JPH11249523A - Electrophotographic system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a cleaning performance, to prolong the life of a blade, to lower a load for a photoreceptor, and to reduce power consumption of a rotary motor, in a high speed electrophotographic system, where frictional force and the torque is respectively raised. SOLUTION: As for the high speed electrophotographic system making the cylindrical photoreceptor rotated, for repeating electrification/exposure/transfer/ cleaning, the system has a constitution of developing the developer on the photoreceptor, transferring the same on transfer material and performing the cleaning the photoreceptor after the developer is transferred thereon by a blade, adopting the photoreceptor provided with a surface layer composed by non-single crystal carbon containing at least, a hydrogen atom for the photoreceptor, using the developer of 0.005 to 0.008 mm average grain size for the developer, and adopting the cleaning blade with JIS hardness from 74 degree to 78 degree, processing speed based on traveling speed of the surface on the photoreceptor is >=400 mm/sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic system (apparatus) which uses a cylindrical photoreceptor and rotates it to continuously perform charging, exposure, development, transfer and cleaning. More specifically, the present invention provides a high-speed electrophotographic process using a cylindrical photoreceptor having an amorphous silicon-based photoconductive layer and a developer having a small particle diameter. A high-quality image without image blur or image deletion can be obtained without the provision of a heating means, and has high durability enough to maintain the characteristics, little fluctuation in potential characteristics, and high-quality images. The present invention relates to an electrophotographic system (apparatus) which is stably obtained and does not cause a ghost phenomenon.

[0002]

2. Description of the Related Art (1) Electrophotographic apparatus: Conventionally, as an electrophotographic method, US Pat. No. 2,297,692, JP-B-42-23910 and JP-B-43 are used.
Numerous methods are known, as described in JP-A-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. Is transferred and fixed by heating, pressure, heating and pressurizing 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. Had been discharged. With an increase in the amount of information processing in recent years, the demand for electrophotographic apparatuses (ie, large high-speed machines) such as copiers and laser beam printers having a large copy volume is increasing.

[0003] As a photoreceptor for electrophotography, an improvement in electrophotographic characteristics corresponding to high speed is required, and in recent years, a more sophisticated image quality is required. Particle size reduction is promoted, and the weight average particle size by a Coulter counter or the like is 0.005 to 0.5.
008 mm is widely 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. The temperature of the fixing device must be increased, and the power consumption of the fixing device, which accounts for about 80% of the power consumption of the entire electrophotographic apparatus, has to be increased. Even in such a situation, reduction of power consumption as a market need is an important issue, and the fixing performance of the toner itself has been improved. However, it is disadvantageous for the fusion which is contrary to the fixing performance. Further, the fact that the particle size of the toner is small is also a more disadvantageous direction for fusing, so that the toner is less likely to adhere to the photoreceptor and to enhance the ability to scrape off the adhered toner, It is necessary to take measures such as increasing the hardness of the blade, but increasing the hardness of the blade
As the characteristics of the blade are changed from a rubbery state to a glassy state, the material becomes brittle and the life of the blade is shortened.

Incidentally, amorphous silicon (a-S)
At present, the surface of the i) type photoreceptor has a large number of projections due to its manufacturing method. The height of such projections is generally about 0.002 to 0.003 mm, but rarely exceeds 0.01 mm, and such projections may damage the blade. Particularly, since the blade having the above-described hardness is brittle, chipping occurs when damaged at high speed, and the cleaning performance may not be maintained. The only means for maintaining the cleaning performance is to set the height of the protrusion to 0.006 mm.
The following is a limitation, and polishing is required in the drum manufacturing process as necessary. The a-Si-based photoreceptor has a high surface hardness, and has not conventionally caused deterioration in image quality such as abrasion of the photoreceptor surface by repeated use. This is because when the cleaning blade scrapes off the toner on the photoreceptor, an extremely small amount of toner slips between the cleaning blade and the photoreceptor and plays a role of a lubricant. FIG.
As shown in FIG. 1, by the cleaning mug roller,
This is achieved by regulating the amount of toner coating on the drum and regulating the convection state and the amount of toner passing through the blade entry portion by the contact angle and pressure of the cleaning blade. However, as shown in FIG. 20, the atomization of the toner is in a disadvantageous direction with respect to fusion and photoreceptor shaving, and as shown in FIG. It is a disadvantageous direction. That is, when the toner in the form of fine particles changes in the degree of agglomeration and the lubricating function is reduced, or when the rush energy of the toner is increased due to an increase in the speed of the apparatus, the convection state of the toner in the portion where the blade enters and the amount of bleeding are greatly affected. And the photoreceptor surface may be scraped by repeated use. It is difficult to avoid this state by the contact angle and pressure of the cleaning blade, and a phenomenon may occur that causes image quality deterioration due to scraping of the photoreceptor surface. On the other hand, in order to improve the cleaning property, a grooved blade as described in JP-A-54-143149 or a grooved blade as disclosed in
For example, a blade with a protrusion as described in Japanese Patent No. 4777, and the like have been devised.
No mention is made of a cleaning system suitable for an electrophotographic apparatus comprising a fine particle toner having a fixing property of 0 mm / sec or more and an a-Si photoreceptor.

[0005] Under the circumstances described above, there is a need for a cleaning system suitable for a high-speed electrophotographic apparatus capable of high image quality. FIG. 1A is a schematic view showing an example of an image forming process of a copying machine, in which the temperature is controlled by a planar inner surface heater 123 rotating in an arrow X direction.
Around the photosensitive member 101, a main charger 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 are provided. Hereinafter, the image forming process will be described with further specific examples. The photoconductor 101 is uniformly charged by the main charger 102 to which a high voltage of +6 to 8 kV is applied.
The light emitted from the electrostatic latent image forming portion, that is, the light emitted from the lamp 110 is reflected on the original 112 placed on the original platen glass 111, passes through mirrors 113, 114, and 115, and is formed by the lens 118 of the lens unit 117. An electrostatic latent image is formed and guided and projected via the mirror 116. The toner is supplied from the developing device 104 to the latent image to form a toner image. Further, the image formation is performed by laser or L
In a digital electrophotographic apparatus performed by the ED, FIG.
As shown in (b), the image information of the document 112 is converted into a digital signal by the CCD 114 via the mirror 113. Based on the signal, a latent image is formed on the photoconductor 101 by the laser 115 / polygon mirror 117. Alternatively, an LED may be used instead of the laser. On the other hand, through the transfer paper supply system 105, the registration rollers 12
0, the leading end timing is adjusted, and the transfer material P supplied in the direction of the photoconductor is opposite in polarity to the toner from the back in the gap between the transfer charger 106 (a) and the photoconductor 101 to which a high voltage of +7 to 8 kV is applied. Is applied, whereby the toner image on the photoreceptor surface is transferred to the transfer material P. 1
The transfer material P is applied by the separation charger 106 (b) to which a high-voltage AC voltage of 300 to 600 Hz is applied at 2 to 14 kVp-p.
Reaches a fixing device (not shown) through the transfer paper transport system 108, and the toner image is fixed and discharged out of the device. The toner remaining on the photoconductor 101 is supplied to the cleaner unit 107.
After the amount of coating on the drum is regulated by the cleaning roller 122, the electrostatic latent image that is scraped off by the cleaning blade 121 and remains is discharged by the charge removing light source 109.
Will be erased by

(2) Electrophotographic photoreceptor: Various materials such as selenium, cadmium sulfide, zinc oxide, phthalocyanine, and amorphous silicon (hereinafter referred to as a-Si) are used as element members for the electrophotographic photoreceptor. Has been proposed. Above all, a non-single-crystal deposited film containing silicon atoms typified by a-Si as a main component, for example, hydrogen and / or
An amorphous deposited film of a-Si or the like compensated with halogen (eg, fluorine, chlorine, etc.) has high performance, high durability,
It has been proposed as a non-polluting photoreceptor, some of which have been put to practical use. For example, JP-A-54-86341 discloses an electrophotographic photoconductor in which a photoconductive layer is mainly formed of a-Si. Such an a-Si photosensitive member has a high surface hardness and a semiconductor laser (770 nm to 800 nm).
m) and has high sensitivity to long-wavelength light such as m), and hardly shows any deterioration due to repeated use. In particular, it is widely used as a photoconductor for electrophotography such as high-speed copying machines and LBPs (laser beam printers). As a method for forming a deposited film for an electrophotographic photoreceptor, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method),
A method of decomposing a source gas by light (photo CVD method), a method of decomposing a source gas by plasma (plasma CVD)
Law) is known. Among them, the plasma CVD method, that is, the raw material gas is DC or high frequency, (RF, VHF)
Decomposition by microwave glow discharge etc. to form a thin film deposition film on a substrate such as glass, quartz, heat resistant synthetic resin film, stainless steel, aluminum etc. is practical for forming amorphous silicon deposition film for electrophotography The technology has been very advanced, and various devices 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 the ability to be used for forming insulating materials such as oxide films and nitride films. Plasma CVD using a high frequency power supply of 50 MHz or more using a parallel plate type plasma CVD apparatus.
There is a report of the law (Plasma Chemistrya
nd Plasma Processing, Vol.
7, No. 3 (1987) pp. 267-273), it has been shown that by increasing the discharge frequency higher than the conventional 13.56 MHz, the deposition rate can be improved without lowering the performance of the deposited film. ing. In addition, reports of increasing the discharge frequency have also been made by sputtering or the like, and their studies have been widely studied in recent years.

