JP2016200746A - Manufacturing method of electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor that comprises a surface layer formed through a polymerization reaction of a photopolymerizable monomer and suppresses a reduction in chargeability due to repetition of image formation.SOLUTION: There is provided a manufacturing method of an electrophotographic photoreceptor comprising a conductive support, a photosensitive layer, and a surface layer. The method includes the steps of: applying a coating liquid containing a polymerizable monomer for forming a surface layer on the photosensitive layer to form a film of the coating liquid on the photosensitive layer; irradiating the film with an infrared ray; and irradiating a portion of the film irradiated with the infrared ray with an active light beam to polymerize the polymerizable monomer, and thereby manufacturing an electrophotographic photoreceptor comprising a conductive support, a photosensitive layer arranged on the conductive support, and a surface layer arranged on the photosensitive layer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an electrophotographic photoreceptor.

  In an electrophotographic image forming apparatus, an electrophotographic photosensitive member (hereinafter also simply referred to as “photosensitive member”) is used to form an electrostatic latent image corresponding to an image to be formed. The photosensitive member has a conductive support and a photosensitive layer disposed on the conductive support. Electric energy, light energy, or mechanical force is supplied to the photoreceptor in each process such as charging, exposure, development, transfer, and cleaning performed for image formation. In the image forming apparatus, a decrease in chargeability of the photosensitive member is not preferable because it causes image defects. Therefore, the photoreceptor is required to have durability that does not impair charging stability, potential holding property, and the like due to repeated image formation.

  Therefore, a technique for providing a surface layer on the surface of the photosensitive layer in order to improve the durability of the photoreceptor is known. In particular, in a surface layer formed by polymerizing a photopolymerizable monomer, the photopolymerizable monomer forms a three-dimensional structure by polymerization, so that a surface layer having high surface strength can be formed. For this reason, a photoreceptor having a surface layer excellent in durability can be obtained.

  As the above photoreceptor, a photoreceptor having a surface layer formed by irradiating light having a wavelength of 500 to 2000 nm to a coating film of a liquid containing a photopolymerizable monomer and a compound that emits up-conversion light is known. (For example, refer to Patent Document 1).

  Further, a photoreceptor having a surface layer formed by irradiating the coating film with ultraviolet rays while heating the coating film of a liquid containing a photopolymerizable monomer is known (for example, Patent Documents). 2).

  Further, the surface of the photoreceptor formed by irradiating the coating film of the liquid containing the photopolymerizable monomer with ultraviolet light with a predetermined irradiation light energy and setting the temperature of the surface of the photoreceptor to 70 to 90 ° C. A photoreceptor having a layer is known (for example, see Patent Document 3).

JP 2014-035527 A JP 2010-008700 A JP 2007-279288 A

  However, since the deactivation rate of the photopolymerization reaction is fast, unreacted groups may remain in the surface layer. If unreacted groups remain in the surface layer, the chargeability of the photoreceptor may be lowered in the process of repeatedly forming an image.

  An object of the present invention is to provide a photoreceptor having a surface layer formed by a polymerization reaction of a photopolymerizable monomer, and in which a decrease in chargeability due to repeated image formation is suppressed.

  The present invention is a method for producing an electrophotographic photosensitive member comprising a conductive support, a photosensitive layer disposed on the conductive support, and a surface layer disposed on the photosensitive layer, wherein the surface A step of coating a coating solution containing a polymerizable monomer for forming a layer on the photosensitive layer to form a film of the coating solution on the photosensitive layer; and irradiating the film with infrared light There is provided a method for producing an electrophotographic photosensitive member, comprising: a step; and a step of irradiating a portion of the film irradiated with infrared light with active light to polymerize the polymerizable monomer.

  The present invention can provide a photoreceptor that has a surface layer formed by a polymerization reaction of a photopolymerizable monomer and that suppresses a decrease in chargeability due to repeated image formation.

FIG. 1 is a diagram schematically showing an example of a layer structure of a photoreceptor manufactured by the manufacturing method according to the present embodiment. FIG. 2 is a diagram schematically illustrating an example of the configuration of an image forming apparatus having the above-described photoconductor.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a diagram schematically showing an example of the layer structure of the photoreceptor 413 manufactured by the manufacturing method according to the present embodiment. As shown in FIG. 1, the photoconductor 413 includes a conductive support 1, an intermediate layer 2 disposed on the conductive support 1, a photosensitive layer 3 disposed on the intermediate layer 2, and a photosensitive layer. 3 and a surface layer 4 disposed on the surface 3. The photosensitive layer 3 has a charge generation layer 5 and a charge transport layer 6.

  The intermediate layer 2 is a layer having a barrier function and an adhesive function.

  The photosensitive layer 3 is a layer for forming an electrostatic latent image of an intended image on the surface by exposure in an image forming apparatus described later. As described above, in the present embodiment, the photosensitive layer 3 is a laminate of the charge generation layer 5 containing a charge generation material and the charge transport layer 6 containing a charge transport material. The photosensitive layer 3 may be a single layer containing a charge transport material and a charge generation material.

  The surface layer 4 is disposed on the photosensitive layer 3 and constitutes the surface of the photoreceptor 413. The surface layer 4 is a layer for protecting the photosensitive layer 3.

  The photosensitive member 413 can be manufactured by a known manufacturing method of an electrophotographic photosensitive member except for the manufacturing process of the surface layer 4. For example, the photoconductor 413 includes 1) a first step of preparing the conductive support 1, 2) a second step of disposing the intermediate layer 2 on the conductive support 1, and 3) photosensitizing on the intermediate layer 2. It can be manufactured by performing the third step of arranging the layer 3 and 4) the fourth step of arranging the surface layer 4 on the photosensitive layer 3 in this order.

  The third step is 3-1) the third step 3-1 in which the charge generation layer 5 is disposed on the intermediate layer 2, and 3-2 the third step in which the charge transport layer 6 is disposed on the charge generation layer 5. Including.

  The fourth step is 4-1) a fourth step in which a coating solution for forming a surface layer containing a polymerizable monomer (hereinafter also referred to as “fourth coating solution”) is applied on the photosensitive layer 3; -2) Step 4-2 for irradiating the film of the fourth coating solution with infrared light; and 4-3) actinic rays for polymerizing the polymerizable monomer on the portion irradiated with infrared light of the film. 4-3 process to irradiate.

  Hereinafter, each process of the manufacturing method of the photoreceptor 413 will be described.

1) 1st process In the 1st process, the electroconductive support body 1 is prepared. The conductive support 1 is a member that supports a photosensitive layer 3 described later and has conductivity. Examples of the type of the conductive support 1 are a metal drum, a metal sheet, a plastic film laminated with a metal foil, a plastic film on which a conductive material is deposited, and a paint containing the conductive material. Metal members, plastic films, paper and the like. The kind of metal will not be specifically limited if it has electroconductivity. Examples of metal types include aluminum, copper, chromium, nickel, zinc and stainless steel. Examples of the conductive material include metals, indium oxide, and tin oxide. In the present embodiment, the conductive support 1 is an aluminum drum.

