JP5921355B2 - Surface processing method of electrophotographic photosensitive member, and manufacturing method of electrophotographic photosensitive member having uneven shape on surface - Google Patents

Description

  The present invention relates to a surface processing method for an electrophotographic photosensitive member, and a method for producing an electrophotographic photosensitive member having an uneven shape on the surface.

  For the purpose of improving the wear resistance of an organic electrophotographic photoreceptor containing an organic photoconductive substance (hereinafter simply referred to as “electrophotographic photoreceptor”), a curable resin is contained in the surface layer of the electrophotographic photoreceptor. There is technology.

  However, increasing the abrasion resistance of the electrophotographic photosensitive member tends to cause image flow. Image flow refers to deterioration of the material used for the surface layer of the electrophotographic photosensitive member due to acidic gas such as ozone and nitrogen oxide generated by charging the electrophotographic photosensitive member. This is a problem that occurs when moisture is adsorbed on the surface and the surface resistance of the electrophotographic photosensitive member decreases.

  As a technique for suppressing the image flow, Patent Document 1 discloses a technique for controlling the temperature of the mold member and the electrophotographic photosensitive member when transferring the uneven shape of the mold member to the surface of the electrophotographic photosensitive member. .

JP 2007-233354 A

  In recent years, installation locations of electrophotographic apparatuses have been expanded globally, and improvement in heat resistance during distribution of electrophotographic apparatuses and electrophotographic photoreceptors is required.

  As a result of the study by the present inventors, the electrophotographic photosensitive member having a concavo-convex shape on the surface described in Patent Document 1 is not sufficiently stable in the concavo-convex shape, and is placed in a high-temperature environment during distribution ( For example, when the temperature inside the physical distribution container rises), it was found that the uneven shape tends to change in a flattening direction. Then, if the uneven shape of the electrophotographic photosensitive member changes in a flattening direction, image flow tends to occur.

  An object of the present invention is to provide a method for processing a surface of an electrophotographic photosensitive member by transferring the concave / convex shape of a mold member onto the surface of the electrophotographic photosensitive member. An object of the present invention is to provide a surface processing method for a photoreceptor. Another object of the present invention is to provide a method for producing an electrophotographic photosensitive member having a concavo-convex shape on the surface, using the surface processing method for the electrophotographic photosensitive member.

  The above object is achieved by the present invention described below.

The present invention pressurizes a mold member having an uneven shape on the surface of an electrophotographic photosensitive member having a charge transport layer containing a thermoplastic resin and a surface layer containing a curable resin formed on the charge transport layer. An uneven shape transfer step for transferring the uneven shape of the mold member to the surface of the electrophotographic photosensitive member by bringing it into contact;
A heat treatment step of heat-treating the electrophotographic photosensitive member having a concavo-convex shape transferred to the surface under the following conditions A and B by the concavo-convex shape transfer step;
The present invention relates to a surface processing method for an electrophotographic photosensitive member.
A: When the temperature of the heat treatment of the electrophotographic photosensitive member is Ta (° C.) and the glass transition temperature of the charge transport layer is Tg (° C.), Tg−20 ≦ Ta ≦ Tg + 20 is satisfied.
B: The heat treatment time of the electrophotographic photosensitive member is 2 minutes or more.

  The present invention also includes a step of processing the surface of the electrophotographic photosensitive member using the surface processing method described above, and forming a concavo-convex shape on the surface of the electrophotographic photosensitive member. The present invention relates to a method for producing an electrophotographic photosensitive member.

  According to the present invention, in a method for processing the surface of an electrophotographic photosensitive member by transferring the concave / convex shape of a mold member onto the surface of the electrophotographic photosensitive member, an electrophotographic film capable of forming a concave / convex shape having high stability in a high temperature environment. It is possible to provide a method for producing an electrophotographic photosensitive member having a concavo-convex shape on the surface using the surface processing method of the photosensitive member and the surface processing method of the electrophotographic photosensitive member.

It is a figure which shows the outline of the output chart of "Fischer scope H100V" (made by Fischer). It is a figure which shows an example of the output chart of "Fischer scope H100V" (made by Fischer). It is a figure which shows an example of the laminated constitution of the electrophotographic photoreceptor of this invention. An example of an apparatus (pressure contact concavo-convex shape transfer device) for transferring the concavo-convex shape of the mold member to the surface of the electrophotographic photosensitive member by bringing a mold member having the concavo-convex shape into pressure contact with the surface of the electrophotographic photosensitive member is shown. FIG. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member. It is a figure which shows the uneven | corrugated shape of the type | mold member used in the Example.

The surface processing method of the electrophotographic photosensitive member of the present invention transfers the uneven shape of the mold member to the surface of the electrophotographic photosensitive member by bringing the mold member having the uneven shape into pressure contact with the surface of the electrophotographic photosensitive member. An uneven shape transfer step. As the electrophotographic photosensitive member, an electrophotographic photosensitive member having a charge transport layer containing a thermoplastic resin and a surface layer containing a curable resin formed on the charge transport layer is used. And after the uneven | corrugated shape transfer process, it has further the heat processing process which heat-processes the electrophotographic photoreceptor by which the uneven | corrugated shape was transferred on the surface on the following conditions A and B.
A: When the temperature of the heat treatment of the electrophotographic photosensitive member is Ta (° C.) and the glass transition temperature of the charge transport layer is Tg (° C.), Tg−20 ≦ Ta ≦ Tg + 20 is satisfied.
B: The heat treatment time of the electrophotographic photosensitive member is 2 minutes or more.

  The present inventors consider the reason why the unevenness formed on the surface of the electrophotographic photosensitive member in the surface processing method of the electrophotographic photosensitive member of the present invention increases the stability in a high temperature environment as follows. .

  In the present invention, by pressing a mold member having an uneven shape on the surface of the electrophotographic photosensitive member under pressure, the uneven shape of the mold member is transferred to the surface of the electrophotographic photosensitive member. When the uneven shape is formed on the surface of the electrophotographic photosensitive member in this manner, the uneven shape corresponding to the uneven shape is also formed on the surface of the charge transport layer (interface between the surface layer and the charge transport layer). The uneven shape on the surface of the electrophotographic photosensitive member is held by the uneven shape formed on the surface of the charge transport layer. Generally, since the curable resin contained in the surface layer has a three-dimensional network structure, it is easily elastically deformed, and the thermoplastic resin contained in the charge transport layer does not have a three-dimensional network structure. It has the property of being easily plastically deformed. By pressing a mold member having a concavo-convex shape on the surface of the electrophotographic photosensitive member, the surface layer is elastically deformed, and the charge transport layer below it is plastically deformed to form a concavo-convex shape on the surface of the charge transport layer. Is done. Since the deformation of the surface layer is mainly an elastic deformation, the surface layer has a force to return to a flat surface, but the charge transport layer that is plastically deformed has an uneven shape on its surface. Since the surface layer adheres to the surface of the charge transport layer, the surface layer remains deformed along the irregular shape of the surface of the charge transport layer. The surface of the body is considered to have an uneven shape. That is, it is considered that the uneven shape on the surface of the electrophotographic photosensitive member is held by the uneven shape on the surface of the charge transport layer.

