JP2000010313A - Electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent cleaning characteristic and attain the higher life of a blade, the reduction in load of a phosphor, and reduction in power consumption of a rotating motor by setting the average particle side of a developing agent to a specified value, and providing a photoreceptor having a surface layer consisting of non-monocrystalline carbon containing hydrogen. SOLUTION: Toner having an average diameter of 0.004-0.012 mm is used, and a material of non-monocrystalline carbon (a-C) or fluorinated non- monocrystalline carbon (a-C: F) having a JIS hardness of 74 deg. or more and 78 deg. or less is used for a photoreceptor. A single layer type phosphor in which a photoconductive layer 403 is not functionally separated is formed by laminating a charge implantation preventing layer 402, the photoconductive layer 403 consisting of amorphous silicon containing hydrogen and a surface layer 404 consisting of a-C on a substrate 401. A phosphor having the surface layer 404 having fluorine dispersed on the surface of the a-C surface layer is formed by laminating the charge implantation preventing layer 402, the photoconductive layer 403, and the surface layer 404 on the substrate 401, and a fluorine diffusion layer 405 is present on the outermost surface of the surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-speed electrophotographic process using a photoreceptor having an amorphous silicon-based photoconductive layer and using a developer having a small particle diameter, and having excellent cleaning characteristics and any environment. A high-quality image with no image blur or image deletion can be obtained without providing a heating means for the photoreceptor even underneath, and has high durability enough to maintain the characteristics, and has little variation in potential characteristics. The present invention relates to an electrophotographic apparatus capable of stably obtaining a high-quality image and causing no ghost phenomenon. In particular, the present invention relates to an image forming method using a system in which untransferred toner remaining on a latent image carrier after development and transfer is collected in a cleaning step and reused.

[0002]

2. Description of the Related Art (1) Electrophotographic apparatus Conventionally, an electrophotographic method is disclosed in US Pat. No. 2,297,692.
Many methods are known, as described in Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used,
An electric latent image is formed on the photoreceptor by various means, then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. Fixing is performed by pressurization or solvent vapor to obtain a copy. In this process, untransferred toner remains on the photoreceptor even after the toner image has been transferred to the transfer material.
07, the untransferred toner was collected and discharged outside the system as so-called waste toner.

With the recent increase in the amount of information processing, the demand for electrophotographic apparatuses (ie, large high-speed machines) such as copiers and laser beam printers having a large copy volume is increasing.

[0004] As the photoreceptor is required to have improved electrophotographic characteristics corresponding to high speed and to be required to have more vivid image quality, not only the photoreceptor characteristics are improved, but also
As the particle size of toner is reduced, those having a weight average particle size of 0.005 to 0.008 mm as measured by a Coulter counter or the like are often used.

On the other hand, the ability to fix the toner image on the transfer material depends on how the toner image on the transfer material is heated in the fixing device. When the time is short, the temperature of the fixing unit must be increased, and the power consumption of the entire electrophotographic apparatus is about 8%.
In this situation, the power consumption of the fixing unit, which is relatively high, has to be increased.

[0006] Even in such a situation, reduction of power consumption as a market need is an important issue, and improvement of the fixing property of the toner itself has been promoted. However, this is disadvantageous to fusion which is incompatible with improvement of the fixing property. Direction.

Since the smaller particle size is also a disadvantageous direction for fusing, it is difficult to adhere the toner to the photoreceptor or to improve the ability to scrape off the adhered toner. Such as increasing the hardness of the blade,
Measures are required. However, increasing the hardness of the blade, as a characteristic of the blade, changes from a rubbery state to a glassy state, so that the material becomes brittle and the life of the blade is shortened.

On the other hand, in order to improve the cleaning property,
A grooved blade described in JP-A-54-143149 and a protruded blade described in JP-A-57-124777 have been devised, but the process speed is 400 mm. No mention is made of a cleaning system suitable for an electrophotographic apparatus comprising a fine particle toner having an improved fixability and an a-Si photoreceptor at or higher than / sec.

[0009] Under these circumstances, there is a demand for the construction of a cleaning system and a waste toner recycling system suitable for a high-speed electrophotographic apparatus capable of high image quality.

FIG. 1 is a schematic view showing an example of an image forming process of a copying machine, in which a main charging is performed around the photosensitive member 101 which is controlled in temperature by a plane inner surface heater 123 rotating in an arrow X direction. Device 102, an electrostatic latent image forming portion 103, a developing device 104, a transfer paper supply system 105, a transfer charger 106 (a), a separation charger 106 (b), a cleaner 107, a transport system 108, a static elimination light source 109, and the like. Has been established.

Hereinafter, the image forming process will be described with reference to a specific example. The photosensitive member 101 is uniformly charged by a main charger 102 to which a high voltage of +6 to 8 kV is applied. That is, the light emitted from the lamp is reflected by the original 112 placed on the original platen glass 111, passes through mirrors 113, 114, and 115, forms an image by the lens 118 of the lens unit 117, passes through the mirror 116, and is guided. Thus, a projected electrostatic latent image is formed. The toner is supplied from the developing device 104 to the latent image to form a toner image.

On the other hand, the leading edge timing is adjusted by the registration roller 122 through the transfer paper supply system 105,
The transfer material P supplied in the direction of the photoreceptor is applied with an electric field having a polarity opposite to that of the toner from the back surface in the gap between the transfer charger 106 (a) to which a high voltage of +7 to 8 kV is applied and the photoreceptor 101. The toner image on the photoreceptor surface is a transfer material P
Transfer to 12-14kVp-p, 300-600H
The transfer material P reaches the fixing device (not shown) through the transfer paper conveying system 108 by the separation charger 106 (b) to which the high AC voltage z is applied, and the toner image is fixed and discharged out of the device. .

The toner remaining on the photosensitive member 101 is scraped off by the cleaning blade 121 of the cleaner unit, and the remaining electrostatic latent image is erased by the charge eliminating light source 109.

(2) Electrophotographic Photoreceptor Various materials such as selenium, cadmium sulfide, zinc oxide, phthalocyanine, and amorphous silicon (hereinafter referred to as a-Si) have been proposed as technologies for element members used in the electrophotographic photoreceptor. Have been. Above all, a non-single crystalline deposited film containing a silicon atom typified by a-Si as a main component, for example, an amorphous deposited film of a-Si compensated with hydrogen and / or halogen (for example, fluorine, chlorine, etc.) has a high performance. , Highly durable and pollution-free photoreceptors, some of which have been put to practical use. Japanese Patent Application Laid-Open No. 54-86341 discloses a technique of an electrophotographic photosensitive member in which a photoconductive layer is mainly formed of a-Si.

The a-Si photoreceptor has a high surface hardness, exhibits high sensitivity to long-wavelength light such as a semiconductor laser (770 nm to 800 nm), and shows little deterioration due to repeated use. (Laser beam printer) is widely used as a photoconductor for electrophotography.

Conventionally, as a method of forming such a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal C)
VD method), a method of decomposing a source gas by light (photo CVD)
Many methods are known, including a method of decomposing a source gas by plasma (plasma CVD method). Among them, a plasma CVD method, that is, a direct current or a high frequency
F, VHF) Decomposition by microwave glow discharge or the like, and forming a thin film deposition film on a substrate such as glass, quartz, heat-resistant synthetic resin film, stainless steel, aluminum, etc. At present, practical application of a forming method and the like has been extremely advanced, and various apparatuses for that purpose have been proposed. Further, in recent years, there has been a strong demand for improvements in film quality and processing capacity, and various devices have been studied.

In particular, a plasma process using high-frequency power is used because of its various advantages, such as high discharge stability and use for forming an insulating material such as an oxide film or a nitride film.

In recent years, using a parallel plate type plasma CVD apparatus, a plasma C
There is a report on the VD method (Plasma Chemistry and Plasma Pr
ocessing, Vi.7, No.3 (1987) p276-273), it is possible to increase the deposition rate without lowering the performance of the deposited film by setting the discharge frequency higher than the conventional 13.56 MHz. It is shown and noted. In addition, reports of increasing the discharge frequency were also made by sputtering and the like,
In recent years, it has been widely studied.

(3) Problems In applying the a-Si photoreceptor prepared by these methods to an electrophotographic apparatus, in most cases, a wire electrode (gold plating of 50 to 100 μmφ) is used as a means for charging and discharging the photoreceptor. Corona charger (corotron, metal wire such as tungsten wire subjected to
Scorotron) is used. That is, a corona current generated by applying a high voltage (approximately 4 to 8 kV) to the wire electrode of the corona charger acts on the surface of the photoreceptor to perform charging and discharging of the surface. The corona charger is excellent in uniform charging and static elimination.

[0020] However, due to the corona discharge ozone (0 ₃₎
Is generated and oxidizes nitrogen in the air to produce nitrogen oxides (NO
_X ) and so on. Furthermore, the generated nitrogen oxides react with moisture in the air to generate nitric acid and the like. Products generated by corona discharge, such as nitrogen oxides and nitric acid, adhere to and accumulate on the photoreceptor and peripheral devices, and contaminate the surfaces thereof.

