JPH05197173A - Electrophotographic photosensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic photosensitive body having high sensitivity and excellent durability. CONSTITUTION:A hydrazone compound expressed by the formula I is contained as a charge transporting material in a photosensitive layer together with a charge generating material such as a perylene pigment expressed by the formula II. In the formula I, R<1>, R<2>, R<3>, R<4>, R<5> indicate the same or different hydrogen atom, halogen atom, alkyl group, or alkoxy group. In the formula II, R<6>, R<7>, R<8>, R<9> indicate the same or different hydrogen atom, alkyl group, alkoxy group, or aryl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in an image forming apparatus utilizing electrophotography such as an electrostatic copying machine and a laser beam printer.

[0002]

2. Description of the Related Art Electrophotographic methods such as the Carlson process are
A step of uniformly charging the surface of the electrophotographic photosensitive member by corona discharge, an exposure step of exposing the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image on the surface, and the formed electrostatic A developing step of bringing a developer into contact with the latent image and developing the electrostatic latent image into a toner image by the toner contained in the developer, and a transfer step of transferring the toner image onto paper or the like are transferred. After the fixing process of fixing the toner image and the transfer process,
And a cleaning step for removing the toner remaining on the photoconductor.

Inorganic photoconductors such as selenium and cadmium sulfide have hitherto been used as the electrophotographic photosensitive member used in the electrophotographic method, but these are toxic and have a high production cost. There is. Therefore, in recent years, so-called organic photoconductors have been widely used, which are safe, have excellent processability and economical efficiency, and have a high degree of freedom in functional design. This organic photoreceptor is one in which a charge generating material that generates a charge upon exposure and a charge transporting material that transports the generated charge are contained in a photosensitive layer made of a binder resin. There are a laminated type photosensitive layer in which a layer containing a generating material and a layer containing a charge transporting material are laminated, and a single layer type photosensitive layer in which both materials are contained in a single layer.

Phthalocyanine pigments, azo pigments, pyrrolopyrrole pigments, etc. are used as charge generating materials, and carbazole compounds, oxadiazole compounds, pyrazoline compounds, hydrazone compounds, etc. are used as charge transport materials. Stilbene compounds, phenylenediamine compounds and the like are used.

[0005]

However, the conventional organic photoreceptor has a problem that the sensitivity and durability are not sufficient. It is believed that the cause of this problem is primarily the conventionally used charge transport materials. In other words, all the conventional charge transport materials have insufficient charge transport ability,
There is a problem that the light stability is poor, or the compatibility with the binder resin that constitutes the photosensitive layer is poor, and it crystallizes with repeated use and precipitates from the photosensitive layer. The resulting photoreceptor has poor sensitivity and durability.

Particularly in the case of a single-layer type photosensitive layer containing a charge generating material and a charge transporting material in a single layer, if the combination of both materials is bad, the functions of the two layers are impaired, The characteristics of each material may not be sufficiently exhibited, and as a result, the sensitivity and durability of the photoreceptor may be further deteriorated. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and excellent durability.

[0007]

Means and Actions for Solving the Problems In order to solve the above problems, the present inventors have studied various compounds, and as a result, the hydrazone compound represented by the following general formula (1) It has been found that it has excellent charge transporting ability (in particular, hole transporting ability) and light stability and can be suitably used as a charge transporting material.

[0008]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.) Therefore, various studies were conducted on the charge generating material to be combined with the hydrazone compound, and as a result, the following general formula (2):

[0010]

[Chemical 7]

(Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group), and a perylene pigment represented by the following general formula (3) :

[0012]

[Chemical 8]

Ansanthuron pigment represented by the formula (wherein X represents a halogen atom), represented by the following general formula (4):

[0014]

[Chemical 9]

A fluorenone bisazo pigment represented by the formula (A represents a coupler residue) and the following general formula
(Five) :

[0016]

[Chemical 10]

(In the formula, A represents a coupler residue, and R ¹⁰
Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The alkyl group, aryl group and heterocyclic group may have a substituent. If any of the bisazo pigments represented by (n represents 0 or 1) is combined with the above-mentioned hydrazone-based compound, there is no risk of interfering with each other's functions, so electrophotographic photosensitive material having high sensitivity and excellent durability. They have found that they can form a body and have completed the present invention.

