JP2000181094A - Electrophotographic photoreceptor and process cartridge and image-forming device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreceptor which has high wear resistance and without filming on which stable copied images of high image quality can be obtained for a long time by incorporating a specified copolymerizable polycarbonate and using a specified imidazole perylene compound for a charge generating material. SOLUTION: In this electrophotographic photoreceptor, the surface layer contains a copolymerizable polycarbonate having at least a repeating unit expressed by formula I as a binder resin, and the charge generating material is at least either imidazole perylene compound expressed by the structural formula II or III. In the formula I, R1 to R6 are each independently a hydrogen atom, halogen atom, 1-6C substituted or unsubstituted alkyl group or the like, X1 and X2 are each independently a single bond, 1-6C substituted or unsubstituted alkylene group or the like, p, q are integers so that the sum of them is in the range of 0 to 200, and m is an integer of 1 to 6.

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 for an image forming apparatus used as a copying machine or a printer, a process cartridge equipped with the photosensitive member, and an image forming apparatus.

[0002]

2. Description of the Related Art In a Carlson method electrophotographic copying machine, a photoreceptor is uniformly charged, and then charge is erased imagewise by exposure to form an electrostatic latent image. The toner is developed and visualized with a toner, and then the toner is transferred and fixed on paper or the like.

The electrophotographic photoreceptor used in the above situation has not only the electrophotographic characteristics such as good charging characteristics and sensitivity and low dark decay, but also printing durability and abrasion resistance in repeated use. It is also required to have good physical properties such as resistance and scratch resistance, and good resistance to ozone, NOx generated during corona discharge, ultraviolet rays during exposure, and the like.

Conventionally, selenium,
Inorganic photoreceptors containing an inorganic photoconductive substance such as zinc oxide and cadmium sulfide as a main component of a photosensitive layer have been widely used. However, these inorganic photoreceptors are harmful to the human body, and thus pose a problem in their disposability.

In recent years, organic photoreceptors using non-polluting organic substances have been actively developed and put to practical use. Above all, charge generation function and charge transport function are shared by different substances,
The development of a function-separated type photoreceptor capable of selecting a substance exhibiting each function from a wide range in view of desired characteristics has been actively developed, and there is a trend to commercialize an organic photoreceptor having high sensitivity and durability.

Conventionally, such an organic photoreceptor of the function sharing type is mainly used for negative charging.
No. 647, a thin carrier generation layer is provided on a support, and a relatively thick carrier transport layer is provided thereon. As a binder used in such a photoreceptor, it is well known that bisphenol A-type or bisphenol Z-type polycarbonate exhibits good characteristics in terms of charging characteristics, sensitivity, residual potential, and repetition characteristics. I have.

On the other hand, not all of the toner on the photoreceptor is transferred, and part of the toner remains on the photoreceptor. When an image is repeatedly formed in this state, the formation of a latent image is disturbed by the effect of the residual toner. Therefore, it is not possible to obtain a high-quality copy without contamination. Therefore, it is necessary to remove the residual toner. The cleaning means is typically a fur brush, a magnetic brush, a blade, or the like, but a blade is mainly used in terms of performance, configuration, and the like. At this time, a plate-shaped rubber elastic body is generally used as the blade member.

When the above-mentioned polycarbonate is used for the surface layer, it has a disadvantage that the surface of the photosensitive layer is scratched by being rubbed by a magnetic brush or a cleaning blade, and the photosensitive layer gradually wears. If the abrasion force of the cleaning means is reduced to reduce such scratches and abrasion, a so-called cleaning failure occurs in which toner additives such as silica and paper powder such as talc pass through the blade. Such a poor cleaning is unlikely to cause a problem on an image in a normal use environment, but it causes a problem such as a character flow and an image blurring under high temperature and high humidity. On the other hand, the photosensitive layer was forcibly shaved to increase the wear rate by increasing the contact load of the blade, or to expose the urethane roller to which the abrasive was added, in order to always expose the clean surface of the photoconductor. It comes in contact with the body. However, when the amount of wear is increased in this way, although the image failure due to poor cleaning is improved, the sensitivity and the charging potential are reduced due to the wear, which shortens the life of the inorganic photosensitive member and hinders high durability. The main cause.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an electrophotographic photosensitive member which is free from filming such as toner components and paper dust, has high abrasion resistance, and provides a high quality and stable copy image for a long period of time. Is to provide the body.

