JP6354230B2 - Image forming apparatus and process cartridge - Google Patents

Description

  The present invention relates to an image forming apparatus and a process cartridge.

  Patent Document 1 discloses an electrophotographic photoreceptor including a support substrate, an intermediate layer, and a photoreceptor layer, in which the intermediate layer includes a phenolic resin, a film-forming resin having a hydroxyl group, and hole transport. An electrophotographic photosensitive member characterized by containing an agent and making the content of the phenolic resin a value within a specific range is disclosed.

  Patent Document 2 discloses an electrophotographic photoreceptor in which an intermediate layer and an organic photosensitive layer are sequentially laminated on a conductive substrate, and the intermediate layer can react with at least a blocked isocyanate compound and an isocyanate group in the blocked isocyanate compound. Obtained by applying and heat-curing a coating solution for forming an intermediate layer in which an active hydrogen-containing group resin, inorganic oxide fine particles, and an electron transport agent are dissolved or dispersed in an aqueous medium. An electrophotographic photosensitive member having a thickness of 50 μm or less is disclosed.

  Patent Document 3 includes a support and an undercoat layer provided on the support, and includes at least a binder resin, metal oxide particles, and an electron-accepting compound having an anthraquinone structure. An electrophotographic photosensitive layer having an undercoat layer in which the content of the compound is in a specific range and a contact angle of the metal oxide particles with water in a specific range, and a photosensitive layer provided on the undercoat layer. The body is disclosed.

JP 2005-215119 A JP 2010-122440 A JP2013-242483A

  An object of the present invention is to provide an image forming apparatus in which image sticking on the surface of an electrophotographic photosensitive member is suppressed.

The above problem is solved by the following means. That is,
The invention according to claim 1
A conductive substrate; an undercoat layer provided on the conductive substrate; and a photosensitive layer provided on the undercoat layer, wherein the undercoat layer comprises a binder resin, metal oxide particles, and the metal oxide. an electrophotographic photosensitive member viewed contains an electron transporting material represented by anthraquinone derivatives and by the following general formula (1), the thickness of the subbing layer is 15μm or more with the surface of the object particles,
Driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more;
Charging means for charging the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member;
Developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner to form a toner image;
Transfer means for transferring the toner image to the surface of the recording medium;
An image forming apparatus.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, Or R ¹⁸ represents an alkyl group, an aryl group, or an aralkyl group.

The invention according to claim 2
The image forming apparatus according to claim 1, wherein a formation start position of the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is synchronized for each electrostatic latent image corresponding to a single image.

The invention according to claim 3
The image forming apparatus according to claim 1, wherein the outermost surface layer of the electrophotographic photosensitive member includes fluorine-containing resin particles and a fluorinated alkyl group-containing copolymer.

The invention according to claim 4
The image forming apparatus according to claim 1, wherein the toner has a volume average particle diameter of 2.0 μm or more and 5.0 μm or less.

The invention according to claim 5
A conductive substrate; an undercoat layer provided on the conductive substrate; and a photosensitive layer provided on the undercoat layer, wherein the undercoat layer comprises a binder resin, metal oxide particles, and the metal oxide. an electrophotographic photosensitive member viewed contains an electron transporting material represented by anthraquinone derivatives and by the following general formula (1), the thickness of the subbing layer is 15μm or more with the surface of the object particles,
Driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more;
With
A process cartridge that can be attached to and detached from an image forming apparatus.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, Or R ¹⁸ represents an alkyl group, an aryl group, or an aralkyl group.

  According to the invention according to claim 1, compared to the case where the undercoat layer does not contain the electron transport material represented by the general formula (1), the undercoat layer contains metal oxide particles and the anthraquinone derivative, In addition, an image forming apparatus capable of suppressing image sticking on the surface of the electrophotographic photosensitive member even when the electrophotographic photosensitive member is provided with a driving unit that drives the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more is provided.

  According to the invention of claim 2, the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is formed as compared with the case where the undercoat layer does not contain the electron transport material represented by the general formula (1). There is provided an image forming apparatus in which image sticking on the surface of an electrophotographic photosensitive member is suppressed even when the start position is synchronized for each of the electrostatic latent images corresponding to a single image.

  According to the invention of claim 3, the outermost surface layer of the electrophotographic photosensitive member is composed of fluorine-containing resin particles and fluoride as compared with the case where the undercoat layer does not contain the electron transport material represented by the general formula (1). There is provided an image forming apparatus in which image sticking on the surface of an electrophotographic photosensitive member is suppressed even in a form including an alkyl group-containing copolymer.

  According to the fourth aspect of the invention, the volume average particle size of the toner is 2.0 μm or more and 5.0 μm or less as compared with the case where the undercoat layer does not contain the electron transport material represented by the general formula (1). Even if it exists, the image forming apparatus in which the burn-in on the surface of the electrophotographic photosensitive member is suppressed is provided.

  According to the invention according to claim 5, the undercoat layer contains metal oxide particles and the anthraquinone derivative as compared with the case where the undercoat layer does not contain the electron transport material represented by the general formula (1). In addition, a process cartridge can be provided in which image sticking on the surface of the electrophotographic photosensitive member is suppressed even when the driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more is provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member used in the image forming apparatus of the present embodiment. FIG. 6 is a schematic cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member used in the image forming apparatus of the present embodiment. It is a schematic block diagram which shows another example of the image forming apparatus which concerns on this embodiment. In the image forming apparatus according to the present embodiment, it is a diagram for explaining the position of the electrostatic latent image formed on the outer peripheral surface of the electrophotographic photosensitive member. It is a photograph which shows the evaluation criteria of the dot reproducibility in an Example. It is a figure which shows the evaluation criteria of the image sticking in an Example. It is a figure which shows the outline of the image formed in abrasion resistance evaluation of an Example.

  Embodiments that are examples of the present invention will be described below.

<Image forming apparatus and process cartridge>
The image forming apparatus according to the present embodiment includes a conductive substrate, an undercoat layer provided on the conductive substrate, and a photosensitive layer provided on the undercoat layer, and the undercoat layer is bound. An electrophotographic photoreceptor (hereinafter referred to as “photoreceptor”) containing a resin, metal oxide particles, an anthraquinone derivative on the surface of the metal oxide particles, and an electron transport material represented by the general formula (1). ), Driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more, charging means for charging the surface of the electrophotographic photosensitive member, and an electrostatic latent image on the surface of the charged electrophotographic photosensitive member An electrostatic latent image forming means for forming the toner, a developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner, and forming the toner image. And transfer means for transferring to the surface of the recording medium.

  The process cartridge according to the present embodiment includes a conductive substrate, an undercoat layer provided on the conductive substrate, and a photosensitive layer provided on the undercoat layer, and the undercoat layer is bound to the process cartridge. An electrophotographic photoreceptor comprising a resin, metal oxide particles, an anthraquinone derivative on the surface of the metal oxide particles, and an electron transport material represented by the general formula (1), and a peripheral speed of 500 mm Driving means for driving at / s or more, and is attached to and detached from the image forming apparatus.

  In this embodiment, the undercoat layer contains metal oxide particles and the anthraquinone derivative as compared with the case where the undercoat layer does not contain the electron transport material represented by the general formula (1), and Even if a driving means for driving at a peripheral speed of 500 mm / s or more is provided, image sticking on the surface of the photoreceptor is suppressed. The reason is not clear, but is presumed as follows.

  In an image forming apparatus (hereinafter sometimes referred to as a “high-speed machine”) provided with a drive unit that drives a photosensitive member at a peripheral speed of 500 mm / s or more, a conventional image forming apparatus (for example, the peripheral speed of the photosensitive member is 440 mm / s) Compared with the image forming apparatus described below, electrical loads such as charging, exposure, and static elimination are repeatedly applied to the photosensitive member in a short time.

In particular, when a photoconductor including metal oxide particles and the anthraquinone derivative in an undercoat layer is applied to a high-speed machine, electrical long-term stability (cycle stability) can be obtained even with a high-speed machine. Burning of the body surface is likely to occur. Here, burn-in on the surface of the photoconductor means that, for example, when a halftone image is formed after repeatedly forming the same image, the history of the same image repeatedly formed appears in the halftone image. This is a phenomenon in which history remains.
That is, since the undercoat layer containing the metal oxide particles and the anthraquinone derivative has excellent charge blocking properties, for example, when the same image is repeatedly formed at a high speed, a specific portion of the photoreceptor continues to receive an electrical load. . For this reason, it is considered that charges are accumulated at the interface between the undercoat layer and the photosensitive layer only at the specific location, and potential unevenness due to a potential difference from the surroundings is likely to occur.

  On the other hand, in the present embodiment, there is provided a photoreceptor in which the undercoat layer includes a binder resin, metal oxide particles, an anthraquinone derivative on the surface of the metal oxide particles, and an electron transport material represented by the general formula (1). Applies to high speed machines. For this reason, even with a high-speed machine, image sticking on the surface of the photoreceptor is suppressed while obtaining the above-described cycle stability. Although the reason is not necessarily clear, the electron transport material represented by the general formula (1) included in the undercoat layer transfers charges accumulated at the interface between the undercoat layer and the photosensitive layer to the photosensitive layer. It is thought that it is from. As a result, it is presumed that charge accumulation is suppressed to such an extent that it can withstand repeated electrical loads in a high-speed machine, and image sticking on the surface of the photoreceptor is suppressed.

In this embodiment, even if the formation start position of the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is synchronized for each electrostatic latent image corresponding to a single image, Burn-in is suppressed.
In particular, high-speed machines often form a large number of images at once, but by synchronizing the electrostatic latent image formation start position for each electrostatic latent image corresponding to a single image, Density unevenness is suppressed. On the other hand, in the image forming apparatus of the above embodiment, since the same electrostatic latent image is formed at the same position on the surface of the photoconductor, it is considered that image sticking on the photoconductor surface is more likely to occur compared to an image forming apparatus that is not synchronized.
However, in the present embodiment, in order to apply a photoreceptor in which the undercoat layer includes metal oxide particles, an anthraquinone derivative that the surface of the metal oxide particles has, and the electron transport material represented by the general formula (1), Even in the image forming apparatus of the above form, image sticking on the surface of the photoreceptor is suppressed.

In this embodiment, even if the outermost surface layer of the photoconductor includes a fluorine-containing resin particle and a fluorinated alkyl group-containing copolymer, image sticking on the surface of the photoconductor is suppressed.
By applying the photoconductor of the above form, the wear resistance of the photoconductor is improved and the life is extended, but compared with the case where the outermost surface layer does not have fluorine-containing resin particles and a fluorinated alkyl group-containing copolymer. Therefore, it is considered that the electrical characteristics are lowered and the surface of the photoreceptor is easily burned.
However, in the present embodiment, in order to apply the photoreceptor in which the undercoat layer includes the metal oxide particles, the anthraquinone derivative that the metal oxide particles have on the surface, and the electron transport material represented by the general formula (1), Even when the photoconductor of the above-described form is applied, image sticking on the surface of the photoconductor is suppressed.

Further, in this embodiment, even when a toner having a volume average particle diameter of 2.0 μm or more and 5.0 μm or less (hereinafter sometimes referred to as “small-diameter toner”) is used, burn-in on the surface of the photoreceptor is suppressed. The
From the viewpoint of achieving high image quality, when the above-mentioned small diameter toner is used, it is necessary to increase the developing potential because the chargeability of the toner is lower than when a conventional toner having a volume average particle diameter exceeding 5 μm is used. For this reason, it is necessary to set the charging potential of the photosensitive member high, and the electrical load applied to the photosensitive member increases, so that it is considered that the surface of the photosensitive member is likely to be burned.
However, in the present embodiment, in order to apply the photoreceptor in which the undercoat layer includes the metal oxide particles, the anthraquinone derivative that the metal oxide particles have on the surface, and the electron transport material represented by the general formula (1), Even when the small-diameter toner is used and the charging potential of the photoconductor is increased, the image sticking on the surface of the photoconductor is suppressed.

  Hereinafter, an image forming apparatus and a process cartridge according to the present embodiment will be described in detail with reference to the drawings.

FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present embodiment.
As shown in FIG. 1, an image forming apparatus 100 according to this embodiment includes a process cartridge 300 including an electrophotographic photosensitive member 7, an exposure device 9 (an example of an electrostatic latent image forming unit), and a transfer device 40 (primary. Transfer device) and an intermediate transfer member 50. In the image forming apparatus 100, the exposure device 9 is disposed at a position where the electrophotographic photosensitive member 7 can be exposed from the opening of the process cartridge 300, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. 7, and a part of the intermediate transfer member 50 is disposed in contact with the electrophotographic photosensitive member 7. Although not shown, it also has a secondary transfer device that transfers the toner image transferred to the intermediate transfer member 50 to a recording medium (for example, paper). The intermediate transfer member 50, the transfer device 40 (primary transfer device), and the secondary transfer device (not shown) correspond to an example of a transfer unit.

  A process cartridge 300 in FIG. 1 includes, in a housing, an electrophotographic photosensitive member 7, a driving device 16 that drives the electrophotographic photosensitive member 7 at a peripheral speed of 500 mm / s or more (an example of a driving unit), and a charging device 8 (a charging unit) An example), a developing device 11 (an example of a developing unit), and a cleaning device 13 (an example of a cleaning unit) are integrally supported. The cleaning device 13 includes a cleaning blade (an example of a cleaning member) 131, and the cleaning blade 131 is disposed so as to contact the surface of the electrophotographic photosensitive member 7. The cleaning member may be a conductive or insulating fibrous member instead of the cleaning blade 131, and may be used alone or in combination with the cleaning blade 131.

  In FIG. 1, as an image forming apparatus, a fibrous member 132 (roll shape) for supplying the lubricant 14 to the surface of the electrophotographic photosensitive member 7 and a fibrous member 133 (flat brush shape) for assisting in cleaning are shown. Examples are provided, but these are arranged as necessary.

  Hereinafter, each configuration of the image forming apparatus according to the present embodiment will be described.

