JP2013242436A - Electrophotographic photoreceptor, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor that has suppressed an increase in residual potential.SOLUTION: An electrophotographic photoreceptor includes a conductive support 2, an undercoat layer 4, and a photosensitive layer 3. The undercoat layer 4 is provided on the conductive support 2, formed of a cured film of a composition containing a binder resin, metal oxide particles, an electron-accepting compound having an anthraquinone structure and is contained in the amount of 1 part by weight or more and 5 parts by weight or less relative to 100 parts by weight of the metal oxide particles, and an isocyanate compound, and has the amount of weight change in a temperature range from 0°C to 230°C of 0.05 weight% or more and 0.8 weight% or less in differential heat/thermogravimetry simultaneous measurement (TG/DTA measurement).

Description

  The present invention relates to an electrophotographic photosensitive member, an image forming apparatus, and a process cartridge.

In recent years, electrophotographic image formation has been widely used in image forming apparatuses such as copying machines and laser printers.
For example, in Patent Document 1, “an undercoat layer is provided between a support and a photosensitive layer, and the undercoat layer is composed of a water-soluble or alcohol-soluble resin, a conductive polymer, an electrolyte-based additive, and an inorganic pigment. An electrophotographic photoreceptor has been proposed in which the undercoat layer has a moisture content of 0.02 g or less per gram of the undercoat layer when placed in an atmosphere of 20 ° C. and 90% RH for 20 hours.

Japanese Patent Laid-Open No. 03-150572

  An object of the present invention is to provide an electrophotographic photosensitive member in which an increase in residual potential is suppressed.

The above problem is solved by the following means. That is,
The invention according to claim 1
A conductive support;
An undercoat layer provided on the conductive support, wherein the binder resin, metal oxide particles, and an anthraquinone structure having a content of 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the metal oxide particles The weight change amount from 0 ° C. to 230 ° C. in the differential heat / thermogravimetric simultaneous measurement (TG / DTA measurement) is 0.05 mass. An undercoat layer that is not less than 0.8% and not more than 0.8% by mass;
A photosensitive layer provided on the undercoat layer;
An electrophotographic photosensitive member having:

The invention according to claim 2
The electrophotographic photoreceptor according to claim 1, wherein the charge-accepting compound is an electron-accepting compound having a hydroxyanthraquinone structure.

The invention according to claim 3
At least the electrophotographic photoreceptor according to claim 1 or 2,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 4
The electrophotographic photosensitive member according to claim 1 or 2,
Charging means for charging the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for exposing the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image;
Developing means for containing a developer and developing the electrostatic latent image with the developer to form a toner image;
Transfer means for transferring the toner image to a transfer medium;
An image forming apparatus comprising at least

According to the first aspect of the present invention, there is provided an electrophotographic photosensitive member in which the increase in residual potential is suppressed as compared with the case where the weight change amount of the undercoat layer formed of the cured film of the composition is outside the above range. it can.
The invention according to claim 2 can provide an electrophotographic photosensitive member in which the increase in residual potential is suppressed as compared with the case where the electron accepting compound is not an electron accepting compound having a hydroxyanthraquinone structure.

  According to the inventions according to claims 3 and 4, the electrophotographic photosensitive member has a weight change amount of the undercoat layer formed of the cured film of the composition as compared with the case where an electrophotographic photosensitive member outside the above range is applied. It is possible to provide a process cartridge and an image forming apparatus that can obtain an image in which image defects due to an increase in residual potential are suppressed.

It is the schematic which shows the cross section of a part of the electrophotographic photoreceptor concerning this embodiment. 1 is a schematic diagram illustrating a basic configuration of an image forming apparatus according to a first embodiment. It is the schematic which shows the basic composition of the image forming apparatus of 2nd Embodiment. It is the schematic which shows the basic composition of an example of a process cartridge.

  Hereinafter, embodiments will be described in detail. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description may be omitted.

<Electrophotographic photoreceptor>
The electrophotographic photoreceptor according to the exemplary embodiment includes a conductive support, an undercoat layer provided on the conductive support, and a photosensitive layer provided on the undercoat layer.
The undercoat layer is a composition containing a binder resin, metal oxide particles, an electron-accepting compound having an anthraquinone structure, and an isocyanate compound, and the electron-accepting compound is 1 in 100 parts by mass of the metal oxide particles. It is comprised with the cured film of the composition contained by 5 to 5 mass parts.
And, in the undercoat layer composed of the cured film of such a composition, the weight change amount from 0 ° C. to 230 ° C. in the simultaneous differential heat / thermogravimetric measurement (TG / DTA measurement) is 0.05% by mass or more. 0.8% by mass or less.

Here, in the electrophotographic photoreceptor, by dispersing metal oxide particles in the undercoat layer, for example, the blocking ability at the interface between the undercoat layer and the photosensitive layer (for example, the charge generation layer) is improved. It is considered that the resistance adjustment function is adjusted to suppress the occurrence of fogging, stabilize the electrical characteristics, and suppress the decrease in density due to repeated use.
And in the structure of the undercoat layer of such an electrophotographic photoreceptor, the electron accepting compound having an anthraquinone structure together with the metal oxide particles is 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the metal oxide particles. When contained in a large amount, for example, in the undercoat layer of the electrophotographic photosensitive member, the progress of corrosion of the conductive support due to the oxidation-reduction reaction between the coupling agent having an amino group and the conductive support is suppressed. It is considered that the afterimage phenomenon (ghost) caused by the history of the previous image remaining is suppressed.
However, in an electrophotographic photoreceptor having an undercoat layer having such advantages, the residual potential may increase.

Therefore, in the electrophotographic photoreceptor according to the exemplary embodiment, the increase in the residual potential is suppressed by setting the weight change amount in the above range in the undercoat layer formed of the cured film of the composition.
The reason is not clear, but it is thought to be as follows.

First, the increase in residual potential is caused by the presence of a reaction residue (for example, unreacted electron-accepting compound, isocyanate compound, etc.) in the subbing layer, which is too small or excessive. This is considered to occur because the resistance value does not fall within a certain range or the resistance value fluctuates over time.
In other words, the increase in the residual potential is caused by the reaction (or coordination) between the metal oxide particles and the electron accepting compound and the reaction of the isocyanate compound proceeding excessively or not sufficiently proceeding in the undercoat layer. This is thought to be caused by
And, the weight change amount of the undercoat layer is in the above range, in the undercoat layer, the reaction (or coordination) between the metal oxide particles and the electron accepting compound and the reaction of the isocyanate compound proceed appropriately. It is considered that the reaction residue (for example, an unreacted electron-accepting compound, an isocyanate compound, etc.) is appropriately present in the undercoat layer.
That is, by setting the weight change amount of the undercoat layer within the above range, it is considered that the resistance value of the undercoat layer falls within an appropriate range and the resistance value hardly changes over time.