  When the electrophotographic photosensitive member having the concavo-convex shape is heated to near the glass transition temperature of the charge transport layer, the thermoplastic resin of the charge transport layer starts to soften, and the power to maintain the concavo-convex shape of the charge transport layer is increased. It drops significantly. Then, it is considered that the force to return the surface layer to the above flatness wins and the uneven shape on the surface of the electrophotographic photosensitive member is easily returned to the flat surface.

  As a result of the study, the inventors have formed an uneven shape on the surface of the electrophotographic photosensitive member, and then performed heat treatment assuming a high-temperature environment during distribution, so that the uneven shape of the surface of the electrophotographic photosensitive member is previously obtained. It has been found that the uneven shape on the surface of the electrophotographic photoreceptor thereafter is stabilized by deforming the charge transport layer and the surface layer to some extent in the flattening direction. In other words, an electrophotographic photosensitive member having a concavo-convex shape on the surface is preliminarily heated under the above conditions A and B assuming a high temperature environment at the time of distribution, and thereafter heated (temperature increase at the time of distribution). However, the uneven shape on the surface of the electrophotographic photosensitive member is not easily deformed in a flattening direction.

  As shown in the above condition A, the temperature (Ta) of the heat treatment of the electrophotographic photosensitive member is set from the glass transition temperature (Tg) of the charge transport layer. If Ta <Tg-20, the thermoplastic resin is less likely to be softened, and the force of the charge transport layer that retains the uneven shape on the surface of the electrophotographic photosensitive member is superior to the force of returning the surface layer to the flat surface. It is thought that it has remained. That is, sufficient heat treatment is not performed. Therefore, when an electrophotographic photosensitive member having a concavo-convex shape on the surface is placed in a high-temperature environment at the time of distribution, the concavo-convex shape on the surface of the electrophotographic photosensitive member tends to return flat. On the other hand, if Tg + 20 <Ta, the temperature of the heat treatment is too high, so the softening of the charge transport layer becomes remarkable, and the uneven shape formed on the surface of the electrophotographic photosensitive member in the uneven shape transfer process is flattened by the heat treatment. Go back to too much.

  More preferably, Ta (° C.) and Tg (° C.) in the condition A satisfy Tg−19 ≦ Ta ≦ Tg + 19, and the uniformity of the plurality of uneven shapes formed on the surface of the electrophotographic photosensitive member is Increase more. When Ta <Tg, it is possible to form a concavo-convex shape having higher stability in a high temperature environment. More preferably, Tg-19 ≦ Ta ≦ Tg + 14.

  The glass transition temperature (Tg) of the charge transport layer is determined by the type and molecular weight of the binder resin constituting the charge transport layer, the type of the charge transport material, the mixing mass ratio of the resin and the charge transport material, and the like. In the present invention, a range of 50 ≦ Tg ≦ 150 is preferable. More preferably, 60 ≦ Tg ≦ 100 is satisfied.

  The glass transition temperature of the charge transport layer can be measured using a differential scanning calorimeter (DSC), for example, a thermal analyzer such as “SSC5200H” manufactured by SII Nanotechnology.

  Specifically, only the film of the charge transport layer (applied directly on the aluminum rough tube or the sheet) is peeled off and the sampled material is put into a measuring pan or the like and placed in the furnace of the DSC apparatus. Measurement is performed by scanning the measurement temperature from 30 ° C. to 300 ° C. at a rate of temperature increase of 5 ° C./min. The glass transition temperature is determined from the obtained differential scanning calorimetry curve.

  Further, as shown in the condition B, the heat treatment time of the electrophotographic photosensitive member is 2 minutes or more. If it is less than 2 minutes, the thermoplastic resin is not sufficiently heated, so that the softening of the thermoplastic resin is difficult to occur, and the charge transport layer that retains the uneven shape on the surface of the electrophotographic photosensitive member by the force of returning to the flat surface layer. It is thought that the power of is still winning. That is, sufficient heat treatment is not performed. Therefore, when an electrophotographic photosensitive member having a concavo-convex shape on the surface is placed in a high-temperature environment at the time of distribution, the concavo-convex shape on the surface of the electrophotographic photosensitive member tends to return flat. More preferably, the heat treatment time of the electrophotographic photosensitive member is 5 minutes or more, and the heat treatment is performed on the entire electrophotographic photosensitive member, thereby improving the stability of the uneven shape. The heating time of the electrophotographic photosensitive member may satisfy the above-described heating time (2 minutes or more), and even if the heating time is further increased, the effect of the present invention can be obtained. Preferably, the heat treatment time of the electrophotographic photosensitive member is 2 minutes or more and 48 hours or less, more preferably 5 minutes or more and 2 hours or less (120 minutes or less). The heat treatment time under the condition B is a time during which the surface temperature of the electrophotographic photosensitive member is in the range of Tg−20 ≦ Ta ≦ Tg + 20.

  In the present invention, for example, heating by an oven, microwave heating, electromagnetic wave heating such as high frequency dielectric heating, or the like is used as the heat treatment, and the temperature or the like is set so as to satisfy the above condition A. The temperature of the surface of the electrophotographic photosensitive member is measured by bringing a temperature sensor such as a thermocouple into contact with the surface of the electrophotographic photosensitive member. A non-contact temperature sensor such as a radiation thermometer may be used.

  In the electrophotographic photoreceptor surface processing method of the present invention, it is preferable to have a cooling step for cooling the electrophotographic photoreceptor between the concavo-convex shape transfer step and the heat treatment step. In this cooling step, cooling until the temperature of the electrophotographic photosensitive member is less than Tg-20 is preferable because the effects of the present invention can be stably obtained.

<Electrophotographic photoconductor>
An outline of a preferred structure of the electrophotographic photosensitive member in the present invention is shown in FIG. In the electrophotographic photosensitive member shown in FIG. 3, 21 is a support, 22 is an undercoat layer, 23 is a charge generation layer, 24 is a charge transport layer, and 25 is a surface layer.