The corona discharge product has a strong hygroscopic property, and the surface of the photoreceptor on which the adsorbed corona discharge product absorbs the adsorbed corona discharge product has a low resistance due to the moisture absorption, so that the charge holding ability substantially or partially decreases. This causes an image defect called image blur or image deletion (charge of the photoreceptor surface leaks in the surface direction to destroy or not form the electrostatic latent image pattern).

Further, the corona discharge products adhering to the inner surface of the shield plate of the corona charger are volatilized and released not only during the operation of the electrophotographic apparatus but also during the stoppage of the apparatus at night or the like. And adheres to the surface of the photoreceptor, and further absorbs moisture to lower the resistance of the surface of the photoreceptor. Therefore, with respect to the first or several copies output first when the apparatus is restarted after the apparatus is stopped, image blur and image deletion are likely to occur in the area corresponding to the charger opening during the apparatus stop. This phenomenon is particularly remarkable when the corona charger is an AC corona charger.

In particular, when the photoreceptor is an a-Si photoreceptor, the problems of image blur and image deletion due to the corona discharge products described above increase. That is, the a-Si photoreceptor has a lower charging and discharging efficiency than the other photoreceptors (the corona charging current required for obtaining a predetermined charging and discharging potential is large). In the charging and discharging process by corona discharge, the voltage applied to the charging device is made higher than in the case of other photoconductors, and the amount of charging current is greatly increased. Since the corona charging current amount and the ozone generation amount are in a proportional relationship, the photoconductor is a
-Si photoreceptor, in a configuration in which it is charged and destaticized by corona charging, the amount of ozone generated is particularly large, and therefore, image blur due to the generation of the corona discharge product,
The problem of image deletion is particularly great. A-Si
In the case of a photoreceptor, the fact that the surface hardness is extremely high as compared with other photoreceptors adversely acts, and the corona discharge products attached to the photoreceptor surface tend to remain forever.

Therefore, the following two methods have been considered as methods for preventing image blur and image deletion.

One of them is to incorporate a heater in the photoreceptor to heat the photoreceptor or to blow warm air to the photoreceptor by a hot air blower to heat the surface of the photoreceptor (30). ~ 50
C.) to reduce the relative humidity.
This method is a process for volatilizing corona discharge products and moisture adhering to the surface of the photoreceptor to suppress a substantial reduction in the resistance of the surface of the photoreceptor, and has been put to practical use.

The second is a method of improving the water repellency of the surface so that a corona discharge product is hardly adhered from the beginning, thereby preventing image deletion. As a prior art, Japanese Patent Application Laid-Open No. 61-289354 discloses an amorphous carbon (hereinafter abbreviated as aC) surface layer whose surface is plasma-treated with a gas containing fluorine. JP-A-64-84257 discloses that the surface of a surface layer made of aC containing fluorine has a depth of 0.1 to
An electrophotographic photosensitive member having irregularities of 0.5 μm and a width of 0.1 to 1 μm and a method of manufacturing the same are disclosed. According to this method, it is possible to further improve the water repellency by increasing the surface area.

Further, in the transfer step, the toner on the photosensitive member (latent image carrier) is not completely transferred,
About 0 to 20% by weight remains on the photoreceptor. As described above, the toner (untransferred toner) remaining on the photoreceptor is collected in the cleaning process and discharged out of the system as a so-called waste toner, and cannot be reused.

In recent years, the demand for copying machines has increased, and the demand for machines having a large copy volume, that is, high-speed copying machines has been increasing. In such a high-speed copying machine, a large amount of waste toner is generated. If all of the waste toner generated in such high-speed copying machines is treated as waste (waste plastic), there is a risk of causing environmental pollution. For this reason, recently, a study of reusing the waste toner, that is, a study of reuse of the toner has been widely performed. If the waste toner becomes reusable, the waste toner can be effectively used, the space in the copying machine can be simplified, and the copying machine can be made compact.

However, when the waste toner is used again in the developing step, there are adverse effects such as a decrease in the reflection image density of the obtained copy, deterioration of ground fog and reversal fog, and occurrence of toner scattering.

The present inventors collect toner from the developing sleeve at any time from the start of copying in order to investigate the cause such as a decrease in the density of the reflected image when the waste toner is used in the reuse system. Was done. As a result, a change was observed in the shape of the toner before and after the above-mentioned adverse effects began to appear.
That is, when the toner on the developer sleeve is observed as needed using a scanning electron microscope (SEM), the surface of the waste toner, which is an adverse toner, may be separated,
Or, it was confirmed that there were many things that were broken from inside.

[0031]

As the speed of an electrophotographic apparatus has been increased, the particle size of toner has been reduced for sharpness of an image, and the fixing property has been improved, the load situation on an electrophotographic photosensitive member has been changed. I have. The first is that the cleaning performance is reduced and the frictional force is increased with the increase in speed. In the electrophotographic process, when the process speed is high, the developer or the like slips through due to chatter of the cleaning blade. As a solution, as the process speed increases, the pressure of the cleaning blade is increased to prevent slipping through.However, as the process speed increases, the frictional force increases, and the photosensitive member and the electrophotographic The load on the device has increased.

As for the reduction of the particle size of the developer, the same problem as the increase in the speed and the problem of fusion occurred. The sharpness of the image increased as the developer particle size decreased, but the load increased when used in a high-speed electrophotographic apparatus.
In addition, the improvement of the fixing property is likely to cause problems such as fusion,
To solve these problems, it was necessary to increase the blade pressure.

For this reason, in the process of obtaining a clear image in a high-speed machine or the like, problems such as shortening of the life of the cleaning blade, damage due to foreign matter inclusion, etc. are more likely to be caused on the photosensitive member, and increase in power of the rotary motor due to increase in load. Caused.

Further studies on the recycling of waste toner were carried out. As a result, untransferred toner (waste toner) on the photoreceptor was scraped off by a cleaning blade in a cleaning process, or developed using a transport screw. It was found that the cause was large due to the mechanical impact applied when transported again to the process. Therefore, the toner applied to the reuse system has the characteristics described above,
That is, in addition to developing properties, low-temperature fixing properties, anti-offset properties, anti-blocking properties, anti-fishing properties and crushing properties, it is also strong against mechanical impact and excellent in durability, and transported to the developing process. In addition to the demand for characteristics such as excellent performance, it is necessary to provide a process with a small load that does not hurt waste toner in the image forming process.

Although the problem of image deletion has been solved by the heating device for the drum, the following problems have newly arisen due to the recent increase in demands for copying machines. That is, from the viewpoint of energy saving and ecology, it has become more desirable not to perform the heating means using the drum heater. Another problem is that high image quality a-
When the Si drum is mounted on a full-color copying machine, there is a high possibility that a low melting point toner such as a color toner is fused to the drum surface. Another problem is that the image density is partially increased or decreased with the rotation cycle of the rotating cylindrical developer carrier. This is because the rotating cylindrical developer carrier expands due to the heat of the photoconductor while the apparatus is at rest, the distance between the rotary cylindrical developer carrier and the photoconductor facing portion is shortened, and the developer is more easily transferred than usual. Due to these problems, there has been a demand for a photoreceptor that does not cause image blur or image deletion without heating.

On the other hand, with respect to the technology for improving water repellency disclosed in the above publication, improvement in water repellency when exposed to ozone is mentioned. However, a durability test was performed by actually performing a large number of copying operations. It is not described whether it is.

Therefore, the present inventors have disclosed in JP-A-61-289.
A follow-up test was performed according to the method disclosed in Japanese Patent Publication No. 354, and a durability test was conducted in which copying operation was continuously performed without using a heating means. As a result, the initial image deletion characteristics were certainly improved. Considering high durability, which is one of the merits of the Si photoreceptor, it was found that it is desirable to maintain more water repellency during a large number of paper passing durability tests.

Further, the method disclosed in JP-A-64-84257 was additionally tested. In this case, it was confirmed that increasing the surface area by providing irregularities on the surface was effective for improving the water repellency, but the effect of the water repellency was reduced by performing paper passing durability. I understood. This is because a-C containing fluorine
However, it is considered that the material is soft and is gradually scraped by rubbing of the peripheral member of the photoreceptor and paper.

From these facts, it is possible to have a highly water-repellent surface layer so as not to cause image blur and image deletion without using a heating means, and the high water repellency can be obtained by a large number of copy operations for a long time. There has been a demand for a photoreceptor that does not deteriorate.

Further, in addition to the problem of image deletion, the demand for copied images has been increasing in recent years, and there is a strong demand for a technique for stably supplying high image quality. The use of copiers has shifted from text-based copy originals to images such as photographs, and the number of halftone-intensive copy originals has increased.As a result, stricter standards have been required for density stability than before. Have been. In the case where the charging potential fluctuates with time when the same charging is desired as described above, the fluctuation of the potential is called a potential shift, and the smaller this is, the higher the stability.

