JP2013003328A - Manufacturing method of organic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of organic photoreceptor providing a protective layer with a sufficient strength and suppressing the occurrence of image memory.SOLUTION: The manufacturing method of organic photoreceptor is a method for manufacturing an organic photoreceptor formed by laminating an organic photosensitive layer and a protective layer comprising a curing resin on a conductive support in this order. The manufacturing method includes a step of applying a coating liquid for protective layer formation that contains a polymerizable compound for forming a curable resin, a hexaaryl bis imidazole, a photoactivated electron-donating agent donating electrons to the hexaaryl bis imidazole, and a curing agent comprising a hydrogen-donating compound, on the organic photosensitive layer, and applying light thereto.

Description

  The present invention relates to a method for producing an organic photoreceptor used in an electrophotographic image forming apparatus.

  In general, a photoreceptor used in an electrophotographic image forming apparatus is repeatedly subjected to a series of image forming processes including a charging process, an exposure process, a developing process, a transfer process, a cleaning process, and a charge eliminating process. Therefore, the photoreceptor is required to have little deterioration in electrical characteristics such as charging property and potential holding property even if the image forming process is repeatedly performed.

Conventionally, as a photoreceptor, for example, zinc oxide (ZnO), cadmium sulfide (CdS), cadmium selenide (CdSe), amorphous selenium-based (a-Se, a-Se-Te, a-As ₂ Se ₃ ), etc. However, in recent years, it has many advantages such as easy manufacturing, high sensitivity design, low cost, and no pollution. Therefore, an organic photoreceptor having an organic compound in the photosensitive layer has become the mainstream.

  Such an organic photoreceptor is generally soft because the surface layer is mainly composed of a low molecular charge transport material and an inert polymer, and when used repeatedly in an image forming process, it is mechanically subjected to a development process and a cleaning process. Wear easily due to excessive load. Such wear of the organic photoconductor causes a deterioration in electrical characteristics such as a deterioration in sensitivity and a decrease in chargeability, thereby causing a problem that a high-quality image cannot be formed over a long period of time.

In order to solve such a problem, a technique of providing a protective layer on the surface of an organic photoreceptor has been proposed (see, for example, Patent Document 1).
The protective layer may or may not include a charge transport material, and the protective layer that does not include the charge transport material has a problem that an image memory is generated although sufficient strength is ensured. . Here, the image memory refers to a phenomenon in which an image in which the density of a printed image is inverted appears in the immediately subsequent image area. On the other hand, the protective layer containing the charge transport material has a problem that sufficient strength cannot be obtained although generation of an image memory is suppressed. The reason why sufficient strength cannot be obtained is that the curing agent used to form the resin constituting the protective layer is generally a cleavage type radical polymerization initiator having high radical generation efficiency, but the protective layer is formed. In this case, it is considered that since the charge transport material absorbs light that should be absorbed by the curing agent, radical generation efficiency is lowered and sufficient curing reaction is not performed.

JP 2008-96528 A

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide a method for producing an organic photoreceptor in which generation of an image memory is suppressed while sufficient strength is obtained in a protective layer. It is to provide.

The organic photoreceptor production method of the present invention is a method for producing an organic photoreceptor in which an organic photoreceptor layer and a protective layer made of a cured resin are laminated in this order on a conductive support,
On the organic photosensitive layer, a polymerizable compound that forms a cured resin, a hexaarylbisimidazole, a photoactive electron donor that donates electrons to the hexaarylbisimidazole, and a curing agent that includes a hydrogen donor compound. It has the process of apply | coating the coating liquid for protective layer formation containing, and irradiating light.

  In the method for producing an organic photoreceptor of the present invention, the photoactive electron donor is a compound having charge transport performance.

  In the method for producing an organic photoreceptor of the present invention, it is preferable that the hydrogen donating compound has a thiol group.

  In the method for producing an organic photoreceptor of the present invention, it is preferable that the protective layer-forming coating solution contains metal oxide fine particles.

  In the method for producing an organophotoreceptor of the present invention, the metal oxide fine particles are preferably alumina fine particles or tin oxide fine particles surface-treated with a surface treatment agent having a reactive group.

  In the method for producing an organic photoreceptor of the present invention, the surface treatment agent is preferably a compound having an acryloyl group or a methacryloyl group as a reactive group.

  In the method for producing an organic photoreceptor of the present invention, the polymerizable compound preferably has an acryloyl group or a methacryloyl group.

  According to the method for producing an organophotoreceptor of the present invention, the protective layer-forming coating solution contains hexaarylbisimidazole (hereinafter also referred to as “HABI”), a photoactive electron donor that donates electrons to the HABI, and By containing a curing agent made of a hydrogen-donating compound, an organic photoreceptor can be produced in which generation of image memory is suppressed while sufficient strength is obtained in the protective layer.

In the present invention, the photoactive electron donor is a so-called sensitizing dye and has charge transport performance.
Therefore, in the production method of the present invention, by using a photoactive electron donor, HABI and a hydrogen donating compound as the curing agent, the electron transfer type increase of the photoactive electron donor as a sensitizing dye is achieved. Since the polymerizable compound is cured using a sensitive reaction, the photoactive electron donation is performed even when the protective layer coating solution contains a photoactive electron donor having charge transport performance. Since the agent does not inhibit the generation of radicals, it is possible to produce an organic photoreceptor in which the generation of image memory is suppressed while sufficient strength is obtained in the protective layer.

