Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
  • G03G5/147—Cover layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0567—Other polycondensates comprising oxygen atoms in the main chain; Phenol resins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0578—Polycondensates comprising silicon atoms in the main chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0664—Dyes
  • G03G5/0696—Phthalocyanines
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/10—Bases for charge-receiving or other layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/10—Bases for charge-receiving or other layers
  • G03G5/102—Bases for charge-receiving or other layers consisting of or comprising metals
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/10—Bases for charge-receiving or other layers
  • G03G5/104—Bases for charge-receiving or other layers comprising inorganic material other than metals, e.g. salts, oxides, carbon
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
  • G03G5/147—Cover layers
  • G03G5/14708—Cover layers comprising organic material
  • G03G5/14713—Macromolecular material
  • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G5/14765—Polyamides; Polyimides

Definitions

• Electrophotographic photosensitive member Process cartridge, and electrophotographic apparatus
• the present invention relates to an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus.
• an electrophotographic photoreceptor As an electrophotographic photoreceptor (hereinafter sometimes simply referred to as “photoreceptor”), a material is used as a photoconductive substance (charge generating substance or charge transporting substance) because of the advantages of low cost and high productivity.
• Organic electrophotographic photoreceptors in which a photosensitive layer (organic photosensitive layer) is provided on a support have become widespread.
• As an organic electrophotographic photosensitive member a laminated photosensitive layer comprising a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material, because of the advantages of high sensitivity and material design diversity.
• An electrophotographic photoreceptor having a mainstream is the mainstream.
• the charge generating substance include a photoconductive dye and a photoconductive pigment
• examples of the charge transport substance include a photoconductive polymer and a photoconductive low molecular weight compound.
• the electrophotographic photoreceptor is required to have durability against these external forces because the surface can be directly charged with electrical and / or mechanical external forces of charging, exposure, development, transfer, and cleaning. Specifically, durability against surface scratches and wear due to these external forces, that is, scratch resistance and wear resistance, is required.
• polycarbonate resin has been often used as the binder resin for the surface layer of the electrophotographic photosensitive member.
• the binder resin for the surface layer it is more than the polycarbonate resin.
• polyarylate resin is a kind of aromatic dicarboxylic acid polyester resin.
• Japanese Patent Application Laid-Open No. 2-1 2 7 6 52 discloses an electrophotographic photosensitive member having a hardened layer using a curable resin as a binder resin as a surface layer.
• Japanese Patent Application Laid-Open Nos. 5-2 1 6 2 4 9 and 7-7 2 6 40 a monomer of a binder resin having a carbon-carbon double bond and a carbon-carbon double bond are disclosed.
• An electrophotographic photosensitive member having a charge transporting cured layer formed by curing and polymerizing a monomer having a charge transporting function with heat or light energy as a surface layer is disclosed.
• Japanese Patent Application Laid-Open No. 2 00-0 6 6 4 2 4 and Japanese Patent Application No. 2 0 0 0 6 6 4 2 5 disclose hole transport having a chain polymerizable functional group in the same molecule.
• An electrophotographic photosensitive member has been disclosed in which a charge transporting cured layer formed by curing and polymerizing a photosensitive compound with the energy of an electron beam is used as a surface layer.
• the surface layer of the electrophotographic photosensitive member is made a hardened layer, thereby improving the mechanical strength of the surface layer.
• the electrophotographic photoreceptor is generally used in an electrophotographic image forming process comprising a charging process, an exposure process, a development process, a transfer process, and a cleaning process as described above.
• the cleaning process that cleans the peripheral surface of the electrophotographic photosensitive member by removing residual toner remaining on the electrophotographic photosensitive member after the transfer step is important for obtaining a clear image. It is a difficult process.
• a cleaning method using a cleaning blade is a tally method that works by rubbing the cleaner blade and the electrophotographic photosensitive member. Depending on the frictional force between the cleaning blade and the electrophotographic photosensitive member, chattering of the cleaning blade and dripping of the cleaning blade may occur.
• the problems with these cleaning blades and electrophotographic photoreceptors tend to become more prominent as the wear resistance of the surface layer of the electrophotographic photoreceptor becomes higher and the peripheral surface of the electrophotographic photoreceptor becomes harder to wear.
• the surface layer of the organic electrophotographic photoreceptor is generally formed by a dip coating method, and the surface of the surface layer formed by this dip coating method tends to be smooth. For this reason, the contact area between the tallying blade and the peripheral surface of the electrophotographic photosensitive member is increased, the frictional resistance between the cleaning blade and the peripheral surface of the electrophotographic photosensitive member is increased, and the above problem tends to become remarkable.
• JP-A-5 3-9 2 1 3 3 discloses that the transfer material can be easily separated from the surface of the electrophotographic photosensitive member.
• a technique for keeping the surface roughness of an electrophotographic photosensitive member within a specified range is disclosed.
• Japanese Patent Application Laid-Open No. Sho 5 3-9 2 1 3 3 discloses a method for roughening the surface of an electrophotographic photosensitive member into a rough skin by controlling the drying conditions when forming the surface layer. Is disclosed.
• Japanese Patent Application Laid-Open No. Sho 5 2-2 6 2 2 6 discloses a technique for roughening the surface of an electrophotographic photosensitive member by incorporating particles in a surface layer.
• Japanese Patent Application Laid-Open No. 5-7-9 4 7 72 discloses a technique for roughening the surface of an electrophotographic photoreceptor by polishing the surface of the surface layer using a metal wire brush.
• Japanese Patent Application Laid-Open No. Hei 9 9 0 60 discloses a technique for roughening the surface of an organic electrophotographic photosensitive member using specific tallying means and toner. Is disclosed. According to Japanese Laid-Open Patent Publication No.
• Japanese Unexamined Patent Publication No. 2-1 39 5 6 6 discloses a technique for roughening the surface of an electrophotographic photosensitive member by polishing the surface of the surface layer using a film-like abrasive.
• Japanese Patent Application Laid-Open No. 02-155085 discloses a technique for roughening the surface of an electrophotographic photosensitive member by blasting.
• roughening is highly effective in improving chattering of the cleaning blade and improvement of cleaning blade deflection.
• An object of the present invention is to provide an electrophotographic photosensitive member having improved cleaning performance and good image reproducibility even during long-term use, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. .
• the electrophotographic photoreceptor of the present invention has a plurality of independent concave portions on the surface, and the major axis diameter of the concave portion is R
• the ratio of the depth to the major axis diameter (R dv / R pc) is 1.0, where R d V is the depth indicating the distance between the deepest part of the pc and the concave part and the aperture surface.
• the present invention relates to an electrophotographic photosensitive member characterized by having a concave-shaped portion which is largely 7.0 or less.
• the present invention is integrally supported by the electrophotographic photosensitive member described above and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. Relates to a process cartridge characterized by
• the present invention relates to an electrophotographic apparatus comprising the electrophotographic photosensitive member described above, a charging unit, an exposing unit, a developing unit, and a transfer unit.
• the electrophotographic photosensitive member of the present invention has an improved cleaning performance and good image reproducibility even when used repeatedly for a long time, and a process cartridge and an electronic device comprising the electrophotographic photosensitive member Photo equipment can be provided.
• FIG. 1A is a diagram showing an example (surface) of the concave shape portion in the present invention
• FIG. IB is a diagram showing an example (surface) of the concave shape portion in the present invention
• FIG. 1C is a diagram of the concave shape portion in the present invention
• FIG. 1D is a diagram showing a shape example (surface) of the concave portion in the present invention
• FIG. 1E is a diagram showing a shape example (surface) ′ of the concave shape portion in the present invention
• FIG. 1F is a diagram showing a shape example (surface) of the concave portion in the present invention
• FIG. 1G is a diagram showing a shape example (surface) of the concave portion in the present invention.
• FIG. 2A is a diagram showing an example (cross section) of the concave shape portion in the present invention
• FIG. 2B is a diagram showing an example (cross section) of the concave shape portion in the present invention
• FIG. 2C is a concave shape portion in the present invention
• FIG. 2D is a diagram showing a shape example (cross section) of the concave shape portion in the present invention
• FIG. 2E is a diagram showing a shape example (cross section) of the concave shape portion in the present invention
• FIG. 2F is a diagram showing a shape example (cross section) of the concave shape portion in the present invention
• FIG. 2G is a diagram showing a shape example (cross section) of the concave shape portion in the present invention.
• FIG. 3 is a view showing an example (partially enlarged view) of an arrangement pattern of masks used in the present invention.
• FIG. 4 is a diagram showing an example of a schematic diagram of a laser processing apparatus used in the present invention.
• FIG. 5 is a view showing an example (partially enlarged view) of an array pattern of concave portions on the outermost surface of the photoreceptor obtained by the present invention.
• FIG. 6 is a diagram showing an example of a schematic view of a pressure contact shape transfer processing apparatus using a mold used in the present invention.
• FIG. 7 is a diagram showing another example of a schematic view of a press-fitting shape transfer processing apparatus using a mold used in the present invention.
• FIG. 8A is a diagram showing an example of the shape of a mold used in the present invention.
• (1) shows a mold shape seen from above, (2) shows a mold shape seen from the side.
• Fig. 8B is a diagram showing another example of the shape of the mold used in the present invention.
• (1) shows the mold shape seen from above, (2) shows It is a figure which shows the mold shape seen from the side.
• FIG. 9 is a diagram showing an outline of the output chart of the fischer scope HI 00 V (manufactured by Fischer).
• FIG. 10 is a diagram showing an example of an output chart of the fischer scope HI 00 V (manufactured by Fischer).
• FIG. 11 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member according to the present invention.
• FIG. 12 is a view showing the shape (partially enlarged view) of the mold used in Example 1.
• FIG. 12 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• FIG. 13 is a diagram showing an array pattern (partially enlarged view) of the concave-shaped portion on the outermost surface of the photoreceptor obtained in Example 1.
• FIG. 13 (1) shows the arrangement of the concave parts formed on the surface of the photoreceptor, and (2) shows the cross-sectional shape of the concave parts.
• FIG. 14 is a view showing the shape (partially enlarged view) of the mold used in Example 7.
• FIG. 14 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• FIG. 15 is a diagram showing an array pattern (partially enlarged view) of the concave portion on the outermost surface of the photoconductor obtained in Example 7.
• FIG. 16 is a view showing the shape (partially enlarged view) of the mold used in Example 8.
• (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• FIG. 17 is a view showing an array pattern (partially enlarged view) of the concave portions on the outermost surface of the photoconductor obtained in Example 8.
• (1) shows the arrangement of the concave portions formed on the surface of the photoreceptor, and (2) shows the cross-sectional shape of the concave portions.
• Figure 18 shows the mold shape (partially enlarged view) used in Example 21. is there.
• (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• FIG. 19 is a diagram showing an array pattern (partially enlarged view) of the concave-shaped portion on the outermost surface of the photoreceptor obtained in Example 21.
• (1) shows the arrangement of the concave portions formed on the surface of the photoreceptor, and (2) shows the cross-sectional shape of the concave portions.
• FIG. 20 is a diagram (partially enlarged view) showing an arrangement pattern of the mask used in Example 24.
• FIG. 20 is a diagram (partially enlarged view) showing an arrangement pattern of the mask used in Example 24.
• FIG. 21 is a diagram showing an array pattern (partially enlarged view) of the concave portion on the outermost surface of the photoreceptor obtained in Example 24.