Therefore, the electrophotographic photoreceptor of the present invention is
On the conductive substrate, the above general formula (1) as a charge transport material
It is characterized in that a photosensitive layer containing a hydrazone compound represented by and a pigment represented by any one of the general formulas (2) to (5) as a charge generating material is provided. The general formula
In the hydrazone-based compound represented by (1), the alkyl groups corresponding to the groups R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the formula include a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, and a hexyloxy group. Be done.

Specific examples of the hydrazone compound include those shown below.

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

The above hydrazone compounds can be synthesized by various methods, for example, by the method shown in the following reaction formula [C. Mannich et al., Ber., 69,
2106, 2112 (1936)].

[0024]

[Chemical 14]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above. ) As shown in the above reaction scheme, an aldehyde compound represented by the general formula (a) and a hydrazine derivative represented by the general formula (b) are acidified by addition of acetic acid or the like,
When the reaction is carried out at a temperature of about 25 ° C, the hydrazone compound represented by the general formula (1) is obtained. Examples of the solvent used in the reaction include ether, tetrahydrofuran, dioxane and the like.

In the perylene pigment represented by the general formula (2), which is contained in the photosensitive layer as a charge generating material together with the hydrazone compound, the groups R ⁶ , R ⁷ and R in the formula
Examples of the alkyl group and alkoxy group corresponding to R ⁸ and R ⁹ include the same groups as described for the hydrazone compound, and examples of the aryl group include a phenyl group, an o-terphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Examples include groups. These alkyl group, aryl group and alkoxy group may have a substituent such as an alkyl group, an alkoxy group and a halogen atom.

Specific examples of the perylene pigment include those represented by the following formula.

[0028]

[Chemical 15]

Examples of the anthanthuron pigment represented by the general formula (3) include dibromoanthanthrone represented by the following formula.

[0030]

[Chemical 16]

In the fluorenone bisazo pigment represented by the general formula (4), examples of the coupler residue corresponding to the group A in the formula include groups represented by the following general formulas (a) to (g). Be done.

[0032]

[Chemical 17]

In each formula, R ³⁰ represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group, and a succinamoyl group. These groups include a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a nitro group, a cyano group, an alkyl group, an alkenyl group, a carbonyl group, a carboxyl group and the like. It may have a substituent.

R ³¹ represents an atomic group necessary for forming an aromatic ring, a polycyclic hydrocarbon or a heterocyclic ring by condensing with R ³⁰ and a benzene ring having a hydroxyl group, and these rings are as described above. You may have the same substituent. R ³² represents an oxygen atom, a sulfur atom or an imino group. R ³³ represents a divalent chain hydrocarbon or aromatic hydrocarbon, and these groups may have the same substituents as described above.

R ³⁴ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituents as described above. R ³⁵ is a divalent chain hydrocarbon, an aromatic hydrocarbon, or the following formula (h) in the above general formulas (e) and (f).

[0036]

[Chemical 18]

It represents an atomic group necessary for forming a heterocycle with the moiety represented by, and these rings may have the same substituents as described above. R ³⁶ is a hydrogen atom, an alkyl group,
It represents an amino group, a carbamoyl group, a sulfamoyl group, an allofanoyl group, a carboxyl group, an ester of a carboxyl group, an aryl group or a cyano group, and groups other than a hydrogen atom may have the same substituents as described above.

R ³⁷ represents an alkyl group or an aryl group, and these groups may have the same substituents as described above.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a te group.
rt-butyl group, pentyl group, hexyl group, etc., having 1 carbon atom
The lower alkyl groups of 6 are mentioned.

As the aryl group, for example, a phenyl group,
Examples thereof include a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. As the alkenyl group, for example, vinyl group, allyl group, 2-butenyl group, 3-butenyl group, 1-methylallyl group, 2-
Examples thereof include lower alkenyl groups having 2 to 6 carbon atoms such as pentenyl group and 2-hexenyl group.

Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom. In R ³¹ , the atomic group necessary for forming an aromatic ring by condensing with R ³⁰ and a benzene ring having a hydroxyl group is, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group or a butylene group. Be done.