[0010]

The above object of the present invention is achieved by the following constitution.

(1) In an electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance, and a binder resin on a conductive support, at least a surface layer of the photosensitive member has at least one of the binder resin as the binder resin. An electrophotographic photosensitive material comprising a copolymerized polycarbonate having a repeating unit represented by the following general formula (A1), and wherein the charge generating substance is at least one of imidazole perylene compounds represented by the structural formulas (G1) and (G2). body.

[0012]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. X ¹ and X ² each independently represent a single bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms,

[0014]

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Wherein p and q are an integer of 0 to 200 in total, and m is an integer of 1 to 6. ]

[0016]

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(2) The binder resin comprises at least a copolymerized polycarbonate having a repeating unit represented by the following general formula (A2), and the imidazole perylene compound has an X-ray diffraction spectrum with respect to Cu-Kα ray (wavelength: 1.54 A). 6.3 ± 0.2 °, 12.4 ± 0.2
結晶, a crystal having peaks at 25.3 ± 0.2 ° and 27.1 ± 0.2 °, wherein the peak intensity at 12.4 ± 0.2 ° is maximum and at the same time the half width of the peaks Is an imidazole perylene compound in a state of not less than 0.65 ° and showing no clear peak at 11.5 ± 0.2 °.

[0018]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Y ₁ and Y ₂ are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or an alkylidene group, and p1 and q1 are an integer of 0 to 200 in total. (3) Using an electrophotographic photosensitive member, charging, image exposure, development,
In a process cartridge used for image formation through a transfer / separation / cleaning step, at least one of the electrophotographic photosensitive member according to the above 1 or 2, and a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit. A process cartridge characterized by being manufactured by combining any one of them.

(4) An image forming apparatus characterized in that an image is formed by using the electrophotographic photosensitive member according to the above (1) or (2), through charging, image exposure, development, transfer / separation, and cleaning.

The present invention will be described in more detail. First, the copolymerized polycarbonate of the present invention will be described.

The polycarbonate copolymer of the present invention comprises, for example, a dihydric amine (1) represented by the following general formula (1) and a dihydric phenol (2) represented by the following general formula (2):
It can be synthesized by reacting a carbonate-forming compound. In synthesizing the polycarbonate copolymer of the present invention, one type of divalent amine (1) may be used alone, two or more types may be used in combination, and one type of dihydric phenol may be used alone. Or two or more of them may be used in combination.

As a synthesis method, for example, a method in which phosgene or the like is used as a carbonate-forming compound and polycondensation with the above divalent amine (1) and dihydric phenol (2) in the presence of a suitable acid binder, A method of performing a transesterification reaction using bisaryl carbonate as the carbonate-forming compound can be applied. These reactions are performed in the presence of a terminal terminating agent and / or a branching agent as necessary.

[0024]

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In the formula, R ¹⁰ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 6 to 12 carbon atoms. Alternatively, it represents an unsubstituted aryl group. X
¹ and X ² represent a group having the same meaning as in the general formula (A1), and n represents an integer of 0 to 200.

[0026]

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In the formula, R ¹¹ and R ¹² are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms or a carbon atom having 6 to 1 carbon atoms.
2 represents a substituted or unsubstituted aryl group, a and b
Each independently represents an integer of 0 to 4, Y ¹⁰ is a single bond,-
O -, - S -, - CO -, - SO -, - SO 2 - shows a.

Specific examples of the above divalent amine (1) include:
For example, the following are mentioned.

