Electrophotographic apparatus, process cartridge and image forming method

Abstract

To provide an electrophotographic device, a process cartridge, and an image formation method which achieve the reduction of streak-like image defects on an image under a high-temperature and humidity environment.SOLUTION: An electrophotographic device includes an electrophotographic photoreceptor, charging means, image exposure means, developing means including toner, transfer means, cleaning means, and fixing means. A surface layer of the electrophotographic photoreceptor is a polymer film of a composition which contains a hole transporting compound with a specific structure and a compound not having a hole transporting skeleton with a specific structure. The toner includes toner particles which contain a resin A having a unit with a specific structure. The resin A is a crystalline resin. A content ratio of the unit with the specific structure in the resin A is 30 mass% or more and 100 mass% or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an electrophotographic apparatus, a process cartridge, and an image forming method. [Background technology]

[0002] In recent years, there has been a demand for longer life for electrophotographic devices, and the durability of the electrophotographic photoreceptors mounted thereon is also being demanded to be improved. In response to this demand, technologies such as curable resins have been used to provide highly abrasion-resistant resins for the surface layer of electrophotographic photoreceptors (Patent Document 1). On the other hand, a problem that arises from increasing the abrasion resistance of the surface of the electrophotographic photoreceptor is a decrease in cleaning performance.

[0003] In addition, there is an increasing demand for faster printing and energy saving for electrophotographic devices. In order to accommodate high-speed printing, technology for melting toner more quickly (hereinafter also referred to as "sharp melt") in the fixing process is being considered. As an energy saving measure, technology for fixing toner at a lower temperature is being considered in order to reduce power consumption in the fixing process. In order to accommodate high-speed printing and improve the low-temperature fixing ability of toner, a toner containing crystalline polyester has been proposed in recent years as a method for lowering the glass transition temperature and softening point of the binder resin of the toner and using a binder resin having sharp melting properties (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-15306 A [Patent Document 2] JP 2004-302458 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the electrophotographic photoreceptor described in Patent Document 1, among the charge transporting substances having a polymerizable functional group, those containing an amine compound having a biphenylene moiety have excellent charge transporting properties and good potential characteristics due to the long conjugation length of the benzene rings bonded to each other. On the other hand, in the toner described in Patent Document 2, when a crystalline polyester is contained in the binder, excellent properties such as low-temperature fixing property and hot offset resistance are obtained. However, it has been found that the techniques described in Patent Documents 1 and 2 leave room for further improvement in that streak-like image defects (hereinafter also referred to as H / H image streaks) occur on images in high-temperature, high-humidity environments.

[0006] SUMMARY OF THE PRESENTLY PREFERRED EMBODIMENTS OF THE PRESENT EMBODIMENT An object of the present invention is to provide an electrophotographic apparatus, a process cartridge and an image forming method which realize a reduction in streak-like image defects on an image in a high-temperature and high-humidity environment. [Means for solving the problem]

[0007] The above object can be achieved by the present invention described below. That is, the electrophotographic apparatus according to the present invention comprises an electrophotographic photosensitive member and a charging means for charging the surface of the electrophotographic photosensitive member. For a charging means for irradiating the charged surface of the electrophotographic photoreceptor with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photoreceptor; For The electrostatic latent image is developed with the toner to form a toner image on the surface of the electrophotographic photoreceptor. For a developing means, a transfer means for transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material, and a cleaning blade for removing residual toner remaining on the surface of the electrophotographic photoreceptor after the toner image has been transferred to the transfer material. For An electrophotographic apparatus having a cleaning means and a fixing means for fixing the toner image transferred onto the transfer material, The electrophotographic photoreceptor has a support, a charge generating layer, a charge transport layer, and a surface layer in this order. death The surface layer comprises a hole transporting compound represented by the following formula (1): As shown in the following formula (4):a polymer film of a composition containing a compound, but Resin A having a unit represented by the following formula (2): and a compound represented by the following formula (3): Toner particles containing death , the resin A but, The resin A is a crystalline resin, and is characterized in that the content of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less. [ka] (In formula (1), R 1 and R 2 each independently represents a hydrogen atom, or 、 It indicates an alkyl group having 1 to 6 carbon atoms. and n is 、 Each independently represents an integer of 0 to 2. 3 R represents a single bond or an alkylene group having 1 to 6 carbon atoms. 4 teeth 、 Hydrogen atom 、 or 、 It indicates a methyl group. [ka] (In formula (2), R Z1 is a hydrogen atom 、 or 、 Methyl group show. R Z2 represents an alkyl group having 18 to 36 carbon atoms. [ka] [ka] (In formula (4), R 41 ~R 43 R represents a hydrogen atom or a methyl group. 44 ~R 46 R represents an alkylene group having 1 to 3 carbon atoms. 47 represents an alkyl group having 1 to 3 carbon atoms.

[0008] Further, an image forming method according to the present invention is an image forming method comprising a charging step of charging the surface of an electrophotographic photoreceptor, an image exposure step of irradiating the charged surface of the electrophotographic photoreceptor with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing step of developing the electrostatic latent image with toner to form a toner image on the surface of the electrophotographic photoreceptor, a transfer step of transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material, a cleaning step of removing residual toner remaining on the surface of the electrophotographic photoreceptor after the transfer step by using a cleaning blade, and a fixing step of fixing the toner image transferred to the transfer material to the transfer material, wherein the electrophotographic photoreceptor has a support, a charge generating layer, a charge transport layer and a surface layer in this order, and the surface layer comprises a hole transport compound represented by the following formula (1), A compound represented by the following formula (4), The toner is a polymerized film of a composition containing but Resin A having a unit represented by the following formula (2): and a compound represented by the following formula (3): The toner particles contain resin A. but, The resin A is a crystalline resin, and is characterized in that the content of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less. [ka] (In formula (1), R 1 and R 2 each independently represents a hydrogen atom, or 、 It indicates an alkyl group having 1 to 6 carbon atoms. and Each n independently represents an integer of 0 to 2. 3 teeth 、 A single bond, or 、 R represents an alkylene group having 1 to 6 carbon atoms. 4 teeth 、 Hydrogen atom 、 or 、 It indicates a methyl group. [ka] (In formula (2), R Z1 is a hydrogen atom 、 or、 Methyl group show. R Z2 represents an alkyl group having 18 to 36 carbon atoms. [ka] [ka] (In formula (4), R 41 ~R 43 R represents a hydrogen atom or a methyl group. 44 ~R 46 R represents an alkylene group having 1 to 3 carbon atoms. 47 represents an alkyl group having 1 to 3 carbon atoms. Effect of the Invention

[0009] According to the present invention, it is possible to provide an electrophotographic apparatus, a process cartridge, and an image forming method in which streak-like image defects on an image in a high-temperature and high-humidity environment are suppressed. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus equipped with a process cartridge having an electrophotographic photosensitive member of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] An embodiment of the present invention is as follows. That is, an electrophotographic apparatus according to the present invention is an electrophotographic apparatus having an electrophotographic photoreceptor, charging means for charging the surface of the electrophotographic photoreceptor, image exposure means for irradiating the charged surface of the electrophotographic photoreceptor with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photoreceptor, developing means having a toner and developing the electrostatic latent image with the toner to form a toner image on the surface of the electrophotographic photoreceptor, transfer means for transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material, cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor after the transfer means has been transferred by using a cleaning blade, and fixing means for fixing the toner image transferred to the transfer material to the transfer material. and a toner having toner particles containing a resin A having a unit represented by the following formula (2), the resin A being a crystalline resin, and the content ratio of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less. [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m and n each independently represent an integer of 0 to 2. R 3 R represents a single bond or an alkylene group having 1 to 6 carbon atoms. 4 represents a hydrogen atom or a methyl group. [ka] (In formula (2), R Z1 represents a hydrogen atom or a methyl group, R Z2 represents an alkyl group having 18 to 36 carbon atoms.

[0012] The mechanism by which the electrophotographic apparatus according to one aspect of the present invention solves the problems is believed to be as follows. In an electrophotographic photoreceptor having a surface layer including a polymerized film of a composition containing a hole transporting compound represented by the above formula (1) and a compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and no hole transporting skeleton, the surface layer of the electrophotographic photoreceptor has improved wear resistance due to the polymerized film. That is, the surface of the surface layer is not easily scraped by rubbing with a cleaning blade. In the surface state of the electrophotographic photoreceptor having improved wear resistance, the frictional force between the cleaning blade and the surface layer increases, and the rubbing state with the cleaning blade becomes unstable. It has been found that in this unstable rubbing state, when an image is output in a high temperature and high humidity environment using a toner that does not contain a unit represented by the above formula (2) as a resin, H / H image streaks may occur. It is believed that these H / H image streaks are caused by an unstable rubbing state that weakens the cleaning blade's ability to block the toner, allowing the toner to slip through the cleaning blade.

[0013] As a result of the study by the present inventors, it was found that the occurrence of H / H image streaks is suppressed when the electrophotographic photoreceptor has a surface layer including a polymer film of a composition containing a hole transporting compound represented by the above formula (1) and a compound having 2 to 6 acryloyloxy or methacryloyloxy groups and no hole transporting skeleton, and the toner has toner particles containing a resin A having a unit represented by the above formula (2), the resin A is a crystalline resin, and the content ratio of the unit represented by the above formula (2) in the resin A is 30% by mass or more and 100% by mass or less. Although the reason is unclear, in the case of the above configuration, it is presumed that the crystalline structure derived from the long-chain alkyl moiety contained in the unit represented by the above formula (2) in the resin A of the toner affects the slipperiness of the cleaning blade. That is, the unit represented by the formula (2) has a crystalline structure due to the long-chain alkyl moiety in the side chain. It is considered that when the side chain has a crystalline structure, cleavage due to the crystalline structure is more likely to occur. Therefore, when a toner having the above-described configuration is present between the surface layer of an electrophotographic photoreceptor having the above-described configuration and a cleaning blade, it is believed that the cleavage of the crystal structure of the toner stabilizes the cleaning condition, suppresses toner slip-through, and suppresses the occurrence of H / H image streaks.

