JPH0594030A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To enhance sensitivity and durability and to reduce residual potential by forming a photosensitive layer containing a specified bishydrazone derivative. CONSTITUTION:The photosensitive layer formed on a conductive substrate contains the bishydrazone derivative represented by formula I in which Q<1> is one of groups represented by formulae III-VII; Q<2> is one of groups represented by formulae IV-VIII; each of Ar<1> and Ar<2> is an optionally substituted alkyl or aryl or heterocyclic group; each of R<1>-R<5> and R<9> is H, alkyl, halogen, or the like; each of R<6> and R<8> is H, alkyl, or the like; each of R<7> and R<10> is an aryl or heterocyclic group; the dotted line 1 indicate that the 2 phenyl groups combined with each other through the nitrogen atom may combine with each other along this dotted line 1, and the dotted line 2 indicate that the 2 phenyl groups combined with each other through the nitrogen atom may combine along this dotted line 2.

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 4]

(In the formula, Q ¹ is represented by the following general formulas [III] to [VI]
I]] represents any group; Q ² represents any group represented by the following general formulas [IV] to [VIII];

[0008]

[Chemical 5]

X represents an aliphatic linking group which may have a substituent, and an oxygen atom or a carbon-carbon double bond may be present in the main chain of the linking group; Ar ¹ and Ar ²
Each is an alkyl group or an aryl group which may have a substituent or a heterocyclic group, which may be the same or different from each other; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁹ represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, or an alkoxy group which may have a substituent, which may be the same or different from each other; R ⁶ and R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and these may be the same or different from each other; R ⁷ and R ¹⁰ Each represents an aryl group or a heterocyclic group which may have a substituent; the dotted line 1 represents 2 bonded to the same nitrogen atom.
In the general formula [IX] or [XI], two phenyl groups are bonded as shown by a dotted line, and a dotted line 2 is two general phenyl groups bonded to the same nitrogen atom as shown by a dotted line in the general formula [X]. ] Or [XII]

[0010]

[Chemical 6]

It is shown that the represented structure can also be taken. And a photosensitive layer containing a bishydrazone compound represented by the formula (1). Hereinafter, the present invention will be described in detail.

The electrophotographic photoreceptor of the present invention contains the bishydrazone compound represented by the above general formula [I] in the photosensitive layer. In the general formula [I], Q ¹ represents any group represented by the following general formulas [III] to [VII]; Q ² represents any group represented by the following general formulas [IV] to [VIII]. Represents a group.

[0013]

[Chemical 7]

X is a lower alkyl group such as a methyl group and an ethyl group, a lower alkoxy group such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, and a substituent group such as an aryl group such as a phenyl group and a naphthyl group. Represents an aliphatic linking group which may have, and these alkyl group, alkoxy group and aryl group may have a substituent, and the substituent includes a hydroxyl group; a chlorine atom, a bromine atom, iodine Halogen atom such as atom; alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group; methoxy,
Alkoxy group such as ethoxy group and butoxy group; allyl group;
Aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group; aryloxy groups such as phenoxy group and triloxy group; arylalkoxy groups such as benzyloxy group and phenethyloxy group; aryl groups such as phenyl group and naphthyl group; styryl group , Arylvinyl groups such as naphthylvinyl group, dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group and dinaphthylamino group; diaralkylamino groups such as dibenzylamino group and diphenethylamino group Group; diheterocyclic amino group such as dipyridylamino group and dithienylamino group; diallylamino group; and disubstituted amino group in which the above-mentioned amino group substituents are combined.

Further, an oxygen atom or a carbon-carbon double bond may be present in the main chain of the linking group. In the case of a carbon-only linking group main chain, the number of constituent carbons is preferably 1 to 9, and in some cases, a hydrocarbon ring such as a cyclohexane ring may be formed on Sp ³ carbon in the linking group chain. .. When an oxygen atom is present in the main chain of the linking group, it is in the form of an ether bond, and the constituent carbon chain length is preferably 1-9.

