JP2000330314A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which is excellent in slidability, has durability to generation of wear or flaw on a surface by rubbing, has no lowering of surface resistance due to adhesion of corona products generated in repeating electrophotographic processes and can hold picture quality of high grade under high humidity and to provide a process cartridge having the electrtophotogarphic photoreceptor and an electrophotographic device. SOLUTION: In the electrophotographic photoreceptor, a protective layer is formed by containing a binding resin and surface-treated conductive metal oxide fine particles in a dispersed state and surface treatment is executed by using a bifunctional or trifunctional silane-series compound as a first processing agent. Further, the surface treatment is executed by using a surface treating agent selected from a group composed of unifunctional chlorosilane compounds, unifunctional alkoxysilane compounds silazane series compounds as a second processing agent. Further the process cartridge and the electrophotographic device having the electrophotographic photoreceptor are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photosensitive member having a surface protective layer, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic device.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors are required to have required sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process to be used. Is applied to the surface layer of the photoreceptor, that is, the outermost layer, which is most isolated from the support, because electrical and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning are directly applied to them. Durability is required.

Specifically, there is a demand for durability against surface abrasion and scratches caused by rubbing and surface deterioration due to ozone generated during corona charging. On the other hand, there is a problem that the toner is easily attached to the surface layer due to the repetition of the development and the cleaning of the toner. For this purpose, it is required to improve the cleaning property of the surface layer.

Attempts have been made to provide a surface protective layer containing a resin as a main component in order to satisfy the characteristics required for the surface layer as described above. For example, JP-A-57-30843 proposes a protective layer in which resistance is controlled by adding a metal oxide as a conductive powder.

However, the conventional methods have problems in the dispersibility and cohesion of the metal oxide particles in the binder resin, and the conductivity and transparency when used for the protective layer. Phenomena such as non-uniformity, image defects due to unevenness, etc., increase in residual potential due to repeated charging, and decrease in sensitivity.

Dispersing a metal oxide in a protective layer for an electrophotographic photoreceptor controls the electrical resistance of the protective layer itself and prevents an increase in the residual potential in the photoreceptor during repetition of the electrophotographic process. Its main purpose is. The appropriate resistivity of the protective layer for the electrophotographic photosensitive member is 10 ¹⁰ to 10 ¹⁵
Ω · cm.

However, when the resistivity is in the above range, the electric resistance of the protective layer is easily affected by ionic conduction, so that the electric resistance tends to greatly change due to a change in environment. In particular, when the metal oxide is dispersed in the film, the water absorption of the metal oxide surface is high, so that the resistance of the protective layer is reduced in various environments and when the electrophotographic process is repeated. Up to this point it has been extremely difficult to maintain.

In general, when particles are dispersed in a protective layer, in order to prevent scattering of incident light by the dispersed particles, the particle diameter of the particles must be smaller than the wavelength of the incident light, that is, 0.3 μm or less. It is necessary to be. However, metal oxide particles generally have a strong tendency to agglomerate in a resin solution, making uniform dispersion difficult, and secondary aggregation or sedimentation occurs even once dispersed, so that fine particles having a particle size of 0.3 μm or less are stable. It has been extremely difficult to produce a film containing the in a dispersed state. Further, in order to improve the transparency and the uniformity of conductivity, ultrafine particles having a finer particle diameter (a primary particle diameter of 0.1 μm) are required.
(1 μm or less) is required to be dispersed, but such ultrafine particle powders tend to have even worse dispersibility and dispersion stability.

