JP2002139857A - Electrophotographic photoreceptor, electrophotographic device and method for manufacturing electrophotogaphic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture an electrophotographic photoreceptor realizing the restraint of the fusion of toner, having a high toner recovering rate, restrained from being unevenly ground by a cleaning blade, and realizing the reduction of the soiling of an electrifier wire and the restraint of the occurrence of a leak spot. SOLUTION: The surface layer of an a-C system is formed under a film deposition condition (area 2) that the deposition rate of the surface layer is lowered with the increase of high frequency applied power for generating plasma.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor having sensitivity to light such as ultraviolet rays, visible rays, infrared rays, X-rays and .gamma.-rays. The present invention relates to an electrophotographic photoreceptor in which an amorphous carbon-based (hereinafter also referred to as aC-based) surface layer is formed on a photoconductive layer of Si-based.

[0002]

2. Description of the Related Art Materials used for a photoconductive layer of an electrophotographic photosensitive member include selenium, cadmium sulfide, zinc oxide, and the like.
Materials such as phthalocyanine and a-Si-based materials can be mentioned. Among them, hydrogenated a-Si (hereinafter, a-Si: H
A-Si) and halogenated a-Si (hereinafter a-Si:
X) is higher in surface hardness than a photoconductive layer made of another material, and has high sensitivity to long-wavelength light (770 nm to 800 nm) generated from a semiconductor laser or the like. Has good durability and photoelectric properties. Furthermore, these photoconductive layers have high sensitivity, high S / N ratio, good absorption spectrum characteristics, fast photoresponse,
A desired dark resistance value can be realized, and it has desirable characteristics such as being harmless to the human body.For these reasons, an electrophotographic photosensitive member having an a-Si-based photoconductive layer is
It is being widely used in electrophotographic apparatuses, such as high-speed copiers and laser printers (hereinafter, also referred to as LBPs), which require high durability and photoelectric properties.

[0003] a-Si: H and a-Si: X are obtained by a sputtering method or a method of decomposing a source gas by heat (thermal CVD).
Method), a method of decomposing a source gas by light (photo CVD)
Method), a method of decomposing a source gas by plasma (plasma CVD method), and the like.
The photoconductive layer of the electrophotographic photoreceptor is manufactured by a plasma CVD method because dense deposition is possible. That is, the raw material gas is decomposed by glow discharge or the like by direct current or high frequency (RF, VHF), microwave, or the like,
Glass, quartz, heat-resistant synthetic resin film, stainless steel,
A-Si: H and a-Si on a conductive substrate such as aluminum
Deposit Si: X to form a photoconductive layer.

[0004] However, a-Si: H and a-S
The surface of the photoconductive layer made of i: X is easily deteriorated by environmental humidity and chemical species generated by corona discharge. Therefore, when an electrophotographic photosensitive member having these photoconductive layers is used, Although a good image was obtained in the early stage, an image defect sometimes occurred after a relatively short period of use.

[0005] In order to solve this problem, it has been proposed to form an amorphous silicon carbide (hereinafter a-SiC) surface layer on the photoconductive layer to protect the photoconductive layer. . For example, in JP-A-57-115551, a silicon atom and a carbon atom are used as a base,
Non-photoconductive amorphous material containing hydrogen atom,
It has been disclosed to form a surface barrier layer. Japanese Patent Application Laid-Open No. 57-115559 discloses that a surface barrier layer composed of a non-photoconductive amorphous material containing a silicon atom and a carbon atom as a base and containing a halogen atom is disclosed. However, despite the provision of these surface layers, the durability of the electrophotographic photoreceptor was sometimes insufficient.

In order to solve the above-mentioned problems, it has been proposed to form an aC-based surface layer as a surface layer having a further excellent protective effect. For example, hydrogenated amorphous carbon containing 10 to 40 atm% hydrogen atoms (hereinafter a-
The formation of a surface layer by C: H was disclosed in JP-A-61-219961. Further, Japanese Patent Application Laid-Open No. Hei 6-317920 discloses that a frequency of 20 MHz to 4 MHz is used.
It has been disclosed that a surface layer is formed from a non-single-crystal carbon-based material having carbon atoms as a base by a plasma CVD method in which a source gas is decomposed by a glow discharge generated by an electromagnetic wave of 50 MHz. Further, Japanese Patent Application Laid-Open No. 8-158050 discloses that a DLC film (diamond-like carbon film) having high hardness is provided as a surface layer by using an ECR plasma method.

[0007]

However, the required performance of an electrophotographic apparatus is continually becoming more sophisticated, and a-C
With respect to the electrophotographic photoreceptor having the system surface layer formed thereon, further improvements in the performance described below have been desired.

First, for the following reasons, toner fusion on the surface of the electrophotographic photosensitive member, that is, toner is prevented from melting and adhering and depositing on the surface of the electrophotographic photosensitive member during long-term use, It has been required to achieve good toner recovery.

In an electrophotographic apparatus, an electric latent image is formed on an electrophotographic photosensitive member by means such as charging, static elimination, exposure, and the like, and then this electric latent image is developed with toner, and a toner image is formed on a transfer material. After the transfer, the toner image is fixed by heat, pressure, solvent vapor or the like. Further, untransferred toner remaining on the electrophotographic photosensitive member is recovered by cleaning.

The weight average particle diameter of the toner used for the above-mentioned development has conventionally been about 10 to 12 μm. However, in recent years, the demand for more vivid and precise images has been increasing. The size reduction of toner particles has been promoted. However, as compared with the conventional toner having a particle size, the toner having a small particle size is more difficult to be removed from the surface of the electrophotographic photosensitive member by cleaning, and thus may sometimes remain on the surface of the electrophotographic photosensitive member. For this reason, a toner having a small particle diameter tends to cause a problem of fusing, and the recovery efficiency is sometimes low.

Further, the fixing efficiency of a toner image on a transfer material can be improved by using a toner having a low melting point, and a toner having a lower melting point is being used in order to cope with a recent increase in printing speed. . Further, with the spread of full-color electrophotographic apparatuses, color toners are being used for general purposes. However, color toners have a lower melting point than conventional black-and-white toners. In addition, the conventional image fixing device has a built-in heater, and the fixing roller is kept at a temperature of 150 ° C. to 200 ° C., and the toner is fixed on the transfer material by melting the toner. In order to reduce the power consumption of the image forming apparatus, it has been studied to lower the temperature of the fixing roller by using a low melting point toner. For the above reasons, the use of low-melting toner is becoming the mainstream in electrophotographic devices, but the low-melting toner softens at low temperatures, so it easily fuses to the surface of the electrophotographic photosensitive member and is recovered by cleaning. In some cases, the efficiency was low.

When the toner is fused to the surface of the electrophotographic photoreceptor, image defects and fusing marks in a solid white image and a halftone image may occur. It is necessary to go out and perform maintenance first, which increases costs. In addition, since the maintenance is performed by removing the electrophotographic photosensitive member from the main body of the electrophotographic apparatus, there is a danger that dent scratches may be made on the electrophotographic photosensitive member during the operation, and the electrophotographic photosensitive member may become unusable.

Such artificial scratches on the surface of the electrophotographic photosensitive member can be suppressed by, for example, increasing the hardness of the surface layer or increasing the thickness of the surface layer itself. However, from the balance between the other properties of the surface layer and the balance between the band gap of the surface layer and the sensitivity of the electrophotographic photosensitive member,
There were restrictions on the hardness and thickness of the surface layer.

