JPH0643675A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body having superior sensitivity and superior repetition characteristics by incoporating a hydrazone compound having a specified bisenamine group in a photosensitive layer. CONSTITUTION:This electrophotographic sensitive body is provided on a conductive substrate with the photosensitive layer containing the hydrazone compound having the bisenamine groups each represented by formula I or II in which each of A and B is optionally substituted aryl, such a substituted heterocyclic group, such aralkyl, or the like: each of R<1> and R<2> is H, optionally substituted aryl, such a heterocyclic group, or the like; a is 1-5C alkyl, such dialkylamino, or the like: n is 1, 2, or 3; b is 1-5C alkyl, such alkoxy, or the like; m is 1, 2, 3, or 4; and Z is a divalent residue necessary to form an optionally substituted and optionally condensed hetero ring together with the N atom of the hydrazone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a photosensitive layer formed on a conductive support and containing a bisenamine group-containing hydrazone compound. Is.

[0002]

2. Description of the Related Art Conventionally, in electrophotographic technology, selenium, cadmium sulfide, amorphous silicon, zinc oxide, etc., which are inorganic substances, have been widely used in the photosensitive layer of electrophotographic photoreceptors. However, in recent years, much research has been conducted using an organic photoconductive material as an electrophotographic photoreceptor.

Here, the basic properties required for an electrophotographic photosensitive member are listed as follows: (1) High chargeability due to corona discharge in a dark place. (2) The resulting charge due to corona charging is less attenuated in a dark place. (3) Charge should be rapidly dissipated by light irradiation. (4) The residual charge after irradiation with light is small. (5) Little increase in residual potential and decrease in initial potential due to repeated use. (6) There are few changes in electrophotographic characteristics due to temperature and humidity.

Conventional inorganic electrophotographic photoreceptors such as selenium and cadmium sulfide have the conditions as a photoreceptor in terms of basic properties, but they are problematic in production, for example, have strong toxicity and film formability. However, there are drawbacks such as difficulty in manufacturing, low plasticity, and high manufacturing cost. Furthermore, in the future, due to the depletion of resources, these inorganic substances, whose production is limited, and also in terms of pollution due to toxicity,
The use of photoreceptors of inorganic to organic materials is desired.

In view of these points, research on electrophotographic photoreceptors made of organic substances has been actively conducted in recent years, and as a result, electrophotographic photoreceptors using various organic substances have been proposed and put to practical use. Some have. Generally speaking, organic type has better transparency than inorganic type, light weight, easy film-forming property, and has both positive and negative electrification property. It has advantages such as being easy.

Typical examples of organic electrophotographic photoreceptors that have been proposed so far include polyvinylcarbazole and its derivatives, but these are not always sufficient in film formability, plasticity, solubility, adhesiveness and the like. In addition, those obtained by sensitizing polyvinyl carbazole with a pyrrolium salt dye (Japanese Patent Publication No. 48-25658) and those obtained by sensitizing polyvinyl carbazole and 2,4,7-trinitroflorenone (US Pat. No. 3,484, No. 237) and the like, but those satisfying the basic properties required for the above-mentioned photoreceptor, mechanical strength, high durability, etc. are still insufficient. Not obtained.

[0007]

According to the present invention, a photosensitive layer formed on a conductive support comprises: i) a general formula (I)

[0008]

[Chemical 3] [Wherein A and B are an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or an alkyl group having 1 to 5 carbon atoms, and R
¹ is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent,
An alkyl group having 1 to 5 carbon atoms or a hydrogen atom, R
² is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent,
An alkyl group having 1 to 5 carbon atoms or a hydrogen atom,
Is an alkyl group having 1 to 5 carbon atoms, a dialkylamino group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and n is an integer of 1 to 3 (where n is When 2 or more, a may be the same or different,
Further, they may form a ring with each other), and b has 1 to 5 carbon atoms.
Is an alkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and m is an integer of 1 to 4 (however, when m is 2 or more, b may be the same or different). ] Or a bisenamine group-containing hydrazone compound (I), or ii) the general formula (II):

[0009]

[Chemical 4] [Wherein R ¹ , R ² , a, b, n and m represent the same contents as in the general formula (I), and Z represents a heterocycle which may have a substituent or a substituent together with the nitrogen atom of hydrazine. And a bisenamine group-containing hydrazone compound (II) represented by the formula (1), which is necessary for forming a condensed heterocycle which may be possessed.

