JP3148571B2 - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and electrophotographic apparatus - 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, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art An electrophotographic photoreceptor needs to have sensitivity, electric characteristics, and optical characteristics according to an applied electrophotographic process. Charge to surface layer, toner development, transfer to paper,
Since an electrical or mechanical external force is directly applied by a process such as cleaning, durability against the external force is required.

[0003] Specifically, it is required to have durability against abrasion of the surface due to friction, generation of scratches, and deterioration of the surface at high temperatures. Another problem is that toner adheres to the surface layer due to repetition of development and cleaning by the toner, and improvement of the cleaning property of the surface layer is required.

Various methods have been studied to satisfy the characteristics required for the surface layer as described above. Among them, a method of providing a resin layer in which fluorine resin particles are dispersed on the surface layer is effective. is there. By dispersing the fluororesin particles, the friction coefficient of the surface layer is reduced, and the cleaning properties and the durability against abrasion and scratches are improved. These effects are further improved by increasing the amount of the fluororesin particles. However, in such a case, in the dispersion of the fluororesin particles, there is a problem in the dispersibility and cohesion thereof, and it is difficult to form a uniform and smooth film . Having image defects was inevitable.

[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 have a cleaning property, a durability against abrasion and scratches, and to provide an improved electrophotographic process. An object of the present invention is to provide an electrophotographic photosensitive member that can always obtain a high-quality image.

[0006]

The present invention SUMMARY OF] In the electrophotographic photosensitive member having a photosensitive layer on a conductive support, electrophotography
4- fluoride instead the surface layer of the photosensitive member as a fluorine-based resin particles
An electrophotographic photoreceptor comprising: a styrene resin particle ; and a half width of a peak (around 2θ = 18) of an X-ray diffraction pattern of the 4- fluoroethylene resin particle is 0.28 or more. You.

FIG. 1 shows the X-ray diffraction pattern of the fluororesin particles.

In general, the half width depends on the crystallinity of the material, and the value becomes smaller as the crystallinity becomes higher. That is, in the present invention, by containing fluorine-based resin particles having a low crystallinity and a high elongation, the friction coefficient is reduced more effectively, the cleaning property is improved, and the durability against abrasion and scratches is improved. It is to improve.

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

As a method for lowering the crystallinity of the fluororesin particles, a method of increasing the cooling rate at the time of molding and heat treatment in the production process may be mentioned.

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

The heat treatment temperature must be higher than Tg (glass transition temperature) of the fluororesin particles and a temperature at which the fluororesin particles do not thermally decompose. Specifically 140
To 280 ° C, and more preferably 160 to 260 ° C. When the heat treatment temperature is 140 ° C. or lower, the crystallinity cannot be reduced even by the heat treatment for a long time, and the cleaning property and the durability against abrasion and scratches cannot be sufficiently improved. On the other hand, when the temperature is 280 ° C. or higher, the fluororesin particles cause thermal decomposition.

The cooling rate during molding must be such that the crystallinity of the fluororesin particles does not increase. Specifically, the temperature is preferably 50 ° C./h or more, and particularly preferably 100 ° C./h or more. When the cooling rate is 50 ° C./h or less, the crystallinity of the fluororesin particles becomes high, so that the cleaning properties and the durability against abrasion and scratches cannot be sufficiently improved.

As an example of the radiation treatment, a method using an electron beam, γ-ray, or the like can be given. The treatment condition with radiation is preferably 10 Mrad or more, particularly preferably 15 Mrad or more. When the treatment conditions are 10 Mrad or less, the crystallinity of the fluororesin particles does not decrease, and the cleaning properties and the durability against abrasion and scratches cannot be sufficiently improved. .

As the fluororesin particles, 4-fluorinated ethylene resin is suitable for improving abrasion resistance. One or more of these resins may be used in combination.
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. If necessary, a dispersing aid, a surfactant and the like may be used. As a good dispersing aid, a fluorine-based comb type graft polymer can be mentioned.

The fluorine-based 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 10,000 and a fluoropolymerizable monomer, wherein the fluoropolymer is used as a trunk and the macromonomer polymer is formed into a plate shape. It has a hanging structure.

The macromonomer is selected from those having affinity for the resin to which the graft polymer is added. For example, polymers or copolymers of acrylates, methacrylates, styrene compounds and the like are used.

