JP3058234B2 - Electrophotographic photoreceptor, electrophotographic apparatus and apparatus unit having the electrophotographic photoreceptor - Google Patents

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, and more particularly, to an electrophotographic photosensitive member having a surface layer containing a resin having a specific structure. Also, the present invention
The present invention relates to an electrophotographic apparatus and an apparatus unit having the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art In recent years, many electrophotographic photoreceptors using an organic photoconductive material have been proposed because of their excellent non-polluting properties, high productivity, ease of material design and future potential. Has been put to practical use.

[0003] Naturally, these electrophotographic photoreceptors have electrical and electrical characteristics corresponding to the applied electrophotographic process.
It is required to have mechanical and further optical characteristics. Particularly, in the case of a photoreceptor that is used repeatedly, the surface layer of the photoreceptor is directly subjected to electrical or mechanical external force such as corona charging, toner development, transfer to paper, and cleaning treatment. Is done.

More specifically, deterioration of characteristics due to ozone generated during corona charging, that is, a decrease in sensitivity, a decrease in charging ability and an increase in residual potential, and a surface rubbing caused by rubbing of the surface of a photoreceptor during transfer or cleaning. Durability against abrasion and scratches is required.

Since the surface of the photoreceptor is a layer containing a resin as a main component, the characteristics of the resin greatly affect the surface of the photoreceptor. As a resin satisfying the above conditions, a polycarbonate resin having bisphenol A as a skeleton (hereinafter referred to as bisphenol A type polycarbonate) has been used.

However, bisphenol A-type polycarbonate resins have not fully satisfied all the properties required for resins for photoreceptors, but have the following problems.

(1) Poor solubility, showing good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane. Since these halogenated aliphatic hydrocarbons have a low boiling point, when a photoreceptor is manufactured using a coating solution prepared with these solvents, the coated surface tends to be whitened. Also, it takes time and effort to control the process such as the solid content of the coating liquid.

(2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrofuran, dioxane, cyclohexanone or a mixed solvent thereof, but the solution gels within a few days. It is not suitable for mass production of photoreceptors due to poor stability over time, for example.

(3) Solvent cracks are liable to occur in polycarbonate resins having a main chain skeleton containing only bisphenol A or a bisphenol A derivative.

(4) In addition, in the conventional polycarbonate resin, since the coating formed of the resin did not have good lubricity, the photosensitive member was liable to be scratched, causing image defects or causing a cleaning blade. In some cases, cleaning failure due to early deterioration and cleaning failure due to reversal of the cleaning blade occur to shorten the life of the photoconductor. Further, since the surface free energy is relatively high, the developer easily adheres to the surface of the photoreceptor, and spot-like image defects (pockets) may occur.

Conventionally, the solution stability described in (1) and (2) has been solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of a polymer. However, as pointed out in (3), the polycarbonate Z resin and the polycarbonate A resin have a relatively large volumetric shrinkage when forming a coating from a solution by a casting method, and may leave stress inside the coating. For this reason, it has a disadvantage that it is relatively vulnerable to stress corrosion. In order to solve this problem, for example, JP-A-61-62040 discloses polycarbonate A
A method for reducing stress corrosion cracking by mixing a resin and a polycarbonate Z resin is disclosed. Japanese Patent Application Laid-Open No. 61-62039 discloses a method for reducing cracks by copolymerizing bisphenol A and bisphenol Z. However, none of these methods has achieved sufficient durability against solvent cracks.

In addition, as shown in the above (4), the ordinary polycarbonate resin has relatively low lubricity to a cleaning blade used in an electrophotographic process, and the cleaning blade is reversed due to the progress of the durability. As a result, it has been pointed out that defective cleaning occurs, and that a strong force is applied to the photoreceptor to easily cause damage. In order to solve this problem, a silicone oil is added or JP-A-61-132954.
As disclosed in Japanese Unexamined Patent Publication, a method of copolymerizing a polydimethylsiloxane block with a polycarbonate resin is known.

However, in the method of adding silicone oil, electrical characteristics in electrophotography, specifically, sensitivity and residual potential characteristics are deteriorated, and silicone oil on the surface is lost due to repeated use, resulting in permanent lubricity. However, there was a drawback that it was not possible to obtain The photoreceptor having a surface layer obtained by copolymerizing the above-mentioned polydimethylsiloxane block has relatively good lubricity,
Conventional polydimethylsiloxane copolymers have drawbacks such as cloudiness when formed into a solution and easy gelation, and have not been satisfactory in terms of durability even when used as a surface layer of an electrophotographic photoreceptor. .