Ar ¹ and Ar ² are each an alkyl group such as a methyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group; a pyrrolyl group, a thiophenyl group, a furyl group or a carbazolyl group. Which may be the same or different from each other, and a phenyl group is 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 A diarylamino group such as a diphenylamino group or a dinaphthylamino group; a dibenzylamino group Group, a diaralkylamino group such as a diphenethylamino group; a diheterocyclic amino group such as a dipyridylamino group or a dithienylamino group; a diallylamino group, or a disubstituted amino group in which the above-mentioned amino group substituents are combined. Can be given.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁹
Represents a hydrogen atom; 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 or a propyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propyloxy group, which are the same as each other. But it can be different. These alkyl groups and alkoxy groups 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, a propyl group or a butyl group Alkyl group such as hexyl group; Alkoxy group such as methoxy group, ethoxy group, butoxy group; Allyl group; Aralkyl group such as benzyl group, naphthylmethyl group and phenethyl group; Aryloxy group such as phenoxy group and triloxy group; Benzyl group Oxy group,
Arylalkoxy group such as phenethyloxy group; aryl group such as phenyl group and naphthyl group; arylvinyl group such as styryl group and naphthylvinyl group, dimethylamino group,
Dialkylamino group such as diethylamino group; Diarylamino group such as diphenylamino group and dinaphthylamino group; Diaralkylamino group such as dibenzylamino group and diphenethylamino group; Dihetero group such as dipyridylamino group and dithienylamino group Ring amino group; diallylamino group,
Examples thereof include di-substituted amino groups in which the above-mentioned amino group substituents are combined.

R ⁶ and R ⁸ represent a hydrogen atom; an alkyl group such as a methyl group, an ethyl group and a propyl group; an aryl group such as a phenyl group, a naphthyl group and an anthracenyl group, which may be the same or different. Especially, a hydrogen atom or a methyl group is preferable. These alkyl group and aryl group may have a substituent, and as the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group Group, alkyl group such as hexyl group; alkoxy group such as methoxy group, ethoxy group, butoxy group; allyl group; aralkyl group such as benzyl group, naphthylmethyl group, phenethyl group; aryloxy group such as phenoxy group and triloxy 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; diphenylamino group Diarylamino group such as dinaphthylamino group; dibenzylamino group, diarylamino group Enechiruamino diaralkylamino groups such as; dipyridyl amino group, di heterocyclic amino groups such as Jichieniruamino group;
A diallylamino group and a disubstituted amino group in which the above-mentioned amino group substituents are combined are also exemplified.

R ⁷ and R ¹⁰ represent an aryl group such as a phenyl group, a naphthyl group and an anthracenyl group; a heterocyclic group such as a pyrrolyl group, a thiophenyl group, a furyl group and a carbazolyl group, which may be the same or different. In particular, a phenyl group or a naphthyl group is preferable. These aryl group and heterocyclic group may have a substituent, and the substituent includes a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group, Alkyl group such as butyl group, hexyl group; alkoxy group such as methoxy group, ethoxy group, butoxy group; allyl group; aralkyl group such as benzyl group, naphthylmethyl group and phenethyl group; aryloxy group such as phenoxy group and triloxy group An arylalkoxy group such as a benzyloxy group and a phenethyloxy group; an aryl group such as a phenyl group and a naphthyl group; an arylvinyl group such as a styryl group and a naphthylvinyl group; a dialkylamino group such as a dimethylamino group and a diethylamino group; diphenylamino Group, diarylamino group such as dinaphthylamino group; dibenzylamino group, diphylamino group Dipyridyl amino group, di heterocyclic amino groups such as Jichieniruamino group; Nechiruamino diaralkylamino group such as addition diallylamino group, di-substituted amino group such as a combination of substituents of the amino group of the above.

The dotted line 1 is the following general formula [IX] or [XI] in which two phenyl groups bonded to the same nitrogen atom are bonded as shown by the dotted line, and the dotted line 2 is two phenyl groups bonded to the same nitrogen atom. Combined as shown by the dotted line, the following general formula [X]
Or [XII]

[0021]

[Chemical 8]

It is also possible to have the structure represented. ) Representative 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.

In the following examples, unless otherwise stated, Ar ¹ and Ar ² are both phenyl groups, R ¹ and R 2.
² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are all hydrogen atoms, Q ¹ is a general formula [III] and Q ² is a general formula [VII].
I], R ⁷ and R ¹⁰ are all phenyl groups,
The bonding position of C (R ⁶ ) = N−Q ¹ and —C (R ⁸ ) = N−Q ² with respect to the benzene nucleus is 1 carbon atom of the benzene nucleus bonded to the nitrogen atom, and the carbon atom adjacent Two atoms
And when it is set to 3, 4, 5, 6 in order, it is assumed to be the position of 4.

Also, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
^The bonding position of ⁹ with respect to the benzene nucleus is set to 1, the carbon atom of the benzene nucleus that is bonded to the nitrogen atom is 2, and the carbon atom next to it is 3, 4, 5, and 6 in sequence. For example, when R ¹ is a methyl group and is bonded to the 2 position of the benzene nucleus, it is represented as R ¹ : 2-methyl group.

