JP2009025459A - Method for manufacturing electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new electrophotographic photoreceptor with high productivity, capable of outputting an image free from image defects such as black spots, white spots, irregularity, stripes, interference fringes and moire on an image. <P>SOLUTION: This invention relates to the method for manufacturing an electrophotographic photoreceptor having, on a support body, at least a base layer comprising either a conductive layer or an intermediate layer or both of a conductive layer and an intermediate layer successively layered from the support body side, and a photosensitive layer. The method includes at least: a first step of applying a coating liquid for the base layer on the support body; a second step of making dew condensation on the surface of the coating film of the coating liquid for the base layer or spraying a liquid on the surface, and then drying the surface of the coating film to form the base layer having a rugged surface; and a third step of applying a coating liquid for the photosensitive layer on the base layer having the rugged pattern to from the photosensitive layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an electrophotographic photoreceptor. More specifically, the present invention relates to a method for manufacturing an electrophotographic photosensitive member having an underlayer surface shape that is effective for suppressing interference fringes.

  At present, electrophotographic apparatuses are widely used in fields such as copying machines and laser beam printers because they can operate at high speed and can obtain high printing quality. As a photoreceptor used in an electrophotographic apparatus, an organic photoreceptor (OPC) using an organic photoconductive material has been actively developed and spread. In addition, regarding the structure of the photoconductor, a function-separated type photoconductor in which a charge generation layer and a charge transport layer are separated from a single-layer type photoconductor in which a charge transfer complex structure or a charge generation material is dispersed in a binder resin. The composition has changed to the body composition. In the function-separated type photoconductor configuration, a configuration in which an underlayer is first formed on an aluminum support, and then a charge generation layer and a charge transport layer are mainly used.

  By the way, when the electrophotographic photosensitive member is exposed with a semiconductor laser, an interference fringe pattern appears in the formed toner image, and density unevenness may occur in the image. The following is considered as one of the causes. The semiconductor laser is not completely absorbed in the photosensitive layer, and the transmitted light is regularly reflected on the surface of the support or the underlying layer, so that multiple reflected light of the laser beam is generated in the photosensitive layer, and this is reflected on the surface of the photosensitive layer. Interference occurs with light.

  As a method for solving the above problem, a method for improving the conductive support and a method for improving the underlayer have been proposed so far. As an improvement of the conductive support, for example, Patent Document 1 discloses a method of roughening the surface of the conductive support by an anodic oxidation method. Patent Document 2 discloses a method of roughening the surface of a conductive support by cutting with a cutting tool. Patent Document 3 proposes that the surface of the support is appropriately roughened by a blast treatment in which an abrasive such as glass beads or alumina is sprayed and irradiated. Patent Document 4 proposes that the surface of the support is appropriately roughened by a humidity honing treatment. This is a method in which a powdery abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. In that case, the surface roughness can be controlled by spraying pressure, speed, amount of abrasive, type, shape, size, hardness, specific gravity, suspension temperature, and the like, and various production conditions have been proposed.

On the other hand, as an improvement of the underlayer, for example, Patent Document 5 discloses a method in which an underlayer is formed on a support, and a conductive metal oxide is dispersed in the underlayer to roughen the surface of the underlayer. Proposed. In Patent Document 6, a base layer composed of two layers of a conductive layer and an intermediate layer is used as a base layer in order to cover the surface of the uncut aluminum support. The conductive layer contains oxygen-deficient SnO ₂ -coated TiO ₂ particles, and further adds rough particles such as silicone resin particles having an average particle size of 1 μm to 3 μm for controlling the roughness of the conductive layer surface. Thus, interference fringes are suppressed. In Patent Document 7, in the step of applying a base layer, the coating layer is blown to the coating layer in an undried state, and a rough surface having an average pitch width of 500 μm or less and a maximum roughness of 0.3 μm or more is applied to the surface of the base layer. A manufacturing method for forming a surface has been proposed.
Japanese Patent Laid-Open No. 05-72785 JP 58-162975 A Japanese Patent Laid-Open No. 08-292592 JP 2002-107958 A JP 2005-140963 A JP 2007-47736 A JP-A-5-88395

  However, in the method of roughening the surface of the conductive support described in Patent Document 1 described above by anodizing, the electrophotographic characteristics depend on the state of the oxide film on the surface of the aluminum support, and the oxide film is The resistance of the thin part is significantly reduced. Therefore, black spots may occur. Further, the unevenness of the oxide film also appears in the unevenness of the surface shape, and the interference fringes may be partially generated. In addition, the apparatus tends to be complicated in production, and it cannot be said that productivity is sufficiently high.

  Further, on the surface of the electrophotographic photosensitive member support processed by the method described in Patent Documents 2 to 4, black spots are generated due to the cutting pieces, abrasive residue or sacrificial material generated by cutting, blasting or honing. Cheap. Further, it is required to provide a cleaning process for removing them, and the manufacturing process tends to be complicated. In this case as well, dirt on the support after washing and unevenness of the oxide film may affect the image, and there are many manufacturing restrictions.

  On the other hand, an underlayer is formed on a support described in Patent Document 5, which is a method for improving the underlayer, and a conductive metal oxide is dispersed in the underlayer to roughen the surface of the underlayer. However, the following problems arise in this method. In other words, the inclusion of fine particles may cause problems such as aggregation and sedimentation of metal oxides, which greatly restricts the dispersion conditions, usable solvents and binder resins, and makes it difficult to achieve compatibility with electrophotographic characteristics. There is a case. In addition, since it is difficult to make the surface roughness uniform, the roughness may partially increase, which causes a rough image or the like. Patent Document 6 discloses a photoreceptor having a base layer composed of two layers, a conductive layer and an intermediate layer. However, when roughening particles are added to effectively roughen the surface of the conductive layer, When used in combination with a thermosetting resin, the film may be easily cracked. Therefore, in order to suppress cracks and black spots, it is necessary to make production restrictions such as the appropriate particle size of coarse particles, the amount added, the dispersion condition of the coating liquid, and the control of the solvent used. The degree of freedom may be reduced. Furthermore, in the method of Patent Document 7, the surface is roughened by air blowing while the underlayer is in an undried state, so it is difficult to obtain a uniform surface roughness due to the manufacturing method, and image defects such as fogging and black spots and partial defects Interference fringes are likely to occur.

  The present invention has been made in view of the above problems. It is another object of the present invention to provide a new and highly productive electrophotographic photosensitive member manufacturing method capable of outputting an image free from image defects such as black spots, white spots, unevenness, streaks, interference fringes, and moire on the image. To do.

  As a result of intensive studies, the present inventors have effectively improved the above-mentioned problems by forming uneven portions on a base layer of an electrophotographic photoreceptor by a predetermined manufacturing method, and a highly productive new manufacturing method I found. Details are described below.

  The present invention comprises, on a support, an underlayer comprising either one of a conductive layer or an intermediate layer, or the conductive layer and the intermediate layer laminated in order from the support side, and a photosensitive layer. A method for producing an electrophotographic photoreceptor comprising: a first step of applying a coating solution for an underlayer on the support; and causing condensation on the coating film surface of the coating solution for the underlayer, or spraying a liquid Then, by drying the surface of the coating film, a second step of forming a ground layer having a concavo-convex shape on the surface, and applying a photosensitive layer coating liquid on the ground layer on which the concavo-convex shape is formed. And a third step of forming a photosensitive layer. The conductive layer contains metal oxide particles and a thermosetting resin. The intermediate layer contains a thermoplastic resin. Further, the metal oxide particles are any one of zinc oxide, tin oxide, and titanium oxide. The underlayer on which the uneven shape is formed in the second step is a conductive layer. The second step includes an intermediate layer applying step of applying an intermediate layer on the conductive layer on which the uneven shape is formed. The underlayer on which the uneven shape is formed in the second step is an intermediate layer. The solvent used in the coating solution for the underlayer contains at least an alcohol solvent having 4 to 8 carbon atoms or a hydrophobic organic solvent. In the second step, the surface of the coating film of the base layer coating solution is maintained in an atmosphere having a relative humidity of 60% to 95% in order to cause condensation. In the second step, the liquid sprayed onto the coating film surface of the base layer coating solution is water or alcohol. Further, in the second step, the liquid sprayed onto the coating layer surface of the base layer coating solution is the same component as the base layer coating solution.

  The present invention also provides an electrophotographic photoreceptor produced by any one of the methods described above.

  In the present invention, the electrophotographic photosensitive member described above and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means are integrally supported and attached to and detached from the main body of the electrophotographic apparatus. It is a process cartridge characterized by being free.

  Furthermore, the present invention is an electrophotographic apparatus comprising at least the electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit.

  According to the present invention, there is provided a novel and highly productive electrophotographic photosensitive member manufacturing method capable of outputting an image free from image defects such as black spots, white spots, unevenness, streaks, interference fringes, and moire on the image. be able to.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  The method for producing an electrophotographic photoreceptor of the present invention comprises the following steps. First, as a 1st process, the coating liquid for base layers is apply | coated on a support body. Next, as a second step, the coating film surface of the coating solution for the base layer after coating is condensed or sprayed with a liquid, and then dried to form a fine uneven shape on the surface of the base layer. Finally, as a third step, a photosensitive layer coating solution is applied onto the base layer on which the shape is formed.

  Here, the underlayer in the present invention refers to all layers present between the support and the photosensitive layer. The configuration of the underlayer may be a single layer or a stacked configuration of two or more layers. In the case of a laminated structure of two or more layers, it has a concavo-convex shape formed by a process of forming the fine concavo-convex shape described above on the surface of the underlayer on the surface of at least one of the layers. In the present invention, the base layer has a structure in which either one of the conductive layer and the intermediate layer, or both are sequentially laminated from the support side.

The support in the present invention may be a support used in a conventional electrophotographic photosensitive member. That is, as the support, a conductive one (conductive cylindrical support) is preferable, and a cylindrical support made of metal such as aluminum, aluminum alloy, or stainless steel can be used. In the case of aluminum or aluminum alloy, ED tube, EI tube, or these are cut, electrolytic composite polishing (electrolysis with electrode having electrolytic action and polishing with grinding stone having polishing action), wet or dry honing treatment Can also be used. Moreover, the said metal cylindrical support body and resin cylindrical support body which have the layer by which aluminum, the aluminum alloy, or the indium oxide tin oxide alloy was formed into a film by vacuum deposition can be used. Here, as the resin-made cylindrical support, polyethylene terephthalate, polybutylene terephthalate, phenol resin, polypropylene, or polystyrene resin can be used. Further, a cylindrical support obtained by impregnating resin or paper with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles, or a plastic having a conductive binder resin can also be used. The volume resistivity including the support and its oxide film is preferably 1 × 10 ¹⁰ Ω · cm or less, and more preferably 1 × 10 ⁶ Ω · cm or less.