2) Second Step In the second step, the intermediate layer 2 is formed on the prepared conductive support 1. Specifically, first, a coating solution for forming an intermediate layer (hereinafter also referred to as “first coating solution”) is prepared. Subsequently, the said 1st coating liquid is apply | coated on the electroconductive support body 1, and the liquid film of a 1st coating liquid is formed. Finally, the intermediate layer 2 can be formed by drying the liquid film.

  For example, the first coating liquid can be prepared by dissolving a binder resin in a known solvent.

  Examples of the binder resin used in the second step include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane and gelatin.

  Examples of the solvent used in the second step include ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol and the like.

  From the viewpoint of adjusting the electric resistance of the intermediate layer 2, the first coating liquid may contain inorganic particles such as conductive particles and metal oxide particles. Examples of types of inorganic particles include metal oxide particles such as alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide; tin-doped indium oxide, antimony-doped tin oxide and oxide Ultrafine particles such as zirconium are included. These inorganic particles may be of one type or more.

  In the case where two or more metal oxide particles are used in combination, the metal oxide particles may be in a solid solution state or in a fused state. The number average primary particle diameter of the metal oxide particles is preferably 0.3 μm or less, and more preferably 0.1 μm or less. The number average primary particle size of the metal oxide particles is randomly captured by a scanner from a 10,000 times magnified photograph taken at an acceleration voltage of 80 kV by a scanning electron microscope “JEM-7500F” (manufactured by JEOL Ltd.). By processing and analyzing photographic images of the 100 metal oxide particles (excluding aggregated particles) with an automatic image processing analyzer “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco Corporation) Calculated.

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

  The means for dispersing the inorganic fine particles in the first coating liquid can be appropriately selected from known dispersing devices. Examples of the means for dispersing the inorganic fine particles include dispersers such as an ultrasonic disperser, a ball mill, a sand grinder, and a homomixer.

  The coating method of the first coating solution can be appropriately selected from known coating methods according to the composition of the first coating solution. Examples of the coating method of the first coating liquid include a dip coating method and a spray coating method.

  The method for drying the liquid film of the first coating liquid can be appropriately selected according to the type of solvent, the desired thickness of the intermediate layer 2, and the like. Examples of the method for drying the liquid film of the first coating liquid include natural drying and heat drying.

  The thickness of the intermediate layer 2 is, for example, 0.1 to 15 μm, and more preferably 0.3 to 10 μm.

3) Third Step In the third step, the photosensitive layer 3 is formed on the intermediate layer 2.

3-1) Step 3-1 In the step 3-1, the charge generation layer 5 is formed on the intermediate layer 2. Specifically, first, a coating solution for forming a charge generation layer (hereinafter, “second coating solution”) is prepared. Next, the second coating liquid is applied onto the intermediate layer 2 to form a liquid film of the second coating liquid. Finally, the charge generation layer 5 can be formed by drying the liquid film.

  The second coating liquid can be prepared, for example, by adding and dispersing a charge generating substance in a binder resin dissolved in a known solvent.

  Examples of the binder resin used in step 3-1 include 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, 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), and poly-vinyl carbazole resin.

  Examples of charge generating 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; and phthalocyanine pigments.

  The amount of the charge generation material added is preferably 1 to 600 parts by mass, and 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 can be appropriately selected from known dispersing devices. Examples of the means for dispersing the charge generating material include dispersing machines such as an ultrasonic dispersing machine, a ball mill, a sand grinder, and a homomixer.

  Examples of the solvent used in Step 3-1 include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl Cellosolve, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, pyridine and diethylamine are included.

  The coating method of the second coating solution can be appropriately selected from known coating methods according to the composition of the second coating solution. Examples of the coating method of the second coating liquid include a dip coating method and a spray coating method.

  The method for drying the liquid film of the second coating solution can be appropriately selected according to the type of solvent, the desired thickness of the charge generation layer, and the like. Examples of the method for drying the liquid film of the second coating liquid include natural drying and heat drying.

  The thickness of the charge generation layer 5 is, for example, 0.01 to 5 μm, and more preferably 0.05 to 3 μm.

3-2) Step 3-2 In step 3-2, charge transport layer 6 is formed on charge generation layer 5. Specifically, first, a coating solution for the charge transport layer (hereinafter also referred to as “third coating solution”) is prepared. Next, the third coating solution is applied onto the charge generation layer to form a liquid film of the third coating solution. Finally, the charge transport layer 6 can be formed by drying the liquid film.

  The third coating liquid can be prepared, for example, by adding and dispersing a charge generating material in a binder resin dissolved in a known solvent.

  Examples of the binder resin used in Step 3-2 include polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylic ester resin, and styrene-methacrylic ester. A copolymer resin.

  Examples of charge transport materials include 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 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 are included.

  Examples of the charge transport material include compounds represented by the following formulas CTM1 to CTM10 and RCTM.

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

  Examples of the solvent used in Step 3-2 include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl Cellosolve, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, pyridine and diethylamine are included.

  The coating method of the third coating solution can be appropriately selected from known coating methods according to the composition of the third coating solution. Examples of the coating method of the third coating liquid include a dip coating method and a spray coating method.

  The method for drying the liquid film of the third coating solution can be appropriately selected according to the type of solvent, the desired thickness of the charge transport layer 6 and the like. Examples of the method for drying the liquid film of the third coating liquid include natural drying and heat drying.

  The thickness of the charge transport layer 6 is, for example, 5 to 40 μm, and more preferably 10 to 30 μm.

4) Fourth Step In the fourth step, the surface layer 4 is formed on the photosensitive layer 3.

4-1) Step 4-1 In Step 4-1, a coating solution for forming a surface layer (fourth coating solution) containing a polymerizable monomer is applied onto the photosensitive layer 3. Specifically, first, a fourth coating solution is prepared. Next, the fourth coating solution is applied onto the photosensitive layer 3 to form a liquid film of the fourth coating solution. Finally, the film of the fourth coating liquid can be formed by drying the liquid film.

  The fourth coating liquid can be prepared, for example, by adding a polymerizable monomer that is a precursor of a cured resin constituting the surface layer 4 and a photopolymerization initiator to a known solvent. The fourth coating liquid may further contain other components such as metal oxide particles, lubricant particles, antioxidants, and resins other than the cured resin, if necessary.

  Examples of polymerizable monomers include styrene monomers, acrylic monomers, methacrylic monomers, vinyl toluene monomers, vinyl acetate monomers, and N-vinyl pyrrolidone monomers. These polymerizable monomers may be of one kind or more.

