JPH05100456A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body having extremely high sensitivity, little residual potential which causes fogging, little accumulation of residual potential due to repeated use and little variation in surface potential and sensitivity because of little photofatigue, and excellent durability. CONSTITUTION:This electrophotographic sensitive body has a photosensitive body containing a bis-hydrozone compd. expressed by formula on a conductive base body. In formula, Ar<1>, Ar<2> Ar<3>, and Ar<4> are aryl groups or heterocyclic groups which may have substituents, Ar<5> and Ar<6> are arylene groups or bivalent heterocyclmc groups which may have substmtuents, R<1> and R<2> are hydrogen atoms, alkyl groups, aryl groups or heterocyclic groups which may have substituents, R<3> and R<4> are alkyl groups, aryl groups or heterocyclic groups which may have substituents (and may form a specified heteroring by connection shown as the dotted lines), and R<5> is a bivalent org. residue which may have substituent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor. More specifically, it relates to a high-sensitivity electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductive substance.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide and zinc oxide have been widely used in the photosensitive layer of electrophotographic photoreceptors. However, selenium and cadmium sulfide need to be recovered as poisons, and selenium is inferior in heat resistance because it is crystallized by heat.
Zinc oxide has inferior moisture resistance, and zinc oxide has the drawback of lacking printing durability, and efforts are being made to develop new photoreceptors. Recently, studies have been conducted on the use of organic photoconductive materials in the photosensitive layer of electrophotographic photoreceptors, and some of them have been put to practical use. Compared to inorganic photoconductive materials, organic photoconductive materials have advantages such as light weight, easy film formation, easy photoconductor production, and transparent photoconductor production depending on the type. Have.

Recently, a so-called function-separated type photoconductor, in which separate functions of charge carrier generation and transfer are shared by different compounds, has become the mainstream of development because it is effective for high sensitivity. The organic photoconductor is also put into practical use. As the charge carrier transfer medium, there are a case where a high molecular weight photoconductive compound such as polyvinylcarbazole is used and a case where a low molecular weight photoconductive compound is dispersed and dissolved in a binder polymer.

[0004]

In particular, organic low-molecular-weight photoconductive compounds can easily select mechanical properties because they can be selected from polymers having excellent film-forming properties, flexibility, adhesiveness, etc. as binders. (See Japanese Patent Application Laid-Open No. 60-196767, Japanese Patent Application Laid-Open No. 60-218652, Japanese Patent Application Laid-Open No. 60-2331).
56, JP-A-63-48552, JP-A-1
-267552). However, it has been difficult to find a compound suitable for producing a highly sensitive photoreceptor.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on an organic low molecular weight photoconductive compound which provides a highly sensitive and durable electrophotographic photoreceptor, and found that a specific bishydrazone compound The present invention has been found to be suitable and has led to the present invention. That is, the gist of the present invention is to provide the following general formula [I] on a conductive support.

[0006]

[Chemical 3]

(Wherein Ar ¹ , Ar ² , Ar ³ and A
r ⁴ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and these may be the same or different from each other; Ar ⁵ and Ar ⁶ are Respectively represent an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent, and these may be the same or different from each other; R
¹ and R ² each represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent,
These may be the same or different from each other; R ³ and R ⁴ each have an alkyl group which may have a substituent, an aryl group which may have a substituent or a substituent which may have a substituent. Optionally represent a heterocyclic group, which may be the same or different from each other; provided that R ³ and R ⁴ are
It forms a heterocycle represented by the following structural formulas [II], [III], [IV] and [V] by combining with adjacent phenyl groups as indicated by a dotted line in the formula [I]. Well;

[0008]

[Chemical 4]

R ⁵ represents a divalent organic residue which may have a substituent. ) A photoconductor for electrophotography, comprising a photosensitive layer containing a bishydrazone compound represented by .