Furthermore, due to recent demands for higher sensitivity of organic electrophotographic photoreceptors, low molecular weight compounds such as charge transport materials are often used in relatively large amounts. In some cases, the above-mentioned low-molecular-weight components are precipitated and separated into layers.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional electrophotographic photosensitive member,
An object of the present invention is to provide an electrophotographic photoreceptor having excellent solvent crack resistance, excellent lubricity, excellent abrasion resistance, excellent toner adhesion resistance, and excellent precipitation resistance.

Another object of the present invention is to provide an electrophotographic apparatus and an apparatus unit having the above electrophotographic photosensitive member.

[0017]

That is, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member has a structural unit represented by the following formula (1): And a copolymer having a structural unit represented by the following formula (2) and a copolymer having a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). An electrophotographic photoreceptor characterized in that:

[0018]

[Outside 6] (Wherein A represents an alkylidene group, an arylene group, an arylenedialkylidene group, -O-, -S-, -CO-, -S
O— and —SO ₂ — are represented, and R _{1-1 to} R _1-8 represent a hydrogen atom, an alkyl group, an aryl group, and a halogen atom. )

[0019]

[Outside 7] (In the formula, R _2-1 represents an alkylene group and an alkylidene group, R _{2-2 to} R _2-5 represent a hydrogen atom, an alkyl group and an aryl group, and n represents an integer of 1 to 200.)

[0020]

[Outside 8] (In the formula, R _{3-1 to} R _3-8 represent a hydrogen atom, an alkyl group, an aryl group, and a halogen atom.)

[0021]

[Outside 9] (Wherein, B represents an alkylidene group, an arylene group, and arylene alkylidene group, R _4-1 to R _4-8 represents a hydrogen atom, an alkyl group, an aryl group and a halogen atom.)

Further, the present invention is an electrophotographic apparatus and an apparatus unit having the electrophotographic photosensitive member.

In the above formulas, the alkyl group includes a methyl group, an ethyl group and a propyl group, the aryl group includes a phenyl group, a naphthyl group and a biphenyl group, and the alkylene group includes a methylene group and an ethylene group. And a propylene group.Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group and a cyclohexylidene group, and examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the group include a phenylenedimethylidene group, and examples of the halogen atom include fluorine, chlorine, and bromine. Each of these groups may have a substituent, and examples of the substituent which may be present include an alkyl group, an aryl group, and a halogen atom as described above.

The copolymer having the structural unit represented by the formula (1) and the structural unit represented by the formula (2) (hereinafter also referred to as copolymer A) used in the present invention is represented by the formula (2). The constituent unit to be used is preferably 0.1 to 50% by weight of the entire copolymer A, and particularly preferably 0.1 to 30% by weight. A in the formula (1) is preferably a propylidene group or a cyclohexylidene group, and the formula (2)
In the formula, R _2-1 is preferably ethylene, propylene and isopropylene, and n is preferably 5 to 100.

The copolymer A can be obtained by interfacially polymerizing a bisphenol represented by the following formula (5) and a bisphenol represented by the following formula (6) in the presence of phosgene, carbon ester or chloroformate. .

[0026]

[Outside 10] (In the formula, A and R _{1-1 to} R _1-8 are the same as above.)

[0027]

[Outside 11] (In the formula, R _{2-1 to} R _2-5 and n are the same as described above.)

Preferred specific examples of the bisphenol represented by the formula (5) are shown below, but the bisphenol used in the present invention is not limited to these.

[0029]

[Outside 12]

[0030]

[Outside 13]

[0031]

[Outside 14]

[0032]

[Outside 15]

[0033]

[Outside 16]

[0034]

[Outside 17]

Among these, (1-4) and (1-
5), (1-11), (1-15), (1-16) and (1-19) are particularly preferred.

Preferred examples of the bisphenol represented by the formula (6) are shown below, but the bisphenol used in the present invention is not limited to these.

[0037]

[Outside 18]

[0038]

[Outside 19]

Synthesis Example (Synthesis of Copolymer A) 3.8 kg of sodium hydroxide was dissolved in 451 of water.
C., while maintaining the temperature at 2,2-bis (4-hydroxyphenyl) cyclohexane (viscosity average molecular weight 2.20 × 10
⁴ ) 7.2 kg and a polydimethylcyclohexane derivative represented by the following formula (X-22-165B, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0040]

[Outside 20] 1.5 kg and 8 g of hydrosulfite were dissolved. To this, add methylene chloride 321 and stir p
158 g of -t-butylphenol were added, and then 3.5 kg of phosgene was blown in over 60 minutes.

After the injection of phosgene was completed, the reaction mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 8 g of triethylamine was added, and stirring was continued for about 1 hour to carry out polymerization.

