JPH1048858A - Electrophotographic photoreceptor, electrophotographic device using same and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity and stable potential characteristics at the time of repetitive use by forming a photosensitive layer contg. a specified azotized calix [n] arene compd. SOLUTION: This photoreceptor has a photosensitive layer contg. an azotized calix [n] arene compd. formed by coupling a calix [n] arene compd. with an azonium compd. having at least two azo groups. The calix [n] arene compd. is preferably represented by formula I, wherein each of R1 -R3 is H or alkyl and (n) is an integer of 4-8. The azonium compd. is preferably represented by formula II, wherein Ar is an arom. hydrocarbon ring which may have a substituent, a hetero ring which may have a substituent, a ring formed by bonding plural arom. hydrocarbon rings or a ring formed by bonding plural hetero rings, X is BF4 , ZnCl2 or halogen and (m) is an integer of 2-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
The present invention relates to an electrophotographic apparatus and a process cartridge provided with the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide, and zinc oxide have been widely used in electrophotographic photosensitive members. On the other hand, as an electrophotographic photoreceptor using an organic photoconductive substance, a photoconductive polymer represented by poly-N-vinylcalibazole or 2,5-bis (p-diethylaminophenyl) -1,3,4- Known are those using a low-molecular organic photoconductive substance such as oxadiazole, and those combining such an organic photoconductive substance with various dyes and pigments.

An electrophotographic photoreceptor using an organic photoconductive substance has good film-forming properties and can be produced by coating, and thus has the advantage of providing an inexpensive electrophotographic photoreceptor with extremely high productivity. In addition, there is an advantage that the photosensitive wavelength range can be freely controlled by selecting a dye or a pigment to be used, and wide studies have been made so far. Particularly recently, with the development of a function-separated type photoconductor in which a charge generation layer containing an organic photoconductive dye or pigment and a charge transport layer containing a photoconductive polymer or a low molecular organic photoconductive substance are laminated,
Significant improvements have been made in sensitivity and durability, which have been disadvantages of conventional organic electrophotographic photosensitive members.

There is an azo pigment as an organic photoconductive substance. However, an azo pigment exhibits excellent photoconductivity, and a compound having various characteristics can be easily obtained by combining an azo component and a coupler component. Numerous compounds have been proposed so far, for example, JP-A-54-22834, JP-A-58-177555, and JP-A-58-17855.
194035, JP-A-61-215556, JP-A-61-241763, JP-A-63-1
No. 7,456, and the like.

[0005]

However, conventional electrophotographic photoreceptors using azo pigments are not necessarily sufficient in terms of sensitivity and potential stability during repeated use, and have been put to practical use. Only very few materials.

An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity characteristics and a stable potential characteristic when repeatedly used, and an electrophotographic apparatus and a process cartridge using the electrophotographic photosensitive member.

[0007]

According to the present invention, there is provided an electrophotographic photosensitive member having at least a photosensitive layer on a support, wherein the photosensitive layer comprises a calix [n] arene compound and at least two azo compounds. Calix [n] formed by coupling with an azonium compound having
It contains an arene compound.

Further, the electrophotographic apparatus of the present invention comprises the above electrophotographic photosensitive member, charging means for charging the electrophotographic photosensitive member, and image exposure of the charged electrophotographic photosensitive member to form an electrostatic latent image. It has an image exposing means for forming and a developing means for developing the electrophotographic photosensitive member on which the electrostatic latent image is formed with toner.

Furthermore, the process cartridge of the present invention is
The electrophotographic photoreceptor includes a charging member for charging the electrophotographic photoreceptor.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photosensitive member of the present invention has at least a photosensitive layer on a support.
An azoxy calix [n] arene compound formed by coupling a calix [n] arene compound with an azonium compound having at least two azos is contained as a charge generating substance.

The calix [n] arene compound is preferably a compound represented by the following general formula (1).

[0012]

[Outside 3]

In the above formula (1), R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group. n shows the integer of 4-8.

The alkyl group is preferably a methyl group, an ethyl group or a propyl group.