  The support used in the present invention is preferably a conductive one (conductive support). Examples of the material of the support include metals or alloys such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, aluminum alloy, and stainless steel. In addition, a metal support or a resin support having a film formed by vacuum deposition of aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can also be used. In addition, a support obtained by impregnating plastic or paper with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, or a support containing a conductive resin can also be used. Examples of the shape of the support include a cylindrical shape, a belt shape, and a sheet shape, and a cylindrical shape is preferable.

  The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, etc. for the purpose of suppressing interference fringes due to scattering of laser light.

  A conductive layer may be provided between the support and the undercoat layer or charge generation layer, which will be described later, for the purpose of suppressing interference fringes due to scattering of a laser or the like and covering the scratches on the support.

  The conductive layer can be formed by applying a coating solution for a conductive layer obtained by dispersing carbon black, a conductive pigment, a resistance adjusting pigment or the like together with a binder resin, and drying the obtained coating film. it can. A compound that is cured and polymerized by heating, ultraviolet irradiation, radiation irradiation, or the like may be added to the conductive layer coating solution. A conductive layer in which a conductive pigment or a resistance adjusting pigment is dispersed tends to have a roughened surface.

  Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less, more preferably 1 μm or more and 35 μm or less, and more preferably 5 μm or more and 30 μm or less. The film thickness of the conductive layer is preferably from 0.1 μm to 50 μm, more preferably from 0.5 μm to 40 μm, and even more preferably from 1 μm to 30 μm.

  Examples of the binder resin used for the conductive layer include styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl compound polymers such as vinylidene fluoride and trifluoroethylene, copolymers, polyvinyl alcohol resins, polyvinyl Examples include acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  Examples of the conductive pigment and the resistance adjusting pigment include particles of metals (alloys) such as aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, and those obtained by vapor deposition on the surfaces of plastic particles. Alternatively, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, indium oxide doped with tin, or metal oxide particles of tin oxide doped with antimony or tantalum may be used. These may be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion.

  Between the support or conductive layer and the charge generation layer, for the purpose of improving the adhesion of the charge generation layer, improving coating properties, improving the charge injection from the support, and protecting the charge generation layer from electrical breakdown An undercoat layer (intermediate layer) having a barrier function or an adhesive function may be provided.

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

  As the resin used for the undercoat layer, polyvinyl alcohol resin, poly-N-vinylimidazole, polyethylene oxide resin, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide resin, N-methoxymethylated 6 nylon resin, co-polymer Examples thereof include polymerized nylon resin, phenol resin, polyurethane resin, epoxy resin, acrylic resin, melamine resin, and polyester resin.

  The undercoat layer may further contain metal oxide particles, and examples thereof include particles containing titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide. The metal oxide particles may be metal oxide particles in which the surface of the metal oxide particles is treated with a surface treatment agent such as a silane coupling agent.

  Examples of the solvent used for the coating solution for the undercoat layer include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, and organic solvents such as aromatic compounds. Can be mentioned. The thickness of the undercoat layer is preferably 0.05 μm or more and 30 μm or less, and more preferably 1 μm or more and 25 μm or less. The undercoat layer may further contain organic resin fine particles and a leveling agent.

  Next, the charge generation layer will be described. The charge generation layer can 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 the obtained coating film. The charge generation layer may be a vapor generation film of a charge generation material.

  Examples of charge generation materials used in the charge generation layer include azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiapyrylium salts, triphenylmethane dyes, quinacridone pigments, azulenium salt pigments, Examples include cyanine dyes, anthanthrone pigments, pyranthrone pigments, xanthene dyes, quinoneimine dyes, and styryl dyes. These charge generation materials may be used alone or in combination of two or more. Among these charge generation materials, phthalocyanine pigments and azo pigments are preferable from the viewpoint of sensitivity, and phthalocyanine pigments are more preferable.

  Among phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine exhibit excellent charge generation efficiency. Furthermore, among the hydroxygallium phthalocyanines, from the viewpoint of sensitivity, the crystal form of the Bragg angle 2θ in CuKα characteristic X-ray diffraction has strong peaks at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 °. A hydroxygallium phthalocyanine crystal is more preferable.

  Examples of the binder resin used for the charge generation layer include polymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol resin, Examples include polyvinyl acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  The mass ratio of the charge generation material and the binder resin is preferably in the range of 1: 0.3 to 1: 4.

  Examples of the dispersion treatment method include a method using a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill, and the like.

  Examples of the solvent used in the coating solution for the charge generation layer include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, and aromatic compounds.

  Next, the charge transport layer will be described. The charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a thermoplastic resin in a solvent to form a coating film, and then drying the obtained coating film. be able to.

  Examples of the charge transport material used in the charge transport layer include carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, and the like, triphenylmethane compounds, pyrazoline compounds, styryl compounds, stilbene compounds. Etc.

  Examples of the thermoplastic resin used for the charge transport layer include acrylic ester, methacrylic ester, polyvinyl alcohol resin, polyvinyl acetal resin, polycarbonate resin, and polyester resin. A polycarbonate resin or a polyester resin is preferable. Solvents used in the charge transport layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aromatic hydrocarbon solvents, etc. Is mentioned.

  The thickness of the charge transport layer is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 40 μm or less.

  The surface layer contains a curable resin. Examples of the curable resin include a curable phenolic resin, a curable melamine resin, a curable epoxy resin, a curable acrylic resin, and a curable methacrylic resin. A curable acrylic resin or a curable methacrylic resin is preferable. . The curable acrylic resin and curable methacrylic resin are preferably resins obtained by polymerizing a charge transporting compound having an acryloyloxy group or a methacryloyloxy group. In addition, when using a charge transporting compound having an acryloyloxy group or a methacryloyloxy group, a polyfunctional monomer (a compound having two or more chain polymerizable functional groups in the same molecule and not having a charge transporting ability) ) May be used in combination. Examples of the polyfunctional monomer include trimethylolpropane triacrylate (product name: Miramer M300, manufactured by Toyo Chemicals Corporation), trimethylolpropane trimethacrylate (product name: Miramer M301, manufactured by Toyo Chemicals Corporation), and the like.

  Examples of the reaction to be cured (polymerized) include radical polymerization, ionic polymerization, thermal polymerization, photopolymerization, radiation polymerization (electron beam polymerization), plasma CVD method, and photo CVD method.

  The surface layer can be formed by applying a surface layer coating solution obtained by dissolving a resin in an organic solvent to form a coating film and drying the resulting coating film.

  The thickness of the surface layer is preferably 0.1 μm or more and 30 μm or less. Further, it is more preferably 0.5 μm or more and 15 μm or less. Examples of the solvent used in the surface layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aromatic compounds, and the like.