The positions at which the following substituents are bonded are represented by the following numbers.

[0026]

[Chemical 9]

When the above naphthyl group, thienyl group or furyl group has a substituent, the number shown in the above formula indicates the bonding position of the substituent. For example, R ⁷ is
A naphthyl group having a substituent having a methyl group bonded to the 4 position of the naphthyl groups, when attached at the 2 position, R ^7: 2- (4- methyl) naphthyl group, and represent.
If X has the following structure,

[0028]

[Chemical 10]

X; --CH _2- [cyclohexane ring] -C
Represented as H ₂ −. Compound Example 1. X; -CH ₂ - _{2. X; -CH 2 CH 2 CH 2} - 3. _{X; -CH 2 CH 2 CH 2} CH 2 CH 2 - 4. _{X; -CH 2 -CH 2 = CH} 2 -CH 2 - 5. _{X; -CH 2 OCH 2 - Ar} 1 and Ar ^2; methyl R ⁶ and R ^8; phenyl R ⁵ and R ^9; 4-methyl 6. X; -CH ₂ - [cyclohexane ring] -CH ₂ - R ¹ and R ^2; 3- chloro groups R ⁶ and R ^8; methyl R ⁷ and R ^10; 3- chloro group 7. _{X; -CH 2 CH 2 - R} 7 and R ^10; 1-naphthyl group 8. _{X; -CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 - R 7 and R ^10; 1- (4- methyl) naphthyl 9. _{X; -CH 2 CH = CHCH 2} - R 1 and R ^2; 2-methoxy and R ⁷ and R ^10; 1-naphthyl group 10. _{X; -CH 2 CH 2 CH 2} CH 2 - Ar 1 and Ar ^2; 2- (5- methyl) thienyl Q ¹ and Q ^2; [IV] 11. _{X; -CH 2 OCH 2 - R} 3 and R ^4; 3- methoxy Q ¹ and Q ^2; [V]

12. X; -CH ₂ - [cyclohexane ring] -CH ₂ - Ar ¹ and Ar ^2; methyl Q ¹ and Q ^2; [VI] 13. X; -CH ₂ - R ¹ and R ^2; 3- methyl Q ¹ and Q ^2; (VII) 14. X; -CH ₂ CH ₂ - Ar ¹ and Ar ^2; methyl dashed 1; [IX] dotted 2; [X] wherein R ⁷ and R ^10; 4-methoxyphenyl group 15. _{X; -CH 2 CH = CHCH 2} - Ar 1 and Ar ^2; methyl dashed 1; [XI] dotted 2; [XII] wherein R ⁷ and R ^10; 2-thienyl group 16. _{X; -CH 2 CH 2 CH 2} - Ar 1 and Ar ^2; 2-furyl group and R ⁷ and R ^10; 2-furyl group 17. _{X; -CH 2 CH 2 CH 2} CH 2 - R 10; 1- naphthyl group 18. X; -CH ₂ OCH ₂ - Ar ^1; methyl R ^3; 3- chloro group R ^6; methyl dotted 2; [X] Ar ^2; methyl 19. _{X; -CH 2 CH 2 - R} 3 and R ^4; 3- methyl R ^6; phenyl Q ^1; (IV) R ^8; methyl Q ^2; [VI] 20. _{X; -CH 2 CH 2 CH 2} CH 2 - Q 1; (VII) R ^10; 1- (4- chloro) naphthyl

The bishydrazone compound represented by the above general formula [I] can be produced by a known method. For example, it is a method in which an arylamine compound is used as a raw material, a known carbonyl introduction reaction is carried out, and then a dehydration reaction with desired hydrazines is carried out to obtain a target compound.

(A-1) In the general formula [I], R⁶and
R⁸When is a hydrogen atom, the following general formula [XIII]
(In the general formulas [XIII] and [XIV], R¹, R²，
R³, R ^Four, Ar¹, Ar², X and dotted line 1, dotted line 2
Has the same meaning as in formula [I]. )
The amine compound

[0033]

[Chemical 11]

By reacting with a formylating agent such as N, N-dimethylformamide or N-methylformanilide in the presence of phosphorus oxychloride, an aldehyde compound represented by the general formula [XIV] can be obtained. (Viral Mayer reaction) A large excess of formylating agent can be used as a reaction solvent, but an inert solvent for the reaction such as o-dichlorobenzene or benzene can also be used.