The present invention will be described in detail below. The electrophotographic photoreceptor of the present invention contains the bishydrazone compound represented by the general formula [I] in the photosensitive layer. In the general formula [I], Ar ¹ , Ar ² , Ar ³ and A
r ⁴ is an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group: or a pyrrolyl group, a thienyl group,
It represents a heterocycle such as a furyl group, which may be the same or different from each other, and a phenyl group and a naphthyl group are particularly preferable. These aryl group and heterocyclic group may have a substituent, and as the substituent, a hydroxyl group; a chlorine atom,
Halogen atom such as bromine atom, iodine atom; alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group; alkoxy group such as methoxy group, ethoxy group, butoxy group; allyl group; benzyl group, naphthyl Aralkyl groups such as methyl group and phenethyl group; aryloxy groups such as phenoxy group and triloxy group; arylalkoxy groups such as benzyloxy group and phenethyloxy group; phenyl group,
Aryl group such as naphthyl group; Divinylamino group such as styryl group, arylvinyl group such as naphthylvinyl group, dimethylamino group, diethylamino group; Diarylamino group such as diphenylamino group, dinaphthylamino group; Dibenzylamino group, Diaralkylamino groups such as diphenethylamino groups; diheterocyclic amino groups such as dipyridylamino groups and dithienylamino groups; diallylamino groups, and disubstituted amino groups in which the above amino group substituents are combined. ..

Ar ⁵ and Ar ⁶ each represent an arylene group such as a phenylene group, a naphthylene group or an anthracenylene group: or a divalent heterocyclic group such as a pyrrolidene group, a thienylidene group or a furylidene group, which are the same as each other. However, they may be different, and a phenyl group and a naphthyl group are particularly preferable. These arylene group and divalent heterocyclic group may have a substituent, and as the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group or a propyl group Group, butyl group, hexyl group, and other alkyl groups; methoxy group, ethoxy group, butoxy group, and other alkoxy groups; allyl group; benzyl group, naphthylmethyl group, phenethyl group, and other aralkyl groups; phenoxy group, triloxy group, and other aryl groups Oxy group; arylalkoxy group such as benzyloxy group and phenethyloxy group; aryl group such as phenyl group and naphthyl group; arylvinyl group such as styryl group and naphthylvinyl group; dialkylamino group such as dimethylamino group and diethylamino group;
Diarylamino groups such as diphenylamino groups and dinaphthylamino groups; diaralkylamino groups such as dibenzylamino groups and diphenethylamino groups; diheterocyclic amino groups such as dipyridylamino groups and dithienylamino groups; diallylamino groups and And di-substituted amino groups in which the above-mentioned amino group substituents are combined.

R ¹ and R ² are each a hydrogen atom;
Represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group; or a heterocyclic group such as a pyrrolyl group, a thienyl group or a furyl group. May be the same or different from each other, and a hydrogen atom and an alkyl group are particularly preferable. These alkyl group, aryl group and heterocyclic group may have a substituent, and as the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, Alkyl groups such as propyl group, butyl group, hexyl group; alkoxy groups such as methoxy group, ethoxy group, butoxy group; allyl group; aralkyl groups such as benzyl group, naphthylmethyl group, phenethyl group; phenoxy group, triloxy group, etc. Aryloxy group; arylalkoxy groups such as benzyloxy group and phenethyloxy group; aryl groups such as phenyl group and naphthyl group; arylvinyl groups such as styryl group and naphthylvinyl group; dialkylamino groups such as dimethylamino group and diethylamino group ;
Diarylamino groups such as diphenylamino groups and dinaphthylamino groups; diaralkylamino groups such as dibenzylamino groups and diphenethylamino groups; diheterocyclic amino groups such as dipyridylamino groups and dithienylamino groups; diallylamino groups and And di-substituted amino groups in which the above-mentioned amino group substituents are combined.