  In general, the underlayer serves to improve the adhesion between the support and the photosensitive layer, and prevents carrier injection from the support to the photosensitive layer, thereby stabilizing the light potential and the dark potential during repeated use. It has a role to enhance sex. Without this function, black spots may occur partially due to partial carrier injection, and fogging may occur in the image.

  First, the first step, that is, the step of applying the base layer coating solution on the support will be described in more detail.

  In order to cover scratches and crusts on the surface of uncut aluminum supports such as ED tubes, a conductive layer is provided between the support and the intermediate layer or photosensitive layer for the purpose of covering flaws and crusts on the support. It may be provided. This is a layer formed by applying a coating liquid in which conductive powder is dispersed in an appropriate binder resin. When the intermediate layer is provided on the conductive layer, in the second step, the intermediate layer may be provided after the uneven shape is formed on the conductive layer, or the intermediate layer laminated on the conductive layer is uneven. A shape may be formed.

Examples of such conductive powder include the following. Metal powders and conductive polymers such as carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper, zinc or silver. Metal oxide particles such as conductive tin oxide, titanium oxide or zinc oxide. For tin oxide, a compound of a metal having a valence different from that of tin, such as antimony oxide, or a nonmetallic element is mixed (doped) to produce a powder resistivity of 1/1000 to 1/100000. It is preferable to make it small. In addition, oxygen-deficient tin oxide in which the resistance of tin oxide is made as low as that of antimony dope without increasing the number of constituent elements is preferable from the viewpoint of reducing resistance. Further, from the viewpoint of dispersibility of the paint, the barium sulfate particles may be coated with oxygen-deficient tin oxide. In addition, using a barium sulfate particle, a titanium oxide (TiO ₂ ) is coated thereon to improve whiteness, and a tin oxide coating is further coated thereon to provide conductivity. Also preferred are powders.

  Furthermore, it is preferable to use titanium oxide particles as the core material particles and to use particles coated with oxygen-deficient tin oxide for the coating liquid for the conductive layer from the viewpoints of reducing the resistance and improving the dispersibility of the particles. By using titanium oxide particles as the core material particles, the bond between the oxygen deficient tin oxide coating layer and the core material is strengthened by the affinity between the oxygen deficient sites of the oxygen deficient tin oxide and the oxide sites on the surface of the titanium oxide particles. It is. In addition, unlike the doped type, the oxygen deficient type may be oxidized in the presence of oxygen and the oxygen deficient site may disappear, resulting in a decrease in conductivity (increase in powder resistivity). By using titanium particles, the oxygen deficient site of the oxygen deficient tin oxide is protected. The coverage is preferably 30% to 70% by mass ratio.

  The average particle size of these conductive powders is preferably 0.05 μm or more and 2.0 μm or less, and more preferably 0.1 μm or more and 0.6 μm or less. If the average particle size is larger than this, unevenness on the surface of the undercoat layer of the present invention is difficult to be formed uniformly, and local surface roughening tends to cause local carrier injection into the photosensitive layer. Black spots tend to occur. In the conventional manufacturing method, when the average particle size is less than 0.20 μm, it is necessary to increase the amount of the conductive powder used in order to keep the volume resistivity of the conductive layer within an appropriate range described later. However, when the amount of the conductive powder used is increased, the surface roughness of the conductive layer should be made suitable in order to suppress the occurrence of interference fringes in the output image due to interference of light reflected from the surface of the conductive layer. It was difficult. However, according to the method for forming a concavo-convex shape of the present invention, it is possible to obtain a good image output in which no interference fringes are generated even when the average particle size is less than 0.20 μm.

  Moreover, as binder resin used simultaneously, the following thermoplastic resins, thermosetting resins, or photocurable resin resins are mentioned. Phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyvinyl acetal, polycarbonate, epoxy resin, acrylic resin, melamine resin, polyester resin, silicone resin, polystyrene, phenoxy resin, cellulose acetate resin. Ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, alkyd resin. Styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, and the like. These can be used alone or in combination of two or more. In addition, among various resins, the conductive layer is used from the viewpoints of suppressing migration (melting) to other layers, adhesion to the support, dispersibility / dispersion stability of the conductive material, solvent resistance after film formation, etc. The binder resin is preferably a curable resin, and more preferably a thermosetting resin. Specifically, thermosetting phenol resin, epoxy resin, urethane resin, melamine resin, siloxane resin, and acrylic resin are more preferable. When a curable resin is used as the binder resin for the conductive layer, the binder material contained in the conductive layer coating solution is a monomer and / or oligomer of the curable resin. When performing such a polycondensation reaction by heating, it is preferable to heat at 100 ° C. or higher so that the polymerization proceeds sufficiently. Moreover, since excessive heating may deteriorate the characteristics of the electrophotographic photosensitive member, it is preferably 200 ° C. or lower. Furthermore, it is preferable that heating is performed at 120 ° C. or higher and 170 ° C. or lower. The time required for the polymerization step is preferably 5 minutes or longer so that the polymerization proceeds sufficiently. In addition, if the heating time is too long, the characteristics of the electrophotographic photosensitive member may be deteriorated. Furthermore, it is more preferable that it is 20 minutes or more and 90 minutes or less.

  The mass ratio (P: B) of the conductive powder (P) and the binder resin (B) in the conductive layer coating solution is in the range of 1.0: 1.0 to 5.0: 1.0. It is preferable. When there is too little conductive powder, it will become difficult to keep the volume resistivity of a conductive layer in the below-mentioned range. When there is too much conductive powder, it becomes difficult to bind the conductive powder in the conductive layer, and cracks in the film are likely to occur.

  Furthermore, in the conventional manufacturing method, in order to further suppress interference fringes, it is common to add a surface roughening agent for roughening the surface of the conductive layer to the coating liquid for the conductive layer. As the rough particles, resin particles having an average particle diameter of 1 μm or more and 3 μm or less are used. Examples thereof include particles of curable resin such as curable rubber, polyurethane, epoxy resin, alkyd resin, phenol resin, polyester, silicone resin, and acrylic-melamine resin. The content of the surface roughening agent in the conductive layer had to be adjusted to 5 to 20% by mass with respect to the binder resin in the conductive layer. This is because, if the content is large, the volume resistivity of the conductive layer is increased and the characteristics of the photoreceptor such as fogging are deteriorated, and cracks of the film due to aggregation of rough particles are likely to occur. However, the method for forming a concavo-convex shape on the surface of the present invention has an advantage that a conductive layer having good film properties can be formed without generating interference fringes without adding rough particles. Therefore, in the present invention, the roughened particles may be added within the above range, or may not be added. Further, a leveling agent may be added to improve the surface property of the conductive layer, and pigment particles may be contained in the conductive layer in order to improve the concealing property of the conductive layer.

  The conductive layer can be formed by dispersing or dissolving the above-described conductive powder and binder resin in an appropriate solvent and applying it. However, after applying the conductive layer, which will be described later, by controlling the surrounding environment to high humidity to promote condensation and creating a concavo-convex shape on the surface, it is more effective in preventing interference fringes by using the solvent conditions described later. Can be formed.

  Specific examples of the solvent used in the conductive layer include the following. Alcohol solvents such as methanol, ethanol, methoxypropanol and isopropanol, 1-butanol, and ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone. Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether and propylene glycol monomethyl ether. Ester solvents such as methyl acetate and ethyl acetate. Aromatic hydrocarbon solvents such as toluene, chlorobenzene and xylene. Moreover, you may use these solvents in mixture of 2 or more types.

  Examples of the dispersion method of the conductive layer coating liquid include a method using a paint shaker, a sand mill, a ball mill, a liquid collision type high-speed disperser, and the like.

  Further, an intermediate layer having a barrier function or an adhesive function against carrier injection from the support may be provided between the support or conductive layer described above and the photosensitive layer. The intermediate layer can be formed by applying a curable resin and then curing to form a resin layer, or applying an intermediate layer coating solution containing a binder resin on the conductive layer and drying.

  Examples of the binder resin for the intermediate layer include the following. Water-soluble resins such as polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acids, methyl cellulose, ethyl cellulose, polyglutamic acid or casein. Polyamide resin, polyimide resin, polyamideimide resin, polyamic acid resin, melamine resin, epoxy resin, polyurethane resin or polyglutamic acid ester resin. A thermoplastic resin is preferable as the binder resin for the intermediate layer in order to effectively develop electric barrier properties and from the viewpoints of coating property, adhesion, solvent resistance, and resistance. Specifically, a thermoplastic polyamide resin is preferable. The polyamide resin is preferably a low crystalline or non-crystalline copolymer nylon that can be applied in a solution state. Also, in order to prevent the flow of electric charges (carriers) in the intermediate layer, the conductive powder as described above is dispersed in the intermediate layer, or an electron transport material (an electron accepting material such as an acceptor). ) May be included.

  However, after application of the intermediate layer, when the surrounding environment is controlled to high humidity to promote condensation and create an uneven shape on the surface, the unevenness more effective in preventing interference fringes can be obtained by using the solvent conditions described below. A shape can be formed.

  Further, the intermediate layer can be formed by dispersing or dissolving the conductive powder or binder resin in an appropriate solvent and applying it.

  Specific examples of the solvent used for the intermediate layer include the following. Alkylamine compounds such as alkylamine compounds, trimethylamine, triethylamine, tributylamine, and triethylamine alkylamine compounds; Alcohol solvents such as methanol, ethanol, 1-butanol, methyl cellosolve and methoxypropanol. Ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone. Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether and propylene glycol monomethyl ether. Ester solvents such as methyl acetate and ethyl acetate. Aromatic hydrocarbon solvents such as toluene, chlorobenzene and xylene. Two or more kinds of these solvents may be mixed and used.

  In the first step of the present invention, in the coating step of applying a base layer coating solution comprising at least one of the conductive layer and the intermediate layer or both on the support, a dip coating method, a spray coating method or a ring coating method is used. The coating method like this can be used. Of these, the dip coating method is preferable from the viewpoint of productivity.

  Next, a second step in the present invention, that is, a step of forming a fine uneven shape on the surface of the underlayer by drying the coating film surface of the coating solution for the underlayer after application by condensing or spraying the liquid. This will be described in more detail.

  In the second step of the present invention, from the viewpoint of productivity and shape uniformity, it is preferable to use the method shown by the following unevenness forming methods 1 to 3. Here, dew condensation in the present invention means that water vapor in the air aggregates on either or both of the surface and / or the inside of the solution.

