JP2017111273A - Electrophotographic photoreceptor and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor capable of obtaining high memory resistance and granularity, and method for manufacturing the same.SOLUTION: The method for manufacturing an electrophotographic photoreceptor includes laminating a photosensitive layer and a protective layer in this order on a conductive support. The protective laye includes P type semiconductor fine particles in a resin, and as the P type semiconductor fine particles, used are fine particles obtained by pulverizing a powdery sintered body consisting of a copper composite oxide by plasma-treatment. In the method for manufacturing an electrophotographic photoreceptor, a compound represented by the general-formula (1): CuMO(where, M represents a group 13 element in the periodic table) is preferably used as the copper composite oxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrophotographic photosensitive member used in an electrophotographic image forming process and a method for manufacturing the same.

An electrophotographic photosensitive member (hereinafter also simply referred to as “photosensitive member”) that constitutes an image forming apparatus such as an electrophotographic copying machine or a printer has a long life and the image quality stability of the formed image. Is required. In the photoconductor, the lifetime of the photoconductor is determined as the surface of the photoconductor is worn.
In recent years, as a photoreceptor that has excellent wear resistance, scratch resistance and environmental stability and has a long life, a photosensitive layer is laminated on a conductive support, and a protective layer made of a cured resin is formed on the photosensitive layer. Photoconductors have been developed.

  In such a photoreceptor, further improvement in memory resistance and graininess is required for further improvement in image quality. In order to improve these, for example, it has been proposed that P-type semiconductor fine particles are further contained in the protective layer as high-strength fine particles having hole transport properties (see, for example, Patent Documents 1 and 2).

  However, the actual situation is that the demands for further improvement in memory resistance and graininess are not sufficiently met.

JP 2013-130603 A Japanese Patent Laying-Open No. 2015-141269

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide an electrophotographic photoreceptor capable of obtaining high memory resistance and graininess and a method for producing the same.

The method for producing an electrophotographic photoreceptor of the present invention is a method for producing an electrophotographic photoreceptor in which a photosensitive layer and a protective layer are laminated in this order on a conductive support,
The protective layer contains P-type semiconductor fine particles in the resin,
As the P-type semiconductor fine particles, a powdered sintered body made of a copper composite oxide is used which is atomized by plasma treatment.

In the method for producing an electrophotographic photoreceptor of the present invention, it is preferable to use a compound represented by the following general formula (1) as the copper composite oxide.
General formula (1): CuMO ₂
[Wherein, M represents an element belonging to Group 13 of the periodic table. ]

  In the method for producing an electrophotographic photosensitive member of the present invention, it is preferable to use a P-type semiconductor fine particle having a number average primary particle size of 10 to 200 nm.

  In the method for producing an electrophotographic photosensitive member of the present invention, it is preferable to use a P-type semiconductor fine particle that has been subjected to a surface treatment.

The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member in which a photosensitive layer and a protective layer are laminated in this order on a conductive support,
The protective layer contains P-type semiconductor fine particles in the resin,
The P-type semiconductor fine particles are obtained by atomizing a powdery sintered body made of a copper composite oxide by plasma treatment.

  According to the method for producing an electrophotographic photosensitive member of the present invention, high memory resistance and granularity can be obtained by introducing P-type semiconductor fine particles having a high particle size and uniform shape into the protective layer. An electrophotographic photoreceptor can be produced.

FIG. 3 is a partial cross-sectional view illustrating an example of a layer configuration of the electrophotographic photoreceptor of the present invention. 1 is a cross-sectional view illustrating the configuration of an example of an image forming apparatus on which an electrophotographic photosensitive member of the present invention is mounted.

  Hereinafter, the present invention will be specifically described.

[Photoreceptor]
The photoconductor of the present invention is a photoconductor mounted on an image forming apparatus including a charging unit, an exposure unit, a developing unit, a transfer unit, and a cleaning unit, and a photosensitive layer and a protective layer are arranged in this order on a conductive support. It is an organic photoreceptor formed by lamination.

  In the present invention, the organic photoreceptor means a structure in which at least one of a charge generation function and a charge transport function essential to the structure of the photoreceptor is exhibited by an organic compound. Or a photosensitive member having an organic photosensitive layer composed of an organic charge transport material, a photosensitive member having all known organic photoreceptors, such as a photosensitive member having an organic photosensitive layer in which a charge generation function and a charge transport function are composed of a polymer complex. Say.

  For example, as shown in FIG. 1, the photoconductor 1 is formed by laminating an intermediate layer 1b, a charge generation layer 1c, a charge transport layer 1d, and a protective layer 1e in this order on a conductive support 1a. The photosensitive layer 1f is composed of the charge generation layer 1c and the charge transport layer 1d.

[Protective layer 1e]
The protective layer 1e constituting the photoconductor 1 of the present invention is obtained by finely pulverizing a powdery sintered body made of a copper composite oxide in a binder resin (hereinafter also referred to as "binder resin for protective layer") by plasma treatment. P-type semiconductor fine particles (hereinafter also referred to as “specific P-type semiconductor fine particles”) 1eA.

[Specific P-type semiconductor fine particles 1eA]
The specific P-type semiconductor fine particle 1eA according to the present invention is obtained by atomizing a powdery sintered body (hereinafter, also referred to as “raw material P-type semiconductor fine particles”) made of a copper composite oxide by plasma treatment.

[Raw material P-type semiconductor fine particles]
The raw material P-type semiconductor fine particles are semiconductor particles in which carriers for transporting charges are holes, and contribute to image quality stability such as memory resistance.

In the present invention, it is preferable to use a compound composed of a compound represented by the following general formula (1) as the copper composite oxide constituting the raw material P-type semiconductor fine particles.
General formula (1): CuMO ₂
[Wherein, M represents an element belonging to Group 13 of the periodic table. ]
As the copper complex oxide constituting the raw material P-type semiconductor fine particles, one obtained from M ₂ O ₃ (wherein M represents an element belonging to Group 13 of the periodic table) and Cu ₂ O is used. Is preferred.
The Cu ₂ O and M ₂ O ₃ as a raw material of the copper compound oxide, it is preferable to use a high purity.

Specific examples of Group 13 elements in the periodic table include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). In the present invention, aluminum Preferably, gallium or indium is used.
In the present invention, preferred examples of the compound represented by the general formula (1) include CuAlO ₂ , CuGaO ₂ , and CuInO ₂ .

The raw material P-type semiconductor fine particles are produced by a solid phase method (sintering method).
Since the raw material P-type semiconductor fine particles produced by the solid phase method contain a small amount of impurities, by atomizing the raw material P-type semiconductor fine particles by plasma treatment, the uniformity of the particle size and shape is high. In addition, specific P-type semiconductor fine particles 1eA in which the generation of impurities is extremely suppressed can be produced.
The particle size of the raw material P-type semiconductor fine particles produced by the solid phase method is, for example, 1 to several tens of μm.

