JP2000247932A - New amino compound, its preparation and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new amino compound useful for a charge transporting material having durability or a luminescent material. SOLUTION: The amino compound is a compound represented by formula I [A is a group represented by formula II (Ar2 is an aryl) or the like; Ar1 is an arylene; n is 1 or 2; R1 and R2 are each an alkyl, aralkyl, aryl or the like], for example a compound of formula III. The compound of formula I is obtained by reacting a halogen compound represented by formula IV (X is a halogen) and an amino compound of formula V. A photoreceptor for electrophotography excellent in initial electrophotographic properties such as sensitivity, charge transporting properties, initial surface potential, damping factor in the dark or the like and low in fatigue caused from repeated use and an organic electroluminescence element having high emission intensity and a low starting voltage for light emission and excellent in durability are obtained by using the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel amino compound, a method for producing the same, and a use thereof. The amino compound of the present invention can be used for a light-emitting material, an organic photoconductive material, and the like, and more specifically, is useful for an organic electroluminescence element and an electrophotographic photosensitive member used for a surface light source and a display.

[0002]

2. Description of the Related Art Organic photoconductive materials which have been developed as photoreceptors and charge transport materials have many advantages such as low cost, various processability, and no pollution, and many compounds have been proposed. ing.

For example, oxadiazole compounds, hydrazone compounds, pyrazoline compounds, oxazole compounds,
Organic photoconductive materials such as arylamine compounds, benzidine compounds, stilbene compounds, and butadiene compounds have been proposed.

[0004] One of the techniques using a charge transport material is an electrophotographic photosensitive member. The electrophotographic method is one of the image forming methods invented by Carlson. In this method, a photoreceptor is charged by corona discharge, image exposure is performed to form an electrostatic latent image on the photoreceptor, toner is adhered onto the electrostatic latent image, and the electrostatic latent image is developed. Is transferred to paper.

[0005] The basic characteristics required of the photoreceptor in such an electrophotographic system are that an appropriate potential is maintained in a dark place, that the electric charge is less dissipated in the dark place, and that the light is promptly irradiated with light. Dissipating the charge may be mentioned. Conventional electrophotographic photoreceptors have used inorganic photoconductors such as selenium, selenium alloys, zinc oxide and cadmium sulfide. These inorganic photoconductors have advantages such as high durability and a large number of printing presses. However, problems such as high production cost, poor workability, and toxicity have been pointed out.

To overcome these drawbacks, organic photoconductors have been developed. However, conventional electrophotographic photoreceptors using an organic photoconductor as a charge transporting material have a chargeability, sensitivity and sensitivity. At present, it cannot be said that electrophotographic characteristics such as residual potential are always satisfied, and development of a charge transport material having excellent charge transport ability and durability has been desired.

As a technique using a charge transport material, there is an organic electroluminescence device. Electroluminescent devices using organic compounds are expected to be used as inexpensive solid-state large-screen full-color display devices of the light-emitting type, and many studies have been made.

In general, an organic electroluminescence element comprises a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from a cathode and holes are injected from an anode. Further, the electrons and holes are recombined in the light emitting layer, and the energy is emitted as light when the energy level returns from the conduction band to the valence band.

A conventional organic electroluminescent device has a higher driving voltage and lower luminous brightness and luminous efficiency than an inorganic electroluminescent device. In addition, the characteristics deteriorated remarkably and did not reach practical use. In recent years, an organic electroluminescence device in which 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 has attracted attention (Applied Physics Letters, 51, 913). P. 198
7 years).

This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injecting layer to obtain high-luminance green light emission.
It achieves 00 cd / m ² and maximum luminous efficiency of 1.5 lm / W, which is close to the practical range.

[0011] However, the organic electroluminescent elements up to the present have improved the luminous efficiency due to the improved structure, but do not yet have a sufficient luminous brightness. In addition, there is a major problem that the stability upon repeated use is poor. Therefore, for the development of an organic electroluminescent device having a higher emission luminance and having excellent stability upon repeated use, it is desired to develop a charge transport material having excellent charge transport ability and durability. ing.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel amino compound, which is useful as a durable charge transporting material or luminescent material. An object of the present invention is to provide a manufacturing method thereof and its use.

[0013]

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

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In the above general formula (I), A represents the following general formula (I)
I);

Embedded image Represents a group represented by In the general formula (II), Ar ² and Ar ³
Each independently represents a substituted or unsubstituted aryl group. The aryl group includes a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and the like, and is preferably a phenyl group, a biphenyl group, or the like. Examples of the substituent include an alkyl group such as methyl group, ethyl group, n-propyl group and isopropyl group, an alkoxy group such as methoxy group, ethoxy group and propoxy group, an aralkyl group such as benzyl group, a phenyl group, a biphenyl group and a naphthyl group. And a heterocyclic group such as an aryl group, a thienyl group, a furyl group, and a pyridyl group. Preferred substituents are alkyl groups or alkoxy groups. Particularly, a methyl group and a methoxy group are preferable.

In the general formula (I), Ar ¹ represents a substituted or unsubstituted arylene group. As an arylene group,
Phenylene group, biphenylene group, terphenylene group, naphthylene group and the like. Preferred are a phenylene group and a biphenylene group. Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, an aralkyl group such as a benzyl group, a phenyl group, a biphenyl group, and a naphthyl group. And aryl, thienyl, furyl, pyridyl and the like. Preferably it is an unsubstituted arylene group.

In the general formula (I), n represents an integer of 1 or 2. That is, the bonding position of the arylene group Ar1 bonded to the benzene ring in the general formula (II) is 3
Or third and fifth place. When n is 2, the general formula (I
The groups bonded to the benzene ring in I) may be the same or different.

[0017] In the general formula ^{(I), R 1, R} 2 each independently represent an alkyl group, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, R ¹ And R ² may together form a ring.
As an alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an aralkyl group as a benzyl group, and an aryl group as a phenyl group, a biphenyl group,
Examples of the aromatic heterocyclic group such as a naphthyl group include a thienyl group, a furyl group, and a pyridyl group. When R ¹ and R ² together form a ring, the ring together with the nitrogen atom to which R ¹ and R ² are attached, for example;

Embedded image May be formed. Preferably phenyl, biphenyl,
Naphthyl or the like, or a ring formed by integrating R ¹ and R ² ;

Embedded image It is.

When R ¹ and R ² may have a substituent, examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, a methoxy group, an ethoxy group and a propoxy group. And the like.

In particular, when R ¹ and R ² are a substituted aryl, one or both of R ¹ and R ² are represented by the following general formula (III):

Embedded image It is preferably an amino-substituted aryl represented by

In the general formula (III), Ar ⁴ represents an arylene group such as a phenylene group, a biphenylene group, a terphenylene group and a naphthylene group, and is preferably a phenylene group, a biphenylene group or the like. These groups include alkyl groups such as methyl group, ethyl group, n-propyl group and isopropyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aralkyl groups such as benzyl group, phenyl group, biphenyl group and naphthyl group. May have a heterocyclic group such as an aryl group, a thienyl group, a furyl group, or a pyridyl group as a substituent, but is preferably unsubstituted.

