JP6540178B2 - Method of manufacturing electrophotographic photosensitive member - Google Patents

Description

  The present invention relates to a method of manufacturing an electrophotographic photosensitive member.

  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 photoreceptor has a conductive support and a photosensitive layer disposed on the conductive support. The photosensitive member is supplied with electrical energy, light energy, or mechanical force at each step of charging, exposure, development, transfer, cleaning, etc., which are performed for image formation. A decrease in the chargeability of the photosensitive member in the image forming apparatus is not preferable because it causes an image defect. Therefore, the photosensitive member is required to have durability such that charging stability and potential holding property are not impaired by repetition of image formation.

  Therefore, in order to improve the durability of the photosensitive member, a technique is known in which a surface layer is provided on the surface of the photosensitive layer. In particular, in the surface layer formed by polymerizing the photopolymerizable monomer, since the photopolymerizable monomer forms a three-dimensional structure by polymerization, a surface layer having high surface strength can be formed. For this reason, it is possible to obtain a photoreceptor having a surface layer excellent in durability.

  As the photosensitive member, there is known a photosensitive member having a surface layer formed by irradiating a light having a wavelength of 500 to 2000 nm to a coating film of a liquid containing a photopolymerizable monomer and a compound that performs upconversion emission. (See, for example, Patent Document 1).

  Further, as the photosensitive member, there is known a photosensitive member having a surface layer formed by irradiating an ultraviolet ray to the coating film while heating a coating film of a solution containing a photopolymerizable monomer (for example, patent document 2).

  Further, the surface of the photosensitive member is formed by irradiating the coating film of a solution containing a photopolymerizable monomer with ultraviolet light with predetermined irradiation light energy to make the temperature of the photosensitive member surface 70 to 90 ° C. A photoreceptor having a layer is known (see, for example, 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, there is a possibility that 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 performing image formation.

  An object of the present invention is to provide a photoreceptor having a surface layer formed by the 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 process 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 is the surface. Applying 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 A process for producing an electrophotographic photosensitive member is provided, which comprises the steps of: irradiating an actinic ray to a portion of the film irradiated with infrared light to polymerize the polymerizable monomer.

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

FIG. 1 is a view schematically showing an example of the layer configuration of a photoreceptor manufactured by the manufacturing method according to the present embodiment. FIG. 2 is a view schematically showing an example of the configuration of an image forming apparatus having the photosensitive member.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a view schematically showing an example of the layer configuration of a photosensitive member 413 manufactured by the manufacturing method according to the present embodiment. As shown in FIG. 1, the photosensitive member 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. And a surface layer 4 disposed on top of the other. Photosensitive layer 3 has charge generation layer 5 and charge transport layer 6.

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

  The photosensitive layer 3 is a layer for forming an electrostatic latent image of a desired image on the surface by exposure in an image forming apparatus to be 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 substance and the charge transport layer 6 containing a charge transport substance. 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 photosensitive member 413. The surface layer 4 is a layer for protecting the photosensitive layer 3.

  The photosensitive member 413 can be manufactured by a known method of manufacturing an electrophotographic photosensitive member other than the manufacturing process of the surface layer 4. For example, the photosensitive member 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) sensitization on the intermediate layer 2. It can be manufactured by performing the third step of disposing the layer 3 and 4) the fourth step of disposing the surface layer 4 on the photosensitive layer 3 in this order.

  Third step: 3-1) 3-1 step of disposing charge generation layer 5 on intermediate layer 2; 3-2) step 3-2 of disposing charge transport layer 6 on charge generation layer 5 And.

  In the fourth step, 4-1) a 4-1 step of applying a coating solution for forming a surface layer containing a polymerizable monomer (hereinafter also referred to as "fourth coating solution") on the photosensitive layer 3; -2) step 4-2 of irradiating the film of the fourth coating solution with infrared light, and 4-3) an actinic ray for polymerizing a polymerizable monomer in the portion of the film irradiated with infrared light. And 4-3 steps of irradiating.

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

1) First Step In the first step, the conductive support 1 is prepared. The conductive support 1 is a member that supports the photosensitive layer 3 described later and has conductivity. Examples of the type of the conductive support 1 include a metal drum, a metal sheet, a plastic film laminated with a metal foil, a plastic film on which a conductive substance is vapor-deposited, and a paint containing a conductive substance Metal members, plastic films, and paper. The type of metal is not particularly limited as long as it has conductivity. Examples of metal types include aluminum, copper, chromium, nickel, zinc and stainless steel. Also, examples of conductive materials include metals, indium oxide and tin oxide. In the present embodiment, the conductive support 1 is a drum made of aluminum.