• FIG. 21 is a diagram showing an array pattern (partially enlarged view) of the concave portion on the outermost surface of the photoreceptor obtained in Example 24.
• FIG. 22 is a diagram (partially large diagram) showing an arrangement pattern of masks used in Example 26.
• FIG. 22 is a diagram (partially large diagram) showing an arrangement pattern of masks used in Example 26.
• FIG. 23 is a diagram showing an array pattern (partially enlarged) of the concave portion on the outermost surface of the photoreceptor obtained in Example 26.
• FIG. 24 shows an image of the concave portion of the surface of the photoconductor produced in Example 27 using a laser microscope.
• the electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member having a photosensitive layer on a support, and has a plurality of independent concave portions on the surface, and the major axis diameter of the concave portion. Is the ratio of depth to major axis diameter (Rd v / Rp c) force S 1.0 where R pc and the depth indicating the distance between the deepest part of the concave-shaped part and the aperture surface are Rd v An electrophotographic photosensitive member having a large concave portion of 7.0 or less.
• each independent concave-shaped part means that each concave-shaped part is another concave-shaped part.
• the concave portion formed on the surface of the electrophotographic photosensitive member in the present invention is constituted by, for example, a shape constituted by a straight line, a shape constituted by a curved line, or a straight line and a curved line when observing the surface of the photosensitive member.
• Shape Examples of shapes formed by straight lines include triangles, quadrilaterals, pentagons, and hexagons. Examples of the shape formed by the curve include a circular shape or an elliptical shape.
• Examples of the shape constituted by a straight line and a curve include a square with a rounded corner, a hexagon with a rounded corner, and a sector.
• the concave portion on the surface of the electrophotographic photosensitive member in the present invention has, for example, a shape constituted by a straight line, a shape constituted by a curve, or a shape constituted by a straight line and a curve in observation of the cross section of the photoreceptor. Can be mentioned.
• Examples of the shape constituted by straight lines include a triangle, a quadrangle, and a pentagon.
• Examples of the shape constituted by the curve include a partial circle shape and a partial ellipse shape.
• Examples of the shape formed by straight lines include a square with a rounded corner or a fan shape.
• Specific examples of the concave portion on the surface of the electrophotographic photosensitive member in the present invention include FIGS. 1A to 1G (shape examples of concave portions (surface)> and FIGS. 2A to 2G (shape examples of concave portions). (Cross section)
• the concave shape portion of the electrophotographic photosensitive member surface in the present invention may have a different shape, size or depth, and In addition, all the concave portions may have the same shape, size, or depth, and the surface of the electrophotographic photosensitive member may have concave shapes having different shapes, sizes, or depths. And a surface in which concave portions having the same shape, size, or depth are combined.
• the major axis diameter in the present invention refers to the length of the maximum straight line among the straight lines crossing the opening of each concave shaped part. Specifically, as shown by the major axis diameter (R pc) in FIGS. 1A to 1G and the major axis diameter (R pc) in FIGS.
• Each concave-shaped part is based on the surface around the opening of the concave-shaped part in the body.
• the maximum length of the surface opening part in is shown. For example, when the surface shape of the concave portion is a circle, the diameter is indicated. When the surface shape is an ellipse, the major axis is indicated. When the surface shape is a square shape, a long diagonal line is shown.
• the depth in this invention shows the distance of the deepest part of each concave shape part, and an aperture surface.
• the surface around the opening of the concave portion of the electrophotographic photosensitive member is defined as a reference (S), It indicates the distance between the deepest part of the concave part and the aperture surface.
• the ratio (R dv ZR pc) of the depth (R dv) to the major axis diameter (R pc) of the concave portion is 1.0 on the surface of the electrophotographic photosensitive member.
• the concave portion of the present invention is formed on at least the surface of the electrophotographic photosensitive member.
• the area of the concave portion on the surface of the photoconductor may be the entire surface of the photoconductor surface or may be formed on a part of the surface, but in order to obtain good cleaning properties, at least contact with the cleaning blade It is preferable that a concave portion is formed on the surface portion.
• the taring performance is maintained well and the occurrence of various image defects is suppressed.
• the reason for this is not clearly understood, but is thought to be due to the fact that the frictional resistance is reduced by having a concave portion having a depth larger than the major axis diameter on the surface of the electrophotographic photosensitive member. It is Specifically, the frictional resistance between the electrophotographic photosensitive member and the cleaning blade tends to decrease as the contact area decreases due to the uneven shape on the surface of the electrophotographic photosensitive member. However, since the tally blade itself is an inertial body, it may be possible to follow the surface shape of the electrophotographic photosensitive member to some extent. If the surface shape is not appropriate, sufficient effects may not be achieved.
• the electrophotographic photosensitive member of the present invention since the depth of the repetitive portion on the surface of the electrophotographic photosensitive member is too large, the tracking of the cleaning blade tends to be suppressed. Therefore, it is considered that the frictional resistance between the electrophotographic photosensitive member and the cleaning blade is greatly reduced. As a result, the cleaning performance is improved, and a good cleaning performance is maintained not only in the initial stage but also in the long-term use, so that it is considered that the occurrence of various image defects is suppressed.
• the friction coefficient between the electrophotographic photoreceptor and the cleaning blade is remarkably reduced, so that good cleaning performance is maintained even without a sufficient amount of developer. It is considered a thing.
• a developer such as a toner or an external additive can be held in the concave portion by having the concave portion having a large major axis diameter. It is thought that it contributes to good cleaning performance.
• good cleaning performance means that a developer such as toner or an external additive that has not been transferred and remains on the surface of the photoconductor is caused by the contact between the cleaning blade and the electrophotographic photoconductor.
• the cleaning performance is exhibited by utilizing a part of the developer remaining without being transferred, and by the increase or decrease in the remaining amount of the developer remaining without being transferred. In some cases, the remaining developer and problems such as fusion caused by increased frictional resistance may occur. More specifically, good cleaning performance was exhibited when there was a sufficient amount of developer such as toner or external additive remaining without being transferred.
• the frictional resistance between the cleaning blade and the electrophotographic photosensitive member tends to increase when printing large amounts of patterns with low print density or when printing monochromatic images in a tandem electrophotographic system, resulting in the melting of the developer. It tends to be easy to wear.
• the toner interposed in the cleaning blade This is probably because the amount of the developer such as one or an external additive is extremely reduced.
• a developer such as toner or an external additive is held in the concave shape portion by having the concave shape portion having a depth larger than the major axis diameter. This can be considered to contribute to good cleaning performance. As a result, it is considered that tally defects are less likely to occur even when single-color continuous printing is performed in a tandem-type electrophotographic system for mass printing with low print density.
• the unit area may have a concave-shaped portion other than the concave-shaped portion in which the ratio of the depth to the major axis diameter (Rd v / Rpc) is greater than 1.0 and 7.0 or less.
• the 100 m square area is obtained by dividing the surface of the electrophotographic photosensitive member into four equal parts in the rotational direction of the photosensitive member and dividing into 25 equal parts in a direction perpendicular to the rotational direction of the photosensitive member. In each area, measure and measure a square area of 100 m on each side. .
• the major axis diameter of all concave-shaped parts included in 100 / m square was measured, and the average major axis diameter (Rpc-A) calculated for the average was measured in 100 zm square.
• the ratio of the average depth (R dv—A) (R d V— AZRp c— A), which is the average of the measured depths of all the convolutions, is: A value larger than 0 and 7.0 or less is preferable from the viewpoint of good cleaning characteristics.
• the ratio (R dv—A) of the average depth (R dv—A) to the average major axis diameter (Rp c—A) A / Rpc-A) is preferably 1.3 or more and 5.0 or less from the viewpoint of good cleaning characteristics.
• the depth (Rd v) of the concave portion in the electrophotographic photosensitive member of the present invention is such that the ratio of the depth to the major axis diameter (Rd v / Rpc) is greater than 1.0 and less than or equal to 7.0 In particular, it is preferable that it is greater than 3. ⁇ and less than 10. ⁇ in view of good cleaning characteristics. Further, the depth (Rd ⁇ ) is preferably 3.5 im or more and 8.0 / im or less.
• the average depth (Rd v—A) calculated by measuring the depth of all the concave-shaped portions included in the 100 m square of the surface of the electrophotographic photosensitive member of the present invention is larger than 3.0 ⁇ m. .. 0 ⁇ or less is preferable from the viewpoint of good cleaning characteristics. Furthermore, the average depth (Rd v— ⁇ ) is preferably 3.5 ⁇ or more and 8.0 ⁇ m or less.
• the major axis diameter (Rpc) in the electrophotographic photosensitive member of the present invention is preferably larger than 3.0 ⁇ and not larger than 10.0 / im. Furthermore, the major axis diameter (R pc) force is preferably 3.5 ⁇ or more and 8.0 m or less.
• the average major axis diameter (Rpc-A) calculated by measuring the major axis diameters of all the concave portions included in 100 ⁇ squares of the surface of the electrophotographic photosensitive member of the present invention is 0.1 ⁇ m or more. 10. Q ⁇ m or less is preferable in terms of good cleaning characteristics. Furthermore, the average major axis diameter is preferably 0.5 ⁇ or more and 8. or less.
• the arrangement of the concave-shaped portions on the surface of the electrophotographic photosensitive member of the present invention in which the ratio of the depth to the major axis diameter (Rd vZRpc) is greater than 1.0 and 7.0 or less is arbitrary.
• the concave portions where the ratio of the depth to the major axis diameter (Rd v / Rpc) is greater than 1.0 and less than or equal to 7.0 may be randomly arranged or arranged with regularity. May be. In order to improve the uniformity of the surface with respect to the cleaning performance, it is preferable to arrange with regularity.
• the concave portion on the surface of the electrophotographic photosensitive member can be measured using, for example, a commercially available laser microscope, optical microscope, electron microscope, or atomic force microscope.
• Ultra-depth shape measurement microscope VK-8550, ultra-depth shape measurement microscope VK-9000 and ultra-depth shape measurement microscope VK-9500 (all manufactured by Keyence Corporation): Surface shape measurement system Surface Ex plorer SX— 520 DR model (manufactured by Ryoka System Co., Ltd.): Scanning confocal laser microscope OLS 3000 (manufactured by Olympus Corp.): Real color confocal microscope Pretex C 130 (manufactured by Laser Teg Co., Ltd.).
• Digital Microscope VHX 500 and Digital Microscope VHX—200 (both made by Keyence Corporation): 3D digital microscope V C-7700 (made by OmKoon Co., Ltd.).
• 3D Real Surface View Microscope VE— 9800 and 3D Real Surface View Microscope VE— 8800 can be used as the electron microscope.
• 3D Real Surface View Microscope VE— 9800 and 3D Real Surface View Microscope VE— 8800 (both manufactured by KEYENCE CORPORATION): Scanning Electron Microscope Convenor / Les ariable Pressure S EM ⁇ Nanotechnology I (manufactured by KK): Scanning electron microscope SUPERS CAN SS—550 (manufactured by Shimadzu Corporation).
• Nanoscale hybrid microscope VN—8000 manufactured by Keyence Co., Ltd.
• Scanning probe microscope Nano NA Vi Station manufactured by SII Nanotechnology Co., Ltd.
• Scanning probe microscope S PM-9600 (Manufactured by Shimadzu Corporation).
• the major axis diameter of the concave part in the measurement visual field at a predetermined magnification And depth can be measured. Furthermore, can calculate the area ratio of the opening portion of the concave portion per unit area by calculation.