The bisenamine group-containing hydrazone compound of the general formula (I) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthetic process.
That is, various substituted p-nitrophenyl ketone derivatives represented by the following structural formula (III) or various substituted p-nitrobenzaldehyde derivatives and various hydrazine compounds represented by the following structural formula (IV) were mixed with acetic acid or potassium acetate in ethanol. It is heated in the presence of a catalyst, and the following structural formula (V)
A hydrazone derivative represented by

[0011]

[Chemical 5] [Each symbol in the formula has the same meaning as defined in formula (I)] Then, this hydrazone derivative is reduced with iron powder / acetic acid in dioxane to obtain an aminohydrazone derivative represented by the following structural formula (VI).

[0012]

[Chemical 6] [Each symbol in the formula has the same meaning as defined in the general formula (I)] Further, the aminohydrazone derivative (VI) and 2 equivalents of various substituted phenylacetaldehyde derivatives represented by the following structural formula (VII) are dehydrated and condensed. Thus, the bisenamine group-containing hydrazone compound (I) of the present invention can be obtained.

[0013]

[Chemical 7] [Each symbol in the formula has the same meaning as defined in the general formula (I)] Next, the bisenamine group-containing hydrazone compound of the general formula (II) according to the present invention can be synthesized by various methods. It is easily synthesized in the process. That is, various substituted p-nitrophenyl ketone derivatives represented by the following structural formula (III), or various substituted p-nitrobenzaldehyde derivatives and various hydrazine compounds represented by the following structural formula (VII) were mixed with acetic acid or potassium acetate in ethanol. By heating in the presence of a catalyst, a hydrazone derivative represented by the following structural formula (VIII) is obtained.

[0014]

[Chemical 8] [Each symbol in the formula has the same meaning as defined in formula (II)] Then, this hydrazone derivative is reduced with iron powder / acetic acid in dioxane to obtain an aminohydrazone derivative represented by the following structural formula (IX).

[0015]

[Chemical 9] [Each symbol in the formula has the same meaning as defined in the general formula (II)] Further, the aminohydrazone derivative (IX) is dehydrated and condensed with 2 equivalents of various substituted phenylacetaldehyde derivatives represented by the following structural formula (VII). Thus, the bisenamine group-containing hydrazone compound (II) of the present invention can be obtained.

[0016]

[Chemical 10] [Each symbol in the formula has the same meaning as defined in formula (II)] An object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and high durability. In particular, the photoreceptor of the present invention is to provide a photoreceptor having excellent stability with respect to temperature and humidity, high charging characteristics, and substantially no deterioration in photosensitivity even after repeated use.

The substituents of the bisenamine group-containing hydrazone compound represented by the general formula (I) and the general formula (II) of the present invention will be described below. R ¹ is phenyl, p-tolyl or p-methoxyphenyl. , P-dimethylaminophenyl, 3,5-xylyl, 1-naphthyl, 2
Aryl groups such as -naphthyl and 2-methyl-1-naphthyl, 1-pyridyl, N-ethyl-3-carbazole, 1
-Furyl, 2-furyl, 4-methyl-1-furyl, 3-
Heterocyclic groups such as methyl-2-furyl, benzyl, aralkyl groups such as p-methylbenzyl, p-methoxybenzyl, 3,5-dimethylbenzyl, etc., methyl, ethyl, n
Alkyl groups such as -propyl, n-butyl, iso-butyl, n-pentyl, and the like.

R ² is a hydrogen atom or methyl,
Ethyl, n-propyl, n-butyl, iso-butyl,
Alkyl groups such as n-pentyl, phenyl, p-tolyl, p-methoxyphenyl, 3,5-xylyl, aryl groups such as 1-naphthyl, 2-naphthyl, 2-methyl-1-naphthyl, 1-pyridyl, 2 -Pyridyl, n-ethyl-3-carbazolyl, 1-furyl, 2-furyl, 4
-Methyl-1-furyl, 1-thienyl, 2-methyl1-
Heterocyclic groups such as cenyl, aralkyl groups such as benzyl, 4-methylbenzyl, p-methoxybenzyl, 3,5-dimethylbenzyl and the like can be mentioned.