When the a-Si photoreceptor prepared by the above-described method is applied to an electrophotographic apparatus, in most cases, a wire electrode (50 to 50) is used as a means for charging and discharging the photoreceptor.
Corona chargers (corotrons, scorotrons) mainly using a 100 μmφ gold-plated metal wire such as a tungsten wire) and a shield plate are used. That is, a high voltage (4 to 8 k) is applied to the wire electrode of the corona charger.
(Approximately V) is applied to the surface of the photoreceptor to cause the corona current to act on the surface of the photoreceptor, thereby performing surface charging and static elimination. The corona charger is excellent in uniform charging and static elimination. However, ozone (O ₃ ) is generated by corona discharge,
Nitrogen in the air is oxidized to generate nitrogen oxides (NOx) and the like. 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. Such corona discharge products have a strong hygroscopic property, and the surface of the photoreceptor which has caused the adsorption has a low or high resistance due to moisture absorption of the corona discharge products, and the charge retention ability is substantially or partially reduced. This causes image defects such as image blurring and image deletion (charge of the photoreceptor surface leaks in the surface direction and the electrostatic latent image pattern is not destroyed or formed). In addition, the corona discharge products adhered to the inner surface of the shield plate of the corona charger volatilized and released not only during the operation of the electrophotographic apparatus but also during the rest of the apparatus such as at night, which corresponded to the discharge opening of the charger. It adheres to the surface of the photoconductor and further absorbs moisture, thereby lowering the resistance of the surface of the photoconductor. 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 above-described 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 amount of corona charging current and the amount of ozone generated are in a proportional relationship,
In a configuration in which the photoconductor is an a-Si photoconductor and is charged and destaticized by corona charging, the amount of ozone generated is particularly large, and therefore, there is a problem of image blur and image deletion due to generation of the corona discharge product. Is particularly large.
In the case of the a-Si photoreceptor, the surface hardness is much higher than that of the other photoreceptors, which is adversely affected, and the corona discharge products adhered to the surface of the photoreceptor easily remain forever.

The following two methods have been proposed as methods for preventing the above-described image blur and image deletion phenomenon. One of them is to incorporate a heater into the photoreceptor to heat the photoreceptor or to blow warm air to the photoreceptor by a hot air blower to heat the photoreceptor surface (30 to 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. Another method is to improve the water repellency of the surface so that the corona discharge products are hardly adhered from the beginning, thereby preventing image deletion. As a conventional technique, Japanese Patent Application Laid-Open No. 61-289354 (hereinafter referred to as Reference 1) discloses an aC surface layer whose surface is plasma-treated with a gas containing fluorine.
JP-A-64-84257 (hereinafter referred to as Reference 2) discloses that a surface layer made of amorphous carbon containing fluorine has a depth of 0.1 to 0.5 μm and a width of 0.1 μm. An electrophotographic photoreceptor having irregularities of about 1 μm and a method of manufacturing the same are disclosed. According to this technique, it is possible to further improve the water repellency by increasing the surface area.

[0009]

The load on the electrophotographic photoreceptor has been reduced by increasing the speed of the electrophotographic apparatus, reducing the toner particle size for improving the sharpness of the image, and improving the fixing property. It is changing. That is, with the speeding up,
The cleaning performance is reduced and the frictional force is increased. In the electrophotographic process, when the process speed is high, the developer or the like easily passes through due to chatter of the cleaning blade. The solution is to increase the pressing pressure of the cleaning blade as the process speed increases, preventing slip-through, etc., but as the process speed increases, the frictional force increases, and the load on the photoconductor and the electrophotographic device increases. growing. Also, regarding the reduction of the particle size of the developer,
Problems similar to those at high speeds and problems with fusion are likely to occur. The sharpness of the image increases as the developer particle size decreases, but when used in a high-speed electrophotographic apparatus, the load increases. In addition, problems such as fusion are likely to occur in the improvement of fixability, and it is necessary to increase the blade pressure in order to solve these problems. Therefore, in the process of obtaining a clear image on a high-speed machine, if the life of the cleaning blade is shortened, scratches due to foreign matter are more likely to stick to the photoconductor, or problems such as increased power of the rotating motor due to increased load are caused. There is. Although the problem of image deletion can be solved by the heating device of the drum, there is a new problem as described below due to an increase in demand for a copying machine in recent years. That is, from the viewpoint of energy saving and ecology, it has become more desirable not to perform heating means using a drum heater. Another problem is that when a high-quality a-Si photosensitive drum is mounted on a full-color copying machine, there is a high possibility that low-melting-point toner such as color toner is fused to the drum surface. Still another problem is that the image density is partially increased or decreased in the rotation cycle of the rotating cylindrical developer carrier. This is because the rotating cylindrical developer carrier expands due to the heat of the photoreceptor while the apparatus is at rest, and the distance between the rotating cylindrical developer carrier and the photoreceptor facing portion is shortened. is there. From these problems, there is a demand for a photoreceptor that does not cause image blur or image deletion without heating.

[0010] With respect to the techniques for improving the water repellency disclosed in the above-mentioned documents 1 and 2, the improvement of the water repellency when exposed to ozone is described, but the durability is increased by actually performing a large number of copying operations. There is no description of the results of the test. Therefore, the present inventors conducted a follow-up test in accordance with the method disclosed in Document 1 and performed a durability test in which a copying operation was continuously performed without using a heating means. However, in consideration of high durability, which is one of the merits of the a-Si photoreceptor, it has been found that there is a need to further improve the water repellency in a paper passing durability test for a large number of sheets. Similarly, an additional test was performed for the method disclosed in Reference 2. In this case, it was confirmed that increasing the surface area by providing irregularities on the surface was effective in improving the water repellency, but the effect of the water repellency was reduced by performing paper passing durability. I understood. It is considered that this is because amorphous carbon containing fluorine is soft and is gradually scraped by sliding of the peripheral member of the photoreceptor and paper.
From these, image blur, without using the heating means,
It has a highly water-repellent surface layer so as not to cause image deletion,
Also, a photoreceptor whose high water repellency does not deteriorate for a long time even by a large number of copying operations is desired. Also, in addition to the problem of image deletion, due to the growing demand for copied images in recent years,
There is a strong need for a technology 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 copy originals that make heavy use of halftones has increased.Therefore, stricter standards have been required for density stability than before. Have been. When the charging potential fluctuates with time when the same charging is desired, the fluctuation of the potential is called a potential shift, and it can be said that the smaller this is, the higher the stability. With regard to photographic originals, demands for the ghost phenomenon as well as the stability of density become severe. 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, and 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. A smaller value indicates that a 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, but there is a strong need for a technique that can further improve the potential shift and the ghost potential.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-speed electrophotographic system (electrophotographic apparatus) in which the frictional force and torque are increased, even when a toner having a small particle size and excellent fixability is used. Improves and reduces friction,
An object of the present invention is to reduce the load applied to the photoconductor and the cleaning blade, thereby providing excellent cleaning properties, prolonging the life of the blade, reducing the load on the photoconductor, and reducing the power of the rotating motor. Another object of the present invention is to provide a high-quality image free of image blur and image deletion without providing a heating means for the photoconductor under any environment, and to maintain the characteristics of the photoconductor in a desired state. To provide an electrophotographic system (electrophotographic apparatus). Another object of the present invention is to provide an electrophotographic system (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.
Is to provide. Another object of the present invention is to achieve prevention of fusing of a low-melting toner such as a color toner and prevention of density unevenness occurring in a rotation cycle of a developer carrying member without using a heating means of a photosensitive member. An object of the present invention is to provide an electrophotographic system (electrophotographic apparatus).

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems in the prior art and to achieve the above object, the present inventors have conducted intensive studies through experiments. The present inventors first focused on improving the cleaning property and tried to increase the slipperiness of the surface of the photoconductor. As a result, it was found that when a photoreceptor having a specific aC surface layer was used, the frictional force was reduced. The present inventors further changed the hardness of the cleaning blade with respect to the cleaning property.
It has been found that by using the S-hardness in the range of 74 to 78 degrees, the cleaning property is excellent, the sliding property is improved, and the load on the photosensitive member and the cleaning blade is reduced. Then, the inventors tried to reduce the pressure of the cleaning 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. In addition, the present inventors, in the cleaning of the photoreceptor surface by the plate cleaning blade of JIS hardness described above,
The angle between the blade and the photoreceptor surface, that is, the blade contact angle [θ1 (degree)], and the rotation of the contact surface between the blade and the photoreceptor surface (hereinafter referred to as “nip”) When the angle [θ2 (degree)] (hereinafter, referred to as a blade drum sandwiching angle) formed by the blade surface continuous with the nip and the photoconductor surface on the upstream side was examined, the blade contact angle θ1 (degree ) Is in the range of 20 ≦ θ1 ≦ 40, and when the blade drum sandwiching angle θ2 (degree) is in the range of 5 ≦ θ2 ≦ 30, the cleaning characteristics are further improved. As a result, even in the process of obtaining a clear image in a high-speed machine, it has become possible to extend the life of the cleaning blade, increase the durability of the photoconductor due to damage caused by foreign matter, and reduce the power consumption by reducing the load on the rotating motor. .

Next, the present inventors have paid attention to the shape of the surface of the non-single-crystal carbon film as a method for maintaining high water repellency on the surface of the photosensitive member to be used. A method for controlling the water repellency by forming an uneven shape on the surface is disclosed in JP-A-64-84257 as described above, but in this method, the surface is gradually cut by a paper passing durability test. The effect of the unevenness could not be confirmed. Therefore, taking into account the surface layer of high hardness that cannot be scraped, that is, the surface layer obtained by etching non-single-crystal carbon not containing fluorine, which is disclosed in Japanese Patent Application Laid-Open No. 61-289354, with fluorine plasma, is taken into consideration by various methods. The experiment was conducted by changing the surface irregularities. Using an atomic force microscope (AFM) to observe the detailed shape of the surface, the surface shape was changed by fluorine plasma etching and examined in detail. As a result, it was found that the surface of the photoreceptor having low durability was very rough at the atomic level, and the surface of the photoreceptor 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 by using the surface roughness as an index. As a result, the durability greatly changed at a boundary of the ten-point average roughness (Rz) of about 1000 ° in a visual field of 5 μm square. Was found. When etching is performed under severe conditions such that Rz exceeds 1000 °, for example, at an extremely high etching rate such as greatly exceeding 100 ° / sec, the surface shape is greatly changed, resulting in a very rough surface, and durability against image deletion. Greatly deteriorated. On the other hand, if Rz is 1000Å
When etching is performed to suppress the following, the surface shape is formed of a gentle curved surface, the durability against image flow is greatly improved, and the less the unevenness on the surface, the longer the image flow characteristics can be maintained. It turned out that there was a tendency.