Specifically, for example, when CuAlO ₂ is used as the copper composite oxide constituting the raw material P-type semiconductor fine particles, the raw material P-type semiconductor fine particles are powdered Al ₂ O ₃ (purity 99.9%) and powdery Cu ₂ O (99.9%) was mixed at a molar ratio of 1: 1, calcined at a temperature of 1100 ° C. for 4 days in an argon gas atmosphere, and further sintered at 1100 ° C. for 2 days, Can be obtained.

The plasma treatment is performed by generating a thermal plasma flame and introducing the raw material P-type semiconductor fine particles together with the carrier gas into the thermal plasma flame.
As the carrier gas, for example, argon gas or nitrogen gas can be used.
The high frequency voltage applied to the high frequency oscillation coil of the plasma torch can be, for example, about 4 MHz and about 80 kVA.
As the plasma gas supplied from the plasma gas supply source, for example, a mixed gas of argon gas and hydrogen gas can be used.
The pressure in the chamber can be, for example, 50 kPa, and the flow rate in the chamber is, for example, 0.25 m / sec.

  The reaction temperature in the plasma torch is preferably 6,000 to 10,000 ° C., for example.

The number average primary particle size of the specific P-type semiconductor fine particles 1eA obtained through the plasma treatment is preferably 10 to 200 nm, more preferably 20 to 100 nm.
When the number average primary particle size of the specific P-type semiconductor fine particles 1eA is less than 10 nm, the specific P-type semiconductor fine particles 1eA aggregate because the dispersibility in the coating liquid for forming the protective layer 1e is low. Therefore, a uniform coating film may not be formed. On the other hand, when the number average primary particle size of the specific P-type semiconductor fine particles 1eA exceeds 200 nm, the dispersion uniformity in the protective layer 1e is low, and the surface roughness tends to increase when used for a long period of time. There is.

  The number average primary particle size of the specific P-type semiconductor fine particles 1eA obtained through the plasma treatment was taken with a scanning electron microscope “JSM-7500F” (manufactured by JEOL Ltd.) at a magnification of 100,000 times. Image data (excluding aggregated particles) captured by a scanner using an automatic image processing analyzer “LUZEX (registered trademark) AP (software version Ver. 1.32)” (manufactured by Nireco) The binarization process is performed on the P-type semiconductor fine particles 1eA, the horizontal ferret diameters for any 100 specific P-type semiconductor fine particles 1eA are calculated, and the average value is taken as the number average primary particle size. Here, the horizontal ferret diameter refers to the length of a side parallel to the x-axis of the circumscribed rectangle when the image of a specific P-type semiconductor fine particle 1eA is binarized.

The number average primary particle size of the specific P-type semiconductor fine particles 1eA can be controlled by adjusting the amount of raw material charged when producing the raw material P-type semiconductor fine particles and / or the plasma output in the plasma treatment. . Specifically, the number average primary particle size of the specific P-type semiconductor fine particles 1eA increases as the amount of raw material charged increases, and the number average of the specific P-type semiconductor fine particles 1eA increases as the plasma output in the plasma processing increases. The primary particle size increases.
In the specific P-type semiconductor fine particle 1eA, the BET specific surface area is measured in the process of performing the plasma treatment, and the number average primary particle diameter is converted from the obtained BET specific surface area into the number average primary particle diameter, thereby feedback control of the number average primary particle diameter. can do.

[Surface treatment of specific P-type semiconductor fine particles]
The specific P-type semiconductor fine particle 1eA is made of a silane coupling agent or the like from the viewpoint of further improving the dispersibility of the specific P-type semiconductor fine particle 1eA in the protective layer 1e to further improve the wear resistance and the anti-blurring property. The surface treatment of the specific P-type semiconductor fine particles 1eA may be performed by stirring the surface treatment agent together. Examples of the surface treatment agent include a silane coupling agent and a titanium coupling agent. In particular, a silane coupling agent having a radical polymerizable reactive group is preferably used for the purpose of further increasing the hardness of the protective layer 1e.
By using a silane coupling agent having a radical polymerizable reactive group, when the protective layer binder resin is a cured resin made of a polymerizable compound described later, a strong protective layer 1e is formed to react with the polymerizable compound. can do.
As the silane coupling agent having a radical polymerizable reactive group, it is preferable to use a silane coupling agent having an acryloyl group or a methacryloyl group. Examples of the silane coupling agent having such a radical polymerizable reactive group include the following. Examples of known compounds are as follows.

_{S-1: CH 2 = CHSi} (CH 3) (OCH 3) 2
_{S-2: CH 2 = CHSi} (OCH 3) 3
S-3: CH ₂ = CHSiCl _{3
S-4: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-5: CH 2 = CHCOO} (CH 2) 2 Si (OCH 3) 3
_{S-6: CH 2 = CHCOO} (CH 2) 2 Si (OC 2 H 5) (OCH 3) 2
_{S-7: CH 2 = CHCOO} (CH 2) 3 Si (OCH 3) 3
_{S-8: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) Cl 2
_{S-9: CH 2 = CHCOO} (CH 2) 2 SiCl 3
_{S-10: CH 2 = CHCOO} (CH 2) 3 Si (CH 3) Cl 2
S-11: CH ₂ = CHCOO (CH ₂ ) ₃ SiCl _{3
S-12: CH 2 = C} (CH 3) COO (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-13: CH 2 = C} (CH 3) COO (CH 2) 2 Si (OCH 3) 3
_{S-14: CH 2 = C} (CH 3) COO (CH 2) 3 Si (CH 3) (OCH 3) 2
_{S-15: CH 2 = C} (CH 3) COO (CH 2) 3 Si (OCH 3) 3
_{S-16: CH 2 = C} (CH 3) COO (CH 2) 2 Si (CH 3) Cl 2
_{S-17: CH 2 = C} (CH 3) COO (CH 2) 2 SiCl 3
_{S-18: CH 2 = C} (CH 3) COO (CH 2) 3 Si (CH 3) Cl 2
_{S-19: CH 2 = C} (CH 3) COO (CH 2) 3 SiCl 3
_{S-20: CH 2 = CHSi} (C 2 H 5) (OCH 3) 2
_{S-21: CH 2 = C} (CH 3) Si (OCH 3) 3
_{S-22: CH 2 = C} (CH 3) Si (OC 2 H 5) 3
_{S-23: CH 2 = CHSi} (OCH 3) 3
_{S-24: CH 2 = C} (CH 3) Si (CH 3) (OCH 3) 2
_{S-25: CH 2 = CHSi} (CH 3) Cl 2
_{S-26: CH 2 = CHCOOSi} (OCH 3) 3
_{S-27: CH 2 = CHCOOSi} (OC 2 H 5) 3
_{S-28: CH 2 = C} (CH 3) COOSi (OCH 3) 3
_{S-29: CH 2 = C} (CH 3) COOSi (OC 2 H 5) 3
_{S-30: CH 2 = C} (CH 3) COO (CH 2) 3 Si (OC 2 H 5) 3
_{S-31: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) 2 (OCH 3)
_{S-32: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OCOCH 3) 2
_{S-33: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (ONHCH 3) 2
_{S-34: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OC 6 H 5) 2
_{S-35: CH 2 = CHCOO} (CH 2) 2 Si (C 10 H 21) (OCH 3) 2
_{S-36: CH 2 = CHCOO} (CH 2) 2 Si (CH 2 C 6 H 5) (OCH 3) 2

  As the surface treatment agent, in addition to S-1 to S-36, a silane compound having a reactive organic group capable of performing a radical polymerization reaction can be used. These surface treatment agents can be used alone or in admixture of two or more.