The polymerizable monomer has a reactive group such as an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) CO—) because it can be polymerized in a small amount of light or in a short time. A compound is preferred. The polymerizable monomer is preferably an acrylic monomer having two or more of these reactive groups. Furthermore, it is preferably an oligomer of a polymerizable monomer.

  The polymerizable monomer 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 polymerizable monomer can be used in combination of 2 or more types, it is preferable to use 50 mass% or more of compounds which have 3 or more of acryloyl groups or methacryloyl groups.

  Examples of the polymerizable monomer having an acryloyl group or a methacryloyl group include compounds represented by the following formulas M1 to M15. In the following formulae, R represents an acryloyl group, and R 'represents a methacryloyl group.

  Examples of photopolymerization initiators 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 Ltd., Irgacure is manufactured by BASF Corp. Registered trademark), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione Acetophenone-based or ketal-based photopolymerization initiators such as 2- (o-ethoxycarbonyl) oxime Benzoin ether photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl Benzophenone photopolymerization initiators such as 4-benzoylphenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, And thioxanthone photopolymerization initiators such as 2,4-dichlorothioxanthone are included.

  Other examples of the photopolymerization initiator 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 Ltd.), bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine Compounds, triazine compounds, and imidazole compounds are included.

  In addition, a photopolymerization accelerator having a photopolymerization promoting effect can be used alone or in combination with the photopolymerization initiator. Examples of photopolymerization accelerators include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, and 4,4′-dimethylamino. Benzophenone is included.

  The addition amount of the photopolymerization initiator is preferably 0.1 to 30 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

From the viewpoint of imparting higher durability to the surface layer 4, the fourth coating liquid preferably contains metal oxide particles. Examples of metal oxide particle materials include silica (silicon oxide), magnesium oxide, zinc oxide, lead oxide, alumina (aluminum oxide), tin oxide, copper aluminum oxide, tantalum oxide, indium oxide, bismuth oxide, oxidation Yttrium, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, titanium dioxide, niobium oxide, molybdenum oxide, and vanadium oxide are included. Among them, the material of the metal particles is preferably tin oxide (SnO ₂₎ or copper aluminum oxide (CuAlO _2).

  The number average primary particle diameter of the metal oxide particles is preferably in the range of 0.01 to 0.2 μm, and more preferably in the range of 0.02 to 0.1 μm. The number average primary particle size of the metal oxide particles is calculated by the same method as the number average primary particle size of the metal oxide particles contained in the intermediate layer 2 described above.

  The means for dispersing the metal oxide particles can be appropriately selected from known dispersing devices. Examples of the means for dispersing the metal oxide particles include an ultrasonic disperser and a disperser such as a ball mill, a sand grinder, and a homomixer.

  The content of the metal oxide particles is preferably 20 to 400 parts by mass and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the content of the metal oxide particles is too small, the electric resistance of the surface 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 particles is too large, good film formability cannot be obtained on the surface layer to be formed, and there is a possibility that deterioration of charging performance and generation of pinholes cannot be prevented.

Further, from the viewpoint of further increasing dispersibility, the metal oxide particles may be surface-treated. In particular, tin oxide (SnO ₂ ) particles or copper aluminum oxide (CuAlO ₂ ) particles surface-treated with a surface treatment agent having metal oxide particles and a reactive group (hereinafter also referred to as “surface treatment agent”). It is preferable. The surface treatment method of the metal oxide particles can be appropriately selected from known methods according to the type of metal, the type of surface treatment agent, and the like. As an example of the surface treatment method, a wet treatment method or a dry treatment method can be adopted.

  For example, the surface-treated metal oxide particles can be treated using a wet media dispersion type apparatus. Specifically, a slurry (a suspension of solid particles) containing metal oxide particles and a surface treatment agent is wet-pulverized. Finally, the surface-treated metal oxide particles can be obtained by removing the solvent and pulverizing.

  A surface treating agent is a compound which has the reactivity with the hydroxyl group which exists in the surface of a metal oxide particle, for example. The surface treatment agent preferably has an acryloyl group or a methacryloyl group. Moreover, the compound shown by the following (S-1)-(S-36) is contained in the example of a surface treating agent.

_{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

  In the wet media dispersion type apparatus, balls, beads, and the like are filled in the container as grinding media, and a stirring disk attached perpendicularly to the rotation shaft is rotated at high speed. Thus, in the wet media dispersion type apparatus, the aggregated particles of the metal oxide are pulverized and dispersed.

  In said surface treatment method, the addition amount of a surface treating agent is 0.1-100 mass parts with respect to 100 mass parts of metal oxide particles, and the addition amount of a solvent is 100 mass parts of metal oxide particles. It is preferable that it is 50-5000 mass parts.

  The wet media dispersion type device is not particularly limited as long as the metal oxide particles can be sufficiently dispersed and surface-treated when performing the surface treatment on the metal oxide particles, for example, vertical / horizontal, continuous Various forms such as a formula and a batch type can be adopted. Examples of wet media dispersing devices include sand mills, ultra visco mills, pearl mills, glen mills, dyno mills, agitator mills, and dynamic mills.

  Examples of the beads used in the wet media dispersion type apparatus include grinding media made of glass, alumina, zircon, zirconia, steel, flint stone and the like as raw materials. In particular, beads such as zirconia and zircon are preferred. The size of the beads is usually about 1 to 2 mm in diameter.

  In addition, 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, and ceramic materials such as zirconia or silicon carbide are particularly preferable.

  Through the above procedure, metal oxide particles having a reactive group capable of reacting with an acryloyl group or a methacryloyl group can be obtained. When the metal oxide particles are surface-treated with the surface treatment agent, the bond with the polymerizable monomer is strengthened, and the durability of the formed surface layer 4 can be further increased.

  Examples of the lubricant particles include resin particles containing fluorine atoms. Examples of resin particle materials containing fluorine atoms include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene chloride propylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride. Included are particles of ethylene resins and copolymers thereof. The lubricant particles are preferably selected from one or more of these as appropriate, but ethylene tetrafluoride 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, and more preferably 0.05 to 0.5 μm.

  The number average primary particle size of the lubricant particles is calculated by the same method as the number average primary particle size of the metal oxide particles described above.

  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 in the fourth coating liquid, and more preferably 0.2 to 10% by mass.

  A known resin may be used as an example of the resin other than the cured resin. Examples of known resins include polyester resins, polycarbonate resins, polyurethane resins, acrylic resins, epoxy resins, silicone resins, alkyd resins, and the like.

  Examples of the solvent used in Step 4-1 include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol, benzyl alcohol, toluene, xylene, methylene chloride, methyl ethyl ketone. Methyl isopropyl ketone, cyclohexane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, pyridine and diethylamine.