For this reason, in the electrophotographic photoreceptor according to this exemplary embodiment, it is considered that the increase in residual potential is suppressed.
In addition, although the mechanism of action is not clear, it is considered that the use of a material having a hydroxyanthraquinone structure as the electron-accepting compound further suppresses the increase in residual potential.
In the image forming apparatus (process cartridge) provided with the electrophotographic photosensitive member according to the present embodiment, image defects (for example, change in image density over time, etc.) due to an increase in residual potential of the m electrophotographic photosensitive member are suppressed. Images are obtained.

  Here, in the electrophotographic photoreceptor according to the exemplary embodiment, the weight change amount of the undercoat layer is 0.05% by mass or more and 0.8% by mass or less, and desirably 0.1% by mass or more and 0.75% by mass. % Or less, more desirably 0.15 mass% or more and 0.6 mass% or less.

The weight change amount of the undercoat layer is the weight change amount from 0 ° C. to 230 ° C. in the simultaneous differential heat / thermogravimetric measurement (TG / DTA measurement), that is, “weight at 230 ° C./weight at 0 ° C.” .
Specifically, the weight change amount of the undercoat layer is measured by using a differential thermal / thermogravimetric simultaneous measuring device with a standard sample: alumina and a temperature rise condition: 10 ° C./min. Ask for.

A method for preparing an undercoat layer sample for measuring a weight change from an electrophotographic photosensitive member is as follows.
For example, an undercoat layer having a target weight is collected from an electrophotographic photosensitive member with a cutter or the like and used as an undercoat layer sample.

Examples of the method for adjusting the amount of change in the weight of the undercoat layer include a method for adjusting the heating and drying conditions for forming the undercoat layer. Specifically, it is preferable to adjust the amount of change in the weight of the undercoat layer by adjusting the heat drying conditions such as the heat drying temperature, the heat drying time, and the heat drying humidity.
In particular, since the reaction (or coordination) between the metal oxide particles and the electron-accepting compound is easily inhibited by moisture in the air, heating is performed in an environment where the heating and drying humidity is reduced (for example, humidity is 50 RH% or less). By adjusting the drying temperature and the heat drying time to form the undercoat layer, it is preferable that the weight change amount of the undercoat layer can be easily controlled within the above range.

  Hereinafter, the electrophotographic photosensitive member according to the exemplary embodiment will be described in detail.

FIG. 1 schematically shows a cross section of a part of the electrophotographic photosensitive member according to this embodiment. The electrophotographic photoreceptor 1 shown in FIG. 1 includes, for example, a function-separated type photosensitive layer 3 in which a charge generation layer 5 and a charge transport layer 6 are separately provided. The layer 4, the charge generation layer 5, and the charge transport layer 6 are stacked in this order.
In addition, in this specification, insulation means the range of 10 ¹² Ωcm or more in volume resistivity. On the other hand, the conductivity means a range of 10 ¹⁰ Ωcm or less in volume resistivity.
Hereinafter, each element of the photoreceptor 1 will be described.

-Conductive support-
Any conductive support 2 may be used as long as it is conventionally used. For example, metals such as aluminum, nickel, chromium, stainless steel, and plastic films provided with thin films such as aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO, etc. Examples thereof include paper and plastic film coated or impregnated with an imparting agent.
The shape of the conductive support 2 is not limited to a drum shape, and may be a sheet shape or a plate shape.

  When a metal pipe is used as the conductive support 2, the surface may remain as it is, or a process such as mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing, etc. is performed in advance. It may be.

-Undercoat layer-
The undercoat layer 4 is a composition containing at least a binder resin, metal oxide particles, an electron accepting compound having an anthraquinone structure, and an isocyanate compound, and the electron accepting compound is contained in 100 parts by mass of the metal oxide particles. On the other hand, it is comprised with the cured film of the composition contained by 1 mass part or more and 5 mass parts or less.
That is, the undercoat layer 4 is configured, for example, by dispersing metal oxide particles and a target amount of an electron-accepting compound in a cured product (cross-linked product) of a binder resin and an isocyanate compound. .
The undercoat layer 4 may contain other materials as necessary.

(Binder resin)
The binder resin contained in the undercoat layer 4 includes acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, and polyvinyl chloride resin. , Polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenolic resin, phenol-formaldehyde resin, melamine resin, urethane resin and other high molecular compounds, charge having charge transporting group A conductive resin such as a transport resin or polyaniline is used.

  As content of binder resin, the range of 5 mass% or more and 60 mass% or less is mentioned, for example with respect to the whole undercoat layer, It is desirable that it is 10 mass% or more and 55 mass% or less, 30 mass% or more More preferably, it is 50 mass% or less.

(Metal oxide particles)
Examples of the metal oxide particles include zinc oxide, titanium oxide, tin oxide, zirconium oxide and the like, and two or more kinds may be mixed and used.
Examples of the volume average particle size of the metal oxide particles include 50 μm to 200 μm, preferably 60 μm to 180 μm, and more preferably 70 μm to 120 μm.

  The volume average particle size of the metal oxide particles is measured using, for example, a laser diffraction type particle size distribution measuring apparatus (LA-700: manufactured by Horiba, Ltd.). As a measuring method, the sample in the state of dispersion is adjusted so as to have a solid content of 2 g, and ion exchange water is added thereto to make 40 ml. This is put into a cell until an appropriate concentration is reached, and measurement is performed after waiting for 2 minutes. The obtained volume average particle diameter for each channel is accumulated from the smaller one, and the place where the accumulation reaches 50% is defined as the volume average particle diameter.

  As content of the metal oxide particle contained in the undercoat layer 4, the range of 2.5 mass% or more is mentioned with respect to the whole undercoat layer, for example, In the range of 10 mass% or more and 70 mass% or less It is desirable that there is a range of 30% by mass or more and 50% by mass or less.

The metal oxide particles are preferably surface-treated with a surface treatment agent. As this surface treating agent, a coupling agent having an amino group is preferably exemplified.
Examples of the coupling agent having an amino group include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a surfactant. In particular, a silane coupling agent (particularly, a silane coupling agent having an amino group) is mentioned as a surface treatment agent that suppresses fogging by adjusting resistance.

  The silane coupling agent is an organic silane compound (an organic compound containing a silicon atom). Specifically, for example, 3-aminopropyltriethoxysilane, N, N-bis (β-hydroxyethyl) -γ- Aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc. Is mentioned.

  Whether the metal oxide particles are surface-treated with a coupling agent is confirmed by molecular structure analysis using FT-IR, Raman spectroscopy, XPS, or the like.

The method for surface treatment of the metal oxide particles is not particularly limited, and examples thereof include a dry method or a wet method.
When the surface treatment is performed by a dry method, for example, the surface treatment agent is directly dropped or dissolved in an organic solvent while stirring the metal oxide particles with a mixer having a large shearing force. Drop and spray with dry air or nitrogen gas. The dropping or spraying is performed at a temperature below the boiling point of the solvent, for example. After dripping or spraying, baking may be performed by further heating to 100 ° C. or higher.