  Moreover, the usage-amount of a surface treating agent is although it does not restrict | limit in particular, It is preferable that it is 0.1-100 mass parts with respect to 100 mass parts of untreated specific P-type semiconductor fine particles 1eA.

The specific P-type semiconductor fine particles 1eA are preferably contained at a ratio of 50 to 120 parts by mass with respect to 100 parts by mass of the protective layer binder resin.
When the content ratio of the specific P-type semiconductor fine particles 1eA is in the above range, an appropriate charge transport property can be obtained in the protective layer and the hardness of the protective layer 1e can be appropriately adjusted.

According to the above photoreceptor, high memory resistance and granularity can be obtained by introducing the specific P-type semiconductor fine particles 1eA into the protective layer 1e.
The reason why high memory resistance and graininess can be obtained in the photoreceptor having such a protective layer 1e is presumed as follows.
That is, when a coarse powdered copper composite oxide produced by a solid phase method is atomized by plasma treatment, a specific P in which the uniformity of particle size and shape is high and the content of impurities is suppressed to be extremely low. Type semiconductor fine particles 1eA can be produced. When this is introduced into the protective layer 1e, the protective layer 1e has high hole transportability and high memory resistance, and the specific P-type semiconductor fine particles 1eA are uniformly dispersed in the protective layer 1e with high dispersibility. Therefore, high graininess is obtained.
Note that the P-type semiconductor fine particles obtained by pulverizing coarse powdered copper composite oxide produced by the solid phase method have large particle size and shape variations, resulting in low dispersibility in the protective layer. Graininess will be lowered.
Further, when a copper composite oxide is produced by a vapor phase method, impurities (for example, CuAl ₂ O ₄ , Cu ₂ O, CuO, etc.) are present in addition to the main component (for example, CuAlO ₂ ) due to the difference in melting point between the metals to be combined. It is easy to generate. As a result, when this is introduced into the protective layer, the hole transport property in the protective layer is lowered and the memory resistance is lowered. In addition, it becomes difficult to uniformly disperse the P-type semiconductor fine particles with high dispersibility in the protective layer due to the presence of impurities.

[Binder resin for protective layer]
The binder resin for the protective layer is preferably a thermoplastic resin or a photocurable resin, and more preferably a photocurable resin because a high film strength can be obtained.
As the protective layer binder resin, for example, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, acrylic resin, melamine resin and the like can be used. When a thermoplastic resin is used, it is preferably a polycarbonate resin. When a photocurable resin is used, a crosslinkable polymerizable compound, specifically a compound having two or more radical polymerizable functional groups (hereinafter also referred to as “polyfunctional radical polymerizable compound”). It is preferably a cured resin obtained by a polymerization reaction by irradiation with active rays such as ultraviolet rays and electron beams.
The above-mentioned materials mentioned as the protective layer binder resin can be used alone or in combination of two or more.

[Polyfunctional radical polymerizable compound]
Since the polyfunctional radical polymerizable compound can be cured in a small amount of light or in a short time, an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═CCH ₃ CO—) is used as the radical polymerizable functional group. ) Is particularly preferably an acrylic monomer having two or more) or oligomers thereof. Accordingly, the curable resin is preferably an acrylic resin formed from an acrylic monomer or an oligomer thereof.

  Examples of these polyfunctional radically polymerizable compounds include the following compounds.

However, in the chemical formulas showing the exemplary compounds M1 to M15, R represents an acryloyl group (CH ₂ ═CHCO—), and R ′ represents a methacryloyl group (CH ₂ ═CCH ₃ CO—).

  In addition to the protective layer binder resin and the specific P-type semiconductor fine particles 1eA as described above, the protective layer 1e may contain lubricant particles, various antioxidants, and the like as necessary.

[Lubricant particles]
Examples of the lubricant particles include fluorine atom-containing resin particles. Examples of the fluorine atom-containing resin particles include ethylene tetrafluoride resin, ethylene trifluoride chloride resin, hexafluoroethylene chloride propylene resin, vinyl fluoride resin, vinylidene fluoride resin, and ethylene difluoride dichloride resin. These copolymers can also be used. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is particularly preferable to use a tetrafluoroethylene resin and a vinylidene fluoride resin.

  The layer thickness of the protective layer 1e is preferably 0.2 to 10 [mu] m, more preferably 0.5 to 6 [mu] m.

(Formation of protective layer)
The protective layer 1e is a coating liquid prepared by adding a polyfunctional radical polymerizable compound, specific P-type semiconductor fine particles 1eA and, if necessary, known resins, polymerization initiators, lubricant particles, antioxidants and the like to a solvent. It can be prepared by coating the surface of the charge transport layer 1d by a known method, forming a coating film, and curing.

(Polymerization initiator)
As a method for polymerizing the polyfunctional radically polymerizable compound, a method using an electron beam cleavage reaction or a method using light or heat in the presence of a radical polymerization initiator can be employed.
Examples of the radical polymerization initiator that initiates the polymerization reaction of the polyfunctional radically polymerizable compound include a thermal polymerization initiator and a photopolymerization initiator, and these can be used in combination.

  As thermal polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylazobisvaleronyl), 2,2′-azobis (2-methylbutyro) Azo compounds such as nitrile); peroxides such as benzoyl peroxide (BPO), di-tert-butyl hydroperoxide, tert-butyl hydroperoxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide An oxide etc. are mentioned.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (“Irgacure 369” (manufactured by BASF Japan)), 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime Acetophenone or ketal photoinitiators such as benzoin, benzoin methyl ether, Benzoin ether photopolymerization initiators such as benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyl Benzophenone photopolymerization initiators such as phenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Examples thereof include thioxanthone photopolymerization initiators such as dichlorothioxanthone.

  Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide (“Irgacure 819” (manufactured by BASF Japan)), bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine series Examples thereof include compounds, triazine compounds, and imidazole compounds. Moreover, what has a photopolymerization promotion effect can be used individually or in combination with the said photoinitiator. Examples of the photopolymerization promoting effect include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′- Examples include dimethylaminobenzophenone.