It is considered that the curing agent used in the present invention exhibits a function as a curing agent by the following process.
That is, when the photoactive electron donor, which is a sensitizing dye, absorbs light, electrons move from the sensitizing dye to HABI, and HABI is cleaved. Then, when the cleaved HABI extracts hydrogen from the hydrogen donating compound, radicals are generated and a curing reaction starts.

It is sectional drawing for description which shows an example of a structure of the circular slide hopper coating device used for the protective layer formation process in the manufacturing method of the organic photoreceptor of this invention. It is a perspective sectional view of the circular slide hopper applicator shown in FIG.

  Hereinafter, the present invention will be described in detail.

[Method for producing organic photoreceptor]
A method for producing an organic photoreceptor in which an organic photosensitive layer and a protective layer made of a cured resin are laminated in this order on a conductive support, wherein the polymerizable resin forms a cured resin on the organic photosensitive layer. Applying a protective layer-forming coating solution containing a compound, HABI, a photoactive electron donor that donates electrons to the HABI, and a curing agent made of a hydrogen-donating compound, and irradiating with light Is the method.

The organic photoreceptor obtained by the production method of the present invention is not particularly limited as long as an organic photosensitive layer and a protective layer are laminated in this order on a conductive support, but specifically, the following (1 ) And (2).
(1) A layer structure in which a charge generation layer, a charge transport layer, and a protective layer are laminated in this order as an intermediate layer and an organic photosensitive layer on a conductive support.
(2) A layer structure in which an intermediate layer, a single layer containing a charge generation material and a charge transport material as an organic photosensitive layer, and a protective layer are laminated in this order on a conductive support.

  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 configuration of the electrophotographic photoreceptor is exhibited by an organic compound. Includes all known organic photoreceptors such as a photoreceptor having a photosensitive layer composed of a generating material or an organic charge transport material, and a photoreceptor having a photosensitive layer in which a charge generating function and a charge transport function are composed of a polymer complex Say.

As a method for producing the organic photoreceptor of the present invention, the case of producing an organic photoreceptor having the layer structure (1) will be specifically described below.
Step (1): A step of forming an intermediate layer by applying and drying an intermediate layer-forming coating solution on the outer peripheral surface of the conductive support.
Step (2): a step of forming a charge generation layer by applying and drying a charge generation layer forming coating solution on the outer peripheral surface of the intermediate layer formed on the conductive support.
Step (3): A step of forming a charge transport layer by applying and drying a charge transport layer forming coating solution on the outer peripheral surface of the charge generation layer formed on the intermediate layer.
Step (4): A step of forming a protective layer by applying a coating liquid for forming a protective layer on the outer peripheral surface of the charge transport layer formed on the charge generation layer and irradiating with light.

[Step (1): Intermediate layer forming step]
In this step (1), for example, a binder resin is dissolved in a known solvent to prepare an intermediate layer forming coating solution, and this intermediate layer forming coating solution is applied to the outer peripheral surface of the conductive support. An intermediate layer can be formed by forming a film and drying the coating film.

  The intermediate layer formed in step (1) provides a barrier function and an adhesive function between the conductive support and the organic photosensitive layer. From the viewpoint of preventing various failures, it is preferable to provide such an intermediate layer.

(Conductive support)
The conductive support on which the intermediate layer is formed is not particularly limited as long as it has conductivity. For example, a metal such as aluminum, copper, chromium, nickel, zinc, and stainless steel is drum-shaped or Sheet shaped, laminated metal foil such as aluminum or copper on plastic film, deposited aluminum, indium oxide and tin oxide etc. on plastic film, or coated with conductive material alone or with binder resin Examples thereof include metals provided with a conductive layer, plastic films, and paper.

(Binder resin)
Examples of the binder resin used in the step (1) include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide resin, polyurethane resin, and gelatin. The binder resin may be an alcohol-soluble polyamide resin. preferable.

(solvent)
As the solvent used in the step (1), those in which inorganic fine particles described later are well dispersed and the polyamide resin is dissolved are preferable. Specifically, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol are used. Alcohols having 2 to 4 carbon atoms such as t-butanol and sec-butanol are particularly preferred from the viewpoints of solubility and applicability of the polyamide resin.
In the step (1), in order to improve the storage stability and dispersibility of the inorganic fine particles, it is preferable to use a co-solvent together with a solvent. Examples of co-solvents that can be used in combination include methanol, benzyl alcohol, toluene, Examples include methylene chloride, cyclohexanone, and tetrahydrofuran.

(Inorganic fine particles)
The coating liquid for forming an intermediate layer may contain inorganic fine particles such as various conductive fine particles and metal oxide fine particles for the purpose of adjusting the resistance of the formed intermediate layer.

  Examples of the inorganic fine particles contained in the coating liquid for forming the intermediate layer include metal oxide fine particles such as alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, and bismuth oxide, and doped with tin. Ultrafine particles such as indium oxide, antimony-doped tin oxide and zirconium oxide can also be used. These metal oxide fine particles can be used singly or in combination of two or more. When two or more metal oxide fine particles are used in combination, the metal oxide fine particles are in a solid solution state. It may be in a fused state.