On the other hand, fluorine-based polymerizable monomers include:
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 invention is not limited thereto. General formula (1)

Embedded image General formula (2)

Embedded image General formula (3)

Embedded image General formula (4)

Embedded image General formula (5)

Embedded image General formula (6)

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

The content of the fluorine monomer residue in the fluorine comb graft polymer is preferably 5 to 90% by weight in the fluorine comb graft polymer, and 10 to 70% by weight.
% By weight is more preferred. Content of fluorine monomer is 5
If the content is less than 90% by weight, the effect of improving the hydrophobicity cannot be sufficiently exhibited, and if the content of the fluorine-based monomer residue exceeds 90% by weight, the solubility with the macromonomer becomes poor.

Examples of the binder resin include thermoplastic resins such as polycarbonate resins, acrylic resins, polyester resins, polyamide resins, polyvinyl acetate resins, polyvinyl butyral resins, polyurethane resins, phenols and the like. Resin, thermosetting resin such as epoxy resin, photocurable resin and the like can be mentioned.

The ratio of the fluororesin particles in the surface layer is appropriately selected depending on the type of the fluororesin particles and the constitution of the photosensitive layer. When the amount of addition is large, the light transmittance is reduced and the sensitivity is reduced, and the light for image exposure is scattered to cause bleeding in an image. On the other hand, if the addition amount is small, it is liable to be worn and the effect of the present invention is not sufficiently exhibited. 0.1 to 50% by weight, particularly preferably 0.2 to 50% by weight, based on the surface layer
４０40% by weight.

Next, preparation of the electrophotographic photosensitive member will be described. Examples of the method of preparing a coating solution for preparing the electrophotographic photoreceptor of the present invention include a method of simultaneously dispersing fluorine-based resin particles together with a solvent such as a binder resin, a charge-transporting substance, and the like, There is a method in which a dispersion is prepared by previously dispersing and then mixed with a coating solution. In preparing the coating solution for the electrophotographic photoreceptor or the fluororesin particle dispersion 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, a sand mill or the like is used.

As the solvent, a binder in the coating solution may be used.
Those having good solubility in resins and charge transport substances, dispersibility in pigments, and applicability are 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, and carbon fibers. -, Carbon black, and a mixture of graphite powder and resin.

Further, a conductive layer can be provided for covering defects on the support and protecting the support . For example, aluminum, copper, metal powder such as nickel, antimony oxide,
Indium oxide, conductive metal oxides such as tin oxide, polypyrrole, polyaniline, polymeric conductive material such as a polymer electrolyte, carbon file Lee bar, carbon black, conductive coating the surface with graphite powder or which such conductive material Thermoplastic resins such as acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, polyvinyl butyral resin, polyurethane resin, phenol resin, epoxy resin, etc.
Examples thereof include those dispersed in a binder resin such as a photocurable resin, and those obtained by adding a necessary additive to a support.

Further, an intermediate layer can be provided to improve the adhesiveness of the photosensitive layer and the charge injection property from the conductive support. Examples of the material of the intermediate layer include gelatin, ethylene-acrylate copolymer, nitrocellulose resin,
Examples thereof include resins such as polyamide resins and polyvinyl alcohol resins, which are dissolved in an appropriate solvent and applied on a conductive support. Further, additives can be added as needed.

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

Examples of the material for the charge generation layer of the laminated photoreceptor include charge generation substances such as azo pigments, phthalocyanine pigments, quinone pigments, perylene pigments and indigo pigments.
A resin dispersed in a binder resin such as a thermoplastic resin such as an acrylic resin, a polyester resin, a polyamide resin, a polyvinyl acetate resin, a polyvinyl butyral resin, and a polyvinyl benzal resin, and a thermosetting resin such as a polyurethane resin, a phenol resin, and an epoxy resin. It can be dispersed in an appropriate solvent to form a coating solution, and further, if necessary, an additive can be added.

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 or a triarylmethane compound may be used. Thermoplastic resins such as polyester resin, polyamide resin, polyvinyl acetate resin, poly, polyvinyl butyral resin, and polyvinyl benzal resin, and thermosetting resins such as polyurethane resin, phenol resin, and epoxy resin. Binder resins such as methanol, ethanol and butanol
Alcohols such as isopropyl alcohol and isopropyl alcohol, ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and propyl acetate, and normal. It is dispersed in a suitable solvent such as hexane, petroleum ether, hydrocarbons such as toluene, and halogenated hydrocarbons such as monochlorobenzene and dichloromethane to prepare a coating solution. Furthermore,
Additives can be added as needed. Further, a conductive polymer can be used as a material for the charge transport layer.