With regard to photographic originals, strict requirements are required for the ghost phenomenon as well as the stability of density. This is because the halftone portion is particularly susceptible to ghosts. Here, the ghost is a phenomenon in which the previously copied image becomes thin and apparent, so that when a halftone potential is applied, the difference between the potential of the portion where the ghost occurs and the halftone potential is called a ghost potential, This indicates that a smaller ghost does not occur.

It is conceivable that these causes are caused by charges being trapped in the film for some reason in the process of performing charging and discharging. Attempts have been made to reduce the potential shift and the ghost potential by various methods so far, but a technique that can further improve the potential has been eagerly desired.

An object of the present invention is to improve cleaning performance and reduce friction even in the case of using a toner having a small particle size and excellent fixability in a high-speed electrophotographic apparatus in which friction force and torque increase. It is another object of the present invention to reduce the load applied to the photosensitive member and the cleaning blade, thereby improving the cleaning property, extending the life of the blade, reducing the load on the photosensitive member, and reducing the power consumption of the rotating motor. It is another object of the present invention to provide an electrophotographic apparatus capable of reducing the load on the photoconductor and the cleaning blade, thereby reducing the load on the waste toner, maintaining the characteristics of the waste toner in the cleaner, and recycling the toner. Aim. Further, under any environment, a high-quality electrophotographic photoreceptor which can obtain a high-quality image without image blur or image deletion without providing a photoreceptor heating unit and has sufficient durability to maintain the characteristics. And a method of manufacturing the same. Further, it is another object of the present invention to prevent the fusion of a low melting point toner such as a color toner and to prevent the occurrence of density unevenness which occurs in the rotation cycle of the developer carrying member without providing a heating unit. Another object of the present invention is to provide an electrophotographic apparatus in which a change in potential characteristics is small, a high-quality image can be stably obtained without changing over time, and a ghost phenomenon does not occur. .

[0044]

Means for Solving the Problems The present inventors first focused on improving the cleaning property and tried to increase the slipperiness of the surface of the photosensitive member. As a result, they have found that the frictional force is reduced when the surface layer of aC of the present invention is used, as compared with conventional a-SiC (non-single-crystal silicon carbide, particularly amorphous silicon carbide).

The present inventors further changed the hardness of the cleaning blade with respect to the cleaning property.
By using in the range of 74 degrees to 78 degrees in IS hardness, it has excellent cleaning properties and good slipperiness,
It has been found that the load on the photoconductor and the cleaning blade is reduced. Then, the present inventors tried to reduce the pressure of the cleaner blade while maintaining the cleaning property. As a result, sufficient cleaning characteristics were obtained at a pressure lower than the pressure performed under the conventional high-speed conditions. Therefore, by improving the slipperiness and reducing the pressing pressure of the cleaning blade, even in the process of obtaining a clear image in a high-speed machine, the life of the cleaning blade is extended, and the scratches due to contamination by foreign matters, etc. Power consumption can be reduced due to the load on the rotating motor.

Further, the present inventors paid attention to the physical properties of the waste toner obtained at this time. As a result, it has been found that when the photoconductor surface layer and the cleaning blade of the present invention are used, deterioration of the physical properties of the waste toner is suppressed. this is,
It is considered that the pressure on the toner can be reduced because the load on the toner can be reduced and the cleaning pressure can be set low, so that the waste toner can be collected without deteriorating.

Next, the present inventors paid attention to the shape of the surface of the non-single-crystal carbon film as a method for maintaining high water repellency. As a method for controlling the water repellency by forming an uneven shape on the surface, as described above, JP-A-64-84257
However, in this method, the surface was gradually shaved by the paper passing durability test, and the effect of the unevenness was not confirmed. Therefore, the starting point is a surface layer of high hardness that cannot be scraped, that is, a surface layer obtained by etching non-single-crystal carbon not containing fluorine, which is disclosed in JP-A-61-289354, using fluorine plasma. The experiment was performed by changing the unevenness. In order to observe the detailed shape of the surface, an atomic force microscope (AFM) was used to investigate in detail what the surface shape was changed by etching with fluorine plasma. As a result, the photoreceptor surface with low durability is a very rough surface at the atomic level,
Conversely, it was found that the surface of the photosensitive member having relatively high durability had high flatness. That is, the change in the durability with respect to the image deletion was examined in more detail using the surface roughness as an index. As a result, the durability greatly changed with a 10-point average roughness (Rz) of about 1000 angstroms in a visual field of 5 μm square. Was found. Intense conditions such that Rz exceeds 1000 angstroms, for example, 10
When the etching was performed with an extremely fast etching blade that greatly exceeded 0 Å / sec, the surface shape was greatly changed, the surface became very rough, and the durability against image deletion was greatly deteriorated. On the other hand, Rz is 1
When the etching is performed so as to be suppressed to 2,000 angstroms or less, the shape of the surface becomes a gentle curved surface,
It was found that the durability against image deletion was greatly improved, and that the less the unevenness of the surface was, the more the image deletion characteristics tended to be maintained for a long time. Such fine irregularities are difficult to measure with a normal surface roughness meter, and were not clear unless a high-resolution measuring means such as AFM was used.
It seems that it has not been revealed so far.

In the case of such a very flat surface,
Although the water repellency is improved as compared with the conventional surface layer, the result is slightly lower as compared with the case having the unevenness. However, with respect to the durability for maintaining the high water repellency, the flatter is improved. The reason for this is not yet clear, but we think as follows.

When the surface has irregularities, the effect of fluorine is large because the surface area is large, and the water repellency is improved. However, when the actual copying operation is performed, the surface is rubbed by various members and papers. However, since the force applied to the convex portion is concentrated, the rubbing condition is considered to be more severe.
If such a concentration of force continues for a long period of time, it is considered that even in the case of a high-hardness film that cannot be scraped, fluorine near the outermost surface and carbon bonded to fluorine are likely to be desorbed. Examination of the surface layer after actually copying a large number of copies showed no change in the film thickness measurement by optical means, but the fluorine content was reduced, and fluorine near the outermost surface was dropped off it is conceivable that.

On the other hand, when the surface is flat, concentration of force does not occur, and it is considered that water repellency is maintained even after long-term use. Normally, the flatness is poorer in slipperiness and the wear characteristics are often deteriorated, but in the case of the present invention, the slipperiness is not deteriorated by the effect of fluorine, and conversely, general electronic The sliding property was improved as compared with the photoreceptor, and an effect that no defective cleaning occurred was obtained. Therefore, the frictional force was further reduced as compared with the case where aC was used for the surface layer.

Next, the amount of fluorine near the surface was examined.

Experiments were conducted by changing the etching conditions so that Rz was substantially the same and the concentration of fluorine was changed. When the content of fluorine was 20% or less, the initial water repellency was reduced. And the effect of preventing image deletion was not sufficient. However, it was found that when fluorine was contained at 20% or more, the water repellency was maintained even after a large number of copying operations. As another effect, an improvement in transfer efficiency due to an improvement in releasability was observed. Therefore, it was found that fluorine was desirably diffused at a concentration of 20% or more with respect to carbon.

On the other hand, as an unexpected effect of the present invention, it has been found that the potential characteristic greatly changes at around 50 Å with respect to the depth at which fluorine is diffused. In particular, the potential shift and the ghost level tended to be greatly improved by controlling the etching conditions with fluorine plasma so that the distribution range of fluorine atoms was within about 50 Å from the outermost surface. The reason why the potential characteristics are improved only under the condition that the fluorine atoms are substantially within 50 Å is that a strong covalent bond of fluorine and carbon is formed on the outermost surface of the surface layer, so that the film becomes denser. It is considered that the injection of the charge is suppressed and the carrier trap is reduced. Further, the existence depth of fluorine atoms is increased by 50
By keeping the thickness within angstrom, desorption of hydrogen atoms when introducing fluorine atoms can be minimized,
It is presumed that the above-mentioned improvement was obtained by an exquisite balance between the two.

From these results, it was found that the diffusion of fluorine is desirably in the range of 50 angstroms (several to several tens of atomic layers), and is desirably diffused in carbon at a concentration of 20% or more. .

The present invention has been made based on the above studies. That is, the electrophotographic photoreceptor and the method of manufacturing the same according to the present invention are characterized in that a plasma is generated between a cathode electrode for applying high-frequency power and a conductive substrate facing the cathode electrode in a reaction vessel capable of reducing pressure. Using a plasma processing apparatus for performing plasma processing on the substrate, a photoconductive layer composed of a non-single-crystal material having silicon atoms as a base is deposited on a substrate to be processed, and at least hydrocarbon is used as a source gas on the photoconductive layer. Using a system gas, a surface layer made of non-single-crystal carbon containing at least hydrogen is provided, and the surface is fluorinated by etching the surface of the surface layer in a plasma in which a gas containing at least fluorine atoms is decomposed. The surface roughness Rz generated on the surface when the reference length is 5 μm is suppressed to less than 1000 Å,
And the fluorine contained in the surface layer is substantially 5
It is characterized in that it is left within 0 Å and the concentration of fluorine with respect to carbon in that region is 20% or more.