[0021] In the general formula (III), R ³ and R ⁴ each independently represents an alkyl group, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, R ³ And R ⁴ may together form a ring. Examples of the alkyl group include a methyl group, an ethyl group, and n-
Examples of the aralkyl group include a benzyl group and the like, examples of the aryl group include a phenyl group, a biphenyl group and a naphthyl group, and examples of the aromatic heterocyclic group include a thienyl group, a furyl group, and a pyridyl group. R ³ and R ⁴
Together form a ring, together with the nitrogen atom to which R ³ and R ⁴ are attached, a ring, for example;

Embedded imageMay be formed. Preferably, phenyl, biphenyl
Or naphthyl or R ¹And R^TwoAre formed together
Ring;

Embedded image It is.

When R ³ and R ⁴ may have a substituent, examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, a methoxy group, an ethoxy group and a propoxy group. And the like.

The amino compound represented by the general formula (I)
It can be manufactured using a specific raw material and utilizing a known chemical reaction. For example, a halogen compound represented by the following general formula (IV);

Embedded image (Wherein A, Ar ¹ and n have the same meanings as above; X represents a halogen atom) and an amino compound represented by the following general formula (V):

Embedded image (Wherein R ¹ and R ² have the same meanings as described above).

Examples of the production of the halogenated compound represented by the general formula (IV) are as shown in the following scheme;

Embedded image A formylated aryl compound represented by the following general formula (VI);

Embedded image (Wherein, Ar ⁵ represents a substituted or unsubstituted arylene group, and X represents a halogen atom) and the following general formula (I
An acetylated aryl compound represented by X);

Embedded image (Wherein, Ar ⁸ represents a substituted or unsubstituted aryl group) to react with a pyrylium salt represented by the following general formula (X);

Embedded image And then subjecting the pyrylium salt to a heat treatment in acetic anhydride in the presence of sodium acetate to obtain a halogenated 1,3,5-triarylbenzene compound represented by the following general formula (XI);

Embedded image (Wherein, Ar ⁵ and Ar ⁸ are as defined above).

In addition, Ar ⁵ is a group represented by A in the general formula (I).
Ar 1 represents the same substituted or unsubstituted arylene group as Ar ^1, and Ar ⁸ represents the same substituted or unsubstituted aryl group as Ar ² in the general formula (II).

In a similar manner, the following general formula (VI)
A formylated aryl compound represented by I);

Embedded image (Wherein, Ar ⁶ represents a substituted or unsubstituted aryl group) and an acetylated aryl compound represented by the following general formula (VIII);

Embedded image (Wherein, Ar ⁷ represents a substituted or unsubstituted arylene group, and X represents a halogen atom), and reacted with the following general formula (XII) pyrylium salt;

Embedded image And subjecting the pyrylium salt to heat treatment in acetic anhydride in the presence of sodium acetate to obtain a halogenated 1,3,5 triarylbenzene compound represented by the following general formula (XIII);

Embedded image (Wherein, Ar ⁶ and Ar ⁷ are in agreement with the above).

Ar ⁶ represents the same substituted or unsubstituted aryl group as Ar ³ in the general formula (II), and Ar ⁷ represents the same substituted or unsubstituted aryl group as Ar ¹ in the general formula (I). Represents an unsubstituted arylene group.

A halogenated 1,3,5-triarylbenzene compound represented by the above general formula (XI) or (XIII) and an amino compound represented by the following general formula (V);

Embedded image (Wherein R ¹ and R ² have the same meanings as in general formula (I)) to give the following general formulas (XIV) and (XV)

Embedded image (Where Ar ^{5 to} Ar ⁸ and R ^{1 to} R ² are as defined above), that is, an amino compound represented by the general formula (I) can be produced.

The synthesis of the above amino compound is carried out in the presence of a basic compound or a transition metal compound catalyst and a solvent in the presence of Ull.
It can be performed by a mann reaction.

The basic compound used for synthesizing the amino compound includes an alkali metal hydroxide, carbonate, and the like.
Bicarbonate, alcoholate and the like are common,
Organic bases such as quaternary ammonium compounds, aliphatic amines and aromatic amines can also be used. In this,
Alkali metal and quaternary ammonium carbonates and bicarbonates are preferably used. In addition, the reaction rate,
From the viewpoints of heat stability and thermal stability, alkali metal carbonates, bicarbonates and alcoholates are most preferred.

As the transition metal or transition metal compound catalyst used in the synthesis, for example, Cu, Fe, Ni, C
Metals such as r, V, Pd, Pt, and Ag, and compounds thereof are used. From the viewpoint of yield, copper, palladium,
Or those compounds 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, cuprous acetate, cupric acetate and the like are preferred. Among them, cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous sulfate, cupric sulfate, cupric chloride, cupric oxide, cupric bromide , Cuprous acetate and cupric acetate are preferred in that they are easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The used amount of the transition metal and its compound is 0.5 to 500 mol% of the halogen compound to be reacted.

The solvent used in the synthesis may be any commonly used solvent, but may be dichlorobenzene, nitrobenzene, dimethylformamide, dimethylsulfoxide,
An aprotic polar solvent such as N-methylpyrrolidone is preferably used.

The reaction is generally carried out at 100 ° C. to 2 ° C. under normal pressure.
The reaction is performed within a temperature range of 50 ° C., but may be performed under pressure. After completion of the reaction, the solid content in the reaction solution is removed, and then the solvent is distilled off under reduced pressure to obtain the desired product.

The following are specific examples of the above-mentioned amino compound. It should be noted that these examples are not intended to limit the amino compounds of the present invention or to disclose them.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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The amino compound represented by the general formula (I) has an excellent charge transport function, particularly an excellent hole transport function, and has excellent 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 can be considered by utilizing such a function. For example, a photoconductor or an organic electroluminescence device Can be suitably used as the charge transport material.

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

The amino compound represented by the general formula (I) is
Although it can be used in any layer of the electrophotographic photoreceptor,
It is desirable to use it as a charge transport material because it has high charge transport properties.

The amino compound acts as a charge transporting substance and can transport the charge generated by light absorption or injected from the electrode very efficiently, so that it is possible to obtain a photoreceptor excellent in sensitivity and high-speed response. is there. Further, since the compound is excellent in ozone resistance and light stability, a photosensitive member having excellent durability can be obtained.

As the electrophotographic photoreceptor, for example, a photoreceptor obtained by forming a single-layer type photosensitive layer in which a charge generating material and a charge transporting material are dispersed in an appropriate binder resin on a conductive support, A photoconductor in which a charge generation layer and a charge transport layer are laminated as a photosensitive layer on a support, and a photoconductor in which a subbing layer or a conductive layer is formed on a support, and a photosensitive layer is formed thereon. ,
Alternatively, a photoreceptor obtained by sequentially laminating an undercoat layer, a photosensitive layer and a surface protective layer on a support may be used.