R ³ and R ⁴ are each a methyl group,
Represents an alkyl group such as an ethyl group, a propyl group, a butyl group or a hexyl group; an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group; or a heterocyclic group such as a pyrrolyl group, a thienyl group or a furyl group, which are the same as each other However, they may be different, and a phenyl group and a naphthyl group are particularly preferable. These alkyl group, aryl group and heterocyclic group may have a substituent, and as the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, Alkyl group such as propyl group, butyl group and hexyl group; alkoxy group such as methoxy group, ethoxy group and butoxy group; allyl group; aralkyl group such as benzyl group, naphthylmethyl group and phenethyl group; phenoxy group,
Aryloxy groups such as triloxy groups; arylalkoxy groups such as benzyloxy groups and phenethyloxy groups; aryl groups such as phenyl groups and naphthyl groups; arylvinyl groups such as styryl groups and naphthylvinyl groups, dimethylamino groups, diethylamino groups, etc. Dialkylamino group; diphenylamino group, dinaphthylamino group, etc. diarylamino group; dibenzylamino group, diphenethylamino group, etc. diaralkylamino group; dipyridylamino group, dithienylamino group, etc. diheterocyclic amino group A diallylamino group, a disubstituted amino group in which the above-mentioned amino group substituents are combined, and the like.

Further, R ³ and R ⁴ are bonded to adjacent phenyl groups as shown by dotted lines, and the above structural formulas [II] and [II]
One of the heterocycles represented by I], [IV], and [V] may be formed. R ⁵ represents a divalent organic residue, for example ^{- (- (R 6) C} (R 7) -) m -; - CH 2 (C 6
_{H 4) CH 2 -; -} CR 8 = CR 9 -; phenylene group,
It represents an arylene group such as a naphthylene group; or a divalent heterocyclic group such as a pyrrolidene group, a thienylidene group or a furylidene group. (R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom; an alkyl group such as a methyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group or a naphthyl group; a pyrrolyl group, a thienyl group or a furyl group. Represents a heterocyclic group such as R ⁶ and R ⁶ which may be the same or different from each other.
It is also possible to form a ring with ⁷ , for example, a cyclohexane ring or the like. m is an integer of 1 to 6. ) These arylene group, divalent heterocyclic group, alkyl group, aryl group, divalent heterocyclic group may have a substituent,
As the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; a methoxy group, an ethoxy group or a butoxy group Alkoxy group; allyl group; aralkyl group such as benzyl group, naphthylmethyl group, phenethyl group; aryloxy group such as phenoxy group, triloxy group; arylalkoxy group such as benzyloxy group, phenethyloxy group; phenyl group, naphthyl group, etc. Aryl group; styryl group, naphthyl vinyl group, etc. aryl vinyl group, dimethylamino group, diethylamino group, etc. dialkylamino group; diphenylamino group, dinaphthylamino group, etc. diarylamino group; dibenzylamino group, diphenethylamino group Diaralkylamino groups such as groups;
Examples thereof include diheterocyclic amino groups such as dipyridylamino group and dithienylamino group; diallylamino groups, and disubstituted amino groups in which the above amino group substituents are combined.

Typical examples of the bishydrazone compounds represented by the general formula [I] are shown below, but the bishydrazone compounds used in the present invention are not limited to these specific examples unless the gist thereof is exceeded. ..

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

The bishydrazone compound represented by the above general formula [I] can be produced by a known method. As a preferred production method, for example, a phenolic compound having two mono-substituted amino groups is linked, then a dinitrosation reaction is performed, and a reduction reaction is performed to obtain a hydrazine compound, followed by dehydration reaction with an aldehyde or a ketone. It is a method of obtaining the target compound by carrying out.