• the electrophotographic photoconductor to be measured Place the electrophotographic photoconductor to be measured on the work table, adjust the tilt to adjust the level, and capture the 3D shape data of the peripheral surface of the electrophotographic photoconductor in wave mode.
• the objective lens magnification may be 50 times, and lOO ⁇ mXlOO / m (10000 ⁇ m 2 ) field of view observation may be used.
• the surface of the photoconductor to be measured is divided into four equal parts in the rotation direction of the photoconductor, and divided into 25 equal parts in the direction orthogonal to the rotation direction of the photoconductor, and each of the total of 100 regions is obtained.
• a square area with a side of 100 ⁇ m is provided for measurement.
• the contour data of the surface of the electrophotographic photosensitive member is displayed using the particle analysis program in the data analysis software.
• the hole angle analysis parameters 1 of the concave portion can be optimized by the formed concave portion.
• the upper limit of the major axis diameter is 15 m
• the lower limit of the major axis diameter is 1 ⁇ m
• the lower limit of the depth is 0.1 ⁇ m
• the volume may be 1 ⁇ 3 or more. Then, the number of concave parts that can be identified as concave parts on the analysis screen is counted, and this is used as the number of concave parts.
• the total aperture area of the concave shape portion is calculated from the total aperture area of each concave shape portion obtained using the particle analysis program, and from the following formula:
• the area ratio of the opening portion of the concave portion may be calculated. (Hereinafter, the area ratio is simply indicated as the area ratio of the opening portion.)
• Examples of the method for forming the surface of the electrophotographic photosensitive member include: a method for forming the surface of the electrophotographic photosensitive member by laser irradiation having an output characteristic having a pulse width of 100 ns (nanoseconds) or less, and a mold having a predetermined shape. Examples thereof include a method for forming a surface that is brought into pressure contact with the surface of an electrophotographic photosensitive member, and a method for forming a surface in which the surface is condensed during formation of the surface layer of the electrophotographic photosensitive member. A method for forming the surface of an electrophotographic photosensitive member by laser irradiation having an output characteristic with a pulse width of 100 ns (nanoseconds) or less will be described.
• lasers used in this method include excimer lasers using a gas such as Ar F, Kr F, Xe F or Xe C 1 or femtosecond lasers using titanium sapphire as a medium.
• the wavelength of the laser beam in the laser irradiation described above is preferably 1,000 nm or less.
• the excimer laser is a laser beam emitted in the following steps. First, a high-energy energy such as discharge, electron beam or X-ray is given to a mixed gas of a rare gas such as Ar, Kr or Xe and a halogen gas such as F or C1, and the above-mentioned Excites and binds elements. After that, excimer laser light is emitted when dissociating by falling to the ground state. Examples of the gas used in the excimer laser include Ar F, Kr F, Xe Cl, and Xe F, and any of them may be used. In particular, Kr Faru is preferably Ar F.
• a mask in which the laser light shielding part a and the laser light transmission part b shown in FIG. 3 are appropriately arranged is used. Penetrated the mask By only condensing the laser beam with the lens and irradiating the surface of the electrophotographic photosensitive member, it becomes possible to form a concave portion having a desired shape and arrangement.
• a large number of concave portions within a certain area can be processed instantaneously and simultaneously regardless of the shape or area of the concave portions. The process can be performed in a short time.
• the electrophotographic photosensitive member f is rotated by a workpiece rotating motor d. While rotating, by moving the laser irradiation position of the excimer laser beam irradiator c in the axial direction of the electrophotographic photosensitive member f by the work moving device e, the concave shape can be efficiently formed over a wide area on the surface of the electrophotographic photosensitive member. Part can be formed.
• the surface layer has a plurality of independent concave portions, and the major axis diameter of the concave portion is Rpc and the deepest portion of the concave portion.
• the ratio of the depth to the major axis diameter (Rd vZRpc) is greater than 1.0 and less than 7.0 m.
• An electrophotographic photoreceptor having the same can be produced.
• the depth of the concave portion is arbitrary within the above range.
• the concave portion When forming the surface of an electrophotographic photosensitive member by laser irradiation, the concave portion can be adjusted by adjusting the manufacturing conditions such as the laser irradiation time and the number of times. The depth of can be controlled. From the viewpoint of manufacturing accuracy or productivity, when forming the surface of an electrophotographic photosensitive member by laser irradiation, the depth of the concave portion by one irradiation is 0. 0 ⁇ or more 2.0 / zm Desirably, it is desirable that the ratio be not less than 0.3 / im and not more than l.2 xm.
• the surface of the electrophotographic photosensitive member is highly precise and highly flexible with high controllability of the size, shape and arrangement of the concave portions. Processing can be realized.
• the above-described surface forming method may be applied to a plurality of portions or the entire surface of the photosensitive member using the same mask pattern. By this method, a highly uniform concave portion can be formed on the entire surface of the photoreceptor. As a result, the mechanical load on the cleaning blade when used in an electrophotographic apparatus is uniform.
• the mask pattern is formed so that the concave portion h and the concave shape non-forming portion g are present on an arbitrary circumferential line of the photosensitive member (indicated by an arrow). By doing so, the uneven distribution of the mechanical load on the cleaning blade can be further prevented.
• FIG. 6 is a diagram showing an example of a schematic diagram of a pressure contact shape transfer processing apparatus using a mold according to the present invention.
• a predetermined amount is applied to the electrophotographic photosensitive member C.
• a predetermined concave shape may be formed over the entire circumference of the photoreceptor by rotating (in the direction indicated by the arrow) and moving (in the direction indicated by the arrow) while applying the pressure of .
• a mold or electrophotographic photosensitive member is added for the purpose of efficient shape transfer. May be heated.
• the heating temperature of the mold and the electrophotographic photosensitive member is arbitrary as long as the shape of the present invention can be formed, but the temperature (° c) of the mold at the time of shape transfer is set to the glass of the photosensitive layer on the support of the photosensitive member. It is preferably heated so as to be higher than the transition temperature (° c).
• the temperature (° C) of the support during shape transfer is controlled to be lower than the glass transition temperature (° C) of the photosensitive layer. This is preferable for stably forming the concave-shaped portion.
• the mold temperature (° C) at the time of shape transfer is set to the glass transition temperature (° C) of the charge transport layer on the support. ) It is preferably heated to be higher. Furthermore, in addition to the heating of the mold, the temperature of the support (° C) during shape transfer is controlled to be lower than the glass transition temperature (° C) of the charge transport layer. It is preferable for stably forming the concave portion.
• the material, size, and shape of the mold itself can be selected as appropriate.
• the materials are metal and silicon wafers patterned with resist on the surface, finely dispersed resin film or resin film with a specified fine surface shape. Can be listed.
• An example of the mold shape is shown in FIGS. 8A and 8B.
• FIG. 8A (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• FIG. 8B (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• an elastic body may be provided between the mold and the pressure device for the purpose of imparting pressure uniformity to the photoreceptor.
• the surface layer has a plurality of independent concave portions by the method of forming a surface by pressing the mold having a predetermined shape against the surface of the electrophotographic photosensitive member and transferring the shape.
• the shaft diameter is RP c, the deepest part of the concave part and the aperture surface
• An electrophotographic photosensitive member having a concave-shaped portion in which the ratio of the depth to the major axis diameter (R dv / R pc) is greater than 1.0 and less than or equal to 7.0, where R dv is the depth indicating the distance of Can be produced.
• the depth of the concave portion is arbitrary within the above range, but when forming a surface that performs shape transfer by pressing a mold having a predetermined shape against the surface of the electrophotographic photosensitive member, the depth is It is desirable to be 0.1 / m or more and 10 ⁇ or less.
• the method of forming the surface that has condensed the surface when forming the surface layer of the electrophotographic photosensitive member includes a binder resin and a specific aromatic organic solvent, and the content of the aromatic organic solvent is the total amount in the coating solution for the surface layer.
• a coating solution for the surface layer containing 50% by mass or more and 80% by mass or less with respect to the mass of the solvent is prepared, followed by an application step of applying the application solution, and then a support coated with the application solution. Condensing step of holding and condensing the surface of the support coated with the coating solution, and then drying to dry the support :! : This is a method for producing a surface layer in which independent concave portions are formed on the surface.
• binder resin examples include acrylic resin, styrene resin, polyester resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyphenylene oxide resin, epoxy resin, polyurethane resin, alkyd resin, and unsaturated resin. It is done. In particular, polymethyl methacrylate resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, polyarylate resin or diallyl phthalate resin are preferable. Furthermore, a polycarbonate resin or a polyarylate resin is preferable. These may be used alone, as a mixture or as a copolymer, or one or more of them may be used.
• the specific aromatic organic solvent is a solvent having a low affinity for water. Specific examples include 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene, 1,3,5-trimethylbenzene, and black benzene.
• the surface layer coating solution contains an aromatic organic solvent.
• the surface layer coating solution further has a high affinity with water.
• the surface layer coating solution may contain a solvent, an organic solvent or water.
• organic solvents with high affinity for water include (methylsulfiel) methane (common name: dimethyl sulfoxide), thiolane 1,1-dione (common name: sulfolane), N, N-dimethylcarboxyamide, N N-jetylcarboxamide, dimethylacetamide, or 1-methylpyrrolidin-2-one is preferred.
• These organic solvents can be contained alone or in admixture of two or more.
• the dew condensation step for dew condensation on the surface of the support refers to a step of holding the support coated with the surface layer coating liquid for a certain period of time in an atmosphere in which the surface of the support is dewed.
• Condensation in this surface formation: ⁇ method means that droplets were formed on the coated support by the action of water.
• the conditions for condensation on the surface of the support are affected by the relative humidity of the atmosphere holding the support and the volatilization conditions of the coating solution solvent (for example, heat of vaporization). Since it is contained in an amount of 50% by mass or more based on the solvent mass, the influence of the volatilization condition of the coating solution solvent is small and mainly depends on the relative humidity of the atmosphere holding the support.
• the relative humidity that condenses the surface of the support is 40% to 100%. Furthermore, the relative humidity is preferably 60% or more and 95% or less. In the support holding process, it suffices if the time required for the formation of droplets by condensation is performed. From the viewpoint of productivity, it is preferably 1 second to 300 seconds, and more preferably about 10 seconds to 180 seconds. Relative humidity is important for the support holding process.
• the temperature is preferably 20 ° C. or higher and 80 ° C. or lower.
• the liquid droplets generated on the surface by the support holding step can be formed as concave portions on the surface of the photoreceptor.
• the drying temperature in the drying step is preferably from 100 ° C to 1550 ° C.
• the drying process time for drying may be a time period for removing the water droplets formed by the coating applied on the support-"solvent in the cloth liquid; and the dew condensation process. 20 minutes for the drying process. It is preferably ⁇ 120 minutes, more preferably 40 minutes to 100 minutes.
• the surface is condensed at the time of forming the surface layer of the electrophotographic photosensitive member
• independent concave portions are formed on the surface of the photosensitive member.
• the method of forming a surface with condensation on the surface of the electrophotographic surface layer of the photoconductor is that the droplets formed by the action of water have low affinity with water, a solvent, and a binding tree.
• This is a method of forming a concave part. Since the individual shapes of the concave portions formed on the surface of the electrophotographic photosensitive member produced by this manufacturing method are formed by the cohesive force of water, the concave portions are highly uniform.
• the concave portion on the surface of the electrophotographic photosensitive member is, for example, a droplet shape or A concave shape with a honeycomb shape (hexagonal shape) is formed.