2) Second Step In the second step, the intermediate layer 2 is formed on the prepared conductive support 1. Specifically, first, a coating liquid for forming an intermediate layer (hereinafter, also referred to as "first coating liquid") is prepared. Then, the first coating liquid is applied onto the conductive support 1 to form a liquid film of the first coating liquid. Finally, the intermediate layer 2 can be formed by drying the liquid film.

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

  Examples of binder resins 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 solution may contain inorganic particles such as conductive particles and metal oxide particles. Examples of inorganic particle types include alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, metal oxide particles such as bismuth oxide; tin-doped indium oxide, antimony-doped tin oxide and oxide It contains ultrafine particles such as zirconium. The type of these inorganic particles may be one or more.

  When 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 taken by a scanner from a 10000 × magnification photograph taken at an accelerating voltage of 80 kV with a scanning electron microscope “JEM-7500F” (manufactured by Nippon Denshi Co., Ltd.) By processing and analyzing the photograph image of the collected 100 metal oxide particles (excluding agglomerated particles) with the automatic image processing and analysis device “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco Co., Ltd.) It is calculated.

  It is preferable that it is 20-400 mass parts with respect to 100 mass parts of binder resin, and, as for the addition amount of inorganic particle, it is more preferable that it is 50-200 mass parts.

  The dispersing means of the inorganic fine particles in the first coating liquid can be appropriately selected from known dispersing devices. Examples of means for dispersing inorganic fine particles include dispersers such as ultrasonic dispersers, ball mills, sand grinders and homomixers.

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

  The method of drying the liquid film of the first coating liquid can be appropriately selected depending on the type of solvent, the desired thickness of the intermediate layer 2 and the like. Examples of the method of drying the liquid film of the first coating liquid include natural drying and thermal drying.

  The thickness of the intermediate layer 2 is, for example, 0.1 to 15 μm, 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) The 3-1 Step In the 3-1 step, the charge generation layer 5 is formed on the intermediate layer 2. Specifically, first, a coating liquid for forming a charge generation layer (hereinafter, "second coating liquid") 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 solution can be prepared, for example, by adding and dispersing the charge generation material 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 resins), and poly-vinylcarbazole resins.

  Examples of charge generating materials include azo raw materials such as sudan red and diane blue; quinone pigments such as pyrene quinone and anthanthrone; quinocyanine pigments; perylene pigments; indigo pigments such as indigo and thioindigo; and phthalocyanine pigments.

  The amount of charge generation substance 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 selected appropriately from known dispersing devices. Examples of means for dispersing the charge generating material include dispersers such as ultrasonic dispersers, ball mills, sand grinders and homomixers.

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

  The method of drying the liquid film of the second coating liquid can be appropriately selected depending on the type of solvent, the desired thickness of the charge generation layer, and the like. Examples of the method of drying the liquid film of the second coating liquid include natural drying and thermal 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, the charge transport layer 6 is formed on the charge generation layer 5. Specifically, first, a coating solution for the charge transport layer (hereinafter, also referred to as "third coating solution") is prepared. Then, 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 solution can be prepared, for example, by adding and dispersing the charge generation 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 acid ester resin, and styrene-methacrylic acid ester Copolymer resins are included.

  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 Vinyl pyrene, and poly-9-vinyl anthracene are included.

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

  The amount of the charge transport substance 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 method of applying the third coating solution include dip coating and spray coating.

  The method of drying the liquid film of the third coating solution can be appropriately selected depending on the type of solvent, the desired thickness of the charge transport layer 6, and the like. Examples of the method of drying the liquid film of the third coating solution include natural drying and thermal 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) Process 4-1 In the process 4-1, a coating solution (fourth coating solution) for forming a surface layer containing a polymerizable monomer is applied onto the photosensitive layer 3. Specifically, first, a fourth coating solution is prepared. Then, 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 solution can be formed by drying the liquid film.

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

  Examples of the polymerizable monomer include styrene-based monomers, acrylic monomers, methacrylic monomers, vinyl toluene-based monomers, vinyl acetate-based monomers, and N-vinyl pyrrolidone-based monomers. The number of types of these polymerizable monomers may be one or more.

The polymerizable monomer has a reactive group of acryloyl group (CH ₂ CHCHCO—) or methacryloyl group (CH ₂ CC (CH ₃ ) CO—) because polymerization is possible with a small amount of light or short time. It is preferably a compound. The polymerizable monomer is preferably an acrylic monomer having two or more of these reactive groups. Furthermore, it is preferable that it is an oligomer of a polymerizable monomer.