[0014] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention will be described in detail. <Electrophotographic photoreceptor> The electrophotographic photoreceptor used in the present invention has a support, a charge generating layer, a charge transport layer, and a surface layer, in this order. The surface layer is a polymerized film of a composition containing a hole transporting compound represented by the following formula (1) and a compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and no hole transporting skeleton. [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m and n each independently represent an integer of 0 to 2. R 3R represents a single bond or an alkylene group having 1 to 6 carbon atoms. 4 represents a hydrogen atom or a methyl group.

[0015] Hereinafter, each of the components of the electrophotographic photoreceptor according to the present invention, such as the support, the undercoat layer, the intermediate layer, the charge generating layer, the charge transport layer, and the surface layer, will be described.

[0016] <Support> The electrophotographic photoreceptor used in the present invention has a support. The support is preferably a conductive support having electrical conductivity. Examples of the support include metal plates containing metals (aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, etc.) or alloys (stainless steel, etc.), metal drums, and metal belts. Examples of the support include paper, resin films, belts, etc. coated, vapor-deposited, or laminated with a conductive compound (e.g., conductive polymer, indium oxide, etc.), a metal (e.g., aluminum, palladium, gold, etc.), or an alloy. Here, "conductive" refers to a material having a volume resistivity of 10 13 This means that the resistance is less than Ωcm.

[0017] When the electrophotographic photoreceptor is used in a laser printer, the surface of the support is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm in order to suppress interference fringes that occur when irradiating with laser light. When non-interfering light is used as the light source, roughening to prevent interference fringes is not particularly necessary, but it is suitable for extending the life of the support since it suppresses the occurrence of defects due to unevenness on the surface.

[0018] Examples of methods for roughening the surface include wet honing, which involves spraying an abrasive suspended in water onto the support, centerless grinding, in which a conductive substrate is pressed against a rotating grindstone and continuously ground, and anodizing.

[0019] In the roughening treatment by anodization, an oxide film is formed on the surface of a conductive substrate by anodizing in an electrolyte solution using a metallic (e.g., aluminum) support as the anode. Examples of electrolyte solutions include sulfuric acid solution and oxalic acid solution. However, the porous anodic oxide film formed by anodization is chemically active in its original state, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, it is preferable to perform a sealing treatment on the porous anodic oxide film, in which the micropores of the oxide film are sealed by volume expansion caused by hydration reaction in pressurized steam or boiling water (metal salts such as nickel may be added) to convert it into a more stable hydrated oxide.

[0020] The thickness of the anodic oxide film is preferably, for example, from 0.3 μm to 15 μm. If the thickness is within this range, the film tends to exhibit a barrier property against injection and tends to suppress an increase in residual potential due to repeated use.

[0021] The support may be subjected to a treatment with an acidic treatment solution or a boehmite treatment. Treatment with an acid treatment liquid is carried out, for example, as follows. First, an acid treatment liquid containing phosphoric acid, chromic acid, and hydrofluoric acid is prepared. For example, phosphoric acid is in the range of 10% by mass to 11% by mass, chromic acid is in the range of 3% by mass to 5% by mass, and hydrofluoric acid is in the range of 0.5% by mass to 2% by mass, and the total concentration of these acids is preferably in the range of 13.5% by mass to 18% by mass. The treatment temperature is preferably, for example, 42° C. to 48° C. The film thickness of the coating is preferably 0.3 μm to 15 μm. The boehmite treatment is carried out, for example, by immersing in pure water at 90° C. or higher and 100° C. or lower for 5 to 60 minutes, or by contacting with heated steam at 90° C. or higher and 120° C. or lower for 5 to 60 minutes.

[0022] The thickness of the coating is preferably 0.1 μm to 5 μm, and may be further anodized using an electrolyte solution that has low coating solubility, such as adipic acid, boric acid, borates, phosphates, phthalates, maleates, benzoates, tartrates, and citrates.

[0023] <Sublayer> In the electrophotographic photoreceptor used in the present invention, an undercoat layer may be provided on the support. By providing the undercoat layer, the adhesion function between layers is improved, and a charge injection blocking function can be imparted to the electrophotographic photoreceptor. The undercoat layer is, for example, a layer containing inorganic particles and a binder resin.

[0024] As inorganic particles, for example, powder resistivity (volume resistivity) of 10 2 Ωcm or more 10 11 Examples of such particles include inorganic particles with a particle size of Ωcm or less. Among these, examples of inorganic particles having the above-mentioned resistance value include metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles, and zinc oxide particles are particularly preferred. The specific surface area of ​​inorganic particles by the BET method is, for example, 10 m 2 / g or higher is preferable. The volume average particle size of the inorganic particles is, for example, 50 nm or more and 2000 nm or less (preferably 60 nm or more and 1000 nm or less). The content of the inorganic particles is, for example, preferably from 10% by mass to 80% by mass, more preferably from 40% by mass to 80% by mass, based on the binder resin.

[0025] The inorganic particles may be surface-treated. Two or more types of inorganic particles having different surface treatments or different particle sizes may be used in combination. Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a surfactant, etc. In particular, a silane coupling agent is preferred, and a silane coupling agent having an amino group is preferred.

[0026] Examples of silane coupling agents having an amino group include, but are not limited to, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane.

[0027] Silane coupling agents may be used in combination of two or more kinds. For example, a silane coupling agent having an amino group may be used in combination with another silane coupling agent. Examples of other silane coupling agents include, but are not limited to, vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane.

[0028] The surface treatment method using the surface treatment agent may be any known method, and may be either a dry method or a wet method. The amount of the surface treatment agent to be used is preferably, for example, 0.5% by mass or more and 10% by mass or less based on the inorganic particles.

[0029] Here, it is preferable that the undercoat layer contains an electron accepting compound (acceptor compound) together with the inorganic particles, from the viewpoints of improving the long-term stability of electrical properties and carrier blocking properties. Examples of the electron-accepting compound include electron-transporting substances such as quinone compounds such as chloranil and bromoanil; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone; oxadiazole compounds such as 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,5-bis(4-naphthyl)-1,3,4-oxadiazole and 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole; xanthone compounds; thiophene compounds; and diphenoquinone compounds such as 3,3',5,5'-tetra-t-butyldiphenoquinone.

[0030] In particular, the electron-accepting compound is preferably a compound having an anthraquinone structure. Examples of the compound having an anthraquinone structure include hydroxyanthraquinone compounds, aminoanthraquinone compounds, and aminohydroxyanthraquinone compounds, and more specifically, anthraquinone, alizarin, quinizarin, anthrarufin, and purpurin.

[0031] The electron accepting compound may be contained in the undercoat layer in a dispersed state together with the inorganic particles, or may be contained in a state of being attached to the surfaces of the inorganic particles. The method for attaching the electron accepting compound to the surface of the inorganic particles may be, for example, a dry method or a wet method. The dry method is, for example, a method in which an electron-accepting compound is attached to the surface of inorganic particles by dropping an electron-accepting compound directly or dissolved in an organic solvent or spraying it together with dry air or nitrogen gas while stirring inorganic particles with a mixer or the like that exerts a large shearing force. The dropping or spraying of the electron-accepting compound is preferably performed at a temperature below the boiling point of the solvent. After dropping or spraying the electron-accepting compound, baking may be performed at 100° C. or higher. The temperature and time of baking are not particularly limited as long as electrophotographic properties can be obtained. The wet method is a method in which, for example, an electron-accepting compound is added while dispersing inorganic particles in a solvent by stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, etc., and the inorganic particles are stirred or dispersed, and then the solvent is removed to attach the electron-accepting compound to the surface of the inorganic particles. The solvent is removed, for example, by filtration or distillation. After the solvent is removed, baking may be performed at 100°C or higher. The baking temperature and time are not particularly limited as long as electrophotographic properties are obtained. In the wet method, moisture contained in the inorganic particles may be removed before adding the electron-accepting compound, and examples of such methods include a method of removing the moisture while stirring and heating in a solvent, and a method of removing the moisture by azeotropy with the solvent.

[0032] The attachment of the electron accepting compound may be carried out before or after the inorganic particles are subjected to a surface treatment with a surface treatment agent, or the attachment of the electron accepting compound and the surface treatment with the surface treatment agent may be carried out simultaneously. The content of the electron accepting compound is, for example, from 0.01% by mass to 20% by mass, and preferably from 0.01% by mass to 10% by mass, based on the inorganic particles.

[0033] Examples of the binder resin used in the undercoat layer include known materials such as acetal resins (e.g., polyvinyl butyral, etc.), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, unsaturated polyester resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate-maleic anhydride resins, silicone resins, silicone-alkyd resins, urea resins, phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, alkyd resins, and epoxy resins; zirconium chelate compounds; titanium chelate compounds; aluminum chelate compounds; titanium alkoxide compounds; organic titanium compounds; and silane coupling agents. Examples of the binder resin used in the undercoat layer include charge transporting resins having charge transporting groups, conductive resins (such as polyaniline, etc.), and the like.

[0034] Among these, the binder resin used in the undercoat layer is preferably a resin that is insoluble in the coating solvent of the upper layer, and in particular, a resin obtained by reacting at least one resin selected from the group consisting of thermosetting resins such as urea resins, phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, unsaturated polyester resins, alkyd resins, and epoxy resins, with a curing agent is preferred. When two or more of these binder resins are used in combination, the mixing ratio is set as necessary.

[0035] The undercoat layer may contain various additives for improving electrical properties, environmental stability, and image quality. Examples of the additives include known materials such as polycyclic condensation and azo-based electron transport pigments, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, silane coupling agents, etc. As described above, silane coupling agents are used for surface treatment of inorganic particles, and may also be added to the undercoat layer as an additive.

[0036] Examples of silane coupling agents as additives include vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethylmethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane.

[0037] Examples of the zirconium chelate compound include zirconium butoxide, zirconium ethyl acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate zirconium butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octanoate, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, and isostearate zirconium butoxide.

[0038] Examples of titanium chelate compounds include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanolamine, and polyhydroxytitanium stearate.

[0039] Examples of aluminum chelate compounds include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, and aluminum tris(ethylacetoacetate).

[0040] These additives may be used alone or as a mixture or polycondensation product of a plurality of compounds.

