Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus

Abstract

This invention relates to an electrophotographic photosensitive element, a method for manufacturing the same, a processing cartridge, and an electrophotographic apparatus. An electrophotographic photosensitive element is provided that suppresses image defects caused by its support and reduces long-term potential fluctuations. The electrophotographic photosensitive element comprises a cylindrical support and a photosensitive layer formed on the support, wherein the support has a surface formed of Al and / or an Al alloy, and wherein the IR peak area ratio A of the surface of the support, determined by Fourier transform infrared spectroscopy, satisfies the following condition: A ≥ 0.50, where the IR peak area ratio A is expressed at 1,016 cm⁻¹. ‑1 Above and 1,130cm ‑1 The peak area "a" in the following range is at 650 cm⁻¹ ‑1 Above and 1,130cm ‑1 The ratio of peak area "z" in the following range, a / z.

Description

Technical Field

[0001] This invention relates to an electrophotographic photosensitive element, a processing box including the electrophotographic photosensitive element, an electrophotographic apparatus, and a method for manufacturing the electrophotographic photosensitive element. Background Technology

[0002] Electrophotographic photosensitive components are used as image-carrying components in electrophotographic image-forming devices (e.g., printers or multifunction peripherals). An electrophotographic photosensitive component includes a support and a photosensitive layer formed on the support. The surface roughness of the support varies depending on the material of the support. The surface roughness of the support can affect the formation of a latent image during electrophotography, causing image defects.

[0003] Japanese Patent Application Publication No. H01-29852 describes a technique that includes processing the surface of a cylindrical support to suppress image defects caused by the roughness of the support surface. Summary of the Invention

[0004] According to the inventors' research, the electrophotographic photosensitive component described in Japanese Patent Application Publication No. H01-29852, while capable of suppressing image defects caused by the support, suffers from the problem of large long-term potential fluctuations. In view of the above, the inventors have researched a technique for processing the surface of a cylindrical support, which enables both the suppression of image defects and the reduction of long-term potential fluctuations.

[0005] One object of the present invention is to provide an electrophotographic photosensitive element that suppresses image defects caused by its support and reduces long-term potential fluctuations.

[0006] This objective is achieved by the invention described below.

[0007] That is, according to the present invention, an electrophotographic photosensitive component is provided, comprising: a cylindrical support; and a photosensitive layer formed on the support, wherein the support has a surface formed of Al and / or an Al alloy, and wherein the IR peak area ratio A of the surface of the support, determined by Fourier transform infrared spectroscopy, satisfies the following condition:

[0008] A≥0.50

[0009] The IR peak area ratio A represents the area at 1,016 cm⁻¹. -1 Above and 1,130cm -1 The peak area "a" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" in the following range, a / z.

[0010] In addition, according to the present invention, a processing box is provided, comprising: the above-described electrophotographic photosensitive component; and at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit, wherein the processing box integrally supports the electrophotographic photosensitive component and the at least one unit, and is detachably mounted to the body of an electrophotographic device.

[0011] In addition, according to the present invention, an electrophotographic apparatus is provided, comprising: the above-described electrophotographic photosensitive component; a charging unit; an exposure unit; a developing unit; and a transfer unit.

[0012] Furthermore, according to the present invention, a method for manufacturing an electrophotographic photosensitive component is provided. The electrophotographic photosensitive component includes a cylindrical support and a photosensitive layer formed on the support. The method for forming the support includes immersing the cylindrical body formed of Al and / or an Al alloy in pure water to obtain the support. The temperature of the pure water is 91°C or higher and 98°C or lower, and the cylindrical body is immersed in the pure water for a time of 60 seconds or higher and 300 seconds or lower. The method further includes the method for determining the IR peak area ratio A of the support surface by Fourier transform infrared spectroscopy, which satisfies the following condition:

[0013] A≥0.50

[0014] The IR peak area ratio A represents the area at 1,016 cm⁻¹. -1 Above and 1,130cm -1 The peak area "a" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" in the following range, a / z.

[0015] According to the present invention, an electrophotographic photosensitive element can be provided that suppresses image defects caused by its support and reduces long-term potential fluctuations.

[0016] Further features of the invention will become apparent from the following description of exemplary embodiments, with reference to the accompanying drawings. Attached Figure Description

[0017] Figure 1 The figure illustrates an example of a schematic configuration of an electrophotographic device, which includes a processing cassette comprising the electrophotographic photosensitive element of the present invention.

[0018] Figure 2 A graph illustrating the IR peak area ratios A and B as defined in this invention is shown for illustrative purposes. Detailed Implementation

[0019] The present invention is described in detail below by way of exemplary embodiments.