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 than the case where the surface layer has irregularities. However, with respect to the durability for maintaining the high water repellency, the flatness is improved. The reason for this is not yet clear, but we think as follows. If the surface has irregularities, the effect of fluorine is large because the surface area increases,
Water repellency is improved. However, by performing the actual copying operation, the surface is rubbed by various members and paper,
Since the force applied to the convex portion is concentrated, it is considered that the sliding condition becomes more severe. If such 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 cut, fluorine near the outermost surface or carbon bonded to fluorine is 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. In contrast, 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, when the surface is flattened, the slipperiness is worsened and the wear characteristics are often deteriorated. The sliding property is improved as compared with the photoreceptor for use, and an effect that no cleaning failure occurs at all can be obtained. Therefore, the friction force is further reduced as compared with the case where aC is used for the surface layer.

Next, the amount of fluorine near the surface was examined. That is, an experiment was performed 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. Further, as an unexpected effect, it has been found that the potential characteristic greatly changes at about 50 ° 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 ° from the outermost surface. The reason why the potential characteristics are improved only under the condition that the fluorine atoms are substantially contained within 50 ° 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 more dense. That is, it is thought that the injection of the charge is suppressed and the carrier trap is reduced. Further, by setting the depth of the fluorine atoms within 50 °, desorption of the hydrogen atoms during the introduction of the fluorine atoms can be minimized, and it is speculated that the above-mentioned improvement was obtained by an exquisite balance between the two. Is done. From these facts, it was found that the diffusion of fluorine is desirably in the range of 50 ° (several to several tens of atomic layers), and is desirably diffused at a concentration of 20% or more with respect to carbon.

The photoreceptor (electrophotographic photoreceptor) used in the electrophotographic system (electrophotographic apparatus) of the present invention includes:
This is based on the facts described above. The preferred embodiment of the electrophotographic photoreceptor in the present invention has the following constitution. That is, in a reaction vessel that can be depressurized, plasma is generated between a cathode electrode to which high-frequency power is applied and a conductive substrate facing the cathode electrode, and a plasma processing apparatus that performs plasma processing on the substrate is used to perform processing. Depositing a photoconductive layer made of a non-single-crystal material having silicon atoms as a base material on a substrate, using at least a hydrocarbon-based gas as a raw material gas on the photoconductive layer, and forming a non-single-crystal containing at least hydrogen; When a surface layer made of carbon 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, and a reference length of 5 μm is generated on the surface by etching. Surface roughness Rz of less than 1000 °, and fluorine contained in the surface layer is substantially present within 50 ° from the surface, and in that region, Characterized in that the concentration of fluorine to carbon at least 20%.

Hereinafter, the electrophotographic system (electrophotographic apparatus) of the present invention will be specifically described. The electrophotographic system of the present invention rotates an electrophotographic photoconductor (a cylindrical photoconductor for electrophotography) (hereinafter simply referred to as a photoconductor or a photoconductor drum in some cases) to perform charging, exposure, development, transfer, and cleaning. An electrophotographic system for repetition, in which a developer is developed on the photoreceptor, then transferred to a transfer material, and the photoreceptor after the developer is transferred is cleaned by a blade. A photoconductor in which a photoconductive layer composed of a non-single-crystal material having silicon atoms as a base and a surface layer composed of non-single-crystal carbon containing at least hydrogen atoms are laminated in this order on a conductive substrate (hereinafter, referred to as The photoconductor is sometimes referred to as “a-Si photoconductor”), and the developer has an average particle diameter of 0.005.
A developer having a JIS hardness of 74 degrees or more and 78 degrees or less, and a process speed based on the moving speed of the surface of the photoreceptor of 400 mm / sec or more. It is characterized by. As a preferred specific example of the photoreceptor used herein, as described above, the surface of the surface layer made of non-single-crystal carbon containing at least hydrogen atoms is etched by etching in a plasma in which fluorine gas is decomposed. Can be mentioned. Further, the photoconductive layer of the photoreceptor may have a configuration described below. That is, the photoconductive layer is made of a non-single-crystal material containing a silicon atom as a base, a hydrogen atom and / or a halogen atom, and an element belonging to Group IIIb of the Periodic Table. Is 25 to 35 atomic%, the optical band gap is 1.80 eV or more, the characteristic energy of the exponential function tail obtained from the light absorption spectrum is 55 meV or less, and a certain amount of light incident on the photoconductive layer is absorbed. And other regions in the Periodic Table III
The contents of elements belonging to group b are different.

The cleaning blade and the developer in the electrophotographic system (electrophotographic apparatus) of the present invention will be described. The cleaning blade (see 121 in FIG. 1) of the present invention has a plate shape made of a material having a JIS hardness of usually 74 degrees or more and 78 degrees or less, and has excellent photoreceptor cleaning properties. 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 chipping of the blade tends to occur. However, aC or a
-C: By using a photoreceptor having a surface layer of F,
Longer blade life can be achieved. Further, as described above, in recent years where finer image quality is required, the particle size of the toner has been reduced, and the toner having a weight average particle size of 0.005 to 0.008 mm by a Coulter counter or the like is often used. It is 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. The temperature of the fixing unit must be increased, and the power consumption of the fixing unit, which accounts for about 80% of the total power consumption of the electrophotographic apparatus, must be increased. Although it is advanced, it is disadvantageous for fusion which is inconsistent with the improvement of fixability. As a result of observing the dependence of the fusion on the toner particle diameter and the dependence on the toner fixability, it can be seen from FIGS. 8, 20 and 21 that the smaller the particle diameter, the better the fixability, the more disadvantageous the fusion. Was. It has been found that such a situation can be countered by using aC or aC: F for the photoreceptor and using a material having a JIS hardness of usually 74 to 78 degrees. Further, the above-described photoreceptor is used, and as described above, the average particle diameter is 0.005 to 0.008.
mm fine particle toner as a developer
In the electrophotographic system of the present invention in which a plate-like elastic blade having a hardness of 74 degrees or more and 78 degrees or less is used as the cleaning blade, the blade contact angle θ1 (degree) is 20 ≦ θ.
In the range of 1 ≦ 40, the blade drum sandwiching angle θ2
It has been found that by satisfying the relationship of (degree) 5 ≦ θ2 ≦ 30, a good cleaning system can be achieved even when the process speed is 500 mm / sec or more.

The cleaner in the electrophotographic system of the present invention will be described. As described above, in the electrophotographic apparatus shown in FIG.
Around the photosensitive member 101, the temperature of which is controlled by the planar inner surface heater 123, a main charger 102, an electrostatic latent image forming light beam 103, a developing device 104, a transfer paper supply system 10
5. Transfer charger 106 (a), separation charger 106
(B), cleaner 107, transport system 108, light source 1
09 and the like are provided. FIG. 4 shows an example of the cleaner unit 107 here. Specifically, FIGS. 9 to 12 show an example of a cleaner according to the present invention. As shown in FIG. 9, a blade 902, a back plate 903, a blade holding plate 904, a support base 905, and the like, which are features of the present invention, are provided around a photoconductor 901 that rotates in the arrow X direction. Blade 902 is a JI
The S hardness is usually 74 to 78 degrees and has a plate-like shape. The back plate 903 and the blade holding plate 90
4 and is fixed to the support base 905 in a state of being sandwiched by the support table 905. The thickness D of the blade is usually about 3 mm, the width a of the blade is usually about 20 mm, the length b from the blade holding plate 904 to the tip of the blade is usually about 6 mm,
The length L from 03 to the tip of the blade is hereinafter referred to as a free length, but is usually set within a range of about 3 mm. With the above configuration, the blade is pressed against the photoconductor, and the blade undergoes pressure deformation at the photoconductor contact portion, and comes into surface contact with the photoconductor. FIG. 10 shows the positional relationship between the blade contact portions.
Blade 10 in contact with the photoreceptor 1001
02, the angle between the blade and the surface of the photoconductor (the blade contact angle) is θ1, and the blade surface continuous with the nip is located upstream of the nip between the blade and the photoconductor. The angle between the surface of the photoconductor and the angle between the blade and the surface of the photoconductor is θ2. In FIG. 11, a blade 1102 comes into contact with a photoconductor 1101 rotating in the direction of arrow X, and a cleaning mag roller 1103 that regulates the amount of toner coating on the photoconductor by providing a constant gap with the photoconductor.
A doctor roller 1104 that regulates the amount of toner coating on the mag roller is provided.
05 is shown. Blade 1102 and photoconductor 1
In the contact portion 101, there is a region where toner convection exists, and a very small part of the region is the blade 1102 and the photoconductor 110.
It passes through the gap 1 and plays the role of a lubricant.
FIG. 12 shows the shape of the blade, and compares an example of the present invention with a conventional example with respect to the state of the blade alone and the state of pressure deformation at the time of contact with the drum.

The electrophotographic photosensitive member in the electrophotographic system (electrophotographic apparatus) of the present invention will be described with reference to the drawings. FIGS. 4A and 4B are schematic cross-sectional views each showing the configuration of an example of an electrophotographic photoconductor (hereinafter, simply referred to as a photoconductor) in the present invention. FIG.
The photoconductor shown in (a) is a photoconductor in which the photoconductive layer is referred to as a single-layer type having no functional separation. The photoconductor is composed of a substrate 4
01, 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 (aC) are stacked in this order. . The photoconductor shown in FIG. 4B is 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. The photoreceptor shown in FIG. 4B has a charge injection blocking layer 40 on a substrate 401.
2. Photoconductive layer 4 made of a-Si containing at least hydrogen
03 and a surface layer 404 made of non-single-crystal carbon are stacked in this order, and 405 indicates a fluorine diffusion region in which fluorine is present, which is present on the outermost surface of the surface layer. The photoconductive layer 403 may be functionally separated into two, 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 photoreceptor shown in FIGS. 1A and 1B, each layer may have a continuous composition change, and may not 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 for the intermediate layer, an SiC layer having an intermediate composition between the photoconductive layer 403 and the surface layer 404 can be cited.
It may be a layer using iN or the like. The composition of the intermediate layer may be changed continuously.