According to the electrophotographic apparatus of the present invention, a photosensitive layer composed of a photoconductive layer composed of a non-single-crystal material mainly composed of silicon atoms and a surface layer composed of a non-single-crystal material is sequentially formed on a conductive substrate. An electrophotographic apparatus which uses a laminated cylindrical photoconductor for electrophotography, rotates the cylindrical photoconductor, and repeats charging, exposing, developing, transferring and cleaning, wherein the average particle size of the developer is 0. 004 to 0.012 mm,
The latent image on the latent image carrier is developed to form a toner image, and the toner image is transferred from the latent image carrier to a transfer material. In an electrophotographic apparatus having an image forming apparatus that collects untransferred toner and supplies the collected toner to a developing unit side and reuses the toner in a developing process, the photoconductor has a surface made of non-single-crystal carbon containing at least hydrogen. An electrophotographic apparatus comprising an electrophotographic photosensitive member having a layer.

The surface layer is preferably amorphous or microcrystalline.

According to the present invention, the electrophotographic apparatus according to the above item 1, wherein the surface layer is an electrophotographic photosensitive member prepared by using plasma obtained by decomposing at least a hydrocarbon gas. .

According to the present invention, the surface layer has a thickness of 1 to 450.
It is preferable that the electrophotographic photosensitive member is formed by decomposing at least a hydrocarbon-based gas by a plasma CVD method using a high frequency of MHz.

According to the invention, said surface is between 50 and 450
It is preferable that the electrophotographic photosensitive member is formed by decomposing at least a hydrocarbon gas by a plasma CVD method using a high frequency of MHz.

According to the present invention, the surface layer has a fluorine-containing surface, has a surface roughness Rz of less than 1000 angstroms when the reference length is 5 μm, and It is preferable that the electrophotographic photoreceptor contains fluorine contained substantially within 50 angstroms from the surface and has a fluorine concentration of 20% or more with respect to carbon in the region.

According to the present invention, it is preferable that the surface layer is an electrophotographic photosensitive member which is fluorinated by being etched in a plasma obtained by decomposing a gas containing at least a fluorine atom.

According to the present invention, the amount of etching of the non-single-crystal carbon caused by the etching with the fluorine-containing gas is 20 Å or more in the film thickness direction as a lower limit, and the remaining non-single-crystal carbon film as an upper limit. It is preferable that the electrophotographic photoreceptor has the thinnest portion in a range of 100 Å or more.

According to the present invention, the compound contains a fluorine atom
CF as gas_Four , CHF_Three , CH _Two F_Two , CH_Three F,
C_Two F₆ , C_Two F_Four , CH_Two CF_Two , CIF_Three , SF
₆ , HF, F_Two Use at least one gas
It is preferable that the electrophotographic photosensitive member is used.

According to the present invention, the gas containing a fluorine atom is preferably diluted with at least one of He, Ne, Ar, and N ₂ .

According to the present invention, the blade preferably has a JIS hardness of 74 degrees or more and 78 degrees or less.

[0067]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to the drawings.

FIG. 1 is a schematic view showing an example of the electrophotographic apparatus according to the present invention.
In the figure, reference numeral 121 denotes a cleaning blade.

The cleaning blade according to the present invention is JIS
The hardness is usually 74 degrees or more and 78 degrees or less and has a plate-like form, and is excellent in cleaning performance of the photoreceptor. FIG. 7 shows the results of evaluating the fusion and the durability of the blade when the hardness was changed. It is more effective to increase the hardness of the blade with respect to fusion, but cleaning failure due to the blade is likely to occur. However, by using a photoreceptor having a surface layer of aC or aC: F (fluorinated non-single-crystal carbon) having good slipperiness, a longer blade life could be achieved. Particularly, the surface layer is preferably made of amorphous carbon. Note that non-single-crystal carbon may include microcrystalline carbon in addition to amorphous carbon.

Further, as described above, in recent years where finer image quality is required, the particle size of the toner has been reduced, and the weight average particle size by a coal tar counter or the like is 0.005 to 0.008 mm. Some are used a lot.

On the other hand, the ability to fix the toner image on the transfer material depends on how the toner image on the transfer material is heated in the fixing device. If it becomes shorter, the temperature of the fixing unit must be increased, and the power consumption of the entire electrophotographic apparatus is about 8%.
In a situation where the power consumption of the fixing unit, which accounts for a large percentage, must be increased, the fixing performance of the toner itself is being improved, but this is disadvantageous for fusing which is incompatible with the improvement of the fixing performance.

As a result of observing the dependence of the fusion on the toner particle diameter and the toner fixing property, FIG.
It was found that the better the fixing property, the more disadvantageous to the fusion. As a result, the practical average particle size was 0.004 to 0.01.
When the toner of 2 mm was used, it was found that the toner could be used without any problem.

It has been found that such a situation can be counteracted by using aC or aC: F for the photoreceptor and using a material whose JIS hardness is usually 74 degrees or more and 78 degrees or less. .

According to the present invention, the toner can be recycled by using the photosensitive member and the cleaning blade. By using aC or aC: F, not only the load on the cleaning blade, but also
It has been found that the load on the toner can be reduced. The waste toner when a-SiC and aC and aC: F of the present invention are used for the surface layer is obtained by scanning electron microscope (SEM).
As a result of the observation, it was revealed that when the photoconductors aC and aC: F of the present invention were used, the surface of the waste toner was improved or the damage from the inside was improved. In addition, as a result of measuring the charge amount of the obtained waste toner, when the photoreceptor of the present invention was used, a decrease in the charge amount was able to be suppressed, and it was possible to approach the initial charge amount.

Photoconductor FIG. 4 is a schematic view illustrating an electrophotographic photoconductor according to the present invention. FIG. 4A shows a photoconductor in which the photoconductive layer is referred to as a single-layer type without function separation. On a substrate 401, a charge injection blocking layer 402, a photoconductive layer made of at least hydrogen-containing a-Si 403, a photoconductor in which a surface layer 404 made of non-single-crystal carbon (aC) is laminated.

FIG. 4B shows a photoconductor having a surface layer (aC: F) in which fluorine is diffused on the surface of a non-single-crystal carbon (aC) surface layer. A charge injection blocking layer 402, a photoconductive layer 403 made of a-Si containing at least hydrogen, and a surface layer 404 made of non-single-crystal carbon are formed on a base 401. Reference numeral 405 denotes a surface layer on the outermost surface of which fluorine is present. It represents the diffused area.

The function of the photoconductive layer 403 may be divided into a charge generation layer and a charge transport layer. When the function separation is performed by changing the composition, the composition may be changed continuously.

In the photoreceptors shown in FIGS. 1A and 1B, each layer may have a continuous composition change.
It is not necessary to have a clear interface. Further, the charge injection blocking layer 402 may be omitted as necessary. In addition, an intermediate layer may be provided between the photoconductive layer 103 and the surface layer 404 made of non-single-crystal carbon, if necessary, for the purpose of improving adhesion. As a material of the intermediate layer, a SiC layer having a composition intermediate between the photoconductive layer 403 and the surface layer 404 can be cited, or SiO, SiN or the like may be used. The composition of the intermediate layer may be changed continuously.

The term “non-single-crystal carbon” mainly means amorphous carbon having an intermediate property between graphite (graphite) and diamond, but partially includes microcrystals and polycrystals. May be. These are plasma CV
Although it can be formed by the D method, the sputtering method, the ion plating method, or the like, the film formed by the plasma CVD method has high transparency and hardness and is preferable for use as a surface layer of an electrophotographic photosensitive member.

Plasma C for forming non-single-crystal carbon film
Any frequency can be used as the discharge frequency using the VD method. Industrially, a high frequency of 1 to 450 MHz, particularly 13.56 MHz, which is called an RF frequency band, can be suitably used. In addition, especially 50 to 450 MH
When a high frequency in a frequency band called VHF of z is used, both transparency and hardness can be further increased, so that it is more preferable when used as a surface layer.

The foot used to obtain the effects of the present invention.
The basic gas is CF_Four , CHF _Three , CH_Three F_Two , C
H_Three F, C_Two F₆ , C_Two F_Four , CH_Two CF_Two , CIF_Three 
SF ₆ , HF, F_Two Fluorine radio active in plasma
Anything that can generate culls can be used
Noh. A mixture of these gases, or
Those diluted with another gas such as a rare gas can also be used.

FIG. 2 is a diagram schematically showing an example of an apparatus for depositing a photosensitive member by a plasma CVD method using a high-frequency power supply according to the present invention.

This apparatus is roughly classified into a deposition apparatus 210
0, a source gas supply device 2200, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 2110. A cylindrical deposition substrate 2112 connected to the ground, a heater 2113 for heating the cylindrical deposition substrate, and a raw material gas introduction pipe 2 are provided in a reaction vessel 2110 in the volume apparatus 2100.
114, and a high-frequency matching box 2
A high frequency power supply 2120 is connected via 115.