The number average primary particle size of such metal oxide fine particles is preferably 0.3 μm or less, more preferably 0.1 μm or less.
In the present invention, the number average primary particle size of the metal oxide fine particles is measured as follows.
That is, a 10000 times magnified photograph was taken with a scanning electron microscope “JSM-7500F” (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 metal oxide fine particles with a scanner. Calculation is performed using an automatic image processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The means for dispersing the inorganic fine particles in the intermediate layer forming coating solution is not particularly limited, and examples thereof include a dispersing machine such as an ultrasonic dispersing machine, a ball mill, a sand grinder, and a homomixer.

  The addition amount of the inorganic fine particles is preferably 20 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

  Although it does not specifically limit as a coating method of the coating liquid for intermediate | middle layer formation, For example, the dip coating method, the spray coating method, etc. are mentioned.

  The method for drying the coating film of the coating solution for forming the intermediate layer can be appropriately selected according to the type of the solvent and the layer thickness of the intermediate layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the intermediate layer formed in the step (1) is preferably 0.1 to 15 μm, more preferably 0.3 to 10 μm.

[Step (2): Charge Generation Layer Formation Step]
In this step (2), for example, a charge generation material is added and dispersed in a binder resin dissolved in a known solvent to prepare a charge generation layer forming coating solution. The charge generation layer can be formed by coating the outer peripheral surface of the intermediate layer formed in the step (1) to form a coating film and drying the coating film.

(Binder resin)
As the binder resin used in the step (2), a known resin 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, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin), poly-vinylcarbazole resin, and the like, but are not limited thereto.

(solvent)
Examples of the solvent used in the step (2) include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, Examples thereof include, but are not limited to, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, diethylamine and the like.

(Charge generating material)
The charge generation material used in the step (2) is not particularly limited. For example, 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 thioindigo; phthalocyanine pigments and the like. These charge generation materials can be used alone or in combination of two or more.

  The amount of the charge generating material added is preferably 1 to 600 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the binder resin.

  The means for dispersing the charge generating material is not particularly limited, and examples thereof include a dispersing machine such as an ultrasonic dispersing machine, a ball mill, a sand grinder, and a homomixer.

  The method for applying the charge generation layer forming coating solution is not particularly limited, and examples thereof include a dip coating method and a spray coating method.

  The method for drying the coating film of the coating solution for forming the charge generation layer can be appropriately selected according to the type of the solvent and the layer thickness of the charge generation layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the charge generation layer formed in the step (2) varies depending on the characteristics of the charge generation material, the characteristics of the binder resin, the mixing ratio, and the like, but is preferably 0.01 to 5 μm, more preferably 0.00. It is 05-3 micrometers. It should be noted that the coating solution for forming the charge generation layer can prevent the occurrence of image defects by filtering foreign matter and aggregates before coating. The pigment can also be formed by vacuum deposition.

[Step (3): Charge Transport Layer Formation Step]
In this step (3), for example, a charge transport material (CTM) is added to a binder resin dissolved in a known solvent to prepare a charge generation layer forming coating solution. Is applied to the outer peripheral surface of the charge generation layer formed in step (2) to form a coating film, and the coating film is dried to form the charge transport layer.

(Binder resin)
As the binder resin used in the step (3), a known resin can be used, and polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylate resin, styrene. -A methacrylic acid ester copolymer resin etc. are mentioned, However, A polycarbonate resin is preferable. Furthermore, bisphenol A (BPA), bisphenol Z (BPZ), dimethyl BPA, BPA-dimethyl BPA copolymer and the like are preferable in terms of crack resistance, wear resistance, and charging characteristics.

(solvent)
Examples of the solvent used in the step (3) include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, tetrahydrofuran, 1,4- Examples include, but are not limited to, dioxane, 1,3-dioxolane, pyridine, diethylamine and the like.

(Charge transport material)
Examples of the charge transport material used in the step (3) include carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, Styryl compound, hydrazone compound, pyrazoline compound, oxazolone derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, triarylamine derivative, phenylenediamine derivative, stilbene derivative, benzidine derivative, poly-N -Vinylcarbazole, poly-1-vinylpyrene and poly-9-vinylanthracene, triphenylamine derivatives Etc., and the like. These charge transport materials can be used alone or in combination of two or more.

  The addition amount of the charge transport material is preferably 10 to 500 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the binder resin.

  The charge transport layer forming coating solution may contain an antioxidant, an electronic conductive agent, a stabilizer and the like as necessary. Examples of the antioxidant include those described in Japanese Patent Application No. 11-200135, and examples of the electronic conductive agent include those described in JP-A Nos. 50-137543 and 58-76483.

  The coating method of the charge transport layer forming coating solution is not particularly limited, and examples thereof include a dip coating method and a spray coating method.

  The method for drying the coating film of the coating liquid for forming the charge transport layer can be appropriately selected according to the type of the solvent and the layer thickness of the charge transport layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the charge transport layer formed in the step (3) varies depending on the characteristics of the charge transport material, the characteristics of the binder resin, the mixing ratio, etc., but is preferably 5 to 40 μm, more preferably 10 to 30 μm. is there.

[Step (4): Protective layer forming step]
In this step (4), it comprises a polymerizable compound forming a cured resin constituting the protective layer, HABI as a curing agent, a photoactive electron donor that donates electrons to the HABI, and a hydrogen donor compound. If necessary, metal oxide fine particles are added to a known solvent to prepare a coating solution for forming a protective layer, and this coating solution for forming a protective layer is used as an outer periphery of the charge transport layer formed in step (3). It is possible to form a protective film by coating the surface to form a coating film, drying the coating film, and irradiating light such as ultraviolet rays to polymerize the polymerizable compound in the coating film to cure. it can.