Secondly, there has been a demand for suppressing the uneven wear of the surface of the electrophotographic photosensitive member by the blade when cleaning, that is, removing the toner from the surface of the electrophotographic photosensitive member.

The cleaning is usually performed using a blade and a mag roller (cleaning roller using a magnetic brush) in combination. However, as described above, in order to efficiently remove and recover toner having a small particle diameter and low melting point, and to reduce the fusion of the toner, the hardness of the blade is increased or the pressing pressure of the blade is reduced. When the height is increased, in the case of an electrophotographic photoreceptor having a high hardness surface layer such as an a-Si system, the surface layer is not polished smoothly, and uneven unevenness is generated in a streak shape,
In some cases, image quality was impaired. Such a phenomenon is
This is particularly noticeable when the blade has a high hardness and a high pressing pressure.Therefore, it is possible to increase the hardness and the pressing pressure of the blade to values necessary for suppressing fusion of the toner and achieving a high recovery rate. It was often difficult.

Thirdly, it is necessary to suppress the contamination of the charger wire of the corona charger and to prevent the occurrence of leak spots on the surface layer due to abnormal discharge. It has been demanded in fields such as copying machines and LBP.

A corona charger is a device that generates a corona discharge by applying a high voltage to a charger wire built in the corona charger and forms an electrophotographic image prior to forming an electric latent image on an electrophotographic photosensitive member. This is provided to uniformly charge the photosensitive member. By performing such a charging process, unevenness in image density and separation / retransfer are suppressed, and a high-quality image can be stably obtained.

However, when the electrophotographic apparatus is operated at a high speed, a minute vibration called chatter may occur on the cleaning blade. If the operation is continued for a long time in a state where chatter has occurred, the cleaning blade cannot withstand vibration, deteriorates rapidly, generates toner slippage, and toner may scatter in the electrophotographic apparatus. Was.

If the operation is further continued in such a state, the scattered toner may adhere to the charger wire of the corona charger, and the charger wire may be stained. As a result, abnormal discharge is induced between the contaminated portion of the charger wire and the electrophotographic photosensitive member, and particularly, when spark discharge occurs, a leak spot is formed on the a-Si type electrophotographic photosensitive member. As a result, image missing such as white spots on a solid black image may occur.

Further, if the charger wire becomes contaminated, potential unevenness may be caused. This causes a problem in normal development (a method of developing a non-exposed portion on the surface of an electrophotographic photosensitive member). In some cases, streak-like white spots, scale-like black haze spreading over the entire image, and black spots that occur locally without periodicity, etc., lower the image quality.

For the above reasons, it has been particularly desired in the fields of high-speed copying machines, LBPs and the like to suppress the contamination of the charger wire of the corona charger and to prevent the deterioration of image quality by preventing leakage spots.

In view of the circumstances described above, fusion of toner is suppressed, toner recovery is high, uneven polishing by the cleaning blade is suppressed, and contamination of the charger wire is reduced. An aC-based surface layer in which the occurrence of leak spots on the electrophotographic photoreceptor is suppressed,
Provided are an electrophotographic photosensitive member formed on an a-Si-based photoconductive layer, an electrophotographic apparatus provided with such an electrophotographic photosensitive member, and a method of manufacturing such an electrophotographic photosensitive member. That is the object of the present invention.

[0023]

According to the present invention, there is provided an amorphous silicon-based photoconductive layer formed on a conductive substrate, and an amorphous carbon layer formed on the photoconductive layer. An electrophotographic photoreceptor comprising at least a plasma CVD under a condition in which the deposition rate of the surface layer decreases with an increase in high-frequency power for plasma generation. An electrophotographic photoreceptor characterized by being formed by a method is provided.

According to the present invention, at least the amorphous silicon-based photoconductive layer formed on the conductive substrate and the amorphous carbon-based surface layer formed on the photoconductive layer are included. A method for manufacturing an electrophotographic photoreceptor, comprising: a step of forming the photoconductive layer by a plasma CVD method; and a step of: And a step of forming the surface layer by a CVD method.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a preferred embodiment of the present invention will be described.

The present inventors have conducted intensive studies on the relationship between the manufacturing conditions for the aC-based surface layer and the characteristics of the obtained surface layer.
By producing the surface layer under the condition that the deposition rate of the surface layer decreases with the increase of the high frequency applied power for plasma generation, the fusion of toner is suppressed, the toner recovery rate is high, and the cleaning blade is used. It has been found that non-uniform polishing is suppressed, contamination of the charger wire is reduced, and an aC-based surface layer in which the occurrence of leak spots is suppressed is obtained.

The reason why the above characteristics can be realized by forming an aC-based surface layer under the above manufacturing conditions is unknown, but can be guessed as follows.

When an aC-based film is formed by plasma CVD, active species (ions and radicals) decomposed by the plasma are adsorbed and bonded to the underlying surface, and are deposited. However, hydrocarbon-based gas plasma is particularly easy to polymerize, and it is considered that polymerized clusters and the like are deposited simultaneously with C atom monomers. These clusters do not form a chemical bond with the base, and are considered to only remain on the base due to a weak adhesive force such as van der Waals force. It is difficult to eliminate these clusters, and it is considered that the film formation proceeds while the clusters are taken in.

Under the deposition conditions disclosed in the present invention, the deposition rate of an aC-based film decreases as the high-frequency power for plasma generation is increased under the deposition conditions disclosed in the present invention. I do. Under such conditions, two antagonistic elementary reactions during film formation, namely, growth and etching of an aC-based film, are proceeding simultaneously, and clusters remaining on the film surface with weak adhesion force are: Removed by an etching elementary reaction,
It is considered that only the C atom monomer contributed to the film growth. According to AFM observation, it has been found that the film surface produced by the production method of the present invention suppresses the occurrence of the fine irregularities as described above, and that a film surface having excellent smoothness is formed. Support the above speculation.

According to the manufacturing method of the present invention, by forming the surface layer under the condition that the etching and the growth of the aC-based film proceed simultaneously, the incorporation of clusters into the surface layer is suppressed. For this reason, generation of minute irregularities on the surface of the surface layer is suppressed. Since the minute irregularities on the surface have an anchor effect on the toner, the toner easily adheres to the irregularities. Then, it is considered that the toner adhered to the irregularities serves as a fusion source, and the adhered lump of the toner grows with the toner as a nucleus, and the fusion proceeds. However, since the surface layer according to the present invention has almost no irregularities that can serve as a fusion source of the toner, the fusion of the toner is significantly suppressed, and at the same time, the releasability of the toner is improved, and a high recovery rate is obtained. It is considered possible.

Further, in the present invention, since the incorporation of clusters into the surface layer is suppressed, the surface layer becomes dense not only on the surface but also as a whole. Further, since the surface layer in the present invention has almost no irregularities, it is considered that the surface layer has a low coefficient of friction and is excellent in lubricity. For this reason, it is considered that the surface layer in the present invention is hardly shaved by the cleaning blade.

Further, the occurrence of chatter on the cleaning blade is suppressed, and the slippage of the toner due to the deterioration of the cleaning blade is suppressed. As a result, contamination of the charger wire built in the corona charger is reduced, so that abnormal discharge is also suppressed, and generation of leak spots on the surface layer is suppressed.