Examples of a and b include a hydrogen atom, an alkyl group such as methyl and ethyl, an alkoxy group such as methoxy and ethoxy, and an electron donating substituent such as N, N, -dimethylamino and N, N-diethylamino group. A and B in the general formula (I) are alkyl groups such as methyl, ethyl, n-propyl, n-butyl, iso-butyl and n-pentyl, phenyl, p-tolyl, p-methoxyphenyl, 1
Examples include aryl groups such as -naphthyl, 2-naphthyl and 9-tetracenyl, and aralkyl groups such as benzyl, p-methylbenzyl, p-methoxybenzyl and 3,5-dimethylbenzyl.

Z in the general formula (II) is 2, 3
-Dihydroindolyl, 1,2,3,4-tetrahydroquinolyl, 2,3,3-trimethyl-1.2-dihydroindolyl, carbazolyl, 1,2,3,4-tetrahydrocarbazolyl, 1- Examples thereof include phenyl and indolenyl. Next, specific examples of the bisenamine group-containing hydrazone compound of the present invention represented by the above general formula (I) include those having the structure shown in Table 1. By this, the bisenamine group-containing hydrazone of the present invention can be mentioned. The compound is not limited.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9] Among these exemplified compounds, R ¹ is a phenyl group, a p-tolyl group or a p-methoxy group, and R ² is a hydrogen atom or a methyl group, which are particularly excellent in electrophotographic properties, cost and synthesis. And a bisenamine group-containing hydrazone compound in which A and B are a methyl group, a phenyl group, and a p-tolyl group, and a and b are hydrogen, a methyl group, and a methoxy group.

Further, specific examples of the bisenamine group-containing hydrazone compound of the present invention represented by the above general formula (II) include those having the structures shown in Table 2. By this, the bisenamine of the present invention can be used. The group-containing hydrazone compound is not limited.

[0031]

[Table 10]

[0032]

[Table 11]

[0033]

[Table 12]

[0034]

[Table 13]

[0035]

[Table 14]

[0036]

[Table 15]

[0037]

[Table 16]

[0038]

[Table 17]

[0039]

[Table 18] Among these exemplified compounds, R ¹ is a phenyl group, a p-tolyl group or a p-methoxy group, and R ² is a hydrogen atom or a methyl group, which are particularly excellent in electrophotographic properties, cost and synthesis. A, b is hydrogen, a methyl group or a methoxy group, and Z is 2,3-dihydroindolyl, 1,2,
Examples thereof include bis enamine group-containing hydrazone compounds which are 3,4-tetrahydroquinolyl and 2,3,3-trimethyl-1.2-dihydroindolyl.

The electrophotographic photosensitive member according to the present invention can be obtained by containing one kind or two or more kinds of the bisenamine group-containing hydrazone compound shown above. In addition, in some cases, other styryl compounds such as β-phenyl- [4- (dibenzylamino)] stilbene, β-phenyl- [4- (N-ethyl-N-phenylamino)] stilbene, 1,1 -Bis (4-diethylaminophenyl) -4,4-diphenylbutadiene}, or the following hydrazone compounds, {for example, 4- (dibenzylamino) benzaldehyde-N,
N-diphenylhydrazone, 4- (ethyl, phenylamino) benzaldehyde-N, N-diphenylhydrazone, 3,3-bis [(4'-diethylamino) phenyl] acrolein-diphenylhydrazone}, or the following triphenylamine compound {For example, 4-methoxy-4 '-(4-methoxystyryl) triphenylamine, 4-methoxy-4'-styryltriphenylamine} and the like can be contained.

Various methods are conceivable as a mode in which these bis enamine group-containing hydrazone compounds are used as an electrophotographic photoreceptor. For example, a bis-enamine group-containing hydrazone compound and a sensitizing dye, and if necessary, a chemical sensitizer or an electron-withdrawing compound are added and dissolved or dispersed in a binder resin to be provided on a conductive support. In the form of a photoconductor or a laminated structure capable of forming a carrier generation layer and a carrier transfer layer with high charge carrier generation efficiency, a sensitizing dye or a pigment represented by an azo pigment or a phthalocyanine pigment is mainly provided on a conductive support. A bisenamine group-containing hydrazone compound of the present invention is added to the carrier generation layer thus prepared, if necessary, by adding an antioxidant compound or an electron-withdrawing compound to dissolve or disperse in the binder, and a laminate is formed by providing this as a carrier transfer layer. There are photoconductors,
It is possible to apply to both cases.