  As a wet method, for example, metal oxide particles are stirred in a solvent, dispersed using an ultrasonic wave, a sand mill, an attritor, a ball mill, etc., and after adding a surface treating agent solution, stirring or dispersing, the solvent is removed. To do. Examples of the solvent removal method include filtration or distillation. After removing the solvent, baking may be performed at 100 ° C. or higher. In the wet method, the water containing the metal oxide particles may be removed before adding the surface treatment agent, for example, a method of removing with stirring and heating in a solvent used for the surface treatment agent solution, or A method of azeotropic removal with a solvent may be used.

The amount of the surface treatment agent attached to the surface of 100 parts by mass of the metal oxide particles (hereinafter sometimes referred to as “surface treatment amount”) is, for example, 0.5 parts by mass or more and 3 parts by mass or less. It is desirable that the amount be from 5 parts by weight to 2.0 parts by weight, and it is more desirable to be from 0.75 parts by weight to 1.30 parts by weight.
Examples of the method for measuring the surface treatment amount (that is, the amount of the surface treatment agent attached to the metal oxide particles) include a method for molecular structure analysis by FT-IR, Raman spectroscopy, XPS, and the like.

(Electron-accepting compound)
As described above, the electron-accepting compound is an electron-accepting compound having an anthraquinone structure. Here, the “compound having an anthraquinone structure” is specifically at least one selected from anthraquinone and anthraquinone derivatives, and more specifically a compound represented by the following general formula (1). It is good.

In General Formula (1), R ¹ and R ² each independently represent a hydroxyl group, a methyl group, a methoxymethyl group, a phenyl group, or an amino group, and m and n each independently represents an integer of 0 or more and 4 or less. Represent.
In general formula (1), a compound in which both m and n are 0 is anthraquinone, and in general formula (1), a compound in which at least one of m and n is an integer of 1 to 4 is an anthraquinone derivative. It is. That is, an anthraquinone derivative means a compound in which at least one hydrogen atom of anthraquinone is substituted with a substituent such as a hydroxyl group, a methyl group, a methoxymethyl group, a phenyl group, or an amino group.

Examples of the electron-accepting compound include, among others, anthraquinone in which m and n are both 0 in the general formula (1), or R ¹ is a hydroxyl group, and m is 1 or more and 3 or less. Suitable examples include hydroxyanthraquinone in which n is 0.
Specific examples of the electron accepting compound include anthraquinone, purpurin, alizarin, ethyl anthraquinone, aminohydroxyanthraquinone, and the like.

  Confirmation that the undercoat layer 4 contains an electron-accepting compound having an anthraquinone structure is performed by an analysis method such as gas chromatography, liquid chromatography, FT-IR, Raman spectroscopy, or XPS.

  The content of the electron accepting compound contained in the undercoat layer 4 is 1 part by mass or more and 5 parts by mass or less, and 2 parts by mass or more with respect to 100 parts by mass of the metal oxide particles contained in the undercoat layer 4. The amount is desirably 4 parts by mass or less.

  The content ratio of the metal oxide particles and the electron-accepting compound contained in the undercoat layer 4 is confirmed by an analysis method such as NMR spectrum, XPS, atomic absorption analysis, or electron beam microanalyzer.

(Isocyanate compound)
The isocyanate compound is a material that functions as a curing agent (crosslinking agent). Specifically, the isocyanate compound is not particularly limited, and examples thereof include a blocked isocyanate compound.
Examples of the blocked isocyanate compound include isocyanates obtained by reacting a polyisocyanate compound with a compound having active hydrogen serving as a blocking agent.
Specific examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane-4,4 ′ diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate.
On the other hand, examples of the blocking agent include lactams such as caprolactam, oximes such as methyl ethyl ketoxime and acetoxime, and β-diketones such as diethyl malonate and diethyl acetoacetate.
In the blocked isocyanate compound, since the isocyanate group is masked with a blocking agent, the coating liquid is prevented from gelling and thickening over time, and is excellent in workability.
The content of the isocyanate compound is preferably 0.1 parts by mass or more and 15 parts by mass or less, and preferably 0.5 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Other additives)
Resin particles may be added to the undercoat layer 4 to adjust the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate (PMMA) resin particles.

In the undercoat layer 4, a curing catalyst may be used in combination with the isocyanate compound (curing agent).
Examples of the curing catalyst include known materials that are generally used, and among these, it is desirable to select from an acid catalyst, an amine catalyst, and a metal compound catalyst. When a blocked isocyanate compound is used, it is desirable to use an amine catalyst or a metal compound catalyst. Examples of the metal compound catalyst include stannous oxide, dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, zinc naphthenate, antimony trichloride, potassium oleate, sodium O-phenylphenate, sodium lead nitrate, Examples thereof include diiron, tetra-n-butyltin, tetra (2-ethylhexyl) titanate, cobalt 2-ethylhexoate, and ferric 2-ethylhexoate iron.
The addition amount of the curing catalyst is desirably 0.0001% by mass or more and 0.1% by mass or less, and more desirably 0.001% by mass or more and 0.01% by mass or less with respect to the isocyanate compound (curing agent).

  The surface of the undercoat layer 4 may be polished for adjusting the surface roughness. Examples of the polishing method include buffing, sandblasting, wet honing, and grinding.

(Formation of undercoat layer)
When the undercoat layer 4 is formed, a coating solution (coating solution for forming the undercoat layer) in which the components of the composition are added to a solvent is used.
Examples of the solvent include organic solvents, and specific examples include aromatic hydrocarbon solvents such as toluene and chlorobenzene; aliphatic alcohols such as methanol, ethanol, n-propanol, iso-propanol, and n-butanol. Solvents; ketone solvents such as acetone, cyclohexanone, 2-butanone; halogenated aliphatic hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride; cyclic or linear ethers such as tetrahydrofuran, dioxane, ethylene glycol, diethyl ether System solvents; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate; and the like. The solvent may be used alone or in combination of two or more, and is not particularly limited, but a solvent that dissolves the binder resin is preferably used.

  The amount of the solvent used in the coating solution for forming the undercoat layer is not particularly limited as long as the binder resin is dissolved therein. For example, 0.05 part by mass or more and 200 parts by mass with respect to 1 part by mass of the binder resin. The following are listed.

Examples of the method for dispersing the metal oxide particles in the coating liquid for forming the undercoat layer include, for example, a media disperser such as a ball mill, a vibration ball mill, an attritor, and a sand mill, an agitator, an ultrasonic disperser, a roll mill, and a high-pressure homogenizer. Medialess dispersers such as the above. In addition, as a high-pressure homogenizer, a method such as a collision method in which a dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high pressure state, or a penetration method in which a fine flow path is dispersed in a high pressure state is used. Also good.
In order to keep the volume resistivity of the obtained undercoat layer 4 within the specified range described later, it is desirable to select an appropriate dispersion method. Specifically, the undercoat layer 4 is dispersed by a sand mill, a ball mill or the like using glass beads. Is preferred. The particle size of the glass beads is adjusted according to the components such as the metal oxide particles and the binder resin used, and specific examples include a particle size of 0.1 mm or more and 10 mm or less.