Also, particularly under high humidity, corona products such as ozone and NOx generated by repeated charging adhere to the surface, causing a reduction in the surface resistance of the photoreceptor, causing problems such as image deletion. At present, no protective layer exhibiting satisfactory electrophotographic characteristics has been obtained.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which meets the above-mentioned requirements. That is, the object of the present invention is excellent in slipperiness,
An object of the present invention is to provide an electrophotographic photosensitive member having durability against abrasion and scratches on the surface due to rubbing, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

Another object of the present invention is to provide an electrophotographic photoreceptor capable of maintaining a high quality image even under a high humidity without a decrease in surface resistance due to the adhesion of corona products generated in a repeated electrophotographic process. An object of the present invention is to provide a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

Still another object of the present invention is to provide an electrophotographic photosensitive member having stable electrophotographic characteristics without accumulation of residual potential and a decrease in sensitivity in a repeated electrophotographic process, and a process cartridge having the electrophotographic photosensitive member. And an electrophotographic apparatus.

[0013]

According to the present invention, there is provided an electrophotographic photoreceptor having a photoconductive layer and a protective layer on a conductive support, wherein the protective layer comprises a binder resin and a surface-treated conductive metal. Such a surface treatment is performed by first using a bifunctional or trifunctional silane-based compound as a first treating agent, and further performing a monofunctional as a second treating agent. And an electrophotographic photosensitive member having a surface treated with a surface treating agent selected from the group consisting of a chlorosilane compound, a monofunctional alkoxysilane compound and a silazane compound, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. You.

[0014]

Embodiments of the present invention will be described below in detail.

As described above, when a film in which conductive metal oxide fine particles are dispersed in a binder resin is used for a protective layer of an electrophotographic photosensitive member, there are problems in dispersibility of fine particles and environmental stability of electric resistance of the film. Sex.

As a means of solving the above problems, the inventors of the present invention have conducted various studies on the surface treatment of conductive metal oxide fine particles. First, the surface treatment was carried out with a bifunctional or trifunctional silane compound. After that, it was found that surface treatment with a surface treatment agent selected from the group consisting of a monofunctional chlorosilane compound, a monofunctional alkoxysilane compound and a silazane compound was very effective. In this case, examples of the first silane-based surface treatment agent include, but are not limited to, bifunctional or trifunctional alkoxysilane compounds and chlorosilane compounds as shown in Table 1 below. .

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

Generally, the reactivity of the silane-based surface treatment agent is S
It is said that the higher the number of functional groups around the i atom, the higher the number of functional groups. However, as a detriment, gelation occurs before or during the surface treatment due to the dehydration / condensation reaction between the treatment agents, and the surface treatment efficiency is reduced or the surface treatment is performed. After that, many unreacted hydroxyl groups which did not participate in the dehydration condensation reaction with the surface of the metal oxide fine particles remain, and the water absorption of the fine particles cannot be sufficiently reduced despite the surface treatment.

On the other hand, it is considered that a monofunctional silane compound may be used to minimize the condensation between the treating agents and the generation of unreacted hydroxyl groups. There is a disadvantage that the reaction efficiency is extremely reduced. This is particularly noticeable when the alkyl chain directly connected to the Si atom is long, etc., and the surface is treated with a modified alkylated silane treating agent such as an alkyl fluoride-based, alkylamino-based, or acrylic silane-based treating agent depending on the application. If not, it is not suitable.

In such a case, the surface treatment efficiency is improved by using a bifunctional or higher-functional silane compound, and the remaining hydroxyl groups are monofunctional chlorosilane compounds and monofunctional alkoxysilane compounds as a second treating agent. The above object can be achieved by capping with a surface treatment agent selected from the group consisting of silazane compounds. In addition, a monofunctional chlorosilane compound, a monofunctional alkoxysilane compound, and a silazane-based compound are considered to work effectively as a capping agent for hydroxyl groups and the like remaining on the surface of the metal oxide. The monofunctional chlorosilane compound, the monofunctional alkoxysilane compound and the silazane-based compound generate monosilanol by hydrolysis, and the monosilanol is dehydrated and condensed with the remaining hydroxyl groups, thereby increasing the hydrophobicity.

Table 2 shows specific examples of the monofunctional chlorosilane compound.
However, if the purpose is merely to cap the remaining hydroxyl groups, Compound Example No. It is generally considered that 1-1 trimethylchlorosilane is used, but other chlorosilane compounds may be used depending on the use, and the present invention is not necessarily limited to these.

