WO2010018725A1 - 有機感光体、画像形成装置及びプロセスカートリッジ - Google Patents
有機感光体、画像形成装置及びプロセスカートリッジ Download PDFInfo
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- WO2010018725A1 WO2010018725A1 PCT/JP2009/062515 JP2009062515W WO2010018725A1 WO 2010018725 A1 WO2010018725 A1 WO 2010018725A1 JP 2009062515 W JP2009062515 W JP 2009062515W WO 2010018725 A1 WO2010018725 A1 WO 2010018725A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14704—Cover layers comprising inorganic material
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14734—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14786—Macromolecular compounds characterised by specific side-chain substituents or end groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14795—Macromolecular compounds characterised by their physical properties
Definitions
- the present invention relates to an organic photoreceptor used in an electrophotographic image forming apparatus, an image forming apparatus using the organic photoreceptor, and a process cartridge.
- organic electrophotographic photoreceptor containing an organic photoconductive substance (hereinafter, also referred to as an organic photoreceptor or simply a photoreceptor) has been most widely used as an electrophotographic photoreceptor.
- Organic photoconductors have advantages over other photoconductors, such as easy development of materials suitable for various exposure light sources from visible light to infrared light, the ability to select materials without environmental pollution, and low manufacturing costs.
- the mechanical strength is weak, the surface of the photoreceptor is easily deteriorated or scratched when copying or printing a large number of sheets, and the durability is insufficient.
- Patent Document 1 a colloidal silica-containing curable siloxane resin is used as a surface layer of a photoreceptor
- the colloidal silica-containing curable siloxane resin includes both a siloxane bond (Si—O—Si bond) curable resin and colloidal silica, which are highly hygroscopic, and the electric resistance of the surface layer is likely to decrease, resulting in image blur and image flow. Likely to happen.
- Patent Document 2 a protective layer of a curable resin obtained by photopolymerization using a compound having an acryloyl group or the like has been proposed (Patent Document 2).
- the protective layer also contains a filler such as a metal oxide in the curable resin, but the bond between the filler and the curable resin is weak, the strength as the protective layer is insufficient, and image blurring is also caused.
- it has not been able to solve the problem of image flow.
- An object of the present invention is to solve the above-described problems, and to improve the wear resistance of an organic photoconductor to a level equivalent to that of an amorphous silicon photoconductor, and to easily generate an image stream under high temperature and high humidity. It is to provide an organic photoreceptor capable of improving image blur and improving durability and obtaining a high-quality electrophotographic image, and to provide an image forming apparatus and a process cartridge using the organic photoreceptor. .
- the inventors of the present application have found out the problems of the conventional protective layer for the protective layer applied to the organic photoreceptor, and as a result, the curable resin and the filler in the protective layer are more strongly bonded to each other and the The present invention has been completed by finding that the curable resin is hydrophobic so as to be necessary for simultaneously solving the wear resistance and image flow and image blur under high temperature and high humidity conditions. That is, the present invention is achieved by having the following configuration.
- An organic photoreceptor having a photosensitive layer on a conductive support and a protective layer on the photosensitive layer, wherein the protective layer is formed using at least alumina particles having a reactive organic group.
- R 3 is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, R 4 is an organic group having a polymerizable double bond, X is a halogen atom, an alkoxy group, an acyloxy group, An aminoxy group and a phenoxy group are shown, and n is an integer of 1 to 3.
- 5 The organic photoreceptor as described in 4 above, wherein the alumina particles have a number average primary particle size of 1 to 300 nm.
- An image forming apparatus that has at least a charging unit, an exposure unit, and a developing unit around an organic photoconductor, and repeatedly forms an image, wherein the organic photoconductor is the organic photoconductor described in 1 above. Image forming apparatus.
- a process cartridge for use in the image forming apparatus described in 15 above comprising at least one of the organic photoreceptor described in 1 and at least one of a charging unit, an image exposing unit, and a developing unit, A process cartridge configured to be removable from and into an image forming apparatus.
- the strength against abrasion and scratching of the photoreceptor surface is remarkably improved, the surface scratch resistance and wear amount of the photoreceptor surface are improved, and image blurring in a high-temperature and high-humidity environment is improved. Etc. are also remarkably improved.
- 1 is a schematic view in which functions of an image forming apparatus of the present invention are incorporated.
- 1 is a cross-sectional configuration diagram of a color image forming apparatus showing an embodiment of the present invention.