Examples of the method for applying the coating solution for forming the undercoat layer onto the conductive support 2 include, for example, 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. Examples thereof include a coating method.
And after apply | coating the coating liquid for undercoat layer formation on the electroconductive support body 2, while removing the solvent in a coating liquid by heat drying, the hardened undercoat layer is formed.

(Physical properties of the undercoat layer)
The thickness of the undercoat layer 4 is preferably 10 μm or more, more preferably 12 μm or more, and further preferably 18 μm or more and 40 μm or less.

The volume resistivity of the undercoat layer 4, from the viewpoint of suppressing an increase in residual potential, as measured by the AC impedance method, often in the range of more than ^{1.0 × 10 8 Ωm, 1.0 ×} 10 8 Ωm or more The range is preferably 1.0 × 10 ¹¹ Ωm or less, and more preferably 2.0 × 10 ⁸ Ωm or more and 1.0 × 10 ¹⁰ Ωm or less.

A detailed method for measuring the volume resistivity of the undercoat layer 4 is as follows.
First, the impedance of the undercoat layer 4 is measured. Using a conductive support such as an aluminum pipe in an impedance measurement sample as a cathode and a gold electrode as an anode, an AC voltage of 1 Vp-p is applied from the high frequency side in the frequency range from 1 MHz to 1 mHz, and the AC impedance of each sample is measured. To do. The volume resistivity of the undercoat layer 4 is obtained by fitting a Cole-Cole plot graph obtained from this measurement to an RC parallel equivalent circuit.

A method for producing an undercoat layer sample for measuring volume resistivity from an electrophotographic photoreceptor is as follows.
For example, a coating such as a charge generation layer and a charge transport layer covering the undercoat layer is removed using a solvent such as acetone, tetrahydrofuran, methanol, ethanol, etc., and a vacuum deposition method or the like is applied to the exposed undercoat layer. By attaching a gold electrode by sputtering or the like, an undercoat layer sample for volume resistivity measurement is obtained.

Examples of a method for adjusting the volume resistivity of the undercoat layer 4 within the above range include a method in which the amount of change in weight of the undercoat layer is within the above range.
Examples of other methods include a method of adjusting the addition amount and particle size of the metal oxide particles and changing the method of dispersing the metal oxide particles in the coating solution for forming the undercoat layer.
As the particle size of the metal oxide particles increases, the volume resistivity of the undercoat layer 4 tends to decrease. Moreover, the volume resistivity of the undercoat layer 4 tends to increase as the addition amount of the metal oxide particles is increased.
Moreover, when the dispersibility of the metal oxide particles in the coating liquid for forming the undercoat layer is improved, the volume resistivity of the undercoat layer 4 tends to increase. Specifically, the volume resistivity of the undercoat layer 4 tends to increase as the dispersion treatment time of the coating solution for forming the undercoat layer is lengthened.

-Intermediate layer-
An intermediate layer (not shown) may be further provided on the undercoat layer 4 as necessary to improve electrical characteristics, improve image quality, improve image quality maintainability, improve photosensitive layer adhesion, and the like. As the binder resin used for the intermediate layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl In addition to polymer resins such as acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, zirconium, titanium, aluminum, manganese, silicon atom, etc. And organometallic compounds containing
For forming the intermediate layer, for example, a coating solution in which the binder resin is dissolved in a solvent is used. As a coating method of the coating solution, known 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.
The thickness of the intermediate layer is set, for example, in the range of 0.1 μm to 3 μm.

-Charge generation layer-
The charge generation layer 5 is formed, for example, by dispersing a charge generation material in a binder resin.
As the charge generation material, for example, phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, titanyl phthalocyanine, and the like are used. ) Chlorogallium phthalocyanine crystal having strong diffraction peaks at least at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, at least a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-rays Metal-free phthalocyanine crystals having strong diffraction peaks at 7.7 °, 9.3 °, 16.9 °, 17.5 °, 22.4 °, and 28.8 °, Bragg angle (2θ ± 0.2 °) at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 , Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 25.1 ° and 28.3 °, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of at least 9.6 °, 24.1 ° and 27. A titanyl phthalocyanine crystal having a strong diffraction peak at 2 ° is used. In addition, quinone pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, anthrone pigments, quinacridone pigments and the like are used as charge generation materials. These charge generation materials are used alone or in admixture of two or more.

Examples of the binder resin in the charge generation layer 5 include polycarbonate resin such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, and acrylonitrile-styrene. Polymer resin, acrylonitrile-butadiene copolymer, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate copolymer resin, Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, poly-N-vinylcarbazole resin, etc. are used. That. These binder resins are used alone or in combination of two or more.
The mixing ratio (mass ratio) of the charge generation material and the binder resin is, for example, in the range of 10: 1 to 1:10, depending on the material used.

When the charge generation layer 5 is formed, a coating solution in which the above components are added to a solvent is used.
In order to disperse the charge generation material in the binder resin, the coating liquid is subjected to a dispersion treatment. As the dispersing means, a media disperser such as a ball mill, a vibrating ball mill, an attritor or a sand mill, or a medialess disperser such as an agitator, an ultrasonic disperser, a roll mill or a high pressure homogenizer is used. Furthermore, examples of the high-pressure homogenizer include a liquid-liquid collision in a high-pressure state, a collision system that disperses the liquid-liquid by colliding with a liquid-wall, and a penetration system that disperses the fine liquid through a high-pressure state.

Examples of a method for applying the coating solution for forming the charge generation layer thus obtained on the undercoat layer 4 include a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, Examples thereof include a knife coating method and a curtain coating method.
The thickness of the charge generation layer 5 is desirably set in a range from 0.01 μm to 5 μm.

-Charge transport layer-
The charge transport layer 6 is formed, for example, by dispersing a charge transport material in a binder resin.
Examples of such charge transport materials include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [Pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline and other pyrazoline derivatives, triphenylamine, N, N′-bis (3,4-dimethylphenyl) biphenyl Aromatic tertiary amino compounds such as -4-amine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline, N, N′-bis (3-methylphenyl) -N, N′-diphenyl Aromatic tertiary dia such as benzidine, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine Mino compounds, 1,2,4-triazine derivatives such as 3- (4′-dimethylaminophenyl) -5,6-di- (4′-methoxyphenyl) -1,2,4-triazine, 4-diethylaminobenzaldehyde Hydrazone derivatives such as -1,1-diphenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran, p- ( 2,2-diphenylvinyl) -N, N-diphenylaniline and other α-stilbene derivatives, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, hole transport materials such as poly-N-vinylcarbazole and its derivatives, chloranil , Quinone compounds such as broanthraquinone, tetraanoquinodimethane compounds Group consisting of electron transport materials such as fluorenone compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone, xanthone compounds and thiophene compounds, and the above compounds. Examples thereof include a polymer having a chain or a side chain. These charge transport materials are used alone or in combination of two or more.