  Generally, dew condensation can be promoted from moisture in the air by using a highly volatile solvent and utilizing the cooling effect of the substrate due to the large heat of vaporization or by cooling the substrate itself. Moreover, effective promotion of dew condensation can be realized by controlling the surrounding environment at high humidity. That is, minute water droplets due to condensation can be formed on the substrate surface by exposing to a high humidity atmosphere or spraying a high humidity gas or a sprayed liquid. In particular, when a hydrophobic solvent is used for the underlayer, when exposed to a high humidity atmosphere, water droplets are formed on the surface due to the cohesive force of water, and individual, uniform concave shapes are formed. It is formed. In addition, when a hydrophilic solvent such as alcohol is used for the underlayer, an alcohol solvent having at least 4 carbon atoms is contained and sprayed in a high-humidity atmosphere or high-humidity gas or sprayed water or alcohol. Thus, the volatility of the solvent is controlled. By doing so, it is preferable because water droplets are easily taken into the interior of the coating liquid, and an uneven shape on the surface of the underlying layer that is effective for interference fringes can be created by performing a drying process in that state.

  In the following, the method for forming irregularities in the underlayer will be specifically described by giving three methods.

(Roughness forming method 1)
What is described here is a method of forming a concavo-convex shape by allowing the coating film surface of the applied underlayer coating solution to condense and then drying.

  As described above, as a method for dewing the coating surface of the coating solution for the underlayer, there is a method for holding the support coated with the coating solution for the underlayer for a certain period of time in an atmosphere where the coating surface is condensed. Condensation in this surface forming method indicates that droplets are formed on the surface of the coating film by the action of water. The conditions for condensation of the coating film are affected by the relative humidity of the atmosphere holding the support and the volatilization conditions of the coating solution solvent (for example, heat of vaporization), so it is important to select appropriate conditions. In particular, it depends mainly on the relative humidity of the atmosphere holding the support. The relative humidity at which the coating surface is condensed is preferably 40% or more and 100% or less. Furthermore, the relative humidity is more preferably 60% or more and 95% or less. The process for condensing the surface of the coating film may have a time required for forming droplets by condensation. From the viewpoint of productivity, it is preferably 1 to 300 seconds, and more preferably about 10 to 180 seconds. By preliminarily cooling the support or base layer coating solution under conditions that are 10 ° C. or more lower than the ambient temperature, droplet formation due to condensation is effectively achieved in a shorter time. Here, relative humidity is important for the process of dew condensation on the coating film surface, but the atmospheric temperature is preferably 20 ° C. or higher and 80 ° C. or lower.

  As the coating solution for the underlayer suitable for the method for forming an uneven shape on the surface of the coating film, a coating solution containing a hydrophobic organic solvent or an alcohol solvent having 4 or more carbon atoms is preferable for the above reasons. Furthermore, it is preferable to contain the above-mentioned binder resin, and if necessary, the above-mentioned conductive powder may be contained.

  Examples of the hydrophobic organic solvent include aromatic organic solvents. Specific examples include toluene, xylene, 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene, 1,3,5-trimethylbenzene, and chlorobenzene. Furthermore, when the content of the aromatic organic solvent is 50% by mass or more based on the total amount of the solvent in the coating solution for the underlayer, water droplets on the surface aggregate to form a uniform shape with independent irregular shapes. Therefore, it is preferable. Here, when a hydrophobic organic solvent is used as the main solvent, the base layer coating solution contains an aromatic organic solvent and has a high affinity with water for the purpose of stably producing the shape portion. An organic solvent or water may be contained in the surface layer coating solution. As the organic solvent having high affinity with water, the following are preferable. (Methylsulfinyl) methane (common name: dimethyl sulfoxide), thiolane-1,1-dione (common name: sulfolane), N, N-dimethylcarboxamide, N, N-diethylcarboxyamide, dimethylacetamide or 1-methylpyrrolidine -2-one. These organic solvents can be contained alone or in admixture of two or more.

  Examples of the alcohol solvent having 4 or more carbon atoms include alcohol solvents having a boiling point of 100 ° C. or higher, such as isobutyl alcohol, 1-butanol, 1-methoxy-2-propanol, and 1-pentanol. Furthermore, the volatility of the solvent is controlled when the content of the alcohol solvent having 4 or more carbon atoms is 50% by mass or more based on the total mass of the solvent in the coating solution for the underlayer. Therefore, it is preferable because water droplets are more easily taken into the interior of the coating liquid, and an uneven shape on the surface of the underlayer effective for interference fringes can be created by performing a drying process in that state. Furthermore, the content of the alcohol solvent having 4 or more carbon atoms is more preferably 80% by mass or more based on the total mass of the solvent in the coating solution for the underlayer. These alcohol solvents having 4 or more carbon atoms can be contained alone or in combination of two or more. Also, when the alcohol solvent has 9 or more carbon atoms, the boiling point tends to increase, and it tends to remain as a residual solvent in the underlayer even after the drying step, and this is preferable in view of electrophotographic characteristics such as an increase in the residual potential of the photoreceptor. There may not be. Therefore, it is more preferable to use an alcohol solvent having 4 to 8 carbon atoms.

(Unevenness forming method 2)
Next, a method of forming an uneven shape by spraying water or alcohol on the coating film surface of the applied underlayer coating solution and then drying it will be described. Specifically, water or alcohol is atomized and sprayed onto the surface of the coating film of the base layer coating solution.

  There are the following methods for spraying water or alcohol by atomization. That is, a spray method in which water or alcohol is mixed with high-pressure air, atomized and sprayed from a nozzle, or a method in which water or alcohol is sprayed on the coating surface using an ink jet unit including a head unit that ejects droplets with particles. is there.

  As alcohol to spray, it is preferable that it is alcohol whose boiling point is lower than water. Of these, methanol, ethanol, n-propanol or isopropanol is preferable. Moreover, you may mix and spray water or the said alcohol.

  By spraying water or the above-described alcohol onto the coating film surface of the applied coating solution for the underlayer, an irregular shape having the size of atomized fine particles is formed on the coating film surface. An example of the spray processing apparatus used in the present invention is shown in FIG. Water or an alcohol solvent stored in a container (not shown) is guided to the nozzle through the route of the instruction number 44, and is injected from the injection nozzle 41 using the compressed air introduced from the route of the instruction number 43. And it is sprayed on the cylindrical support body 47 which apply | coated the coating liquid for base layers currently supported by the workpiece | work support body 46 and rotating. At this time, the distance between the nozzle and the cylindrical support is adjusted and determined by the nozzle fixing jig 42 and the arm 49. The nozzle usually forms an uneven shape while moving relative to the direction of the rotation axis of the cylindrical support, and the nozzle support 48 moves in the direction of the rotation axis of the cylindrical support so that the workpiece is uneven without unevenness. Shape formation can be performed. At this time, the shortest distance between the nozzle and the surface of the cylindrical support is required to be adjusted to an appropriate interval. The pressure of the compressed air used for the power of injection is also required to be adjusted to an appropriate pressure.

  Examples of the method of drying after spraying water or alcohol as described above include heat drying, air drying, and vacuum drying, and a method combining these possible methods can also be used. In particular, heat drying and air blowing drying are preferable from the viewpoint of productivity. Moreover, in order to form a highly uniform concavo-convex shape, it is important to perform rapid drying, and thus it is preferable to perform heat drying. It is preferable that the drying temperature in a drying process is 100 to 150 degreeC. The drying process time to dry should just be the time in which the solvent in the coating liquid apply | coated on the support body, the water sprayed on the coating-film surface, or alcohol is removed. The drying process time is preferably 5 minutes to 120 minutes, and more preferably 10 minutes to 100 minutes.

(Unevenness forming method 3)
Next, a method of forming an uneven shape by spraying the same component as the coating solution for the underlayer onto the coating film surface of the applied coating solution for the underlayer and then drying it. In detail, the same component as the coating liquid for base layers is atomized and sprayed with respect to the coating-film surface of the coating liquid for base layers.

  As a method of spraying the same components as the coating solution for the underlayer, a spray method in which the coating solution for the underlayer is mixed with high-pressure air, atomized, and sprayed from a nozzle, or an inkjet including a head unit that ejects droplets as particles The method using a unit is mentioned. It is also possible to carry out dilution with a solvent contained in the coating solution for underlayer coating, if necessary, so that the viscosity of the coating solution for ground layer to be sprayed becomes an appropriate viscosity.

  An example of a spray processing apparatus used in the present invention is shown in FIG. The base layer coating liquid stored in a container (not shown) is guided to the nozzle through the route of the instruction number 54 and is sprayed from the spray nozzle 51 using the compressed air introduced from the route of the instruction number 53. And it is sprayed by the cylindrical support body 57 apply | coated with the coating liquid for base layers currently supported by the workpiece | work support body 56 and rotating. At this time, the distance between the nozzle and the cylindrical support is adjusted and determined by the nozzle fixing jig 52 and the arm 59. The nozzle normally forms an uneven shape while moving with respect to the rotational axis direction of the cylindrical support, and the nozzle support 58 moves in the rotational axis direction of the cylindrical support so that the workpiece is uneven without unevenness. Shape formation can be performed. At this time, the shortest distance between the nozzle and the surface of the cylindrical support is required to be adjusted to an appropriate interval. It is required to adjust the pressure of compressed air used for the power of injection to an appropriate pressure.

  By spraying the same component as the coating solution for the under layer on the surface of the coating film, the same unevenness of the size of the fine particles is obtained when the same component as the coating solution that has become fine particles is sprayed on the coating surface. A shape is formed on the coated surface.

  Examples of the method of drying after spraying the same components as the coating solution for the underlayer include heat drying, air drying, and vacuum drying, and a method combining these possible methods can be used. In particular, heat drying and air blowing drying are preferable from the viewpoint of productivity. It is preferable that the drying temperature in a drying process is 100 to 150 degreeC. The drying process time for drying may be a time for removing the solvent in the coating solution coated on the support. The drying process time is preferably 5 minutes to 120 minutes, and more preferably 10 minutes to 100 minutes.

  In this way, the thickness of the base layer on which the concavo-convex shape is formed by applying the base layer, in the case of the conductive layer, the average thickness of the conductive layer is 0.5 μm or more from the viewpoint of covering the scratches on the support. It is preferably 100.0 μm or less. Furthermore, it is more preferably 1.0 μm or more and 50.0 μm or less, and further more preferably 5.0 μm or more and 35.0 μm or less.

  The average film thickness of the intermediate layer is preferably 0.05 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 5.0 μm or less.

  Here, the reference point for the film thickness of the surface is a convex vertex in the convex shape, and the film thickness from the upper surface of the concave in the concave shape.

  In the present invention, the film thickness of each layer of the electrophotographic photosensitive member including the base layer can be measured by FISHERSCOPE manufactured by Fisher Instruments Co., Ltd. The film thickness is measured after the irregular shape is formed.