After the polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing was repeated until the pH of the washing became neutral. Thereafter, 351 was added with isopropanol to precipitate a polymer. The precipitate is filtered and then dried to obtain the following formula (where the copolymerization ratio is represented by the polymerization ratio)
A white powdery copolymer (viscosity average molecular weight: 2.8 × 10 ⁴ ) having the structure represented by the following formula was obtained. Composition analysis was obtained by measuring the infrared absorption spectrum. In addition, the copolymerization ratio was shown by weight ratio.

[0043]

[Outside 21]

In the copolymer having the structural unit represented by the formula (3) and the structural unit represented by the formula (4) (hereinafter, also referred to as copolymer B) used in the present invention, the compound represented by the formula (3)
Is preferably 5:95 to 95: 5, more preferably 30:70 to 70:30, and preferably 4:95 to 95: 5.
The ratio is preferably from 0:60 to 60:40.

The copolymer B can be synthesized in the same manner as the copolymer A, using a bisphenol represented by the following formula (7) and a bisphenol represented by the following formula (8).

[0046]

[Outside 22] (In the formula, R _{3-1 to} R _3-8 are the same as above.)

[0047]

[Outside 23] (In the formula, B and R _{4-1 to} R _4-8 are the same as above.)

Preferred specific examples of the bisphenol represented by the formula (7) are the same as those of the above formulas (1-31) to (1-35), in which (1-31) and (1-34) are particularly preferable. preferable.

Preferred specific examples of the bisphenol represented by the formula (8) are the above formulas (1-1) to (1-24)
And (1-4), (1-5) and (1-15) are particularly preferred.

In the present invention, the mixing ratio of the copolymer A and the copolymer B is preferably from 1:99 to 70:30, more preferably from 5:95 to 50:50 in terms of polymerization ratio. preferable.

Further, in the present invention, from the viewpoint of improving solvent crack resistance and toner adhesion resistance, the surface layer further comprises a polycarbonate resin having a structural unit represented by the following formula (9) (hereinafter referred to as polymer C). ) Is preferable.

[0052]

[Outside 24] (In the formula, D represents an alkylidene group, an arylene group, or an arylenedialkylidene group, and R _{9-1 to} R _9-8 represent a hydrogen atom, an alkyl group, an aryl group, and a halogen atom.)

In this case, the mixing ratio of copolymer A, copolymer B and polymer C is such that A is 5 to 20 with respect to the total weight of the resin.
%, B is preferably 5 to 40%, and it is preferable that the mixing ratio of A and the mixing ratio of B do not exceed the mixing ratio of C.

The resin represented by the formula (9) can be synthesized in the same manner as the copolymer A using the corresponding bisphenol. Preferred specific examples of the bisphenol are the same as those of the above formulas (1-1) to (1-24), in which (1-4), (1-5), (1-8), (1-8) 1
5), (1-16) and (1-21) are particularly preferred,
Further, (1-4) and (1-15) are preferable.

The molecular weight of each copolymer and polymer used in the present invention may be in any range as long as the viscosity is such that a suitable film thickness can be obtained when forming a coating film. From the viewpoint of the mechanical properties of the film, the viscosity average molecular weight is preferably from 10,000 to 100,000, particularly preferably from 20,000 to 60,000.

According to the present invention, a film having excellent lubricity can be obtained. Further, the copolymer has high solubility in very common solvents such as tetrahydrofuran, dioxane, cyclohexanone, benzene, toluene, xylene, monochlorobenzene, dichloromethane, dichlorobenzene or a mixture thereof, and It also has good characteristics in electrophotographic characteristics, production stability, quality stability, etc., such that problems such as reduction in pot life due to gelation hardly occur.

In the present invention, the copolymer used in the present invention comprises two components represented by the formula (1) or (3).
And may have at least one species, and similarly, formula (2) or (4)
May have two or more types of constituent components represented by

The present invention is intended to improve various properties as described above, that is, solvent cracking property, toner adhesion, surface lubricity and the like. Naturally, the polymers A and B and the polymer C The characteristics which are much better than the system using only each of the above are obtained.

The component represented by the formula (2) contained in the copolymer A of the present invention is introduced for imparting suitable flexibility to the polycarbonate resin and lowering the surface free energy. Is introduced for the purpose of improving the properties and toner adhesion resistance.

The copolymer B is introduced to further lower the polymer crystallinity of the surface layer.

Since the mixture of the polycarbonate resin used in the present invention has the above-mentioned structure, the crystallinity is lower than that of the conventional polycarbonate, and the internal stress during film formation is extremely small. It is considered that the toner hardly generates cracks and the surface free energy is reduced to improve the toner adhesion and lubricity.