[0020] [Electronic photographic sensor]

[0021] The electrophotographic photosensitive component according to this embodiment is an electrophotographic photosensitive component whose support body undergoes surface treatment such that the IR peak area ratio A of the support body surface can exhibit a predetermined range. It has been found that while prior art electrophotographic photosensitive components with such an oxidized surface treatment of the support body exhibit excellent properties in shielding image defects originating from the support body, these photosensitive components are subject to the problem of amplifying long-term potential fluctuations due to repeated charging. To solve this problem, the inventors of the present invention conducted research aimed at optimizing the surface composition of the support body by improving the surface treatment method. As a result of the research, the inventors discovered that when the IR peak area ratio A of the support body surface, determined by Fourier transform infrared spectroscopy, is controlled under the following conditions through surface treatment, long-term potential fluctuations of the photosensitive component can be suppressed compared to conventional electrophotographic photosensitive components that shield image defects caused by the support body:

[0022] A≥0.50

[0023] The IR peak area ratio A represents the area at 1,016 cm⁻¹. -1 Above and 1,130cm -1 The peak area "a" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" in the following range, a / z.

[0024] Furthermore, the inventors have revealed that as the value of A increases, the suppression effect on long-term potential fluctuations becomes more effective.

[0025] Although some aspects of the true cause of suppressing long-term potential fluctuations have not yet been elucidated, as a mechanism inferred from the above results, it is conceivable that, despite the potential fluctuations caused by charge accumulation in the oxidized portions of electrophotographic photosensitive components constructed by the prior art, in a construction with this IR peak area ratio, such a composition in which almost no charge accumulation occurs grows sufficiently on the surface of the support. As stated above, the effects of the present invention can be achieved when a suitable method for processing the support is selected and the composition of the support surface is set to an optimal composition.

[0026] A more preferred scenario is where the IR peak area ratio A is controlled under the following conditions.

[0027] A≥0.75

[0028] Furthermore, it is preferable to control the IR peak area ratio B of the support surface determined by Fourier transform infrared spectroscopy under the following conditions:

[0029] B≤0.20

[0030] The IR peak area ratio B represents the area at 831 cm⁻¹. -1 Above and 1,015cm -1 The peak area "b" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" to b / z within the following range.

[0031] [Electronic photographic sensor]

[0032] The electrophotographic photosensitive component of the present invention is characterized in that it includes a support and a photosensitive layer.

[0033] An example of the manufacturing method of the electrophotographic photosensitive component of the present invention includes the following steps: preparing coating liquids for each layer described below; applying the liquids in a desired layer sequence; and drying the liquids. In this case, examples of coating methods for each coating liquid include dip coating, spray coating, inkjet coating, roller coating, die coating, doctor blade coating, curtain coating, wire rod coating, and ring coating. From the viewpoint of efficiency and productivity, dip coating is preferred.

[0034] The following describes each layer.

[0035] <Support Body>

[0036] In this invention, the electrophotographic photosensitive component includes a support. Regarding the shape of the support, a cylindrical support is used. Furthermore, the surface of the support can be sandblasted or machined, etc.

[0037] Regarding the material of the support, an aluminum support made of aluminum (Al) and / or an Al alloy is used. Although there are no particular limitations on the aluminum alloy used, examples include A3003 series aluminum alloys, A5052 series aluminum alloys, and A6063 series aluminum alloys. Among these, A3003 series aluminum alloys are preferred because this alloy has latitude for the IR peak area ratio A of the support surface. The Al alloy preferably contains the following components as components other than Al relative to the total mass of the Al alloy: less than 0.6 wt% Si, less than 0.7 wt% Fe, more than 0.05 wt% and less than 0.20 wt% Cu, more than 1.0 wt% and less than 1.5 wt% Mn, and less than 0.10 wt% Zn.

[0038] In this invention, although there are no particular limitations on the methods for setting the IR peak area ratio A of the support surface to the following conditions, examples include: hot water treatment with pure water at a temperature exceeding 90°C; and treatment with an alkaline aqueous solution with appropriate control of the pH of the solution and the immersion time therein.

[0039] A≥0.50

[0040] A preferred method, for example, includes immersing a cylindrical body made of Al and / or Al alloy in pure water, wherein the temperature of the pure water is above 91°C and below 98°C, and the immersion time of the cylindrical body in the pure water is above 60 seconds and below 300 seconds.

[0041] <Conductive Layer>

[0042] In this invention, a conductive layer can be provided on the support. The conductive layer can shield scratches and unevenness on the surface of the support and control light reflection on the surface of the support.

[0043] The conductive layer preferably comprises conductive particles and resin.

[0044] The conductive particles are made of materials such as metal oxides, metals, or carbon black.

[0045] Examples of metal oxides include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, and bismuth oxide. Examples of metals include aluminum, nickel, iron, nickel-chromium alloys, copper, zinc, and silver.

[0046] Metal oxides are preferably used as conductive particles, and in particular, titanium oxide, tin oxide, and zinc oxide are more preferred.

[0047] When metal oxides are used as conductive particles, the surface of the metal oxides can be treated with silane coupling agents, or the metal oxides can be doped with elements such as phosphorus or aluminum or their oxides.

[0048] Furthermore, each conductive particle can be a stacked structure having a core particle and a coating layer covering the particle. Examples of core particles include titanium oxide, barium sulfate, and zinc oxide. The coating layer is, for example, a metal oxide such as tin oxide.

[0049] Furthermore, when metal oxides are used as conductive particles, their volume average particle size is preferably 1 nm or more and 500 nm or less, more preferably 3 nm or more and 400 nm or less.