[0024]

[Table 4]

Specific examples of the monofunctional alkoxysilane compound are shown in Table 3. If the purpose is merely to cap the remaining hydroxyl groups, Compound Example No. It is generally considered that 2-1 trimethylmethoxysilane is used, but other alkoxysilane compounds may be used depending on the use, and the present invention is not necessarily limited to these.

[0026]

[Table 5]

Specific examples of the silazane compound are shown in Table 4. If the purpose is merely to cap remaining hydroxyl groups, Compound Example No. It is generally considered to use 3-1 hexamethyldisilazane, but other silazane compounds may be used depending on the use, and the present invention is not necessarily limited to these.

[0028]

[Table 6]

As a method of surface treatment, there are a wet method and a dry method. Furthermore, the first silane compound, the second monofunctional chlorosilane compound, the monofunctional alkoxysilane compound, and the silazane compound can be combined. In the wet method, the conductive metal oxide fine particles and the first silane-based compound are first dispersed in a solvent, and the silane compound is attached to the surface of the fine particles. As the dispersing means, general dispersing means such as a ball mill and a sand mill can be used. Next, after the dispersion solution is dried by a dryer to remove the solvent, heat treatment is further performed to fix the silane compound on the surface of the conductive metal oxide fine particles.

Further, as for the treatment of the second monofunctional chlorosilane compound, monofunctional alkoxysilane compound and silazane compound, the wet method of dispersing, drying and heat-treating in a solvent in the same manner as in the first treatment, Any of dry methods of directly mixing, kneading, drying, and heat-treating without using a solvent may be used. At this time, in order to sufficiently hydrolyze the monofunctional chlorosilane compound, the monofunctional alkoxysilane compound, and the silazane-based compound, it is important to absorb the fine particle powder before the second treatment. If necessary, fine particles may be pulverized before each treatment. As another method, it is possible to first treat the silane compound in a dry manner and then perform the second treatment in a wet or dry manner, and the method can be the same as described above.

Examples of the conductive metal oxide used in the present invention include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony-doped tin oxide, oxide Zirconium and the like can be mentioned. One type or two or more types of these ultrafine particles of metal oxide are used in combination. When two or more types are used, they may be fine particles in the form of a solid solution or fusion. The average particle size of such a metal oxide is preferably 0.3 μm or less, more preferably 0.1 μm or less.

In the present invention, the ratio of the silane compound to the conductive metal oxide fine particles depends on the particle size of the fine particles, the structure and the molecular weight of the surface treating agent, and is 1 to 50% by weight.
Is more preferable, and more preferably 3 to 40% by weight. The ratio of the monofunctional chlorosilane compound, the monofunctional alkoxysilane compound, and the silazane-based compound as the second treating agent depends on the amount of the remaining hydroxyl group, but the amount depends on the amount of the silane-based compound as the first treating agent. On the other hand, the minimum amount may be about the same as the number of moles of the functional group.

In particular, when trimethylchlorosilane, trimethylmethoxysilane, and hexamethyldisilazane are used, the excess of them is all hydrolyzed to produce trimethylsilanol, and thereafter, these two molecules gather to form trimethylsilyl ether. Since it is inert and has a low boiling point, it can be removed by the final heat treatment.

Examples of the binder resin for the protective layer used in the present invention include commercially available resins such as acrylic resins, polyesters, polycarbonates, polystyrenes, celluloses, polyethylene, polypropylene, polyurethanes, epoxy resins, silicone resins, and polyvinyl chloride. Can be used. Among these resins, it is preferable to use a curable resin in view of the surface hardness and abrasion resistance of the protective layer, the dispersibility of fine particles, and the stability after dispersion. That is, the conductive metal oxide fine particles subjected to the above-mentioned surface treatment are dispersed in a solution of a resin containing a monomer or an oligomer which is cured by heat or light to form a coating liquid for a protective layer. The protective layer formed by coating and curing on the
It is more excellent in hardness, abrasion resistance and the like.