- 1 is a cross-sectional view of a color image forming apparatus using an organic photoreceptor of the present invention.
- the alumina particles having a reactive organic group used in the present invention will be described.
- the reactive organic group used in the present invention includes radical polymerizable functional groups such as acryloyl group and methacryloyl group.
- radical polymerizable functional groups such as acryloyl group and methacryloyl group.
- cyclic ether structures such as epoxy and oxetane can also be cited as the cationic polymerizable functional group.
- the alumina particles having a reactive organic group used in the present invention can be produced as follows.
- R 3 is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, R 4 is an organic group having a polymerizable double bond, X is a halogen atom, an alkoxy group, an acyloxy group, It represents an aminoxy group and a phenoxy group, and n is an integer of 1 to 3.
- R 3 is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms
- R 4 is an organic group having a polymerizable double bond
- X is a halogen atom, an alkoxy group, an acyloxy group, It represents an aminoxy group and a phenoxy group
- n is an integer of 1 to 3.
- the silane compound to be reacted with the alumina particles is not particularly limited as long as it is a compound having a silyl group, particularly a hydrolyzable silyl group, and capable of radical polymerization thereafter. Examples of the compound represented by the general formula (1) will be given below.
- silane compounds can be used alone or in admixture of two or more.
- Alumina particles having a reactive organic group according to the present invention are obtained by subjecting alumina particles to a surface treatment using a silane compound represented by the general formula (1) or the like, Can be obtained.
- a wet media dispersion type apparatus is used with 100 to 100 parts by mass of alumina particles using 0.1 to 100 parts by mass of a silane compound as a surface treating agent and 50 to 5000 parts by mass of a solvent. It is preferable.
- the following describes a surface treatment method for producing alumina particles that have been surface-coated with a silane compound more uniformly and finely.
- a slurry a suspension of solid particles
- a silane compound surface treatment agent a silane compound surface treatment agent
- wet pulverization the alumina particles are refined and the surface treatment of the alumina particles proceeds at the same time. Thereafter, the solvent is removed and the mixture is pulverized, so that alumina particles surface-treated with a uniform and finer silane compound can be obtained.
- the wet media dispersion type apparatus which is a surface treatment apparatus used in the present invention, is an aggregated particle of alumina by filling beads in a container as a medium and rotating a stirring disk mounted perpendicularly to a rotation axis at high speed.
- the apparatus has a step of crushing and pulverizing / dispersing, as long as the alumina particles are sufficiently dispersed and subjected to surface treatment when the surface treatment is performed on the alumina particles.
- Various styles such as mold, horizontal, continuous, batch, etc. can be adopted. Specifically, a sand mill, ultra visco mill, pearl mill, glen mill, dyno mill, agitator mill, dynamic mill and the like can be used.
- These dispersive devices are pulverized and dispersed by impact crushing, friction, cutting, shear stress, etc., using a grinding medium such as balls and beads.
- beads used in the sand grinder mill balls made of glass, alumina, zircon, zirconia, steel, flint stone, etc. can be used, but those made of zirconia or zircon are particularly preferable.
- the size of the beads is usually about 1 to 2 mm in diameter, but in the present invention, it is preferable to use about 0.3 to 1.0 mm.
- the disk and container inner wall used in the wet media dispersion type apparatus can be used for the disk and container inner wall used in the wet media dispersion type apparatus.
- the disk and container inner wall made of ceramic such as zirconia or silicon carbide are particularly used. Is preferred.
- alumina particles having a reactive organic group can be obtained by surface treatment with the silane compound of the general formula (1).
- the thus-obtained alumina particles having a reactive organic group can form a protective layer by a mutual reaction between these alumina particles. More preferably, the protective layer is formed by a reaction with the curable compound according to the present invention described below. Form.
- the compound that reacts with the reactive organic group of the alumina particles (the curable compound according to the present invention)
- the curable compound is preferably a monomer that is polymerized (cured) by irradiation with actinic rays such as ultraviolet rays or electron beams and becomes a resin generally used as a binder resin for a photoreceptor, such as polystyrene and polyacrylate.
- a resin generally used as a binder resin for a photoreceptor, such as polystyrene and polyacrylate.
- the monomers styrene monomers, acrylic monomers, methacrylic monomers, vinyl toluene monomers, vinyl acetate monomers, and N-vinyl pyrrolidone monomers are particularly preferable.