  In addition, the surface layer of the electrophotographic photosensitive member contains a lubricant such as conductive particles, silicone oil, wax, fluorine atom-containing resin particles such as polytetrafluoroethylene particles, silica particles, alumina particles, and boron nitride. Also good.

  Various additives can be added to each layer of the electrophotographic photoreceptor of the present invention. Additives include deterioration inhibitors such as antioxidants and UV absorbers, coatability improvers such as leveling agents, organic resin particles such as fluorine atom-containing resin particles and acrylic resin particles, silica, titanium oxide, Examples thereof include inorganic particles such as alumina.

  When applying the coating liquid for each of the above layers, for example, a coating method such as a dip coating method (dip coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, or a blade coating method should be used. Can do.

  The present invention includes a concavo-convex shape transfer step of transferring the concavo-convex shape of the mold member to the surface of the electrophotographic photosensitive member by bringing a mold member having the concavo-convex shape into pressure contact. From the viewpoint of transferring the uneven shape of the mold member to the electrophotographic photosensitive member, the elastic deformation rate is important. From the viewpoint of performing the uneven shape transfer step described above, the elastic deformation rate of the surface of the electrophotographic photosensitive member is preferably 45 to 65%. When the elastic deformation rate is within this range, it is possible to efficiently form a concavo-convex shape on the surface of the electrophotographic photosensitive member.

  The elastic deformation rate of the surface of the electrophotographic photosensitive member can be determined based on a measurement method defined by a universal hardness test. The universal hardness test (Martens hardness test) is a measurement method defined by ISO 14577 (JIS Z 2255: 2003). The surface of the electrophotographic photosensitive member can be measured using a microhardness measuring device (trade name: Fischerscope H100V, manufactured by Fischer) in an environment of a temperature of 25 ° C. and a humidity of 50% RH. A load is applied with a diamond indenter with a face angle of 136 ° at the tip of the square pyramid, the indenter is pushed into the surface of the electrophotographic photosensitive member to be measured, and the indentation depth in the state where the indenter is loaded is electrically detected. Thus, the elastic deformation rate can be calculated.

  The final load (final load) continuously applied to the diamond indenter was 6 mN, and the time during which the final load 6 mN was applied to the indenter (retention time) was 0.1 second. The measurement points were 273 points. The holding time at each measurement point was also 0.1 seconds.

  An outline of the output chart of the “Fisherscope H100V” is shown in FIG. FIG. 2 shows an example of an output chart of “Fischer Scope H100V” when the electrophotographic photosensitive member of the present invention is a measurement object. 1 and 2, the vertical axis represents the load F (mN) applied to the indenter, and the horizontal axis represents the indentation depth h (μm). In FIG. 1, the load F applied to the indenter is increased stepwise to maximize the load (from point A to point B), and then the load is decreased stepwise (from point B to point C). Shows the results. FIG. 2 shows the results when the load F applied to the indenter is increased stepwise to finally set the load to 6 mN, and then the load is decreased stepwise.

  In FIG. 2, the universal hardness value (HU) can be obtained from the indentation depth of the indenter when a final load of 6 mN is applied to the indenter by the following formula. In the following formula, HU means universal hardness (HU), Ff means the final load, Sf means the surface area of the indented portion when the final load is applied, and hf is the final value. It means the indentation depth of the indenter when a load is applied.

  The elastic deformation rate is the amount of work (energy) performed by the indenter with respect to the measurement target (electrophotographic photosensitive member surface), that is, the energy due to the increase or decrease of the load with respect to the measurement target (electrophotographic photosensitive member surface). It can be obtained from the change of. Specifically, a value (We / Wt) obtained by dividing the elastic deformation work We by the total work Wt is the elastic deformation rate. The total work Wt is the area of the region surrounded by A-B-D-A in FIG. 1, and the elastic deformation work We is the area of the region surrounded by C-B-D-C in FIG. It is.

  Next, the uneven shape transfer process will be described.

  FIG. 4 shows an apparatus for transferring the concavo-convex shape of the mold member to the surface of the electrophotographic photosensitive member by press-contacting the mold member having the concavo-convex shape on the surface of the electrophotographic photosensitive member (pressure contact concavo-convex shape transfer device). It is a figure which shows an example.

  According to the press-contact uneven shape transfer apparatus shown in FIG. 4, while rotating the electrophotographic photosensitive member 4-1, which is a workpiece, the mold member 4-2 is continuously brought into contact with the surface (circumferential surface), and the processing is performed. The mold member 4-2 is moved while being pressed. As a result, while rotating the electrophotographic photosensitive member 4-1, the mold member is continuously brought into pressure contact with the surface (circumferential surface), and the concave and convex shape of the mold member is transferred to the surface of the electrophotographic photosensitive member. Irregularities can be formed on the surface of the photographic photoreceptor. Note that the electrophotographic photosensitive member and the mold member may be heated from the viewpoint of efficiently transferring the uneven shape onto the surface of the electrophotographic photosensitive member.

  Moreover, the mold member 4-2 is preferably a mold member composed of three layers including a transfer layer having a convex portion on the surface, a metal layer, and an elastic layer. Further, it may be a mold member composed of two layers, a layer in which a transfer layer and an elastic layer are integrated, and an elastic layer.

  Examples of the material of the pressure member 4-3 include metal, metal oxide, plastic, and glass. Among these, stainless steel (SUS) is preferable from the viewpoint of mechanical strength, dimensional accuracy, and durability. A mold member 4-2 is installed on the upper surface of the pressure member 4-3. In addition, the mold member 4-2 is pressed to a predetermined pressure on the surface of the electrophotographic photosensitive member 4-1 supported by the support member 4-4 by a support member (not shown) on the lower surface side and a pressure system (not shown). Can be contacted. Further, the support member 4-4 may be pressed against the pressure member 4-3 with a predetermined pressure, or the support member 4-4 and the pressure member 4-3 may be pressed against each other.

  The convex part on the surface of the mold member (the surface of the transfer layer) is, for example, a fine surface-processed metal (having a convex part), a surface patterned with a resist, a resin film in which fine particles are dispersed, Examples thereof include a resin film having fine convex portions and a metal coating applied thereto. In addition, the transfer layer is preferably the same as the material forming the above-described convex portions, and aluminum, nickel, various stainless steels, and the like are used. As the metal layer, aluminum, nickel, various stainless steels or the like are used. Examples of the elastic layer include silicon rubber, fluorine rubber, urethane rubber, and the like.

  Note that it is preferable to heat the mold member 4-2 and the electrophotographic photosensitive member 4-1, from the viewpoint of efficiently performing the uneven shape transfer.