  The polymerizable monomer is more preferably a compound having two or more acryloyl groups or methacryloyl groups, and particularly preferably a compound having three or more acryloyl groups or methacryloyl groups. Moreover, although a polymerizable monomer can be used combining 2 or more types, it is preferable to use 50 mass% or more of compounds which have 3 or more of acryloyl group 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 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 or ketal 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-based photopolymerization initiators such as 4-benzoylphenyl ether, acrylated benzophenone and 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, And thioxanthone photopolymerization initiators such as 2,4-dichlorothioxanthone.

  Other examples of the photopolymerization initiator include ethyl anthraquinone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6- trimethyl benzoyl phenyl ethoxy phosphine oxide, bis (2,4,6- trimethyl benzoyl) Phenyl phosphine oxide ("IRGACURE 819": manufactured by BASF Japan Ltd.), bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, methylphenylglyoxy ester, 9,10-phenanthrene, acridine It includes compounds, triazine compounds, and imidazole compounds.

  Also, 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, ethyl (2-dimethylamino) benzoate and 4,4'-dimethylamino It contains benzophenone.

  It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymerizable monomers, and, as for the addition amount of a photoinitiator, it is more preferable that it is 0.5-10 mass parts.

From the viewpoint of imparting higher durability to the surface layer 4, the fourth coating solution 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, oxide Included are yttrium, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, titanium dioxide, niobium oxide, molybdenum oxide, and vanadium oxide. 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 diameter of the metal oxide particles is calculated by the same method as the number average primary particle diameter 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 means for dispersing metal oxide particles include ultrasonic dispersers, and dispersers such as ball mills, sand grinders and homomixers.

  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. If the content of the metal oxide particles is too low, the electrical resistance of the surface layer to be formed will be low, and it may not be possible to prevent the increase in residual potential and the occurrence of fogging. On the other hand, when the content of the metal oxide particles is too large, a good film formability can not be obtained in the surface layer to be formed, and there is a possibility that the deterioration of the charging performance and the generation of pinholes can not be prevented.

In addition, the metal oxide particles may be surface-treated from the viewpoint of enhancing the dispersibility. In particular, tin oxide (SnO ₂ ) particles or copper aluminum oxide (CuAlO ₂ ) particles surface-treated with a metal oxide particle and a surface treatment agent having a reactive group (hereinafter also referred to as “surface treatment agent”) Is preferred. 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, surface-treated metal oxide particles can be treated using a wet media dispersion type apparatus. Specifically, a slurry (suspension of solid particles) containing metal oxide particles and a surface treatment agent is wet milled. Finally, the solvent is removed and powderization is carried out to obtain surface-treated metal oxide particles.

  The surface treatment agent is, for example, a compound having reactivity with a hydroxyl group present on the surface of the metal oxide particle. The surface treatment agent preferably has an acryloyl group or a methacryloyl group. Moreover, the compound shown by following (S-1)-(S-36) is contained in the example of a surface treatment 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 CHCHCOO (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 CC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
S-15: CH ₂ CC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃
S-16: CH ₂ CC (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 CC (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 CC (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 CC (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 the stirring disk mounted vertically to the rotating shaft is rotated at high speed. Thereby, in the wet media dispersion type apparatus, pulverization and dispersion of the agglomerated particles of the metal oxide are performed.

  In the above-mentioned surface treatment method, the addition amount of the surface treatment agent is 0.1 to 100 parts by mass with respect to 100 parts by mass of the metal oxide particles, and the addition amount of the solvent is 100 parts by mass with respect to the 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 the metal oxide particles are subjected to surface treatment, for example, vertical type, horizontal type, continuous Various modes such as a formula, a batch, etc. can be adopted. Examples of wet media dispersive devices include sand mills, ultravisco mills, pearl mills, grain mills, dyno mills, agitator mills, and dynamic mills.

  Examples of 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. Also, the size of the bead is usually about 1 to 2 mm in diameter.

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

  By the above procedure, metal oxide particles having a reactive group capable of reacting with an acryloyl group or a methacryloyl group can be obtained. By surface-treating the metal oxide particles with a surface treatment agent, the bond with the polymerizable monomer becomes strong, and the durability of the surface layer 4 to be formed can be further enhanced.

  Examples of lubricant particles include resin particles containing fluorine atoms. Examples of the material of resin particles containing fluorine atoms include tetrafluoroethylene resin, trifluorochlorinated ethylene resin, hexafluorochlorinated ethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride Included are particles of ethylene resin, and copolymers thereof. As the lubricant particles, one or more kinds of lubricant particles are preferably selected from these, and in particular, tetrafluoroethylene resin particles and vinylidene fluoride resin particles are preferable.

  The number average primary particle diameter 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 diameter of the lubricant particles is calculated by the same method as the number average primary particle diameter 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 in the fourth coating solution is preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass.