  Examples of the binder resin in the charge transport layer 6 include polycarbonate resin such as biphenyl copolymerized polycarbonate resin, bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, Polystyrene resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer resin, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride -Vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, insulating resin such as chlorine rubber, and poly Alkenyl carbazole, polyvinyl anthracene, organic photoconductive polymers such as polyvinyl pyrene, and the like, used alone or in admixture of two or more.

  Further, when the charge transport layer 6 is a surface layer of an electrophotographic photoreceptor (a layer disposed on the side farthest from the conductive support 2 of the photosensitive layer), the charge transport layer 6 has lubricating particles (for example, silica particles). , Alumina particles, fluorine resin particles such as polytetrafluoroethylene (PTFE), and silicone resin particles). These lubricating particles may be used as a mixture of two or more.

  Furthermore, when the charge transport layer 6 is a surface layer of an electrophotographic photosensitive member, a fluorine-modified silicone oil may be added to the charge transport layer 6. Examples of the fluorine-modified silicone oil include compounds having a fluoroalkyl group.

  In addition, as mass ratio of the charge transport material and binder resin in the charge transport layer 6, the range of 10: 1 to 1: 5 is mentioned, for example. That is, the content of the charge transport material with respect to the entire charge transport layer 6 is, for example, in the range of 17% by mass to 91% by mass.

The charge transport layer 6 is formed using a coating liquid for forming a charge transport layer in which the above components are added to a solvent.
Examples of the solvent include known organic solvents, for example, aromatic hydrocarbon solvents such as toluene and chlorobenzene, aliphatic alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, and n-butanol, acetone, and cyclohexanone. , Ketone solvents such as 2-butanone, halogenated aliphatic hydrocarbon solvents such as methylene chloride, chloroform and ethylene chloride, cyclic or linear ether solvents such as tetrahydrofuran, dioxane, ethylene glycol and diethyl ether, methyl acetate, Examples thereof include ester solvents such as ethyl acetate and n-butyl acetate. Moreover, you may use these solvents individually or in mixture of 2 or more types. Any solvent can be used as long as it can dissolve the binder resin as a mixed solvent.

  Examples of a dispersion method for dispersing the lubricant particles in the coating liquid for forming the charge transport layer include, for example, a media disperser such as a ball mill, a vibration ball mill, an attritor, and a sand mill, and a stirrer, an ultrasonic disperser, and a roll mill. And a method using a medialess disperser such as a high-pressure homogenizer or a nanomizer. Further, examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high pressure state, and a penetration method in which the fine liquid is penetrated and dispersed in a high pressure state.

As a method for forming the charge transport layer 6, for example, the charge transport layer forming coating solution is applied onto the charge generation layer 5 of the conductive support 2 on which the undercoat layer 4 and the charge generation layer 5 are formed. And a method of forming the charge generation layer 6 by drying.
Examples of the method for applying the coating liquid for forming the charge transport layer on the charge generation layer 5 include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain. Examples thereof include a coating method.
And after apply | coating the said coating liquid on the electric charge generation layer 5, the solvent in a coating liquid is removed by a heat drying process. Examples of the film thickness of the charge transport layer 6 include a range of 5 μm to 50 μm.

  For the purpose of preventing deterioration of the photoreceptor due to ozone, nitrogen oxide, or light or heat generated in the image forming apparatus, an antioxidant, a light stabilizer, a heat stabilizer, etc. are included in each layer constituting the photosensitive layer 3. Additives may be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and their derivatives, organic sulfur compounds, and organic phosphorus compounds. Examples of light stabilizers include derivatives such as benzophenone, benzoazole, dithiocarbamate, and tetramethylpipen.

The photoreceptor 1 of the present embodiment has the charge transport layer 6 as the outermost surface layer, but may have a configuration in which a protective layer is further formed on the charge transport layer.
Further, the photoreceptor 1 of the present embodiment is a function separation type as the photosensitive layer 3, but the photosensitive layer 3 is a single layer type (photosensitive layer having charge generation ability / charge transport ability). Also good.

<Image forming apparatus>
Next, an image forming apparatus provided with the electrophotographic photosensitive member according to this embodiment will be described.
-First embodiment-
FIG. 2 schematically shows the basic configuration of the image forming apparatus according to the first embodiment.
An image forming apparatus 200 shown in FIG. 2 includes, for example, the electrophotographic photosensitive member 1 of the above embodiment, a charging device 208 (charging means) that is connected to the power source 209 and charges the electrophotographic photosensitive member 1, and a charging device 208. An exposure device 210 (electrostatic latent image forming means) for exposing the charged electrophotographic photosensitive member 1 to form an electrostatic latent image, and developing the electrostatic latent image formed by the exposure device 210 with toner A developing device 211 (developing means) that forms a toner image by developing with an agent; a transfer device 212 (transfer means) that transfers the toner image formed on the surface of the electrophotographic photosensitive member 1 to a transfer medium 500; Thereafter, a toner removing device 213 (toner removing means) that removes toner remaining on the surface of the electrophotographic photoreceptor 1 and a fixing device 215 that fixes the toner image transferred to the transfer medium 500 to the transfer medium 500. Comprising a fixing means), a.
The image forming apparatus 200 shown in FIG. 3 does not include an erasing-less image forming apparatus that does not include a charge removing unit that removes charges remaining on the surface of the electrophotographic photosensitive member after the toner image on the surface of the electrophotographic photosensitive member is transferred. It is.

The charging device 208 includes a charging member. For example, when charging the photoreceptor 1, a DC voltage is applied to the charging member. As a voltage range, when a DC voltage is applied, positive or negative 50V or more and 2000V or less is desirable, and 100V or more and 1500V or less is more desirable according to the photosensitive member charging potential.
When the AC voltage is superimposed, the peak-to-peak voltage is 400 V to 1800 V, preferably 800 V to 1600 V, and more preferably 1200 V to 1600 V. The frequency of the AC voltage is 50 Hz to 20000 Hz, preferably 100 Hz to 5000 Hz.

Examples of the charging member include a roller, a brush, and a film. Among them, as the roller-shaped charging member (hereinafter sometimes referred to as “charging roller”), for example, a member composed of a material whose electric resistance is adjusted to a range of 10 ³ Ω to 10 ⁸ Ω can be mentioned. . The charging roller may be a single layer or may be composed of a plurality of layers.
When a charging roller is used as the charging member, examples of the pressure that contacts the photoreceptor 1 include a range of 250 mgf to 600 mgf (2.45 mN to 5.88 mN).