The monomer or oligomer which is cured by heat or light has, for example, a functional group which causes a polymerization reaction at the end of the molecule by the energy of heat or light. The monomer is a monomer, and the structural unit of the monomer is a monomer. Are relatively large molecules having a repetition of about 2 to 20 are oligomers. Examples of the functional group that causes a polymerization reaction include acryloyl groups, methacryloyl groups, vinyl groups, groups having a carbon-carbon double bond such as an acetophenone group, silanol groups, and those that cause ring-opening polymerization such as a cyclic ether group, or phenol. And those in which two or more types of molecules react and cause polymerization, such as formaldehyde.

The ratio between the resin and the surface-treated conductive metal oxide fine particles is a value that directly determines the resistance of the protective layer, and the resistivity of the protective layer is in the range of 10 ¹⁰ to 10 ¹⁵ Ω · cm. Set to be.

In the photoreceptor of the present invention, additives such as a coupling agent and an antioxidant may be added to the protective layer for the purpose of improving dispersibility, binding property and weather resistance.
The protective layer is formed by applying a solution in which a metal oxide is dispersed in the binder resin and curing the solution.

Next, the photosensitive layer will be described. The configuration of the photoconductive layer of the electrophotographic photoreceptor of the present invention may be a single layer type containing both a charge generating material and a charge transporting material, or a laminated type in which the charge generating layer and the charge transporting layer are laminated on a conductive substrate. Is one of Hereinafter, a laminated electrophotographic photosensitive member will be described.

The laminated photosensitive layer may be a layer in which a charge generation layer and a charge transport layer are laminated on a conductive support in this order, or may be a layer in which a charge transport layer and a charge generation layer are laminated in this order. Good.

The support in the electrophotographic photoreceptor of the present invention is not particularly limited as long as it has conductivity. For example, a metal such as aluminum, copper, chromium, nickel, zinc and stainless steel is formed into a drum or sheet. Molded, aluminum or copper metal foil laminated on plastic film, aluminum, indium oxide, tin oxide, etc. deposited on plastic film, conductive material applied alone or with binder resin to form conductive layer Metal, plastic film, paper and the like.

The charge transport layer of the laminated electrophotographic photoreceptor is made of a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene, or phenanthrene in a main chain or a side chain thereof, such as indole, carbazole, oxadiazole, and pyrazoline. It is formed using a coating solution in which a charge transporting material such as a nitrogen-containing ring compound, a hydrazone compound, a styryl compound or the like is dissolved in a resin having a film-forming property.

As the resin having such a film forming property,
For example, polyester, polycarbonate, polystyrene, polymethacrylate and the like can be mentioned. The thickness of the charge transport layer is preferably from 5 to 40 μm, and more preferably from 10 to 30 μm.

The charge generation layer of the laminated electrophotographic photoreceptor is made of an azo pigment such as Sudan Red or Diane Blue, a quinone pigment such as pyrenequinone or anthantrone, a quinocyanine pigment, a perylene pigment, an indigo pigment such as indigo or thioindigo, or a phthalocyanine pigment. Or the like is dispersed in a binder resin such as polyvinyl butyral, polystyrene, polyvinyl acetate, and an acrylic resin, and this dispersion is applied, or the pigment is formed by vacuum evaporation. The thickness of such a charge generating layer is preferably 5 μm or less, more preferably 0.05 to 3 μm.

In the electrophotographic photoreceptor of the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the conductive layer and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, alcohol-soluble amide, polyurethane, gelatin or the like. The thickness of the undercoat layer is suitably from 0.1 μm to 3 μm.