As the azonium compound having at least two azos, a compound represented by the following general formula (2) is preferable.

Ar- (N ₂ · X) _m (2)

In the above formula (2), Ar represents an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent,
It shows a structure in which a plurality of aromatic hydrocarbon rings are bonded or a structure in which a plurality of heterocycles are bonded. X is BF ₄ , ZnCl ₂
Or a halogen atom. m shows the integer of 2-4.

The aromatic hydrocarbon ring or heterocyclic ring includes hydrocarbon aromatic rings such as benzene, naphthalene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene; furan, thiophene, pyridine and the like.
Aromatic heterocycles such as indole, benzothiazole, carbazole, benzocarbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, phenazine, cinnoline and benzocinnoline are preferred. Ar may be one in which a plurality of aromatic hydrocarbon rings or a plurality of heterocycles are bonded with an aromatic or non-aromatic bonding group or directly. Examples of such Ar include triphenylamine, diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl,
Fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenylether, benzophenone, stilbene, distyrylbenzene, tetraphenyl-p-
Examples include phenylenediamine and tetraphenylbenzidine.

As the substituent for Ar, for example, methyl,
Ethyl, propyl, butyl and other alkyl groups, methoxy,
Examples include an alkoxy group such as ethoxy, a dialkylamino group such as dimethylamino and diethylamino, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a hydroxy group, a nitro group, a cyano group, and a halomethyl group.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The azoxy calix [n] arene compound contained in the electrophotographic photoreceptor of the present invention has the general formula (1)
Is a coupling product of a calix [n] arene compound of formula (1) and an azonium compound of the above general formula (2). Further, as the azotized calix [n] arene compound, a compound represented by the following general formula (3) is preferable.

[0022]

[Outside 4]

[0023] are those having the same meaning as R ₁ -R ₃ and n in formula (3), R ₁ -R ₃ and n have the general formula (1). R ₄ -R ₆ represent a hydrogen atom or an alkyl group, and the alkyl group is preferably a methyl group, an ethyl group or a propyl group.

Preferred examples of the azoxy calix [n] arene compound used in the present invention are described below. In addition, among the following examples, the exemplified compounds (1) to (15) are compounds belonging to the general formula (3), and include Ar, R ₁ -R ₆ ,
It was expressed only by n.

[0025]

[Outside 5]

[0026]

[Outside 6]

[0027]

[Outside 7]

[0028]

[Outside 8]

[0029]

[Outside 9]

[0030]

[Outside 10]

[0031]

[Outside 11]

The azylated calix [n] arene compound used in the present invention can be obtained by subjecting an amine to tetrazotization by an ordinary method and coupling the calix [n] arene with an aqueous system in the presence of an alkali, or by converting an azonium salt into a borofluoride or chloride. After conversion into a double zinc salt or the like, calix [n] arene is reacted with an organic solvent such as N, N-dimethylformamide, dimethylsulfoxide or tetrahydrofuran in the presence of a base such as sodium acetate, triethylamine, pyridine and N-methylmorpholine. It can be easily synthesized by coupling.

Synthesis Example (Synthesis of Exemplified Compound (1)) In a 300 ml beaker, 75 ml of water, 15 ml of concentrated hydrochloric acid and 10.5 g (0.05 mol) of 2,7-diaminofluorenone are added, and the mixture is heated to 0 ° C. Cool. 7.6 g of sodium nitrite into this solution
(0.11 mol) dissolved in 17 g of water was added dropwise over 10 minutes while maintaining the solution temperature at 5 ° C. or lower. After stirring for 20 minutes, the mixture was filtered with carbon, and a solution prepared by dissolving 19.8 g (0.18 mol) of sodium borofluoride in 60 ml of water was dropped into this solution with stirring, and the precipitated borofluoride was collected by filtration. After washing with cold water, the mixture was washed with cold acetonitrile-isopropylether and dried at room temperature under reduced pressure. Yield 18.
3 g, yield 90.0%.