(Polymerizable compound)
Although it does not specifically limit as a polymeric compound used in a process (4), For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, a vinyl toluene monomer, a vinyl acetate monomer, an N-vinyl pyrrolidone monomer, etc. Is mentioned. These polymerizable compounds can be used alone or in combination of two or more.

Since the polymerizable compound can be cured with a small amount of light or in a short time, it is composed of a compound having a reactive group of an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═CCH ₃ CO—). It is preferable.

  Specific examples of the compound having an acryloyl group or a methacryloyl group as the polymerizable compound include those shown in the following exemplified compounds (1) to (44). Moreover, the number of groups shown below is the number of acryloyl groups or methacryloyl groups.

  In the exemplary compounds (1) to (44), R is an acryloyl group represented by the following formula (1), and R ′ is a methacryloyl group represented by the following formula (2).

The polymerizable compound is more preferably composed of a compound having two or more acryloyl groups or methacryloyl groups, and particularly preferably composed of a compound having three or more acryloyl groups or methacryloyl groups.
Moreover, although a polymeric compound can be used in combination of 2 or more types, also in this case, it is preferable to use 50 mass% or more of compounds which have 3 or more of acryloyl groups or methacryloyl groups.

(Hexaarylbisimidazole)
Specifically as HABI which comprises the hardening | curing agent used in a process (4), the following exemplary compound (HABI-1)-(HABI-3) is mentioned.
This HABI can be detected by peeling off the formed protective layer, extracting with deuterated chloroform, and measuring the ¹ H-NMR spectrum.
For the NMR measurement, “FT-NMR LA-400” (manufactured by JEOL Ltd.) is used.

(Photoactive electron donor)
The photoactive electron donor constituting the curing agent used in the step (4) has a function as a sensitizing dye in the coating liquid for forming the protective layer.
The photoactive electron donor is a compound having charge transport performance, and specific examples thereof include the following exemplified compounds (X-1) to (X-4).

(Hydrogen donating compound)
Examples of the hydrogen donating compound constituting the curing agent used in the step (4) include those having a thiol group or an amino group, but those having a thiol group are preferable. Specific examples of the hydrogen-donating compound include the following exemplary compounds (Y-1) to (Y-5).

It is preferable that the addition amount of the hardening | curing agent used in this invention is 3-60 mass parts with respect to 100 mass parts of polymeric compounds, More preferably, it is 5-45 mass parts.
Further, the curing agent is added at a ratio of 5 to 30 parts by mass of the photoactive electron donor and 1 to 10 parts by mass of the total of HABI and the hydrogen donor compound with respect to 100 parts by mass of the polymerizable compound. It is preferable.
Furthermore, it is preferable that the ratio (HABI / hydrogen-donating compound) of HABI and the hydrogen-donating compound is 1 to 5.

(solvent)
Examples of the solvent used in the step (4) include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol, benzyl alcohol, toluene, xylene, methylene chloride, methyl ethyl ketone, and methyl. Examples include, but are not limited to, isopropyl ketone, cyclohexane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, and diethylamine.

(Metal oxide fine particles)
The coating liquid for forming the protective layer preferably contains metal oxide fine particles for the purpose of imparting high durability to the formed protective layer.
Such metal oxide fine particles may be metal oxide particles including transition metals. For example, silica (silicon oxide), magnesium oxide, zinc oxide, lead oxide, alumina (aluminum oxide), tin oxide, oxide Metal oxides such as tantalum, indium oxide, bismuth oxide, yttrium oxide, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, tin oxide, titanium dioxide, niobium oxide, molybdenum oxide, vanadium oxide Among these, fine particles of alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), and titanium dioxide (TiO ₂ ) are preferable, and alumina and tin oxide are more preferable.

The number average primary particle size of the metal oxide fine particles is preferably in the range of 1 to 300 nm, more preferably 3 to 100 nm.
In the present invention, the number average primary particle size of the metal oxide fine particles is measured as follows.
That is, a 10000 times magnified photograph was taken with a scanning electron microscope “JSM-7500F” (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 metal oxide fine particles with a scanner. Calculation is performed using an automatic image processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The means for dispersing the metal oxide fine particles is not particularly limited, and examples thereof include a disperser such as an ultrasonic disperser, a ball mill, a sand grinder, and a homomixer.

The content of the metal oxide fine particles is preferably 20 to 400 parts by mass, more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymerizable compound.
When the content of the metal oxide fine particles is too small, the electrical resistance of the protective layer to be formed becomes low, and it may not be possible to prevent an increase in residual potential and occurrence of fog. On the other hand, when the content of the metal oxide fine particles is excessive, there is a possibility that good film formability cannot be obtained in the formed protective layer, and it is impossible to prevent deterioration of charging performance or occurrence of pinholes. is there.

The metal oxide fine particles are preferably those that have been surface-treated with a surface treatment agent having a reactive group (hereinafter also referred to as “reactive group-containing surface treatment agent”). Alumina fine particles or tin oxide fine particles surface-treated with a treating agent are preferred.
Such a reactive group-containing surface treatment agent may be any one having reactivity with a hydroxyl group or the like present on the surface of the metal oxide fine particles, and specifically, one having an acryloyl group or a methacryloyl group is preferable.
When the metal oxide fine particles are surface-treated with the reactive group-containing surface treatment agent, the bond with the polymerizable compound becomes strong, and the formed protective layer has higher durability.