As described above, the electrophotographic photoreceptor of the present invention has a protective layer on the photosensitive layer, and the conductive metal oxide fine particles contained in the protective layer contain bifunctional or trifunctional silane. After the surface treatment with the compound, the surface treatment is performed with a surface treatment agent selected from the group consisting of a monofunctional chlorosilane compound, a monofunctional alkoxysilane compound and a silazane-based compound as a second treatment agent. It is an electrophotographic photosensitive member. Therefore, in the present invention, it was possible to form a uniform protective layer having good dispersibility of the metal oxide fine particles and small fluctuation in the resistance environment. As a result,
It has become possible to provide an electrophotographic photoreceptor having no image defects such as fog and black spots, extremely high abrasion resistance and environmental resistance, and excellent electrophotographic characteristics.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus using a process cartridge having an 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 a shaft 2 at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 rotates during the rotation process.
The peripheral surface is uniformly charged at a predetermined positive or negative potential by the primary charging means 3, and then, the time-series electricity of target image information output from exposure means (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 which has been enhanced and modulated according to the digital image signal is received. Thus, an electrostatic latent image corresponding to the target image information 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 7 taken out of the paper supply unit (not shown) between the photoreceptor 1 and the transfer unit 6 in synchronization with the rotation of the photoreceptor 1 and fed. The formed and carried toner images are sequentially transferred by the transfer means 6.

The transfer material 7 to which the toner image has been transferred is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing to be printed out of the apparatus as an image formed product (print, copy). You.

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by removing the untransferred toner by the cleaning means 9, and is further cleaned by a pre-exposure light 10 from a pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, among the components such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9 described above, a plurality of components are housed in a container 11 and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and is detachably attached to the apparatus main body using a guide unit 12 such as a rail of the apparatus main body. It can be a process cartridge.

When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam is emitted in accordance with the signal. Beam scanning, LED
Light emitted by driving the array, driving the liquid crystal shutter array, and the like.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as CRT printers, LED printers, faxes, liquid crystal printers, and laser plate making.

[0054]

The present invention will be described below in more detail with reference to specific examples. In addition, "part" in an Example shows a weight part.

Example 1-1 On an aluminum cylinder (30 mmφ × 260 mm), 10 parts of an alcohol-soluble polyamide resin (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) and a methokidimethylated 6 nylon resin ( Product name: Toresin EF-30T, manufactured by Teikoku Science Co., Ltd.) 30 parts was dissolved in a mixed solvent of 150 parts of methanol / 150 parts of butanol, and the mixture was applied by dipping.
By drying at 10 ° C. for 10 minutes, an undercoat layer having a thickness of 1 μm was formed.

Next, the compound is represented by the following structural formula (1).

[0057]

Embedded image After dispersing 4 parts of disazo pigment, 2 parts of butyral resin (trade name: Eslex BL-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone for 48 hours using a sand mill, 100 parts of tetradrofuran (THF) are dispersed. Was added to prepare a dispersion for the charge generation layer. This dispersion was applied on the undercoat layer by an immersion method and dried at 80 ° C. for 5 minutes to form a charge generation layer having a thickness of 0.15 μm.

Next, the compound is represented by the following structural formula (2).

[0059]

Embedded image 10 parts of styryl compound and polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
10 parts of dichloromethane 20 parts / monochlorobenzene 6
The solution was dissolved in 0 parts of a mixed solvent, the solution was applied on the charge generation layer by an immersion method, and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 18 μm.

Next, a preparation liquid for the protective layer was prepared according to the following procedure.

Antimony-containing tin oxide fine particles having an average particle size of 0.02 μm (trade name: T-1, Mitsubishi Materials Corporation)
50 parts, Compound Example No. Compound 10 of 3
And 300 parts of methanol were stirred for 48 hours with a stirrer, and the solution was filtered and washed, dried, and further heat-treated at 150 ° C. for 2 hours. After that, once the fine particles were sufficiently absorbed by humidification treatment, Compound Example No.
30 parts of the compound 1-1 and 300 parts of toluene were added, and the mixture was stirred for 48 hours with a stirrer. Then, the solution was filtered, washed, dried, and further heat-treated at 150 ° C. for 2 hours.

