JPH1078673A - Electrophotographic photoreceptor, process cartridge with same and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure a superior wear resistance, to suppress a deterioration of image quality even in an environment at a high humidity and to ensure high durability by incorporating a curable resin and one or more kinds of materials selected from among glass materials and ceramic materials each having a specified Mohs hardness into a protective layer formed on a photosensitive layer. SOLUTION: This electrophotographic photoreceptor has a photosensitive layer and a protective layer on the electrically conductive substrate and the protective layer contains a curable resin and one or more kinds of materials selected from among glass materials and ceramic materials each having a Mohs hardness of >=3. Especially effective examples of the glass materials are soda glass, borosilicate glass, potash glass and quartz glass. Especially effective examples of the ceramic materials are sintered compacts each made of one or more kinds of compds. such as zirconium compds. (zirconia, zirconium carbide, zirconium boride and zircon), silicon compds. (silicon nitride, silicon carbide and silica), tantalum compds., alumina and titania.

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 photosensitive member is required to have required sensitivity, electric characteristics and optical characteristics according to an electrophotographic process to be used. Further, in the electrophotographic photoreceptor that is used repeatedly, the surface layer of the photoreceptor, that is, the layer that is most isolated from the support, has durability against damage received from charging means, developing means, cleaning means and transfer means. Required. Specifically, surface friction due to friction,
Durability against scratching, surface deterioration due to electric discharge, and the like is required. In order to satisfy the characteristics required for the surface layer as described above, a method of providing a function-separated type photoconductor in which a charge transport layer is provided on a charge generation layer is performed. However, even in the case of a function-separated type photoreceptor, the material used for the charge transport layer is limited, and the number of durable sheets is limited. It has been practiced to provide a protective layer containing a resin as a main component on a photosensitive layer in order to obtain a higher durable number of sheets. For example, as proposed in JP-A-57-30843, there is provided a protective layer in which resistance is controlled by adding a conductive powder.

However, if the conventional protective layer is used repeatedly, the surface of the protective layer is deteriorated by discharge when used repeatedly, and paper powder or the like adheres to the surface of the protective layer from transfer paper during transfer. When the electrophotographic photoreceptor to which paper dust adheres and deteriorates is used in a high humidity environment, the surface resistance decreases,
There is a problem that image blur occurs. As a countermeasure, if the deteriorated surface is scraped every time it is used, a new surface is always formed on the surface, so that there is no problem that image blur occurs even when used in a high humidity environment. However, excessive shaving results in shortening the life of the electrophotographic photosensitive member. Conventionally, it has not been possible to achieve both durability against shaving and image quality in a high humidity environment.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to reduce surface friction even after long-term repeated use, and
Provided is a highly durable electrophotographic photoreceptor which can always obtain high-quality images with little image deterioration in a high humidity environment after repeated use. Also, a process cartridge and an electronic device using the electrophotographic photoreceptor are provided. A photographic device is provided.

[0005]

According to the present invention, there is provided an electrophotographic photosensitive member having a protective layer provided on a photosensitive layer, wherein the protective layer comprises at least one material selected from glass materials and ceramic materials having a Mohs hardness of 3 or more. It is composed of an electrophotographic photosensitive member containing a material and a curable resin.

[0006] The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member having a photosensitive layer and a protective layer on a conductive support.

[0007] The protective layer is provided on the photosensitive layer in order to impart higher durability. The characteristics required for the protective layer include the basic characteristics of the photosensitive layer as an electrophotographic photoreceptor, such as chargeability, residual potential, sensitivity, etc., as well as exposure to damage caused by a predetermined electrophotographic process. The layer must be protected, and furthermore, the protective layer itself must be robust against damage from certain electrophotographic processes.
Furthermore, it is mentioned that paper powder or the like does not easily adhere to the surface.

In the electrophotographic photoreceptor of the present invention, first, the protective layer contains a glass material or a ceramic material particle having a Mohs hardness of 3 or more and a curable resin, thereby enhancing abrasion resistance. Curable resins have higher abrasion resistance than general non-curable resins, and a glass material or a ceramic material particle having a Mohs hardness of 3 or more is added to the resin to exhibit a synergistic effect and exhibit high abrasion resistance. Secondly, the protective layer is abraded to remove glass powder having a Mohs hardness of 3 or more, which is deposited on the surface, and to remove paper dust or the like adhered to the surface, thereby abrading the surface even for long-term repeated use. This has made it possible to provide a highly durable electrophotographic photoreceptor which has little image deterioration under high humidity environment after repeated use and can always obtain high quality images.