  Specific examples of the reactive group-containing surface treatment agent include those shown in the following exemplary compounds (S-1) to (S-36).

_{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

Moreover, as a surface treating agent, the silane compound which has a reactive group in which radical polymerization reaction is possible other than what is shown to the said exemplary compound (S-1)-(S-36) can be used.
These silane compounds can be used alone or in combination of two or more.

  The surface treatment method using a reactive group-containing surface treatment agent for metal oxide fine particles is not particularly limited, and wet treatment or dry treatment can be adopted, but treatment using a wet media dispersion type apparatus is preferable. .

Hereinafter, a surface treatment method using a wet media dispersion type apparatus will be specifically described.
That is, by subjecting a slurry (suspension of solid particles) containing metal oxide fine particles and a reactive group-containing surface treatment agent to wet pulverization, the metal oxide fine particles are refined and the surface treatment of the metal oxide fine particles is performed. Progresses. After that, the surface-treated metal oxide fine particles are obtained by removing the solvent and pulverizing.

  In the surface treatment method as described above, the addition amount of the reactive group-containing surface treatment agent is 0.1 to 100 parts by mass with respect to 100 parts by mass of the metal oxide fine particles, and the addition amount of the solvent is the metal oxide fine particles. It is preferable that it is 50-5000 mass parts with respect to 100 mass parts.

Wet media dispersion type device is a device that crushes and disperses the aggregated particles of metal oxide by filling beads in the container as media and rotating the stirring disk mounted perpendicular to the rotation axis at high speed. The structure is not particularly limited as long as the metal oxide fine particles can be sufficiently dispersed and subjected to the surface treatment when the surface treatment is performed on the metal oxide fine particles. For example, vertical and horizontal types, Various modes such as a continuous type and a batch type can be adopted. Specifically, a sand mill, an ultra visco mill, a pearl mill, a glen mill, a dyno mill, an agitator mill, a dynamic mill, or the like can be used.
In these dispersion-type apparatuses, pulverization and dispersion are performed by impact crushing, friction, shearing, shear stress, and the like using a pulverizing medium (media) such as balls and beads.

  Examples of the beads used in the wet media dispersion type apparatus include pulverization media made of glass, alumina, zircon, zirconia, steel, flint stone, etc., and those made of zirconia or zircon are particularly preferable. The size of the beads is usually about 1 to 2 mm in diameter, but in the present invention, about 0.1 to 1.0 mm is preferable.

  For example, stainless steel, nylon, and ceramic materials are used for the stirring disk and the inner wall of the container used in the wet media dispersion type apparatus, but ceramic materials such as zirconia or silicon carbide are particularly preferable.

  By the surface treatment with the reactive group-containing surface treatment agent as described above, metal oxide fine particles having a reactive group capable of reacting with a reactive acryloyl group and a reactive methacryloyl group can be obtained.

  The protective layer-forming coating solution may contain lubricant particles, an antioxidant, or the like, if necessary.

(Lubricant particles)
Examples of the lubricant particles include fluorine atom-containing resin particles. Examples of the fluorine atom-containing resin particles include tetrafluoroethylene resin, trifluorinated ethylene chloride resin, hexafluoroethylene chloride propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride dichloride resin, and these It is preferable to select one or two or more of these copolymer particles as appropriate, but tetrafluoroethylene resin particles and vinylidene fluoride resin particles are particularly preferable.

The number average primary particle size of the lubricant particles is preferably 0.01 to 1 μm, more preferably 0.05 to 0.5 μm.
In the present invention, the number average primary particle size of the lubricant particles is measured as follows.
In other words, a 10000x magnified photograph was taken with a scanning electron microscope "JSM-7500F" (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 lubricant particles with a scanner was automatically displayed. Calculation is performed using a processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The molecular weight of the resin constituting the lubricant particles can be appropriately selected and is not particularly limited.

  The content of the lubricant particles is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass in the protective layer forming coating solution.

The liquid viscosity of the protective layer-forming coating solution is preferably 5 to 50 mP · s, more preferably 10 to 25 mP · s.
When the viscosity of the coating liquid for forming the protective layer is too small, coating unevenness occurs, and there is a possibility that a protective layer having a desired layer thickness and a uniform layer thickness cannot be formed. . On the other hand, when the liquid viscosity of the coating liquid for forming the protective layer is excessive, good fluidity cannot be obtained in the coating liquid for forming the protective layer, causing liquid breakage on the coated surface and forming a uniform coated film. There is a risk that it cannot be done.
The liquid viscosity of the coating liquid for forming the protective layer is measured using “E-type viscometer VISCONIC ELD type” (manufactured by Tokyo Keiki Co., Ltd.).

  In the step (4), as a coating method of the coating solution for forming the protective layer, for example, a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, a beam coating method, a slide hopper method, etc. The method is mentioned. Among these, the application method by the slide hopper method is preferable.

  Hereinafter, a method of applying by a slide hopper method using a circular slide hopper applicator will be specifically described.

FIG. 1 is an explanatory cross-sectional view showing an example of the configuration of a circular slide hopper coating apparatus used in the protective layer forming step in the method for producing an organic photoreceptor of the present invention, and FIG. 2 is a circular slide hopper shown in FIG. It is a perspective sectional view of a coating device.
This circular slide hopper coating apparatus includes a cylindrical base material 251, an annular coating head 260 provided so as to surround the periphery thereof, and a storage tank 254 that stores the coating liquid L.