As the support, copper, aluminum, iron,
A foil of nickel, stainless steel, or the like, or a plate or drum shape is used. These metals are vacuum-deposited or electroless-plated on paper or plastic drums, or a layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide is applied or deposited on paper or plastic drums. Can also be used. In general, aluminum is used.For example, after extrusion processing, a drawn aluminum pipe is cut, and the outer surface thereof is cut to about 0.2 to 0.3 mm using a cutting tool such as a diamond tool. After finishing (cutting tube) or deep drawing of aluminum disc into cup shape, then ironing the outer surface (DI tube), impact processing of aluminum disc into cup shape After that, the outer surface is finished by ironing (EI tube), and the outer surface is subjected to cold drawing after extrusion (ED tube). Further, those obtained by further cutting these surfaces may be used.

When an undercoat layer is formed 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 an undercoat layer. Alternatively, it is 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. In this case, as a material used for the undercoat layer, polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, or the like is appropriate, 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 organic metal complexes are preferably used. The thickness of the undercoat layer is 0.1 to 5 μm.
m, 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 vacuum-deposited,
Alternatively, it is formed by dissolving in an appropriate solvent and applying, or by applying and drying a coating solution prepared by dispersing the pigment in an appropriate solvent or, if necessary, in a solution in which a binder resin is dissolved. From the standpoint of adhesiveness, those dispersed in a resin are good. The thickness of the charge generation layer is desirably about 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 resins may be used in combination.

Examples of the charge generating material used in the charge generating layer include azo pigments (including bisazo pigments and trisazo pigments), triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, and cyanine dyes. Organic dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indathrone pigments, squarium pigments, and phthalocyanine pigments Pigments and dyes. Other than these, any material can be used as long as it absorbs light and generates charge carriers at an extremely high probability, but in particular, azo-based (bis-based, tris-based) pigments and phthalocyanine pigments can be used. Is preferred.

Examples of the resin used together with the charge generating material include a saturated polyester resin, a polyamide resin, an acrylic resin, an ethylene-vinyl acetate copolymer, an ion-crosslinked olefin copolymer (ionomer),
Styrene-butadiene block copolymer, polyarylate, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin, polyacetal resin, thermoplastic binder such as phenoxy resin, epoxy resin, urethane resin, silicone Thermosetting binders such as resins, phenolic resins, melamine resins, xylene resins, alkyd resins, thermosetting acrylic resins, photocurable resins, photoconductive resins such as poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene Can be used.

The above-mentioned charge generating material is used together with these resins together with alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylacetamide and sulfoxides such as dimethyl sulfoxide. , Tetrahydrofuran, dioxane, ethers such as ethylene glycol monomethyl ether, methyl acetate,
Esters such as ethyl acetate, chloroform, methylene chloride, dichloroethane, carbon tetrachloride, aliphatic halogenated hydrocarbons such as trichloroethylene, or benzene,
A photosensitive coating solution prepared by dispersing or dissolving in an organic solvent such as aromatics such as toluene, xylene, ligroin, monochlorobenzene, and dichlorobenzene is coated on the conductive support and dried to form a charge generation layer. Is provided. A charge transport layer containing a charge transport material and a binder resin is provided on the charge generation layer formed as described above.

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

In forming the charge transport layer of the photoreceptor, a coating solution obtained by dissolving the charge transport material and the binder resin in an appropriate solvent is applied on the above-mentioned charge generation layer, and dried. The thickness of the charge transport layer is 5 to 60 μm.
m, preferably about 10 to 50 μm.

Further, the content of the charge transporting material in the charge transporting layer cannot be specified unconditionally depending on the kind thereof, but it is generally 0.02 to 2 parts by weight, preferably 0.5 to 2 parts by weight with respect to 1 part by weight of the binder resin. It is desirable to add 〜1.2 parts by weight. The charge transporting material used for the photoreceptor has a general formula (I)
May be used alone or in combination with another charge transporting material.

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,
Hole transport materials such as tetraphenylbenzidine compounds and azine compounds, fluorenone compounds, anthraquinodimethane compounds, diphenoquinone compounds, stilbenequinone compounds, thiopyran dioxide compounds, oxadiazole compounds, perylenetetracarboxylic acid compounds, and fullerene compounds. Electron transport materials such as olenylidenemethane compounds, anthraquinone compounds, anthrone compounds, cyanovinyl compounds, etc.
Various compounds can be used.

Examples of the solvent used for forming the charge transport layer include ketones such as benzene, toluene, xylene, and chlorobenzene, alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl acetate and ethyl cellosolve; Examples thereof include halogenated hydrocarbons such as carbon chloride, carbon tetrabromide, chloroform, dichloromethane, and tetrachloroethane; ethers such as tetrahydrofuran and dioxane; dimethylformamide, dimethylsulfoxide, and diethylformamide.
These solvents may be used alone or in combination of two or more.

In the case of forming a laminated photosensitive layer as described above, the application of the charge transport layer and the charge generation layer can be performed by a known method using various coating apparatuses. Specifically, dip coating, spray coating,
Various coating methods such as a spinner coating method, a blade coating method, a roller coating method, and a wire bar coating method can be used. Also,
In the case of the laminated photosensitive layer as described above, especially in the charge transport layer, an additive for improving film formability or flexibility, an additive for suppressing accumulation of residual potential, and the like are known. May be added.

Specific examples of these compounds include halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, o-terphenyl, m-terphenyl, p-terphenyl, diethylbiphenyl, hydrogenated terphenyl,
Plasticizers such as diisopropylbiphenyl, benzylbiphenyl, diisopropylnaphthalene, dibenzofuran, 9,10-dihydroxyphenanthrene, chloranil, tetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, dicyanobenzoquinone, tetrachlorophthalic anhydride, 3,5 -Electron-withdrawing sensitizers such as dinitrobenzoic acid and cyanovinyl compounds, and sensitizers such as methyl violet, rhodamine B, cyanine dyes, pyrylium salts and thiapyrylium salts can be used.

The greater the amount of the plasticizer added, the more the internal stress of the layer is reduced. Therefore, when the photosensitive layer is formed by laminating the charge transport layer and the charge generation layer, the charge transport layer and the charge generation layer The adhesion between the photosensitive layer and the support is improved, and 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.
Parts by weight, preferably 5 to 80 parts by weight, more preferably 1 to
It is desirable to add about 0 to 50 parts by weight. The sensitizer is added in an amount of 0.01 to 100 parts by weight of the charge transport material.
It is desirable to add about 20 to 20 parts by weight, preferably about 0.1 to 10 parts by weight, more preferably about 0.5 to 8 parts by weight.

Further, an antioxidant may be added to the photosensitive layer of the photosensitive member, particularly to the charge transport layer, for the purpose of preventing ozone deterioration. Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, hydroquinone, spirochroman, spiroidanone, hydroquinoline and derivatives thereof, and organic phosphorus compounds and organic sulfur compounds.