Next, it is represented by the following structural formula (3)

[0063]

Embedded image 50 parts of an acrylic curable monomer, 0.1 part of 2-methylthioxanthone as a photopolymerization initiator, 40 parts of the conductive fine particles subjected to the surface treatment, and 50 parts of toluene were mixed and dispersed in a sand mill for 96 hours, A preparation for the protective layer was prepared.

Using this mixture, a film was formed on the charge transport layer by spray coating, and after drying, 8 mw with a high pressure mercury lamp.
UV irradiation for 20 seconds at a light intensity of 5 μm / cm ²
m of the protective layer was formed to obtain an electrophotographic photosensitive member.

The electrophotographic photosensitive member produced in this manner was mounted on a copying machine in which a charging-exposure-development-transfer-cleaning process was repeated in a cycle of 1.5 seconds.
The electrophotographic properties were evaluated at room temperature and normal humidity of 50 ° C./50% RH, and at low temperature and low humidity of 10 ° C./15% RH and at 35 ° C./85.
Image evaluation under high temperature and high humidity of% RH, and repeated 100,000 times of surface exposure under normal temperature and normal humidity and 10,000 times of repeated surface exposure under high temperature and high humidity.

As a result, as compared with the electrophotographic photosensitive member without the protective layer shown in Comparative Example 1-1, the sensitivity and the residual potential were equivalent, and an image free from unevenness and black spots could be obtained. In addition, a stable image could be maintained even after 100,000 repetitions of normal temperature and normal humidity and 10,000 repetitions of high temperature and high humidity. The results are shown in Table 1-1.

The dark part potential is the surface potential of the electrophotographic photosensitive member when discharged at a corona discharge voltage +5 KV, and the larger the value, the better the charging ability. The sensitivity is indicated by an exposure amount required to attenuate the surface potential from 700 V to 200 V, and a smaller value indicates higher sensitivity.

(Example 1-2) In Example 1-1,
Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the treatment of the monofunctional chlorosilane compound of 1-1 was changed to a dry method. The results are shown in Table 1-1.

(Example 1-3) In Example 1-1,
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that Example 21 was used. The results are shown in Table 1-1.

(Example 1-4) In Example 1-1,
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that Example 19 was used. The results are shown in Table 1-1.

(Example 1-5) In Example 1-1,
Compound Example No. 1-1 as Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that 1-5 was used. The results are shown in Table 1-1.

(Example 1-6) In Example 1-1,
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the curable acrylic monomer was changed to 40 parts of the following structural formula (4). The results are shown in Table 1-1.

[0073]

Embedded image

(Comparative Example 1-1) In Example 1-1,
An electrophotographic photosensitive member was prepared in the same manner as in Example 1-1 except that the protective layer was not provided, and the same evaluation was performed. As a result, the electrophotographic characteristics were good at the initial stage, but when durability was performed at normal temperature and normal humidity, the charging ability was reduced, and a good image could not be obtained from about 70,000 sheets. The results are shown in Table 1-1.

(Comparative Example 1-2) In Example 1-1,
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the surface treatment of the conductive fine particles used for the protective layer was not performed. As a result, image blurring occurred from an early stage in a high-temperature and high-humidity environment, and image blurring was observed in durability at normal temperature and normal humidity. The results are shown in Table 1-1.

(Comparative Example 1-3) In Example 1-1,
Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the second chlorosilane surface treatment according to 1-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 1-1.

(Comparative Example 1-4) In Example 1-3,
Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-3, except that the second chlorosilane surface treatment according to 1-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 1-1.

(Comparative Example 1-5) In Example 1-4,
Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-4, except that the second chlorosilane surface treatment according to 1-1 was not performed. As a result, under high temperature and high humidity, image blur was observed after 10,000 times of image output durability. The results are shown in Table 1-1.

