Electrophotographic photoreceptor, process cartridge, and electrophotographic apparatus

Abstract

To provide an electrophotographic photoreceptor which suppresses peeling between an undercoat layer and a support, after storage in an environment of a large temperature / humidity change such as a high temperature and high humidity and a low temperature and low humidity.SOLUTION: An electrophotographic photoreceptor contains a polymer obtained by polymerization of a composition containing an electron transport substance having a specific structure in an undercoat layer formed right above a cylindrical support, wherein a surface of the support is formed of Al and an Al alloy, the surface of the support is composed of crystal grains of Al having (α) a surface in {001} orientation of -15° or more and less than +15° and (γ) a surface in {111} orientation of -15° or more and less than +15°, a ratio of an area occupied by the crystal grains of the Al having the (α) to a total area of the surface of the support is 10% or less, and a ratio of the area occupied by the crystal grains of the Al having the (γ) exceeds 10%.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus having the electrophotographic photoreceptor. [Background technology]

[0002] Currently, the dominant type of electrophotographic photoreceptor used in process cartridges and electrophotographic devices is an organic photoconductive material (organic photoreceptor, OPC). Generally, an electrophotographic photoreceptor has a support and a photosensitive layer formed on the support. In order to suppress charge injection from the support to the photosensitive layer and reduce the occurrence of image defects such as black spots, an undercoat layer is often provided between the support and the photosensitive layer.

[0003] The undercoat used in negatively charged electrophotographic photoreceptors is preferably electron-transporting due to its required functionality. For example, Patent Document 1 describes an electrophotographic photoreceptor using a material containing an electron-transporting substance of a specific structure in the undercoat. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-46640 [Overview of the project] [Problems that the invention aims to solve]

[0005] According to the inventors' investigation, electrophotographic photoreceptors in which an undercoat containing an electron transport material described in Patent Document 1 is formed directly on a support showed delamination between the undercoat and the support after storage in environments with large temperature and humidity fluctuations, such as high temperature and high humidity and low temperature and low humidity. In other words, it was found that there is room for improvement in the adhesion between the undercoat and the support.

[0006] Therefore, the object of the present invention is to provide an electrophotographic photoreceptor that suppresses peeling between the undercoat layer and the support after storage in an environment with large temperature and humidity fluctuations, and improves the adhesion between the undercoat layer and the support. [Means for solving the problem]

[0007] The above objective is achieved by the present invention as follows. That is, an electrophotographic photoreceptor according to one aspect of the present invention is an electrophotographic photoreceptor having a cylindrical support, an undercoat layer formed directly above the support, and a photosensitive layer formed on the undercoat layer, wherein the undercoat layer contains a cured product of a composition containing a compound represented by the following formula (A1) and / or a compound represented by the following formula (A2), the surface of the support is formed of aluminum (hereinafter abbreviated as Al) and / or an Al alloy, and the surface of the support in the surface direction of the texture of Al on the surface of the support is (α){001}Face with orientation -15° or greater and less than +15° (γ){111}Face with orientation -15° or greater and less than +15° The material is characterized by being composed of Al crystal grains having (α), wherein the area occupied by the Al crystal grains having (α) is 10% or less of the total surface area of ​​the support, and the area occupied by the Al crystal grains having (γ) is greater than 10%. [ka] (In formulas (A1) and (A2), R 101 ~R 106 , R 201 ~R 210 Each of these independently represents a monovalent group, a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group represented by the following formula (B). However, R 101 ~R 106 At least one of the following, and R 201 ~R 210At least one of the groups is a monovalent group represented by the following formula (B). One of the CH2 groups of the alkyl group may be substituted with O or S, or one of the CH groups of the alkyl group may be substituted with N. The substituent of the substituted alkyl group is at least one group selected from the group consisting of aryl groups, alkoxycarbonyl groups, halogen atoms, and hydroxyl groups. The substituent of the substituted aryl group and the substituted heterocycle is at least one group selected from the group consisting of halogen atoms, nitro groups, cyano groups, alkyl groups, halogen-substituted alkyl groups, and alkoxy groups. [ka] (In formula (B), at least one of a, b, and c has at least one group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. l and m are each independently 0 or 1, and the sum of l and m is between 0 and 2.) a represents an alkylene group having 1 to 6 carbon atoms in the main chain, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkylocarbonyl group, or an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a phenyl group. These alkylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. One of the CH2s in the main chain of these alkylene groups may be substituted with O or S, or one of the CHs in the main chain of these alkylene groups may be substituted with N. b represents a phenylene group, a C1-C6 alkyl-substituted phenylene group, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy-substituted phenylene group, and these phenylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. c represents a hydrogen atom, a carboxy group, an alkyl group having 1 to 6 carbon atoms in the main chain, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 5 carbon atoms, and these alkyl groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as substituents.)

[0008] Further, a process cartridge according to another aspect of the present invention integrally supports the electrophotographic photoreceptor and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus.

[0009] Furthermore, an electrophotographic apparatus according to still another aspect of the present invention is characterized by having the electrophotographic photoreceptor, as well as a charging means, an exposure means, a developing means, and a transfer means.

Advantages of the Invention

[0010] As described above, according to the present invention, after storage in an environment with large temperature and humidity changes such as high temperature and high humidity and low temperature and low humidity, peeling between the undercoat layer and the support is suppressed, and an electrophotographic photoreceptor with improved adhesion between the undercoat layer and the support can be provided. Also, according to the present invention, a process cartridge and an electrophotographic apparatus that can exhibit the same effects can be provided.

Brief Description of the Drawings

[0011] [Figure 1] It is a diagram showing the distribution of crystal grains of Al. [Figure 2] It is a diagram showing the measurement position on the support surface in the measurement of the crystal orientation of crystal grains of Al. [Figure 3] It is a diagram showing an example of the schematic configuration of an electrophotographic apparatus having a process cartridge equipped with an electrophotographic photoreceptor.

Embodiments for Carrying Out the Invention

[0012] The present invention will be described in detail below with reference to preferred embodiments. [Embodiment 1] The compounds represented by formula (A1) or (A2) above have π-conjugated molecules and a rigid skeleton structure, and the undercoat containing the cured product of a composition containing these compounds has excellent electron transport properties.

[0013] On the other hand, the inventors found that in electrophotographic photoreceptors in which these undercoating layers are formed directly on the support, the adhesion between the undercoating layer and the support is somewhat low after storage in environments with large temperature and humidity fluctuations, such as high temperature and high humidity and low temperature and low humidity.

[0014] The compounds represented by formulas (A1) or (A2) above lack flexibility due to their rigid structure. Therefore, under harsh conditions where the thermal strain of the support is large, it is thought that the undercoat containing the cured product of a composition containing these compounds becomes unable to follow the strain of the support, resulting in reduced adhesion and increased susceptibility to delamination.

[0015] To solve the above technical problems, the inventors considered the properties of the surface of the aluminum support for the electrophotographic photoreceptor to be important, and investigated the orientation of the crystal grains of the polycrystalline material on the surface of the aluminum support.

[0016] Aluminum crystal orientations can be broadly categorized into three: {10¹} orientation, {00¹} orientation, and {11¹} orientation. As described in "Koberniks" ([No.28] Vol.14 2005.OCT), crystal grains with each crystal orientation are usually distributed randomly, as shown in Figure 1(a), for example.