- a curable compound having an acryloyl group or a methacryloyl group is particularly preferable because it can be cured in a small amount of light or in a short time.
- examples of the cationic polymerizable monomer include epoxy compounds, vinyl ether compounds, oxetane compounds, and the like, and oxetane compounds are preferable.
- these curable compounds may be used alone or in combination.
- curable compounds examples are shown below.
- the following acrylic compounds can be preferably used as the curable compound.
- An acrylic compound is a compound having an acryloyl group (CH 2 ⁇ CHCO—) or a methacryloyl group (CH 2 ⁇ CCH 3 CO—). Further, the number of Ac groups (the number of acryloyl groups) described below represents the number of acryloyl groups or methacryloyl groups in the molecule.
- R and R ′ are respectively shown below.
- Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
- the curable compound preferably has 2 or more functional groups, particularly preferably 4 or more.
- the ratio of the molecular weight M of the compound having an acryloyl group or methacryloyl group to the number Ac of the acryloyl group or methacryloyl group; Ac / M is preferably in the following relationship. By using this ratio: Ac / M, the crosslink density is increased and the abrasion resistance of the photoreceptor is improved.
- two or more kinds of curable compounds having different curable reactive group equivalents may be mixed and used.
- alumina particles used in the present invention are not particularly limited as long as they are aluminum oxides, but it is preferable to use alumina particles purified and sintered from bauxite, which are widely produced industrially.
- the number average primary particle size of the alumina particles used in the present invention is preferably in the range of 1 to 300 nm. Particularly preferred is 3 to 100 nm.
- the wear resistance is not sufficient, and when the particle size is large, writing light may be scattered, or the particles may hinder photocuring and the wear resistance may be insufficient.
- the number average primary particle size of the alumina particles is a photographic image (excluding aggregated particles) obtained by taking an enlarged photograph of 10,000 times with a scanning electron microscope (manufactured by JEOL) and randomly capturing 300 particles with a scanner.
- Automatic image processing analyzer LUZEX AP Neco Corporation software version Ver. The number average primary particle size was calculated using 1.32.
- the proportion of the alumina particles in the protective layer is preferably 0.5% by mass to 80% by mass, and particularly preferably 1% by mass to 50% by mass with respect to the protective layer.
- the ratio of the alumina particles is 1 to 200 parts by mass, particularly preferably 30 to 120 parts by mass with respect to 100 parts by mass of the curable compound.
- the protective layer can form a cured film by applying and reacting with a coating liquid containing a polymerization initiator, a filler, lubricant particles, an antioxidant and the like, if necessary, in addition to the curable compound and alumina particles.
- a method of reacting by electron beam cleavage a method of reacting with light or heat by adding a radical polymerization initiator or a cationic polymerizable initiator, and the like are used.
- a radical polymerization initiator either a photopolymerization initiator or a thermal polymerization initiator can be used. Further, both light and heat initiators can be used in combination.
- a photopolymerization initiator As a radical polymerization initiator of these photocurable compounds, a photopolymerization initiator is preferable, and among them, an alkylphenone compound or a phosphine oxide compound is preferable. In particular, a compound having an ⁇ -hydroxyacetophenone structure or an acylphosphine oxide structure is preferable.
- the compound that initiates cationic polymerization include B (C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , and SbF 6 ⁇ of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium.
- CF 3 SO 3 - ionic polymerization initiator or sulfonic acid sulfonated materials that generate a such as salts, halides or generates hydrogen halide can be mentioned nonionic polymerization initiator such as iron arene complex.
- nonionic polymerization initiator such as iron arene complex.
- a sulfonate that generates a sulfonic acid that is a nonionic polymerization initiator and a halide that generates a hydrogen halide are preferable.
- the photoinitiator used preferably below is illustrated.
- Examples of ⁇ -aminoacetophenone series ⁇ -aminoacetophenone series
- the protective layer coating solution (the above composition) is applied on the photosensitive layer, and then dried to the extent that the fluidity of the coating film is lost, and then the protective layer is irradiated with ultraviolet rays.
- a method of curing and performing secondary drying to make the amount of volatile substances in the coating film a specified amount is preferable.
- a device for irradiating ultraviolet rays a known device used for curing an ultraviolet curable resin can be used.