[0050] Examples of resins include polyester resins, polycarbonate resins, polyvinyl acetal resins, acrylic resins, silicone resins, epoxy resins, melamine resins, polyurethane resins, phenolic resins, and alkyd resins.

[0051] In addition, the conductive layer may further contain a masking agent, such as silicone oil, resin particles, or titanium dioxide.

[0052] The average thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

[0053] The conductive layer can be formed by preparing a coating liquid containing the above-mentioned materials and solvents, forming a coating film thereon, and drying the coating film. Examples of solvents used in the coating liquid include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. As a dispersion method for dispersing conductive particles in the coating liquid for the conductive layer, methods using paint mixers, sand mills, ball mills, and liquid collision type high-speed dispersers are provided.

[0054] <Undercoat>

[0055] In this invention, a primer layer can be applied to the support or conductive layer. The primer layer improves the adhesion between layers, thereby providing a charge injection barrier.

[0056] The primer layer preferably comprises a resin. Alternatively, the primer layer can be formed into a cured film by polymerizing a composition comprising monomers having polymerizable functional groups.

[0057] Examples of resins include polyester resins, polycarbonate resins, polyvinyl alcohol acetal resins, acrylic resins, epoxy resins, melamine resins, polyurethane resins, phenolic resins, polyvinylphenol resins, alkyd resins, polyvinyl alcohol resins, polyethylene oxide resins, polypropylene oxide resins, polyamide resins, polyamic acid resins, polyimide resins, polyamide-imide resins, and cellulose resins.

[0058] Examples of polymerizable functional groups in monomers include isocyanate groups, terminal isocyanate groups, hydroxymethyl groups, alkylated hydroxymethyl groups, epoxy groups, metal alkoxide groups, hydroxyl groups, amino groups, carboxyl groups, thiol groups, carboxylic anhydride groups, and carbon-carbon double bond groups.

[0059] Furthermore, to improve electrical properties, the base coating may further include electron transport materials, metal oxides, metals, and conductive polymers. Among these, electron transport materials and metal oxides are preferred.

[0060] Examples of electron transport materials include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienyl compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aromatic compounds, thiophene compounds, and boron-containing compounds. Electron transport materials having polymerizable functional groups can be used as electron transport materials and copolymerized with the aforementioned monomers having polymerizable functional groups to form a base coating as a cured film.

[0061] 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.

[0062] In addition, the base coat may contain additives.

[0063] The average thickness of the base coating is preferably 0.1 μm or more and 50 μm or less, more preferably 0.2 μm or more and 40 μm or less, and particularly preferably 0.3 μm or more and 30 μm or less.

[0064] The primer layer can be formed by preparing a primer coating solution containing the above-mentioned materials and solvents, forming the coating film thereon, and drying and / or curing the coating film. Examples of solvents used in the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

[0065] <Photosensitive layer>

[0066] The photosensitive layer of an electrophotographic photosensitive component is mainly classified into (1) stacked photosensitive layer and (2) single-layer photosensitive layer. (1) Stacked photosensitive layer has a charge-generating layer containing charge-generating material and a charge-transporting layer containing charge-transporting material. (2) Single-layer photosensitive layer has a photosensitive layer containing both charge-generating material and charge-transporting material.

[0067] (1) Layered photosensitive layer

[0068] A stacked photosensitive layer includes a charge generation layer and a charge transport layer.

[0069] (1-1) Charge generation layer

[0070] The charge-generating layer preferably comprises a charge-generating substance and a resin.

[0071] Examples of charge-generating substances include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferred. Of the phthalocyanine pigments, titanium dioxide phthalocyanine pigments, gallium chloride phthalocyanine pigments, and hydroxy gallium phthalocyanine pigments are preferred.

[0072] The content of charge-generating material in the charge-generating layer is preferably 40% by mass or more and 85% by mass or less relative to the total mass of the charge-generating layer, more preferably 60% by mass or more and 80% by mass or less.

[0073] Examples of resins include polyester resins, polycarbonate resins, polyvinyl acetal resins, polyvinyl butyral resins, acrylic resins, silicone resins, epoxy resins, melamine resins, polyurethane resins, phenolic resins, polyvinyl alcohol resins, cellulose resins, polystyrene resins, polyvinyl acetate resins, and polyvinyl chloride resins. Among these, polyvinyl butyral resins are more preferred.

[0074] In addition, the charge-generating layer may further contain additives such as antioxidants or UV absorbers. Specific examples include hindered phenolic compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

[0075] The average thickness of the charge generation layer is preferably 0.1 μm or more and 1 μm or less, more preferably 0.15 μm or more and 0.4 μm or less.

[0076] The charge-generating layer can be formed by preparing a coating solution containing the above-described materials and solvents, forming a coating film thereon, and drying the coating film. 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.

[0077] (1-2) Charge transport layer

[0078] The charge transport layer preferably comprises a charge transport material and a resin.

[0079] Examples of charge-transporting substances include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from each of these substances. Among these, triarylamine compounds and benzidine compounds are preferred.