  The substrate 251 here is a substrate for forming a protective layer to which a coating solution for forming a protective layer is to be applied. For example, the substrate 251 has a state in which an intermediate layer and an organic photosensitive layer are formed on a conductive support. Thus, the protective layer is not formed.

The coating head 260 has a narrow coating liquid distribution slit 262 having a coating liquid outlet 261 that opens to the base 251 side along the entire direction of the annular coating head 260 along the direction perpendicular to the longitudinal direction of the base 251. Is formed over. The coating liquid distribution slit 262 communicates with the annular coating liquid distribution chamber 263, and the coating liquid distribution chamber 263 is supplied with the coating liquid L in the storage tank 254 through the supply pipe 264 by the pumping pump 255. Is formed.
On the lower side of the coating liquid outlet 261 of the coating liquid distribution slit 262, there is formed a slide surface 265 that is continuously inclined downward and is formed with a dimension slightly larger than the outer dimension of the substrate 251. Furthermore, a lip portion (bead; liquid reservoir portion) 266 extending downward from the end of the slide surface 265 is formed.

  In such a circular slide hopper coating apparatus, when the coating liquid L is pushed out from the coating liquid distribution slit 262 and allowed to flow down along the slide surface 265 in the process of moving the base 251 in the direction of the arrow, the slide surface 265 ends. The resulting coating liquid L forms a bead between the end of the slide surface 265 and the outer peripheral surface of the substrate 251, and is then applied to the surface of the substrate 251 to form a coating film F. Is discharged from the discharge port 267.

  In such a coating method using a circular slide hopper coating apparatus, the slide surface end and the base material are arranged with a certain gap (about 2 μm to 2 mm), so that the base material is not damaged and the layers have different properties. Even in the case of forming a multilayer, it can be applied without damaging the already applied layer. Furthermore, when multiple layers with different properties and dissolved in the same solvent are formed, the time in the solvent is much shorter than in the dip coating method. Since it can be applied without elution, for example, it can be applied without deteriorating the dispersibility of the metal oxide fine particles.

In the step (4), the coating film of the protective layer forming coating solution can be dried before and after the light irradiation and during the light irradiation, and the timing of the drying should be appropriately selected by combining them. Can do.
The method for drying the coating film of the coating liquid for forming the protective layer can be appropriately selected depending on the type of the solvent, the layer thickness of the protective layer to be formed, etc. The drying temperature is preferably room temperature to 180 ° C., for example. More preferably, it is 80-140 degreeC. The drying time is preferably, for example, 1 to 200 minutes, and more preferably 5 to 100 minutes.

In the step (4), it is preferable that the light irradiated when polymerizing the polymerizable compound in the coating film has a wavelength of 250 to 450 nm.
Such a light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a flash (pulse) xenon, and an LED lamp.
Although the irradiation conditions vary depending on the type of each lamp, the light irradiation amount is usually 5 to 500 mJ / cm ² , preferably 5 to 100 mJ / cm ² . The power of the lamp is preferably 0.1 to 5 kW, more preferably 0.5 to 3 kW.

  The irradiation time for obtaining the necessary light irradiation amount is preferably 0.1 second to 10 minutes, and more preferably 0.1 second to 5 minutes from the viewpoint of work efficiency.

  The thickness of the protective layer formed by the step (4) is preferably 0.2 to 10 μm, more preferably 0.5 to 5 μm.

The protective layer formed by this process (4) can also be comprised using together well-known resin with the cured resin formed of a polymeric compound.
Examples of known resins include polyester resins, polycarbonate resins, polyurethane resins, acrylic resins, epoxy resins, silicone resins, alkyd resins, and the like.

[Image forming apparatus]
The organic photoreceptor obtained by the production method of the present invention can be used in various known electrophotographic image forming apparatuses such as a monochrome image forming apparatus and a full color image forming apparatus.
The image forming apparatus using the organic photoreceptor according to the present invention includes, for example, a charging unit that applies a uniform charging potential on the organic photoreceptor, and an electrostatic latent image on the organic photoreceptor to which the uniform charging potential is applied. A developing unit that develops the electrostatic latent image with a toner and visualizes the toner image, a transfer unit that transfers the toner image onto the transfer material, and a toner image on the transfer material that is fixed. The image forming apparatus includes a fixing unit and a cleaning unit that removes toner remaining on the organic photoreceptor.

〔toner〕
The electrostatic latent image formed on the organic photoreceptor obtained by the production method of the present invention is visualized as a toner image by development. The toner used for the development may be a pulverized toner or a polymerized toner, but a polymerized toner produced by a polymerization method is preferable from the viewpoint of obtaining a stable particle size distribution.

  Polymerized toner is formed by the formation of a binder resin (hereinafter also referred to as “binder resin for toner”) and the shape of the toner by polymerization reaction of the raw material monomer of the toner binder resin and, if necessary, subsequent chemical treatment. Specifically, it means a material formed through a polymerization reaction such as suspension polymerization or emulsion polymerization and, if necessary, a step of fusing the particles thereafter.