[0041] The undercoat layer preferably has a Vickers hardness of 35 or more. The surface roughness (ten-point average roughness) of the undercoat layer is preferably adjusted to between 1 / 4n (n is the refractive index of the upper layer) and 1 / 2λ of the wavelength λ of the exposure laser used in order to suppress moire images.

[0042] Resin particles or the like may be added to the undercoat layer to adjust the surface roughness. Examples of the resin particles include silicone resin particles and crosslinked polymethyl methacrylate resin particles. The surface of the undercoat layer may be polished to adjust the surface roughness. Examples of the polishing method include buffing, sandblasting, wet honing, grinding, and the like.

[0043] The formation of the undercoat layer is not particularly limited, and a well-known formation method can be used. For example, the undercoat layer can be formed by forming a coating film of a coating solution for forming the undercoat layer in which the above-mentioned components are added to a solvent, drying the coating film, and heating it as necessary. Examples of the solvent for preparing the coating liquid for forming the undercoat layer include known organic solvents, such as alcohol-based solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone-based solvents, ketone alcohol-based solvents, ether-based solvents, and ester-based solvents. Specific examples of these solvents include ordinary organic solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.

[0044] Examples of the method for dispersing the inorganic particles when preparing the coating liquid for forming the undercoat layer include known methods such as those using a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker. Examples of the method for applying the coating liquid for forming the undercoat layer onto the support include ordinary methods such as blade coating, wire bar coating, spray coating, dip coating, bead coating, air knife coating, and curtain coating.

[0045] The thickness of the undercoat layer is set, for example, preferably at least 15 μm, and more preferably within the range of from 20 μm to 50 μm.

[0046] <Middle Class> Although not shown, an intermediate layer may be further provided between the undercoat layer and the charge generating layer. The intermediate layer is, for example, a layer containing a resin. Examples of the resin used in the intermediate layer include polymer compounds such as acetal resins (e.g., polyvinyl butyral, etc.), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate-maleic anhydride resins, silicone resins, silicone-alkyd resins, phenol-formaldehyde resins, and melamine resins.

[0047] The intermediate layer may be a layer containing an organometallic compound. Examples of the organometallic compound used in the intermediate layer include organometallic compounds containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon. The compounds used in the intermediate layer may be used alone or as a mixture or polycondensation product of a plurality of compounds.

[0048] Among these, the intermediate layer is preferably a layer containing an organometallic compound containing zirconium atoms or silicon atoms.

[0049] The formation of the intermediate layer is not particularly limited, and a well-known formation method can be used. For example, the intermediate layer can be formed by forming a coating film of a coating liquid for forming an intermediate layer in which the above components are added to a solvent, drying the coating film, and heating it if necessary. The intermediate layer can be formed by any of the usual coating methods, such as dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating and curtain coating. The thickness of the intermediate layer is preferably set in the range of, for example, 0.1 μm or more and 3 μm or less. The intermediate layer may be used as an undercoat layer.

[0050] <Charge generation layer> The charge generating layer preferably contains a charge generating material and a resin.

[0051] Examples of the charge generating material 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.

[0052] In addition, when the charge transport layer contains a compound represented by formula (6) described below, it is preferable that the charge generation layer contains an oxytitanium phthalocyanine pigment from the viewpoint of suppressing the fluctuation in the bright area potential. It is presumed that the effect of suppressing the fluctuation in the bright area potential is caused by the efficient injection of holes from the oxytitanium phthalocyanine pigment in the charge generation layer to the compound represented by formula (6) in the charge transport layer.

[0053] The content of the charge generating material in the charge generating layer is preferably from 40% by mass to 85% by mass, and more preferably from 60% by mass to 80% by mass, based on the total mass of the charge generating layer.

[0054] Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin, polyvinyl chloride resin, etc. Among these, polyvinyl butyral resin is more preferable.

[0055] The charge generating layer may further contain additives such as an antioxidant and an ultraviolet absorbing agent, etc. Specific examples of such additives include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

[0056] The average thickness of the charge generating layer is preferably from 0.1 μm to 1 μm, and more preferably from 0.15 μm to 0.4 μm. The charge generating layer can be formed by preparing a coating solution for the charge generating layer containing the above-mentioned materials and solvent, forming a coating film of this, and drying it. Examples of the solvent 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.

[0057] <Charge transport layer> The charge transport layer preferably contains a charge transport material and a resin.

[0058] Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these materials. Among these, triarylamine compounds and benzidine compounds are preferred. The content of the charge transport material in the charge transport layer is preferably from 25% by weight to 70% by weight, and more preferably from 30% by weight to 55% by weight, based on the total weight of the charge transport layer.

[0059] Examples of the resin include polyester resin, polycarbonate resin, acrylic resin, polystyrene resin, etc. Among these, polycarbonate resin and polyester resin are preferable. As the polyester resin, polyarylate resin is particularly preferable. The content ratio (mass ratio) of the charge transport material to the resin is preferably from 4:10 to 20:10, and more preferably from 5:10 to 12:10.

[0060] The charge transport layer may also contain additives such as antioxidants, ultraviolet absorbers, plasticizers, leveling agents, slipping agents, and abrasion resistance improvers. Specific examples of such additives 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.

[0061] The average thickness of the charge transport layer is preferably from 5 μm to 50 μm, more preferably from 8 μm to 40 μm, and particularly preferably from 10 μm to 30 μm. The charge transport layer can be formed by preparing a coating solution for the charge transport layer containing the above-mentioned materials and solvent, forming a coating film of this, and drying it. Examples of the solvent 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.

[0062] From the viewpoint of suppressing fluctuations in the bright area potential, it is preferable to contain a compound represented by the following formula (6) as an additive. [ka]

[0063] It is speculated that the effect of suppressing the fluctuation of the bright area potential is due to the fact that the compound represented by the above formula (6) is contained in the charge transport layer, thereby promoting the injection of holes from the charge generation layer to the charge transport layer. The content of the compound of the above formula (6) is preferably 0.5% by mass or more and 5.0% by mass or less based on the total amount of materials contained in the charge transport layer.

[0064] <Surface layer> The electrophotographic photoreceptor used in the present invention has a surface layer on the charge transport layer. The surface layer is a polymerized film of a composition containing a hole-transporting compound represented by the following formula (1) and a compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and no hole-transporting skeleton. [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m and n each independently represent an integer of 0 to 2. R3 R represents a single bond or an alkylene group having 1 to 6 carbon atoms. 4 represents a hydrogen atom or a methyl group.

[0065] Specific examples of the compound represented by the above formula (1) of the present invention are listed below, but the present invention is not limited to these. [ka]

[0066] Examples of the compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and no hole-transporting skeleton include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane acrylate, trimethylolpropane methacrylate, and ditrimethylolpropane tetraacrylate.

[0067] The compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and no hole transporting skeleton is preferably a compound represented by the following formula (4) or (5).

[0068] The compound represented by formula (4) will be described. [ka] (In formula (4), R 41 ~R 43 R represents a hydrogen atom or a methyl group. 44 ~R 46 R represents an alkylene group having 1 to 3 carbon atoms. 47 represents an alkyl group having 1 to 3 carbon atoms.

[0069] Specific examples of the compound represented by the above formula (4) of the present invention are listed below, but the present invention is not limited to these. [ka]

[0070] Next, the compound represented by formula (5) will be described. [ka] (In formula (5), R 51 ~R 56 is a hydrogen atom or a methyl group; k is an integer of 1 or more and 9 or less, and m is an integer of 0 or more and 3 or less.

[0071] Specific examples of the compound represented by the above formula (5) are listed below, but the present invention is not limited to these. [ka]

[0072] The surface layer may contain metal oxide particles such as titanium oxide, zinc oxide, tin oxide, indium oxide, and aluminum oxide (alumina) as conductive particles. Among them, alumina particles are preferred from the viewpoint of suppressing H / H image streaks. It is speculated that the suppression of H / H image streaks occurs through the following mechanism. When alumina particles are contained in the surface layer, the charged state of the surface layer changes, and the interaction between the toner having the unit of formula (2) and the surface layer increases. The increased interaction increases the probability of the toner being present in the surface layer of the electrophotographic photoreceptor, and the effect of improving the slipperiness due to the crystal cleavage of the toner increases. As a result, the rubbing state between the surface layer of the electrophotographic photoreceptor and the cleaning blade becomes stable, and H / H image streaks are suppressed. The content of the alumina particles is preferably 5.0 mass % or more and 15.0 mass % or less with respect to the total amount of substances contained in the surface layer.

[0073] The surface layer may contain, as a charge transport material, a polycyclic aromatic compound, a heterocyclic compound, a hydrazone compound, a styryl compound, an enamine compound, a benzidine compound, a triarylamine compound, or a resin having a group derived from these materials. The surface layer may contain, as the resin, polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, epoxy resin, or the like.

[0074] The surface layer is formed by polymerizing a composition containing a monomer having a polymerizable functional group to form a polymerized film. Examples of the reaction include thermal polymerization, photopolymerization, and radiation polymerization. Examples of the polymerizable functional group of the monomer having a polymerizable functional group include an acryloyloxy group and a methacryloyloxy group. The surface layer may contain additives such as antioxidants, ultraviolet absorbers, plasticizers, leveling agents, etc. Specific examples of additives include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, and silicone oils.

[0075] The average thickness of the surface layer is preferably from 0.5 μm to 10 μm, and more preferably from 1 μm to 7 μm. The surface layer can be formed by preparing a coating solution for the surface layer containing the above-mentioned materials and solvent, forming a coating film from the coating solution, and drying and / or curing the coating solution. Examples of the solvent 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.

[0076] <Toner> The toner used in the present invention has toner particles containing resin A having a unit represented by the following formula (2), where resin A is a crystalline resin, and the content of the unit represented by the following formula (2) in resin A is 30% by mass or more and 100% by mass or less. [ka] (In formula (2), R Z1 represents a hydrogen atom or a methyl group, R Z2 represents an alkyl group having 18 to 36 carbon atoms.

[0077] Hereinafter, each of the components of the toner according to the present invention, such as the resin A, the release agent, the colorant, the crystal cleavage accelerator, the charge control agent, and the inorganic fine particles, will be described.

