JP4447968B2 - Method for producing electrophotographic photosensitive member - Google Patents

Description

  The present invention relates to a method for producing an electrophotographic photosensitive member having a photoconductive layer made of a non-single crystal material based on silicon atoms.

  The electrophotographic photosensitive member is mounted on an electrophotographic apparatus and is subjected to a series of processes including a charging process, an exposure process, a development process, a transfer process, and a cleaning process for residual toner. In the cleaning process in this series of processes, the surface state of the photoconductor is an important parameter for determining the cleaning property of the electrophotographic photoconductor, and various technical developments have been made in designing the electrophotographic photoconductor.

  As a material of the photoconductor, there is hydrogenated amorphous silicon (hereinafter also referred to as “amorphous Si”), which is a non-single crystal material having a silicon atom as a base material and defect compensation with hydrogen. A problem in the cleaning process of the photoconductor using amorphous Si is an image flow in a high-temperature and high-humidity environment caused by insufficient removal of charged products.

  Another problem is that the toner particles or additives contained in the toner remain or adhere to the surface of the photoreceptor without being sufficiently cleaned in the cleaning process.

  In recent years, with the progress of digitalization of electrophotographic apparatuses, the print length (number of pages printed at one time) and the print volume (total number of pages printed during a predetermined period) tend to increase greatly, and the cleaning process is started. The load is increasing. Further, the colorization of the output image tends to increase the printing ratio, and in this respect also, the load of the cleaning process tends to increase.

  On the other hand, pixel density tends to increase year by year in order to improve image quality and increase definition. Since digital images are formed by a collection of fine dots, dots are miniaturized by improving image quality and high definition, and reproduction of non-uniformities and disturbances on light latent images, which did not become apparent in the past, are reproduced in halftones. May appear as degradation of image quality, such as lowering of image quality, uniformity, and lower-case reproducibility.

In order to solve these problems, as for the cleaning property of an electrophotographic photosensitive member containing amorphous Si, a photosensitive member is disclosed in which toner adhesion and cleaning failure are prevented by paying attention to microscopic surface roughness ( For example, see Patent Document 1). Also disclosed is an image forming apparatus provided with a polishing means for polishing the surface of the photoreceptor (for example, see Patent Document 2).
JP 2001-330978 A JP 08-076663

  Based on such a technique, the inventors have studied to further improve the cleaning property by paying attention to the surface of the photoreceptor, and the following problems have arisen.

  When the microscopic surface roughness Ra of the surface of the electrophotographic photosensitive member is increased, the following problems in the cleaning process are more likely to occur.

  That is, the charged product is likely to be accumulated in the concave and convex valley portions, so that the resistance is reduced in a high-temperature and high-humidity environment, thereby causing image flow.

  In addition, fine particles (so-called external additives) added to the toner in order to improve functions such as developability, cleaning properties, and transferability may not be firmly fixed to the toner particles. In the formation process, it is detached and cannot be completely cleaned, and tends to remain in the concave and convex valleys on the surface of the photoreceptor.

  Further, it has been found that when this process is repeated, the remaining external additive accumulates and may cause uneven exposure reaching the photoreceptor.

  The microscopic surface roughness of the amorphous Si photoconductor greatly depends on the film forming conditions for depositing the film. However, due to restrictions for obtaining sufficient electrophotographic characteristics, it is difficult to control to a desired surface roughness only by film formation conditions. In this case, it is conceivable to polish the surface after film formation.

  However, since the polishing process takes a long time, improvement of productivity becomes a problem. Furthermore, in order to perform polishing uniformly over the entire surface of the photoreceptor, it is preferable to use a polishing sheet coated with abrasive grains. In this case, a binder or a dispersion aid in which abrasive grains are dispersed is used. There is a possibility that it adheres to the photoconductor, which is a problem associated with a longer processing time.

  On the other hand, as an image forming apparatus that attempts to supplement cleaning properties by providing a means for forcibly removing deposits that cause image flow, a rubbing means using an abrasive tape is brought into contact with the surface of the photoreceptor. Means such as adding an abrasive to the developer have been proposed. However, in these cases, process design and mechanism design become complicated, and problems such as an increase in apparatus cost, maintainability, and influence on image quality remain.

  As another method for suppressing image flow, the surface of the photoconductor may be provided by incorporating a heater in the photoconductor to heat the photoconductor itself or by blowing warm air to the photoconductor by a hot air blower. There is a method of lowering the relative humidity by heating (30-50 ° C.). This method is a treatment that volatilizes corona discharge products and moisture adhering to the surface of the photosensitive member to suppress substantial reduction in resistance of the surface of the photosensitive member.

  However, this method increases the power consumption of the copying machine main body, and it may be difficult to operate the high-speed copying machine within the power of 100 V / 15 A, which is a general office power supply situation.

  The object of the present invention is to solve the above-mentioned problems of the prior art, to prevent image defects related to cleaning properties such as image flow, and to reduce the load on the image forming apparatus side. It aims at providing the manufacturing method of a body.

  The present inventor has studied a simple manufacturing method for solving these problems, and found that a method of polishing after forming a low hardness film on the outermost surface of the electrophotographic photosensitive member is effective. It came to.

The present invention relates to a method for producing an electrophotographic photosensitive member by depositing a photoconductive layer composed of a non-single crystal material based on silicon atoms and a surface layer on a conductive substrate. A first layer region composed of silicon carbide having a dynamic hardness of 790 to 800 kgf / mm ² , and a dynamic hardness composed of amorphous silicon carbide having a hardness smaller than that of the first layer region of 250 to 270 kgf After the second layer region having a thickness of / mm ² is laminated in this order and the surface layer is formed, the first layer region is partially exposed on the outermost surface of the electrophotographic photosensitive member. The surface after forming the second layer region is polished using a polishing sheet coated with abrasive grains whose material dispersed in the binder is silicon carbide and the particle size is 6 μm. Electrophotographic photoreceptor It is a manufacturing method.