This method will be described in detail as follows. In the general formula [VI] (in the general formulas [VI] and [VIII], R ³ , R ^3
4 and R ⁵ have the same meaning as in the general formula [I] shown above. ). A phenolic compound having a mono-substituted amino group and a general formula [VII] (wherein R ⁵ has the same meaning as in the general formula [I] shown above. X is
Represents a halogen atom such as a chlorine atom, a bromine atom and an iodine atom. ) In the presence of a base such as sodium amide, potassium carbonate, triethylamine, sodium hydroxide, barium oxide, silver oxide, sodium hydride, dimethyl sulfoxide, N, N-dimethylformamide, dimethoxyethane, Tetrahydrofuran,
By reacting in a solvent inert to the reaction such as nitrobenzene, the compound represented by the general formula [VIII] can be obtained. In some cases, copper powder may be added to accelerate the reaction.

[0025]

[Chemical 12]

By the above-mentioned production method, a compound of R ³ = R ⁴ can be obtained, but if two or more compounds are used as the general formula [VI], R ³ and R ⁴ are different from each other in the general formula [VIII ]
A compound represented by can be obtained. During this reaction,
In some cases, in addition to the general formula [VIII], it may be a mixture with a compound represented by the following general formulas [IX] and [X].

[0027]

[Chemical 13]

Next, the compound represented by the general formula [VIII] is dinitrosated by adding an aqueous solution of sodium nitrite in a solvent inert to the reaction such as acetic acid to give a nitroso compound represented by the general formula [XI]. Is obtained.

[0029]

[Chemical 14]

Next, the compound represented by the general formula [XI] is treated with zinc-unacetic acid, sodium-ethanol, sodium-
Reduction with a reducing agent such as liquid ammonia or lithium aluminum hydride gives a hydrazine compound represented by the general formula [XII].

[0031]

[Chemical 15]

Next, the general formula [XII] and the general formula [XIII]
(In the formula, Ar ¹ , Ar ₂ , Ar ⁵ and R ¹ have the same meanings as in the above-mentioned general formula [I].), If necessary, at 50 ° C. to 15 ° C.
Under heating at 0 ° C, methanol, ethanol, tetrahydrofuran, cellosolve, N, N-dimethylformamide,
By reacting in a solvent inert to the reaction such as benzene and toluene, the compound represented by the general formula [I] can be obtained. During this reaction, auxiliary agents such as paratoluenesulfonic acid, acetic acid, hydrochloric acid, sodium acetate may be used as a reaction accelerator, if desired.

[0033]

[Chemical 16]

In the above manufacturing method, Ar ¹ = Ar ³ , A
A compound of r ² = Ar ⁴ , Ar ⁵ = Ar ⁶ , and R ³ = R ⁴ can be obtained. If two or more compounds are used in the general formula [XIII], Ar ¹ and Ar ³ , Ar ² and Ar ⁴ are obtained. ⁴ , Ar ⁵
And Ar ⁶ , and R ³ and R ⁴ are different from each other, a compound represented by the general formula [I] can be obtained.

In these reactions, in some cases,
After each step, or after all steps, recrystallization purification,
It is also possible to obtain a highly purified product by a known purification means such as sublimation purification or column purification. The electrophotographic photoreceptor of the present invention has a photosensitive layer containing one or more bishydrazone compounds represented by the general formula [I].

The bishydrazone compound represented by the general formula [I] exhibits extremely excellent performance as an organic photoconductor. In particular, when it is used as a charge transfer medium, it gives a photoreceptor having high sensitivity and excellent durability. Various forms of the photosensitive layer of the electrophotographic photosensitive member are known, and any of them may be used as the photosensitive layer of the electrophotographic photosensitive member of the present invention. For example, a photosensitive layer in which a bishydrazone compound and optionally a sensitizer dye or an electron-withdrawing compound are added to a binder, photoconductive particles and a bishydrazone system that generate charge carriers with extremely high efficiency when absorbing light. A photosensitive layer in which a compound is added to a binder, a charge transfer layer including a bishydrazone compound and a binder, and a photoconductive particle that generates charge carriers with extremely high efficiency when absorbing light, or a charge generation layer including this and a binder. Examples include a photosensitive layer in which and are laminated.