[0078] <Resin A, etc.> Resin A may be a vinyl resin, or a hybrid resin in which a resin other than a vinyl resin is bonded to a unit represented by formula (2). When resin A is a vinyl resin, it may be a random copolymer resin of the polymerizable monomers forming each unit, or it may be a block copolymer. From the viewpoint of low-temperature fixability and ease of control of other properties, it is preferable to use a vinyl resin as the resin A.

[0079] In the present invention, resin A is a crystalline resin that has a melting point, for example, a resin that exhibits an endothermic peak in differential scanning calorimetry (DSC). The unit of formula (2) has R Z2 The presence of this moiety makes it easier for resin A to exhibit sharp melting properties, and a toner containing resin A has an advantage in low-temperature fixing properties. When the content of the unit of formula (2) in the resin A is 30% by mass or more and 100% by mass or less, the effect of suppressing H / H image streaks is improved. When the content of the unit of formula (2) in resin A is less than 30% by mass, the crystallinity is likely to decrease, and therefore the effect of suppressing H / H image streaks is likely to decrease.

[0080] The composition of resin A was determined by the general method of 1 This can be confirmed by a conversion method using the peak area ratio of hydrogen atoms (hydrogen atoms that make up the resin) obtained by H-NMR measurement.

[0081] From the viewpoint of suppressing H / H image streaks, the unit represented by formula (2) is preferably a unit derived from at least one acrylic ester selected from the group consisting of (meth)acrylic esters having an alkyl group having 18 to 36 carbon atoms. Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a straight-chain alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myrisyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.]. More preferably, it is at least one selected from the group consisting of linear stearyl (meth)acrylate and linear behenyl (meth)acrylate. The unit represented by formula (2) may be used alone or in combination of two or more kinds.

[0082] Resin A may contain units other than the unit represented by the above formula (2). When resin A is a vinyl resin, examples of the polymerizable monomer that forms a unit other than the unit represented by formula (2) include the following. The polymerizable monomer that forms a unit other than the unit represented by formula (2) may be used alone or in combination of two or more kinds.

[0083] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Monomers having an amide group: for example, acrylamide, a monomer obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method. Monomers having a urea group: for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as di-normal ethylamine, di-normal propylamine, and di-normal butylamine), aniline, and cycloxylamine] with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond by a known method. Monomers having a urethane group: for example, monomers obtained by reacting diols having 3 to 22 carbon atoms and isocyanates having ethylenically unsaturated bonds and having 2 to 30 carbon atoms by a known method. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.

[0084] Vinyl esters; such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octoate.

[0085] Further examples include styrene and its derivatives such as styrene and o-methylstyrene, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0086] Also included are unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; and unsaturated polyenes such as butadiene, isoprene.

[0087] Aromatic divinyl compounds; alkyl chain linked diacrylate compounds; alkyl chain linked diacrylate compounds containing ether linkages; aromatic and ether linkage linked diacrylate compounds; polyester type diacrylates; polyfunctional crosslinkers. Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate of the above compounds is replaced with methacrylate.

[0088] When the resin A is a vinyl resin, it can be produced using the exemplified polymerizable monomer and polymerization initiator. From the viewpoint of efficiency, it is preferable to use 0.05 parts by mass or more and 10 parts by mass or less of the polymerization initiator with respect to 100 parts by mass of the polymerizable monomer.

[0089] Examples of the polymerization initiator include the following. 2,2'-Azobisisobutyronitrile, 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2-methylbutyronitrile), Dimethyl-2,2'-azobisisobutyrate, 1,1'-Azobis(1-cyclohexanecarbonitrile), 2-Carbamoylazoisobutyronitrile, 2,2'-Azobis(2,4,4-trimethylpentane), 2-Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-Azobis(2-methylpropane), Methyl ethyl ketone peroxide, Acetone Ketone peroxides such as ethyl acetone peroxide and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-Trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxy diisobutyrate, tert-butyl peroxy neodecanoate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxy laurate, tert-butyl peroxy benzoate, tert-butyl peroxy isopropyl carbonate, di-tert-butyl peroxy isophthalate, tert-butyl peroxy allyl carbonate, tert-amyl peroxy 2-ethylhexanoate, di-tert-butyl peroxy hexahydroterephthalate, di-tert-butyl peroxy azelate.

[0090] In addition, when resin A is a hybrid resin in which a resin other than a vinyl resin is bonded to a unit represented by formula (2), the resin other than the vinyl resin can be a silicone resin, a polyester resin, a polyurethane, a polyamide resin, a furan resin, an epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin, a coumarone-indene resin, a petroleum-based resin, etc. Among these, it is preferable to use a polyester resin from the viewpoint of low-temperature fixing property and charge control. The polyester resin can be either an amorphous polyester or a crystalline polyester, but an amorphous polyester is more preferable.

[0091] A polyester resin is a resin having a "polyester unit" in the resin chain, and specific examples of components constituting the polyester unit include divalent or higher alcohol monomer components and acid monomer components such as divalent or higher carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters. For example, examples of dihydric or higher alcohol monomer components include alkylene oxide adducts of bisphenol A such as polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, and polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, and 1,6-hexanediol. Examples of suitable glycerol include 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

[0092] Among these, the alcohol monomer component that is preferably used is an aromatic diol, and the alcohol monomer component that constitutes the polyester resin preferably contains the aromatic diol in a proportion of 80 mol % or more. On the other hand, examples of acid monomer components such as divalent or higher carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or anhydrides thereof; alkyl dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, or anhydrides thereof; succinic acid or anhydrides thereof substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; and unsaturated dicarboxylic acids or anhydrides thereof such as fumaric acid, maleic acid, and citraconic acid. Among these, preferred acid monomer components are polyvalent carboxylic acids such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and anhydrides thereof.

[0093] A preferred method for obtaining the hybrid resin is to carry out a polymerization reaction of either or both of the vinyl resin, vinyl copolymer unit, and polyester resin in the presence of a polymer containing a monomer component capable of reacting with each of the vinyl resin, vinyl copolymer unit, and polyester resin.

[0094] The content of resin A in the toner particles of the toner is not particularly limited to an upper limit, but taking into consideration the contents of colorant and release agent contained in the toner particles, it is preferably 90.0% by mass or less.

[0095] In the toner according to the present invention, if necessary, for the purpose of improving pigment dispersibility, etc., a resin other than Resin A may be contained to an extent that does not impair the effects of the present disclosure. Resins other than Resin A include the following. Polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin.

[0096] The content of the resin other than the resin A in the toner particles of the toner is preferably 0% by mass or more and 30.0% by mass or less. In the present invention, the above-mentioned resin A and the resin other than the resin A correspond to the binder resin of the toner.

[0097] <Release agent> The toner particles may contain a wax as a release agent. Examples of such wax include the following:

[0098] Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes whose main component is fatty acid esters such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bi saturated fatty acid bisamides such as stearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, and N,N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'-distearyl isophthalic acid amide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0099] Among these waxes, from the viewpoint of improving low-temperature fixing property and fixing separation property, preferred are hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax, and more preferred are hydrocarbon waxes from the viewpoint of further improving hot offset resistance.

[0100] The content of the wax is preferably 3 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

[0101] <Coloring agent> The toner may contain a colorant, if necessary. Examples of the colorant include the following.

[0102] Examples of black colorants include carbon black; yellow colorants, magenta colorants, and cyan colorants used to tone the color to black. As colorants, pigments may be used alone, or dyes and pigments may be used in combination. From the viewpoint of image quality of full-color images, it is preferable to use dyes and pigments in combination. Examples of pigments for magenta toner include the following. CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0103] Dyes for magenta toners include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0104] Pigments for cyan toners include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45; copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. Dyes for cyan toners include CI Solvent Blue 70.

[0105] Yellow toner pigments include: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20. Yellow toner dyes include CI Solvent Yellow 162.

[0106] These colorants may be used alone or in mixture, or further in the form of a solid solution. The colorant is selected in consideration of hue angle, chroma, brightness, light resistance, OHP transparency, and dispersibility in toner. The content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0107] <Crystal cleavage promoter> The toner may contain a crystal cleavage accelerator as necessary. Examples of the crystal cleavage accelerator include CI Pigment Red 260 (formula (A) below), CI Pigment Orange 66 (formula (B) below), and CI Pigment Yellow 185 (formula (3) below). [ka]

[0108] These crystal cleavage promoters have an isoindoline skeleton and a cyano group. The crystal cleavage promoters can be used alone or in mixtures, and even in their individual forms. The crystal cleavage accelerator is selected from the viewpoint of accelerating the cleavage of the crystalline resin. The content of the crystal cleavage accelerator is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0109] <Charge control agent> The toner particles may contain a charge control agent, if necessary. By blending a charge control agent, the charge characteristics can be stabilized and the amount of triboelectric charge can be controlled to an optimum level according to the development system. As the charge control agent, known substances can be used, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount. Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass, more preferably 0.5 parts by mass to 10.0 parts by mass, based on 100 parts by mass of the binder resin.

[0110] <Inorganic fine particles> The toner may contain inorganic fine particles as necessary. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner as an external additive. Examples of the inorganic fine particles include silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0111] From the viewpoint of improving fluidity, inorganic fine particles as external additives should have a specific surface area of ​​50 m 2 / g or more 400m 2 From the viewpoint of improving durability and stability, the inorganic fine particles as the external additive preferably have a specific surface area of ​​10 m 2 / g or more 50m 2 In order to achieve both improved fluidity and durability and stability, inorganic fine particles having a specific surface area within the above range may be used in combination. The content of the external additive is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0112] <Toner softening point (Tm)> From the viewpoint of low-temperature fixability and storage stability, the toner of the present invention preferably has a softening point of 70° C. or more and 120° C. or less, more preferably 75° C. or more and 110° C. or less, and even more preferably 100° C. or less.

[0113] The softening point of the toner is measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual that comes with the device. With this device, a constant load is applied from above the measurement sample with a piston while the measurement sample filled in a cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and temperature can be obtained.

