JP2013214064A - Film, device including film, electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film that is resistant to an increase in a frictional coefficient resulting from wearing in a surface rugged pattern even in long-term use, and to provide a device having the film.SOLUTION: The film includes a first portion and a second portion having different hardness degrees from each other: the first portion shows a hardness degree (H[GPa]) of 0.01 to 3 GPa by a continuous stiffness measurement method, and a ratio (H/H) of a hardness degree (H[GPa]) of the second portion by the continuous stiffness measurement method to the hardness degree (H[GPa]) of the first portion by the continuous stiffness measurement method is 1.2 to 30. The surface of the film includes a surface portion composed of the first portion and a surface portion composed of the second portion, in which the first portion and the second portion are each continuously extended in a film thickness direction to a depth of 75% or more of the film thickness. In a 1-mm square region disposed at any position of the film surface, an area ratio of the surface composed of the second portion is 10 to 80%, and the total area ratio of the surfaces composed of the first portion and the second portion is 50% or more.

Description

  The present invention relates to a membrane having a novel structure and an apparatus having the membrane. The present invention also relates to an electrophotographic photosensitive member having the film as a surface layer, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  Conventionally, a technique for controlling friction by providing a specific shape on the surface of a member is known. For example, in the field of industrial mechanical materials, as described in Patent Document 1, there is a technique for reducing friction with a shaft that is a contact member by providing a convex shape on the surface of a bearing member.

  Further, as described in Patent Document 3, there is a technique for reducing the frictional force by providing a honeycomb-shaped texture on the slider surface of the magnetic head.

  In addition, as an application to an organic functional member, Patent Document 2 discloses that an uneven shape is provided on the surface (outer peripheral surface) of a toner image carrier such as an electrophotographic photosensitive member or an intermediate transfer member, so that the toner remaining on the surface is protected. A technique is disclosed that achieves both high cleaning performance and suppression of entrainment of a cleaning blade that is a contact member (blade curling).

  Patent Document 4 discloses a technique for suppressing the reversal of the cleaning blade and the like by making the surface of the electrophotographic photosensitive member an uneven surface having smooth curved protrusions.

  Furthermore, as another technique for controlling friction, a technique for incorporating a lubricant into a member is also known.

JP 2002-106578 A JP 2005-128510 A JP 09-219077 A Japanese Patent Laid-Open No. 07-092697

  However, a member having a concavo-convex shape on the surface may cause concavo-convex wear due to long-term contact with the contact member. The unevenness on the surface of the member is worn and removed by long-term use, and the coefficient of friction on the surface of the member increases.

  An object of the present invention is to provide a film and an apparatus having the film that are less likely to increase in the coefficient of friction due to the disappearance of the irregular shape on the surface even after long-term use. Another object of the present invention is to provide an electrophotographic photosensitive member having the film as a surface layer, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

The present invention has a first portion and a second portion having different hardness, and the hardness (H ₁ [GPa]) of the first portion measured by a continuous stiffness measurement method is 0.01 to 3 GPa, The ratio (H ₂ / H ₁ ) of the ratio of hardness (H ₂ [GPa]) of the second portion to the hardness (H ₁ [GPa]) of the second portion relative to the hardness (H ₁ [GPa]) of the continuous stiffness measurement method is 1.2 to 30 A film,
The surface of the membrane has a surface composed of the first portion and a surface composed of the second portion;
Each of the first portion and the second portion continuously extends in the film thickness direction of the film by 75% or more of the film thickness;
In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the membrane, the area ratio of the surface constituted by the second portion is 10 to 80%, and the first portion is constituted. The total area ratio of the surface formed by the second portion and the surface formed by the second portion is 50% or more.

  Moreover, this invention is an apparatus characterized by having the member containing the said film | membrane and the contact member which can contact with the surface of this film | membrane with a relative speed.

  The present invention also provides an electrophotographic photoreceptor having the above film as a surface layer.

  The present invention also provides an electrophotographic photosensitive member in a process cartridge that integrally supports an electrophotographic photosensitive member and a cleaning unit for cleaning the surface of the electrophotographic photosensitive member and is detachable from the main body of the electrophotographic apparatus. The process cartridge is characterized in that the body is the electrophotographic photosensitive member, and the cleaning means has a cleaning blade capable of contacting the surface of the electrophotographic photosensitive member.

  The present invention also provides an electrophotographic photosensitive member comprising an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, a transferring unit, and a cleaning unit for cleaning the surface of the electrophotographic photosensitive member. The electrophotographic apparatus is characterized in that the body is the electrophotographic photosensitive member, and the cleaning means has a cleaning blade capable of contacting the surface of the electrophotographic photosensitive member.

  In the film of the present invention, the first part has a lower hardness than the second part and is easy to wear, so that the first part becomes a concave part and the second part becomes a convex part by use. The area in contact with the contact member on the surface of the membrane can be reduced. Therefore, it is possible to reduce friction with the contact member. In addition, the first portion having a low hardness is more sharpened by use than the second portion having a high hardness, so that the difference in height between the first portion and the second portion is substantially constant even when used for a long time. It becomes possible to maintain the concavo-convex shape with the portion as a convex portion. This makes it possible to maintain a small coefficient of friction on the film surface for a long period of time.

It is the figure which looked at the example of the film | membrane of this invention from the upper direction of the surface of the film | membrane. It is the figure which looked at the example of the film | membrane of this invention from the cross-sectional direction. It is the figure which used the example of the film | membrane of this invention and looked at the state in which the uneven | corrugated shape was formed from the cross-sectional direction. It is the figure which looked at another example of the film | membrane of this invention from the direction right above the film | membrane surface. It is the figure which looked at another example of the film | membrane of this invention from the direction right above the surface of the film | membrane. It is the figure which looked at another example of the film | membrane of this invention from the cross-sectional direction. It is the figure which looked at the state where the uneven | corrugated shape was formed using the further another example of the film | membrane of this invention, and the lubricating powder with which lubricity accumulated in the recessed part from the cross-sectional direction. It is a figure which shows the line | wire width and aperture size in a square type nickel mesh / plain weave type stainless steel mesh. It is a figure which shows the line | wire width and aperture size in a honeycomb type nickel mesh. It is a figure explaining the method of winding a photomask around the surface of an electrophotographic photoreceptor. It is a figure explaining the method of making a braid | blade made from urethane rubber contact | abut with respect to an electrophotographic photoreceptor, and measuring a friction coefficient. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

  FIG. 1 is a view of an example of the film of the present invention as viewed from directly above the surface of the film, and FIG. 2 is a view as viewed from a cross-sectional direction. Moreover, FIG. 3 is the figure which looked at the state in which the uneven | corrugated shape was formed from the cross-sectional direction using the example of the film | membrane of this invention. 1-3, 10 is the 2nd part of a film | membrane, 11 is a 1st part of a film | membrane. Moreover, the upper side of the film | membrane in FIG. 2 and 3 is the surface which contacts a contact member.

  Since the first part 11 of the film has a lower hardness than the second part 10, the first part 11 is more in comparison with the second part 10 by using the film in contact with the contact member at a relative speed. As shown in FIG. 3, an uneven shape is formed in which the second portion 10 is a convex portion and the first portion 11 is a concave portion. Thereby, friction can be reduced by reducing the contact area of the membrane with the contact member. And since the 1st part 11 can be shaved rapidly by the part which the 2nd part 10 was worn, since the uneven | corrugated shape of the surface of a film | membrane is maintained, even if it uses for a long period of time, it can maintain an uneven | corrugated shape. Become. For this reason, it is possible to maintain a small coefficient of friction on the surface of the film.

  In addition, it is preferable to select the material so that the refractive index of the first portion 11 is approximately the same as the refractive index of the second portion 10, since changes in appearance due to light scattering can be suppressed. In this case, since an optical member can suppress a reduction in resolution, a field in which the present invention can be suitably used includes an electrophotographic field.

  Further, for example, as shown in FIG. 4, the surface constituted by the first portion 411 may be surrounded by the surface constituted by the second portion 410 on the surface of the film. FIG. 4 is a view of another example of the film of the present invention as viewed from directly above the surface of the film. As shown in FIG. 4, the first portion 411 (first portion) that becomes a concave portion by use is surrounded by the surface constituted by the second portion 410 on the surface of the film. 411) forms a closed space surrounded by the second portion 410 serving as a convex portion, and air can be confined between the membrane and the contact member. Therefore, a repulsive force due to compressed air is likely to occur. By this repulsive force, the load pressure (contact pressure between the membrane and the contact member) is reduced, and friction with the contact member can be further reduced. Here, the closed space means a closed space formed by the recess and the contact member when the membrane comes into contact with the contact member.

  As a method for producing the film of the present invention, for example, an ultraviolet curable resin such as acrylate, unsaturated polyester, epoxy, oxetane, vinyl ether, or a monomer of an electron beam curable resin (and a lubricant described later if necessary) is used. By irradiating the formed resin film with ultraviolet rays or electron beams through a photomask or electron beam mask to change the crosslink density in the resin film, a hardness difference is given to each part, and the first part and the second part A method of forming a part is mentioned.

  Examples of the monomer of the ultraviolet curable resin or the electron beam curable resin include the following compounds.

  In addition, polycarbonate (containing lubricant as described below if necessary) on micro swords made of brass, etc., which are fine in the order of micrometers or even nanometers, with many rods pointing in a certain direction. It can also be produced by pouring a resin solution such as polyarylate, polystyrene or polyethylene and drying.

  Further, for example, as shown in FIGS. 5 to 7, the film may contain a lubricant. FIG. 5 is a view of still another example of the film of the present invention viewed from directly above the surface of the film, and FIG. 6 is a view of still another example of the film of the present invention viewed from the cross-sectional direction. . Moreover, FIG. 7 is the figure which used the other example of the film | membrane of this invention, and was the figure which looked at the state where uneven | corrugated shape was formed and lubricous abrasion powder collected in the recessed part from the cross-sectional direction. The upper side of the membrane in FIGS. 6 and 7 is the surface in contact with the contact member. As shown in FIGS. 5 and 6, when the surface of the film is worn by use because the film contains the lubricant 512, wear powder 513 having lubricity is generated on the surface of the film as shown in FIG. . The lubricating powder 513 having lubricity accumulates in a concave-convex recess having the second portion 510 as a convex portion and the first portion 511 as a concave portion, and therefore does not easily flow out of the friction system and exists in the friction system for a long time. become. Therefore, the friction coefficient of the film surface is further reduced, and the small friction coefficient can be maintained for a long time. From the viewpoint of further reducing friction with the contact member due to the lubricating wear powder accumulated in the recesses, the surface constituted by the first portion is surrounded by the surface constituted by the second portion on the surface of the film. It is preferable. Since the surface constituted by the first portion is surrounded by the surface constituted by the second portion, the first portion that becomes a concave portion by use (the surface constituted by the first portion) becomes the second portion that becomes a convex portion. A closed space surrounded by the portion is formed, and by allowing the wear powder having lubricity to accumulate in the closed space, the outflow of the wear powder from the wear system can be further suppressed. Further, the lubricant 512 is preferably contained in at least one of the first portion 511 and the second portion 510.

  The lubricant contained in the film is preferably a solid lubricant or a semisolid lubricant.

  Examples of solid lubricants include polymers of fluorine atom-containing compounds, layered oxides such as mica and talc, layered hydrocarbon compounds such as graphite, metal sulfides such as molybdenum disulfide, silicone, and melamine Examples of the particles include cyanurate and boron nitride. Examples of the fluorine atom-containing compound include ethylene tetrafluoride, ethylene trifluoride chloride, hexafluoroethylene propylene, vinyl fluoride, vinylidene fluoride, and ethylene difluoride chloride. Among these, as the solid lubricant, polymer particles of ethylene tetrafluoride, that is, polytetrafluoroethylene particles are preferable.

  When the lubricant is particles, the average particle diameter is preferably 0.01 to 10 μm.

  Examples of semi-solid lubricants include fluorine grease (thickener: polytetrafluoroethylene, base oil: perfluoropolyether, etc.), silicone grease (thickener: lithium soap, etc.), base oil: phenylmethylpolysiloxane. , Dimethylpolysiloxane, etc.), fluorosilicone grease (thickener: lithium soap, etc.), base oil: fluorosilicone, etc., ester grease (thickener: urea, lithium soap, etc.), pentaphenyl ether, tetraphenyl ether, etc. Examples include polyphenyl ether-based grease (thickener: bentonite, etc.) based on polyphenyl ether.

  The lubricant content in the film is preferably 20% by volume or less with respect to the total volume of the film. As the amount of lubricant in the film increases, it tends to be difficult to make a difference in hardness by irradiation with ultraviolet rays or electron beams. These lubricants may be used alone or in combination of two or more and may be used together with a lubricant dispersant.

  The size of the lubricant is preferably equal to or smaller than the size of the second portion. The larger the size of the lubricant, the more difficult it is to make a hardness difference in the film by irradiation with ultraviolet rays or electron beams.

  In addition, from the viewpoint of reducing the contact area and reducing the friction, any shape can be selected as the shape of the first part and the second part. Examples of the shape when the two portions are convex include a hole type, a pillar type, a line & space (L & S) type, a square type, and a honeycomb type. Among these, as described above, when the friction with the contact member is reduced by the air confined in the closed space, or the wear powder with lubricity is retained in the closed space to suppress the outflow of the wear powder from the wear system. In this case, examples of the shape of the closed space when the surface of the film is viewed from directly above include a hole type, a square type, and a honeycomb type. Among these, a honeycomb type is preferable.

  In the present invention, as described above, the area ratio of the surface constituted by the second portion must be 10 to 80% in a square region having a side of 1 mm arranged at an arbitrary position on the surface of the film. From the viewpoint of being effective in reducing friction and being less likely to wear, the content is preferably 20 to 70%. When the area ratio of the surface constituted by the second part is less than 10%, the contact area with the contact member becomes small, so that the second part that has become a protrusion is not easily able to withstand the load of the contact member and is easily destroyed. Become. When the area ratio of the surface constituted by the second portion is more than 80%, the contact area with the contact member is increased, so that the friction reduction effect cannot be sufficiently obtained and the friction coefficient is increased.