[0017] In this invention, for crystal grains having the three crystal orientations described above, (α){001}Face with orientation -15° or greater and less than +15° (β){10¹}Face with orientation -15° or greater and less than +15° (γ){111}Face with orientation -15° or greater and less than +15° This is how it is written. For example, (α), that is, a plane with a {001} orientation of -15° or more and less than +15°, refers to a crystal plane in an aluminum (Al) crystal that has variation in the planes of -15° or more and less than +15° from the {001} plane.

[0018] In this invention, the notation for the crystal orientation of Al on the support surface, for example, a {001} oriented plane, is a representation of the Al crystal plane using Miller indices. That is, a {001} oriented plane is a comprehensive expression of Miller indices representing any of the crystal lattice planes (001), (010), (100), (00-1), (0-10), or (-100).

[0019] It is known that crystals exhibit crystal orientation dependence due to the arrangement and density of atoms. The inventors hypothesize that because the properties of thermal shrinkage differ slightly depending on the crystal orientation, the adhesion to the undercoat differs depending on the crystal orientation, and that crystal grains (γ) and (β) exhibit higher adhesion to the undercoat under a wide range of temperature and humidity conditions compared with crystal grains (α). Furthermore, they hypothesize that crystal grains (γ) exhibit higher resin adhesion under an even wider range of temperature and humidity conditions compared with crystal grains (β).

[0020] In conventional aluminum supports, the presence of randomly arranged crystal grains with three different crystal orientations creates minute differences in adhesion between the undercoat and the support. This is thought to have caused the undercoat to peel off, especially under storage conditions with high thermal stress.

[0021] Therefore, the surface of the aluminum support is formed in a state rich in crystal grains having a (γ) plane, which is presumed to have high film adhesion, as shown in Figure 1(b). This is thought to suppress thermal distortion on the surface of the aluminum support and improve minute differences in adhesion, thereby suppressing delamination of the underlying layer.

[0022] [Electrophotographic photoconductor] The electrophotographic photoreceptor according to the present invention comprises a cylindrical support, an undercoat layer, and a photosensitive layer. A method for manufacturing an electrophotographic photoreceptor according to the present invention involves preparing coating solutions for each layer, as described later, applying them to a support in the desired layer order, and then drying them. Methods for applying the coating solutions include immersion coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, and ring coating. Among these, immersion coating is preferred from the viewpoint of efficiency and productivity. The support structure and each layer will be described below.

[0023] <Support> The electrophotographic photoreceptor according to the present invention has a cylindrical support, the surface of which is formed of Al and / or an Al alloy. The surface of the support may also be subjected to cutting, hot water treatment, blasting, or the like.

[0024] (1) Crystal orientation In the present invention, the surface of the support is formed of Al and / or an Al alloy, and the surface of the support in the surface direction of the Al texture of the support surface is (α){001}Face with orientation -15° or greater and less than +15° (γ){111}Face with orientation -15° or greater and less than +15° The support is characterized by being composed of Al crystal grains having (α), wherein the area occupied by the Al crystal grains having (α) is 10% or less of the total surface area of ​​the support, and the area occupied by the Al crystal grains having (γ) is greater than 10%.

[0025] From the viewpoint of increasing the area of ​​the support with low thermal distortion, it is preferable that the area occupied by Al crystal grains having (γ) is 11% or more, and more preferably 50% or more. Furthermore, it is even more preferable that the area occupied by Al crystal grains having (γ) is 75% or more. In particular, the effects of the present invention can be better obtained when the area occupied by Al crystal grains having (γ) is 75% or more.

[0026] Furthermore, from the viewpoint of reducing surfaces with large thermal distortion, it is preferable that the proportion of the area occupied by Al crystal grains having (α) is 5% or less.

[0027] (Method for measuring the crystal orientation of Al crystal grains on the surface of a support) In the present invention, the crystal orientation of the Al crystal grains on the surface of the support can be measured, for example, as follows.

[0028] First, the surface of the support is treated with buff polishing and an aqueous sodium hydroxide solution, and the crystal orientation of the Al crystal grains is measured at points within 20 μm of the surface of the support before treatment. The crystal orientation is preferably measured by the SEM-EBSP method.

[0029] Measurements using the SEM-EBSP method employ a FE-SEM (Field Emission-Scanning Electron Microscope) equipped with an EBSP (Electron Backscatter Diffraction Pattern) detector. Here, SEM-EBSP refers to the Kikuchi pattern (Kikuchi lines) obtained from backscattered electrons generated when an electron beam is incident on the surface of a specimen. By analyzing this pattern, the crystal orientation at the electron beam incident position can be determined. The Kikuchi pattern refers to the pattern that appears behind the electron diffraction image as a pair of parallel lines, bands, or arrays when an electron beam that strikes a crystal is scattered and diffracted. As an FE-SEM equipped with an EBSP detector, for example, a field emission scanning electron microscope (product name: JSM-6500F, manufactured by JEOL Ltd.) can be used.

[0030] (2) Area of ​​Al crystal grains on the surface of the support In the present invention, the surface of the support is (α){001}Face with orientation -15° or greater and less than +15° (γ){111}Face with orientation -15° or greater and less than +15° It consists of Al crystal grains having [α], and the ratio of the area occupied by the Al crystal grains having [α] to the total surface area of the support is 10% or less, and the ratio of the area occupied by the Al crystal grains having [γ] exceeds 10%.

[0031] The ratio of the area occupied by the Al crystal grains having each of the above crystal orientations can be determined as follows. As shown in Figure 2, first, positions corresponding to 1 / 8, 2 / 8, 3 / 8, 4 / 8, 5 / 8, 6 / 8, 7 / 8 of the total length in the axial direction are determined from one end of the support. Further, at each of these positions, it is divided into 4 equal parts at 90° intervals in the circumferential direction. At each of the 28 points where the axial division line and the circumferential division line intersect, a 100 μm square region is set with the intersection of the axial division line and the circumferential division line as the center, and the crystal orientation is measured by the above SEM-EBSP method. Subsequently, for the Al crystal grains having the crystal orientations of (α), (β), and (γ), the area occupied by each orientation is calculated, and the obtained value is divided by 10000 μm 2 to determine the ratio of the area occupied by the Al crystal grains having each crystal orientation in each region. Finally, the average value of each value obtained from the 28 regions is determined as the ratio of the area occupied by (α), (β), and (γ) of the support.

[0032] The calculation of the area occupied by the Al crystal grains having each crystal orientation may use the attached software. For example, the obtained orientation by measurement may be defined such that the range of (α) is 0 ≤ h < 60 and 300 ≤ h < 360, the range of (β) is 60 ≤ h < 180, and the range of (γ) is 180 ≤ h < 300 using the hue h of the HSV color space, and the area may be calculated by performing hue mapping of the regions of the Al crystal grains having each crystal orientation. [[ID=**14**]]

[0033] [[ID=**15**]] (3) Aluminum alloy for use as a support The support in this invention may be Al or an Al alloy. Generally, for electrophotographic photoreceptors, wrought Al alloys such as the JIS designation 3000 series, 5000 series, and 6000 series are used. Among these, from the viewpoint of controlling the crystal orientation, it is preferable to use a support formed of a 3000 series Al alloy containing 0.05 mass% to 0.2 mass% Cu and 1.0 mass% to 1.5 mass% Mn, or a 5000 series or 6000 series Al alloy containing 0.45 mass% to 6.0 mass% Mg.