The above-mentioned non-single-crystal carbon mainly refers to amorphous carbon having an intermediate property between graphite (diamond) and diamond, but may partially include microcrystals or polycrystals. . These are plasma CVD,
Although it can be formed by a sputtering method, an ion plating method, or the like, a film formed by a plasma CVD method has high transparency and hardness and is preferable to be used as a surface layer of a photoreceptor. Any frequency can be used as the discharge frequency when the non-single-crystal carbon film is formed by the plasma CVD 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. Also, especially 50 to 450
When a high frequency in a frequency band called VHF of MHz is used, both transparency and hardness can be further increased, so that it is more preferable when used as a surface layer. Surface layer 404
Examples of the fluorine-based gas used for forming the fluorine diffusion region on the outermost surface include CF ₄ , CHF ₃ , CH ₂ F ₂ , and the like.
CH ₃ F, C ₂ F ₆ , C ₂ F ₄ , CH ₂ CF ₂ , ClF ₃ , SF
Any material, such as ₆ , HF, and F ₂ , can be used as long as it can generate an active fluorine radical by plasma conversion. Further, a mixture of these gases or a mixture diluted with another gas such as a rare gas may 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 device is roughly classified into a deposition device 21
The system comprises a source gas supply system 2200 and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 2110. A cylindrical substrate 2112 connected to the ground, a heater 2113 for heating the cylindrical substrate, and a raw material gas introduction pipe 2114 are provided in a reaction vessel 2110 in the deposition apparatus 2100. A high-frequency matching box 2115 is provided on the cathode electrode 2111 also serving as a peripheral wall of the reaction vessel 2110.
The high frequency power supply 2120 is connected via the. The source gas supply system 2200 includes SiH ₄ , H ₂ , CH ₄ , NO, B ₂
A gas cylinder for a source gas such as H ₆ , CF _{4 and the} like and a gas cylinder 2221 to 2226 for an etching gas, and a valve 2
231 to 2236, 2241 to 2246, 2251-2
256 and mass flow controllers 2211-22
16 and each gas cylinder has an auxiliary valve 2260
Is connected to a gas introduction pipe 2114 in the reaction vessel 2110 via the. As the high frequency power supply 2120, 10 W
Any output can be used as long as it can generate power in the range of 5000 W or more. Further, the effect of the present invention can be obtained regardless of the output fluctuation rate of the high-frequency power supply 2120. As the matching box 2115, any configuration that can match the load with the high-frequency power supply 2120 can be suitably used. Further, as a method of obtaining the matching, a method of automatically adjusting is preferable, but a method of adjusting manually may be used. Examples of the material of the cathode electrode 2111 to which high-frequency power is applied include copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and a composite of two or more of these materials. Materials can be used. Also,
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 as needed. As specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element, or the like is used as necessary. Cylindrical substrate 2112
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. Regarding the surface shape of the cylindrical substrate 2112, unevenness at a relatively large cycle due to cutting with a tool, dimple processing, or the like is performed so as not to deteriorate the durability against image blur in a high-temperature and high-humidity environment, and to prevent interference. It is possible to have for purpose. The effect of the present invention can be obtained if Rz is less than 1000 ° when the roughness of the outermost surface of the photoconductor 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, it is not necessary to consider the roughness of the substrate surface before film formation.

Hereinafter, an example of a procedure of a method of forming a photoreceptor using the apparatus of FIG. 2 will be described. Reaction vessel 2110
The inside of the reaction vessel 2110 is evacuated by a not-shown exhaust device (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 cylindrical substrate heating heater 2113. Raw material gas for photoreceptor formation is supplied to reaction vessel 2
To make the gas flow into 110, the valve 2231 of the gas cylinder is used.
2236, the leak valve 2117 of the reaction vessel was confirmed to be closed, and the inflow valves 2241 to 2224 were confirmed.
46, outflow valves 2251 to 2256, auxiliary valve 22
Check that 60 is open, and
8 to open the inside of the reaction vessel 2110 and the gas supply pipe 21
Exhaust into 16. Next, the gauge 2119 reads 5 × 1
When the pressure reaches 0 ^-6 Torr, the auxiliary valve 2260
Outflow valves 2251 to 2256 are closed. After that, each gas is supplied from the gas cylinders 2221 to 2226 to the valves 2231 to 2231.
2236 is opened and introduced and pressure regulators 2261 to 2266 are introduced.
To adjust each gas pressure to 2 kg / cm ² . 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, formation of each layer on the cylindrical substrate 2112 is performed as follows.
When the temperature of the cylindrical base 2112 reaches a predetermined temperature, a necessary one of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened, and each gas cylinder 222 is opened.
A predetermined raw material gas is supplied from the gas inlet pipe 2114
And introduced into the reaction vessel 2110. Next, each mass flow controller 2211 to 2216 adjusts each raw material gas to a predetermined flow rate. that time,
The main valve 21 is monitored while observing the vacuum gauge 2119 so that the inside of the reaction vessel 2110 has a predetermined pressure of 1 Torr or less.
Adjust 18 openings. When the internal pressure is stabilized, the high-frequency power supply 2120 is set to a desired power, and high-frequency power is supplied into the reaction vessel 2110 via the high-frequency matching box 2115 and the cathode electrode 2111 to generate high-frequency glow discharge. The raw material gas introduced into the reaction vessel 2110 is decomposed by the discharge energy, and a deposited film mainly containing predetermined silicon atoms is formed on the cylindrical base 2112. After the formation of the desired film thickness, the supply of the high-frequency power is stopped, and the outflow valves 2251 to 225
6 is closed, the flow of each source gas into the reaction vessel 2110 is stopped, and the formation of the deposited film is completed. Thus, the formation of the photoconductive layer can be performed.

The formation of the surface layer can also be performed basically by repeating the above operation. Specifically, a necessary one of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened, and each gas cylinder 2221 to 2256 is opened.
From 2226, the raw material gas necessary for the surface layer is
Introduced into the reaction vessel 2110 via. Next, each mass flow controller 2211 to 2216 adjusts each raw material gas to 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 into the reaction vessel 2110 via the high-frequency matching box 2115 and the cathode electrode 2111 to generate a high-frequency glow discharge. The source gas introduced into the reaction vessel 2110 is decomposed by the discharge energy, and a surface layer is formed. After the desired film thickness is formed, the supply of the high-frequency power is stopped, and each of the outflow valves 2251 to
By closing 2256, the flow of each source gas into the reaction vessel 2110 is stopped, 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 etching process is performed from each gas cylinder 2221 to 2226. Gas containing at least fluorine atoms necessary for gas introduction pipe 2
It is introduced into the reaction vessel 2110 via 114. next,
Each of the mass flow controllers 2211 to 2216 is adjusted so that the gas containing a fluorine atom has 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 into the reaction vessel 2110 via the high-frequency matching box 2115 and the cathode electrode 2111 to generate a high-frequency glow discharge. The gas containing fluorine atoms introduced into the reaction vessel 2110 is decomposed by the discharge energy, and reacts with the surface layer to perform an etching process on the surface layer. The control of the surface shape and the fluorine atom content depth 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 the desired film thickness is performed, the supply of the high-frequency power is stopped, and the outflow valves 2251 to 2256 are closed to close the reaction vessel 211.
Stop the flow of each source gas to zero. During the film formation, the cylindrical base 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 view of an example of an electrophotographic photoconductor forming apparatus (mass production type) by a VD method. FIG. 3 is a schematic sectional view of the deposition apparatus. In FIG. 3, reference numeral 301 denotes a reaction vessel;
It has a vacuum tight structure. An exhaust pipe 302 has one end opened into the reaction vessel 301 and the other end connected to an exhaust device (not shown). Reference numeral 303 denotes a discharge space surrounded by the cylindrical substrate 304. The high frequency power supply 305 is electrically connected to the electrode 307 via the high frequency matching box 306. The cylindrical substrate 304 is the holder 3
08 and set on the rotating shaft 309. The cylindrical substrate 304 on the holder 308 can be rotated by a motor 310 as needed. The source gas supply system (not shown) may be the same as 2200 shown in FIG. The source gas from the source gas supply system is
The gas is introduced into the reaction vessel 301 through a gas introduction pipe 311 having a valve 312. As the high-frequency power supply 305 of the apparatus shown in FIG. Furthermore, the effect of the present invention can be obtained regardless of the output fluctuation rate of the high-frequency power supply 305. As the matching box 306, any structure can be suitably used as long as it can match the load with the high frequency power supply 305. Further, as a method of obtaining the matching, a method of automatically adjusting is preferable, but a method of adjusting manually may be used. Materials of the electrode 307 to which the high-frequency power is applied include copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron,
Chromium, molybdenum, titanium, stainless steel, and composite materials of two or more 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 electrode 307 may be provided with a cooling means as needed. 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 and 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 the material, copper, aluminum, gold, silver, platinum, lead,
Nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel and composite materials of two or more of these materials, as well as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass An insulating material such as quartz, ceramics, paper, or the like coated with a conductive material can be used. The film formation by the apparatus of FIG. 3 can be performed in the same manner as the film formation method by the apparatus of FIG. 2 described above.

[0027]

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

[0028]

EXPERIMENTAL 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. A photoconductor having an a-SiC surface layer was prepared in the same manner except that the surface layer was made of a-SiC by a conventional method. The prepared photoreceptor was evaluated for cleaning performance using an evaluation apparatus obtained by modifying a Canon copier NP6060. The process speed was 400 mm / sec, and the toner particle size was 6.5 μm. The results are shown in Tables 4 to 7.
In the table, ○ indicates that there is no problem in cleaning properties and durability, and X indicates that there is a problem. Chatter and slippage occurred when the pressure applied to the cleaning blade was small. When the aC film of the present invention was used for the surface layer, 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, it was found that the pressure range of the cleaning blade can be widely used in the system of the present invention.