As the amount of the antioxidant added increases, the adhesiveness improves. However, when the amount is too large, problems such as a decrease in mechanical strength and sensitivity are caused. When the amount is too small, a sufficient effect of antioxidation is obtained. I can't. Therefore, it is desirable to add about 0.1 to 50 parts by weight, preferably about 1 to 30 parts by weight, more preferably about 3 to 20 parts by weight based on 100 parts by weight of the charge transporting material. When the antioxidant and the plasticizer are used in combination, the total amount of the additives is 1 to 120 parts by weight, preferably 5 to 120 parts by weight.
It is desirable to add 100 parts by weight, more preferably about 10 to 80 parts by weight. If the solubility of the plasticizer or antioxidant is low or the melting point is high, crystal precipitation is caused or the adhesiveness is not improved so much. Preferably, it is used.

A conductive layer may be provided between the support constituting the photosensitive member and the undercoat layer. As the conductive layer, aluminum,
Iron, nickel and other metal materials dispersed in resin,
A material obtained by dispersing a metal oxide such as conductive tin oxide, titanium oxide, antimony oxide, zirconium oxide, and ITO (indium, tin oxide solid solution) in a resin is preferably used.

Further, 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 the material used for the surface protective layer, a polymer such as an acrylic resin, a polyaryl resin, a polycarbonate resin, a urethane resin, a thermosetting resin, a photocurable resin, or a low-resistance substance such as tin oxide or indium oxide may be used. Dispersed materials can be used. Further, an organic plasma polymerized film may be used as the surface protective layer. The organic plasma polymerized film may optionally contain oxygen, nitrogen, halogen, and atoms of Group 3 and 5 of the periodic table.

When a single-layer type photosensitive layer is formed,
The charge generating material and the charge transporting material may be formed by dip coating or spin coating using a solution dissolved in an appropriate resin together with a binder resin.

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

FIGS. 1 to 4 schematically show an embodiment of an organic electroluminescence device. In FIG. 1, reference numeral (1) denotes 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 organic hole injecting and transporting layer contains the amino compound represented by the general formula (I).

In FIG. 2, (1) is an anode, on which an organic hole injecting and transporting layer (2) and an organic light emitting layer (3), an electron injecting and transporting layer (5) and a cathode (4) are provided. The organic hole injecting / transporting layer and / or the organic light emitting layer contains the amino compound represented by the general formula (I).

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

In FIG. 4, (1) denotes an anode, on which an organic light emitting layer (3) and a cathode (4) are sequentially laminated, and an organic light emitting material is provided on the organic light emitting layer. (6) and a charge transport material (7) are used, 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 a lead wire (8), and a voltage is applied to the anode (1) and the cathode (4) to form an organic light emitting layer. (3) emits light.

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

The specific amino compound represented by the general formula (I) has a small ionization potential and a large hole transporting ability, so that the light emission starting voltage required for causing the organic electroluminescence device to emit light may be low. It is considered that stable long-term light emission is possible. When an amino compound is used as an organic luminous body, it is considered that the function of the amino compound itself as a luminescent material and the thermal stability contribute.

As the conductive substance used as the anode (1) of the organic electroluminescence element, those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc,
Tungsten, silver, gold, platinum and their alloys,
Tin oxide, indium oxide, antimony oxide, zinc oxide,
A conductive metal compound such as zirconium oxide and an organic conductive resin such as polythiophene and polypyrrole are used.

As the metal forming the cathode (4), 4e
Those having a work function smaller than V are preferable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, and alloys thereof are used. The anode and the cathode may be formed by two or more layers if necessary.

In the organic electroluminescence element, at least one of the anode (1) and the cathode (4) must 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 easily impaired, so that the anode is preferably a transparent electrode.

In the case of forming a transparent electrode, the above-mentioned conductive substance is used on a transparent substrate by means of vacuum deposition, sputtering, or the like, or by means of a sol-gel method or a method of dispersing and applying in a resin or the like. In this case, a desired light-transmitting property and conductivity may be ensured.

The transparent substrate is not particularly limited as long as it has a proper strength and is transparent without being affected by heat due to vapor deposition or the like when an organic electroluminescent device is manufactured. Alternatively, a transparent resin such as polyethylene, polypropylene, polyethersulfone, polyetheretherketone, or polyester can be used. Examples of transparent electrodes formed on a glass substrate include ITO and NESA.
Etc. are known, but these may be used.

As an example of manufacturing an organic electroluminescence device, a structure (FIG. 1) in which an amino compound is used for an organic hole injection / transport layer will be described. First, an organic hole injection / transport layer (2) is formed on the above-mentioned anode (1).
The organic hole injecting and transporting layer (2) may be formed by vapor deposition of the amino compound represented by the general formula (I),
A solution in which the amino compound is dissolved or a solution in which the amino compound is dissolved together with an appropriate resin may be formed by a coating method such as dip coating or spin coating.

When the film is formed by a vapor deposition method, the film thickness is usually about 1 to 500 nm.
It may be formed to about 1000 nm. As the film thickness is larger, the applied voltage for emitting light needs to be higher, and the luminous efficiency is poor, and the organic electroluminescent element is likely to be deteriorated. Further, when the film thickness is small, the luminous efficiency is improved, but the breakdown is easy, and the life of the element is shortened.

The compound of the formula (I) can be used in combination with other charge transporting materials. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazoline, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane, Stilbene, butadiene,
Examples include benzidine-type triarylamines, diamine-type triarylamines, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. Any compound can be used as long as it has a hole injection effect, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron transport material, and has excellent thin film forming ability.

An organic light emitting layer is formed on the organic hole injecting and transporting layer (2). As the organic light emitting material used for the organic light emitting layer, a known light emitting auxiliary material 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-phenylbenzo Oxazole, aluminum trisoxine, magnesium bisoxin, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8-quinolinolate) aluminum oxide, indium trisoxin, aluminum tris (5-methyloxin), lithium oxine, gallium Trisoxin, calcium bis (5-chlorooxin), polyzinc-bis (8-hydroxy-5)
-Quinolinolyl) methane, dilithium epindridione, zinc bisoxin, 1,2-phthaloperinone, 1,
Examples thereof include 2-naphthaloperinone and tris (8-hydroxyquinoline) aluminum complex.

Further, general fluorescent dyes such as coumarin dyes, perylene dyes, pyran dyes, thiopyran dyes, polymethine dyes, merocyanine dyes, imidazole dyes and the like can also be used. Among these, particularly preferred materials include chelated oxinoid compounds. The organic light-emitting layer may have a single-layer structure of the above-described light-emitting substance, or may have a multi-layer structure in order to adjust characteristics such as emission color and emission intensity. Also, mixing two or more kinds of luminescent substances,
The light emitting layer may be doped.

The organic light-emitting layer (3) may be formed by vapor deposition of the above-described light-emitting substance, or a solution in which the light-emitting substance is dissolved or a solution in which a suitable resin is dissolved is subjected to dip coating or spin coating. It may be formed by such a coating method. Further, an amino compound represented by the general formula (I) may be used as a light emitting substance.