  Further, in the present invention, as described above, in a square region having a side of 1 mm arranged at an arbitrary position on the surface of the film, the total of the surface composed of the first portion and the surface composed of the second portion. The area ratio must be 50% or more, preferably 90% or more, and more preferably 100%. When the total area ratio of the surface composed of the first part and the surface composed of the second part is less than 50%, the surface of the film is formed by the concavo-convex shape in which the first part is a recess and the second part is a protrusion. The effect of maintaining a small coefficient of friction for a long time becomes poor.

In the present invention, as described above, the value of the ratio of the hardness (H ₂ [GPa]) of the second portion to the hardness (H ₁ [GPa]) of the first portion to the hardness (H ₁ [GPa]) of the second portion of the first portion. (H ₂ / H ₁ ) must be 1.2 to 30, but is preferably 1.5 to 30 in order to more appropriately maintain the height difference between the first portion and the second portion. The value (H ₂ / H ₁ ) of the ratio of the hardness (H ₂ [GPa]) of the second part to the hardness (H ₁ [GPa]) of the first part to the hardness (H ₁ [GPa]) of the second part is 1.2. If it is less than 1, the difference in wear rate between the first part and the second part is not sufficient, so that the height difference between the first part and the second part cannot be sufficiently obtained, and the friction reducing effect cannot be sufficiently obtained. . When the value (H ₂ / H ₁ ) of the ratio of the hardness (H ₂ [GPa]) of the second part to the hardness (H ₁ [GPa]) of the first part to the hardness (H ₁ [GPa]) of the second part is more than 30 The height difference between the first portion and the second portion is increased, so that the second portion that is a convex portion is not easily able to withstand the load of the contact member and is easily destroyed.

In the present invention, as described above, the hardness by a continuous rigidity measuring method of the first portion _(H 1 [GPa]) is 0.01～3GPa. If the hardness (H ₁ [GPa]) of the first portion measured by the continuous stiffness measurement method is 0.01 GPa or more, the difference in height between the first portion and the second portion is appropriately maintained. If the hardness (H ₁ [GPa]) by the continuous stiffness measurement method of the first part is 3 GPa or less, the second part becomes a moderately convex part by the above use.

In the present invention, as described above, the first portion and the second portion must continuously extend in the film thickness direction by 75% or more of the film thickness. In order to maintain a concave / convex shape with the second part as a convex part, it is preferable to extend 90% or more, and further, the first part and the second part each penetrate the film. (= Extending 100% of the film thickness). If the film thickness is less than 75% of the film thickness, it is difficult to maintain a concavo-convex shape with the first portion as a recess and the second portion as a protrusion for a long period of time.
The film thickness is preferably 1 to 100 μm.

  The size of the first part and the second part when the first part becomes a space-like concave part and the second part becomes a line-like convex part by the above use is 0.1 to 50 μm, respectively. preferable. Here, the size of the second portion can be the width of the line portion in the line & space type, the hole diameter in the hole type, the pillar diameter in the pillar type, or the distance between the opposing vertices in the honeycomb type. Even in other shapes, for example, the narrowest distance can be used in the continuous region of the second portion on the surface.

  In addition, when the surface constituted by the first portion is surrounded by the surface constituted by the second portion on the surface of the film, the most of the closed space surrounded by the second portion which becomes a convex portion by use. The major axis is preferably 0.1 to 100 μm from the viewpoint of reducing friction with the contact member by trapped air. Here, the longest diameter of the closed space is, for example, the diameter of the hole when the shape of the closed space is a circular hole type, and the distance between the opposing vertices when the shape of the closed space is a honeycomb type. The longest distance. Even in other shapes, for example, when two parallel lines sandwiching the closed space are drawn, the distance when the distance between these parallel lines is the longest is the longest diameter of the closed space.

  These values (sizes) can be easily calculated by an image analysis apparatus such as an image analysis apparatus (trade name: LuzexAP) manufactured by Nireco Corporation.

In the present invention, the various hardnesses of the film mean hardnesses by a continuous stiffness measurement method unless otherwise specified. The hardness by the continuous stiffness measurement method can be measured according to the continuous stiffness measurement method using an ultra-micro hardness meter. The hardness measured by the continuous stiffness measurement method of the first part so measured is H ₁ [GPa], and the hardness of the second part measured by the continuous stiffness measurement method is H ₂ [GPa]. Here, the continuous stiffness measurement method means that the indenter is microvibrated during the indentation test, the response amplitude and phase difference with respect to the vibration are obtained as a function of time, and it is removed corresponding to the continuous change in the indentation depth. This is a method of continuously calculating the initial gradient at loading. A specific measurement method is a method of performing an indentation load / unloading test on a sample using a regular triangular pyramid indenter (Berkovich indenter) and obtaining a load-indentation depth diagram.

  The area ratio of the surface composed of the first part and the surface composed of the second part is to detect the deflection amplitude of the cantilever that changes due to the difference in viscoelasticity of the surface by applying a minute vibration in the vertical direction to the sample. Thus, a viscoelastic image can be obtained, whereby the area ratio of the second portion can be calculated.

  The field in which the present invention is preferably used includes the field of electrophotography. The film of the present invention can be suitably used in a surface layer (outermost layer) such as a charge transport layer or a protective layer of an electrophotographic photoreceptor. In that case, a cleaning blade etc. are mentioned as a contact member. A member made of urethane rubber is generally used for the cleaning blade.

  Other fields in which the present invention is preferably used include functional parts of automobiles. For example, the film of the present invention is used on the surface of the wiper or the window glass that can be opened and closed so that rain and snow do not slip through the surface. The film of the present invention can be used on the side of the member to be used.

  Hereinafter, the material and layer structure of the electrophotographic photoreceptor will be described.

  An electrophotographic photoreceptor generally has a support and a photosensitive layer formed on the support.

  The photosensitive layer may be a single-layer type photosensitive layer containing a charge transport material and a charge generation material in the same layer, or a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. It may be a laminated type (functionally separated type) photosensitive layer separated. From the viewpoint of electrophotographic characteristics, a laminated photosensitive layer is preferable. The laminated photosensitive layer has a normal layer type photosensitive layer laminated in the order of the charge generation layer and the charge transport layer from the support side, and a reverse layer type photosensitive layer laminated in the order of the charge transport layer and the charge generation layer from the support side. is there. From the viewpoint of electrophotographic characteristics, a normal layer type photosensitive layer is preferred. Further, the charge generation layer and the charge transport layer itself can each have a laminated structure.

  As the support, it is only necessary to have conductivity (conductive support), and for example, a support made of metal (made of alloy) such as aluminum, aluminum alloy, and stainless steel can be used. Further, a metal support or a plastic support having a coating such as aluminum, aluminum alloy, indium oxide-tin oxide alloy formed by vacuum deposition can be used. Further, a plastic support or paper support containing conductive particles such as carbon black, tin oxide particles, titanium oxide particles, silver particles, a support made of conductive binder resin, or the like can also be used. . In addition, examples of the shape of the support include a cylindrical shape and a belt shape, and a cylindrical shape is preferable.

  Between the support and the photosensitive layer (charge generation layer, charge transport layer) or the undercoat layer described later, for the purpose of suppressing interference fringes due to scattering of laser light or the like, covering the scratches on the support, A conductive layer may be provided.

  The conductive layer is obtained by applying a conductive layer coating solution obtained by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles together with a binder resin and a solvent, and drying and drying the obtained coating film. It can be formed by curing.

  Examples of the binder resin used for the conductive layer include phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, and polyester.

  Examples of the solvent used in the conductive layer coating solution include organic solvents such as alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, halogenated aromatic compounds, and aromatic compounds.

  The film thickness of the conductive layer is preferably 1 to 40 μm, and more preferably 2 to 20 μm.

  In addition, between the support or conductive layer and the photosensitive layer (charge generation layer, charge transport layer), improvement of adhesion of the photosensitive layer, improvement of charge injection from the support, protection against electrical breakdown of the photosensitive layer, etc. For this purpose, an undercoat layer having a barrier function or an adhesive function may be provided.

  The undercoat layer can be formed by applying an undercoat layer coating solution obtained by dissolving a resin (binder resin) in a solvent, and drying and / or curing the obtained coating film.

  Examples of the resin used for the undercoat layer include acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenol resin, butyral resin, polyacrylate. , Polyacetal, polyamideimide, polyamide, polyallyl ether, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl alcohol, polybutadiene, polypropylene, urea resin and the like.

  Further, the undercoat layer may be formed using a material such as aluminum oxide.

  Examples of the solvent used in the coating solution for the undercoat layer include alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, and aromatic compounds.

  The thickness of the undercoat layer is preferably 0.05 to 7 μm, and more preferably 0.1 to 2 μm.

  Examples of the charge generating material used in the electrophotographic photoreceptor include azo pigments such as monoazo, disazo, and trisazo, phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, indigo pigments such as indigo and thioindigo, and perylene acid anhydride. , Perylene pigments such as perylene imide, polycyclic quinone pigments such as anthraquinone and pyrenequinone, squarylium dyes, pyrylium and thiapyrylium salts, triphenylmethane dyes, selenium, selenium-tellurium, amorphous silicon, etc. Examples include inorganic substances, quinacridone pigments, azurenium salt pigments, cyanine dyes, xanthene dyes, quinoneimine dyes, styryl dyes, cadmium sulfide, and zinc oxide. These charge generation materials may be used alone or in combination of two or more.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used for the charge generation layer include acrylic resins, allyl resins, alkyd resins, epoxy resins, diallyl phthalate resins, silicone resins, styrene-butadiene copolymers, phenols. Resin, butyral resin, benzal resin, polyacrylate, polyacetal, polyamideimide, polyamide, polyallyl ether, polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl acetal, polybutadiene, polypropylene, methacrylic resin, urea Resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin and the like. Among these, a butyral resin is preferable. These may be used alone or in combination as a mixture or copolymer.

  The charge generation layer may be formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent, and drying and / or curing the obtained coating film. it can. Examples of the dispersion method include a method using a homogenizer, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, a liquid collision type high-speed disperser, and the like. The ratio between the charge generating material and the binder resin is preferably in the range of 1: 0.5 to 1: 4 (mass ratio).

  Examples of the solvent used in the charge generation layer coating solution include organic solvents such as alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, halogenated aromatic compounds, and aromatic compounds.

  The thickness of the charge generation layer is preferably 0.001 to 6 μm, and more preferably 0.01 to 2 μm.

  In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, and the like can be added to the charge generation layer as necessary.

  Examples of the charge transport material used in the electrophotographic photoreceptor include triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds. These charge transport materials may be used alone or in combination of two or more.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used for the charge transport layer include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenol resin, phenoxy resin, and butyral. Resin, polyacrylamide, polyacetal, polyamideimide, polyamide, polyallyl ether, polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl butyral, polyphenylene oxide, polybutadiene, polypropylene, methacrylic resin, urea resin, chloride A vinyl resin, a vinyl acetate resin, etc. are mentioned. Among these, polyarylate and polycarbonate are preferable. These may be used alone or in combination as a mixture or copolymer.

  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 and / or curing the obtained coating film. . The ratio between the charge transport material and the binder resin is preferably in the range of 2: 1 to 1: 2 (mass ratio).

  Examples of the solvent used in the charge transport layer coating solution include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, 1,4-dioxane, and tetrahydrofuran. Examples thereof include hydrocarbons substituted with halogen atoms such as ether, chlorobenzene, chloroform, and carbon tetrachloride.

  The thickness of the charge transport layer is preferably 5 to 30 μm, and more preferably 6 to 25 μm.

  In addition, an antioxidant, an ultraviolet absorber, a plasticizer, and the like can be added to the charge transport layer as necessary.

  When the photosensitive layer is a single-layer type photosensitive layer, the single-layer type photosensitive layer is obtained by dispersing the charge generating substance and the charge transporting substance together with the binder resin and the solvent. It can form by apply | coating the coating liquid for coating and drying and / or hardening the obtained coating film.

  Further, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. The protective layer can be formed by applying a protective layer coating solution obtained by dissolving the above-described various binder resins in a solvent, and drying and / or curing the obtained coating film.

  The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 7 μm.

  When applying the coating liquid for each layer, for example, a coating method such as a dip coating method (a dip coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, a blade coating method, or the like is used. be able to.

  It is common to clean the residual toner by strongly pressing the cleaning blade, which is a contact member, against the surface of the electrophotographic photosensitive member. However, by strongly pressing, the rotational torque of the electrophotographic photosensitive member is reduced. growing. In addition, the concavo-convex shape formed on the surface of the electrophotographic photosensitive member (particularly, the convex portion is easily broken).

  By using the film of the present invention for the surface layer of the electrophotographic photosensitive member, friction can be reduced, so that the rotational torque of the electrophotographic photosensitive member can be reduced. In addition, since the uneven shape on the surface of the electrophotographic photosensitive member can be maintained for a long period of time, it is possible to maintain contact with a small coefficient of friction, and to prevent the cleaning blade from being caught (blade twisting).

  FIG. 12 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 12, a cylindrical electrophotographic photosensitive member 1201 of the present invention is driven to rotate around a shaft 1202 in the direction of the arrow at a predetermined peripheral speed.

  The surface (circumferential surface) of the electrophotographic photosensitive member 1201 that is driven to rotate is charged to a positive or negative potential by a charging unit 1203, and then exposure light (image exposure light) 1204 output from an exposure unit (not shown). Receive. Thus, an electrostatic latent image corresponding to the target image is formed on the surface of the electrophotographic photosensitive member 1201. Examples of charging means include corona charging means using corotron, scorotron, etc., and contact charging means using rollers, brushes, films, and the like. Further, the voltage applied to the charging means may be only a DC voltage or a DC voltage on which an AC voltage is superimposed. Examples of the exposure means include slit exposure and laser beam scanning exposure.

  The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1201 is developed with toner from the developing unit 1205 and becomes a toner image. Examples of the developing method include a method in which magnetic or non-magnetic one-component or two-component toner is contacted or non-contacted and developed. Examples of the toner include polymerized toner by suspension polymerization, emulsion polymerization, and the like, and toner that has been spheroidized by mechanical pulverization or spheronization. The weight average particle diameter of the toner is preferably 4 to 7 μm, and the average circularity of the toner is preferably 0.95 to 0.99.