Examples of the material constituting the charging member include urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, EPDM (ethylene-propylene-diene copolymer rubber), epichlorohydrin rubber and other synthetic rubber, polyolefin, polystyrene, chloride Examples thereof include an elastomer composed of vinyl or the like as a main material and a suitable amount of a conductivity imparting agent such as conductive carbon, metal oxide, or ionic conductive agent.
Furthermore, a resin such as nylon, polyester, polystyrene, polyurethane, silicone is made into a paint, and an appropriate amount of a conductivity imparting agent such as conductive carbon, metal oxide, and ionic conductive agent is blended therein, and the resulting paint is dipped, sprayed, You may use it, laminating | stacking by methods, such as roll coating.

When a charging roll is used as the charging member, the charging roll is brought into contact with the surface of the photoreceptor 1 so that the charging means is driven and rotated even if the charging means does not have a driving means. A means may be attached and rotated at a peripheral speed different from that of the photoreceptor 1.
The charging member is not limited to the contact charging type charging member, and may be a non-contact charging type charging member such as corotron or scorotron.

As the exposure apparatus 210, known exposure means is used. Specifically, for example, an optical system device that performs exposure with a light source such as a semiconductor laser, an LED (Light Emitting Diode), or a liquid crystal shutter is used. The amount of time writing, for example, range from 0.5 mJ / ^{m 2} or more 5.0mJ / ^{m 2} and the like on the photosensitive member surface.

As the developing device 211, for example, a developing brush (developer holding body) to which a developer containing a carrier and toner adheres is brought into contact with an electrostatic latent image holding body and developed, and conductive rubber, conductive rubber Examples include a contact-type one-component developing unit that attaches toner onto an elastic-conveying roll (developer holder) and develops the toner on the electrostatic latent image holder.
The toner is not particularly limited as long as it is a known toner. Specifically, for example, the toner may include at least a binder resin and, if necessary, a colorant, a release agent, and the like.

  The method for producing the toner is not particularly limited. For example, a known pulverization method, a wet melt spheronization method prepared in a dispersion medium, suspension polymerization, dispersion polymerization, emulsion polymerization aggregation method and the like are known. Examples thereof include a toner production method using a polymerization method.

  When the developer is a two-component developer containing a toner and a carrier, the carrier is not particularly limited. For example, a core material such as a magnetic metal such as iron oxide, nickel or cobalt, or a magnetic oxide such as ferrite or magnetite. And a carrier coated with a resin layer on the surface of the core material (non-coated carrier). In the two-component developer, for example, the mixing ratio (mass ratio) of the toner and the carrier is in the range of toner: carrier = 1: 100 to 30: 100, and even in the range of 3: 100 to 20: 100. Good.

  Examples of the transfer device 212 include a roller-type contact-type charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger using a corona discharge or a corotron transfer charger. Can be mentioned.

The toner removing device 213 is for removing residual toner adhering to the surface of the electrophotographic photosensitive member 1 after the transfer process, and the electrophotographic photosensitive member 1 thus cleaned is repeatedly subjected to the above image forming process. Provided. As the toner removing device 213, a foreign matter removing member (cleaning blade), brush cleaning, roll cleaning, and the like are used. Among these, it is desirable to use a cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.
Note that the toner removing device 213 need not be provided when residual toner is not a problem, for example, when the toner hardly remains on the surface of the photoreceptor 1.

A basic image forming process of the image forming apparatus 200 will be described.
First, the charging device 208 charges the surface of the photoreceptor 1 to a predetermined potential. Next, the surface of the charged photoreceptor 1 is exposed by the exposure device 210 based on the image signal to form an electrostatic latent image.

Next, the developer is held on the developer holding member of the developing device 211, the held developer is conveyed to the photosensitive member 1, and the developer holding member and the photosensitive member 1 are in proximity (or contact). It is supplied to the electrostatic latent image. As a result, the electrostatic latent image is visualized and becomes a toner image.
The developed toner image is conveyed to the position of the transfer device 212 and transferred directly to the transfer medium 500 by the transfer device 212.

  Next, the transfer medium 500 to which the toner image is transferred is conveyed to the fixing device 215, and the toner image is fixed to the transfer medium 500 by the fixing device 215. Examples of the fixing temperature include 100 ° C. or higher and 180 ° C. or lower.

On the other hand, after the toner image is transferred to the transfer medium 500, the toner particles that are not transferred and remain on the photoreceptor 1 are transported to the contact position with the toner removing device 213 and collected by the toner removing device 213.
As described above, image formation by the image forming apparatus 200 is performed.

-Second Embodiment-
FIG. 3 schematically shows the basic configuration of the image forming apparatus according to the second embodiment. An image forming apparatus 220 shown in FIG. 3 is an intermediate transfer type image forming apparatus. In the housing 400, four electrophotographic photosensitive members 1a, 1b, 1c, and 1d are arranged in parallel along the intermediate transfer belt 409. ing. For example, an image is formed in which the photoreceptor 1a is yellow, the photoreceptor 1b is magenta, the photoreceptor 1c is cyan, and the photoreceptor 1d is black.
Further, the image forming apparatus 220 shown in FIG. 3 is an erase-less type image forming apparatus that does not include a charge removing unit that removes charges remaining on the surface of the electrophotographic photosensitive member after the toner image on the surface of the electrophotographic photosensitive member is transferred. It is.

Here, the electrophotographic photoreceptors 1a, 1b, 1c, and 1d mounted on the image forming apparatus 220 are the electrophotographic photoreceptors of this embodiment, respectively.
Each of the electrophotographic photoreceptors 1a, 1b, 1c, and 1d rotates in one direction (counterclockwise on the paper surface), and charging rolls 402a, 402b, 402c, and 402d, and developing devices 404a, 404b, and 404c along the rotation direction. 404d, primary transfer rolls 410a, 410b, 410c, 410d and cleaning blades 415a, 415b, 415c, 415d. The developing devices 404a, 404b, 404c, and 404d supply toners of four colors, yellow, magenta, cyan, and black, which are accommodated in toner cartridges 405a, 405b, 405c, and 405d, respectively, and also include primary transfer rolls 410a, 410b, 410c and 410d are in contact with the electrophotographic photoreceptors 1a, 1b, 1c and 1d through the intermediate transfer belt 409, respectively.

  Further, a laser light source (exposure device) 403 is disposed in the housing 400, and irradiates the surfaces of the electrophotographic photoreceptors 1a, 1b, 1c, and 1d after charging with laser light emitted from the laser light source 403. As a result, in the rotation process of the electrophotographic photoreceptors 1a, 1b, 1c, and 1d, the charging, exposure, development, primary transfer, and cleaning (removal of foreign matters such as toner) are sequentially performed, and the toner images of the respective colors are intermediate. The image is transferred onto the transfer belt 409 in an overlapping manner. The electrophotographic photoreceptors 1a, 1b, 1c, and 1d after the toner image is transferred onto the intermediate transfer belt 409 are subjected to the next image forming process without passing through the process of removing the surface charge.

  The intermediate transfer belt 409 is supported with tension by a drive roll 406, a back roll 408, and a support roll 407, and rotates without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to be in contact with the back roll 408 through the intermediate transfer belt 409. The intermediate transfer belt 409 that has passed through the position sandwiched between the back roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed facing the drive roll 406, and then forms the next image. Used repeatedly in the process.