In preparing photoreceptors using the compounds of the present invention, the aid of a polymeric film-forming binder on a support such as a metal drum, metal plate, electrically conductive processed paper, or plastic film. Borrow and make a film. In this case, in order to further increase the sensitivity, it is desirable to add a sensitizer and a substance that imparts plasticity to the polymerizable film-forming binder as described below to form a uniform photoreceptor film.

As these polymerizable film-forming binders, various ones can be mentioned depending on the field of application. That is, in the field of photoconductors for copiers or printers,
Polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, polyphenylene oxide resin, polyester resin, alkyd resin, polyarylate resin and the like are preferable. These are alone or 2
You may use it in mixture of 2 or more types. Among them, polystyrene,
Resins such as polycarbonate, polyarylate, and polyphenylene oxide have a volume resistance value of 10 ¹³ Ω or more, and also have excellent film-forming properties and potential characteristics.

The amount of these binders to be added to the bisenamine group-containing hydrazone compound of the present invention is 0.2 to 20 times by weight, preferably 0.5 to 5 times. When it is 5 or less, a bisenamine group-containing hydrazone compound is precipitated from the surface of the photoreceptor, and when it is 5 times or more, the sensitivity is remarkably lowered. Especially for use in printing plates an alkaline binder is required. The alkaline binder is an acidic group soluble in water or an alcoholic alkaline solvent (including mixed systems), such as an acid anhydride group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, or a sulfonimide group. Is a polymer substance having

These alkaline binders usually have an acid value of 10
It is preferable to have a high value of 0 or more. The binder resin having a large acid value is easily dissolved or easily swelled in an alkaline solvent. Examples of these binder resins include styrene: maleic anhydride copolymer, vinyl acetate: maleic anhydride copolymer, vinyl acetate: crotonic acid copolymer, methacrylic acid: methacrylic acid ester copolymer, phenol resin, methacrylic acid. Acid: styrene: methacrylic acid ester copolymer and the like.

The ratio of these resins added to the photoconductive organic substance may be approximately the same as in the case of the photoconductor for a copying machine.
Next, as the sensitizing dye added to the photosensitive layer, methyl violet, crystal violet, night blue,
Triphenylmethane dyes represented by Victoria Blue, erythrosine, rhodamine B, rhodamine 3R,
Acridine dye typified by acridine orange and flapeosin, thiazine dye typified by methylene blue and methylene green, oxazine dye typified by capri blue and meldora blue, cyanine dye, styryl dye, pyrylium salt dye, thiopyrylium There are salt dyes.

In the photosensitive layer, as photoconductive pigments that generate charge carriers with extremely high efficiency by light absorption, phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines and halogenated metal-free phthalocyanines, perylene imides and perylenes. Examples include perylene pigments such as acid anhydrides, bisazo pigments, azo pigments such as trisazo pigments, quinacridone pigments, and anthraquinone pigments.

In particular, the charge-generating pigments are metal-free phthalocyanine pigments, titanyl phthalocyanine pigments, fluorenylidene, bisazo pigments containing a phlorenone ring,
Those using bisazo pigments and trisazo pigments composed of aromatic amines give excellent electrophotographic photoreceptors showing high sensitivity. Also, the above-mentioned dye may be used as the charge carrier generating substance. These dyes may be used alone, but in many cases, the coexistence of a pigment generates charge carriers with higher efficiency.

In addition to the above-mentioned spectral sensitizers, it is necessary to add various chemical substances for the purpose of preventing an increase in residual potential, a decrease in charging potential, a decrease in sensitivity, etc., due to repeated use. Is coming. These added substances include tribenzylamine, 1-chloroanthraquinone, benzoquinone, 2,3-dichloronaphthoquinone, naphthoquinone, 4,4'-dinitrobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dichlorobenzophenone, 4-nitrobenzophenone, 4-nitrobenzalmalondinitrile, α-cyano-β- (p-cyanophenyl) ethyl acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano-1- (p-nitro Phenyl) -2- (p-chlorophenyl) ethylene, 2,7-
Examples thereof include electron-withdrawing compounds such as dinitrofluorenone.

In addition, an antioxidant, an anti-curl agent, a leveling agent and the like can be added as an additive to the photosensitive member, if necessary. The bisenamine group-containing hydrazone compound of the present invention is dissolved or dispersed in a suitable solvent together with the above-mentioned various additives according to the form of the photoreceptor, and the coating solution is coated on the conductive support described above, Dry to produce a photoreceptor.