[0029]

[Experimental Example 2] For each of the two types of photoconductors obtained in Experimental Example 1, the evaluation device used in Experimental Example 1 was used. The loading force on the friction of the steel was examined. The blade pressure was 14 g / cm, and the toner used had a particle size of 6.5 μm. FIG. 5 shows the results. 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 performed,
When the pressure of the cleaning blade was reduced to 8 gf / cm, slip-through and fusion occurred, except that a-C was used for the surface layer and that of the present invention was used for the cleaning blade. Using aC or aC: F for the surface layer,
The cleaning blade of the present invention is used, and the pressure is 8
FIG. 6 shows the case where gf / cm was set. By lowering the pressure of the cleaning blade, the load applied to the drum rotation motor was further reduced.

[0030]

EXPERIMENTAL EXAMPLE 3 Using the plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1, and three photoconductors were prepared. Next, etching was performed under the conditions shown in Table 2 while changing the high-frequency power so that the etched surface Rz was about 200 °, 500
３ Three kinds of items were prepared. In this range of power, the penetration depth of fluorine is around 20 ° and the concentration is 30 to 40.
%. In order to evaluate the water repellency of the photoreceptor, a contact angle meter (CA-S manufactured by Kyowa Interface Science Co., Ltd.) was used.
When the contact angle of the surface was measured with pure water using a (roll type), the contact angles of all three were 100 ° or more and high water repellency was obtained. Next, the potential characteristics were evaluated. That is, each photoconductor was mounted on a measuring instrument, and the change in surface potential was measured under various conditions. To evaluate the potential shift, a constant current was applied to the charger, and the electric potential was shifted for 2 minutes (Canon copier NP-50).
(Equivalent to 100 sheets for 60), the charged potential on the surface of the photoreceptor was observed, and the state of the fluctuation was examined. Also, with regard to the ghost potential, after charging, it goes through a process similar to the copying process such as exposure and static elimination, gives a halftone potential after one round, and observes the potential difference between the exposed part and the unexposed part It is obtained by doing. Next, this photoreceptor was mounted on a modified Canon copier NP-6060, which was modified for experiments, and was used in a high-temperature, high-humidity environment at 30 ° C. and 80% without using any heating means such as a drum heater. Copies were made for a durability test. At this time, rotate the mag roller in the counter direction at a higher speed than normal use to make contact,
The pressing pressure of the cleaner blade was set higher than usual, and the environment where the load on the surface due to sliding was more severe was set. The copy manuscript contains a Canon test chart (part number: FY
99058) was used. 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 collected after the durability test, and the weight was accurately measured and compared. Regarding the easiness of occurrence of scratches, a forced jam test was performed 10 times after the endurance, 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. Table 8 shows the obtained results based on the following criteria. ◎: very good ○: good △: no practical problem ×: practical problem

[0031]

Comparative Example 1 A deposited film was sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. Thus, two photosensitive members were prepared. Next, etching was performed under the conditions shown in Table 2 while increasing the high-frequency power as compared with Experimental Example 3, thereby producing two types of etched surfaces having an Rz of about 1000 ° and an Rz of about 2000 °. It is known that in this condition range, the penetration depth of fluorine is around 35 ° and the concentration is 40 to 50%. Next, the same durability and evaluation as in Experimental Example 3 were performed. Evaluation results are shown in Experimental Example 3.
The results are shown in Table 8 together with In the potential measurement, it was found that there was no problem in both the potential shift and the ghost potential for all the photoconductors. With respect to the photoreceptor having an Rz of up to 800 °, no image deletion occurred at 100,000 sheets of durability. However, when the roughness was 1000 °, the image was slightly reduced in resolution, and at 2000 °, image deletion occurred. It is considered that this is because the bonding state of the surface was greatly changed at a boundary of Rz of 1000 °, and fluorine was easily dropped. Roughness 1000 at which image deletion occurred
In the case of the photoreceptor of {2000}, the contact angle after 100,000 sheets had been degraded to 45 and 35, respectively. In addition, in the forced jam test, no scratch was found on any of the photoconductors, and it was confirmed that the hardness as the surface layer was sufficient.

[0032]

EXPERIMENTAL EXAMPLE 4 Using the plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1. Thus, three photosensitive members were prepared. Next, etching was performed under the conditions shown in Table 3, and the depth of penetration of fluorine was set to 5Å, 25 by changing the reaction temperature and pressure.
{, 50}. The surface roughness accompanying the etching is set to be approximately 500 °. This 3
The content of fluorine relative to carbon in the surface layer of the photoreceptor is
22,37,45% respectively as measured by S
Met. Next, the same durability and evaluation as in Experimental Example 3 were performed. Table 9 shows the obtained evaluation results.

[0033]

Comparative 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. Thus, three photosensitive members were prepared. Next, etching was performed under the conditions shown in Table 3, and the depth of penetration of fluorine was 5 °, 55 ° C. by changing the reaction temperature and pressure.
{, 70}. The surface roughness accompanying the etching is set to be approximately 500 °. This 3
The content of fluorine relative to carbon in the surface layer of the photoreceptor is
As measured by S, 15,46,55% respectively
Met. Next, the same durability and evaluation as in Experimental Example 3 were performed. Experimental Example 4
Table 9 also shows the results. From the results of Experimental Example 4 and Comparative Example 2, even when the penetration depth is the same of 5 °, the fluorine content is 20%.
It can be seen that when the amount is smaller, the water repellency after durability decreases. As a result, a slight but blurred image occurred. In addition, the fluorine content is 20% less than that of 20% or less.
It was found that the transfer efficiency of the above-described materials was further improved by the improvement of the releasability. On the other hand, when the penetration depth exceeds 50 ° and the case where the penetration depth is kept within 50 ° even when the amount of fluorine is more than 20%, the potential shift and the ghost potential are further improved when the penetration depth is kept within 50 °. I understood. From these results, it was found that the penetration depth of fluorine was 5
It was found that the content of fluorine had to be 20% or more based on carbon within 0 °.

[0034]

EXPERIMENTAL EXAMPLE 5 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. Thus, five photosensitive members were prepared. Next, etching was performed under the conditions shown in Table 2. At this time, by changing the etching time, the etching film thickness is set to 20 °, 1
00, 500, 2000, and 2900. Since the thickness of the surface layer is 3000 Å, the thickness after etching is 2980 Å, 2900 Å, and 250 そ れ ぞ れ, respectively.
0 °, 1000 °, and 100 °. Next, Experimental Example 3
The same durability and evaluation as described above were performed for each. Table 10 shows the obtained evaluation results.

[0035]

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. Thus, two photosensitive members were prepared. Next, etching was performed under the conditions shown in Table 2. At this time, the etching film thickness is changed to 5 °
It was changed to 50 °. Since the thickness of the surface layer is 3000 °, the thickness after etching is 2995 ° and 595, respectively.
0 °. Next, the same durability and evaluation as in Experimental Example 3 were performed. Table 10 shows the obtained evaluation results together with the results of Experimental Example 5. When the etched film thickness is small, the amount of fluorine contained is expected to be small. Comparing the etched film having a thickness of 5 ° and the etched film having a thickness of 20 °, the image having a thickness of 5 ° caused a slight image deletion after the durability test, while the image having a thickness of 20 ° did not. From the analysis of the drum made under the same conditions, the etching film thickness was 5 mm,
The amount of fluorine contained in the 20 ° surface layer is 11
% And 28%. In addition, it was found that the transfer efficiency was further improved in the case where the etching film thickness was 20 ° or more as compared with the case where the etching film thickness was 5 ° because the mold releasability was improved. From this, it was found that the etching film thickness was desirably 20 ° 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 etching film thickness of 2900 ° (the remaining film thickness of the surface layer is 100 °);
0 °). When the presence or absence of scratches was examined by the forced jam test, when the residual film thickness was 50 °, the surface was sometimes scratched by the forced jam test.
On the other hand, no scratch was observed when the residual film thickness was 100 ° or more. From these facts, it was found that the film thickness to be removed by etching needs to be at least 20 °, and the thickness of the surface layer remaining on the surface is desirably 100 ° or more.

[0036]

EXPERIMENTAL EXAMPLE 6 Using the plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1. Thus, six photosensitive members were prepared. Next, under the conditions shown in Table 2, the gas species was CF ₄ , CHF ₃ , C
It was etched using the six types of gases _{2 F 6, CF 2 = CF} 2, ClF 3, SF 6. Next, the same durability and evaluation as in Experimental Example 3 were performed. Table 11 shows the obtained evaluation results. 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.

[0037]

EXPERIMENTAL EXAMPLE 7 Using the plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1. Thus, four photosensitive members were prepared. Next, the gas was changed to He, Ne, Ar and N _{2 under} the conditions shown in Table 2.
Etching was performed by diluting (50%) by type. Next, the same durability and evaluation as in Experimental Example 3 were performed. Table 12 shows the obtained evaluation results. 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.

[0038]

EXPERIMENTAL EXAMPLE 8 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. Next, fluorination was performed by etching under the conditions shown in Table 2. Under these conditions, it is known that Rz is diffused by about 500 ° and fluorine is diffused by about 20 °, and about 40% is contained in the same region. Next, the obtained photoreceptor was mounted on a modified copy machine NP-5060 manufactured by Canon Inc., and durability of 500,000 sheets was performed in the same manner as in Experimental Example 3. However, the surface of the drum was maintained at about 50 ° C. using a heating device for the drum. Table 13 shows the obtained evaluation results.

[0039]

COMPARATIVE EXAMPLE 4 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. No fluorination was performed. The obtained photoconductor was mounted on a modified copy machine NP-5060 manufactured by Canon Inc.
The durability of 100,000 sheets was performed in the same manner as in Experimental Example 3. However, the surface of the drum was maintained at about 50 ° C. using a heating device for the drum. Table 13 shows the evaluation results 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 Experimental 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.