The aromatic ring formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group includes
Examples thereof include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, and naphthacene ring. In R ³¹ , the atomic group necessary for condensing with R ³⁰ and a benzene ring having a hydroxyl group to form a polycyclic hydrocarbon is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, or a carbon atom. Examples include alkylene groups of the numbers 1 to 4.

The polycyclic hydrocarbon formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group is, for example, a carbazole ring, a benzocarbazole ring,
Examples include a dibenzofuran ring. Further, in R ³¹ , an atomic group necessary for forming a heterocycle by condensing with R ³⁰ and a benzene ring having a hydroxyl group is, for example, a benzofuranyl group, a benzothiophenyl group, an indolyl group,
1H-indolyl group, bezoxazolyl group, benzothiazolyl group, 1H-indaryl group, benzimidazolyl group, chromenyl group, chromanyl group, isochromanyl group,
Quinolinyl group, isoquinolinyl group, cinnolinyl group, phthalazinyl group, quinazonilyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, xanthenyl group,
Examples thereof include an acridinyl group, a phenanthridinyl group, a phenazinyl group, a phenoxazinyl group and a thianthrenyl group.

Examples of the aromatic heterocyclic group formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group include, for example, thienyl group, furyl group, pyrrolyl group, oxazolyl group, isoxazolyl group and thiazolyl group. , Isothiazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group and thiazolyl group. In addition, it may be a heterocyclic group condensed with another aromatic ring (for example, a benzofuranyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group).

In the above R ³³ and R ³⁵ , examples of the divalent chain hydrocarbon include ethylene group, propylene group and butylene group, and examples of the divalent aromatic hydrocarbon include phenylene group, naphthylene group, Examples thereof include a phenanthrylene group. Examples of the heterocyclic group for R ³⁴ include a pyridyl group, a pyrazyl group, a thienyl group, a pyranyl group and an indolyl group.

In R ³⁵ , the atomic group necessary for forming a heterocycle with the moiety represented by the formula (h) is, for example, phenylene group, naphthylene group, phenanthrylene group, ethylene group, propylene group, butylene. Examples include groups. Examples of the aromatic heterocyclic group formed by R ³⁵ and the portion represented by the formula (h) include a benzimidazole group, a benzo [f] benzimidazole group, a dibenzo [e, g] benzimidazole group. Group, benzopyrimidine group and the like. These groups may have the same substituents as described above.

Examples of the carboxyl group ester in R ³⁶ include methyl ester, ethyl ester, propyl ester, butyl ester and the like. Specific examples of the coupler residue A represented by the above general formulas (a) to (g) include the following groups.

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

Specific examples of the above fluorenone bisazo pigment include those represented by the following formula.

[0052]

[Chemical formula 23]

In the bisazo pigment represented by the general formula (5), the alkyl group corresponding to the group R ¹⁰ in the formula is
The same groups as those explained for the hydrazone compounds are given,
Examples of the aryl group include the same groups as described for the perylene pigment. Examples of the heterocyclic group include a thienyl group, a pyrrolyl group, a pyrrolidinyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a 2H-imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, and a pyranyl group. , Pyridyl group, piperidyl group, piperidino group, 3-morpholinyl group, morpholino group, thiazolyl group and the like. It may also be a heterocyclic group condensed with an aromatic ring.

Examples of the substituent substituting for the above group include a halogen atom, an amino group, a hydroxyl group, an optionally esterified carboxyl group, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Examples thereof include an alkenyl group having 2 to 6 carbon atoms which may have an alkoxy group or an aryl group. Examples of the coupler residue corresponding to the group A in the formula include the same coupler residues as described for the fluorenone bisazo pigment.

The bisazo pigment represented by the general formula (5) is prepared by azotization of a corresponding divalent amino compound by a conventional method.
Then, the corresponding coupler is coupled in the presence of an alkali, or the diazonium salt of the divalent amino compound is formed in the form of a borofluoride salt or a zinc chloride double acid salt.
Once isolated, in a suitable solvent in the presence of alkali,
It can be synthesized by coupling with a coupler.

Specific examples of the bisazo pigment include those represented by the following formula.

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

The photoconductor of the present invention comprises, as a charge transport material,
In addition to containing one or more hydrazone compounds represented by the general formula (1), as a charge generating material, a perylene pigment represented by the general formula (2), a general formula
(3) Anthanthuron pigment represented by the general formula (4) fluorenone bisazo pigment represented by, and a photosensitive layer containing any of the bisazo pigment represented by the general formula (5) It is a thing. The pigments represented by the general formulas (2) to (5) are usually used alone as charge generating materials, but in the present invention, two or more pigments represented by the general formulas are used in combination. You can also do it.