  The rotational speed at the time of processing is optimized together with the temperature control and the applied pressure, but is generally adjusted in the range of 1 mm / second to 200 mm / second as the surface moving speed of the electrophotographic photosensitive member. The number of press contact processes can be set as necessary, and may be one or more times.

  Next, as for the convex part of the surface of a type | mold member, the shape by which many convex parts are formed in the plane part is mentioned, for example. Examples of the shape of the convex portion include a circle, an ellipse, a square, a rectangle, a triangle, a quadrangle, and a hexagon when the convex portion is viewed from above. In addition, the cross-sectional shape of the convex portion may be, for example, those having edges such as triangles, quadrilaterals, polygons, corrugations consisting of continuous curves, and some or all of the edges of triangles, quadrilaterals, polygons as curves. Deformed ones are listed.

  Moreover, it is preferable to install an elastic body between the mold member 4-2 and the pressure member 4-3 from the viewpoint of making the pressure on the electrophotographic photosensitive member uniform.

  The longest diameter of the recess formed on the surface of the surface layer is preferably 0.1 μm or more and 100 μm or less. Moreover, the depth of the recess is preferably 0.1 μm or more and 10 μm or less, and the area ratio of the recess is preferably 0.1% or more and 100% or less with respect to the entire surface layer. Observation of the surface of the electrophotographic photosensitive member having a concavo-convex shape formed on the surface, such as the longest diameter, depth, and area ratio of these concave portions, is possible with a commercially available laser microscope, optical microscope, electron microscope, or atomic force microscope. .

  As a laser microscope, for example, ultra-deep shape measurement microscopes VK-8550, VK-9000, VK-9500 (manufactured by Keyence Corporation), surface shape measurement system Surface Explorer SX-520DR type machine (Ryokai System Co., Ltd.) Co., Ltd.), scanning confocal laser microscope OLS3000 (manufactured by Olympus Corporation), and real color confocal microscope Oplitex C130 (manufactured by Lasertec Corporation).

  Examples of the optical microscope include a digital microscope VHX-500, a digital microscope VHX-200 (both manufactured by Keyence Corporation), and a 3D digital microscope VC-7700 (manufactured by OMRON Corporation).

  Examples of the electron microscope include a 3D real surface view microscope VE-9800, a 3D real surface view microscope VE-8800 (both manufactured by Keyence Corporation), a scanning electron microscope conventional / variable pre sure SEM (SII Nanotechnology). And a scanning electron microscope SUPERSCAN SS-550 (manufactured by Shimadzu Corporation).

  Examples of the atomic force microscope include a nanoscale hybrid microscope VN-8000 (manufactured by Keyence Corporation), a scanning probe microscope NanoNavi station (manufactured by SII NanoTechnology Corporation), and a scanning probe microscope SPM-9600 (Shimadzu). (Manufactured by Seisakusho Co., Ltd.).

  Using the above microscope, it is possible to obtain the cross-sectional profile by observing the uneven shape in the measurement visual field at a predetermined magnification, and by analyzing the cross-sectional profile with the image analysis software attached to the microscope. . As an example, a measurement example using an analysis program by the Surface Explorer SX-520DR type machine will be described. The electrophotographic photosensitive member to be measured is placed on the work table, and the tilt is adjusted to adjust the horizontal, and the three-dimensional shape data of the peripheral surface of the electrophotographic photosensitive member is captured in the wave mode. At this time, the magnification of the objective lens may be 50 times or 20 times. Next, the contour data of the surface of the electrophotographic photoreceptor can be displayed using a particle analysis program in the data analysis software.

  Next, FIG. 5 shows an example of a schematic configuration of an electrophotographic apparatus provided with the electrophotographic photosensitive member and the process cartridge of the present invention.

  In FIG. 5, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is driven to rotate at a predetermined peripheral speed in the direction of the arrow about the shaft 2. The peripheral surface of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined positive or negative potential by a charging unit (primary charging unit: charging roller or the like) 3. Next, exposure light (image exposure light) 4 output from exposure means (not shown) such as slit exposure or laser beam scanning exposure is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1. The voltage applied to the charging means 3 may be either a voltage obtained by superimposing an AC component on a DC component or a voltage containing only a DC component.

  The electrostatic latent image formed on the peripheral surface of the electrophotographic photosensitive member 1 is developed with toner contained in the developer of the developing unit 5 to become a toner image. Next, the toner image formed and supported on the peripheral surface of the electrophotographic photosensitive member 1 is sequentially transferred onto a transfer material (such as paper) 7 by a transfer bias from a transfer unit (such as a transfer roller) 6. The transfer material 7 is taken out from a transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1 and fed. .

  The transfer material 7 that has received the transfer of the toner image is separated from the peripheral surface of the electrophotographic photosensitive member 1, introduced into the fixing means 8, and subjected to image fixing to be printed out of the apparatus as an image formed product (print, copy). Out.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by receiving a developer (toner) remaining after the transfer by a cleaning means (cleaning blade or the like) 9. Next, after being subjected to charge removal processing by pre-exposure light 10 from a pre-exposure means (not shown), the electrophotographic photosensitive member 1 is repeatedly used for image formation. As shown in FIG. 5, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  Further, as the transfer unit, for example, an intermediate transfer type transfer unit using a belt-shaped or drum-shaped intermediate transfer member may be employed.

  Among the components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 9, a plurality of components are housed in a container and integrally supported as a process cartridge, and the process cartridge is copied. It may be configured to be detachable from the main body of an electrophotographic apparatus such as a machine or a laser beam printer. In FIG. 5, the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5 and the cleaning unit 9 are integrally supported to form a cartridge, and the electrophotographic apparatus is used by using a guide unit 12 such as a rail of the main body of the electrophotographic apparatus. The process cartridge 11 is detachable from the main body.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “part” means “part by mass”.

Example 1
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a wall thickness of 1 mm was used as a support (conductive support).

Next, 100 parts of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) as a metal oxide are stirred and mixed with 500 parts of toluene, and this is mixed with a silane coupling agent. (Compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8 part was added and stirred for 6 hours. Thereafter, toluene was distilled off under reduced pressure, followed by heating and drying at 130 ° C. for 6 hours to obtain surface-treated zinc oxide particles.

  Next, 15 parts of polyvinyl butyral resin (weight average molecular weight: 40000, trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and blocked isocyanate (trade name: Sumidur 3175, Sumika Bayer Urethane ( 15 parts) was dissolved in a mixed solution of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol. 80.8 parts of the surface-treated zinc oxide particles and 0.8 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to this solution, and this is added to a glass having a diameter of 0.8 mm. Dispersion was performed in a sand mill apparatus using beads in an atmosphere of 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning), cross-linked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-102, manufactured by Sekisui Plastics Co., Ltd.) 5.6 parts of an average primary particle size of 2.5 μm) was added and stirred to prepare an undercoat layer coating solution.