The particle diameter of the toner particles constituting the toner is preferably 2 to 9 μm, more preferably 3 to 7 μm in terms of volume average particle diameter (Dv50).
When the particle diameter of the toner particles is in the above range, the resolution of the formed image can be increased. Furthermore, although the toner particles have a small particle size, the abundance of fine toner particles can be reduced, the dot image reproducibility is improved over a long period of time, and a stable image with good sharpness. Can be formed.
The volume average particle diameter (Dv50) of the toner particles is measured and calculated using a measuring device in which a computer system for data processing (manufactured by Beckman Coulter) is connected to “Multisizer 3” (manufactured by Beckman Coulter). Is.

(Developer)
The toner according to the present invention may be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. can do.

  Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable.

The magnetic particles constituting the carrier preferably have a volume average particle size (Dv50) of 15 to 100 μm, more preferably 25 to 80 μm.
In the present invention, the volume average particle diameter (Dv50) of the magnetic particles is measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser. is there.

  The carrier is preferably a resin-coated type in which magnetic particles are further coated with a resin, or a so-called resin-dispersed type in which magnetic particles are dispersed in a resin. The coating resin for constituting the resin-coated carrier is not particularly limited. For example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, ester resin, fluorine-containing resin Examples thereof include polymer resins. In addition, the dispersing resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin Etc.

  According to the method for producing an organophotoreceptor of the present invention, the coating liquid for forming the protective layer contains a curing agent comprising HABI, a photoactive electron donor and a hydrogen donor compound, so that the protective layer is sufficient. It is possible to manufacture an organic photoreceptor that can suppress the generation of image memory while obtaining strength.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

[Example 1: Production Example 1 of Organic Photoreceptor]
(1) Production of conductive support The surface of a drum-like aluminum support was cut to produce a conductive support [1] having a surface roughness Rz = 1.5 (μm).

(2) Intermediate layer forming step Using a sand mill with the following raw materials as a disperser, dispersion was performed for 10 hours by a batch method to prepare an intermediate layer forming coating solution [1].
-Binder resin: Polyamide resin "X1010" (manufactured by Daicel Degussa) 1 part by mass-Solvent: 20 parts by mass of ethanol-Metal oxide fine particles: Titanium oxide fine particles "SMT500SAS" (manufactured by Teika) 1.1 parts by mass On the conductive support [1], the intermediate layer-forming coating solution [1] is applied by a dip coating method to form a coating film, and the coating film is formed at 110 ° C. for 20 minutes. Dried to form an intermediate layer [1] having a layer thickness of 2 μm.

(3) Organic photosensitive layer forming step (charge generating layer forming step)
Dispersion for 10 hours was performed using a sand mill with the following raw materials as a disperser to prepare a coating solution [1] for forming a charge generation layer.
Charge generating material: titanyl phthalocyanine pigment (having a maximum diffraction peak at a position of 5 at least 27.3 ° by Cu-Kα characteristic X-ray diffraction spectrum measurement) 20 parts by mass Binder resin: polyvinyl butyral resin “# 6000-C (Electric Chemical Industry 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 On the intermediate layer [1], this coating solution for forming a charge generation layer [1] ] Was applied by a dip coating method to form a coating film, and a charge generation layer [1] having a layer thickness of 0.3 μm was formed.

(Charge transport layer forming step)
The following raw materials were mixed and dissolved to prepare a charge transport layer forming coating solution [1].
-Charge transport material: 150 parts by mass of the compound represented by the following formula (A)-Binder resin: 300 parts by mass of polycarbonate resin "Z300" (manufactured by Mitsubishi Gas Chemical Company)-Solvent: Toluene / tetrahydrofuran = 1/9% by volume 2000 parts by mass Antioxidant: “Irganox 1010” (manufactured by Ciba Geigy Japan) 6 parts by mass Leveling agent: Silicone oil “KF-54” (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass On this charge generation layer [1] The layer forming coating solution [1] was applied by a dip coating method to form a coating film, and this coating film was dried at 120 ° C. for 70 minutes to form a charge transport layer [1] having a layer thickness of 20 μm.

(4) Protective layer forming step The following polymerizable compound, solvent, curing agent and metal oxide fine particles are dispersed for 10 hours using a sand mill as a disperser under light shielding, and a protective layer forming coating solution [1] is prepared. Prepared.
Polymerizable compound: Exemplified compound (42) 100 parts by mass Solvent: sec-butanol 500 parts by mass Solvent: tetrahydrofuran 100 parts by mass HABI: Exemplified compound (HABI-1) 4 parts by mass Photoactive electron donor: Exemplified compound (X-1) 20 parts by mass / hydrogen donating compound: Exemplified compound (Y-5) 2 parts by mass / metal oxide fine particles: Number subjected to surface treatment with the surface treating agent shown in Exemplified compound (S-15) 100 parts by mass of tin oxide fine particles having an average primary particle size of 20 nm The coating solution [1] for forming the protective layer was applied onto the charge transport layer [1] using a circular slide hopper coating device to form a coating film. . Thereafter, this coating film was dried at room temperature for 20 minutes, and a distance between the light source and the surface of the photosensitive member was set to 100 mm under a nitrogen stream using a xenon lamp, and ultraviolet light was irradiated for 1 minute at a lamp output of 4 kW. A protective layer [1] of 3.5 μm was formed to obtain an organic photoreceptor [1].