  A well-known resin may be used for the example of resin other than 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 solution viscosity of the fourth coating solution is preferably 2 to 50 mP · s, and more preferably 3 to 25 mP · s. When the liquid viscosity of the fourth coating solution is too small, coating unevenness may occur, and a surface layer having a desired thickness and a uniform thickness may not be formed. On the other hand, when the liquid viscosity of the fourth coating liquid is too high, good fluidity can not be obtained for the fourth coating liquid, which may cause liquid breakage on the coated surface, making it impossible to form a uniform liquid film. There is. The liquid viscosity of the fourth coating solution can be measured using “E-type viscosity meter 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 method of applying the fourth coating solution 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 drying method of the liquid film of the fourth coating solution can be appropriately selected according to the type of the solvent, the desired thickness of the surface layer 4 and the like. Examples of the method of drying the liquid film of the fourth coating solution include natural drying and thermal drying.

  A film of the fourth application liquid can be formed on the photosensitive layer 3 by the above steps. 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, the film of the fourth coating solution formed on the photosensitive layer 3 of the work is irradiated with infrared light.

  One feature of the method for manufacturing a photosensitive member according to the present embodiment is that it includes a step of irradiating infrared light. The present inventors irradiated the film of the fourth coating solution with infrared light and then irradiated the actinic light described later, as compared with the case where the infrared light was not irradiated before the actinic light irradiation. It has been found that the decrease in chargeability due to repeated image formation can be significantly suppressed (see Examples). Although the principle by which the decrease in chargeability is suppressed is unknown, the irradiation of infrared light causes the polymerizing monomers in the film to undergo molecular vibration and sequence, thereby promoting the polymerization reaction. It is guessed. This is considered to be because the amount of unreacted groups in the surface layer 4 is reduced, and the bond between the discharge product generated in the charging step for forming an image and the unreacted groups is suppressed.

Irradiation conditions such as irradiation energy and irradiation time of infrared light may 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 performed sufficiently, but if the infrared light is irradiated excessively, the polymerizable monomer may be damaged by the heat generated by the irradiation of the infrared light. And the film may dry and solidify. On the other hand, if the irradiation of infrared light is insufficient, the intended 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. 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 which irradiates infrared light is 0.1 second-5 minutes before irradiating the below-mentioned actinic light.

  Examples of types of infrared light sources include infrared halogen lamps, carbon lamps and colche 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 the 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 using a long pass filter, a short pass filter or a band pass filter for the light emitted from the light source.

  The irradiation method of infrared light is not particularly limited. For example, the work may be irradiated with infrared light from the entire circumferential direction of the conductive support 1 using a light irradiation device described in Japanese Patent Application Laid-Open No. 2013-125121. The said light irradiation apparatus is formed with the light emission window which radiate | emits infrared light so that the circumference | surroundings of a cylindrical workpiece | work may be surrounded. Thus, the workpiece can be irradiated with infrared light simultaneously from the entire circumferential direction of the conductive support 1. When the surface area of the work is larger than the irradiated area of the light irradiation device, the fourth coating liquid is irradiated with infrared light by the light irradiation device while conveying the work in the axial direction of the conductive support 1. The entire film of can be irradiated with infrared light. At this time, the speed at which the workpiece is transported is adjusted so that infrared light can be irradiated with 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 transport speed of the work is 1 to 30 mm / sec. From the viewpoint of irradiating the workpiece with infrared light more uniformly, the workpiece may be rotated with the axis of the conductive support 1 as the central axis.

4-3) Step 4-3 In step 4-3, an actinic ray is applied to polymerize the polymerizable monomer. Irradiation of the work with actinic radiation can be carried out under known conditions for forming a surface layer by polymerization of a polymerizable monomer.

The irradiation energy and irradiation time of the actinic light may 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. The irradiation time is preferably 0.1 seconds to 10 minutes, and more preferably 0.1 seconds to 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 (pulsed) xenon, and ultraviolet LEDs. The output of the actinic ray light source is preferably 0.1 to 5 kW, and more preferably 0.5 to 3 kW. The wavelength of the actinic radiation is preferably 250 to 400 nm (ultraviolet light).

  The irradiation method of the actinic light is not particularly limited as long as the portion irradiated with the infrared light in the film of the fourth coating liquid can be irradiated with the actinic light. For example, the active light beam may be sequentially irradiated from the portion irradiated with the infrared light toward the work being transported while being irradiated with the infrared light using the above-described light irradiation device, or the entire film The entire film may be irradiated after the end of the irradiation of the infrared light. In the case of sequentially emitting actinic light 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, the polymerizable monomer can be polymerized to form the surface layer 4.

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

  The photosensitive member 413 can be manufactured by the above procedure. In the method of manufacturing the photosensitive member 413, the film of the fourth coating solution is irradiated with infrared light before the surface layer 4 is cured. As a result, even if image formation is repeated, it is possible to suppress the decrease in the chargeability of the photosensitive member.