By such a method, the time required to obtain an appropriate surface roughness can be remarkably shortened as compared with the case of directly polishing a hard surface layer. In addition, since a surface layer having a high hardness remains even after polishing processing with an appropriate surface roughness, the photoconductor is mounted on an electrophotographic apparatus as compared with the case of using only a surface layer having a low hardness. The amount of abrasion on the surface of the photoreceptor can be suppressed, and the life of the photoreceptor can be further extended. That is, in the present invention, a surface layer having the above-described configuration along the surface shape is formed on the surface having a certain degree of roughness formed in the process of forming the photoconductive layer. When this photoconductor is polished, the layer region having a low hardness is scraped off in a short time, and the convex portion of the layer region having a high hardness is exposed. At this stage, a layer region having a low hardness remains in the concave portion of the layer region having a high hardness, and the surface roughness of the entire surface of the photoreceptor is reduced.
Further, in the present invention, after the polishing process, it is preferable to polish the outermost surface of the electrophotographic photosensitive member so that the layer region having the high hardness is partially exposed on the outermost surface.

  Even if it is partially in this manner, the effect of suppressing toner fusion is enhanced by exposing the layer region having a high hardness on the surface of the photoreceptor. Although the details of the mechanism for increasing the effect of suppressing the fusion are not known, it is presumed that it is difficult for the fusion nucleus to grow due to the presence of regions having different surface free energies on the surface of the photoreceptor.

As described above, according to the present invention, a photoconductive layer made of a non-single crystal material having a silicon atom as a base material and a surface layer are deposited on a conductive substrate to form an electrophotographic photosensitive member. In the manufacturing method, the first layer region composed of amorphous silicon carbide and having a dynamic hardness of 790 to 800 kgf / mm ² and the amorphous silicon carbide having a smaller hardness than the first layer region. And the second layer region having a dynamic hardness of 250 to 270 kgf / mm ² is laminated in this order to form the surface layer, and then the first layer region is partially formed on the outermost surface of the electrophotographic photosensitive member. A polishing sheet coated with abrasive grains having a particle size of 6 μm made of silicon carbide as a material dispersed in the binder is formed on the surface after the second layer region is formed so as to be exposed to the surface. Polishing using It was possible to obtain a more or less of the effect.

  First, the production of an electrophotographic photosensitive member capable of suppressing the occurrence of image defects such as image blurring and image flow in a high temperature and high humidity environment to a practically negligible level without providing a means for heating the electrophotographic photosensitive member is significant. This is possible without extending the manufacturing time.

  Furthermore, even when a toner having a small particle size and excellent fixability is used, the cleaning property is good, and the production of an electrophotographic photosensitive member capable of suppressing the fusion of the toner to a practically negligible time greatly increases the production time. It becomes possible without.

  Details of the present invention will be described below.

  The method for producing an electrophotographic photosensitive member of the present invention first includes a step of forming a photosensitive layer by depositing a photoconductive layer made of a non-single crystal material having at least silicon atoms as a base on a conductive substrate.

Further, according to the present invention, the second layer region (also referred to as “second layer region having low hardness”) formed of a material having low hardness is the first layer region (“hardness”) formed of material having high hardness. The dynamic hardness is preferably 50 kgf / mm ² or more, or 2/3 times or less than the first layer region having a large. As a result, in the process in which the first layer region having a high hardness exposed on the outermost surface of the photosensitive member is retracted due to wear, the second layer region having a lower hardness is less likely to be peeled off, and the entire outermost surface of the photosensitive member is always uniform. Since it is worn out, the amount of abrasion on the surface of the photoreceptor can be suppressed, and the life of the photoreceptor can be further extended.

  In addition, the dynamic hardness in this invention prescribed | regulated here is measured using the Shimadzu Corporation dynamic hardness meter (model number DUH-201). In the present invention, the dynamic hardness was evaluated by forming a sample film having a thickness of 1 μm on 7059 glass (manufactured by Corning) set on a cylindrical aluminum substrate and measuring the dynamic hardness of the sample film. The dynamic hardness was measured using a triangular pyramid diamond stylus having a ridge angle of 115 ° with a tip radius of 0.1 μm and an indentation depth of 1/10 (0.1 μm) of the sample film thickness.

Also, dynamic hardness of greater first layer region of the hardness Ru Ah at 790 ~ 800 kgf / mm ^2. The dynamic hardness of greater first layer region of hardness 300 kgf / mm ² or more, preferably 500 kgf / mm ² or more, more preferably by a 700 kgf / mm ² or more, scraping streaky unevenness As you use Can effectively be prevented. In addition, by setting it to 1000 kgf / mm ² or less, it becomes possible to make toner fusion less likely to occur even if environmental conditions change.

  In the present invention, after the polishing process, the electrophotographic photosensitive member is polished so that the center line average roughness (Ra) in a 10 μm × 10 μm field of view is 1.0 nm to 40.0 nm. It is preferable for obtaining the effect more remarkably.

  The center line average roughness in the present invention refers to the value of the surface roughness Ra measured using an atomic force microscope (also referred to as AFM) [Q-Scope 250 manufactured by Questant Co., Ltd.]. In order to measure the thickness with high accuracy and good reproducibility, it is desirable that the result is in a measurement range of 10 μm × 10 μm.

  By setting Ra to 40.0 nm or less, fine irregularities on the surface can be suppressed, and it becomes difficult for charged products to accumulate in the valleys of the irregularities, so that image flow in high-temperature and high-humidity environments is less likely to occur. . Further, the fine particles (so-called external additives) added to the toner are suppressed from remaining in the concave and convex valley portions on the surface of the photoreceptor, and the cleaning property is improved.

  In addition, by suppressing the surface from becoming excessively smooth with Ra of 1.0 nm or more, an excessive increase in the contact area between the toner particles, external additive particles, etc. and the photoreceptor surface is suppressed. It becomes easy to maintain the adhesion force of the toner particles, external additive particles, and the like to the surface of the photoreceptor in an appropriate range, and it becomes easy to maintain good cleaning properties.

  In the present invention, it is preferable that the thickness of the second layer region having a low hardness of the electrophotographic photoreceptor before polishing is 5 nm or more and 300 nm or less in order to obtain the effects of the present invention remarkably. If the thickness exceeds 300 nm, the polishing time required to partially expose the first layer region having a high hardness becomes longer, and the effect of the present invention may be reduced. When the thickness is less than 5 nm, the second layer region having a small hardness remaining in the concave portion is reduced, and it may be difficult to obtain an appropriate surface roughness.