As the coating solvent, halogenated hydrocarbons such as methylene chloride and dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene, and solvents such as dioxane, dimethoxymethyl ether and dimethylformamide, either alone or in combination. The above mixed solvent or, if necessary, a solvent such as alcohols, acetonitrile and methyl ethyl ketone can be further added and used.

Next, the specific synthesis of the bisenamine group-containing hydrazone compound of the present invention will be described, but the synthesis examples are not limited thereto. Synthesis Example 1 (Exemplified Compound No. 2) By heating p-nitrobenzaldehyde and N, N-diphenylhydrazine hydrochloride in ethanol using a potassium acetate catalyst, p-nitrobenzaldehyde N,
N-diphenylhydrazone is obtained. Then, the compound thus obtained is subjected to reduction reaction with iron powder in 1,4 dioxane / water to give p-3 aminobenzaldehyde N, N-
Get diphenylhydrazone. Then, in benzene, α
-Exemplified compound No. was obtained by dehydration condensation with 2 equivalents of phenylpropionaldehyde. 2 (melting point, 182.0-
183.0 ° C.) (the recrystallization was carried out from a mixed solvent of ethanol / ethyl acetate).

Synthesis Example 2 (Exemplified Compound No. 82) By heating p-nitrobenzaldehyde and 1,2,3,4-tetrahydroquinolylhydrazine in ethanol using an acetic acid catalyst, p-nitrobenzaldehyde-
1,2-dihydroindolenylhydrazone is obtained. Then, the compound thus obtained is subjected to a reduction reaction with iron powder in 1,4-dioxane / water to obtain p-aminobenzaldehyde-1,2-dihydroindolenylhydrazone. Then, by dehydration condensation with 2 equivalents of α-phenylpropionaldehyde in benzene, the exemplified compound N
o. 10 (melting point, 105 to 106 ° C.) is obtained (recrystallized from ethanol).

[0054]

【Example】

Examples 1 to 5 An aluminum vapor-deposited polyester film (film thickness 80 μ) was used as a support, and the following structural formula

[0055]

[Chemical 11] The bisazo pigment represented by is added to a 1% THF solution in which a polyvinyl butyral resin (manufactured by Nissin Chemical Industry Co., Ltd .; Eslec B) is dissolved in the same amount as the resin by weight, and then the diameter is measured in a paint conditioner (manufactured by Red Level). 1.5
mm glass beads were dispersed together for about 2 hours, applied by the doctor blade method, and dried. The film thickness after drying was 0.2μ.

On the pigment layer (charge generation layer), the exemplified compound No. 2, No. 3, No. 8, No. Three
7, No. 57 g of each 1 g of polyarylate resin (manufactured by Unitika; U-100), 1.2 g of which was dissolved in methylene chloride, was applied with a 15% solution using a squeegee doctor to obtain a resin-styryl compound solid solution phase having a dry film thickness of 25 μm ( A charge transfer layer) was prepared.

The laminated electrophotographic photosensitive member thus prepared was used as an electrostatic recording paper tester (Kawaguchi Denki; SP-428).
To evaluate the electrophotographic characteristics. Measurement conditions are applied voltage:
-6 kV, static: No. 3 is -700V to -100V by white light irradiation (irradiation light: 5lux)
The amount of exposure E ₁₀₀ (lux · sec) and the initial potential V ₀ (-volt) required to attenuate the light were measured, and the values are shown in Table 3.

Further, using the same apparatus, the initial potential V ₀ (-volt) after carrying out the same operation 10,000 times with charge-discharge (charge removal light: irradiation with white light at 40 lux for 1 second) as one cycle ) And E ₁₀₀ (lux seconds) were measured and V ₀ and E
Examine ₁₀₀ changes.

[0059]

[Table 19] From Table 3, it was found that the bisenamine group-containing hydrazone compound of the present invention had good sensitivity repeating characteristics. Example 6 0.4 g of x-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals; Fastgen Blue 8120) was placed on a polyester film vapor-deposited on aluminum and vinyl chloride: vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .; S-Rex M). ) Add 0.3 g of ethyl acetate to 30 ml of ethyl acetate solution, disperse in paint conditioner for about 20 minutes, apply by doctor blade method, and form charge generation layer to have a film thickness of 0.4 μm after drying. Let

On the charge generation layer, the exemplified compound No. Three
50% by weight of hydrazone compound containing bis enamine group
It is composed of two layers by laminating the contained polyarylate layer.
A photoconductor was created. 780nm spectral light of this photoreceptor
Energy required to reduce the potential to half (E ₅₀) And early
Electric potential (-V₀), V₀ = 880 (Bol
G), E₅₀= 2.7 (erg / cm²) And very sensitive
It was also a highly charged photoreceptor.