  The toner image formed on the surface of the electrophotographic photosensitive member 1201 is sequentially transferred onto a transfer material (paper or the like) 1207 by the transfer unit 1206. The transfer material 1207 is taken out from a transfer material supply unit (not shown) between the electrophotographic photosensitive member 1201 and the transfer unit 1206 (contact portion) in synchronization with the rotation of the electrophotographic photosensitive member 1201 and fed. .

  The transfer material 1207 onto which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1201, introduced into the fixing means 1208, and subjected to image fixing, whereby the image forming product (print, copy) is taken out of the electrophotographic apparatus. Printed out.

  After the toner image is transferred, the surface of the electrophotographic photosensitive member 1201 is subjected to removal of the transfer residual toner by a cleaning blade 1209 provided in the cleaning unit, and then subjected to charge removal processing by pre-exposure light 1210 from a pre-exposure unit (not shown). Used repeatedly for image formation.

  Among the components selected from the above-described electrophotographic photosensitive member 1201, charging unit 1203, developing unit 1205, transfer unit 1206, cleaning unit (cleaning blade 1209), etc., a plurality of components are housed in a container and integrated as a process cartridge. The process cartridge may be configured to be detachable from the main body of the electrophotographic apparatus. In FIG. 12, an electrophotographic photosensitive member 1201, a charging unit 1203, a developing unit 1205, and a cleaning blade 1209 are integrally supported to form a cartridge, and an electrophotographic apparatus using a guide unit 1212 such as a rail of an electrophotographic apparatus main body. The process cartridge 1211 is detachable from the main body.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these.

(1) Measurement of hardness For the measurement of hardness by the above-mentioned continuous stiffness measurement method, an ultrafine hardness meter (trade name: Nano Indenter DCM) manufactured by MTS Systems Co., Ltd. was used. The working indenter was a diamond regular triangular pyramid indenter, and the hardness was measured by a continuous stiffness measurement method at room temperature (25 ° C.) and in the air.

(2) Calculation of area ratio of second part The area ratio of the surface constituted by the second part is determined by using a scanning probe microscope (trade name: S-image) manufactured by SII Nanotechnology. Calculated.

(3) Production of membrane (Example 1-1)
A photosensitive silicone polymer (trade name: SINR-3170PX), which is a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd., was spinner coated on a silicon wafer to form a coating film. Subsequently, ultraviolet irradiation was performed twice with respect to the coating film. The first ultraviolet irradiation was performed on the entire surface of the coating film, and at the second ultraviolet irradiation, irradiation was performed using a photomask having a line width of 4 μm and a space width of 4 μm. The amount of UV irradiation and the time of UV irradiation for the first and second times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.5. And it adjusted so that the hardness of a 1st part (low-hardness part) might be set to about 0.15 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-2)
The ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.2, and the hardness of the first part (low hardness part) is about 0. A film was obtained in the same manner as in Example 1-1 except that the first and second ultraviolet irradiation amounts and the ultraviolet irradiation time were adjusted to 15 GPa. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 53%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.2, and the first part (low hardness) The hardness of the (hardness part) was 0.16 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-3)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

-Coating liquid for charge transport layer Bisphenol Z type polycarbonate: 10 parts by mass Compound (charge transport material) represented by the following structural formula (101): 9 parts by mass

Chlorobenzene: 100 parts by mass Next, a coating film having a film thickness of 5 μm was obtained by spray coating a coating solution for a surface layer having the following composition on the charge transport layer.

-Surface layer coating solution Compound represented by the above structural formula (28) (radical polymerizable compound having a charge transporting structure): 10 parts by weight Trimethylolpropane triacrylate: 10 parts by weight 2,2-dimethoxy-1,2 -Diphenylethane-1-one (photopolymerization initiator, trade name: IRGACURE651, manufactured by BASF): 1 part by mass Chlorobenzene: 100 parts by mass Next, the coating film was irradiated with ultraviolet rays twice. The first ultraviolet irradiation was performed on the entire surface of the coating film, and at the second ultraviolet irradiation, irradiation was performed using a photomask having a line width of 4 μm and a space width of 4 μm. The amount of UV irradiation and the time of UV irradiation for the first time and the second time are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 10, and The first part (low hardness part) was adjusted to have a hardness of about 0.15 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained surface layer (film) was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 8.6. The hardness of one part (low hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-4)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

-Coating liquid for charge transport layer Bisphenol Z-type polycarbonate: 10 parts by weight Compound (charge transport material) represented by the above structural formula (101): 9 parts by weight Chlorobenzene: 100 parts by weight Next, on the charge transport layer A coating film having a film thickness of 5 μm was obtained by spray coating a surface layer coating solution having the following composition.

-Surface layer coating solution Compound represented by the above structural formula (28) (radical polymerizable compound having a charge transporting structure): 10 parts by mass Methyl ethyl ketone: 100 parts by mass Next, the coating film was irradiated twice with an electron beam. went. The first electron beam irradiation was performed on the entire surface of the coating film, and during the second electron beam irradiation, irradiation was performed using a metal mask having a line width of 4 μm and a space width of 4 μm. At the time of electron beam irradiation, nitrogen purge was performed and the acceleration voltage was set to 30 kV. The first and second electron beam irradiation doses and electron beam irradiation times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 30. And it adjusted so that the hardness of a 1st part (low-hardness part) might be set to about 0.15 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 50%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained surface layer (film) was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 27.3. The hardness of one part (low hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-5)
The ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.5, and the hardness of the first part (low hardness part) is about 0. A film was obtained in the same manner as in Example 1-1 except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted so as to be 0.05 GPa. The film thickness obtained by drying was 15 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.5, and the hardness of the low hardness part Was 0.05 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-6)
The ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.7, and the hardness of the first part (low hardness part) is about 0. A film was obtained in the same manner as in Example 1-1 except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted to 50 GPa. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 49%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.51 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-7)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 20 μm and a space width of 20 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.13 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-8)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 22.7 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 16%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-9)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 1.3 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 77%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 1-10)
The amount of the photopolymerization initiator in the surface layer coating solution is 3 parts by mass, and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.5. The length extending in the film thickness direction of the film of the second portion (high hardness portion) so that the hardness of the first portion (low hardness portion) is about 0.15 GPa A film was obtained in the same manner as in Example 1-3 except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted so as to be about 4 μm. The film thickness obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. The first portion (low hardness portion) penetrated the film, and the second portion (high hardness portion) extended 75% of the film thickness in the film thickness direction.

(Comparative Example 1-1)
Example 1-1, except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted so that the film surface hardness was about 0.22 GPa by the first ultraviolet irradiation, and the second ultraviolet irradiation was not performed. In the same manner, a film was obtained. The film thickness obtained by drying was 17 μm.

  When the hardness of the obtained film was measured, the presence of the first portion and the second portion having different hardness was not recognized, and the hardness of the film surface was 0.22 GPa.

(Comparative Example 1-2)
The same as Example 1-1, except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted so that the hardness of the film surface was about 0.15 GPa by the first ultraviolet irradiation, and the second ultraviolet irradiation was not performed. A film was obtained. The film thickness obtained by drying was 17 μm.

  When the hardness of the obtained film was measured, the presence of the first part and the second part having different hardness was not recognized, and the hardness of the film surface was 0.15 GPa.

(Comparative Example 1-3)
A 81 mm diameter, 1 mm thick polycarbonate substrate with a 51 mm diameter circular cavity in the center, line width: 4 μm, space width: 4 μm, height difference between lines and spaces: 85 mm vertically with a pattern of 2 μm X Using a stamper mold made of nickel with a width of 85 mm and a thickness of 0.8 mm, the substrate side of the polycarbonate is heated to 100 ° C, the stamper mold side is heated to 190 ° C, and imprinting is performed at a load of 6500 N for 5 minutes. The film was obtained by transferring the stamper mold pattern onto a polycarbonate substrate.

  When the hardness of the obtained film was measured, the presence of the first part and the second part having different hardness was not recognized, and the hardness of the film surface was 0.18 GPa.

(Comparative Example 1-4)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 500 μm and a space width of 2000 μm (2 mm) was used during the second ultraviolet irradiation. The film thickness obtained by drying was 19 μm.

  In a square region with a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) may be 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, and the first portion (low hardness) The hardness of the (hardness part) was 0.19 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 1-5)
The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.1, and the hardness of the first part (low hardness part) is about 0 A film was obtained in the same manner as in Example 1-1 except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted to 15 GPa. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.1, and the first portion (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 1-6)
The ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 35, and the hardness of the first part (low hardness part) is about 0.15 GPa. A film was obtained in the same manner as in Example 1-1 except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted so that The film thickness obtained by drying was 15 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 34.5, and the first portion (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 1-7)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 76 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 6%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 1-8)
A film was obtained in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 0.7 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 85%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 1-9)
The photopolymerization initiator in the surface layer coating solution is 5 parts by mass, and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.5. Thus, the length of the first portion (low hardness portion) is about 0.15 GPa and the length of the second portion (high hardness portion) extending in the film thickness direction is about 0. A film was obtained in the same manner as in Example 1-3, except that the ultraviolet irradiation amount and the ultraviolet irradiation time were adjusted to 2 μm. The film thickness obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 GPa. The first portion (low hardness portion) penetrates the film, and the second portion (high hardness portion) extends 4% of the film thickness in the film thickness direction.

(Comparative Example 1-10)
The following solution 1 and solution 2 were filled in two solution tanks of an inkjet coating apparatus (trade name: PixelJet128, manufactured by Trident), respectively. This ink jet coating apparatus has two liquid ejection means, and each of the two liquid ejection means has a plurality of nozzles.

-Solution 1
A solution 1 was prepared by mixing the following components.

Fluorocarbonsiloxane rubber composition (trade name: Seifer 610, manufactured by Shin-Etsu Chemical Co., Ltd.): 75% by mass
Fluorine-based solvent (trade name: X-70-580, manufactured by Shin-Etsu Chemical Co., Ltd.): 25% by mass
-Solution 2-
A solution 2 was prepared by mixing the following components.

Fluorocarbon siloxane rubber composition (trade name: Seifer 650, manufactured by Shin-Etsu Chemical Co., Ltd.): 75% by mass
Fluorine-based solvent (trade name: X-70-580, manufactured by Shin-Etsu Chemical Co., Ltd.): 25% by mass
20 nozzles of each of the two liquid discharge means are used, and the nozzle discharge surface and the polyimide plate (a square plate having a thickness of 1 mm (length 100 mm × width 100 mm)) are arranged to be 10 mm, The solution 1 and the solution 2 from the two liquid discharge means are respectively formed in a line shape with a width of 4 μm for each of the solution 1 and the solution 2 under the conditions of a driving frequency of 2.6 kHz and a moving speed of the liquid discharge means of 450 mm / min. And from one end of the polyimide plate so that the distance between the solution 1 line and the solution 2 line is close, and the solution 1 line and the solution 2 line are parallel to one side of the polyimide plate. The other end was discharged. By repeating this process, the line width of the solution 1 was 4 μm, the line width of the solution 2 was 4 μm, and the line of the solution 1 and the line of the solution 2 were closely arranged in parallel, as viewed from directly above. Occasionally, a coating film having a pattern as shown in FIG. 1 was obtained on a polyimide plate. Thereafter, the coating film was primarily heated at 120 ° C. for 30 minutes, and then secondarily heated at 200 ° C. for 120 minutes. The film thickness on the polyimide plate obtained by heating was 20 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 2.8, and the first part (low hardness) The hardness of the (hardness part) was 0.00038 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

  Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10 are collectively shown in Table 1.

(Example 2-1)
A photosensitive silicone polymer (trade name: SINR-3170PX), which is a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd., was spinner coated on a silicon wafer to form a coating film. Subsequently, ultraviolet irradiation was performed twice with respect to the coating film. The first UV irradiation is performed on the entire surface of the coating film, and the second UV irradiation is performed using a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 2 μm. It was. The amount of UV irradiation and the time of UV irradiation for the first and second times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.6. And it adjusted so that the hardness of a 2nd part (high-hardness part) might be set to about 0.22 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 23%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa, and the hardness of the second part (high hardness part) was 0.22 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-2)
A film was obtained in the same manner as in Example 2-1, except that a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 1 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 18 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 12%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 (0.135) GPa, and the hardness of the second part (high hardness part) was 0.23 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-3)
A film was obtained in the same manner as in Example 2-1, except that a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 6 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 69%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa, and the hardness of the second part (high hardness part) was 0.23 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-4)
The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.2, and the hardness of the second part (high hardness part) is about 0 A film was obtained in the same manner as in Example 2-1, except that the UV irradiation amount and the UV irradiation time for the first and second times were adjusted to 19 GPa. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 23%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.2, and the first part (low hardness) The hardness of the (hardness part) was 0.15 GPa, and the hardness of the second part (high hardness part) was 0.18 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-5)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

Bisphenol Z-type polycarbonate: 10 parts by mass Compound (charge transport material) represented by the above structural formula (101): 9 parts by mass Chlorobenzene: 100 parts by mass Next, on the charge transport layer, for the surface layer having the following composition A coating film having a thickness of 5 μm was obtained by spray coating the coating solution.

-Coating liquid for surface layer Compound represented by the above structural formula (14) (radical polymerizable compound having a charge transporting structure): 10 parts by mass Trimethylolpropane triacrylate: 10 parts by mass Photopolymerization initiator: 1 part by mass Chlorobenzene : 100 parts by mass Next, the coating film was irradiated with ultraviolet rays twice. The first UV irradiation is performed on the entire surface of the coating film, and the second UV irradiation is performed using a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 2 μm. It was. The amount of UV irradiation and the time of UV irradiation for the first and second times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 30, and It adjusted so that the hardness of 2 part (high hardness part) might be set to about 0.30 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 23%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 26.8, and the first portion (low hardness) The hardness of the (hardness part) was 0.01 (0.01044) GPa, and the hardness of the second part (high hardness part) was 0.28 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-6)
The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.4, and the hardness of the second part (high hardness part) is about 0. A film was obtained in the same manner as in Example 2-1, except that the first and second ultraviolet irradiation amounts and the ultraviolet irradiation time were adjusted to 0.02 GPa. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 23%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.4, and the first portion (low hardness) The hardness of the (hardness part) was 0.01 (0.014) GPa, and the hardness of the second part (high hardness part) was 0.02 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-7)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

Bisphenol Z-type polycarbonate: 10 parts by mass Compound (charge transport material) represented by the above structural formula (101): 10 parts by mass Chlorobenzene: 100 parts by mass Next, on the charge transport layer, for the surface layer having the following composition A coating film having a thickness of 5 μm was obtained by spray coating the coating solution.

