JPH08328287A - Electrophotographic photoreceptor, process cartridge with the same and electrophotographic device - Google Patents

Abstract

PURPOSE: To effectively reduce the coefft.. of friction of a surface layer and to obtain an electrophotographic photoreceptor excellent in cleanability and wear and scuffing resistances and always giving a high grade image in a repetitive electrophotographic process. CONSTITUTION: This electrophotographic photoreceptor has a photoreceptive layer on the electrically conductive substrate and contains fluororesin particles in the surface layer. The half-width of a peak (2θ≈18) of the X-ray diffraction pattern of the fluororesin particles is >=0.28.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor and an electrophotographic apparatus.

[0002]

2. Description of the Related Art An electrophotographic photosensitive member is required to have sensitivity, electrical characteristics and optical characteristics according to an electrophotographic process to be applied. Charge the surface layer, toner development, transfer to paper,
Since electrical and mechanical external forces are directly applied by a process such as cleaning, durability against them is required.

Specifically, it is required to have durability against abrasion of the surface due to friction, generation of scratches, deterioration of the surface at high temperature and the like. Further, there is a problem that the toner adheres to the surface layer due to repeated development and cleaning by the toner, and it is required to improve the cleaning property of the surface layer.

Various methods have been studied in order to satisfy the properties required for the surface layer as described above, and among them, the means for providing the surface layer with the resin layer in which the fluorine-based resin particles are dispersed is effective. is there. By dispersing the fluorine-based resin particles, the friction coefficient of the surface layer is reduced, and the cleaning property and the durability against abrasion and scratch are improved. These effects are further improved by increasing the amount of fluororesin particles. However, in the case of dispersing the fluorine-based resin particles in such a case, there is a problem in dispersibility and cohesiveness, and it becomes difficult to form a uniform and smooth film, and the obtained surface layer has image unevenness or pinhole nadono image. It was unavoidable to have defects.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to effectively reduce the coefficient of friction of a surface layer, to provide cleaning properties, durability against abrasion and scratches, and in repeated electrophotographic processes. An object is to provide an electrophotographic photosensitive member that can always obtain a high-quality image.

[0006]

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 contains fluorine-containing resin particles. The peak of the line diffraction pattern (near 2θ = 18) has a half value width of 0.28 or more.

The X-ray diffraction pattern of the fluorine-based resin particles is shown in FIG.

Generally, the full width at half maximum depends on the crystallinity of the material, and the higher the crystallinity, the smaller the half width. That is, in the present invention, the crystallinity is low, and by containing the fluorine resin particles having a high elongation rate, the friction coefficient is more effectively reduced, the cleaning property is improved, and the durability against abrasion and scratches is improved. To improve.

As the crystallinity of the fluorine-based resin particles, it is preferable that the half-width of the X-ray diffraction pattern around 2θ = 18 is 0.28 or more. Since the fluorine-based resin particles having a half width of 0.28 or less have high crystallinity, the elongation rate of the fluorine-based resin particles is poor and the surface layer cannot be sufficiently covered. As a result, since the friction coefficient cannot be effectively reduced, the cleaning property and the durability against abrasion and scratch cannot be sufficiently improved.

As a method for reducing the crystallinity of the fluorine-based resin particles, there may be mentioned a method such as a heat treatment in the manufacturing process thereof, and a method of increasing the cooling rate during molding.

Examples of the heat treatment include a warm air dryer, a vacuum dryer, an electric furnace, an infrared heating furnace, a far infrared heating furnace and the like.

The heat treatment temperature needs to be a temperature not lower than the Tg (glass transition temperature) of the fluororesin particles and at which the fluororesin particles are not thermally decomposed. Specifically, 140
-280 degreeC is preferable and 160-260 degreeC is especially preferable. When the heat treatment temperature is 140 ° C. or lower, the crystallinity cannot be lowered even by the heat treatment for a long time, and the cleaning property and the durability against abrasion or scratch cannot be sufficiently improved. Further, when the temperature is 280 ° C. or higher, the fluorine-based resin particles cause thermal decomposition.