The volume resistivity of the underlayer of the present invention is preferably more than 1.0 × 10 ⁶ Ω · cm and not more than 1.0 × 10 ¹⁴ Ω · cm from the viewpoint of the repeated potential stability of the photoreceptor. Among these, the volume resistivity of the conductive layer is preferably more than 1.0 × 10 ⁶ Ω · cm and 1.0 × 10 ¹¹ Ω · cm or less, and the volume resistivity of the intermediate layer is 1.0 × 10 10. It is preferably more than ⁹ Ω · cm and 1.0 × 10 ¹⁴ Ω · cm or less.

  The method for measuring the volume resistivity of the underlayer in the present invention is as follows.

  First, a base layer sample (the film thickness is set to the same thickness as the base layer) is formed on the aluminum sheet using the base layer coating solution. A gold thin film is formed on the underlayer sample by vapor deposition. The current value flowing between the aluminum sheet and the gold thin film electrode is measured with a pA meter. The measurement environment is 23 ° C./60% RH, and the applied voltage is 0.1 V for the conductive layer and 100 V for the intermediate layer. A stable value 1 minute after the start of current value measurement is read to derive the volume resistivity of the underlayer.

  Next, the third step in the present invention, that is, the step of applying the photosensitive layer coating solution on the underlayer on which the uneven shape is formed will be described in more detail.

  Even if the photosensitive layer is a single-layer type photosensitive layer containing the charge transport material and the charge generation material in the same layer, the charge generation layer containing the charge generation material and the charge transport layer containing the charge transport material Separated layered (functionally separated type) photosensitive layers may be used. The electrophotographic photoreceptor according to the present invention is preferably a laminated photosensitive layer from the viewpoint of electrophotographic characteristics. In addition, even if the laminated type photosensitive layer is a normal type photosensitive layer in which the charge generation layer and the charge transport layer are laminated in this order from the support side, the reverse layer type photosensitive layer in which the charge transport layer and the charge generation layer are laminated in order from the support side. It may be a layer. In the electrophotographic photoreceptor according to the present invention, when a laminated type photosensitive layer is employed, a normal layer type photosensitive layer is preferable from the viewpoint of electrophotographic characteristics. Further, the charge generation layer may have a laminated structure, and the charge transport layer may have a laminated structure. Furthermore, it is possible to provide a protective layer on the photosensitive layer for the purpose of improving the durability performance.

  Examples of the charge generating material used in the electrophotographic photosensitive member of the present invention include the following. Azo pigments such as monoazo, disazo or trisazo. Phthalocyanine pigments such as metal phthalocyanine or non-metal phthalocyanine. Indigo pigments such as indigo or thioindigo. Perylene pigments such as perylene anhydride or perylene imide. Polycyclic quinone pigments such as anthraquinone or pyrenequinone. Squarylium dye, pyrylium salt or thiapyrylium salt, triphenylmethane dye. Inorganic materials such as selenium, selenium-tellurium or amorphous silicon. Quinacridone pigment, azulenium salt pigment, cyanine dye, xanthene dye, quinoneimine dye or styryl dye. These charge generation materials may be used alone or in combination of two or more. Among these, metal phthalocyanines such as oxytitanium phthalocyanine, hydroxygallium phthalocyanine or chlorogallium phthalocyanine are particularly preferable because of their high sensitivity.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used for the charge generation layer include the following. Polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin, phenol resin, silicone resin. Polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin or vinyl chloride-vinyl acetate copolymer resin. In particular, a butyral resin is preferred. These can be used singly or in combination of two or more as a mixture or copolymer.

  The charge generation layer can be formed by applying and drying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent. The charge generation layer may be a vapor generation film of a charge generation material. Examples of the dispersion method include a method using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor, or a roll mill. The ratio between the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10 (mass ratio), and more preferably in the range of 3: 1 to 1: 1 (mass ratio).

  The solvent used for the charge generation layer coating solution is selected from the solubility and dispersion stability of the binder resin and charge generation material used. Examples of the organic solvent include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  The average film thickness of the charge generation layer is preferably 5 μm or less, and more preferably 0.1 to 2 μm.

  In addition, various sensitizers, antioxidants, ultraviolet absorbers and / or plasticizers can be added to the charge generation layer as necessary. In order to prevent the flow of charges (carriers) in the charge generation layer from stagnation, the charge generation layer may contain an electron transport material (an electron accepting material such as an acceptor).

  In the case of a multilayer type photoreceptor, a charge transport layer is formed on the charge generation layer. The charge transport layer contains a charge transport material. Examples of the charge transport material 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. Further, in general, the charge transport layer is formed by blending a binder resin for imparting durability, applying a solution dissolved using an appropriate solvent, and drying. The drying temperature is preferably 80 ° C. or higher.

  Examples of the binder resin used for the charge transport layer include the following. Acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, nylon, phenol resin, phenoxy resin, butyral resin, polyacrylamide resin, polyacetal resin, polyamideimide resin. Polyamide resin, polyallyl ether resin, polyarylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polystyrene resin, polysulfone resin, polyvinyl butyral resin. Polyphenylene oxide resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, vinyl chloride resin, vinyl acetate resin, etc. In particular, the use of modified polycarbonates and polyesters in which polyarylate resins, polycarbonate resins, etc. are modified with silicon or fluorine compounds means compatibility, electrophotographic characteristics, and the sustainability of effects due to the combination of surface migration and surface shape And more preferable. These may be used alone or in combination of two or more.

  The ratio between the charge transport material and the binder resin is preferably in the range of 2: 1 to 1: 2 (mass ratio). The thickness of the charge transport layer is preferably 5 to 50 μm, and more preferably 7 to 30 μm. The charge transport layer may contain additives such as an antioxidant, an ultraviolet absorber, and a plasticizer.

  Further, when the photosensitive layer is a single layer type, it can be formed by applying a solution in which the above-described charge generating material or charge transporting material is dispersed and dissolved in the above binder resin and drying it.

  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, a blade coating method, or the like should be used. Can do. The liquid viscosity at the time of coating is preferably 5 mPa · s or more and 500 mPa · s or less from the viewpoint of coating properties.

  The following are mentioned as a solvent used for the coating liquid for charge transport layers. Ketone solvents such as acetone or methyl ethyl ketone. Ester solvents such as methyl acetate or ethyl acetate. Ether solvents such as tetrahydrofuran, dioxolane, dimethoxymethane or dimethoxyethane. Aromatic hydrocarbon solvents such as toluene, xylene or chlorobenzene. These solvents may be used alone or in combination of two or more. Among these solvents, it is preferable to use an ether solvent or an aromatic hydrocarbon solvent from the viewpoint of resin solubility.

  The average film thickness of the charge transport layer is preferably 5 to 50 μm, more preferably 10 to 35 μm. In addition, for example, an antioxidant, an ultraviolet absorber and / or a plasticizer may be added to the charge transport layer as necessary.

  When further improvement in durability is required, a configuration in which a second charge transport layer or a protective layer is formed on the charge transport layer may be used. The second charge transport layer or protective layer can be formed of a charge transport material exhibiting plasticity and a binder resin, as in the case of the charge transport layer. It is effective to use a resin.

  Examples of the method for constituting the surface layer with a curable resin include, for example, a method for constituting the charge transport layer with a curable resin, and forming a curable resin layer as a second charge transport layer or a protective layer on the charge transport layer. A method is mentioned. Since the characteristic required for the curable resin layer is to satisfy both the strength of the film and the charge transport capability, it is generally composed of a charge transport material and a polymerized or crosslinkable monomer or oligomer.

  In the method of constituting these surface layers with a curable resin, known hole transporting compounds and electron transporting compounds can be used as charge transporting materials. Examples of materials for synthesizing these compounds include chain polymerization materials having an acryloyloxy group or a styrene group. In addition, a material such as a sequential polymerization system having a hydroxyl group, an alkoxysilyl group or an isocyanate group can be used. In particular, a combination of a hole transporting compound and a chain polymerization material is preferable from the viewpoints of electrophotographic characteristics, versatility, material design, and production stability of an electrophotographic photoreceptor having a surface layer made of a curable resin. Furthermore, an electrophotographic photoreceptor constituted by a surface layer obtained by curing a compound having both a hole transporting group and an acryloyloxy group in the molecule is particularly preferable.

  As the curing means, known means such as heat, light or radiation can be used.

  In the case of a charge transport layer, the average thickness of the cured layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 35 μm or less. In the case of the second charge transport layer or protective layer, the thickness is preferably 0.3 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less.

  Various additives can be added to each layer of the electrophotographic photoreceptor of the present invention. Examples of the additive include antioxidants such as antioxidants and ultraviolet absorbers.

  By the method of the present invention described above, an electrophotographic photosensitive member having a plurality of concave and convex shapes on the surface of the underlayer can be produced.

  Examples of the concavo-convex shape of the underlayer of the electrophotographic photoreceptor include, for example, a shape constituted by a straight line, a shape constituted by a curve, or a shape constituted by a straight line and a curve in the observation of the surface of the underlayer. Examples of the shape constituted by straight lines include a triangle, a quadrangle, a pentagon, and a hexagon. Examples of the shape constituted by the curve include a circular shape or an elliptical shape. Examples of the shape formed by straight lines and curves include a square with a rounded corner, a hexagon with a rounded corner, and a sector. Further, in the observation of the cross section of the photoreceptor, the uneven shape of the ground surface of the electrophotographic photoreceptor in the present invention includes, for example, a shape constituted by straight lines, a shape constituted by curves, or a shape constituted by straight lines and curves. It is done. Examples of the shape constituted by straight lines include a triangle, a quadrangle, and a pentagon. Examples of the shape constituted by the curve include a partial circular shape and a partial elliptical shape. Examples of the shape constituted by straight lines and curves include a square with a rounded corner or a fan shape. Among these, it is more preferable that the concavo-convex shape is constituted by a portion having a curve. This is because the irregular reflection of the laser beam is more likely to occur more effectively when the unevenness of the surface of the photoreceptor underlayer has a curved portion. When the concavo-convex shape is a straight line or when the concavo-convex linear portion is large to some extent, the laser light is likely to be regularly reflected, and multiple reflected light is easily generated in the photosensitive layer, and interference fringes are likely to occur. In the above-described concavo-convex forming methods 1 to 3 on the surface of the underlayer, the concavo-convex shape having a curved portion is generally formed on the concavo-convex shape formed on the surface of the photoreceptor underlayer.