[0029]

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[0030]

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[0031]

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[0032]

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Examples of the dihydric phenol (2) represented by the general formula (2) include, for example, 4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 4'-dihydroxy-3,3 '
-Dimethylbiphenyl, 4,4'-dihydroxy-2,
2'-dimethylbiphenyl, 4,4'dihydroxy-
3,3'-dicyclohexylbiphenyl, 4,4'-dihydroxy-3,3'-divinylbiphenyl, 3,3 '
4,4'-dihydroxybiphenyls such as -diallyl-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylmethane,
Bis (4-hydroxy-3-methylphenyl) methane,
Bis (4-hydroxy-3-nonylphenyl) methane,
Bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane,
Bis (3-chloro-4-hydroxyphenyl) methane,
Bis (3-fluoro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (4-hydroxy-3-vinylphenyl) methane, bis (3-allyl-4-hydroxy Phenyl) methane, bis (4-hydroxy-5-methyl-3-
Vinylphenyl) methane, bis (3-allyl-4-hydroxy-5-methylphenyl) methane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4
-Hydroxyphenylmethane, bis (2-hydroxy-
4-methylphenyl) methane, bis (6-tert-butyl-2-hydroxy-4-methylphenyl) methane,
Bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-
(Hydroxy-3-phenylphenyl) -1-phenylethane, 2- (4-hydroxy-3-methylphenyl)-
2- (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-
1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (alias: bisphenol A), 1,1
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, , 2-bis (4-hydroxy-2-methylphenyl) propane,
1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-
sec-butyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4
-Hydroxyphenyl) propane, 2,2-bis (3,
5-difluoro-4-hydroxyphenyl) propane (alias: tetrafluorobisphenol A), 2,2-
Bis (3,5-dichloro-4-hydroxyphenyl) propane (alias: tetrachlorobisphenol A), 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane (alias: tetrabromobisphenol A), 2,2-bis (3-bromo-5-chloro-4-hydroxyphenyl) propane, 2,2- Bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxy-3-
Phenylphenyl) propane, 2,2-bis (4-hydroxy-3-vinylphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-5-methyl-3-vinylphenyl) propane, 2,2-bis (3-allyl-4
-Hydroxy-5-methylphenyl) propane, 2,2
-Bis (2-hydroxy-4,6-dimethylphenyl)
Propane, 2,2-bis (4-sec-butyl-2-hydroxyphenyl) propane, 1,1-bis (2-te
rt-butyl-5-methyl-4-hydroxyphenyl)
-2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 2,2-bis (4-
(Hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl)
Butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (4-hydroxy-2-methyl-5-tert-pentylphenyl) butane, 2, 2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3- Methylbutane, 1,1-bis (4-hydroxyphenyl)
-3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 2,2-bis (4-hydroxyphenyl) hexane, 2-ethyl-1 , 1-bis (4-
Hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (2-te
rt-butyl-4-hydroxy-5-methylphenyl)
Heptane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-
3,5-dimethylphenyl) cyclohexane, 1,1-
Bis (4-hydroxy-3-vinylphenyl) cyclohexane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-5-methyl-3-vinylphenyl) cyclohexane , 1,1-bis (3-allyl-4-hydroxy-5-
Methylphenyl) cyclohexane, 1,1-bis (4-
Bis (hydroxyphenyl) alkanes such as hydroxy-3-cyclohexylphenyl) cyclohexane and 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane; bis (4-hydroxyphenyl) ether, bis (3-fluoro- 4-hydroxyphenyl)
Bis (4-hydroxyphenyl) ethers such as ethers; bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (4-hydroxy-3-methylphenyl) sulfide; bis (4- Bis (4-hydroxyphenyl) sulfones such as hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxy-3-phenylphenyl) sulfone; 4,4′-dihydroxybenzophenone Bis (hydroxyphenyl) ketones; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-
Methylphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-vinylphenyl) fluorene, 9,9-bis (3-allyl-4) -Hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-5-
Methyl-3-vinylphenyl) fluorene, 9,9-bis (3-allyl-4-hydroxy-5-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-
Bis (hydroxyphenyl) fluorenes such as phenylphenyl) fluorene; 4,4'-dihydroxy-p-
Dihydroxy-p-terphenyls such as terphenyl;
Dihydroxy-p-quarterphenyls such as 4,4'-dihydroxy-p-quarterphenyl; 2,5-bis (4-hydroxyphenyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6- Dimethylpyrazine, 2,5-bis (4-hydroxyphenyl) -2,6
Bis (hydroxyphenyl) pyrazines such as diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (4-hydroxy-3-methylphenyl) menthane, 1,8-bis (4 -Hydroxy-
Bis (4-hydroxyphenyl) menthanes such as 3,5-dimethylphenyl) menthane; and the like.