  The polymerization initiator is preferably a photopolymerization initiator, more preferably an alkylphenone compound or a phosphine oxide compound, and a photopolymerization initiator having an α-hydroxyacetophenone structure or an acylphosphine oxide structure. More preferably, an agent is used.

These polymerization initiators may be used alone or in combination of two or more.
The usage-amount of a polymerization initiator is 0.1-40 mass parts with respect to 100 mass parts of polyfunctional radically polymerizable compounds, Preferably it is 0.5-20 mass parts.

〔solvent〕
Solvents used for forming the protective layer 1e include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, benzyl alcohol, methyl isopropyl ketone, and methyl isobutyl. Ketone, methyl ethyl ketone, cyclohexane, toluene, xylene, methylene chloride, ethyl acetate, butyl acetate, 2-methoxyethanol, 2-ethoxyethanol, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine and diethylamine, etc. It is not limited to these.
These can be used individually by 1 type or in mixture of 2 or more types.

  In the curing process, the coating film is irradiated with actinic rays to generate radicals, polymerize, and form a cross-linking bond by a cross-linking reaction between molecules and within the molecule to form a binder resin for the protective layer. Is preferred. As an actinic ray, it is preferable to use light such as ultraviolet light and visible light and an electron beam, and it is particularly preferable to use ultraviolet light from the viewpoint of ease of use.

As the ultraviolet light source, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a flash (pulse) xenon, an ultraviolet LED, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 1 to 20 mJ / cm ² , preferably 5 to 15 mJ / cm ² . The output voltage of the light source is preferably 0.1 to 5 kW, and particularly preferably 0.5 to 3 kW.

  As the electron beam source, for example, a curtain beam type electron beam irradiation apparatus can be preferably used. The acceleration voltage at the time of irradiation with an electron beam is preferably 100 to 300 kV. The absorbed dose is preferably 0.005 Gy to 100 kGy (0.5 to 10 Mrad).

  The irradiation time of the actinic radiation may be a time for obtaining the necessary irradiation amount of the actinic radiation, specifically 0.1 seconds to 10 minutes is preferable, and 1 second to 5 minutes is preferable from the viewpoint of curing efficiency or work efficiency. More preferred.

  The coating film may be dried before and after irradiation with active rays and during irradiation with active rays. The timing for performing the drying process can be appropriately selected in combination with the irradiation condition of the active rays. The drying conditions for the protective layer 1e can be appropriately selected depending on the type of solvent used in the coating solution, the film thickness of the protective layer 1e, and the like. The drying temperature is preferably room temperature to 180 ° C, particularly preferably 80 to 140 ° C. The drying time is preferably 1 to 200 minutes, particularly preferably 5 to 100 minutes. By drying the coating film under such drying conditions, the amount of solvent contained in the protective layer 1e can be controlled in the range of 20 ppm to 75 ppm.

  Hereinafter, the configuration of the photoreceptor other than the protective layer 1e will be described.

[Conductive support 1a]
The conductive support 1a may be anything as long as it has conductivity, for example, a metal such as aluminum, copper, chromium, nickel, zinc, and stainless steel formed into a drum or a sheet, or a metal foil such as aluminum or copper. Laminated on plastic film, aluminum, indium oxide, tin oxide, etc. deposited on plastic film, metal with conductive layer applied alone or with binder resin, plastic film and paper It is done.

[Intermediate layer 1b]
The intermediate layer 1b provides a barrier function and an adhesive function between the conductive support 1a and the photosensitive layer 1f. From the viewpoint of preventing various failures, it is preferable to provide such an intermediate layer.

  Such an intermediate layer 1b contains, for example, a binder resin (hereinafter also referred to as “binder resin for intermediate layer”) and, if necessary, conductive particles and metal oxide particles.

  Examples of the intermediate layer binder resin include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide resin, polyurethane resin, and gelatin. Among these, alcohol-soluble polyamide resins are preferable.

The intermediate layer 1b can contain various conductive particles and metal oxide particles for the purpose of resistance adjustment. For example, various metal oxide particles such as alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, and bismuth oxide can be used. Ultrafine particles such as indium oxide doped with tin, tin oxide doped with antimony, and zirconium oxide can be used.
The number average primary particle size of such metal oxide particles is preferably 0.3 μm or less, and more preferably 0.1 μm or less.
You may use a metal oxide particle individually by 1 type or in mixture of 2 or more types. When two or more kinds are mixed, it may take the form of a solid solution or fusion.

  It is preferable that the content rate of electroconductive particle or metal oxide particle is 20-400 mass parts with respect to 100 mass parts of binder resin for intermediate | middle layers, More preferably, it is 50-200 mass parts.

The intermediate layer 1b as described above is prepared, for example, by dissolving a binder resin for an intermediate layer in a known solvent, and dispersing conductive particles or metal oxide particles as necessary to prepare a coating solution for forming an intermediate layer. The intermediate layer forming coating solution can be formed by coating the surface of the conductive support to form a coating film and drying the coating film.
The density | concentration of the binder resin for intermediate | middle layers in the coating liquid for intermediate | middle layer formation can be suitably selected according to the layer thickness of the intermediate | middle layer 1b, and the coating method.

  The solvent used for forming the intermediate layer 1b is not particularly limited, and various known organic solvents can be used. However, good solubility and coating with respect to a polyamide resin that is preferable as a binder resin for the intermediate layer. In order to express performance, it is preferable to use alcohols having 2 to 4 carbon atoms such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol and the like. Moreover, in order to improve preservability and the dispersibility of electroconductive particle or metal oxide particle, a cosolvent can be used together with the said solvent. Preferred examples of the cosolvent include methanol, benzyl alcohol, toluene, cyclohexanone, tetrahydrofuran and the like. These solvents and cosolvents can be used alone or in combination of two or more.

  As a means for dispersing the conductive particles and metal oxide particles, an ultrasonic disperser, a ball mill, a sand grinder, a homomixer, or the like can be used.

  The coating method for the intermediate layer forming coating solution is not particularly limited. For example, dip coating method, spray coating method, spinner coating method, bead coating method, blade coating method, beam coating method, circular amount regulation type coating method ( A circular slide hopper coating method).

  As a method for drying the coating film, a known drying method can be appropriately selected according to the type of solvent and the film thickness of the intermediate layer to be formed, and thermal drying is particularly preferable.

  The layer thickness of the intermediate layer 1b is preferably 0.1 to 15 μm, and more preferably 0.3 to 10 μm.

[Charge generation layer 1c]
The charge generation layer 1c contains a charge generation material and a binder resin (hereinafter also referred to as “binder resin for charge generation layer”).

  Examples of charge generation materials include azo raw materials such as Sudan Red and Diane Blue, quinone pigments such as pyrenequinone and anthanthrone, quinocyanine pigments, perylene pigments, indigo pigments such as indigo and thioindigo, pyranthrone and diphthaloylpyrene. Examples thereof include, but are not limited to, ring quinone pigments and phthalocyanine pigments. Among these, polycyclic quinone pigments and titanyl phthalocyanine pigments are preferable. These charge generation materials may be used alone or in combination of two or more.