The photosensitive layer includes a single layer type and a laminated type as described above, but the present invention can be applied to any of these. However, the effect of the combination of the charge transporting material and the charge generating material becomes more remarkable particularly in the single-layer type photosensitive layer in which both materials are contained in the same layer. It can be said that it is more preferable to apply to an electrophotographic photosensitive member having a layer.

In order to obtain a single-layer type photoreceptor, any one of the compounds represented by the general formula (1), which is a charge transport material, and the general formulas (2) to (5), which is a charge generation material, can be used. A photosensitive layer containing the pigment represented by and a binder resin or the like may be formed on the conductive substrate by means of coating or the like. Further, in order to obtain a laminated type photoreceptor, a charge generation layer containing a pigment represented by any one of the general formulas (2) to (5) is formed on a conductive substrate by means such as vapor deposition or coating. Then, a charge transport layer containing the compound represented by the general formula (1) and a binder resin may be formed on the charge generation layer. Alternatively, conversely to the above, the charge transport layer may be formed on the conductive substrate, and then the charge generation layer may be formed. Further, in the above-mentioned laminated type photosensitive layer, the charge generating layer may also contain a charge transport material.

As the charge generating material, the above general formula is used.
In addition to the pigment represented by any one of (2) to (5), for the purpose of expanding the sensitivity region of the electrophotographic photosensitive member so as to have an absorption wavelength region in a desired region, further known in the art. Other charge generating materials can also be used together. Other charge generation materials include selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salts, perylene pigments other than those represented by the general formula (2), and the general formula (3). Ansanthuron-based pigments other than those described above, the general formula
(4) Bisazo pigments other than those represented by (5), azo pigments, phthalocyanine pigments, indigo pigments, triphenylmethane pigments, slene pigments, toluidine pigments,
Examples thereof include pyrazoline-based pigments, quinacridone-based pigments and pyrrolopyrrole-based pigments.

However, the above-mentioned other charge generating materials are represented by the general formula
When used in combination with the hydrazone compound represented by (1), the functions may interfere with each other. Therefore, the amount used is preferably as small as possible, and preferably not used. The hydrazone compound represented by the general formula (1), which is a charge transport material, can be used alone or in combination with other conventionally known charge transport materials. As the conventionally known charge transport material, various electron-withdrawing compounds and electron-donating compounds can be used.

Examples of the electron-withdrawing compound include 2,
Diphenoquinone derivatives such as 6-dimethyl-2 ′, 6′-ditert-dibutyldiphenoquinone, malononitrile, thiopyran compounds, tetracyanoethylene, 2,
4,8-trinitrothioxanthone, 3,4,5,7-
Tetranitro-9-fluorenone, dinitrobenzene,
Examples include dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, and dibromomaleic anhydride.

As the electron donating compound, 2,5
-Oxadiazole compounds such as di (4-methylaminophenyl) and 1,3,4-oxadiazole, 9- (4
A styryl compound such as -diethylaminostyryl) anthracene, a carbazole compound such as polyvinylcarbazole, a pyrazoline compound such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, and the above general formula
(1) hydrazone compounds other than those represented by, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazoles Examples thereof include nitrogen-containing cyclic compounds such as compounds and condensed polycyclic compounds.

These charge transport materials are used alone or in combination of two or more. When a charge transporting material having film-forming property such as polyvinylcarbazole is used,
The binder resin is not always necessary. As a binder resin,
Various resins can be used. For example, styrene-based polymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer , Chlorinated polyethylene, polyvinyl chloride, polypropylene,
Thermoplastic resin such as vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy Examples thereof include resins, phenol resins, urea resins, melamine resins, other crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins may be used alone or in combination of two or more.

The organic photosensitive layers of single-layer type and laminated type include
A sensitizer, a fluorene compound, an antioxidant, a deterioration inhibitor such as an ultraviolet absorber, and an additive such as a plasticizer can be contained. Further, in order to improve the sensitivity of the charge generation layer, known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generation material.