As a 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 layer containing the fluororesin particles to the surface layer of the photosensitive layer (a layer directly in contact with a toner, a developing device, a cleaning device, etc.). That is, as the layer configuration of the photosensitive layer, the charge generation layer is laminated on the charge transport layer in the case of a single layer structure, the charge transport layer in the laminate structure in which the charge transport layer is laminated on the charge generation layer, and the charge generation layer 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 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 an electrophotographic apparatus such as a copying machine, a laser beam printer, an LED printer, and a liquid crystal shutter printer.

According to the present invention, the electrophotographic photoreceptor of the present invention and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and attached to and detached from an electrophotographic apparatus main body. It is composed of a process cartridge characterized by being flexible.

Further, the present invention comprises an electrophotographic apparatus comprising the electrophotographic photoreceptor of the present invention, a charging unit, an image exposing unit, a developing unit and a transferring unit.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in the direction of an arrow. In the rotation process, the photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3, and then the image exposure means (such as a slit exposure or a laser beam scanning exposure) is used. (See FIG. 1). Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
Is transferred to the transfer material 6 from the paper supply unit (not shown) and fed between the photosensitive member 1 and the transfer means 6 in synchronization with the rotation of the photosensitive member 1. Are sequentially transferred by the transfer means 6. The transfer material 7 having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out as a copy (copy) outside the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the transfer residual toner by the cleaning means 9, and further subjected to a static elimination process by the pre-exposure light 10 from the pre-exposure means (not shown). After that, it is repeatedly used for image formation. Incidentally, the primary charging means 3 is a charging roller.
In the case of a contact charging means using a liner or the like, pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the photosensitive member 1, the primary charging means 3, the developing means 5, and the cleaning means 9 are integrally connected as a process cartridge. Alternatively, the process cartridge may be configured to be detachable from a main body of an 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 together with the photoreceptor 1 to form a cartridge, and the apparatus is guided by a guide means such as a rail 12 of the apparatus body. The process cartridge 11 can be detachably attached to the main body. When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor.
The light is emitted by laser beam scanning, driving of an LED array, driving of a liquid crystal shutter array, and the like performed in accordance with this signal.

On the other hand, when used as a facsimile printer, the image exposure light 4 becomes exposure light for printing 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. 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 a remote terminal connected via the line) is demodulated by the receiving circuit 15 and then decoded by the CPU 20 and sequentially stored in the image memory 19. Is done. When at least one page of the image is stored in the image memory 19, the image of the page is recorded. CPU 20
Reads out one page of image information from the image memory 19 and sends out the decoded one-page image information to the printer controller 21. Printer controller
Upon receiving one page of image information 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. Thus, reception and recording of an image are performed.

[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 used. The resultant was dispersed in a sand mill using a φ1 mm glass bead for 2 hours to prepare a conductive layer coating solution. Aluminum cylinder (φ3
(0 mm × 360 mm, wall thickness: 5 mm) by dip coating, and dried at 160 ° C. for 25 minutes to form a conductive layer having a thickness of 20 μm.

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

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

Embedded image 200 parts by weight of polyvinyl butyral resin (butyralization degree: 68%, average molecular weight: 24,000) and 5,000 parts by weight of cyclohexanone were dispersed by a sand mill using a φ1 mm glass bead, and further tetrahydrofuran 5000
By weight, a coating solution for a charge generation layer was prepared. Further, this solution was subjected to centrifugal separation (at 7000 rpm for 30 minutes) to remove beads, dust and the like. This coating solution was applied by dip coating on the aluminum cylinder on which the intermediate layer had been formed.
After drying for a minute, a charge generation layer having a thickness of 0.15 μm was formed.

Next, as a charge transporting layer coating step, first, 200 parts by weight of a 4-fluoroethylene resin which had been subjected to a heat treatment at 250 ° C. to prepare a fluororesin particle dispersion,
After thoroughly mixing 200 parts by weight of a polycarbonate resin, 600 parts by weight of monochlorobenzene, and 8 parts by weight of a fluorine-based comb graft polymer (trade name: GF300, manufactured by Toa Gosei Chemical Co., Ltd.), a glass bead is used. The mixture was dispersed by a sand grinder (manufactured by Amex Co., Ltd.) to prepare a dispersion of 4-fluoroethylene resin particles. When the X-ray diffraction pattern of the 4-fluoroethylene resin powder used at this time was measured, the half-width value of the peak near 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 and 1500 parts by weight of the 4-fluoroethylene resin particle dispersion 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 liquid 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 thickness of 25 μm, thereby producing an electrophotographic photoreceptor.