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

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

  Further, the photosensitive member 413 supplies toner to the surface of the photosensitive member 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 photosensitive member 413, thereby forming a toner image The present invention is applied to an image forming method in which a toner is transferred to the recording medium from the surface 413 and remaining on the surface of the photosensitive member 413 with a cleaning device. The image forming method is performed, for example, by the above-described image forming apparatus.

  FIG. 2 is a view schematically showing an example of the configuration of the image forming apparatus 100 having the photosensitive member 413. As shown in FIG. The 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 sheet conveyance unit 50, and a fixing device 60.

  The image forming unit 40 includes image forming units 41Y, 41M, 41C, and 41K that form images with toners of Y (yellow), M (magenta), C (cyan), and K (black). Since all of these components have the same configuration except for the toner to be stored, symbols representing 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 transfer devices.

  The image forming unit 41 includes an exposure device 411, a developing device 412, the above-described photosensitive member 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 that brings a contact charging member such as a charging roller, a charging brush, or a charging blade into contact with the photosensitive member 413 for charging. The exposure device 411 includes, for example, a semiconductor laser as a light source, and a light deflection device (polygon motor) that irradiates the photosensitive member 413 with a laser beam according 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 for containing a two-component developer, and a developing container capable of communicating the two-component developer with a developing roller (magnetic roller) rotatably disposed at an opening of the developing container. It has a partition dividing the inside, a conveyance roller for conveying the two-component developer on the opening side of the developing container toward the developing roller, and a stirring roller for stirring the two-component developer in the developing container. . The developer container contains, for example, a two-component developer described later.

  The intermediate transfer unit 42 includes an intermediate transfer belt 421, a primary transfer roller 422 for pressing the intermediate transfer belt 421 against the photosensitive member 413, a plurality of support rollers 423 including a backup roller 423A, and a belt cleaning device 426. The intermediate transfer belt 421 is stretched around a plurality of support rollers 423 in a loop. By rotating at least one drive roller of the plurality of support rollers 423, the intermediate transfer belt 421 travels at a constant speed in the arrow A direction.

  The secondary transfer unit 43 has 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 covers, for example, the fixing roller 62 and the outer peripheral surface of the fixing roller 62, and heats and melts toner forming the toner image on the sheet S, fixing the sheet S and the sheet S And a pressure roller 64 for pressing the roller 62 and the heat generating belt 63. The sheet 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 sheet conveyance unit 50. The image reading unit 110 has a sheet feeding device 111 and a scanner 112.

  The sheet conveyance unit 50 includes a sheet feeding unit 51, a sheet discharge unit 52, and a conveyance path unit 53. In the three sheet feeding tray units 51a to 51c constituting the sheet feeding unit 51, sheets S (standard sheets and special sheets) identified based on basis weight, size, and the like are accommodated for each preset type. . The transport path portion 53 has a plurality of transport roller pairs such as a registration roller pair 53a.

  The 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. The mixing ratio of these components is, for example, 5 to 10% by mass in terms of the concentration of toner particles in the two-component developer.

  The carrier particles are composed of a magnetic material. In the example of the carrier particle, a coated carrier particle having a core particle made of the magnetic substance and a layer of a coating material that coats the surface, and a resin in which fine powder of the magnetic substance is dispersed in a resin Dispersed carrier particles are included. From the viewpoint of suppressing the adhesion of the carrier particles to the photosensitive member 413, the carrier particles are preferably the coated carrier particles.

  The toner particles have 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, based on 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 dispersedly contained therein. The type of the binder resin may be one or more.

  The type of the colorant may be one or more kinds. As the coloring agent, known inorganic coloring agents or organic coloring agents used for coloring agents of color toners are used. Examples of the colorant include carbon black, magnetic substances, pigments and dyes.

  The toner base particles may further contain other components in addition to the binder resin and the colorant, as long as the effects of the exemplary embodiment can be achieved. The other components may be one or more, and the other components include known components known to be used for color toners. Examples of such other components include mold release agents and charge control agents.

  The toner base particles can be produced, for example, by an emulsion association aggregation method of producing toner base particles by aggregating and fusing particles of a binder resin dispersed in an aqueous medium and particles of a colorant. . In the method of producing toner base particles by the emulsion association aggregation method, for example, a step of preparing a binder resin particle dispersion liquid in which binder resin particles are dispersed in an aqueous medium, and the coloring agent 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 is 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 112 a 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 photosensitive member 413 rotates at a constant circumferential speed. The charging device 414 uniformly charges the surface of the photosensitive member 413 to a negative polarity. As described above, in the photosensitive member 413 manufactured by the manufacturing method according to the present embodiment, discharge at the time of charging is compared with a photosensitive member manufactured without irradiation of infrared light before irradiation with an actinic ray. The number of functional groups that can react with the product is small. Therefore, even if the image formation is repeated, the chargeability is unlikely to be reduced.