In the multi-layer type photoreceptor, the charge generating material and the binder resin constituting the charge generating layer can be used in various ratios, but the charge generating material 5 is added to 100 parts by weight of the binder resin. It is preferably used in an amount of about 500 parts by weight, particularly 10 to 300 parts by weight. The charge generation layer may have an appropriate film thickness, but it is preferably formed to a thickness of 0.01 to 5 μm, particularly 0.1 to 3 μm.

The hydrazone compound (charge-transporting material) represented by the general formula (1) constituting the charge-transporting layer and the binder resin may be mixed in various amounts within a range that does not inhibit charge transport and a range that does not crystallize. Can be used in a proportion of 100 parts by weight of the binder resin so that the charges generated in the charge generation layer by light irradiation can be easily transported.
It is preferable to use the hydrazone compound represented by (1) in an amount of 10 to 500 parts by weight, particularly 25 to 200 parts by weight. The thickness of the laminated photosensitive layer is 0.
The thickness of the charge transport layer is preferably about 1 to 5 μm, more preferably about 0.1 to 3 μm.
The thickness is preferably about 50 μm.

In the single-layer type photoreceptor, the binder resin 10
0.1 to 50 parts by weight, particularly 0.5 to 30 parts by weight of the pigment (charge generating material) represented by any one of the general formulas (2) to (5) relative to 0 part by weight, The hydrazone compound (charge transport material) represented by (1) is 40 to 200 parts by weight,
Particularly, 50 to 100 parts by weight is suitable. Also,
The thickness of the single-layer type photosensitive layer is 5 to 100 μm, particularly 10 to 5 μm.
The thickness is preferably about 0 μm.

In the case of a single-layer type photoreceptor, it is between a conductive substrate and a photosensitive layer, and in the case of a laminated type photoreceptor, it is between a conductive substrate and a charge generation layer, and a conductive substrate. A barrier layer may be formed between the charge transport layer and the charge transport layer or between the charge generation layer and the charge transport layer to the extent that the characteristics of the photoreceptor are not impaired. It may be formed.

As the conductive substrate on which each of the above layers is formed, various conductive materials can be used.
For example, simple metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, and iodide Examples thereof include glass coated with aluminum, tin oxide, indium oxide, or the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, the conductive substrate is preferably one having sufficient mechanical strength when used. When each of the above layers is formed by a coating method, the charge generation material, charge transport material, and
A binder resin and the like are mixed with a suitable solvent by a known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser to prepare a coating solution, which is prepared by a known means. It may be applied and dried.

As the solvent for forming the coating liquid, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol,
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran, Examples thereof include ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the charge transport material or the charge generating material and the smoothness of the surface of the photosensitive layer, a surfactant, a leveling agent, etc. may be used. The charge generation layer may be formed by depositing the charge generation material.

[0076]

The present invention will be described in detail below with reference to examples and comparative examples. Example 1 100 parts by weight of a hydrazone compound represented by the above formula (12) as a charge transport material, 6 parts by weight of a perylene pigment represented by the above formula (21) as a charge generating material, and a binder 100 parts by weight of a polycarbonate resin as a resin was dispersed with a predetermined amount of tetrahydrofuran by using an ultrasonic disperser for 2 minutes to prepare a coating liquid for a single-layer type photosensitive layer. The perylene pigment used was previously crushed with a ball mill. Then, this coating solution is applied to the surface of an aluminum sheet as a conductive substrate by a bar coating method using a wire bar so that the film thickness is 25 to 30 μm, and dried at 110 ° C. for 30 minutes. A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared.

The coating solution was applied to the surface of an aluminum base tube (outer diameter 78 mm, length 350 mm) as a conductive substrate by dip coating to give a film thickness of 25 to 30 μm.
And then dried at 110 ° C for 30 minutes,
A drum-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer was produced. Example 2 Example 1 was repeated except that 100 parts by weight of the hydrazone compound represented by the formula (15) was used as the charge transport material instead of the hydrazone compound represented by the formula (12). In the same manner as above, a sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Example 3 The above Example except that 6 parts by weight of the perylene pigment represented by the above formula (22) was used as the charge generating material in place of the perylene pigment represented by the above formula (21). Similar to 1,
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Example 4 The above Example except that 6 parts by weight of the perylene pigment represented by the formula (23) was used as the charge generating material in place of the perylene pigment represented by the formula (21). Similar to 1,
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Comparative Example 1 As a charge transport material, a compound 100 represented by the following formula (B1) was used in place of the hydrazone compound represented by the above formula (12).
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 1 except that parts by weight were used.