When the film is formed by the vapor deposition method, the film thickness is usually about 1 to 500 nm.
The thickness may be about 000 nm. It is necessary to increase the applied voltage for emitting light as the film thickness to be formed is larger,
The luminous efficiency is poor, and the organic electroluminescent element is likely to be deteriorated. Further, when the film thickness is small, the luminous efficiency is improved, but the breakdown is easy, and the life of the element is shortened.

Next, the above-mentioned cathode (4) is formed on the organic light emitting layer (3) to obtain an organic electroluminescence device.

As shown in FIG. 2, when the hole injecting and transporting layer (2), the organic light emitting layer (3), and the electron injecting and transporting layer (5) are laminated, the hole injecting and transporting layer and the organic light emitting layer are stacked. An amino compound can be used for either one or both. In this case, the hole injecting / transporting layer can be formed using the same procedure as described above with or without using an amino compound. The organic light emitting layer can be formed in the same procedure as described above, and an amino compound may be used as the light emitting substance. When an amino compound is used as a light emitting substance, it is preferable to mix another light emitting substance or dope the organic light emitting layer.

The electron injecting / transporting layer can be formed by a conventionally known method such as a vapor deposition method and a coating method using an electron transporting material, similarly to the hole injecting / transporting layer and the organic light emitting layer.

Examples of the electron transporting material include fluorenone, anthraquinodimethane, diphenoquinone, stilbenquinone, thiopyrandioxide, oxadiazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinone, anthrone and derivatives thereof. However, it has the ability to transport electrons, has an excellent electron-injection effect on the light-emitting layer or the light-emitting substance, and transfers excitons generated in the light-emitting layer to the hole-injection layer or the hole-transport material. The compound is not limited to these as long as it is a compound that prevents and is excellent in the ability to form a thin film. In addition, sensitization can be achieved by adding an electron accepting substance or an electron donating substance to the charge transporting material.

As shown in FIG. 3, when the organic light emitting layer (3) and the electron injection / transport layer (5) are laminated on the anode (1), an amino compound is used in the same procedure as described above. An organic light emitting layer can be formed. Further, the electron injection / transport layer can be formed in the same manner as described above.

In each of the above structures, the hole injecting and transporting layer may have a two-layered structure of a hole injecting layer and a hole transporting layer by separating the hole injecting function and the hole transporting 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.

As the hole transporting layer, known hole transporting materials can be used. For example, N, N'-diphenyl-
N, N'-bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-bis (4-methylphenyl) -1,1 '-
Diphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-bis (1-naphthyl) -1,1'-diphenyl-4,4'-diamine, N, N'-diphenyl-
N, N'-bis (2-naphthyl) -1,1'-diphenyl-4,4'-diamine, N, N'-tetra (4-methylphenyl) -1,1'-diphenyl-4,4 ' -Diamine, N, N'-tetra (4-methylphenyl) -1,
1'-bis (3-methylphenyl) -4,4'-diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-bis (3-methylphenyl)
-4,4'-diamine, N, N'-bis (N-carbazolyl) -1,1'-diphenyl-4,4'-diamine,
4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, N, N ′, N ″ -triphenyl-N,
N ′, N ″ -tris (3-methylphenyl) -1,3,
5-tri (4-aminophenyl) benzene, 4,4 ',
4 "-tris [N, N ', N" -triphenyl-N,
N ', N "-tris (3-methylphenyl)] triphenylamine, N, N'-diphenyl-N, N'-bis (4-methylphenyl) -1,1'-bis (3-methylphenyl) -4,4'-diamine, N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine and the like. You may mix and use more than one kind.

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.

In order to form a single-layer organic light emitting layer as shown in FIG. 4, an organic light emitting material and a charge transporting material may be mixed and formed by a co-evaporation method, or an organic light emitting material and a charge transporting material may be mixed. It may be formed by dip coating or spin coating using a solution in which a transport material is dissolved or a solution in which a transport material is dissolved. As the charge transporting material, the above-described electron transporting material or hole transporting material is used, and these may be used as a mixture, or two or more materials having the same transportability may be used as a mixture. When the organic light emitting layer is formed by a vapor deposition method, the thickness is usually 5 to 200 nm. When the organic light emitting layer is formed by a coating method, the thickness may be about 10 to 500 nm. In the case of the coating method, particularly good characteristics can be obtained when a photoconductive resin such as polyvinyl carbazole or polyvinyl acetylene is used as the resin to be mixed and used. The case where each layer is formed on the anode (1) has been described above as an example. However, each layer may be formed on the cathode (4) in the same procedure as described above.

Nichrome wire, gold wire, copper wire,
By connecting an appropriate lead wire (8) such as a platinum wire and applying an appropriate voltage (Vs) to both electrodes, the organic electroluminescence element emits light.

The organic electroluminescence device of the present invention is applicable to various display devices, display devices, and the like. Hereinafter, the present invention will be described with reference to Examples. In the examples, “parts” means, unless otherwise specified.
Represents "parts by weight".

Synthesis Example 1 (Synthesis of Compound (58)) A 200 ml three-necked flask equipped with a water-cooled condenser was charged with p-
Tolualdehyde (5.0 g, 0.042 mol) and 4′-bromoacetophenone (16.6 g, 0.083 mol) were added, and toluene (20 ml) was added and dissolved. next,
Boron trifluoride-diethyl ether complex 17.7g
(0.125 mol) was dissolved in 10 ml of toluene, and this solution was added with stirring at room temperature, and then heated to reflux for 8 hours. The reaction solution was cooled to room temperature, 200 ml of 1,4-dioxane was added thereto, and the precipitated crystals were filtered and dried under reduced pressure to obtain 13.7 g (yield 58%) of the following pyrylium salt as yellow crystals.

Embedded image

Next, 8.0 g (0.014 mol) of the above pyrylium salt and 2.3 g (0.028 mol) of sodium acetate were placed in a 100 ml three-necked flask, and 25 ml of acetic anhydride was added thereto. Heated to reflux for hours. The reaction solution is cooled to room temperature, water and dichloromethane are added thereto, and the product is extracted into an organic layer. After that, the solvent is distilled off under reduced pressure. The obtained reaction mixture is subjected to silica gel column chromatography (developing solvent: hexane / toluene). = 1/1
(Vol / vol)) to obtain 3.2 g (yield 48%) of the following brominated triphenylbenzene derivative as pale brown needle-like crystals.

Embedded image

Then, in a 100 ml three-necked flask,
1.5 g of the above brominated triphenylbenzene derivative
(0.003 mol), the following benzidine derivatives;

Embedded image 2.7 g (0.006 mol), 0.75 g (0.0078 mol) of sodium-t-butoxide, 0.04 g (0.00017 mol) of palladium acetate, and 0.14 g (0.00067 mol) of tri-t-butylphosphine are added. After adding 15 ml of o-xylene as a solvent thereto,
The mixture was stirred at 120 ° C. for 3 hours under a nitrogen atmosphere. The solution was cooled to room temperature, 100 ml of dichloromethane was added to dissolve the contents, and the insolubles were filtered off. The solvent of the residue was distilled off under reduced pressure. The obtained reaction mixture is subjected to silica gel column chromatography (developing solvent: hexane / toluene =
1/1 (vol / vol)), and purify the target compound (5
8) 3.1 g (83% yield) were obtained as pale yellow crystals.