  The liquid viscosity of the fourth coating liquid is preferably 2 to 50 mP · s, and more preferably 3 to 25 mP · s. If the liquid viscosity of the fourth coating solution is too small, coating unevenness may occur, and it may not be possible to form a surface layer having a desired thickness and a uniform thickness. On the other hand, if the liquid viscosity of the fourth coating liquid is too large, the fluidity of the fourth coating liquid cannot be obtained, and the liquid may run out on the coated surface, so that a uniform liquid film cannot be formed. There is. The liquid viscosity of the fourth coating liquid can be measured using an “E-type viscometer VISCONIC ELD type” (manufactured by Tokyo Keiki Co., Ltd.).

  The coating method of the fourth coating solution can be appropriately selected from known coating methods according to the composition of the fourth coating solution. Examples of the coating method of the fourth coating liquid include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, a beam coating method, and a slide hopper method.

  The method for drying the liquid film of the fourth coating solution can be appropriately selected according to the type of solvent, the desired thickness of the surface layer 4 and the like. Examples of the method for drying the liquid film of the fourth coating solution include natural drying and heat drying.

  Through the above steps, a film of the fourth coating solution can be formed on the photosensitive layer 3. Hereinafter, the photosensitive layer 3 on which the film of the fourth coating solution is formed is referred to as “work”.

4-2) Step 4-2 In Step 4-2, infrared light is irradiated to the film of the fourth coating solution formed on the photosensitive layer 3 of the workpiece.

  One feature of the method for producing a photoreceptor according to the present embodiment is that it includes a step of irradiating infrared light. The inventors of the present invention irradiate the film of the fourth coating solution with infrared light and then irradiate with actinic rays described later, as compared with the case of not irradiating infrared light before irradiating with actinic rays. The inventors have found that a decrease in chargeability due to repeated image formation can be remarkably suppressed (see Examples). The principle of suppressing the decrease in chargeability is unknown, but the polymerization reaction in the film was promoted by the molecular vibration and alignment of the polymerizable monomers in the film by irradiation with infrared light. It is guessed. This is presumably because the amount of unreacted groups in the surface layer 4 is reduced, and the binding between the unreacted groups and the discharge product generated in the charging step for forming an image is suppressed.

Irradiation conditions such as irradiation energy and irradiation time of infrared light can be appropriately set according to the type of light source used, the output of the light source, the type of polymerizable monomer, and the like. Irradiation of the infrared light to the film of the fourth coating solution needs to be sufficiently performed, but if the infrared light is excessively irradiated, the polymerizable monomer may be damaged by the heat generated by the infrared light irradiation. In addition, the film may dry and solidify. On the other hand, if the infrared light irradiation is insufficient, the desired effect may not be obtained. From this point of view, the irradiation energy of the infrared light is preferably 0.1~5J / cm ^2, more preferably 0.5 to 3 J / cm ^2. Further, the irradiation time of infrared light is preferably 0.1 to 60 seconds, and more preferably 1 to 10 seconds. Furthermore, it is preferable that the timing of irradiating infrared light is 0.1 second to 5 minutes before irradiating an actinic ray described later.

  Examples of types of infrared light sources include infrared halogen lamps, carbon lamps and Korce lamps. The output of the infrared light source is preferably 0.1 to 10 kW, and more preferably 3 to 7 kW. The wavelength of infrared light is preferably 750 to 3500 nm, and more preferably 1500 to 2500 nm (near infrared light). The wavelength of the infrared light can be adjusted by using a long-pass filter, a short-pass filter, or a band-pass filter for light emitted from the light source.

  The irradiation method of infrared light is not particularly limited. For example, what is necessary is just to irradiate a workpiece | work with infrared light from the perimeter direction of the electroconductive support body 1 using the light irradiation apparatus described in Unexamined-Japanese-Patent No. 2013-125121. In the light irradiation device, a light emission window for emitting infrared light is formed so as to surround the periphery of the cylindrical workpiece. Thereby, an infrared light can be irradiated to a workpiece | work simultaneously from the perimeter direction of the electroconductive support body 1. FIG. When the surface area of the workpiece is larger than the irradiated region of the light irradiation device, the fourth coating liquid is obtained by irradiating infrared light with the light irradiation device while conveying the workpiece in the axial direction of the conductive support 1. The whole film can be irradiated with infrared light. At this time, the speed at which the workpiece is conveyed is adjusted so that infrared light can be irradiated with a desired irradiation energy according to the output of the infrared light source, the distance between the workpiece and the light source, and the like. For example, the workpiece conveyance speed is 1 to 30 mm / sec. From the viewpoint of more uniformly irradiating the work with infrared light, the work may be rotated about the axis of the conductive support 1 as the central axis.

4-3) Step 4-3 In Step 4-3, actinic rays for polymerizing the polymerizable monomer are irradiated. Irradiation of actinic rays to the workpiece can be performed under known conditions for forming a surface layer by polymerization of a polymerizable monomer.

The irradiation energy and irradiation time of actinic rays can be appropriately set according to the type of light source used, the output of the light source, the type of polymerizable monomer for forming the surface layer 4 and the like. Irradiation energy of active rays is preferably 5~500mJ / cm ^2, more preferably 5~10mJ / cm ^2. Moreover, it is preferable that irradiation time is 0.1 second-10 minutes, and it is more preferable that it is 0.1 second-5 minutes. Examples of types of actinic light sources include low pressure mercury lamps, medium pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, flash (pulse) xenon, and ultraviolet LEDs. The output of the active light source is preferably 0.1 to 5 kW, and more preferably 0.5 to 3 kW. The wavelength of the actinic ray is preferably 250 to 400 nm (ultraviolet light).

  The actinic ray irradiation method is not particularly limited as long as it is possible to irradiate the portion irradiated with infrared light in the film of the fourth coating solution. For example, actinic rays may be irradiated sequentially from the portion irradiated with infrared light toward the workpiece being conveyed while being irradiated with infrared light using the above-described light irradiation device, or the entire film The entire film may be irradiated after the infrared light irradiation to the film is finished. In addition, in the case of sequentially irradiating actinic rays from the portion irradiated with infrared light, the portion irradiated with infrared light and the portion irradiated with actinic light may partially overlap, It does not have to overlap. Thereby, a polymerizable monomer can be polymerized and the surface layer 4 can be formed.

  The thickness of the surface layer 4 formed in the fourth step is, for example, 2 to 15 μm, and more preferably 4 to 8 μm.

  The photoconductor 413 can be manufactured by the above procedure. In the method for manufacturing the photoconductor 413, the film of the fourth coating solution is irradiated with infrared light before the surface layer 4 is cured. Thereby, even if image formation is repeatedly performed, it is possible to suppress a decrease in chargeability of the photoreceptor.

  In the above embodiment, the photoconductor 413 having the intermediate layer 2 has been described. However, the photoconductor may not have the intermediate layer 2. In this case, the photosensitive layer 3 is disposed on the conductive support 1.