[0034] (4) Method for manufacturing the support The method for manufacturing the support is not particularly limited, as long as it is a method that can manufacture a support that satisfies the requirements of the present invention. One example of a method for manufacturing a support is a method that includes the following four steps: • The first step involves preparing a specific aluminum alloy and performing hot extrusion to obtain a molded body. • The second step involves cold drawing of the molded body obtained in the first step. • The third step involves annealing after the second step. • The fourth step involves machining the surface after annealing.

[0035] When controlling crystal orientation by annealing, it is possible to control the crystal orientation by adjusting the heating time, annealing temperature, holding time, and cooling time. In particular, by maintaining a cooling rate of 5°C / min or higher until the support temperature reaches 150°C, the appearance of Al crystal grains with (α) crystal orientation on the surface is suppressed, while the appearance of Al crystal grains with (γ) crystal orientation on the surface becomes easier. As a result, the proportion of the surface area occupied by Al crystal grains with (α) crystal orientation on the support surface decreases, and the proportion of the surface area occupied by Al crystal grains with (γ) crystal orientation increases.

[0036] Furthermore, since variations occur depending on the heating rate and annealing temperature, it is preferable to control the heating rate to 40°C / min or less and the annealing temperature to be between 400°C and 450°C. Furthermore, it is preferable that the annealing temperature be maintained for no more than one hour. Furthermore, since thermal history is important in controlling the crystal orientation, it is preferable to use materials that have undergone the above-mentioned hot extrusion and cold drawing processes, and then be annealed.

[0037] In the method for manufacturing the support of this embodiment, other steps may be included as needed before, after, between, or during each of the above-described steps for manufacturing the support. For example, processing steps such as cutting for dimensional adjustment, chamfering / spigot formation, mirror finishing / roughening, honing, blasting, and grinding may be performed as needed.

[0038] Generally, the rotation axis of an electrophotographic photoreceptor is secured by fitting flange members to both ends of a cylindrical support and attaching the rotation axis to these flange members. Generally, the inner diameter dimensions of both ends of the support are set to approximately H8 (or similar) of the fit tolerance of JIS B 0401-1999. Furthermore, while a smaller surface roughness is preferable from the standpoint of fit tolerance, due to manufacturing cost considerations, the arithmetic mean roughness Ra of both ends of the support is set to 1.6 μm or less and the maximum height Rz to 6.3 μm or less (or above the old JIS finish symbol ▽▽▽) of JIS B 0601-2001.

[0039] If cutting oil or dust is adhering to the surface of the support, cleaning may be performed. A known method for cleaning the support includes a degreasing cleaning step to remove oil and foreign matter adhering to the surface of the support, a rinsing step to wash away the degreasing cleaning agent, and a drying step to dry the water remaining on the support and complete the cleaning.

[0040] In the degreasing and cleaning process, the support material is immersed in a cleaning solution containing a degreasing agent such as a surfactant or alkaline electrolyzed water. Using ultrasound and increasing the temperature of the cleaning solution are effective in enhancing the degreasing and cleaning ability. The ultrasonic frequency is preferably between 10 kHz and 100 kHz for optimal effectiveness. The temperature is preferably between 30°C and 60°C for optimal effectiveness.

[0041] In the rinsing process, the support material is immersed in a rinsing solution. The rinsing solution can be tap water or distilled water, but distilled water is preferred. Using ultrasound and increasing the temperature of the rinsing solution are effective in improving the rinsing cleaning ability. The ultrasonic frequency is preferably between 10 kHz and 1 MHz for optimal effectiveness. The temperature is preferably between 20°C and 60°C for optimal effectiveness. The rinsing tank may be a single tank or multiple tanks. Using a shower when removing the material after immersion further enhances the rinsing effect.

[0042] While any drying method, such as hot air drying, vacuum drying, or hot water drying, is effective for the drying process, pull-up drying with warm pure water is preferred to reduce dust. The temperature of the warm pure water should be between 30°C and 99°C.

[0043] <Underlayer> The undercoat layer in the present invention is formed directly on the support and contains a cured product of a composition comprising the compound represented by formula (A1) or the compound represented by formula (A2). Having the compound represented by formula (A1) or (A2) makes it possible to ensure excellent electron transport properties. [ka] (In formulas (A1) and (A2), R 101 ~R 106 , R 201 ~R 210 Each of these independently represents a monovalent group, a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group represented by the following formula (B). However, R 101 ~R 106At least one of the following, and R 201 ~R 210 At least one of the groups is a monovalent group represented by the following formula (B). One of the CH2 groups of the alkyl group may be substituted with O or S, or one of the CH groups of the alkyl group may be substituted with N. The substituent of the substituted alkyl group is at least one group selected from the group consisting of aryl groups, alkoxycarbonyl groups, halogen atoms, and hydroxyl groups. The substituent of the substituted aryl group and the substituted heterocycle is at least one group selected from the group consisting of halogen atoms, nitro groups, cyano groups, alkyl groups, halogen-substituted alkyl groups, and alkoxy groups.

[0044] [ka] (In formula (B), at least one of a, b, and c has at least one group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. l and m are each independently 0 or 1, and the sum of l and m is between 0 and 2.) a represents an alkylene group having 1 to 6 carbon atoms in the main chain, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkylocarbonyl group, or an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a phenyl group. These alkylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. One of the CH2s in the main chain of these alkylene groups may be substituted with O or S, or one of the CHs in the main chain of these alkylene groups may be substituted with N. b represents a phenylene group, a C1-C6 alkyl-substituted phenylene group, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy-substituted phenylene group, and these phenylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. c represents a hydrogen atom, a carboxyl group, an alkyl group with 1 to 6 carbon atoms in the main chain, or an alkyl group with 1 to 6 carbon atoms in the main chain substituted with an alkyl group with 1 to 5 carbon atoms. These alkyl groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group.

[0045] For a and b, the main chain refers to the chain with the minimum number of carbon atoms extending from the carbon or nitrogen atom of the skeletal structure of (A1) or (A2) to c. For c, the main chain refers to the chain with the maximum number of carbon atoms from the atom bonded to a or b to the end. Note that the alkylene group with 1 to 6 carbon atoms in the main chain of a and the alkyl group with 1 to 6 carbon atoms in the main chain of c are straight-chain alkylene groups and straight-chain alkyl groups, respectively, and alkyl groups that may be present as substituents become side chains bonded to the above straight chains.

[0046] The undercoat layer according to the present invention can be formed as a cured film by polymerizing a composition containing the above compound and a monomer having a polymerizable functional group.

[0047] Polymerizable functional groups found in monomers possessing polymerizable functional groups include isocyanate groups, blocked isocyanate groups, methylol groups, alkylated methylol groups, epoxy groups, metal alkoxide groups, hydroxyl groups, amino groups, carboxyl groups, thiol groups, carboxylic acid anhydride groups, and carbon-carbon double bond groups.