  Specific examples of the concave shape on the surface of the electrophotographic photosensitive member are shown in FIGS. FIG. 1 shows an example of the uneven shape (surface). FIG. 2 shows an example of a concave shape (cross section). FIG. 3 shows a convex shape example (cross section). The uneven shape on the surface of the electrophotographic photosensitive member may have different shapes, sizes, depths / heights, and all the uneven shapes have the same shape, size, or depth. May be. Further, the surface of the underlayer of the electrophotographic photosensitive member is a surface in which concave and convex shapes having different shapes, sizes or depths / heights and concave shapes having the same shape, size or depth are combined. There may be. Further, these shapes may have overlapping portions or may overlap each other.

  Next, the size of the uneven shape on the surface of the electrophotographic photoreceptor underlayer will be described. In the case of a concave shape, the major axis diameter (L1) is used as an index of size. The major axis diameter (L1) indicates the length of the maximum straight line among the straight lines crossing the apertures of the concave portions. Specifically, as indicated by the major axis diameter (L1) in FIG. 2, the surface opening of each concave shape is defined with reference to the surface surrounding the concave hole portion on the surface of the electrophotographic photosensitive member. Indicates the maximum length of the hole. For example, when the concave surface shape is circular, the diameter is indicated, when the surface shape is elliptical, the major axis is indicated, and when the surface shape is quadrilateral, a long diagonal line is shown among the diagonal lines. The major axis diameter (L1) of the concave shape on the surface of the electrophotographic photosensitive member base is arbitrary, but is preferably 0.1 μm or more and 7.0 μm or less. Furthermore, it is more preferably 0.3 μm or more and 5.0 μm or less, and even more preferably 3.0 μm or less.

  The depth in the case of a concave shape will be described. The depth (D) is used as the concave shape index. The depth (D) indicates the distance between the deepest part of each concave shape and the aperture surface. Specifically, as shown by the depth (D) in FIG. 2, the surface around the concave hole portion on the surface of the electrophotographic photosensitive member underlayer is used as a reference and the deepest portion of the concave shape Indicates the distance to the aperture surface. The depth (D) of the concave shape on the surface of the electrophotographic photosensitive member base is arbitrary, but is preferably 0.1 μm or more and 10 μm or less. Furthermore, it is more preferably 0.3 μm or more and 7 μm or less, and further preferably 5 μm or less.

  The size of the convex shape on the surface of the electrophotographic photoreceptor underlayer will be described. The major axis diameter (L2) is used as the convex index. The major axis diameter (L2) refers to the maximum length of a portion where each convex shape and the surrounding surface are in contact with each other on the basis of the surface around each convex shape portion. Specifically, it indicates that the length is indicated by the major axis diameter (L2) in FIG. For example, when the convex surface shape is circular, the diameter is indicated, when the surface shape is elliptical, the major axis is indicated, and when the surface shape is quadrilateral, a long diagonal line is shown among the diagonal lines. The major axis diameter (L2) of the convex shape on the surface of the electrophotographic photosensitive member base is arbitrary, but is preferably 0.5 μm or more and 7.0 μm or less. Furthermore, it is preferably 1 μm or more and 5.0 μm or less, and more preferably 3.0 μm or less.

  The height of the convex shape will be described. The height (H) is used as the convex shape index. The height (H) indicates the distance between the top of each convex shape and the surrounding surface. Specifically, the distance indicated by the height (H) in FIG. 3 is shown. The height (H) of the convex shape on the surface of the electrophotographic photosensitive member base is arbitrary, but is preferably 0.1 μm or more and 10 μm or less. Furthermore, it is more preferably 0.3 μm or more and 7 μm or less, and further preferably 5 μm or less.

  In addition, the region where the concavo-convex shape of the surface of the electrophotographic photosensitive member base layer is formed may be the entire surface of the photosensitive member, or may be formed on a part of the surface. It is preferable from the viewpoint of preventing interference fringe images that unevenness is formed in the entire region. Moreover, even if it is only convex shape or only concave shape, both may be mixed. Further, it is preferable that the uneven shape on the surface of the electrophotographic photosensitive member base has 10 or more and 40,000 or less in a 100 μm square of the surface of the electrophotographic photosensitive member base. Furthermore, it is more preferable to have 100 or more and 20,000 or less. The 100 μm square area is a total of 100 areas obtained by dividing the surface of the electrophotographic photosensitive member into four equal parts in the direction of rotation of the photosensitive member and 25 parts in the direction orthogonal to the rotational direction of the photosensitive member. Measurement is performed by providing a square region of 100 μm on each side.

  The uneven shape on the surface of the electrophotographic photoreceptor underlayer can be measured using, for example, a commercially available laser microscope, optical microscope, electron microscope, or atomic force microscope.

  As the laser microscope, for example, the following devices can be used. Ultra-deep shape measurement microscope VK-8550, ultra-deep shape measurement microscope VK-9000, and ultra-deep shape measurement microscope VK-9500 (all manufactured by Keyence Corporation). Surface shape measuring system Surface Explorer SX-520DR type machine (manufactured by Ryoka Systems Inc.). Scanning confocal laser microscope OLS3000 (manufactured by Olympus Corporation). Real color confocal microscope Oplitex C130 (manufactured by Lasertec Corporation).

  As the optical microscope, for example, the following devices can be used. Digital microscope VHX-500 and digital microscope VHX-200 (both manufactured by Keyence Corporation). 3D digital microscope VC-7700 (manufactured by OMRON Corporation).

  As the electron microscope, for example, the following devices can be used. 3D real surface view microscope VE-9800 and 3D real surface view microscope VE-8800 (both manufactured by Keyence Corporation). Scanning electron microscope conventional / variable pressure SEM (manufactured by SII Nanotechnology Co., Ltd.). Scanning electron microscope SUPERSCAN SS-550 (manufactured by Shimadzu Corporation).

  As the atomic force microscope, for example, the following devices can be used. Nanoscale hybrid microscope VN-8000 (manufactured by Keyence Corporation). Scanning probe microscope NanoNavi station (manufactured by SII Nanotechnology Inc.). Scanning probe microscope SPM-9600 (manufactured by Shimadzu Corporation).

  Using the microscope, the major axis diameter, depth, and height of the concavo-convex shape in the measurement visual field can be measured with a predetermined magnification.

As an example, a measurement example using an analysis program by the Surface Explorer SX-520DR type machine will be described. First, an electrophotographic photosensitive member to be measured is placed on a work table, tilted to adjust the level, and three-dimensional shape data of the peripheral surface of the electrophotographic photosensitive member is captured in a wave mode. At that time, the magnification of the objective lens may be 50 times, and the field of view may be 100 μm × 100 μm (10000 μm ² ). In this method, the surface of the photoconductor to be measured is divided into four equal parts in the direction of rotation of the photoconductor and divided into 25 equal parts in a direction perpendicular to the direction of rotation of the photoconductor, Measurement is performed by providing a square region having a side of 100 μm. Next, the contour line data of the ground surface of the electrophotographic photosensitive member is displayed using a particle analysis program in the data analysis software.

The analysis parameters of the concavo-convex shape such as the concavo-convex shape, major axis diameter, depth and height can be optimized by the formed concavo-convex shape. For example, in the case of observing and measuring a concavo-convex shape having a major axis diameter of about 10 μm, the major axis diameter upper limit may be 15 μm, the major axis diameter lower limit may be 1 μm, the depth lower limit may be 0.1 μm, and the volume lower limit may be 1 μm ³ or more. Then, the number of concavo-convex shapes that can be determined as concavo-convex shapes on the analysis screen is counted, and this is used as the number of concavo-convex shapes. In addition, although the concave / convex shape with the major axis diameter of about 1 μm or less can be observed with a laser microscope and an optical microscope, in order to further increase the measurement accuracy, observation and measurement with an electron microscope should be used in combination. Is desirable.

  Next, a process cartridge and an electrophotographic apparatus on which the electrophotographic photosensitive member produced by the manufacturing method of the present invention is mounted will be described. FIG. 6 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member according to the present invention.

  In FIG. 6, a cylindrical electrophotographic photosensitive member 1 is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed. The surface of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined positive or negative potential by a charging unit (primary charging unit: for example, a charging roller) 3. 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 surface of the electrophotographic photosensitive member 1. Then, the electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in the developer of the developing unit 5 to become a toner image. The toner image is transferred from a transfer material supply unit (not shown) between the electrophotographic photosensitive member 1 and the transfer unit 6 (contact portion) by a transfer bias from a transfer unit (for example, a transfer roller) 6. The images are sequentially transferred onto a transfer material (for example, paper) P fed in synchronism with the rotation of 1. Then, the transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and is introduced into the fixing unit 8 to be subjected to image fixing, and as an image formed product (print, copy), is taken out of the apparatus. Printed 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 transfer by a cleaning means (for example, a cleaning blade) 7.

  Further, the surface of the electrophotographic photoreceptor 1 is subjected to charge removal processing by pre-exposure light (not shown) from pre-exposure means (not shown), and then repeatedly used for image formation. As shown in FIG. 6, when the charging unit 3 is a contact charging unit using, for example, a charging roller, pre-exposure is not always necessary.

  Of the above-described group of components of the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7, a plurality of components may be housed in a container and integrally coupled as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 6, the electrophotographic photosensitive member 1, the charging means 3, the developing means 5 and the cleaning means 7 are integrally supported to form a cartridge, and the electrophotographic apparatus is electrophotographic using a guide means 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the apparatus main body.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the examples, “part” means “part by mass”.

Example 1
In this example, an electrophotographic photosensitive member was manufactured according to the manufacturing method of the present invention.

  An aluminum cylinder with a length of 260.5 mm and a diameter of 30 mm obtained by hot extrusion in an environment of 23 ° C. and 60% RH (an aluminum alloy ED tube specified as material symbol A3003 in JIS, Showa Aluminum ( Co., Ltd.) was used as a support. It was 0.8 micrometer when Rzjis of the support surface of the area | region of 100-150 mm from this support body edge part was measured. Here, the measurement of Rzjis is according to JIS-B0601 (1994), using a surface roughness meter Surfcoder SE3500 manufactured by Kosaka Laboratory Ltd., feed rate 0.1 mm / second, cutoff λc 0.8 mm, The measurement length was set to 2.50 mm. The following measurement of Rzjis was performed under the same conditions.

  Next, the coating material for conductive layers was prepared as follows.

First, 55 parts of oxygen-deficient SnO ₂ -coated TiO ₂ particles, 36.5 parts of phenol resin as a binder resin, 30 parts of methoxypropanol as a solvent, and 5 parts of methanol were mixed with a sand mill using glass beads having a diameter of 1 mm. A dispersion was prepared by time dispersion. Here, the oxygen-deficient SnO ₂ -coated TiO ₂ particles have a powder resistivity of 100 Ω · cm, and the SnO ₂ coverage (mass ratio) is 40%. Moreover, the said phenol resin is a brand name: Praiofen J-325, Dainippon Ink and Chemicals Co., Ltd., and resin solid content is 60%.