[0081]

[Chemical formula 26]

Comparative Example 2 As a charge transport material, a compound 100 represented by the following formula (B2) was used in place of the hydrazone compound represented by the above formula (12).
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 1 except that parts by weight were used.

[0083]

[Chemical 27]

The following tests were carried out on the electrophotographic photosensitive members of the above-mentioned respective Examples and Comparative Examples to evaluate their characteristics. Measurement of initial surface potential Electrostatic copying tester (EPA-810 manufactured by Kawaguchi Electric Co., Ltd.
By adjusting the flow current value according to 0), the surface of the sheet-shaped electrophotographic photosensitive member produced in Examples and Comparative Examples is adjusted to +800.
The initial surface potential Vs.p. (V) when charged around V was measured.

Measurement of residual potential The sheet-shaped electrophotographic photosensitive member charged in the above-mentioned measurement of the initial surface potential was exposed to an exposure intensity of 10 lux by using a white halogen lamp as an exposure light source of an electrostatic copying tester. Exposure was performed under the conditions, and the surface potential at the time point 0.3 seconds after the start of exposure was measured and defined as the residual potential Vr.p. (V).

Durability Test After measuring the initial surface potential V1s.p. (V) of the drum-shaped electrophotographic photosensitive members produced in the Examples and Comparative Examples in the same manner as described above, the electrostatic copying machine (Sanda) Industrial company product number DC165
7), and the charging-exposure-discharging process is performed for 100
Repeated 0 times, then again surface potential V2s.p.
(V) is measured and the amount of change in surface potential Δ
Vs.p. (V) was determined and the durability of the electrophotographic photosensitive member was evaluated.

ΔVs.p. = V2s.p.-V1s.p. The above results are shown in Table 1.

[0088]

[Table 1]

From the results shown in Table 1 above, the electrophotographic photosensitive members of Examples 1 to 4 all have a small residual potential when set to substantially the same surface potential (about 800 V) as compared with Comparative Example 2. It was found that the sensitivity was high because it was very low. Further, as compared with Comparative Examples 1 and 2, the amount of change in surface potential due to repeated exposure was small, and thus it was found that the durability was excellent.

Example 5 The procedure of Example 5 was repeated except that 6 parts by weight of dibromoanthanthurone represented by the above formula (31) was used as the charge generating material in place of the perylene pigment represented by the above formula (21). In the same manner as in Example 1, a sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Comparative Example 3 As a charge transport material, instead of the hydrazone compound represented by the formula (12), the compound 100 represented by the formula (B1) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 5 except that parts by weight were used.

Comparative Example 4 As the charge transport material, instead of the hydrazone compound represented by the formula (12), the compound 100 represented by the formula (B2) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 5 except that parts by weight were used.

The above-mentioned respective tests were conducted on the electrophotographic photosensitive members of the above-mentioned respective Examples and Comparative Examples, and the characteristics thereof were evaluated. The results are shown in Table 2.

[0094]

[Table 2]

From the results in Table 2 above, the electrophotographic photosensitive member of Example 5 has a slightly lower residual potential when set to a surface potential (about 800 V) that is substantially equal to that of Comparative Example 4, It was found that the sensitivity was high. Further, it was found that the durability was excellent because the amount of change in surface potential due to repeated exposure was small as compared with Comparative Examples 3 and 4. Example 6 Example 1 was repeated except that 6 parts by weight of the fluorenone bisazo pigment represented by the formula (41) was used as the charge generation material instead of the perylene pigment represented by the formula (21). In the same manner as above, a sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Comparative Example 5 As the charge transport material, instead of the hydrazone compound represented by the formula (12), the compound 100 represented by the formula (B1) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 6 except that parts by weight were used.

Comparative Example 6 As a charge transport material, instead of the hydrazone compound represented by the formula (12), the compound 100 represented by the formula (B2) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 6 except that parts by weight were used.