- the amount of ultraviolet light (mJ / cm 2 ) for curing the applied coating solution with ultraviolet light is preferably controlled by the ultraviolet irradiation intensity and the irradiation time.
- thermal polymerization initiator ketone peroxide compounds, peroxyketal compounds, hydroperoxide compounds, dialkyl peroxide compounds, diacyl peroxide compounds, peroxydicarbonate compounds, peroxyester compounds Compounds and the like are used, and these thermal polymerization initiators are disclosed in company product catalogs.
- thermal polymerization initiators are mixed with alumina particles having a reactive organic group or a curable compound to prepare a coating solution for the protective layer, The coating solution is applied onto the photosensitive layer and then dried by heating to form the protective layer according to the present invention.
- the thermal polymerization initiator the above-mentioned other radical polymerization initiators can be used.
- a coating method such as a quantity-regulating type (circular slide hopper type is a typical example) from the viewpoint of preventing dissolution of the photosensitive layer film.
- the circular amount regulation type coating is described in detail in, for example, Japanese Patent Application Laid-Open No. 58-189061.
- polymerization initiators may be used alone or in combination of two or more.
- the content of the polymerization initiator is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the acrylic compound.
- the protective layer of the present invention can further contain various charge transport materials.
- various lubricant particles can be added.
- fluorine atom-containing resin particles can be added.
- Fluorine atom-containing resin particles include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluorochloroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride dichloride resin, and these One or two or more types are preferably selected from the copolymers, but tetrafluoroethylene resin and vinylidene fluoride resin are particularly preferable.
- the ratio of the lubricant particles in the protective layer is preferably 5 to 70 parts by mass, more preferably 10 to 60% by mass with respect to 100 parts by mass of the acrylic resin.
- the lubricant particles preferably have an average primary particle size of 0.01 ⁇ m to 1 ⁇ m. Particularly preferred is 0.05 to 0.5 ⁇ m.
- the molecular weight of the resin can be appropriately selected and is not particularly limited.
- Solvents for forming the protective layer include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol, benzyl alcohol, toluene, xylene, methylene chloride, methyl ethyl ketone, cyclohexane, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, and diethylamine.
- the protective layer of the present invention is preferably reacted by irradiating actinic radiation after natural drying or heat drying after coating.
- a known method such as 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 can be used as in the case of the intermediate layer and the photosensitive layer. .
- the protective layer of the organophotoreceptor of the present invention is irradiated with actinic rays on the coating to generate radicals and polymerize, and forms a cross-linking bond by a cross-linking reaction between molecules and within the molecule, and cures the cured resin. It is preferable to form by producing.
- actinic rays As the active ray, ultraviolet rays and electron beams are particularly preferable.
- any light source that generates ultraviolet light can be used without limitation.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a flash (pulse) xenon, or the like can be used.
- Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 .
- the power of the lamp is preferably 0.1 kW to 5 kW, particularly preferably 0.5 kW to 3 kW.
- an electron beam accelerator for electron beam irradiation is a curtain beam type that is relatively inexpensive and can provide a large output. Used.
- the acceleration voltage during electron beam irradiation is preferably 100 to 300 kV.
- the absorbed dose is preferably 0.5 to 10 Mrad.
- the irradiation time for obtaining the necessary irradiation amount of active rays is preferably 0.1 second to 10 minutes, and more preferably 0.1 second to 5 minutes from the viewpoint of work efficiency.
- ultraviolet rays are particularly easy to use.
- the organophotoreceptor of the present invention can be dried before and after irradiating with active rays and during irradiation with active rays, and the timing of drying can be appropriately selected by combining these.
- Drying conditions can be appropriately selected depending on the type of solvent and the film thickness.
- the drying temperature is preferably from room temperature to 180 ° C., particularly preferably from 80 ° C. to 140 ° C.
- the drying time is preferably 1 minute to 200 minutes, particularly preferably 5 minutes to 100 minutes.
- the film thickness of the protective layer is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m.
- the support used in the present invention may be any one as long as it has conductivity, for example, a metal such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or a sheet, aluminum or copper Metal foils such as those laminated on plastic films, aluminum, indium oxide and tin oxide deposited on plastic films, metals with conductive layers applied alone or with a binder resin, plastic films and For example, paper.
- a metal such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or a sheet
- Metal foils such as those laminated on plastic films, aluminum, indium oxide and tin oxide deposited on plastic films, metals with conductive layers applied alone or with a binder resin, plastic films and For example, paper.