  To the dispersion, 0.001 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) as a leveling agent was added and stirred to prepare a coating solution for a conductive layer.

The average particle diameter of the oxygen-deficient SnO ₂ -coated TiO ₂ particles in this conductive layer coating solution is 0.36 μm, and the ratio of the particles having a particle diameter in the range of 0.10 to 0.40 μm is as follows. It was 61.2 mass%.

  The conductive layer coating prepared by the above method was directly dip coated on a support whose surface temperature was adjusted to 20 ° C., and the conductive layer coating solution was applied on the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in the support holding process apparatus that had been previously set to a relative humidity of 80% and an atmospheric temperature of 60 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed.

  Next, an intermediate layer coating material having the following components dissolved in 600 parts of methanol is dip-coated on the conductive layer, and immediately dried by heating in an oven heated to 100 ° C. for 30 minutes. An intermediate layer having an average film thickness of 1.0 μm at a position of 130 mm from the upper end was formed.

Copolymer nylon resin 10 parts (Product name: Amilan CM8000, manufactured by Toray Industries, Inc.)
30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.)

  Next, the following components were dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 4 hours, and then 700 parts of ethyl acetate was added to prepare a charge generation layer coating material.

20 parts of hydroxygallium phthalocyanine (in CuKα characteristic X-ray diffraction, 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 °, 28.3 ° (Bragg angle (2θ ± 0. Having a strong diffraction peak at 2 °))
0.2 parts of calixarene compound represented by the following structural formula (1)

10 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical)
600 parts of cyclohexanone

  The charge generation layer coating material is applied onto the intermediate layer by a dip coating method and dried by heating in an oven heated to 100 ° C. for 10 minutes, whereby the average film thickness at a position of 130 mm from the upper end of the support is 0.17 μm. The charge generation layer was formed.

  Next, the following components were dissolved in a mixed solvent of 350 parts of chlorobenzene and 150 parts of methylal to prepare a charge transport layer coating material.

35 parts of the compound represented by the following structural formula (2)

5 parts of the compound represented by the following structural formula (3)

50 parts of copolymerized polyarylate resin represented by the following structural formula (4)

(In the formula, m and n represent the ratio (copolymerization ratio) of the repeating unit in the resin, and in the resin, m: n = 7: 3)

  The molar ratio of the terephthalic acid structure to the isophthalic acid structure (terephthalic acid skeleton: isophthalic acid skeleton) in the polyarylate resin is 50:50. The weight average molecular weight (Mw) is 120,000.

  Using this, the charge transport layer is dip-coated on the charge generation layer and dried in an oven heated to 110 ° C. for 30 minutes, whereby the average film thickness at a position of 130 mm from the upper end of the support is 20 μm. A charge transport layer was formed. Thus, an electrophotographic photosensitive member having a support, a conductive layer, an intermediate layer, a charge generation layer, and a charge transport layer in this order, and the charge transport layer being a surface layer was produced.

  Moreover, in this invention, the weight average molecular weight of resin was measured as follows according to a conventional method.

  First, the measurement target resin was placed in tetrahydrofuran and allowed to stand for several hours, and then the measurement target resin and tetrahydrofuran were mixed well while shaking (mixed until the measurement target resin was not united), and then allowed to stand for 12 hours or more. . Then, what passed the sample processing filter Mysori disk H-25-5 by Tosoh Corporation was made into the sample for GPC (gel permeation chromatography). Next, the column is stabilized in a heat chamber at 40 ° C., tetrahydrofuran is flowed through the column at this temperature at a flow rate of 1 ml / min, 10 μl of GPC sample is injected, and the weight average molecular weight of the measurement target resin Was measured. A column TSKgel Super HM-M manufactured by Tosoh Corporation was used as the column.

  In the measurement of the weight average molecular weight of the measurement target resin, the molecular weight distribution of the measurement target resin was calculated from the relationship between the logarithmic value of the calibration curve prepared by several kinds of monodisperse polystyrene standard samples and the count number. The following were used as standard polystyrene samples for preparing a calibration curve. That is, it is a monodisperse polystyrene manufactured by Aldrich, and has a molecular weight of 3,500, 12,000, 40,000, 75,000, 98,000, 120,000, 240,000, 500,000, 800,000, 1,800,000 was used. An RI (refractive index) detector was used as the detector.

  Next, the volume resistivity of the underlayer was measured as follows.

Using the conductive layer coating solution and the intermediate layer coating solution, a 20 μm thick conductive layer and a 3 μm thick intermediate layer sample were respectively formed on an aluminum sheet. A gold thin film was formed on the sample by vapor deposition, and the volume resistivity of the conductive layer and the intermediate layer was measured by the method described above. As a result, the volume resistivity of the conductive layer was 8.5 × 10 ⁸ Ω · cm, and the volume resistivity of the intermediate layer was 2.0 × 10 ¹² Ω · cm.

<Measurement of surface shape of electrophotographic photosensitive member conductive layer surface>
The surface of the underlayer of the produced electrophotographic photosensitive member (the surface of the conductive layer when the concavo-convex shape was formed on the conductive layer, or the surface of the intermediate layer when the concavo-convex shape was formed on the intermediate layer) was measured using the ultra-deep shape measuring microscope VK-9500 ( (Manufactured by Keyence Corporation). First, the electrophotographic photosensitive member to be measured is placed on a pedestal that has been processed so that the cylindrical support can be fixed, the objective lens magnification is 50 times, and the surface of the base layer at a position of 130 mm from the upper end of the electrophotographic photosensitive member is 100 μm. The field was observed in all directions, and the uneven portion was measured. Each of the above 100 μm square areas is divided into four equal parts in the rotation direction of the photosensitive member on the base surface of the electrophotographic photosensitive member, and divided into 25 equal parts in a direction perpendicular to the rotational direction of the photosensitive member. In the measurement, a square region having a side of 100 μm was provided. Within the range evaluated in this way, the unevenness of the surface of the underlayer was observed. About the observed uneven | corrugated shaped part, the maximum length (L1) of an opening part and the length from an opening part to the deepest part, ie, depth (D), were measured, and the average value was computed. For the convex portion, the maximum length (L2) of the portion where the convex shape and the surrounding surface are in contact with each other, and the distance between the top of the convex shape and the surrounding surface, that is, the height (H), are measured, and the average The value was calculated. In addition, it measured similarly about the case where both concave shape and convex shape exist, and calculated the average value of L1, L2, D, and H as an absolute value. In addition, the number of concavo-convex shapes around 100 μm square was also calculated. The measurement results are shown in Table 1 below.

<Image evaluation of electrophotographic photoreceptor>
The electrophotographic photosensitive member produced according to the examples was evaluated for interference fringes and image defects using the following evaluation apparatus.

  As an evaluation apparatus, LBP-2510 manufactured by Canon Inc. (primary charging: contact withstand voltage method applying only DC voltage, process speed: 94.2 mm / second) was modified and used. The modification was performed as follows so that the image exposure amount could be adjusted and the resolutions of 600 dpi and 1200 dpi could be obtained. That is, a laser beam capable of outputting a resolution of 600 dpi at a wavelength of 780 nm and a laser spot diameter of 60 μm and a laser beam capable of outputting a resolution of 1200 dpi at a wavelength of 780 nm and a laser spot diameter of 40 μm were used.

Evaluation is performed in a normal temperature and humidity environment (23 ° C., 65%), halftone images (PBS, 1 dot / 2 space, 2 dots / 3 space) are output at respective resolutions, and interference fringes are visually observed. Leveling was performed according to the following criteria. Also, image defects such as black spots and fog were evaluated. The evaluation results are shown in Table 1 below.
A: No interference fringe pattern is observed.
B: An interference fringe pattern is observed only slightly in a specific image.
C: An interference fringe pattern is observed in a part of the image.
D: An interference fringe pattern is observed on the entire surface of the image.

(Example 2)
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in a support holding process apparatus that had been previously set to a relative humidity of 95% and an atmospheric temperature of 50 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 3)
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in the support holding process apparatus that had been previously set to a relative humidity of 60% and an atmospheric temperature of 65 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

Example 4
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. Then, the support body which has the coating-film surface of the apply | coated coating liquid for conductive layers was rotated at 120 rpm, and the water made into the droplet of diameter 50 micrometers was sprayed for 5 second. After completion of the shape forming step by water spraying, the surface has an uneven shape by heating and curing in an oven preliminarily heated to 140 ° C., and the average film thickness at a position 130 mm from the upper end of the support is 20 μm. A conductive layer was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 5)
Conductive layer having an uneven shape on the surface in the same manner as in Example 4 except that methanol was sprayed instead of spraying water on the conductive layer coating surface, and the average film thickness at a position 130 mm from the upper end of the support was 20 μm. A photoconductor composed of layers was prepared and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 6)
It was produced and prepared by the same method as in Example 4 until the coating liquid for the conductive layer was prepared.

  The conductive layer coating solution was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. Thereafter, for the purpose of drying the coating film surface of the applied coating solution for conductive layer, drying was performed for 15 minutes in a drier maintained at 50 ° C. to form a coating film surface.

  Dilution was performed by adding 5 parts by mass of methanol to 1 part by mass of the coating liquid for the conductive layer coating liquid of Example 1. Then, the support body which has the coating-film surface of the apply | coated coating liquid for conductive layers was rotated at 120 rpm, and the coating liquid for conductive layers diluted with respect to the coating-film surface was sprayed for 5 seconds. After completion of the shape forming step by spraying the conductive layer dilution liquid, the surface has an uneven shape by heating and curing in an oven preliminarily heated to 140 ° C., and the average film thickness at a position of 130 mm from the upper end of the support. Formed a conductive layer of 20 μm. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 7)
In the preparation of the coating liquid for the conductive layer in Example 1, preparation of the coating liquid for the conductive layer was conducted in the same manner as in Example 1 except that the solvent used was changed from 30 parts methoxypropanol and 5 parts methanol to 35 parts toluene. Produced. A conductive layer having a concave shape on the surface of the conductive layer and an average film thickness of 20 μm at a position 130 mm from the upper end of the support was formed. Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

(Example 8)
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. Immediately after that, the inside of the apparatus is heated and cured in an oven heated to 140 ° C. for 60 minutes, so that the surface does not have an uneven shape, and the conductive layer has an average film thickness of 20 μm at a position 130 mm from the upper end of the support. Formed.

  Next, an intermediate layer coating material in which the following components were dissolved in a mixed solution of 350 parts of 1-butanol and 50 parts of methanol was dip-coated on the conductive layer.

Copolymer nylon resin 10 parts (Product name: Amilan CM8000, manufactured by Toray Industries, Inc.)
30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.)