Radical polymerizable compound having a charge transporting structure (Exemplary Compound No. 9 (compound represented by the above structural formula (9))): 10 parts by mass Methyl ethyl ketone: 100 parts by mass I went twice. The first electron beam irradiation is performed on the entire surface of the coating film, and at the time of the second electron beam irradiation, a honeycomb type electron beam mask having a regular hexagonal side length of 10 μm and a wall thickness of 2 μm is used. Irradiation was performed. At the time of electron beam irradiation, nitrogen purge was performed and the acceleration voltage was set to 30 kV. The first and second electron beam irradiation doses and electron beam irradiation times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.6. In addition, the hardness of the second portion (high hardness portion) was adjusted to be about 5.00 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 23%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.8, and the first portion (low hardness) The hardness of the (hardness part) was 2.69 GPa, and the hardness of the second part (high hardness part) was 4.84 GPa.

(Example 2-8)
A film was obtained in the same manner as in Example 2-1, except that a circular hole-type photomask having a diameter of 0.2 μm and a center-to-center distance of 0.4 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 21%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.13 GPa, and the hardness of the second part (high hardness part) was 0.22 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 2-9)
A film was obtained in the same manner as in Example 2-1, except that a honeycomb type photomask having a regular hexagonal side length of 50 μm and a wall thickness of 10 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 18 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 23%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa, and the hardness of the second part (high hardness part) was 0.23 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 2-1)
The first UV irradiation was not performed on the entire surface of the coating film, and the UV irradiation was performed using a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 2 μm. A film was obtained in the same manner as in Example 2-1, except that the part that did not exist was etched. The film thickness obtained by drying was 17 μm.

  Moreover, when the hardness was measured about the obtained film | membrane, presence of the 1st part and 2nd part from which hardness differs was not recognized, but the hardness of the surface of a film | membrane was 0.24 GPa. Further, irregularities were observed, and the height difference of the irregularities was 17 μm.

(Comparative Example 2-2)
A film was obtained in the same manner as in Example 2-1, except that a honeycomb-type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 0.5 μm was used during the second ultraviolet irradiation. . The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 6%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa, and the hardness of the second part (high hardness part) was 0.23 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 2-3)
A film was obtained in the same manner as in Example 2-1, except that a honeycomb type photomask having a regular hexagonal side length of 10 μm and a wall thickness of 8 μm was used during the second ultraviolet irradiation. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 92%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, and the first portion (low hardness) The hardness of the (hardness part) was 0.15 GPa, and the hardness of the second part (high hardness part) was 0.22 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 2-4)
The ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 40.0, and the hardness of the second part (high hardness part) is about 5 A film was obtained in the same manner as in Example 2-1, except that the UV irradiation amount and the UV irradiation time for the first and second times were adjusted to 0.000 GPa. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 23%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 37.3, and the first part (low hardness) The hardness of the (hardness part) was 0.13 GPa, and the hardness of the second part (high hardness part) was 4.85 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 2-5)
The photopolymerization initiator in the surface layer coating solution is 5 parts by mass, and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.6. As described above, the length of the second portion (high hardness portion) is about 0.22 GPa and the length of the second portion (high hardness portion) extending in the film thickness direction is about 1 μm. A film was obtained in the same manner as in Example 2-5 except that the first and second ultraviolet irradiation amounts and the ultraviolet irradiation time were adjusted so that The film thickness obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the surface area ratio of the surface constituted by the second portion (high hardness portion) is 23%, and the first portion (low The total area ratio of the surface composed of the (hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, and the first portion (low hardness) The hardness of the (hardness part) was 0.13 GPa, and the hardness of the second part (high hardness part) was 0.20 GPa. The first portion (low hardness portion) penetrated the film, and the second portion (high hardness portion) extended 20% of the film thickness in the film thickness direction.

(Example 3-1)
A photosensitive silicone polymer (trade name: SINR-3170PX), a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd., and a polytetrafluoropolymer having an average particle size of 0.5 μm manufactured by Daikin Industries, Ltd. as a lubricant. Ethylene (PTFE) particles (trade name: Lubron L-2) and a surfactant (trade name: GF-300) manufactured by Toa Gosei Co., Ltd. were added to obtain a mixed solution. The amount (dispersion concentration) of polytetrafluoroethylene particles in the mixed solution was set to 10% by volume. This was spinner coated on a silicon wafer, and the resulting coating film was dried (pre-dried) at 90 ° C. for 2 minutes.

  Subsequently, ultraviolet irradiation was performed twice with respect to the coating film. The first ultraviolet irradiation was performed on the entire surface of the coating film, and at the second ultraviolet irradiation, irradiation was performed using a photomask having a line width of 4.0 μm and a space width of 4.0 μm. The amount of UV irradiation and the time of UV irradiation for the first and second times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.6. And it adjusted so that the hardness of a 1st part (low-hardness part) might be set to about 0.14 GPa. Thereafter, the coating film was dried (post-dried) at 90 ° C. for 2 minutes. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-2)
A film was obtained in the same manner as in Example 3-1, except that polytetrafluoroethylene particles having an average particle diameter of 1.0 μm were used as the lubricant. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 53%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-3)
A film was obtained in the same manner as in Example 3-1, except that polytetrafluoroethylene particles having an average particle diameter of 4.0 μm were used as the lubricant. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 40%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-4)
A film was obtained in the same manner as in Example 3-1, except that polytetrafluoroethylene particles having an average particle diameter of 10 μm were used as the lubricant. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 20%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-5)
A membrane was obtained in the same manner as in Example 3-1, except that the dispersion concentration of the polytetrafluoroethylene particles was 1% by volume. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 55%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-6)
A membrane was obtained in the same manner as in Example 3-1, except that the dispersion concentration of the polytetrafluoroethylene particles was 5% by volume. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-7)
A film was obtained in the same manner as in Example 3-1, except that the dispersion concentration of the polytetrafluoroethylene particles was 20% by volume. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 30%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-8)
A film was obtained in the same manner as in Example 3-2 except that a photomask having a hole structure with a diameter of 4.0 μm was used as the photomask. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 52%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.13 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-9)
A film was obtained in the same manner as in Example 3-2 except that a photomask having a honeycomb structure with a maximum vertex distance of 4.0 μm was used as the photomask. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-10)
A film was obtained in the same manner as in Example 3-1, except that mica particles (trade name: MK-100) having an average particle diameter of 0.5 μm manufactured by Coop Chemical Co., Ltd. were used as the lubricant. The film thickness obtained by drying was 16 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-11)
A film was obtained in the same manner as in Example 3-1, except that boron nitride (BN) particles (trade name: AP-20S) manufactured by MARUKA having an average particle size of 0.5 μm were used. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the first portion (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-12)
A film was formed in the same manner as in Example 3-1, except that melamine cyanurate (MCN) particles (trade name: MC-5F) manufactured by Sakai Chemical Industry Co., Ltd. having an average particle diameter of 0.5 μm were used as the lubricant. Obtained. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-13)
A film was obtained in the same manner as in Example 3-1, except that silica particles having an average particle size of 0.5 μm (trade name: High Plessica) manufactured by Ube Nitto Kasei Co., Ltd. were used as the lubricant. The film thickness obtained by drying was 17 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained film, the area ratio of the surface composed of the second portion (high hardness portion) is 50%, and the first portion (low hardness) The total area ratio of the surface composed of the portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-14)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

-Charge transport layer coating solution Bisphenol Z-type polycarbonate: 10 parts by mass Compound (charge transport material) represented by the above structural formula (101): 9 parts by mass Chlorobenzene: 100 parts by mass Next, on the charge transport layer, A coating film having a thickness of 5 μm was obtained by spray coating a coating solution for the surface layer having the following composition.

-Surface layer coating liquid Compound represented by the above structural formula (28) (radical polymerizable compound having a charge transporting structure): 10 parts by mass Trimethylolpropane triacrylate: 10 parts by mass Polytetrafluoroethylene particles (average particle diameter) 1.0 μm): 1 part by mass (equivalent to 10% by volume)
Surfactant (trade name: GF-300) manufactured by Toa Gosei Co., Ltd .: 0.05 part by mass 2.2-dimethoxy-1.2-diphenylethane-1-one (photopolymerization initiator, trade name: IRGACURE651) , Manufactured by BASF): 1 part by mass Chlorobenzene: 100 parts by mass Next, the coating film was irradiated with ultraviolet rays twice. The first ultraviolet irradiation was performed on the entire surface of the coating film, and at the second ultraviolet irradiation, irradiation was performed using a photomask having a line width of 4.0 μm and a space width of 4.0 μm. The amount of UV irradiation and the time of UV irradiation for the first and second times are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.5. And it adjusted so that the hardness of a 1st part (low-hardness part) might be set to about 0.15 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 51%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.14 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Example 3-15)
On a 100 mm long x 100 mm wide x 0.75 mm thick aluminum plate, a charge transport layer coating solution having the following composition is coated with a Meyer bar, and the resulting coating is dried, thereby transporting the charge with a thickness of 20 μm. A layer was formed.

Bisphenol Z-type polycarbonate: 10 parts by mass Compound (charge transport material) represented by the above structural formula (101): 10 parts by mass Chlorobenzene: 100 parts by mass Next, a coating for a surface layer having the following composition is applied on the charge transport layer. By spray coating the liquid, a coating film having a thickness of 5 μm was obtained.

-Surface layer coating solution Compound represented by the above structural formula (28) (radical polymerizable compound having a charge transporting structure): 10 parts by mass Polytetrafluoroethylene particles (average particle size: 1.0 μm): 1 part by mass ( 10 volume% equivalent)
Toa Gosei Co., Ltd. surfactant (trade name: GF-300): 0.05 parts by mass Methyl ethyl ketone: 100 parts by mass Next, the coating film was subjected to electron beam irradiation twice. The first electron beam irradiation was performed on the entire surface of the coating film, and an electron beam mask (metal mask) having a line width of 4.0 μm and a space width of 4.0 μm was used during the second electron beam irradiation. At the time of electron beam irradiation, nitrogen purge was performed and the acceleration voltage was set to 30 kV. The first and second electron beam irradiation doses are such that the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is about 1.6, and The hardness of one part (low hardness part) was adjusted to be about 0.15 GPa. Thereafter, the coating film was dried at 90 ° C. for 2 minutes. The film thickness of the surface layer (film) obtained by drying was 5 μm.

  In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the obtained surface layer (film), the area ratio of the surface constituted by the second portion (high hardness portion) is 50%, The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Further, when the hardness of the obtained film was measured, the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) was 1.6, and the first part (low hardness) The hardness of the (hardness part) was 0.15 GPa. Further, both the first portion (low hardness portion) and the second portion (high hardness portion) penetrated the film.

(Comparative Example 3-1)
A photosensitive polyimide silicone (trade name: SPS-7750), a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd., and a polytetrafluoropolymer having an average particle size of 0.5 μm manufactured by Daikin Industries, Ltd. as a lubricant. Ethylene particles (trade name: Lubron L-2) and a surfactant (trade name: GF-300) manufactured by Toa Gosei Co., Ltd. were added to obtain a mixed solution. The amount (dispersion concentration) of polytetrafluoroethylene particles in the mixed solution was set to 10% by volume. This was spinner coated on a silicon wafer, and the resulting coating film was dried (pre-dried) at 90 ° C. for 2 minutes. The film thickness obtained by drying was 17 μm.

  When the hardness of the obtained film was measured, the presence of the first part and the second part having different hardness was not recognized, and the hardness of the film surface was 0.14 GPa.

(Comparative Example 3-2)
A film was obtained in the same manner as in Comparative Example 3-1, except that mica particles (trade name: MK-100) having an average particle diameter of 0.50 μm manufactured by Coop Chemical Co., Ltd. were used as the lubricant. The film thickness obtained by drying was 17 μm.

  When the hardness of the obtained film was measured, the presence of the first part and the second part having different hardness was not recognized, and the hardness of the film surface was 0.14 GPa.

  Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-2 are collectively shown in Table 2.

(4) Evaluation of Friction Coefficient (Dynamic Friction Coefficient) Evaluation of the friction coefficient of the film surface was performed using a torque type frictional resistance measuring machine (trade name: TYPE: 20) manufactured by Shinto Kagaku Co., Ltd. A film to be measured is placed on a turntable (diameter 12.7 mm) of a measuring machine, and a urethane rubber member (JIS-A hardness: 70 degrees) having a thickness of 3 mm, a width of 1 cm, and a length of 1 cm is attached to the circumferential edge of the film. 24 ° (when the rubber member and the membrane are in parallel contact with each other, the angle is 0 °) in contact with the driven direction (with direction), a load of 30 g is applied, and the membrane installed on the turntable (radius 33 mm) Was rotated at a rotational speed of 47.8 rpm, and the friction coefficient (dynamic friction coefficient) was determined from the force applied between the membrane and the urethane rubber member.

  As Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10 as the value of the friction coefficient (dynamic friction coefficient), the urethane rubber member was brought into contact with the member and rotated for 10 hours or 30 hours. With respect to Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-5, Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-2, The value when the member was brought into contact and rotated for 1 hour or 20 hours was used.

(5) Evaluation of surface unevenness The surface unevenness evaluation of the film was performed using a surface shape measuring device (trade name: TENCORP-10) manufactured by TENCOR. The width of each of the convex portion by the second portion and the concave portion by the first portion and the height difference between the convex portion and the concave portion were evaluated.

(6) Evaluation of stick-and-slip Evaluation of stick-and-slip was performed with respect to Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-9. Torque friction resistance measuring machine manufactured by Shinto Kagaku Co., Ltd. (Product name: TYPE: 20). After rotating the urethane rubber member for 30 hours, the urethane rubber member is rotated at an angle of 24 ° to the circumferential end of the membrane (when the rubber member and the membrane are in parallel contact with each other, the angle is 0 °). Abutting in the reverse direction (counter direction), a load of 30 g was applied, and the film (radius 33 mm) placed on the turntable was rotated at 23.9 rpm (slow rotation) and 47.8 rpm (fast rotation). The behavior of the urethane rubber member was used for stick and slip evaluation. The evaluation results of stick and slip were classified into the following three stages.
A: The behavior of rotating without any problem at the rotation speeds of 23.9 rpm and 47.8 rpm is shown.
B: The rotation of the urethane rubber member shows a continuous jumping behavior at a rotation speed of 23.9 rpm, but a behavior of rotating without a problem at a rotation speed of 47.8 rpm.
C: The urethane rubber member continuously jumps up at both rotation speeds of 23.9 rpm and 47.8 rpm.