  This undercoat layer coating solution was dip-coated on the aluminum cylinder to form a coating film, and the resulting coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

  Next, 20 parts of a crystalline hydroxygallium phthalocyanine crystal (charge transport material) having strong peaks at 7.4 ° and 28.2 ° of black angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction, the following formula (1) ), 10 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 600 parts of cyclohexanone in a sand mill using 1 mm diameter glass beads. After dispersion for 4 hours, 700 parts of ethyl acetate was added to prepare a coating solution for charge generation layer. This coating solution for charge generation layer was dip coated on the undercoat layer, and the resulting coating film was heated and dried in an oven at a temperature of 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.17 μm. .

  Next, 60 parts of a compound (charge transport material) represented by the following formula (2), 40 parts of a compound (charge transport material) represented by the following formula (3), and polycarbonate resin (Iupilon Z400, Mitsubishi Engineering Plastics ( The charge transport layer coating solution was prepared by dissolving 100 parts) in a mixed solvent of 600 parts monochlorobenzene and 200 parts methylal. The charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was dried by heating in an oven at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

  In order to measure the Tg of the charge transport layer, the same charge transport layer coating solution was directly applied on the same aluminum cylinder under the same conditions and dried to form a charge transport layer. Thereafter, the charge transport layer was peeled off from the aluminum cylinder, folded and put into an aluminum pan for differential scanning calorimetry (DSC) measurement, and covered.

  This sample for DSC measurement is installed in a DSC measurement apparatus manufactured by Seiko Electronics Industry Co., Ltd., and measurement is performed by scanning the measurement temperature from 30 ° C. to 300 ° C. at a temperature increase rate of 5 ° C./min. The glass transition temperature (Tg) was determined from the obtained differential scanning calorimetry curve. Tg was 69 ° C.

  Next, 30 parts of a compound represented by the following formula (4) (a hole transporting compound having a chain polymerizable functional group), 35 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane ( Product name: Zeorora H, manufactured by Nippon Zeon Co., Ltd.), 1-propanol 35 parts, and fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) 0.09 parts may be mixed and stirred well. did. This was filtered with a polyflon filter (trade name: PF-06, manufactured by Advantech Toyo Co., Ltd.) to prepare a surface layer coating solution.

  This coating solution for surface layer was dip coated on the charge transport layer to form a coating film, and the obtained coating film was dried in an oven at a temperature of 50 ° C. for 10 minutes in the atmosphere. Thereafter, in a nitrogen atmosphere, the coating film was irradiated with an electron beam for 1.6 seconds while rotating the support (object to be irradiated) at 200 rpm under conditions of an acceleration voltage of 150 kV and a beam current of 3.0 mA. Subsequently, in a nitrogen atmosphere, the coating film was heated for 30 seconds until the temperature of the coating film reached 25 ° C. from 25 ° C. to heat the coating film. In addition, when the absorbed dose of the electron beam at this time was measured, it was 15 kGy. Moreover, the oxygen concentration from electron beam irradiation to heat treatment under a nitrogen atmosphere was 15 ppm or less. Next, in the air, the coating film was naturally cooled until the temperature reached 25 ° C., and heat treatment was performed for 30 minutes under the condition that the temperature of the coating film reached 100 ° C. in the atmosphere to form a surface layer having a thickness of 5 μm.

  In this manner, an electrophotographic photosensitive member before forming a concavo-convex shape on the surface (an electrophotographic photosensitive member before forming the concavo-convex shape) was produced.

  Next, a mold member was installed in the press-contact uneven shape transfer apparatus having a configuration generally shown in FIG. As the mold member, an elastic layer (silicone rubber), a metal layer (stainless steel), and a transfer layer (nickel) were used. As the concavo-convex shape of the transfer layer, a random convex portion (by an error diffusion method (Floyd & Steinberg method)) having a shape shown in FIG. In FIG. 6, the convex shape of the transfer layer is the longest diameter (the longest diameter when the convex portion on the mold member is viewed from above) Xm: 50 μm, and the height H is 8.0 μm. It was a shape. Using this mold member, surface processing was performed on the surface of the electrophotographic photosensitive member produced above. During processing, the temperatures of the electrophotographic photosensitive member and the mold member were controlled so that the surface temperature of the electrophotographic photosensitive member was 23 ° C. (room temperature). The electrophotographic photosensitive member was rotated in the circumferential direction while pressing the electrophotographic photosensitive member and the pressure member so that the pressure applied to the electrophotographic photosensitive member was 1280 kgf. An uneven shape (concave shape) was formed on the entire surface (circumferential surface) of the electrophotographic photosensitive member.

  In this way, an electrophotographic photosensitive member having an uneven shape on the surface was produced. When the elastic deformation rate of the surface of the electrophotographic photosensitive member was measured using the above-mentioned “Fischerscope H100V”, it was 53%.

  The concave shape was measured immediately after the surface processing of the obtained electrophotographic photosensitive member. The concave shape on the surface of the electrophotographic photosensitive member was measured while marking the concave shape and specifying the position so that the concave shape could be traced even after time and processing steps.

  The concave shape was measured with a surface shape measurement system Surface Explorer SX-520DR type machine (manufactured by Ryoka System Co., Ltd.) with a 20 × objective lens, and the concave shape was measured. At the time of observation, the electrophotographic photosensitive member was adjusted so that there was no inclination in the longitudinal direction and the circumferential direction was focused on the apex of the peripheral surface of the electrophotographic photosensitive member. The measurement data was subjected to noise removal processing, curvature correction processing, etc., as necessary, by using the attached shape image analysis software, and concave shape data was extracted. The measured concave shape had an average longest diameter of 50 μm and a depth of 2.72 μm.

  The electrophotographic photosensitive member having a concavo-convex shape formed on the surface was subjected to heat treatment for shape stabilization of the present invention. Using a hot air dryer, the surface of the electrophotographic photoreceptor was heated for 15 minutes under the condition that the temperature was 75 ° C. In the electrophotographic photosensitive member after the heat treatment, the uneven shape (concave shape) on the surface was measured. The concave shape was measured by the same method as the measurement of the concave shape immediately after the surface processing. The measured concave shape had an average longest diameter of 50 μm and a depth of 1.71 μm. Thus, surface processing was performed and the electrophotographic photoreceptor was manufactured.

(Evaluation of uneven shape stability under high temperature environment)
The evaluation of the stability of the uneven shape under a high temperature environment is based on the assumption of a high temperature environment such as a temperature rise during distribution, and the electrophotographic photoreceptor after the above heat treatment is stored for 14 days in a constant temperature bath at a temperature of 60 ° C. , Called severe storage test).