Further, in addition to these dihydric phenols represented by the general formula (2), hydroquinone, resorcinol,
Dihydroxybenzenes such as catechol and methylhydroquinone; dihydroxynaphthalenes such as 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; 6,
Dihydroxybisindanes such as 6'-dihydroxy-3,3,3 ', 3'-tetramethylbisindane;
4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene and the like can also be used.

Among these various dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) )-
1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1,1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) ) Propane, 2,2-bis (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone, 2,2
-Bis (4-hydroxy-3-methoxyphenyl)-
1,1,1,3,3,3-hexafluoropropane and the like are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

As the terminal terminating agent that can be used in the production of the polycarbonate copolymer used in the present invention, monovalent carboxylic acids and derivatives thereof, and monovalent phenols can be used. For example, p- (tert-butyl) phenol, p-cumylphenol, p-phenylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert-perfluorobutylphenol,
1- (p-hydroxybenzyl) perfluorodecane,
p- (2- (1H, 1H-perfluorotridecyloxy) -1,1,1,3,3,3-hexafluoropropyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p -Perfluorododecyl hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-
Perfluorononanoic acid and the like are preferably used.

The preferred range of the total amount of the terminal terminator is 1 to 30 mol%, more preferably 1 to 1 as a copolymer composition ratio.
0 mol%. If it exceeds 30 mol%, the photosensitive layer is liable to be worn due to insufficient surface hardness, and the printing life is shortened.
If it is less than 1 mol%, the solution viscosity increases, and it may be difficult to produce a photoreceptor by a liquid coating method. As a branching agent,
Trivalent or higher phenols or carboxylic acids can be used. Examples of branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,4-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 1,3,5-tris (2-hydroxyphenyl) benzene, 1,3 5-
Tris (4-hydroxyphenyl) benzene, 1,1,
1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-
Bis (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane, 2,4-bis {2- (4-hydroxyphenyl) -2-propyl} phenol, 2,6-
Bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2
-(2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis (4- (4-hydroxyphenylisopropyl) phenoxy) methane, 1,4-bis (4 ', 4 "-dihydroxytriphenyl Methyl) benzene, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin and the like.

Of these, phloroglysin, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are preferably used. A preferred range of the amount of the branching agent is 30 mol% or less, more preferably 5 mol% or less as a copolymer composition ratio. If it exceeds 30 mol%, the viscosity of the solution increases, and it may be difficult to produce the photoconductor by the liquid coating method.

The reaction of performing polycondensation in the presence of an acid binder using various carbonyl halides such as phosgene, haloformates such as chloroformate, etc., as the carbonate-forming compound, Usually, it is carried out in a solvent. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed.

The proportion of the carbonate-forming compound used is as follows:
What is necessary is just to adjust suitably considering the stoichiometric ratio (equivalent) of reaction. Examples of the acid binder include sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine and mixtures thereof are used.

The proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 or more equivalents, preferably 2 to 10 equivalents, of the acid binder relative to the number of moles of the dihydric phenol to be used (1 mol is usually equivalent to 2 equivalents).

Specific examples of the copolymerized polycarbonate having a repeating unit of the general formula (A1) and the general formula (A2) which can be preferably used in the present invention are shown below.

[0043]

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[0044]

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As the charge generating substance, at least one of the imidazole perylene compounds represented by the structural formulas (G1) and (G2) is preferable.

In particular, the electrophotographic photoreceptor of the present invention contains Cu
6.3 ± 0.2 °, 12.4 ± 0.2 °, 25.3 of X-ray diffraction spectrum with respect to −Kα ray (wavelength 1.54 A)
A crystal having peaks at ± 0.2 ° and 27.1 ± 0.2 °, wherein the peak intensity at 12.4 ± 0.2 ° is the maximum and the half width of the peak is 0.65 °. That's it,
When at least one of the imidazole perylene compounds of the structural formulas (G1) and (G2) does not show a clear peak at 11.5 ± 0.2 °, the sensitivity, durability and image quality are remarkably improved. Show the effect.