  Stick-and-slip is unlikely to occur with a low coefficient of friction and tends to occur with a high coefficient of friction.

(7) Evaluation of destruction of convex part Evaluation of the destruction of the 2nd part which became the convex part on the surface of a film | membrane is Example 1-1 to 1-10, Comparative example 1-1 to 1-10, Example 2 Regarding -1 to 2-9 and Comparative Examples 2-1 to 2-5, an ultra-deep shape measuring microscope (trade name: VK-9510) manufactured by Keyence Corporation and an image analysis apparatus (trade name) manufactured by Nireco Corporation : LuzexAP).

For Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10, the evaluation results of the destruction of the convex portions of the film after rotating the urethane rubber member for 30 hours, It was classified into the following two stages.
A: The area where the shape of the convex part was destroyed is less than 20% of the total area of the convex part per square of 1 mm on each side.
C: The area where the shape of the convex part was destroyed is 30% or more of the total area of the convex part per square with a side of 1 mm.

  Moreover, regarding Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-5, the evaluation results of the destruction of the convex portions of the film after the urethane rubber member was brought into contact and rotated for 20 hours Were classified into the following three stages.

  A: The area where the shape of the convex part was destroyed is less than 10% of the total area of the convex part per square with a side of 1 mm.

  B: The area where the shape of the convex part was destroyed is 10% or more and less than 20% of the whole convex part per square with a side of 1 mm.

  C: The area where the shape of the convex portion was destroyed is 20% or more of the entire convex portion per square with a side of 1 mm.

(8) Evaluation result 1
(Example 1-1)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.44.

  Further, when the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the 4 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex part and the concave part was 0.24 μm, and the friction coefficient of the film surface was 0.42. Neither stick-and-slip was observed in both the slow rotation and the fast rotation, and the protrusion was not broken. It was found that the surface shape was maintained and the low coefficient of friction was maintained even after the urethane rubber member was brought into contact and rotated for 30 hours.

(Example 1-2)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the portion and the recess was 0.18 μm, and the friction coefficient of the film surface was 0.56.

  Further, when the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the 4 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex part and the concave part was 0.19 μm, and the friction coefficient of the film surface was 0.50. Neither stick-and-slip was observed in both the slow rotation and the fast rotation, and the protrusion was not broken. Even after the urethane rubber member was brought into contact and rotated for 30 hours, the shape of the surface was maintained and a low coefficient of friction was maintained, but the coefficient of friction was higher than that of Example 1-1.

(Example 1-3)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.30 μm, and the friction coefficient of the film surface was 0.49.

  Further, when the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the 4 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex portion and the concave portion was 0.31 μm, and the friction coefficient of the film surface was 0.52. Neither stick-and-slip was observed in both the slow rotation and the fast rotation, and the protrusion was not broken. It was found that the surface shape was maintained and the low coefficient of friction was maintained even after the urethane rubber member was brought into contact and rotated for 30 hours.

(Example 1-4)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.38 μm, and the friction coefficient of the film surface was 0.68.

  Further, when the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the 4 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex part and the concave part was 0.39, and the friction coefficient of the film surface was 0.73. Stick and slip was observed at slow rotation, but no stick and slip was observed at high rotation. Moreover, the destruction of the convex part was not seen. The friction coefficient of the surface of the film after the urethane rubber member was brought into contact and rotated for 10 hours and 30 hours was higher than that of Example 1-1.

(Example 1-5)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.36 μm, and the friction coefficient of the film surface was 0.62.

  When the surface of the film after the urethane rubber member was contacted and rotated for 30 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.36 μm, and the friction coefficient of the film surface was 0.68. Stick and slip was observed at slow rotation, but no stick and slip was observed at high rotation. Moreover, the destruction of the convex part was not seen. The friction coefficient of the surface of the film after the urethane rubber member was brought into contact and rotated for 10 hours and 30 hours was higher than that of Example 1-1.

(Example 1-6)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.27 μm, and the friction coefficient of the film surface was 0.61.

  When the surface of the film after the urethane rubber member was contacted and rotated for 30 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.28 μm, and the friction coefficient of the film surface was 0.66. Stick and slip was observed at slow rotation, but no stick and slip was observed at high rotation. Moreover, the destruction of the convex part was not seen. The friction coefficient of the surface of the film after the urethane rubber member was brought into contact and rotated for 10 hours and 30 hours was higher than that of Example 1-1.

(Example 1-7)
When the surface of the film after the urethane rubber member was contacted and rotated for 10 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 20 μm and a convex portion due to the second portion having a width of 20 μm were recognized. The height difference between the part and the concave part was 0.51 μm, and the friction coefficient of the film surface was 0.71.

  When the surface of the film after rotating the urethane rubber member for 30 hours after contact was confirmed and evaluated, a concave portion due to the first portion having a width of 20 μm and a convex portion due to the second portion having a width of 20 μm were recognized. The height difference between the portion and the recess was 0.51 μm, and the friction coefficient of the film surface was 0.70. Stick and slip was observed at slow rotation, but no stick and slip was observed at high rotation. Moreover, the destruction of the convex part was not seen. The friction coefficient of the surface of the film after the urethane rubber member was brought into contact and rotated for 10 hours and 30 hours was higher than that of Example 1-1.

(Example 1-8)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the 22.7 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex part and the concave part was 0.57 μm, and the friction coefficient of the film surface was 0.53.

  After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 30 hours, a concave portion due to the 22.7 μm wide first portion and a convex portion due to the 4 μm wide second portion were observed. The height difference between the convex portion and the concave portion was 0.58 μm, and the friction coefficient of the film surface was 0.54. Neither stick-and-slip was observed in both the slow rotation and the fast rotation, and the protrusion was not broken. It was found that the surface shape was maintained and the low coefficient of friction was maintained even after the urethane rubber member was brought into contact and rotated for 30 hours.

(Example 1-9)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion formed by a first portion having a width of 1.3 μm and a convex portion formed by a second portion having a width of 4 μm were recognized. The height difference between the convex part and the concave part was 0.15 μm, and the friction coefficient of the film surface was 0.75.

  When the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the first portion having a width of 1.3 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the convex part and the concave part was 0.16 μm, and the friction coefficient of the film surface was 0.73. Stick and slip was observed at slow rotation, but no stick and slip was observed at high rotation. Moreover, the destruction of the convex part was not seen. The friction coefficient of the surface of the film after the urethane rubber member was brought into contact and rotated for 10 hours and 30 hours was higher than that of Example 1-1.

(Example 1-10)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.45.

  When the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, an unevenness of 4.0 μm width was observed, and the height difference between the convex part and the concave part was 0.26 μm. The coefficient of friction of the film surface was 0.43. Neither stick-and-slip was observed in both the slow rotation and the fast rotation, and the protrusion was not broken. It was found that the surface shape was maintained and the low coefficient of friction was maintained even after the urethane rubber member was brought into contact and rotated for 30 hours.

(Comparative Example 1-1)
When the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours was confirmed and evaluated, no irregularities were observed and the coefficient of friction of the film surface was 1.77.

  When the surface of the film after the urethane rubber member was brought into contact with and rotated for 30 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 1.74. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed.

(Comparative Example 1-2)
When the surface of the film after the urethane rubber member was contacted and rotated for 10 hours was confirmed and evaluated, irregularities were not observed and the coefficient of friction of the film surface was 0.95.

  When the surface of the film after the urethane rubber member was brought into contact with it and rotated for 30 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 0.91. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed.

(Comparative Example 1-3)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 1.68 μm, and the friction coefficient of the film surface was 0.99.

  When the surface of the film after the urethane rubber member was contacted and rotated for 30 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 1.05 μm, and it was found that the concave and convex shape was disappearing because the convex part was worn by rotating the urethane rubber member abutted for 30 hours. The coefficient of friction on the surface of the film was 1.24. Stick-and-slip occurred in both slow rotation and fast rotation, unstable friction behavior was observed, and the area where the convex shape was destroyed was found to be 41% of the total area of the convex.

(Comparative Example 1-4)
When the surface of the film after the urethane rubber member was contacted and rotated for 10 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 2000 μm and a convex portion due to the second portion having a width of 500 μm were recognized. The height difference between the part and the concave part was 1.89 μm, and the friction coefficient of the film surface was 1.88.

  When the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the first portion having a width of 2000 μm and a convex portion due to the second portion having a width of 500 μm were recognized. The height difference between the part and the concave part was 1.93 μm, and the friction coefficient of the film surface was 1.86. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed. The destruction of the convex part was not seen.

(Comparative Example 1-5)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.11 μm, and the friction coefficient of the film surface was 0.97.

  When the surface of the film after the urethane rubber member was contacted and rotated for 30 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.10 μm, and the friction coefficient of the film surface was 0.97. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed. The destruction of the convex part was not seen.

(Comparative Example 1-6)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.66 μm, and the friction coefficient of the film surface was 0.99.

  When the surface of the film after the urethane rubber member was contacted and rotated for 30 hours was confirmed and evaluated, a concave portion due to the first portion having a width of 4 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.64 μm, and the friction coefficient of the film surface was 0.92. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed. The destruction of the convex part was not seen.

(Comparative Example 1-7)
When the surface of the film after rotating for 10 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the first portion having a width of 76 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the part and the concave part was 0.77 μm, and the friction coefficient of the film surface was 0.95.

  When the surface of the film after rotating for 30 hours with the urethane rubber member in contact was confirmed and evaluated, a concave portion due to the first portion having a width of 76 μm and a convex portion due to the second portion having a width of 4 μm were recognized. The height difference between the portion and the recess was 0.75 μm, and the friction coefficient of the film surface was 1.23. Stick-and-slip occurred in both slow rotation and fast rotation, unstable friction behavior was observed, and the area where the shape of the convex portion was broken was found to be 36% with respect to the total area of the convex portion.

(Comparative Example 1-8)
After confirming and evaluating the surface of the film after the urethane rubber member was brought into contact with it and rotated for 10 hours, a concave portion formed by a first portion having a width of 0.7 μm and a convex portion formed by a second portion having a width of 4 μm were recognized. The height difference between the convex portion and the concave portion was 0.11 μm, and the friction coefficient of the film surface was 1.05.

  After confirming and evaluating the surface of the film after rotating the urethane rubber member for 30 hours, a concave portion due to the 0.7 μm wide first portion and a convex portion due to the 4 μm wide second portion are recognized. The height difference between the convex portion and the concave portion was 0.13 μm, and the friction coefficient of the film surface was 1.03. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed. The destruction of the convex part was not seen.

(Comparative Example 1-9)
When the surface of the film after the urethane rubber member was contacted and rotated for 10 hours was confirmed and evaluated, no irregularities were observed and the friction coefficient of the film surface was 1.06.

  When the surface of the film after the urethane rubber member was brought into contact with and rotated for 30 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 1.02. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed.

(Comparative Example 1-10)
When the surface of the film after the urethane rubber member was contacted and rotated for 10 hours was confirmed and evaluated, no irregularities were observed and the coefficient of friction of the film surface was 1.90.

  When the surface of the film after the urethane rubber member was brought into contact with and rotated for 30 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 1.88. Stick-and-slip occurred in both slow and fast rotations, and unstable friction behavior was observed.

(Example 2-1)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.22 μm, and the friction coefficient of the film surface is 0.44. .

  Further, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.25 μm. The coefficient of friction of the film surface was 0.43. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Example 2-2)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 1 μm, the height difference between the convex part and the concave part is 0.33 μm, and the friction coefficient of the film surface is 0.48. .

  In addition, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.34 μm. The coefficient of friction of the film surface was 0.52. The area where the shape of the convex portion was destroyed per square with a side of 1 mm was 14% of the total area of the convex portion.

(Example 2-3)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 6 μm, the height difference between the convex portion and the concave portion is 0.11 μm, and the friction coefficient of the film surface is 0.75. .

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.12 μm. The coefficient of friction of the film surface was 0.72. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Example 2-4)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.16 μm, and the friction coefficient of the film surface is 0.81. .

  Further, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.17 μm. The friction coefficient of the film surface was 0.81. The area where the shape of the convex portion was destroyed per square with a side of 1 mm was 12% of the total area of the convex portion.

(Example 2-5)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.24 μm, and the friction coefficient of the film surface is 0.45. .

  In addition, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.34 μm. The coefficient of friction of the film surface was 0.85. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Example 2-6)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.16 μm, and the friction coefficient of the film surface is 0.81. .

  Further, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.16 μm. The coefficient of friction of the film surface was 0.86. The area where the shape of the convex portion was destroyed per square with a side of 1 mm was 15% of the total area of the convex portion.

(Example 2-7)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.27 μm, and the friction coefficient of the film surface is 0.53. .

  Further, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.35 μm. The coefficient of friction of the film surface was 0.88. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Example 2-8)
When the surface of the film after rotating for 1 hour with the urethane rubber member in contact was confirmed and evaluated, a circular hole with a diameter of 0.2 μm on the surface and a center-to-center distance of 0.4 μm. Mold irregularities were observed, the height difference between the convex and concave portions was 0.03 μm, and the friction coefficient of the film surface was 0.85.

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, hole-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.03 μm. The coefficient of friction of the film surface was 0.84. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Example 2-9)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon was 50 μm, the thickness of the wall was 10 μm, the height difference between the convex part and the concave part was 0.84 μm, and the friction coefficient of the film surface was 0.83. .

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.89 μm. The coefficient of friction of the film surface was 0.86. The area where the shape of the convex portion was destroyed per square with a side of 1 mm was 15% of the total area of the convex portion.

(Comparative Example 2-1)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the convex part and the concave part was 17 μm, and the friction coefficient of the film surface was 0.78.

  In addition, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 16 μm. The surface friction coefficient was 0.92. The area where the shape of the convex portion was destroyed per square with a side of 1 mm was 23% of the total area of the convex portion.