- an intermediate layer having a barrier function and an adhesive function may be provided between the conductive layer and the photosensitive layer.
- the intermediate layer can be formed by dip coating or the like by dissolving a binder resin such as casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane and gelatin in a known solvent. Of these, an alcohol-soluble polyamide resin is preferred.
- a binder resin such as casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane and gelatin.
- an alcohol-soluble polyamide resin is preferred.
- various conductive fine particles and metal oxides can be included for the purpose of adjusting the resistance of the intermediate layer.
- various metal oxides such as alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, and bismuth oxide.
- Ultrafine particles such as indium oxide doped with tin, tin oxide doped with antimony, and zirconium oxide can be used.
- metal oxides may be used alone or in combination of two or more. When two or more types are mixed, it may take the form of a solid solution or fusion.
- the average particle diameter of such a metal oxide is preferably 0.3 ⁇ m or less, more preferably 0.1 ⁇ m or less.
- a solvent in which inorganic particles are well dispersed and the polyamide resin is dissolved is preferable.
- alcohols having 2 to 4 carbon atoms such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol and the like are preferable because of excellent solubility and coating performance of the polyamide resin.
- co-solvents examples include methanol, benzyl alcohol, toluene, methylene chloride, cyclohexanone, and tetrahydrofuran.
- the concentration of the binder resin is appropriately selected according to the film thickness of the intermediate layer and the production rate.
- the mixing ratio of the inorganic particles to the binder resin is preferably 20 to 400 parts by weight, more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the binder resin.
- an ultrasonic disperser As the means for dispersing the inorganic particles, an ultrasonic disperser, a ball mill, a sand grinder, a homomixer, and the like can be used, but are not limited thereto.
- the method for drying the intermediate layer can be appropriately selected according to the type of solvent and the film thickness, but thermal drying is preferred.
- the film thickness of the intermediate layer is preferably from 0.1 to 15 ⁇ m, more preferably from 0.3 to 10 ⁇ m.
- the photosensitive layer according to the present invention is preferably composed of at least two layers of a charge generation layer and a charge transport layer.
- the charge generation layer used in the present invention preferably contains a charge generation material and a binder resin, and is formed by dispersing and coating the charge generation material in a binder resin solution.
- the charge generation material examples include azo raw materials such as Sudan Red and Diane Blue, quinone pigments such as bilenquinone and anthanthrone, quinocyanine pigments, perylene pigments, indigo pigments such as indigo and thioindigo, and phthalocyanine pigments. It is not something. These charge generating substances can be used alone or in a form dispersed in a known resin.
- a known resin can be used, for example, polystyrene resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, Polyurethane resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of these resins (eg, vinyl chloride-vinyl acetate copolymer resins, chlorides) Vinyl-vinyl acetate-maleic anhydride copolymer resin) and poly-vinyl carbazole resin, but are not limited thereto.
- polystyrene resin polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, Polyurethane resins, phenol resins, polyester resins, alkyd resins, polycarbonate resin
- the charge generation layer is formed by dispersing a charge generation material in a solution in which a binder resin is dissolved in a solvent using a disperser to prepare a coating solution, and applying the coating solution to a certain film thickness using a coating device. It is preferable to prepare the film by drying.
- Solvents for dissolving and applying the binder resin used in the charge generation layer include, for example, toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methanol, ethanol, propanol, Examples include butanol, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, and diethylamine, but are not limited thereto.
- an ultrasonic disperser As a means for dispersing the charge generating substance, an ultrasonic disperser, a ball mill, a sand grinder, a homomixer, or the like can be used, but is not limited thereto.
- the mixing ratio of the charge generating material to the binder resin is preferably 1 to 600 parts by weight, more preferably 50 to 500 parts by weight based on 100 parts by weight of the binder resin.
- the film thickness of the charge generation layer varies depending on the characteristics of the charge generation material, the characteristics of the binder resin, the mixing ratio, and the like, but is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 3 ⁇ m. It should be noted that the coating solution for the charge generation layer can prevent the occurrence of image defects by filtering foreign matter and aggregates before coating.
- the pigment can also be formed by vacuum deposition.
- the charge transport layer used in the photoreceptor of the present invention contains a charge transport material and a binder resin, and is formed by dissolving and coating the charge transport material in a binder resin solution.