In the present invention, the glass material refers to a substance obtained by quenching a molten liquid appropriately and solidifying it without crystallization. Particularly effective examples of the glassy material include soda glass, borosilicate glass, potash glass, soda glass, and quartz glass. For these materials, the hardness of the fine powder is appropriate, and the fine powder is easily available.

In the present invention, a ceramic material refers to a sintered body of a nonmetallic inorganic material. Particularly effective examples of ceramic materials include single or composite sintered bodies of zirconium compounds (zirconia, zirconium carbide, zirconium boride, zircon), silicon compounds (silicon nitride, silicon carbide compounds, silica), tantalum compounds, alumina, titania, etc. Is mentioned. For these materials, the hardness of the fine powder is appropriate, and the fine powder is easily available.

In the present invention, a composite material of the above glass material or ceramic material and another material, or a material mixed with another material can be used.

When the glass material or the ceramic material particles used in the protective layer of the electrophotographic photosensitive member of the present invention are too soft, the effect of imparting abrasion resistance is small, and the effect of removing paper dust and the like attached to the surface is also reduced. Few. Mohs hardness of 3 or more is required as hardness. As the particles dispersed in the protective layer, one kind of glass material or ceramic material may be used as needed, and a mixture of two or more kinds of glass material and ceramic material particles is also effective.

In the present invention, the glass or ceramic material particles dispersed in the protective layer may be conductive or non-conductive. In particular, a conductive glass or ceramic material may be used to control the resistance. It is possible.

In the present invention, the effect is recognized when the volume average particle diameter of the glass material or ceramic material particles dispersed in the protective layer is 0.01 μm or more. If the particle size is more than 5 μm, the photoreceptor will be scratched by repeated use. Therefore, it is preferable that the particle size of 5 μm or more be 10% by volume. If the particle size is smaller than the above range, the polishing effect is small. In an electrophotographic photoreceptor that requires higher image quality, in order to prevent the incident light from being scattered by the particles in the protective layer and causing image deterioration, the wavelength of the incident light is less than the wavelength, that is, the volume average particle diameter is not more than 0.1. 01μm or more, 0.9μ
m or less is particularly preferred.

The content ratio of the glass material and the ceramic material particles in the protective layer is preferably 0.001% to 5% by volume. If the content is high, the incident light is scattered by the particles in the protective layer, causing image deterioration.

The curable resin contained in the protective layer in the present invention includes a thermosetting resin, a photocurable resin, an electron beam curable resin, and the like. Particularly preferred are ultraviolet curable resins. UV curable resins are easy to handle and have a long pot life.

The protective layer in the present invention may contain a dispersant for dispersing the glass material and the ceramic material particles in the resin. The type of the dispersant is selected according to the type of the glass material and the ceramic material particles and the resin, and examples thereof include anionic, cationic, nonionic, and metallic soaps.

As a method of dispersing the glass material and the ceramic material particles in the coating solution for the protective layer, it is possible to simply mix and agitate the fine particles in the coating solution, but the glass material, the ceramic material, the curable monomer, and an appropriate solvent And the like may be charged into a dispersing means to perform pulverization and dispersion. Examples of the dispersing means include a sand mill, a ball mill, a roll mill, and a high-pressure homogenizer.

Further, as a method of dispersing the glass material and the ceramic material particles in the coating solution for the protective layer, a sand mill,
It is also possible to employ a method in which a glass material and a ceramic material are used as the vessel material of the ball mill or the medium material, and the vessel material or the medium material is ground and simultaneously dispersed in the coating solution for the protective layer. Especially when it is necessary to disperse a material other than the glass material and the ceramic material particles in the coating liquid for the protective layer using a mill, this method does not increase the number of steps, and the glass material and the ceramic material particles having an appropriate particle size are used. Can be dispersed in the protective layer coating solution.

As the vessel material or the medium material, a glass material having three or more moths and a ceramic material contained in the protective layer of the present invention and which can be formed into a vessel material or a medium material are used. . Examples of materials include soda glass, borosilicate glass, potash glass, quartz glass, and the like, and zirconium compounds (zirconia, zirconium carbide, zirconium boride, zircon) and silicon compounds (silicon nitride, silicon carbide compounds, (Silica), a tantalum compound, alumina, titania and the like, or a composite sintered body.