The raw material gas supply device 2200 includes SiH ₄ ,
Source gas cylinders such as H ₂ , CH ₄ , NO, B ₂ H ₆ , CF ₄ and etching gas cylinders 2221-2226
And valves 2231 to 2236, 2241 to 2246, 2
251-2256 and mass flow controller 22
Each component gas cylinder is connected to a gas introduction pipe 2114 in a reaction vessel 2110 via a valve 2260.

The output of the high-frequency power supply used in the present invention is 1
Any output can be used as long as power suitable for the device used in the range of 0 W to 5000 W or more can be generated. Furthermore, the effect of the present invention can be obtained regardless of the value of the output fluctuation rate of the high-frequency power supply.

As the matching box 2115 to be used, any structure can be suitably used as long as it can match the load with the high frequency power supply 2120.
Further, as a method for obtaining the matching, it is preferable that the adjustment is performed automatically. However, even if the adjustment is performed manually, the effect of the present invention is not affected at all.

Cathode electrode 21 to which high frequency power is applied
Materials of 11 include copper, aluminum, gold, silver, platinum,
Lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel and two or more composite materials of these materials can be used. The shape is preferably a cylindrical shape, but an elliptical shape or a polygonal shape may be used if necessary.

The cathode electrode 2111 may be provided with a cooling means if necessary. As specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

A cylindrical film-forming substrate 2112 used in the present invention.
May have any material or shape according to the purpose of use. For example, the shape is preferably cylindrical when an electrophotographic photoreceptor is manufactured, but may be flat or another shape if necessary. In addition, in the material, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and a composite material of two or more of these materials,
Furthermore, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass,
A material obtained by coating an insulating material such as quartz, ceramics, paper, or the like with a conductive material can be used.

As for the surface shape, unevenness with a relatively large cycle such as cutting tool and dimple processing is not deteriorated in durability against image blur in a high-temperature and high-humidity environment. It is possible. The effect of the present invention can be obtained when Rz is less than 1000 angstroms when the roughness of the outermost surface of the electrophotographic photosensitive member is set to a reference length of 5 μm. Since the surface roughness can be flattened by etching with fluorine plasma after the photoreceptor is deposited, the substrate surface roughness before film formation is not so sensitive.

Hereinafter, an example of a procedure of a method for forming a photoreceptor using the apparatus shown in FIG. 2 will be described.

In the reaction vessel 2110, the cylindrical substrate 2 is formed.
The reactor 112 is installed, and the inside of the reaction vessel 2110 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical substrate 2112 is controlled to a predetermined temperature of 20 ° C. to 500 ° C. by the heater 2113 for heating the cylindrical substrate.

A raw material gas for forming a photoreceptor is supplied to a reaction vessel 211.
To allow the gas to flow into the chamber 0, the valves 2231 to 2
236, confirming that the leak valve 2117 of the reaction vessel is closed, and checking the inflow valves 2241 to 224
6. Outflow valves 2251-2256, auxiliary valve 226
0 is opened, the main valve 2118
To open the reaction vessel 2110 and the gas supply pipe 2116
Exhaust.

Next, the reading of the vacuum system 2119 is 5 × 1 ⁻⁶ T.
When it reaches orr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed. Then gas cylinder 222
Valves 2231 to 2236 are introduced by opening valves 2231 to 2236 from 1 to 2226, and each gas pressure is adjusted to ² kgf / cm ² by pressure regulators 2261 to 2266. Next, the gas is introduced into the mass flow controllers 2211 to 2216 by gradually opening the inflow valves 2241 to 2246.

After preparation for film formation is completed by the above procedure, a photoconductive layer is formed on the cylindrical substrate 2112 for film formation.

When the temperature of the cylindrical film-forming substrate 2112 reaches a predetermined temperature, a necessary one of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened.
A predetermined raw material gas is introduced from each gas cylinder 2221 to 2226 into the reaction vessel 2110 via the gas introduction pipe 2144. Next, each mass flow controller 2211-2
In step 216, each source gas is adjusted to have a predetermined flow rate. At this time, the opening of the main valve 2118 is adjusted while watching the vacuum gauge 2119 so that the inside of the reaction vessel 2110 has a predetermined pressure of 1 Torr or less. When the internal pressure is stabilized, the high frequency power supply 2120 is set to a desired power and supplied to the cathode electrode 2111 through the high frequency matching box 2115 to generate a high frequency glow discharge. The respective source gases introduced into the reaction vessel 2110 are decomposed by the discharge energy, and the cylindrical substrate 2 is formed.
A deposited film mainly containing predetermined silicon atoms is formed on 112. After the desired film thickness is formed, the supply of high-frequency power is stopped, the outflow valves 2251 to 2256 are closed to stop the flow of each source gas into the reaction vessel 2110, and the formation of the deposited film is completed.

Also, when the surface layer of the present invention is formed, basically, the above operation may be repeated, and a film forming gas and an etching gas may be supplied.

More specifically, each of the outflow valves 2251 to 225
6 and the auxiliary valve 2260 are gradually opened, and the raw material gas necessary for the surface layer is supplied from the gas cylinders 2221-2226 through the gas introduction pipe 2114 to the reaction vessel 2.
Introduced into 110. Next, each mass flow controller 2211 to 2216 adjusts each raw material gas to a predetermined flow rate. At this time, the vacuum gauge 2 is controlled so that the inside of the reaction vessel 2110 has a predetermined pressure of 1 Torr or less.
The opening of the main valve 2118 is adjusted while looking at 119. When the internal pressure is stabilized, the high-frequency power supply 2120 is set to a desired power, and the high-frequency power is supplied to the cathode electrode 2111 through the high-frequency matching box 2115 to generate a high-frequency glow discharge. Each source gas introduced into the reaction vessel 2110 is decomposed by this discharge energy, and a surface layer is formed. After the desired film thickness is formed, the supply of high-frequency power is stopped, and each outflow valve 2251
Is closed to stop the flow of each raw material gas into the reaction vessel 2110, and the formation of the surface layer is completed.

After sufficiently exhausting the gas used for film formation from the inside of the reaction vessel, the necessary one of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened, and the gas cylinders 222 to 2226 are used for etching. A necessary gas containing at least a fluorine atom is supplied to the gas introduction pipe 21.
Introduced into the reaction vessel 2110 via. Next, the gas containing the fluorine atom is adjusted by the respective mass flow controllers 2211 to 2216 so as to have a predetermined flow rate. At this time, the opening of the main valve 2118 is adjusted while watching the vacuum gauge 2119 so that the inside of the reaction vessel 2110 has a predetermined pressure of 1 Torr or less. When the internal pressure is stabilized, the high-frequency power supply 2120 is set to a desired power and the high-frequency power is supplied to the cathode electrode 2111 through the high-frequency matching box 2115 to generate a high-frequency glow discharge. This discharge energy causes the reaction vessel 21
The gas containing fluorine atoms introduced into 10 is decomposed,
The surface layer is etched by reacting with the surface layer. The control of the surface shape and the depth of the fluorine atom content can be arbitrarily set by changing the internal pressure, the high-frequency power, the substrate temperature, and the like, so that desired conditions can be set. After the etching of a desired film thickness is performed, the supply of the high-frequency power is stopped, and the outflow valves 2251 to 225
6 is closed to stop the flow of each source gas into the reaction vessel 2110.

During film formation, the cylindrical substrate 2112 may be rotated at a predetermined speed by a driving device (not shown).

FIG. 3 shows another embodiment of the plasma C of FIG.
FIG. 2 is a schematic diagram of an example of an electrophotographic photosensitive member forming apparatus (mass production type) by a VD method. FIG. 3 shows a cross-sectional view of the reaction vessel section.

In FIG. 3, reference numeral 300 denotes a reaction vessel, which has a vacuum tight structure. An exhaust pipe 302 has one end open into the reaction vessel 301 and the other end communicating with an exhaust device (not shown). Reference numeral 303 denotes a discharge space surrounded by the cylindrical substrate 304. High frequency power supply 3
05 is electrically connected to the electrode 307 via the high frequency matching box 306. Cylindrical film-forming substrate 3
04 is set on the rotating shaft 309 while being set in the holders 308 (a) and 308 (b). Motor 3 if necessary
It can be rotated at 10.

As the raw material gas supply device (not shown), the same device as 2200 shown in FIG. 2 may be used. The constituent gases are mixed and connected to a gas introduction pipe 311 in the reaction vessel 301 via a valve 312.

The output of the high-frequency power supply in the image forming apparatus of the present invention can be used with any output as long as it can generate power suitable for the apparatus used in the range of 10 W to 5000 W or more.

Further, the effect of the present invention can be obtained regardless of the value of the fluctuation rate of the high frequency power supply.

As the matching box 306 to be used, any structure can be suitably used as long as it can match the load with the high frequency power supply 306. Further, as a method for obtaining the matching, it is preferable that the adjustment is performed automatically. However, even if the adjustment is performed manually, the effect of the present invention is not affected at all.