The copolymer of the present invention is contained in the surface layer of an electrophotographic photosensitive member. The surface layer may be a photosensitive layer or a surface protective layer provided on the photosensitive layer. Is also good.

The photosensitive layer, even if it is a so-called single layer type containing a charge generating substance and a charge transporting substance in the same layer, is functionally separated into a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. Also, a so-called laminated type may be used.

The charge generation layer can be obtained by applying a liquid in which a charge generation substance is dispersed in a binder resin, and the charge generation substance is exemplified by azo pigments such as Sudan Red and Diane Blue; pyrenequinone, anthantrone and the like. Quinone pigments; quinocyanine pigments; perylene pigments;
And indigo pigments such as indigo and thioindigo; azulenium salt pigments; and phthalocyanine pigments such as copper phthalocyanine. As the binder resin, when the charge generation layer is a surface layer, at least the copolymer of the present invention is used, but when the charge generation layer is not a surface layer, another resin may be used without using the copolymer of the present invention. it can. Such other resins include polyester resin, acrylic resin, polyethylene resin, polypropylene resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polyvinyl butyral resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin, and vinylidene chloride-acrylonitrile. And copolymer resins.

The ratio of the charge generating substance to the binder resin is preferably from 1: 5 to 5: 1 by weight, more preferably from 1: 2 to 3: 1. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.05 to 2 μm.

The charge transporting substance which can be used in the present invention includes an electron transporting substance and a hole transporting substance. Examples of the electron transporting substance include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 4,5,
7-tetranitro-9-fluorenone, 2,4,5,7
And electron-withdrawing substances such as tetranitroxanthone and 2,4,8-trinitrothioxanth, and those obtained by polymerizing these electron-withdrawing substances.

As the hole transporting substance, pyrene, N-ethylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-
Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone and p-
Hydrazones such as diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone; 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- (p- Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (3)] -3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3-
(P-Diethylaminostyryl) -4-methyl-5-
Pyrazolines such as (p-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazolin and spiropyrazolin; a-phenyl-4-N, N Styryl such as -diphenylaminostilbene, N-ethyl-3 (d-phenylstyryl) carbazole, 9-dibenzylaminobenzylidene-9H-fluorenone and 5-p-ditolylaminobenzylidene-5H-dibenzo [a, d] cycloheptene Compound; 2
-(P-diethylaminostyryl) -6-diethylaminobenzoxazole and 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5-
Oxazo- such as (2-chlorophenyl) oxazole
2- (p-diethylaminostyryl) -6
Thiazole compounds such as -diethylaminobenzothiazole; triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) -phenylmethane; 1,1-bis (4-N, N-diethylamino-2-
Methylphenyl) heptane, 1,1,2,2-tetrakis (4-N, N-dimethylamino-2-methylphenyl)
Polyarylalkanes such as ethane; triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine,
Poly-9-vinylanthracene, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin and the like can be mentioned. In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon, and cadmium sulfide can be used.

Among these, particularly preferred are the following 10 types.

[0069]

[Outside 25]

[0070]

[Outside 26]

In general, since the charge transporting substance has poor film-forming properties, it is used after being dissolved in a suitable binder resin. As such a resin, when the charge transport layer is the surface layer of the photoreceptor, the copolymer of the present invention is used, but when the charge transport layer is not the surface layer, another resin may be used without using the copolymer of the present invention. it can. Such other resins are the same as those described above.

The charge transport layer is formed by dissolving the charge transport material and the binder resin in an appropriate solvent, applying the solution, and drying. The mixing ratio of the charge transport material and the binder resin is preferably from 3: 1 to 1: 3, more preferably from 2: 1 to 1: 2 by weight.

The charge transport layer has a thickness of 5 to 40 μm,
In particular, the thickness is preferably 10 to 30 μm.

When the photoreceptor is of a single layer type, it can be obtained by applying a solution in which the above-described charge generating substance and charge transporting substance are dispersed and dissolved in a binder resin, and then drying.

When the photosensitive layer is a surface layer, at least the copolymer of the present invention is used as the binder resin. When the photosensitive layer is not the surface layer, another resin is used without using the copolymer of the present invention. Can be used. Such other resins are the same as those described above.

The single-layer type photosensitive layer preferably has a thickness of 5 to 40 μm, more preferably 10 to 30 μm.

Further, in the present invention, a surface protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer from external adverse mechanical, chemical or electrical adverse effects. This protective layer contains at least the copolymer of the present invention.