  As the binder resin for the charge generation layer, known resins can be used. For example, polystyrene resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, Polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and copolymer resin containing two or more of these resins (for example, vinyl chloride-vinyl acetate copolymer resin, chloride) Vinyl-vinyl acetate-maleic anhydride copolymer resin), poly-vinylcarbazole resin, and the like, but are not limited thereto. Among these, polyvinyl butyral resin is preferable.

  The mixing ratio of the charge generation layer binder resin and the charge generation material is preferably 1 to 600 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the charge generation layer binder resin. Part by mass. When the mixing ratio of the charge generating layer binder resin and the charge generating material is in the above range, high dispersion stability is obtained in the coating solution for forming the charge generating layer, which will be described later. The resistance is suppressed to be low, and an increase in residual potential due to repeated use can be extremely suppressed.

  The charge generation layer 1c as described above is prepared by, for example, adding a charge generation material into a charge generation layer binder resin dissolved in a known solvent and dispersing it to prepare a charge generation layer forming coating solution. It can be formed by coating the generating layer forming coating solution on the surface of the intermediate layer to form a coating film and drying the coating film.

  As the solvent used for forming the charge generation layer 1c, a solvent capable of dissolving the charge generation layer binder resin may be used. For example, ketone solvents such as methyl ethyl ketone and cyclohexanone, tetrahydrofuran, 1-dioxane, 1, Ether solvents such as 3-dioxolane, alcohol solvents such as methyl cellsolve, ethyl cellsolve, methanol, ethanol, propanol and butanol, ester solvents such as ethyl acetate and t-butyl acetate, aromatics such as toluene and xylene Although a solvent etc. can be mentioned, it is not limited to these. These may be used alone or in combination of two or more.

Examples of the means for dispersing the charge generating substance include the same method as the means for dispersing the conductive particles and metal oxide particles in the coating liquid for forming the intermediate layer.
Examples of the coating method for the charge generation layer forming coating solution include the same methods as those mentioned as the coating method for the intermediate layer forming coating solution.

  The layer thickness of the charge generation layer 1c varies depending on the characteristics of the charge generation material, the characteristics and the content ratio of the binder resin for the charge generation layer, but is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm. .

[Charge transport layer 1d]
The charge transport layer 1d contains a charge transport material and a binder resin (hereinafter also referred to as “binder resin for charge transport layer”).

  As the charge transport material of the charge transport layer 1d, for example, carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline compounds, oxazolone derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, benzidine Derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like. That. These may be used alone or in combination of two or more.

  A known resin can be used as the binder resin for the charge transport layer. Polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylic ester resin, styrene-methacrylic ester Examples of the resin include a copolymer resin, and a polycarbonate resin is preferable. Furthermore, BPA (bisphenol A) type, BPZ (bisphenol Z) type, dimethyl BPA type, BPA-dimethyl BPA copolymer type polycarbonate resin and the like are preferable in terms of crack resistance, wear resistance, and charging characteristics.

  The content ratio of the charge transport material in the charge transport layer 1d is preferably 10 to 500 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the charge transport layer binder resin.

  In the charge transport layer 1d, an antioxidant, an electronic conductive agent, a stabilizer, silicone oil, or the like may be added. As the antioxidant, those disclosed in JP-A No. 2000-305291 and as the electronic conductive agent are disclosed in JP-A Nos. 50-137543 and 58-76483.

  The layer thickness of the charge transport layer 1d varies depending on the characteristics of the charge transport material, the characteristics and the content ratio of the binder resin for the charge transport layer, and is preferably 5 to 40 μm, more preferably 10 to 30 μm.

For the charge transport layer 1d as described above, for example, a charge transport material (CTM) is added and dispersed in a charge transport layer binder resin dissolved in a known solvent to prepare a charge transport layer forming coating solution. The coating liquid for forming the charge transport layer can be applied to the surface of the charge generation layer 1c to form a coating film, and the coating film can be dried.
Examples of the solvent used in the formation of the charge transport layer 1d include the same solvents as those used in the formation of the charge generation layer 1c.
In addition, as the method for applying the charge transport layer forming coating solution, the same method as the method for applying the charge generating layer forming coating solution can be used.

[Image forming apparatus]
The photoconductor of the present invention includes, for example, a charging unit that charges the surface of the photoconductor, an exposure unit that exposes the photoconductor charged by the charging unit to form an electrostatic latent image, and a toner on the photoconductor. A developing means for supplying and developing the electrostatic latent image with toner to form a toner image; a transfer means for transferring the toner image formed on the photoreceptor; and a cleaning for removing the toner remaining on the surface of the photoreceptor. And an image forming apparatus.

FIG. 2 is a cross-sectional view illustrating the configuration of an example of the image forming apparatus according to the present invention.
This image forming apparatus is called a tandem type color image forming apparatus, and includes four sets of image forming units (image forming units) 10Y, 10M, 10C, and 10Bk, an intermediate transfer body unit 70, a paper feeding unit 21, and And fixing means 24. A document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.

The four sets of image forming units 10Y, 10M, 10C, and 10Bk are centered around the photoreceptors 1Y, 1M, 1C, and 1Bk, charging means 2Y, 2M, 2C, and 2Bk, and exposure means 3Y, 3M, 3C, and 3Bk, Rotating developing means 4Y, 4M, 4C, 4Bk, primary transfer rollers 5Y, 5M, 5C, 5Bk as primary transfer means, and cleaning means 6Y, 6M, 6C, cleaning the photoreceptors 1Y, 1M, 1C, 1Bk It is composed of 6Bk.
The image forming apparatus according to the present invention uses the above-described photoreceptors of the present invention as the photoreceptors 1Y, 1M, 1C, and 1Bk.

  The image forming units 10Y, 10M, 10C, and 10Bk have the same configuration except that the colors of the toner images formed on the photoreceptors 1Y, 1M, 1C, and 1Bk are different from yellow, magenta, cyan, and black, respectively. The forming unit 10Y will be described in detail as an example.

  The image forming unit 10Y includes a charging unit 2Y, an exposing unit 3Y, a developing unit 4Y, and a cleaning unit 6Y around a photoconductor 1Y as an image forming body, and a yellow (Y) toner image is formed on the photoconductor 1Y. To form.

  The charging unit 2Y is a unit that uniformly charges the surface of the photoreceptor 1Y to a negative polarity. As the charging unit 2Y, for example, a corona discharge type charger is used.

  The exposure unit 3Y is a unit that performs exposure based on an image signal (yellow) on the photoreceptor 1Y to which a uniform potential is applied by the charging unit 2Y, and forms an electrostatic latent image corresponding to a yellow image. As the exposure means 3Y, a device composed of an LED having light emitting elements arranged in an array in the axial direction of the photoreceptor 1Y and an imaging element, a laser optical system, or the like is used.