[Examples 2 to 10 and Comparative Example 1: Production Examples 2 to 11 of Organic Photoreceptor]
In the same manner as in Production Example 1 of the organic photoreceptor, except that the polymerizable compound, the curing agent, and the metal oxide fine particles in the protective layer forming step were changed to the types and addition amounts shown in Table 1 in the same manner. [2] to [11] were obtained.

  The organic photoreceptors [1] to [11] obtained as described above were subjected to full color image forming apparatus “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies, Inc .; 780 nm semiconductor laser exposure / reverse development / intermediate transfer member) The following evaluations 1 to 3 were performed. The results are shown in Table 2.

[Evaluation 1: Image memory]
A monochrome halftone image (average relative reflection density of 0.4 with a Macbeth densitometer) was copied on the entire surface of A3 neutral paper under the conditions of a temperature of 10 ° C. and a humidity of 20% RH. A total of 8 points at a distance of 180 mm from the corner and 33 mm from the end in the vertical direction are a1, a2,... A8, respectively, and a total of 8 points at a position of 195 mm in the horizontal direction from the corner and 33 mm from the vertical end. Are similarly b1, b2,..., B8, and the reflection density at each point was measured with a Macbeth densitometer. The difference between the measured values of a1 and b1, the difference between the measured values of a2 and b2, and the difference in the measured values of eight combinations in total were calculated and evaluated according to the following evaluation criteria. In addition, it is thought that generation | occurrence | production of an image memory is suppressed, so that the maximum value of the difference of a measured value is small.
-Evaluation criteria-
A: Maximum difference in measured values is less than 0.01 (good)
○: The maximum difference between measured values is 0.01 or more and less than 0.02 (no problem in practical use)
Δ: The maximum difference between the measured values is 0.02 or more and less than 0.04 (practical use)
×: The maximum difference in measured values is 0.04 or more (there is a problem in practical use)

[Evaluation 2: Scratch resistance]
After the evaluation of the image memory, an A4 plate image with a print area ratio of 5% for each color of yellow (Y), magenta (M), cyan (C), and black (K) under the conditions of a temperature of 20 ° C. and a humidity of 50% RH One million sheets were printed on the neutral plate. Thereafter, a halftone image (relative reflection density of 0.4 with Macbeth densitometer) was printed on the entire surface of A3 neutral paper. Thereafter, the organic photoreceptor and the formed halftone image were observed and evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: No noticeable scratches are observed on the surface of the organic photoreceptor, and no image defects corresponding to the scratches are found in the halftone image (good).
○: Minor scratches are visually observed on the surface of the organophotoreceptor, but no image defects corresponding to the scratches are found in the halftone image (no problem in practical use).
×: The surface of the organic photoconductor is clearly scratched, and the occurrence of image defects corresponding to the scratch is also observed in the halftone image (practically problematic).

[Evaluation 3: Abrasion resistance]
Under the conditions of the initial organic photoconductor thickness, temperature 20 ° C., humidity 50% RH, yellow (Y), magenta (M), cyan (C), black (K) A4 version with 5% each color printing area ratio The film thickness of the organic photoconductor after printing 1 million sheets of images on A4 neutral paper was measured, and this film thickness difference was evaluated according to the following evaluation criteria as the amount of wear of the protective layer of the organic photoconductor.
In addition, the film thickness of the organic photoconductor was measured at 10 points at random on the uniform film thickness portion (the film thickness tends to be non-uniform at both ends of the organic photoconductor), and the average value thereof was measured. Was the film thickness of the organic photoreceptor. The film thickness was measured using an eddy current film thickness measuring instrument “EDDY560C” (manufactured by HELMUT FISCHER GMBTE CO).
-Evaluation criteria-
A: The amount of wear is 1 μm or less (good)
○: Amount of wear is greater than 1 μm and less than 3 μm (no problem in practical use)
X: The amount of wear is larger than 3 μm (there is a practical problem)

251 Substrate 254 Storage tank 255 Pressure pump 260 Application head 261 Application liquid outlet 262 Application liquid distribution slit 263 Application liquid distribution chamber 264 Supply pipe 265 Slide surface 266 Lip portion 267 Discharge port L Application liquid F Application film

Claims (7)

A method for producing an organic photoreceptor in which an organic photosensitive layer and a protective layer made of a cured resin are laminated in this order on a conductive support,
On the organic photosensitive layer, a polymerizable compound that forms a cured resin, a hexaarylbisimidazole, a photoactive electron donor that donates electrons to the hexaarylbisimidazole, and a curing agent that includes a hydrogen donor compound. A method for producing an organic photoreceptor, comprising a step of applying a coating liquid for forming a protective layer and irradiating light.   2. The method for producing an organic photoreceptor according to claim 1, wherein the photoactive electron donor is a compound having charge transport performance.   The method for producing an organic photoreceptor according to claim 1, wherein the hydrogen-donating compound has a thiol group.   The method for producing an organic photoreceptor according to any one of claims 1 to 3, wherein the coating liquid for forming the protective layer contains metal oxide fine particles.   5. The method for producing an organophotoreceptor according to claim 4, wherein the metal oxide fine particles are alumina fine particles or tin oxide fine particles surface-treated with a surface treatment agent having a reactive group.   6. The method for producing an organic photoreceptor according to claim 5, wherein the surface treatment agent is a compound having an acryloyl group or a methacryloyl group as a reactive group.   The method for producing an organic photoreceptor according to claim 1, wherein the polymerizable compound has an acryloyl group or a methacryloyl group.