  The photoreceptor 413 is used as an organic photoreceptor in an electrophotographic image forming apparatus. For example, the image forming apparatus includes a photoconductor 413, a charging device for charging the surface of the photoconductor 413, and an exposure device for forming an electrostatic latent image by irradiating light on the surface of the charged photoconductor 413. A developing device for supplying toner to the photoconductor 413 on which the electrostatic latent image is formed to form a toner image, and a transfer device for transferring the toner image on the surface of the photoconductor 413 to a recording medium. And a cleaning device for removing the toner remaining on the surface of the photoconductor 413 after the toner image is transferred to the recording medium.

  In addition, the photoconductor 413 supplies toner to the surface of the photoconductor 413 on which the electrostatic latent image is formed to form a toner image corresponding to the electrostatic latent image on the surface of the photoconductor 413, and the toner image is formed on the photoconductor. The image forming method is applied to an image forming method in which toner transferred to a recording medium from the surface of 413 and remaining on the surface of the photoreceptor 413 is removed by a cleaning device. The image forming method is performed by, for example, the image forming apparatus described above.

  FIG. 2 is a diagram schematically illustrating an example of the configuration of the image forming apparatus 100 having the photoconductor 413. An image forming apparatus 100 illustrated in FIG. 2 includes an image reading unit 110, an image processing unit 30, an image forming unit 40, a paper transport unit 50, and a fixing device 60.

  The image forming unit 40 includes image forming units 41Y, 41M, 41C, and 41K that form images of toners of Y (yellow), M (magenta), C (cyan), and K (black). Since these have the same configuration except for the toner to be accommodated, the symbols representing the colors may be omitted hereinafter. The image forming unit 40 further includes an intermediate transfer unit 42 and a secondary transfer unit 43. These correspond to a transfer device.

  The image forming unit 41 includes an exposure device 411, a developing device 412, the above-described photoreceptor 413, a charging device 414, and a drum cleaning device 415. The charging device 414 is, for example, a corona charger. The charging device 414 may be a contact charging device in which a contact charging member such as a charging roller, a charging brush, or a charging blade is brought into contact with the photosensitive member 413 to be charged. The exposure device 411 includes, for example, a semiconductor laser as a light source and a light deflecting device (polygon motor) that irradiates the photoconductor 413 with laser light corresponding to an image to be formed.

  The developing device 412 is a two-component developing type developing device. The developing device 412 includes, for example, a developing container that contains a two-component developer, a developing roller (magnetic roller) that is rotatably disposed in an opening of the developing container, and a developing container that allows the two-component developer to communicate with each other. A partition partitioning the inside, a transport roller for transporting the two-component developer on the opening side of the developing container toward the developing roller, and an agitation roller for stirring the two-component developer in the developing container . For example, a two-component developer described later is accommodated in the developing container.

  The intermediate transfer unit 42 includes an intermediate transfer belt 421, a primary transfer roller 422 that presses the intermediate transfer belt 421 against the photoconductor 413, a plurality of support rollers 423 including a backup roller 423A, and a belt cleaning device 426. The intermediate transfer belt 421 is looped around the plurality of support rollers 423. When at least one drive roller of the plurality of support rollers 423 rotates, the intermediate transfer belt 421 travels at a constant speed in the arrow A direction.

  The secondary transfer unit 43 includes a plurality of support rollers 431 including a secondary transfer roller 431A, and an endless secondary transfer belt 432. The secondary transfer belt 432 is stretched in a loop by the secondary transfer roller 431A and the support roller 431.

  The fixing device 60 fixes, for example, the fixing roller 62, an endless heating belt 63 that covers the outer peripheral surface of the fixing roller 62, and heats and melts the toner constituting the toner image on the paper S, and the paper S. And a pressure roller 64 that presses toward the roller 62 and the heat generating belt 63. The paper S corresponds to a recording medium.

  The image forming apparatus 100 further includes an image reading unit 110, an image processing unit 30, and a paper transport unit 50. The image reading unit 110 includes a paper feeding device 111 and a scanner 112.

  The paper transport unit 50 includes a paper feed unit 51, a paper discharge unit 52, and a transport path unit 53. In the three paper feed tray units 51a to 51c constituting the paper feed unit 51, paper S (standard paper, special paper) identified based on basis weight, size, or the like is stored for each preset type. . The conveyance path unit 53 includes a plurality of conveyance roller pairs such as registration roller pairs 53a.

  The above two-component developer can be appropriately selected from, for example, known two-component developers as long as the effects of the present embodiment can be obtained. The two-component developer has toner particles and carrier particles. These mixing ratios are 5-10 mass% in the density | concentration of the toner particle in a two-component developer, for example.

  The carrier particles are made of a magnetic material. Examples of the carrier particles include coated carrier particles having core material particles made of the magnetic material and a coating material layer covering the surface thereof, and a resin in which fine powder of the magnetic material is dispersed in the resin. Dispersed carrier particles are included. The carrier particles are preferably the coated carrier particles from the viewpoint of suppressing the adhesion of carrier particles to the photoreceptor 413.

  The toner particles include toner base particles and an external additive. The toner base particles contain, for example, a binder resin, a colorant, a release agent, and a charge control agent. The external additive is, for example, silica particles. The amount of the external additive added is, for example, 0.1 to 10.0% by mass, and more preferably 1.0 to 3.0% by mass with respect to the entire toner particles.

  The toner base particles contain a binder resin and a colorant. The binder resin constitutes toner base particles and includes a colorant dispersed therein. The kind of the binder resin may be one kind or more.

  The type of the colorant may be one type or more. As the colorant, known inorganic colorants or organic colorants used for color toners are used. Examples of the colorant include carbon black, a magnetic material, a pigment, and a dye.

  The toner base particles may further contain components other than the binder resin and the colorant as long as the effects of the present embodiment are exhibited. The other component may be one kind or more, and a known component known to be used for a color toner is used as the other component. Examples of the other components include a release agent and a charge control agent.

  The toner base particles can be manufactured, for example, by an emulsion association aggregation method in which toner base particles are manufactured by aggregating and fusing binder resin particles dispersed in an aqueous medium and colorant particles. . The toner base particle manufacturing method by the emulsion association aggregation method includes, for example, a step of preparing a binder resin particle dispersion in which binder resin particles are dispersed in an aqueous medium, and the colorant in the aqueous medium. And dispersing the binder resin particles to prepare resin particles to be toner base particles. The toner base particles are removed from the aqueous medium by, for example, cooling and filtration of the aqueous medium, washed, and dried.

  The toner particles can be obtained, for example, by mixing the toner base particles and the external additive using a known mixing device such as a Henschel mixer. The two-component developer can be obtained, for example, by mixing the toner particles and the carrier particles using a known mixing device such as a V-type mixer.

  Next, a method of using the image forming apparatus 100 (image forming method) will be described.

  First, the scanner 112 optically scans and reads the document D on the contact glass. Reflected light from the document D is read by the CCD sensor 112a and becomes input image data. The input image data is subjected to predetermined image processing in the image processing unit 30 and sent to the exposure device 411.