The cooling rate during molding is required to be such that the crystallinity of the fluorine-based resin particles does not increase. Specifically, 50 ° C./h or more is preferable, and 100 ° C./h or more is particularly preferable. When the cooling rate is 50 ° C./h or less, the crystallinity of the fluorine-based resin particles becomes high, so that the cleaning property and the durability against abrasion and scratch cannot be sufficiently improved.

As an example of the radiation treatment, a method using electron beam, γ-ray or the like can be mentioned. The radiation treatment condition is preferably 10 Mrad or more, and particularly preferably 15 Mrad or more. When the treatment condition is 10 Mrad or less, the crystallinity of the fluorine-based resin particles is not lowered, and the cleaning property and the durability against abrasion or scratch cannot be sufficiently improved. .

As the fluorinated resin particles, 4-fluorinated ethylene resin is suitable for improving abrasion resistance. You may use these resin 1 type or in mixture of 2 or more types.
The molecular weight of the resin and the particle size of the particles can be appropriately selected and are not particularly limited. Moreover, you may mix with antiwear agents and lubricants other than the above. Moreover, you may use a dispersion aid, a surfactant, etc. as needed. Fluorine-based graft polymer is a good example of the dispersion aid.

The fluorine-type comb-type graft polymer has a molecular weight of 100 having a polymerizable functional group at one end of each molecular chain.
It is obtained by copolymerizing a macromonomer consisting of an oligomer having a relatively low molecular weight of about 0 to 10000 and a fluoropolymerizable monomer, and the fluoropolymer is a backbone and the macromonomer polymer is a plate-shaped product. It has a dangling structure.

The macromonomer is selected such that the resin to which the graft polymer is added has an affinity, and for example, polymers or copolymers of acrylic acid esters, methacrylic acid esters or styrene compounds are used.

On the other hand, as the fluorine-based polymerizable monomer,
One or more polymerizable monomers having a fluorine atom in the side chain as described in the following general formulas (1) to (6) are used, but the present invention is not limited thereto. General formula (1)

Embedded image General formula (2)

Embedded image General formula (3)

Embedded image General formula (4)

[Chemical 4] General formula (5)

Embedded image General formula (6)

[Chemical 6] In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitrile group, and a combination of several kinds thereof may be used. n is an integer of 1 or more, m is an integer of 1 to 5, k is 1
It is an integer of 4 and m + k = 5.

The content of the fluorine-type monomer residue in the fluorine-type comb-type graft polymer is preferably 5 to 90% by weight, and 10-70% by weight in the fluorine-type comb-type graft polymer.
Weight percent is even more preferred. Fluorine monomer content is 5
If it is less than wt%, the effect of modifying hydrophobicity cannot be sufficiently exerted, and if the content of the fluorine-based monomer residue exceeds 90 wt%, the solubility with the macromonomer becomes poor.

Examples of the binder resin include thermoplastic resins such as polycarbonate resin, acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, polyvinyl butyral resin, polyurethane resin, and phenol resin. Examples of the resin include thermosetting resins such as resins and epoxy resins, and photocurable resins.

The ratio of the fluororesin particles in the surface layer is appropriately selected depending on the kind of the fluororesin particles and the constitution of the photosensitive layer. When the addition amount is large, there are disadvantages such as a decrease in light transmittance and a decrease in sensitivity, and scattering of image exposure light to cause blurring of an image. On the other hand, if the amount of addition is small, it is easily worn and the effect of the present invention is not sufficiently exhibited. Generally 0.1 to 50% by weight, particularly preferably 0.2, relative to the surface layer.
-40% by weight.

Next, the production of the electrophotographic photosensitive member will be described. As an example of a method for preparing a coating liquid for preparing the electrophotographic photosensitive member of the present invention, a binder resin, a method of simultaneously dispersing a fluorine-based resin particle with a solvent such as a charge transport substance, and a fluorine-based resin particle Examples include a method of previously dispersing to prepare a dispersion liquid and mixing the dispersion liquid with a coating liquid. In the preparation of the coating liquid for an electrophotographic photosensitive member or the fluororesin particle dispersion liquid of the present invention, simple stirring and mixing may be used, but if necessary, a dispersing means such as a ball mill, a roll mill or a sand mill is used.

As the solvent, the binder in the coating liquid is used.
A resin having good solubility with respect to the resin and the charge transport material, dispersibility with the pigment, and coating property is selected.