  The developing means 4Y includes, for example, a developing sleeve that contains a magnet and rotates while holding the developer, and a voltage applying device that applies a DC and / or AC bias voltage between the photosensitive member and the developing sleeve.

  The cleaning unit 6Y is a unit that removes toner remaining on the surface of the photoreceptor 1Y. The cleaning means 6Y in this example includes a cleaning blade and a brush roller provided on the upstream side of the cleaning blade.

  In the image forming apparatus of FIG. 2, the photosensitive member 1Y, the charging unit 2Y, the developing unit 4Y, and the cleaning unit 6Y of the image forming unit 10Y are integrally supported and provided as a process cartridge. It may be configured to be detachable from the main body A of the image forming apparatus via a guide means such as a rail.

  The image forming units 10Y, 10M, 10C, and 10Bk are arranged in tandem in the vertical direction, and an intermediate transfer body unit 70 is arranged on the left side of the photoreceptors 1Y, 1M, 1C, and 1Bk in the drawing. The intermediate transfer body unit 70 is wound around a plurality of rollers 71, 72, 73, and 74, and is supported by a semiconductive endless belt-like intermediate transfer body 77, and a secondary transfer means. It consists of a next transfer roller 5b and a cleaning means 6b.

  The image forming units 10Y, 10M, 10C, and 10Bk and the intermediate transfer body unit 70 are housed in a housing 80. The housing 80 is pulled out from the main body A of the image forming apparatus via support rails 82L and 82R. It is configured to be possible.

  The fixing unit 24 is, for example, a heat roller fixing configured by a heating roller having a heating source therein and a pressure roller provided in pressure contact with the heating roller so as to form a fixing nip portion. One of the methods is mentioned.

  In FIG. 2, the image forming apparatus according to the present invention is shown as a color laser printer, but may be configured as a monochrome laser printer or a copy. In the image forming apparatus according to the present invention, a light source other than a laser, for example, an LED light source can be used as the exposure light source.

In the image forming apparatus as described above, image formation is performed as follows. That is, first, the charging means 2Y, 2M, 2C, and 2Bk are discharged to the surface of the photoreceptors 1Y, 1M, 1C, and 1Bk to be negatively charged (charging process). Next, the exposure means 3Y, 3M, 3C, and 3Bk expose the surfaces of the photoreceptors 1Y, 1M, 1C, and 1Bk based on the image signal to form an electrostatic latent image (exposure process). Next, with the developing means 4Y, 4M, 4C, and 4Bk, toner is applied to the surface of the photoreceptors 1Y, 1M, 1C, and 1Bk and developed to form a toner image (developing process).
Next, the primary transfer rollers 5Y, 5M, 5C, and 5Bk are brought into contact with the rotating intermediate transfer body 77. Thus, the color toner images formed on the photoreceptors 1Y, 1M, 1C, and 1Bk are sequentially transferred onto the rotating intermediate transfer body 77 to form a color toner image (primary transfer process). During the image forming process, the primary transfer roller 5Bk is always in contact with the photoreceptor 1Bk. On the other hand, the other primary transfer rollers 5Y, 5M, and 5C abut against the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

Then, after separating the primary transfer rollers 5Y, 5M, 5C, and 5Bk from the intermediate transfer body 77, the toner remaining on the surfaces of the photoreceptors 1Y, 1M, 1C, and 1Bk is cleaned with the cleaning means 6Y, 6M, 6C, and 6Bk. To remove (cleaning step). Thereafter, in preparation for the next image forming process, the surfaces of the photoreceptors 1Y, 1M, 1C, and 1Bk are neutralized by a neutralizing unit (not shown) as necessary.
As described above, this image forming apparatus is configured such that the lubricant is supplied to the surfaces of the photoreceptors 1Y, 1M, 1C, and 1Bk for each image forming process.

On the other hand, a transfer material P (for example, a support for carrying a final image such as plain paper or a transparent sheet) accommodated in the paper feed cassette 20 is fed by the paper feed means 21 and a plurality of intermediate rollers 22A, 22B, 22C. , 22D, and the registration roller 23, and is conveyed to a secondary transfer roller 5b as a secondary transfer unit. The secondary transfer roller 5b is brought into contact with the intermediate transfer member 77, whereby a color toner image is formed on the transfer material P. Are transferred at once. The transfer material P onto which the color toner image has been transferred is fixed by the fixing means 24, is sandwiched between the paper discharge rollers 25, and is placed on a paper discharge tray 26 outside the apparatus. The secondary transfer roller 5b is brought into contact with the intermediate transfer member 77 only when secondary transfer is performed.
After the color toner image is transferred to the transfer material P by the secondary transfer roller 5b, the residual toner is removed by the cleaning means 6b from the intermediate transfer body 77 from which the transfer material P is separated by curvature.

[Toner and developer]
The toner used in the image forming apparatus according to the present invention is not particularly limited, but includes toner particles containing a binder resin and a colorant. The toner particles may include other components such as a release agent as desired. It may be contained.

  As the toner, either a pulverized toner or a polymerized toner can be used. However, in the image forming apparatus according to the present invention, it is preferable to use a polymerized toner from the viewpoint of obtaining a high quality image.

  The average particle diameter of the toner is preferably 2 to 8 μm in terms of volume-based median diameter. By setting this range, the resolution can be increased.

  In addition, an appropriate amount of inorganic fine particles such as silica and titania having an average particle diameter of about 10 to 300 nm and an abrasive of about 0.2 to 3 μm can be externally added to the toner particles as external additives.

The toner can be used as a magnetic or nonmagnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
In the case where the toner is used as a two-component developer, the carrier may be a conventionally known material such as a ferromagnetic metal such as iron, an alloy such as ferromagnetic metal and aluminum and lead, and a compound of ferromagnetic metal such as ferrite and magnetite. In particular, ferrite is preferable.

  As mentioned above, although embodiment of this invention was described concretely, embodiment of this invention is not limited to said example, A various change can be added.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[P-type semiconductor fine particle production example 1]
(1) Production of sintered body Powdered Al ₂ O ₃ (purity 99.9%) and powdered Cu ₂ O (purity 99.9%) were mixed at a molar ratio of 1: 1, and argon was mixed. After calcining at 1100 ° C. for 4 days in a gas atmosphere, sintering was further performed at 1100 ° C. for 2 days to obtain a powdery sintered body [1] made of CuAlO ₂ .