  The photoconductor 413 rotates at a constant peripheral speed. The charging device 414 uniformly charges the surface of the photoreceptor 413 to a negative polarity. As described above, the photoconductor 413 manufactured by the manufacturing method according to the present embodiment has a discharge during charging as compared with a photoconductor manufactured without irradiation with infrared light before irradiation with actinic rays. The number of functional groups that can react with the product is small. For this reason, even if image formation is repeated, the chargeability is unlikely to decrease.

  In the exposure apparatus 411, the polygon mirror of the polygon motor rotates at high speed, and laser light corresponding to the input image data of each color component is developed along the axial direction of the photoconductor 413, and the photoconductor 413 along the axial direction. Irradiated to the outer peripheral surface of. Thus, an electrostatic latent image is formed on the surface of the photoconductor 413.

  In the developing device 412, the toner particles are charged by stirring and transporting the two-component developer in the developing container, and the two-component developer is transported to the developing roller, and forms a magnetic brush on the surface of the developing roller. The charged toner particles are detached from the magnetic brush and electrostatically attached to the electrostatic latent image portion on the photoconductor 413. Thus, the electrostatic latent image on the surface of the photoconductor 413 is visualized, and a toner image corresponding to the electrostatic latent image is formed on the surface of the photoconductor 413. The “toner image” refers to a state where toner is gathered in an image form.

  As described above, the photoreceptor 413 manufactured by the manufacturing method according to the present embodiment can suppress a decrease in chargeability due to repeated image formation. For this reason, even if image formation is repeated, the toner particles can be appropriately attached to the photoreceptor 413 during the development process. Therefore, it is possible to suppress a decrease in density and occurrence of defects in the formed image.

  The toner image on the surface of the photoreceptor 413 is transferred to the intermediate transfer belt 421 by the intermediate transfer unit 42. Transfer residual toner remaining on the surface of the photoconductor 413 after the transfer is removed by a drum cleaning device 415 having a drum cleaning blade that is in sliding contact with the surface of the photoconductor 413.

  When the intermediate transfer belt 421 is pressed against the photoconductor 413 by the primary transfer roller 422, a primary transfer nip is formed for each photoconductor 413 by the photoconductor 413 and the intermediate transfer belt 421. In the primary transfer nip, the toner images of the respective colors are sequentially transferred onto the intermediate transfer belt 421.

  On the other hand, the secondary transfer roller 431A is pressed against the backup roller 423A via the intermediate transfer belt 421 and the secondary transfer belt 432. Accordingly, a secondary transfer nip is formed by the intermediate transfer belt 421 and the secondary transfer belt 432. The sheet S passes through the secondary transfer nip. The sheet S is conveyed to the secondary transfer nip by the sheet conveying unit 50. The correction of the inclination of the sheet S and the adjustment of the conveyance timing are performed by a registration roller unit provided with a registration roller pair 53a.

  When the sheet S is conveyed to the secondary transfer nip, a transfer bias is applied to the secondary transfer roller 431A. By applying the transfer bias, the toner image carried on the intermediate transfer belt 421 is transferred onto the paper S. The sheet S on which the toner image is transferred is conveyed toward the fixing device 60 by the secondary transfer belt 432.

  The fixing device 60 forms a fixing nip by the heat generating belt 63 and the pressure roller 64, and heats and presses the conveyed paper S at the fixing nip portion. Thus, the toner image is fixed on the paper S. The paper S on which the toner image has been fixed is discharged out of the apparatus by a paper discharge unit 52 having a paper discharge roller 52a.

  Note that transfer residual toner remaining on the surface of the intermediate transfer belt 421 after the secondary transfer is removed by a belt cleaning device 426 having a belt cleaning blade that is in sliding contact with the surface of the intermediate transfer belt 421.

  As is clear from the above description, the manufacturing method according to the present embodiment includes a conductive support, a photosensitive layer disposed on the conductive support, a surface layer disposed on the photosensitive layer, A coating solution containing a polymerizable monomer for forming the surface layer is applied on the photosensitive layer, and a film of the coating solution is formed on the photosensitive layer. Forming a film, irradiating the film with infrared light, and irradiating a portion of the film irradiated with infrared light with active light to polymerize the polymerizable monomer. Therefore, the photoreceptor manufactured by the manufacturing method can suppress a decrease in chargeability due to repeated image formation. Therefore, an image forming apparatus having this photoconductor can suppress image defects due to a decrease in chargeability, and can form a high-quality image over a long period of time.

  Further, after irradiating the entire surface of the film with infrared light and then irradiating the entire surface of the film with actinic light, it is possible to activate molecular vibration without generating a portion irradiated with infrared light and active light simultaneously. Since the polymerization reaction can be started in a converted state, it is more effective from the viewpoint of increasing the reactivity of the polymerization reaction on the entire surface of the film.

  Moreover, it is much more effective that infrared light is near-infrared light from a viewpoint of activating molecular vibration more.

  The polymerizable monomer having an acryloyl group or methacryloyl group is more effective from the viewpoint of polymerizing the polymerizable monomer in a small amount of light or in a short time, and from the viewpoint of imparting higher durability to the surface layer. .

  Moreover, it is much more effective that a 4th coating liquid contains a metal oxide particle from a viewpoint of providing higher durability to a surface layer.

  Furthermore, the fact that the actinic ray is ultraviolet light is even more effective from the viewpoint of activating the photopolymerization initiator with high energy.

1. Production of photoconductor (Production of photoconductor 1)
(1) Preparation of conductive support The surface of a drum-shaped aluminum support (outside diameter φ30 mm, length 360 mm) was cut to prepare a conductive support having a surface roughness Rz of 1.5 μm.

(2) Formation of intermediate layer Next, the following components were dispersed in the following amounts to prepare a first coating solution. At this time, a sand mill was used as a disperser, and the dispersion was carried out for 10 hours by a batch method.
Polyamide resin 1 part by mass Titanium oxide 1.1 parts by mass Ethanol 20 parts by mass

  X1010 (manufactured by Daicel Degussa Co., Ltd.) was used as the polyamide resin (binder resin), and SMT500SAS (manufactured by Teika Co., Ltd.) was used as the titanium oxide (metal oxide particles). The number average primary particle diameter of titanium oxide is 0.035 μm.

  The prepared first coating solution was applied to the outer peripheral surface of the prepared conductive support by a dip coating method and dried in an oven at 110 ° C. for 20 minutes. As a result, an intermediate layer having a thickness of 2 μm was formed on the surface of the conductive support.