[0080] The content of charge transport material in the charge transport layer is preferably 25% by mass or more and 70% by mass or less relative to the total mass of the charge transport layer, more preferably 30% by mass or more and 55% by mass or less.

[0081] Examples of resins include polyester resins, polycarbonate resins, acrylic resins, and polystyrene resins. Polycarbonate resins and polyester resins are preferred. Polyaryl ester resins are particularly preferred as polyester resins.

[0082] The content ratio (mass ratio) between the charge transport material and the resin is preferably 4:10 to 20:10, more preferably 5:10 to 12:10.

[0083] In addition, the charge transport layer may contain additives such as antioxidants, UV absorbers, plasticizers, leveling agents, lubricants, or abrasion improvers. Specific examples include hindered phenolic compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluoropolymer particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, and boron nitride particles.

[0084] The average thickness of the charge transport layer is 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 30 μm or less.

[0085] The charge transport layer can be formed by preparing a coating solution containing the above-described materials and solvents, forming a coating film thereon, and drying the coating film. 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.

[0086] (2) Single-layer photosensitive layer

[0087] A single-layer photosensitive layer can be formed by preparing a coating solution containing a charge-generating substance, a charge-transporting substance, a resin, and a solvent, forming a coating film thereon, and drying the coating film. Examples of the charge-generating substance, the charge-transporting substance, and the resin are the same as those of the materials in the section "(1) Laminated Photosensitive Layers".

[0088] <Protective Layer>

[0089] In this invention, a protective layer can be formed on the photosensitive layer. The protective layer can improve durability.

[0090] The protective layer preferably comprises conductive particles and / or charge-transporting substances, and resin.

[0091] Examples of conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide, and indium oxide.

[0092] Examples of charge-transporting substances include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from each of these substances. Among these, triarylamine compounds and benzidine compounds are preferred.

[0093] Examples of resins include polyester resins, acrylic resins, phenoxy resins, polycarbonate resins, polystyrene resins, phenolic resins, melamine resins, and epoxy resins. Among these, polycarbonate resins, polyester resins, and acrylic resins are preferred.

[0094] Alternatively, the protective layer can be formed into a cured film by polymerizing a composition containing monomers having polymerizable functional groups. Examples of reactions in this case include thermal polymerization, photopolymerization, and radiation polymerization. Examples of polymerizable functional groups in monomers include acrylate and methacrylate groups. Materials with charge-transporting capabilities can be used as monomers having polymerizable functional groups.

[0095] The protective layer may contain additives such as antioxidants, UV absorbers, plasticizers, leveling agents, lubricants, or abrasion improvers. Specific examples include hindered phenolic compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluoropolymer particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, and boron nitride particles.

[0096] The average thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less.

[0097] The protective layer can be formed by preparing a coating solution containing the above-described materials and solvents, forming the coating film thereon, and drying and / or curing the coating film. 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.

[0098] [Processing box and electrophotographic equipment]

[0099] The processing box of the present invention is characterized in that the processing box integrally supports the above-mentioned electrophotographic photosensitive component and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit and a cleaning unit, and the processing box is detachably mounted to the main body of the electrophotographic device.

[0100] Furthermore, the electrophotographic apparatus of the present invention is characterized in that it includes the aforementioned electrophotographic photosensitive component, charging unit, exposure unit, developing unit, and transfer unit.

[0101] An example of the schematic configuration of an electrophotographic device is shown in Figure 1 In this context, the electrophotographic device includes a processing box containing an electrophotographic photosensitive component.

[0102] A cylindrical electrophotographic photosensitive element 1 is driven to rotate about axis 2 at a predetermined circumferential speed in the direction indicated by the arrow. The surface of the electrophotographic photosensitive element 1 is charged to a predetermined positive or negative potential by charging unit 3. Although a roller charging system based on a roller-type charging element is shown in the figure, charging systems such as corona charging systems, contact charging systems, or injection charging systems can also be used. The charged surface of the electrophotographic photosensitive element 1 is irradiated with exposure light 4 from an exposure unit (not shown), thus forming an electrostatic latent image corresponding to the target image information thereon. The electrostatic latent image formed on the surface of the electrophotographic photosensitive element 1 is developed using toner stored in the developing unit 5, and a toner image is formed on the surface of the electrophotographic photosensitive element 1. The toner image formed on the surface of the electrophotographic photosensitive element 1 is transferred to transfer material 7 by transfer unit 6. The transfer material 7, on which the toner image has been transferred, is conveyed to fixing unit 8 for processing to fix the toner image and then printed to the outside of the electrophotographic device. Electrophotographic equipment may include a cleaning unit 9 for removing, for example, toner residues remaining on the surface of the electrophotographic photosensitive member 1 after transfer. Alternatively, a so-called cleanerless system may be used, configured to remove residues using a developing unit or similar device without a separate cleaning unit. Electrophotographic equipment may include a static removal mechanism configured to perform static removal treatment on the surface of the electrophotographic photosensitive member 1 using pre-exposure light 10 from a pre-exposure unit (not shown). Additionally, a guide unit 12, such as a guide rail, may be provided for detachably mounting the processing cartridge 11 of the present invention to the main body of the electrophotographic equipment.