• the concave portion of the droplet shape is, for example, a concave portion that is observed in a circular shape or an elliptical shape.
• the cross section of the photosensitive member for example, a partial circular shape or a partial elliptical shape It shows the concave part observed in the shape.
• the honeycomb-shaped (hexagonal) concave-shaped portion is, for example, a concave-shaped portion formed by close-packing droplets on the surface of the electrophotographic photosensitive member.
• the concave portion is circular, hexagonal, or hexagonal with a rounded corner, and in observation of the cross section of the photoreceptor, for example, partial circle or prismatic Such a concave-shaped part is shown.
• the surface layer has a plurality of independent concave portions, and the major axis diameter of the concave portions is reduced.
• the ratio of the depth to the major axis diameter (Rd v / R pc) is greater than 1.0, where R _d V is the depth that indicates the distance between the deepest portion of R pc and the concave shape portion and the aperture surface.
• An electrophotographic photosensitive member having a concave-shaped portion that is 7.0 or less can be produced.
• the depth of the concave-shaped portion is arbitrary within the above range, but the depth of each concave-shaped portion is preferably a manufacturing condition of 0.5 Aim or more and 10 ⁇ or less. It is more preferably greater than 0.0 m and not greater than 10.0 ⁇ , and even more preferably not less than 3.5 ⁇ and not greater than 8.0 Aim.
• the concave portion can be controlled by adjusting the manufacturing conditions within the range shown in the manufacturing method.
• the concave shape portion can be controlled by, for example, the solvent type, the solvent content, the relative humidity in the condensation process, the holding time in the condensation process, and the drying temperature in the surface layer coating solution described in the present invention.
• the electrophotographic photosensitive member of the present invention includes a support and an organic photosensitive layer (hereinafter also simply referred to as “photosensitive layer”) provided on the support.
• the electrophotographic photosensitive member according to the present invention is generally a cylindrical organic electrophotographic photosensitive member in which a photosensitive layer is formed on a cylindrical support. However, a belt-like or sheet-like shape is also possible. .
• the photosensitive layer is a single-layer type light-sensitive layer containing a charge transport material and a charge generation material in the same layer, a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material Separated layers (functional separation type) photosensitive layer may be used.
• the electrophotographic photosensitive member according to the present invention is preferably a laminated type photosensitive layer from the viewpoint of electrophotographic characteristics.
• the laminated photosensitive layer is a normal layer type photosensitive layer laminated in the order of the charge generation layer and the charge transport layer from the support side
• the reverse layer type photosensitive layer is laminated in the order of the charge transport layer and the charge generation layer from the support side. It can be a layer.
• Electrophotographic photosensitive When a laminated photosensitive layer is used in the body, a normal photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. Further, the charge generation layer may have a laminated structure, and the charge transport layer may have a laminated structure. Furthermore, a protective layer can be provided on the photosensitive layer for the purpose of improving durability.
• conductive support those having conductivity (conductive support) are preferable.
• a support made of metal such as aluminum, aluminum alloy or stainless steel can be used.
• electrolytic composite polishing electrolysis with electrode having electrolytic action and electrolytic stone with polishing solution
• wet or dry houng treatment Things can also be used.
• the above-mentioned metal support or resin support polyethylene terephthalate, polybutylene terephthalate, phenolic resin, or the like
• conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles are impregnated with resin or paper, or a plastic having conductive '14 binder resin.
• the surface of the support may be subjected to cutting treatment, roughening treatment, anodizing treatment, etc. for the purpose of preventing interference fringes due to scattering of laser light or the like.
• the volume resistivity of the layer may be 1 X 10 0 10 ⁇ ⁇ cm or less. In particular, it is more preferably 1 X 10 6 ⁇ ⁇ cm or less.
• a conductive layer for the purpose of preventing interference fringes due to scattering of laser light, etc., and covering scratches on the support May be provided.
• This is a layer formed by applying a coating liquid in which conductive powder is dispersed in an appropriate binder resin. Examples of such conductive powder include the following. Carbon black, acetylene black; metal powder such as aluminum, nickel, iron, dichrome, copper, zinc or silver; metal oxide powder such as conductive tin oxide or ITO.
• binder resin examples include the following thermoplastic resins, thermosetting resins, and photocurable resin resins.
• the conductive layer consists of the conductive powder and the binder resin, an ether solvent such as tetrahydrofuran or ethylene glycol dimethyl ether; an alcohol solvent such as methanol; a ketone solvent such as methyl ethyl ketone; and toluene. It can be formed by dispersing or dissolving in a simple aromatic hydrocarbon solvent and applying it.
• the average thickness of the conductive layer is preferably 0.2 ⁇ or more and 40 ⁇ or more, more preferably 1 m or more and 35 or less, and even more preferably 5 Aim or more and 30 m or less. It is even more preferable that the surface of the conductive layer in which the conductive pigment or the resistance adjusting pigment is dispersed tends to be roughened.
• An intermediate layer having a barrier function or an adhesive function may be provided between the support or the conductive layer and the photosensitive layer (charge generation layer, charge transport layer).
• the intermediate layer can be, for example, improved adhesion of the photosensitive layer, improved coatability, improved charge injection from the support, 'Formed for protection against erosion.
• the intermediate layer may be formed by applying a curable resin and then curing to form a resin layer, or by applying an intermediate layer coating solution containing a binder resin on the conductive layer and drying. it can.
• binder resin for the intermediate layer examples include the following. Water-soluble resins such as polybutyl alcohol, polyvinyl methyl ether, polyacrylic acids, methyl cellulose, ethyl cellulose, polyglutamic acid or casein; polyamide resins, polyimide resins, polyamide resins, polyamide resins, Melamine resin, epoxy resin, polyurethane resin or polyglutamic acid 10 ester resin.
• the binder resin of the intermediate layer is preferably a thermoplastic resin from the viewpoints of coating property, adhesion, solvent resistance and resistance. Specifically, a thermoplastic polyamide resin is preferable.
• the polyamide resin is preferably a low crystalline or non-crystalline copolymerized nylon that can be applied in a solution state.
• the average film thickness of the intermediate layer is preferably not less than 0.05 ⁇ m and not more than 15 7 / m, more preferably not less than 0.1 im and not more than 2 ⁇ .
• semiconductive particles are dispersed in the intermediate layer, or an electron transport material (electron-accepting material such as an acceptor) is added. You may make it contain.
• Examples of the charge generating material used in the electrophotographic photosensitive member of the present invention include the following. Azo pigments such as monoazo, disazo or trisazo; phthalocyanine pigments such as metal phthalocyanines or non-metal phthalocyanines; Unindigo pigments; perylene anhydride or peri
• Una polycyclic quinononone facial pigments Susukuri Liri Lumum chromophore, Pipiriri Lillium salt or Tithiaapipyril Lilli Salts, triphenylmethane dyes; inorganic substances such as selenium, selenium monotellurium or amorphous silicon; quinacridone pigments, azurenium salt pigments, cyanine dyes, xanthene dyes, quinonimine dyes or styryl dyes. These charge generating materials may be used alone or in combination of two or more.
• metal phthalocyanines such as oxytitanium phthalocyanine, hydroxygallium phthalocyanine or chlorogallium phthalocyanine are preferable because of their high sensitivity.
• binder resin used for the charge generation layer examples include the following. Polycarbonate resin, Polyester resin, Polyarylate resin, Petranolate resin, Polystyrene resin, Polyvinylacetal resin, Diallyl phthalate resin, Acrylic resin, Methacrylic resin, Acetate butyl resin, Phenolic resin, Silicone resin, Polysulfone resin, Styrene Butadiene copolymer resin, alkyd resin, epoxy resin, urea resin or butyl chloride-vinyl acetate copolymer resin. In particular, petital resin is preferred. These may be used alone, as a mixture or as a copolymer, or one or more of them may be used.
• the charge generation layer can be formed by applying and drying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent.
• the charge generation layer may be a vapor deposition film of a charge generation material.
• the dispersion method include a method using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor, or a mouthful mill.
• the ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1: 10 (mass ratio), and more preferably in the range of 3: 1 to 1: 1 (mass ratio).
• the solvent used in the charge generation layer coating solution is selected based on the solubility and dispersion stability of the binder resin and charge generation material used.
• organic solvents include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, and ester solvents. Or an aromatic hydrocarbon solvent is mentioned.
• the average film thickness of the charge generation layer is preferably 5 ⁇ or less, and more preferably 0.1 to 2.
• the charge generation layer various sensitizers, antioxidants, ultraviolet absorbers and Z or a plasticizer can be added as necessary. Further, in order to prevent the flow of charges (carriers) in the charge generation layer, the charge generation layer may contain an electron transport material (electron-accepting material such as an acceptor). '
• Examples of the charge transport material used in the electrophotographic photosensitive member of the present invention include triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, virazoline compounds, oxazole compounds, thiazole compounds, and triallyl methane compounds. These charge transport materials may be used alone or in combination of two or more.
• the charge transport layer can be formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent, and drying it. Further, among the above charge transporting substances, those having film-forming properties alone may be formed as a charge transporting layer by itself without using a binder resin.
• examples of the binder resin used for the charge transport layer include the following. Acrylic resin, styrene resin, polyester resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyphenylene oxide resin, epoxy resin, polyurethane resin, alkyd resin or unsaturated resin.
• a polymethyl methacrylate resin, a polystyrene resin, a styrene-acrylonitrile copolymer resin, a polycarbonate resin, a polyarylate resin, or a diallyl phthalate resin is preferable. These may be used alone or as a mixture or copolymer.
• the charge transport layer can be formed by applying and drying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent.
• the ratio between the charge transport material and the binder resin is preferably in the range of 2: 1 to 1 : 2 (mass ratio).
• Ketone solvents such as aceton or methyl ethyl ketone; ester solvents such as methyl acetate or ethyl acetate; ether solvents such as tetrahydrofuran, dioxolane, dimethoxymethane or dimethoxetane; toluene, xylene or black mouth
• Aromatic hydrocarbon solvents such as benzene.
• solvents may be used alone or in combination of two or more.
• the average film thickness of the charge transport layer is preferably from 5 to 50 ⁇ , more preferably from 10 to 35 ⁇ m. '
• an antioxidant for example, an ultraviolet absorber and / or a plasticizer can be added to the charge transport layer as necessary.
• the material design of the charge transport layer serving as the surface layer is important in the case of the above-mentioned function separation type photosensitive member. For example, a method using a high-strength binder resin, a method for optimizing the ratio of the charge transport material exhibiting plasticity and the binder resin, and a method using a polymer charge transport material ⁇ are more durable. In order to achieve performance, it is effective to form the surface layer with a curable resin.
• the charge transport layer may be constituted with a curable resin, and as the second charge transport layer or protective layer on the charge transport layer.
• a curable resin layer may be formed.
• the characteristics required for the cured resin layer are both the strength of the film and the charge transport capability. It is generally composed of a cargo transport material and a polymerized or crosslinkable monomer.
• known hole transporting compounds and electron transporting compounds can be used as the charge transporting material.
• the material for synthesizing these compounds include chain polymerization materials having an talyloyloxy group or a styrene group.
• a material such as a sequential polymerization system having a hydroxyl group, an alkoxysilanol group or an isocyanate group can be mentioned.
• a combination of a hole transporting compound and a chain polymerization material is preferable from the viewpoints of electrophotographic characteristics, versatility, material design, and production stability of an electrophotographic photoreceptor having a surface layer made of a curable resin.