[0048] Furthermore, it may contain resins. Examples of resins include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenolic resin, polyvinylphenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, polyamide resin, polyamic acid resin, polyimide resin, polyamideimide resin, and cellulose resin.

[0049] Furthermore, the undercoat layer may contain, in addition to the electron transport material represented by formula (A1) or (A2) above, metal oxides, metals, conductive polymers, etc., for the purpose of improving electrical properties. Among these, the use of metal oxides is preferred. Furthermore, it is preferable that the thickness of the undercoat layer is 2.5 μm or less.

[0050] Tables 1-1 to 1-6 show specific examples of compounds represented by formula (A1), and Tables 2-1 to 2-2 show specific examples of compounds represented by formula (A2). In the tables, if "(H)" is written in the column for c, it indicates that c is a hydrogen atom in the structure shown in column a or b, and that the structure of formula (B) is the structure shown in column a or b. If column a or b is (-), it indicates that l or m is 0. The following are specific examples, and the effects of the present invention are not limited to these examples. These compounds may be used individually or in combination.

[0051] [Table 1-1]

[0052] [Table 1-2]

[0053] [Table 1-3]

[0054] [Table 1-4]

[0055] [Table 1-5]

[0056] [Table 1-6]

[0057] [Table 2-1]

[0058] [Table 2-2]

[0059] Examples of metal oxides include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, and silicon dioxide. Examples of metals include gold, silver, and aluminum. Furthermore, the underlayer may contain additional additives.

[0060] The thickness of the undercoat layer is particularly preferably 0.1 μm or more and 3.5 μm or less. The undercoat can be formed by preparing an undercoat coating solution containing the above-mentioned materials and solvents, forming a coating film, and then drying and / or curing it. Examples of solvents used in the coating solution include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.

[0061] <Photosensitive layer> The photosensitive layers of electrophotographic photoreceptors are mainly classified into (1) multilayer photosensitive layers and (2) single-layer photosensitive layers. (1) A multilayer photosensitive layer has a charge generating layer containing a charge generating material and a charge transport layer containing a charge transport material. (2) A single-layer photosensitive layer has a photosensitive layer containing both a charge generating material and a charge transport material.

[0062] (1) Stacked photosensitive layer The stacked photosensitive layer comprises a charge generation layer and a charge transport layer.

[0063] (1-1) Charge generation layer The charge generation layer preferably contains a charge generation material and a resin.

[0064] Examples of charge-generating materials include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferred. Among phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments, and hydroxygallium phthalocyanine pigments are preferred. The content of the charge generating material in the charge generating layer is preferably 40% to 85% by mass, and more preferably 60% to 80% by mass, relative to the total mass of the charge generating layer.

[0065] Examples of resins include polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenolic resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin, and polyvinyl chloride resin. Among these, polyvinyl butyral resin is more preferred.

[0066] Furthermore, the charge generation layer may contain additives such as antioxidants and ultraviolet absorbers. Specifically, these include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

[0067] The thickness of the charge generation layer is preferably 0.1 μm or more and 1 μm or less, and more preferably 0.15 μm or more and 0.4 μm or less.

[0068] The charge generation layer can be formed by preparing a coating solution for the charge generation layer containing the above-mentioned materials and solvents, forming a coating film, and drying it. Examples of solvents used in the coating solution include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.

[0069] (1-2) Charge transport layer The charge transport layer preferably contains a charge transport material and a resin.

[0070] Examples of charge transport materials include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferred. The content of the charge transport material in the charge transport layer is preferably 25% to 70% by mass, and more preferably 30% to 55% by mass, relative to the total mass of the charge transport layer.

[0071] Examples of resins include polyester resin, polycarbonate resin, acrylic resin, and polystyrene resin. Among these, polycarbonate resin and polyester resin are preferred. Polyarylate resin is particularly preferred among polyester resins. The content ratio (mass ratio) of the charge transport material to the resin is preferably 4:10 to 20:10, and more preferably 5:10 to 12:10.

[0072] Furthermore, the charge transport layer may contain additives such as antioxidants, ultraviolet absorbers, plasticizers, leveling agents, lubrication agents, and wear resistance enhancers. Specifically, examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, and boron nitride particles.

[0073] The thickness of the charge transport layer is preferably 5 μm to 50 μm, more preferably 8 μm to 40 μm, and particularly preferably 10 μm to 30 μm.

[0074] The charge transport layer can be formed by preparing a coating solution for the charge transport layer containing the above-mentioned materials and solvents, forming a coating film, and drying it. Examples of solvents used in the coating solution include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. Among these solvents, ether-based solvents or aromatic hydrocarbon-based solvents are preferred.

[0075] (2) Single-layer photosensitive layer A single-layer photosensitive layer can be formed by preparing a coating solution for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin, and a solvent, forming this coating film, and drying it. The charge generating substance, charge transporting substance, and resin are the same as the examples of materials in "(1) Multilayer Photosensitive Layer" above.

[0076] <Protective layer> In this invention, a protective layer may be provided on the photosensitive layer. Providing a protective layer can improve durability. The protective layer preferably contains conductive particles and / or charge transport material and a resin.

[0077] Examples of conductive particles include metal oxide particles such as titanium oxide, zinc oxide, tin oxide, and indium oxide. Examples of charge transport materials include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferred. Examples of resins include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenolic resin, melamine resin, and epoxy resin. Among these, polycarbonate resin, polyester resin, and acrylic resin are preferred.

[0078] Furthermore, the protective layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. Examples of reactions in this process include thermal polymerization, photopolymerization, and radiation polymerization. Examples of polymerizable functional groups in monomers having a polymerizable functional group include acryloyl groups and methacryloyl groups. Materials with charge transport ability may be used as monomers having a polymerizable functional group.

[0079] The protective layer may contain additives such as antioxidants, UV absorbers, plasticizers, leveling agents, lubrication agents, and wear resistance enhancers. Specifically, examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, and boron nitride particles.

[0080] The thickness of the protective layer is preferably 0.5 μm to 10 μm, and more preferably 1 μm to 7 μm.

[0081] The protective layer can be formed by preparing a protective coating solution containing the above-mentioned materials and solvents, forming a coating film, and then drying and / or curing it. Examples of solvents used in the coating solution include alcohol-based solvents, ketone-based solvents, ether-based solvents, sulfoxide-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.

[0082] [Process cartridges, electrophotographic equipment] The process cartridge according to the present invention is characterized in that it integrally supports the electrophotographic photoreceptor described above and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachably attached to the electrophotographic apparatus body.

[0083] Furthermore, the electrophotographic apparatus according to the present invention is characterized by having the electrophotographic photoreceptor described above, as well as a charging means, an exposure means, a developing means, and a transfer means.

[0084] Figure 3 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge equipped with an electrophotographic photoreceptor. The cylindrical electrophotographic photoreceptor 1 is driven to rotate at a predetermined peripheral speed in the direction of the arrow around the axis 2. The surface of the electrophotographic photoreceptor 1 is charged to a predetermined positive or negative potential by the charging means 3. Although the diagram shows a roller-type charging method using a roller-type charging member, other charging methods such as corona charging, proximity charging, and injection charging may also be used.