-Electrophotographic photoreceptor-
In this embodiment, the photoreceptor only needs to have at least a conductive substrate, an undercoat layer, and a photosensitive layer. The photoreceptor may have a function-integrated photosensitive layer having both charge transporting ability and charge generating ability as the photosensitive layer, or a function-separated photosensitive layer including the charge transporting layer and the charge generating layer. You may have. Furthermore, you may provide other layers, such as a protective layer.

FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the photoreceptor in this embodiment. In FIG. 2, 1 is a conductive substrate, 2 is a photosensitive layer, 2A is a charge generation layer, 2B is a charge transport layer, 2C represents a protective layer and 4 represents an undercoat layer.
The photoreceptor shown in FIG. 2 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, a charge transport layer 2B, and a protective layer 2C are laminated on a conductive substrate 1 in this order. It is composed of three layers including a generation layer 2A, a charge transport layer 2B, and a protective layer 2C (the photoreceptor of the first embodiment).
In the photoreceptor shown in FIG. 2, the protective layer 2C is the outermost surface layer constituting the outermost surface.
Next, each element of the electrophotographic photoreceptor will be described. In some cases, the reference numerals are omitted.

(Conductive substrate)
Examples of the conductive substrate include metal plates (eg, aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, etc.) or alloys (stainless steel, etc.), metal drums, metal belts, etc. Is mentioned. In addition, as the conductive substrate, for example, paper, resin film, belt, etc. coated, vapor-deposited or laminated with a conductive compound (for example, conductive polymer, indium oxide, etc.), metal (for example, aluminum, palladium, gold, etc.) or an alloy, etc. Also mentioned. Here, “conductive” means that the volume resistivity is less than 10 ¹³ Ωcm.

  When the electrophotographic photosensitive member is used in a laser printer, the surface of the conductive substrate has a center line average roughness Ra of 0.04 μm or more and 0.5 μm for the purpose of suppressing interference fringes generated when laser light is irradiated. The surface is preferably roughened below. When non-interfering light is used as a light source, roughening for preventing interference fringes is not particularly required, but it is suitable for extending the life because it suppresses generation of defects due to irregularities on the surface of the conductive substrate.

  As a roughening method, for example, wet honing performed by suspending an abrasive in water and spraying it on a support, centerless grinding in which a conductive substrate is pressed against a rotating grindstone, and grinding is continuously performed, Anodizing treatment etc. are mentioned.

  As a roughening method, without roughening the surface of the conductive substrate, conductive or semiconductive powder is dispersed in the resin to form a layer on the surface of the conductive substrate. A method of roughening with particles dispersed in the layer may also be mentioned.

  In the roughening treatment by anodic oxidation, a metal (for example, aluminum) conductive substrate is used as an anode, and an oxide film is formed on the surface of the conductive substrate by anodizing in an electrolyte solution. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores of the oxide film are blocked by the volume expansion due to the hydration reaction in pressurized water vapor or boiling water (a metal salt such as nickel may be added) against the porous anodic oxide film, and more stable hydration oxidation It is preferable to perform a sealing treatment for changing to a product.

  The thickness of the anodized film is preferably, for example, 0.3 μm or more and 15 μm or less. When this film thickness is within the above range, the barrier property against implantation tends to be exhibited, and the increase in residual potential due to repeated use tends to be suppressed.

The conductive substrate may be treated with an acidic treatment liquid or boehmite treatment.
The treatment with the acidic treatment liquid is performed as follows, for example. First, an acidic treatment liquid containing phosphoric acid, chromic acid and hydrofluoric acid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is, for example, in the range of 10% by mass to 11% by mass of phosphoric acid, in the range of 3% by mass to 5% by mass of chromic acid, The concentration of these acids is preferably in the range of 13.5% by mass or more and 18% by mass or less. The treatment temperature is preferably 42 ° C. or higher and 48 ° C. or lower, for example. The film thickness is preferably from 0.3 μm to 15 μm.

  The boehmite treatment is performed, for example, by immersing in pure water of 90 ° C. or higher and 100 ° C. or lower for 5 minutes to 60 minutes, or by contacting with heated steam of 90 ° C. or higher and 120 ° C. or lower for 5 minutes to 60 minutes. The film thickness is preferably 0.1 μm or more and 5 μm or less. This may be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

(Undercoat layer)
As described above, the undercoat layer includes a binder resin, metal oxide particles, an anthraquinone derivative on the surface of the metal oxide particles, and an electron transport material represented by the general formula (1). Other components may be included as necessary.

Examples of the binder resin used for the undercoat layer include acetal resins (eg, polyvinyl butyral), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, and unsaturated polyesters. Resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, urea resin, phenol resin, phenol-formaldehyde resin, melamine resin, Known polymer compounds such as urethane resin, alkyd resin, epoxy resin; zirconium chelate compound; titanium chelate compound; aluminum chelate compound; titanium alkoxide compound ; Organic titanium compounds; known materials silane coupling agent, and the like.
Examples of the binder resin used for the undercoat layer include a charge transport resin having a charge transport group, a conductive resin (for example, polyaniline) and the like.

Among these, as the binder resin used for the undercoat layer, a resin insoluble in the upper coating solvent is preferable, and in particular, a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, and an unsaturated polyester. Thermosetting resins such as resins, alkyd resins, and epoxy resins; at least one resin selected from the group consisting of polyamide resins, polyester resins, polyether resins, methacrylic resins, acrylic resins, polyvinyl alcohol resins, and polyvinyl acetal resins; Resins obtained by reaction with curing agents are preferred.
When these binder resins are used in combination of two or more, the mixing ratio is set as necessary.

・ Metal oxide particles (inorganic particles)
In this embodiment, metal oxide particles are included as inorganic particles in the undercoat layer.
Examples of the metal oxide particles include particles of antimony oxide, indium oxide, tin oxide, titanium oxide, zinc oxide, zirconium oxide, and the like.
Among these, as the metal oxide particles, tin oxide, titanium oxide, and zinc oxide particles are preferable from the viewpoint of fine line reproducibility and suppression of increase in residual potential.

As the metal oxide particles, a conductive powder having a particle size of 100 nm or less, particularly 10 nm or more and 100 nm or less is preferably used. The particle size here means an average primary particle size. The average primary particle size of the metal oxide particles is a value observed and measured by SEM (scanning electron microscope).
When the particle diameter of the metal oxide particles is 10 nm or more, the surface area of the metal oxide particles does not become too large, and the occurrence of unevenness in the dispersion is suppressed. On the other hand, when the particle size of the metal oxide particles is 100 nm or less, secondary particles or higher order particles are effectively suppressed from having a particle size of about 1 μm. A portion where oxide particles are present and a portion where oxide particles are not present, that is, a so-called sea-island structure, is suppressed, and generation of image quality defects such as uneven halftone density is suppressed.

In addition, the specific surface area by the BET method of the metal oxide particles is, for example, preferably 10 m ² / g or more.
Moreover, the volume average particle diameter of the metal oxide particles is, for example, preferably from 50 nm to 2000 nm (preferably from 60 nm to 1000 nm).

The metal oxide particles preferably have a powder resistance of 10 ⁴ Ω · cm to 10 ¹⁰ Ω · cm. As a result, it becomes easy for the undercoat layer to obtain an appropriate impedance at a frequency corresponding to the electrophotographic process speed.

The metal oxide particles are preferably surface-treated with at least one coupling agent for the purpose of improving various properties such as dispersibility.
The coupling agent may be at least one selected from silane coupling agents, titanate coupling agents, and aluminate coupling agents.
Specific examples of the coupling agent include vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid. Xylpropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Silane coupling agents such as ethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, acetoalkoxyaluminum diisopropyl Rate etc. Examples include, but are not limited to, aluminate coupling agents, isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate), titanate coupling agents such as isopropyl tri (N-aminoethyl-aminoethyl) titanate, and the like. It is not a thing. Moreover, you may use these coupling agents in mixture of 2 or more types.

  The treatment amount of the coupling agent is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.3% by mass or more and 2.0% by mass or less, more preferably, based on the metal oxide particles. It is 0.5 mass% or more and 1.5 mass% or less.

In addition, the processing amount of a coupling agent is measured as follows.
There are analysis methods such as FT-IR method, 29Si solid state NMR method, thermal analysis, XPS, etc., but FT-IR method is the simplest. In the FT-IR method, the normal KBr tablet method or the ATR method may be used. A small amount of the treated metal oxide particles are mixed with KBr and the FT-IR is measured to measure the throughput of the coupling agent.

  The metal oxide particles may be subjected to heat treatment after the surface treatment with the above-mentioned coupling agent in order to improve the environmental dependency of the resistance value. The heat treatment temperature is preferably, for example, 150 ° C. or more and 300 ° C. or less, and the treatment time is 30 minutes or more and 5 hours or less.

The content of the metal oxide particles is desirably 30% by mass or more and 85% by mass or less, and more desirably 40% by mass or more and 80% by mass or less with respect to the entire undercoat layer, from the viewpoint of maintaining electrical characteristics.
In addition, only 1 type may be used for a metal oxide particle, and 2 or more types from which a material, a particle size, surface treatment, etc. differ may be used together.

Anthraquinone derivative Examples of the anthraquinone derivative on the surface of the metal oxide particle include, for example, an anthraquinone skeleton and a material that chemically reacts with the surface of the metal oxide particle, or an anthraquinone skeleton, and a metal oxide. Examples include materials that adsorb on the surface of particles.
Specific examples of the anthraquinone derivative include, for example, hydroxyanthraquinone compounds, aminoanthraquinone compounds, aminohydroxyanthraquinone compounds, and more specifically, for example, anthraquinone, alizarin, quinizarin, anthralfin, and purpurin. .

  The anthraquinone derivative is preferably an anthraquinone derivative represented by the following general formula (11) or the following general formula (12) from the viewpoint of material availability and electron transport capability.

In general formula (11), n1 and n2 each independently represent an integer of 0 or more and 3 or less. However, at least one of n1 and n2 represents an integer of 1 or more and 3 or less (that is, n1 and n2 do not simultaneously represent 0). m1 and m2 each independently represents an integer of 0 or 1. R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

In general formula (12), n1, n2, n3, and n4 each independently represent an integer of 0 or more and 3 or less. However, at least one of n1 and n2 represents an integer of 1 or more and 3 or less (that is, n1 and n2 do not simultaneously represent 0). At least one of n3 and n4 represents an integer of 1 or more and 3 or less (that is, n3 and n4 do not represent 0 at the same time). m1 and m2 each independently represents an integer of 0 or 1. R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. r represents an integer of 1 or more and 10 or more.

Among the anthraquinone derivatives represented by the general formula (11), a compound in which R ¹ and R ² each independently represents an alkoxy group having 1 to 10 carbon atoms is preferable from the viewpoint of fine line reproducibility and suppression of increase in residual potential.

Here, the general formula (11) was ^{R 1} and ^{R 2} carbon atoms represents 1 to 10 alkyl group, and as a general formula (12) an alkyl group having 1 to 10 carbon atoms which is medium ^{R 1} and ^{R 2} represents May be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The general formula (11) was ^{R 1} and ^{R 2} represents the number 1 to 10 alkoxy group carbon, and the general formula (12) was ^{R 1} and alkoxy group having 1 to 10 carbon atoms represented ^{by R 2,} a straight Either chain or branched may be used, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an octoxy group. The alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms.

Here, specific examples of the anthraquinone derivative represented by the general formula (11) are shown in the following (1-1) to (1-11), and specific examples of the compound represented by the general formula (12) are shown in the following (1-12). To (1-13). However, it is not limited to these.
In addition, the following specific example compound is called "exemplary compound" below, for example, if it is a compound of the following (1-1), it will be called "exemplary compound (1-1)."
In the exemplified compounds below, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents an n-butyl group, and “C ₈ H ₁₇ ” represents an n-octyl group.

  Specific examples of anthraquinone derivatives other than the anthraquinone derivative represented by the general formula (11) or the general formula (12) are shown in the following (1-14). However, it is not limited to these.

These anthraquinone derivatives may be used alone or in combination of two or more.
Further, the anthraquinone derivative and an electron accepting compound other than the anthraquinone derivative may be used in combination. As the electron-accepting compound other than the anthraquinone derivative, for example, an electron-accepting compound having an acidic group is applied. Examples of the acidic group include a hydroxyl group (phenolic hydroxyl group), a carboxyl group, and a sulfonyl group.

Specific examples of electron accepting compounds other than anthraquinone derivatives include, for example, quinones other than anthraquinones, coumarins, phthalocyanines, triphenylmethanes, anthocyanins, flavones, fullerenes, ruthenium complexes, xanthenes, benzoxazines. And porphyrin compounds.
Specific examples of the electron-accepting compound that can be used in combination with the anthraquinone derivative are shown in the following (1-15) to (1-22).

The content of all electron-accepting compounds including anthraquinone derivatives is determined by the surface area of metal oxide particles and the content of metal oxide particles that are a chemical reaction or adsorption partner, and the electron transport ability of each material. Is preferably in the range of 0.01% by mass or more and 20% by mass or less, more preferably in the range of 0.1% by mass or more and 10% by mass or less with respect to the entire undercoat layer.
When the content of the electron-accepting compound is 0.1% by mass or more, the effect of the acceptor substance is efficiently expressed. In addition, when the content of the electron-accepting compound is 20% by mass or less, aggregation of the metal oxide particles is suppressed, and uneven distribution in the undercoat layer of the metal oxide particles is suppressed, which is favorable. A conductive path is formed.

  Moreover, the ratio of the anthraquinone derivative in the contained electron-accepting compound is desirably 50% by mass or more, and is desirably as close to 100% by mass.

  Examples of the method for allowing the anthraquinone derivative to exist on the surface of the metal oxide particles (that is, the method of chemically reacting with the surface of the metal oxide particles, or the method of physically adsorbing the metal oxide particles on the surface of the metal oxide particles) Method or wet method.

  In the dry method, for example, while stirring the metal oxide particles with a mixer having a large shearing force, an anthraquinone derivative dissolved directly or in an organic solvent is dropped and sprayed with dry air or nitrogen gas to oxidize the anthraquinone derivative. It is a method of making it exist on the surface of an object particle. When the anthraquinone derivative is dropped or sprayed, it is preferably performed at a temperature not higher than the boiling point of the solvent. After dripping or spraying the anthraquinone derivative, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics.