Next, 800 ml of N, N-dimethylformamide and 4.24 g (0.01 mol) of calix [n] arene are placed in a beaker of 1000 ml, cooled to 0 ° C., and put into this solution. 2.04 g (0.005 mol) of the obtained borofluoride was added, and then N 2
4.5 g of methyl morpholine were slowly added. After stirring for 2 hours while maintaining the liquid temperature at 5 ° C or lower, the mixture was further cooled
Stirred for hours. The precipitate was collected by filtration, purified with N, N-dimethylformamide, washed with water, and dried at room temperature under reduced pressure. The yield was 4.71 g, and the yield was 53.0%.

With respect to the thus obtained exemplary compound (1),
Elemental analyzer (CARLO ERBA INSTRUUM)
Elemental analysis was carried out using EA-1108 manufactured by ENTS. The results are shown below.

[0036]

The electrophotographic photoreceptor of the present invention has a photosensitive layer containing an azide calix [n] arene compound on a conductive support. The photosensitive layer may be a single layer, but a function-separated type photosensitive layer in which a layer containing an azide calix [n] arene compound is used as a charge generation layer, and a charge transport layer containing a charge transport substance is laminated thereon is preferable. .

The charge generation layer is formed by applying a coating solution obtained by dispersing the above-mentioned azoxy calix [n] arene compound together with a binder resin in an appropriate solvent onto a conductive support by a known method. Can be.
The thickness of the charge generation layer is 5 μm or less, preferably 0.1 to 1 μm.
μm is desirable. The content of the azotized calix [n] arene compound is preferably from 40 to 85% by weight, more preferably from 50 to 80% by weight, based on the layer containing the azotized calix [n] arene compound.

The binder resin used for the charge generation layer is selected from a wide range of insulating resins or organic photoconductive polymers. For example, substituted or unsubstituted polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy Resins, cellulose resins, acrylic resins, polyurethanes and the like are preferred, and the substituents are preferably halogen atoms, alkyl groups, alkoxy groups, nitro groups, trifluoromethyl groups, cyano groups and the like.

As the solvent to be used, it is preferable to select a solvent that dissolves the binder resin and does not dissolve the charge transport layer and the undercoat layer described below. For example, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as cyclohexanone and methylethyl ethyl ketone, N, N-
Amides such as dimethylformamide; esters such as methyl acetate and ethyl acetate; aromatic hydrocarbon compounds such as toluene, xylene and chlorobenzene; alcohols such as methanol, ethanol and 2-propanol; aliphatics such as chloroform and methylene chloride. And hydrocarbon compounds.

The charge transport layer is laminated on or under the charge generation layer. The charge transport layer is formed by applying a coating solution in which a charge transport material is dissolved in a solvent together with an appropriate binder resin as required. The thickness of the charge generation layer is 5
４０40 μm, preferably 10-30 μm.

The charge transport material includes an electron transport material and a hole transport material. Examples of the electron transport material include 2, 4, 7
-Electron-withdrawing substances such as -trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil, and tetracyanoquinodimethane, and those obtained by polymerizing these electron-withdrawing substances. Further, as the hole transporting substance, for example, polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole,
Heterocyclic compounds such as pyrazoline, thiadiazole and triazole compounds, hydrazone compounds such as p-diethylamidobenzaldehyde-N, N-diphenylhydrazone, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, α-phenyl -4'-N, N
-Diphenylaminostilbene, 5- [4- (di-p-
Tolylamino) benzylidene] -5H-dibenzo [a,
b] styryl compounds such as cycloheptene, benzidine compounds, triarylmethane compounds, tri (p-tolyl) amine, 2- [di (p-tolyl)]-aminobiphenyl, 1- [di- (p-tolyl) )]-Aminopyrene and the like, or polymers having a group consisting of these compounds in the main chain or side chain (for example, poly-N-vinylcarbazole, polyvinylanthracene, etc.).

In addition to these organic charge transport materials, selenium,
Inorganic materials such as selenium-tellurium, amorphous silicon, and cadmium sulfide can also be used. These charge transport materials can be used alone or in combination of two or more. The content of the charge transport material is preferably 30 to 70% by weight based on the charge transport layer.