  The concave shape of the surface of the electrophotographic photosensitive member after storage for 14 days was measured. About the same recessed part shape which measured initial shape, shape measurement was performed by the same method. The measured concave shape had an average longest diameter of 50 μm and a depth of 1.63 μm. The surface shape maintenance ratio of this electrophotographic photosensitive member was 95.3% when compared before and after the severe storage test. The surface shape maintenance ratio indicates the ratio of the depth of the concave shape after the severe leaving test when the depth of the concave shape before the severe standing test is 100%. The obtained results are shown in Table 1.

(Example 2)
The heat treatment after forming the uneven shape of the electrophotographic photosensitive member was the same as in Example 1 except that the heat treatment was performed for 120 minutes (2 hours) under the condition that the surface temperature of the electrophotographic photosensitive member was 65 ° C. Photoconductors were manufactured and evaluated for the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Example 3)
The height (H) of the mold member when forming the uneven shape of the electrophotographic photosensitive member was changed to 7.0 μm. The electrophotographic photosensitive member was processed in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed by heating for 15 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 70 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

Example 4
An electrophotographic photosensitive member is produced in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member is performed by heating for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member is 65 ° C. Then, the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 5)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 6.2 μm, and the heat treatment after forming the concavo-convex shape of the electrophotographic photosensitive member is performed at the surface temperature of the electrophotographic photosensitive member. The heat treatment was performed for 15 minutes under the condition of 67 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 6)
The electrophotographic photosensitive member was formed in the same manner as in Example 5 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 60 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 65 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Comparative Example 1)
Example 1 except that the height (H) of the mold member when forming the uneven shape of the electrophotographic photosensitive member was changed to 4.8 μm and the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was not performed. In the same manner as above, an electrophotographic photoreceptor was produced, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Comparative Example 2)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 6.2 μm, and the heat treatment after forming the concavo-convex shape of the electrophotographic photosensitive member is performed at the surface temperature of the electrophotographic photosensitive member. The heat treatment was performed for 480 minutes under the condition of 45 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 7)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 8.0 μm, and the heat treatment after the formation of the concavo-convex shape of the electrophotographic photosensitive member is performed. The heat treatment was performed for 15 minutes under the condition of 70 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 8)
The electrophotographic photosensitive member was formed in the same manner as in Example 7 except that the heat treatment after formation of the uneven shape of the electrophotographic photosensitive member was performed for 60 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 67 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

Example 9
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 7.0 μm, and the heat treatment after the concavo-convex shape formation of the electrophotographic photosensitive member is performed, the surface temperature of the electrophotographic photosensitive member is changed. The heat treatment was performed for 15 minutes under the condition of a temperature of 68 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 10)
The electrophotographic photosensitive member was formed in the same manner as in Example 9 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 60 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 65 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Comparative Example 3)
Example 1 except that the height (H) of the mold member when forming the uneven shape of the electrophotographic photosensitive member was changed to 6.2 μm and the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was not performed. In the same manner as above, an electrophotographic photoreceptor was produced, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 11)
The temperature was adjusted so that the surface temperature of the mold member when the concavo-convex shape was formed was 150 ° C., and the pressure applied to the electrophotographic photosensitive member was changed to 800 kgf. Thereafter, as a cooling step, the electrophotographic photosensitive member having the irregular shape formed thereon was allowed to stand for 10 minutes in a room temperature environment (23 ° C., 1 atm) so that the temperature of the electrophotographic photosensitive member became 40 ° C. or lower. . The electrophotographic photosensitive member was the same as in Example 1 except that the heat treatment after the formation of the concavo-convex shape of the electrophotographic photosensitive member and the heat treatment for 15 minutes were performed under the condition that the surface temperature of the electrophotographic photosensitive member was 83 ° C. And the stability of the irregular shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 12)
The electrophotographic photosensitive member was formed in the same manner as in Example 11 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 77 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 2.

(Example 13)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 7.0 μm, and the heat treatment after the concavo-convex shape formation of the electrophotographic photosensitive member is performed, the surface temperature of the electrophotographic photosensitive member is changed. Was heat-treated for 15 minutes under the condition of 80 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 14)
The electrophotographic photosensitive member was formed in the same manner as in Example 13 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 75 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 2.

(Example 15)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 6.2 μm, and the heat treatment after forming the concavo-convex shape of the electrophotographic photosensitive member is performed at the surface temperature of the electrophotographic photosensitive member. The heat treatment was performed for 15 minutes under the condition of a temperature of 77 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 16)
The electrophotographic photosensitive member was formed in the same manner as in Example 15 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 70 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 2.

(Comparative Example 4)
Example 11 except that the height (H) of the mold member when forming the uneven shape of the electrophotographic photosensitive member was changed to 4.2 μm and the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was not performed. In the same manner as above, an electrophotographic photoreceptor was produced, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Comparative Example 5)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 6.2 μm, and the heat treatment after forming the concavo-convex shape of the electrophotographic photosensitive member is performed at the surface temperature of the electrophotographic photosensitive member. The heat treatment was performed for 480 minutes under the condition of 45 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 17)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 8.0 μm, and the heat treatment after the formation of the concavo-convex shape of the electrophotographic photosensitive member is performed. A heat treatment was performed for 15 minutes under the condition of 78 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 18)
The electrophotographic photosensitive member was formed in the same manner as in Example 17 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 75 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 2.

(Example 19)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 7.0 μm, and the heat treatment after the concavo-convex shape formation of the electrophotographic photosensitive member is performed, the surface temperature of the electrophotographic photosensitive member is changed. Was heat-treated for 15 minutes under the condition of 75 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 20)
The electrophotographic photosensitive member was formed in the same manner as in Example 19 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 120 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 72 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 2.

(Comparative Example 6)
Example 11 except that the height (H) of the mold member when forming the uneven shape of the electrophotographic photosensitive member was changed to 6.2 μm and the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was not performed. In the same manner as above, an electrophotographic photoreceptor was produced, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 2.

(Example 21)
The electrophotographic photosensitive member was processed in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed by heating for 2 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 83 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Example 22)
The electrophotographic photosensitive member was processed in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed by heating for 5 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 80 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Example 23)
The aluminum cylinder used in Example 1 was used as a support. Next, 60 parts of barium sulfate particles coated with tin oxide (trade name: Pastoran PC1, manufactured by Mitsui Kinzoku Mining Co., Ltd.), 15 parts of titanium oxide particles (trade name: TITANIX JR, manufactured by Teika Co., Ltd.), Resole type phenolic resin (trade name: Phenolite J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content 70%) 43 parts, silicone oil (trade name: SH28PA, manufactured by Toray Silicone Co., Ltd.) 0.015 3.6 parts of silicone resin particles (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.) in a mixed solvent of 50 parts 2-methoxy-1-propanol / 50 parts methanol and ball-milled for about 20 hours. Dispersed to prepare a coating solution for a conductive layer. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was heated at 140 ° C. for 1 hour to cure, thereby forming a conductive layer having a thickness of 15 μm.