  Furthermore, after the polishing process, a larger effect can be obtained by polishing the electrophotographic photosensitive member so that the thickness of the concave portion of the first layer region having a high hardness is not less than 200 nm and not more than 1000 nm. Here, the concave portion is a concave portion of the first layer region having a high hardness after the formation of the first layer region having a high hardness and before the polishing process. After the polishing process, the concave portion has a high hardness with the photoconductive layer. The position can be specified by the recess in the interface portion of the first layer region.

In addition, it is preferable that the surface layer of the electrophotographic photosensitive member is formed of amorphous silicon carbide or amorphous carbon from the viewpoint that the hardness of the surface layer can be easily adjusted within the range of the present invention. More preferably, the surface layer is made of amorphous silicon carbide, and the carbon atom content is less than 95 atomic% with respect to the sum of the carbon atom content and the silicon atom content.
(Conductive substrate)
The substrate of the conductive substrate may be conductive or electrically insulating. Examples of the conductive substrate include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Conductive surface of at least the photosensitive layer of electrically insulating substrates such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc. The treated one can also be used as a conductive substrate.
(Photoconductive layer, surface layer)
The photoconductive layer is made of a non-single crystal material based on silicon atoms, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, microwave CVD method or other AC discharge CVD method, or direct-current discharge CVD method). It can be formed by a number of thin film deposition methods such as sputtering, vacuum deposition, ion plating, photo CVD, and thermal CVD.

  Among these, a high-frequency glow discharge method using frequencies in the RF band, in particular, the VHF band to the microwave band is preferable.

  If necessary, a lower charge injection blocking layer made of a non-single-crystal silicon material that functions to block charge injection from the conductive substrate side may be provided below the photoconductive layer. The lower charge injection blocking layer has a function of effectively blocking charge injection from the conductive substrate side to the photoconductive layer side when the surface layer is subjected to charging treatment with a constant polarity on its free surface.

  The lower charge injection blocking layer is an atom that controls conductivity, such as an atom belonging to Group 13 of the periodic table (abbreviated as Group 13 atom) or an atom belonging to Group 15 of the periodic table (abbreviated as Group 15 atom). In addition, atoms such as nitrogen, oxygen, and carbon are included as necessary. By comprising a non-single-crystal silicon film containing these atoms, it is possible to effectively prevent charge injection from the conductive substrate side, and to improve the adhesion between the photoconductive layer and the conductive substrate. Excellent electrophotographic characteristics can be realized.

  The layer thickness of the lower charge injection blocking layer is preferably 0.1 μm or more and 10 μm or less from the viewpoint of desired electrophotographic characteristics and economic effects. If the layer thickness is 0.1 μm or more, the injection of charges from the substrate can be sufficiently prevented, and if it is 10 μm or less, the production time of the electrophotographic photosensitive member can be shortened without reducing the electrophotographic characteristics, and the production cost can be reduced.

  The photoconductive layer preferably contains hydrogen and / or halogen atoms, but these atoms compensate for dangling bonds of silicon atoms, improving the layer quality, particularly improving photoconductivity and charge retention characteristics. Let The total amount of these atoms to be added is preferably 10 to 40 atomic% with respect to the total amount of silicon atoms and added atoms.

In addition, atoms for controlling conductivity can be introduced into the photoconductive layer. As atoms for controlling conductivity, group 13 atoms or group 15 atoms can be used. By containing these atoms, the electrophotographic characteristics can be optimized by controlling the runnability and generation degree of carriers. The total amount of these atoms to be added is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ atom% with respect to the total amount of silicon atoms and added atoms.

It is also effective to incorporate one or more atoms of carbon, oxygen and nitrogen into the photoconductive layer. By containing these atoms, the electrophotographic characteristics can be optimized by controlling the runnability and generation degree of carriers. The total amount of these atoms to be added is preferably 1 × 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁻⁴ to 8 atom%, based on the total amount of silicon atoms and added atoms, Optimally, 1 × 10 ^{−3 to} 5 atomic% is desirable.

  The layer thickness of the photoconductive layer is determined from the viewpoint of desired electrophotographic characteristics and economic effects, and is preferably 10 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm. If the layer thickness is 10 μm or more, sufficient charging ability, sensitivity, etc. can be secured, and if it is 50 μm or less, the production time of the electrophotographic photosensitive member can be shortened without reducing the electrophotographic characteristics, and the production cost can be reduced.

  An upper charge injection blocking layer may be provided between the photoconductive layer and the surface layer as necessary. The upper charge injection blocking layer prevents the injection of charges from the upper part, improves the charging ability, and also improves the image quality by preventing the photocarriers from moving quickly and accumulating charges in unnecessary areas. Plays.

  As the base material of the upper charge injection blocking layer, any material can be used as long as it is a non-single crystal silicon material. For example, an amorphous material containing hydrogen (H) and / or halogen (X) and further containing carbon atoms. Silicon (a-SiC: abbreviated as H, X) is preferable.

  When carbon is contained in the upper charge injection blocking layer, it is preferably less than the carbon content in the surface layer, and the stay of charge between the photoconductive layer and the surface layer is suppressed, reducing the cause of residual potential. it can. As a result, the lateral flow of accumulated charges is suppressed, and adverse effects such as image flow are suppressed.

  Furthermore, the upper charge injection blocking layer preferably contains atoms that control conductivity, such as Group 13 atoms or Group 15 atoms, and by containing these atoms, charge injection from the surface layer is blocked. In addition, accumulation of optical carriers can be prevented more effectively.

  The layer thickness of the upper charge injection blocking layer is determined by comprehensive judgment based on the layer thicknesses of the photoconductive layer and the surface layer, required electrophotographic characteristics, and the like. From the viewpoint of sufficiently exhibiting the ability to prevent charge injection from the surface and not affecting the image quality, the design is usually from 0.01 μm to 0.5 μm.

In the present invention, on the photoconductive layer obtained above to form a first layer region, the surface layer obtained by laminating a lower second layer region hardness in the order than the first layer region There is a need.
The surface layer preferably from the viewpoint that it is easy to be formed by amorphous carbide silicon down to adjust the scope of the present invention the hardness of the surface layer, and further a surface layer with amorphous silicon carbide, carbon atoms The content of is more preferably less than 95 atomic% with respect to the sum of the carbon atom content and the silicon atom content.

  The surface layer preferably contains hydrogen atoms, and may further contain halogen (X) as necessary.