Examples of the material of the conductive support include metals such as aluminum, copper, nickel and silver or alloys thereof, conductive metal oxides such as indium oxide, antimony oxide and tin oxide, carbon fiber. -, Carbon black, a mixture of graphite powder and resin, and the like.

Further, a conductive layer can be provided for covering defects on the support and protecting the support. For example, metal powder of aluminum, copper, nickel or the like, antimony oxide,
Conductive metal oxides such as indium oxide and tin oxide, polymer conductive materials such as polypyrrole, polyaniline, and polymer electrolytes, carbon fiber over, carbon black, graphite powder, or a conductive substance such as these for the surface A conductive substance such as coated conductive powder is a thermoplastic resin such as acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, poly, polyvinyl butyral resin, polyurethane resin, phenol resin, epoxy resin. , Etc. dispersed in a binder resin such as a thermosetting resin such as
Furthermore, the thing which added the additive as needed and which apply | coated on the support is mentioned.

Further, an intermediate layer may be provided in order to improve the adhesiveness of the photosensitive layer and the charge injection property from the conductive support. Examples of the material for the intermediate layer include gelatin, ethylene / acrylic acid copolymer, nitrocellulose resin,
Examples of the resin include polyamide resin and polyvinyl alcohol resin, which are dissolved in a suitable solvent and applied onto the conductive support. Further, additives can be added if necessary.

The photosensitive layer may have a single structure or a laminated structure in which the charge generation layer and the charge transport layer are functionally separated.

Examples of the material for the charge generating layer of the laminated structure photoreceptor include charge generating substances such as azo pigments, phthalocyanine pigments, quinone pigments, perylene pigments and indigo pigments.
Acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, poly, polyvinyl butyral resin,
Examples thereof include those dispersed in a binder resin such as a thermoplastic resin such as a polyvinylbenzal resin, a polyurethane resin, a phenol resin, a thermosetting resin such as an epoxy resin, and a dispersion in an appropriate solvent to prepare a coating solution. Further, additives may be added as required.

As the material for the charge transport layer, for example, a charge transport material such as a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a thiazole compound, and a triarylmethane compound is used as an acrylic resin. Thermoplastic resin such as polyester resin, polyamide resin, polyvinyl acetate resin, poly, polyvinyl butyral resin, polyvinyl benzal resin, thermosetting resin such as polyurethane resin, phenol resin, epoxy resin, etc. The binder resin is methanol, ethanol or butano.
Alcohol, isopropyl alcohol, etc., methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc. ketones, diethyl ether, tetrahydrofuran, etc. ethers, ethyl acetate, propyl acetate, etc. esters, normal Disperse in hydrocarbons such as hexane, petroleum ether, toluene, etc., halogenated hydrocarbons such as monochlorobenzene, dichloromethane, etc. dispersed in other suitable solvent to prepare a coating solution. Furthermore,
Additives can be added as required. Further, a conductive polymer can be used as the material for the charge transport layer.

As the coating method used in the present invention, a dip coating method, a spray coating method, a roll coater coating method, a gravure coater coating method and the like can be applied.

In the present invention, it is effective to apply the surface layer of the photosensitive layer (the layer directly in contact with the toner and the developing device, the cleaning device, etc.) as the layer containing the fluorine resin particles. That is, as the layer structure of the photosensitive layer, a single layer structure has a photosensitive layer, a charge transport layer has a charge transport layer laminated on the charge generation layer, and a charge transport layer has a charge generation layer laminated on the charge transport layer. Further, it is used as a conductive layer in a laminated photoreceptor having a structure in which a conductive layer is further formed thereon, and as a protective layer in a photoreceptor having a protective layer formed on the photosensitive layer.

The electrophotographic photosensitive member of the present invention can be applied to a photosensitive drum generally used in electrophotographic devices such as copying machines, laser beam printers, LED printers, liquid crystal shutters and printers.

The present invention integrally supports the electrophotographic photosensitive member of the present invention and at least one means selected from the group consisting of charging means, developing means and cleaning means, and is attachable to and detachable from the main body of the electrophotographic apparatus. It is composed of a process cartridge characterized by being flexible.