In the protective layer of the present invention, conductive particles may be dispersed in the protective layer, if necessary, in addition to the glass material and ceramic material particles in order to control the layer resistance. When the glass material and the ceramic material particles for increasing the durability are already contained in the protective layer, the conductive particles for controlling the layer resistance may not be the glass material and the ceramic material. Examples of the conductive particles include zinc oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, and the like, and tin oxide and zirconium oxide obtained by doping antimony and the like into these materials.

According to the present invention, the electrophotographic photosensitive member 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 the figure, reference numeral 1 denotes a drum-shaped electrophotographic photoreceptor of the present invention, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow around a flick 2. 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 developed.
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. When the primary charging means 3 is a contact charging means using a charging roller 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 main body is guided by a guide means such as the rail 12 of the apparatus main body. The process cartridge 11 can be detachably mounted on the cartridge. When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal. This is light emitted by scanning of the laser beam, driving of the LED array, driving of the liquid crystal shutter array, and the like.

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 the image of at least one page is stored in the image memory 19, the image of the page is recorded. The CPU 20 reads out the image information of one page from the image memory 19 and sends out the decoded image information of one page to the printer-controller-21. When receiving the image information of one page from the CPU 20, the printer controller 21 controls the printer 22 to record the image information of the page. CPU 20
Is receiving the next page during recording by the printer-22. Thus, reception and recording of an image are performed.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photosensitive member of the present invention is prepared, for example, as follows.

A solution prepared by dissolving alcohol-soluble copolymerized nylon in a mixture of methanol and methoxymethyl 6 nylon in a mixture of methanol and butanol is applied to an aluminum cylinder and dried to form an undercoat layer. Next, a coating liquid obtained by dispersing a disazo pigment as a charge generating substance together with polyvinyl butyral, tetrahydrofuran, and cyclohexanone is dip-coated on the undercoat layer to form a charge generating layer, and then charge transport is performed. A coating solution prepared from a styryl compound as a substance from polycarbonate, chlorobenzene, and dichloromethane is dip-coated on the charge generation layer to form a charge transport layer, and then a curable acrylic is formed to form a protective layer. A coating solution prepared by dispersing a monomer, soda glass powder, tin oxide, and toluene by a sand mill and further adding a photopolymerization initiator is coated on the charge transport layer. Le - coated, irradiated with ultraviolet rays to form a protective layer to an electrophotographic photoreceptor.

Further, the cartridge of the present invention integrally supports at least one means selected from the group consisting of the electrophotographic photoreceptor of the present invention, and a charging means, a developing means and a cleaning means. It is configured to be detachable from the photographic apparatus main body.

In the electrophotographic apparatus having the process cartridge having the electrophotographic photosensitive member of the present invention, the drum-shaped electrophotographic photosensitive member of the present invention is driven to rotate at a predetermined peripheral speed. In the rotation process, the photoreceptor is uniformly charged on its peripheral surface with a predetermined positive or negative potential by the primary charging means, and then is subjected to image exposure from image exposure means such as slit exposure or laser beam scanning exposure. Upon receiving the light, an electrostatic latent image is sequentially formed on the peripheral surface of the photoreceptor, and the formed electrostatic latent image is then toner-developed by the developing means, and the developed toner is developed.
The developed image is sequentially transferred by the transfer means to the transfer material fed from the paper supply section between the photoconductor and the transfer means in synchronization with the rotation of the photoconductor. The transfer material having undergone the image transfer is separated from the photoreceptor surface, introduced into an image fixing means, and subjected to image fixing to be printed out as a copy (copy) outside the apparatus. The surface of the photoreceptor after image transfer is clean.
After the transfer residual toner is removed by the polishing means, the surface is cleaned, and after being subjected to a static elimination treatment by the pre-exposure light from the pre-exposure means, it is repeatedly used for image formation.

[0032]

【Example】

Example 1 Alcohol-soluble copolymerized nylon resin (average molecular weight 29
000) and 30 parts of methoxymethyl 6 nylon (average molecular weight: 32,000) in a mixture of 240 parts of methanol and 80 parts of butanol, to give an undercoat layer coating solution. Was prepared. This coating solution was applied onto an aluminum cylinder (φ30 mm × 260 mm) by dip coating, and dried at 100 ° C. for 20 minutes to form an undercoat layer having a thickness of 1 μm.