(A-2) Then, the obtained general formula [XIV]
A bishydrazone represented by the general formula [I] can be produced by subjecting the compound of the formula (I) to a dehydration condensation reaction with hydrazines represented by the following general formulas [XV] a and b. Where [XV] a,
R ⁷ and R ⁵ , and R ⁹ and R ^{10 in} b may contain a nitrogen atom to form a heterocycle represented by the above general formulas [IV], [V], [VI] and [VII]. ..

[0036]

[Chemical formula 12]

The dehydration condensation reaction may be carried out at a temperature of 50 ° C. to 1 if necessary.
Under heating at 50 ° C., in a solvent inert to the reaction such as methanol, ethanol, tetrahydrofuran, cellosolve, N, N-dimethylformamide, benzene and toluene,
Paratoluene sulfonic acid as a reaction accelerator, if desired,
You may use auxiliary agents, such as hydrochloric acid and sodium acetate. (Hydrazonization reaction) [XV] a and [XV] b may be used alone or in combination, or may be reacted stepwise in some cases.

(B-1) R in the general formula [I]⁶and
R⁸Is a hydrogen atom other than the general formula [XIII] as shown below.
(In the general formulas [XIII] and [XVI], R¹, R²，
R³, R ^Four, R⁶, R⁸, Ar¹, Ar², X and dots
Line 1 and dotted line 2 have the same meaning as in the general formula [I] shown above.
Have a righteousness, R⁶And R⁸Can be the same or different
Yes. ) An arylamine compound represented by

[0039]

[Chemical 13]

An acid chloride represented by the general formula Cl-CO-R ⁶ or Cl-CO-R ⁸ in the presence of a Lewis acid such as aluminum chloride, iron chloride or zinc chloride in a solvent such as nitrobenzene, dichloromethane or carbon tetrachloride. A ketone body represented by the general formula [XVI] is obtained by reacting with a substance. R ⁶ and R ⁸ may be the same as or different from each other, and in the case of R ⁶ ≠ R ⁸ , it is achieved by mixing the acid chlorides to be added or adding them stepwise.

(B-2) [XVI] → [I] is (A-
It is achieved by the same reaction as in 2). In these reactions, a high-purity compound can be obtained by a known purification means such as recrystallization purification, sublimation purification, column purification, etc. after each step or after all steps in some cases.

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 containing a hydrazone compound in a binder and optionally a sensitizer dye or an electron-withdrawing compound, photoconductive particles and a hydrazone compound that generate charge carriers with extremely high efficiency when absorbing light. A photosensitive layer added to a binder, a charge transfer layer composed of a hydrazone compound and a binder, and photoconductive particles that generate charge carriers with extremely high efficiency when absorbing light, or a charge generation layer composed of a binder is laminated. Photosensitive layers and the like.

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, a 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 pigments, and electron-withdrawing compounds added to the photosensitive layer, known ones can be used. Photoconductive particles that generate charge carriers with extremely high efficiency when attracting light include selenium, selenium-tellurium alloys, selenium-arsenic alloys, cadmium sulfide,
Inorganic photoconductive particles such as amorphous silicon; metal-containing phthalocyanine, perinone resin, thioindigo dye, quinacridone pigment, perylene pigment, anthraquinone pigment, azo pigment, bisazo pigment, trisazo pigment, tetrakis azo pigment , And organic photoconductive particles such as cyanine pigments. (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, 1-nitroanthraquinone, and 1-chloro-
Quinones such as 5-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone; aldehydes such as 4-nitrobenzaldehyde; 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 2,4,7-trinitrofluorenone , 2,
4,5,7-tetranitrofluorenone, 3,3 ',
Ketones such as 5,5′-tetranitrobenzophenone;
Acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride; tetracyanoethylene, terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, 4- (p-nitrobenzoyloxy) ) Cyano compounds such as benzalmalononitrile; 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,5,6,7-tetrachlorophthali Examples thereof include electron-withdrawing compounds such as phthalides.

Further, the photosensitive layer of the electrophotographic photosensitive member of the present invention may contain known plasticity 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 hydrazone 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. .. 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.

[0050]

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) Bis (p-diphenylamino) -1,8-
Diphenyl-1,7-octadiene

[0051]

[Chemical 14]

1.0 g was dissolved in 20 ml of N, N-dimethylformamide and then 0.53 ml of phosphorus oxychloride.
Was added, and then the mixture was reacted at 60 ° C. for 1 hour and 30 minutes. After cooling, the reaction solution was released into 150 g of ice water, hydrolyzed with sodium hydroxide, and then extracted and concentrated by a conventional method.
By purifying, 0.9 g of a yellow oily matter was obtained.