  In the wet method, for example, the anthraquinone derivative is added while the metal oxide particles are dispersed in the solvent by stirring, ultrasonic wave, sand mill, attritor, ball mill, etc. In this method, the derivative is present on the surface of the metal oxide particles. The solvent removal method is distilled off by filtration or distillation, for example. After removing the solvent, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics. In the wet method, the water content of the metal oxide particles may be removed before the anthraquinone derivative is added. Examples thereof include a method of removing by stirring and heating in a solvent, and a method of removing by azeotropic distillation with a solvent. Can be mentioned.

  The treatment for allowing the anthraquinone derivative to exist on the surface of the metal oxide particles may be performed before or after the surface treatment with the surface treatment agent is performed on the metal oxide particles, or may be performed simultaneously with the surface treatment with the surface treatment agent. .

-Electron transport material represented by the general formula (1) As described above, the undercoat layer includes an electron transport material represented by the following general formula (1).

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, Or R ¹⁸ represents an alkyl group, an aryl group, or an aralkyl group.

In the general formula (1), examples of the halogen atom represented by R ^{11 to} R ¹⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In general formula (1), examples of the alkyl group represented by R ^{11 to} R ¹⁷ include linear or branched alkyl groups having 1 to 4 carbon atoms (preferably 1 to 3 carbon atoms), Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

In the general formula (1), examples of the alkoxy group represented by R ^{11 to} R ¹⁷ include an alkoxy group having 1 to 4 carbon atoms (preferably 1 to 3 carbon atoms). Specifically, a methoxy group, An ethoxy group, a propoxy group, a butoxy group, etc. are mentioned.

In the general formula (1), examples of the aryl group represented by R ^{11 to} R ¹⁷ include a phenyl group and a tolyl group.
In the general formula (1), examples of the aralkyl group represented by R ^{11 to} R ¹⁷ include a benzyl group.
Among these, a phenyl group is preferable.

In the general formula (1), examples of the alkyl group represented by R ¹⁸ include a linear alkyl group having 5 to 10 carbon atoms and a branched alkyl group having 5 to 10 carbon atoms.
Examples of the linear alkyl group having 5 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -An octyl group, n-nonyl group, n-decyl group, etc. are mentioned.
Examples of the branched alkyl group having 5 to 10 carbon atoms include isopropyl group,
Isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, sec-hexyl group, tert-hexyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, Examples include isooctyl group, sec-octyl group, tert-octyl group, isononyl group, sec-nonyl group, tert-nonyl group, isodecyl group, sec-decyl group, tert-decyl group and the like.

In the general formula (1), examples of the aryl group represented by R ¹⁸ include a phenyl group, a methylphenyl group, and a dimethylphenyl group.

In general formula (1), examples of the aralkyl group represented by R ¹⁸ include a group represented by —R ¹⁹ —Ar. However, R ¹⁹ represents an alkylene group, and Ar represents an aryl group.
Examples of the alkylene group represented by R ¹⁹ include a linear or branched alkylene group having 1 or more carbon atoms, such as a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, Examples include sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, tert-pentylene group and the like.
Examples of the aryl group represented by Ar include a phenyl group, a methylphenyl group, and a dimethylphenyl group.

Specific examples of the aralkyl group represented by R ¹⁸ in the general formula (1) include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a phenylethyl group, a methylphenylethyl group, a phenylpropyl group, and a phenylbutyl group. .

As an electron transport material represented by the general formula (1), an electron transport material in which R ¹⁸ represents a linear or branched alkyl group having 5 to 10 carbon atoms from the viewpoint of suppressing image sticking on the surface of the photoreceptor. In particular, R ^{11 to} R ¹⁷ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹⁸ represents a linear or branched alkyl group having 5 to 10 carbon atoms. Electron transport materials are preferred.

  Hereinafter, although the exemplary compound of the electron transport material represented by the general formula (1) is shown, it is not limited thereto. In addition, the following exemplary compound numbers are described as an exemplary compound (11-number) below. Specifically, for example, Exemplified Compound 15 is represented below as “Exemplified Compound (11-15)”.

In addition, the abbreviations in the above exemplary compounds have the following meanings.
・ Ph: Phenyl group

The content of the electron transport material represented by the general formula (1) with respect to the entire undercoat layer is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less.
When the content of the electron transport material represented by the general formula (1) is within the above range, image sticking on the surface of the photoreceptor is suppressed as compared with the case where the content is less than the above range, and the content is larger than the above range. There is an advantage that the potential stability is superior.

The undercoat layer may contain various additives for improving electrical characteristics, improving environmental stability, and improving image quality.
Additives include known materials such as electron transport pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents. It is done. The silane coupling agent is used for the surface treatment of the inorganic particles as described above, but may be further added to the undercoat layer as an additive.

  Examples of the silane coupling agent as the additive 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, 3-chloropropyltrimethoxysilane and the like can be mentioned.

  Examples of the zirconium chelate compound include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, Zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of titanium chelate compounds include tetraisopropyl titanate, tetranormal 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 triethanolamate, polyhydroxy titanium stearate and the like.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.

  These additives may be used alone or as a mixture or polycondensate of a plurality of compounds.

The undercoat layer preferably has a Vickers hardness of 35 or more.
The surface roughness (ten-point average roughness) of the undercoat layer is adjusted from 1 / 4n (n is the refractive index of the upper layer) to 1 / 2λ of the exposure laser wavelength λ used to suppress moire images. It should be done.
Resin particles or the like may be added to the undercoat layer for adjusting the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished for adjusting the surface roughness. Examples of the polishing method include buffing, sandblasting, wet honing, and grinding.

  There is no particular limitation on the formation of the undercoat layer, and a well-known formation method is used. For example, a coating film for forming an undercoat layer in which the above components are added to a solvent is formed, and the coating film is dried. And heating as necessary.

Solvents for preparing the coating solution for forming the undercoat layer include known organic solvents such as alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, ketone alcohol solvents, ether solvents. Examples include solvents and ester solvents.
Specific examples of these solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Examples include ordinary organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.

  Examples of the dispersion method of the inorganic particles when preparing the coating liquid for forming the undercoat layer include known methods such as a roll mill, a ball mill, a vibration 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 conductive substrate include, for example, a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. The usual methods, such as these, are mentioned.

  The thickness of the undercoat layer is, for example, preferably set in the range of 15 μm or more, more preferably 20 μm or more and 50 μm or less.

(Middle layer)
Although illustration is omitted, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer.
An intermediate | middle layer is a layer containing resin, for example. Examples of the resin used for the intermediate layer include an acetal resin (for example, polyvinyl butyral), polyvinyl alcohol resin, polyvinyl acetal resin, casein resin, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, Polymer compounds such as polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, and the like can be given.
The intermediate layer may be a layer containing an organometallic compound. Examples of the organometallic compound used for the intermediate layer include organometallic compounds containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon.
The compounds used for these intermediate layers may be used alone or as a mixture or polycondensate of a plurality of compounds.

  Among these, the intermediate layer is preferably a layer containing an organometallic compound containing a zirconium atom or a silicon atom.

The formation of the intermediate layer is not particularly limited, and a well-known formation method is used. For example, a coating film of an intermediate layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried and necessary. It is performed by heating according to.
As the coating method for forming the intermediate layer, usual methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method, and a curtain coating method are used.

  For example, the thickness of the intermediate layer is preferably set in a range of 0.1 μm to 3 μm. An intermediate layer may be used as the undercoat layer.

(Charge generation layer)
The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. The charge generation layer may be a vapor deposition layer of a charge generation material. The vapor-deposited layer of the charge generation material is suitable when an incoherent light source such as an LED (Light Emitting Diode) or an organic EL (Electro-Luminescence) image array is used.

  Examples of the charge generating material include azo pigments such as bisazo and trisazo; fused aromatic pigments such as dibromoanthanthrone; perylene pigments; pyrrolopyrrole pigments; phthalocyanine pigments; zinc oxide;

  Among these, in order to cope with near-infrared laser exposure, it is preferable to use a metal phthalocyanine pigment or a metal-free phthalocyanine pigment as the charge generation material. Specifically, for example, hydroxygallium phthalocyanine disclosed in JP-A-5-263007, JP-A-5-279591, etc .; chlorogallium phthalocyanine disclosed in JP-A-5-98181; More preferred are dichlorotin phthalocyanines disclosed in JP-A No. 140472, JP-A No. 5-140473 and the like; and titanyl phthalocyanine disclosed in JP-A No. 4-189873.

  On the other hand, in order to cope with laser exposure in the near-ultraviolet region, as the charge generation material, condensed aromatic pigments such as dibromoanthanthrone; thioindigo pigments; porphyrazine compounds; zinc oxide; trigonal selenium; Bisazo pigments and the like disclosed in 2004-78147 and JP-A-2005-181992 are preferred.

  The above-described charge generation material may also be used in the case of using an incoherent light source such as an LED having a central wavelength of light emission of 450 nm to 780 nm and an organic EL image array. However, from the viewpoint of resolution, the photosensitive layer is 20 μm or less. When the thin film is used, the electric field strength in the photosensitive layer is increased, and a charge reduction due to charge injection from the base material, so-called image defects called black spots are likely to occur. This becomes conspicuous when a charge generating material that easily generates a dark current is used in a p-type semiconductor such as trigonal selenium or a phthalocyanine pigment.

On the other hand, when an n-type semiconductor such as a condensed ring aromatic pigment, perylene pigment, azo pigment or the like is used as the charge generation material, dark current hardly occurs and even a thin film can suppress image defects called black spots. . Examples of the n-type charge generation material include compounds (CG-1) to (CG-27) described in paragraphs [0288] to [0291] of JP2012-155282A. It is not limited.
The n-type determination is performed by using a time-of-flight method that is usually used, and is determined by the polarity of the flowing photocurrent, and an n-type is more likely to flow electrons as carriers than holes.

The binder resin used for the charge generation layer is selected from a wide range of insulating resins, and the binder resin is selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinyl anthracene, polyvinyl pyrene, and polysilane. You may choose.
As the binder resin, for example, polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol and aromatic divalent carboxylic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, Examples thereof include polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, and the like. Here, “insulating” means that the volume resistivity is 10 ¹³ Ωcm or more.
These binder resins are used singly or in combination of two or more.

  The mixing ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass ratio.

  In addition, the charge generation layer may contain a known additive.

  The formation of the charge generation layer is not particularly limited, and a known formation method is used. For example, a coating film of a charge generation layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried. And heating as necessary. The charge generation layer may be formed by vapor deposition of a charge generation material. Formation of the charge generation layer by vapor deposition is particularly suitable when a condensed ring aromatic pigment or perylene pigment is used as the charge generation material.

  Solvents for preparing the charge generation layer forming coating solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-acetate. -Butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like. These solvents are used alone or in combination of two or more.

Examples of a method for dispersing particles (for example, a charge generation material) in a coating solution for forming a charge generation layer include, for example, a media disperser such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, a stirring, an ultrasonic disperser, etc. Medialess dispersers such as roll mills and high-pressure homogenizers are used. Examples of the high-pressure homogenizer include a collision method in which a dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high pressure state, and a penetration method in which a fine flow path is dispersed in a high pressure state.
In this dispersion, it is effective that the average particle size of the charge generation material in the coating solution for forming the charge generation layer is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. .

  Examples of methods for applying the charge generation layer forming coating solution on the undercoat layer (or on the intermediate layer) include blade coating, wire bar coating, spray coating, dip coating, bead coating, and air knife coating. And usual methods such as a curtain coating method.

  The film thickness of the charge generation layer is, for example, preferably set in the range of 0.1 μm to 5.0 μm, more preferably 0.2 μm to 2.0 μm.

(Charge transport layer)
The charge transport layer is, for example, a layer containing a charge transport material and a binder resin. The charge transport layer may be a layer containing a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone compounds; benzophenone compounds A cyanovinyl compound; an electron transporting compound such as an ethylene compound; Examples of the charge transporting material include hole transporting compounds such as triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, and hydrazone compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto.

  As the charge transport material, from the viewpoint of charge mobility, a triarylamine derivative represented by the following structural formula (a-1) and a benzidine derivative represented by the following structural formula (a-2) are preferable.

In Structural Formula (a-1), Ar ^T1 , Ar ^T2 , and Ar ^T3 are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ^T4 ) ═C (R ^T5 ) (R ^T6), or _{-C 6 H 4 -CH = CH-} CH = C (R T7) shows the ^{(R T8).} R ^T4 , R ^T5 , R ^T6 , R ^T7 , and R ^T8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Examples of the substituent for each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Examples of the substituent of each group also include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

In Structural Formula (a-2), R ^T91 and R ^T92 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ^T101 , R ^T102 , R ^T111 and R ^T112 are each independently ^substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. A substituted amino group, a substituted or unsubstituted aryl group, —C (R ^T12 ) ═C (R ^T13 ) (R ^T14 ), or —CH═CH— ^CH═C (R ^T15 ) (R ^T16 ), R ^T12 , R ^T13 , R ^T14 , R ^T15 and R ^T16 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Tm1, Tm2, Tn1, and Tn2 each independently represent an integer of 0 or more and 2 or less.
Examples of the substituent for each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Examples of the substituent of each group also include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

Here, among the triarylamine derivative represented by the structural formula (a-1) and the benzidine derivative represented by the structural formula (a-2), in particular, “—C ₆ H ₄ —CH═CH—CH═ Triarylamine derivatives having “C (R ^T7 ) (R ^T8 )” and benzidine derivatives having “—CH═CH— ^CH═C (R ^T15 ) (R ^T16 )” are preferable from the viewpoint of charge mobility.

  As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane are used. In particular, polyester-based polymer charge transport materials disclosed in JP-A-8-176293, JP-A-8-208820 and the like are particularly preferable. The polymer charge transport material may be used alone or in combination with a binder resin.

The binder resin used for the charge transport layer is polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N -Vinylcarbazole, polysilane, etc. are mentioned. Among these, as the binder resin, a polycarbonate resin or a polyarylate resin is preferable. These binder resins are used alone or in combination of two or more.
The mixing ratio of the charge transport material and the binder resin is preferably 10: 1 to 1: 5 by mass ratio.