[0040]

[Experiment 9] Using the plasma CVD apparatus shown in FIG.
Under a condition shown in Table 14 at a discharge frequency of 105 MHz, a deposited film was sequentially laminated on a cylindrical Al substrate to prepare a plurality of photoconductors. For comparison, a photoreceptor was prepared under the conditions shown in Table 15 using an RF plasma CVD apparatus having a discharge frequency of 13.56 MHz shown in FIG. Next, etching was performed using fluorine plasma under the conditions shown in Table 2. Experimental Example 3 for each of the obtained photoconductors
The same durability and evaluation as described above were performed. Table 1 shows the obtained results.
6 is shown. The one made with 105MHz VHF is 1
There is no inferiority in all characteristics as compared with the one made at a high frequency of 3.56 MHz. In addition, it was found that the sensitivity and hardness were further improved as compared with those prepared at 13.56 MHz.

[0041]

[Experimental Example 10] The drum and cleaning blade generated by the rotation of the drum with respect to the process speed using the evaluation device used in Experimental Example 1 in the same manner as in Experimental Example 2 for the photosensitive members produced in Experimental Examples 3 to 9 The load force on the friction with the was investigated. 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 aC of the surface layer. Next, when the same experiment was performed by lowering the pressure of the cleaning blade, when the pressure of the cleaning blade was reduced to 8 g / cm, even when any of the photoconductors prepared in Experimental Examples 3 to 9 was used, the photoconductor passed through. There was no occurrence of fusion or the like.

[0042]

[Experimental example 11] Photoreceptors having different heights of protrusions with respect to the average surface, various toners having different particle diameters, and different fixing properties were prepared.
Further, as for the blades, those having different JIS hardness, different thicknesses and different shapes, that is, as shown in FIG. 12, the blade contact edge is dropped, and the blade drum sandwich angle at the time of the drum contact can be selected. I prepared several kinds of things. An electrophotographic apparatus (Canon NP-6060 was modified for testing) as shown in FIG. 1A was modified so that the process speed could be changed and the blade pressing pressure could be changed. The photoconductor, toner and blade thus set were set, and the image quality, fusion, cleaning properties, chipping of the blade, blade life, and scraping of the photoconductor were evaluated. FIG. 13 shows the blade contact angle (θ in FIG.
1) Dependencies are shown. The cleaning performance was evaluated by evaluating the amount of toner remaining on the drum surface after passing through the cleaner. The scraping of the photoreceptor was evaluated by rank by visually observing the surface of the photoreceptor. The cleaning property has an appropriate range with respect to the blade contact angle, and does not depend on the blade drum sandwiching angle. However, the photoreceptor abrasion is better when the blade drum sandwiching angle is 20 degrees than when it is 65 degrees. It was found that the contact angle was wide in a favorable range. Also, FIG.
The blade drum clamping angle for the photoreceptor shaving (θ in FIG. 10)
2) Dependencies are shown. If the blade drum included angle is too small or too large, the photoreceptor tends to be shaved, and it can be seen that there is an appropriate range of the blade drum included angle for the photoreceptor shaved. Further, those having high blade hardness have a narrow usable range. On the other hand, as can be seen from FIG. 10, in order to reduce the blade drum sandwiching angle while keeping the normal plate-like blade, the contact angle must be increased, and cleaning performance is deteriorated. Therefore, the present inventors paid attention to the shape, and used a shape in which the drum abutting edge was dropped as shown in FIG. 12, so that the optimum range in which the blade abutting angle and the blade drum sandwiching angle were compatible could be sufficiently obtained. Has found that it is possible. FIG. 15 shows the results of measuring the process speed dependency of fusion and photoreceptor shaving. Both the fusing and the photoreceptor shaving deteriorate as the process speed increases. However, as described above, the problem is solved by setting the blade drum holding angle to an optimum value. Furthermore,
The results of evaluating the fusing, cleaning properties, and blade life by changing the blade thickness and pressing pressure are shown in FIGS.
It is shown in FIG. It was found that the higher the blade hardness, the wider the suitable range of the blade thickness for the fusing and cleaning properties, and the wider the range of the pressing pressure for the fusing and the blade life.

FIGS. 16 and 17 show the results of evaluation of poor cleaning and fusion due to chipping of the blade using a photoreceptor in which the height of the protruding portion with respect to the average surface was changed and a blade in which the JIS hardness was changed. . From this result, a blade having a low JIS hardness has a wide allowable range of blade chipping with respect to the height of the projection, but is disadvantageous in terms of fusion. On the other hand, a blade having a high JIS hardness is effective for fusing, but is liable to cause poor cleaning due to chipping of the blade. I understood. Furthermore, using various toners having different particle diameters and fixing properties,
FIG. 20 shows the results of evaluation of fusion, photoreceptor shaving, and image quality.
As shown in FIG. The fixability is defined as the rubbing rate when the image after fixing is rubbed with silk paper, and the image density is defined as D.
0, when the density after rubbing is D1, (D0−D1) / D
An amount represented by 0 * 100 (%), and the larger the value, the worse the fixability. From this result, it was found that when the toner particle diameter is small, there is a disadvantage in fusing and abrasion of the photoconductor, but when the toner particle diameter is large, the image quality is deteriorated. Further, it was found that when the fixing property of the toner is improved, the fusion is disadvantageous, but by increasing the hardness of the blade, there is no problem with the fusion. Regarding the above representative examples, ☆: very good, ◎: good,
：: No problem in practical use, Δ: Slightly difficult in practical use, X: Poor in practical use, judged in 5 stages. The results are shown in Table 17.

Hereinafter, the present invention will be further described with reference to examples. However, the present invention is not limited to these examples.

[0045]

EXAMPLE 1 Using a plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 to prepare two types of photosensitive members having surfaces a to C. The produced photoreceptor is used with a Canon copier NP-6060.
Was evaluated using a modified evaluation device. The process speed was 450 mm / sec, the toner particle size was 7 μm, the cleaning blade had a JIS hardness of 76, and the cleaning blade pressure was 14 g / cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good.

[0046]

Example 2 Using a plasma CVD apparatus shown in FIG. 2, deposition films were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 to prepare three such photoconductors. Next, etching was performed under the conditions shown in Table 2 while changing the high-frequency power, thereby producing a photoreceptor having an etched surface having an Rz of about 200 °. The penetration depth of this fluorine is about 20Å
And the concentration was 35%. The produced photoreceptor was evaluated using an evaluation device obtained by modifying a Canon copier NP-6060. Process speed is 510mm / se
c, toner particle size is 6 μm, cleaner blade is JIS
The pressure was set to 16 g / cm using a material having a hardness of 75 degrees. At this time, no chattering, slippage, or fusion occurred. 10
The cleaning blade after using 10,000 sheets was also good. Next, the ghost potential measurement 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.

[0047]

Example 3 Using a plasma CVD apparatus shown in FIG. 3, a photosensitive film was formed by sequentially depositing deposited films on a cylindrical Al substrate at a discharge frequency of 105 MHz under the conditions shown in Table 14. Next, etching was performed using fluorine plasma under the conditions shown in Table 2. The produced photoreceptor was evaluated using an evaluation device obtained by modifying a Canon copier NP-6060. The process speed was 420 mm / sec, the toner particle size was 7.5 μm, and the cleaner blade had a JIS hardness of 78 and the pressure was 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 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.

[0048]

Embodiment 4 Using the plasma CVD apparatus shown in FIG.
A photoreceptor comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared on a mirror-finished aluminum cylinder having a diameter of 108 mm under the conditions shown in Table 18. The entire surface of the photoreceptor is observed, and a portion having a different height of the protrusion from the average surface is searched. A photoreceptor having a height of the protrusion of 0.005 mm is used. toner,
Using a blade with JIS hardness of 76 degrees, contact angle 25de
g, sandwich angle 20 deg, blade thickness 3 mm, pressing pressure 400 g / cm ² , process speed 520 mm / sec, image quality, fusion, cleaning properties, blade chipping, blade life, and photosensitivity When the body scraping was evaluated, good results were obtained. Table 17 shows the results.

[0049]

Embodiment 5 A mechanism for reciprocating the blade in the generatrix direction of the photoconductor is provided, and a blade having a JIS hardness of 76 degrees is used.
The contact angle was set to 25 deg, the included angle was set to 20 deg, the blade thickness was set to 3 mm, and the pressing pressure was set to 400 g / cm ² .
The height of the protruding portion was 0.005, which was created in the same manner as in Example 1.
mm, a toner having a particle diameter of 0.007 mm and a fixing property of 10%, and a process speed of 520 m.
m / sec, image quality, fusion, cleaning properties,
When the chipping of the blade, the blade life, and the scraping of the photoreceptor were evaluated, good results were obtained. Table 17 shows the results.

[0050]

Embodiment 6 Using the plasma CVD apparatus shown in FIG.
A photoreceptor comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared on a mirror-finished aluminum cylinder having a diameter of 108 mm under the conditions shown in Table 18. Observe the entire surface of the photoreceptor, search for a portion where the height of the protrusions with respect to the average surface is different, and grind the surface of the photoreceptor with the height of the protrusions of 0.02 mm with lapping tape, and adjust the height of the protrusions. 0.005
mm, particle size 0.007 mm, fixability 1
Using a 0% toner, a blade having a JIS hardness of 76 degrees, a contact angle of 25 deg, a sandwich angle of 20 deg, a blade thickness of 3 mm, a pressing pressure of 400 g / cm ² and a process speed of 520 mm / sec. hand,
When image quality, fusing, cleaning properties, blade chipping, blade life, and scraping of the photoreceptor were evaluated, good results were obtained. Table 17 shows the results.