  In addition, hydrogen and halogen in the surface layer compensate for dangling bonds of constituent atoms such as silicon, and improve the layer quality, particularly the photocarrier runnability and charge retention characteristics. From such a viewpoint, the hydrogen content is preferably 30 to 70 atomic%, more preferably 35 to 65 atomic%, and still more preferably 40 to 60 atomic% with respect to the total amount of constituent atoms. Further, the preferable content of, for example, fluorine as a halogen is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and optimally 0.6 to 4 atomic%.

  The layer thickness of the surface layer is preferably 0.010 to 3.00 μm, more preferably 0.050 to 2.00 μm, and particularly preferably 0.10 to 1.00 μm. If the layer thickness is 0.010 μm or more, sufficient durability of the surface layer can be secured, and if it is 3.00 μm or less, an increase in residual potential is suppressed and sufficient electrophotographic characteristics can be realized.

  For example, in order to form a photoconductive layer and a surface layer by a glow discharge method, a source gas that can supply atoms necessary for forming each layer, for example, a source gas for supplying Si that can supply silicon atoms (Si) A source gas for supplying C that can supply carbon atoms (C), a source gas for supplying H that can supply hydrogen atoms (H), etc., in a desired gas state in a reaction vessel capable of reducing the pressure inside Then, a glow discharge is generated in the reaction vessel, and a layer made of a-Si: H, a-SiC: H, aC: H, or the like is sequentially formed on the conductive substrate.

For example, as a substance that can serve as a silicon (Si) supply gas, silicon hydride (silanes) that is in a gas state such as SiH ₄ or Si ₂ H ₆ or can be gasified can be effectively used. Further, these source gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Examples of substances that can serve as a carbon supply gas include those in which gaseous hydrocarbons such as CH ₄ , C ₂ H ₂ , C ₂ H ₆ , or the like that can be gasified are effectively used. Further, these source gases for supplying C may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

  Examples of the substance that can serve as a hydrogen supply gas include hydrogen gas, a silicon compound gas containing hydrogen atoms, and a carbon compound containing hydrogen atoms. Each gas is not limited to a single species but may be a mixture of a plurality of species at a predetermined mixing ratio.

Preferable examples of the halogen-supplied source gas include gaseous or gasatable halogen compounds such as halogen gas, halides, halogen-containing interhalogen compounds, and halogen-substituted silane derivatives. It is done. For the formation of the photoconductive layer and the surface layer, a silicon hydride compound containing a halogen atom which is gaseous or can be gasified containing silicon atoms and halogen atoms as a mixed element is also effective. Specific examples of the halogen compound that can be preferably used include interhalogen compounds such as fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , and IF _7. . Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon fluorides such as SiF ₄ and Si ₂ F ₆ .

  Specific examples of atoms that control conductivity, such as Group 13 atoms, include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). B, Al, and Ga are preferable.

In order to structurally introduce Group 13 atoms, other materials for forming a photoconductive layer, a surface layer, etc. in the reaction vessel in a gas state with a raw material for introducing Group 13 atoms in the layer formation. What is necessary is just to introduce with other gas. As a raw material for introducing a Group 13 atom, it is desirable to employ a material that is gaseous at normal temperature and pressure or that can be easily gasified at least under the conditions of layer formation. Specifically, as a raw material for introducing such a group 13 atom, for introducing boron atom, boron hydrides such as B ₂ H ₆ and B ₄ H ₁₀ , BF ₃ , BCl ₃ , BBr _{3 and the} like are used. Examples thereof include boron halide. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned.

  Specific examples of atoms that control conductivity, such as Group 15 atoms, include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). P is particularly preferred. is there.

In order to structurally introduce Group 15 atoms, other materials for forming a photoconductive layer, a surface layer, or the like in the reaction vessel in a gaseous state with a raw material for introducing Group 15 atoms in the formation of the layer. What is necessary is just to introduce with other gas. As a raw material for introducing a Group 15 atom, it is desirable to employ a material that is gaseous at normal temperature and pressure or that can be easily gasified at least under the conditions of layer formation. Specifically, as the raw material for introducing the Group 15 atom, for introducing the phosphorus atom, phosphorus hydride such as PH ₃ and P ₂ H ₄ , PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , Examples thereof include phosphorus halides such as PBr ₃ and PI ₃ , and PH ₄ I. Other examples include AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like.

Further, the starting material for introducing an atom for controlling the conductivity may be diluted with H ₂ and / or He if necessary.

The flow rate when using a diluent gas such as H ₂ , He, Ar, Ne, etc. is appropriately selected in accordance with the layer design, but the diluent gas is usually set to 0.3 to 20 for the Si supply gas. It is desirable to control within a range of double, preferably 0.5 to 15 times, and most preferably 1 to 10 times.

Similarly, the optimum gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the normal case, 1.0 × 10 ^{−2 to} 1.0 × 10 ³ Pa, preferably 5.0 × 10. ^{−2 to} 5.0 × 10 ² Pa, most preferably 1.0 × 10 ^{−1 to} 1.0 × 10 ² Pa.

  Further, the discharge power is similarly selected as appropriate in accordance with the layer design. For example, in the case of a photoconductive layer, the discharge power (W) with respect to the flow rate of gas for supplying Si (ml / min (normal)). It is desirable to normally set the ratio of 0.3 to 30, preferably 0.5 to 15, and most preferably 1 to 10. For example, when amorphous silicon carbide is used as the surface layer, The ratio of the discharge power (W) to the total flow rate (ml / min (normal)) of the gas for supplying Si and the gas for supplying carbon is usually 1 to 100, preferably 3 to 30, and most preferably 7 to It is desirable to set in the range of 20.

  In addition, the optimum temperature range of the substrate is appropriately selected according to the layer design. In a normal case, the temperature is preferably 100 to 350 ° C, more preferably 150 to 330 ° C, and most preferably 200 to 310 ° C. Is desirable.

  Although the above-mentioned ranges are mentioned as desirable numerical ranges of the dilution gas mixing ratio, gas pressure, discharge power, and substrate temperature for forming the photoconductive layer, surface layer, etc., these layer preparation factors are usually independent. Rather than being determined separately, it is desirable to determine the optimum value of each layer fabrication factor based on mutual and organic relevance to form each layer having the desired characteristics.