The material of the electrode 307 to which high-frequency power is applied is copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, or a composite of two or more of these materials. Materials can be used. The shape is preferably a cylindrical shape, but an elliptical shape or a polygonal shape may be used if necessary.

The electrode 307 may be provided with a cooling means if necessary. As specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

The cylindrical substrate 304 used in the present invention.
May have any material or shape according to the purpose of use. For example, the shape is preferably cylindrical when an electrophotographic photoreceptor is manufactured, but may be flat or another shape if necessary. In addition, in the material, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and a composite material of two or more of these materials,
Furthermore, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass,
A material obtained by coating an insulating material such as quartz, ceramics, paper, or the like with a conductive material can be used.

[0110]

EXAMPLES The present invention will be specifically described below with reference to experimental examples and examples, but the present invention is not limited thereto.

Experimental Example 1 Using a plasma CVD apparatus shown in FIG. 2, a deposition film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1, and two types of photosensitive materials having surfaces a-SiC and a-C were formed. Created body. The preparation conditions are shown in Table 1. The produced photoreceptor was evaluated using an evaluation device obtained by modifying a Canon copier NP6060.
The cleaning property was evaluated. Process speed is 4
The toner was manufactured under the conditions shown in Table 18 at 00 mm / s. The toner particle size is 6.5 μm. The results are shown in Tables 4 to 7.

In the table, ○ indicates a level at which there is no problem in cleaning performance and durability, and X indicates a level at which there is a problem.
Chatter and slippage occurred when the pressure applied to the cleaning blade was small. The surface layer according to the present invention
When the -C film was used, no slip-through occurred even when the pressure applied to the cleaning blade was small. When the cleaning blade of the present invention was used, no fusion occurred even when the pressure of the cleaning blade was small. As described above, in the system of the present invention, it was found that the pressure range of the cleaning blade can be widely used.

EXPERIMENTAL EXAMPLE 2 Using the photosensitive member and the evaluator used in Experimental Example 1, the load on the friction between the drum and the cleaning blade caused by the rotation of the drum with respect to the process speed was examined. All blade pressures were unified to 14 g / cm. The toner particle size is 6.5 μm. The results are shown in FIGS. By using aC for the surface layer and using the cleaning blade of the present invention, the load applied to the drum rotation motor was reduced.

Next, when the pressure of the cleaning blade was lowered and the same experiment was carried out, when the pressure of the cleaning blade was lowered to 8 g / cm, the surface layer was made of aC and the cleaning blade was replaced with a cleaning blade other than that of the present invention. Slip-through and fusion occurred. The surface layer is made of aC, the cleaning blade of the present invention is used, and the pressure is 8 g / c.
The case where m is set is added to FIG. By reducing the pressure of the cleaning blade, the load applied to the drum rotation motor was further reduced.

Experimental Example 3 Deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. 2 to prepare three such photoconductors. Next, etching was performed by changing the high-frequency power under the conditions shown in Table 2 to prepare three types having an etched surface Rz of about 200 Å and about 500 Å. At a power in this range, the penetration depth of fluorine is around 20 angstroms and the concentration is known to be 30-40%.

To evaluate the water repellency of the photoreceptor, the contact angle of the surface was measured with pure water using a contact angle meter (CA-S-roll type) manufactured by Kyowa Interface Science Co., Ltd.
The contact angle was 0 ° or more, and high water repellency was obtained.

Next, the potential characteristics were evaluated. For the evaluation, a change in the surface potential was measured under various conditions by mounting on a measuring instrument imitating a copying machine. To evaluate the potential shift, a constant current was passed through the charger, and the copy was performed for 2 minutes (a Canon copier NP-506).
The charge potential on the surface of the photoreceptor (0: equivalent to 100 sheets) was observed, and the state of the fluctuation was examined. Also, with regard to the ghost potential, after charging, through a process similar to the copying process such as exposure and static elimination, a halftone potential is applied after one round, and the potential difference between the exposed part and the unexposed part is observed. It is obtained by doing.

Next, this photoreceptor was mounted on a modified Canon copier NP-6060, which was modified for experiment,
In an environment of high temperature and high humidity of 80%, 100,000 sheets were continuously copied without using any heating means such as a drum heater and the durability test was performed. At this time, the mag roller was rotated in the counter direction at a higher speed than in normal use to make contact therewith, the pressing pressure of the cleaner blade was set higher than usual, and an environment was set in which the addition to the surface by rubbing was more severe. A test chart (part number: FY99058) manufactured by Canon was used for the copy original.

Before and after such a durability test, the contact angle and the image deletion characteristics were evaluated. The contact angle was evaluated in the same manner as described above, and the image deletion was evaluated based on whether the thin line of the test chart was not blurred.

Further, in order to examine the transfer efficiency, the waste toner was recovered after the durability test, and the weight was accurately measured and compared.

Regarding the easiness of occurrence of scratches, a forced jam test after the durability test was performed 10 times, and then a halftone image was displayed to check the state of the scratches.

Table 8 shows the results of various characteristics obtained by the above evaluation.
Shown in

In the table, each evaluation shows: ◎ very good ◎ good △ good, no practical problem × no practical problem.

Comparative Example 1 Using the plasma CVD apparatus shown in FIG. 2, a deposited film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Two such photoconductors were prepared. Next, the etching was performed under the conditions shown in Table 2 while increasing the high-frequency power as compared with Experimental Example 3, so that the Rz of the etched surface was 100%.
Two types of about 0 Å and about 2,000 Å were prepared. It is known that in this condition range, the fluorine penetration depth is around 35 Å and the concentration is 40 to 50%.

Next, the same durability and evaluation as those in Experimental Example 3 were performed.

Table 8 shows the results of the above change in characteristics together with the results of Experimental Example 3.

In the potential measurement, it was found that there was no problem in both the potential shift and the ghost potential for all the photosensitive members.

With respect to the photoreceptor having an Rz of up to 800 angstroms, no image deletion occurred at 100,000 sheets of durability. However, when the roughness was 1,000 angstroms, an image with a slightly reduced resolution was obtained, and at 2000 angstroms, image deletion occurred. I have. This means that Rz is 1
This is considered to be because the bonding state of the surface changed significantly after the boundary at 000 Å, and fluorine was easily dropped off. In the case of the photoreceptors having a roughness of 1000 Å and 2000 Å where image deletion occurred, the contact angles after 100,000 sheets of durability were deteriorated to 45 and 35, respectively. Also, in the forced jam test, no damage was found on any of the photoconductors.
It was confirmed that the hardness as the surface layer was sufficient.

Experimental Example 4 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Three such photoconductors were prepared. Next, etching was performed under the conditions shown in Table 3, and the penetration temperature of fluorine was changed to 5 Å, 25 Å, and 50 Å by changing the reaction temperature and pressure. The surface roughness accompanying the etching is set to be approximately 500 angstroms.

The fluorine content of these three surface layers with respect to carbon was measured by XPS to find that they were 22, 37, and 22, respectively.
45%.

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 9 shows the results of the obtained characteristics.

Comparative Example 2 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Three such photoconductors were prepared. Next, etching is performed under the conditions shown in Table 3, and the depth and depth of fluorine penetration are 5 Å and 55 Å by changing the reaction temperature and pressure.
Angstrom and 70 Å. The surface roughness accompanying the etching is set to be approximately 500 angstroms.

When the fluorine contents of these three surface layers with respect to carbon were measured by XPS, they were 15, 46,
55%.

Next, the same durability and evaluation as those of Experimental Example 3 were performed.

Table 9 shows the results of the obtained characteristics together with those of Experimental Example 4.

The results of Experimental Example 4 and Comparative Example 2 show that even if the penetration depth is the same, that is, 5 Å, the fluorine content is 20%.
%, The water repellency after durability is reduced. As a result, a slight but blurred image occurred. In addition, compared to those having a fluorine content of 20% or less,
% Or more, it was found that the transfer efficiency was further improved due to the improvement of the releasability.

On the other hand, comparing the case where the penetration depth exceeds 50 Å and the case where the penetration depth is kept within 50 Å even when the amount of fluorine is more than 20%, the potential shift and the ghost potential are found to be kept at 50 Å. Both were found to improve further. From these results, it was found that the depth of penetration of fluorine should be within 50 Å and the amount of fluorine should be 20% or more with respect to carbon.

Experimental Example 5 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Five such photoconductors were prepared. Next, etching was performed under the conditions shown in Table 2. At this time, the etching film thickness was changed to 20 angstroms by changing the etching time.
100 angstroms, 500 angstroms, 2
2,000 angstroms and 2900 angstroms. Since the thickness of the surface layer is 3000 Å, the thickness after etching is 2980,
2900, 2500, 1000, and 100 angstroms.

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 10 shows the results of the obtained image deletion characteristics.