In addition, since the surface layer in the present invention has almost no irregularities, the surface layer has high smoothness. For this reason, the surface layer in the present invention has a high electric breakdown voltage, and abnormal discharge is suppressed, and occurrence of peak spots is suppressed.

Note that it is difficult to remove the above minute irregularities having a diameter of several tens to several hundreds of nanometers by, for example, mechanical polishing. Even if the surface is etched after the film formation is completed, It is impossible to remove clusters dispersed in the film. Therefore, it is considered that the above-described characteristics of the surface layer can be realized only by forming the surface layer in which the incorporation of clusters is suppressed according to the manufacturing conditions disclosed in the present invention.

The production conditions of the present invention will be described in more detail. In forming the aC-based surface layer, high-frequency applied power for plasma generation, its frequency, temperature of the conductive substrate,
By setting the film forming parameters such as pressure, gas type, and gas flow rate in the reaction vessel to predetermined values, it is possible to realize a condition in which the deposition rate of the surface layer decreases with an increase in the high-frequency power for plasma generation. The present inventors have found. That is, when only the high-frequency power for plasma generation is changed while other film formation parameters are kept constant, the deposition rate of the surface layer can be changed as shown in FIG.

In the region 1 of FIG. 1, the deposition rate of the surface layer increases as the high-frequency power for plasma generation increases.
That is, in the region 1, since the elementary reaction of the growth of the surface layer is proceeding preferentially, the cluster attached to the surface of the surface layer during the deposition contributes to the growth of the surface layer without detaching again.
For this reason, clusters are also taken into the surface layer. On the other hand, in the region 2, since the etching element reaction proceeds preferentially, the cluster adhered by a weak adhesive force such as van der Waals force is detached again. For this reason, when the surface layer is formed under the film formation conditions corresponding to the region 2, the incorporation of clusters into the surface layer is suppressed.

The upper and lower limits of the high-frequency applied power for plasma generation are not particularly limited as long as the film forming conditions corresponding to region 2 in FIG. 1 can be realized. From the viewpoint, it is preferably at least 5 W / ml, more preferably at least 10 W / ml, even more preferably at least 15 W / ml, based on the hydrocarbon source gas. In addition, the upper limit needs to be suppressed to a power that does not cause abnormal discharge.

The upper and lower limits of the frequency of the high frequency applied power for plasma generation are not particularly limited as long as the film forming conditions corresponding to region 2 in FIG. 1 can be realized. From the viewpoint of balance, when the RF band is used, 1 MHz or more and 20 MHz or less, preferably 13.56 MHz is used. When the VHF band is used, the frequency may be 50 MHz or more, at a higher frequency it may be 60 MHz or more, or even 80 MHz or more.
Hz or lower, 200 MHz or lower for lower frequencies, and even 150 MHz or lower.

The upper and lower limits of the temperature of the conductive substrate are not particularly limited as long as the film forming conditions corresponding to region 2 in FIG. 1 can be realized, but from the viewpoint of the balance of the characteristics of the obtained surface layer. The temperature of the conductive substrate is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, preferably 400 ° C. or lower, more preferably 380 ° C. or lower, and even more preferably 350 ° C. or lower.

The upper and lower limits of the pressure in the reaction vessel are not particularly limited as long as the film formation conditions corresponding to the region 2 in FIG. 1 can be realized. 56 MHz), it is generally not less than 13.3 Pa and not more than 1333 Pa.
In the case of electric power (typically 50 MHz to 450 MHz), the electric power is generally 13.3 mPa to 13.3 Pa. In the present invention, from the viewpoint of the balance of the properties of the obtained surface layer, the pressure in the reaction vessel is 665 Pa or less, and when the pressure is lower, 133 Pa or less, and further 66.5 P or less.
a or less. Further, the lower limit of the pressure in the reaction vessel is generally equal to or higher than the pressure at which plasma is stably generated.

The upper and lower limits of the deposition rate of the surface layer are not particularly limited as long as the film formation conditions corresponding to the region 2 in FIG. 1 can be realized. In light of the above, 0.01 nm / sec or more is preferable, 0.05 nm / sec or more is more preferable, 0.1 nm / sec or more is still more preferable, and 2 nm / sec or more.
sec or less, preferably 1 nm / sec or less, more preferably 0.5 nm / sec or less.

With respect to the change (ΔPwr) of the high-frequency applied power
Ratio (ΔDr) of the change in the deposition rate (ΔDr) of the surface layer.
ΔPwr) corresponds to the area 2 in FIG.
There is no particular limitation as long as the film forming conditions can be realized.
Is -1 from the viewpoint of the balance of the properties of the obtained surface layer.
× 10^-3nm / sec · W or more, preferably -8 × 10
^-Fournm / sec · W or more is more preferable, and −5 × 10^-Four
nm / sec · W or more is more preferable, and^-Fiven
m / sec · W or less, preferably -5 × 10^-Fivenm / s
ec · W or less, more preferably -8 × 10^-Fivenm / se
It is more preferably cW or less.

By optimizing the film forming conditions described above and forming the surface layer under the optimum film forming conditions, the incorporation of clusters can be sufficiently suppressed, and the film formed under the conventional film forming conditions can be obtained. Unlike the surface layer, a surface layer having few tens to hundreds of nanometers of minute irregularities on the surface can be manufactured. For example, when the surface of the obtained surface layer is observed by AFM, the height is 10 μm and the width is 10 μm.
The average number of irregularities having a diameter of 100 nm or more in the region
It can be set to 0 or less. Note that the diameter of the unevenness refers to the diameter of a circle circumscribing the region where the unevenness exists.

FIG. 2 schematically shows a cross section of an example of the electrophotographic photosensitive member of the present invention. Reference numeral 210 denotes a conductive substrate having a shape such as a cylinder or a sheet, and can be made of a metal such as aluminum and stainless steel, or a glass and a resin subjected to a conductive treatment.

Reference numeral 220 denotes a photoconductive layer made of an a-Si-based material. a-Si based materials are a-Si: H, a-
Si: X, hydrogenated a-Si (hereinafter a-S)
i: H, X), and specific examples thereof include a-Si: H, a-Si: F, a-Si: Cl, a
-Si: Br, a-Si: I, a-Si: H, F, a-
Si: H, Cl, a-Si: H, Br, a-Si: H,
I and the like. If necessary, these a-Si-based materials may be doped with a Group 13 or Group 15 element. From the viewpoint of the balance of the properties of the photoconductive layer, the ratio of hydrogen or halogen to the entire surface layer (when both hydrogen and halogen are present,
The total ratio) is preferably 10 atm% or more and 40 atm% or less. Further, from the viewpoint of the balance of the characteristics of the entire electrophotographic photosensitive member, the thickness of the photoconductive layer is preferably 1 μm or more,
5 μm or more is more preferable, 100 μm or less is preferable, and 50 μm or less is more preferable.