In these photosensitive layers, a bishydrazone compound represented by the general formula [I] is mixed with another known hydrazone compound having excellent performance as an organic photoconductor and a stilbenzene compound. Good. In the present invention, when the bishydrazone compound represented by the above general formula [I] is used in the charge transfer layer of the photosensitive layer comprising the charge generation layer and the charge transfer layer, the sensitivity is particularly high and the residual potential is small. Further, when repeatedly used, it is possible to obtain a photoreceptor having excellent durability with little fluctuation in surface potential, decrease in sensitivity, accumulation of residual potential and the like.

In the electrophotographic photoreceptor of the present invention, the bishydrazone compound represented by the above general formula [I] is dissolved in a suitable solvent together with a binder according to a conventional method, and light is absorbed if necessary, resulting in extremely high efficiency. Photoconductive particles that generate charge carriers, sensitizing dyes, electron-withdrawing compounds, or coating liquids obtained by adding plasticizers, pigments and other additives are coated on a conductive support and dried. , Several μ ~
It can be manufactured by forming a photosensitive layer having a film thickness of several tens of μ. In the case of a photosensitive layer composed of two layers, a charge generation layer and a charge transfer layer, the above-mentioned coating solution is applied onto the charge generation layer, or the charge generation layer is applied onto the charge transfer layer obtained by applying the above coating solution. It can be manufactured by forming.

As the solvent for preparing the coating solution, ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone,
Aprotic polar solvents such as dimethyl sulfoxide; esters such as ethyl acetate, methyl formate and methyl cellosolve acetate; solvents that dissolve hydrazone compounds such as chlorinated hydrocarbons such as dichloroethane and chloroform. Of course, it is necessary to select one that dissolves the binder from these. Further, as the binder, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester and butadiene, polyvinyl acetal,
Examples include various polymers compatible with styrene compounds such as polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose ester, cellulose ether, phenoxy resin, silicon resin, and epoxy resin. The amount of the binder used is usually 0.5 to 30 times by weight, preferably 0.7 to 10 times by weight, that of the hydrazone compound.

As the photoconductive particles, dye pigment, and electron-withdrawing compound added to the above-mentioned photosensitive layer, known ones can be used. Photoconductive particles that generate charge carriers with extremely high efficiency when absorbing light include selenium, selenium-tellurium alloys, selenium-arsenic alloys, cadmium sulfide,
Inorganic photoconductive particles such as amorphous silicon; metal-containing phthalocyanine, perinone pigment, thioindigo, quinacridone, perylene pigment, anthraquinone pigment, azo pigment, bisazo pigment, trisazo pigment, tetrakis azo pigment, cyanine pigment Organic photoconductive particles such as (In particular, when combined with a metal-containing phthalocyanine, a photoreceptor having improved sensitivity to laser light can be obtained.) Examples of dyes include triphenylmethane dyes such as methyl violet, brilliant green, and crystal violet, thiazine dyes such as methylene blue, and quinizarin. And quinone dyes and cyanine dyes, pyrylium salts, thiabilylium salts, benzopyrylium salts and the like. Examples of the electron-withdrawing compound that forms a charge transfer complex with a hydrazone compound include chloranil, 2,3-dichloro-1,4-naphthoquinone,
Quinones such as 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone; aldehydes such as 4-nitrobenzaldehyde; 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, Two
Ketones such as 4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 3,3 ', 5,5'-tetranitrobenzophenone; phthalic anhydride, 4
Acid anhydrides such as chloronaphthalic anhydride; tetracyanoethylene, terephthalalmalononitrile, 9-anthrylmethylidene malononitrile, 4-nitrobenzalmalononitrile, 4- (p-nitrobenzoyloxy) benzalmalononitrile A cyano compound such as 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,
Examples thereof include electron-withdrawing compounds such as phthalides such as 5,6,7-tetrachlorophthalide.

Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention may contain a well-known plasticizer in order to improve film-forming property, flexibility and mechanical strength. Therefore, examples of the plasticizer added to the coating liquid include phthalic acid esters, phosphoric acid esters, epoxy compounds, chlorinated paraffins, chlorinated fatty acid esters, and aromatic compounds such as methylnaphthalene. When the bishydrazone compound is used as the charge transfer medium in the charge transfer layer, the coating solution may have the above composition, but the photoconductive particles, dye pigment, electron withdrawing compound, etc. may be removed or added in a small amount. Good. As the charge generation layer in this case, a coating solution obtained by dissolving or dispersing in the solvent such as the photoconductive particles and a binder polymer or an organic photoconductive substance, a dye pigment, and an electron-withdrawing compound as necessary is applied and dried. Examples thereof include a thin layer or a layer in which the photoconductive particles are formed by a means such as vapor deposition.

It goes without saying that the photoreceptor thus formed may also have an adhesive layer, an intermediate layer, a transparent insulating layer, etc., if necessary. As the conductive support on which the photosensitive layer is formed, any of those known in electrophotographic photoreceptors can be used. Specific examples thereof include metal drums such as aluminum, stainless steel, and copper, sheets, laminates of these metal foils, and vapor-deposited materials. Further, there may be mentioned plastic films, plastic drums, papers, paper tubes, etc. which have been subjected to a conductive treatment by coating a conductive material such as metal powder, carbon black, copper iodide, and a polymer electrolyte with a suitable binder. In addition, a conductive plastic sheet or drum containing a conductive substance such as metal powder, carbon black or carbon fiber can be used.

[0043]

The electrophotographic photosensitive member of the present invention has a very high sensitivity and a small residual potential that causes fogging. Particularly, since light fatigue is small, accumulation of residual potential due to repeated use, surface potential and It is characterized by small fluctuations in sensitivity and excellent durability.

[0044]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following production examples and examples as long as the gist thereof is not exceeded. In the examples, "parts" means "parts by weight".

Production Example 1 p-hydroxydiphenylamine

[0046]

[Chemical 17]

10 g of N, N-dimethylformamide 1
Dissolve in 00 ml, then 4.3 g of sodium hydroxide
Was added and then stirred at room temperature for 30 minutes. Then, with ice cooling, O-xylylene dibromide (7.1 g) of N, N
20 ml of dimethylformamide solution was added and then stirred at room temperature for 5 hours and 30 minutes. Then, the reaction solution was poured into 400 ml of ice water, and extraction and purification treatments were carried out by a conventional method to obtain 10 g of light brown crystals (melting point 105-107 ° C)
Got

This compound was found to be a compound represented by the following structural formula by the following elemental analysis values, mass spectrometric measurements and infrared absorption spectrum measurements.

[0049]

[Chemical 18]

Production Example 2 1.5 g of the amino compound synthesized in Production Example 1 was added to 30 ml of acetic acid.
, And then 1.3 ml of an aqueous solution of 1.0 g of sodium nitrite was added, followed by stirring at room temperature for 2 hours.
After that, 30 ml of water is added to the reaction system to precipitate crystals, and then filtration and purification treatment are carried out by a conventional method.
1.7 g of brown crystals (melting point 50-52 ° C.) were obtained.

This compound was found to be a compound represented by the following structural formula by the following elemental analysis values, mass spectrometric measurements and infrared absorption spectrum measurements.

[0052]

[Chemical 19]

Production Example 3 1.7 g of the nitroso compound synthesized in Production Example 2 was dissolved in a mixed solution of 7 ml of methanol and 9 ml of tetrahydrofuran, and 1.5 g of zinc powder was added thereto. Then under ice cooling,
2.8 g of acetic acid was added dropwise, and then the mixture was stirred at room temperature for 1 hour and 30 minutes. Then, zinc acetate was removed by filtration and the filtrate was directly used in the next reaction.