[0079]

[Table 7]

(Example 2-1) In Example 1-1,
Compound Example No. The monofunctional chlorosilane compound of No. 1-1 was used as a compound example No. in Table 3. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1 except that the monofunctional alkoxysilane compound of 2-1 was used. Table 2-
It is shown in FIG.

(Example 2-2) In Example 2-1
Compound Example No. in Table 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that the treatment of the 2-1 monofunctional alkoxysilane compound was changed to a dry method. The results are shown in Table 2-1.

(Example 2-3) In Example 2-1,
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that the photosensitive member was replaced with 21. The results are shown in Table 2-1.

(Example 2-4) In Example 2-1,
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that 19 was used. The results are shown in Table 2-1.

(Example 2-5) In Example 2-1,
Compound Example No. in Table 3 2-1 is a compound example no. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that 2-2 was used. The results are shown in Table 2-1.

(Example 2-6) In Example 2-1,
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that the curable acrylic monomer was replaced with 40 parts of the structural formula (4). The results are shown in Table 2-1.

(Comparative Example 2-1) In Example 2-1.
An electrophotographic photosensitive member was prepared in the same manner as in Example 2-1 except that the protective layer was not provided, and the same evaluation was performed. As a result, the electrophotographic characteristics were good at the initial stage, but when durability was performed at normal temperature and normal humidity, the charging ability was reduced, and a good image could not be obtained from about 70,000 sheets. The results are shown in Table 2-1.

(Comparative Example 2-2) In Example 2-1
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that the surface treatment of the conductive fine particles used for the protective layer was not performed. As a result, image blurring occurred from an early stage in a high-temperature and high-humidity environment, and image blurring was observed in durability at normal temperature and normal humidity. The results are shown in Table 2-1.

(Comparative Example 2-3) In Example 2-1,
Compound Example No. in Table 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that the second alkoxysilane surface treatment according to 2-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 2-1.

(Comparative Example 2-4) In Example 2-3,
Compound Example No. in Table 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-3, except that the second alkoxysilane surface treatment according to 2-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 2-1.

(Comparative Example 2-5) In Example 2-4,
Compound Example No. in Table 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-4, except that the second alkoxysilane surface treatment according to 2-1 was not performed. As a result, under high temperature and high humidity, image blur was observed after 10,000 times of image output durability. The results are shown in Table 2-1.

[0091]

[Table 8]

(Example 3-1) In Example 1-1,
Compound Example No. The monofunctional chlorosilane compound of 1-1 was used as the compound example No. in Table 4. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that the silazane compound of 3-1 was used. The results are shown in Table 3-1.

(Example 3-2) In Example 3-1
Compound Example No. in Table 4 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3-1 except that the treatment of the silazane compound of 3-1 was changed to a dry method. The results are shown in Table 3-1.

(Example 3-3) In Example 3-1
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-1 except that 21 was used. The results are shown in Table 3-1.

(Example 3-4) In Example 3-1
Compound Example No. Compound No. 3 as Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-1 except that 19 was used. The results are shown in Table 3-1.

(Example 3-5) In Example 3-1
Compound Example No. in Table 4 3-1 is a compound example No. 3-1. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-1 except that 3-2 was used. The results are shown in Table 3-1.

(Example 3-6) In Example 3-1
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3-1 except that the curable acrylic monomer was changed to 40 parts of the structural formula (4). The results are shown in Table 3-1.

(Comparative Example 3-1) In Example 3-1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-1 except that the protective layer was not used. As a result, the electrophotographic characteristics were good at the initial stage, but when durability was performed at normal temperature and normal humidity, the charging ability was reduced, and a good image could not be obtained from about 70,000 sheets. The results are shown in Table 3-1.

(Comparative Example 3-2) In Example 3-1
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3-1 except that the surface treatment of the conductive fine particles used for the protective layer was not performed. As a result, image blurring occurred from an early stage in a high-temperature and high-humidity environment, and image blurring was observed in durability at normal temperature and normal humidity. The results are shown in Table 3-1.