Next, disazo pigment 1 having the following structural formula
0 copies,

Embedded image 5 parts of a polyvinyl butyral resin (trade name: BX1, manufactured by Sekisui Chemical Co., Ltd.), 600 parts of tetrahydrofuran, and 300 parts of cyclohexanone were dispersed in a sand mill for 20 hours to prepare a coating solution for a charge generation layer. This coating solution was dip-coated on the undercoat layer, dried at 100 ° C. for 20 minutes, and dried.
A charge generation layer having a thickness of 15 μm was formed.

Next, 10 parts of a styryl compound having the following structural formula

Embedded image Further, 10 parts of a polycarbonate resin (trade name: Panlite, manufactured by Teijin Chemicals Ltd.) was dissolved in 60 parts of chlorobenzene and 20 parts of dichloromethane to prepare a coating solution for a charge transport layer.
This coating solution was dip-coated on the charge generation layer,
It dried at 30 degreeC for 30 minutes, and formed the 20-micrometer-thick charge transport layer.

Next, 55 parts of a curable acrylic monomer having the following structural formula:

Embedded image 5 parts of soda glass (Mohs hardness 5) powder having an average particle diameter of 5 μm, 40 parts of tin oxide having an average particle diameter of 0.01 μm for controlling resistance, and 100 parts of toluene were sand-milled (Vessel, medium co-agate). For 58 hours. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 2 μm (10% of particles having a size of 5 μm or more) and a content of 5%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. This coating solution was spray-coated on the charge transport layer to form a film, dried at 70 ° C. for 5 minutes and then 100 mW with a high-pressure mercury lamp.
UV irradiation for 15 seconds at a high intensity of / cm ²
m was formed to form an electrophotographic photosensitive member.

The prepared electrophotographic photosensitive member was attached to a laser printer in which a process of charging-exposure-development-transfer-cleaning was repeated at a cycle of 1.5 seconds, and an initial image was evaluated. Next, 10,000 sheets of A4 size high-quality paper were durable under an environment of 23 ° C. and 50%. After the electrophotographic photoreceptor was left for 8 hours in an environment of 30 ° C. and 85%, image evaluation was performed in this environment. Table 1 shows the results. Furthermore,
After returning to an environment of 23 ° C. and 50%, the durability of 90000 sheets of A4 size high quality paper was measured, and then the thickness of the protective layer was measured. The results are shown in Tables 1 and 2.

Example 2 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, that is, 55 parts of curable acrylic monomer, 5 parts of soda glass powder having an average particle diameter of 2 μm, and resistance For control, 40 parts of tin oxide having an average particle diameter of 0.01 μm and 100 parts of toluene were dispersed in a sand mill (Vessel, manufactured by Amenow Corporation) for 58 hours. The soda glass powder contained in the protective layer coating solution had a volume average particle size of 0.9 μm (5 μm).
The ratio of particles having a particle size of 2 μm or more was 2%), and the content was 5%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1,
The same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Example 3 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, ie, 55 parts of curable acrylic monomer, 5 parts of soda glass powder having an average particle diameter of 0.02 μm, Further, tin oxide 40 having an average particle diameter of 0.01 μm for resistance control.
Parts and 100 parts of toluene were dispersed in a sand mill (Vessel, Medium Co., Ltd., Menow) for 58 hours. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 0.0
The content was 1 μm (the ratio of particles having a particle size of 5 μm or more was 0%) and the content was 5%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. Table 1 shows the results
And 2.

Example 4 In Example 1, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer 59.999 was used.
Parts, soda glass powder having an average particle diameter of 0.5 μm 0.00
One part, 40 parts of tin oxide having an average particle diameter of 0.01 μm for controlling the resistance, and 100 parts of toluene were dispersed in a sand mill (Vessel, medium and agate) for 58 hours. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 0.2 μm (proportion of particles having a particle size of 5 μm or more 1%) and a content of 0.001%. Further, as a photopolymerization initiator, 2
-1 part of methylthioxanthone was added to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Example 5 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, ie, 60 parts of curable acrylic monomer, tin oxide having an average particle diameter of 0.01 μm for controlling the resistance. 40
Parts, 100 parts of toluene with a sand mill (Vessel super steel,
(Medium soda glass) for 58 hours. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 0.5 μm (the ratio of particles having a volume average particle size of 5 μm or more was 0.01 μm).
%), And the content was 0.04%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Example 6 In Example 1, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer having the following structural formula was used.
55 parts,