  In addition, the charge transport layer may contain a known additive.

  The formation of the charge transport layer is not particularly limited, and a known formation method is used. For example, a coating film of a charge transport layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried. This is done by heating as necessary.

  Solvents for preparing the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ketones such as acetone and 2-butanone; methylene chloride, chloroform and ethylene chloride. Halogenated aliphatic hydrocarbons: Usual organic solvents such as cyclic or linear ethers such as tetrahydrofuran and ethyl ether. These solvents are used alone or in combination of two or more.

  Coating methods for applying the charge transport layer forming coating solution on the charge generation layer include blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method may be mentioned.

  The thickness of the charge transport layer is, for example, preferably set in the range of 5 μm to 50 μm, more preferably 10 μm to 30 μm.

(Protective layer)
The protective layer is provided on the photosensitive layer as necessary. The protective layer is provided, for example, for the purpose of preventing chemical change of the photosensitive layer during charging or further improving the mechanical strength of the photosensitive layer.
Therefore, it is preferable to apply a layer composed of a cured film (crosslinked film) as the protective layer. Examples of these layers include the layers shown in 1) or 2) below.

1) A layer composed of a cured film of a composition containing a reactive group-containing charge transporting material having a reactive group and a charge transporting skeleton in the same molecule (that is, a polymer or cross-linking of the reactive group-containing charge transporting material) Layer containing body)
2) a layer composed of a cured film of a composition comprising a non-reactive charge transport material and a reactive group-containing non-charge transport material having a reactive group and having no charge transport skeleton (that is, A layer comprising a non-reactive charge transport material and a polymer or a cross-linked product of the reactive group-containing non-charge transport material)

The reactive group of the reactive group-containing charge transport material includes a chain polymerizable group, an epoxy group, —OH, —OR [wherein R represents an alkyl group], —NH ₂ , —SH, —COOH, —SiR. ^Q1 _3-Qn (OR ^Q2 ) _Qn [wherein R ^Q1 represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and R ^Q2 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. _Qn represents an integer of 1 to 3], and the like, and other well-known reactive groups.

  The chain polymerizable group is not particularly limited as long as it is a functional group capable of radical polymerization. For example, it is a functional group having a group containing at least a carbon double bond. Specific examples include groups containing at least one selected from a vinyl group, vinyl ether group, vinyl thioether group, styryl group, acryloyl group, methacryloyl group, and derivatives thereof. Among them, the chain polymerizable group is preferably a group containing at least one selected from a vinyl group, a styryl group, an acryloyl group, a methacryloyl group, and derivatives thereof because of its excellent reactivity. .

  The charge transporting skeleton of the reactive group-containing charge transporting material is not particularly limited as long as it is a known structure in an electrophotographic photoreceptor, and examples thereof include triarylamine compounds, benzidine compounds, hydrazone compounds, and the like. And a structure conjugated from a nitrogen-containing hole transporting compound and conjugated with a nitrogen atom. Among these, a triarylamine skeleton is preferable.

  The reactive group-containing charge transport material having a reactive group and a charge transport skeleton, a non-reactive charge transport material, and a reactive group-containing non-charge transport material may be selected from well-known materials.

  The protective layer preferably contains fluorine-containing resin particles and a fluorinated alkyl group-containing copolymer from the viewpoint of wear resistance, and more preferably contains a charge transport material. Further, as the charge transport material, a reactive charge transport material (that is, the reactive group-containing charge transport material) is desirable. That is, the protective layer is composed of a charge transportable cured film containing a polymer (or a crosslinked product) of a reactive charge transport material, fluorine-containing resin particles, and a fluorinated alkyl group-containing copolymer. desirable.

Reactive charge transport material Among the reactive group-containing charge transport materials, the reactive charge transport material is —OH, —OR ¹⁰ (R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms), —NH _2. , —SH, —COOH, and at least one of charge transport materials having at least one substituent selected from a group having a functional group having a carbon double bond. In particular, the reactive charge transport material includes at least two substituents selected from —OH, —OR ¹⁰ , —NH ₂ , —SH, —COOH, and a group having a functional group having a carbon double bond. A charge transport material having three more is desirable. As described above, the reactive functional group (substituent) increases in the charge transport material, so that the crosslink density is increased and a cross-linked film having higher strength is easily obtained.

The reactive charge transport material is preferably a compound represented by the following general formula (C).
Fr- (D) _n3 ... General formula (C)
In general formula (C), Fr represents an organic group (charge transport skeleton) derived from a compound having a charge transporting ability, and D represents — (— R ¹¹ —Z) _n1 (R ¹² ) _n2 —Y (provided that , R ¹¹ and R ¹² each independently represents a linear or branched alkylene group having 1 to 5 carbon atoms, Z represents an oxygen, NH or sulfur atom, Y represents —OH, —OR ¹⁰ ( R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms), —NH ₂ , —SH or —COOH, n1 represents 0 or 1, n2 represents 0 or 1, and carbon double A group having a functional group having a bond is represented, and n3 represents an integer of 1 or more and 4 or less.

  Examples of the group having a functional group having a carbon double bond represented by D include acryloyl group, methacryloyl group, styryl group (vinylphenyl group), allyl group, vinyl group, vinyl ether group, allyl vinyl ether group, and the like. And a group having at least one selected from the derivatives. In particular, a group having these groups at the terminal is desirable.

  In general formula (C), an arylamine derivative is preferably exemplified as the compound having charge transporting ability in the “organic group derived from the compound having charge transporting ability” represented by Fr. Preferred examples of the arylamine derivative include a triphenylamine derivative and a tetraphenylbenzidine derivative.

  The compound represented by the general formula (C) is preferably a compound represented by the following general formula (C-1).

In general formula (C-1), Ar ^C1 , Ar ^C2 , Ar ^C3 and Ar ^C4 each independently represent a substituted or unsubstituted aryl group, and may be the same or different.
Ar ^C5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group.

D represents — (— R ¹¹ —Z) _n1 (R ¹² ) _n2 —Y (where R ¹¹ and R ¹² each independently represents a linear or branched alkylene group having 1 to 5 carbon atoms; Z represents an oxygen, NH, or sulfur atom, Y represents —OH, —OR ¹⁰ (R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms), —NH ₂ , —SH, or —COOH, n 1 Represents 0 or 1, and n2 represents 0 or 1.), or — (CH ₂ ) _d — (O—CH ₂ —CH ₂ ) _f —O—CO—C (R ′) ═CH ₂ (provided that , R ′ represents a hydrogen atom or a methyl group, d represents an integer of 1 to 5, and f represents 0 or 1. e represents 0 or 1 independently at each position, and the total number of D is 1 or more and 4 or less. k represents 0 or 1;

Regarding Ar ^{C1 to} Ar ^C5 , the substituent in the substituted aryl group and the substituted arylene group, other than D, is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted And an aryl group having 6 to 10 carbon atoms.

In the general formula (C-1), when D is “— (— R ¹¹ —Z) _n1 (R ¹² ) _n2 —Y”, R ¹¹ and R ¹² are each independently a straight chain having 1 to 5 carbon atoms. A branched or branched alkylene group, n1 is preferably 1, n2 is preferably 1, and Z is preferably oxygen.

  In the general formula (C-1), the total number of D corresponds to n3 in the general formula (C), preferably 2 or more and 4 or less, and more preferably 3 or more and 4 or less. When the total number of D is 2 or more and 4 or less, preferably 3 or more and 4 or less in one molecule, the crosslinking density increases and a crosslinked film with higher strength can be obtained.

In general formula (C-1), Ar ^C1 , Ar ^C2 , Ar ^C3 and Ar ^C4 are preferably any of the following formulas (1) to (7). The following formulas (1) to (7) are shown together with “— (D) _e ” which can be linked to each of Ar ^C1 , Ar ^C2 , Ar ^C3 and Ar ^C4 .

In the formulas (1) to (7), R ¹³ is phenyl substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents one selected from the group consisting of a group, an unsubstituted phenyl group, and an aralkyl group having 7 to 10 carbon atoms, wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, 1 to 4 carbon atoms An alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. 1 represents one selected from the group, Ar represents a substituted or unsubstituted arylene group, D and e are the same as “D” and “e” in formula (C-1), and s is 0 or 1 The table , T is an integer of 1 to 3.

  Here, as Ar in Formula (7), what is represented by following formula (8) or (9) is desirable.

In Formula (8) or (9), R ¹⁷ and R ¹⁸ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. This represents one selected from the group consisting of a substituted phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and t represents an integer of 1 to 3.

  Z ′ in the formula (7) is preferably represented by any one of the following formulas (10) to (17).

In formulas (10) to (17), R ¹⁹ and R ²⁰ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It represents one selected from the group consisting of a substituted phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, W represents a divalent group, and q and r are respectively Represents an integer of 1 to 10, and t represents an integer of 1 to 3.

  W in the formulas (16) and (17) is preferably any one of divalent groups represented by the following (18) to (26). However, in formula (25), u represents an integer of 0 or more and 3 or less.

In the general formula (C-1), Ar ^C5 is an aryl group of the above formulas (1) to (7) exemplified in the description of Ar ^{C1 to} Ar ^C4 when k is 0, and when k is 1 Is an arylene group obtained by removing a hydrogen atom from the aryl groups of the above formulas (1) to (7).

  Specific examples of the compound represented by the general formula (C) include compounds i-1 to i-25, compounds ii-1 to ii-56, and iii-1 to iii described in JP2011-175038A. -19, iv-1 to iv-49, v-1 to v-3, vi-1 to vi-6, compound I-1 to compound I-31 described in JP 2011-112801 A, and JP Compound I-1 thru | or Compound I-34 as described in 2011-27808 gazette are mentioned.

The reactive charge transport material includes at least one of a reactive charge transport material having an alkoxy group and a reactive charge transport material having a hydroxyl group from the viewpoint of wear resistance, image quality characteristics, electrical characteristics, and the like of the electrophotographic photosensitive member. It is desirable. Furthermore, it is more desirable to include both a reactive charge transport material having an alkoxy group and a reactive charge transport material having a hydroxyl group.
The addition amount of the reactive charge transport material having an alkoxy group with respect to the total solid content of the outermost surface layer (protective layer 2C in the first embodiment) excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer is The content is preferably 10% by mass to 40% by mass, more preferably 10% by mass to 35% by mass, and particularly preferably 10% by mass to 30% by mass.

  Here, specific examples of the reactive charge transport material having a hydroxyl group and the reactive charge transport material having an alkoxy group among the compounds represented by the general formula (C-1) are given. However, it is not limited to the following.

  The content of the reactive charge transport material is, for example, 80 mass as a solid content concentration in the forming composition with respect to all the constituent components (solid content) excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer. % Or more, desirably 90% by mass or more, and more desirably 95% by mass or more.

Fluorine-containing resin particles The fluorine-containing resin particles are not particularly limited. For example, polytetrafluoroethylene (PTFE, also known as “tetrafluoroethylene resin”), perfluoroalkoxy fluororesin, polychlorotrifluoro Ethylene, polyvinylidene fluoride, polydichlorodifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene -Particles such as a perfluoroalkyl vinyl ether copolymer and a tetrafluoroethylene-perfluoroalkoxyethylene copolymer.

Among these, polytetrafluoroethylene and a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene are desirable from the viewpoint of wear resistance and cleaning properties of the electrophotographic photosensitive member.
Fluorine-containing resin particles may be used alone or in combination of two or more.

  The weight average molecular weight of the fluororesin constituting the fluorine-containing resin particles is, for example, preferably from 3000 to 5 million.

The average primary particle size of the fluorine-containing resin particles is desirably 0.05 μm or more and 10 μm or less, and more desirably 0.1 μm or more and 5 μm or less.
The average primary particle size of the fluorine-containing resin particles was measured using a laser diffraction particle size distribution measuring device LA-920 (manufactured by Horiba) and diluted in the same solvent as the dispersion in which the fluorine-containing resin particles were dispersed. Is a value measured at a refractive index of 1.35.

  Examples of commercially available fluorine-containing resin particles include the Lubron series (manufactured by Daikin Industries, Ltd.), the Teflon (registered trademark) series (manufactured by DuPont), and the Dinion series (manufactured by Sumitomo 3M).

  The content of the fluorine-containing resin particles is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and more preferably 3% with respect to the entire layer constituent (solid content). It is not less than 15% by mass.

-Fluorinated alkyl group-containing copolymer The fluorinated alkyl group-containing copolymer maintains the dispersion stability of the fluorine-containing resin particles. Examples of the fluorinated alkyl group-containing copolymer include fluorinated alkyl group-containing copolymers having repeating units represented by the following structural formula (E) and structural formula (F). The fluorinated alkyl group-containing copolymer is desirable from the viewpoint of improving the wear resistance and cleaning properties of the electrophotographic photoreceptor.

In the structural formula (E) and the structural formula (F), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or an alkyl group. X ′ represents an alkylene chain, a halogen-substituted alkylene chain, —S—, —O—, —NH—, or a single bond. Y ′ represents an alkylene chain, a halogen-substituted alkylene chain, — (C _z H _2z-1 (OH)) —, or a single bond. Q represents -O- or -NH-. g, h and i each independently represents an integer of 1 or more. p ′, q ′, r ′ and s ′ each independently represent 0 or an integer of 1 or more. t ′ represents an integer of 1 to 7. z represents an integer of 1 or more.

Here, as a group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ , a hydrogen atom, a methyl group and an ethyl group are desirable, and a methyl group is more desirable.

The alkylene chain represented by X ′ and Y ′ (unsubstituted alkylene chain, halogen-substituted alkylene chain) is preferably an alkylene chain having 1 to 10 carbon atoms.
Z in — (C _z H _2z-1 (OH)) — represented by Y ′ is preferably an integer of 1 or more and 10 or less.
p ′, q ′, r ′ and s ′ are each independently preferably 0 or an integer of 1 or more and 10 or less.

