JP2000169448A - New amino compound and its production, and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new amino compound useful as a durable charge transfer material or a durable light-emitting material. SOLUTION: An amino compound of formula I [A is a group of formula II (Ar2 is an aryl) or the like; Ar1 is an arylene; (n) is 1-3; R1, R2 are each an alkyl, an aralkyl, an aryl or the like], for example, a compound of formula III. The compound of formula I can be obtained by reacting a halogen compound of formula IV with an amino compound of formula V. For example, the compound of formula III is obtained by reacting p-tolualdehyde with 4'- bromoacetophenone in the presence of boron trifluoride-diethyl ether complex, converting the obtained pyrylium salt into a bromotriphenylpyridine derivative, and further adding and reacting p,p'-ditolylamine, sodium-t-butoxide, palladiumm acetate, and tri-t-butylphosphine with the obtained bromotriphenylpyridine derivative. The compound of formula I is a compound useful as a hole transport material.

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).

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

Embedded image In the general formula (II), Ar ² and Ar ³ represent an aryl group such as a phenyl group, a biphenyl group, a terphenyl group and a naphthyl group, and are preferably a phenyl group, a biphenyl group and the like. These groups 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,
Aryl group such as naphthyl group, thienyl group, furyl group,
It may have a heterocyclic group such as a pyridyl group as a substituent.

In the general formula (I), Ar ¹ is a phenylene group,
It represents an arylene group such as a biphenylene group, a terphenylene group, a naphthylene group and the like, 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. It may have an aryl group such as a group, a heterocyclic group such as a thienyl group, a furyl group or a pyridyl group as a substituent.

In the general formula (I), n represents an integer of 1, 2 or 3. That is, the bonding position of Ar ¹ is an arylene group bonded to the pyridine ring, 4-position of the pyridine ring, or 2,6-position, or a position 2,4,6, if a plurality of Ar ¹ binds to A In the above, the portions up to Ar ¹ , R ¹ and R ² may be the same or different.

In the general formula (I), R ¹ and R ² each independently represent an alkyl group such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group, an aralkyl group such as a benzyl group,
A substituted or unsubstituted phenyl group, a biphenyl group, an aryl group such as a naphthyl group, a substituted or unsubstituted thienyl group, a furyl group, an aromatic heterocyclic group such as pyridyl group, R ¹ and R ² together And a ring together with the nitrogen atom to which R ¹ and R ² are attached, for example;

Embedded image May be formed. More preferably, a phenyl group which may have a substituent, a ring formed by combining R ¹ and R ² ;

Embedded image It is.

These rings are methyl, ethyl, n-
It may have an alkyl group such as a propyl group or an isopropyl group, or an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group as a substituent.

Further, ^one or both of R ¹ and R ² are represented by the following general formula (III):

Embedded image If an aryl group having in represented by a substituent, Ar ⁴
Is a phenylene group, a biphenylene group, a terphenylene group,
It represents an arylene group such as a naphthylene group, and is preferably a phenylene group, a biphenylene group or the like.

These groups are methyl, ethyl, n-
Propyl group, alkyl group such as isopropyl group, methoxy group, ethoxy group, alkoxy group such as propoxy group,
It may have an aralkyl group such as a benzyl group, an aryl group such as a phenyl group, a biphenyl group, or a naphthyl group, or a heterocyclic group such as a thienyl group, a furyl group, or a pyridyl group as a substituent. R ³ and R ⁴ are each independently a methyl group,
Ethyl group, alkyl group such as n-propyl group, isopropyl group, aralkyl group such as benzyl group, aryl group such as substituted or unsubstituted phenyl group, biphenyl group, naphthyl group, substituted or unsubstituted thienyl group, furyl group , Represents an aromatic heterocyclic group such as a pyridyl group, and R ³ and R ⁴ are taken together to form a ring together with the nitrogen atom to which R ³ and R ⁴ are bonded;
For example;

Embedded image May be formed. More preferably, a phenyl group which may have a substituent, a ring formed by combining R ³ and R ⁴ ;

Embedded image It is.

These rings are methyl, ethyl, n-
It may have an alkyl group such as a propyl group or an isopropyl group, or an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group as a substituent.