  In addition, a container 411 that houses a transfer medium is provided in the housing 400, and the transfer medium 500 such as paper in the container 411 is sandwiched between the intermediate transfer belt 409 and the secondary transfer roll 413 by the transfer roll 412. Then, the sheet is sequentially transferred to a position sandwiched between two fixing rolls 414 that are in contact with each other, and then discharged to the outside of the housing 400.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. May be. In the case of a belt shape, a known resin is used as the resin material constituting the base material of the intermediate transfer member. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Further, a resin material and an elastic material may be blended and used.

The transfer medium according to the above embodiment is not particularly limited as long as it is a medium that transfers a toner image formed on an electrophotographic photosensitive member.
In the above embodiment, the charging rolls 402a, 402b, 402c, and 402d employ a system that applies only a DC voltage.

<Process cartridge>
FIG. 4 schematically shows a basic configuration of an example of a process cartridge including the electrophotographic photosensitive member of the present embodiment. The process cartridge 300 develops the electrostatic latent image formed on the electrophotographic photosensitive member 1 by exposure with a developer including toner, together with the electrophotographic photosensitive member 1, a charging device 208 for charging the electrophotographic photosensitive member 1. A developing device 211 that forms a toner image, a toner removing device 213 that removes toner remaining on the surface of the electrophotographic photosensitive member 1 after transfer, and an opening 218 for exposure are combined using an attachment rail 216. It is an integrated one.

The process cartridge 300 includes a transfer device 212 that transfers the toner image formed on the surface of the electrophotographic photosensitive member 1 to the transfer medium 500, and the toner image transferred to the transfer medium 500 to the transfer medium 500. The image forming apparatus main body is composed of a fixing device 215 to be fixed and other components not shown, and constitutes the image forming apparatus together with the image forming apparatus main body.
In addition to the electrophotographic photosensitive member 1, the charging device 208, the developing device 211, the toner removing device 213, and the opening 218 for exposure, the process cartridge 300 exposes the surface of the electrophotographic photosensitive member 1 (see FIG. (Not shown).
It should be noted that the process cartridge of the present embodiment only needs to include at least the electrophotographic photoreceptor 1.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” is based on mass.

[Production of electrophotographic photosensitive member]
<Example 1>
-Formation of undercoat layer-
60 parts by mass of zinc oxide particles (manufactured by Teika, volume average particle size: 70 nm, specific surface area value: 15 m ² / g) are stirred and mixed with 500 parts by mass of tetrahydrofuran, and KBM603 (surface treatment agent) is used as a silane coupling agent (surface treatment agent). 1.25 parts by mass of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of the zinc oxide particles, and the mixture was stirred for 2 hours. Thereafter, tetrahydrofuran was removed by distillation under reduced pressure, baking was performed at 120 ° C. for 3 hours, and zinc oxide particles surface-treated with a silane coupling agent were obtained.

  100 parts by mass of zinc oxide particles surface-treated with a silane coupling agent, 1 part by mass of anthraquinone as an electron-accepting compound, 22.5 parts by mass of blocked isocyanate (Sumijoule 3173, manufactured by Sumitomo Bayern Urethane) as a curing agent, and butyral 38 parts by mass of a resin (ESLEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) in 38 parts by mass dissolved in 142 parts by mass of methyl ethyl ketone and 25 parts by mass of methyl ethyl ketone were mixed, and a glass bead having a diameter of 1 mm was used in a sand mill. Dispersion was performed for 4 hours to obtain a dispersion. To the obtained dispersion, 0.008 parts by mass of dioctyltin dilaurate and 6.5 parts by mass of silicone resin particles (Tospearl 145, manufactured by GE Toshiba Silicone) are added as a catalyst, and coating for forming an undercoat layer. A liquid was obtained. This coating solution is applied onto an aluminum substrate having a diameter of 30 mm by a dip coating method, and heat drying (dry curing) is performed under the conditions of a heat drying temperature of 175 ° C., a heat drying humidity of 40 RH%, and a heat drying time of 20 minutes, A subbing layer having a thickness of 15 μm was obtained.

-Formation of charge generation layer-
Next, as a charge generation 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 °. Using a glass bead having a diameter of 1 mm, a mixture of 15 parts by mass of chlorogallium phthalocyanine crystal, 10 parts by mass of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Union Carbide) and 300 parts by mass of n-butyl alcohol was used. Then, it was dispersed in a sand mill for 4 hours to obtain a coating solution for forming a charge generation layer. This coating solution for forming the charge generation layer was dip-coated on the undercoat layer and dried to obtain a charge generation layer having a thickness of 0.2 μm.

-Formation of charge transport layer-
Next, 8 parts by mass of tetrafluoroethylene resin particles (average particle size: 0.2 μm), 0.015 parts by mass of fluorinated alkyl group-containing methacrylic copolymer (weight average molecular weight: 30000), 4 parts by mass of tetrahydrofuran, 1 part by mass of toluene was kept at a liquid temperature of 20 ° C. and stirred for 48 hours to obtain a tetrafluoroethylene resin particle suspension A.

  Next, 4 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine as a charge transport material, and bisphenol Z type 6 parts by mass of a polycarbonate resin (viscosity average molecular weight: 40,000) and 0.1 part by mass of 2,6-di-tert-butyl-4-methylphenol as an antioxidant are mixed to obtain 24 parts by mass of tetrahydrofuran. And 11 mass parts of toluene was mixed and dissolved, and the mixed solution B was obtained.

After adding the tetrafluoroethylene resin particle suspension A to this mixed solution B and stirring and mixing it, using a high-pressure homogenizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) equipped with a through-type chamber having a fine flow path, The dispersion treatment by increasing the pressure to 4900 N / cm ² (500 kgf / cm ² ) was repeated 6 times. A fluorine-modified silicone oil (trade name: FL-100, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto so as to be 5 ppm, and stirred to obtain a coating liquid for forming a charge transport layer.

  This coating solution was applied onto the charge generation layer and dried at 140 ° C. for 25 minutes to form a charge transport layer, whereby an electrophotographic photoreceptor 1 having a thickness of 32.0 μm was obtained.

<Example 2>
An electrophotographic photoreceptor 2 was produced in the same manner as in Example 1 except that the amount of the electron-accepting compound was 5 parts by mass and the volume average particle diameter of the zinc oxide fine particles was 100 nm.
However, when the undercoat layer was formed, the heating and drying humidity was changed to 20 RH%.

<Example 3>
An electrophotographic photoreceptor 3 was produced in the same manner as in Example 2 except that the amount of the electron-accepting compound was 1 part by mass in the production of the undercoat layer.
However, when forming the undercoat layer, the heating and drying humidity was changed to 40 RH%, and the heating and drying time was changed to 15 minutes.