The charge transporting substance is not particularly limited, but may be, for example, an oxazole derivative, an oxadiazole derivative, a thiazole derivative, a thiadiazole derivative, a triazole derivative, an imidazole derivative, an imidazolone derivative, an imidazolidine derivative, a bisimidazolidine derivative, a styryl compound. Hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, Poly-9
-Vinyl anthracene and the like.

Further, as the charge transporting substance, those which are excellent in the ability to transport holes generated upon light irradiation and which are suitable for combination with oxytitanyl phthalocyanine are preferable.

Since the charge generating substance and the charge transporting substance by themselves have poor film-forming ability, the photosensitive layer may be formed by using various binders.

As the binder resin used for forming the photosensitive layer in combination with the above-described copolymerized polycarbonate of the present invention, any binder resin can be used, but the binder resin is hydrophobic, has a high dielectric constant, and is electrically insulating. It is preferable to use a film-forming polymer. Examples of such a high-molecular polymer include polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, and vinylidene chloride having a structure other than that of the present invention. -Acrylonitrile copolymer, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole,
Polyvinyl acetal (eg polyvinyl butyral)
And the like. These binder resins can be used as a mixture of two or more kinds in combination with the resin of the present invention.

In the organic photoreceptor, an auxiliary layer such as a protective layer, an intermediate layer, a barrier layer, and an adhesive layer may be further laminated on the support, if necessary, in addition to the charge generation layer and the charge transport layer.

The intermediate layer functions as an adhesive layer or a blocking layer. In addition to the binder resin, for example, polyvinyl alcohol, ethyl cellulose,
Carboxymethyl cellulose, casein, copolymerized nylon, N-alkoxymethylated nylon, starch and the like are used.

Solvents or dispersion media used for forming the charge generation layer and the charge transport layer include butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, and the like.
N, N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,
2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl Sulfoxide, methylcellosolve and the like.

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Among them, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube usually formed by extrusion or drawing is often used.

Examples of the form of the organic photoreceptor are shown in FIGS.

As shown in FIGS. 1 (1) and (2), the organic photoreceptor comprises, on a conductive support 1, CGL 2 containing CGM as a main component and CTL 3 containing CTM as a main component according to the present invention. Is provided.

The photosensitive layer 4 may be provided via an intermediate layer 5 provided on the conductive support 1, as shown in FIGS.

Thus, when the photosensitive layer 4 has a two-layer structure, an electrophotographic photosensitive member having excellent electrophotographic characteristics can be obtained.

In the present invention, as shown in FIGS. 5 and 6, the photosensitive layer 4 formed by dispersing fine-grained CGM 7 in the layer 6 containing CTM as a main component is electrically conductive. It may be provided directly on the body 1 or via the intermediate layer 5.

Further, a protective layer 8 may be provided on the photosensitive layer 4 if necessary.

Here, when the photosensitive layer 4 has a two-layer structure as shown in FIG. 1A, the CGL 2 is
It can be formed by the following method directly on the TL3 or after providing an intermediate layer such as an adhesive layer or a blocking layer as necessary.

(1) Vacuum evaporation method (2) Method of applying a solution in which CGM is dissolved in an appropriate solvent (3) CGM is converted into fine particles in a dispersion medium by a ball mill, a sand grinder or the like, and if necessary, a binder is prepared. And applying a dispersion obtained by mixing and dispersing.

That is, specifically, a vapor deposition method such as vacuum evaporation, sputtering, or CVD, or a coating method such as dipping, spray, blade, or roll method is used arbitrarily.

The thickness of the CGL thus formed is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm.

The CTL 3 can be formed in the same manner as the CGL 2.