Embedded image Zirconia (Mohs hardness 8) powder 5 having an average particle diameter of 3 μm 5
And 40 parts of tin oxide having an average particle diameter of 0.01 μm for controlling the resistance, and 100 parts of toluene were dispersed in a sand mill (Vessel, medium and agate) for 58 hours. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. The zirconia powder contained in the protective layer coating solution had a volume average particle size of 2 μm (ratio of particles having a size of 5 μm or more: 10%) and a content of 5%. Photopolymerization An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the protective layer coating solution, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Example 7 In Example 6, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 4) 60
Parts, 40 parts of tin oxide having an average particle diameter of 0.01 μm for resistance control, and 100 parts of butanol were dispersed in a sand mill (Vessel, made of zirconia with medium) for 58 hours. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 0.5 μm (the ratio of particles having a volume average particle size of 5 μm or more was 0.01 μm).
%), And the content was 0.01%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Example 8 In Example 6, the preparation of the coating solution for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 4) 60
Parts, 40 parts of tin oxide having an average particle size of 0.01 μm for controlling resistance and 100 parts of butanol were dispersed in a sand mill (Vessel, made of zirconia with medium) for 28 hours. The soda glass powder contained in this protective layer coating solution has a volume average particle size of 0.01 μm (the ratio of particles having a volume average particle size of 5 μm or more is 0.0 μm).
1%), and the content was 0.001%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Example 9 In Example 6, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 4) 60
Parts, 40 parts of tin oxide having an average particle diameter of 0.01 μm for resistance control, and 100 parts of butanol were manufactured by a sand mill (vessel: tungsten carbon (Mohs hardness 9)), medium: potash glass (Mohs hardness) 6.5)) for 78 hours. The potash glass powder contained in this protective layer coating solution had a volume average particle size of 0.9 μm (ratio of particles having a size of 5 μm or more: 10%) and a content of 5%. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for this protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are shown in Tables 1 and 2.

Example 10 In Example 1, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer having the following structural formula was used.
50 copies,

Embedded image Tin oxide 6 having an average particle diameter of 0.01 μm for resistance control
0 parts and 100 parts of butanol were mixed with a sand mill (Vessel: made of zirconia, medium: zircon (ZrO ₂ : SiO ₂₎
= 67:32) (Moth hardness 7.5)) for 68 hours. The zircon and zirconia powders contained in this protective layer coating solution had a volume average particle size of 0.5 μm (the ratio of particles having a size of 5 μm or more was 0.1%), and the content was 0.5% of the solid content. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Comparative Example 1 In Example 1, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 3) 60
And 40 parts of tin oxide having an average particle diameter of 0.01 μm for controlling the resistance, and 100 parts of toluene were dispersed in a sand mill (Vessel, medium and agate) for 58 hours. The content of the agate powder contained in the protective layer coating solution was 0.001% based on the solid content. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 2 In Example 1, the preparation of the coating liquid for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 4) 60
And 40 parts of tin oxide having an average particle diameter of 0.01 μm for controlling the resistance, and 100 parts of butanol were dispersed in a sand mill (Vessel, manufactured by Amenou Corporation) for 58 hours. The content of the agate powder contained in the protective layer coating solution was 0.001% based on the solid content. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 3 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 5) 40
Parts, and 60 parts of tin oxide having an average particle diameter of 0.01 μm for controlling resistance and 100 parts of butanol were dispersed by a sand mill (Vessel, medium co-agate (Mohs hardness: 8)) for 58 hours. The content of the agate powder contained in the protective layer coating solution was 0.001% based on the solid content. Further, 1 part of 2-methylthioxanthone was added as a photopolymerization initiator to prepare a coating solution for a protective layer. Except for the protective layer coating solution, an electrophotographic photosensitive member was prepared in the same manner as in Example 1,
The same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 4 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, ie, a non-curable polymethyl methacrylate resin (trade name: J-899, manufactured by Seiko Chemical Co., Ltd.) 55 parts, 5 parts of soda glass powder having an average particle diameter of 5 μm, 40 parts of tin oxide having an average particle diameter of 0.01 μm for resistance control, and 100 parts of toluene by a sand mill (Vessel, made of agate with medium). Time dispersed. The soda glass powder contained in this protective layer coating solution had a volume average particle size of 2 μm (5 μm).
m, the content was 5%. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 5 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, that is, a curable acrylic monomer (formula 3) 55
Parts, 5 parts of gypsum (Moth hardness 2) powder having an average particle diameter of 5 μm, 40 parts of tin oxide having an average particle diameter of 0.01 μm for resistance control, and 100 parts of toluene were sand-milled (Vessel, medium co-agate). For 58 hours. The gypsum powder contained in the protective layer coating solution has a volume average particle size of 2 μm (proportion of particles having a particle size of 5 μm or more 10%) and a content of 5%.
Met. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except for the coating liquid for the protective layer, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 6 In Example 1, the preparation of the coating solution for the protective layer was changed as follows, ie, a non-curable polymethyl methacrylate resin (trade name: J-899, manufactured by Seiko Chemical Co., Ltd.) 60 parts), 40 parts of tin oxide having an average particle diameter of 0.01 μm for resistance control, and 100 parts of toluene were dispersed for 58 hours by a sand mill (Vessel, manufactured by Amenow Corporation). The content of the agate powder contained in the protective layer coating solution was 0.001% based on the solid content. Other than this coating solution for the protective layer,
An electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