The melting point of the obtained compound is 167 ° -169 ° C.
Met. The following results were obtained by analyzing the molecular formula. The molecular formula was analyzed using a CHN analyzer. The same applies to the following synthesis examples. Molecular formula: C ₈₇ H ₆₈ N ₄ Calculated value (%) C: 89.35% H: 5.86%
N: 4.79% Analysis value (%) C: 89.29% H: 5.90%
N: 4.81%

Synthesis Example 2 (Synthesis of Compound (57)) The same procedure as in Synthesis Example 1 was repeated except that 4′-bromoacetophenone was used instead of 4′-bromoacetophenone to synthesize the desired compound (57). 4. In a 200 ml three-necked flask equipped with a water-cooled condenser, p-tolualdehyde was added.
0 g (0.042 mol) and 20.4 g (0.083 mol) of 4'-iodoacetophenone were added, and 20 ml of toluene was added thereto to dissolve. Next, 17.7 g (0.125 mol) of a boron trifluoride-diethyl ether complex was dissolved in 10 ml of toluene, and this solution was added with stirring at room temperature, followed by heating to reflux for 8 hours. The reaction solution was cooled to room temperature, 200 ml of 1,4-dioxane was added thereto, and the precipitated crystals were filtered and dried under reduced pressure.
14.5 g (yield 52%) was obtained as yellow crystals.

Embedded image

Next, 9.3 g (0.014 mol) of the above pyrylium salt and 2.3 g (0.028 mol) of sodium acetate were placed in a 100 ml three-necked flask, and 25 ml of acetic anhydride was added thereto. Heated to reflux for hours. The reaction solution is cooled to room temperature, water and dichloromethane are added thereto, and the product is extracted into an organic layer. After that, the solvent is distilled off under reduced pressure. The obtained reaction mixture is subjected to silica gel column chromatography (developing solvent: hexane / toluene). = 1/1
(Vol / vol)) to obtain 3.7 g (yield 49%) of the following iodinated triphenylbenzene derivative as light brown needle-like crystals.

Embedded image

Subsequently, in a 100 ml three-necked flask,
1.7 g of the above iodinated triphenylbenzene derivative
(0.003 mol), the following benzidine derivatives;

Embedded image 2.7 g (0.006 mol), 0.75 g (0.0078 mol) of sodium-t-butoxide, 0.04 g (0.00017 mol) of palladium acetate, and 0.14 g (0.00067 mol) of tri-t-butylphosphine are added. After adding 15 ml of o-xylene as a solvent thereto,
The mixture was stirred at 120 ° C. for 3 hours under a nitrogen atmosphere. The solution was cooled to room temperature, 100 ml of dichloromethane was added to dissolve the contents, and the insolubles were filtered off. The solvent of the residue was distilled off under reduced pressure. The obtained reaction mixture is subjected to silica gel column chromatography (developing solvent: hexane / toluene =
1/1 (vol / vol)), and purify the target compound (5
7) 3.1 g (83% yield) were obtained as pale yellow crystals.

The results of analysis of the obtained compound were the same as those in Synthesis Example 1.

Application of Electrophotographic Photoreceptor to Charge Transport Material Example 1 Trisazo compound represented by the following structural formula

Embedded image 0.45 parts of a polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.) and 0.45 parts of the resin were dispersed together with 50 parts of cyclohexanone by a sand mill. The obtained dispersion of the trisazo compound was applied on an aluminum drum of 80φ by a dip coating method so that a dry film thickness became 0.3 g / m ^2, and then dried. On the charge generation layer thus obtained, 50 parts of the amino compound (2) and a polycarbonate resin (Panlite K-1300; manufactured by Teijin Chemicals Ltd.)
A solution prepared by dissolving 50 parts in 400 parts of 1,4-dioxane was applied to a dry film thickness of 20 μm and dried to form a charge transport layer. Thus, an electrophotographic photoreceptor having two photosensitive layers was obtained.

The photoreceptor thus obtained was subjected to -6K using a commercially available electrophotographic copying machine (EP-540, manufactured by Minolta Co.).
V, the initial surface potential V ₀ (V), and the exposure amount E _1/2 (lux ·
sec) The decay rate DDR ₁ (%) of the initial potential when left in a dark place for 1 second was measured.

Examples 2 to 4 In the same manner and in the same manner as in Example 1, the amino compound (6) was used in place of the amino compound (2) used in Example 1.
Photoconductors using (7) and (8) were produced. The obtained photoreceptor was treated in the same manner as in Example 1,
V ₀ , E _1/2 and DDR ₁ were measured.

Example 5 Bisazo compound represented by the following structural formula

Embedded image0.45 parts, polystyrene resin (molecular weight 40,000)
0.45 parts with 50 parts of cyclohexanone
Disperse with water. Dispersion of the obtained bisazo compound
Is dried on a 80φ aluminum drum by dip coating.
0.3g / m thickness ^TwoAfter applying so that it becomes
Let dry.

On the charge generation layer thus obtained, 50 parts of the amino compound (13) and 50 parts of a polyarylate resin (U-100; manufactured by Unitika) were dissolved in 400 parts of 1,4-dioxane. The solution was dried to a thickness of 25 μm.
And dried to form a charge transport layer. Thus, an electrophotographic photoreceptor having two photosensitive layers was obtained.

Examples 6 to 8 In the same manner and in the same manner as in Example 5, the amino compound (1) was used in place of the amino compound (13) used in Example 5.
4), (17), and photoconductors using (20) were prepared.
With respect to the photoreceptor thus obtained, V ₀ , E _1/2 , and DDR ₁ were measured in the same manner as in Example 1.

Example 9 Polycyclic quinone pigment represented by the following structural formula

Embedded image 0.45 parts, polycarbonate resin (Panlite K-1
3000: manufactured by Teijin Chemicals Ltd.) 0.45 part was dispersed with a sand mill together with 50 parts of dichloroethane, and the resulting dispersion of the polycyclic quinone pigment was placed on an 80φ aluminum drum.
It was applied so that the dry film thickness was 0.4 g / m ^2, and then dried. A solution-dried film in which 60 parts of the amino compound (25) and 50 parts of a polyarylate resin (U-100: manufactured by Unitika) are dissolved in 400 parts of 1,4-dioxane on the charge generation layer thus obtained. It was applied to a thickness of 18 μm and dried to form a charge transport layer. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was produced.

Examples 10 to 11 In the same manner as in Example 9, the same structures were used, except that the amino compounds (26) and (33) were used instead of the amino compound (25) used in Example 9. A photoreceptor was produced. With respect to the photoreceptor thus obtained, V ₀ , E _1/2 , and DDR ₁ were measured in the same manner as in Example 1.