The electrophotographic photosensitive member is charged, exposed, developed,
The apparatus was mounted on a copying machine in which the transfer and cleaning processes were repeated in a 0.5 second cycle, and 10,000 sheets were continuously output at 35 ° C. and 80% high temperature and high humidity. As a result, a high-quality image free from image defects was obtained both in the initial stage and on the 10,000th sheet. Further, the wear amount of the surface layer after 10,000 sheets was measured. The results are shown in Table 1 below.

Example 2 As a process for preparing a fluororesin particle dispersion, 30 Mra
100 parts by weight of 4-fluorinated ethylene resin, 100 parts by weight of polycarbonate resin, 500 parts by weight of monochlorobenzene, fluorine-based comb type graft polymer
After sufficiently mixing 6 parts by weight (trade name: GF150, manufactured by Toa Gosei Chemical Co., Ltd.), the mixture was dispersed by a sand grinder (manufactured by Amex Co., Ltd.) using a glass bead, and 4-fluoroethylene resin particles were dispersed. A liquid was prepared. 4-
When the X-ray diffraction pattern of the fluorinated ethylene resin particles was measured, the half-width value of the peak near 2θ = 18 was 0.3.
It was 6.

A coating solution for the charge transport layer was prepared in exactly the same manner as in Example 1 except that this 4-fluoroethylene resin particle dispersion was used, and this solution was applied onto the charge generation layer by dip coating.
After drying at 130 ° C. for 30 minutes, a charge transport layer having a thickness of 25 μm was formed to prepare an electrophotographic photoreceptor. The electrophotographic photoreceptor 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 same styryl compound and 1,100 parts by weight of a polycarbonate resin as in Example 1 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 dip-coated on the charge generation layer formed in the same manner as in Example 1, and dried at 130 ° C. for 30 minutes to form a charge transport layer having a thickness of 25 μm.

Next, as a preparation step of the fluororesin particle dispersion, 50 parts by weight of 4-fluoroethylene resin, 100 parts by weight of polycarbonate resin, 500 parts by weight of monochlorobenzene, After thoroughly mixing 4 parts by weight of a comb type graft polymer (trade name: LF40, manufactured by Soken Chemical Co., Ltd.), the mixture is dispersed by a sand grinder (manufactured by Amex Co., Ltd.) using a glass bead, and 4-fluorinated. An ethylene resin particle dispersion was prepared. The solid content of the 4-fluoroethylene resin particles is 33% by weight.

Further, the 4-fluoroethylene resin particle dispersion was spray-coated on the charge transport layer,
For 20 minutes to form a protective layer having a thickness of 4 μm, and an electrophotographic photoreceptor was prepared. The electrophotographic photoreceptor prepared in exactly the same manner as in Example 1 was evaluated. The results are shown in Table 1 below.

Example 4 As a process for preparing a fluororesin particle dispersion, 200 parts by weight of a 4-fluoroethylene resin, 200 parts by weight of a polycarbonate resin, and a cooling temperature of 300 ° C./h during molding were used. 600 parts by weight of chlorobenzene, fluorine comb type graft polymer (trade name: GT100, manufactured by Toa Gosei Chemical Co., Ltd.) 8
After sufficiently mixing the parts by weight, the mixture was dispersed with a sand grinder (manufactured by Amex Co., Ltd.) using a glass bead to prepare a dispersion of 4-fluoroethylene resin particles. When the X-ray diffraction pattern of the 4-fluoroethylene resin particles used at this time was measured, the half-width value of the peak near 2θ = 18 was 0.32.