• an electrophotographic photoreceptor constituted by a surface layer obtained by curing a compound having both a hole transporting group and an acryloyloxy group in the molecule is particularly preferable.
• the curing means known means such as heat, light or radiation can be used.
• the average thickness of the cured layer is preferably 5 ⁇ m or more and 50 ⁇ m or less, and more preferably 10 ⁇ or more and 35 im or less.
• the second charge transport layer or the protective layer it is preferably 0.1 / z m or more and 20 ⁇ or less, more preferably 1 / im or more and 10 im or less.
• Additives include deterioration inhibitors such as antioxidants, UV absorbers or light stabilizers, and organic and inorganic particulates.
• deterioration inhibitors include hindered phenol-based antioxidants, hindered amine-based light stabilizers, sulfur atom-containing antioxidants, and phosphorus atom-containing antioxidants.
• organic fine particles include polymer resin particles such as fluorine atom-containing resin particles, polystyrene fine particles, and polyethylene resin particles.
• the inorganic fine particles include metal oxides such as silica and alumina.
• the electrophotographic photosensitive member of the present invention has a specific concave portion on the surface of the electrophotographic photosensitive member. The concave portion of the present invention works effectively when applied to a photoconductor whose surface is hard to wear.
• the elastic deformation rate of the surface layer of the electrophotographic photoreceptor of the present invention is preferably 40% or more and 70% or less, more preferably 45% or more and 65% or less, and 50% or more and 60% or less. Is even more preferable.
• the universal hardness value (HU) of the surface of the electrophotographic photosensitive member of the present invention is preferably 14 ON / mm 2 or more and 2 40 mm 2 or less, and more preferably 15 ON / mm 2 or more and 22 ON / mm. It is preferably 2 or less.
• the universal hardness value (HU) and elastic deformation rate of the surface of the electrophotographic photosensitive member are measured under the environment of an ambient temperature of 25 ° C and a relative humidity of 50%. (Measured using Fischer).
• This Fischer Scope HI 00V has an indenter abutting against the object to be measured (the peripheral surface of the electrophotographic photosensitive member), a continuous load is applied to this indenter, and the indentation depth under the load is read directly to continuously harden This is a device that requires high speed.
• a Vickers square pyramid diamond indenter having a facing angle of 136 ° was used as the indenter, and the indenter was pressed against the peripheral surface of the electrophotographic photosensitive member, and the following conditions were used.
• the number of measurement points was 273.
• FIG. 9 is a diagram showing an outline of the output chart of the Fischer Scope HI 00 V (Fischer).
• FIG. 10 is a view showing an example of an output chart of the Fischer scope HI 0 OV (manufactured by Fischer) when the electrophotographic photosensitive member according to the present invention is used as a measurement object.
• the axis represents the load F (mN) applied to the indenter, and the horizontal axis represents the indentation depth h ( ⁇ m).
• Figure 9 shows the results when the load applied to the indenter is increased stepwise to maximize the load (A ⁇ B) and then decreased gradually (B ⁇ C).
• Fig. 10 shows the results when the load applied to the indenter is increased stepwise and finally the load is 6 mN, and then the load is decreased stepwise.
• the universal hardness value can be obtained from the indentation depth of the indenter when a final load of 6 mN is applied to the indenter by the following formula.
• HU indicates universal hardness
• F f indicates the final load (unit N)
• S f indicates the surface area (mm 2 ) of the indented part when the final load is applied.
• H f is the indenter depth (mm) when the final load is applied.
• the elastic deformation rate is the amount of work (energy) performed by the indenter on the measurement target (electrophotographic photosensitive member peripheral surface), that is, the load on the indenter measurement target (electrophotographic photosensitive member peripheral surface) It can be obtained from the change in energy due to increase or decrease.
• the value obtained by dividing the elastic deformation work W e by the total work W t (W e ZW t) is the elastic deformation rate.
• the total work W t is the area of the area surrounded by A—B—D—A in FIG. 9, and the elastic deformation work W e is surrounded by C—B—D—C in FIG. It is the area of the area to be. .
• FIG. 11 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member according to the present invention.
• reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is driven to rotate about a shaft 2 in the direction of an arrow at a predetermined peripheral speed.
• the surface of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined positive or negative potential by a charging unit (primary charging unit: for example, a charging roller) 3.
• a charging unit primary charging unit: for example, a charging roller
• exposure light (image exposure light) 4 output from an exposure means (not shown) such as slit exposure or laser beam scanning exposure is received.
• electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.
• the electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in the developer of the developing means 5 to become a toner image.
• the toner image formed and supported on the surface of the electrophotographic photoreceptor 1 is transferred from the transfer material supply means (not shown) to the electrophotographic photoreceptor 1 by the transfer bias from the transfer means (for example, transfer roller 1) 6.
• the image is sequentially transferred to a transfer material (for example, paper) P fed between the transfer means 6 (abutting portion) in synchronism with the rotation of the electrophotographic photosensitive member 1.
• the transfer material P that has received the toner image transfer is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to undergo image fixing, and as an image formed product (print, copy) outside the apparatus. Printed out.
• the surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the developer (toner) remaining after the transfer by a cleaning means (for example, a cleaning blade) 7. Further, the surface of the electrophotographic photosensitive member 1 is subjected to charge removal processing by pre-exposure light (not shown) from pre-exposure means (not shown), and then used repeatedly for image formation. As shown in FIG. 11, when the charging means 3 is a contact charging means using, for example, a charging roller, pre-exposure is not necessarily required.
• the charging unit 3, the developing unit 5, and the cleaning unit 7, a plurality of components may be housed in a container and integrally combined as a process cartridge.
• the process cartridge may be configured to be detachable from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.
• an electrophotographic apparatus such as a copying machine or a laser beam printer.
• the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7 are integrally supported to form a cartridge, and a guide unit 10 such as a rail of the electrophotographic apparatus main body is used.
• the process cartridge 9 is removable from the main body of the electrophotographic apparatus.
• part means “part by mass”.
• the support body (cylindrical support body) was an aluminum cylinder with a diameter of 3 O mm and a length of 3 57.5 mm.
• Powder made of barium sulfate particles with tin oxide coating layer 60 parts (trade name: Pastoran P C 1, manufactured by Sankei Metal Mining Co., Ltd.)
• Titanium oxide 15 parts (Product name: T I T AN I X J R, manufactured by Tika Corporation)
• Resole type phenolic resin 4 3 parts (Product name: Phenolite J 1 3 2 5, manufactured by Dainippon Ink & Chemicals, solid content 70%)
• an intermediate layer coating solution in which the following components are dissolved in a mixed solution of 400 parts of methanol and 200 parts of Zn-butanol is dip-coated on the conductive layer and heated in an oven heated to 100 ° C. for 30 minutes.
• an intermediate layer having an average film thickness of 0.45 ⁇ m at a position of 170 mm from the upper end of the support was formed.
• Hexanone 60.0 parts The above coating for the charge generation layer is applied onto the intermediate layer by dip coating, and heated and dried in an oven heated to 80 ° C for 15 minutes, thereby A charge generation layer having an average film thickness of 0.17 ⁇ m at a position of 1700 mm was formed.
• the following components were dissolved in a mixed solvent of 600 parts of black-end benzene and 200 parts of methylal to prepare a coating for a charge transport layer. Using this, the charge transport layer was dip-coated on the charge generation layer and dried by heating in an oven heated to 100 ° C. for 30 minutes. A charge transport layer having an average film thickness of 15 ⁇ m was formed.
• tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) was added to the solution in which the fluorine atom-containing resin was dissolved. After that, the solution containing tetrafluorinated styrene resin powder was added four times at a pressure of 60 O kgf / cm 2 with a high-pressure disperser (product name: Mic mouth fluidizer M-110 EH, manufactured by Microfluidics, USA). Was applied and dispersed uniformly. Further, the dispersion-treated solution was filtered with a polyflon filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.) to prepare a dispersion.
• PF-040 manufactured by Advantech Toyo Co., Ltd.
• the second charge transport layer coating material was applied onto the charge transport layer, and then dried in an atmosphere at 50 ° C. for 10 minutes. After that, electron beam irradiation was performed for 1.6 seconds in a nitrogen atmosphere while rotating the support at 200 rpm under the conditions of an acceleration voltage of 150 KV and a beam current of 3. O mA. Subsequently, the temperature around the support was raised from 25 to 125 ° C. over 30 seconds in a nitrogen atmosphere, and the curing reaction of the material contained in the second charge transport layer was performed. At this time, the absorbed dose of the electron beam was measured and found to be 15 K Gy. The oxygen concentration in the electron beam irradiation and heat curing reaction atmosphere was 15 ppm or less.
• the support subjected to the above treatment is naturally cooled to 25 ° C in the air, and then subjected to heat treatment in the air for 30 minutes in an oven heated to 100 ° C.
• a protective layer having an average film thickness of 5 ⁇ m at a position of 17 O mm from the upper end of the support was formed to obtain an electrophotographic photosensitive member.
• the module shown in FIG. In a press-contacting shape transfer processing device using a mold, the shape transfer mold shown in Fig. 12 was installed and surface processing was performed. The temperature of the electrophotographic photosensitive member and monored at the time of processing was controlled at 110 ° C., and the shape was transferred by rotating the photosensitive member in the circumferential direction while applying a pressure of 5 MPa.
• FIG. 12 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• the mold shown in Fig. 1 2 has a cylindrical shape, the major axis diameter D is 1.0 / X m, the height F is 3. ⁇ ⁇ , and the distance E between the molds is 1.0.
• the electrophotographic photosensitive member produced by the above method was subjected to surface observation using an ultra-deep shape measuring microscope VK-9 500 (manufactured by Keyence Corporation).
• the electrophotographic photosensitive member to be measured was placed on a pedestal that was processed so that the cylindrical support could be fixed.
• the objective lens magnification was 50 times, and 100 ⁇ m square on the surface of the photoconductor was used for visual field observation.
• the concave shape observed in the measurement field was analyzed using an analysis program.
• the average distance I between the concave shape portion and the concave shape portion closest to the concave shape portion (hereinafter also referred to as the concave shape portion interval) is formed at an interval of 1.0 in. It was.
• the average depth (R dv ⁇ A) of the concave part in the above 100 / m square is 1.5 ⁇ m. there were.
• the area ratio was calculated to be 20%. The results are shown in Table 1. (In Table 1, the number is the ratio of depth to major axis diameter (Rdv / Rpc) is 1.
• R p c— ⁇ indicates the average major axis diameter of the concave portion in a 100 ⁇ m square.
• R d V—A represents the average depth of the concave portion in 100 ⁇ squares.
• R d V—AZR pc —A represents the ratio of the average depth to the average major axis diameter of the concave portion in 100 ⁇ square.
• the electrophotographic photosensitive member produced by the above method was left in an environment at an ambient temperature of 23 ° C and a relative humidity of 50% for 24 hours. Thereafter, the elastic deformation rate and the universanore hardness were measured. As a result, the elastic deformation rate value is 55% and the universal hardness value is
• the electrophotographic photosensitive member produced by the above method was mounted on an Canon electrophotographic copying machine GP 55 (corona charging method) and evaluated as follows.
• the electrophotographic photoconductor has an area potential (Vd) of -700 V and a light area potential (VI) of -200 V in an environment with an ambient temperature of 23 ° C and a relative humidity of 50%.
• the initial potential of the electrophotographic photosensitive member was adjusted.