The surface protective layer may be formed of only a resin, or may be formed by adding a charge transporting material as described above or a conductive material such as a conductive powder for the purpose of lowering the residual potential. Good. Aluminum, copper,
Metal powders such as nickel and silver, flaky metal powders and short metal fibers, conductive metal oxides such as antimony oxide, indium oxide and tin oxide, polymer conductive agents such as polypyrrole, polyaniline and polymer electrolytes, Examples thereof include carbon black, carbon fiber, graphite powder, organic and inorganic electrolytes, and conductive powders whose surfaces are coated with these conductive substances.

The thickness of the protective layer is determined in consideration of electrophotographic characteristics and durability, but is preferably 0.2 μm to 15 μm, particularly preferably 0.5 μm to 15 μm.

In the present invention, an undercoat layer having both a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer.

Examples of materials for the undercoat layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenolic resin polyamides (nylon 6, nylon 66, nylon 610, copolymer nylon, Alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is 0.1 to 10 μm.
m, more preferably 0.1 to 5 μm.

In the present invention, a coating for compensating for surface defects of the support is provided between the support and the undercoat layer, and interference fringes which are problematic particularly when the image input is a laser beam. A conductive layer can be provided for the purpose of preventing the occurrence of, for example. This conductive layer can be formed by applying a solution in which a conductive powder such as carbon black, metal particles or metal oxide particles is dispersed in an appropriate binder resin, and drying the solution. The thickness of the conductive layer is 5
４０40 μm, especially 10-30 μm
m is preferable.

The various layers described above can be applied by a coating method such as a dipping method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method and a beam coating method.

As the conductive support used in the present invention, a support having conductivity itself, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, Although gold and platinum can be used, aluminum, an aluminum alloy, indium oxide, tin oxide and an indium oxide-tin oxide alloy having a conductive layer obtained by vacuum evaporation, paper,
Alternatively, a support in which conductive particles are impregnated in plastic or paper, a plastic having a conductive polymer, and the like can be given.

The shape of the support may be a drum shape, a sheet shape, or a belt shape, and is preferably a shape optimal for the applied electrophotographic apparatus.

The image holding member of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

Referring to FIG. 1, reference numeral 1 denotes an electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 1a in a direction indicated by an arrow at a predetermined peripheral speed. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on the peripheral surface thereof by a charging means 2 during the rotation process, and then applies an image exposure L (slit) to an exposure unit 3 by an image exposure means (not shown). Exposure and laser beam scanning exposure). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor.

The formed electrostatic latent image is then transferred to developing means 4
The toner developed image is transferred from a paper supply unit (not shown) to the transfer material P fed between the photoconductor 1 and the transfer unit 5 in synchronization with the rotation of the photoconductor 1 by a transfer unit. 5 are sequentially transferred.

The transfer material P having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy (copy) outside the machine.

The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning means 6, and is further subjected to a static elimination treatment by the pre-exposure means 7 to be repeatedly used for image formation. Is done.

As the uniform charging means 2 for the photosensitive member 1, a corona charging device is generally widely used. The transfer device 5 also generally uses a corona transfer unit. In the present invention, a plurality of components such as the photoreceptor 1, the developing unit 4 and the cleaning unit 6 are integrally connected as an apparatus unit, and this unit is detachably attached to the apparatus body. May be configured. For example,
A unit is formed by integrally supporting at least one of the charging means 2, the developing means 4 and the cleaning means 6 together with the photoreceptor, and as a single unit detachable from the apparatus main body using guide means such as rails of the apparatus main body. Is also good.

In the case where the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L involves irradiating the photosensitive member with reflected light or transmitted light from the original, or reading the original with a sensor and converting it into a signal. In accordance with this signal, scanning of a laser beam, driving of an LED array, driving of a liquid crystal shutter array, and the like are performed to irradiate the photosensitive member with light.

When used as a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 11 controls the image reading unit 10 and the printer 19. The whole controller 11 is CP
It is controlled by U17. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 13. Data received from the partner station is sent to the printer 19 through the receiving circuit 12. Predetermined image data is stored in the image memory. The printer controller 18 is the printer 1
9 is controlled. 14 is a telephone.

The image received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, and then the CPU 17 performs a decoding process of the image information and sequentially executes the image memory 16 Is stored in Then, when the image of at least one page is stored in the memory 16,
The image of the page is recorded. The CPU 17 is a memory 1
6 to read out the one-page image information and send out the decoded one-page image information to the printer controller 18. The printer controller 18 receives 1
When the image information of the page is received, the printer 19 is controlled to record the image information of the page.

The CPU 17 receives the next page during recording by the printer 19.

As described above, image reception and recording are performed.