In the fluorinated alkyl group-containing copolymer, the content ratio of structural formula (E) to structural formula (F), that is, g: h is preferably 1: 9 to 9: 1, and 3: 7 to 7: 3. More desirable.
The fluorinated alkyl group-containing copolymer may further contain a repeating unit represented by the structural formula (G). The content of structural formula (G) is preferably the sum of the contents of structural formula (E) and structural formula (F), that is, the ratio of g + h, preferably 10: 0 to 7: 3 as g + h: j, 9: 1 To 7: 3 is more desirable.

In Structural Formula (G), R ¹⁰⁵ and R ¹⁰⁶ represent a hydrogen atom or an alkyl group. j represents an integer of 1 or more.

The group represented by R ¹⁰⁵ or R ¹⁰⁶ is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a methyl group.

  Commercially available fluorinated alkyl group-containing copolymers include, for example, GF300, GF400 (manufactured by Toagosei Co., Ltd.), Surflon series (manufactured by AGC Seikekikal Co., Ltd.), footent series (manufactured by Neos), and PF series (Kitamura Chemical). Co., Ltd.), Mega Fuck Series (manufactured by DIC), FC Series (manufactured by 3M), and the like.

  The fluoroalkyl group-containing copolymer may be used alone or in combination of two or more.

The weight average molecular weight of the fluorinated alkyl group-containing copolymer is, for example, 2000 or more and 250,000 or less, preferably 3000 or more and 150,000 or less, more preferably 10,000 or more and 100,000 or less, and further preferably 30000 or more and 100,000 or less. is there.
The weight average molecular weight of the fluorinated alkyl group-containing copolymer is measured by gel permeation chromatography (GPC).

The content of the fluorinated alkyl group-containing copolymer is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 7% by mass with respect to the mass of the fluorine-containing resin particles.
Further, the total content of the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer in the surface protective layer is desirably 1% by mass or more and 40% by mass or less with respect to the layer total constituent components (solid content total amount). More preferably, it is more than 20% by mass.

-Guanamine compound, melamine compound In order to further improve the abrasion resistance and electrical stability of the electrophotographic photosensitive member, the composition for forming the protective layer includes a compound having a guanamine structure (hereinafter referred to as "guanamine compound"). And at least one selected from a compound having a melamine structure (hereinafter also referred to as “melamine compound”) may be included. That is, the protective layer may include a cross-linked product (cross-linked product) of a reactive charge transport material and at least one selected from a guanamine compound and a melamine compound.

  A guanamine compound is a compound having a guanamine skeleton (structure), and examples thereof include acetoguanamine, benzoguanamine, formoguanamine, steroguanamine, spiroguanamine, and cyclohexylguanamine.

  The guanamine compound is particularly preferably at least one of a compound represented by the following general formula (H) and a multimer thereof. Here, the multimer is an oligomer polymerized using the compound represented by the general formula (H) as a structural unit, and the degree of polymerization thereof is, for example, 2 or more and 200 or less (desirably 2 or more and 100 or less). The compound represented by the general formula (H) or a multimer thereof may be used alone or in combination of two or more. When the compound represented by the general formula (H) is used as a mixture of two or more kinds or used as a multimer (oligomer) having the structural unit as a structural unit, the solubility in a solvent is improved.

In General Formula (H), R ^H1 represents a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, or a substituted or unsubstituted carbon. This represents an alicyclic hydrocarbon group having a number of 4 or more and 10 or less. R ^{H2 to} R ^H5 each independently represents a hydrogen atom, —CH ₂ —OH, or —CH ₂ —O—R ^H6 . R ^H6 represents a linear or branched alkyl group having 1 to 10 carbon atoms.

When R ^H1 is a linear or branched alkyl group having 1 to 10 carbon atoms, the carbon number is preferably 1 to 8 and more preferably 1 to 5 carbon atoms.
When R ^H1 is a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, it preferably has 6 to 8 carbon atoms. Examples of the substituent when the phenyl group is substituted include a methyl group, an ethyl group, and a propyl group.

When R ^H1 is a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 10 carbon atoms, it preferably has 5 to 8 carbon atoms. Examples of the substituent when the alicyclic hydrocarbon group is substituted include a methyl group, an ethyl group, and a propyl group.
The linear or branched alkyl group having 1 to 10 carbon atoms represented by R ^H6 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms (for example, methyl Group, ethyl group, butyl group, etc.).

In the compound represented by the general formula (H), it is particularly desirable that R ^H1 is a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and R ^{H2 to} R ^H5 are each independently —CH ₂ —O—. a compound represented by R ^{H6, R H6} is a methyl group or an n- butyl group.
The compound represented by the general formula (H) is synthesized by, for example, a known method (for example, “Experimental Chemistry Course”, 4th edition, Volume 28, page 430) using guanamine and formaldehyde.

  Although the specific example of a compound represented by general formula (H) below is shown, it is not necessarily restricted to these. Moreover, although the following specific examples show a monomer, the multimer (oligomer) which uses these as a structural unit may be sufficient.

  Examples of commercially available compounds represented by the general formula (H) include superbecamine (R) L-148-55, superbecamine (R) 13-535, and superbecamine (R) L-145. 60, Superbecamine (R) TD-126 (manufactured by DIC Corporation), Nicarak BL-60, Nicarac BX-4000 (manufactured by Nippon Carbide Corporation), and the like.

  The compound represented by the general formula (H) (including multimers) is dissolved in an appropriate solvent such as toluene, xylene or ethyl acetate after synthesis or after purchasing a commercial product in order to remove the influence of residual catalyst. It may be washed with distilled water, ion exchange water or the like, or may be removed by treatment with an ion exchange resin.

  The melamine compound is a compound having a melamine skeleton (structure), and is particularly preferably at least one of a compound represented by the following general formula (J) and a multimer thereof. Here, the multimer is an oligomer polymerized using the compound represented by the general formula (J) as a structural unit, and the degree of polymerization thereof is, for example, 2 or more and 200 or less (desirably 2 or more and 100 or less). The compound represented by the general formula (J) or a multimer thereof may be used alone or in combination of two or more. When the compound represented by the general formula (J) is used as a mixture of two or more kinds or used as a multimer (oligomer) having the same as a structural unit, the solubility in a solvent is improved.

In General Formula (J), R ^{J6 to} R ^J11 each independently represent a hydrogen atom, —CH ₂ —OH, —CH ₂ —O—R ^J12 , or —O—R ^J12 , and R ^J12 represents the number of carbon atoms. 1 or more and 5 or less linear or branched alkyl group is represented. Examples of the alkyl group include a methyl group, an ethyl group, and a butyl group.

The compound represented by the general formula (J) is synthesized by a known method (for example, “Experimental Chemistry Course”, 4th edition, Volume 28, page 430) using, for example, melamine and formaldehyde.
Although the specific example of a compound represented by general formula (J) below is shown, it is not necessarily restricted to these. Moreover, although the following specific examples show a monomer, the multimer (oligomer) which uses these as a structural unit may be sufficient.

  As a commercial item of the compound represented by the general formula (J), for example, Super Melami No. 90 (manufactured by NOF Corporation), Super Becamine (R) TD-139-60 (manufactured by DIC), Uban 2020 (Mitsui Chemicals), Sumitex Resin M-3 (Sumitomo Chemical Industries), Nicarak MW-30 (Japan) Carbide).

  The compound represented by the general formula (J) (including multimers) is dissolved in an appropriate solvent such as toluene, xylene or ethyl acetate after synthesis or after purchasing a commercial product in order to remove the influence of residual catalyst. It may be washed with distilled water, ion exchange water or the like, or may be removed by treatment with an ion exchange resin.

  When using at least one selected from a guanamine compound and a melamine compound, it is desirable to use at least one selected from reactive charge transport materials having an alkoxy group as the reactive charge transport material. It is more desirable to use at least one selected from reactive charge transport materials.

In this case, the total addition amount of the guanamine compound and the melamine compound is based on the total solid content in the composition for forming the outermost surface layer (protective layer) excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer. It is preferably 0.1% by mass or more and 25% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and further preferably 1% by mass or more and 20% by mass or less.
By setting the protective layer to the above configuration, the protective layer becomes a denser cured film, and the wear resistance and electrical characteristics of the electrophotographic photosensitive member are further improved.

  The total content of reactive charge transport materials in the protective layer and the total content of guanamine compounds and melamine compounds are controlled by adjusting the solid content concentration of these compounds in the composition for forming the protective layer. The

  In this embodiment, the protective layer is a polymer obtained by polymerizing at least one selected from a guanamine compound and a melamine compound, a reactive charge transport material having an alkoxy group, and a reactive charge transport material having a hydroxyl group. The total content of the guanamine compound and the melamine compound with respect to the total solid content of the protective layer excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer (that is, the component derived from the guanamine compound and the melamine compound) The total alkoxy group with respect to the total solid content of the protective layer excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer is 0.1% by mass or more and 20% by mass or less. Content of the reactive charge transporting material having a component (that is, a component derived from the reactive charge transporting material having an alkoxy group) The amount) is it is particularly desirable greater than 40 wt% to 10 wt%.

Hereinafter, the protective layer will be described in more detail.
In the protective layer, a phenol resin, a urea resin, an alkyd resin, or the like may be used in combination with a reactive charge transport material (for example, a compound represented by the general formula (C)). In order to improve the strength, a compound having a larger number of functional groups in one molecule such as spiroacetal guanamine resin (for example, “CTU-guanamine” manufactured by Ajinomoto Fine Techno Co., Ltd.) It is also effective to copolymerize the material.

  The protective layer may be mixed with other thermosetting resins such as phenol resin for the purpose of effectively suppressing oxidation by the discharge generated gas so that the discharge generated gas is not excessively adsorbed.

An antioxidant may be added to the protective layer. The antioxidant is an additive used for the purpose of suppressing deterioration due to an oxidizing gas such as ozone generated in the charging device.
Examples of antioxidants include hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphite antioxidants, and dithiocarbamate antioxidants. And known antioxidants such as oxidants, thiourea antioxidants, and benzimidazole antioxidants.

  A surfactant is preferably added to the protective layer. The surfactant is not particularly limited as long as it is a surfactant containing at least one of a fluorine atom, an alkylene oxide structure, and a silicone structure. It is preferable because it has high affinity and compatibility, improves the film-forming property of the coating solution for the protective layer, and suppresses wrinkles and unevenness of the protective layer.

  The protective layer may be mixed with a coupling agent or a fluorine compound for the purpose of adjusting the film formability, flexibility, lubricity, and adhesion. As this compound, various silane coupling agents and commercially available silicone hard coat agents are used.

The protective layer is made of alcohol for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life (storability of coating liquid for layer formation), etc. A dissolving resin may be added.
Here, the resin that dissolves in alcohol means a resin that dissolves 1% by mass or more in an alcohol having 5 or less carbon atoms. As resin which melt | dissolves in alcohol, polyvinyl acetal resin and polyvinyl phenol resin are mentioned, for example.

Various particles may be added to the protective layer for the purpose of lowering the residual potential or improving the strength. An example of the particles is silicon-containing particles. Silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles.
Further, a lubricant such as silicone oil may be added to the protective layer.

  Metals, metal oxides, carbon black, and the like may be added to the protective layer.

  The protective layer is preferably a cured film (cross-linked film) obtained by polymerizing (cross-linking) a reactive charge transporting material and, if necessary, a guanamine compound and a melamine compound using an acid catalyst. Acid catalysts include aliphatic carboxylic acids such as acetic acid, chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, maleic acid, malonic acid, and lactic acid; aromatics such as benzoic acid, phthalic acid, terephthalic acid, and trimellitic acid Carboxylic acids: Aliphatic or aromatic sulfonic acids such as methanesulfonic acid, dodecylsulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc. are used, but sulfur-containing materials (especially organic sulfonic acids) And derivatives thereof).

  Here, the compounding amount of the catalyst is in the range of 0.1% by mass or more and 50% by mass or less with respect to all the constituent components (solid content) excluding the fluorine-containing resin particles and the fluorinated alkyl group-containing copolymer. In particular, the content is preferably 10% by mass to 30% by mass. When the amount is less than the above range, the catalytic activity may be too low, and when it exceeds the above range, the light resistance may be deteriorated. The light resistance refers to a phenomenon in which the irradiated portion causes a decrease in density when the photosensitive layer is exposed to light from the outside such as room light. The cause is not clear, but it is presumed that a phenomenon similar to the optical memory effect occurs as disclosed in JP-A-5-099737.

  The protective layer having the above structure is formed using a protective layer-forming coating solution in which the above components are mixed. The coating liquid for forming the protective layer may be prepared without a solvent, or may be performed using a solvent as necessary. Such solvents are used singly or in combination of two or more, and preferably have a boiling point of 100 ° C. or lower. As the solvent, it is particularly preferable to use a solvent having at least one hydroxyl group (for example, alcohol).

  In addition, when a coating solution is obtained by reacting the above components, it may be simply mixed and dissolved, but it is room temperature (for example, 25 ° C.) to 100 ° C., preferably 30 ° C. to 80 ° C., for 10 minutes to 100 Heating may be performed for a period of time or less, preferably 1 hour or more and 50 hours or less. It is also desirable to irradiate ultrasonic waves at this time. Thereby, it is likely that a partial reaction proceeds, and it becomes easy to obtain a film with few coating film defects and little variation in thickness.

  Then, the coating liquid for forming the protective layer is applied by a known method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc. Accordingly, for example, the protective layer is obtained by heating and curing at a temperature of 100 ° C. or higher and 170 ° C. or lower.

  The film thickness of the protective layer is desirably 1 μm or more and 15 μm or less, and more desirably 3 μm or more and 10 μm or less.

  2 has been described above, the photoconductor applied to the image forming apparatus and the process cartridge of the present embodiment is not limited to the above configuration.

FIG. 3 is a schematic cross-sectional view showing another example of the layer structure of the photoreceptor in the present embodiment, and the reference numerals shown in FIG. 3 are synonymous with those shown in FIG.
3 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, and a charge transport layer 2B are laminated in this order on a conductive substrate 1, and the photosensitive layer 2 includes the charge generation layer 2A and the charge generation layer 2A. It is composed of two layers of the charge transport layer 2B (photoconductor of the second aspect).
In the photoreceptor shown in FIG. 3, the charge transport layer 2B is the outermost surface layer constituting the outermost surface.