  And as a method of changing the hardness of the surface layer, for example, when using a surface layer mainly composed of silicon and carbon, the carbon content is changed, the electric power at the time of forming the surface layer is changed, at the time of forming the surface layer A method of changing the deposition rate by changing the gas flow rate can be suitably used. These suitability values differ depending on the configuration of the apparatus to be used and are not uniquely determined.In general, however, the direction in which the carbon content is increased, the direction in which the power is decreased, and the direction in which the deposition rate is increased are directions in which the hardness is decreased. Become. The adjustment of hardness may be performed by adjusting a single condition among these conditions, or may be performed by combining several conditions. Furthermore, the adjustment of the film formation temperature and pressure during the surface layer formation may be combined with these.

  FIG. 2 is a schematic cross-sectional view of a plasma CVD (also referred to as PCVD) apparatus that can be used in the present invention.

  An exhaust pipe 209 is connected to the lower part of the reaction vessel 201, and the other end of the exhaust pipe 209 is connected to an exhaust device (not shown) (for example, a vacuum pump). Six cylindrical substrates 205 on which deposited films are formed are arranged on the same circumference so as to be parallel to each other at equal intervals so as to surround the central portion of the reaction vessel 201. The six cylindrical substrates 205 are each held by a substrate support 206 having a substrate heating heater 207 built therein. The reaction vessel 201 has a gas supply means 210 connected to a gas supply device (not shown). The reaction vessel 201 is connected to the high-frequency power branching means 211 through the matching box 204 to which the high-frequency power source 203 is connected. The high frequency electrode 202 is installed. The cylindrical base body 205 can be rotated by each rotation mechanism 208.

  Formation of the deposited film in the apparatus of FIG. 2 is performed as follows.

  First, the cylindrical substrate 205 is installed in the reaction vessel 201, and the inside of the reaction vessel 201 is evacuated by an unillustrated exhaust device (for example, a vacuum pump). Thereafter, an inert gas such as Ar or He is introduced into the reaction vessel 201 from the gas supply means 210, and the flow rate and the exhaust speed are adjusted so that a predetermined pressure is obtained. Subsequently, the substrate heating heater 207 is heated and controlled so that the temperature of the cylindrical substrate 205 becomes a predetermined temperature.

Thereafter, a gas such as SiH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ , etc. is introduced from the gas supply means 210 into the reaction vessel 201, and a flow rate and an exhaust rate so as to obtain a desired gas component and pressure. Adjust.

  After the preparation for film formation is completed as described above, each layer is formed according to the following procedure.

  For example, a high frequency power source 203 of 105 MHz is set to desired power, high frequency power is introduced into the reaction vessel 201 through the matching box 204, the high frequency power branching means 211, and the high frequency electrode 202, and the cylindrical substrate 205 is made to act as an anode. Causes a glow discharge. The gas introduced into the reaction vessel 201 is decomposed by this discharge energy, and a predetermined deposited film is formed on the cylindrical substrate 205. After the formation of the desired film thickness, the supply of high-frequency power is stopped, the inflow of gas into the reaction vessel 201 is stopped, and the formation of the deposited film is completed.

  By repeating the same operation, the photoconductive layer and the surface layer are laminated on the substrate. In addition to the conductive layer and the surface layer, the same operation is repeated a plurality of times as necessary, so that the substrate and the photoconductive layer are laminated. A charge injection blocking layer or the like is laminated between the photoconductive layer and the surface layer to form an electrophotographic photosensitive member having desired characteristics.

  In order to achieve uniform deposition film formation, it is desirable to rotate the cylindrical substrate 205 at a predetermined speed by the rotation mechanism 208 during the layer formation.

Furthermore, it goes without saying that the above gas species are changed according to the production conditions of each layer.
(Polishing)
Polishing is performed after the surface layer is formed. As a polishing method, a method in which a polishing tape is pressed against a rotating photoreceptor is preferable from the viewpoint of uniformity and efficiency. As an abrasive tape, what is normally called a lapping sheet is preferable, and SiC is used as an abrasive grain.

  An outline of such a polishing apparatus is shown in FIG.

  The photoconductor 300 is supported by a photoconductor support mechanism 307 fixed on the holding table 308, and is driven to rotate by a rotation mechanism (not shown).

  Adjacent to the photoconductor 300 is a pressure elastic roller 306 that winds the polishing tape 301 and presses it against the photoconductor 300. The polishing tape 301 is fed from the feed roll 302 by a fixed quantity feed roll 304 and a capstan roller 305, passes between the photosensitive member 300 and the pressure elastic roller 306, and is taken up by the take-up roll 303. The feed speed of the polishing tape 301 is controlled by controlling the rotational speed of the fixed delivery roll 304.

  The state of the surface of the photoconductor in the polishing process is shown in FIG. 1 as a schematic diagram of the cross section of the photoconductor. FIG. 1A shows a state before polishing, FIG. 1B shows a state after polishing, 101 is a conductive substrate, 102 is a photosensitive layer including a photoconductive layer formed of amorphous Si, and 103 is a first surface layer. The layer region (high hardness region), 104 indicates the second layer region (low hardness region) of the surface layer.

  As shown in FIG. 1B, the first layer region (high hardness region) of the surface layer is exposed on the surface by the polishing process, and a part of the second layer region (low hardness region) of the surface layer remains. It is preferable to polish as described above.

Hereinafter, the effect of the present invention will be specifically described with reference to examples. The present invention is not limited to these examples.
Example 1
Using the amorphous silicon photosensitive film forming apparatus shown in FIG. 2, it is shown in Table 1 on six cylinders in which an aluminum conductive substrate having an outer diameter of 80 mm and a length of 358 mm is mirror-finished by the method described above. Under the conditions, a lower charge injection blocking layer (abbreviated as a lower blocking layer), a photoconductive layer, and a surface layer were formed in this order. The VHF power used was a VHF power supply having a power supply frequency of 105 MHz and 50 MHz, and the VHF power of each power supply frequency was introduced at a ratio of 1: 1.

  As a result of measuring the carbon concentration of the surface layer of the electrophotographic photosensitive member thus produced by Auger electron spectroscopy, the carbon concentration (C / (Si + C) of the first layer region (high hardness region) was obtained. ) Was 65 atomic%, and the carbon concentration (C / (Si + C)) of the second layer region (low hardness region) was 78 atomic%. The carbon concentration in the first layer region (high hardness region) was measured by preparing an electrophotographic photosensitive member in which the second layer region (low hardness region) was not deposited.