Hereinafter, the present invention will be described in more detail with reference to examples. The copolymerization ratio of copolymer A is shown by weight ratio, and the copolymerization ratio of copolymer B is shown by molar ratio.

[0100]

【Example】

Example 1 10 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (parts by weight, the same applies hereinafter), 10 parts of conductive titanium oxide, 10 parts of methanol, 10 parts of methyl cellosolve, and silicone oil 0.001 part to φ1
By dispersing for 2 hours in a sand mill using mm glass beads, a conductive solution was obtained. This solution is φ3
A conductive layer having a thickness of 18 μm was formed by applying the solution on a 0 × 260 mm aluminum cylinder by dipping and heat curing at 140 ° C. for 30 minutes.

Next, 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon were combined with 65 parts of methanol and n-
A solution prepared by dissolving 30 parts of butanol in a mixed solvent was applied onto the previously formed conductive layer by dipping, and dried to form a 0.5 μm-thick undercoat layer.

Next, 3 parts of oxytitanium phthalocyanine pigment, polyvinyl butyral (butyralization degree of 66
%, Weight average molecular weight 110000) and 80 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 24 hours.
By adding 5 parts, a solution for a charge generation layer was obtained. This solution was applied on the previously formed undercoat layer by dipping and dried to form a charge generation layer having a thickness of 0.2 μm.

Next, a charge transport material 10 represented by the following formula:
Department,

[0104]

[Outside 27] 2 parts of a copolymer represented by the following formula (viscosity average molecular weight: 2.0 × 10 ⁴ ) as copolymer A

[0105]

[Outside 28] 2 parts of a copolymer (viscosity average molecular weight 2.3 × 10 ⁴ ) represented by the following formula as copolymer B

[0106]

[Outside 29] And 6 parts of a polymer (viscosity average molecular weight 2.5 × 10 ⁴ ) represented by the following formula as polymer C:

[0107]

[Outside 30] Was dissolved in a mixed solvent of 50 parts of monochlorobenzene and 10 parts of dichloromethane to obtain a solution for a charge transport layer. This solution was applied on the previously formed charge generation layer by dipping and dried to form a film having a thickness of 20 μm.
m of the charge transport layer was formed.

The obtained electrophotographic photosensitive member was evaluated for surface lubricity, precipitation resistance, solvent crack resistance, toner adhesion resistance, surface layer scraping property and sensitivity.

The surface lubricating property was determined by contacting a urethane rubber cleaning blade for a copying machine to the surface of the photoreceptor at a contact angle of 30 °, and measuring the slip resistance of the surface with a HEIDON-14 type surface tester (Shinto Chemical Co., Ltd.). )). The measured value is in the unit of mV / 10 g, and a smaller value indicates better lubricity.

The deposition resistance was measured by pressing a urethane cleaning blade against the surface of the photoreceptor, storing at 60 ° C., conducting an acceleration test for the deposition property, observing the presence or absence of the deposition with a 50 × microscope, and confirming the deposition of the low molecular weight compound. Evaluation was made based on the number of days until the completion (up to 30 days).

The solvent cracking resistance is determined by adhering finger grease and lubricating oil (PS-158, manufactured by Sanwa Oil Chemical Co., Ltd.) to the surface of the photoreceptor, and after 48 hours, using a microscope with a magnification of 50.times. Observation was performed, and an image obtained when the photoconductor was used was visually observed. The evaluation was performed in the following five stages.

A: No cracks were observed on the photoreceptor, and no image defects due to cracks were found in the image.

：: Cracks were observed on the photoreceptor,
No image defect confirmed.

Δ: Cracks are observed on the photoreceptor, and one image defect is observed.

X: Cracks were observed on the photoreceptor, and 2 to 10 image defects were observed.

XX: Cracks are observed on the photoreceptor, and 11 or more image defects are observed.

The toner adhesion resistance was measured using a laser beam printer (manufactured by Hewlett-Packard, Laserjet I).
II-Si) with photoreceptor, 35 ° C, 70% RH
A continuous image of 5,000 sheets was output below, and the evaluation was made based on the number of sheets when 10 or more image defects due to the uncleanable deposits were confirmed.

The shaving property of the surface layer was evaluated based on the shaving amount of the surface layer before and after the above-mentioned image output durability test. The evaluation was performed using a film thickness measuring apparatus (EC-8E2TY, manufactured by FISCHER).

The sensitivity was evaluated by installing the photoreceptor in the above-described laser beam printer and measuring the amount of light required to change the surface potential of the photoreceptor from -700 V to -200 V.

Table 1 shows the results.