(Comparative Example 2-2)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the wall thickness is 0.5 μm, the height difference between the convex part and the concave part is 0.35 μm, and the friction coefficient of the film surface is 0.54. there were.

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.39 μm. The coefficient of friction of the film surface was 0.94. The area where the shape of the convex portion was destroyed per square of 1 mm on one side was 27% of the total area of the convex portion.

(Comparative Example 2-3)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the wall thickness is 8 μm, the height difference between the convex part and the concave part is 0.07 μm, and the friction coefficient of the film surface is 0.96. .

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, honeycomb-shaped unevenness was observed, and the height difference between the protrusion and the recess was 0.07 μm. The coefficient of friction of the film surface was 0.95. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Comparative Example 2-4)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.27 μm, and the friction coefficient of the film surface is 0.49. .

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, honeycomb-shaped irregularities were observed, and the height difference between the convex and concave portions was 0.42 μm. The coefficient of friction of the film surface was 0.99. The area where the shape of the convex portion was destroyed per 1 mm square was less than 10% of the total area of the convex portion.

(Comparative Example 2-5)
After confirming and evaluating the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact with the surface, honeycomb-shaped irregularities were recognized with a regular hexagonal recess on the surface and a wall surrounding it as a protrusion. The length of one side of the regular hexagon is 10 μm, the thickness of the wall is 2 μm, the height difference between the convex part and the concave part is 0.22 μm, and the friction coefficient of the film surface is 0.47. .

  Moreover, when the surface of the film | membrane after making the said urethane rubber member contact | abut and rotating for 20 hours was confirmed and evaluated, the unevenness | corrugation was not recognized but the friction coefficient of the film | membrane surface was 1.61.

(Classification of friction coefficient values)
Regarding Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-9, the friction coefficient values were classified into the following three stages.
A: The value of the coefficient of friction on the surface of the film after contacting the urethane rubber member and rotating for 10 hours or 30 hours is 0.60 or less.
B: The value of the coefficient of friction on the surface of the film after contacting the urethane rubber member and rotating for 10 hours or 30 hours is 0.61 or more and 0.80 or less.
C: The value of the coefficient of friction on the surface of the film after contacting the urethane rubber member and rotating for 10 hours or 30 hours is 0.81 or more.

  For Examples 2-1 to 1-9 and Comparative Examples 2-1 to 2-5, the friction coefficient values were classified into the following three stages.

  A: The value of the friction coefficient of the surface of the film after the urethane rubber member is brought into contact with and rotated for 1 hour or 20 hours is 0.60 or less.

  B: The value of the coefficient of friction on the surface of the film after contacting the urethane rubber member and rotating for 1 hour or 20 hours is 0.61 or more and 0.90 or less.

  C: The value of the coefficient of friction on the surface of the film after the urethane rubber member is brought into contact and rotated for 1 hour or 20 hours is 0.91 or more.

  The above is summarized in Table 3.

(9) Evaluation result 2
(Example 3-1)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex portion and the concave portion was 0.25 μm, and the friction coefficient of the film surface was 0.33.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.24 μm, and the friction coefficient of the film surface was 0.33. When the concave and convex portions were confirmed, it was confirmed that the wear powder (the wear powder with lubricity generated by the abrasion of the film containing the lubricant. The same applies hereinafter) is accumulated in the concave portion with an optical microscope. I was able to confirm.

(Example 3-2)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex part and the concave part was 0.22 μm, and the friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.21 μm, and the friction coefficient of the film surface was 0.27. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-3)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex portion and the concave portion was 0.28 μm, and the friction coefficient of the film surface was 0.37.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.24 μm, and the friction coefficient of the film surface was 0.35. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-4)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex portion and the concave portion was 0.23 μm, and the friction coefficient of the film surface was 0.35.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.23 μm, and the friction coefficient of the film surface was 0.35. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-5)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The height difference between the convex part and the concave part was 0.27 μm, and the friction coefficient of the film surface was 0.65.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.64. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-6)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The difference in height between the convex and concave portions was 0.25 μm, and the friction coefficient of the film surface was 0.53.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.50. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-7)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The height difference between the convex part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.26.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.26. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-8)
When the surface of the film after rotating for 1 hour with the urethane rubber member in contact was confirmed and evaluated, a hole shape was observed with a diameter of 4.0 μm, and the height difference between the convex part and the concave part was 0.25 μm. The friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after rotating for 20 hours by contacting the urethane rubber member was confirmed and evaluated, a hole shape having a diameter of 4.0 μm was observed, and the height difference between the convex part and the concave part was 0.00. The friction coefficient of the film surface was 0.22. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-9)
When the surface of the membrane after rotating for 1 hour with the urethane rubber member in contact was confirmed and evaluated, a honeycomb shape with a maximum apex distance of 4.0 μm was observed, and the difference in height between the convex and concave portions was It was 0.24 μm, and the friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after rotating for 20 hours with the urethane rubber member in contact was confirmed and evaluated, a honeycomb shape with a maximum apex distance of 3.9 μm was observed, and the height of the convex and concave portions was The difference was 0.24 μm, and the friction coefficient of the film surface was 0.20. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-10)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The height difference between the convex part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.35.

  Further, when the surface of the film after the urethane rubber member was contacted and rotated for 20 hours was confirmed and evaluated, the concave portion formed by the first portion having a width of 4.2 μm and the convex portion formed by the second portion having a width of 3.8 μm. The height difference between the convex part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.31. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-11)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex part and the concave part was 0.26 μm, and the friction coefficient of the film surface was 0.52.

  Further, when the surface of the film after the urethane rubber member was contacted and rotated for 20 hours was confirmed and evaluated, the concave portion formed by the first portion having a width of 4.1 μm and the convex portion formed by the second portion having a width of 3.9 μm. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.47. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-12)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The difference in height between the convex and concave portions was 0.25 μm, and the friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.28. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-13)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. As a result, the difference in height between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.42.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex portion and the concave portion was 0.25 μm, and the friction coefficient of the film surface was 0.38. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-14)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The difference in height between the convex and concave portions was 0.25 μm, and the friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.27. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Example 3-15)
After confirming and evaluating the surface of the film after the urethane rubber member was contacted and rotated for 1 hour, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion were found. The difference in height between the convex and concave portions was 0.25 μm, and the friction coefficient of the film surface was 0.32.

  Further, when the surface of the film after the urethane rubber member was brought into contact with and rotated for 20 hours was confirmed and evaluated, a concave portion formed by a 4.0 μm wide first portion and a convex portion formed by a 4.0 μm wide second portion. The height difference between the convex part and the concave part was 0.25 μm, and the friction coefficient of the film surface was 0.28. When the concave and convex portions were confirmed, it was confirmed with an optical microscope that the abrasion powder accumulated in the concave portions.

(Comparative Example 3-1)
When the surface of the film after the urethane rubber member was contacted and rotated for 1 hour was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 0.33.

  Further, when the surface of the film after the urethane rubber member was contacted and rotated for 20 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 0.52. The generation of abrasion powder due to rubbing was confirmed, but it immediately disappeared from the friction system.

(Comparative Example 3-2)
When the surface of the film after the urethane rubber member was brought into contact with it and rotated for 1 hour was confirmed and evaluated, irregularities were not recognized and the coefficient of friction of the film surface was 0.35.

  Further, when the surface of the film after the urethane rubber member was contacted and rotated for 20 hours was confirmed and evaluated, no irregularities were observed, and the coefficient of friction of the film surface was 0.53. The generation of abrasion powder due to rubbing was confirmed, but it immediately disappeared from the friction system.

  As an index of the effect of suppressing the increase in the coefficient of friction due to the outflow of the wear powder from the wear system, evaluation was made using a reduction rate defined as follows. When the reduction rate is less than 0%, it means that an increase in the coefficient of friction occurs due to use.

Reduction rate = {(Friction coefficient of film surface after rotating urethane rubber member for 1 hour-Friction coefficient of film surface after rotating urethane rubber member for 20 hours after contact) ) ÷ Friction coefficient of film surface after rotating urethane rubber member for one hour} × 100
The above is summarized in Table 4.

(Photomask for producing electrophotographic photosensitive member)
A photomask for preparing an electrophotographic photosensitive member was prepared as follows. In addition, the line width and the opening size in the square type nickel mesh / plain weave type stainless steel mesh are as shown in FIG. 8, and the line width and the opening size in the honeycomb type nickel mesh are as shown in FIG.

<Photomask 1 for producing electrophotographic photosensitive member>
A square-shaped nickel mesh (trade name: # 1500, manufactured by Kuraba Co., Ltd.) having a line width of 10 μm, an aperture size of 6 μm, and an aperture ratio of 14% is used for producing an electrophotographic photoreceptor. The photomask 1 was obtained.

<Photomasks 2 to 5 for producing an electrophotographic photosensitive member>
Square-shaped nickel meshes having the line width, hole size, and hole area ratio shown in Table 5 were used as photomasks 2 to 5 for producing an electrophotographic photosensitive member, respectively.

<Photomasks 6 to 8 for producing electrophotographic photosensitive member>
The honeycomb type nickel meshes having the line width, the hole size and the hole area ratio shown in Table 5 were used as photomasks 6 to 8 for producing an electrophotographic photosensitive member, respectively.

<Photomask 9 for producing electrophotographic photosensitive member>
The surface of a transparent resin film (trade name: ZEONOR film ZF14-040, manufactured by Optes Co., Ltd.) having a thickness of 40 μm is hydrophilized by corona treatment, and then the photomask 1 is placed on the transparent resin film to a thickness of 100 nm. The square pattern (area ratio of the deposited gold pattern: 64%) was produced by performing the gold deposition. This was designated as a photomask 9 for producing an electrophotographic photosensitive member. The area ratio of the gold pattern deposited on the photomask 9 is 64%. The size of the square pattern of the photomask 9 (corresponding to the aperture size in FIG. 8) is 15 μm.

<Photomasks 10 to 16 for producing electrophotographic photosensitive member>
In the production of the photomask 9 for producing an electrophotographic photosensitive member, a square pattern was produced in the same manner except that the photomasks 2 to 8 were used as the photomask covered on the transparent resin film at the time of gold deposition. These were designated as photomasks 10 to 16 for producing an electrophotographic photosensitive member, respectively. The area ratio of the gold pattern deposited on the photomask 10 is 36%, the area ratio of the gold pattern deposited on the photomask 11 is 46%, and the area ratio of the gold pattern deposited on the photomask 12 is 64%. The area ratio of the gold pattern deposited on the photomask 13 is 78%, the area ratio of the gold pattern deposited on the photomask 14 is 34%, and the area ratio of the gold pattern deposited on the photomask 15 is 23%. Yes, the area ratio of the gold pattern deposited on the photomask 16 is 62%. Further, the size of the square pattern of the photomask 10 (corresponding to the opening size of FIG. 8) is 15 μm, and the size of the square pattern of the photomask 11 (corresponding to the opening size of FIG. 8) is 17 μm. Yes, the size of the square pattern of the photomask 12 (corresponding to the aperture size of FIG. 8) is 25 μm, and the size of the square pattern of the photomask 13 (corresponding to the aperture size of FIG. 8) is 45 μm. Yes, the size of the honeycomb pattern of the photomask 14 (corresponding to the aperture size of FIG. 9) is 16 μm, and the size of the honeycomb pattern of the photomask 15 (corresponding to the aperture size of FIG. 9) is 16 μm. In addition, the size of the honeycomb pattern of the photomask 16 (corresponding to the aperture size in FIG. 9) is 21 μm.

<Photomask 101 for Electrophotographic Photoconductor Preparation>
A square-type plain weave type stainless steel mesh having a line width of 1000 μm, an aperture size of 1500 μm, and an aperture ratio of 36% was used as a photomask 101 for producing an electrophotographic photosensitive member.

<Photomask 102 for Electrophotographic Photoconductor Preparation>
A square-shaped nickel mesh (trade name: # 1000, manufactured by Kuraba Co., Ltd.) with a line width of 18 μm, an aperture size of 7 μm, and an aperture ratio of 8% is used for producing an electrophotographic photoreceptor. The photomask 102 was obtained.

<Photomask 103 for producing electrophotographic photosensitive member>
Electrophotography of a square nickel mesh (trade name: # 500, manufactured by Kuraba Co., Ltd.) with a line width of 4.5 μm, an aperture size of 46.5 μm, and an aperture ratio of 83%. A photomask 103 for producing a photoconductor was obtained.

<Photomasks 104 to 106 for producing an electrophotographic photosensitive member>
In producing the photomask 9 for producing the electrophotographic photosensitive member, a square pattern was produced in the same manner except that the photomasks 101 to 103 were used as the photomasks covered on the transparent resin film at the time of gold deposition. These were designated as photomasks 104 to 106 for producing an electrophotographic photosensitive member. The area ratio of the gold pattern deposited on the photomask 104 is 22%, the area ratio of the gold pattern deposited on the photomask 105 is 8%, and the area ratio of the gold pattern deposited on the photomask 106 is 83%. . Further, the size of the square pattern of the photomask 104 (corresponding to the opening size of FIG. 8) is 1500 μm, and the size of the square pattern of the photomask 105 (corresponding to the opening size of FIG. 8) is 7 μm. In addition, the size of the square pattern of the photomask 106 (corresponding to the aperture size in FIG. 8) is 46.5 μm.

(Electrophotographic photoreceptor)
<Electrophotographic photoreceptor 1>
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a thickness of 0.75 mm was used as a support (conductive support).

  Next, the undercoat layer coating solution (containing 5% by mass of polyamide) was prepared by dissolving in polyamide (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) in methanol. This undercoat layer coating solution was dip-coated on a support, and the resulting coating film was dried to form an undercoat layer having a thickness of 0.5 μm.

  Next, 3.5 parts by mass of a hydroxygallium phthalocyanine crystal (charge generation material) having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα, 1 part by weight of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 120 parts by weight of cyclohexanone are placed in a sand mill using glass beads having a diameter of 1 mm, followed by a dispersion treatment for 3 hours. Then, 120 parts by mass of ethyl acetate was added thereto to prepare a charge generation layer coating solution. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

  Next, the charge transport layer coating solution prepared in the same manner as in Example 1-3 was dip-coated on the charge generation layer, and the obtained coating film was dried at 125 ° C. for 80 minutes, whereby the film thickness was 20 μm. A charge transport layer was formed. The electrophotographic photoreceptor thus obtained was designated as an electrophotographic photoreceptor 1. A plurality of electrophotographic photoreceptors 1 were produced.