[0085] Exposure light 4 is shone onto the surface of the charged electrophotographic photoreceptor 1 from an exposure means (not shown), forming an electrostatic latent image corresponding to the desired image information. The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in the developing means 5, and a toner image is formed on the surface of the electrophotographic photoreceptor 1. The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to a transfer material 7 by a transfer means 6. The transfer material 7 with the transferred toner image is transported to a fixing means 8, where the toner image is fixed and printed out outside the electrophotographic device.

[0086] The electrophotographic apparatus may have a cleaning means 9 for removing toner and other deposits remaining on the surface of the electrophotographic photoreceptor 1 after transfer. Alternatively, a so-called cleanerless system may be used in which the deposits are removed by developing means 5 or the like, without a separate cleaning means 9.

[0087] The electrophotographic apparatus may have a static elimination mechanism that removes static electricity from the surface of the electrophotographic photoreceptor 1 using pre-exposure light 10 from a pre-exposure means (not shown). Furthermore, guide means 12, such as rails, may be provided for attaching and detaching the process cartridge 11 according to the present invention to the electrophotographic apparatus body.

[0088] The electrophotographic photoreceptor according to the present invention can be used in laser beam printers, LED printers, photocopiers, facsimile machines, and multifunction devices thereof. [Examples]

[0089] The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited in any way by the following examples unless it exceeds the gist of the invention. In the following examples, "parts" refers to mass unless otherwise specified.

[0090] [Manufacturing of support structures] The support was manufactured using the following method.

[0091] (Example of manufacturing support A-1) A hot-extruded extruded tube made of JIS designated A3003 alloy was cold-drawn to obtain a drawn tube with an outer diameter of 30.8 mm, an inner diameter of 28 mm, and a length of 371 mm. Next, the drawn tube was placed in an electric furnace and heated at a rate of 40°C / min, then maintained at 435°C for 1 hour. Subsequently, it was cooled at 15°C / min until the drawn tube reached 150°C, and then removed from the electric furnace after 24 hours. By performing machining after annealing, a support structure "Support A-1" was obtained, having an outer diameter of 30.5 mm, a length of 370 mm, and spigot sections at both ends with an inner diameter of 28.5 mm and a depth of 20 mm. The manufacturing conditions for support structure A-1 are shown in Table 3.

[0092] Elemental analysis of the drawn tubes used revealed that they were an Al alloy consisting of 0.3 mass% Si, 0.4 mass% Fe, 0.1 mass% Cu, 1.2 mass% Mn, 0.05 mass% Zn, with the remainder being Al and impurities.

[0093] (Manufacturing examples of supports A-2 to A-10) In the manufacturing example of support A-1, the support was manufactured in the same manner as in the manufacturing example of support A-1, except that the same drawn tube was used and the annealing conditions were changed as shown in Table 3. The resulting supports are referred to as "Supports A-2 to A-10". The manufacturing conditions for supports A-2 to A-10 are shown in Table 3.

[0094] (Example of manufacturing support A-11) A hot-extruded extruded tube made of a JIS-designated 5000 series alloy (Al-Mg alloy) containing 2.5% by mass of magnesium was cold-drawn to obtain a drawn tube with an outer diameter of 30.8 mm, an inner diameter of 28 mm, and a length of 371 mm. Next, the drawn tube was placed in an electric furnace and heated at a rate of 5°C / min, then maintained at 450°C for 1 hour. Subsequently, it was cooled at 15°C / min until the drawn tube reached 150°C, and then removed from the electric furnace after 24 hours. By performing machining after annealing, a "support A-11" with the same dimensions as support A-1 was obtained. The manufacturing conditions for support A-11 are shown in Table 3.

[0095] Elemental analysis of the drawn tubes used revealed that they were an Al alloy containing 0.1 mass% Si, 0.1 mass% Fe, 0.02 mass% Cu, 2.5 mass% Mg, and 0.01 mass% Zn.

[0096] (Manufacturing example of support A-12) A hot-extruded extruded tube made of JIS-designated 6000 series alloy (Al-Mg-Si alloy) was cold-drawn to obtain a drawn tube with an outer diameter of 30.8 mm, an inner diameter of 28 mm, and a length of 371 mm. Next, the drawn tube was placed in an electric furnace and heated at a rate of 5°C / min, then maintained at 450°C for 30 minutes. Subsequently, it was cooled at 20°C / min until the drawn tube reached 150°C, and then removed from the electric furnace after 24 hours. By performing machining after annealing, a "support A-12" with the same dimensions as support A-1 was obtained. The manufacturing conditions for support A-12 are shown in Table 3.

[0097] Elemental analysis of the drawn tubes used revealed that they were an Al alloy containing 0.5 mass% Si, 0.6 mass% Fe, 0.2 mass% Cu, 0.1 mass% Mn, 1.0 mass% Mg, and 0.8 mass% Zn.

[0098] (Manufacturing examples of support B-1 to support B-12) In the manufacturing example of support A-1, the support was manufactured in the same manner as in the manufacturing example of support A-1, except that the annealing conditions were changed as shown in Table 3. The obtained supports will be referred to as "supports B-1 to B-12". The manufacturing conditions for supports B-1 to B-12 are shown in Table 3.

[0099] (Manufacturing examples of support B-13 and support B-14) A drawn tube with an outer diameter of 30.8 mm, an inner diameter of 28 mm, and a length of 371 mm, made of a JIS-designated 5000 series alloy (Al-Mg alloy) containing 2.5 mass% magnesium, was annealed under the conditions shown in Table 3. After annealing, machining was performed to obtain "supports B-13 and B-14" with the same dimensions as support A-1. The manufacturing conditions for supports B-13 and B-14 are shown in Table 3.

[0100] [Table 3]

[0101] [(A1)(A2) Manufacturing Examples] Derivatives having the structure of formula (A1) above (derivatives of electron transport materials) can be synthesized, for example, using known synthesis methods described in U.S. Patent No. 4,442,193, U.S. Patent No. 4,992,349, U.S. Patent No. 5,468,583, and Chemistry of Materials, Vol. 19, No. 11, 2703-2705 (2007). They can also be synthesized by the reaction of naphthalenetetracarboxylic dianhydride, which can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Ltd., and Johnson Matthey Japan, Incorporated, with monoamine derivatives.

[0102] The compound represented by (A1) has polymerizable functional groups (hydroxyl group, thiol group, amino group, and carboxyl group) that can polymerize with the isocyanate group of the isocyanate compound. Methods for introducing these substituents to a derivative having the structure of (A1) include directly introducing the polymerizable functional group to the derivative having the structure of (A1), and introducing a structure having the polymerizable functional group or a functional group that can serve as a precursor to the polymerizable functional group. As an example of the method described later, there is a method of introducing a functional group-containing aryl group using a cross-coupling reaction with a palladium catalyst and a base, based on a halide of a naphthylimide derivative. Another method is to introduce a functional group-containing alkyl group using a cross-coupling reaction with an FeCl3 catalyst and a base, based on a halide of a naphthylimide derivative. For example, there is a method of introducing a hydroxyalkyl group or carboxyl group by reacting an epoxy compound or CO2 after lithiation, based on a halide of a naphthylimide derivative. One method for synthesizing naphthylimide derivatives involves using a naphthalenetetracarboxylic dianhydride derivative or monoamine derivative having the polymerizable functional group or a functional group that can serve as a precursor to a polymerizable functional group as a raw material.