Examples of the binder resin used for the charge transporting material include insulating resins such as acrylic resin, polyarylate, polycarbonate, polyester, polystyrene, acrylonitrile-styrene copolymer, polyacrylamide, polyamide, and chlorinated rubber;
Organic photoconductive polymers such as vinyl carbazole and polyvinyl anthracene are exemplified.

When the photosensitive layer is a single layer, the thickness of the photosensitive layer is 5
-40 μm, more preferably 10-30 μm.

When the photosensitive layer is a single layer, it can be prepared by applying a solution obtained by dispersing the above-mentioned azoxy calix [n] arene compound and a charge transport material in an appropriate resin solution on a conductive support and drying. it can.

As a coating method for coating each layer,
General coating materials can be used, and for example, coating methods such as dip coating, spray coating, spinner coating, roller coating, Meyer bar coating, and blade coating can be used.

As the material of the conductive support on which the photosensitive layer is formed, for example, aluminum, aluminum alloy, copper,
Zinc, stainless steel, vanadium, molybdenum, chromium,
Titanium, nickel, indium, gold and platinum are used. In addition, plastics (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) obtained by vacuum-depositing these metals or alloys, and conductive particles (for example, carbon black, silver particles, etc.) together with a suitable binder resin, together with plastic or A support coated on a metal substrate, a support in which conductive particles are impregnated in plastic or paper, or the like can be used.

An undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer.
The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like. The film thickness is 5 μm or less, preferably 0.1 μm.
1-3 μm is appropriate.

Azotis calix [n] used in the present invention
The crystalline form of the arene compound may be amorphous or crystalline. If necessary, two or more of the above-mentioned azoxy calix [n] arene compounds may be used in combination, or a known charge generating substance such as phthalocyanine It can be used in combination with a series pigment, an azo pigment, a perylene pigment or the like.

The electrophotographic photoreceptor of the present invention is used not only for electrophotographic copying machines and facsimile printers, but also for
Laser beam printer, CRT printer, LED
It can be widely used in electrophotographic applications such as printers, liquid crystal printers, and laser plate making.

A protective layer may be provided on the photosensitive layer if necessary. The protective layer is made of a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer or the like. It can be formed by dissolving with a solvent, coating and drying on the photosensitive layer. The thickness of the protective layer is preferably 0.05 to 20 μm.
Further, the protective layer may contain conductive particles, an ultraviolet absorber, and the like. As the conductive particles, for example, metal oxides such as tin oxide particles are preferable.

Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.

In FIG. 1, reference numeral 1 denotes a drum type photosensitive member of the present invention, which is driven to rotate around an axis 1a at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on its peripheral surface by a charging means 2 during the rotation process,
Next, the exposure unit 3 receives light image exposure L (slit exposure or laser beam scanning exposure) by an image exposure unit (not shown). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor. The electrostatic latent image is then developed with toner by a developing unit 4, and the developed toner image is transferred by a corona transfer unit 5 between a photosensitive unit 1 and a transfer unit 5 from a paper feeding unit (not shown). The recording material 9 is sequentially transferred onto the surface of the recording material 9 fed in synchronization. The recording material 9 to which the image has been transferred is separated from the surface of the photoreceptor, and
And the image is fixed and printed out of the machine as a copy. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning unit 6, subjected to a charge removal process by the pre-exposure unit 7, and used repeatedly for image formation.

In the apparatus shown in FIG. 2, at least the photosensitive member 1, the charging means 2 and the developing means 4 are housed in a container 20 to form a process cartridge, and this process cartridge is formed by using a guide means 12 such as a rail of the apparatus body. It is configured to be removable. The cleaning means 6 may or may not be disposed in the container 20.

As shown in FIGS. 3 and 4, a direct charging member 10 is used as charging means, and the photosensitive member 1 is charged by bringing the direct charging member 10 to which a voltage is applied into contact with the photosensitive member 1. (This charging method is hereinafter referred to as direct charging). 3 and 4, the toner image on the photoconductor 1 is also directly transferred to the recording material 9 by the charging member 23. That is, the direct charging member 23 to which the voltage is applied is
To transfer the toner image on the photoconductor 1 to the recording material 9.