  As the conductive substrate 1, the undercoat layer 4 and the charge generation layer 2A in the photoreceptor of the second embodiment, the conductive substrate 1, the undercoat layer 4 and the charge in the photoreceptor of the first embodiment shown in FIG. The generation layer 2A is applied as it is. As the charge transport layer 2B in the photoconductor of the second mode, the protective layer 2C in the photoconductor of the first mode shown in FIG. 2 is applied as it is.

  In the embodiment shown in FIG. 2, the photosensitive layer 2 is composed of three layers of the charge generation layer 2A, the charge transport layer 2B, and the protective layer 2C as described above. In the embodiment shown in FIG. An embodiment in which the layer 2 is composed of two layers of the charge generation layer 2A and the charge transport layer 2B is shown. However, in addition to this, in FIGS. 2 and 3, the charge generation layer 2 </ b> A and the charge transport layer 2 </ b> B may be stacked in the order of the charge transport layer 2 </ b> B and the charge generation layer 2 </ b> A from the conductive substrate 1 side. .

The function separation type electrophotographic photosensitive member has been described above as an example. For example, instead of the charge generation layer 2A and the charge transport layer 2B, a function-integrated type photosensitive layer having both charge transport capability and charge generation capability is provided. An aspect etc. may be sufficient. When the function-integrated single-layer type photosensitive layer is formed, the content of the charge generation material is preferably about 1% by mass to 10% by mass, and more preferably 1.5% by mass to 5% by mass. The content of the charge transport material is desirably 20% by mass or more and 70% by mass or less.
The method for forming the single-layer type photosensitive layer is performed according to the method for forming the charge generation layer or the charge transport layer. The thickness of the single-layer type photosensitive layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.

-Drive device-
The driving device 16 drives the photosensitive member at a peripheral speed of 500 mm / s or more.
Here, the peripheral speed means the speed on the outer peripheral surface of the photoconductor, and is obtained from the angular speed of the photoconductor rotated by the driving device 16 and the distance from the rotation axis of the photoconductor to the outer peripheral surface.
Examples of the peripheral speed include 500 mm / s to 800 mm / s, and preferably 500 mm / s to 700 mm / s.
Examples of the driving device 16 include a motor and the like. However, the driving device 16 is not particularly limited as long as it drives the photosensitive member. Rotating motion, pendulum motion, reciprocating motion, etc. using excitation force, air pressure, hydraulic pressure, etc. Any structure that operates repeatedly may be used.

-Charging device-
As the charging device 8, for example, a contact type charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like is used. Further, a non-contact type roller charger, a known charger such as a scorotron charger using a corona discharge or a corotron charger may be used.

-Exposure device-
Examples of the exposure device 9 include optical system devices that expose the surface of the electrophotographic photoreceptor 7 with light such as semiconductor laser light, LED light, and liquid crystal shutter light in a predetermined image-like manner. The wavelength of the light source is set within the spectral sensitivity region of the electrophotographic photosensitive member. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength of 400 nm to 450 nm as a blue laser may be used. In addition, a surface-emitting type laser light source that can output a multi-beam is also effective for color image formation.

-Developer-
Examples of the developing device 11 include a general developing device that performs development by bringing a developer into contact or non-contact with the developer. The developing device 11 is not particularly limited as long as it has the functions described above, and is selected according to the purpose. For example, a known developing device having a function of attaching a one-component developer or a two-component developer to the electrophotographic photosensitive member 7 using a brush, a roller, or the like can be used. Among these, those using a developing roller holding the developer on the surface are preferable.

  The developer used in the developing device 11 may be a one-component developer including a toner alone or a two-component developer including a toner and a carrier. Further, the developer may be magnetic or non-magnetic. A well-known thing is applied for these developers.

(toner)
Hereinafter, the toner used in the developing device 11 will be described.
The volume average particle diameter of the toner is, for example, in the range of 2.0 μm to 12 μm, and is preferably 2.0 μm to 5.0 μm from the viewpoint of achieving high image quality, and is 2.0 μm to 4 μm. More preferably, it is 5 μm or less.
The volume average particle diameter of the toner corresponds to the volume average particle diameter of the toner particles, for example, in the case of toner containing toner particles and an external additive.

The volume average particle diameter of the toner (toner particles) is measured as follows.
First, 0.5 mg to 50 mg of a measurement sample was added to 2 ml of a 5 mass% aqueous solution of a surfactant (desirably sodium alkylbenzenesulfonate) as a dispersant, and this was added to 100 ml to 150 ml of an electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for 1 minute, and a particle size of 100 μm is used with an aperture having a diameter of 100 μm by a Coulter Multisizer II type (manufactured by Beckman-Coulter). The particle size distribution of particles in the range of 2.0 μm to 60 μm is measured. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

The average circularity of the toner (toner particles) is preferably 0.900 or more and 0.998 or less, and more preferably 0.950 or more and 0.980 or less.
The average circularity of the toner (toner particles) is determined by (equivalent circumference of circle) / (perimeter) [(perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)]. . Specifically, a flow-type particle image analyzer (for example, a particle image is captured as a still image by sucking and collecting the toner to be measured, forming a flat flow, and emitting light with a strobe light, and analyzing the particle image (for example, It is obtained by FPIA-2100) manufactured by Sysmex Corporation. The number of samplings when obtaining the average circularity is 3500.

The shape factor SF1 of the toner (toner particles) is preferably 100 or more and 130 or less, and more preferably 110 or more and 120 or less.
The shape factor SF1 of the toner (toner particles) is obtained by the following formula.
Formula: SF1 = 100π × (ML) ² / (4 × A)
In the above formula, ML is the maximum particle length, and A is the projected area of the particle. The maximum length and projected area of the particles are determined by observing the particles sampled on the slide glass with an optical microscope, taking them into an image analysis apparatus (LUZEX III, manufactured by NIRECO) through a video camera, and performing image analysis. In this case, the number of sampling is 100 or more, and the shape factor shown in the above equation is obtained using the average value.

-Constitution of toner The toner may be composed of toner particles alone, or may be composed of toner particles and an external additive.

  The toner particles are configured to contain, for example, a binder resin, a colorant, a release agent, and other internal additives.

  The binder resin is not particularly limited, but styrenes (eg, styrene, chlorostyrene, etc.), monoolefins (eg, ethylene, propylene, butylene, isoprene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, Vinyl benzoate, vinyl butyrate, etc.), 1-methylene aliphatic monocarboxylic acid esters (for example, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, methacrylic acid) Ethyl acetate, butyl methacrylate, dodecyl methacrylate, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, vinyl isopro) Homopolymers and copolymers of Niruketon etc.), etc., and polyester resins by copolymerization of dicarboxylic acids and diols.

Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include a polymer, a polyethylene resin, a polypropylene resin, and a polyester resin.
Typical binder resins include polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  Examples of the colorant include magnetic powder (eg, magnetite, ferrite, etc.), carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is a typical example.

  Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. However, it is not limited to this.

  Examples of other internal additives include magnetic materials, charge control agents, inorganic powders, and the like.

Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, and CaO. , K ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like. .

  The surface of the external additive may be hydrophobized in advance. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.

Toner Production Method For example, toner particles may be obtained and then mixed with an external additive.
The method for producing the toner particles is not particularly limited by the production method. For example, kneading and pulverization in which a binder resin, other colorant, release agent, and other internal additives are added and kneaded, pulverized, and classified. Method: Method of changing the shape of particles obtained by kneading and pulverization method by mechanical impact force or thermal energy; Emulsion polymerization of polymerizable monomer of binder resin, and formed dispersion or other coloring An emulsion polymerization aggregation method in which a dispersing agent, a release agent and other internal additives are mixed, agglomerated, and heat-sealed; a polymerizable monomer for obtaining a binder resin, other colorants, a release agent Suspension polymerization method in which a solution of an agent and other internal additives is suspended in an aqueous solvent for polymerization; a binder resin, a solution of other colorants, a release agent, and other internal additives are suspended in an aqueous solvent Examples thereof include a dissolution suspension method in which granulation is performed.
The toner particles may be core-shell toner particles obtained by using the toner particles obtained by the above method as a core, and further adhering and aggregating aggregated particles.
As a method for producing the toner particles, a suspension polymerization method, an emulsion polymerization aggregation method, and a dissolution suspension method in which an aqueous solvent is used are desirable from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly desirable.

  When the toner includes an external additive, the toner is manufactured by mixing the toner particles and the external additive with a Henschel mixer or a V blender. Further, when the toner particles are produced by a wet method, they may be externally added by a wet method.

(Career)
Examples of the carrier include iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof.
The mixing ratio (mass ratio) of the toner and the carrier is, for example, in the range of toner: carrier = 1: 100 to 30: 100.

-Cleaning device-
As the cleaning device 13, a cleaning blade type device including a cleaning blade 131 is used.
In addition to the cleaning blade method, a fur brush cleaning method and a simultaneous development cleaning method may be employed.

-Transfer device-
Examples of the transfer device 40 include known transfer chargers such as a contact transfer charger using a belt, a roller, a film, a rubber blade, and the like, a scorotron transfer charger using a corona discharge, and a corotron transfer charger. Can be mentioned.

-Intermediate transfer member-
As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) containing polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member, a drum-like member may be used in addition to the belt-like member.

In the image forming apparatus 100 of the present embodiment, first, the surface of the electrophotographic photosensitive member 7 rotated by the driving device 16 is charged by the charging device 8, and the exposure device 9 is charged on the outer peripheral surface of the electrophotographic photosensitive member 7. Write an electrostatic latent image. The electrostatic latent image is developed by the developing device 11 to be visualized as a toner image, and then the toner image is conveyed to a position where the transfer device 40 is disposed, and is transferred onto the surface of the intermediate transfer member 50 by the transfer device 40. Electrostatically transferred.
Then, the outer peripheral surface of the electrophotographic photosensitive member 7 after the toner image is transferred by the transfer device 40 is cleaned by the cleaning device 13 and then charged, formed of an electrostatic latent image, developed, transferred, and cleaned. The process is repeated.
On the other hand, the toner image transferred to the surface of the intermediate transfer member 50 is transferred to a recording medium by a secondary transfer device (not shown), and is fixed to the recording medium by a fixing device (not shown) if necessary. An image is obtained.

As described above, the image forming apparatus 100 according to the present embodiment is a position where the exposure device 9 starts forming an electrostatic latent image (hereinafter referred to as “latent”) from the viewpoint of suppressing image density unevenness in one formed image. It is desirable that the image forming start position is sometimes synchronized for each electrostatic latent image corresponding to a single image.
Here, “single image” refers to each formed image when, for example, the same image is repeatedly formed.

As a form in which the latent image formation start position is synchronized for each electrostatic latent image corresponding to a single image, for example, a form provided with a control unit (control means) that controls the driving device 16 and the exposure device 9 can be cited.
The control unit is configured as a computer that controls the entire image forming apparatus 100 and performs various calculations. Specifically, although not shown, the control unit includes, for example, a CPU (Central Processing Unit), a ROM (Read Only Memory) storing various programs, and a RAM (RAM) used as a work area when executing the programs. Random Access Memory), a nonvolatile memory for storing various information, and an input / output interface (I / O). Each of the CPU, ROM, RAM, nonvolatile memory, and I / O is connected via, for example, a bus.

  Here, each device in the image forming apparatus 100 (for example, the driving device 16 that drives the electrophotographic photosensitive member 7, the charging device 8, the exposure device 9, the transfer device 40, etc.) is connected to the I / O of the control unit. Yes. For example, the control unit exchanges information with each device in the image forming apparatus 100 to control each device.

  Hereinafter, an operation of synchronizing the latent image formation start position on the surface of the electrophotographic photoreceptor 7 for each electrostatic latent image corresponding to a single image will be described with reference to the drawings. This operation is controlled by the control unit.

FIG. 5 is a view showing the positional relationship of the electrostatic latent image formed on the outer peripheral surface of the electrophotographic photosensitive member 7 by the exposure device 9. In FIG. 5, S represents the circumference on the outer circumferential surface of the electrophotographic photosensitive member 7, G _{1 to} G ₃ represent electrostatic latent images corresponding to single images to be formed, and A _{1 to} A ₃ represent Respectively, the latent image formation start positions of the electrostatic latent images G ₁ to G ₃ are shown. The _{P 1} and _{P 2,} respectively, the distance between the latent image formation start position _{A 2} of the latent image formation starting position of the electrostatic latent image _{G 1 A 1} and the electrostatic latent image _{G 2,} and the electrostatic latent image _{G 2} It indicates the distance between the latent image formation start position a ₂ and the latent image formation start position a ₃ of the electrostatic latent image G _3.
FIG. 5 shows the circumference of the electrophotographic photosensitive member 7 in the electrostatic latent image corresponding to a single image (that is, each of the electrostatic latent image G ₁ , the electrostatic latent image G ₂ , and the electrostatic latent image G ₃ ). Although the length in the direction is longer than the circumferential length S of the electrophotographic photoreceptor 7, the same applies to the case where the length is shorter than the circumferential length S.

In the form shown in FIG. 5, the electrostatic latent image G ₁ , the electrostatic latent image G ₂ , and the electrostatic latent image G ₃ are formed on the outer peripheral surface of the electrophotographic photosensitive member 7 rotated by the driving device 16 by the exposure device 9. They are formed one after another in this order.
The control unit may, for example, a latent image forming start position A _1, the latent image formation start position A _2, the latent image formation start position A _3, but so as to be synchronized, controls the driving unit 16 and the exposure apparatus 9 . Specifically, for example, the interval P ₂ between the distance P _1, and the latent image formation start position A ₂ and the latent image forming start position A ₃ of the latent image formation start position A ₁ and the latent image forming start position A ₂ The control unit controls the driving device 16 and the exposure device 9 so as to be an integral multiple of the circumferential length S of the electrophotographic photoreceptor 7. Thereby, formation of the electrostatic latent images G _{1 to} G ₃ is started from the latent image formation start positions A _{1 to} A ₃ corresponding to the same position on the outer peripheral surface of the electrophotographic photoreceptor 7.
Therefore, for example, when the electrostatic latent images G _{1 to} G ₃ are the same image, the electrostatic latent image G ₃ is developed even if the history of the electrostatic latent image G ₁ and the electrostatic latent image G ₂ remains. As a result, density unevenness or the like in the obtained image is less likely to occur.