Further, the present invention comprises an electrophotographic apparatus characterized by having the electrophotographic photosensitive member of the present invention, a charging means, an image exposing means, a developing means and a transferring means.

FIG. 1 shows a schematic structure of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. In the course of rotation of the photoconductor 1, the peripheral surface of the photoconductor 1 is uniformly charged to a predetermined positive or negative potential by a primary charging means 3, and then an image exposure means (non-exposure means) such as slit exposure or laser beam scanning exposure is used. Image exposure light 4 from the drawing is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed by the developing means 5.
The toner-developed toner image developed and developed by the transfer material 7 is fed from a sheet feeding unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1. Then, the image is sequentially transferred by the transfer means 6. The transfer material 7 that has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 to undergo the image fixing, and is printed out as a copy (copy) to the outside of the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned by the cleaning means 9 after removal of the residual toner after transfer, and is further neutralized by the pre-exposure light 10 from the pre-exposure means (not shown). And then repeatedly used for image formation. The primary charging means 3 is a charging roller.
In the case of a contact charging means using a wire or the like, pre-exposure is not always necessary.

In the present invention, a plurality of constituent elements such as the photoconductor 1, the primary charging means 3, the developing means 5 and the cleaning means 9 are integrally combined as a process cartridge. However, the process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported with the photoconductor 1 to form a cartridge, and a guide means such as a rail 12 of the apparatus main body is used. The process cartridge 11 can be attached to and detached from the main body. Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 uses reflected light or transmitted light from a document, or a document is read by a sensor,
It is the light emitted by the signalization and the scanning of the laser beam, the driving of the LED array, the driving of the liquid crystal shutter array, etc., performed according to this signal.

On the other hand, when used as a printer for a facsimile, the image exposure light 4 becomes exposure light for printing the received data. FIG. 2 is a block diagram showing an example of this case. The controller 14 controls the image reading unit 13 and the printer 22. The entire controller 14 is controlled by the CPU 20. The read data from the image reading unit 13 is transmitted to the partner station through the transmission circuit 16. The data received from the partner station is sent to the printer 22 through the receiving circuit 15. Predetermined image data is stored in the image memory. The printer controller 21 controls the printer 22. 17 is a telephone. The image received from the line 18 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 15, and then the image information is decoded by the CPU 20 and sequentially stored in the image memory 19. To be done. Then, when at least one page of image is stored in the image memory 19, the image of that page is recorded. CPU20
Reads one page of image information from the image memory 19 and sends the decoded one page of image information to the printer controller -21. Printer controller
When the printer 21 receives the image information of one page from the CPU 20, the printer 21 prints the image information of the page.
22 is controlled. The CPU 20 receives the next page during recording by the printer 22. In this way, the image is received and recorded.

[0039]

【Example】

Example 1 As a conductive layer coating step, 2000 parts by weight of conductive titanium oxide coated with tin oxide containing 10% antimony oxide, 2500 parts by weight of phenol resin, 2000 parts by weight of methyl cellosolve, and 500 parts by weight of methanol were applied. A coating solution for a conductive layer was prepared by dispersing for 2 hours in a sand mill using a φ1 mm glass bead. Aluminum cylinder- (φ3
0 mm × 360 mm, wall thickness 5 mm), the above coating solution was dip-coated and dried at 160 ° C. for 25 minutes to form a conductive layer having a film thickness of 20 μm.

Next, in an intermediate layer coating step, 1000 parts by weight of N-methoxymethylated nylon 6 reprecipitated and purified, and 250 parts by weight of 6,12,66,610 copolymerized nylon were added to 5000 parts by weight of methanol and butanol. Solution was dissolved in 5000 parts by weight to prepare an intermediate layer coating solution. The above coating solution was dip-coated on the aluminum cylinder having the conductive layer formed thereon, and dried at 95 ° C. for 7 minutes to form an intermediate layer having a film thickness of 0.5 μm.