  In the exposure device 411, the polygon mirror of the polygon motor rotates at high speed, and the laser light corresponding to the input image data of each color component is developed along the axial direction of the photosensitive member 413, and the photosensitive member 413 along the axial direction. The outer peripheral surface of the Thus, an electrostatic latent image is formed on the surface of the photosensitive member 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 a magnetic brush is formed on the surface of the developing roller. The charged toner particles separate from the magnetic brush and electrostatically adhere to the portion of the electrostatic latent image on the photosensitive member 413. Thus, the electrostatic latent image on the surface of the photosensitive member 413 is visualized, and a toner image corresponding to the electrostatic latent image is formed on the surface of the photosensitive member 413. Note that "toner image" refers to a state in which toner is gathered in the form of an image.

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

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

  The intermediate transfer belt 421 is pressed against the photosensitive member 413 by the primary transfer roller 422, whereby a primary transfer nip is formed for each photosensitive member 413 by the photosensitive member 413 and the intermediate transfer belt 421. At the primary transfer nip, toner images of the respective colors are sequentially overlapped and transferred onto the intermediate transfer belt 421.

  On the other hand, the secondary transfer roller 431A is in pressure contact with the backup roller 423A via the intermediate transfer belt 421 and the secondary transfer belt 432. Thus, 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 by the sheet conveyance unit 50 to the secondary transfer nip. The correction of the inclination of the sheet S and the adjustment of the timing of conveyance are performed by the registration roller unit in which the registration roller pair 53a is disposed.

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

  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 sheet S at the fixing nip portion. Thus, the toner image is fixed on the sheet S. The sheet S on which the toner image is fixed is discharged to the outside of the machine by the paper discharge unit 52 provided with the paper discharge roller 52a.

  The 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 in sliding contact with the surface of the intermediate transfer belt 421.

  As apparent from the above description, the manufacturing method according to the present embodiment comprises a conductive support, a photosensitive layer disposed on the conductive support, and a surface layer disposed on the photosensitive layer. And a coating solution containing a polymerizable monomer for forming the surface layer is coated on the photosensitive layer, and a film of the coating solution is formed on the photosensitive layer. Forming the film, irradiating the film with infrared light, and irradiating the 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 the decrease in the chargeability due to the repetition of the image formation. Therefore, the image forming apparatus having the photosensitive member can suppress the defect of the image due to the decrease in the chargeability, and can form a high quality image over a long period of time.

  Further, irradiating the entire surface of the film with actinic light after irradiating the entire surface of the film with infrared light does not produce a portion to which infrared light and actinic light are simultaneously irradiated, thereby activating molecular vibration. Since the polymerization reaction can be initiated in the solidified state, it is more effective from the viewpoint of enhancing the reactivity of the polymerization reaction on the entire surface of the film.

  Further, it is more effective that the infrared light is near infrared light from the viewpoint of further activating molecular vibration.

  In addition, it is more effective that the polymerizable monomer has an acryloyl group or a methacryloyl group 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. .

  In addition, it is more effective that the fourth coating solution contains metal oxide particles from the viewpoint of imparting higher durability to the surface layer.

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

1. Production of Photoreceptor (Production of Photoreceptor 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 Subsequently, 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 dispersing machine, and dispersion was performed for 10 hours by a batch system.
Polyamide resin 1 part by mass Titanium oxide 1.1 parts by mass Ethanol 20 parts by mass

  As polyamide resin (binder resin), X1010 (made by Daicel Degussa Co., Ltd.) was used, and as titanium oxide (metal oxide particles), SMT500SAS (made by Tayca Co., Ltd.) was used. The number average primary particle size 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 dip coating, and dried at 110 ° C. for 20 minutes in an oven. Thus, an intermediate layer with a film thickness of 2 μm was formed on the surface of the conductive support.