The amino compound represented by the general formula (I) is
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 in general formula (I), and X represents a halogen atom) and the following general formula (V)
An amino compound represented by the formula:

Embedded image (Wherein R ¹ and R ² have the same meanings as in formula (I)).

Examples of the production of the halogen compound represented by the general formula (IV) include a formylated aryl compound represented by the following general formula (VI);

Embedded image (Wherein, Ar ⁵ represents an arylene group such as a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, and is preferably a phenylene group, a biphenylene group or the like; these groups are a methyl group, an ethyl group, an n- Alkyl groups such as propyl group and isopropyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aralkyl groups such as benzyl group, aryl groups such as phenyl group, biphenyl group and naphthyl group, thienyl group, furyl group, pyridyl A heterocyclic group such as a group; X represents a halogen atom) and the following general formula (I
An acetylated aryl compound represented by X);

Embedded image

(Wherein, Ar ⁸ represents an aryl group such as a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group, and is preferably a phenyl group, a biphenyl group, and the like;
These groups are methyl, ethyl, n-propyl,
Alkyl groups such as isopropyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aralkyl groups such as benzyl group, aryl groups such as phenyl group, biphenyl group and naphthyl group, thienyl group, furyl group, pyridyl group, etc. May have a heterocyclic group as a substituent. ) To give a pyrylium salt, and then heat-treated in an aqueous solution of ammonia or an ammonia salt to obtain a halogenated 2,4,4 represented by the following general formula (X).
6 triarylpyridine compounds;

Embedded image (Wherein, Ar ⁵ and Ar ⁸ are as defined above, and X represents a halogen atom).

Embedded image Indicated by

In the same manner, the following general formula (VII)
A formylated aryl compound represented by the formula:

Embedded image (Wherein, Ar ⁶ represents an aryl group such as a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group, and is preferably a phenyl group, a biphenyl group, and the like; those groups are a methyl group, an ethyl group, an n- Alkyl groups such as propyl group and isopropyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aralkyl groups such as benzyl group, aryl groups such as phenyl group, biphenyl group and naphthyl group, thienyl group, furyl group, pyridyl And a acetylated aryl compound represented by the following general formula (VIII);

Embedded image

(Wherein, Ar ⁷ represents an arylene group such as a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group and the like, preferably a phenylene group, a biphenylene group and the like; these groups are a methyl group, an ethyl group , N
-Alkyl group such as propyl group, isopropyl group, methoxy group, ethoxy group, alkoxy group such as propoxy group, aralkyl group such as benzyl group, phenyl group, biphenyl group, aryl group such as naphthyl group, thienyl group,
It may have a heterocyclic group such as a furyl group or a pyridyl group as a substituent; X represents a halogen atom. ) To react with the halogenated 2,2 represented by the general formula (XI).
4,6 triarylpyridine compounds;

Embedded image

Wherein Ar ⁶ and Ar ⁷ are as defined above, and X represents a halogen atom, or a formylated aryl compound represented by the following general formula (VI):

Embedded image (Wherein, Ar ⁵ and X are as defined above) and an acetylated aryl compound represented by the following general formula (VIII);

Embedded image (Wherein, Ar ⁷ and X have the same meanings as described above), and halogenated 2,4,6 triarylpyridine compound represented by the following general formula (XII);

Embedded image (Wherein, Ar ⁵ and Ar ⁷ are as defined above, and may be the same or different; X represents a halogen atom).

These halogen compounds 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), whereby the amino compound represented by the general formula (I) can be produced. Synthesis of the amino compound, in the presence of a basic compound or a transition metal compound catalyst and a solvent,
It can be performed by the Ullmann 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.

Examples of the transition metal or transition metal compound catalyst used in the synthesis include 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 under normal pressure.
The reaction is carried out within a temperature range of -250 ° C, but may be carried out 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 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.

[0032]

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[0033]

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[0034]

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[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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The amino compound represented by the general formula (I) has an excellent charge transport function, especially 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) can be used in any layer of an electrophotographic photoreceptor, but is preferably used as a charge transporting material because it has high charge transporting properties.

The above-mentioned 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.