• the cleaning blade made of polyurethane rubber was set so that the contact angle was 25 ° and the contact pressure was 30 gZ cm with respect to the surface of the electrophotographic photosensitive member.
• the initial driving current value (current value A) of the rotating motor of the electrophotographic photosensitive member having the above-mentioned surface finish was measured.
• This evaluation is an evaluation of the load amount between the electrophotographic photosensitive member and the cleaning blade.
• the magnitude of the current value obtained is the magnitude of the load between the electrophotographic photosensitive member and the cleaning blade. Indicates.
• the electrophotographic photosensitive member obtained by the same method was subjected to an initial driving current value (current value B) of the rotating motor of the electrophotographic photosensitive member using an electrophotographic photosensitive member that was not subjected to surface addition. ) was measured.
• the driving current value (current value A) of the rotation motor of the electrophotographic photosensitive member with the surface added thus obtained and the driving current value (current value) of the rotating motor of the electrophotographic photosensitive member whose surface is not processed are obtained.
• the obtained '(current value A) / (current value B) values were compared as relative torque ratios.
• This relative torque ratio value indicates the increase or decrease in the load amount between the surface-processed electrophotographic photosensitive member and the cleaning blade.
• the torque ratio value is smaller. This indicates that the load amount is small.
• Blade noise is a cleaning blade when the electrophotographic photosensitive member and the cleaning blade are rubbed, when the electrophotographic photosensitive member starts rotating, or when the rotation of the electrophotographic photosensitive member stops. Shows the phenomenon of making a sound.
• the main cause of blade noise is thought to be high friction between the electrophotographic photosensitive member and the cleaning blade.
• the torque ratio is used for evaluating the frictional force between the electrophotographic photosensitive member and the cleaning blade. The results are shown in Table 1. (In Table 1, the torque ratio indicates the relative torque ratio obtained by the above method.
• Blade squeal after 5 0 ', 0 0 0 indicates the presence or absence of blade squeaking or the number of blade squeaking in the paper passing durability test by the above method.
• Example 2 An electrophotographic photosensitive member was prepared in the same manner as in Example 1. In the mold used in Example 1, the height indicated by F in FIG. Processing was performed in the same manner as in Example 1 except that ⁇ was selected. Surface shape measurement as in Example 1. As a result, it was confirmed that a cylindrical concave portion was formed. Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 1.0 m, and the area ratio was calculated to be 20%. In the same manner as in Example 1, the elastic deformation rate and the universal hardness were measured. Result, the elastic deformation ratio value is 55% and Yunibasa Le hardness value was 180 NZmm 2. In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1.
• the major axis diameter indicated by D in FIG. 12 was changed from 1. to 0.5 ⁇ , ⁇ .
• Example 1 was processed in the same manner as in Example 1 except that the height represented by 1.0 111 to 0.5 ⁇ and F was changed from 3.0 zm to 2.0 im.
• the surface shape was measured in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed.
• the measurement results are shown in Table 1.
• the interval between the concave portions was formed at an interval of 0.5 m, and the area ratio was calculated to be 20%.
• the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive film was prepared in the same manner as in Example 1.
• the major axis diameter indicated by D in FIG. 12 was changed from 1.0 111 to 0.2 // ⁇ , E.
• Processing was carried out in the same manner as in Example 1, except that the indicated interval was changed from 1.0 111 to 0.2 ⁇ and the height indicated by F from 3. O zm to 2. O im.
• surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed. Table 1 shows the measurement results. The interval between the concave parts is
• Example Similar to 1 the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1.
• the major axis diameter indicated by D in FIG. 12 was indicated by 1.0 111 to 0.5 ⁇ , E.
• the processing was carried out in the same manner as in Example 1 except that the interval indicated by 1.0 to 111 / 0.2 / zm and the height indicated by F was changed from 3. ⁇ to 2. ⁇ .
• Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 0.2 ⁇ m, and the area ratio was calculated to be 40%.
• the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1.
• the major axis diameter indicated by D in FIG. 12 was expressed as 1. ⁇ ⁇ to 0.5 ⁇ , ⁇ .
• Example 3 Processing was performed in the same manner as in Example 1 except that ⁇ to 2. O / m.
• Table 1 shows the measurement results.
• the interval between the concave portions was formed at an interval of 0.1 m, and the area ratio was calculated to be 55%.
• the elastic deformation rate and universal hardness were measured.
• the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 .
• Ma The characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was produced in the same manner as in Example 1, and the same processing as in Example 1 was carried out except that the mold used in Example 1 was replaced with the chevron-shaped mold shown in FIG.
• FIG. 14 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• the mold shown in Fig. 14 has a chevron shape, the major axis diameter D is 1. ⁇ ⁇ , the height F is 3.0 xm, and the distance E between the molds is 1.0 / m.
• the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that the mountain-shaped concave portion shown in FIG. 15 was formed.
• FIG. 14 shows the mold shape seen from above
• FIG. 14 shows the mold shape seen from the side.
• the mold shown in Fig. 14 has a chevron shape, the major axis diameter D is 1. ⁇ ⁇ , the height F is 3.0 xm, and the distance E between the molds is 1.0 /
• Example 15 (1) shows the arrangement of the concave portions formed on the surface of the photoreceptor, and (2) shows the cross-sectional shape of the concave portions.
• Table 1 shows the measurement results.
• the concave-shaped portion interval I was formed at an interval of 1. ⁇ / iin, and the area ratio was calculated to be 20%.
• the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was produced in the same manner as in Example 1, and the same processing as in Example 1 was performed except that the mold used in Example 1 was replaced with the conical mold shown in FIG.
• FIG. 16 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• the mold shown in FIG. 16 has a conical shape, the major axis diameter D is 0.2; um, the height F is 2.0 m, and the distance E between the molds is 0.2. ⁇ .
• the conical concave portion shown in FIG. 17 was formed.
• Figure 17 (1) is formed on the surface of the photoconductor (2) shows the cross-sectional shape of the concave-shaped part.
• Table 1 shows the measurement results. Further, the interval I between the concave portions was formed at intervals of 0.2 ⁇ , and the area ratio was calculated to be 20%. In the same manner as in Example 1, the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation value was 55%, and the universal hardness value was 18 ON / mm 2 . In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 1 fluorine atom-containing resin (trade name: GF-300, manufactured by Tojo Gosei Co., Ltd.) and tetrafluoroethylene resin powder (trade name: Lubron L 1-2, Daikin Industries, Ltd.) ) A second charge transport layer coating was prepared without adding. Otherwise, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the surface was processed in the same manner as in Example 7 using the mold used in Example 7. When surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a mountain-shaped concave portion was formed. Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 1. ⁇ , and the area ratio was calculated to be 20%.
• Example 1 In the same manner as in Example 1, the bowing deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 6 2% and the universal hardness value was 20 ON / mm 2 . In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) and tetrafluorinated styrene resin powder (trade name: Lubron L 2 and Daikin Industries, Ltd.) were prepared as 2.0 parts and 40 parts, respectively. Otherwise, an electrophotographic photoreceptor was produced in the same manner as in Example 1, and the surface was processed in the same manner as in Example 7 using the mold used in Example 7. When the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a mountain-shaped concave portion was formed. Table 1 shows the measurement results.
• the interval between the shape portions was formed at an interval of 1.0 m, and the area ratio was calculated to be 20%.
• the elastic deformation rate and universal hardness were measured.
• the elastic deformation rate value was 50% and the universal hardness value was 1 75 N / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) and tetrafluorinated styrene resin powder (trade name: Lubron L 2 and Daikin Industries, Ltd.) were prepared as 3.0 parts and 60 parts, respectively. Otherwise, an electrophotographic photoreceptor was produced in the same manner as in Example 1, and the surface was processed in the same manner as in Example 7 using the mold used in Example 7. When the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a mountain-shaped concave portion was formed. Table 1 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.0 ⁇ , and the area ratio was calculated to be 20%.
• the elastic deformation rate and universal hardness were measured.
• the elastic deformation rate value was 45% and the universal hardness value was 1 65 N / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support. Subsequently, the following components were dissolved in a mixed solvent of 600 parts by weight of benzene and 20 parts by weight of methylal to prepare a coating for a charge transport layer. Using this, the charge transport layer was dip-coated on the charge generation layer and dried by heating in an oven heated to 110 ° C for 30 minutes. A charge transport layer with an average film thickness of 15 m was formed.
• Electrotransport material represented by the above formula (2) 70 parts
• the molar ratio of the terephthalic acid structure to the isophthalic acid structure (terephthalic acid structure: isophthalic acid structure) in the polyarylate resin is 50:50.
• the weight average molecular weight (Mw) is 1 3 0, 0 0 0.
• the weight average molecular weight of the resin is measured as follows according to a conventional method.
• the molecular weight distribution of the resin to be measured was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.
• the standard polystyrene samples used for preparing calibration curves include Aldrich monodisperse polystyrene molecular weights of 3, 500, 12,000, 40, 000, 75, 000, 98, 000, 120, 000, 240, Ten points of 000, 500,000, 800, 000, 1,800,000 were used.
• An RI (refractive index) detector was used as the detector.
• Example 1 For the electrophotographic photosensitive member produced by the above method, in the mold used in Example 1, the height indicated by F in Fig. 12 was changed from 3. O ⁇ um to 6.0 ⁇ m. The processing was performed in the same manner as in Example 1 except that. When surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed. Table 1 shows the measurement results. The interval between the concave portions was 1. O / m, and the area ratio was calculated to be 20%. In the same manner as in Example 1, the elastic deformation rate and the universal hardness were measured. As a result, the elastic deformation rate value was 42% and the universal hardness value was 23 ON / mm 2 . In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 12.
• the major axis diameter indicated by D in Fig. 12 was changed from 1.
• ⁇ ⁇ to 2.5 ⁇ m E in height was shown a shown expired interval 1.0 from M m 2. in 0 m and F a 3.
• Processing was performed in the same manner as in Example 1 except that im ⁇ to 7.0 im.
• the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed.
• Table 1 shows the measurement results.
• the interval between the concave portions was 2.0 ⁇ m, and the “area ratio” was calculated to be 24%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 12, and the major axis indicated by D in FIG. 12 was changed from 1.0 ⁇ to 4.5 ⁇ m and E in the monored used in Example 1. Processing was performed in the same manner as in Example 1 except that the indicated interval was changed from 1. ⁇ ⁇ to 5.0 ⁇ m and the height indicated by F was changed from 3.0 ⁇ to 10. ⁇ .
• Table 1 shows the measurement results. The interval between the concave portions was formed at intervals of '5.0 ⁇ , and the area ratio was calculated to be 18%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 12.
• the major axis diameter indicated by D in FIG. 12 ′ was changed from 1. O m to 2.0 ⁇ m and Processing was performed in the same manner as in Example 1 except that the height indicated by F was changed from 3.0 // m to 5.0 ⁇ m.
• Table 1 shows the measurement results. Further, concave portions interval is formed at intervals of 1. 0 M m, the area ratio ⁇ : was that the 35% out.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1. (Example 16)
• An electrophotographic photosensitive member was produced in the same manner as in Example 12.
• the major axis diameter indicated by D in Fig. 12 was changed from 1. ⁇ ⁇ to 3.0 ⁇ m
• E Processing was performed in the same manner as in Example 1 except that the indicated interval was changed from 1. ⁇ ⁇ to 2.0 m and the height indicated by F was changed from 3.0 / im to 9.0 m.
• Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 2.0 Aim, and the area ratio was calculated to be 28%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• the polyarylate resin has a weight average molecular weight (Mw) of 120, 0-00.
• Example 1 For the electrophotographic photosensitive member produced by the above method, in the mold used in Example 1, the major axis diameter indicated by D in FIG. 12 was changed from 1. ⁇ to 5.5 ⁇ m, E The same processing as in Example 1 was performed except that the indicated interval was changed from 1. ⁇ ⁇ to 5.0 ⁇ m and the height indicated by F was changed from 3. ⁇ ⁇ to 12.0 / ⁇ .
• Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 5.0 / m, and the area ratio was calculated to be 22%. In the same manner as in Example 1, the elastic deformation rate and universal hardness were measured.
• Example 1 the elastic deformation rate value was 43% and the universal hardness value was 24 ON / mm 2 . Further, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1. (Example 1 8)
• An electrophotographic photosensitive member was prepared in the same manner as in Example 17.
• the major axis diameter indicated by D in Fig. 12 was changed from 1. 1. ⁇ to 3.0 ⁇ in the mode / read used in Example 1.
• ⁇ Processing was performed in the same manner as in Example 1 except that the interval indicated by ⁇ was changed from 1. ⁇ ⁇ to 2.0 m and the height indicated by F was changed from 3.0 im to 7.0 At m. It was.
• Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 2.0 / zm, and the area ratio was calculated to be 28%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 1 An electrophotographic photosensitive member was prepared in the same manner as in Example 7, and the major axis diameter indicated by D in Fig. 12 was changed from 1. D ⁇ to 2.0 im in the mold used in Example 1. Processing was performed in the same manner as in Example 1 except that the height indicated by chopstick F was changed from 3. 3. ⁇ to 6. ⁇ . When surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a circular columnar concave portion was formed. Table 1 shows the measurement results. The interval between the concave portions was formed at an interval of 1. ⁇ , and the area ratio was calculated to be 34%. In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 17.
• the distance indicated by ⁇ in Fig. 12 was changed from 1.0 m to 2.
• Processing was performed in the same manner as in Example 1 except that the height indicated by 3 was changed from 3. ⁇ ⁇ to 4. ⁇ ⁇ .
• Table 1 shows the measurement results.
• the concave part interval is formed at an interval of 2.0 / m, and the area ratio is calculated It was 20%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that the height indicated by F in FIG. 12 was changed from 3.0 / m to 1.4 ⁇ in the mold used in Example 1. The same processing as in Example 1 was performed. When surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed. When the total number of concave parts in 100 ⁇ m squares on the surface of the electrophotographic photosensitive member was calculated, 2,500 parts were formed, but the ratio of the depth to the major axis diameter (R The formation of a concave part with a dv (R pc) greater than 1.0 and less than 7.0 was not observed.
• Table 1 shows the average major axis diameter (R pc ⁇ A) and average depth (R dv ⁇ A) in the 100 ⁇ m square of the concave shape. Further, the interval between the concave portions was formed at a distance of 1.0 / m, and the area ratio was calculated to be 20%. In the same manner as in Example 1, the elastic deformation rate and the universal hardness were measured. As a result, the elastic deformation rate value was 55% and the universal hardness value was 18 ON / mm 2 . In addition, the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• An electrophotographic photosensitive member was produced in the same manner as in Example 1.
• the major axis diameter indicated by D in FIG. 12 was changed from 1. ⁇ ⁇ ⁇ to 5.
• ⁇ ⁇ and Processing was performed in the same manner as in Example 1 except that the height indicated by F was changed from 3. Oim to 1.0 m.
• the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed.
• the total number of concave parts in 100 ⁇ m square on the surface of the electrophotographic photosensitive member was calculated, 2 78 8 concave parts were formed, but the ratio of the depth to the major axis diameter (R d vZR pc ) was not larger than 1.0 but not more than 7.0.
• the average major axis diameter (R pc—A) and average depth (R dv—A) in the 100 ⁇ m square of the concave part are shown. Shown in 1.
• the interval between the concave portions was formed at an interval of 1.0 m, and the area ratio was calculated to be 55%.
• the elastic deformation rate and the universal hardness were measured. Result, the elastic deformation ratio value 55% and a universal hardness value was 1 8 ONZmm 2. Further, in the same manner as in Example 1, the electrophotographic photoconductor was evaluated for special characteristics. The results are shown in Table 1.
• Example 1 An electrophotographic photosensitive member was produced in the same manner as 2 and the height indicated by F in Fig. 1 2 was changed from 3. ⁇ 2 to 1.6 ⁇ in the mold used in Example 1. Except for this, the same processing as in Example 1 was performed. When the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed. When the total number of concave parts in 100 ⁇ m square on the surface of the electrophotographic photosensitive member was calculated, 2,500 concave parts were formed, but the ratio of the depth to the major axis diameter (Rd V / There was no formation of a concave part with Rp c) greater than 1.0 and less than 7.0.
• Table 1 shows the average major axis diameter (Rpc-A) and average depth (Rdv- ⁇ ) in the 100 ⁇ m square of the concave part.
• the interval between the concave portions was 1. O wm, and the area ratio was calculated to be 20%.
• the elastic deformation rate and universal hardness were measured. As a result, the elastic deformation rate value was 42% and the universal hardness value was 2 3 ON / mm 2 .
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 1.
• An electrophotographic photosensitive member was produced in the same manner as in Example 1, and the surface was not processed. In the same manner as in Example 1, the occurrence of blade squeal during the paper passing durability test of the electrophotographic photosensitive member was evaluated. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the electrophotographic photosensitive member was formed by a sand plast method in which glass beads having an average particle size of 35 ⁇ m were sprayed on the surface of the photosensitive member. The surface was sparse.
• surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a partially spherical concave portion was formed.
• the total number of concave parts in 100 ⁇ m square on the surface of the electrophotographic photosensitive member was calculated, six concave parts were formed, but the ratio of the depth to the major axis diameter (Rd v / Rpc) was The formation of a concave portion larger than 1.0 and not larger than 7.0 was not observed.
• Table 1 shows the average major axis diameter (Rp c—A) and average depth (Rd v—A) in the 100 ⁇ square of the concave part.
• the ratio of the depth to the major axis diameter (Rd vZRpc) is greater than 1 1.0 and less than or equal to 7.0, but the number of concave parts in 100 ⁇ square is completely included in 100 ⁇ square. The number of concave-shaped portions that were present was calculated and used.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 1.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the surface of the electrophotographic photosensitive member was roughened by a sand plast method in which glass beads having an average particle size of 70 ⁇ m were sprayed on the surface of the photosensitive member.
• a partially spherical concave portion was formed.
• the total number of concave-shaped portions in a 100 ⁇ m square on the surface of the electrophotographic photosensitive member was calculated, one concave-shaped portion was formed, but the ratio of the depth to the major axis diameter (Rd v / Rpc) was The formation of a concave portion larger than 1.0 and not larger than 7.0 was not observed.
• Table 1 shows the average major axis diameter (Rp c—A) and average depth (Rd v—A) in the 100 ⁇ square of the concave part.
• the ratio of the depth to the major axis diameter (Rd vZRp c) force is greater than 1.0 and less than 7.0, but the number of concave shapes in 100 ⁇ squares is completely contained within 10 squares. The number of concave portions was calculated and used.
• Table 1 shows the average major axis diameter (Rp c—A) and average depth (Rd v—A) in the 100 ⁇ square of the concave part.
• the ratio of the depth to the major axis diameter (Rd vZRp c) force is greater than 1.0 and less than 7.0, but the number of concave shapes in 100 ⁇ squares is completely contained within 10 squares. The number of concave portions was calculated and used.
• Table 1 shows the average major axis diameter (Rp c—A) and average depth (Rd
• the durability of 50,000 sheets was evaluated for a photosensitive member having a photosensitive layer formed on a support having a diameter of 3 Omm.
• the effect of reducing was confirmed.
• the concave surface is formed on the body surface, there is a tendency that the blade squeal does not occur.
• the effect persistence varies depending on the shape of the concave surface portion. This is because the effect of reducing the load with the cleaning blade is maintained by having a specific concave shape on the surface, and it is considered that the result of improving the blade squeal is obtained.
• An electrophotographic photosensitive member was produced in the same manner as in Example 1.
• the electrophotographic photosensitive member produced by the above method was subjected to surface processing in the apparatus shown in FIG. 7 by installing the mold for mold transfer made of nickel material shown in FIG.
• FIG. 18 (1) shows the mold shape seen from above, and (2) shows the mold shape seen from the side.
• the mold shown in FIG. 18 has a cylindrical shape, the major axis diameter D is 2. C m, the height F is 6., and the distance E between the mold and the mold is 1. ⁇ . .
• the temperature of the electrophotographic photosensitive member during processing and the temperature of the mold were controlled to 110 ° C, and the shape was transferred by rotating the photosensitive member in the circumferential direction while pressurizing the mold with a pressure of 5 MPa.
• FIG. 19 showing the arrangement of the concave-shaped portions, (1) is a view of the surface of the photoconductor from above, and (2) is a cross-sectional shape of the concave-shaped portions.
• the concave portion interval I was formed at an interval of 1.0 m, and the area ratio was calculated to be 46%.
• the electrophotographic photosensitive member produced by the above method was evaluated for the characteristics of the electrophotographic photosensitive member in the same manner as in Example 1. The results are shown in Table 2.
• Table 2 the number indicates the number of concave parts with a ratio of depth to major axis diameter (Rd v / Rpc) greater than 1.0 and less than 7.0 in 100 m square.
• Rp c— A is ⁇ ⁇ ⁇ ⁇
• the average major axis diameter of the concave-shaped part in four directions is shown.
• R dv— ⁇ indicates the average depth of the concave part in the square of ⁇ ⁇ ⁇ ⁇ m.
• R d V—A / R, pc—A represents the ratio of the average depth to the average major axis diameter of the concave portion in the l OO ⁇ um square.
• the torque ratio indicates a relative torque ratio according to the method described in Example 1.
• the blade noise after 5 000 sheets indicates the presence or absence of blade squeaking or the number of blade squeaking during the paper passing durability test according to the method described in Example 1. )
• An electrophotographic photosensitive member was prepared in the same manner as in Example 21.
• the major axis diameter indicated by D in Fig. 12 was changed from 2.0 111 to 1.5 ⁇ m.
• surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a cylindrical concave portion was formed.
• Table 2 shows the measurement results.
• the 'concave part interval was formed at an interval of 0.8 / m, and the area ratio was calculated to be 39%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. Table 2 shows the results.
• Example 21 An electrophotographic photosensitive member was produced in the same manner as in Example 21.
• the major axis diameter indicated by D in Fig. 12 was changed from 2.
• E was processed in the same manner as in Example 1 except that the interval shown by 1.0 to 2.0 m and the height shown by F was changed from 6. to 9. ⁇ ⁇ .
• Table 2 shows the measurement results.
• the interval between the W-shaped parts was colored with an interval of 2.0 ⁇ , and the area ratio was calculated to be 63%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 2. (Example 2 4)
• An electrophotographic photosensitive member was produced in the same manner as in Example 1.
• a quartz glass mask having a pattern in which circular laser light transmitting portions having a diameter of 1 are arranged at intervals of 5.0 ⁇ m as shown in the figure is used.
• the irradiation area per irradiation was 2 mm square, and 3 laser irradiations were performed per 2 mm square irradiation area.
• a similar concave-shaped portion was formed on the surface of the photosensitive member by rotating the electrophotographic photosensitive member and shifting the irradiation position in the axial direction.