- Charge transport materials include, for example, carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline compounds Oxazolone derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, benzidine derivatives, poly-N-vinylcarbazole, poly-1- A mixture of two or more of vinylpyrene and poly-9-vinylanthracene may be used.
- charge transport material As the charge transport material (CTM), it is preferable to use a charge transport material having an atomic weight ratio of N atoms of less than 4.5%.
- a charge transport material As the basic structure of the charge transport material, a triphenylamine derivative, a styryl compound, a benzidine compound, a butadiene compound, and the like can be used, and among them, a styryl compound is preferable.
- binder resin for the charge transport layer a known resin can be used.
- Polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylic ester resin, and styrene-methacrylic acid Examples include ester copolymer resins, and polycarbonate is preferred.
- BPA, BPZ, dimethyl BPA, BPA-dimethyl BPA copolymer and the like are preferable in terms of crack resistance, wear resistance, and charging characteristics.
- the charge transport layer is formed by dissolving the binder resin and the charge transport material to prepare a coating solution, applying the coating solution to a certain film thickness with a coating machine, and drying the coating film.
- Examples of the solvent for dissolving the binder resin and the charge transport material include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, and tetrahydrofuran. 1,4-dioxane, 1,3-dioxolane, pyridine, diethylamine and the like, but are not limited thereto.
- the mixing ratio of the charge transport material to the binder resin is preferably 10 to 500 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the binder resin.
- the film thickness of the charge transport layer varies depending on the characteristics of the charge transport material, the characteristics of the binder resin, the mixing ratio, etc., but is preferably 5 to 40 ⁇ m, more preferably 10 to 30 ⁇ m.
- an antioxidant In the charge transport layer, an antioxidant, an electronic conductive agent, a stabilizer and the like may be added.
- the antioxidants described in Japanese Patent Application No. 11-200135 and the electronic conductive agents described in JP-A Nos. 50-137543 and 58-76483 are preferable.
- An image forming apparatus 1 shown in FIG. 1 is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B, an image forming unit C, and a transfer paper transport unit D as a transfer paper transport unit. Yes.
- An automatic document feeder that automatically conveys the document is provided above the image reading unit A.
- the document placed on the document table 11 is separated and conveyed by the document conveyance roller 12 to the reading position 13a.
- the image is read.
- the document after the document reading is completed is discharged onto the document discharge tray 14 by the document transport roller 12.
- the image of the original when placed on the platen glass 13 is read at a speed v of the first mirror unit 15 including the illumination lamp and the first mirror constituting the scanning optical system, and the V-shaped first image is located. Reading is performed by the movement of the second mirror unit 16 including the two mirrors and the third mirror in the same direction at the speed v / 2.
- the read image is formed on the light receiving surface of the image sensor CCD, which is a line sensor, through the projection lens 17.
- the line-shaped optical image formed on the image sensor CCD is sequentially photoelectrically converted into an electric signal (luminance signal) and then A / D converted, and the image processing unit B performs processing such as density conversion and filter processing. Then, the image data is temporarily stored in the memory.
- a drum-shaped photoconductor 21 as an image carrier, a charging means (charging step) 22 for charging the photoconductor 21 on the outer periphery thereof, and a surface potential of the charged photoconductor.
- PCL (precharge lamp) 27 as a process is arranged in the order of operation.
- a reflection density detecting means 222 for measuring the reflection density of the patch image developed on the photosensitive member 21 is provided.
- the photosensitive member 21 the organic photosensitive member according to the present invention is used, and the photosensitive member 21 is driven and rotated in the clockwise direction shown in the drawing.
- an image based on an image signal called from the memory of the image processing unit B by an exposure optical system as an image exposure unit (image exposure step) 30 is used. Exposure is performed.
- the exposure optical system as the image exposure means 30 as the writing means uses a laser diode (not shown) as a light source, and the optical path is bent by the reflection mirror 32 via the rotating polygon mirror 31, the f ⁇ lens 34, and the cylindrical lens 35, and main scanning is performed. Therefore, image exposure is performed on the photoconductor 21 at the position Ao, and an electrostatic latent image is formed by rotation (sub-scanning) of the photoconductor 21.
- the character portion is exposed to form an electrostatic latent image.
- the image forming apparatus of the present invention it is preferable to use a semiconductor laser or light emitting diode having an oscillation wavelength of 350 to 800 nm as an image exposure light source when an electrostatic latent image is formed on a photoreceptor.