<Example 4>
An electrophotographic photosensitive member 4 was produced in the same manner as in Example 2 except that in the formation of the undercoat layer, the electron accepting compound was 5 parts by mass and the dispersion time by the sand mill was 2 hours.
However, when forming the undercoat layer, the heating and drying temperature was changed to 185 ° C. and the heating and drying humidity was changed to 40 RH%.

<Example 5>
In the production of the undercoat layer, an electrophotographic photoreceptor 5 was produced in the same manner as in Example 1 except that the electron accepting compound was 1 part by mass of purpurin.

<Example 6>
In the production of the undercoat layer, an electrophotographic photoreceptor 6 was produced in the same manner as in Example 3 except that the electron accepting compound was 1 part by mass of purpurin.

<Comparative Example 1>
An electrophotographic photosensitive member C1 was produced in the same manner as in Example 1, except that the electron-accepting compound was 2 parts by mass and the dispersion time by the sand mill was 7 hours.
However, the heat drying temperature was changed to 165 ° C. when forming the undercoat layer.

<Comparative example 2>
An electrophotographic photosensitive member C2 was produced in the same manner as in Example 2 except that in the production of the undercoat layer, the electron-accepting compound was 2 parts by mass and the dispersion time by the sand mill was 3 hours.
However, when forming the undercoat layer, the heating and drying temperature was changed to 195 ° C., the heating and drying humidity was changed to 10 RH%, and the heating and drying time was changed to 40 minutes.

[Measurement of weight change of undercoat layer]
-Preparation of measurement sample-
The undercoat layer coating solutions used in preparing the photoreceptors of the above examples and comparative examples were each applied onto an aluminum plate by a blade coating method, and heat dried (dry cured) under the heat drying conditions of each example. About 7 mg of a sample was taken from this monolayer film, and this was weighed on an aluminum dish for TG measurement to measure the weight loss rate.

-Measuring method-
For measurement of the amount of change in weight, “EXSTER TG / DTA 6200” manufactured by SII Nano Technology was used.
Then, using alumina as a standard substance, measurement was performed from 30 ° C. to 500 ° C. at a temperature increase rate of 10 ° C./min, and the weight change (weight reduction rate) from 30 ° C. to 230 ° C. was measured. Table 1 shows the amount of change in weight in Examples and Comparative Examples.

[Measurement of resistivity of undercoat layer]
-Preparation of measurement sample-
The undercoat layer coating solutions used in preparing the photoreceptors of the above examples and comparative examples were each applied onto an aluminum plate by a blade coating method, and heat dried (dry cured) under the heat drying conditions of each example. About this undercoat single layer film, a gold electrode with a thickness of 100 nm was attached as a counter electrode by a vacuum deposition method, and was used for resistivity measurement.

-Measurement method-
For measurement of impedance, SI 1287 electrochemical interface (manufactured by Toyo Technica) was used as a power source, SI 1260 inpedance / gain phase analyzer (manufactured by Toyo Technica) was used as an ammeter, and 1296 dielectric interface (manufactured by Toyo Technica) was used as a current amplifier.
Using the aluminum pipe in the impedance measurement sample as the cathode and the gold electrode as the anode, an AC voltage of 1 Vp-p is applied from the high frequency side in the frequency range from 1 MHz to 1 mHz, and the AC impedance of each sample is measured. The volume resistivity was obtained by fitting the obtained Cole-Cole plot graph to an RC parallel equivalent circuit. Table 1 shows the volume resistivity in Examples and Comparative Examples.

[Evaluation]
-Residual potential evaluation-
The following measurements were performed on the residual potential of the photoreceptors obtained in the above examples and comparative examples.
Under normal temperature and normal humidity (20 ° C., 40 RH%), with the photoconductor rotated at 100 rpm, the photoconductor was charged to −700 V with a scorotron charger, and a semiconductor laser having a wavelength of 780 nm was used 1 second after charging. It was discharged by irradiating with 10 mJ / m ² light. Subsequently, the photoconductor 3 seconds after the discharge was irradiated with 50 mJ / m ² of red LED light to perform slow charging. Then, the surface potential V of the photosensitive member 100 msec after slow current was measured, and this was used as the value of the residual potential.
After the measurement, the above-mentioned measurement was performed after repeating 1000 cycles of exposure, charging, discharging, and slow charging on the photoreceptor, and the difference between the obtained residual potential and the initial residual potential was defined as the residual potential increase.

-Image quality evaluation-
The photoreceptors obtained in the above examples and comparative examples were incorporated into a modified machine of the image forming apparatus DocuCentre 505a. And the following evaluation was performed using this image forming apparatus.
Continuously form 50,000 images (A4 size) while changing the environment of high temperature and high humidity (28 ° C, 85RH%) and low temperature and low humidity (15 ° C, 10RH%) alternately every 10 images. went. Thereafter, the ghost was evaluated based on the following method.
In a 20 ° C, 40% RH environment, an arbitrary number of 15 mm square patterns are printed as an image for ghost evaluation for one round of the electrophotographic photosensitive member, and then the entire halftone image is printed in the next cycle. The ghost image that appeared on the halftone image was evaluated based on the following criteria.
The evaluation criteria are as follows. The results are shown in Table 1.
A: No ghost is seen in the image.
○: Slight ghost is seen in the image.
Δ: A ghost is seen in the image.
X: A terrible ghost is seen in the image.

From the above results, it can be seen that the increase in the residual potential is suppressed in this example as compared with the comparative example.
In addition, in this example, it can be seen that a better result was obtained for the evaluation of image quality than in the comparative example.

1, 1a, 1b, 1c, 1d Electrophotographic photoreceptor, 2 conductive support, 3 photosensitive layer, 4 undercoat layer, 5 charge generation layer, 6 charge transport layer, 200 image forming apparatus, 208 charging apparatus, 210 exposure Device, 211 developing device, 212 transfer device, 213 toner removing device, 215 fixing device, 220 image forming device, 404a, 404b, 404c, 404d developing device, 500 medium to be transferred

Claims (4)

A conductive support;
An undercoat layer provided on the conductive support, wherein the binder resin, metal oxide particles, and an anthraquinone structure having a content of 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the metal oxide particles The weight change amount from 0 ° C. to 230 ° C. in the differential heat / thermogravimetric simultaneous measurement (TG / DTA measurement) is 0.05 mass. An undercoat layer that is not less than
A photosensitive layer provided on the undercoat layer;
An electrophotographic photosensitive member having:   The electrophotographic photoreceptor according to claim 1, wherein the charge-accepting compound is an electron-accepting compound having a hydroxyanthraquinone structure. At least the electrophotographic photoreceptor according to claim 1 or 2,
A process cartridge attached to and detached from the image forming apparatus. The electrophotographic photosensitive member according to claim 1 or 2,
Charging means for charging the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for exposing the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image;
Developing means for containing a developer and developing the electrostatic latent image with the developer to form a toner image;
Transfer means for transferring the toner image to a transfer medium;
An image forming apparatus comprising at least