Moreover, the dynamic hardness first layer region (high hardness region) 800 kgf / mm ^2, the second layer region (low hardness region) was 250 kgf / mm ^2. Hereinafter, the dynamic hardness is formed by forming a 1 μm-thick sample film on 7059 glass (manufactured by Corning) set on a cylindrical aluminum substrate, and using a dynamic hardness meter (model number DUH-201) manufactured by Shimadzu Corporation. A triangular pyramid diamond stylus having a radius of 0.1 μm and an angle between ridges of 115 ° is used, and the indentation depth is a value measured under measurement conditions of 1/10 (0.1 μm) of the sample film thickness.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member is elastically applied through a wrapping tape (Fuji Film C2000: abrasive grain silicon carbide, abrasive grain diameter 6 μm) which is a polishing tape having a width of 380 mm. After pressing with a roller, polishing was performed for 15 minutes at a tape speed of 50 mm / min and a photosensitive member rotation speed of 40 rpm.

When the microscopic surface roughness Ra of the electrophotographic photoreceptor thus obtained in the range of 10 μm × 10 μm was measured by AFM in the axial direction from one end to one end, an average of 35. It was 3 nm. In addition, when mapping analysis was performed on the surface state of the electrophotographic photosensitive member by EPMA (Electron Probe Micro-Analysis), it was observed that the portion where the carbon concentration was locally low was localized and distributed. As shown in FIG. 1B, it was observed that a portion where the first layer region having a high hardness was exposed and a second layer region having a low hardness were mixed.
(Comparative Example 1)
In the same manner as in Example 1, an electrophotographic photosensitive member comprising a lower blocking layer, a photoconductive layer, and a surface layer was formed under the conditions shown in Table 2. The VHF power used was a VHF power supply having a power supply frequency of 105 MHz and 50 MHz, and the VHF power of each power supply frequency was introduced at a ratio of 1: 1.

  As a result of measuring the carbon concentration of the surface layer of the electrophotographic photoreceptor thus produced by Auger electron spectroscopy, the carbon concentration (C / (Si + C)) was 65 atomic%.

The dynamic hardness of the surface layer was 800 kgf / mm ² .

Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was adjusted to 50 mm / The polishing process was performed at min and the photosensitive member rotation speed of 40 rpm, and the average of 10 positions of Ra from the axial end to the other end of the electrophotographic photosensitive member was set to 35.0 nm. The time required was 50 minutes.
(Comparative Example 2)
In the same manner as in Comparative Example 1, an electrophotographic photosensitive member comprising a lower blocking layer, a photoconductive layer, and a surface layer was formed under the conditions shown in Table 2, and this polishing apparatus shown in FIG. The surface was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fujifilm), which was a polishing tape having a width of 380 mm, and then polished for 15 minutes at a tape speed of 50 mm / min and a photosensitive member rotation speed of 40 rpm.

When the microscopic surface roughness Ra of the electrophotographic photoreceptor thus obtained in the range of 10 μm × 10 μm was measured by AFM in the axial direction from one end to one end, an average of 45. 1 nm.
(Comparative Example 3)
In the same manner as in Example 1, an electrophotographic photosensitive member comprising a lower blocking layer, a photoconductive layer, and a surface layer was formed under the conditions shown in Table 3. The VHF power used was a VHF power supply having a power supply frequency of 105 MHz and 50 MHz, and the VHF power of each power supply frequency was introduced at a ratio of 1: 1.

    As a result of measuring the carbon concentration of the surface layer of the electrophotographic photoreceptor thus produced by Auger electron spectroscopy, the carbon concentration (C / (Si + C)) was 78 atomic%.

The dynamic hardness of the surface layer was 250 kgf / mm ² .

Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was adjusted to 50 mm / The polishing process was performed at min and the photosensitive member rotation speed of 40 rpm, and the average of 10 positions of Ra from the axial end to the other end of the electrophotographic photosensitive member was set to 35.0 nm. The travel time was 9 minutes.
(Comparative Example 4)
In the same manner as in Comparative Example 3, an electrophotographic photosensitive member comprising a lower blocking layer, a photoconductive layer, and a surface layer was formed under the conditions shown in Table 3, and this polishing apparatus shown in FIG. The surface was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fujifilm), which was a polishing tape having a width of 380 mm, and then polished for 15 minutes at a tape speed of 50 mm / min and a photosensitive member rotation speed of 40 rpm.

When the microscopic surface roughness Ra of the electrophotographic photoreceptor thus obtained in the range of 10 μm × 10 μm was measured by AFM from one end to one end in the axial direction, an average of 26. It was 2 nm.
The electrophotographic photoreceptors of Example 1 and Comparative Examples 1, 2, 3, and 4 thus prepared were evaluated as follows.

・ Image flow An electrophotographic photoconductor was installed in an acceleration test machine modified from Canon's electrophotographic device iR-6000 for experiments. The electrophotographic photoconductor was not heated, and the temperature was 32 ° C and the humidity was 80%. Under the environment, 20,000 copies of a Canon test chart with Iroha characters printed on the entire surface were copied using A4 paper. Thereafter, the copying machine was once stopped, and in this state, the environment was changed to a temperature of 35 ° C. and a humidity of 90%, and left for 5 hours.

  Thereafter, the operation of copying 20,000 sheets of the previous chart with A4 paper and stopping the copying machine for 5 hours was repeated, and the durability test was performed up to a total of 100,000 sheets.

  The image flow was determined by determining the character outline of the image obtained in this way, and it was determined how many copies of the image recovered after 5 hours of rest.

  The evaluation results are shown in Table 4. The evaluation results were A when the A4 paper was recovered within 50 sheets, A when it was recovered with 51 to 100 sheets, C when it was recovered with 101 to 300 sheets, and D when it was not recovered with 300 sheets.

-Evaluation of toner fusion By making the pressing pressure of the cleaning blade of the Canon electrophotographic apparatus iR-6000 1/3 times and setting the surface temperature of the drum to 50 ° C., fusion is likely to occur. Created an environment. The drum after the 100,000 sheet durability test is installed on the acceleration test machine modified in this way, and 10% of A4 paper is used with a 1% original (original with only a straight line having a width of about 0.2 mm in the A4 diagonal direction). A 10,000 sheet durability test was performed.