<Electrophotographic photoreceptor 2>
60 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayalad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.03 μm before dispersion treatment, 2 as a photopolymerization initiator , 2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) 20 parts by mass and 400 parts by mass of methanol were placed in a sand mill and dispersed for 66 hours to obtain a surface layer. A coating solution was prepared. By dip-coating the coating solution for the surface layer on the charge transport layer of the electrophotographic photoreceptor 1, and irradiating the obtained coating film with ultraviolet rays with a high-pressure mercury lamp so that its hardness is about 0.14 GPa, A surface layer was formed. The electrophotographic photosensitive member thus obtained was designated as an electrophotographic photosensitive member 2. A plurality of electrophotographic photoreceptors 2 were produced. The surface hardness of each electrophotographic photosensitive member 2 was 0.14 GPa, and the film thickness of each surface layer was 3 μm.

<Electrophotographic photoreceptor 3>
One of the electrophotographic photoreceptors 2 is again subjected to photocuring by irradiating the surface with ultraviolet rays with a high-pressure mercury lamp, and then post-baking at 130 ° C. for 1 hour, whereby the electrophotographic photoreceptor 3 is obtained. Was made. The surface hardness of the electrophotographic photosensitive member 3 was 0.52 GPa, and the film thickness of the surface layer was 3 μm.

<Electrophotographic photoreceptor 4>
A photomask 1 for producing an electrophotographic photosensitive member is cut into a width of 5 cm, and as shown in FIG. 10 (in FIG. 10, 1001 is an electrophotographic photosensitive member and 1002 is a photomask), the electrophotographic photosensitive member 2 is formed. It was wound around the surface of one of them, and again was irradiated with ultraviolet rays with a high-pressure mercury lamp and photocured. Next, after peeling off the wound photomask 1, post-baking treatment was performed at 130 ° C. for 1 hour to produce an electrophotographic photosensitive member 4. When the hardness of the surface of the electrophotographic photosensitive member 4 was measured, the hardness of the first portion (low hardness portion) was 0.18 GPa, and the hardness of the second portion (high hardness portion) was 0.48 GPa. The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the part (low hardness part) was 2.7. In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 4, the area ratio of the surface constituted by the second portion (high hardness portion) is 14%. The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photoreceptor 4 penetrated the surface layer.

<Electrophotographic photoreceptors 5-9 and 101-105>
The electrophotographic photosensitive members 5 to 9 and the electrophotographic photosensitive member 4 are the same as the electrophotographic photosensitive member 4 except that the photomask 1 for producing the electrophotographic photosensitive member used in the production of the electrophotographic photosensitive member 4 is changed to the photomask shown in Table 6. 101-105 were produced. The area ratio of the surface composed of the second portion (high hardness portion) in a square region of 1 mm on a side arranged at an arbitrary position on the surface of the surface layers of the electrophotographic photoreceptors 5 to 9 and 101 to 105, and The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the hardness of the first part (low hardness part) on the surfaces of the electrophotographic photosensitive members 5 to 9 and 101 to 105 Table 6 shows the value of the hardness ratio of the two parts (high hardness part). In each of the electrophotographic photosensitive members 5 to 9 and 101 to 105, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer penetrated the surface layer. In each of the electrophotographic photoreceptors 5 to 9 and 101 to 105, the total area ratio of the surface composed of the first portion (low hardness portion) and the surface composed of the second portion (high hardness portion) is 100%.

<Electrophotographic photoreceptor 10>
60 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayalad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.03 μm before dispersion treatment, 2 as a photopolymerization initiator , 2-Dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE651, manufactured by BASF) 20 parts by mass and 400 parts by mass of methanol were placed in a sand mill and dispersed for 66 hours to apply for the surface layer. A liquid was prepared. By dip-coating the coating solution for the surface layer on the charge transport layer of the electrophotographic photoreceptor 1, and irradiating the obtained coating film with ultraviolet rays with a high-pressure mercury lamp so that its hardness is about 0.31 GPa, A surface layer having a thickness of 3 μm was formed to obtain an electrophotographic photosensitive member.

  Next, the photomask 12 for producing the electrophotographic photosensitive member is cut into a width of 5 cm, wrapped around the surface of the electrophotographic photosensitive member as shown in FIG. 10, and again irradiated with ultraviolet rays with a high-pressure mercury lamp to be photocured. It was. Next, after the photomask 12 that had been wound was peeled off, the post-baking process was performed at 130 ° C. for 1 hour to produce the electrophotographic photoreceptor 10. The area ratio of the surface constituted by the second portion (high hardness portion) in a square region having a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 10, and the electrophotographic photosensitive member 10 The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) Table 6 shows the values. Both the first part (low hardness part) and the second part (high hardness part) of the surface layer of the electrophotographic photoreceptor 10 penetrated the surface layer. The total area ratio of the surface constituted by the first portion (low hardness portion) and the surface constituted by the second portion (high hardness portion) on the surface of the electrophotographic photoreceptor 10 was 100%.

<Electrophotographic photoreceptor 11>
An electrophotographic photoreceptor 11 was produced in the same manner as the electrophotographic photoreceptor 2 except that the surface layer coating solution used in the production of the electrophotographic photoreceptor 2 was changed to the surface layer coating solution prepared as follows. . A plurality of electrophotographic photoreceptors 11 were produced.

  60 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.04 μm before dispersion treatment, polytetrafluoroethylene particles (average particles) (Diameter 0.18 μm) 50 parts by mass, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE651, manufactured by BASF) as a photopolymerization initiator, and 400 parts by mass of methanol A portion was placed in a sand mill and dispersed for 66 hours to prepare a surface layer coating solution. The surface hardness of the electrophotographic photoreceptor 11 was 0.14 GPa, and the film thickness of the surface layer was 3 μm.

<Electrophotographic photoreceptor 12>
An electrophotographic photoreceptor 12 was produced in the same manner as the electrophotographic photoreceptor 3, except that the surface layer coating solution used in the production of the electrophotographic photoreceptor 3 was changed to the surface layer coating solution prepared as follows. . The electrophotographic photosensitive member 12 had a surface hardness of 0.52 GPa and a surface layer thickness of 3 μm.

  60 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.04 μm before dispersion treatment, polytetrafluoroethylene particles (average 50 parts by mass of particle size 0.18 μm), 20 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE651, manufactured by BASF) as a photopolymerization initiator, and methanol 400 The coating solution for the surface layer was prepared by putting a mass part into a sand mill and carrying out a dispersion treatment for 66 hours.

<Electrophotographic photoreceptor 13>
A photomask 1 for producing an electrophotographic photosensitive member is cut into a width of 5 cm, wound around one surface of the electrophotographic photosensitive member 11 as shown in FIG. 10, and again irradiated with ultraviolet rays with a high-pressure mercury lamp to be photocured. I let you. Next, after peeling off the wound photomask, post-baking treatment was performed at 130 ° C. for 1 hour to produce an electrophotographic photoreceptor 13. When the surface hardness of the electrophotographic photosensitive member 13 was measured, the hardness of the first portion (low hardness portion) was 0.19 GPa, and the hardness of the second portion (high hardness portion) was 0.48 GPa. The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the part (low hardness part) was 2.5. In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 13, the area ratio of the surface constituted by the second portion (high hardness portion) is 13%. The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photosensitive member 13 penetrated the surface layer.

<Electrophotographic photoreceptors 14 to 27>
The electrophotographic photosensitive members 14 to 27 are formed in the same manner as the electrophotographic photosensitive member 13 except that the photomask 1 for producing the electrophotographic photosensitive member used in the production of the electrophotographic photosensitive member 13 is changed to the photomask shown in Table 7. Produced. The area ratio of the surface composed of the second portion (high hardness portion) in the square region with a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photoreceptors 14 to 27, and electrophotographic photosensitive The hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the second portion (high hardness portion) relative to the hardness of the first portion (low hardness portion) of the surfaces of the bodies 14 to 27 Table 7 shows the hardness ratio values. In each of the electrophotographic photoreceptors 14 to 27, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer penetrated the surface layer. In each of the electrophotographic photoreceptors 14 to 27, the total area ratio of the surface constituted by the first portion (low hardness portion) and the surface constituted by the second portion (high hardness portion) was 100%. It was.

<Electrophotographic photoreceptors 28 and 29>
In the production of the electrophotographic photosensitive member 24, the irradiation intensity of the ultraviolet light after the photomask is wound is increased so that the hardness of the first portion (low hardness portion) and the second portion (high hardness portion) of the surface of the electrophotographic photosensitive member are increased. And the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is changed as shown in Table 7, except that the electrophotographic photosensitive member 24 is changed. In the same manner, electrophotographic photosensitive members 28 and 29 were produced. The area ratio of the surface composed of the second portion (high hardness portion) in the square region of 1 mm on a side arranged at an arbitrary position on the surface layer of the electrophotographic photosensitive members 28 and 29, and electrophotographic photosensitive The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the second part (high hardness part) relative to the hardness of the first part (low hardness part) of the surfaces of the bodies 28 and 29 Table 7 shows the hardness ratio values. In each of the electrophotographic photoreceptors 28 and 29, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer penetrated the surface layer. In each of the electrophotographic photosensitive members 28 and 29, the total area ratio of the surface composed of the first portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. It was.

<Electrophotographic photoreceptor 30>
5 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayalad DPHA, manufactured by Nippon Kayaku Co., Ltd.) A coating solution for the surface layer was prepared by dissolving 20 parts by mass of 14 (compound represented by the above structural formula (14)) in a mixed solvent of 60 parts by mass of ethanol / 15 parts by mass of methyl ethyl ketone. This surface layer coating solution is dip-coated on the charge transport layer of the electrophotographic photoreceptor 1, and the resulting coating film is irradiated with an electron beam so that its hardness is about 0.20 GPa. Formed. The electrophotographic photosensitive member thus obtained was designated as an electrophotographic photosensitive member 30. A plurality of electrophotographic photoreceptors 30 were produced. The electrophotographic photosensitive member 30 had a surface hardness of 0.20 GPa and a surface layer thickness of 3 μm.

<Electrophotographic photoreceptor 31>
In the production of the electrophotographic photosensitive member 30, the electron beam irradiation dose was increased, and then post-baking treatment was performed at 120 ° C. for 1 hour, thereby producing the electrophotographic photosensitive member 31. The surface hardness of the electrophotographic photoreceptor 31 was 0.75 GPa, and the film thickness of the surface layer was 3 μm.

<Electrophotographic photoreceptor 32>
The photomask 1 for producing an electrophotographic photosensitive member was cut into a width of 5 cm, wound around one surface of the electrophotographic photosensitive member 30 as shown in FIG. 10, and again irradiated with an electron beam to be cured with an electron beam. . Next, after the photomask that had been wound was peeled off, the post-baking process was performed at 120 ° C. for 1 hour to produce the electrophotographic photosensitive member 32. When the hardness of the surface of the electrophotographic photosensitive member 32 was measured, the hardness of the first portion (low hardness portion) was 0.20 GPa, and the hardness of the second portion (high hardness portion) was 0.74 GPa. The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the part (low hardness part) was 3.7. In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 32, the area ratio of the surface constituted by the second portion (high hardness portion) is 15%. The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photoreceptor 32 penetrated the surface layer.

<Electrophotographic photosensitive members 33 to 39 and 201 to 203>
The electrophotographic photosensitive members 33 to 39 and the electrophotographic photosensitive member 32 are the same as the electrophotographic photosensitive member 32 except that the photomask 1 for producing the electrophotographic photosensitive member used in the production of the electrophotographic photosensitive member 32 is changed to the photomask shown in Table 8. 201-203 were produced. The area ratio of the surface composed of the second part (high hardness part) in a square area of 1 mm on a side arranged at an arbitrary position on the surface of the surface layers of the electrophotographic photosensitive members 33 to 39 and 201 to 203, and The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the hardness of the first part (low hardness part) of the surfaces of the electrophotographic photoreceptors 33 to 39 and 201 to 203 Table 8 shows the value of the hardness ratio of the second part (high hardness part). In each of the electrophotographic photoreceptors 33 to 39 and 201 to 203, the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer both penetrated the surface layer. In each of the electrophotographic photoreceptors 33 to 39 and 201 to 203, the total area ratio of the surface composed of the first portion (low hardness portion) and the surface composed of the second portion (high hardness portion) is 100%.

<Electrophotographic photoreceptor 40>
In the production of the electrophotographic photosensitive member 34, the irradiation dose of the electron beam after the photomask is wound is increased so that the hardness of the first portion (low hardness portion) and the second portion (high hardness portion) of the surface of the electrophotographic photosensitive member are increased. ), And the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is changed so as to be as shown in Table 8. In the same manner as in Example 34, an electrophotographic photoreceptor 40 was produced. The area ratio of the surface composed of the second portion (high hardness portion) in a square area of 1 mm on a side arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photoreceptor 40, and the electrophotographic photoreceptor 40 The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) Table 8 shows the values. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photoreceptor 40 penetrated the surface layer. The total area ratio of the surface constituted by the first portion (low hardness portion) and the surface constituted by the second portion (high hardness portion) on the surface of the electrophotographic photoreceptor 40 was 100%.

<Electrophotographic photoreceptor 41>
1.25 parts by mass of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) was added to 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H , Manufactured by Nippon Zeon Co., Ltd.) 37.5 parts by mass / 1-propanol 37.5 parts by mass, and then dissolved in a polytetrafluoroethylene particle (trade name: Lubron L-2, Daikin) 25 parts by mass of Kogyo Co., Ltd.) was added, and this was placed in a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA), and 3 times at a pressure of 58.8 MPa (600 kgf / cm ² ). A lubricant dispersion was prepared by performing the dispersion treatment.