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

[0054] (Mass spectrometry measurements) C ₄₆ H ₄₀ O ₂ as N ₂ MW
= 652, M ⁺ = 652

[0055]

[Chemical 15]

(Production Example 2) 0.9 g of the compound synthesized in Production Example 1 and 1.0 g of 1,1-diphenylhydrazine were mixed with 9 ml of tetrahydrofuran and 5 ml of methanol in the presence of an acetic acid catalyst.
The mixture was reacted for 12 hours at room temperature.

Then, the reaction solution was poured into 200 ml of methanol, and filtered and purified by a conventional method to obtain 0.7 g of a yellow oily substance. This compound was found to be a bishydrazone-based compound represented by the following structural formula, based on the following elemental analysis values, mass spectrometric measurements, and infrared absorption spectrum measurements (FIG. 1).

[0058] (Mass spectrometric measurement result) C ₇₀ H ₆₀ N ₆ MW = 9
84, M ⁺ +1 = 985

[0059]

[Chemical 16]

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 KK) were added to 30 parts of 4-part.
Methoxy-4-methylpentanone-2 (Mitsubishi Kasei Co., Ltd.)
(Manufactured by the company).

This dispersion was applied on an aluminum vapor-deposited layer vapor-deposited on a polyester film having a thickness of 100 μm by 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 2 and the following polycarbonate resin

[0062]

[Chemical 17]

A coating liquid having 100 parts dissolved in 900 parts dioxane 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, of the electrophotographic photosensitive member having the photosensitive layer composed of two layers thus obtained was measured and found to be 2.2 (μW / cm ² ) ^-1 .

The half-exposure amount is as follows.
It was determined by charging with 8 kV corona discharge, then exposing with 775 nm light, and measuring the amount of exposure required to decay the surface potential from 500V to 250V.

Example 2 Instead of the phthalocyanine pigment used in Example 1, a naphthalic acid 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.

[0066]

[Chemical 18]

Examples 3 to 10 Instead of the bishydrazone compound used in Example 1,
An electrophotographic photoconductor obtained by using the bishydrazone compounds shown in Table 1 below synthesized in the same manner as in Production Example 2 and using the titanium oxyphthalocyanine pigment used in Example 1 in the charge generation layer. The sensitivity of is shown in Table 1.

Table 1 Example Example Compound No. Sensitivity (μW / cm ² ) ^-1 3 2 2.2 4 4 2.0 5 7 7 2.0 6 10 1.0 1.0 7 11 1.5 1.5 8 12 1.4 9 15 15 0.9 10 20 1.6

Comparative Example 1 In the same manner as in Example 1 except that the bishydrazone compound shown in Table 2 below was used in place of the bishydrazone compound used in Example 1,
An electrophotographic photoreceptor was obtained. Each photoconductor was charged by a corona discharge of -4.8 kV in the dark, and the surface potential at that time was measured as the initial surface potential. Then, as in Example 1,
After measuring the sensitivity, the surface potential after sufficient exposure is taken as the residual potential. These results are shown in Table 2 together with the measurement results for the photoconductor of Example 1.

[0070]

[Table 1]

It can be seen that the present invention is particularly excellent in residual potential as compared with the comparative example.

[0072]

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.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of a bishydrazone compound obtained in Production Example 2.

Claims (1)

[Claims] 1. A compound represented by the following general formula [I] on a conductive support: (In the formula, Q ¹ represents any group represented by the following general formulas [III] to [VII]; Q ² represents the following general formula [IV] to
Represents any group represented by [VIII]; X represents an aliphatic linking group which may have a substituent, and an oxygen atom or a carbon-carbon double bond may be present in the main chain of the linking group; Ar ¹ and Ar ² are each a substituent. An alkyl group, an aryl group or a heterocyclic group which may have a group, which may be the same or different from each other; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁹ are each A hydrogen atom, an alkyl group which may have a substituent, a halogen atom, or an alkoxy group which may have a substituent, which may be the same or different from each other; R ⁶ and R ⁸ are each represents a hydrogen atom, an optionally substituted alkyl group or a substituted group aryl group which may have a, these may be the same or different from each other; R ⁷ and R ¹⁰ are each substituted May have a group Represents a reel group or a heterocyclic group; dotted line 1 is the following general formula [IX] or [XI] in which two phenyl groups bonded to the same nitrogen atom are bonded as shown by the dotted line, and dotted line 2 is bonded to the same nitrogen atom. The two phenyl groups are bonded as shown by a dotted line, and are represented by the following general formula [X] or [XII] It shows that the structure represented can also be taken. ) An electrophotographic photoreceptor having a photosensitive layer containing a bishydrazone compound represented by the formula (1).