The composition ratio in this CTL is CTM1
The binder is preferably used in an amount of 0.1 to 5 parts by weight based on the weight of the photosensitive layer 4 in which fine particle CGM is dispersed.
Is preferably used in an amount of 5 parts by weight or less based on 1 part by weight of CGM.

When the CGL is of a dispersion type in a binder, the binder is preferably used in an amount of 5 parts by weight or less based on 1 part by weight of CGM.

The electrophotographic photoreceptor of the present invention is applicable to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers.
Further, the present invention can be widely applied to apparatuses using electrophotography, such as displays, recording, light printing, plate making, and facsimile.

[0069]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Polyamide resin Amilan CM-8000 (manufactured by Toray Industries, Inc.) 3
0 g of methanol 900 ml, 1-butanol 100 m
1 and mixed at 50 ° C. under heating. This liquid was applied on a cylindrical aluminum conductive support having an outer diameter of 80 mm and a length of 360 mm to form a 0.5 μm thick intermediate layer.

Next, 2 g of polyvinyl butyral resin ESLEK BX-1 (manufactured by Sekisui Chemical Co., Ltd.) is dissolved in a mixed solvent of 700 ml of methyl ethyl ketone and 300 ml of cyclohexanone, and 3 g of the imidazole perylene compound according to claim 2 is mixed therein and a sand mill is used. For 10 hours,
A charge generating layer coating liquid (CGL liquid-1) was obtained. This liquid was used to coat the intermediate layer to form a 0.3 μm thick charge generation layer.

Next, as CTM, 1 of the following compound T-1
50 g of the resin of the structural formula (1) shown in Chemical formula 15 (Mv = 8
(000) 200 g of 1,2-dichloroethane 100
This was dissolved in 0 ml to obtain a charge transport layer coating solution (CTL solution-1). Using this solution, coating was performed on the charge generation layer, and the coating was dried at 100 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.

Thus, a photoreceptor sample (OPC-1) comprising the intermediate layer, the charge generation layer and the charge transport layer was obtained.

[0074]

Embedded image

Example 2 A photoconductor sample was prepared in the same manner as in Example 1 except that the resin (1) of the charge transport layer was replaced with the resin of the structural formula (2) (Mv = 78,000) shown in Chemical Formula 15. (OPC-2) was produced.

Example 3 A photoreceptor sample was prepared in the same manner as in Example 1 except that the resin (1) of the charge transport layer was replaced with the resin of the structural formula (3) shown in Chemical Formula 15 (Mv = 73,000). (OPC-3) was produced.

Example 4 A photoconductor sample was prepared in the same manner as in Example 1, except that the resin (1) of the charge transport layer was replaced with the resin of the structural formula (4) shown in Chemical Formula 16 (Mv = 96,000). (OPC-4) was produced.

Example 5 A photoconductor sample was prepared in the same manner as in Example 1 except that the resin (1) of the charge transport layer was replaced with the resin of the structural formula (5) shown in Chemical Formula 16 (Mv = 10,000). (OPC-5) was produced.

Example 6 In Example 1, the Mv of the resin (1) of the charge transport layer was changed to 8
A photoreceptor sample (OPC-6) was prepared in the same manner except that the amount was changed from 000 to 30,000.

Comparative Example 1 A photoreceptor sample (OP) was prepared in the same manner as in Example 1 except that the resin (1) of the charge transport layer was replaced with the resin of Comparative Example 1 below.
C-7) was produced.

Comparative Example 2 A photoreceptor sample (OP) was prepared in the same manner as in Example 1 except that the resin (1) of the charge transport layer was changed to the resin of Comparative Example 2 below.
C-8) was produced.

[0082]

Embedded image

Comparative Example 3 A photoconductor sample (OPC-9) was prepared in the same manner as in Example 1 except that the perylene compound was used in place of the perylene compound and the azo pigment having the following structure was used.

[0084]

Embedded image

Comparative Example 4 A photoconductor sample (OPC-10) was prepared in the same manner as in Example 1, except that τ-phthalocyanine was used instead of the perylene compound as the charge generating substance.

<Evaluation> The photoconductor thus obtained was mounted on a digital copying machine Konica 7050 manufactured by Konica Corporation, and the following evaluation was performed.