[0103] The electrophotographic photosensitive component of the present invention can be used, for example, in laser beam printers, LED printers, copiers, fax machines, and their multifunctional peripheral devices.

[0104] <Example>

[0105] The present invention is described in more detail below by way of examples and comparative examples. The present invention is by no means limited to the following examples, and various modifications can be made without departing from the spirit of the invention. In the following description of the examples, unless otherwise stated, "parts" are based on mass.

[0106] <Example of the production of surface-treated supports>

[0107] [Production Examples 1 to 4]

[0108] An aluminum cylinder made of A3003 alloy, with a diameter of 30.5 mm and a length of 370 mm, was used as a support. The cylinder was ultrasonically cleaned for 80 seconds at 100 kHz in a water bath containing a surfactant (trade name: CHEMICOL CT, manufactured by Tokiwa Chemical Industries Co., Ltd.) at 35°C, followed by ultrasonic cleaning for 80 seconds at 100 kHz in pure water at 40°C. Subsequently, the cylinder was surface-treated by immersion in a pure water bath while appropriately adjusting the water temperature and immersion time. This yielded a support, and the IR peak area ratio A on the support surface was then varied to satisfy A ≥ 0.75. Through the above steps, supports S1 to S4 with the surface treatment according to the present invention, used for the production of photosensitive components, were obtained. The conditions are shown in Table 1.

[0109] [Production Examples 5 to 7]

[0110] Instead, the cylindrical body was immersed in hot water at 95°C for 180 seconds. The hot water temperature and immersion time were appropriately adjusted to change the IR peak area ratios A and B on the support surface, ensuring that A ≥ 0.50 and B ≤ 0.20. Supports S5 to S7 were obtained under the same conditions as in Production Example 1, except as described above. These conditions are shown in Table 1.

[0111] [Production Examples 8 to 11]

[0112] Instead, the cylindrical body was immersed in hot water at 95°C for 180 seconds. The hot water temperature and immersion time were appropriately adjusted to change the IR peak area ratios A and B on the surface of the support, so that A ≥ 0.50 and B > 0.20. Supports S8 to S11 were obtained under the same conditions as in Production Example 1, except as described above. These conditions are shown in Table 1.

[0113] [Comparative Production Examples 1 to 5]

[0114] Except for appropriately adjusting the water temperature and immersion time to change the IR peak area ratio A so that A < 0.50, supports R1 to R5 were obtained in the same manner as in production example 1. The conditions are shown in Table 1.

[0115] [Comparative Production Example 6]

[0116] Except that, after ultrasonic cleaning, the cylindrical body is immersed in pure water at room temperature instead of in hot water for surface treatment, the support body R6 is obtained in the same manner as in Production Example 1. The production conditions are shown in Table 1.

[0117] [Comparative Production Example 7]

[0118] Except that after ultrasonic cleaning, the support surface is anodized instead of surface treatment by hot water immersion, the support R7 is obtained in the same manner as in Production Example 1. An electrolyte solution with a sulfuric acid concentration of 180 g / L and a dissolved aluminum concentration of 7 g / L is used at 1.2 A / dm³. 2 Anodizing was performed at a specific current density. Further, the anodized support was sealed by washing it with water and then immersing it in an aqueous solution of nickel acetate at 95°C for 30 minutes. Production conditions are shown in Table 1.

[0119] [Comparative Production Example 8]

[0120] Except that after ultrasonic cleaning, the cylinder is immersed in hot water at 95°C for 20 seconds and then further oxidized in an oven heated to 120°C for 20 minutes, the support R8 is obtained in the same manner as in Production Example 1. The production conditions are shown in Table 1.

[0121] Table 1

[0122]

[0123] <Example of the production of electrophotographic photosensitive components>

[0124] [Example 1]

[0125] Use support body S1 as support body.

[0126] 100 parts of zinc oxide granules (specific surface area: 19m²) 2 / g, powder resistivity: 4.7×10 6 The zinc oxide (O2) was stirred and mixed with 500 parts of toluene (Ω·cm), and 0.8 parts of silane coupling agent were added to the mixture, followed by stirring for 6 hours. Subsequently, the toluene was evaporated under reduced pressure, and the residue was dried at 130°C for 6 hours to obtain surface-treated zinc oxide particles. KBM-602 (compound name: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used as the silane coupling agent.

[0127] Next, 15 parts of polyvinyl butyral resin (weight average molecular weight: 40,000, product name: BM-1, manufactured by Sekisui Chemical Company, Limited) and 15 parts of end-capped isocyanate (trade name: Sumidur 3175, manufactured by Sumika Covestro Urethane Co., Ltd. (formerly Sumika Bayer Urethane Co., Ltd.)) were dissolved in a mixed solution of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol. 80.8 parts of surface-treated zinc oxide particles and 0.8 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the solution, and the mixture was dispersed at 23°C ± 3°C under atmospheric conditions for 3 hours using a sand mill with glass beads of 0.8 mm diameter. After dispersion, 0.01 parts of silicone oil (product name: SH28PA, manufactured by DowCorning Toray Co., Ltd.) and 5.6 parts of cross-linked polymethyl methacrylate (PMMA) particles (product name: TECHPOLYMER SSX-103, manufactured by Sekisui Kasei Co., Ltd., average primary particle size: 3 μm) were added to the dispersion product, and the mixture was stirred to prepare a coating liquid for the primer layer.