  After the endurance test, a halftone image was copied and examined for fusing. Specifically, the number of black spots due to toner fusion in the A4 halftone image was counted.

  The evaluation results are shown in Table 5. The obtained results were subjected to relative evaluation with the value of the electrophotographic photosensitive member produced in Comparative Example 1 being 100, 90 or less being A, 91 to 110 being B, 111 to 130 being C, and 131 or more being D.

Evaluation of wear amount After measuring the film thickness of the surface layer of the electrophotographic photosensitive member, the electrophotographic photosensitive member was installed in the Canon electrophotographic apparatus iR-6000, and the room temperature / normal humidity was 23 ° C. and 60% humidity. In the environment, 250,000 copies of Canon test charts were copied. Thereafter, the electrophotographic photosensitive member was taken out from the electrophotographic apparatus, the thickness of the surface layer of the electrophotographic photosensitive member was measured, and the wear amount of the surface layer was measured from the difference from the surface layer thickness before 1 million copies.

  The evaluation results are shown in Table 6. The obtained results were subjected to relative evaluation with the value of the electrophotographic photosensitive member prepared in Comparative Example 1 being 100. 50 or less was A, 51 to 70 was B, 71 to 100 was C, and 101 or more was D.

  As shown in Tables 4, 5, and 6, the electrophotographic photosensitive member produced in Example 1 was shorter in production time than the photosensitive member produced in Comparative Example 1, and image flow was less likely to occur. The amount of wear on the body surface was small and good. In addition, the image was less likely to occur as compared with the photoconductor produced in Comparative Example 2 and was good. Furthermore, it was a good one with less wear compared to the photoconductor produced in Comparative Example 3. Compared to the photoconductor produced in Comparative Example 4, fusion was less likely to occur and the amount of wear was good.

As described above, it was found that the electrophotographic photosensitive member produced in Example 1 was good in all aspects of image flow, toner fusion, and the amount of wear on the surface of the electrophotographic photosensitive member. Further, the electrophotographic image obtained by the electrophotographic photosensitive member produced in Example 1 was satisfactory without any problems .

( Example 3)
Using the amorphous silicon photosensitive film forming apparatus shown in FIG. 2, it is shown in Table 13 on six cylinders in which an aluminum conductive substrate having an outer diameter of 80 mm and a length of 358 mm is mirror-finished by the method described above. Under the conditions, a lower blocking layer, a photoconductive layer, and a surface layer were formed in this order. The VHF power used was a VHF power supply with a power supply frequency of 90 MHz and 50 MHz, and the VHF power of each power supply frequency was superimposed and introduced at a ratio of 1: 1.

  The carbon concentration of the surface layer of the electrophotographic photosensitive member thus produced was measured by Auger electron spectroscopy in the same manner as in Example 1. As a result, the carbon concentration (C / (Si + C) of the first layer region (high hardness region) was measured. )) Was 68 atomic%, and the carbon concentration (C / (Si + C)) of the second layer region (low hardness region) was 74 atomic%.

Moreover, the dynamic hardness first layer region (high hardness region) 790kgf / mm ^2, the second layer region (low hardness region) was 270 kgf / mm ^2.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. When the surface state of the electrophotographic photosensitive member was 35.0 nm and mapping analysis was performed with EPMA, the portion where the carbon concentration was locally low was localized and distributed.

The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, Ra of the six electrophotographic photosensitive members was in the range of 32.3 nm to 34.5 nm. The polishing time was 18 minutes.
(Example 4)
A lower blocking layer, a photoconductive layer, and a surface layer are formed in this order in the same manner as in Example 3 except that the thickness of the high hardness region of the surface layer is 0.795 μm and the thickness of the low hardness region is 0.005 μm. did.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. When the surface state of the electrophotographic photosensitive member was 35.0 nm and mapping analysis was performed with EPMA, the portion where the carbon concentration was locally low was localized and distributed.

The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, the Ra of the six electrophotographic photosensitive members was in the range of 31.2 nm to 32.9 nm. The polishing time was 13 minutes.
(Example 5)
Except that the thickness of the first layer region (high hardness region) of the surface layer is 0.500 μm and the thickness of the second layer region (low hardness region) is 0.300 μm, the same as in Example 3, A lower blocking layer, a photoconductive layer, and a surface layer were formed in this order.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. When the surface state of the electrophotographic photosensitive member was 35.0 nm and mapping analysis was performed with EPMA, the portion where the carbon concentration was locally low was localized and distributed.

The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, Ra of the six electrophotographic photosensitive members was in the range of 30.3 nm to 31.5 nm. The polishing time was 20 minutes.
(Example 6)
Except that the film thickness of the first layer region (high hardness region) of the surface layer is 0.797 μm and the film thickness of the second layer region (low hardness region) is 0.003 μm, the same as in Example 3, A lower blocking layer, a photoconductive layer, and a surface layer were formed in this order.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. When the surface state of the electrophotographic photosensitive member was 35.0 nm and mapping analysis was performed with EPMA, the portion where the carbon concentration was locally low was localized and distributed.

The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, Ra of the six electrophotographic photosensitive members was in the range of 30.5 nm to 34.7 nm. The polishing time was 26 minutes.
(Example 7)
In the same manner as in Example 3 except that the thickness of the first layer region (high hardness region) of the surface layer is 0.400 μm and the thickness of the second layer region (low hardness region) is 0.400 μm, A lower blocking layer, a photoconductive layer, and a surface layer were formed in this order.

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm. However, if the pressure applied by the elastic roller is the same as in Examples 3, 4, 5, and 6, the surface of the electrophotographic photosensitive member may be unevenly scraped. 80% for 5 and 6.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. When the surface state of the electrophotographic photosensitive member was 35.0 nm and mapping analysis was performed with EPMA, the portion where the carbon concentration was locally low was localized and distributed.

The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, Ra of the six electrophotographic photosensitive members was in the range of 24.5 nm to 25.8 nm. The polishing time was 27 minutes.
(Comparative Example 9)
In the same manner as in Example 3, an electrophotographic photosensitive member comprising a lower blocking layer, a photoconductive layer, and a surface layer was formed under the conditions shown in Table 14. The VHF power used was a VHF power supply with a power supply frequency of 90 MHz and 50 MHz, and the VHF power of each power supply frequency was superimposed and introduced at a ratio of 1: 1.