Further, in the apparatus shown in FIG. 4, at least the photosensitive member 1 and the direct charging member 10 are housed in a first container 21 to form a first process cartridge, and at least the developing means 4
Are contained in a second container 22 to form a second process cartridge, and the first process cartridge and the second process cartridge are configured to be detachable. The cleaning means 6 may or may not be disposed in the container 21.

In the case where the electrophotographic apparatus is used as a copier or a printer, the light image exposure L uses reflected light or transmitted light from the original, or reads the original and converts the signal into a laser beam. This is performed by performing scanning, driving a light emitting diode array, driving a liquid crystal shutter array, or the like.

The electrophotographic photoreceptor of the present invention has a remarkable effect that it has high sensitivity and has stable and excellent potential characteristics even when used repeatedly. In addition, it can be mounted on a process cartridge and an electrophotographic apparatus to provide the same excellent effects.

[0060]

【Example】

Examples 1 to 8 5 g of methoxymethylated nylon (weight average molecular weight 32,000) and alcohol-soluble copolymerized nylon (weight average molecular weight 29000) 1 on a sheet-like aluminum support
A solution prepared by dissolving 0 g in 95 g of methanol was applied with a Meyer bar, and an undercoat layer having a dried film thickness of 1 μm was formed.

Next, 6 g of Exemplified Compound (1) was added to a solution of 2 g of butyral resin (degree of butyralization: 63 mol%) dissolved in 95 g of cyclohexanone.
Dispersed for 0 hours. This dispersion was applied to the undercoat layer with a Meyer bar so that the film thickness after drying was 0.2 μm to form a charge generation layer.

Next, 5 g of a hydrazone compound having the following structural formula

[0063]

[Outside 12] And polymethyl methacrylate (number average molecular weight 10,000
0) A solution in which 5 g was dissolved in 40 g of chlorobenzene was applied on the above-mentioned charge generating layer with a Meyer bar, and dried to form a 16 μm-thick charge photosensitive layer, thereby preparing an electrophotographic photosensitive member of the present invention.

The electrophotographic photoreceptors of Examples 2 to 8 were prepared in exactly the same manner as in Example 1 except that the exemplified compounds shown in Table 1 were used instead of the exemplified compound (1).

The electrophotographic photoreceptor thus prepared was subjected to an electrostatic copying paper tester (SP-428, manufactured by Kawaguchi Electric Co., Ltd.).
And negatively charged by a corona discharge of -5 KV using the above method, left in a dark place for 1 second, and then exposed to an illuminance of 10 lux using a halogen lamp to evaluate the charging characteristics. As the charging characteristics, the surface potential V ₀ immediately after the charging and the exposure material E _1/2 required to attenuate the surface potential after leaving in a dark place for 1 second to _1/2 were measured. The results are shown in Table 1.

[0066]

[Table 1]

Comparative Examples 1 and 2 An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 1 except that the following comparative pigments 1 and 2 were used in place of the exemplary compound (1) used in Example 1. Then, the charging characteristics of each photoconductor were evaluated in the same manner as in Example 1. Table 2 shows the results
It was shown to.

Comparative pigment 1

[0069]

[Outside 13]

Comparative pigment 2

[0071]

[Outside 14]

[0072]

[Table 2]

From these results, it is known that all of the electrophotographic photoreceptors of the present invention have a sufficient chargeability and improved excellent sensitivity characteristics.

Examples 9 to 13 The electrophotographic photosensitive member prepared in Example 1 was attached to the cylinder of the electrophotographic copying machine shown in FIG. For the corona charger-
A voltage of 7.0 kV was applied. Near the initial dark potential V _D and light portion potential V _L, respectively -700 V, was set to be around -200 V, charging, exposure, the cycle of neutralization using repeated 5000 times, with initial and repeat after use The durability was evaluated by measuring the variation ΔV _D of the dark portion potential and the variation ΔV _L of the bright portion potential. The results are shown in Table 3. Note that a negative sign in the potential fluctuation indicates that the absolute value of the potential has decreased, and a positive sign indicates that the absolute value of the potential has increased.