A laser printer (WD-580P) manufactured by Sharp Corporation was remodeled, and the main photosensitive member was attached to the drum portion, and continuous blank copy (Non Copy Agin) was performed.
After performing g) 10,000 times, the degree of initial potential drop and sensitivity drop was examined. The result is V ₀ = 870 (volts),
E ₅₀ = 2.7 (erg / cm ² ), which showed almost no change in the value compared with the first time.

Examples 7 to 10 Anodized aluminum substrate surface (alumite layer: 7)
1 g each of the bisenamine group-containing hydrazone compound of the present invention, 1.1 g of polyarylate resin represented by the following structural formula and N, N-3,5-xylyl-
A solution prepared by dissolving 0.15 g of 3,4,9,10-perylenetetracarboxylic imide and 0.05 g of an ultraviolet absorber in methylene chloride (the imide compound was partly dispersed) was applied with an applicator to obtain a dry film having a thickness of 20 μ. A layer photoreceptor was obtained.

[0063]

[Chemical 12]In this way, the photoconductor is electronically copied by the electrostatic recording paper testing device.
The true property was measured. Measurement condition is applied voltage: + 5.5k
V, static: No. I went in 3. With white light irradiation
Dew required to reduce from + 700V to + 100V
Light intensity E ₁₀₀(Looks / second) was measured and the value is shown in Table 4.
did. In addition, the sensitivity (E
₁₀₀The degree of decrease in () is also shown in Table 4.

[0064]

[Table 20] It has been found that the photoconductor using the bisenamine group-containing hydrazone compound of the present invention is a photoconductor having excellent sensitivity and repetitive characteristics even in positive charging. Examples 11 to 15 A polyester film (thickness 80 μm) vapor-deposited on aluminum was used as a support, and the following structural formula

[0065]

[Chemical 13] The bisazo pigment represented by is added to a 1% THF solution in which a polyvinyl butyral resin (manufactured by Nissin Chemical Industry Co., Ltd .; Eslec B) is dissolved in the same amount as the resin by weight, and then the diameter is measured in a paint conditioner (manufactured by Red Level). 1.5
mm glass beads were dispersed together for about 2 hours, applied by the doctor blade method, and dried. The film thickness after drying was 0.2μ.

On the pigment layer (charge generation layer), the exemplified compound No. 82, No. 76, No. 79, N
o. 91, No. A 15% solution of 1.2 g of polyarylate resin (Unitika U-100; 1.2 g) was coated with a squeegee doctor to give a resin-styryl compound solid solution phase having a dry film thickness of 25 μm ( A charge transfer layer) was prepared.

The laminated electrophotographic photosensitive member thus prepared was used as an electrostatic recording paper tester (Kawaguchi Denki; SP-428).
To evaluate the electrophotographic characteristics. Measurement conditions are applied voltage:
-6 kV, static: No. 3 is -700V to -100V by white light irradiation (irradiation light: 5lux)
The amount of exposure E ₁₀₀ (lux · sec) and the initial potential V ₀ (-volt) required to attenuate the light were measured, and the values are shown in Table 5.

Further, using the same apparatus, the initial potential V ₀ (-volt) after carrying out the same operation 10,000 times with charge-discharge (charge removal light: irradiation with white light at 40 lux for 1 second) as one cycle ) And E ₁₀₀ (lux seconds) were measured and V ₀ and E
Examine ₁₀₀ changes.

[0069]

[Table 21] From Table 5, it was found that the bisenamine group-containing hydrazone compound of the present invention had good sensitivity repeating characteristics. Example 16 0.4 g of x-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals; Fastgen Blue 8120) was placed on a polyester film vapor-deposited on aluminum, and vinyl chloride: vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .; S-Rex M). ) Add 0.3 g of ethyl acetate to 30 ml of ethyl acetate solution, disperse in paint conditioner for about 20 minutes, apply by doctor blade method, and form charge generation layer to have a film thickness of 0.4 μm after drying. Let

On the charge generation layer, the exemplified compound No. 1
The bis enamine group-containing hydrazone compound of No. 03 was added in a weight ratio of 5
From a two-layer structure by laminating a polyarylate layer containing 0%
A photoconductor was made. 780nm spectrum of this photoreceptor
Energy required to reduce the potential to half (E ₅₀)as well as
Initial potential (-V₀), V₀ = 870 (bol
G), E₅₀= 2.6 (erg / cm²) And very sensitive
It was also a highly charged photoreceptor.