Examples of the electrophotographic photoreceptor include a photoreceptor having a single-layer type photosensitive layer formed by dispersing a charge generating material and a charge transporting material 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 for 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 a charge transport material and a binder resin in an appropriate solvent is applied on the 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 unconditionally defined depending on the kind thereof, but it is generally 0.02 to 2 parts by weight, preferably 0.5 to 2 parts by weight, based on 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 transporting 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 the above-mentioned laminated type photosensitive layer, the application of the charge transport layer and the charge generation layer can be carried out 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 larger the amount of the plasticizer, the lower the internal stress of the layer. 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 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 photoreceptor 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. 1 to 4 schematically show an embodiment of the organic electroluminescence element. In FIG.
(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 transport 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) is 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. Organic light emitting layer,
For 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) 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 easily impaired, so that the anode is preferably a transparent electrode. When forming a transparent electrode, using a conductive substance as described above on a transparent substrate, vacuum evaporation, means such as sputtering, or a sol-gel method or using a means such as dispersing in a resin or the like to apply the desired What is necessary is just to form so that translucency and electroconductivity may be ensured.

The transparent substrate is not particularly limited as long as it has a suitable strength and is transparent without being adversely affected by heat due to vapor deposition or the like at the time of manufacturing an organic electroluminescence device. 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 electroluminescent device, a structure (FIG. 1) in which an amino compound is used for an organic hole injecting and transporting 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 the 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 compounds of the general 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 dye, perylene dye, pyran dye, thiopyran dye, polymethine dye, merocyanine dye, imidazole dye and the like can 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 evaporating the above-mentioned light emitting substance, or dip coating or spin coating a solution in which the light emitting substance is dissolved or a solution in which a suitable resin is dissolved. 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 formed by a vapor deposition method, the film thickness is usually about 1 to 500 nm, and when formed by a coating method, the film thickness may be about 5 to 1000 nm. It is necessary to increase the applied voltage for emitting light as the thickness of the formed film increases, so that 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 using an electron transporting material by a conventionally known method such as an evaporation method or a coating method, similarly to the hole injecting / transporting layer or 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 has an excellent ability to form a thin film.

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 an organic light emitting layer having a single layer structure 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 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.

A nichrome wire, a gold wire, a 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 element 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 “parts by weight” unless otherwise specified.

Synthesis Example 1 (Synthesis of Compound (19)) In a 200 ml three-necked flask equipped with a water-cooled condenser, 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, 10.0 g (0.018 mol) of the above pyrylium salt was placed in a 1000 ml three-necked flask.
To this was added 100 ml of tetrahydrofuran to dissolve. Further, after adding 300 ml of 14% ammonia water,
Stirred at 50 ° C. for 1 hour. After the product was extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the obtained crystals were recrystallized with a mixed solvent of dichloromethane / hexane to obtain 4.5 g of the following brominated triphenylpyridine derivative (yield: 54).
%) As red-brown crystals.

Embedded image

Subsequently, 1.5 g of the above brominated triphenylpyridine derivative (0.1 g) was placed in a 100 ml three-necked flask.
003 mol), 1.4 g of p, p'-ditolylamine
(0.069 mol), sodium t-butoxide 0.
8 g (0.0083 mol), palladium acetate 0.04 g
(0.00017 mol) and 0.14 g (0.00067 mol) of tri-t-butylphosphine, and 5 ml of o-xylene as a solvent was added thereto.
The mixture was stirred at 20 ° C for 3 hours. 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 / vo)
l)) and 1.96 g of the target compound (19)
(89% yield) as pale yellow crystals.

The melting point of the obtained compound is 167 to 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 ₅₂ H ₄₅ N ₃ Calculated value (%) C: 87.73% H: 6.37% N: 5.90% Analysis value (%) C: 87.61% H: 6.40% N: 5.99%

Synthesis Example 2 (Synthesis of Compound (76)) The following brominated triphenylpyridine derivative obtained by the same operation as in Example 1 in a 100 ml three-necked flask;

Embedded image 1.0 g (0.0021 mol) of the following benzidine derivative;

Embedded image 1.8 g (0.0043 mol), 0.5 g (0.0051 mol) of sodium-t-butoxide, 0.026 g (0.00012 mol) of palladium acetate, and 0.09 g (0.00046 mol) of tri-t-butylphosphine are added. After adding 5 ml of o-xylene as a solvent, 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 separated by filtration. 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)) to give the desired compound (76)
2.2 g (yield 90%) were obtained as pale yellow crystals.