(Comparative Example 3-3) In Example 3-1.
Compound Example No. in Table 4 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3-1 except that the second silazane surface treatment according to 3-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 3-1.

(Comparative Example 3-4) In Example 3-3,
Compound Example No. in Table 4 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3-3, except that the second silazane surface treatment according to 3-1 was not performed. As a result, under high temperature and high humidity, the charging ability was reduced and a good image could not be obtained. The results are shown in Table 3-1.

(Comparative Example 3-5) In Example 3-4,
Compound Example No. in Table 4 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-4, except that the second silazane surface treatment according to 3-1 was not performed. As a result, under high temperature and high humidity, image blur was observed after 10,000 times of image output durability. The results are shown in Table 3-1.

[0103]

[Table 9]

[0104]

As described above, according to the present invention,
Excellent slipperiness, durability against surface abrasion and scratches caused by rubbing, and no reduction in surface resistance due to corona product adhesion repeatedly generated in the electrophotographic process, even under high humidity It has become possible to provide a photoconductor for electrophotography capable of maintaining high-quality image quality, a process cartridge having the electrophotographic photoconductor, and an electrophotographic apparatus.

[Brief description of the drawings]

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoconductor 2 shaft 3 charging means 4 exposure light 5 developing means 6 transfer means 7 transfer material 8 fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge container 12 guide means

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Michiyo Sekiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Shoji Amemiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon F term (reference) 2H068 AA04 BA58 CA22 CA37 CA40 FA03 FA07 FA27 FC08

Claims (9)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer and a protective layer on a conductive support, wherein the protective layer contains a binder resin and surface-treated conductive metal oxide fine particles in a dispersed state. The surface treatment is performed by first performing a surface treatment using a bifunctional or trifunctional silane-based compound as a first treatment agent, and further performing a surface treatment with a monofunctional chlorosilane compound as a second treatment agent. An electrophotographic photoreceptor, comprising: 2. An electrophotographic photoreceptor having a photoconductive layer and a protective layer on a conductive support, wherein the protective layer contains a binder resin and surface-treated fine particles of a conductive metal oxide in a dispersed state. The surface treatment is performed by first performing a surface treatment using a bifunctional or trifunctional silane-based compound as a first treatment agent, and further performing a surface treatment with a monofunctional alkoxysilane compound as a second treatment agent. An electrophotographic photoreceptor, characterized in that: 3. An electrophotographic photoreceptor having a photoconductive layer and a protective layer on a conductive support, wherein the protective layer contains a binder resin and surface-treated fine particles of a conductive metal oxide in a dispersed state. The surface treatment is performed by first performing a surface treatment using a bifunctional or trifunctional silane-based compound as a first treatment agent, and further performing a surface treatment with a silazane-based compound as a second treatment agent. An electrophotographic photosensitive member characterized by the following. 4. The electrophotographic photoconductor according to claim 1, wherein the first processing agent is an alkoxysilane compound or a chlorosilane compound. 5. The electrophotographic photosensitive member according to claim 1, wherein the second processing agent is trimethylchlorosilane. 6. The electrophotographic photosensitive member according to claim 1, wherein the second processing agent is trimethylmethoxysilane. 7. The electrophotographic photosensitive member according to claim 1, wherein the second processing agent is hexamethyldisilazane. 8. An electrophotographic photosensitive member according to claim 1, a charging means for charging the electrophotographic photosensitive member, and a developing device for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner. Means and at least one means selected from the group consisting of a cleaning means for recovering the toner remaining on the photoreceptor after the transfer step, and are integrally supported and detachable from the main body of the electrophotographic apparatus. Process cartridge. 9. An electrophotographic photoreceptor according to claim 1, a charging means for charging said electrophotographic photoreceptor, and exposing the charged electrophotographic photoreceptor to form an electrostatic latent image. An electrophotographic apparatus comprising: an exposure unit; a developing unit that develops an electrophotographic photosensitive member on which an electrostatic latent image is formed with a toner; apparatus.