Production Example 4 Triphenylamine aldehyde

[0055]

[Chemical 20]

0.7 g was dissolved in 14 ml of tetrahydrofuran, the filtrate obtained in Preparation Example 3 was added dropwise thereto, and then,
The reaction was carried out at room temperature for 10 hours. Next, this reaction solution was added dropwise to 300 ml of methanol and filtered and purified by a conventional method to give 0.5 g of pale yellow crystals (melting point: 118
-120 ° C) was obtained.

This compound was found to be a compound represented by the following structural formula (Compound Example No. 5) by the following elemental analysis values, mass spectrometric measurements and infrared absorption spectrum measurements.

[0058]

[Chemical 21]

Example 1 1.0 part of titanium oxyphthalocyanine pigment and 0.5 part of polyvinyl butyral (trade name: polyvinyl butyral # 6000 manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to 30 parts of 4-
Methoxy-4-methylpentanone-2 (Mitsubishi Kasei Co., Ltd.)
(Manufactured by the company).

This dispersion was coated on a vapor-deposited aluminum layer on a polyester film having a thickness of 100 μm with a wire bar so that the weight after drying would be 0.2 g / m ² , and then dried to charge. A generator layer was formed. 70 parts of the bishydrazone compound prepared in Preparation Example 4 and the following polycarbonate resin

[0061]

[Chemical formula 22]

A coating liquid prepared by dissolving 100 parts in 900 parts of tetrahydrofuran was applied and dried to form a charge transfer layer having a film thickness of 17 μm.

The sensitivity, that is, the half-exposure amount was measured for the electrophotographic photosensitive member having the photosensitive layer consisting of two layers thus obtained, and it was 2.1 (μW / cm ² ) ^-1 . The half-exposure amount is obtained by first charging the photoreceptor in the dark with a corona discharge of -4.8 KV, then exposing it with light of 775 nm, and measuring the exposure amount required for the surface potential to decay from 500V to 250V. I asked.

Example 2 Instead of the phthalocyanine-based pigment used in Example 1, a naphthalic acid-based bisazo pigment represented by the following structural formula was used to expose a photoreceptor prepared in the same manner as in Example 1 to white light. The half-dose exposure was measured and found to be 1.3 lux · sec.

[0065]

[Chemical formula 23]

Examples 3 to 10 Instead of the bishydrazone compound used in Example 1,
The bishydrazone compounds shown in Table 1 below, which were synthesized in the same manner as in Production Examples 2 to 4, were used.
Table 1 shows the sensitivity of the electrophotographic photosensitive member obtained by using the titanium oxyphthalocyanine pigment used in Example 1.

Table 1 Example Example Compound No. Sensitivity (μW / cm ² ) ⁻¹ 3 1 1 1.0 4 4 2.0 5 6 6 2.0 6 7 1.9 7 8 1.8 1.8 8 9 1.5 9 9 11 2.0 10 10 14 1.7

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of a bishydrazone compound obtained in Production Example 4.

Claims (1)

[Claims] 1. A conductive support having the following general formula [I]: (In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and these are the same as each other. Or may be different; Ar ⁵ and Ar ⁶ each represent an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent, and these are the same as each other. Or they may be different; R ¹ and R ²
Each represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and these are the same as each other. R ³ and R ⁴ are each an alkyl group which may have a substituent, an aryl group which may have a substituent or a hetero group which may have a substituent. Represents a ring group, which may be the same or different from each other; provided that R ³ and R ⁴ are bonded to adjacent benzene rings as shown by the dotted line in the formula [I], and the following structural formula [II], Any one of the heterocycles represented by [III], [IV] and [V] may be formed; R ⁵ represents a divalent organic residue which may have a substituent. ) An electrophotographic photoreceptor having a photosensitive layer containing a bishydrazone compound represented by