Reference numeral 230 denotes a surface layer made of an aC-based material. The aC-based materials are aC: H, aC: X,
It means hydrogenated halogenated aC (hereinafter also referred to as aC: H, X) and the like, and specific examples thereof include aC: H,
aC: F, aC: Cl, aC: Br, aC:
I, aC: H, F, aC: H, Cl, aC: H,
Br, aC: H, I and the like. Also,
If necessary, these aC-based materials may be doped with a Group 13 or Group 15 element. From the viewpoint of the balance of the properties of the surface layer, the ratio of hydrogen or halogen to the entire surface layer (the total ratio when both hydrogen and halogen are present) is 40 atm% or more and 60 atm% or more.
atm% or less is preferable. In addition, from the viewpoint of the balance of the characteristics of the entire electrophotographic photosensitive member, the thickness of the surface layer is preferably 5 nm or more, more preferably 10 nm or more, and 1000 n
m or less, and more preferably 500 nm or less.

In the electrophotographic photoreceptor of the present invention, the photoconductive layer 22 is used for the purpose of relaxing material heterogeneity between the photoconductive layer 220 and the surface layer 230 and improving the adhesion.
The buffer layer 260 may be formed between the zero and the surface layer 230. The buffer layer 260 is made of, for example, an amorphous silicon carbide (a-Si _{1 -X} C _X , 0 <X <1) -based material, specifically, a-Si _{1 -X} C _X : H, a-Si
_1-X C _X : X, a-Si _{1 -X} C _X : H, X; amorphous silicon nitride (a-Si _{1 -Y} N _Y , 0 <Y <4/3) based material, specifically , A-Si _1-Y N _Y : H, a-Si
_{1-Y N Y: X,} a-Si 1- Y N Y: H, X; amorphous silicon oxide _{(a-Si 1-Z O} Z, 0 <Z <2) based material,
Specifically, a-Si _{1 -Z} O _Z : H, a-Si _{1 -Z} O _Z :
X, a-Si _{1 -Z} O _Z : can be formed from H, X and the like. If necessary, these materials may be added to the group 13 or 1
Group 5 elements may be doped. Note that the thickness of the buffer layer 260 is preferably 10 nm or more and 10000 nm or less from the viewpoints of spectral sensitivity, residual potential, electrical consistency, and the like.

In the electrophotographic photoreceptor of the present invention, a blocking layer is provided between the conductive substrate 210 and the photoconductive layer 220 for the purpose of preventing electrons from flowing from the conductive substrate 210 to the photoconductive layer 220. 240 may be formed. The blocking layer 240 is made of aluminum oxide, aluminum nitride, silicon oxide, silicon nitride, a-Si _1-X C _X :
H, a-Si _1-X C _X : X, a-Si _{1 -X} C _X : H, X, a
-Si _{1-Y NY} : H, a-Si _{1-Y NY} : X, a-Si _1-Y
N _Y : H, X, a-Si _{1 -Z} O _Z : H, a-Si _{1 -Z} O _Z :
X, a-Si _{1 -Z} O _Z : can be formed from H, X and the like. If necessary, these materials may be added to the group 13 or 1
Group 5 elements may be doped. The thickness of the blocking layer 240 is preferably 10 nm or more and 10000 nm or less in order to suppress the inflow of electrons without impairing the characteristics of the entire electrophotographic photosensitive member.

In the electrophotographic photoreceptor of the present invention, a charge transport layer 250 may be formed as a lower layer in contact with the photoconductive layer 220. At this time, the photoconductive layer 220 functions as a charge generating layer. It can also be considered that the photoconductive layer is functionally separated into the charge generation layer and the charge transport layer. That is, the charges generated in the charge generation layer are transported to the conductive substrate via the charge transport layer. The charge transport layer 250 having such a function can be made of an a-Si-based material, and the thickness of the charge transport layer 250 can be adjusted with high efficiency without impairing the characteristics of the entire electrophotographic photosensitive member. Is preferably 1 μm or more and 100 μm or less.

FIG. 3 shows an example of an apparatus for manufacturing an electrophotographic photosensitive member having an aC-based surface layer. Using this apparatus, an aC-based surface layer can be formed by a plasma CVD method using a high-frequency power supply.

This apparatus comprises a reaction vessel 301 and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 301. In the reaction vessel 301, a cylindrical conductive base 302 is mounted on a conductive support 303 connected to the ground. A heater (not shown) for heating is built in the conductive receiving table 303 so that the conductive base 302 can be heated to an arbitrary temperature. The conductive pedestal 303 is connected to a rotating motor 312 by a rotating shaft 304, rotates the conductive substrate 302 during film formation, and deposits the film over the entire circumferential direction. A source gas introduction pipe 306 is attached to the reaction vessel 301 so that the source gas can be supplied from a source gas supply device (not shown). The reaction vessel 301 is provided with a cathode electrode 305, and the cathode electrode 305 is
8 to a high frequency power supply 309. A vacuum gauge 310 is attached to the reaction vessel 301 so that the pressure inside the reaction vessel can be measured. Reaction vessel 3
Numeral 01 is connected to an exhaust device (not shown) via an exhaust port 311 and has a structure capable of vacuum exhaust.

Using such an apparatus, an electrophotographic photosensitive member can be produced, for example, by the following procedure. First, a conductive base 302 whose surface is mirror-finished by lathing or the like is mounted on a conductive support 303, and a raw material gas introduction valve 3 is provided.
07 is closed, the reaction vessel 301 is once evacuated by an exhaust device (not shown) through the exhaust port 311, and then the source gas introduction valve 307 is opened to introduce an inert gas for heating, for example, argon gas as a source gas. The gas is introduced into the reaction vessel 301 through the pipe 306, and the evacuation speed of the evacuation device (not shown) and the flow rate of the heating gas are adjusted while monitoring the vacuum gauge 310 so that the inside of the reaction vessel 301 has a desired pressure. Thereafter, a heater (not shown) built in the conductive receiving base 303 is operated to heat the conductive base 302,
The conductive substrate 302 is controlled to a predetermined temperature. When the conductive substrate 302 is heated to a desired temperature, the source gas introduction valve 307 is closed to stop the gas from flowing into the reaction vessel 301.

Next, a predetermined raw material gas, for example, a material gas such as silane gas, disilane gas, methane gas and ethane gas, and a doping gas such as diborane gas and phosphine gas are mixed from a gas supply device (not shown) by a mixing panel (not shown). After that, the mixture is gradually introduced into the reaction vessel 301 through the source gas introduction valve 307. next,
Each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At that time, the evacuation speed is adjusted while watching the vacuum gauge 310 so that the inside of the reaction vessel 301 has a predetermined pressure.

After the preparation for film formation is completed by the above procedure, a photoconductive layer is formed on the conductive substrate 302. After confirming that the pressure has stabilized, the high-frequency power supply 309 is set to a desired power, high-frequency power is supplied to the cathode electrode 305 through the matching box 308, and high-frequency glow discharge is generated as plasma. At this time, the matching box 308 is operated to adjust the reflected wave to be minimum,
A value obtained by subtracting the reflected power from the high-frequency incident power is set as a desired value. This discharge energy causes the reaction vessel 301
Each raw material gas introduced into the inside is decomposed, and the conductive substrate 30 is decomposed.
A predetermined deposited film is formed on the surface 2. After the formation of the desired film thickness, the supply of the high-frequency power is stopped, and the reaction vessel 301 is stopped.
After the flow of each source gas into the reaction vessel 301 is stopped and the inside of the reaction vessel 301 is once pulled up to a high vacuum, the formation of the layer is terminated. In addition, a blocking layer, a charge transport layer, a buffer layer, and the like can be formed in addition to the photoconductive layer by the same operation as described above.