(3) Formation of Charge Generating Layer Subsequently, the following components were mixed and dispersed in the following amounts to prepare a second coating liquid. At this time, dispersion was performed for 10 hours using a sand mill as a dispersing machine.
Titanyl phthalocyanine pigment 20 parts by mass polyvinyl butyral resin 10 parts by mass t-butyl acetate 700 parts by mass 4-methoxy-4-methyl-2-pentanone 300 parts by mass

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

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

(4) Formation of Charge Transport Layer Subsequently, the following components were mixed and dissolved in the following amounts to prepare a third coating liquid.
Charge transport substance 150 parts by mass Polycarbonate resin 300 parts by mass Tetrahydrofuran / toluene = 1/9 volume% 2000 parts by mass Antioxidant 6 parts by mass Silicone oil 1 part by mass

  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, Ltd.) Gas Chemical Co., Ltd.) Irganox 1010 (manufactured by BASF; "Irganox" is a registered trademark of the company) was used as an antioxidant. As 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 dip coating, and dried in an oven at 120 ° C. for 70 minutes. Thus, 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 Then, under light shielding, the polymerizable monomer, the metal oxide particles and the solvent were mixed in the following amounts. At this time, dispersion was performed for 10 hours using a sand mill as a dispersing machine. Then, under light shielding, the polymerization initiator was further mixed in the following amounts, stirred, and dissolved to prepare a fourth coating solution.
Polymerizable monomer 100 parts by mass Polymerization initiator 10 parts by mass Metal oxide particles 100 parts by mass sec-butanol 400 parts by mass Methyl isopropyl ketone 100 parts by mass

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

As metal oxide particles, tin oxide particles surface-treated with a compound represented by the above formula (S-15) and 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. at a rotational speed of 1500 rpm. Further, the treated mixture was taken out, charged 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

According to the above surface treatment, the surface of the tin oxide particles is coated with the surface treatment agent represented by the above-mentioned formula (S-15) by the fluorescent X-ray analyzer “XRF-1700 (manufactured by Shimadzu Corporation) It confirmed by detecting the peak of Si by "." As tin oxide, tin oxide (number average primary particle diameter: 20 nm, volume resistivity: 1.05 × 10 ⁵ Ω · cm) manufactured by CIK Nanotech Co., Ltd. was used.

  The prepared fourth coating solution was applied to the surface of the charge transport layer by a dip coating method and naturally dried at room temperature for 20 minutes to produce a work.

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

(Production of Photoreceptor 2)
A photoconductor 2 was produced in the same manner as the photoconductor 1 except that the charge transport substance was mixed in the surface layer, not the metal oxide particles, and the wavelength range 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. When preparing the fourth coating solution, a polymerizable monomer was used. Further, 20 parts by mass of the charge transport material was further mixed with 100 parts by mass.

(Production of Photoreceptor 3)
A photoconductor 3 was produced in the same manner as the photoconductor 1 except that Irgacure 184 (Irg 184; manufactured by BASF Japan Ltd.) was used as a polymerization initiator.

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

(Preparation of Photoreceptor 5)
The compound represented by the formula (M1) is used as the polymerizable monomer, the metal oxide fine particles are contained in the surface layer, and the compound represented by the following formula (CTM-10) is used as the charge transport material. A photoreceptor 5 was produced in the same manner as the photoreceptor 2. At the time of preparation of a 4th coating liquid, 100 mass parts metal oxide fine particles were further mixed. As metal oxide particles, the same tin oxide particles as those used in preparation of the photosensitive member 1 were used.

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

As metal oxide particles, copper aluminum oxide (CuAlO ₂ ) particles surface-treated with a compound represented by the above formula (S-15) and 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 of 0.5 mm in diameter, and mixed at about 30 ° C. for 6 hours. The methyl ethyl ketone and alumina beads were then filtered and dried at 60.degree.
Copper aluminum oxide 100 parts by mass Surface treatment agent 10 parts by mass Methyl ethyl ketone 1000 parts by mass

According to the above surface treatment, the surface of the copper aluminum oxide particles is coated with the surface treatment agent represented by the above chemical formula (S-15), as shown by the fluorescent X-ray analyzer “XRF-1700 (Shimadzu Corporation) Made by detecting the peak of Si. The number average primary particle diameter of copper aluminum oxide is 20 nm, and the volume resistivity is 1 × 10 ⁷ Ω · cm.

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

(Production of Photoreceptor 8)
A photosensitive member 7 was produced in the same manner as the photosensitive member 1 except that heat drying was performed instead of natural drying and infrared light irradiation before irradiation with ultraviolet light. Thermal drying was performed in an oven at 120 ° C. for 20 minutes.

(Preparation of Photoreceptor 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 the irradiation of the infrared light and the irradiation of the ultraviolet light were simultaneously performed.

(Production of Photoreceptor 10)
A photoconductor 10 was produced in the same manner as the photoconductor 1 except that the wavelength range of the infrared light was changed to 1000 to 2500 nm and the ultraviolet light was irradiated and then the infrared light was irradiated.

  About each photoreceptor, division, photoreceptor no. , Types of polymerizable monomers and reactive groups, types of polymerization initiators, types of metal oxide particles, types of charge transport materials, irradiation timing of infrared light, wavelength range of infrared light, and timing of thermal drying Shown in 1.