Using this 4-fluoroethylene resin particle dispersion, a coating solution for a charge transport layer was prepared in exactly the same manner as in Example 1. This solution was dip-coated on the charge generation layer formed in the same manner as in Example 1, dried at 130 ° C. for 30 minutes,
A 5 μm charge transport layer was formed, and an electrophotographic photoreceptor was prepared. 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 a 4-fluorinated ethylene resin which was not subjected to heat treatment was used in the preparation process of the fluororesin particle dispersion in Example 1. It was created. When the X-ray diffraction pattern of the 4-fluoroethylene 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 at the initial stage, but fogging occurred on the 10,000th sheet, and a good image was obtained. Could not be obtained. Further 1000
The wear amount of the surface layer after the endurance of 0 sheets 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 the 4-fluoroethylene resin particles was 55% by weight. When this electrophotographic photosensitive member was evaluated in the same manner as in Example 1, image unevenness occurred at the initial stage, and a good image was not obtained. Further, the wear amount 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 An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 2 except that a 4-fluorinated ethylene resin not subjected to γ-ray treatment was used in the preparation step of the fluororesin particle dispersion in Example 2. Created body. When the X-ray diffraction pattern of the 4-fluoroethylene resin particles used at this time was measured, 2θ = 1
The half width value of the peak near 8 was 0.24.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. As a result, a good image was obtained at the initial stage, but fogging occurred on the 10,000th sheet. Could not be obtained. Further 1000
The wear amount of the surface layer after the endurance of 0 sheets was measured. The results are shown in Table 1 below.

Comparative Example 4 1200 parts by weight of the same styryl compound and 1014 parts by weight of a polycarbonate resin as in Example 1 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 liquid was dip-coated on the charge generation layer formed in the same manner as in Example 1 and dried at 130 ° C. for 40 minutes to form a charge transport layer.
An electrophotographic photoreceptor was prepared.

The electrophotographic photosensitive member was evaluated in the same manner as in Example 1. As a result, a good image was obtained in the initial stage. And the photosensitive drum was damaged, and a good image was not obtained. Further, the wear amount 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]

When Examples 1 to 4 and Comparative Examples 1 to 4 are compared, the fluororesin having a half width value of 0.28 or less of the peak (around 2θ = 18) of the X-ray diffraction pattern on the surface layer is shown. Electrophotographic photoreceptors containing particles are excellent in durability against abrasion and scratches on the surface due to friction, and can be charged, exposed, developed, transferred, and cleaned.
High-quality images were always obtained for the repetition of the shining process. 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 of 0.28 or more (around 18), the durability against abrasion and scratches on the surface due to friction is not sufficient, and high-quality images free from image defects even when used repeatedly. No image was obtained. On the other hand, if the content of the fluorine-based resin particles is more than 50% by weight, a uniform and smooth film cannot be formed. In this case, problems such as large wear of the photosensitive drum, poor cleaning properties, and easy damage are caused.
In each case, good images without image defects were not obtained.

[0061]

The electrophotographic photoreceptor of the present invention has durability against abrasion and scratches on the surface due to friction, and can provide a high-quality image stably even when used repeatedly. It has a remarkable effect of being excellent in shining properties. The same applies to a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[Brief description of the drawings]

FIG. 1 shows an X-ray diffraction pattern of fluororesin particles.

FIG. 2 is a process card having the electrophotographic photosensitive member of the present invention.
FIG. 2 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a cartridge.

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

[Explanation of symbols]

 DESCRIPTION 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 Rail 13 Image reading unit 14 Controller 15 Receiving circuit 16 Transmitting circuit 17 Telephone 18 Line 19 Image memory 20 CPU 21 Printer controller 22 Printer

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 5/00-5/16

Claims (9)

(57) [Claims] 1. A electrophotographic photosensitive member having a photosensitive layer on a conductive support, containing 4-fluorinated ethylene resin particle surface layer of the electrophotographic photosensitive member as a fluorine-based resin particles
An electrophotographic photoreceptor , wherein the 4-fluoroethylene resin particles have a half value width of 0.28 or more at a peak (around 2θ = 18) of an X-ray diffraction pattern. 2. The 4-fluoroethylene resin particles which have been heat-treated at 140 to 280 ° C. during the production process thereof.
The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is a fluoroethylene resin particle. 3. A 4-fluoroethylene resin particle whose cooling rate is set to 50 ° C./h or more in the production process.
The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is a fluoroethylene resin particle. 4. The electrophotographic photoreceptor according to claim 1, wherein the 4-fluoroethylene resin particles are radiation-treated 4-fluoroethylene resin particles during the production process. 5. The electrophotographic photosensitive member according to claim 1, wherein the content of 4-fluoroethylene resin particles is 0.1 to 50% by weight. 6. The electrophotographic photoreceptor according to claim 1, wherein the surface layer contains a fluorine-based comb type graft polymer. 7. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer. 8. The 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 are integrally supported and detachably attached to the electrophotographic apparatus main body. A process cartridge. 9. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposing unit, a developing unit, and a cleaning unit.