[0103] Derivatives having the structure of formula (A2) above can be synthesized, for example, using known synthesis methods described in the Journal of the American Chemical Society, Vol. 129, No. 49, 15259-78 (2007). Alternatively, they can be synthesized by the reaction of perylenetetracarboxylic dianhydride, which can be purchased as a reagent from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., or Johnson Matthey Japan, Inc., with a monoamine derivative.

[0104] The compound represented by (A2) has a polymerizable functional group (hydroxyl group, thiol group, amino group, and carboxyl group) that can be polymerized with the isocyanate group of the isocyanate compound. Methods for introducing these polymerizable functional groups into a derivative having the structure of (A2) include directly introducing the polymerizable functional group into the derivative having the structure of (A2), as well as introducing a structure having the polymerizable functional group or a functional group that can serve as a precursor to the polymerizable functional group. Methods described later include, for example, a method using a palladium catalyst and a base to perform a cross-coupling reaction based on a halide of a peryleneimide derivative, or a method using an FeCl3 catalyst and a base to perform a cross-coupling reaction based on a halide of a peryleneimide derivative. Furthermore, when synthesizing peryleneimide derivatives, there is a method of using a perylenetetracarboxylic dianhydride derivative or monoamine derivative having the polymerizable functional group or a functional group that can serve as a precursor to the polymerizable functional group as a raw material.

[0105] (Synthesis Example 1) To 200 parts of dimethylacetamide, 5.4 parts of naphthalenetetracarboxylic dianhydride, 4 parts of 2-methyl-6-ethylaniline, and 3 parts of 2-amino-1-butanol were added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour to prepare the solution. After preparing the solution, refluxing was performed for 8 hours, the precipitate was filtered off, and recrystallization with ethyl acetate was performed to obtain 1.0 part of compound A101.

[0106] (Synthesis Example 2) To 200 parts of dimethylacetamide, 5.4 parts of naphthalenetetracarboxylic dianhydride, 4 parts of 4-heptylamine, and 3 parts of 2-amino-1,3-propanediol were added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour to prepare the solution. After preparing the solution, it was refluxed for 8 hours and separated by silica gel column chromatography (eluent: ethyl acetate / toluene). The fraction containing the target compound was then concentrated. The concentrate was recrystallized in an ethyl acetate / toluene mixed solution to obtain 2.0 parts of the target compound A154.

[0107] (Synthesis Example 3) To 200 parts of dimethylacetamide, 7.4 parts of perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 4 parts of 2,6-diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4 parts of 2-amino-1-phenylethanol were added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour to prepare the solution. After preparing the solution, the mixture was refluxed for 8 hours, the precipitate was filtered off, and recrystallization was performed with ethyl acetate to obtain 5.0 parts of compound A203.

[0108] [Manufacturing of electrophotographic photoreceptors] (Manufacturing example of photoreceptor C-1) Support material A-1 was used as the support material.

[0109] Next, 4 parts of the exemplary compound (A101), 1.5 parts of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 0.0005 parts of zinc(II) octoate as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of tetrahydrofuran. Block isocyanate (trade name: BL3175, manufactured by Sumika Bayer Co., Ltd.) equivalent to 6 parts of solids was added to this solution to prepare a coating solution for the undercoat layer. This undercoat layer coating solution was applied to a support by immersion to form a coating film, and the resulting coating film was heat-cured at 165°C for 30 minutes to form an undercoat layer with a thickness of 0.8 μm.

[0110] Next, I prepared the following materials. 20 parts of hydroxygallium phthalocyanine crystals (charge-generating material) in a crystalline form exhibiting peaks at 7.4° and 28.2° of the Bragg angle 2θ±0.2° in CuKα characteristic X-ray diffraction. • 0.2 parts of the calixarene compound represented by the following formula (C), [ka] • Polyvinyl butyral (product name: S-Rec BX-1, manufactured by Sekisui Chemical Co., Ltd.) 10 units 600 parts of cyclohexanone These materials were placed in a sand mill using 1 mm diameter glass beads and dispersed for 4 hours. Subsequently, 700 parts of ethyl acetate were added to prepare a coating solution for the charge generation layer. This coating solution for the charge generation layer was applied to the undercoat layer by immersion, and the resulting coating film was dried at 80°C for 15 minutes to form a charge generation layer with a thickness of 0.17 μm.

[0111] Next, I prepared the following materials. • 30 parts of the compound represented by the following formula (D) (charge transport material) • 60 parts of the compound represented by the following formula (E) (charge transport material) • 10 parts of the compound represented by the following formula (F) (charge transport material) [ka] • Polycarbonate resin (product name: Yupiron Z400, manufactured by Mitsubishi Engineering Plastics Corporation, bisphenol Z type polycarbonate) 100 units • 0.02 parts of polycarbonate represented by the following formula (G) (viscosity-average molecular weight Mv: 20000) [ka] These were dissolved in a mixed solvent of 600 parts mixed xylene and 200 parts dimethoxymethane to prepare a coating solution for the charge transport layer. This coating solution for the charge transport layer was applied to the charge generating layer by immersion to form a coating film, and the resulting coating film was dried at 100°C for 30 minutes to form a charge transport layer with a thickness of 18 μm.

[0112] Next, a mixed solvent of 20 parts 1,1,2,2,3,3,4-heptafluorocyclopentane (product name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) and 20 parts 1-propanol was filtered through a polyflon filter (product name: PF-040, manufactured by Advantec Toyo Co., Ltd.). In addition, the following materials were prepared. • 90 parts of the hole transport compound represented by the following formula (H) [ka] 70 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane 70 parts of 1-propanol These were added to the above mixed solvent. This was filtered through a polyflon filter (product name: PF-020, manufactured by Advantec Toyo) to prepare a coating solution for the second charge transport layer (protective layer). This coating solution for the second charge transport layer was applied to the charge transport layer by immersion, and the resulting coating film was dried in air at 50°C for 6 minutes. Subsequently, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an accelerating voltage of 70kV and an absorbed dose of 8000Gy, while the support (irradiated object) was rotated at 200rpm in nitrogen. Following this, the coating film was heated in nitrogen from 25°C to 125°C over 30 seconds. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15ppm. Next, a second charge transport layer (protective layer) with a thickness of 5μm, hardened by electron beam, was formed by heat treatment at 100°C in air for 30 minutes.

[0113] Next, linear grooves were formed on the surface of the protective layer using an abrasive sheet (product name: GC3000, manufactured by Riken Corundum). The feed speed of the abrasive sheet was set to 40 mm / min, the rotation speed of the workpiece to 240 rpm, and the pressure of the abrasive sheet against the workpiece to 7.5 N / m 2 The feeding direction of the abrasive sheet and the rotation direction of the workpiece were set to be the same. In addition, a backup roller with an outer diameter of 40 cm and an Asker C hardness of 40 was used. Under these conditions, linear grooves were formed on the circumferential surface of the workpiece over a period of 10 seconds. In this way, the photoreceptor C-1 was manufactured.