[0128] The primer layer is applied to the support by dip coating to form a coating film, and the resulting coating film is dried at 160°C for 40 minutes to form a primer layer with a thickness of 18 μm.

[0129] Next, four parts of hydroxy gallium phthalocyanine crystal (charge-generating material) in crystalline form with strong peaks at Bragg angles of 7.4° and 28.1° at 2θ±0.2° in CuKα characteristic X-ray diffraction, and 0.04 parts of the compound represented by formula (1) were added to a liquid obtained by dissolving 2 parts of polyvinyl butyral (product name: S-LEC BX-1, manufactured by Sekisui Chemical Company, Limited) in 100 parts of cyclohexanone.

[0130]

[0131] Subsequently, the mixture was dispersed for 1 hour at 23℃±3℃ under atmospheric conditions using a sand mill with glass beads of 1.0 mm diameter each. After dispersion, 100 parts of ethyl acetate were added to the dispersion product to prepare a coating solution for the charge generation layer. The coating solution for the charge generation layer was applied to the base layer by dip coating, and the resulting coating was dried at 90℃ for 10 minutes to form a charge generation layer with a thickness of 0.21 μm.

[0132] Next, 30 parts of the compound represented by formula (2) (charge transport material), 60 parts of the compound represented by formula (3) (charge transport material), 10 parts of the compound represented by formula (4), 100 parts of polycarbonate (product name: IUPILON Z400, manufactured by Mitsubishi Engineering-Plastics Corporation, bisphenol Z type), and 0.02 parts of polycarbonate having two structural units represented by formula (5) (viscosity average molecular weight Mv: 20,000) were mixed with 272 parts of o-xylene, 256 parts of methyl benzoate, and 272 parts of dimethoxymethane (methyl acetal) to prepare a coating solution for the charge transport layer. The coating solution for the charge transport layer was applied to the charge generation layer by dip coating to form a coating film, and the resulting coating film was dried at 115°C for 50 minutes to form a charge transport layer with a thickness of 18 μm.

[0133]

[0134] Next, 95 parts of the compound represented by formula (6), 5 parts of the vinyl ester compound represented by formula (7) (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.5 parts of the siloxane-modified acrylic compound (BYK-3550, manufactured by BYK-Chemie Japan KK), and 5 parts of the urea compound represented by formula (8) were mixed with 200 parts of 1-propanol and 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (product name: ZEORORA H, manufactured by Zeon Corporation), and the mixture was stirred.

[0135] Subsequently, the solution was filtered using a polytetrafluoroethylene filter (product name: PF-020, manufactured by Advantec Toyo Kaisha, Ltd.) to prepare a coating solution for the surface layer (coating solution for the protective layer).

[0136] A surface layer was applied to the charge transport layer using an immersion coating to form a coating film, and the resulting coating film was dried at 50°C for 10 minutes. Subsequently, under a nitrogen atmosphere, with an accelerating voltage of 70 kV and a beam current of 5.0 mA, the coating film was irradiated with an electron beam for 1.6 seconds while the support (the irradiated target) rotated at 200 rpm. The absorbed dose of the electron beam at this time was measured to be 15 kGy. The coating film was then heated by increasing its temperature from 25°C to 117°C over 30 seconds under a nitrogen atmosphere. The oxygen concentration during the period from electron beam irradiation to the subsequent heat treatment was below 15 ppm. Next, the coating film was allowed to cool naturally in the atmosphere until its temperature reached 25°C, and then heat-treated for 30 minutes at a temperature of 105°C. This resulted in a protective layer (surface layer) with a thickness of 5 μm.

[0137]

[0138] The surface of the manufactured electrophotographic photosensitive component can be subjected to surface processing to reduce friction using a component that can abut against the surface of the photosensitive component. Examples of surface processing include grinding and shaping.

[0139] [evaluate]

[0140] <Preparation of the support plate for evaluation>

[0141] Evaluation support sheets are prepared by cutting a 1 cm square piece from the upper end of the support of a surface-treated cylindrical support or an electrophotographic photosensitive element after the application of a photosensitive layer, at a distance of 180 mm from the layer. In this evaluation, eight sample sheets are prepared circumferentially along the support, and the average value of the measurements from each sample sheet is used. When the support sheets are collected from the photosensitive element, the photosensitive layer is removed to expose the surface of the support. Examples of removal methods include dissolution with an organic solvent and removal with a polishing machine. When removal is performed by grinding, an appropriate grinding time and appropriate abrasive are determined from the grinding rate of the photosensitive layer to avoid excessive scraping of the outermost surface of the support.