- a semiconductor laser or light emitting diode having an oscillation wavelength of 350 to 800 nm as an image exposure light source when an electrostatic latent image is formed on a photoreceptor.
- the exposure dot diameter in the writing direction is narrowed down to 10 to 100 ⁇ m, and digital exposure is performed on the organic photoreceptor, so that it is 400 dpi (dpi: the number of dots per 2.54 cm) or more.
- dpi the number of dots per 2.54 cm
- the exposure dot diameter refers to the length of the exposure beam along the main scanning direction (Ld: measured at the maximum length) in a region where the intensity of the exposure beam is 1 / e 2 or more of the peak intensity.
- the light beams used have a solid scanner such as the scanning optical system and LED using a semiconductor laser, there is a Gaussian distribution and Lorentz distribution, etc. also the light intensity distribution is in each 1 / e 2 or more regions of peak intensity
- the exposure dot diameter according to the present invention is used.
- the electrostatic latent image on the photoconductor 21 is subjected to reversal development by the developing means 23, and a visible toner image is formed on the surface of the photoconductor 21.
- the electrostatic latent image formed on the organic photoreceptor of the present invention is visualized as a toner image by development.
- the toner used for development may be a pulverized toner or a polymerized toner, but the toner according to the present invention is preferably a polymerized toner that can be prepared by a polymerization method from the viewpoint of obtaining a stable particle size distribution.
- Polymerized toner means a toner whose toner binder resin is formed and the toner shape is formed by polymerization of a raw material monomer of the binder resin and, if necessary, subsequent chemical treatment. More specifically, it means a toner formed through a polymerization reaction such as suspension polymerization or emulsion polymerization, and if necessary, a step of fusing particles between them.
- the volume average particle diameter of the toner that is, the 50% volume particle diameter (Dv50) is desirably 2 to 9 ⁇ m, more preferably 3 to 7 ⁇ m.
- Dv50 50% volume particle diameter
- the volume average particle diameter of the toner is desirably 2 to 9 ⁇ m, more preferably 3 to 7 ⁇ m.
- the toner according to the present invention may be used as a one-component developer or a two-component developer.
- a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 ⁇ m of magnetic particles in the toner can be used. be able to.
- the magnetic particles of the carrier can be mixed with a carrier and used as a two-component developer.
- conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable.
- the magnetic particles preferably have a volume average particle diameter of 15 to 100 ⁇ m, more preferably 25 to 80 ⁇ m.
- the measurement of the volume average particle diameter of the carrier can be typically performed by a laser diffraction type particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.
- HELOS laser diffraction type particle size distribution measuring apparatus
- the carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin.
- the resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, ester resin, or fluorine-containing polymer resin is used.
- the resin for constituting the resin-dispersed carrier is not particularly limited, and known resins can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. be able to.
- paper feed units 41 (A), 41 (B), and 41 (C) are provided below the image forming unit as transfer paper storage means for storing transfer paper P of different sizes.
- a manual paper feeding unit 42 for manually feeding paper is provided on the side, and the transfer paper P selected from any of them is fed along the transport path 40 by the guide roller 43 and fed.
- the transfer paper P is temporarily stopped by a pair of paper feed registration rollers 44 that correct the inclination and bias of the transfer paper P to be transferred, and then fed again.
- the transport path 40, the pre-transfer roller 43a, and the paper feed path 46 The toner image on the photosensitive member 21 is guided to the transfer guide belt 47 and is transferred to the transfer paper P while being transferred to the transfer transport belt 454 of the transfer transport belt device 45 by the transfer pole 24 and the separation pole 25 at the transfer position Bo. Photographed, transfer sheet P is separated from the photosensitive member 21 surface, it is conveyed to the fixing unit 50 by the transfer conveyor belt device 45.
- the fixing unit 50 includes a fixing roller 51 and a pressure roller 52, and the toner is fixed by heating and pressure by passing the transfer paper P between the fixing roller 51 and the pressure roller 52. After the toner image has been fixed, the transfer paper P is discharged onto the paper discharge tray 64.
- the transfer paper P is transported downward by the transport mechanism 178 and switched back by the transfer paper reversing unit 179, and the rear end portion of the transfer paper P becomes the leading end portion and transported into the duplex copying paper supply unit 130.