Next, as a charge generation layer coating step, 400 parts by weight of a disazo pigment having the following structural formula,

[Chemical 7] 200 parts by weight of polyvinyl butyral resin (degree of butyralization 68%, average molecular weight 24000) and 5000 parts by weight of cyclohexanone were dispersed in a sand mill using a φ1 mm glass bead, and tetrahydrofuran 5000 was further added.
Parts by weight were added to prepare a charge generation layer coating liquid. Furthermore, beads and dust were removed from this liquid by a centrifuge (7000 rpm, 30 minutes). This coating solution is dip-coated on the aluminum cylinder on which the intermediate layer has been formed, and the coating is performed at 85 ° C for 7 hours.
After drying for a minute, a charge generation layer having a film thickness of 0.15 μm was formed.

Next, in the charge transport layer coating step, first, 200 parts by weight of a 4-fluorinated ethylene resin heat-treated at 250 ° C. to prepare a fluororesin particle dispersion liquid,
200 parts by weight of polycarbonate resin, 600 parts by weight of monochlorobenzene, 8 parts by weight of fluorine-type comb-type graft polymer (trade name GF300, manufactured by Toagosei Kagaku Co., Ltd.) were thoroughly mixed, and then glass beads were used. Was dispersed with a sand grinder (manufactured by Amex Co., Ltd.) to prepare a 4-fluorinated ethylene resin particle dispersion liquid. When the X-ray diffraction pattern of the 4-fluorinated ethylene resin powder used at this time was measured, the half-width value of the peak around 2θ = 18 was 0.30.
Met.

Next, a styryl compound 1200 having the following structural formula
Parts by weight,

Embedded image 800 parts by weight of the polycarbonate resin, 1500 parts by weight of the 4-fluorinated ethylene resin particle dispersion liquid were dissolved and mixed in 5000 parts by weight of monochlorobenzene and 3000 parts by weight of dichloromethane to prepare a charge transport layer coating solution. This solution was applied onto the charge generation layer by dip coating and dried at 130 ° C. for 40 minutes to form a charge transport layer having a film thickness of 25 μm to prepare an electrophotographic photoreceptor.

This electrophotographic photoreceptor is charged, exposed, developed,
The transfer and cleaning processes were mounted on a copying machine that repeats every 0.5 seconds, and images were continuously output on 10000 sheets under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet. Further, the amount of wear of the surface layer after 10,000 sheets was measured. The results are shown in Table 1 below.

Example 2 As a step of preparing a fluororesin particle dispersion liquid, 30 Mra was used.
100 parts by weight of 4-fluorinated ethylene resin treated with γ-ray in d, 100 parts by weight of polycarbonate resin, 500 parts by weight of monochlorobenzene, fluorine-type comb-type graft polymer
(Product name: GF150, manufactured by Toagosei Kagaku Co., Ltd.) 6 parts by weight were thoroughly mixed and dispersed with a sand grinder (made by Amex Co., Ltd.) using a glass bead to disperse 4-fluorinated ethylene resin particles. A liquid was prepared. I used 4-
When the X-ray diffraction pattern of the fluorinated ethylene resin particles was measured, the half-width value of the peak around 2θ = 18 was 0.3.
It was 6.

A charge transport layer coating liquid was prepared in exactly the same manner as in Example 1 except that this 4-fluorinated ethylene resin particle dispersion liquid was used, and this liquid was dip coated on the charge generation layer,
The film was dried at 130 ° C. for 30 minutes to form a charge transport layer having a film thickness of 25 μm, an electrophotographic photosensitive member was prepared, and the electrophotographic photosensitive member prepared in exactly the same manner as in Example 1 was evaluated. The results are shown in Table 1 below.

Example 3 1200 parts by weight of the styryl compound as in Example 1 and 1100 parts by weight of a polycarbonate resin were dissolved in 5000 parts by weight of monochlorobenzene and 3000 parts by weight of dichloromethane to prepare a coating solution for the charge transport layer. did. This solution was applied onto the charge generation layer formed in the same manner as in Example 1 by dip coating, and dried at 130 ° C. for 30 minutes to form a charge transport layer having a film thickness of 25 μm.

Next, in the step of preparing the fluororesin particle dispersion, 50 parts by weight of the same 4-fluoroethylene resin as in Example 2, 100 parts by weight of polycarbonate resin, 500 parts by weight of monochlorobenzene, and fluorine system are used. 4 parts by weight of comb-type graft polymer (trade name LF40, manufactured by Soken Chemical Industry Co., Ltd.) was thoroughly mixed, and then dispersed with a sand grinder (manufactured by Amex Co., Ltd.) using a glass bead, and 4-fluorinated. An ethylene resin particle dispersion liquid was prepared. The solid content of the 4-fluorinated ethylene resin particles is 33% by weight.