  Next, 20 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayalad DPHA, manufactured by Nippon Kayaku Co., Ltd.), Exemplified Compound No. 14 (compound represented by the above structural formula (14)) 80 parts by mass, 45 parts by mass of the lubricant dispersion, 1,6,2 parts by mass of 1,1,2,2,3,3,4-heptafluorocyclopentane Then, 66.7 parts by mass of 1-propanol were mixed and stirred, and then subjected to pressure filtration with a 5 μm membrane filter made of PTFE (polytetrafluoroethylene) to prepare a surface layer coating solution. By using this surface layer coating solution, dip-coating on the charge transport layer of the electrophotographic photoreceptor 1, and irradiating the resulting coating film with an electron beam so that its hardness is about 0.19 GPa, A surface layer was formed. The electrophotographic photoreceptor thus obtained was designated as an electrophotographic photoreceptor 41. A plurality of electrophotographic photoreceptors 41 were produced. The electrophotographic photosensitive member 41 had a surface hardness of 0.19 GPa and a surface layer thickness of 3 μm.

<Electrophotographic photoreceptor 42>
In the production of the electrophotographic photosensitive member 41, the electron beam irradiation dose was increased, and then post-baking treatment was performed at 120 ° C. for 1 hour, whereby the electrophotographic photosensitive member 42 was produced. The electrophotographic photosensitive member 42 had a surface hardness of 0.74 GPa and a surface layer thickness of 3 μm.

<Electrophotographic photoreceptor 43>
The photomask 1 for producing the electrophotographic photosensitive member was cut into a width of 5 cm, wound around one surface of the electrophotographic photosensitive member 41 as shown in FIG. 10, and again irradiated with an electron beam to be cured with an electron beam. . Next, after peeling off the wound photomask, post-baking treatment was performed at 120 ° C. for 1 hour to produce an electrophotographic photoreceptor 43. When the hardness of the surface of the electrophotographic photosensitive member 43 was measured, the hardness of the first portion (low hardness portion) was 0.19 GPa, and the hardness of the second portion (high hardness portion) was 0.75 GPa. The value of the ratio of the hardness of the second part (high hardness part) to the hardness of the part (low hardness part) was 3.9. In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 43, the area ratio of the surface constituted by the second portion (high hardness portion) is 13%. The total area ratio of the surface composed of the portion (low hardness portion) and the surface composed of the second portion (high hardness portion) was 100%. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photosensitive member 43 penetrated the surface layer.

<Electrophotographic photosensitive members 44 to 58, 62 and 301 to 303>
The electrophotographic photoreceptors 44 to 58, 62 are the same as the electrophotographic photoreceptor 43 except that the photomask for producing the electrophotographic photoreceptor used in the production of the electrophotographic photoreceptor 43 is changed to the photomask shown in Table 9. And 301-303 were prepared. Area ratio of the surface composed of the second portion (high hardness portion) in a square region of 1 mm on a side arranged at an arbitrary position on the surface of the surface layers of the electrophotographic photosensitive members 44 to 58, 62 and 301 to 303 And the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the first portion (low hardness portion) of the surfaces of the electrophotographic photosensitive members 44 to 58, 62 and 301 to 303. Table 9 shows values of the ratio of the hardness of the second portion (high hardness portion) to the hardness of). In each of the electrophotographic photoreceptors 44 to 58, 62, and 301 to 303, the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer both penetrated the surface layer. Each of the electrophotographic photoreceptors 44 to 58, 62, and 301 to 303 has a total area of a surface composed of a first portion (low hardness portion) and a surface composed of a second portion (high hardness portion). The rate was 100%.

<Electrophotographic photoreceptor 59>
10 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayalad DPHA, Nippon Kayaku Co., Ltd.) A coating solution for the surface layer was prepared by dissolving 10 parts by mass of 27 (compound represented by the above structural formula (27)) in a mixed solvent of 60 parts by mass of ethanol / 15 parts by mass of methyl ethyl ketone. This surface layer coating solution is dip-coated on the charge transport layer of the electrophotographic photoreceptor 1, and the resulting coating film is irradiated with an electron beam so that its hardness is about 0.10 GPa. Formed. The electrophotographic photoreceptor thus obtained was designated as an electrophotographic photoreceptor 41-2. A plurality of electrophotographic photoreceptors 41-2 were produced. The electrophotographic photoreceptor 41-2 had a surface hardness of 0.10 GPa and a surface layer thickness of 3 μm.

  Next, the photomask 3 for producing the electrophotographic photosensitive member is cut into a width of 5 cm, wound around one surface of the electrophotographic photosensitive member 41-2 as shown in FIG. 10, and again irradiated with an electron beam, Electron beam curing was performed. Next, after the photomask that had been wound was peeled off, a post-baking process was performed at 120 ° C. for 1 hour to produce an electrophotographic photoreceptor 59. The area ratio of the surface composed of the second portion (high hardness portion) in a square area of 1 mm on a side arranged at an arbitrary position on the surface of the surface layer of the electrophotographic photosensitive member 59, and the electrophotographic photosensitive member 59 The hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) Table 9 shows the values. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer of the electrophotographic photoreceptor 59 penetrated the surface layer. The total area ratio of the surface composed of the first portion (low hardness portion) and the surface composed of the second portion (high hardness portion) on the surface of the electrophotographic photosensitive member 59 was 100%.

<Electrophotographic photoreceptors 60, 61 and 63>
In the production of the electrophotographic photosensitive member 59, the irradiation dose of the electron beam after winding the photomask is increased, and the hardness of the first portion (low hardness portion) and the second portion (high hardness portion) of the surface of the electrophotographic photosensitive member are increased. ), And the ratio of the hardness of the second part (high hardness part) to the hardness of the first part (low hardness part) is changed so as to be as shown in Table 9. In the same manner as in 59, electrophotographic photoreceptors 60, 61 and 63 were produced. The area ratio of the surface composed of the second portion (high hardness portion) in the square region with a side of 1 mm arranged at an arbitrary position on the surface layer of the electrophotographic photoreceptors 60, 61 and 63, and the electron The second part (the hardness of the first part (low hardness part), the hardness of the second part (high hardness part), and the hardness of the first part (low hardness part) of the surface of the photoconductor 60, 61 and 63 ( Table 9 shows the value of the hardness ratio of the high hardness portion. In each of the electrophotographic photoreceptors 60, 61 and 63, the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer both penetrated the surface layer. In each of the electrophotographic photoreceptors 60, 61, and 63, the total area ratio of the surface constituted by the first portion (low hardness portion) and the surface constituted by the second portion (high hardness portion) is 100%. Met.

<Electrophotographic photoreceptor 64>
The surface of the electrophotographic photosensitive member 3 was polished with a wrapping tape and roughened to a state of Rz = 0.5 μm, whereby an electrophotographic photosensitive member 64 was produced.

<Electrophotographic photoreceptor 65>
The surface of the electrophotographic photosensitive member 31 was polished with a wrapping tape and roughened to a state of Rz = 0.5 μm, whereby an electrophotographic photosensitive member 65 was produced.

<Electrophotographic photoreceptor 66>
By rotating the electrophotographic photosensitive member 1 while pressing the surface of the electrophotographic photosensitive member 1 against a metal mold having a concave portion on the surface, a rectangular columnar convex portion (the bottom surface of the rectangular column: 6 μm × 6 μm, high The area occupied by the quadrangular prism in a square region having a thickness of 0.2 μm and a side of 1 mm was 14%). This was designated as an electrophotographic photosensitive member 66.

(Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8)
The electrophotographic photoreceptors 2 to 10 and 101 to 105 were evaluated.

<Evaluation of the condition of the cleaning blade>
The electrophotographic photosensitive members 2 to 10 and 101 to 105 are mounted on a GP-215 (trade name) of a monochrome copying machine manufactured by Canon Inc., and 10,000 sheets are printed in an environment of a temperature of 30 ° C./humidity of 80% RH. An image was output and the state of the cleaning blade (blade made of urethane rubber) that contacted (contacted) the electrophotographic photosensitive member (blade curling and blade squeal) was evaluated. Note that GP-215 (trade name) of the monochrome copying machine used for the evaluation has a cleaning means for cleaning the surface of the electrophotographic photosensitive member, and the cleaning means comes into contact with the surface of the electrophotographic photosensitive member. A copier having a blade.

  For both the blade whirl and the blade squeal, B is the case where the blade squeezes and the blade squeaks before outputting 10,000 images, and A is the case where the blade squeaks.

<Evaluation of friction coefficient>
As shown in FIG. 11 after outputting the above 10,000 images, using a surface property measuring machine (trade name: Type 14FW) manufactured by Shinto Kagaku Co., Ltd. under conditions of a vertical load of 30 g and a rubbing speed of 100 mm / min. Then, a blade made of urethane rubber (urethane blade) was brought into contact with the electrophotographic photosensitive member at an angle of 26 °, and a friction coefficient was measured by applying a vertical load. In FIG. 11, 3a is an electrophotographic photosensitive member, 3b is a urethane rubber blade (urethane blade), and 3c is a fastener for the electrophotographic photosensitive member.

<Evaluation of wear amount>
After outputting the above 10,000 images, electrophotography using an ultra-deep shape measuring microscope (trade name: VK-9510) manufactured by Keyence Corporation and an image analyzer (trade name: LuzexAP) manufactured by Nireco Corporation. The amount of wear on the surface of the photoreceptor was measured.

  Table 10 shows the results of Examples 4-1 to 4-6 and Comparative examples 4-1 to 4-8.

  In Examples 4-1 to 4-6, the value of the ratio of the hardness of the second part to the hardness of the first part is in the range of 1.2 to 30, and the area ratio of the surface constituted by the second part is 10 Since it is in the range of ˜80%, the coefficient of friction was low even after outputting 10,000 images.

  In Comparative Examples 4-1 and 4-2, since the first part and the second part were not formed, the friction reduction effect due to the height difference between the first part and the second part could not be obtained.

  In Comparative Example 4-3, since the value of the ratio of the hardness of the second part to the hardness of the first part is less than 1.2, the level difference between the first part and the second part cannot be sufficiently obtained, A sufficient friction reducing effect was not obtained.

  In Comparative Example 4-5, since the area ratio of the surface formed by the second portion is less than 10%, the contact area with the cleaning blade that is the contact member is reduced, so that the second portion that is a convex portion However, it could not withstand the load of the contact member and was easily destroyed, and the friction reduction effect was not sufficiently obtained.

  In Comparative Examples 4-6 and 4-8, since the area ratio of the surface constituted by the second portion is more than 80%, the contact area with the cleaning blade that is the contact member is increased, and the friction reduction effect is sufficient. It was not obtained.

  In Comparative Examples 4-4 and 4-7, the area ratio of the surface composed of the second part is less than 10%, and the area ratio of the surface composed of the second part is more than 80%. The friction reduction effect could not be obtained sufficiently.

(Examples 4-7 to 4-23 and Comparative Examples 4-9 to 4-10)
The electrophotographic photoreceptors 11 to 29 were evaluated in the same manner as in Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8.

  Table 11 shows the results of Examples 4-7 to 4-23 and Comparative examples 4-9 to 4-10.

(Examples 4-24 to 4-32 and Comparative Examples 4-11 to 4-15)
The electrophotographic photoreceptors 30 to 40 and 201 to 203 were evaluated in the same manner as in Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8. However, the electrophotographic apparatus used for the evaluation was changed from GP-215 (trade name) of a monochrome copier manufactured by Canon Inc. to GP-405 (product name) of a monochrome copier manufactured by Canon Inc. Also, the number of output images was changed from 10,000 to 20000. GP-405 (trade name) is also a copier having a cleaning unit for cleaning the surface of the electrophotographic photosensitive member, and a cleaning blade that contacts the surface of the electrophotographic photosensitive member.

  Table 12 shows the results of Examples 4-24 to 4-32 and Comparative examples 4-11 to 4-15.

(Examples 4-33 to 4-51 and Comparative Examples 4-16 to 4-25)
The electrophotographic photoreceptors 41 to 63 and 301 to 303 were evaluated in the same manner as in Examples 4-24 to 4-32 and Comparative Examples 4-11 to 4-15.

  Table 13 shows the results of Examples 4-33 to 4-51 and Comparative examples 4-16 to 4-25.

Claims (12)

A first portion and a second portion having different hardnesses, and the hardness (H ₁ [GPa]) of the first portion by a continuous stiffness measurement method is 0.01 to 3 GPa, and the continuous stiffness measurement method of the first portion The ratio (H ₂ / H ₁ ) of the ratio of hardness (H ₂ [GPa]) according to the continuous stiffness measurement method of the second portion to the hardness (H ₁ [GPa]) of the second part is 1.2 to 30. And
The surface of the membrane has a surface composed of the first portion and a surface composed of the second portion;
Each of the first portion and the second portion continuously extends in the film thickness direction of the film by 75% or more of the film thickness;
In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the membrane, the area ratio of the surface constituted by the second portion is 10 to 80%, and the first portion is constituted. And a total area ratio of the surface constituted by the second portion is 50% or more.   The membrane of claim 1, wherein the second portion penetrates the membrane.   In a square region having a side of 1 mm arranged at an arbitrary position on the surface of the film, a total area ratio of a surface constituted by the first portion and a surface constituted by the second portion is 100%. Item 3. The membrane according to Item 1 or 2.   The film | membrane of any one of Claims 1-3 in which the surface comprised by the said 1st part is surrounded by the surface comprised by the said 2nd part in the surface of the said film | membrane.   The film according to any one of claims 1 to 4, wherein the film contains a lubricant.   An apparatus comprising: a member including the film according to claim 1; and a contact member capable of contacting the surface of the film with a relative speed.   The apparatus according to claim 6, wherein the contact member is a urethane rubber member.   An electrophotographic photosensitive member having the film according to claim 1 as a surface layer. In a process cartridge that integrally supports an electrophotographic photosensitive member and a cleaning means for cleaning the surface of the electrophotographic photosensitive member, and is detachable from an electrophotographic apparatus main body,
9. The process cartridge according to claim 8, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 8, and the cleaning means has a cleaning blade that contacts the surface of the electrophotographic photosensitive member.   The process cartridge according to claim 9, wherein the cleaning blade is a urethane rubber member. In an electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, a transferring unit, and a cleaning unit for cleaning the surface of the electrophotographic photosensitive member.
9. The electrophotographic apparatus according to claim 8, wherein the electrophotographic photoreceptor is the electrophotographic photoreceptor according to claim 8, and the cleaning unit has a cleaning blade that contacts the surface of the electrophotographic photoreceptor.   The electrophotographic apparatus according to claim 11, wherein the cleaning blade is a urethane rubber member.

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