[0142] <Evaluation of Surface Composition>

[0143] FT-IR spectroscopy was used as a method for evaluating the composition of the support surface. FT-IR spectra were measured by ATR using a Fourier transform infrared spectrophotometer (Spectrum One; manufactured by PerkinElmer, Inc.) equipped with a universal ATR sampling accessory. The specific measurement procedures, and the methods for calculating peak areas "a", "b", and "z" and IR peak area ratios A and B, are described below.

[0144] The incident angle of the infrared light was set to 45°, and a Ge ATR crystal (refractive index = 4.0) was used as the ATR crystal. Other conditions are as follows.

[0145] scope

[0146] Starting point: 4,000cm -1

[0147] End: 600cm -1 (Ge ATR crystal)

[0148] continued

[0149] Number of scans: 16

[0150] Resolution: 4.00cm -1

[0151] Later stage: CO2 / H2O correction exists.

[0152] [Method for calculating peak intensity ratio]

[0153] (1) Install the Ge ATR crystal (refractive index = 4.0) into the device.

[0154] (2) Set the device's scan type to "background" and its unit to "EGY", followed by a background measurement.

[0155] (3) Set the scan type to "sample" and its unit to "A".

[0156] (4) Each support sheet is placed on the ATR crystal so that its surface is on the ATR crystal side.

[0157] (5) Apply pressure to the sample using the pressure arm of the device (set its force gauge to 80).

[0158] (6) Measure the FT-IR spectrum of the sample.

[0159] (7) Baseline correction is performed on the obtained FT-IR spectrum using the automatic calibration of the device.

[0160] (8) Perform ATR correction on the spectrum after baseline correction.

[0161] (9) Calculate 1,016 cm -1 Above and 1,130cm -1 The integral value "a" of the absorption peak intensity within the following range.

[0162] (10) Calculate 831cm -1 Above and 1,015cm -1The integral value "b" of the absorption peak intensity within the following range.

[0163] (11) Calculate 650cm -1 Above and 1,130cm -1 The integral value "z" of the absorption peak intensity within the following range.

[0164] (12) The ratio a / z is defined as the IR peak area ratio A.

[0165] (13) The ratio b / z is defined as the IR peak area ratio B.

[0166] (14) Calculate the magnitude of the calculated values ​​of A and B respectively.

[0167] A schematic diagram of the IR spectrum is shown in Figure 2 In this study, it was found that as the value of A increases, long-term potential fluctuations in the electrophotographic photosensitive component can be suppressed to a greater extent. This is likely because the proportion of components that are difficult to cause charge accumulation on the support surface becomes larger, thus establishing a favorable state for suppressing long-term potential fluctuations. It was also found that long-term potential fluctuations are easily suppressed even in the range of A ≥ 0.5 and B ≤ 0.2. This is likely because the proportion of components that are easy to cause charge accumulation on the support surface becomes smaller.

[0168] The evaluation results are shown in Table 2.

[0169] <Evaluation of Depth-Directional Composition>

[0170] ESCA, as an X-ray photoelectron spectroscopy method, is used to evaluate the depth-direction composition of the support. The analytical conditions are as follows.

[0171] Equipment used: VersaProbe II manufactured by ULVAC-PHI, Inc.

[0172] X-ray source: Al Kα 1,486.6 eV (25 W, 15 kV)

[0173] Measurement area: φ100μm

[0174] Spectral region: 300μm × 200μm, angle: 45°

[0175] Energy: 58.70 eV

[0176] Step size: 0.125eV

[0177] Sputtering gas: Ar

[0178] Sputtering conditions: 1kV, 4×4

[0179] The surface atomic concentration (atomic %) was calculated from the peak intensities of each element measured under the above conditions using relative sensitivity coefficients provided by ULVAC-PHI, Inc. The peak top ranges for each element were used as described above.

[0180] O: Energy of photoelectrons originating from electron orbit 1s: 525eV to 545eV

[0181] Al: Energy of photoelectrons originating from the 2p electron orbital: 68 eV to 80 eV

[0182] The elemental ratio O / Al of the outermost surface of the support is represented by X, and the region satisfying X ± 0.1X along its depth direction from the outermost surface of the support is evaluated as depth D. D is preferably 40 nm or more and 1 μm or less. This is because when D is less than 40 nm, the image defect-masking property of the electrophotographic photosensitive element decreases, or its suppression effect on long-term potential fluctuations becomes smaller; and when D exceeds 1 μm, the suppression effect on long-term potential fluctuations becomes smaller. The evaluation results are shown in Table 2.

[0183] Evaluation of electrical properties

[0184] A modified version of an electrophotographic device (copier) (product name: imagePRESS C910) manufactured by Canon Inc. was used as the evaluation device.

[0185] The surface potential of the electrophotographic photosensitive component is measured as follows: the developing cartridge is removed from the evaluation device; a potential probe (product name: model 6000B-8, manufactured by Trek, Inc.) is fixed in place of the cartridge; and the measurement is performed using a surface potentiometer (model 344: manufactured by Trek, Inc.).