[0051]

Example 7 A charge injection blocking layer and a photoconductive layer were formed on a mirror-finished aluminum cylinder having a diameter of 108 mm by VHF-plasma CVD using the plasma CVD apparatus shown in FIG. A photoreceptor comprising a surface layer was prepared. Observe the entire surface of the photoreceptor, search for a portion where the height of the protrusions with respect to the average surface is different, and grind the surface of the photoreceptor with the height of the protrusions of 0.02 mm with lapping tape, and adjust the height of the protrusions. A toner having a particle size of 0.007 mm and a fixing property of 10%,
Using a blade with JIS hardness of 76 degrees, contact angle 25de
g, sandwich angle 20 deg, blade thickness 3 mm, pressing pressure 400 g / cm ² , process speed 520 mm / sec, image quality, fusion, cleaning properties, blade chipping, blade life, and photosensitivity When the body scraping was evaluated, good results were obtained. Table 17 shows the results.

[0052]

Comparative Example 1 The JIS hardness of the blade is out of the range of 74 to 78 degrees, or the blade contact angle (degree, FIG.
Is not 20 ≦ θ1 ≦ 40 or the blade drum sandwiching angle (degree, θ2 in FIG. 10) is 5
≦ θ2 ≦ 30, or a toner whose particle height is not more than 0.006 mm with respect to the average surface of the photoreceptor surface, is 0.007 mm, and the toner has a fixing property of 10%, and the process speed is 520 mm. When used at / sec, any of the characteristics was inferior, and good electrophotographic characteristics could not be obtained. Table 17 shows the results.

[0053]

Example 8 A blocking layer / photosensitive layer was sequentially formed on a support under the conditions shown in Table 20 using the plasma CVD apparatus shown in FIG.
A -C surface layer was provided. Ch, Eg, and Eu of the photosensitive layer were 25 atomic%, 1.81 eV, and 57 meV, respectively.
The photoconductive layer has a mixture ratio of SiH ₄ gas and H ₂ gas,
_By changing the ratio of the ₄ gas to the discharge power and the temperature of the support variously, Ch, Eg, and Eu become 22 atomic%, 1.81 eV, 60 meV (a), 10 atomic%, respectively.
1.75 eV, 55 meV (b), 28 atomic%, 1.8
3 eV, 62 meV (c) and 30 atomic%, 1.85
eV, 65 meV (d), Ch is 10 to 30 atomic%, E
g is 1.75 eV or more and less than 1.85 eV, Eu is 55 m
Various photoreceptors of eV to 65 meV, and Ch, Eg, E
u is 20 atomic%, 1.75 eV and 55 meV, respectively.
(E) 10 atom%, 1.68 eV, 47 meV
(F), 15 atom%, 1.70 eV, 50 meV (g)
And 19 at%, 1.74 eV, 53 meV (h), 10 to 20 at% of Ch, Eg of 1.75 eV or less, E
various photoconductors having u of 55 meV or less, and further, Ch, E
g and Eu are 32 atom%, 1.85 eV and 53 m, respectively.
eV (i), 25 atom%, 1.80 eV, 47 meV
(J), 34 atomic%, 1.85 eV, 54 meV (k)
And 35 atomic%, 1.87 eV, 55 meV (l), 25 to 35 atomic% of Ch, Eg of 1.80 eV or more, E
Various photosensitive members having u of 55 meV or less were prepared.

For each of the obtained photoreceptors, the photoreceptors were set in an electrophotographic apparatus (NP-6650 manufactured by Canon) modified for experiments, and the potential characteristics were evaluated. At this time, first, the process speed is 300 mm / sec.
c, Pre-exposure (700 nm wavelength LED) 4lux · se
c, set to NP-6650 for image exposure (680 nm LED and laser light can be exchanged) and set the current value of the charger to 1
Under the condition of 000 μA, the surface potential of the photoreceptor was measured by a potential sensor of a surface voltmeter (Model 344, TREK Co.) set at the developing device position of the electrophotographic apparatus. The surface potential at the time of was measured, and it was regarded as a residual potential. Further, the temperature was changed from room temperature (about 25 ° C.) to 50 ° C. by a drum heater built in the photoconductor, and the charging ability was measured under the above conditions.
The change in the charging ability per 1 ° C. of the temperature at that time was defined as a temperature characteristic. Then, charging conditions are set so that the dark potential is 400 V at each of room temperature and 45 ° C., and EV characteristics (curve) are measured using a 680 nm LED as an image exposure light source, and the temperature characteristics of sensitivity and The linearity of sensitivity was evaluated. Further, the memory potential is set to a wavelength of 680 n for the image exposure light source.
Under the above-mentioned conditions, the potential difference between the surface potential in the non-exposed state and the potential after the exposure and the recharging was measured by using the same potential sensor under the above conditions. Thereafter, the image characteristics were evaluated by setting a 680 nm LED to NP-6650. Regarding the respective characteristics, the chargeability, the temperature characteristic, the memory potential, the temperature characteristic of the sensitivity, and the linearity of the sensitivity are based on the case where the photoconductive layer (layer thickness: 30 μm) is composed of only the first layer region or the second layer region. The property was evaluated. As a result, good results were obtained for charging ability, residual potential, temperature characteristics, memory potential, sensitivity temperature characteristics, sensitivity linearity, and cleaning properties (chattering, slip-through, fusion, blade and drum durability). Was done. It was also found that similar results were obtained when a semiconductor laser (wavelength 680 nm) was used instead of the LED as the exposure light source. Further, the produced photoreceptor was evaluated using an evaluation apparatus obtained by modifying a Canon copier NP-6060. The condition is that the process speed is 450 mm / s
ec, toner particle size is 7 μm, and cleaner blade is JI
The pressure was set to 14 g / cm using an S hardness of 76 degrees.
At this time, no chattering, slippage, or fusion occurred. 1
The cleaning blade after using 100,000 sheets was also good.
That is, it has been found that good electrophotographic characteristics can be obtained even when the surface layer in which the content of silicon atoms and carbon atoms in the surface layer is non-uniformly distributed in the layer thickness direction is provided in the present invention. Next, the surface layer was etched by changing the high frequency power under the conditions shown in Table 22 so that the Rz of the etched surface was about 200 °, the fluorine penetration depth was about 20 °, and the concentration was 35%. a-C
A photoreceptor having a surface layer was prepared. The produced photoreceptor was evaluated using an evaluation device obtained by modifying a Canon copier NP-6060. Process speed is 510mm / se
c, toner particle size is 6 μm, cleaner blade is JIS
The pressure was set to 16 g / cm using a material having a hardness of 75 degrees. At this time, no chattering, slippage, or fusion occurred. 10
The cleaning blade after using 10,000 sheets was also good. In addition, a ghost potential measurement, a contact angle, an image flow characteristic, and a forced jam test were performed before and after the durability test, and good results were obtained in all cases.

[0055]

Embodiment 9 Similarly to Embodiment 8, the charge injection blocking layer and the photoconductive layer (the first layer region and
the light of m was prepared a photosensitive member having a B ₂ H ₆ and distribution) in the second layer region corresponding to the thickness capable of absorbing 50%. afterwards,
The photoreceptor is VHF using a plasma CVD apparatus shown in FIG.
-A light receiving member having a surface layer made of non-single-crystal carbon was prepared by a plasma CVD method. The preparation conditions were based on Table 21. When the various photoconductors thus produced were evaluated in the same manner as in Example 8, the charging ability and
Residual potential, temperature characteristics, memory potential, temperature characteristics of sensitivity,
Good results were obtained for both sensitivity linearity and image characteristics. It was also found that similar results were obtained when a semiconductor laser (wavelength: 680 nm) was used instead of the LED as the exposure light source. That is, only the surface layer is VH
It has been found that good electrophotographic characteristics can be obtained even when a non-single-crystal carbon film is formed by using the F-plasma CVD method. Also, the created photoreceptor is used with a Canon copier N
The evaluation was performed using an evaluation device obtained by modifying P-6060. The conditions are that the process speed is 450 mm / sec,
The toner particle size was 7 μm, and the cleaner blade had a JIS hardness of 76 degrees and the pressure was 14 g / cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good. That is, it has been found that good electrophotographic characteristics can be obtained even when a surface layer in which the content of silicon atoms and carbon atoms in the surface layer is non-uniformly distributed in the layer thickness direction is provided in the present invention. Also, by etching the surface layer while changing the high frequency power under the conditions shown in Table 22,
A photoreceptor having an aC surface layer having a fluorine penetration depth of about 20 ° and a concentration of 35% was prepared with the etched surface having an Rz of about 200 °. The produced photoreceptor was evaluated using an evaluation device obtained by modifying a Canon copier NP-6060. The process speed was 510 mm / sec, the toner particle size was 6 μm, and the cleaner blade had a JIS hardness of 75 and the pressure was 16 g / cm. At this time, no chattering, slippage, or fusion occurred. The cleaning blade after using 100,000 sheets was also good. Next, a contact angle, an image flow characteristic, and a forced jam test were performed before and after the ghost potential measurement and the durability test, and good results were obtained in each case.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4] Cleaning properties (chatter)

[0060]

[Table 5] Blade slippage

[0061]

[Table 6] Fusion

[0062]

[Table 7] Blade durability

[0063]

[Table 8] Changes in properties due to surface roughness

[0064]

Table 9: Changes in properties due to changes in fluorine penetration depth and concentration

[0065]

[Table 10] Changes in characteristics depending on etching film thickness

[0066]

[Table 11] Change in image flow characteristics due to difference in etching gas

[0067]

[Table 12] Change in image flow characteristics due to difference in dilution gas

[0068]

[Table 13] Comparison of fusion etc. when heated by drum heater

[0069]

[Table 14]

[0070]

[Table 15]

[0071]

[Table 16] Comparison by surface layer preparation method

[0072]

[Table 17]

[0073]

[Table 18]

[0074]

[Table 19]

[0075]

[Table 20]

[0076]

[Table 21]

[0077]

[Table 22]

[0078]

As described above, according to the present invention,
A surface layer made of non-single-crystal carbon is provided on the photoconductive layer, and the surface layer has a fluorinated surface. By using a cleaning blade having a JIS hardness of 74 degrees or more and 78 degrees or less, the frictional force is increased. Even when a high-speed electrophotographic apparatus with a high torque or a small particle size toner is used, the cleaning property is improved and the friction can be reduced. The surface roughness Rz of the surface layer made of non-single-crystal carbon on the photoreceptor is less than 1000 ° 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
Å exists within, and the concentration of fluorine with respect to carbon in that region is set to 20% or more, so that water repellency is excellent,
A photoreceptor that provides a high-quality image under a high-temperature and high-humidity environment without a heating means was obtained with very high 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. Further, an a-Si photoreceptor having a height of a protrusion of 0.006 mm or less with respect to the average surface of the surface, a fine particle toner having an average particle size of 0.005 to 0.008 mm, and a JIS hardness of 74 effective for fusing. The blade contact angle θ1 (degree) is in the range of 20 ≦ θ1 ≦ 40, and the blade drum sandwiching angle θ2 (degree) is 5 ≦ θ2 ≦ 30, using a plate-like elastic blade having a degree of not less than 78 degrees and not more than 78 degrees. 400m process speed by satisfying the relationship
At m / sec or more, a high-speed electrophotographic system capable of achieving high image quality, in which a cleaning system suitable for the a-Si photosensitive member is established.