A laser printer (WD-580P) manufactured by Sharp Corporation was remodeled, and the main photosensitive member was attached to the drum portion, and continuous blank copy (Non Copy Agin) was performed.
After performing g) 10,000 times, the degree of initial potential drop and sensitivity drop was examined. The result is V ₀ = 865 (volts),
E ₅₀ = 2.6 (erg / cm ² ), which showed almost no change in the value compared with the first time.

Examples 17 to 20 The surface of an aluminum substrate was anodized (alumite layer: 7).
1 g each of the bisenamine group-containing hydrazone compound of the present invention, 1.1 g of polyarylate resin represented by the following structural formula and N, N-3,5-xylyl-
A solution prepared by dissolving 0.15 g of 3,4,9,10-perylenetetracarboxylic imide and 0.05 g of an ultraviolet absorber in methylene chloride (the imide compound was partly dispersed) was applied with an applicator to obtain a dry film having a thickness of 20 μ. A layer photoreceptor was obtained.

[0073]

[Chemical 14]In this way, the photoconductor is electronically copied by the electrostatic recording paper testing device.
The true property was measured. Measurement condition is applied voltage: + 5.5k
V, static: No. I went in 3. With white light irradiation
Dew required to reduce from + 700V to + 100V
Light intensity E ₁₀₀(Looks / second) was measured and the value is shown in Table 6.
did. In addition, the sensitivity (E
₁₀₀The degree of decrease in () is also shown in Table 6.

[0074]

[Table 22] It has been found that the photoconductor using the bisenamine group-containing hydrazone compound of the present invention is a photoconductor having excellent sensitivity and repetitive characteristics even in positive charging.

[0075]

It has been found that the photoconductor using the bisenamine group-containing hydrazone compound of the present invention is a photoconductor having excellent sensitivity and repeatability even in positive charging.

Claims (3)

[Claims] 1. A photosensitive layer formed on a conductive support comprises: i) a compound represented by the general formula (I): [Wherein A and B are an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or an alkyl group having 1 to 5 carbon atoms, and R
¹ is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent,
An alkyl group having 1 to 5 carbon atoms or a hydrogen atom, R
² is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent,
An alkyl group having 1 to 5 carbon atoms or a hydrogen atom,
Is an alkyl group having 1 to 5 carbon atoms, a dialkylamino group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and n is an integer of 1 to 3 (however, n Are 2 or more, a may be the same or different and may form a ring with each other), b is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or hydrogen. Is an atom, and m is an integer of 1 to 4 (however, when m is 2 or more, b may be the same or different). ] The hydrazone group-containing hydrazone compound (I) represented by: or ii) the general formula (II): [R ¹ is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom. And R ² is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group having 1 to 5 carbon atoms, or A hydrogen atom, a is an alkyl group having 1 to 5 carbon atoms, a dialkylamino group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and n is an integer of 1 to 3. (However, when n is 2 or more, a's may be the same or different and may form a ring with each other), b has 1 carbon atom
To an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and m is an integer of 1 to 4 (provided that when m is 2 or more, b may be the same or different). , Z is a divalent residue necessary for forming a heterocyclic ring which may have a substituent together with the nitrogen atom of hydrazine or a condensed heterocyclic ring which may have a substituent]. An electrophotographic photoreceptor containing a hydrazone compound (II). 2. A photosensitive layer formed on a conductive support contains a carrier transfer substance and a carrier generation substance, and the carrier transfer substance is a bisenamine group-containing hydrazone of the general formula (I) or general formula (II). The electrophotographic photoreceptor according to claim 1, which is a compound. 3. In a laminate of a photosensitive layer formed on a conductive support, a carrier generating layer containing a carrier generating substance and a carrier moving layer containing a carrier moving substance, the carrier moving substance is represented by the general formula: The electrophotographic photosensitive member according to claim 1, which is a hydrazone compound containing a bisenamine group represented by (I) or general formula (II).