  After 60 seconds from the end of the coating process, the support coated with the intermediate layer coating liquid was held for 120 seconds in a support holding process apparatus that had been previously set to a relative humidity of 80% and an atmospheric temperature of 60 ° C. After 60 seconds from the end of the support holding process, the surface of the apparatus has an uneven shape by heating and drying in an oven preheated to 100 ° C. for 30 minutes, and an average film at a position of 130 mm from the upper end of the support An intermediate layer having a thickness of 4.0 μm was formed. Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

Example 9
A conductive layer / intermediate layer coating solution was prepared and prepared in the same manner as in Example 8, and the conductive layer coating solution was dip coated on the support. A conductive layer having an average film thickness of 20 μm was formed. Thereafter, the intermediate layer coating solution was applied onto the conductive layer by dip coating. Then, the support which has the coating-film surface of the coating liquid for intermediate | middle layers was rotated at 120 rpm, and the process which sprayed the water made into the droplet of 40 micrometers in diameter for 5 second was performed. After completion of the shape forming process by water spraying, the surface has an uneven shape by heating and drying in an oven preheated to 100 ° C. for 30 minutes, and the average film thickness at a position of 130 mm from the upper end of the support Formed an intermediate layer of 4.0 μm. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 10)
The surface has an uneven shape by the same method as in Example 9 except that methanol was sprayed instead of spraying water on the surface of the intermediate layer coating film, and the average film thickness at a position 130 mm from the upper end of the support was 4.0 μm. A photoconductor composed of an intermediate layer was prepared and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 11)
A conductive layer / intermediate layer coating solution was prepared and prepared by the same method as in Example 8, and the conductive layer coating solution was applied onto the support and dried to form a conductive layer having no irregularities on the surface. Next, the intermediate layer coating solution was applied onto the conductive layer by dip coating. In order to dry the coating film surface of the applied coating solution for intermediate layer, the coating film surface was formed by performing simple drying for 15 minutes in a drier heated and held at 40 ° C.

  Next, dilution was performed by adding 2 parts by mass of methanol to 1 part by mass of the intermediate layer coating liquid in the intermediate layer coating liquid of Example 1. Then, the support body which has the coating-film surface of the apply | coated intermediate | middle layer coating liquid was rotated at 120 rpm, and the coating liquid for intermediate | middle layers diluted with respect to the coating-film surface was sprayed for 5 seconds.

  After completion of the shape forming step by spraying the intermediate layer dilution liquid, the surface has an uneven shape by heating and drying in an oven heated to 100 ° C. in advance, and the surface has an uneven shape and is positioned 130 mm from the upper end of the support. A conductive layer having an average film thickness of 4.2 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

Example 12
In the preparation of the intermediate layer coating solution in Example 8, the resin used was 40 parts of polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., ESREC BM-S), and the solvent used was 350 parts of 1-butanol, methanol. The mixture was changed from 50 parts to 400 parts toluene. Other than that, the coating liquid for intermediate | middle layer was prepared and produced similarly to Example 1, the intermediate | middle layer surface has a concave shape, and the intermediate | middle layer whose average film thickness of the position of 130 mm from a support upper end is 4.0 micrometers is obtained. Formed. Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the intermediate layer by the same method as described in Example 1, it was 8.5 × 10 ¹⁴ Ω · cm.

(Example 13)
The preparation of the conductive layer coating solution in Example 1 was changed as follows.

  Disperse 55 parts of zinc oxide particles, 36.5 parts of phenol resin as a binder resin, 30 parts of methoxypropanol as a solvent and 5 parts of methanol in a sand mill using glass beads having a diameter of 1 mm for 3 hours. Prepared. Here, the said zinc oxide particle is a brand name: Passette 23K, the product made from Hakusui Tech Co., Ltd. The phenol resin is trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., and has a resin solid content of 60%.

  To this dispersion, 0.001 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) as a leveling agent was added and stirred to prepare a coating solution for a conductive layer.

  The average particle diameter of the zinc oxide particles after dispersion in this conductive layer coating solution is 0.37 μm, and among these particles, the proportion of particles having a particle diameter in the range of 0.10 to 0.40 μm is 71.5. It was mass%.

  The conductive layer coating prepared by the above method was dip-coated directly on the support, and the conductive layer coating solution was applied on the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in the support holding process apparatus that had been previously set to a relative humidity of 80% and an atmospheric temperature of 60 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the conductive layer by the same method as that described in Example 1, it was 8.5 × 10 ⁹ Ω · cm.

(Example 14)
In the preparation of the conductive layer coating solution in Example 13, the solvent used was changed from 30 parts methoxypropanol and 5 parts methanol to 35 parts toluene. Otherwise, a conductive layer coating solution was prepared and produced in the same manner as in Example 1, and a conductive layer having a concave shape on the surface of the conductive layer and an average film thickness of 20 μm at a position 130 mm from the upper end of the support was formed. . Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 13, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

(Example 15)
It was produced and prepared by the same method as in Example 13 until the coating liquid for the conductive layer was prepared.

  The conductive layer coating solution was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. Then, for the purpose of drying the coating film surface of the applied conductive layer coating solution, the coating film surface was formed by performing simple drying for 15 minutes in a drier heated and held at 50 ° C.

  Dilution was performed by adding 5 parts by mass of methanol to 1 part by mass of the coating liquid for the conductive layer coating liquid of Example 13. Then, the support which has the coating-film surface of the apply | coated coating liquid for conductive layers was rotated at 120 rpm, and the process which sprayed the coating liquid for conductive layers diluted with respect to the coating-film surface for 5 second was performed.

  After completion of the shape forming step by spraying the conductive layer dilution liquid, the surface of the apparatus is heat-cured for 60 minutes in an oven heated to 140 ° C., so that the surface has an uneven shape and is 130 mm from the upper end of the support. A conductive layer having an average film thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 16)
The preparation of the coating liquid for the conductive layer in Example 1 was changed as follows.

  A dispersion was prepared by dispersing 55 parts of zinc oxide particles, 36.5 parts of phenol resin as a binder resin, and 35 parts of toluene as a solvent in a sand mill using glass beads having a diameter of 1 mm for 3 hours. Here, the said zinc oxide particle is a brand name: Passetto CK, the product made from Hakusui Tech Co., Ltd. The phenol resin is trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., and has a resin solid content of 60%.

  To this dispersion, 0.001 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) as a leveling agent was added and stirred to prepare a coating solution for a conductive layer.

  The average particle diameter of the zinc oxide particles after dispersion in the conductive layer coating solution is 0.11 μm, and the ratio of the particles having a particle diameter in the range of 0.10 to 0.40 μm is 25.3. It was mass%.

  The conductive layer coating prepared by the above method was dip-coated directly on the support, and the conductive layer coating solution was applied on the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in the support holding process apparatus that had been previously set to a relative humidity of 80% and an atmospheric temperature of 60 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the conductive layer by the same method as described in Example 1, it was 1.0 × 10 ¹¹ Ω · cm.

(Example 17)
The preparation of the coating liquid for the conductive layer in Example 1 was changed as follows.

  55 hours of conductive powder composed of barium sulfate particles having a tin oxide coating layer, 36.5 parts of phenol resin as a binder resin, and 35 parts of toluene as a solvent in a sand mill using glass beads having a diameter of 1 mm for 5 hours Dispersed to prepare a dispersion. Here, the conductive powder made of the barium sulfate particles having the tin oxide coating layer is a trade name: Pastoran PC1, manufactured by Mitsui Mining & Smelting Co., Ltd. The phenol resin is trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., and has a resin solid content of 60%.

  To this dispersion, 0.001 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) as a leveling agent was added and stirred to prepare a coating solution for a conductive layer.

  The average particle size of the dispersed particles in this conductive layer coating solution is 0.22 μm, and the proportion of the particles having a particle size in the range of 0.10 to 0.40 μm is 45.3 mass%. Met.

  The conductive layer coating prepared by the above method was dip-coated directly on the support, and the conductive layer coating solution was applied on the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in the support holding process apparatus that had been previously set to a relative humidity of 80% and an atmospheric temperature of 60 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the conductive layer by the same method as that described in Example 1, it was 3.0 × 10 ¹² Ω · cm.

(Example 18)
In the preparation of the conductive layer coating solution in Example 13, the following changes were made. That is, the resin used was changed from 36.5 parts of phenol resin to 36.5 parts of acrylic melamine resin, and the solvent was changed from 10 parts methoxypropanol and 25 parts methanol to 30 parts xylene and 5 parts methoxypropanol. Here, the said acrylic melamine resin is a brand name: brand name: Acrose # 6000, Dainippon Paint Co., Ltd., and resin solid content is 60%. Other than that, the coating liquid for conductive layers was prepared and produced similarly to Example 13, and the conductive layer surface had an uneven | corrugated shape, and formed the conductive layer with an average film thickness of 20 micrometers in the position of 130 mm from the support upper end. . Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

The volume resistivity of the conductive layer was measured by the same method as that described in Example 1, and the result was 4.4 × 10 ¹⁰ Ω · cm.

Example 19
The support in Example 1 was changed to the following cutting tube.

  First, an aluminum base tube having an outer diameter of 30.5 mm, an inner diameter of 28.5 mm, a length of 260.5 mm, a runout accuracy of 100 μm, and Rzjis of 10 μm, obtained by hot extrusion, was mounted on a lathe. Then, the aluminum tube was cut with a diamond sintered tool to obtain a cutting tube having an outer diameter of 30.0 ± 0.02 mm, runout accuracy of 15 μm, and Rzjis 0.2 μm. The aluminum base tube is made of an aluminum alloy specified as a material symbol A6063 in JIS H4000: 1999.

  In the cutting process, the spindle rotation speed was 3000 rpm, the bite feed rate was 0.3 mm / rev, and the machining time was 24 seconds except for the attachment / detachment of the workpiece.

  The cutting tube was used as a support, the conductive layer was not applied, and an intermediate layer coating solution was prepared and prepared on the support in the same manner as in Example 8. Then, the intermediate layer coating material was directly dip coated on the support to form an intermediate layer having an uneven surface on the surface and an average film thickness of 4.0 μm at a position of 130 mm from the upper end of the support.

  Subsequent steps were carried out in the same manner as in Example 1, and an electrophotographic photosensitive member in which an intermediate layer, a charge generation layer, and a charge transport layer were laminated in this order on a support was produced. The produced photoreceptor was measured and evaluated in the same manner as in Example 1. The measurement and evaluation results are shown in Table 1 below.