Incidentally, for example, latent image forming start position A ₁ is a non-volatile memory storage on the basis of image formation information, stored latent image forming start position A ₂ and the latent image formation start position on the basis of the latent image formation start position A ₁ A ₃ may be determined.
As mentioned above, although the form which synchronizes a latent image start position for every electrostatic latent image corresponding to a single image was demonstrated, the image forming apparatus of this embodiment is not limited to the said form.

FIG. 4 is a schematic configuration diagram illustrating another example of the image forming apparatus according to the present embodiment.
An image forming apparatus 120 shown in FIG. 4 is a tandem multicolor image forming apparatus equipped with four process cartridges 300. In the image forming apparatus 120, four process cartridges 300 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member is used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  The image forming apparatus according to the present embodiment is not limited to the above configuration. For example, the cleaning apparatus 13 is around the electrophotographic photosensitive member 7 and downstream of the transfer device 40 in the rotation direction of the electrophotographic photosensitive member 7. Alternatively, the first static eliminating device may be provided on the upstream side of the rotation direction of the electrophotographic photosensitive member so that the polarity of the remaining toner is aligned and easily removed by the cleaning brush. A configuration in which a second static elimination device for neutralizing the surface of the electrophotographic photosensitive member 7 may be provided on the downstream side in the rotation direction of the electrophotographic photosensitive member and on the upstream side in the rotational direction of the electrophotographic photosensitive member with respect to the charging device 8.

In addition, the image forming apparatus according to the present embodiment is not limited to the above-described configuration, and a known configuration, for example, a direct transfer type image forming device that directly transfers a toner image formed on the electrophotographic photosensitive member 7 to a recording medium is employed. May be.
In addition, the process cartridge according to the present embodiment only needs to include the electrophotographic photosensitive member 7 and the driving device 16, and may not include the charging device 8, the developing device 11, and the cleaning device 13, or as necessary. Further, a transfer means may be provided.

  The image forming apparatus according to the present embodiment may be either a dry developing type image forming apparatus or a wet developing type (developing type using a liquid developer).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all. In the following description, “parts” and “%” are based on mass unless otherwise specified.

<< Photoconductor >>
[Preparation of Photoreceptor 1]
-Production of undercoat layer-
100 parts of zinc oxide (average particle size: 70 nm, manufactured by Teica, specific surface area value: 15 m ² / g) is stirred and mixed with 500 parts of toluene, and 1.25 parts of KBM603 (Shin-Etsu Chemical Co., Ltd.) is used as a silane coupling agent. Added and stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure, and baking was performed at 120 ° C. for 3 hours to obtain zinc oxide particles subjected to surface treatment with a silane coupling agent.

41.39 parts of the zinc oxide particles subjected to the surface treatment, 10 parts of blocked isocyanate (Sumijoule 3173, manufactured by Sumitomo Bayern Urethane Co., Ltd.) as a curing agent, and exemplified compound (1-8) of the aforementioned anthraquinone derivative 0. 6 parts and 35 parts of methyl ethyl ketone were stirred and mixed for 30 minutes, and further 5 parts of the exemplary compound (11-2) of the electron transport material represented by the above general formula (1), butyral resin (ESREC BM) -1, Sekisui Chemical Co., Ltd.) 5 parts, Tospearl 120 (manufactured by Toshiba Silicone) as silicone resin particles, and silicone oil SH29PA (manufactured by Toray Dow Corning Silicone) as leveling agent (surface conditioner) 0.01 And dispersion was performed for 3 hours with a sand mill to obtain a dispersion (coating liquid for forming the undercoat layer).
Further, this dispersion was applied on an aluminum substrate having a diameter of 84 mm, a length of 357 mm, and a thickness of 1 mm by dip coating, followed by drying and curing at 180 ° C. for 40 minutes, and an undercoat layer having a thickness of 21 μm. Got.

-Fabrication of charge generation layer-
Next, as a charge generating material, it has strong diffraction peaks at Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of at least 7.4 °, 16.6 °, 25.5 ° and 28.3 °. Add 1 part of chlorogallium phthalocyanine crystal to 100 parts of butyl acetate together with 1 part of polyvinyl butyral resin (Sekisui Chemical Co., Ltd. S-REC BM-S), and disperse with a paint shaker for 1 hour using glass beads with a diameter of 1 mm to generate charges A layer forming coating solution was obtained. This charge generation layer forming coating solution was dip coated on the undercoat layer and dried at 100 ° C. for 8 minutes to obtain a charge generation layer having a thickness of 0.2 μm.

-Preparation of charge transport layer-
A polymer compound (viscosity average molecular weight 39000) composed of 2.1 parts of a compound represented by the following structural formula (2B-1) as a charge transport material and a repeating unit represented by the following structural formula (2B-2) 2.9 parts was dissolved in 10 parts of tetrahydrofuran and 5 parts of toluene to obtain a coating solution for forming a charge transport layer.
This coating solution for forming a charge transport layer was dip coated on the charge generation layer and dried at 135 ° C. for 35 minutes to obtain a charge transport layer having a thickness of 23 μm.

-Production of surface protective layer (protective layer)-
10 parts of Lubron L-2 (manufactured by Daikin Industries) as tetrafluoroethylene resin particles, a repeating unit represented by the following structural formula (E) -1 and a repeating unit represented by the following structural formula (F) -1 0.5 part of a fluorinated alkyl group-containing copolymer (weight average molecular weight 50,000, l: m = 1: 1, s = 1, n = 60) is added to 40 parts of cyclopentanone and mixed with stirring. Then, a tetrafluoroethylene resin particle suspension was prepared.

  Next, 80 parts of the exemplary compound (I-8) of the reactive charge transport material described above, 20 parts of the exemplary compound (I-26) of the reactive charge transport material described above, and a benzoguanamine resin (Nicarac BL-60, three 4 parts) (manufactured by Wa Chemical Co., Ltd.) was added to 220 parts of cyclopentanone and dissolved and mixed, and then the tetrafluoroethylene resin particle suspension was added and stirred and mixed to obtain a dispersion.

Thereafter, the obtained dispersion is subjected to a dispersion treatment by increasing the pressure to 700 kgf / cm ² using a high-pressure homogenizer (YSNM-1500AR manufactured by Yoshida Kikai Kogyo Co., Ltd.) equipped with a through-type chamber having a fine flow path. After repeating several times, 0.1 part of NACURE 5225 (manufactured by King Industry) was added to obtain a coating solution for forming a surface protective layer.
This coating solution for forming a surface protective layer was dip coated on the charge transport layer and dried by heating at 159 ° C. for 34 minutes to obtain a surface protective layer having a thickness of 6 μm.
As described above, the photoreceptor 1 was obtained.

[Preparation of Photoreceptor 2]
Photosensitive material other than benzoguanamine resin was changed to methylated melamine resin (Nicarac MW-30HM, manufactured by Sanwa Chemical Co., Ltd., the exemplified compound (J) -2), instead of benzoguanamine resin. The photoconductor 2 was obtained in the same manner as the photoconductor 1.

[Preparation of Photoreceptor 3]
Photoreceptor 3 was obtained in the same manner as Photoreceptor 1 except that Exemplified Compound (1-2) was used instead of Exemplified Compound (1-8) as an anthraquinone derivative in preparation of the undercoat layer in Receptor 1. It was.

[Preparation of Photoreceptor 4]
Photoreceptor 4 was obtained in the same manner as Photoreceptor 1 except that Exemplified Compound (1-6) was used instead of Exemplified Compound (1-8) as an anthraquinone derivative in preparation of the undercoat layer in Receptor 1. It was.

[Preparation of Photoreceptor 5]
In the production of the undercoat layer in the photoreceptor 1, the photoreceptor 5 is obtained in the same manner as the photoreceptor 1 except that the exemplified compound (1-11) is used instead of the exemplified compound (1-8) as an anthraquinone derivative. It was.

[Production of Photosensitive Member 6]
In preparation of the surface protective layer in the photoreceptor 1, the addition amount of the exemplary compound (I-8) of the reactive charge transport material is 41 parts, and the addition amount of the exemplary compound (I-26) of the reactive charge transport material is 44 parts. A photoconductor 6 was obtained in the same manner as the photoconductor 1 except that:

[Preparation of Photoreceptor 7]
In preparation of the surface protective layer in the photoreceptor 1, the addition amount of the exemplary compound (I-8) of the reactive charge transport material is 50 parts, and the addition amount of the exemplary compound (I-26) of the reactive charge transport material is 19 parts. The photoreceptor 7 was obtained in the same manner as the photoreceptor 1 except that the addition amount of the benzoguanamine resin was changed to 20.4 parts.

[Preparation of Photoreceptor 8]
In preparation of the surface protective layer in the photoreceptor 1, the addition amount of the exemplary compound (I-8) of the reactive charge transport material is 70.25 parts, the addition amount of Lubron L-2 is 5 parts, and the fluoroalkyl group-containing co-polymer is included. A photoconductor 8 was obtained in the same manner as the photoconductor 1, except that the addition amount of the polymer was changed to 0.25 part.

[Preparation of Photoreceptor 9]
Except for using the reactive charge transporting material exemplified compound (I-16) instead of the reactive charge transporting material exemplified compound (I-8) in the preparation of the surface protective layer in the photoreceptor 1, the photosensitive member 1 and Similarly, a photoreceptor 9 was obtained.

[Production of Photoreceptor 10]
Photoconductor 10 was obtained in the same manner as Photoconductor 1, except that the preparation of the surface protective layer was changed to the following method in preparation of Photoconductor 1.

-Preparation of surface protective layer-
10 parts of Lubron L-2 (manufactured by Daikin Industries) as tetrafluoroethylene resin particles, a repeating unit represented by the structural formula (E) -1 and a repeating unit represented by the structural formula (F) -1 0.5 part of a fluorinated alkyl group-containing copolymer (weight average molecular weight 50,000, l: m = 1: 1, s = 1, n = 60) is added to 40 parts of cyclopentanone and mixed with stirring. Then, a tetrafluoroethylene resin particle suspension was prepared.

Next, the following constituent materials were dissolved in 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran, and 0.3 part of distilled water, 0.5 parts of an ion exchange resin (Amberlyst 15E manufactured by Organo) was added, and room temperature (25 The mixture was stirred at 24 ° C. for 24 hours for hydrolysis.
(Constituent materials)
-Compound (6) represented by the following structural formula: 37 parts-Methyltrimethoxysilane 37 parts-Tetramethoxysilane 8.4 parts-Colloidal silica 6 parts In the following structural formula, "Me" represents a methyl group, “iPr” represents an isopropyl group.

In the solution obtained by filtering and separating the ion exchange resin after hydrolysis, 0.1 parts of aluminum trisacetylacetonate (Al (aqaq) ₃ ) and 3,5-di-t-butyl-4- After adding 0.4 part of hydroxytoluene (BHT) and mixing and dissolving, the tetrafluoroethylene resin particle suspension was added and mixed by stirring to obtain a dispersion.

Next, the obtained dispersion is subjected to a dispersion treatment in which the pressure is increased to 700 kgf / cm ² using a high-pressure homogenizer (YSNM-1500AR manufactured by Yoshida Kikai Kogyo Co., Ltd.) equipped with a through-type chamber having a fine flow path. After repeating several times, 1 part of dimethylpolysiloxane (Kyoeisha Chemical Granol 450) and 0.1 part of NACURE 5225 (King Industries) were added to obtain a coating solution for forming a surface protective layer.
This surface protective layer forming coating solution is applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature (25 ° C.) for 30 minutes, and then cured by heat treatment at 180 ° C. for 1 hour, A surface protective layer having a thickness of 5 μm was formed.

[Preparation of Photoreceptor 11]
Photoreceptor 11 was obtained in the same manner as Photoreceptor 1 except that the preparation of the surface protective layer was changed to the following method in preparation of Photoreceptor 1.

-Preparation of surface protective layer-
75.5 parts of exemplary compound (I-8) of reactive charge transport material, 20 parts of exemplary compound (I-26) of reactive charge transport material, and benzoguanamine resin (Nicarac BL-60, manufactured by Sanwa Chemical Co., Ltd.) After adding 4.4 parts to 220 parts of cyclopentanone and mixing and dissolving, 0.1 part of NACURE 5225 (manufactured by King Industry) was added to obtain a coating solution for forming a surface protective layer.
This surface protective layer forming coating solution was dip coated on the charge transport layer and dried by heating at 159 ° C. for 34 minutes to form a surface protective layer having a thickness of 6 μm.

[Production of Photoreceptor 12]
Photoconductor 12 was obtained in the same manner as Photoconductor 1, except that an anthraquinone derivative was not used in the production of the undercoat layer in Photoconductor 1.

[Preparation of Photoreceptor 13]
Photoconductor 13 was obtained in the same manner as Photoconductor 1, except that the electron transport material represented by the general formula (1) was not used in the production of the undercoat layer in Photoconductor 1.

[Preparation of Photoreceptor 14]
In the production of the undercoat layer in the photoreceptor 1, a compound represented by the exemplary compound (1-15) which is an electron accepting compound other than the anthraquinone derivative is used instead of the exemplary compound (1-8) which is an anthraquinone derivative. A photoconductor 14 was obtained in the same manner as the photoconductor 1 except that.

[Production of Photoreceptor 15]
In preparation of the undercoat layer in the photoreceptor 1, an electron transport material represented by the following structural formula (4-1) is used instead of the exemplified compound (11-2) of the electron transport material represented by the general formula (1). A photoconductor 14 was obtained in the same manner as the photoconductor 1 except that was used.

[Production of Photosensitive Member 16]
Photoconductor 16 was obtained in the same manner as photoconductor 11 except that the electron transport material represented by the general formula (1) was not used in the production of the undercoat layer on photoconductor 11.

[Preparation of Photoconductor 17]
In preparing the undercoat layer in the photoreceptor 1, the photoreceptor except that the exemplified compound (11-14) was used instead of the exemplified compound (11-2) as the electron transport material represented by the general formula (1). 1 was obtained.