Comparative Example 3 Using the plasma CVD apparatus shown in FIG. 2, a deposited film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Two such photoconductors were prepared. Next, etching was performed under the conditions shown in Table 2. At this time, the etching thickness is changed by changing the etching time to 5 Å, 2 Å,
It was changed to 950 angstroms. Since the thickness of the surface layer is 3000 angstroms, the thickness after etching is 2995, 50 angstroms, respectively.

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 10 shows the obtained results together with the results of Experimental Example 5.

When the etching film thickness is small, the amount of fluorine contained is expected to be small. Comparing the etched film thicknesses of 5 angstroms and 20 angstroms, the ones of 5 angstroms caused slight image deletion after the durability test, while those of 20 angstroms did not. From the analysis of the drum created under the same conditions, the etching film thickness was 5 Å,
The amount of fluorine contained in the surface layer of 20 angstroms is
They were 11% and 28%, respectively. Further, it was found that the transfer efficiency was further improved because the releasability was improved for those having an etching film thickness of 20 angstroms or more as compared with those having an etching film thickness of 5 angstroms. From this,
It has been found that the etching film thickness is desirably 20 angstroms or more.

Conversely, it was found that when the etching film thickness was large, the remaining film thickness was small, and scratches were likely to occur. An etched film having a thickness of 2900 angstroms (having a surface layer with a remaining film thickness of 100 angstroms) and a 2,950 angstroms (having a remaining film thickness of 50 angstroms) were compared. When the presence or absence of scratches was examined by the forced jam test, when the residual film thickness was 500 Å, the surface was sometimes damaged by the forced jam test. On the other hand, when the residual film thickness is 10
No scratches were found when the thickness was 0 Å or more.

From these results, it was found that the film thickness to be removed by etching needs to be at least 20 angstroms or more, and the thickness of the surface layer remaining on the surface is desirably 100 angstroms or more.

Experimental Example 6 Deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG.
Six such photoconductors were prepared. Next, under the conditions listed in Table 2, the gas species was CF ₄ , CHF ₃ , C ₂ F ₆ , and CF ₂ = C
Etching was performed using six types of gases, F ₂ , CIF ₃ , and SF ₆ .

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 11 shows the results of the obtained image deletion characteristics. From these results, it was found that the effects of the present invention can be obtained regardless of the type of the fluorine-containing gas used for etching.

Experimental Example 7 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Four such photoconductors were prepared. Next, under the conditions listed in Table 2, the gas was diluted with four types of He, Ne, and N ₂ (50%).
Then, etching was performed.

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 12 shows the results of the obtained image deletion characteristics. From this result, it was found that the effects of the present invention can be obtained regardless of the dilution of the fluorine-containing gas with the rare gas.

Experimental Example 8 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
Next, etching and fluorination were performed under the conditions shown in Table 2. Under these conditions, Rz is 500 angstroms,
It is known that fluorine diffuses about 200 angstroms, and that about 40% is contained in the same region.

Next, this photoreceptor was transferred to a Canon copier N
It was mounted on a modified P-5060 and 500,000 sheets were durable in the same manner as in Experimental Example 3. However, the surface of the drum was maintained at about 50 ° C. using a humidifier for the drum. Table 13 shows the results.

Comparative Example 4 Using the plasma CVD apparatus shown in FIG. 2, deposited films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1.
No fluorination was performed.

Next, this photoreceptor was transferred to a Canon copier N
It was mounted on a modified P-5060 and 500,000 sheets were durable in the same manner as in Experimental Example 3. However, the surface of the drum was maintained at about 50 ° C. using a humidifier for the drum. The results are shown in Table 13 together with Experimental Example 8.

In Comparative Example 4, traces of fusion appeared on the image, and minute fusion was found on the drum surface. Because the blade pressure is higher than normal use conditions, fusing is likely to occur in the environment. However, when the copying process is performed up to the durable number of sheets required for the a-Si drum, the image can become apparent in the image. There is also. On the other hand, in the drum of Example 8, no fusion occurred even when the drum surface temperature was raised to about 50 ° C. This is presumably because the fluorine existing on the surface improved the slipperiness.

Experimental Example 9 Using the VHF plasma apparatus shown in FIG. 3, a deposited film was sequentially laminated on a cylindrical Al substrate at a discharge frequency of 105 MHz under the conditions shown in Table 14 as an example. Further, for comparison, R of the discharge frequency of 13.56 MHz shown in FIG.
A photoreceptor was prepared under the conditions shown in Table 15 using an F plasma CVD apparatus. Next, etching was performed with fluorine plasma under the same conditions as listed in Table 2.

Next, the same durability and evaluation as in Experimental Example 3 were performed.

Table 16 shows the results of the obtained image deletion characteristics. The one made with 105MHz VHF is 13.5
There is no inferiority in all characteristics as compared with the one made at a high frequency of 6 MHz. In addition, 13. in terms of sensitivity and hardness.
It was found that the quality was further improved as compared with that made at 56 MHz.

Experimental Example 10 The photosensitive members prepared in Experimental Examples 3 to 9 were replaced with
Using the evaluator used in Experimental Example 1, the load force related to the friction between the drum and the cleaning blade, which is generated by the rotation of the drum, was examined according to the process speed. All blade pressures were unified to 14 g / cm. The toner particle size is 6.5 μm. In each case, the load applied to the rotary motor was further reduced as compared with the case of the surface layer a-C.

Next, the same experiment was conducted by lowering the pressure of the cleaning blade. When the pressure of the cleaning blade was reduced to 8 g / cm, the results were as follows when any of the photoconductors produced in Experimental Examples 3 to 9 was used. Also, no slip-through or fusion occurred.

Experimental Example 11 The waste toner used in Experimental Example 10 was collected and observed with a scanning electron microscope (SEM). When aC or aC: F was used for the photoreceptor, the surface of the toner was peeled off, or the damage from the inside could be greatly improved.

Next, the charge amount of this toner was measured. The charge amount was measured as follows. Iron carrier (BF
V200-300) Mix 9.5 g with 0.5 g of toner,
Packed in 50cc polybins. This is agitator (Yayoi YS)
-LD), a measurement sample is put in a conductive screen 53 of 500 mesh (which can be appropriately changed to a size that does not allow magnetic particles to pass through) or a metal container 52, and a metal lid is placed thereon. (See FIG. 9) The entire mainity of the measuring container 52 at this time is weighed to be W1 (g). Next, in the suction device 51 (at least the portion in contact with the measurement container 52 is an insulator), the pressure of the vacuum gauge 55 that is suctioned from the suction port 57 and the air volume control valve 56 is adjusted to 250 mmAq (2452
Pa). In this state, suction is sufficiently performed (about 2 minutes) to remove the toner by suction. The potential of the electrometer 59 at this time is set to V (volt). Here, 58 is a capacitor, whose capacity is C (μF). In addition, the weight of the entire measurement container after suction is weighed and set as W2 (g). This triboelectric charge amount T
(MC / kg) is calculated as follows.

T (mC / kg) = (C × V) / (W1-W2)

Table 17 shows the results of the charge amounts measured as described above. In the conventional photoconductor, the charge amount of the waste toner is smaller than the charge amount of the new toner. However, under the conditions of the present invention, although a decrease in the charge amount was observed, a great improvement was recognized as compared with the related art.

Next, the obtained waste toner was mixed with a new toner, and a check was made on the image. The mixing conditions were as follows: new toner: waste toner = 8: 2. Table 17 shows the results of measuring fog on solid white. In the case of the present invention, fog was greatly improved, and a clear image was obtained even under the waste toner mixing condition.

Example 1 Using a plasma CVD apparatus shown in FIG. 2, a deposited film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 to prepare a photoreceptor having a surface layer of aC. Table 1
It was shown to. The created photoreceptor is copied by Canon copier NP60
The evaluation was performed using 60 modified evaluation devices. The process speed is 450 mm / s. The toner was manufactured under the conditions shown in Table 18, and the particle size was 7 μm. The cleaning blade had a JIS hardness of 76 degrees and the pressure of the cleaning blade was 14 g / cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good. Next, as a result of recycling the untransferred waste toner, no problem such as fogging occurred, and a good image was obtained.

Example 2 Using the plasma CVD apparatus shown in FIG. 2, a deposited film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 to produce such a photoreceptor. Next, etching was performed under the conditions listed in Table 2 while changing the high-frequency power, thereby producing a photoreceptor having an etched surface Rz of about 200 angstroms. The penetration depth of this fluorine was about 20 angstroms, and the concentration was 35%.

The photoreceptor thus prepared was used with a Canon copier NP6
060 was evaluated using a modified evaluation apparatus. The process speed is 510 mm / s. The toner was manufactured under the conditions shown in Table 18 and had a particle size of 6 μm. The cleaner blade has a JIS hardness of 75 degrees and the pressure is 16 g /
cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good.

Next, the ghost potential was measured and the contact angle and the image flow characteristics were evaluated before and after the durability test. Forced jam tests were performed and good results were obtained in all cases. Next, as a result of recycling the untransferred waste toner, no problem such as fogging occurred, and a good image was obtained.