The melting point of the obtained compound is 187 to 189 ° C.
Met. The following results were obtained by analyzing the molecular formula. Molecular formula: C ₈₆ H ₆₇ N ₅ Calculated value (%) C: 88.25% H: 5.77% N: 5.98% Analysis value (%) C: 88.21% H: 5.80% N: 5.99%

Synthesis Example 3 (Synthesis of Compound (38)) In a 200 ml three-necked flask equipped with a water-cooled condenser, p-
15.0 g (0.081 mol) of bromobenzaldehyde
And 4'-bromoacetophenone 32.3 g (0.16mo
l) was added thereto, and 50 ml of toluene was added thereto and dissolved. Next, boron trifluoride-diethyl ether complex 3
4.5 g (0.24 mol) are dissolved in 15 ml of toluene,
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, and 1,4-
400 ml of dioxane was added, and the precipitated crystals were filtered and dried under reduced pressure. The following pyrylium salt, 28.2 g (yield 55%)
Was obtained as yellow crystals.

Embedded image

Next, 20.0 g (0.032 mol) of the above pyrylium salt was placed in a 2000 ml three-necked flask.
To this was added 150 ml of tetrahydrofuran to dissolve. Furthermore, after adding 400 ml of 14% ammonia water,
Stirred at 50 ° C. for 1 hour. After the product was extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the obtained crystals were recrystallized with a mixed solvent of dichloromethane / hexane to give 9.9 g of the following brominated triphenylpyridine derivative (yield: 58).
%) As red-brown crystals.

Embedded image

Subsequently, 1.8 g of the above brominated triphenylpyridine derivative (0.1 g) was placed in a 100 ml three-necked flask.
003 mol), 2.2 g of p, p'-ditolylamine
(0.011 mol), sodium t-butoxide 1.
3 g (0.013 mol), palladium acetate 0.06 g
(0.00017 mol) and 0.23 g (0.0011 mol) of tri-t-butylphosphine, and 10 ml of o-xylene as a solvent.
The mixture was stirred at 20 ° C for 3 hours. The solution was cooled to room temperature, 100 ml of dichloromethane was added to dissolve the contents, and the insolubles were removed by filtration. 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 / vo)
l)) to give 2.7 g (yield 91%) of the target compound (38) as pale yellow crystals.

The melting point of the obtained compound is 315-317 ° C.
Met. The following results were obtained by analyzing the molecular formula. Molecular formula: C ₆₅ H ₅₆ N ₄ Calculated value (%) C: 87.41% H: 6.32% N: 6.27% Analysis value (%) C: 87.47% H: 6.28% N: 6.25%

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, an amino compound (4) was used instead of the amino compound (2) used in Example 1.
Photoconductors using (5) 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 image 0.45 parts, polystyrene resin (molecular weight 40,000)
0.45 parts were dispersed together with 50 parts of cyclohexanone by a sand mill. The obtained dispersion of the bisazo 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. A solution prepared by dissolving 50 parts of the amino compound (13) and 50 parts of a polyarylate resin (U-100; manufactured by Unitika) in 400 parts of 1,4-dioxane was obtained on the charge generation layer thus obtained. Coating was performed so that the dry film thickness became 25 μm, followed by drying 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.
5), (16) and (19) 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 (27) and (31) 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 phthalocyanine pigment dispersion was dispersed at 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 compounds (45) and (48) 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.

[0112]

[Table 1]

As can be seen from Table 1, the photoreceptor of this example has a sufficient charge retention ability even in a laminated type or a single-layer type, and the dark decay rate is small enough to be used as a photoreceptor. Is also excellent. Further, a repetitive actual shooting test at the time of positive charging was performed on the photoconductor of Example 13 using a commercially available electrophotographic copying machine (manufactured by Minolta; EP-350Z). In, 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 (15) 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 (16), (19) and (26) were used instead of using amino compound (15).
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 (31) was deposited on an indium-tin oxide-coated glass substrate as an organic hole injecting and transporting layer 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 (38), (44) or (50) was used instead of the compound (31). An organic electroluminescence device was manufactured.