[0114] The softening point is the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow property evaluation device Flow Tester CFT-500D." The melting temperature in the 1 / 2 method is calculated as follows. First, calculate half the difference between the amount of piston descent when the outflow ends (end of outflow, Smax) and the amount of piston descent when the outflow starts (minimum point, Smin) (this is X. X=(Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of piston descent is the sum of X and Smin is the melting temperature in the 1 / 2 method. The measurement sample is prepared by compressing approximately 1.0 g of resin at approximately 10 MPa for approximately 60 seconds using a tablet molding machine (e.g., NT-100H, manufactured by NPA Systems) in an environment of 25°C to form a cylindrical shape with a diameter of approximately 8 mm. The specific operations for the measurement are carried out according to the manual that comes with the device. The measurement conditions for the CFT-500D are as follows. Test mode: Temperature rise method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm2 Test load (piston load): 10.0kgf (0.9807MPa) Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0115] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and provide stable images over a long period of time, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer. As the magnetic carrier, generally known carriers can be used, such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) that contain a magnetic material and a binder resin that holds the magnetic material in a dispersed state. When the toner is mixed with a magnetic carrier to be used as a two-component developer, the mixing ratio of the magnetic carrier in this case is preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less, in terms of the toner concentration in the two-component developer.

[0116] <Toner manufacturing method> The method for producing the toner of the present invention is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used.

[0117] <Method of measuring weight average particle size (D4) of toner> The weight-average particle size (D4) of the toner is calculated as follows. The measurement device used is a precision particle size distribution measurement device using the narrow hole electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000 channels. The electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter).

[0118] Before performing measurements and analysis, the dedicated software is set up as follows. In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count number in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the "Measure Threshold / Noise Level" button to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement." In the "Pulse to particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0119] The specific measurement method is as follows. (1) Pour about 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Tube Flush" function of the dedicated software to remove dirt and air bubbles from inside the aperture tube. (2) Place about 30 mL of the electrolyte solution in a 100 mL flat-bottom glass beaker. Add about 0.3 mL of a solution of "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made from nonionic surfactants, anionic surfactants, and organic builders, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times with ion-exchanged water as a dispersant. (3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W. Place 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add about 2 mL of the above-mentioned Contaminon N to this water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, add the electrolyte solution (5) in which the toner particles are dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume%, the "Average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4).

[0120] <Method for measuring average circularity of toner> The average circularity of the toner is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration process. The measurement principle of the flow-type particle image analyzer "FPIA-3000" (Sysmex Corporation) is to capture still images of flowing particles and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent to the flat sheath flow is sandwiched between the sheath liquid and forms a flat flow. The sample passing through the flat sheath flow cell is irradiated with a strobe light at 1 / 60 second intervals, making it possible to capture still images of the flowing particles. In addition, since the flow is flat, the image is captured in focus. The particle images are captured by a CCD camera, and the captured images are processed with an image processing resolution of 512 x 512 pixels (0.37 x 0.37 μm per pixel), and the contours of each particle image are extracted, and the projected area S and perimeter L of the particle image are measured.

[0121] Next, the equivalent circle diameter and circularity are calculated using the above area S and perimeter L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of ​​the particle image, and the circularity C is defined as the perimeter of the circle calculated from the equivalent circle diameter divided by the perimeter of the projected particle image, and is calculated using the following formula. Circularity C=2×(π×S)1 / 2 / L When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness on the outer periphery of the particle image, the smaller the circularity value. After calculating the circularity of each particle, the range of circularity between 0.200 and 1.000 is divided into 800, the arithmetic mean of the resulting circularities is calculated, and this value is the average circularity.

[0122] The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impurities such as solids have been removed is placed in a glass container, and about 0.2 mL of a solution of "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made from a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries) diluted about three times by mass with ion-exchanged water is added as a dispersant. Add approximately 0.02 g of the measurement sample and disperse it for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At this time, cool the dispersion appropriately so that the temperature is between 10°C and 40°C.

[0123] As the ultrasonic disperser, a tabletop ultrasonic cleaner disperser ("VS-150" (manufactured by Velvoclear)) with an oscillation frequency of 50 kHz and an electrical output of 150 W was used. A specified amount of ion-exchanged water was placed in the water tank, and approximately 2 mL of Contaminon N was added to the water tank.

[0124] For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10x) is used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and total count mode. Then, the binarization threshold value during particle analysis is set to 85%, the analyzed particle diameter is set to a circle-equivalent diameter of 1.98 μm to 39.96 μm, and the average circularity of the toner is calculated.

[0125] Before starting the measurement, automatic focus adjustment is performed using standard latex particles (e.g., Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water). After that, it is preferable to perform focus adjustment every 2 hours from the start of the measurement.

[0126] [Process cartridges, electrophotographic devices] The process cartridge having the electrophotographic photosensitive member of the present invention is characterized in that it integrally supports the electrophotographic photosensitive member described above and a developing means having toner and for forming a toner image on the surface of the electrophotographic photosensitive member, and is detachably mountable to the main body of the electrophotographic apparatus. The electrophotographic apparatus of the present invention is characterized by comprising the toner, electrophotographic photosensitive member, charging means, exposure means, developing means and transfer means described above.

[0127] FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge 11 equipped with an electrophotographic photosensitive member 1. In FIG. A cylindrical electrophotographic photoreceptor 1 is driven to rotate around an axis 2 at a predetermined peripheral speed in the direction of the arrow. The surface of the electrophotographic photoreceptor 1 is charged to a predetermined positive or negative potential by a charging means 3. Although FIG. 1 shows a roller charging method using a roller-type charging member, a corona charging method, a proximity charging method, an injection charging method, or other charging methods may be adopted. Exposure light 4 is irradiated from an exposure means (not shown) onto the charged surface of the electrophotographic photoreceptor 1, and an electrostatic latent image corresponding to the target image information is formed. The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in a 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 to which the toner image has been transferred is transported to a fixing means 8, where the toner image is fixed, and the transfer material is printed out outside the electrophotographic device. The electrophotographic device may have a cleaning means 9 for removing deposits such as toner remaining on the surface of the electrophotographic photoreceptor 1 after transfer. Also, a so-called cleanerless system may be used in which the deposits are removed by a developing means or the like without providing a separate cleaning means. The electrophotographic apparatus may have a charge eliminating mechanism that eliminates charge on the surface of the electrophotographic photoreceptor 1 by pre-exposure light 10 from a pre-exposure means (not shown). Also, a guide means 12 such as a rail may be provided in order to attach and detach the process cartridge 11 to and from the main body of the electrophotographic apparatus.

[0128] The electrophotographic photoreceptor produced by the production method of the present invention can be used in laser beam printers, LED printers, copiers, facsimiles, and combination machines thereof. EXAMPLES

[0129] The present invention will be described in more detail below with reference to Production Examples and Examples, which are not intended to limit the scope of the present invention. Note that the numbers of parts in the following formulations are all by weight unless otherwise specified. Moreover, Examples 7, 12, and 19 are reference examples.

[0130] <Production Example of Electrophotographic Photoreceptor 1> ·Support An aluminum cylinder having a length of 357.5 mm, a thickness of 0.7 mm, and an outer diameter of 30 mm was prepared as a support (conductive support). The surface of the prepared aluminum cylinder was machined using a lathe. The cutting conditions were a R0.1 bit, a spindle speed of 10,000 rpm, and a bit feed rate that was continuously changed within the range of 0.03 to 0.06 mm / rpm.

[0131] · Formation of undercoat layer Next, 5 parts of N-methoxymethylated nylon (FR101, manufactured by Lead City Co., Ltd.), 70 parts of methanol, and 30 parts of n-butanol were mixed to prepare a coating solution for undercoat layer 1. This coating solution for undercoat layer 1 was dip-coated onto the above-mentioned aluminum cylinder to form a coating film, and the resulting coating film was dried by heating at 130° C. for 10 minutes to form undercoat layer 1 with a thickness of 0.7 μm. Next, 24 parts of an alkyd resin (Beckolite M6401-50, manufactured by DIC Corporation), 16 parts of a melamine resin (Amidea L-150-60, manufactured by DIC Corporation), 160 parts of titanium oxide particles (CR-EL, manufactured by Ishihara Sangyo Kaisha, Ltd.), and 500 parts of methyl ethyl ketone were mixed. Thereafter, the mixture was dispersed for 10 hours using a sand mill using glass beads having a diameter of 0.8 mm as a dispersing machine to prepare a coating liquid for an undercoat layer 2. This coating liquid for an undercoat layer 2 was dip-coated on the above undercoat layer 1 to form a coating film, and the resulting coating film was dried by heating at 130° C. for 20 minutes to form an undercoat layer 2 having a thickness of 3.5 μm.

[0132] Formation of charge generating layer Next, 2.5 parts of oxytitanyl phthalocyanine crystals having a maximum diffraction peak at a Bragg angle of 27.2°±0.2° in CuKα characteristic X-ray diffraction, 0.5 parts of polyvinyl butyral resin (S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 280 parts of methyl ethyl ketone were mixed. After that, the mixture was dispersed for 1 hour using a sand mill using glass beads with a diameter of 1 mm as a dispersing machine to prepare a coating solution for a charge generating layer. This charge generating layer coating liquid was dip coated onto the undercoat layer, and the resulting coating was dried at 90° C. for 10 minutes to form a charge generating layer having a thickness of 0.2 μm.

[0133] Formation of charge transport layer Next, 10 parts of polycarbonate resin (Panlite TS-2050, Teijin Chemical Co., Ltd.), 10 parts of 4,4'-dimethyl-4"-(β-phenylstyryl)triphenylamine, 0.5 parts of the compound represented by formula (6), 0.1 parts of silicone oil (KF50-100CS, Shin-Etsu Chemical Co., Ltd.), and 80 parts of tetrahydrofuran were mixed to prepare a coating liquid for the charge transport layer. This coating liquid for the charge transport layer was dip-coated on the charge generation layer to form a coating film, and the resulting coating film was dried by heating at 110°C for 60 minutes to form a charge transport layer with a thickness of 28 μm.

[0134] Surface layer formation Next, 10.0 parts of a hole transport compound represented by formula (1-4), 10.0 parts of a compound represented by formula (4-1), 2.0 parts of alumina particles (Sumicorundum AA03, manufactured by Sumitomo Chemical Co., Ltd.), 0.05 parts of a surfactant (BYK-P105, manufactured by BYK Japan Co., Ltd.), 0.5 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by BASF Japan Co., Ltd.), and 80 parts of tetrahydrofuran were mixed to prepare a coating liquid for a surface layer.