(3) Formation of charge generation layer Next, the following components were mixed and dispersed in the following amounts to prepare a second coating solution. At this time, a sand mill was used as a disperser and dispersion was performed for 10 hours.
Titanyl phthalocyanine pigment 20 parts by weight Polyvinyl butyral resin 10 parts by weight t-butyl acetate 700 parts by weight 4-methoxy-4-methyl-2-pentanone 300 parts by weight

  The titanyl phthalocyanine pigment (charge generating substance) has a maximum diffraction peak at a position of at least 27.3 ° by Cu-Kα characteristic X-ray diffraction spectrum measurement. Moreover, as a polyvinyl butyral resin (binder resin), # 6000-C (made by Denki Kagaku Kogyo Co., Ltd.) was used.

  The prepared second coating solution was applied onto the intermediate layer by a dip coating method and dried in an oven at room temperature for 10 minutes. As a result, a charge generation layer having a thickness of 0.3 μm was formed on the surface of the intermediate layer.

(4) Formation of charge transport layer Next, the following components were mixed and dissolved in the following amounts to prepare a third coating solution.
Charge transport material 150 parts by weight Polycarbonate resin 300 parts by weight Tetrahydrofuran / toluene = 1/9% by volume 2000 parts by weight Antioxidant 6 parts by weight Silicone oil 1 part by weight

  As the charge transport material, (4,4′-dimethyl-4 ″-(β-phenylstyryl) triphenylamine) represented by the following formula (RCTM) was used. As the polycarbonate (binder resin), Z300 (Mitsubishi) As an antioxidant, Irganox 1010 (manufactured by BASF; “Irganox” is a registered trademark of the same company) was used. As the silicone oil, KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

  The prepared third coating solution was applied onto the charge generation layer by a dip coating method and dried in an oven at 120 ° C. for 70 minutes. As a result, a charge transport layer having a thickness of 20 μm was formed on the surface of the charge generation layer.

(5) Formation of surface layer Next, the polymerizable monomer, the metal oxide particles, and the solvent were mixed in the following amounts under light shielding. At this time, a sand mill was used as a disperser and dispersion was performed for 10 hours. Subsequently, under the light shielding, the 4th coating liquid was prepared by further mixing a polymerization initiator with the following quantity, stirring and dissolving.
Polymerizable monomer 100 parts by weight Polymerization initiator 10 parts by weight Metal oxide particles 100 parts by weight sec-butanol 400 parts by weight Methyl isopropyl ketone 100 parts by weight

  As the polymerizable monomer, a compound represented by the following formula (M4) was used. As the polymerization initiator, Irgacure 819 (Irg819; manufactured by BASF Japan Ltd.) was used.

As the metal oxide particles, tin oxide particles surface-treated with a compound represented by the above formula (S-15) having a number average primary particle diameter of 20 nm were used. The surface-treated tin oxide particles were obtained by the following method. The following components were mixed in the following amounts, placed in a sand mill with zirconia beads, and stirred at about 40 ° C. and a rotational speed of 1500 rpm. Further, the treated mixture was taken out, put into a Henschel mixer, stirred at a rotational speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours.
Tin oxide 100 parts by mass Surface treatment agent 30 parts by mass Toluene 150 parts by mass Isopropyl alcohol 150 parts by mass

By the above surface treatment, the surface of the tin oxide particles is covered with the surface treatment agent represented by the above formula (S-15). XRF analyzer “XRF-1700 (manufactured by Shimadzu Corporation)” This was confirmed by detecting the Si peak. As tin oxide, tin oxide manufactured by CIK Nanotech Co., Ltd. (number average primary particle size: 20 nm, volume resistivity: 1.05 × 10 ⁵ Ω · cm) was used.

  The prepared 4th coating liquid was apply | coated to the surface of the electric charge transport layer with the dip coating method, and the workpiece | work was produced by air-drying for 20 minutes at room temperature.

Next, a surface layer was formed by irradiating infrared light and ultraviolet light in this order while conveying the workpiece in the axial direction. Thereby, infrared light is irradiated to the workpiece | work surface before irradiating an ultraviolet light. Irradiation conditions of infrared light and ultraviolet light are shown below. The wavelength range of infrared light and ultraviolet light was adjusted using a long pass filter and a short pass filter.
Distance between workpiece and light exit window of light irradiation device: 100mm
Work transfer speed: 20 mm / sec Infrared light source, output: halogen lamp, 5 kW
Infrared wavelength: 2500-5000 nm
Irradiation time of infrared light: 5 seconds Irradiation energy of infrared light on the workpiece surface: 4 J / cm ²
Ultraviolet light source, output: xenon lamp, 4kW
Ultraviolet light wavelength: 250-400 nm
Irradiation time of ultraviolet light: 2 seconds Irradiation energy of ultraviolet light on the workpiece surface: 3 J / cm ²
Interval between infrared light irradiation and ultraviolet light irradiation: 30 seconds

(Preparation of photoconductor 2)
Photoreceptor 2 was produced in the same manner as Photoreceptor 1, except that the surface layer was mixed with a charge transport material instead of metal oxide particles and the wavelength region of infrared light was changed to 1000 to 2500 nm.

  As the charge transport material, (4,4′-dimethyl-4 ″-(β-phenylstyryl) triphenylamine) represented by the above formula (RCTM) was used. At the time of preparing the fourth coating solution, a polymerizable monomer was used. 20 parts by mass of charge transport material was further mixed with 100 parts by mass.

(Preparation of photoreceptor 3)
Photoconductor 3 was prepared in the same manner as Photoconductor 1, except that Irgacure 184 (Irg184; manufactured by BASF Japan Ltd.) was used as the polymerization initiator.

(Preparation of photoconductor 4)
Photoreceptor 4 was produced in the same manner as Photoreceptor 1, except that the compound represented by the following formula (M1) was used as the polymerizable monomer and the wavelength range of infrared light was changed to 1000 to 2500 nm.

(Preparation of photoconductor 5)
Except for using a compound represented by the above formula (M1) as a polymerizable monomer, containing metal oxide fine particles in the surface layer, and using a compound represented by the following formula (CTM-10) as a charge transport material. A photoconductor 5 was produced in the same manner as the photoconductor 2. When preparing the fourth coating solution, 100 parts by mass of metal oxide fine particles were further mixed. As the metal oxide particles, the same tin oxide particles as those used in the production of the photoreceptor 1 were used.

(Preparation of photoreceptor 6)
A photoconductor 6 was produced in the same manner as the photoconductor 4 except that CuAlO ₂ particles surface-treated with the compound represented by the above formula (S-15) were used as metal oxide particles.

As the metal oxide particles, copper aluminum oxide (CuAlO ₂ ) particles surface-treated with a compound represented by the above formula (S-15) having a number average primary particle diameter of 20 nm were used. The surface-treated copper aluminum oxide particles were obtained by the following method. The following components were mixed in the following amounts, placed in a sand mill with alumina beads having a diameter of 0.5 mm, and mixed at about 30 ° C. for 6 hours. Thereafter, methyl ethyl ketone and alumina beads were filtered and dried at 60 ° C.
Copper aluminum oxide 100 parts by mass Surface treatment agent 10 parts by mass Methyl ethyl ketone 1000 parts by mass

As a result of the surface treatment, the surface of the copper aluminum oxide particles is coated with the surface treatment agent represented by the chemical formula (S-15). XRF-1700 (Shimadzu Corporation) It was confirmed by detecting the Si peak in “manufactured)”. The number average primary particle diameter of the copper aluminum oxide is 20 nm, and the volume resistivity is 1 × 10 ⁷ Ω · cm.