(Example 20)
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After 60 seconds from the end of the coating process, the support coated with the conductive layer coating liquid was held for 120 seconds in a support holding process apparatus that had been previously set to a relative humidity of 40% and an atmospheric temperature of 30 ° C. After 60 seconds from the end of the support holding process, the surface is uneven by heating and curing in an oven preheated to 140 ° C. for 60 minutes, and the average film at a position of 130 mm from the upper end of the support A conductive layer having a thickness of 20 μm was formed. Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Example 21)
In the preparation of the conductive layer coating solution in Example 1, the solvent used was changed from 30 parts methoxypropanol and 5 parts methanol to 35 parts methanol. Otherwise, a conductive layer coating solution was prepared and produced in the same manner as in Example 1, and a conductive layer having a concave shape on the surface of the conductive layer and an average film thickness of 20 μm at a position 130 mm from the upper end of the support was formed. . Also in the subsequent steps, an electrophotographic photosensitive member was prepared in the same manner as in Example 1, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

(Comparative Example 1)
The conductive layer coating material prepared and prepared in the same manner as in Example 1 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After that, without conducting the shape forming step, the device is immediately heated and cured in an oven preheated to 140 ° C. for 60 minutes to form a conductive layer having an average film thickness of 20 μm at a position 130 mm from the upper end of the support. did.

  Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Comparative Example 2)
The preparation of the coating liquid for the conductive layer in Example 1 was changed as follows.

Disperse 55 parts of oxygen-deficient SnO ₂ -coated TiO ₂ particles, 36.5 parts of phenol resin as a binder resin, 30 parts of methoxypropanol as a solvent, and 5 parts of methanol in a sand mill using glass beads with a diameter of 1 mm for 3 hours. A dispersion was prepared. Here, the oxygen-deficient SnO ₂ -coated TiO ₂ particles have a powder resistivity of 100 Ω · cm, and the SnO ₂ coverage (mass ratio) is 40%. The phenol resin is trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., and has a resin solid content of 60%.

  To this dispersion, 1.0 part of silicone resin particles as a surface roughening agent and 0.001 part of silicone oil as a leveling agent were added and stirred to prepare a coating solution for a conductive layer. Here, the silicone resin particles have a trade name: Tospearl 120, manufactured by GE Toshiba Silicone Co., Ltd., and an average particle diameter of 2 μm. The silicone oil is trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.

The average particle diameter of the oxygen-deficient SnO ₂ -coated TiO ₂ particles in this conductive layer coating solution is 0.33 μm, and among these particles, the proportion of particles having a particle diameter in the range of 0.10 to 0.40 μm is It was 63.1% by mass.

  The conductive layer coating prepared by the above method was dip-coated directly on the support, and the conductive layer coating solution was applied on the support. After that, without conducting the shape forming step, the device is immediately heated and cured in an oven preheated to 140 ° C. for 60 minutes to form a conductive layer having an average film thickness of 20 μm at a position 130 mm from the upper end of the support. did.

  Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the conductive layer by the same method as that described in Example 1, it was 2.2 × 10 ¹⁰ Ω · cm.

(Comparative Example 3)
The preparation of the coating liquid for the conductive layer in Example 1 was changed as follows.

Disperse 55 parts of oxygen-deficient SnO ₂ -coated TiO ₂ particles, 36.5 parts of phenol resin as a binder resin, 30 parts of methoxypropanol as a solvent, and 5 parts of methanol in a sand mill using glass beads with a diameter of 1 mm for 3 hours. A dispersion was prepared. Here, the oxygen-deficient SnO ₂ -coated TiO ₂ particles have a powder resistivity of 100 Ω · cm, and the SnO ₂ coverage (mass ratio) is 40%. The phenol resin is trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., and has a resin solid content of 60%.

  To this dispersion, 13 parts of silicone resin particles as a surface roughening agent and 0.001 part of silicone oil as a leveling agent were added and stirred to prepare a coating solution for a conductive layer. Here, the silicone resin particles have a trade name: Tospearl 120, manufactured by GE Toshiba Silicone Co., Ltd., and an average particle diameter of 2 μm. The silicone oil is trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.

The average particle diameter of the oxygen-deficient SnO ₂ -coated TiO ₂ particles in this conductive layer coating solution is 0.30 μm, and among these particles, the proportion of particles having a particle diameter in the range of 0.10 to 0.40 μm is It was 66.1 mass%.

  The conductive layer coating prepared by the above method was dip-coated directly on the support, and the conductive layer coating solution was applied on the support. After that, without performing the shape forming step, the surface is not uneven, by heating and curing in an oven heated in advance to 140 ° C. for 60 minutes. A conductive layer having a thickness of 20 μm was formed.

  Except for these, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

In addition, as a result of measuring the volume resistivity of the conductive layer by the same method as that described in Example 1, it was 2.3 × 10 ¹⁴ Ω · cm.

(Comparative Example 4)
In the production of the electrophotographic photosensitive member in Example 19, the conductive layer was not applied on the support, the intermediate layer was directly dip coated on the support, and the shape forming step was not performed on the surface of the intermediate layer. In the same manner as in Example 19, an electrophotographic photosensitive member was prepared and measured and evaluated. The measurement and evaluation results are shown in Table 1 below.

(Comparative Example 5)
The preparation of the intermediate layer coating solution in Example 8 was changed as follows.

Copolymer nylon resin 10 parts (Product name: Amilan CM8000, manufactured by Toray Industries, Inc.)
30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.)
Titanium oxide SMT500SAS (first time: silica / alumina treatment, second time: methyl hydrogen polysiloxane treatment, number average primary particle size 35 nm: manufactured by Teica) 5 parts

  The above materials were added to 600 parts of methanol in the same container and dispersed using an ultrasonic homogenizer to prepare an intermediate layer coating solution.

  The intermediate layer coating material thus prepared was dip-coated on the conductive layer, and without being subjected to the shape forming step, the coating material was immediately dried by heating in an oven preheated to 100 ° C. for 10 minutes. By doing so, an intermediate layer having an average film thickness of 0.8 μm at a position 130 mm from the upper end of the support was formed.

  Otherwise, an electrophotographic photoreceptor was prepared in the same manner as in Example 8, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

(Comparative Example 6)
The process after applying the conductive layer on the support in Example 13 was changed as follows.

  The conductive layer coating material prepared in Example 13 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After that, without conducting the shape forming step, the device is immediately heated and cured in an oven preheated to 140 ° C. for 60 minutes to form a conductive layer having an average film thickness of 20 μm at a position 130 mm from the upper end of the support. did.

  Otherwise, an electrophotographic photoreceptor was prepared in the same manner as in Example 13, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

(Comparative Example 7)
The process after applying the conductive layer on the support in Example 17 was changed as follows.

  The conductive layer coating material prepared in Example 17 was directly dip coated on the support, and the conductive layer coating solution was applied onto the support. After that, without conducting the shape forming step, the device is immediately heated and cured in an oven preheated to 140 ° C. for 60 minutes to form a conductive layer having an average film thickness of 20 μm at a position 130 mm from the upper end of the support. did.

  Otherwise, an electrophotographic photoreceptor was prepared in the same manner as in Example 17, and measurement and evaluation were performed. The measurement and evaluation results are shown in Table 1 below.

  From the above results, it is possible to easily produce a high-quality electrophotographic photosensitive member that has excellent film properties and does not generate interference fringes by the method of forming irregularities on the surface of the underlayer of the electrophotographic photosensitive member according to the present invention. all right.

It is a figure which shows the example of a shape (surface) of the uneven | corrugated shaped part in this invention. It is a figure which shows the example of a shape (cross section) of the concave shape part in this invention. It is a figure which shows the example of a shape (cross section) of the convex-shaped part in this invention. It is the schematic of a water or alcohol spraying apparatus. It is the schematic of the apparatus which sprays base layer application | coating. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means 41 Injection nozzle 42 Nozzle fixing jig 43 Path 44 Water or alcohol solvent 45 Spray liquid 46 Workpiece support body 47 Cylindrical support body 48 Nozzle support body 49 Arm 51 Injection nozzle 52 Nozzle fixing jig 53 Path 54 Underlayer coating liquid 55 Spray liquid 56 Work support body 57 Cylindrical support body 58 Nozzle support body 59 Arm L1 Concave Major long axis diameter L2 Convex major axis diameter D Depth H Height

Claims (14)

An electrophotographic photosensitive member having at least a photosensitive layer and a base layer comprising either a conductive layer or an intermediate layer on the support, or an underlying layer in which the conductive layer and the intermediate layer are sequentially laminated from the support side. A method for manufacturing a body,
A first step of applying an undercoat layer coating solution on the support;
A second step of forming a base layer having a concavo-convex shape on the surface by causing condensation on the coating surface of the coating liquid for the base layer or spraying the liquid and then drying the surface of the coating film; and
A third step of forming a photosensitive layer by applying a photosensitive layer coating solution on the underlying layer on which the uneven shape is formed;
A method for producing an electrophotographic photosensitive member, comprising:   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the conductive layer contains metal oxide particles and a thermosetting resin.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the intermediate layer contains a thermoplastic resin.   The method for producing an electrophotographic photoreceptor according to claim 2, wherein the metal oxide particles are any one of zinc oxide, tin oxide, and titanium oxide.   5. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the base layer on which the uneven shape is formed in the second step is a conductive layer. 6.   6. The method of manufacturing an electrophotographic photosensitive member according to claim 5, wherein the second step includes an intermediate layer applying step of applying an intermediate layer on the conductive layer on which the uneven shape is formed.   5. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the base layer on which the uneven shape is formed in the second step is an intermediate layer. 6.   The solvent used in the coating liquid for the underlayer contains at least an alcohol solvent having 4 to 8 carbon atoms or a hydrophobic organic solvent. The method for producing an electrophotographic photosensitive member according to Item.   In the second step, in order to cause dew condensation, the coating film surface of the base layer coating solution is maintained in an atmosphere having a relative humidity of 60% to 95%. The method for producing an electrophotographic photosensitive member according to any one of the above.   9. The electrophotographic photosensitive member according to claim 1, wherein in the second step, the liquid sprayed on the coating film surface of the coating solution for the underlayer is water or alcohol. Production method.   The said 2nd process WHEREIN: The liquid sprayed on the coating-film surface of the said coating liquid for base layers is the same component as this coating liquid for base layers, The any one of Claim 1 to 10 characterized by the above-mentioned. A method for producing the electrophotographic photosensitive member according to the description.   An electrophotographic photosensitive member produced by the method according to claim 1.   The electrophotographic photosensitive member according to claim 12 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means are integrally supported and are detachable from the main body of the electrophotographic apparatus. A process cartridge characterized by being.   An electrophotographic apparatus comprising at least the electrophotographic photosensitive member according to claim 12, a charging unit, an exposure unit, a developing unit, a fixing unit, and a transfer unit.