2. Evaluation of Photosensitive Member The chargeability of each photosensitive member was repeatedly evaluated. Specifically, each photoreceptor is mounted on a modified machine of the image forming apparatus "Bizuhub C 554 (made by Konica Minolta Business Technologies Co., Ltd.)", and charged and exposed in a high temperature and high humidity environment (temperature 30.degree. C., humidity 80%). Was repeated 30,000 times. At this time, the evaluation of repeated charging property, the charge time of the grid voltage _{(V g)} is 700 V, the exposure amount is adjusted each 0.4μJ / cm ^2, the distance of the charging and exposure to 0.4 seconds, repeated before ( Before and after the evaluation of the repeated chargeability, the surface potential (V _H ) of the unexposed area of the photoreceptor and the surface potential (V _L ) of the exposed area after the initial cycle and after 30,000 repetitions The differences (| ΔV _H |, | ΔV _L |) after the measurement were respectively determined. Then, each photoreceptor was evaluated according to the following criteria. For the photosensitive member, there is no problem in practical use if | ΔV _H | is less than 30 and there is no practical problem if | ΔV _L | is less than 40V.
(Evaluation criteria for | ΔV _H |)
:: less than 15 V :: 15 V or more and less than 30 V 30: 30 V or more and less than 40 V ×: 40 V or more (evaluation criteria for | ΔV _L |)
:: Less than 20 V ○: More than 20 V and less than 40 V Δ: More than 40 V and less than 60 V ×: More than 60 V

  Here, the modified machine of the image forming apparatus refers to an apparatus in which the developing mechanism, the transfer mechanism, the cleaning mechanism and the charge removing mechanism are removed from the image forming apparatus so that the evaluation of the chargeability can be repeatedly performed.

  About each photoreceptor, division, photoreceptor no. The evaluation results of the repeated chargeability are shown in Table 2.

  As shown in Table 2, for the photosensitive members 7 to 10 according to Comparative Examples 1 to 4, the reduction in repetitive chargeability could not be sufficiently suppressed. The photoconductor 7 according to Comparative Example 1 is considered to be because infrared light is not irradiated when forming the surface layer. Moreover, about the photoreceptor 8 which concerns on the comparative example 2, when forming a surface layer, although it heated before irradiation of an ultraviolet light, it is thought that it is because it has not irradiated infrared light. Further, the photosensitive member 9 according to Comparative Example 3 is considered to be because infrared light and ultraviolet light were simultaneously conducted when forming the surface layer. Furthermore, it is considered that the photosensitive member 10 according to Comparative Example 4 is 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 photosensitive members 2 and 4 to 6 according to Examples 1 to 4 , deterioration in repetitive chargeability can be sufficiently suppressed.

From the comparison of Examples 1 to 4 and Comparative Examples 1 to 4, when the surface layer is formed, the decrease in repetitive chargeability is suppressed by irradiating the infrared light before irradiating the ultraviolet light. It turned out that a photoreceptor can be manufactured. Further, from the comparison of Examples 1 to 4 and Comparative Example 2, it is understood that the improvement of the repetitive chargeability is not due to the heat generated by the irradiation of the infrared light.

  According to the present invention, since the temporal deterioration of the chargeability of the photosensitive member 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 electrophotographic image forming apparatuses are expected.

DESCRIPTION OF SYMBOLS 1 conductive support 2 middle layer 3 photosensitive layer 4 surface layer 5 charge generation layer 6 charge transport layer 30 image processing part 40 image forming part 41Y, 41M, 41C, 41K image forming unit 42 intermediate transfer unit 43 secondary transfer unit 50 Paper conveyance unit 51 Paper feed unit 51a, 51b, 51c Paper feed tray unit 52 Discharge unit 52a Discharge roller 53 Conveyance path portion 53a Registration roller pair 60 Fixing device 62 Fixing roller 63 Heat generation 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 Development device 413 Photoconductor 414 Charging device 415 Drum cleaning device 421 Intermediate transfer belt 422 Primary transfer roller 423, 431 Support roller 423A Backup Roller 426 belt cleaning device 431A secondary transfer roller 432 Secondary transfer belt D document S Paper

Claims (5)

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,
Applying a coating solution containing a polymerizable monomer for forming the surface layer on the photosensitive layer to form a film of the coating solution on the photosensitive layer;
Irradiating the film with near infrared light ;
Irradiating the portion of the film irradiated with near infrared light with an actinic ray to polymerize the polymerizable monomer;
A method of producing an electrophotographic photosensitive member, comprising: The method for producing an electrophotographic photosensitive member according to claim 1, wherein the whole surface of the film is irradiated with an actinic ray after the whole surface of the film is irradiated with 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 any one of claims 1 to 3 , wherein the coating solution further contains metal oxide particles. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 4 , wherein the actinic ray is ultraviolet light.

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