  Next, 10 parts of copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.) are mixed with methanol. An undercoat layer coating solution was prepared by dissolving in a mixed solvent of 400 parts / 200 parts of n-butanol. This undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was heated and dried in an oven at a temperature of 100 ° C. for 30 minutes to form an undercoat layer having a thickness of 0.45 μm.

  Next, a charge generation layer similar to that in Example 1 was formed on the undercoat layer.

  Next, 70 parts of a compound represented by the following formula (5) (charge transporting substance (hole transporting compound)) and 100 parts of a polycarbonate resin (Iupilon Z400, manufactured by Mitsubishi Engineering Plastics) were added to 510 parts of monochlorobenzene and A charge transport layer coating solution was prepared by dissolving in 170 parts of methylal mixed solvent. The charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was heated and dried in an oven at 105 ° C. for 60 minutes to form a charge transport layer having a thickness of 20 μm.

  The glass transition temperature (Tg) of the charge transport layer was measured in the same manner as in Example 1. Tg was 82 ° C.

  Next, 30 parts of the compound represented by the formula (4), 35 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 35 parts of 1-propanol were mixed and stirred well. This was filtered with a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a surface layer coating solution. Using this surface layer coating solution, a surface layer having a thickness of 5 μm was formed in the same manner as in Example 1.

  Next, the surface shape was formed under the same conditions as in Example 1 with the height (H) of the mold member at the time of forming the uneven shape of the electrophotographic photosensitive member being 8.0 μm. The depth of the formed initial shape was 2.90 μm. The elastic deformation rate of the surface of this electrophotographic photosensitive member was 51% when measured using the above-described microhardness measuring apparatus (trade name: Fischerscope H100V, manufactured by Fischer).

  Next, the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed for 15 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 80 ° C. As in Example 1, the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Comparative Example 7)
The electrophotographic photosensitive member was processed in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed by heating for 1 minute under the condition that the surface temperature of the electrophotographic photosensitive member was 83 ° C. Manufactured and evaluated the stability of the irregular shape in a high temperature environment. The results are shown in Table 1.

(Example 24)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 6.2 μm, and the heat treatment after forming the concavo-convex shape of the electrophotographic photosensitive member is performed at the surface temperature of the electrophotographic photosensitive member. The heat treatment was performed for 480 minutes under the condition of 50 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Example 25)
The height (H) of the mold member when forming the concavo-convex shape of the electrophotographic photosensitive member is changed to 8.0 μm, and the heat treatment after the formation of the concavo-convex shape of the electrophotographic photosensitive member is performed. The heat treatment was performed for 3 minutes under the condition of 88 ° C. Other than this, an electrophotographic photosensitive member was produced in the same manner as in Example 11, and the stability of the uneven shape in a high temperature environment was evaluated. The results are shown in Table 1.

(Reference Example 1)
The electrophotographic photosensitive member was treated in the same manner as in Example 1 except that the heat treatment after forming the uneven shape of the electrophotographic photosensitive member was performed by heating for 15 minutes under the condition that the surface temperature of the electrophotographic photosensitive member was 95 ° C. Manufactured. As a result, the depth of the concave shape (initial shape) before the heat treatment was 2.72 μm, but the depth of the concave shape after the heat treatment step was 0.3 μm or less, and the concave shape (uneven shape) was Almost lost.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means 21 Support body 22 Undercoat layer 23 Charge generation layer 24 Charge transport layer 25 Surface layer 4-1 Electrophotographic photosensitive member 4-2 Mold member 4-3 Pressure member 4-4 Electrophotographic photosensitive member support member

Claims (10)

By bringing a mold member having an uneven shape into pressure contact with the surface of an electrophotographic photosensitive member having a charge transport layer containing a thermoplastic resin and a surface layer containing a curable resin formed on the charge transport layer. , A concavo-convex shape transfer step for transferring the concavo-convex shape of the mold member to the surface of the electrophotographic photosensitive member,
A heat treatment step of heat-treating the electrophotographic photosensitive member having a concavo-convex shape transferred to the surface under the following conditions A and B by the concavo-convex shape transfer step;
And a surface processing method for an electrophotographic photosensitive member.
A: When the temperature of the heat treatment of the electrophotographic photosensitive member is Ta (° C.) and the glass transition temperature of the charge transport layer is Tg (° C.), Tg−20 ≦ Ta ≦ Tg + 20 is satisfied.
B: The heat treatment time of the electrophotographic photosensitive member is 2 minutes or more.   The surface processing method for an electrophotographic photosensitive member according to claim 1, wherein Ta (° C.) and Tg (° C.) in the condition A satisfy Tg-19 ≦ Ta ≦ Tg + 14.   The surface processing method for an electrophotographic photosensitive member according to claim 1, wherein Ta (° C.) and Tg (° C.) in the condition A satisfy Ta <Tg.   The surface processing method for an electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the time for the heat treatment of the electrophotographic photosensitive member under the condition B is 5 minutes or more.   5. The surface processing method for an electrophotographic photosensitive member according to claim 1, wherein the time for the heat treatment of the electrophotographic photosensitive member under the condition B is 2 hours or less.   6. The surface processing method of an electrophotographic photosensitive member according to claim 1, wherein Tg (° C.) in the condition A satisfies 60 ≦ Tg ≦ 100.   The cooling process of further cooling the electrophotographic photosensitive member until the temperature of the electrophotographic photosensitive member becomes less than Tg-20 (° C.) between the uneven shape transfer step and the heat treatment step. 7. The surface processing method for an electrophotographic photosensitive member according to any one of 6 above.   The surface processing method for an electrophotographic photosensitive member according to any one of claims 1 to 7, wherein the thermoplastic resin is a polycarbonate resin or a polyester resin.   The surface processing method for an electrophotographic photosensitive member according to claim 1, wherein the curable resin is a curable acrylic resin or a curable methacrylic resin.   It has the process of processing the surface of an electrophotographic photosensitive member using the said surface processing method of any one of Claim 1 to 9, and forming uneven | corrugated shape on the surface of this electrophotographic photosensitive member, It is characterized by the above-mentioned. A method for producing an electrophotographic photosensitive member having a concavo-convex shape on a surface thereof.