(2) Plasma treatment A high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and a mixed gas of argon gas 80 liter / min and hydrogen gas 5 liter / min from the plasma gas supply source. Was introduced to generate an argon / hydrogen thermal plasma flame in the plasma torch. The reaction temperature was controlled to be about 8000 ° C.
In the chamber, argon gas of 150 liters / min is injected toward the end of the argon / hydrogen thermal plasma flame, and from the side where the argon / hydrogen thermal plasma flame is formed along the inner wall of the chamber to the discharge port. Then, 50 liters / min of argon gas was injected. The pressure in the chamber was 50 kPa. At this time, the flow velocity in the chamber was 0.25 m / sec.
Under the above conditions, the sintered body [1] is introduced into the argon / hydrogen thermal plasma flame in the plasma torch together with the carrier gas (10 liter / min of argon gas) to perform plasma treatment. A powder of CuAlO ₂ fine particles [1] subjected to plasma treatment having an average primary particle size of 10 nm was obtained.

(3) Surface treatment 100 parts by mass of the above CuAlO ₂ fine particles [1], surface treatment agent: 7 parts by mass of 3-methacryloxypropyltrimethoxysilane “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1000 parts by mass of methyl ethyl ketone, P type semiconductor fine particles that have been surface-treated by placing in a wet sand mill (zirconia beads having a diameter of 0.5 mm), mixing at 30 ° C. for 6 hours, and then filtering off methyl ethyl ketone and zirconia beads and drying at 60 ° C. The powder of [1] was obtained.

[P-type semiconductor fine particle production examples 2 to 5]
In Production Example 1 of P-type semiconductor fine particles, P-type semiconductor fine particles (CuAlO) obtained by controlling (1) the amount of raw material charged in the production process of the sintered body and (2) plasma intensity in the plasma treatment step A powder of P-type semiconductor fine particles [2] to [5] subjected to surface treatment was obtained in the same manner except that the number average primary particle size of ₂ ) was changed to that shown in Table 1.

[P-type semiconductor fine particle production example 6]
In the production process of P type semiconductor fine particles (1) sintered body, Ga ₂ O ₃ (purity 99.9%) is used instead of Al ₂ O ₃ (purity 99.9%), and ( Table 1 shows the number average primary particle size of the obtained P-type semiconductor fine particles (CuGaO ₂ ) by controlling the amount of raw materials charged in the sintered body production process and (2) the plasma intensity in the plasma treatment process. A powder of P-type semiconductor fine particles [6] subjected to the surface treatment was obtained in the same manner except that those described above were used.

[P-type semiconductor fine particle production example 7]
In the manufacturing process of P type semiconductor fine particles (1) sintered body, In ₂ O ₃ (purity 99.9%) is used instead of Al ₂ O ₃ (purity 99.9%), and ( Table 1 shows the number average primary particle size of the obtained P-type semiconductor fine particles (CuInO ₂ ) by controlling the amount of raw material charged in the production process of the sintered body and (2) the intensity of the plasma in the plasma treatment process. A powder of P-type semiconductor fine particles [7] subjected to the surface treatment was obtained in the same manner as described above.

[Preparation Example 8 of P-type semiconductor fine particles]
By applying a high frequency voltage of about 4 MHz and about 80 kVA to the high frequency oscillation coil of the plasma torch and introducing a mixed gas of argon gas 80 liter / min and oxygen gas 5 liter / min from the plasma gas supply source. An argon / oxygen thermal plasma flame was generated in the plasma torch. The reaction temperature was controlled to be about 8000 ° C.
In the chamber, 150 liters / min of argon gas is injected toward the end of the argon / oxygen thermal plasma flame, and from the side where the argon / oxygen thermal plasma flame is formed along the inner wall of the chamber to the discharge port. Then, 50 liters / min of argon gas was injected. The pressure in the chamber was 50 kPa. At this time, the flow velocity in the chamber was 0.25 m / sec.
Under the conditions as described above, Cu (purity 99.9%) and Al (99.9%) are mixed at a weight ratio of 1: 1, and this is mixed with a carrier gas (10 liter / min argon gas) and plasma. Plasma treatment was performed by introducing it into an argon / oxygen thermal plasma flame in the torch, whereby a CuAlO ₂ fine particle [8] powder produced by a vapor phase method having a number average primary particle size of 20 nm was obtained. Obtained.
100 parts by mass of the above CuAlO ₂ fine particles [8], surface treatment agent: 7 parts by mass of 3-methacryloxypropyltrimethoxysilane “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1000 parts by mass of methyl ethyl ketone were added to a wet sand mill (diameter 0). 0.5 mm zirconia beads) and mixed at 30 ° C. for 6 hours, and then the methyl ethyl ketone and zirconia beads are filtered off and dried at 60 ° C., whereby the surface-treated P-type semiconductor fine particles [8] powder Got the body.

[Preparation Example 9 of P-type semiconductor fine particles]
(1) Production of sintered body Powdered Al ₂ O ₃ (purity 99.9%) and powdered Cu ₂ O (purity 99.9%) were mixed at a molar ratio of 1: 1, and argon was mixed. After calcining at 1100 ° C. for 4 days in a gas atmosphere, sintering was further performed at 1100 ° C. for 2 days to obtain a powdery sintered body [9] made of CuAlO ₂ .
(2) Wet pulverization treatment Then, after coarsely pulverizing to several hundred μm, the obtained coarse particles and a solvent are put into a wet media dispersion type apparatus and subjected to wet pulverization treatment, whereby P-type semiconductor fine particles made of CuAlO ₂ [ 9] powder was obtained.
(3) Surface treatment 100 parts by mass of the above CuAlO ₂ fine particles [9], a surface treatment agent: 7 parts by mass of 3-methacryloxypropyltrimethoxysilane “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1000 parts by mass of methyl ethyl ketone, P type semiconductor fine particles that have been surface-treated by placing in a wet sand mill (zirconia beads having a diameter of 0.5 mm), mixing at 30 ° C. for 6 hours, and then filtering off methyl ethyl ketone and zirconia beads and drying at 60 ° C. A powder of [9] was obtained.

[Photosensitive body preparation example 1]
(1) Production of conductive support The surface of a drum-shaped aluminum support (outer diameter 60 mm) was cut to obtain a conductive support [1].

(2) Formation of Intermediate Layer A dispersion was obtained by dispersing the following composition in a batch mode for 5 hours using a sand mill as a disperser.
・ Binder resin for intermediate layer: 100 parts by mass of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) ・ Metal oxide particles: Titanium oxide “SMT500SAS” (manufactured by Teica) 120 parts by mass ・ Metal oxide particles: titanium oxide “SMT150MK” (Manufactured by Teica) 155 parts by mass / solvent: ethanol / n-propyl alcohol / tetrohydrofuran (volume ratio 60/20/20) 1290 parts by mass This dispersion was diluted 1.5 times with the same mixed solvent, After standing overnight, the mixture was filtered (filter; using a lysh mesh 5 μm filter manufactured by Nippon Pole Co., Ltd.) to prepare a coating solution for forming an intermediate layer. This intermediate layer forming coating solution was applied to the outer peripheral surface of the washed conductive support [1] by dip coating, and dried to form an intermediate layer [1] having a dry film thickness of 2 μm.