[0052]

[Table 1]

[Table 2]

In Example 1, by including a glass material in the protective layer, an electrophotographic photoreceptor having excellent abrasion resistance and having little deterioration in image quality even in a high humidity environment was obtained.
In Example 2, by setting the average particle diameter of the glass material to an appropriate value, higher image quality was obtained from the beginning. In Comparative Examples 1 to 3, since the contents of the glass material and the ceramic material were 0.001% or less, image quality deterioration in a high humidity environment was observed.
When a non-curable resin was used as in Comparative Examples 4 and 6, abrasion was large, and a highly durable electrophotographic photosensitive member could not be obtained. In the case of a material having a Mohs hardness of not more than 3 as in Comparative Example 5, abrasion was large and a highly durable electrophotographic photosensitive member could not be obtained.

[0054]

According to the electrophotographic photoreceptor of the present invention, the protective layer provided on the photosensitive layer contains at least one material selected from glass materials and ceramic materials having a Mohs hardness of 3 or more and a curable resin. By doing so, there is a remarkable effect that the abrasion resistance is excellent, the image quality is less deteriorated even in a high humidity environment, and the durability is high.

[Brief description of the drawings]

FIG. 1 is a process car having an electrophotographic photoreceptor of the present invention.
FIG. 2 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a cartridge.

FIG. 2 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

Claims (9)

[Claims] 1. An electrophotographic photosensitive member having a protective layer provided on a photosensitive layer, wherein the protective layer contains one or more materials selected from glass materials and ceramic materials having a Mohs hardness of 3 or more and a curable resin. An electrophotographic photoreceptor characterized in that: 2. A glass material having a Mohs hardness of 3 or more and ceramic material particles are made of borosilicate glass, potash glass,
2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is at least one material selected from the group consisting of douglas, quartz glass, zirconium compounds, silicon nitride, silicon carbide compounds, and polycrystalline sintered bodies of silica. 3. A glass material having a Mohs hardness of 3 or more and a ceramic material particle having a volume average particle diameter of 0.01 μm or more, and a particle diameter of 5 μm or more having a volume average of 1 μm.
The electrophotographic photoreceptor according to claim 1, wherein the content is 0% or less. 4. The electrophotographic photoreceptor according to claim 1, wherein the volume average particle diameter of the glass material and the ceramic material particles having a Mohs hardness of 3 or more is 0.01 μm or more and 0.9 μm or less. 5. The protective layer has a glass material having a Mohs hardness of 3 or more and a ceramic material particle content of 0.001% or more,
2. The electrophotographic photosensitive member according to claim 1, wherein the content is 5% or less. 6. In the step of dispersing the coating liquid for a protective layer, the mill material or the medium material is a glass material and a ceramic material having a Mohs hardness of 3 or more.
The electrophotographic photoreceptor according to claim 1, wherein the glass material and the ceramic material particles generated by abrasion of the mill material or the medium material are used as the glass material and the ceramic material having a Mohs hardness of 3 or more in the protective layer. 7. The glass material and ceramic material particles having a Mohs hardness of 3 or more contained in the protective layer are materials selected from a zirconium compound, alumina, soda glass and potash glass, and the curable resin is an ultraviolet curable resin. 2. The electrophotographic photosensitive member according to claim 1, wherein 8. The electrophotographic photoreceptor 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 are integrally supported, and are detachably attached to an electrophotographic apparatus main body. A process cartridge characterized by the following. 9. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.