Example 3 Using the plasma CVD apparatus shown in FIG. 2, a deposited film was sequentially laminated on a cylindrical Al substrate at a discharge frequency of 105 MHz under the conditions shown in Table 14 as an example. Also, for comparison, R of the discharge frequency of 13.56 Z MHz shown in FIG.
A photoreceptor was prepared under the conditions shown in Table 15 using an F plasma CVD apparatus. Next, etching was performed with fluorine plasma under the same conditions as listed in Table 2.

The photoreceptor thus produced was used with a Canon copier NP6
The evaluation was performed using a modified evaluation apparatus of No. 060. The process speed is 420 mm / s. The toner was manufactured under the conditions shown in Table 19, and the particle size was 7.5 μm. Use a cleaner blade with a JIS hardness of 78 degrees and a pressure of 10 g.
/ Cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good.

Next, the ghost potential measurement and the contact angle and image flow characteristics were evaluated before and after the durability test. Forced jam tests were performed and good results were obtained in all cases. Next, as a result of recycling the untransferred waste toner, no problem such as fogging occurred, and a good image was obtained.

[0176]

According to the present invention, a surface layer made of non-single-crystal carbon is provided on a photoconductive layer, and the surface layer has a fluorinated surface.
By using the S hardness of 74 degrees or more and 78 degrees or less, the friction force and the torque are increased,
Even when a toner having a small particle diameter was used, the cleaning property was improved and the friction was able to be reduced. Also, by reducing the load on the photosensitive member and the cleaning blade, the load on the waste toner was reduced, and the characteristics of the waste toner in the cleaner could be improved. Therefore, there is no difference in physical properties between the newly replenished toner and the recycled toner when the toner is recycled, and problems such as fogging and low density caused by toner recycling can be solved.
The surface layer made of non-single-crystal carbon of the photoreceptor has a roughness Rz of less than 1000 angstroms when observed within a minute range when the reference length is 5 μm, and the fluorine contained in the surface layer Is substantially 50 from the surface
Angstroms are present within the region, and the concentration of fluorine to carbon in the region is set to 20% or more,
A photoreceptor having excellent water repellency and providing high-quality images without a heating means in a high-temperature and high-humidity environment was obtained with very good reproducibility. The corona discharge product is less likely to adhere, and there is no need to provide a heating means, so that toner fusion hardly occurs.

[0177]

[Table 1]

[0178]

[Table 2]

[0179]

[Table 3]

[0180]

[Table 4]

[0181]

[Table 5]

[0182]

[Table 6]

[0183]

[Table 7]

[0184]

[Table 8]

[0185]

[Table 9]

[0186]

[Table 10]

[0187]

[Table 11]

[0188]

[Table 12]

[0189]

[Table 13]

[0190]

[Table 14]

[0191]

[Table 15]

[0192]

[Table 16]

[0193]

[Table 17]

[0194]

[Table 18]

[0195]

[Table 19]

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an electrophotographic apparatus.

FIG. 2 is a schematic view of a deposition apparatus for forming a photoreceptor on a substrate by the PCVD method of the present invention.

FIG. 3 is a schematic diagram of a deposition apparatus for forming a photoconductor using a VHF-PCVD method.

FIG. 4A is a schematic cross-sectional view illustrating a layer configuration of an electrophotographic photosensitive member. (B) A schematic cross-sectional view illustrating a layer configuration of the electrophotographic photosensitive member when the surface is subjected to a fluorine treatment.

FIG. 5 is a diagram illustrating a load applied to a rotary motor at the time of stopping and rotating when a blade and a surface layer are changed when a process speed is changed.

FIG. 6 is a diagram illustrating a load applied to a rotary motor at the time of stopping and rotating when a blade and a surface layer are changed when a process speed is changed.

FIG. 7 is a diagram showing the relationship between the JIS hardness of the blade of the present invention and the cleaning failure due to fusion and chipping of the blade.

FIG. 8 is a diagram showing a relationship between toner particle size, fusing, and image quality.

FIG. 9 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of toner.

[Explanation of symbols]

 Reference Signs List 101 photosensitive member 102 main charger 103 electrostatic latent image forming portion 104 developing device 105 transfer paper supply system 106 (a) transfer charger 106 (b) separation charger 107 cleaner 108 transport system 109 static elimination light source 110 electrostatic latent image formation Part 111 Platen glass 112 Document 113, 114, 115, 116 Mirror 117 Lens unit 118 Lens 121 Cleaning blade 122 Registration roller 123 Heat source (internal heater) 2100 Deposition device 2110 Reaction vessel 2111 Cathode electrode 2112 Conductive substrate 2113 Heater for substrate heating 2114 Gas inlet pipe 2115 High frequency matching box 2116 Gas pipe 2117 Leak valve 2118 Main valve 2119 Vacuum system 2120 High frequency power supply 2200 Gas supply device 2211-2216 Mass Flow Controllers 2221 to 2226 Bombs 2231 to 2236 Valves 2241 to 2246 Inflow valves 2251 to 2256 Outflow valves 2260 Auxiliary valves 2261 to 2266 Pressure regulators 300 Deposition equipment using VHF (mass production type) 301 Reaction vessel 302 Exhaust pipe 303 Discharge space 304 Cylindrical film-formed substrate 305 High-frequency power supply 306 Matching box 307 Electrode 308 (a), (b) Substrate holder 309 Rotating shaft 310 Motor 311 Gas introduction tube 312 Gas introduction valve 401 Conductive substrate 402 Charge injection blocking layer 403 Photoconductive layer 404 Surface layer 405 Area where fluorine is diffused

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideaki Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Makoto Shinbayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Yuji Mikituri 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H034 BA00 BF05 CA04 CB01 2H068 CA03 DA04 DA14 DA20 DA25 EA24 FA01 FA03 FA15 FA16 FC15

Claims (11)

[Claims] 1. An electrophotographic method in which a photoconductive layer composed of a non-single-crystal material mainly composed of silicon atoms and a photosensitive layer composed of a surface layer composed of a non-single-crystal material are sequentially laminated on a conductive substrate. An electrophotographic apparatus that uses a cylindrical photoreceptor, rotates the cylindrical photoreceptor, and repeats charging, exposure, development, transfer, and cleaning, wherein the average particle size of the developer is 0.0
04 to 0.012 mm, the latent image on the latent image carrier is developed to form a toner image, and the toner image is transferred from the latent image carrier to a transfer material, and then the latent image carrier is cleaned with a blade. An electrophotographic apparatus having an image forming apparatus that collects untransferred toner on the latent image carrier and supplies the collected toner to the developing unit side and reuses the toner in the developing process. An electrophotographic photoreceptor having a surface layer made of non-single-crystal carbon. 2. The electrophotographic apparatus according to claim 1, wherein the surface layer is amorphous or microcrystalline. 3. The electrophotographic apparatus according to claim 1, wherein said surface layer is an electrophotographic photosensitive member formed by using plasma obtained by decomposing at least a hydrocarbon-based gas. 4. The electrophotographic photoreceptor according to claim 1, wherein said surface layer is formed by decomposing at least a hydrocarbon gas by a plasma CVD method using a high frequency of 1 to 450 MHz. 4. The electrophotographic apparatus according to 1 or 3. 5. The electrophotographic photoreceptor according to claim 4, wherein the surface is formed by decomposing at least a hydrocarbon gas by a plasma CVD method using a high frequency of 50 to 450 MHz. Electrophotographic equipment. 6. The surface layer has a fluorine-containing surface, has a surface roughness Rz of less than 1000 Å when a reference length is 5 μm, and has a fluorine content contained in the surface layer. 2. The electrophotographic apparatus according to claim 1, wherein the electrophotographic photoreceptor substantially exists within 50 angstroms from the surface, and the concentration of fluorine to carbon in the region is 20% or more. 7. The electrophotographic apparatus according to claim 6, wherein said surface layer is an electrophotographic photosensitive member fluorinated by being etched in plasma obtained by decomposing a gas containing at least fluorine atoms. . 8. An etching amount generated in the non-single-crystal carbon by etching with the gas containing a fluorine atom is not less than 20 angstroms in a film thickness direction as a lower limit, and is the thinnest film thickness of the remaining non-single-crystal carbon as an upper limit. 8. The electrophotographic apparatus according to claim 6, wherein the portion is an electrophotographic photosensitive member having a range of 100 angstrom or more. 9. The gas containing a fluorine atom as CF
_Four , CHF_Three , CH _Two F_Two , CH_Three F, C_Two F₆ , C_Two 
F_Four , CH_Two CF_Two , CIF_Three , SF₆ , HF, F_Two of
Electrophotographic photosensitive using at least one gas
9. The method according to claim 6, wherein the body is a body.
Electrophotographic device. 10. The gas containing a fluorine atom is He,
Ne, Ar, electrophotographic apparatus according to any one of claims 6-9, characterized in that is obtained by dilution with at least one or more gases of N _2. 11. The blade according to claim 7, wherein said blade has a JIS hardness of 74 degrees or more.
The electrophotographic apparatus according to claim 1, wherein the angle is 8 degrees or less.