<< Developer >>
[Developer 1]
(Preparation of toner particles 1)
-Preparation of resin particle dispersion-
A nonionic surfactant (Nonpol 400: manufactured by Sanyo Chemical Co., Ltd.) prepared by mixing 370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol, and 4 g of carbon tetrabromide was dissolved. 6 g and 10 g of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added to a flask containing an aqueous solution dissolved in 550 g of ion-exchanged water, and emulsion polymerization was performed while slowly mixing for 10 minutes. An aqueous solution in which 4 g of ammonium persulfate was dissolved in 50 g of ion-exchanged water was added.
After carrying out nitrogen substitution, while stirring the liquid in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours.
As a result, a resin particle dispersion was obtained in which resin particles having a volume average particle size of 150 nm, a glass transition temperature Tg of 58 ° C., and a weight average molecular weight Mw of 11500 were dispersed. The solid content concentration of this dispersion was 40% by mass.

-Preparation of colorant dispersion-
・ Carbon black (Mogal L: Cabot) 60g
-Nonionic surfactant (Nonipol 400: Sanyo Kasei Co., Ltd.) 6g
・ Ion exchange water 240g
The above components are mixed and dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then dispersed with an optimizer to give a colorant having a volume average particle diameter of 250 nm ( Carbon black) A colorant dispersant in which particles were dispersed was prepared.

-Preparation of release agent dispersion-
・ 100 g of paraffin wax (HNP0190: manufactured by Nippon Seiwa Co., Ltd., melting temperature 85 ° C.)
・ Cationic surfactant (Sanisol B50: manufactured by Kao Corporation) 5g
・ Ion exchange water 240g
The above components were dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then dispersed with a pressure discharge homogenizer, and the volume average particle diameter was 550 nm. A release agent dispersion liquid in which release agent particles are dispersed was prepared.

-Production of toner particles 1-
-234 parts of resin particle dispersion-30 parts of colorant dispersion-40 parts of release agent dispersion-0.5 part of polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.)-600 parts of ion-exchanged water After mixing and dispersing in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), the flask was heated to 30 ° C. with stirring in an oil bath for heating. After holding at 30 ° C. for 20 minutes, it was confirmed that aggregated particles having a volume average particle diameter D50 of 3.0 μm were produced.

  Further, the temperature of the heating oil bath was raised and maintained at 45 ° C. for 1 hour, and the volume average particle diameter D50 was 3.8 μm. Thereafter, 26 parts of the resin particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 20 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the system to 5.0, the stainless steel flask is sealed, and the stirring is continued to 80 ° C. using a magnetic seal. Heated and held for 3 hours. After cooling, the resulting toner particles were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner particles 1. Toner particles 1 had a volume average particle diameter D50 of 4.1 μm and a shape factor SF1 of 105.

(Preparation of carrier 1)
• Ferrite particles (average particle size: 50 μm) 100 parts • Toluene 14 parts • Styrene / methacrylate copolymer (component ratio: 90/10) 2 parts • Carbon black (R330: manufactured by Cabot) 0.2 parts First, ferrite The above components except the particles were stirred with a stirrer for 10 minutes to prepare a dispersed coating solution. Next, the coating liquid and the ferrite particles were put in a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes, and then degassed and degassed while heating, and dried to obtain a carrier 1. This carrier 1 had a volume resistivity value of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm was applied.

(Preparation of developer 1)
1100 parts of the toner particles 1, 1 part of rutile titanium oxide (particle size 20 nm, n-decyltrimethoxysilane treatment), 2.0 parts of silica (particle size 40 nm, silicone oil treatment, gas phase oxidation method), Jet mill of 1 part of cerium oxide (average particle size 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and tetrafluoroethylene resin (Lublon L-2) in a mass ratio of 5: 1 After mixing with 0.3 parts of an average particle diameter of 8.0 μm by pulverization at 15 m / s with a 5 L Henschel mixer, using a sieve with 45 μm openings Coarse particles were removed to obtain toner 1.
Further, 100 parts of the carrier 1 and 5 parts of the toner 1 were stirred with a V-blender for 20 minutes under a condition of 40 rpm, and sieved with a sieve having an opening of 212 μm, thereby developing agent 1. Got.

[Developer 2]
(Preparation of toner particles 2)
-234 parts of resin particle dispersion-30 parts of colorant dispersion-40 parts of release agent dispersion-0.5 part of polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.)-600 parts of ion-exchanged water After mixing and dispersing in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), the flask was heated to 40 ° C. with stirring in a heating oil bath. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a volume average particle diameter D50 of 4.5 μm were generated.

  Further, the temperature of the heating oil bath was raised and maintained at 53 ° C. for 1 hour, and the volume average particle diameter D50 was 5.2 μm. Thereafter, 26 parts of the resin particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the system to 7.0, the stainless steel flask is sealed, and the stirring is continued to 80 ° C. using a magnetic seal. Heated and held for 3.5 hours. After cooling, the obtained toner particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner particles 2. Toner particles 2 had a volume average particle diameter D50 of 6.0 μm and a shape factor SF1 of 135.

(Preparation of developer 2)
Toner 2 was obtained in the same manner as toner 1 except that toner particle 2 was used instead of toner particle 1.
Further, 100 parts of the carrier 1 and 5 parts of the toner 2 were stirred with a V-blender for 20 minutes at 40 rpm, and sieved with a sieve having an opening of 212 μm, thereby developing agent 2. Got.

<< Example 1 >>
Subsequently, the photosensitive member 1 and the developer 1 were combined and loaded into an image forming apparatus (“Color 1000 Press” manufactured by Fuji Xerox Co., Ltd.). In the image forming apparatus, the peripheral speed (process speed) of the photoconductor is usually 440 mm / s and an image is formed on 100 sheets of A4 paper per minute, but the peripheral speed of the photoconductor is 528 mm / s (120 sheets / second). Min) or 660 mm / s (150 sheets / min), and evaluated at the peripheral speeds shown in the table below.
In addition, the function (synchronization function) for synchronizing the latent image formation start position on the surface of the photoconductor for each electrostatic latent image corresponding to a single image is enabled (ON) and disabled (OFF). Remodeling was performed to make the settings to be free, and the settings shown in the table below were evaluated.
Unless otherwise specified, image formation was performed using an unused photoreceptor for each evaluation. Moreover, Fuji Xerox J paper (basis weight: 82 g / m ² , paper thickness: 97 μm, ISO whiteness: 89%) was used as a recording medium for evaluation.

[Electrical characteristics evaluation]
The following settings and measurements were performed in an environment of room temperature 22 ° C. and humidity 55% RH.
First, as an initial evaluation of the electrical characteristics of the photoconductor, the grid voltage of the scorotron (non-contact type charging means) was adjusted using a potential monitor built in the image forming apparatus so that the surface potential of the photoconductor was -700V. Next, the amount of exposure light was set so that the exposure portion potential was -250V. After performing later-described wear resistance evaluation using this exposure light quantity, the exposed portion potential was measured again, and the difference from the initial value was expressed by ΔVL. The evaluation criteria are as follows. The values of ΔVL (numeric values in parentheses in the table) and evaluation results are shown in the following table.
A: ΔVL <10
B: 10 ≦ ΔVL <15
C: 15 ≦ ΔVL

[Concentration stability evaluation]
The following settings and measurements were performed in an environment of room temperature 22 ° C. and humidity 55% RH.
In the photoconductor having the same configuration and the same prototype as the photoconductor used for the electrical property evaluation, the grid voltage and the exposure light amount were adjusted in the same manner as the electrical property evaluation. After that, the photoconductor is mounted, 1000 images with an image density Cin of 50% are formed on an A3 size recording medium, the reflection density is measured for the first image and the 1000th image, and the difference ΔDout is expressed as follows: Evaluation was performed according to the criteria.
The reflection density is an image density (Dout) measured using a spectrocolorimeter (X-Rite 938). Specifically, a total of five locations at the center and four corners of the image are displayed on the first sheet. And it measured about each of the 1000th sheet, and evaluated using the difference of the average of 5 places. The evaluation criteria are as follows. The values of ΔDout (numeric values in parentheses in the table) and evaluation results are shown in the following table.
A: ΔDout <0.10
B: 0.10 ≦ ΔDout <0.15
C: 0.15 ≦ ΔDout

[Dot reproducibility evaluation]
The dot reproducibility of the 100th image formed by the density stability evaluation was evaluated according to the following criteria. The photograph shown in FIG. 6 is a photograph obtained by magnifying an image with an image density Cin of 30% formed by the density stability evaluation 100 times with a microscope (manufactured by KEYENCE, model number: VHX-900). The evaluation results are shown in the following table.
A: The dots are not disturbed as shown in FIG. 6A. B: The toner is slightly scattered as shown in FIG. 6B. C: The toner is scattered as shown in FIG. 6C.

[Burn-in evaluation]
In the environment of 28 ° C./85% RH, the grid voltage and the amount of exposure light were adjusted in the same manner as in the electrical characteristic evaluation.
Thereafter, after 1000 grid-like chart images as shown in FIG. 7A are formed, images having an image density Cin of 20% are continuously output, and the appearance of the grid-like image (ghost) is visually observed. Observed and evaluated according to the following criteria. All images were formed on an A3 recording medium. The evaluation results are shown in the following table.
A: A grid-like image is not confirmed as shown in FIG.
B: As shown in FIG. 7B, a lattice-like image is slightly confirmed. No problem level C: As shown in FIG. 7C, a lattice-like image is clearly confirmed.

[Abrasion resistance evaluation]
The grid voltage and the amount of exposure light were adjusted in the same manner as in the electrical characteristic evaluation. Thereafter, the image shown in FIG. 8 was output until the photoconductor rotated 100,000 times (within 1% error) (that is, an image was formed on 50,000 A3-sized recording media).
Note that the image shown in FIG. 8 specifically has a portion having an image density Cin of 100% (a portion having an “image density of 100%” in FIG. 8) in the center of the recording medium and two portions sandwiching this portion. The image density Cin is a 30% portion (“image density 30%” portion in FIG. 8) and the entire image density Cin is 7.5%.

The difference between the film thickness of the photoreceptor before use (film thickness of the protective layer) measured in advance and the film thickness of the photoreceptor (film thickness of the protective layer) after 100,000 rotations was obtained, and the photoreceptor The amount of wear per 1000 revolutions (nm / 1000 revolutions) was calculated and evaluated according to the following criteria.
The film thickness of the photoconductor is 4 points in the circumferential direction (4 points of 0 °, 90 °, 180 °, and 270 ° are arbitrarily set as the base point) and 33 points in the axial direction from the top 20 mm position at a 10 mm pitch. A total of 132 points were measured, and an average value of 132 points was obtained. For the measurement, a film thickness measuring device (for example, a permascope manufactured by Fischerscope) may be used. The amount of wear (numerical values in parentheses in the table) and the evaluation results are shown in the following table.
A: Less than 2.5 nm / 1000 rotations B: 2.5 nm / 1000 rotations or more, less than 3.5 nm / 1000 rotations C: 3.5 nm / 1000 rotations or more

<< Examples 2 to 15 >>
Example 1 except that the photoconductor and developer used were changed to those shown in the following table, and the setting of the synchro function in evaluation, the peripheral speed of the photoconductor, and the surface potential of the photoconductor were as shown in the following table. Evaluation was performed in the same manner as above. The evaluation results are shown in the following table.

<< Comparative Examples 1-6 >>
Example 1 except that the photoconductor and developer used were changed to those shown in the following table, and the setting of the synchro function in evaluation, the peripheral speed of the photoconductor, and the surface potential of the photoconductor were as shown in the following table. Evaluation was performed in the same manner as above. The results are shown in the table below.

  From the above results, it can be seen that in this example, image sticking on the surface of the photoreceptor is suppressed as compared with the comparative example.

DESCRIPTION OF SYMBOLS 1 Conductive substrate, 2 Photosensitive layer, 2A Charge generation layer, 2B Charge transport layer, 2C Protective layer, 4 Undercoat layer, 7 Electrophotographic photoreceptor, 8 Charging device, 9 Exposure device, 11 Developing device, 13 Cleaning device, 14 Lubricant, 40 Transfer device, 50 Intermediate transfer body, 100 Image forming device, 120 Image forming device, 131 Cleaning blade, 132 Fibrous member, 133 Fibrous member, 300 Process cartridge, A _{1 to} A ₃ latent image formation start _position, G 1 ~G ₃ electrostatic latent _image, P 1 to P ₂ spacing, S circumference,

Claims (5)

A conductive substrate; an undercoat layer provided on the conductive substrate; and a photosensitive layer provided on the undercoat layer, wherein the undercoat layer comprises a binder resin, metal oxide particles, and the metal oxide. an electrophotographic photosensitive member viewed contains an electron transporting material represented by anthraquinone derivatives and by the following general formula (1), the thickness of the subbing layer is 15μm or more with the surface of the object particles,
Driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more;
Charging means for charging the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member;
Developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner to form a toner image;
Transfer means for transferring the toner image to the surface of the recording medium;
An image forming apparatus.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, Or R ¹⁸ represents an alkyl group, an aryl group, or an aralkyl group.   The image forming apparatus according to claim 1, wherein a formation start position of the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is synchronized for each electrostatic latent image corresponding to a single image.   The image forming apparatus according to claim 1, wherein the outermost surface layer of the electrophotographic photosensitive member includes fluorine-containing resin particles and a fluorinated alkyl group-containing copolymer.   The image forming apparatus according to claim 1, wherein the toner has a volume average particle diameter of 2.0 μm or more and 5.0 μm or less. A conductive substrate; an undercoat layer provided on the conductive substrate; and a photosensitive layer provided on the undercoat layer, wherein the undercoat layer comprises a binder resin, metal oxide particles, and the metal oxide. an electrophotographic photosensitive member viewed contains an electron transporting material represented by anthraquinone derivatives and by the following general formula (1), the thickness of the subbing layer is 15μm or more with the surface of the object particles,
Driving means for driving the electrophotographic photosensitive member at a peripheral speed of 500 mm / s or more;
With
A process cartridge that can be attached to and detached from an image forming apparatus.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, Or R ¹⁸ represents an alkyl group, an aryl group, or an aralkyl group.