Example 12 0.45 part of titanyl phthalocyanine and 0.45 part of a butyral resin (BX-1 manufactured by Sekisui Chemical Co., Ltd.) were dispersed together with 50 parts of dichloroethane by a sand mill, and the resulting dispersion of the phthalocyanine pigment was mixed with 80φ. And dried on the aluminum drum having a dry film thickness of 0.3 μm. A solution obtained by dissolving 50 parts of an amino compound (35) and 50 parts of a polycarbonate resin (PC-Z: manufactured by Mitsubishi Gas Chemical Company) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained. Was applied to a dry film thickness of 18 μm and dried to form a charge transport layer. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was produced. For the photoreceptor thus obtained, V ₀ , E _1/2 , D
It was measured RR _1.

Example 13 50 parts of copper phthalocyanine and 0.2 parts of tetranitro copper phthalocyanine were dissolved in 500 parts of 98% concentrated sulfuric acid with sufficient stirring, and the mixture was poured into 5000 parts of water. After precipitating the conductive material composition, it was filtered, washed with water, and dried at 120 ° C. under reduced pressure. 10 parts of the photoconductive composition thus obtained are 22.5 parts of a thermosetting acrylic resin (Acryduk A405: manufactured by Dainippon Ink) and 7.5 parts of a melamine resin (Super Beckamine J820: manufactured by Dainippon Ink). Then, 15 parts of the amino compound (43) were put in a ball mill pot together with 100 parts of a mixed solvent in which the same amounts of methyl ethyl ketone and xylene were mixed, and dispersed for 48 hours to prepare a photosensitive coating solution. It was spray-coated on a drum and dried to form a photosensitive layer of about 15 μm. In this way,
A single-layer photoreceptor was prepared. The photosensitive member thus obtained was subjected to the same method as in Example 1, except that the corona charge was + 6K.
V, V ₀ , E _1/2 , and DDR ₁ were measured.

Examples 14 to 15 In the same manner as in Example 13, except that the amino compound (44) and (49) were used in place of the amino compound (43) used in Example 13, respectively. The body was made. With respect to the photoreceptor thus obtained, V ₀ , E _1/2 , and DDR ₁ were measured in the same manner as in Example 13. Table 1 summarizes the measurement results of V ₀ , E _1/2 , and DDR ₁ of the photoreceptors obtained in Examples 1 to 15.

[0125]

[Table 1]

As can be seen from Table 1, the photoreceptor of this embodiment has a sufficient charge retention ability even in a laminated type or a single-layer type, and has a dark decay rate small enough to be usable as a photoreceptor. Is also excellent. Further, a repetitive real-photographing test was performed on the photoreceptor of Example 15 at the time of positive charging using a commercially available electrophotographic copying machine (manufactured by Minolta; EP-350Z). In the final image, a clear image was obtained with excellent gradation and no change in sensitivity. This shows that the photoreceptor of the present invention has stable repetition characteristics.

Example 16 Application to Organic Electroluminescence Device Example 16 A thin film having a thickness of 50 nm was formed on an indium-tin oxide-coated glass substrate by vapor deposition of an amino compound (10) as an organic hole injecting and transporting layer. Next, as an organic light emitting layer, aluminum trisoxine was deposited to a thickness of 50 nm by evaporation.
A thin film was formed to have a thickness of. Further, as the cathode, a thin film was formed by vapor deposition of magnesium to have a thickness of 200 nm. As described above, an organic electroluminescence device was manufactured.

Examples 17 to 19 In Example 16, amino compounds (13), (18) and (20) were used instead of using amino compound (10).
An organic electroluminescent device was produced in exactly the same manner as in Example 16 except for changing the above.

Example 20 An amino compound (25) was deposited as an organic hole injecting and transporting layer on a substrate of indium-tin oxide-coated glass by vapor deposition.
A thin film was formed so as to have a thickness of 0 nm. Next, 100 nm of aluminum trisoxine was used as an organic light emitting layer.
A thin film was formed to have a thickness of. Next, as an organic electron injection / transport layer, the following oxadiazole compound;

Embedded image Was deposited to a thickness of 50 nm to form a thin film. Further, as a cathode, magnesium is deposited by vapor deposition.
A thin film was formed to a thickness of 00 nm. As described above, an organic electroluminescence device was manufactured.

Examples 21 to 23 The procedure of Example 20 was repeated, except that the amino compound (30), (38) or (46) was used instead of the compound (25). An organic electroluminescence device was manufactured.

Example 24 On a substrate of indium-tin oxide-coated glass, an amino compound (48) was deposited as an organic light emitting layer by evaporation to a thickness of 50 nm.
To form a thin film. Next, the following oxadiazole compound as an organic electron injection / transport layer;

Embedded image Was formed to a thickness of 20 nm by vapor deposition. Further, as a cathode, a thin film was formed by vapor deposition of Mg and Ag at an atomic ratio of 10: 1 so that the thickness became 20 nm. As described above, an organic electroluminescence device was manufactured.

Example 25 A compound (50) was vacuum-deposited on a glass substrate coated with indium-tin oxide to form a hole injection layer having a thickness of 20 nm. Next, N, N'-diphenyl-N, N '-(3
-Methylphenyl) -1,1'-biphenyl-4,4 '
-Diamine was vacuum deposited to form a hole transport layer having a thickness of 40 nm. Next, tris (8-hydroxyquinoline)
A thin film was formed by vapor deposition of an aluminum complex so as to have a thickness of 50 nm. Further, as a cathode, a thin film was formed by vapor deposition of Mg and Ag at an atomic ratio of 10: 1 so as to have a thickness of 200 nm. As described above, an organic electroluminescence device was manufactured.

Example 26 On an indium-tin oxide coated glass substrate, N, N'-
Diphenyl-N, N '-(3-methylphenyl) -1,
1′-biphenyl-4,4′-diamine was vacuum-deposited to form a 60-nm-thick hole injection / transport layer. next,
Tris (8-hydroxyquinine) aluminum complex and amino compound (53) were mixed at a ratio of 3: 1 by vacuum evaporation to give 6
The light emitting layer was formed so as to have a thickness of 0 nm. further,
As a cathode, a thin film was formed by vapor deposition of Mg and Ag at an atomic ratio of 10: 1 to a thickness of 200 nm. As described above, an organic electroluminescence device was manufactured.

Example 27 On a glass substrate coated with indium-tin oxide, compound (5
5) was dissolved in dichloromethane, and a hole injection / transport layer having a thickness of 50 nm was obtained by spin coating. further,
After forming a light emitting layer to a thickness of 20 nm by vapor deposition of a tris (8-hydroxyquinoline) aluminum complex, the following oxadiazole compound;

Embedded image Was formed into a 20 nm-thick electron injection / transport layer by vapor deposition. Further, as a cathode, a thin film was formed by vapor deposition of Mg and Ag at an atomic ratio of 10: 1 so as to have a thickness of 200 nm. As described above, an organic electroluminescence device was manufactured.