[0135] Next, the surface layer coating liquid was dip-coated on the charge transport layer to form a coating film, and the resulting coating film was dried for 5 minutes at 60° C. After drying, the coating film was irradiated with light at an irradiation intensity of 700 mW / cm using a metal halide lamp with an output of 160 W / cm. 2 The coated layer was then irradiated with ultraviolet light at 130° C. for 120 seconds, and then heat-treated at 130° C. for 30 minutes to form a surface layer with a thickness of 5.0 μm, thereby producing the electrophotographic photoreceptor 1.

[0136] <Production Example of Electrophotographic Photoreceptor 2> In the manufacturing example of the electrophotographic photoreceptor 1, the amount of the compound represented by the above formula (4-1) was changed from 10.0 parts to 5.0 parts, and 5.0 parts of the compound represented by the formula (5-3) was further added to prepare a coating liquid for a surface layer. In the same manner as in the manufacturing example of the electrophotographic photoreceptor 1, an electrophotographic photoreceptor 2 was manufactured, except that

[0137] <Production Example of Electrophotographic Photoreceptor 3> An electrophotographic photoreceptor 3 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that the compound represented by the above formula (1-2) was added instead of the compound represented by the formula (1-4) to prepare a coating liquid for a surface layer.

[0138] <Production Example of Electrophotographic Photoreceptor 4> An electrophotographic photoreceptor 4 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that the surface layer coating liquid was prepared without adding the alumina particles and the surfactant.

[0139] <Production Example of Electrophotographic Photoreceptor 5> Electrophotographic photoreceptor 5 was produced in the same manner as in the production example of electrophotographic photoreceptor 1, except that in the production example of electrophotographic photoreceptor 1, metal-free phthalocyanine crystals were added instead of oxytitanyl phthalocyanine crystals to prepare a coating liquid for a charge generating layer.

[0140] <Production Example of Electrophotographic Photoreceptor 6> An electrophotographic photoreceptor 6 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that the coating liquid for the charge transport layer was prepared without adding the compound represented by formula (6).

[0141] <Production Example of Electrophotographic Photoreceptor 7> Electrophotographic photoreceptor 7 was produced in the same manner as in the production example of electrophotographic photoreceptor 5, except that the coating liquid for the charge transport layer was prepared without adding the compound represented by formula (6).

[0142] <Production Example of Electrophotographic Photoreceptor 8> An electrophotographic photoreceptor 8 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that a compound represented by formula (5-1) was added instead of the compound represented by formula (4-1) to prepare a coating liquid for a surface layer.

[0143] <Production Example of Electrophotographic Photoreceptor 9> In the manufacturing example of the electrophotographic photoreceptor 1, except that 10.0 parts of the hole transporting compound represented by the formula (1-4) was changed to 14.0 parts, and further, 10.0 parts of the compound represented by the formula (4-1) was changed to 6.0 parts to prepare a surface layer coating solution, the same procedure as in the manufacturing example of the electrophotographic photoreceptor 1 was repeated to manufacture the electrophotographic photoreceptor 9.

[0144] <Production Example of Electrophotographic Photoreceptor 10> An electrophotographic photoreceptor 10 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that in the production example of the electrophotographic photoreceptor 1, 10.0 parts of the hole transporting compound represented by the formula (1-4) was changed to 8.0 parts, and further, 10.0 parts of the compound represented by the formula (4-1) was changed to 12.0 parts to prepare a surface layer coating solution.

[0145] <Production Example of Electrophotographic Photoreceptor 11> Electrophotographic photoreceptor 11 was produced in the same manner as in the production example of electrophotographic photoreceptor 1, except that in the production example of electrophotographic photoreceptor 1, 2.0 parts of alumina particles were changed to 1.0 part to prepare a surface layer coating liquid.

[0146] <Production Example of Electrophotographic Photoreceptor 12> An electrophotographic photoreceptor 12 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that in the production example of the electrophotographic photoreceptor 1, 2.0 parts of alumina particles were changed to 3.0 parts to prepare a surface layer coating liquid.

[0147] <Production Example of Electrophotographic Photoreceptor 13> An electrophotographic photoreceptor 13 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that in the production example of the electrophotographic photoreceptor 1, 0.5 parts of the compound represented by formula (6) was changed to 0.1 parts to prepare the coating solution for the charge transport layer.

[0148] <Production Example of Electrophotographic Photoreceptor 14> An electrophotographic photoreceptor 14 was produced in the same manner as in the production example of the electrophotographic photoreceptor 1, except that in the production example of the electrophotographic photoreceptor 1, 0.5 parts of the compound represented by formula (6) was changed to 1.0 parts to prepare the coating solution for the charge transport layer.

[0149] [Developer manufacturing example] As the resin A, resins A1 to A9 were produced by the following method.

[0150] <Measuring method for resin melting point> The melting point of the resin is measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ End of measurement temperature: 180℃ The melting points of indium and zinc are used for temperature correction of the device detection section, and the heat of fusion of indium is used for heat correction. Specifically, about 5 mg of a sample is weighed out and placed in an aluminum pan, and differential scanning calorimetry is performed using an empty silver pan as a reference. The peak temperature of the maximum endothermic peak in the first heating process is taken as the melting point. The maximum endothermic peak refers to the peak with the largest amount of endothermic heat when there are multiple peaks.

[0151] (Production example of resin A1) Toluene 150.0 parts Behenyl acrylate (compound represented by structural formula (a-1)) 48.0 parts (Content of units derived from structural formula (a-1) in resin A1: 80% by mass) Acrylic acid 12.0 parts Polymerization initiator: Azoisobutyronitrile (AIBN) 1.5 parts The above materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm to carry out a polymerization reaction for 12 hours, and a solution in which the polymer of the monomer composition was dissolved in toluene was obtained. Next, the temperature of the solution was lowered to 25°C, and then the solution was poured into 1000.0 parts of methanol while stirring, and the methanol insoluble matter was precipitated. The obtained methanol insoluble matter was filtered, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain resin A1. [ka]

[0152] (Production example of resin A2) Toluene 150.0 parts Behenyl acrylate (compound represented by structural formula (a-1)) 18.0 parts (Content of units derived from structural formula (a-1) in resin A2: 30% by mass) Acrylic acid 42.0 parts Polymerization initiator: Azoisobutyronitrile (AIBN) 1.5 parts The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Resin A2 was produced in the same manner as Resin A1 except for the above.

[0153] (Resin A3 manufacturing example) Toluene 150.0 parts Behenyl acrylate (compound represented by structural formula (a-1)) 60.0 parts (Content of units derived from structural formula (a-1) in resin A3: 100% by mass) Polymerization initiator: Azoisobutyronitrile (AIBN) 1.5 parts The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Resin A3 was produced in the same manner as Resin A1.

[0154] (Resin A4 manufacturing example) Resin A4 was produced in the same manner as Resin A1 except that the following structural formula (a-2) was used instead of behenyl acrylate and methacrylic acid was used instead of acrylic acid in the production example of Resin A1. [ka]

[0155] (Resin A5 manufacturing example) Resin A5 was produced in the same manner as Resin A1 except that the following structural formula (a-3) was used instead of behenyl acrylate in the production example of Resin A1. [ka]

[0156] (Production example of resin A6) Resin A6 was produced in the same manner as Resin A1 except that the following structural formula (a-4) was used instead of behenyl acrylate in the production example of Resin A1. [ka]

[0157] (Resin A7 manufacturing example) Resin A7 was produced in the same manner as Resin A1 except that the following structural formula (a-5) was used instead of behenyl acrylate in the production example of Resin A1. [ka]

[0158] (Resin A8 manufacturing example) Resin A8 was produced in the same manner as Resin A1 except that the following structural formula (a-6) was used instead of behenyl acrylate in the production example of Resin A1. [ka]

[0159] (Resin A9 manufacturing example) Toluene 150.0 parts Behenyl acrylate (compound represented by structural formula (a-1)) 16.8 parts (Content of units derived from structural formula (a-1) in Resin A9: 28% by mass) Acrylic acid 43.2 parts Polymerization initiator: Azoisobutyronitrile (AIBN) 1.5 parts Resin A9 was produced in the same manner as Resin A1 except that the above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere.

[0160] [Table 1]

[0161] (Production Example of Microparticle Dispersion 1) Ion-exchanged water 683.0 parts Sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.) 11.0 parts Styrene 130.0 parts Methacrylic acid 138.0 parts -n-Butyl acrylate 184.0 parts Ammonium persulfate 1.0 parts The above materials were placed in a reaction vessel equipped with a stirrer and a thermometer. After stirring at 400 rpm for 15 minutes, a white suspension was obtained. The mixture was heated to 75°C and reacted for 5 hours. Further, 30.0 parts of 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75° C. for 5 hours to obtain a vinyl polymer microparticle dispersion 1. The 50% particle size (D50) based on the volume distribution of the microparticle dispersion 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

[0162] (Production Example of Release Agent Dispersion) Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro) 20.0 parts Ethyl acetate 80.0 parts The above materials were weighed and put into a mixing vessel equipped with a stirrer, and then heated and stirred at 80°C. Next, the system was cooled to 25°C over 3 hours while stirring at 50 rpm, and the milky liquid was separated by ethanol. This solution was put into a heat-resistant vessel together with 30.0 parts of glass beads having a diameter of 1 mm, and dispersed for 3 hours using a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and the glass beads were removed using a nylon mesh to obtain a release agent dispersion. The 50% particle size (D50) based on the volume distribution of the release agent dispersion was measured using a dynamic light scattering particle size distribution meter Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and was found to be 0.23 μm.

[0163] (Production Example of Microparticle Dispersion 2) CI Pigment Yellow 185 (formula (3) below) 100.0 parts Ethyl acetate 150.0 parts Glass beads (1mm) 200.0 parts [ka] The above materials were placed in a heat-resistant glass container and dispersed for 5 hours using a paint shaker. The glass beads were removed using a nylon mesh to obtain a fine particle dispersion 2. The 50% particle size (D50) based on volume distribution of the fine particle dispersion 2 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

[0164] <Production of Toner 1> Preparation of oil phase Resin A1 100.0 parts Ethyl acetate 85.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 1 minute using a Disper (manufactured by Tokushu Kika Co., Ltd.). Release agent dispersion (20% solids) 50.0 parts ·Fine particle dispersion 2 (solid content 40%) 162.5 parts Ethyl acetate 5.0 parts The above materials were then placed in a beaker and stirred at 6,000 rpm for 3 minutes using a Disper (manufactured by Tokushu Kika Co., Ltd.) to prepare an oil phase.