The following evaluations were all made at 30 ° C. and 80% R
H.

First, the above copying machine was equipped with a surface voltmeter, and the unexposed portion potential and the potential after exposure (VH and V
L) was modified so that it could be measured, and the potential characteristics were evaluated.

Further, an elastic rubber blade having a rubber hardness of JIS A 65 °, a rebound resilience of 40%, a thickness of 2 mm and a free length of 9 mm is pressed against the rotation of the photosensitive member in a counter direction at a contact angle of 20 °. The contact was performed at a pressure of 18 g / cm.

Next, a real copy test of 10,000 copies was carried out under the above conditions, and the surface potential fluctuation of the photoreceptor before and after the test and the thickness loss of the photosensitive layer were measured. At this time, the printing rate was 5%.

Further, 10,000 copies were actually photographed with the image printing ratio reduced to 1%, and a forced test of filming on paper dust and toner was performed. Filming was evaluated by visually observing the surface of the photoreceptor and the halftone image after the 10,000 copy forced test.

<Evaluation Criteria> A: No filming on the photosensitive member surface. No image defect due to filming ：: Filming on photoreceptor surface, but no image defect and no problem in practical use △: Minor streak-like unevenness on image ×: Clear black streak-like defect on image Table 1 shows the results of the test.

[0093]

[Table 1]

As shown in Examples 1 to 6, in the present invention,
2. Description of the Related Art An electrophotographic photoreceptor which is free from filming such as toner components and paper powder, has high abrasion resistance, and can provide a high-quality and stable copy image for a long period of time has been obtained.

[0095]

According to the present invention, it is possible to provide an electrophotographic photosensitive member which is free from filming such as toner components and paper dust, has high abrasion resistance, and can provide a high quality and stable copy image for a long period of time. .

[Brief description of the drawings]

FIG. 1 is a sectional view of a layer structure of an electrophotographic photosensitive member applicable to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive support 2 charge generation layer (CGL) 3 charge transport layer (CTL) 4 photosensitive layer 5 intermediate layer 6 layer containing charge transport material (CTM) as main component 7 charge generation material (CGM) 8 protective layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masahiko Kurachi 2970, Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H068 AA13 AA59 BB20 BB25 FA03 FA27 FC01 FC05 FC08 FC11 FC15

Claims (4)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance, and a binder resin on a conductive support, wherein a surface layer of the photosensitive body is
At least the following general formula (A) is used as the binder resin.
An electrophotographic photoreceptor comprising a copolymerized polycarbonate having the repeating unit of 1) and wherein the charge generating substance is at least one of an imidazole perylene compound of the structural formula (G1) or (G2). Embedded image Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, 6 represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. X ¹ and X ² each independently represent a single bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, And p and q are an integer of 0 to 200 in total;
Is an integer of 1 to 6. [Chemical formula 3] 2. The binder resin comprises a copolymerized polycarbonate having at least a repeating unit represented by the following general formula (A2), and the imidazole perylene compound has an X-ray diffraction spectrum of 6 to X-ray (1.54 A). 0.3 ± 0.2 °, 12.4 ± 0.2 °, 2
A crystal having peaks at 5.3 ± 0.2 ° and 27.1 ± 0.2 °, wherein the peak intensity at 12.4 ± 0.2 ° is maximum and the half-width of the peak is 0. 2. The electrophotographic photoreceptor according to claim 1, wherein the imidazole perylene compound has a temperature of 0.65 ° or more and does not show a clear peak at 11.5 ± 0.2 °. Embedded image Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, 6 represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Y ₁ and Y ₂ each independently represent a single bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or an alkylidene group;
It is an integer of 200. ] 3. An electrophotographic photosensitive member, comprising charging, image exposure,
3. An electrophotographic photosensitive member according to claim 1 or 2, and a charging device, an image exposing device, a developing device, a transferring or separating device, and a cleaning device. A process cartridge manufactured by combining at least one of the above. 4. An image forming apparatus using the electrophotographic photoreceptor according to claim 1 to form an image through charging, image exposure, development, transfer / separation, and cleaning.