Next, the aC-based surface layer of the present invention is formed. Once the inside of the reaction vessel 301 is pulled up to a high vacuum,
A predetermined source gas, for example, CH
₄ , a reaction gas after mixing hydrocarbon gases such as C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ and other material gases such as hydrogen gas, helium gas, and argon gas as required by a mixing panel (not shown). Introduced into 301. Next, each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At that time, the evacuation speed is adjusted while watching the vacuum gauge 310 so that the inside of the reaction vessel 301 has a predetermined pressure. After confirming that the pressure has stabilized, the high-frequency power supply 309 is set to a desired power, and the power is reduced to the cathode electrode 30.
5 to generate high-frequency glow discharge as plasma. At this time, operating the matching box 308,
Adjustment is made so that the reflected wave is minimized, and a value obtained by subtracting the reflected power from the high-frequency incident power is set as a desired value. Each source gas introduced into the reaction vessel 301 is decomposed by this discharge energy, and a predetermined aC-based deposited film is formed on the photoconductive layer. After the desired film thickness is formed, the supply of the high-frequency power is stopped, the flow of each source gas into the reaction vessel 301 is stopped, and the deposition chamber is once pulled up to a high vacuum, and then the formation of the surface layer is completed.

During the film formation, the conductive substrate 302 is rotated at a predetermined speed by the rotating motor 312 so that the film is deposited on the entire circumference of the conductive substrate 302.

In the present invention, in the step of forming the surface layer, the reaction apparatus is controlled so that the deposition rate of the surface layer decreases as the power of the high-frequency power for plasma generation increases. In this case, as a manufacturing condition of the aC-based film, the relationship between the high-frequency applied power for plasma generation and the deposition rate may be examined in advance, and the film forming condition may be set so that the two are inversely proportional. The surface layer may be formed under the manufacturing conditions, and thereafter, the relationship between the high-frequency applied power for plasma generation at the time of forming the surface layer and the deposition rate may be examined.

Substances that can serve as a carbon supply gas used in the present invention include CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ ,
Hydrocarbon compounds in the gaseous state at normal temperature and normal pressure, such as C ₂ H ₂ ,
Hydrocarbon compounds that can be gasified under film forming conditions can be mentioned. From the viewpoint of carbon supply efficiency, CH ₄ , C ₂ H ₆ ,
C ₃ H ₈ and C ₂ H ₂ are preferred. Further, these raw material gases for supplying carbon may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary. Further, as a halogen atom supply gas, F ₂ , BrF, ClF, Cl
In some cases, halogen compounds such as F ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ may be mixed. From the viewpoint of halogen supply efficiency, CF ₄ , CHF ₃ , C ₂ F ₆ , ClF ₃ , CHClF ₂ ,
Fluorine-containing gases such as C ₃ F ₈ and C ₄ F ₁₀ are preferably used.

In the electrophotographic photoreceptor of the present invention, fusion of the toner is suppressed, the recovery rate of the toner is high, uneven polishing by the cleaning blade is suppressed, and contamination of the charger wire is reduced. Since the occurrence of pinholes in the surface layer is suppressed, the electrophotographic photoreceptor of the present invention can be provided in an electrophotographic apparatus, and an electrophotographic apparatus with excellent performance can be provided.

FIG. 4 shows an electrophotographic photosensitive member 501 of the present invention.
A high-speed copying machine is shown as an example of the electrophotographic apparatus provided with. Around the electrophotographic photosensitive member 501, a corona charger 502 having a built-in charger wire, an electric latent image forming portion 5
03, developing unit 504, transfer material supply system 505, transfer unit 50
6 (a), an image fixing device 506 (b) incorporating a heater for image fixing, a toner collecting device 525 incorporating a cleaning blade 521, a transport system 508, a light source 50 for static elimination.
9 and so on.

In such a high-speed copying machine, the lamp 5
Light emitted from 10 is reflected on a document 512 placed on a document table glass 511, is imaged by a lens 518 in a lens unit 517 via mirrors 513, 514, 515, and is formed via a mirror 516. The light carrying the information is projected onto the electric latent image forming portion 503, and the optical information is converted into electrostatic information on the electrophotographic photoreceptor 501 to form an electric latent image. Prior to the formation of the electric latent image, the electrophotographic photosensitive member 501 is uniformly charged by the corona charger 502 to which a high voltage of +6 to 8 kv has been applied.

In the developing unit 504, a toner is supplied to the electric latent image and developed to form a toner image. On the other hand, the transfer material P such as paper is supplied to the transfer device 506 (a) via the transfer material supply system 505, the timing of leading end supply being adjusted by the registration roller 522. In the transfer unit 506 (a), the toner image is transferred to the transfer material P, and heated in the image fixing unit 506 (b) to fix the toner image. Thereafter, the transfer material P is transferred to the feeding system 50.
8 and is scattered out of the apparatus.

The toner remaining on the electrophotographic photosensitive member 501 is removed by a cleaning blade 521 made of an elastic material such as silicone rubber or urethane rubber, and is collected by a toner collecting device 525. Electrophotographic photoreceptor 501
The electric latent image remaining on the upper surface is erased by the light source 509 for static elimination. A blank exposure LED 520 is provided for exposing the electrophotographic photosensitive member 501 in order to prevent toner from adhering to an area exceeding the width of the transfer material P on the electrophotographic photosensitive member 501.

[0064]

The present invention will be described in more detail with reference to the following examples. (Method of Analyzing Characteristics of Surface Layer and Electrophotographic Photoreceptor) (A) Evaluation of Fusing In a modified machine of Canon high-speed copying machine NP-6085, the surface temperature of the electrophotographic photoreceptor was controlled to be 60 ° C. In an environment where the relative humidity was 10% and the moving speed of the electrophotographic photosensitive member was 400 mm / sec, 100,000 sheets of A4 size continuous copy paper were passed, and the fusion was evaluated. As a document for copying, a one-line chart in which black lines of 1 mm width are printed in a cross pattern on a white background is used, and a toner having a small particle size (6.5 μm), which is liable to be fused, is used as the toner. used.

After the end of the endurance, the charging current of the corona charger is adjusted so that the potential of the dark portion at the developing device position becomes 400 V, a solid white document is placed on the platen glass, and the potential of the bright portion becomes 50 V. The lighting voltage of the lamp was adjusted as described above, and an A3-size solid white document was copied. Black spots due to toner fusion were observed on the obtained image, and the surface layer of the electrophotographic photoreceptor was observed with a microscope.

The degree of fusion was quantified by a relative value where the number of fusion generated on the surface layer of a-SiC: H was 100. The smaller the numerical value, the smaller the number of occurrences of fusion,
It shows that it is good.

(A) Evaluation of Non-uniform Polishing by Cleaning Blade (Evaluation of Uneven Shaving) To evaluate uneven shaving of the surface layer of an electrophotographic photosensitive member by using a modified high-speed copying machine NP-6086 made by Canon. An original on which a solid black vertical line of 5 cm width and a solid white vertical line of 5 cm width are alternately printed is placed on a platen glass, and toner is always applied in the generatrix direction of the surface layer of the electrophotographic photosensitive member. A portion to be rubbed and a portion not to be rubbed were provided, and 100,000 sheets of A4 size continuous copy paper were passed at a moving speed of the electrophotographic photosensitive member of 400 mm / sec. In order to increase the frictional resistance between the electrophotographic photoreceptor and the cleaning blade, copying continuous paper passing durability was performed without heating under an environment condition of 30 ° C. and a relative humidity of 80%.