The electrophotographic photosensitive members prepared in Examples 2, 3, 5, and 8 were similarly evaluated. Table 3 shows the results
It was shown to.

[0076]

[Table 3]

Comparative Examples 3 and 4 With respect to the electrophotographic photosensitive members prepared in Comparative Examples 1 and 2, the amount of potential fluctuation during repeated use was measured in the same manner as in Example 9. The results are shown in Table 4.

[0078]

[Table 4]

From the results of Examples 9 to 13 and Comparative Examples 3 and 4, it can be seen that the electrophotographic photosensitive member of the present invention has little potential fluctuation when repeatedly used.

Example 14 An undercoat layer of polyvinyl alcohol having a thickness of 0.5 μm was formed on a sheet-like aluminum support.

On the undercoat layer, a dispersion of the same exemplified compound (18) as used in Example 7 was applied with a Meyer bar and dried to form a charge generation layer having a thickness of 0.2 μm. .

Next, 5 g of a compound having the following structural formula

[0083]

[Outside 15] And polycarbonate (weight average molecular weight 55000) 5g
Was dissolved in 40 g of tetrahydrofuran and applied onto the charge generation layer and dried to form a charge transport layer having a thickness of 16 μm, whereby an electrophotographic photoreceptor of the present invention was prepared.

The sensitivity of this electrophotographic photosensitive member was measured as follows.

A laser beam printer (trade name: LBP-
SX, manufactured by Canon Inc.) and charged so that the dark area potential was -700 V. Thereafter, a laser beam having a wavelength of 802 nm is irradiated on the electrophotographic photosensitive member.
The sensitivity was determined by measuring the amount of light required to reduce the 700 V potential to -150 V.

Next, the dark part potential -700 V, the light part potential -1.
A continuous paper endurance test of 4000 sheets was performed with the voltage set to 50 V, and the dark portion potential variation ΔV _D and the light portion potential variation ΔV
_L was measured. The measurement results of the sensitivity and the amount of potential fluctuation are shown below.

Sensitivity: 1.25 μJ / cm ² ΔV _D : 0 V ΔV _L : +5 V

Example 15 An undercoat layer of polyvinyl alcohol having a thickness of 0.5 μm was formed on a sheet-like aluminum support.

On the undercoat layer, a dispersion liquid of the same compound (14) as used in Example 5 was applied by a Meyer bar and dried to form a charge generation layer having a thickness of 0.2 μm.

Next, 5 g of a compound having the following structural formula

[0091]

[Outside 16] And polycarbonate (weight average molecular weight 55000) 5g
Was dissolved in 40 g of tetrahydrofuran and applied onto the charge generating layer and dried to form a charge transporting layer having a thickness of 17 μm, whereby an electrophotographic photoreceptor of the present invention was prepared.

The sensitivity of this electrophotographic photoreceptor and the amount of potential fluctuation in a durability test were measured in the same manner as in Example 14.
The measurement results are shown below.

Sensitivity: 1.10 μJ / cm ² ΔV _D : 0 V ΔV _L : +5 V

Example 16 An electrophotographic photosensitive member of the present invention was prepared by laminating the charge generation layer and the charge transport layer of the electrophotographic photosensitive member prepared in Example 5 in reverse order. The charging characteristics were evaluated.
However, the charging was positive. The results are shown below.

V ₀ : + 620V E _1/2 : 2.75 lux · sec

Example 17 A charge generation layer was formed in the same manner as in Example 5. On top of that, 5 g of 2,4,7-trinitro-9-fluorenone and poly-4,4-dioxydiphenyl-2,2-
Propane carbonate (weight average molecular weight 300,000)
A solution in which 5 g was dissolved in 50 g of tetrahydrofuran was applied and dried with a Meyer bar to form a charge transporting layer having a thickness of 16 μm, thereby producing an electrophotographic photosensitive member. The charging characteristics were evaluated in the same manner as in Example 1. However, the charging was positive. The results are shown below.