[0165] (Preparation of aqueous phase) ·Fine particle dispersion 1 15.0 parts 30.0 parts of sodium dodecyl diphenyl ether disulfonate solution (Eleminol MON7, Sanyo Chemical Industries, Ltd.) Ion-exchanged water 955.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using a Disper (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.

[0166] The oil phase was added to the aqueous phase and dispersed at 10,000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). The solvent was then removed for 30 minutes at 30°C and a reduced pressure of 50 mmHg. The mixture was then filtered, and the surfactant was removed by repeating the steps of filtering and redispersing in ion-exchanged water until the electrical conductivity of the slurry reached 100 μS, to obtain a filter cake. The filter cake was vacuum-dried and then air-classified to obtain toner particles 1. Next, the following materials were mixed in a Henschel mixer FM-10C type (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s-1 for a rotation time of 10 min to obtain toner 1. 100 parts of toner particles Hydrophobic silica (HDK-2000, Wacker Chemie) 0.7 parts Titanium oxide (MT-150AI, manufactured by Teika Co., Ltd.) 0.3 parts

[0167] <Production Examples of Toner 2 to Toner 9> In the production example of toner 1, resins A2 to A9 were used instead of resin A1. Otherwise, toners 2 to 9 were produced in the same manner as toner 1.

[0168] <Production Example of Toner 10> In the production example of Toner 1, carbon black was used in place of CI Pigment Yellow 185 contained in Fine Particle Dispersion Liquid 2. Except for the above, Toner 10 was produced in the same manner as Toner 1.

[0169] <Production Example of Toner 11> In the production example of Toner 1, 5.0 parts of CI Pigment Yellow 185 and 95.0 parts of CI Pigment Yellow 180 (formula (C) below) were used instead of 100.0 parts of CI Pigment Yellow 185 contained in the fine particle dispersion 2. Otherwise, Toner 11 was produced in the same manner as Toner 1. [ka]

[0170] <Production Example of Toner 12> In the production example of Toner 1, 50.0 parts of CI Pigment Yellow 185 and 50.0 parts of CI Pigment Yellow 180 were used instead of 100.0 parts of CI Pigment Yellow 185 contained in Fine Particle Dispersion Liquid 2. Except for the above, Toner 12 was produced in the same manner as Toner 1.

[0171] <Production Example of Toner 13> In the production example of Toner 1, 95.0 parts of CI Pigment Yellow 185 and 5.0 parts of CI Pigment Yellow 180 were used instead of 100.0 parts of CI Pigment Yellow 185 contained in Fine Particle Dispersion Liquid 2. Otherwise, Toner 13 was produced in the same manner as Toner 1.

[0172] <Production Example of Toner 14> In the production example of Toner 1, 5.0 parts of CI Pigment Yellow 185 and 95.0 parts of carbon black were used instead of 100.0 parts of CI Pigment Yellow 185 contained in Fine Particle Dispersion Liquid 2. Except for the above, Toner 14 was produced in the same manner as Toner 1.

[0173] <Production Example of Toner 15> In the production example of Toner 1, carbon black was used in place of CI Pigment Yellow 185 contained in Fine Particle Dispersion Liquid 2. Except for the above, Toner 13 was produced in the same manner as Toner 1.

[0174] <Production Example of Toner 16> (Synthesis of organic fine particle emulsion) In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, resulting in a white emulsion. The mixture was heated to an internal temperature of 75°C and reacted for 5 hours. Furthermore, 30 parts of a 1% aqueous ammonium persulfate solution was added, and the mixture was aged at 75°C for 5 hours to obtain an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-sodium salt of methacrylic acid ethylene oxide adduct sulfate) [fine particle dispersion 16].

[0175] (Preparation of aqueous phase) 990 parts of water, 83 parts of [fine particle dispersion 16], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries), and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [aqueous phase 16].

[0176] (Synthesis of low molecular weight polyester) Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mol adduct, 529 parts of bisphenol A propylene oxide 3-mol adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, and 2 parts of dibutyltin oxide were placed and reacted at normal pressure at 230°C for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours. After that, 44 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180°C and normal pressure for 2 hours to obtain [low molecular weight polyester 16].

[0177] (Synthesis of intermediate polyester) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 682 parts of bisphenol A ethylene oxide 2 mole adduct, 81 parts of bisphenol A propylene oxide 2 mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were placed and reacted at normal pressure at 230°C for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [intermediate polyester 16]. Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 410 parts of [intermediate polyester 16], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate were placed and reacted at 100°C for 5 hours to obtain [prepolymer 16].

[0178] (Synthesis of crystalline polyester) 25 mol of 1,4-butanediol, 23.75 mol of fumaric acid, 1.65 mol of trimellitic anhydride, and 5.3 g of hydroquinone were placed in a 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and reacted at 160°C for 5 hours, then heated to 200°C and reacted for 1 hour, and further reacted at 8.3 KPa for 1 hour to obtain [crystalline polyester resin 16].

[0179] (Ketimine synthesis) In a reaction vessel equipped with a stirring bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50° C. for 5 hours to obtain [ketimine compound 16].

[0180] (Masterbatch (MB) synthesis) 1,200 parts of water, 540 parts of CI Pigment Yellow 185, and 1,200 parts of polyester resin were added and mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded using two rolls at 150°C for 30 minutes, then rolled and cooled, and pulverized in a pulverizer to obtain [Masterbatch 16].

[0181] (Preparation of oil phase) In a vessel equipped with a stirring rod and a thermometer, 378 parts of [low molecular weight polyester 16], 110 parts of carnauba wax, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged, and the mixture was heated to 80°C under stirring, and then kept at 80°C for 5 hours, and then cooled to 30°C in 1 hour. Next, 500 parts of [master batch 16] and 500 parts of ethyl acetate were charged in the vessel, and mixed for 1 hour to obtain [raw material solution 16]. 1324 parts of [raw material solution 16] were transferred to the vessel, and carbon black and wax were dispersed using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.) under the conditions of a liquid delivery speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume of 0.5 mm zirconia beads, and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [Low molecular weight polyester 16] was added, and the mixture was passed once through the bead mill under the above conditions to obtain [Pigment / WAX dispersion 16].

[0182] (Preparation of crystalline polyester dispersion) 100g of [Crystalline polyester resin 16] and 400g of ethyl acetate were placed in a 2L metal container, and dissolved or dispersed by heating at 79℃, then quenched in an ice-water bath. 500ml of glass beads (3mmφ) were added to the mixture, and the mixture was stirred for 10 hours in a batch-type sand mill (Kanpe Hapio Co., Ltd.) to obtain [Crystalline polyester dispersion 16] with a volume average particle size of 0.4μm.

[0183] (Emulsification - Desolvation) 664 parts of [Pigment / WAX Dispersion 16], 109.4 parts of [Prepolymer 16], 73.9 parts of [Crystalline Polyester Dispersion 16], and 4.6 parts of [Ketimine Compound 16] were placed in a container and mixed with a TK Homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, after which 1,200 parts of [Aqueous Phase 16] was added to the container and mixed with a TK Homomixer at a rotation speed of 13,000 rpm for 20 minutes to obtain [Emulsified Slurry 16]. [Emulsified slurry 16] was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 8 hours, and then aged at 45° C. for 8 hours to obtain [Dispersed slurry 16].

[0184] (Washing~Drying) 100 parts of [emulsified slurry 16] was filtered under reduced pressure, and then (1): 100 parts of ion-exchanged water was added to the filter cake, which was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and filtered. (2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (at 12,000 rpm for 30 minutes), and then filtered under reduced pressure. (3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (4): 300 parts of ion-exchanged water was added to the filter cake of (3), and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes), followed by filtering twice to obtain [filter cake 16]. The filtered cake 16 was dried in a circulating air dryer at 45° C. for 48 hours, and sieved through a 75 μm mesh to obtain toner particles 16. Next, mix the following materials in a Henschel mixer FM-10C (manufactured by Mitsui Miike Chemical Industry) at a rotation speed of 30 s. -1 The mixture was mixed at a rotation time of 10 minutes to obtain toner 16. Toner particles 16 100 parts Hydrophobic silica (HDK-2000, Wacker Chemie) 0.7 parts Titanium oxide (MT-150AI, manufactured by Teika Co., Ltd.) 0.3 parts

[0185] [Table 2]

[0186] <Magnetic carrier manufacturing example> As the core material, 5000 parts of Mn ferrite particles (weight average diameter: 35 μm) were used. As the coating material, a coating liquid was used, which was prepared by dispersing 300 parts of toluene, 300 parts of butyl cellosolve, 60 parts of an acrylic resin solution (composition ratio (molar ratio) methacrylic acid: methyl methacrylate: 2-hydroxyethyl acrylate = 5: 9: 3, solid content 50% toluene solution, Tg 38 ° C.), 15 parts of an N-tetramethoxymethylbenzoguanamine resin solution (polymerization degree 1.5, solid content 77% toluene solution), and 15 parts of alumina particles (average primary particle diameter 0.30 μm) with a stirrer for 10 minutes. The core material and the coating liquid were put into a coating device that was equipped with a rotating bottom plate disk and stirring blades in a fluidized bed to form a swirling flow, and the coating liquid was applied onto the core material. The resulting coating was baked in an electric furnace at 220°C for 2 hours to obtain magnetic carrier 1.

[0187] <Production example of two-component developer 1> 92.0 parts of magnetic carrier 1 and 8.0 parts of toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1.

[0188] <Production Examples of Two-Component Developers 2 to 16> In the production example of the two-component developer 1, toner 2 to toner 16 were used instead of toner 1. Except for that, two-component developer 2 to two-component developer 1 were produced in the same manner as two-component developer 1.