After the end of the durability, the thickness of the surface layer corresponding to the solid black vertical line and the solid white vertical line was measured with a spectral reflectometer [MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.] The difference in the amount of wear was evaluated. The obtained result is a-S
The degree of uneven polishing was quantified as a relative value with the difference in the amount of wear in the surface layer of iC: H being 100.
The smaller the numerical value, the lower the degree of uneven polishing and the better.

(C) Evaluation of Dirt on Charger Wire In order to evaluate dirt on the charger wire using a modified machine of Canon high-speed copying machine NP-6086, a solid black vertical line having a width of 5 cm and a vertical line having a width of 5 cm were evaluated. An original on which a solid white vertical line is alternately printed is placed on a platen glass, and a portion which is always rubbed with toner and a portion which is not rubbed in the generatrix direction of the surface layer of the electrophotographic photosensitive member are provided. At a moving speed of the photoreceptor of 400 mm / sec, 100,000 sheets of A4 size continuous copy paper were passed. In order to increase the frictional resistance between the electrophotographic photosensitive member and the cleaning blade,
Under continuous environmental conditions of 0 ° C. and a relative humidity of 80%, continuous copying durability was performed without heating.

After the end of the durability, the charging current amount of the corona charger is adjusted so that the potential of the dark portion at the developing device position becomes 400 V, a solid white document is placed on the platen glass, and the potential of the bright portion becomes 50 V. After adjusting the lighting voltage of the lamp as described above, a document having a reflection density of 0.3 was placed, and the potential unevenness at this time was measured as a potential difference using Model 344 manufactured by Trek Japan.

The degree of contamination of the charger wire was determined by a-Si
It was quantified by a relative value with the potential difference in the surface layer of C: H being 100. The smaller the numerical value is, the smaller the contamination of the charger wire is, indicating that it is good.

(D) Evaluation of Leak Potch Corona with a mixture of aluminum chips and paper powder adhered to the electrodes provided on the corona charger of a modified high-speed copying machine NP-6085 manufactured by Canon Inc. The applied voltage of the charger is increased to twice the normal voltage, and the A4 size 100
The charging process corresponding to zero sheets was repeated.

Thereafter, the potential of the dark portion at the developing device position becomes 4
The charging current amount of the corona charger was adjusted to be 00 V, a solid black original was placed on a document table, and this was copied to produce an A3-size solid black image. An image omission called a white spot-like white spot generated on the solid black image was observed.

The evaluation of leak spots was quantified by a relative value where the number of white spots on the surface layer of a-SiC: H was 100. The smaller the numerical value, the smaller the number of leak spots generated, which indicates that the number is good.

(Experimental Example 1) In order to find a film forming condition in which the deposition rate of the surface layer decreases with an increase in the applied high frequency power for plasma generation, the high frequency applied power for plasma generation was set to 4
00W, 700W, 900W, 1100W, 1500W
An aC: H film was formed on a Si wafer under the following conditions, and the deposition rate was measured: CH ₄ 200 ml / min (Normal) Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 270 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.5 μm The obtained results are plotted in FIG. From this figure, it can be seen that, under the above-mentioned film forming parameters, the film forming condition in which the deposition rate of the surface layer decreases with an increase in the high frequency applied power for plasma generation by setting the high frequency applied power for plasma generation to 900 W or more. I can do it.

(Experimental Example 2) a-
An electrophotographic photoreceptor having a surface layer made of SiC: H was prepared by the following procedure. First, a blocking layer was formed on a cylindrical Al substrate under the following conditions: SiH ₄ 300 ml / min (Normal) H ₂ 500 ml / min (Normal) NO 8 ml / min (Normal) B ₂ H ₆ 2000 ppm 100 W Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 250 ° C. Pressure in reaction vessel 53.2 Pa Film thickness 1 μm.

Next, a photoconductive layer was formed under the following conditions: SiH ₄ 500 ml / min (Normal) H ₂ 5000 ml / min (Norma
l) High frequency applied power 400 W Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 250 ° C. Pressure in reaction vessel 66.5 Pa Film thickness 20 μm.

Subsequently, a surface layer made of a-SiC: H was formed under the following conditions: SiH ₄ 10 ml / min (Normal) CH ₄ 500 ml / min (Normal) High frequency applied power 200 W High frequency applied power frequency 13 .56 MHz Temperature of conductive substrate 250 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.5 μm.

(Examples 1 to 3 and Comparative Examples 1 and 2) Electrophotographic Photoreceptors A to E After forming a blocking layer and a photoconductive layer in the same manner as in Experimental Example 2, the high-frequency applied power for plasma generation was shown. 1
The electrophotographic photoreceptors A to E were produced in the same manner as in Experimental Example 1 while changing as shown in FIG.

The high frequency applied power for plasma generation is 150
In the case of 0 W, the hydrogen content in the obtained surface layer is 4
It was 4 atm%. Similarly, for 1100W, 48
atm%; in the case of 900 W, it was 52 atm%.

Examples 1 to 3 (Electrophotographic photosensitive members A to
C) and Comparative Examples 1 and 2 (Electrophotographic photoreceptors D and E)
Table 1 shows the evaluation results. Thus, by forming the surface layer of aC: H under film-forming conditions in which the deposition rate of the surface layer decreases as the high-frequency power for plasma generation increases, fusion of the toner is suppressed, It has been found that an electrophotographic photoreceptor having a high toner recovery rate, suppressing non-uniform polishing by a cleaning blade, reducing contamination of a charger wire, and suppressing occurrence of leak spots can be produced.

[0082]

[Table 1]

(Examples 4 to 6, Comparative Examples 3 and 4) Electrophotographic photoreceptors F to J After forming a blocking layer and a photoconductive layer in the same manner as in Experimental example 2, the applied high frequency power for plasma generation was shown. 2
While changing as shown in FIG.
-C: Form a surface layer composed of H and F to form electrophotographic photosensitive members F to H (Examples 4 to 6) and electrophotographic photosensitive members I and J
(Comparative Examples 3 and 4) were prepared: CH ₄ 200 ml / min (Normal) CF ₄ 50 ml / min (Normal) Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 270 ° C. Pressure in reaction vessel 53 Pa Film thickness 1.0 μm.

FIG. 6 shows the relationship between the deposition rate of the surface layer and the high-frequency applied power for plasma generation. Thus, the electrophotographic photosensitive members F to H are manufactured under the condition that the deposition rate of the surface layer decreases as the applied high frequency power for plasma generation increases, and the electrophotographic photosensitive members manufactured as described above are manufactured. As shown in Table 2, it was found that the characteristics of the electrophotographic photosensitive members F to H were excellent. When the applied high frequency power for plasma generation is 1400 W, the total content of hydrogen and F in the obtained surface layer is 60 a.
tm%. Similarly, for 1000 W, 56 at
m%; In the case of 700 W, it was 47 atm%.

[0085]

[Table 2]

(Examples 7 to 9, Comparative Examples 5 and 6) The high-frequency power supply and the matching box of the electrophotographic photosensitive members K to O
Electrophotographic photoreceptors K to O were produced by the following procedure, with the frequency of the high frequency applied power being 105 MHz.