[0114] (Manufacturing examples of photoreceptors C-2 to C-12 and D-1 to D-14) Except for using the support structures shown in Table 4, the electrophotographic photoreceptors were manufactured in the same manner as photoreceptor C-1. The obtained electrophotographic photoreceptors were designated as "photoreceptors C-2 to C-12, and photoreceptors D-1 to D-14."

[0115] [Table 4]

[0116] (Manufacturing examples of photoreceptors C-13 to C-24) Using the support shown in Table 4, electrophotographic photoreceptors were manufactured in the same manner as photoreceptor C-1, except that example compound (A101) was replaced with example compound (A154). The obtained electrophotographic photoreceptors were designated as "photoreceptors C-13 to C-24".

[0117] (Manufacturing examples of photoreceptors C-25 to C-36) Using the support shown in Table 4, electrophotographic photoreceptors were manufactured in the same manner as photoreceptor C-1, except that example compound (A101) was changed to example compound (A203) and the thickness of the undercoat layer was changed to 1.0 μm. The obtained electrophotographic photoreceptors were designated as "photoreceptors C-25 to C-36".

[0118] (Manufacturing examples of photoreceptors C-37 to C-48) Using the support shown in Table 4, electrophotographic photoreceptors were manufactured in the same manner as photoreceptor C-1, except that example compound (A101) was changed to example compound (A205) and the thickness of the undercoat layer was changed to 1.0 μm. The obtained electrophotographic photoreceptors were designated as "photoreceptors C-37 to C-48".

[0119] (Manufacturing examples of photoreceptors C-49 to C-58) Electrophotographic photoreceptors were manufactured in the same manner as photoreceptor C-1, except that the support and example compounds shown in Table 4 were used and the film thickness was changed as shown in Table 4. The obtained electrophotographic photoreceptors were designated as "photoreceptors C-49 to C-58".

[0120] (Manufacturing example of photoreceptor D-15) The supports shown in Table 4 were used. 20 parts of blocked isocyanate (Sumijule BL3175, manufactured by Sumika Bayer Urethane Co., Ltd., 75% solids by mass) and 7.5 parts of butyral resin (Eslec BL-1, manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 150 parts of methyl ethyl ketone. Next, 34 parts of pigment orange 43 (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed into the solution and dispersed in a sand mill for 10 hours to obtain a dispersion. To this dispersion, 0.005 parts of bismuth carboxylate (K-KAT XK-640, manufactured by King Industries Co., Ltd.) and 2 parts of silicone resin particles (Tospar 145, manufactured by Momentive Performance Materials Co., Ltd.) were added to obtain a coating solution for the undercoat layer. This coating solution was immersed on support B-1 and cured at 160°C for 60 minutes to form an undercoat layer with a thickness of 7 μm. Next, the layers above the charge generation layer were formed in the same manner as those of photoreceptor C-1. The resulting electrophotographic photoreceptor will be designated as "Photoreceptor D-15".

[0121] (Manufacturing example of photoconductor D-16) The supports shown in Table 4 were used. 20 parts of blocked isocyanate (Sumijule BL3175, manufactured by Sumika Bayer Urethane Co., Ltd., 75% solids by mass) and 7.5 parts of butyral resin (Eslec BL-1, manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 150 parts of methyl ethyl ketone. Next, 34 parts of pigment orange 43 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 parts of anthraquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed into the above solution and dispersed in a sand mill for 10 hours to obtain a dispersion. To this dispersion, 0.005 parts of bismuth carboxylate (K-KAT XK-640, manufactured by King Industries Co., Ltd.) and 2 parts of silicone resin particles (Tospar 145, manufactured by Momentive Performance Materials Co., Ltd.) were added to obtain a coating solution for the undercoat layer. This coating solution was immersed and applied onto support B-1 and cured at 160°C for 60 minutes to form an undercoat layer with a thickness of 7 μm. Next, the layers above the charge generation layer were formed in the same manner as those of photoreceptor C-1. The resulting electrophotographic photoreceptor will be designated as "Photoreceptor D-16".

[0122] [evaluation] The resulting photoreceptor was subjected to adhesion tests using the following method. First, the samples were stored at 40°C / 90%RH for 5 days, followed by 5°C / 20%RH for 5 days. Then, the samples were moved to 23°C / 50%RH, the protective layer was removed with a polishing sheet, and the photosensitive layer was removed using methyl ethyl ketone to expose the undercoat, thus obtaining samples for scratch evaluation. As shown in Figure 2, the evaluation positions were determined at 1 / 8, 2 / 8, 3 / 8, 4 / 8, 5 / 8, 6 / 8, and 7 / 8 of the total length in the axial direction from one end of the evaluation sample. Furthermore, at each of these positions, four positions were determined by dividing the circumferential direction by 90°. At each of the 28 points where the axial division line and the circumferential division line intersect, a 5mm square was scratched with a cutter so that the intersection of the axial and circumferential division lines was at the center, and then the inside of that square was further divided into 25 1mm squares. Next, transparent adhesive tape was applied to the 25 divided sections and rubbed with a finger to ensure adhesion. Within 5 minutes, the transparent adhesive tape was peeled off in about 1 second to check whether a 1mm square undercoat layer peeled off from the support. Based on the average number of 1mm squares that peeled off within each 5mm square, the evaluation rank was determined as follows. A...Less than 1 B...1 or more but less than 5 C... 5 to less than 10 D...10 or more but less than 15 E...15 or more Next, each of the 28 points evaluated above was cut out as a 5mm square fragment.

[0123] Subsequently, the undercoat was removed by buff polishing, exposing the support surface and giving it a mirror finish. Next, the sample was immersed in a sodium hydroxide aqueous solution for 1 minute to obtain a sample for crystal orientation measurement. Measurements were taken using the SEM-EBSP method on a 100 μm square region centered on the surface of the obtained sample, specifically at the intersection of the axial and circumferential dividing lines of the support material. The percentage of the area occupied by each crystal grain in each orientation within the 100 μm square region was then calculated.

[0124] Similar adhesion tests and crystal orientation measurements were performed on photoreceptors C-2 to C-58 and D-1 to D-16. The results are shown in Tables 5 and 6.