[0189] Example 1 A modified copy machine of Canon iR-ADV-C5255 was used for the evaluation of the image forming apparatus. The evaluation machine, iR-ADV-C5255, was modified so that the control operation before the image output was not performed so that the electrophotographic photosensitive member would not rotate in contact with the cleaning blade before the image output.

[0190] [Evaluation 1: Evaluation of H / H image streaks] The evaluation was performed under an environment of 30°C / 80% RH. An electrophotographic photoreceptor 1 was attached to the yellow station of the evaluation machine. The cleaning blade of the electrophotographic photoreceptor was a cleaning blade made of polyurethane rubber with a hardness of 77°, and was set to contact the peripheral surface of the electrophotographic photoreceptor at a contact angle of 28° and a contact pressure of 30 g / cm (29.4 N / m). Two-component developer 1 was set in the developing device of the yellow station of the evaluation machine. In addition, the conditions of the charging device and the exposure device were set in advance so that the dark area potential (Vd) of the electrophotographic photoreceptor was -500V and the light area potential (Vl) was -200V. Next, with the heater (drum heater) for the electrophotographic photoreceptor turned on, 10 sheets of A4 evaluation charts with a density of 30% were continuously output. The output images were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3.

[0191] (Evaluation Criteria) A: No streaks are observed on the image. (Excellent) B: Images that give the impression of streaks are obtained, but are at a level where it is not possible to determine whether they are clear streaks or not. (Slightly better) C: Very slight streaks are observed on the image (level acceptable in the present invention). D: Clear streaks are observed on the image (a level that is unacceptable in this invention).

[0192] [Evaluation 2: Evaluation of light area potential fluctuation] The evaluation was performed under an environment of 23°C / 5%RH. The electrophotographic photoreceptor 1 was mounted on the yellow station of the evaluation machine. The cleaning blade of the electrophotographic photoreceptor was a cleaning blade made of polyurethane rubber with a hardness of 77°, and was set to contact the peripheral surface of the electrophotographic photoreceptor at a contact angle of 28° and a contact pressure of 30 g / cm (29.4 N / m). The two-component developer 1 was set in the developing device of the yellow station of the evaluation machine. In addition, as the charging conditions of the electrophotographic photoreceptor, the AC component applied to the charging roller was set to a peak-to-peak voltage of 1500V and a frequency of 1500Hz, and the DC component (initial dark potential (Vda)) was set to -750V. In addition, as the exposure conditions of the electrophotographic photoreceptor, the exposure conditions were adjusted so that the initial bright potential (Vla) in 780 nm laser exposure irradiation was -200V. The surface potential of the electrophotographic photoreceptor was measured by removing the developing cartridge from the evaluation device and inserting a potential measuring device therein. The potential measuring device is configured by arranging a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe relative to the electrophotographic photoreceptor was the center in the generating line direction of the electrophotographic photoreceptor, with a gap of 3 mm from the surface of the electrophotographic photoreceptor.

[0193] Next, the evaluation will be described. Each electrophotographic photoreceptor was evaluated under the charging conditions and exposure conditions set above. The developing cartridge with the electrophotographic photoreceptor mounted thereon was attached to the evaluation device, and the electrophotographic photoreceptor was repeatedly used for 100,000 continuous revolutions under a 23°C / 5% RH environment. After the 100,000 revolutions were repeatedly used, the electrophotographic photoreceptor was left for 5 minutes, the developing cartridge was replaced with a potential measuring device, and the dark potential (VDb) and light potential (VLb) after the repeated use were measured. The difference between the light potential after the repeated use and the initial light potential was determined as the light potential fluctuation (ΔVL=|VLb|-|VLa|), and the difference between the dark potential after the repeated use and the initial dark potential was determined as the dark potential fluctuation (ΔVD=|VDb|-|VDa|). The results of evaluating ΔVL according to the following evaluation criteria are shown in Table 3.

[0194] (Evaluation Criteria) A: ΔVL is 0V or more and less than 30V (excellent) B: ΔVL is 30V or more and less than 40V (slightly better) C: ΔVL is 40V or more and less than 50V (the acceptable level in the present invention) D: ΔVL is 50V or more (a level that is not acceptable in the present invention)

[0195] [Examples 2 to 25, Comparative Examples 1 to 4] As Examples 2 to 25 and Comparative Examples 1 to 4, the combinations of electrophotographic photoreceptors and two-component developers shown in Table 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0196] [Table 3] [Explanation of symbols]

[0197] 1. Electrophotographic photoreceptor 2. Axis 3. Charging means 4‥‥Exposure light 5. Developing method 6. Transfer means 7. Transfer material 8. Fixing means 9. Cleaning means 10. Pre-exposure light 11. Process cartridge 12. Guidance means

Claims

1. An electrophotographic photoreceptor; a charging means for charging the surface of the electrophotographic photoreceptor; an image exposure means for irradiating the charged surface of the electrophotographic photosensitive member with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photosensitive member; a developing means having a toner and for developing the electrostatic latent image with the toner to form a toner image on the surface of the electrophotographic photoreceptor; a transfer means for transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material; a cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor by using a cleaning blade after the toner image is transferred to the transfer material; a fixing means for fixing the toner image transferred onto the transfer material; An electrophotographic apparatus having the electrophotographic photoreceptor has a support, a charge generating layer, a charge transport layer, and a surface layer in this order; The surface layer is a polymerized film of a composition containing a hole transporting compound represented by the following formula (1) and a compound represented by the following formula (4), The toner has toner particles containing a resin A having a unit represented by the following formula (2) and a compound represented by the following formula (3), The resin A is a crystalline resin, The content of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less: Electrophotographic apparatus characterized in that 【Chemistry 1】 (In formula (1), R １ and R ２ Each of m and n independently represents an integer of 0 to 2. ３ R represents a single bond or an alkylene group having 1 to 6 carbon atoms. ４ represents a hydrogen atom or a methyl group. 【Chemistry 2】 (In formula (2), R Ｚ１ represents a hydrogen atom or a methyl group. Ｚ２ represents an alkyl group having 18 to 36 carbon atoms. 【Chemistry 3】 【Chemistry 4】 (In formula (4), R 41 to R 43 each represent a hydrogen atom or a methyl group. R 44 to R 46 each represent an alkylene group having 1 to 3 carbon atoms. R 47 represents an alkyl group having 1 to 3 carbon atoms.) 2. The electrophotographic apparatus according to claim 1, wherein the compound represented by the formula (4) is a compound represented by the following formula (4-1): 【Chemistry 5】

3. 3. The electrophotographic apparatus according to claim 1, wherein the surface layer contains alumina particles.

4. 4. The electrophotographic apparatus according to claim 1, wherein the charge transport layer contains a compound represented by the following formula (6): 【Chemistry 6】

5. 5. The electrophotographic apparatus according to claim 1, wherein the charge generating layer contains oxytitanium phthalocyanine.

6. An electrophotographic photoreceptor; a developing means having a toner and for developing an electrostatic latent image formed on the surface of the electrophotographic photoreceptor with the toner to form a toner image on the surface of the electrophotographic photoreceptor; a process cartridge which is detachably mountable to a main body of an electrophotographic apparatus and which integrally supports the the electrophotographic photoreceptor has a support, a charge generating layer, a charge transport layer, and a surface layer in this order; The surface layer is a polymerized film of a composition containing a hole transporting compound represented by the following formula (1) and a compound represented by the following formula (4), The toner has toner particles containing a resin A having a unit represented by the following formula (2) and a compound represented by the following formula (3), The resin A is a crystalline resin, The content of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less: A process cartridge comprising: 【Chemistry 7】 (In formula (1), R １ and R ２ Each of m and n independently represents an integer of 0 to 2. ３ R represents a single bond or an alkylene group having 1 to 6 carbon atoms. ４ represents a hydrogen atom or a methyl group. 【Chemistry 8】 (In formula (2), R Ｚ１ represents a hydrogen atom or a methyl group. Ｚ２ represents an alkyl group having 18 to 36 carbon atoms. 【Chemistry 9】 【Chemistry 10】 (In formula (4), R 41 to R 43 each represent a hydrogen atom or a methyl group. R 44 to R 46 each represent an alkylene group having 1 to 3 carbon atoms. R 47 represents an alkyl group having 1 to 3 carbon atoms.) 7. The process cartridge according to claim 6, wherein the compound represented by the formula (4) is a compound represented by the following formula (4-1): 【Chemistry 11】

8. a charging step of charging the surface of an electrophotographic photoreceptor; an image exposure step of irradiating the charged surface of the electrophotographic photoreceptor with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photoreceptor; a developing step of developing the electrostatic latent image with a toner to form a toner image on the surface of the electrophotographic photoreceptor; a transfer step of transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material; a cleaning step of removing residual toner remaining on the surface of the electrophotographic photoreceptor after the transfer step by using a cleaning blade; a fixing step of fixing the toner image transferred onto the transfer material; An image forming method comprising: The electrophotographic photoreceptor has a support, a charge generating layer, a charge transport layer, and a surface layer in this order, The surface layer is a polymerized film of a composition containing a hole transporting compound represented by the following formula (1) and a compound represented by the following formula (4), The toner has toner particles containing a resin A having a unit represented by the following formula (2) and a compound represented by the following formula (3), The resin A is a crystalline resin, The content of the unit represented by the following formula (2) in the resin A is 30% by mass or more and 100% by mass or less:

1. An image forming method comprising: 【Chemistry 12】 (In formula (1), R １ and R ２ Each of m and n independently represents an integer of 0 to 2. ３ R represents a single bond or an alkylene group having 1 to 6 carbon atoms. ４ represents a hydrogen atom or a methyl group. 【Chemistry 13】 (In formula (2), R Ｚ１ represents a hydrogen atom or a methyl group. Ｚ２ represents an alkyl group having 18 to 36 carbon atoms. 【Chemistry 14】 【Chemistry 15】 (In formula (4), R 41 to R 43 each represent a hydrogen atom or a methyl group. R 44 to R 46 each represent an alkylene group having 1 to 3 carbon atoms. R 47 represents an alkyl group having 1 to 3 carbon atoms.) 9. The image forming method according to claim 8, wherein the compound represented by formula (4) is a compound represented by the following formula (4-1): 【Chemistry 16】

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