Example 24 On a substrate of indium-tin oxide-coated glass, an amino compound (55) 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 The compound (61) 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 N, N′- was formed on an indium-tin oxide coated glass substrate.
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 (63) were prepared by vacuum evaporation at a ratio of 3: 1 by vacuum evaporation.
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 (6
7) 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 conducted in the same manner as in Example 27 except that amino compounds (69) and (73) were used instead of compound (67). An element was manufactured.

Example 30 A compound (77), 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 was used 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 the anode, the maximum light emission luminance and the light emission start voltage at that time Was measured. Table 2 summarizes the measurement results.

[0126]

[Table 2]

As can be seen from Table 2, the organic electroluminescent device of the present invention exhibited high 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.

[0128]

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 417/12 213 C07D 417/12 213 417/14 213 417/14 213 C09K 11/06 645 C09K 11/06 645 G03C 1/72 G03C 1/72 H05B 33/14 H05B 33/14 A 33/22 33/22 D (72) Inventor Keiichi Furukawa 2-13-13 Azuchicho, Chuo-ku, Osaka City, Osaka Osaka International Building Minolta In-house F-term (Reference) 2H123 AA00 AA52 3K007 AB02 AB03 AB06 AB11 CA01 CB01 DA01 DB03 EB00 4C055 AA01 BA03 BA05 BA08 BA16 BA27 BB01 BB02 BB04 BB10 CA01 DA08 DA16 DA27 DB01 DB02 DB04 DB10 FA23 FA37 4C063AA A13 BB01 DD08 DD12 EE10

Claims (9)

[Claims] An amino compound represented by the following general formula (I): (In the formula, A represents a group represented by the following general formula (II); (Ar ² and Ar ³ represent a substituted or unsubstituted aryl group); Ar ¹ represents a substituted or unsubstituted arylene group; n represents an integer of ¹ , 2 or 3; R ¹ , R ²
Each independently represents 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 may together form a ring When a plurality of Ar ¹ is bonded to A,
The portions up to r ¹ , R ¹ and R ² may be the same or different). 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); (In the formula, Ar ⁸ represents a substituted or unsubstituted aryl group) to obtain a pyrylium salt; (b) heat-treating the pyrylium salt in ammonia or an aqueous solution of an ammonium salt to obtain a compound represented by the following general formula ( A halogenated 2,4,6 triarylpyridine compound represented by X); Wherein Ar ⁵ and Ar ⁸ are as defined above; and (c) the obtained halogenated 2,4,6 triarylpyridine compound and a compound represented by the following general formula (V) An amino compound; (Wherein R ¹ and R ² have the same meanings as defined in claim 1 or claim 2), a process 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; (b) heating the pyrylium salt in an aqueous solution of ammonia or ammonium salt Treated, and a halogenated 2,4,6 triarylpyridine compound represented by the following general formula (XI); Wherein Ar ⁶ and Ar ⁷ are as defined above; and (c) the obtained halogenated 2,4,6 triarylpyridine compound and an amino compound represented by the following general formula (V) Compound; Wherein R ¹ and R ² have the same meanings as defined 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). (A) a formylated aryl compound represented by the following general formula (VI): (Wherein, Ar ⁵ represents a substituted or unsubstituted arylene group, X represents a halogen atom) and the following general formula (V
Acetylated aryl compound represented by III); (Wherein, Ar ⁷ represents a substituted or unsubstituted arylene group and X represents a halogen atom) to obtain a pyrylium salt; (b) heating the pyrylium salt in an aqueous solution of ammonia or ammonium salt A halogenated 2,4,6 triarylpyridine compound represented by the following general formula (XII): (Wherein, Ar ⁵ and Ar ⁷ represent a substituted or unsubstituted arylene group); and (c) the obtained halogenated 2,4,6 triarylpyridine compound and the following general formula (V) An amino compound represented by the formula: Wherein R ¹ and R ² have the same meanings as defined in claim 1 or claim 2, and comprising the step of reacting the amino compound represented by the following general formula: (Wherein, Ar ⁵ , Ar ⁷ , R ¹ , and R ² are as defined above). 7. A hole transport material comprising the amino compound according to claim 1. 8. An organic electroluminescence device comprising a light emitting layer or a plurality of organic compound thin films including a 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. 9. An electrophotographic photosensitive member using a charge generation material and a charge transport material on a conductive support, wherein the charge transport material is the hole transport material according to claim 7. Electrophotographic photoreceptor.