[0186] First, the dark area potential (Vd) of the electrophotographic photosensitive element used in the evaluation was adjusted to -600V. Next, the bright area potential (Vl) of the electrophotographic photosensitive element's surface was measured under constant exposure conditions of the exposure equipment. The average value of the bright area potential was taken as the value of the photosensitive element's bright area potential at a position 180mm from the top of the photosensitive element, and this was evaluated. Next, the surface potential was measured similarly after passing through 100,000 sheets of paper using an imagePRESS C910 at 27°C and 60%RH. The evaluation criteria were set as described below.

[0187] ◎: The photosensitive element is far superior to existing photosensitive elements (its potential fluctuation is less than 5V).

[0188] ○: The photosensitive element is superior to existing photosensitive elements (its potential fluctuation is above 5V and less than 10V).

[0189] ●: The photosensitive element is slightly superior to existing photosensitive elements (its potential fluctuation is above 10V and less than 15V).

[0190] △: The photosensitive element is comparable to that of existing photosensitive elements (its potential fluctuation is above 15V and less than 30V).

[0191] The evaluation results are shown in Table 2.

[0192] <Image Evaluation>

[0193] Subsequently, the halftone image was output onto A3 paper under constant exposure conditions, and the presence or absence of image defects was confirmed. Evaluation criteria were set as described below.

[0194] ○: No image defects exist.

[0195] △: There are image defects that do not cause practical problems.

[0196] The evaluation results are shown in Table 2.

[0197] [Examples 2 to 11]

[0198] Except that supports S2 to S11 are used as supports instead of support S1, each of the electrophotographic photosensitive components is produced in the same manner as in Example 1, and then evaluated. The evaluation results are shown in Table 2.

[0199] [Comparative Examples 1 to 8]

[0200] Except that each of the supports R1 to R8 is used as a support instead of support S1, the electrophotographic photosensitive components are each manufactured in the same manner as in Example 1, and then evaluated. The evaluation results are shown in Table 2.

[0201] Table 2

[0202]

[0203] The evaluation results showed that a larger IR peak area ratio (A) resulted in greater suppression of long-term potential fluctuations. Furthermore, when the IR peak area ratios (A) of the two electrophotographic photosensitive components were at the same level, a smaller IR peak area ratio (B) resulted in greater suppression of long-term potential fluctuations. Additionally, it was found that sufficient surface treatment of the support in each embodiment effectively suppressed image defects.

[0204] Although the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the appended claims should be interpreted in the broadest sense to cover all such modifications and equivalent structures and functions.

Claims

1. An electrophotographic photosensitive component, characterized in that, It includes: A cylindrical support; and The photosensitive layer formed on the support, The support body has a surface formed of Al and / or an Al alloy, and The IR peak area ratio A of the surface of the support, determined by Fourier transform infrared spectroscopy, satisfies the following condition: A≥0.75 The IR peak area ratio A is expressed as 1,016 cm⁻¹. -1 Above and 1,130cm -1 The peak area "a" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" in the following range, a / z.

2. The electrophotographic photosensitive component according to claim 1, wherein the IR peak area ratio B of the surface of the support, determined by Fourier transform infrared spectroscopy, satisfies the following condition: B≤0.20 The IR peak area ratio B is indicated at 831 cm⁻¹. -1 Above and 1,015cm -1 The peak area "b" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" to b / z within the following range.

3. The electrophotographic photosensitive component according to claim 1 or 2, wherein, In the support, when the elemental ratio O / Al of the outermost surface of the support, as determined by X-ray photoelectron spectroscopy, is represented by X, and the depth of the region satisfying the value of X ± 0.1X is represented by D, D is greater than 40 nm and less than 1 μm.

4. The electrophotographic photosensitive component according to claim 1 or 2, wherein the support body is formed of an Al alloy, and the Al alloy comprises, relative to the total mass of the Al alloy, the following components: less than 0.6% by mass of Si, less than 0.7% by mass of Fe, more than 0.05% by mass and less than 0.20% by mass of Cu, more than 1.0% by mass and less than 1.5% by mass of Mn, and less than 0.10% by mass of Zn.

5. A processing box, characterized in that, Its integrated support comprises an electrophotographic photosensitive component according to any one of claims 1 to 4 and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit, and the processing box is detachably mounted to the body of the electrophotographic device.

6. An electrophotographic device, characterized in that, It includes an electrophotographic photosensitive element, a charging unit, an exposure unit, a developing unit, and a transfer unit according to any one of claims 1 to 4.

7. A method for manufacturing an electrophotographic photosensitive component, characterized in that, The electrophotographic photosensitive component includes a cylindrical support and a photosensitive layer formed on the support. The formation of the support body includes impregnating a cylindrical body made of Al and / or Al alloy with pure water to obtain the support body. The temperature of the pure water is above 91°C and below 98°C, and the cylindrical body is immersed in the pure water for a time of 60 seconds to 300 seconds. The IR peak area ratio A of the surface of the support, determined by Fourier transform infrared spectroscopy, satisfies the following condition: A≥0.75 The IR peak area ratio A is expressed as 1,016 cm⁻¹. -1 Above and 1,130cm -1 The peak area "a" in the following range is at 650 cm⁻¹ -1 Above and 1,130cm -1 The ratio of peak area "z" in the following range, a / z.

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