The above-mentioned respective tests were conducted on the electrophotographic photosensitive members of the above-mentioned respective Examples and Comparative Examples, and the characteristics thereof were evaluated. The results are shown in Table 3.

[0099]

[Table 3]

From the results in Table 3 above, the electrophotographic photosensitive member of Example 6 has a slightly lower residual potential than that of Comparative Example 6 when the surface potential (about 800 V) is set to be substantially equal. It was found that the sensitivity was high. Further, as compared with Comparative Examples 5 and 6, the amount of change in surface potential due to repeated exposure was small, and thus it was found that the durability was excellent. Example 7 The same as Example 1 except that 6 parts by weight of the bisazo pigment represented by the formula (51) was used as the charge generation material instead of the perylene pigment represented by the formula (21). And then
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Example 8 As described above, except that 100 parts by weight of the hydrazone compound represented by the above formula (15) was used as the charge transport material instead of the hydrazone compound represented by the above formula (12). In the same manner as in Example 7, a sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Example 9 The above Example except that 6 parts by weight of the bisazo pigment represented by the formula (52) was used as the charge generating material in place of the bisazo pigment represented by the formula (51). Similar to 7,
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Example 10 As described above, except that 100 parts by weight of the hydrazone compound represented by the above formula (15) was used as the charge transport material instead of the hydrazone compound represented by the above formula (12). In the same manner as in Example 9, a sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced.

Comparative Example 7 As a charge transport material, instead of the hydrazone compound represented by the formula (12), the compound 100 represented by the formula (B1) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 7 except that the parts by weight were used.

Comparative Example 8 Instead of the hydrazone compound represented by the formula (12) as the charge transport material, the compound 100 represented by the formula (B2) was used.
A sheet-shaped electrophotographic photosensitive member having a single-layer type photosensitive layer and a drum-shaped electrophotographic photosensitive member were produced in the same manner as in Example 7 except that the parts by weight were used.

The above-mentioned respective tests were conducted on the electrophotographic photoreceptors of the above-mentioned respective Examples and Comparative Examples, and the characteristics thereof were evaluated. The results are shown in Table 4.

[0107]

[Table 4]

From the results shown in Table 4, the electrophotographic photosensitive members of Examples 7 to 10 all have a small residual potential when set to a surface potential (about 800 V) which is almost equal to that of Comparative Example 8. It was found that the sensitivity was high because it was very low. Also,
As compared with Comparative Examples 7 and 8, the amount of change in surface potential due to repeated exposure was small, and thus it was found that the durability was excellent.

[0109]

INDUSTRIAL APPLICABILITY As described above, the electrophotographic photoreceptor of the present invention is provided with a photosensitive layer containing a hydrazone compound having excellent charge transporting ability and photostability, and a specific charge generating material. Therefore, it has high sensitivity and excellent durability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Iwasaki 1-2-2 Tamatsukuri, Chuo-ku, Osaka City, Osaka Prefecture Mita Kogyo Co., Ltd. No. 28 Mita Industry Co., Ltd. (72) Inventor Tsuneo Oki 1-2-2 Tamatsukuri Chuo-ku, Osaka City, Osaka Prefecture Mita Industry Co., Ltd.

Claims (4)

[Claims] 1. A general formula (1) as a charge transporting material on a conductive substrate: (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group) and a charge generating material. The following general formula (2): (Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group) and a photosensitive layer containing a perylene pigment An electrophotographic photosensitive member. 2. A hydrazone compound represented by the above general formula (1) on a conductive substrate and the following general formula (3): An electrophotographic photoreceptor comprising a photosensitive layer containing an anthanthrone pigment represented by the formula (X represents a halogen atom). 3. A hydrazone compound represented by the above general formula (1) on a conductive substrate and the following general formula (4): An electrophotographic photoreceptor comprising a photosensitive layer containing a fluorenone bisazo pigment represented by the formula (A represents a coupler residue). 4. A hydrazone compound represented by the above general formula (1) on a conductive substrate and the following general formula (5): (In the formula, A represents a coupler residue, R ¹⁰ is a hydrogen atom,
An alkyl group, an aryl group, or a heterocyclic group is shown. The alkyl group, aryl group and heterocyclic group may have a substituent. and n is 0 or 1), and an electrophotographic photoreceptor comprising a photosensitive layer containing a bisazo pigment.