(Preparation of photoconductor 7)
A photoconductor 7 was produced in the same manner as the photoconductor 1 except that infrared light was not irradiated.

(Preparation of photoconductor 8)
Photoconductor 7 was prepared in the same manner as Photoconductor 1, except that natural drying and heat drying were performed instead of irradiation with infrared light before irradiation with ultraviolet light. Thermal drying was performed in an oven at 120 ° C. for 20 minutes.

(Preparation of photoconductor 9)
A photoconductor 9 was produced in the same manner as the photoconductor 1 except that the wavelength region of infrared light was changed to 1000 to 2500 nm and infrared light irradiation and ultraviolet light irradiation were performed simultaneously.

(Preparation of photoconductor 10)
The photoconductor 10 was produced in the same manner as the photoconductor 1 except that the wavelength region of infrared light was changed to 1000 to 2500 nm, and the ultraviolet light was applied and then the infrared light was applied.

  For each photoreceptor, category, photoreceptor No. , Type of polymerizable monomer and reactive group, type of polymerization initiator, type of metal oxide particles, type of charge transport material, irradiation timing of infrared light, wavelength range of infrared light, and timing of thermal drying It is shown in 1.

2. Evaluation of Photoreceptor Each of the photoreceptors was repeatedly evaluated for chargeability. Specifically, each photoconductor is mounted on a modified machine of an image forming apparatus “Bizhub C554 (manufactured by Konica Minolta Business Technologies)”, and is charged and exposed in a high temperature and high humidity environment (temperature 30 ° C., humidity 80%). Was repeated 30,000 times. At this time, the evaluation of repetitive charging was carried out by adjusting the grid voltage (V _g ) at the time of charging to 700 V, the exposure amount to 0.4 μJ / cm ² , and the interval between charging and exposure to 0.4 seconds. (Initial) and after 30,000 repetitions, the surface potential (V _H ) of the unexposed portion of the photoreceptor and the surface potential (V _L ) of the exposed portion are measured, and before repeated charging evaluation is performed, Differences (| ΔV _H |, | ΔV _L |) after the determination were obtained. Each photoconductor was evaluated according to the following criteria. For the photoreceptor, if | ΔV _H | is less than 30, there is no practical problem, and if | ΔV _L | is less than 40 V, there is no practical problem.
(Evaluation criteria for | ΔV _H |)
◎: Less than 15V ○: 15V or more and less than 30V △: 30V or more and less than 40V ×: 40V or more (Evaluation criteria of | ΔV _L |)
◎: Less than 20V ○: 20V or more and less than 40V △: 40V or more and less than 60V ×: 60V or more

  The remodeling machine for the image forming apparatus refers to an apparatus in which the developing mechanism, the transfer mechanism, the cleaning mechanism, and the charge eliminating mechanism are removed from the image forming apparatus so that the chargeability can be repeatedly evaluated.

  For each photoreceptor, category, photoreceptor No. Table 2 shows the results of repeated chargeability evaluation.

  As shown in Table 2, with respect to the photoreceptors 7 to 10 according to Comparative Examples 1 to 4, it was not possible to sufficiently suppress the repeated chargeability reduction. The photoreceptor 7 according to Comparative Example 1 is considered to be because infrared light is not irradiated when the surface layer is formed. In addition, regarding the photoconductor 8 according to Comparative Example 2, it was considered that when the surface layer was formed, heating was performed before irradiation with ultraviolet light, but infrared light was not irradiated. In addition, it is considered that the photosensitive member 9 according to Comparative Example 3 was obtained by simultaneously performing infrared light and ultraviolet light when forming the surface layer. Further, it is considered that the photosensitive member 10 according to Comparative Example 4 was irradiated with infrared light after being irradiated with ultraviolet light when forming the surface layer.

  On the other hand, it can be seen that for the photoreceptors 1 to 6 according to Examples 1 to 6, it is possible to sufficiently suppress the decrease in repeated chargeability.

  From the comparison between Examples 1 to 6 and Comparative Examples 1 to 4, when forming the surface layer, the irradiation with infrared light is irradiated before irradiating with ultraviolet light, so that repeated deterioration in chargeability is suppressed. It has been found that a photoreceptor can be produced. Moreover, it turns out from the comparison with Examples 1-6 and the comparative example 2 that the improvement of repetitive charging property is not based on the heat | fever generate | occur | produced by irradiating infrared light.

  According to the present invention, since the deterioration of the charging property of the photoconductor with time is suppressed, it is possible to provide an image forming apparatus capable of stably forming a high-quality image over a long period of time. Therefore, further improvement in performance and further spread in the electrophotographic image forming apparatus are expected.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Intermediate | middle layer 3 Photosensitive layer 4 Surface layer 5 Charge generation layer 6 Charge transport layer 30 Image processing part 40 Image formation part 41Y, 41M, 41C, 41K Image formation unit 42 Intermediate transfer unit 43 Secondary transfer unit 50 Paper transport unit 51 Paper feed unit 51a, 51b, 51c Paper feed tray unit 52 Paper discharge unit 52a Paper discharge roller 53 Transport path part 53a Registration roller pair 60 Fixing device 62 Fixing roller 63 Heating belt 64 Pressure roller 100 Image forming device 110 Image reading unit 111 Paper feeding device 112 Scanner 112a CCD sensor 411 Exposure device 412 Developing device 413 Photoconductor 414 Charging device 415 Drum cleaning device 421 Intermediate transfer belt 422 Primary transfer roller 423, 431 Support roller 423A Back-up Roller 426 belt cleaning device 431A secondary transfer roller 432 Secondary transfer belt D document S Paper

Claims (6)

An electrophotographic photosensitive member having a conductive support, a photosensitive layer disposed on the conductive support, and a surface layer disposed on the photosensitive layer,
Applying a coating solution containing a polymerizable monomer to form the surface layer on the photosensitive layer, and forming a film of the coating solution on the photosensitive layer;
Irradiating the film with infrared light;
Irradiating a portion of the film irradiated with infrared light with active light to polymerize the polymerizable monomer; and
A process for producing an electrophotographic photoreceptor comprising:   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the entire surface of the film is irradiated with infrared light and then the entire surface of the film is irradiated with actinic rays.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the infrared light is near infrared light.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the polymerizable monomer has an acryloyl group or a methacryloyl group.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the coating liquid further contains metal oxide particles.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the actinic ray is ultraviolet light.

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