(3) Formation of Charge Generation Layer Dispersion for 10 hours was performed using a sand mill using the following raw materials as a disperser to prepare a charge generation layer forming coating solution [1].
Charge generation material: titanyl phthalocyanine pigment (having a maximum diffraction peak at a position of at least 27.3 ° by Cu-Kα characteristic X-ray diffraction spectrum measurement) 20 parts by mass Binder resin for charge generation layer: polyvinyl butyral resin # 6000-C "(manufactured by Denki Kagaku Kogyo Co., Ltd.) 10 parts by mass. Solvent: 700 parts by mass of t-butyl acetate. Solvent: 300 parts by mass of 4-methoxy-4-methyl-2-pentanone Above the intermediate layer [1] Then, this charge generation layer forming coating solution [1] was applied by a dip coating method to form a coating film, thereby forming a charge generation layer [1] having a dry film thickness of 0.3 μm.

(4) Formation of charge transport layer The following raw materials were mixed and dissolved to prepare a charge transport layer forming coating solution [1].
Charge transport material: 4,4′-dimethyl-4 ″-(β-phenylstyryl) triphenylamine) 225 parts by mass Binder resin for charge transport layer: polycarbonate resin “Z300” (Mitsubishi Gas Chemical Co., Ltd.) 300 mass Part / Antioxidant: “Irganox 1010” (manufactured by BASF Japan) 6 parts by mass / solvent: 1600 parts by mass of tetrahydrofuran / solvent: 400 parts by mass of toluene / leveling agent: silicone oil “KF-54” (manufactured by Shin-Etsu Chemical) 1 Part by weight The charge transport layer forming coating solution [1] is applied onto the charge generation layer [1] by a dip coating method to form a coating film, the coating film is dried, and a charge transport layer having a thickness of 20 μm is formed. Layer [1] was formed.

(5) Formation of protective layer P-type semiconductor fine particles [1] 50 parts by mass Polymerizable compound (Exemplary compound (M1)) 100 parts by mass Polymerization initiator “Irgacure 819” (manufactured by BASF Japan) 6 parts by mass -Solvent: 313 parts by mass of 2-butanol-Solvent: 35 parts by mass of tetrahydrofuran A coating liquid composition consisting of 35 parts by mass was mixed and stirred to sufficiently dissolve and disperse to prepare a coating liquid [1] for forming a protective layer.
This protective layer-forming coating solution [1] is applied onto the charge transport layer [1] using a circular slide hopper coating machine, irradiated with ultraviolet rays for 1 minute using a xenon lamp, and then dried at 80 ° C. for 70 minutes. As a result, a protective layer [1] having a layer thickness of 3.0 μm was formed, thereby producing a photoreceptor [1].

[Photoconductor Preparation Examples 2 to 11]
Photoreceptors [2] to [2] in the same manner except that the type and amount of the P-type semiconductor fine particles were changed as shown in Table 1 in the protective layer formation step in Photoconductor Preparation Example 1. 11] was produced.

[Examples 1 to 9, Comparative Examples 1 and 2]
Evaluation was carried out by mounting the photoreceptors [1] to [11] on a commercially available full-color multifunction peripheral “bizhub PRESS C1070” (manufactured by Konica Minolta Co., Ltd.) basically having the configuration shown in FIG.
First, an endurance test was performed in which 300,000 double-sided continuous printing was performed for each character image with an image area ratio of 6% in an A4 horizontal feed under an environment of a temperature of 30 ° C. and a humidity of 80% RH. Before and after, the memory resistance and graininess were evaluated as follows. The results are shown in Table 1.

(1) Memory resistance (image memory)
After the endurance test, 10 test images in which a solid black image portion and a solid white image portion are mixed are continuously printed, then a uniform halftone image is printed, and the solid black image is included in the halftone image. And the solid white image part history (memory generation) or not (no memory generation) was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: No memory generated (passed)
B: Minor memory is visible, but there is virtually no problem (pass)
C: Memory is visually recognized and there is a problem in practice (failed)
D: Clear memory is generated, and there is a practical problem (fail)

(2) Graininess Before and after the endurance test, a gradation pattern with a gradation ratio of 32 steps is output, and this gradation pattern is subjected to Fourier transform processing in consideration of MTF (Modulation Transfer Function) correction on the read value by the CCD. The maximum GI value is obtained by measuring the GI value (Graininess Index) according to the human specific visual sensitivity, and the fluctuation value Δ of the GI value before the endurance test (initial printing) and after printing 100,000 sheets in the endurance test Evaluation was performed according to the following evaluation criteria.
-Evaluation criteria-
A: GI value variation Δ is less than 0.02 (pass)
B: Variation value Δ of GI value is 0.02 or more and less than 0.04 (pass)
C: Variation value Δ of GI value is 0.04 or more and less than 0.06 (pass)
D: The variation value Δ of the GI value is 0.06 or more (failed)

1a conductive support 1b intermediate layer 1c charge generation layer 1d charge transport layer 1e protective layer 1eA specific P-type semiconductor fine particles 1f photosensitive layer 1, 1Y, 1M, 1C, 1Bk photosensitive member 2Y, 2M, 2C, 2Bk charging means 3Y , 3M, 3C, 3Bk Exposure means 4Y, 4M, 4C, 4Bk Developing means 5Y, 5M, 5C, 5Bk Primary transfer roller 5b Secondary transfer rollers 6Y, 6M, 6C, 6Bk, 6b Cleaning means 10Y, 10M, 10C, 10Bk Image forming unit 20 Paper feed cassette 21 Paper feed means 22A, 22B, 22C, 22D Intermediate roller 23 Registration roller 24 Fixing means 25 Paper discharge roller 26 Paper discharge tray 70 Intermediate transfer body units 71, 72, 73, 74 Roller 77 Intermediate transfer Body 80 Cases 82L, 82R Support rail A Main body SC Document image reading device P Transfer material

Claims (5)

A method for producing an electrophotographic photosensitive member in which a photosensitive layer and a protective layer are laminated in this order on a conductive support,
The protective layer contains P-type semiconductor fine particles in the resin,
A method for producing an electrophotographic photosensitive member, characterized in that a powdered sintered body made of a copper composite oxide is used as the P-type semiconductor fine particles, which are atomized by plasma treatment. The method for producing an electrophotographic photosensitive member according to claim 1, wherein a compound represented by the following general formula (1) is used as the copper complex oxide.
General formula (1): CuMO ₂
[Wherein, M represents an element belonging to Group 13 of the periodic table. ]   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the P-type semiconductor fine particles have a number average primary particle size of 10 to 200 nm.   4. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the P-type semiconductor fine particles are subjected to a surface treatment. An electrophotographic photosensitive member in which a photosensitive layer and a protective layer are laminated in this order on a conductive support,
The protective layer contains P-type semiconductor fine particles in the resin,
An electrophotographic photosensitive member, wherein the P-type semiconductor fine particles are obtained by atomizing a powdery sintered body made of a copper composite oxide by plasma treatment.

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