First, a blocking layer was formed on a cylindrical Al substrate under the following conditions: SiH ₄ 300 ml / min (Normal) H ₂ 500 ml / min (Normal) B ₂ H ₆ 2000 ppm High-frequency applied power 100 W Conductive substrate Temperature 270 ° C. Pressure in reaction vessel 26.6 Pa Film thickness 1 μm.

Next, a charge transport layer was formed under the following conditions: SiH ₄ 500 ml / min (Normal) H ₂ 500 ml / min (Normal) CH ₄ 50 ml / min (Normal) High frequency applied power 300 W Temperature 270 ° C. Pressure in reaction vessel 26.6 Pa Film thickness 15 μm.

Subsequently, a charge generation layer was formed under the following conditions: SiH ₄ 500 ml / min (Normal) H ₂ 500 ml / min (Normal) High-frequency applied power 300 W Temperature of conductive substrate 270 ° C. Pressure in reaction vessel 26 0.6 Pa film thickness 5 μm.

An aC: H surface layer was formed on the charge generation layer manufactured as described above under the following conditions while changing the applied high frequency power for plasma generation as shown in Table 3. : CH ₄ 500 ml / min (Normal) H ₂ 200 ml / min (Normal) Frequency of high frequency applied power 105 MHz Temperature of conductive substrate 270 ° C. Pressure in reaction vessel 2.7 Pa Film thickness 1.0 μm.

FIG. 7 shows the relationship between the deposition rate of the surface layer and the high frequency applied power for plasma generation. Thus, the electrophotographic photoconductors K to M are manufactured under the condition that the deposition rate of the surface layer decreases as the applied high frequency power for plasma generation increases, and the electrophotographic photoconductors manufactured as described above are manufactured. As shown in Table 3, it was found that the characteristics of the electrophotographic photosensitive members K to M were excellent.

[0092]

[Table 3]

(Examples 10 to 12, Comparative Examples 7 and 8) Electrophotographic photosensitive members P to T
The charge transport layer and the charge generation layer were laminated. Then, Table 4
While changing the frequency applied power for plasma generation, as shown in, a-C under the following conditions: H, to form a surface layer of the _{F: CH 4 400ml / min (} Normal) C 2 F 6 200ml / min ( Normal) Frequency of high frequency applied power 105 MHz Temperature of conductive substrate 270 ° C. Pressure in reaction vessel 2.7 Pa Film thickness 1.0 μm.

FIG. 8 shows the relationship between the deposition rate of the surface layer and the high-frequency applied power for plasma generation. Thus, the electrophotographic photoconductors P to R are manufactured under the condition that the deposition rate of the surface layer decreases as the applied high frequency power for plasma generation increases, and the electrophotographic photoconductors manufactured as described above are manufactured. As shown in Table 4, it was found that the characteristics of the electrophotographic photosensitive members P to R were excellent.

[0095]

[Table 4]

Example 13 Electrophotographic Photoreceptor U First, a blocking layer was formed on a cylindrical Al substrate under the following conditions: SiH ₄ 300 ml / min (Normal) H ₂ 500 ml / min (Normal) B ₂ H ₆ 2000 ppm High frequency applied power 100 W Frequency of high frequency applied power 105 MHz Temperature of conductive substrate 200 ° C. Pressure in reaction vessel 27 Pa Film thickness 1 μm.

Next, a photoconductive layer was formed under the following conditions: SiH ₄ 500 ml / min (Normal) H ₂ 5000 ml / min (Normal) High frequency applied power 300 W High frequency applied power frequency 105 MHz Conductive substrate temperature 200 ℃ Pressure in reaction vessel 27 Pa Film thickness 20 μm.

Subsequently, a buffer layer made of a-SiC was formed under the following conditions: SiH ₄ 10 ml / min (Normal) CH ₄ 500 ml / min (Normal) High frequency applied power 200 W Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 200 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.3 μm.

A surface layer is formed on the buffer layer formed as described above in the same manner as in the case of the electrophotographic photosensitive member B.
An electrophotographic photosensitive member U was produced. When the performance of the obtained electrophotographic photoreceptor U was evaluated, fusing: 5, uneven shaving: 1
0, the charger wire dirt: 10, the leak spot: 6, indicating excellent performance.

(Comparative Example 9) Electrophotographic photosensitive member U 'In the same manner as in the case of the electrophotographic photosensitive member U, after the blocking layer, the photoconductive layer and the buffer layer were laminated, in the same manner as in the case of the electrophotographic photosensitive member D A surface layer was formed to produce an electrophotographic photoreceptor U ′. When the performance of the obtained electrophotographic photoreceptor U ′ was evaluated, it was found that fusing: 50, uneven shaving: 70, charging wire stain: 40, leak spot: 30.

Example 14 Electrophotographic Photoreceptor V A blocking layer and a photoconductive layer were laminated in the same manner as in the case of the electrophotographic photoreceptor U, and then a buffer layer made of a-SiN was formed under the following conditions. SiH ₄ 50 ml / min (Normal) N ₂ 900 ml / min (Normal) High frequency applied power 200 W Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 200 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.3 μm. Thereafter, a surface layer was formed in the same manner as in the case of the electrophotographic photosensitive member B, and an electrophotographic photosensitive member V was produced. When the performance of the obtained electrophotographic photosensitive member V was evaluated, fusing: 5, uneven shaving: 10, charging device wire stain: 10, leak spot: 6
It turned out to be excellent performance.

(Comparative Example 10) Electrophotographic photosensitive member V 'In the same manner as in the case of the electrophotographic photosensitive member V, after the blocking layer, the photoconductive layer and the buffer layer were laminated, in the same manner as in the case of the electrophotographic photosensitive member D A surface layer was formed to produce an electrophotographic photoreceptor V ′. When the performance of the obtained electrophotographic photoreceptor V ′ was evaluated, it was found that fusing: 50, uneven shaving: 70, charger wire stain: 40, and leak spot: 30.

Example 15 Electrophotographic Photoreceptor W A blocking layer and a photoconductive layer were laminated in the same manner as in the case of the electrophotographic photoreceptor U, and then a buffer layer made of a-SiO was formed under the following conditions. SiH ₄ 50 ml / min (Normal) NO 900 ml / min (Normal) High frequency applied power 200 W Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 200 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.3 μm. Thereafter, a surface layer was formed in the same manner as in the case of the electrophotographic photosensitive member B, and an electrophotographic photosensitive member W was produced. When the performance of the obtained electrophotographic photosensitive member W was evaluated, fusing: 5, uneven shaving: 10, charging device wire stain: 10, leak spot: 6
It turned out to be excellent performance.

(Comparative Example 11) Electrophotographic photosensitive member W 'In the same manner as in the case of the electrophotographic photosensitive member W, after the blocking layer, the photoconductive layer and the buffer layer were laminated, in the same manner as in the case of the electrophotographic photosensitive member D A surface layer was formed, and an electrophotographic photosensitive member W ′ was produced. When the performance of the obtained electrophotographic photoreceptor W ′ was evaluated, it was found that fusing: 50, uneven scraping: 70, charging wire stain: 40, leak spot: 30.