Examples 28 to 29 Organic electroluminescence was carried out in the same manner as in Example 27 except that amino compounds (57) and (58) were used instead of compound (55). An element was manufactured.

Example 30 A compound (62), a tris (8-hydroxyquinoline) aluminum complex and polymethyl methacrylate were dissolved in tetrahydrofuran at a weight ratio of 3: 2: 5 on an indium-tin oxide-coated glass substrate. A light emitting layer having a thickness of 100 nm was formed by spin coating. Next, as a cathode, a thin film was formed to a thickness of 200 nm by vapor deposition of Mg and Ag at an atomic ratio of 10: 1.
As described above, an organic electroluminescence device was manufactured.

Comparative Example 1 The following amino compound as an organic hole injecting and transporting layer on an indium-tin oxide coated glass substrate:

Embedded image Was formed into a thin film having a thickness of 50 nm by vacuum evaporation. Next, as an organic light emitting layer, a thin film was formed by vacuum deposition of aluminum trisoxine to a thickness of 50 nm. As described above, an organic electroluminescence device was manufactured.

Evaluation Regarding the organic electroluminescent devices obtained in Examples 16 to 30 and Comparative Example 1, the light emission starting voltage when a DC voltage was applied using the glass electrode as an anode, the maximum light emission luminance and the light emission start voltage at that time Was measured. Table 2 summarizes the measurement results.

[0139]

[Table 2]

As can be seen from Table 2, the organic electroluminescence device of the present invention exhibited high light emission luminance even at a low voltage. Further, when the organic electroluminescent device of Example 21 of the present invention was continuously emitted at a current density of 1 mA / cm ² , stable emission was observed for 1000 hours or more. The organic electroluminescent device of the present invention achieves an improvement in luminous efficiency, luminous luminance and a long life of the device, and is used together with a luminescent material, a luminescent auxiliary material, a charge transport material, a sensitizer, and a resin. However, the present invention is not limited to element constituent materials such as an electrode material and an element manufacturing method.

[0141]

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

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of one configuration example of an organic electroluminescence element.

FIG. 2 is a schematic cross-sectional view of one configuration example of an organic electroluminescence element.

FIG. 3 is a schematic cross-sectional view of one configuration example of an organic electroluminescence element.

FIG. 4 is a schematic cross-sectional view of one configuration example of an organic electroluminescence 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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 471/06 C07D 471/06 4C204 C09K 11/06 620 C09K 11/06 620 4H006 655 655 G03G 5/06 312 G03G 5/06 312 H05B 33/14 H05B 33/14 A 33/22 33/22 D (72) Inventor Keiichi Furukawa 2-13-13 Azuchicho, Chuo-ku, Osaka-shi, Osaka Osaka International Building Minolta F Term (Reference) 2H068 AA20 AA21 BA12 BA14 BA16 3K007 AB02 AB06 AB11 CA01 CB01 DA01 DB03 EB00 4C036 AA02 AA11 AA12 AA14 AA17 AA18 4C056 AA01 AB02 AC07 AD01 AE03 AF05 FA04 FB01 FC01 4C0 BB01 PP08 BB05 BB09 CB25 DB01 EB01 FB08 FB16 GB01 4H006 AA01 AA02 AB76 AC28 AC52 BA02 BA32 BB17 BC1 0

Claims (8)

[Claims] An amino compound represented by the following general formula (I): (Wherein A is the following general formula (II): (Ar ^2, Ar ³ represents a substituted or unsubstituted aryl group) represent a group represented by; Ar ¹ represents a substituted or unsubstituted arylene group; n is an integer of 1 or 2; R ¹ , R ² each independently represent an alkyl group, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, and R ¹ and R ² together form a ring May be). 2. In the general formula (I), one or both of R ¹ and R ² are represented by the following general formula (III)
The amino compound according to claim 1, which is a group represented by the following formula: (Wherein, Ar ⁴ represents a substituted or unsubstituted arylene group; R ³ and R ⁴ each independently represent an alkyl group, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group; And R ³ and R ⁴ may be combined to form a ring). 3. A halogen compound represented by the following general formula (IV): (Wherein A, Ar ¹ and n have the same meanings as described in claim 1; X represents a halogen atom) and an amino compound represented by the following general formula (V): Wherein R ¹ and R ² have the same meanings as described in claim 1 or claim 2, wherein the amino compound is represented by the following general formula (I): Formula 6 (Wherein, A, Ar ¹ , n, R ¹ and R ² are as defined above). (A) a formylated aryl compound represented by the following general formula (VI): (Wherein, Ar ⁵ represents a substituted or unsubstituted arylene group, and X represents a halogen atom) and the following general formula (I
An acetylated aryl compound represented by X); (Wherein Ar ⁸ represents a substituted or unsubstituted aryl group) to obtain a pyrylium salt represented by the following general formula (X): (B) a heat treatment of the pyrylium salt in acetic anhydride in the presence of sodium acetate to give a halogenated 1,3,5-triarylbenzene compound represented by the following general formula (XI); Wherein Ar ⁵ and Ar ⁸ are as defined above; and (c) represented by the following general formula (V) and the obtained halogenated 1,3,5-triarylbenzene compound. An amino compound; Wherein R ¹ and R ² have the same meanings as those described in claim 1 or claim 2. A method for producing an amino compound represented by the following general formula: (Wherein, Ar ⁵ , Ar ⁸ , R ¹ , and R ² are as defined above). 5. (a) a formylated aryl compound represented by the following general formula (VII): (Wherein, Ar ⁶ represents a substituted or unsubstituted aryl group) and an acetylated aryl compound represented by the following general formula (VIII): (Wherein, Ar ⁷ represents a substituted or unsubstituted arylene group, and X represents a halogen atom) to obtain a pyrylium salt represented by the following general formula (XII); (B) a heat treatment of the pyrylium salt in acetic anhydride in the presence of sodium acetate to obtain a halogenated 1,3,5 triarylbenzene compound represented by the following general formula (XIII); Wherein Ar ⁶ and Ar ⁷ are as defined above; and (c) the obtained halogenated 1,3,5 triarylbenzene compound and an amino compound represented by the following general formula (V) Compound; Wherein R ¹ and R ² have the same meanings as those described in claim 1 or claim 2. A method for producing an amino compound represented by the following general formula: (Wherein, Ar ⁶ , Ar ⁷ , R ¹ , and R ² are as defined above). 6. A hole transport material comprising the amino compound according to claim 1. 7. An organic electroluminescence device comprising a light emitting layer or a plurality of organic compound thin films including the light emitting layer between a pair of electrodes, wherein at least one layer is a layer containing the amino compound according to claim 1. Characteristic organic electroluminescent element. 8. An electrophotographic photoreceptor comprising a charge generation material and a charge transport material on a conductive support,
An electrophotographic photosensitive member, wherein the charge transport material is the hole transport material according to claim 6.