Further, this 4-fluorinated ethylene resin particle dispersion is spray-coated on the above charge transport layer, and the temperature is set to 130 ° C.
Was dried for 20 minutes to form a protective layer having a film thickness of 4 μm, an electrophotographic photosensitive member was prepared, and the electrophotographic photosensitive member prepared in exactly the same manner as in Example 1 was evaluated. The results are shown in Table 1 below.

Example 4 200 parts by weight of a 4-fluorinated ethylene resin and 200 parts by weight of a polycarbonate resin obtained by cooling the molding resin at a cooling temperature of 300 ° C./h as a step of preparing a fluororesin particle dispersion liquid, 600 parts by weight of chlorobenzene, fluorine-type comb-type graft polymer (trade name GT100, manufactured by Toagosei Kagaku Co., Ltd.) 8
After sufficiently mixing the parts by weight, the mixture was dispersed with a sand grinder (manufactured by Amex Co., Ltd.) using glass beads to prepare a 4-fluorinated ethylene resin particle dispersion liquid. When the X-ray diffraction pattern of the 4-fluorinated ethylene resin particles used at this time was measured, the half-width value of the peak around 2θ = 18 was 0.32.

Using this 4-fluorinated ethylene resin particle dispersion liquid, a coating liquid for charge transport layer was prepared in exactly the same manner as in Example 1. This solution was applied onto the charge generation layer formed in the same manner as in Example 1 by dip coating and dried at 130 ° C. for 30 minutes to give a film thickness of 2
A 5 μm charge transport layer was formed to prepare an electrophotographic photoreceptor. This electrophotographic photosensitive member was evaluated in exactly the same manner as in Example 1. The results are shown in Table 1 below.

Comparative Example 1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 4-fluoroethylene resin which was not subjected to heat treatment was used in the step of preparing the fluororesin particle dispersion liquid in Example 1. It was created. When the X-ray diffraction pattern of the 4-fluorinated ethylene resin particles used at this time was measured, 2θ = 1
The half-width value of the peak near 8 was 0.26.

When this electrophotographic photosensitive member was evaluated in the same manner as in Example 1, a good image was obtained in the initial stage, but fogging occurred on the 10000th sheet, and a good image was obtained. I couldn't get it. 1000 more
The amount of wear of the surface layer of 0 sheets after running was measured. The results are shown in Table 1 below.

Comparative Example 2 An electrophotographic photosensitive member was prepared in the same manner as in Example 3, except that the solid content of 4-fluorinated ethylene resin particles was changed to 55% by weight. When this electrophotographic photosensitive member was evaluated in the same manner as in Example 1, image unevenness occurred in the initial stage and a good image could not be obtained. Further, the amount of abrasion of the surface layer of 10,000 sheets after the durability test was measured. The results are shown in Table 1 below.

Comparative Example 3 Electrophotographic sensitization was carried out in the same manner as in Example 2 except that 4-fluoroethylene resin not subjected to γ-ray treatment was used in the step of preparing the fluororesin particle dispersion liquid in Example 2. Created the body. When the X-ray diffraction pattern of the 4-fluorinated ethylene resin particles used at this time was measured, 2θ = 1
The half-width value of the peak around 8 was 0.24.

When this electrophotographic photosensitive member was evaluated in the same manner as in Example 1, a good image was obtained in the initial stage, but fogging occurred on the 10000th sheet, and a good image was obtained. I couldn't get it. 1000 more
The amount of wear of the surface layer of 0 sheets after running was measured. The results are shown in Table 1 below.

Comparative Example 4 1200 parts by weight of the same styryl compound as in Example 1 and 1014 parts by weight of a polycarbonate resin were dissolved in 5000 parts by weight of monochlorobenzene and 3000 parts by weight of dichloromethane to prepare a coating solution for the charge transport layer. did. This solution is applied onto the charge generation layer formed in the same manner as in Example 1 by dip coating and dried at 130 ° C. for 40 minutes to form a charge transport layer,
An electrophotographic photoreceptor was created.