[0125] [Table 5]

[0126] [Table 6]

[0127] This embodiment includes the following configuration. [Configuration 1] An electrophotographic photoreceptor having a cylindrical support, an undercoat formed directly above the support, and a photosensitive layer formed on the undercoat, The undercoat contains a cured product of a composition comprising a compound represented by the following formula (A1) and / or a compound represented by (A2), The surface of the support is formed of Al and / or an Al alloy, and the surface of the support in the surface direction of the Al texture of the support surface is (α){001}Face with orientation -15° or greater and less than +15° (γ){111}Face with orientation -15° or greater and less than +15° An electrophotographic photoreceptor characterized by comprising Al crystal grains having (α), wherein the ratio of the area occupied by the Al crystal grains having (α) to the total surface area of ​​the support is 10% or less, and the ratio of the area occupied by the Al crystal grains having (γ) exceeds 10%. [ka] (In formulas (A1) and (A2), R 101 ~R 106 , R 201 ~R 210Each of these independently represents a monovalent group, a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group represented by the following formula (B). However, R 101 ~R 106 At least one of the following, and R 201 ~R 210 At least one of the groups is a monovalent group represented by the following formula (B). One of the CH2 groups of the alkyl group may be substituted with O or S, or one of the CH groups of the alkyl group may be substituted with N. The substituent of the substituted alkyl group is at least one group selected from the group consisting of aryl groups, alkoxycarbonyl groups, halogen atoms, and hydroxyl groups. The substituent of the substituted aryl group and the substituted heterocyclic group is at least one group selected from the group consisting of halogen atoms, nitro groups, cyano groups, alkyl groups, halogen-substituted alkyl groups, and alkoxy groups. [ka] (In formula (B), at least one of a, b, and c has at least one group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. l and m are each independently 0 or 1, and the sum of l and m is between 0 and 2.) a represents an alkylene group having 1 to 6 carbon atoms in the main chain, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkylocarbonyl group, or an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a phenyl group. These alkylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. One of the CH2s in the main chain of these alkylene groups may be substituted with O or S, or one of the CHs in the main chain of these alkylene groups may be substituted with N. b represents a phenylene group, a C1-C6 alkyl-substituted phenylene group, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy-substituted phenylene group, and these phenylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. c represents a hydrogen atom, a carboxyl group, an alkyl group with 1 to 6 carbon atoms in the main chain, or an alkyl group with 1 to 6 carbon atoms in the main chain substituted with an alkyl group with 1 to 5 carbon atoms. These alkyl groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. [Configuration 2] The electrophotographic photoreceptor according to configuration 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 11% or more. [Configuration 3] The electrophotographic photoreceptor according to configuration 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 50% or more. [Structure 4] The electrophotographic photoreceptor according to configuration 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 75% or more. [Composition 5] An electrophotographic photoreceptor according to any one of configurations 1 to 4, wherein the ratio of the area occupied by Al crystal grains having (α) to the total surface area of ​​the support is 5% or less. [Composition 6] The electrophotographic photoreceptor according to any one of configurations 1 to 5, wherein the thickness of the undercoat layer is 2.5 μm or less. [Composition 7] The electrophotographic photoreceptor according to any one of configurations 1 to 6, wherein the surface of the support is formed of an Al alloy containing 0.05% by mass or more and 0.2% by mass or less of Cu, and 1.0% by mass or more and 1.5% by mass or less of Mn. [Structure 8] The electrophotographic photoreceptor according to any one of configurations 1 to 6, wherein the surface of the support is formed of an Al alloy containing 0.45% by mass or more and 6.0% by mass or less of Mg. [Composition 9] A process cartridge that integrally supports an electrophotographic photoreceptor as described in any one of configurations 1 to 8, and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachably attached to the body of an electrophotographic apparatus. [Configuration 10] An electrophotographic photoreceptor according to any one of configurations 1 to 8, and an electrophotographic apparatus having a charging means, an exposure means, a developing means, and a transfer means. [Explanation of Symbols]

[0128] 1...Electrophotographic photoreceptor 2...axis 3. Charging methods 4‥‥Exposure light 5. Development methods 6. Transfer method 7. Transfer material 8. Fixation methods 9. Cleaning methods 10...Previous exposure light 11... Process cartridge 12... Means of guidance

Claims

1. An electrophotographic photoreceptor having a cylindrical support, an undercoat formed directly above the support, and a photosensitive layer formed on the undercoat, The undercoat contains a cured product of a composition comprising a compound represented by the following formula (A1) and / or a compound represented by (A2), The surface of the support is formed of Al and / or an Al alloy, and the surface of the support in the surface direction of the Al texture of the support surface is (α) {001} plane with an orientation of -15° or more and less than +15° (γ) {111} plane with an azimuth of -15° or greater and less than +15° An electrophotographic photoreceptor characterized by comprising Al crystal grains having (α), wherein the ratio of the area occupied by the Al crystal grains having (α) to the total surface area of ​​the support is 10% or less, and the ratio of the area occupied by the Al crystal grains having (γ) exceeds 10%. 【Chemistry 1】 (In Formula (A1) and Formula (A2), R １０１ ~R １０６ 、R ２０１ ~R ２１０ each independently represents a monovalent group represented by the following formula (B), a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of R １０１ ~R １０６ , and at least one of R ２０１ ~R ２１０ is a monovalent group represented by the following formula (B). One of the CH ２ of the alkyl group may be substituted with O or S, or one of the CH of the alkyl group may be substituted with N. The substituent of the substituted alkyl group is at least one kind of group selected from the group consisting of an aryl group, an alkoxycarbonyl group, a halogen atom, and a hydroxy group. The substituent of the substituted aryl group and the substituted heterocyclic group is at least one kind of group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen-substituted alkyl group, and an alkoxy group.) 【Chemistry 2】 (In formula (B), at least one of a, b, and c has at least one group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. l and m are each independently 0 or 1, and the sum of l and m is 0 or greater and 2 or less.) a represents an alkylene group having 1 to 6 carbon atoms in the main chain, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 carbon atoms in the main chain substituted with an alkylcarbonyl group, or an alkylene group having 1 to 6 carbon atoms in the main chain substituted with a phenyl group. These alkylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. CH in the main chain of these alkylene groups ２ One of these groups may be substituted with O or S, or one of the CH groups in the main chain of these alkylene groups may be substituted with N. b represents a phenylene group, a C1-C6 alkyl-substituted phenylene group, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy-substituted phenylene group. These phenylene groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group. c represents a hydrogen atom, a carboxyl group, an alkyl group with 1 to 6 carbon atoms in the main chain, or an alkyl group with 1 to 6 carbon atoms in the main chain substituted with an alkyl group with 1 to 5 carbon atoms. These alkyl groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and a carboxyl group.

2. The electrophotographic photoreceptor according to claim 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 11% or more.

3. The electrophotographic photoreceptor according to claim 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 50% or more.

4. The electrophotographic photoreceptor according to claim 1, wherein the ratio of the area occupied by Al crystal grains having (γ) to the total surface area of ​​the support is 75% or more.

5. The electrophotographic photoreceptor according to any one of claims 1 to 4, wherein the ratio of the area occupied by Al crystal grains having (α) to the total surface area of ​​the support is 5% or less.

6. The electrophotographic photoreceptor according to claim 1, wherein the thickness of the undercoat layer is 2.5 μm or less.

7. The electrophotographic photoreceptor according to claim 1, wherein the surface of the support is formed of an Al alloy containing 0.05% by mass or more and 0.2% by mass or less of Cu and 1.0% by mass or more and 1.5% by mass or less of Mn.

8. The electrophotographic photoreceptor according to claim 1, wherein the surface of the support is formed of an Al alloy containing 0.45% by mass or more and 6.0% by mass or less of Mg.

9. A process cartridge that integrally supports an electrophotographic photoreceptor according to any one of claims 1 to 4 and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachably attached to the main body of an electrophotographic apparatus.

10. An electrophotographic photoreceptor according to any one of claims 1 to 4, and an electrophotographic apparatus having a charging means, an exposure means, a developing means, and a transfer means.

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