Examples 2 to 5 Copolymer A, copolymer B and polymer C were each 4 parts,
3 parts and 3 parts (Example 2); 5 parts, 5 parts and 0 parts (Example 3); 4.5 parts, 4.5 parts and 1 part (Example 4); 1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the parts were 4.5 parts and 4.5 parts (Example 5).

Table 1 shows the results.

Comparative Examples 1 to 5 Copolymer A, copolymer B and polymer C
Parts, 0 parts and 0 parts (Comparative Example 1); 0 parts, 10 parts and 0 parts (Comparative Example 2); 0 parts, 0 parts, and 10 parts (Comparative Example 3);
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 0 part, 5 parts and 5 parts (Comparative Example 4); 5 parts, 0 parts and 5 parts (Comparative Example 5) were evaluated.

Table 1 shows the results.

Examples 6 to 10 and Comparative Examples 6 to 10 As a charge transport material, 7 parts of a compound represented by the following formula was used.

[0126]

[Outside 31] And 3 parts of the compound represented by the following formula, 10 parts in total

[0127]

[Outside 32] An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5 except that it was used.

Table 1 shows the results.

[0129]

[Table 1]

Example 11 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% of antimony oxide, 25 parts of phenol resin,
20 parts of methyl cellosolve, 5 parts of ethanol, and 0.002 part of silicone oil were dispersed in a sand mill using φ1 mm glass beads for 2 hours to obtain a conductive layer solution. This solution was applied on an aluminum cylinder by a dipping method, and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, a solution for an intermediate layer was obtained by dissolving 5 parts of N-methoxymethylated nylon in 95 parts of methanol. This solution was applied on the previously formed conductive layer by dipping and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

Next, the following formula

[0133]

[Outside 33] 3 parts of disazo pigment represented by the following formula, polyvinyl benzal (degree of benzalization 80%, weight average molecular weight 11000)
After 2 parts and 35 parts of cyclohexanone were dispersed for 12 hours by a sand mill using φ1 mm glass beads, 60 parts of methyl ethyl ketone was added to obtain a solution for a charge generation layer. This solution was applied onto the previously formed intermediate layer by a dipping method, and dried at 80 ° C. for 20 minutes to form a charge generation layer having a thickness of 0.2 μm.

Next, a charge transport material 1 represented by the following formula:
0 copies,

[0135]

[Outside 34] The following formula is used as the copolymer B.

[0136]

[Outside 35] (Viscosity average molecular weight 2.15 × 10
⁴ ) 5 parts and the following formula as copolymer A:

[0137]

[Outside 36] To obtain a solution for the charge transport layer by dissolving the polymer (viscosity-average molecular weight 2.2 × 10 ⁴⁾ 5 parts of a mixed solvent of 20 parts of monochlorobenzene and 40 parts of dichloromethane. This solution was applied on the previously formed charge generation layer by dipping, and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 23 μm.

The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1 for the surface lubricity, precipitation resistance, solvent crack resistance, toner adhesion resistance and surface layer scraping property.

Table 2 shows the results.

Example 12 As a copolymer B, a copolymer represented by the following formula:

[0141]

[Outside 37] (Viscosity average molecular weight 2.5 × 10 ⁴ ) 5 parts and copolymer A
A copolymer represented by the following formula:

[0142]

[Outside 38] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11 except that 5 parts (viscosity average molecular weight 2.0 × 10 ⁴ ) were used.

Table 2 shows the results.

Example 13 As a copolymer B, a copolymer represented by the following formula:

[0145]

[Outside 39] (Viscosity average molecular weight 8.3 × 10 ⁴ ) 8 parts and copolymer A
A copolymer represented by the following formula:

[0146]

[Outside 40] An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 11 except that 2 parts (viscosity average molecular weight 2.3 × 10 ⁴ ) were used.

Table 2 shows the results.

Example 14 Copolymer represented by the following formula as copolymer B

[0149]

[Outside 41] (Viscosity average molecular weight 3.0 × 10 ⁴ ) 2 parts and copolymer A
A copolymer represented by the following formula:

[0150]

[Outside 42] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11 except that 8 parts (viscosity average molecular weight 2.3 × 10 ⁴ ) were used.

Table 2 shows the results.

Example 15 Copolymer represented by the following formula as copolymer B

[0153]

[Outside 43] (Viscosity average molecular weight 3.8 × 10 ⁴ ) 5 parts and copolymer A
A copolymer represented by the following formula:

[0154]

[Outside 44] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11, except that 5 parts (viscosity average molecular weight 3.1 × 10 ⁴ ) were used.

Table 2 shows the results.