[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 a plasma CVD method of the present invention.

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

FIG. 4A is a schematic cross-sectional view illustrating a layer configuration of an electrophotographic photosensitive member. FIG. 2B is 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 on a rotating motor during stationary and rotating when a blade and a surface layer are changed when a process speed is changed.

FIG. 6 is a diagram showing a load on a rotating motor applied 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 view 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 illustrating a relationship between a toner particle size, fusing, and image quality.

FIG. 9 is a schematic cross-sectional view around a blade for explaining an electrophotographic apparatus according to one embodiment of the present invention.

FIG. 10 is a schematic cross-sectional view illustrating a contact positional relationship between a blade and a drum according to one embodiment of the present invention.

FIG. 11 is a schematic cross-sectional view illustrating a peripheral state when a blade and a drum are in contact according to an embodiment of the present invention.

FIG. 12 is a schematic cross-sectional view illustrating a blade shape according to one embodiment of the present invention.

FIG. 13 is a diagram illustrating the dependence of blade contact angle on cleaning performance and photoreceptor scraping.

FIG. 14 is a diagram illustrating the dependency of blade scraping angle on photoreceptor scraping.

FIG. 15 is a diagram showing the process speed dependency on fusion and photoreceptor shaving.

FIG. 16 is a diagram illustrating the dependency of the height of the protrusion of the photosensitive member on the cleaning failure due to chipping of the blade.

FIG. 17 is a diagram showing the JIS hardness dependency of a blade on cleaning failure due to fusion and chipping of the blade.

FIG. 18 is a diagram showing the dependence of the blade thickness on the fusing and cleaning properties.

FIG. 19 is a diagram showing dependence of blade pressing pressure on fusing and blade life.

FIG. 20 is a diagram showing toner particle size dependence on photoreceptor shaving, fusing, and image quality.

FIG. 21 is a diagram showing the dependency of toner fixing property on fusing.

[Explanation of symbols]

Reference Signs List 101 electrophotographic 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 forming portion 111 Platen glass 112 Documents 113, 114, 115, 116 Mirror 117 Lens unit 118 Lens 121 Cleaning blade 122 Resistor 123 Heat source (internal heater) 2100 Deposition device 2110 Reaction vessel 2111 Cathode electrode 2112 Conductive substrate 2113 Substrate Heating heater 2114 Gas introduction 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 controller 2221 to 2226 Bomb 2231 to 2236 Valve 2241 to 2246 Inflow valve 2251 to 2256 Outflow valve 2260 Auxiliary valve 2261 to 2266 Pressure regulator 300 Deposition device using VHF (mass production type) 301 Reaction vessel 302 Exhaust pipe 303 Discharge space 304 Cylindrical film-forming 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 Fluorine diffusion region 901 Photoconductor 902 Blade 903 Back plate 904 Blade holding plate 905 Support base D Blade thickness L Free length a Blade length b blade pressing plate from 904 to blade tip length 1001 photoconductor 1002 blade θ1 blade contact angle θ2 blade drum included angle 1101 photoconductor 1102 blade 1103 cleaning roller 1004 doctor roller 1005 Toner

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Takaaki Kaya, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Hironori Owaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Makoto Aoki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (21)

[Claims] 1. Rotating a cylindrical photoreceptor to charge, expose,
An electrophotographic system that repeats development, transfer, and cleaning, wherein the developer is developed on the photoconductor, transferred to a transfer material, and the photoconductor after the developer is transferred is cleaned by a blade, A photoconductive layer composed of a non-single-crystal material containing silicon atoms as a matrix and a surface layer composed of non-single-crystal carbon containing at least hydrogen atoms are formed in this order on a cylindrical conductive substrate as a photoreceptor. A laminated cylindrical photoreceptor is used, a developer having an average particle size of 0.005 to 0.008 mm is used as the developer, and a JIS hardness of 74 degrees or more 7 is used as the blade.
Using a cleaning blade of 8 degrees or less, the process speed based on the moving speed of the surface of the photoconductor is 400 m.
m / sec or more. 2. The electrophotographic system according to claim 1, wherein the surface layer of the photoreceptor is formed by using plasma obtained by decomposing at least a hydrocarbon gas. 3. The photoconductor according to claim 1, wherein a surface layer of the photoconductor is 1 to 450 MH.
The electrophotographic system according to claim 1, wherein the electrophotographic system is formed by decomposing at least a hydrocarbon-based gas by a plasma CVD method using a high frequency of z. 4. The photoconductor according to claim 1, wherein the surface layer has a thickness of 50 to 450M.
The electrophotographic system according to claim 3, wherein the electrophotographic system is formed by decomposing at least a hydrocarbon gas by a plasma CVD method using a high frequency of Hz. 5. The surface layer of the photoreceptor has a surface containing fluorine, the surface has a surface roughness Rz of less than 1000 ° when a reference length is 5 μm, and the surface layer Is substantially 50 ° away from the surface.
The electrophotographic system according to claim 1, wherein the concentration of fluorine to carbon in the region is 20% or more. 6. The electrophotographic system according to claim 5, wherein the surface layer is fluorinated by being etched in a plasma obtained by decomposing a gas containing at least a fluorine atom. 7. An etching layer formed on the non-single-crystal carbon by etching with the gas containing a fluorine atom has a lower limit of 20 ° or more in a film thickness direction, and an upper limit of the thickness of the remaining non-single-crystal carbon. 7. A thin portion having a range of not less than 100 [deg.].
2. The electrophotographic system according to 1. 8. A blade contact angle θ1 (degree) between the blade and the surface of the photoconductor is in a range of 20 ≦ θ1 ≦ 40, and a rotation upstream side of a contact surface between the blade and the photoconductor. 8. The method according to claim 1, wherein an angle .theta.2 (degree) between a blade surface continuous with the contact surface and the surface of the photoreceptor is in a range of 5.ltoreq..theta.2.ltoreq.30. Electrophotographic system. 9. The electrophotographic system according to claim 8, further comprising a mechanism for periodically reciprocating the blade in a direction perpendicular to a rotation direction of the photoconductor. 10. The electrophotographic system according to claim 8, wherein the photoreceptor is used after being prepared and then its surface is polished. 11. The electrophotographic system according to claim 8, wherein the height of the projections on the surface of the photoconductor is 0.006 mm or less. 12. The process speed is 500 mm /
The electrophotographic system according to any one of claims 8 to 10, wherein the time is sec. 13. The photoconductive layer of the photoreceptor is made of a non-single-crystal material containing silicon atoms as base materials and containing hydrogen atoms and / or halogen atoms and elements belonging to Group IIIb of the periodic table. The photoconductive layer has a hydrogen content of 25 to 35 atomic% and an optical band gap of 1.80.
eV or more, characteristic energy of an exponential function tail obtained from a light absorption spectrum is 55 meV or less, and belongs to Group IIIb of the periodic table in a region where a certain amount of light incident on the photoconductive layer is absorbed and other regions. 13. The electrophotographic system according to claim 1, wherein the contents of the elements are different. 14. A region on the light incident side of the photoconductive layer, which is necessary to absorb 50% or more and 90% or less, of the element belonging to Group IIIb of the periodic table, more than other regions. 14. The electrophotographic system according to claim 13, wherein the content is small. 15. In a region of the photoconductive layer on which light is incident and necessary for absorbing light of 50% or more and 90% or less, the content of the element belonging to Group IIIb of the periodic table is silicon. 0.03ppm or more to atom and 5pp
The electrophotographic system according to claim 14, wherein m is equal to or less than m. 16. In a region of the photoconductive layer on which light is incident and which is necessary to absorb more than 90% of the light, the content of the element belonging to Group IIIb of the periodic table is set to silicon atoms. The electrophotographic system according to claim 14, wherein the content is 0.2 ppm or more and 25 ppm or less. 17. The light-incident side of the photoconductive layer, which is required to absorb 50% or more and 90% or less of light, has a region other than the content of the element belonging to Group IIIb of the periodic table. 15. The electrophotographic system according to claim 14, wherein the ratio of the content of the element belonging to Group IIIb of the periodic table in a region is 1.2 to 200. 18. The method according to claim 18, wherein the content of the element belonging to Group IIIb of the periodic table contained in the photoconductive layer decreases stepwise from the conductive substrate side to the surface side. The electrophotographic system according to any one of claims 13 to 17, wherein: 19. The method according to claim 19, wherein the content of the element belonging to Group IIIb of the periodic table contained in the photoconductive layer decreases smoothly from the conductive substrate side toward the surface side. An electrophotographic system according to any one of claims 13 to 17. 20. The electrophotographic system according to claim 13, wherein the photoconductive layer contains at least one of carbon, oxygen, and nitrogen. 21. The photoreceptor contains a hydrogen atom and / or a halogen atom based on a silicon atom, and contains carbon,
At least one of oxygen and nitrogen and Periodic Table IIIb
21. The electrophotograph according to claim 13, further comprising a charge injection blocking layer made of a non-single-crystal material containing an element selected from the group between the conductive substrate and the photoconductive layer. system.