V ₀ : + 650V E _1/2 : 2.50 lux · sec

Example 18 0.5 g of Exemplified Compound (2) was added to cyclohexanone 9.5.
g and dispersed with a paint shaker for 5 hours. To this dispersion, a solution in which 5 g of the same charge transporting substance as used in Example 1 and 5 g of polycarbonate were dissolved in 40 g of tetrahydrofuran was added, and the mixture was further shaken for 1 hour. The prepared coating solution was applied on an aluminum substrate with a Meyer bar and dried to form a photosensitive layer having a thickness of 20 μm, thereby preparing an electrophotographic photosensitive member of the present invention. The charging characteristics of this electrophotographic photosensitive member were evaluated in the same manner as in Example 1. However, the charging was positive. The results are shown below.

V ₀ : + 640V E _1/2 : 2.20 lux · sec

[0100]

The electrophotographic photoreceptor of the present invention has a remarkable effect that it has high sensitivity and has excellent potential characteristics stably even when used repeatedly. In addition, it can be mounted on a process cartridge and an electrophotographic apparatus to provide the same excellent effects.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of an electrophotographic apparatus according to the present invention.

FIG. 2 is a diagram illustrating another example of the electrophotographic apparatus of the present invention.

FIG. 3 is a diagram showing another example of the electrophotographic apparatus of the present invention.

FIG. 4 is a diagram showing another example of the electrophotographic apparatus of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Charging means 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 9 Recording material 10 Direct charging member

Claims (11)

[Claims] 1. An electrophotographic photosensitive member having at least a photosensitive layer on a support, wherein said photosensitive layer is calix [n].
An electrophotographic photoreceptor comprising an azoxy calix [n] arene compound formed by coupling an arene compound with an azonium compound having at least two azo compounds. 2. The electrophotographic photosensitive material according to claim 1, wherein the calix [n] arene compound is represented by the following general formula (1), and the azonium compound is represented by the following general formula (2). body. [Outside 1] In the formula (1), R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group. n shows the integer of 4-8. Ar- (N ₂ · X) _m (2) In the formula (2), X represents BF ₄ , ZnCl ₂ or a halogen atom, and Ar represents an aromatic hydrocarbon ring which may have a substituent, a substituent. Or a combination of a plurality of aromatic hydrocarbon rings or a plurality of heterocycles. m shows the integer of 2-4. 3. The electrophotographic photoreceptor according to claim 1, wherein said azylated calix [n] arene compound is represented by the following general formula (3). [Outside 2] In the above (3), R ₁ -R ₆ represent a hydrogen atom or an alkyl group. n shows the integer of 4-8. 4. The electrophotographic photosensitive material according to claim 1, wherein the content of the azoxy calix [n] arene compound is 40 to 85% by weight based on the layer containing the azoxy calix [n] arene compound. body. 5. The electrophotographic photoreceptor according to claim 4, wherein said content is 50 to 80% by weight. 6. The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer has a structure in which at least a charge generation layer and a charge transport layer are laminated, and the charge generation layer contains the azoxy calix [n] arene compound. . 7. The method according to claim 1, wherein said photosensitive layer is composed of one layer.
The electrophotographic photosensitive member according to the above. 8. An electrophotographic photosensitive member according to claim 1, charging means for charging said electrophotographic photosensitive member, and image exposure for forming an electrostatic latent image by performing image exposure on said charged electrophotographic photosensitive member. And an developing device for developing the electrophotographic photosensitive member on which the electrostatic latent image is formed with toner. 9. An electrophotographic apparatus according to claim 8, wherein said charging means is a direct charging member. 10. A process cartridge comprising: the electrophotographic photosensitive member according to claim 1; and a charging member for charging the electrophotographic photosensitive member. 11. The process cartridge according to claim 10, further comprising developing means for developing an electrostatic latent image formed on said electrophotographic photosensitive member.