  As a result of measuring the carbon concentration of the surface layer of the electrophotographic photoreceptor thus produced by Auger electron spectroscopy, the carbon concentration (C / (Si + C)) was 68 atomic%.

The dynamic hardness of the surface layer was 790 kgf / mm ² .

  Next, using the polishing apparatus shown in FIG. 3, the surface of the electrophotographic photosensitive member was pressed with an elastic roller through a wrapping tape (C2000 manufactured by Fuji Film), which is a polishing tape having a width of 380 mm, and then the tape speed was changed to 60 mm / Polishing was performed at min, the photosensitive member rotation speed of 60 rpm.

  The polishing time is an average of 25.0 nm to 10 μm × 10 μm of the electrophotographic photosensitive member when the microscopic surface roughness Ra is measured by AFM from one end to one end in the axial direction. Until it became 35.0 nm.

  The six electrophotographic photosensitive members were polished in this manner, and the microscopic surface roughness Ra of the obtained electrophotographic photosensitive member in the range of 10 μm × 10 μm was measured by the AFM in the axial direction from one end to the other end. The average Ra was obtained by measuring 10 points to the part. As a result, Ra of the six electrophotographic photosensitive members was in the range of 26.5 nm to 34.7 nm. The polishing time was 48 minutes.

The electrophotographic photoreceptors of Examples 3, 4, 5, 6, 7 and Comparative Example 9 thus prepared were evaluated for image flow, toner fusion, and wear amount in the same manner as in Example 1.
The evaluation results are shown in Tables 15, 16, 17, and 18. The evaluation results of the toner fusion and the amount of wear were evaluated relative to the evaluation value of Comparative Example 9 as 100.

  Further, Ra variation after polishing was evaluated as follows. Six electrophotographic photoconductors are polished, and the microscopic surface roughness Ra of the obtained electrophotographic photoconductor in the range of 10 μm × 10 μm is 10 positions from one end to one end in the axial direction by AFM. The average Ra was measured. From the results, the variation width of Ra ((maximum value of Ra) − (minimum value of Ra)) was examined. The evaluation results are shown in Table 17. The obtained results were subjected to relative evaluation with the value of the electrophotographic photosensitive member produced in Comparative Example 9 being 100, 20 or less being A, 21 to 50 being B, 50 to 100 being C, and 101 or more being D.

  Table 17 shows the polishing time in Examples 3, 4, 5, 6, 7, and Comparative Example 9. In the table, relative evaluation was performed by setting the polishing time in Comparative Example 9 as 100, and 50 or less was A, 51 to 75 was B, 76 to 100 was C, and 101 or more was D.

  As described above, the electrophotographic photoreceptors produced in Examples 3, 4, 5, 6, and 7 have a shorter production time and a high image flow suppression effect compared to the electrophotographic photoreceptor produced in Comparative Example 9, It was revealed that the electrophotographic photosensitive member surface was a good one with a small amount of wear. In particular, when the thickness of the second layer region (low hardness region) of the surface layer is 5 nm or more and 300 nm or less, the polishing time can be further shortened, and the variation of Ra on the surface of the produced electrophotographic photoreceptor is smaller. Thus, it has been clarified that the effect of the present invention appears more remarkably.

  Further, the electrophotographic images obtained by the electrophotographic photosensitive members produced in Examples 3, 4, 5, 6, and 7 were good without any problems.

FIG. 1A schematically shows a cross section of an electrophotographic photosensitive member of the present invention. FIG. 1A shows a state before polishing, FIG. 1B shows a state after polishing, 101 is a conductive substrate, and 102 is amorphous Si. , A photosensitive layer including a photoconductive layer comprising 103, 103 a first layer region (high hardness region) of the surface layer, and 104 a second layer region (low hardness region) of the surface layer. It is the figure which showed typically an example of the deposition apparatus for forming the electrophotographic photoreceptor of this invention. It is the figure which showed typically an example of the grinding | polishing apparatus for forming the electrophotographic photoreceptor of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 ... Conductive base | substrate 102 ... Photosensitive layer 103 ... 1st layer area | region (high hardness area | region) of a surface layer
104 ... second layer region of the surface layer (low hardness region)
DESCRIPTION OF SYMBOLS 201 ... Reaction container 202 ... High frequency electrode 203 ... High frequency power supply 204 ... Matching box 205 ... Cylindrical base body 206 ... Base substrate support 207 ... Substrate heating heater 208 ... Rotating mechanism 209 ... exhaust pipe 210 ... gas supply means 211 ... high frequency power branching means 300 ... photoconductor 301 ... polishing tape 302 ... delivery roll 303 ... take-up roll 304 ..Quantitative feed roll 305 ... Capstan roller 306 ... Pressure elastic roller

Claims (5)

In a method for producing an electrophotographic photosensitive member by depositing a photoconductive layer composed of a non-single crystal material having a silicon atom as a base material and a surface layer on a conductive substrate,
A first layer region composed of amorphous silicon carbide having a dynamic hardness of 790 to 800 kgf / mm ² , and a dynamic hardness composed of amorphous silicon carbide having a smaller hardness than the first layer region A state in which the first layer region is partially exposed on the outermost surface of the electrophotographic photosensitive member after forming the surface layer by laminating the second layer region of 250 to 270 kgf / mm ² in this order. The surface after the formation of the second layer region is polished using a polishing sheet coated with abrasive grains whose material dispersed in the binder is silicon carbide and the grain size is 6 μm. A method for producing an electrophotographic photosensitive member. The method for producing an electrophotographic photosensitive member according content in 請 Motomeko 1 Ru der less than 95 atomic% with respect to the sum of the content of content and silicon atom of the carbon atoms of the carbon atoms in the prior Symbol table surface layer. The method for producing an electrophotographic photosensitive member according to 請 Motomeko 1 or 2 center line average roughness (Ra) of Ru der than 40.0nm less 1.0nm in 10 [mu] m × 10 [mu] m field of view after the polishing. Method for producing a polishing before the previous SL second thickness of the layer region is Ru der than 300nm or less 5nm 請 Motomeko 1 electrophotographic photosensitive member any crab described 3. The method for producing an electrophotographic photosensitive member prior SL any crab description of the first thickness of the concave portion of the layer region is Ru der than 1000nm or less 200nm 請 Motomeko 1-4 after the polishing.

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