• Example 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.4 ⁇ , and the area ratio was 41%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• An electrophotographic photosensitive member was produced in the same manner as in Example 24, and the surface shape was formed in the same manner as in Example 24, except that the laser beam was irradiated 5 times per 2 mm square irradiation site.
• the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that a concave portion was formed.
• Table 2 shows the measurement results. The interval between the concave portions was formed at an interval of 1.4 / m, and the area ratio was 41%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 24, and a pattern in which circular laser light transmitting portions having a diameter of 5.0 ⁇ m shown in FIG. 22 were arranged at intervals of 2.0 ⁇ as shown in the figure. Except for using a quartz glass mask with Surface shape formation was performed. When the surface shape measurement was performed in the same manner as in Example 1, it was confirmed that the concave portion shown in FIG. 23 was formed. Table 2 shows the measurement results. In addition, the concave portion interval I was formed at intervals of 0.6 m, and the area ratio was 44%. The characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 2.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• a surface layer coating solution containing a charge transporting substance was prepared by dissolving in a mixed solvent of 65 parts of chlorobenzene and 35 parts of dimethoxymethane.
• the surface layer coating solution thus prepared was dip-coated on the charge layer and the surface layer coating solution was applied on the support.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C.
• the support coated with the surface layer coating liquid is placed in the apparatus for the dew condensation process, where the relative humidity is 70% and the ambient temperature is 60 ° C in advance. Hold for 1 20 seconds.
• the support was placed in a blower dryer that had been heated to 120 ° C. in advance, and the drying process was performed for 60 minutes. In this way, an electrophotographic photoreceptor having a charge transport layer as a surface layer was produced.
• FIG. 24 shows an image of the surface of the electrophotographic photosensitive member produced in Example 27 using a laser microscope.
• Table 2 shows the measurement results. The interval between the concave portions was formed at an interval of 1.8 ⁇ , and the area ratio was 44%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 2 except that a conductive layer, an intermediate layer, and a charge generation layer were prepared on a support in the same manner as in Example 7 and the relative humidity in the condensation process was changed to 70% and the ambient temperature to 45 ° C.
• An electrophotographic photoreceptor was prepared in the same manner as in Example 7.
• Table 2 shows the measurement results. The interval between the concave portions was formed at an interval of 0.6 ⁇ , and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 1. The results are shown in Table 2.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• a coating solution for the surface layer containing a charge transporting substance was prepared by dissolving in a mixed solvent of 30 parts of oxolane and 20 parts of dimethoxymethane.
• the surface layer coating solution thus prepared was dip coated on the charge generation layer, and the surface layer coating solution was coated on the support.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C.
• the inside of the device is preliminarily set to a relative humidity of 70% and the ambient temperature is 60 ° C.
• the support on which the coating solution for the surface layer is coated is placed in the device for the condensation process Hold for 1 20 seconds.
• the support was placed in an air dryer where the inside of the apparatus had been heated to 12.degree. C. in advance, and the drying process was performed for 60 minutes.
• an electrophotographic photoreceptor having a charge transport layer as a surface layer was produced.
• Example 2 the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• the surface layer coating solution is applied to the support in the photoconductor manufacturing process described above, where the concave portion is not processed on the surface in the torque ratio evaluation of the electrophotographic photoconductor. After that, a drying process was immediately performed for 60 minutes, and a photoconductor having no concave portion on the surface was used.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• the polyarylate resin represented by the formula (10) (the molar ratio of the terephthalic acid structure to the isophthalic acid structure in the polyarylate resin described above (terephthalic acid structure: isophthalic acid structure) is 50:50.
• the weight average molecular weight (Mw) is 1 3 0, 0 0 0), 70 parts of black-ended benzene, 2 parts of dimethoxymethane 3 2 parts (methylsulfier) 3 parts of methane dissolved in a mixed solvent
• a coating solution for the surface layer containing a transport substance was prepared.
• the surface layer coating solution thus prepared is dip coated on the charge generation layer, and the surface layer coating solution is coated on the support. It was.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C.
• the support coated with the surface layer coating liquid is placed in the apparatus for the dew condensation process that has been previously set to a relative humidity of 50% and an atmospheric temperature of 30 ° C. Hold for 10 seconds.
• the support was placed in a blower dryer that had been heated to 120 ° C. in advance, and the drying process was performed for 60 minutes. In this way, an electrophotographic photosensitive member having a charge transport layer as a surface layer was produced.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support. '
• a charge transport material having a structure represented by the above formula (1) 10 parts of a polyarylate resin represented by the above formula (6) as a binding resin (terephthalic acid in the above polyarylate resin)
• the molar ratio between the forged and isophthalic acid structure is 50:50
• the weight average molecular weight (Mw) is 130,000.
• a coating solution for the surface layer containing a charge transporting substance was prepared by dissolving in a mixed solvent of 70 parts of black mouth benzene and 3 parts of dimethoxymethane 3 parts.
• the surface layer coating solution thus prepared is cooled so that the coating solution temperature becomes 15 ° C, and the charge generation layer
• the surface coating solution was applied by dip coating on the support and cooled on the support.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C.
• the substrate coated with the surface layer coating liquid is placed in the apparatus for the dew condensation process, where the relative humidity is 50% and the ambient temperature is 28 ° C. Hold for 60 seconds.
• the support was placed in a blower dryer that had been heated to 120 ° C. in advance, and the drying process was performed for 60 minutes. In this way, an electrophotographic photosensitive member having a charge transport layer as a surface layer was produced.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• a charge transport material having a structure represented by the following formula: 10 parts of a polyarylate resin represented by the above formula (4) (where m and n represent the ratio (copolymerization ratio) of the repeating unit in the resin)
• m : n 7: 3
• the molar ratio of the terephthalic acid structure to the isophthalenolic acid structure is 50:50
• the weight average molecular weight (Mw) is 1 RGANOX 1330 (manufactured by Ciba Specialty Chemicals) as an antioxidant, dissolved in a mixed solvent of 70 parts of kuroguchi benzene and 35 parts of dimethoxymethane, and charge transport A coating solution for the surface layer containing the substance was prepared.
• the charge transport layer was dip-coated on the charge generation layer, and was heated and dried in an open heated to 110 ° C for 30 minutes, so that the average film thickness at 170 mm from the upper end of the support was A 15 ⁇ m charge transport layer was formed.
• the electrophotographic photosensitive member produced by the above method was processed in the same manner as in Example 1 using the mold used in Example 18.
• Example 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.0 ⁇ , and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 32 The same as Example 32, except that TI NUV IUV622 LD (Ciba Specialty Chemicals) was used instead of the antioxidant used in Example 32. Thus, an electrophotographic photosensitive member was produced and processed in the same manner as in Example 32.
• TI NUV IUV622 LD Ciba Specialty Chemicals
• Example 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.0 ⁇ ⁇ ⁇ m, and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• PF_040 manufactured by Advantech Toyo Co., Ltd.
• a charge transport material having a structure represented by the above formula (1) 4 parts of a charge transport material having a structure represented by the above formula (7), 10 parts of a polyarylate resin represented by the above formula (4)
• the molar ratio (terephthalic acid structure: isophthalic acid structure) is 50:50, and the weight average molecular weight (Mw) is 130,000).
• a coating solution for the surface layer containing a charge transport material was prepared.
• the electrophotographic photosensitive member produced by the above method was processed in the same manner as in Example 1 using the mold used in Example 18.
• Example 2 shows the measurement results.
• the interval between the concave portions was 1.0; m, and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 2 -Surface shape measurement was performed in the same manner as in Example 1, and it was confirmed that a concave portion was formed.
• Table 2 shows the measurement results. The interval between the concave portions was formed at an interval of 1.'0 ⁇ m, and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 3 Conducted except that alumina fine particles (average particle size 0.1 l / im, trade name: LS-2 31, manufactured by Nippon Light Metal Co., Ltd.) were used in place of the tetrafluoroethylene resin powder used in 4
• An electrophotographic photoreceptor was prepared in the same manner as in Example 34, and the same processing was performed.
• Table 2 shows the measurement results. The interval between the concave portions was formed at an interval of 1.0 ⁇ m, and the area ratio was 46%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 2 As in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were prepared on a support. It was.
• a coating solution for the surface layer containing the same charge transport material as in Example 32 was prepared.
• the surface layer coating solution prepared as described above was dip coated on the charge generation layer, and the surface layer coating solution was coated on the support.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C. 10 seconds after the end of the coating process, a support in which the coating solution for the surface layer has been coated in the apparatus for the dew condensation process, where the relative humidity is 70% and the ambient temperature is 35 ° C. was held for 120 seconds.
• the support was placed in a blower dryer that had been heated to 120 ° C. in advance, and the drying process was performed for 60 minutes. In this way, an electrophotographic photoreceptor having a charge transport layer as a surface layer was produced.
• An electrophotographic photosensitive member was prepared in the same manner as in Example 37, except that TI NU VIN 6 2 2 LD (manufactured by Ciba Specialty Chemicals) was used instead of the antioxidant used in Example 37. did.
• Example 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.8 Atm, and the area ratio was 44%.
• Electronic as in Example 1 The characteristics of the photographic photoconductor were evaluated. The results are shown in Table 2.
• the drying process was performed for 60 minutes, and a photoconductor without a concave portion on the surface was used.
• Example 2 In the same manner as in Example 1, a conductive layer, an intermediate layer, and a charge generation layer were produced on a support.
• a surface layer coating solution containing the same charge transport material as in Example 34 was prepared.
• the surface layer coating solution thus prepared was dipped on the charge generation layer, and the surface layer coating solution was coated on the support.
• the step of applying the surface layer coating solution was performed at a relative humidity of 45% and an ambient temperature of 25 ° C. 10 seconds after the end of the coating process, a support in which the coating solution for the surface layer has been coated in the apparatus for the dew condensation process, where the relative humidity is 70% and the ambient temperature is 35 ° C. was held for 120 seconds.
• the support was placed in a blower dryer that had been heated to 120 ° C. in advance, and the drying process was performed for 60 minutes. In this way, an electrophotographic photoreceptor having a charge transport layer as a surface layer was produced.
• Example 39 Except that instead of the tetrafluoroethylene resin powder used in Example 39, surface-treated silli force fine particles (average particle size 0.1 ⁇ , product name: LS-2 3 1, made by Nippon Light Metal Co., Ltd.) were used. An electrophotographic photosensitive member was produced in the same manner as in Example 39, and the same processing was performed.
• silli force fine particles average particle size 0.1 ⁇ , product name: LS-2 3 1, made by Nippon Light Metal Co., Ltd.
• Example 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.8 / im, and the area ratio was 44%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• Example 3 Except for the use of alumina fine particles (average particle size 0.1 // m, product name: LS—2 3 1, Nippon Light Metal Co., Ltd.) instead of the tetrafluorinated styrene resin powder used in Example 9.
• An electrophotographic photosensitive member was produced in the same manner as in Example 39, and the same processing was performed.
• Table 2 shows the measurement results.
• the interval between the concave portions was formed at an interval of 1.8 ⁇ , and the area ratio was 44%.
• the characteristics of the electrophotographic photosensitive member were evaluated. The results are shown in Table 2.
• the surface of the electrophotographic photosensitive member has a concave portion with a ratio of the depth to the major axis diameter (Rd v / Rpc) greater than 1.0 and less than or equal to 7.0.
• Rd v / Rpc major axis diameter

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