(Examples 16 to 20) Electrophotographic photosensitive member AA
AE In the same manner as in Experimental Example 2, after laminating the blocking layer and the photoconductive layer, CH ₄ was used as a gas for supplying carbon, and the deposition rate of the surface layer was reduced with an increase in the high-frequency power for plasma generation. ΔDr / ΔPwr by changing the carbon supply gas flow rate and the high frequency applied power within the range of
Is changed as shown in Table 5, and a-
C: H surface layer was formed: Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 150 ° C. Pressure in reaction vessel 53 Pa Film thickness 0.2 μm.

The electrophotographic photosensitive members AA to AE produced as described above were evaluated, and the results are shown in Table 5. Than this,
When ΔDr / ΔPwr was -1 × 10 ⁻³ nm / sec · W or more and −1 × 10 ⁻⁵ nm / sec · W or less, it was found that the characteristics of the electrophotographic photosensitive member were particularly excellent.

[0107]

[Table 5]

(Examples 21 to 25) Electrophotographic photosensitive member AF
AJ After stacking the blocking layer and the photoconductive layer in the same manner as in Experimental Example 2, C ₂ H ₂ was used as a gas for supplying carbon, and the deposition rate of the surface layer was increased with an increase in the high-frequency power for plasma generation. The flow rate of the carbon supply gas and the high-frequency applied power were changed within the range of the film forming conditions in which
The surface layer of aC: H was formed under the following conditions while changing as shown in the following: Frequency of high frequency applied power 13.56 MHz Temperature of conductive substrate 200 ° C. Pressure in reaction vessel 40 Pa Film thickness 0.5 μm .

The electrophotographic photosensitive members AF to AJ prepared as described above were evaluated. The results are shown in Table 6. Than this,
It was found that when the deposition rate of the surface layer was 2 nm / sec or less, the characteristics of the electrophotographic photosensitive member were particularly excellent. On the other hand, when the deposition rate is less than 0.01 nm / sec, it takes a long time to form a film, which is not practical.

[0110]

[Table 6]

[0111]

As is apparent from the above description, a-C
By forming the surface layer of the system under film-forming conditions in which the deposition rate of the surface layer decreases with an increase in the high-frequency applied power for plasma generation, the fusion of the toner is suppressed, and the toner recovery rate is increased. In addition, it is possible to manufacture an electrophotographic photoreceptor in which uneven polishing by a cleaning blade is suppressed, contamination of a charger wire is reduced, and occurrence of leak spots is suppressed.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a relationship between a deposition rate of a surface layer and a high-frequency applied power for plasma generation.

FIG. 2 is a schematic sectional view for explaining an example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic diagram for explaining an apparatus for forming an electrophotographic photosensitive member.

FIG. 4 is a schematic diagram for explaining the electrophotographic apparatus of the present invention.

FIG. 5 is a diagram showing an experimental example of a relationship between a deposition rate of a surface layer and a high-frequency applied power for plasma generation.

FIG. 6 is a diagram illustrating an experimental example of a relationship between a deposition rate of a surface layer and a high-frequency applied power for plasma generation.

FIG. 7 is a diagram illustrating an experimental example of a relationship between a deposition rate of a surface layer and a high-frequency applied power for plasma generation.

FIG. 8 is a diagram showing an experimental example of a relationship between a deposition rate of a surface layer and a high-frequency applied power for plasma generation.

[Explanation of symbols]

 210 conductive substrate 220 photoconductive layer 230 surface layer 240 blocking layer 250 charge transport layer 260 buffer layer 301 reaction vessel 302 conductive substrate 303 conductive pedestal 304 rotating shaft 305 cathode electrode 306 source gas introduction pipe 307 source gas introduction valve 308 Matching box 309 High-frequency power supply 310 Vacuum gauge 311 Exhaust port 312 Rotating motor 501 Electrophotographic photosensitive member 502 Corona charger 503 Electrical latent image forming portion 504 Developing device 505 Transfer material supply system 506 (a) Transfer device 506 (b) Image fixing Container 508 Transport system 509 Light source for static elimination 510 Lamp 511 Platen glass 512 Document 513 Mirror 514 Mirror 515 Mirror 516 Mirror 517 Lens unit 518 Lens 520 Blank exposure LED 521 Cleaner Grayed blade 522 resist roller 525 the toner recovery unit P transfer material

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/08 360 G03G 5/08 360 C23C 16/26 C23C 16/26 16/505 16/505 G03G 5 / 00 101 G03G 5/00 101 (72) Inventor Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 CA03 DA05 DA06 DA07 DA12 DA19 DA46 DA51 EA24 EA34 EA36 4K030 AA09 AA17 AA20 BA27 BB12 CA02 CA07 CA16 FA01 GA07 JA01 JA12 JA16 JA18 KA04 LA17

Claims (12)

[Claims] 1. An electrophotographic photoreceptor comprising at least an amorphous silicon-based photoconductive layer formed on a conductive substrate and an amorphous carbon-based surface layer formed on the photoconductive layer. The electrophotographic photoreceptor is characterized in that the surface layer is formed by a plasma CVD method under a condition in which the deposition rate of the surface layer decreases with an increase in applied power for high frequency power for plasma generation. . 2. The thickness of the surface layer is 5 nm or more and 100 or more.
2. The electrophotographic photosensitive member according to claim 1, wherein the thickness is 0 nm or less. 3. The photoconductive layer has a thickness of 1 μm or more and 10 μm or more.
3. The electrophotographic photoreceptor according to claim 1, wherein the thickness is 0 μm or less. 4. Between the photoconductive layer and the surface layer,
2. A buffer layer is formed.
4. The electrophotographic photosensitive member according to any one of items 1 to 3, 5. The electrophotographic photosensitive member according to claim 1, wherein the buffer layer is made of an amorphous silicon carbide, an amorphous silicon nitride, or an amorphous silicon oxide. 6. The electrophotographic photoreceptor according to claim 1, wherein a blocking layer is formed between the conductive substrate and the photoconductive layer. 7. The electrophotographic photoreceptor according to claim 1, wherein a charge transport layer is formed as a lower layer in contact with said photoconductive layer. 8. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1. 9. Production of an electrophotographic photoreceptor comprising at least an amorphous silicon-based photoconductive layer formed on a conductive substrate and an amorphous carbon-based surface layer formed on the photoconductive layer. Forming the photoconductive layer by a plasma CVD method, and forming the photoconductive layer by a plasma CVD method under a condition in which the deposition rate of the surface layer decreases with an increase in applied high frequency power for plasma generation. And a step of forming an electrophotographic photosensitive member. 10. In the step of forming the surface layer,
The frequency of the high frequency applied power is 50 MHz or more and 450 M
10. The method for producing an electrophotographic photosensitive member according to claim 9, wherein the frequency is lower than or equal to Hz. 11. In the step of forming the surface layer,
The deposition rate of the surface layer is 0.01 nm / sec or more and 2 n
10. The method according to claim 9, wherein the speed is not more than m / sec.
0. The method for producing an electrophotographic photosensitive member according to item 0. 12. The step of forming the surface layer,
The ratio (ΔDr / ΔPw) of the deposition rate change (ΔDr) of the surface layer to the change (ΔPwr) of the high-frequency applied power
r) is -1 × 10 ⁻³ nm / sec · W or more and −1 × 10 ^−5.
10. The value of nm / sec · W or less.
12. The method for producing an electrophotographic photosensitive member according to any one of items 1 to 11.