When this electrophotographic photosensitive member was evaluated in the same manner as in Example 1, a good image was obtained in the initial stage, but at the 10000th sheet, sensitivity was insufficient, fogging, and toner were observed. No good image could be obtained due to the adherence of scratches and scratches on the photosensitive drum. Further, the amount of abrasion of the surface layer of 10,000 sheets after the durability test was measured. The results are shown in Table 1 below.

[0059]

[Table 1]

Comparing Examples 1 to 4 with Comparative Examples 1 to 4, a fluorine resin having a half width value of 0.28 or less in the peak of the X-ray diffraction pattern (near 2θ = 18) on the surface layer. The electrophotographic photoreceptor containing particles has excellent durability against abrasion and scratches on the surface due to friction, and is charged, exposed, developed, transferred, and cleared.
High quality images were always obtained for repeated training processes. On the other hand, the peak of the X-ray diffraction pattern (2θ =
In the case of using fluorine-based resin particles having a half width value of 0.28 or more (near 18), durability against surface abrasion and scratches due to friction is not sufficient, and high quality without image defects in repeated use. I couldn't get a good image. Further, if the content of the fluorine-based resin particles is more than 50% by weight, a uniform and smooth film cannot be formed, so that image unevenness occurs from the beginning, and the fluorine-based resin particles are not contained. Then, problems such as large abrasion of the photosensitive drum, poor cleaning property, and easy scratching occur,
In any case, good images without image defects could not be obtained.

[0061]

The electrophotographic photosensitive member of the present invention has durability against abrasion and scratches on the surface due to friction and can stably obtain a high-quality image even after repeated use. It has a remarkable effect of being excellent in turning property. The same applies to a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[Brief description of drawings]

FIG. 1 shows an X-ray diffraction pattern of fluorine-based resin particles.

FIG. 2 is a process chart having the electrophotographic photoreceptor of the present invention.
It is a figure which shows schematic structure of the electrophotographic apparatus which has a triggle.

FIG. 3 is a diagram showing an example of a block of a facsimile having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Electrophotographic Photoreceptor of the Present Invention 2 Axis 3 Primary Charging Means 4 Image Exposure Light 5 Developing Means 6 Transfer Means 7 Transfer Material 8 Image Fixing Means 9 Cleaning Means 10 Pre-Exposure Light 11 Process Cartridge 12 Rails 13 Image reading unit 14 Controller 15 Receiver circuit 16 Transmitter circuit 17 Telephone 18 Line 19 Image memory 20 CPU 21 Printer-Controller 22 Printer-

Claims (10)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the surface of the electrophotographic photoreceptor contains fluororesin particles, the fluororesin particles of the electrophotographic photoreceptor have an X-ray diffraction pattern pattern. An electrophotographic photosensitive member characterized by having a half width of 0.28 or more in the region (2θ = 18). 2. The electrophotographic photosensitive member according to claim 1, wherein the fluororesin particles according to claim 1 are fluororesin particles which are heat-treated at 140 to 280 ° C. in the manufacturing process. 3. The electrophotographic photosensitive member according to claim 1, wherein the fluororesin particles according to claim 1 are fluororesin particles whose cooling rate during molding is 50 ° C./h or more in the manufacturing process. 4. The electrophotographic photosensitive member according to claim 1, wherein the fluororesin particles according to claim 1 are fluororesin particles that have been subjected to radiation treatment in the manufacturing process thereof. 5. The fluororesin particles according to claim 1 are 4-
The electrophotographic photosensitive member according to claim 1, which is a fluorinated ethylene resin. 6. The electrophotographic photosensitive member according to claim 1, wherein the content of the fluororesin particles according to claim 1 is 0.1 to 50% by weight. 7. The electrophotographic photosensitive member according to claim 1, wherein the surface layer according to claim 1 contains a fluorine-based comb-type graft polymer. 8. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer according to claim 1 has a laminated structure of a charge generation layer and a charge transport layer. 9. An electrophotographic photosensitive member according to claim 1, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means, which are integrally supported and are detachably attached to the main body of the electrophotographic apparatus. A process cartridge characterized by the following. 10. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit and a cleaning unit.