Example 16 Copolymer represented by the following formula as copolymer A

[0157]

[Outside 45] (Viscosity average molecular weight 2.5 × 10 ⁴ ) 5 parts, copolymer represented by the following formula as copolymer B

[0158]

[Outside 46] (Viscosity average molecular weight 3.0 × 10 ⁴ ) 5 parts and a compound represented by the following formula as a charge transporting substance:

[0159]

[Outside 47] An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 11 except for using.

The results are shown in Table 2.

Comparative Example 11 An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 11 except that a polycarbonate Z resin (viscosity average molecular weight: 1.9 × 10 ⁴ ) was used instead of the copolymers A and B. evaluated.

Table 2 shows the results.

Comparative Example 12 Instead of copolymers A and B, a copolymer represented by the following formula:

[0164]

[Outside 48] An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 11 except that (viscosity average molecular weight 2.5 × 10 ⁴ ) was used.

Table 2 shows the results.

Example 17 A charge transport layer was formed in the same manner as in Comparative Example 1. next,
Copolymer represented by the following formula as copolymer B

[0167]

[Outside 49] (Viscosity average molecular weight 2.4 × 10 ⁴ ) 2 parts, a copolymer represented by the following formula as copolymer A (viscosity average molecular weight 2.0
× 10 ⁴ ) 4.5 parts

[0168]

[Outside 50] And 1 part of a compound represented by the following formula as a charge transport material:

[0169]

[Outside 51] Was dissolved in 190 parts of monochlorobenzene to obtain a solution for a protective layer. This solution was applied onto the previously formed charge transport layer by a spray coating method, and dried to form a surface protective layer having a thickness of 3 μm.

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11.

Table 2 shows the results.

[0172]

[Table 2]

[0173]

As described above, according to the present invention, an electrophotograph having excellent solvent crack resistance, excellent lubricity, excellent abrasion resistance, excellent toner adhesion resistance, and excellent precipitation resistance. A photoconductor, an electrophotographic apparatus having the electrophotographic photoconductor, and an apparatus unit can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram illustrating an example of a block diagram of a facsimile having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of the present invention 1a shaft 2 Charging means 3 Exposure unit 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means L Optical image exposure P Transfer material 10 Image reading unit 11 Controller 12 Receiving circuit 13 Transmission circuit 14 Telephone 15 Line 16 Image memory 17 CPU 18 Printer controller 19 Printer

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Aoki Kasumi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kiyoshi Sakai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Naoto Fujimura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-6-220181 (JP, A) JP-A-6-136108 (JP) JP-A-5-158249 (JP, A) JP-A-5-127411 (JP, A) JP-A-5-72753 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB G03G 5/05 101 G03G 5/147 502

Claims (6)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member has a structural unit represented by the following formula (1) and a constitution represented by the following formula (2): Containing a copolymer having a unit and having the following formula (3)
An electrophotographic photoreceptor comprising a copolymer having a structural unit represented by the following formula and a structural unit represented by the following formula (4). [Outside 1] (Wherein A represents an alkylidene group, an arylene group, an arylenedialkylidene group, -O-, -S-, -CO-, -S
O- and -SO ₂ - shows the shows R _{1 -1} to R _1-8 is a hydrogen atom, an alkyl group, an aryl group, and a halogen atom. [Outside 2] (In the formula, R _2-1 represents an alkylene group and an alkylidene group, R _{2-2 to} R _2-5 represent a hydrogen atom, an alkyl group and an aryl group, and n represents an integer of 1 to 200.) Outside 3] (In the formula, R _{3-1 to} R _3-8 represent a hydrogen atom, an alkyl group, an aryl group, and a halogen atom.) (Wherein, B represents an alkylidene group, an arylene group, and arylene alkylidene group, R _4-1 to R _4-8 represents a hydrogen atom, an alkyl group, an aryl group and a halogen atom.) 2. The method according to claim 1, wherein the surface layer further has the following formula (9). (In the formula, D represents an alkylidene group, an arylene group or an arylenedialkylidene group, and R _{9-1 to} R _9-8 represent a hydrogen atom, an alkyl group, an aryl group, and a halogen atom.) The electrophotographic photoreceptor according to claim 1, further comprising: 3. The electrophotographic photoconductor according to claim 1, wherein the photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer is a surface layer. 4. The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoconductor has a protective layer on a photosensitive layer, and the protective layer is a surface layer. 5. An electrophotographic photoreceptor according to claim 1, comprising means for forming an electrostatic latent image, means for developing the formed electrostatic latent image, and means for transferring the developed image to a transfer material. An electrophotographic apparatus characterized by the above-mentioned. 6. An electrophotographic photosensitive member according to claim 1, and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit, integrally supporting
An apparatus unit, which is detachable from the apparatus body.