- the transfer paper P is moved in a paper feed direction by a conveyance guide 131 provided in the double-sided copy paper supply unit 130, the transfer paper P is re-fed by the paper supply roller 132, and the transfer paper P is guided to the conveyance path 40. .
- the transfer paper P is conveyed in the direction of the photoconductor 21, the toner image is transferred to the back surface of the transfer paper P, fixed by the fixing means 50, and then discharged onto the paper discharge tray 64.
- the image forming apparatus of the present invention is configured by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge, and this unit is configured to be detachable from the apparatus main body. Also good.
- a process cartridge is formed by integrally supporting at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device together with a photosensitive member, and a single unit that is detachable from the apparatus main body. It is good also as a structure which can be attached or detached using guide means, such as a rail of an apparatus main body.
- FIG. 2 is a cross-sectional configuration diagram of a color image forming apparatus showing an embodiment of the present invention.
- This color image forming apparatus is called a tandem type color image forming apparatus, and includes four sets of image forming units (image forming units) 10Y, 10M, 10C, and 10Bk, an endless belt-shaped intermediate transfer body unit 7, and a feeding unit. It comprises a paper conveying means 21 and a fixing means 24.
- a document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.
- the image forming unit 10Y that forms a yellow image includes a charging unit (charging step) 2Y, an exposure unit (exposure step) 3Y, and a developing unit disposed around a drum-shaped photoconductor 1Y as a first image carrier.
- An image forming unit 10M that forms a magenta image includes a drum-shaped photosensitive member 1M as a first image carrier, a charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roller 5M as a primary transfer unit, It has a cleaning means 6M.
- An image forming unit 10C for forming a cyan image includes a drum-shaped photoreceptor 1C as a first image carrier, a charging unit 2C, an exposure unit 3C, a developing unit 4C, and a primary transfer roller 5C as a primary transfer unit. It has cleaning means 6C.
- the image forming unit 10Bk that forms a black image includes a drum-shaped photoreceptor 1Bk as a first image carrier, a charging unit 2Bk, an exposure unit 3Bk, a developing unit 4Bk, a primary transfer roller 5Bk as a primary transfer unit, and a cleaning unit. 6Bk.
- the four sets of image forming units 10Y, 10M, 10C, and 10Bk include charging means 2Y, 2M, 2C, and 2Bk that rotate around the photosensitive drums 1Y, 1M, 1C, and 1Bk, and image exposure means 3Y, 3M, 3C and 3Bk, rotating developing means 4Y, 4M, 4C and 4Bk, and cleaning means 5Y, 5M, 5C and 5Bk for cleaning the photosensitive drums 1Y, 1M, 1C and 1Bk.
- the image forming units 10Y, 10M, 10C, and 10Bk have the same configuration except that the colors of toner images formed on the photoreceptors 1Y, 1M, 1C, and 1Bk are different, and the image forming unit 10Y is taken as an example in detail. explain.
- the image forming unit 10Y has a charging unit 2Y (hereinafter simply referred to as a charging unit 2Y or a charger 2Y), an exposure unit 3Y, a developing unit 4Y, and a cleaning unit 5Y (around a photosensitive drum 1Y as an image forming body).
- a charging unit 2Y or a charger 2Y the cleaning means 5Y or the cleaning blade 5Y
- the cleaning means 5Y or the cleaning blade 5Y is simply disposed, and a yellow (Y) toner image is formed on the photosensitive drum 1Y.
- at least the photosensitive drum 1Y, the charging unit 2Y, the developing unit 4Y, and the cleaning unit 5Y are provided so as to be integrated.
- the charging means 2Y is a means for applying a uniform potential to the photosensitive drum 1Y.
- a corona discharge type charger 2Y is used for the photosensitive drum 1Y.
- the image exposure means 3Y performs exposure based on the image signal (yellow) on the photosensitive drum 1Y given a uniform potential by the charger 2Y, and forms an electrostatic latent image corresponding to the yellow image.
- the exposure means 3Y includes an LED in which light emitting elements are arranged in an array in the axial direction of the photosensitive drum 1Y and an imaging element (trade name; Selfoc lens), or A laser optical system or the like is used.
- the image forming apparatus of the present invention is configured by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge (image forming unit), and this image forming unit is connected to the apparatus main body. It may be configured to be detachable.
- at least one of a charging device, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge (image forming unit), which is detachable from the apparatus main body.
- a single image forming unit may be detachable using guide means such as a rail of the apparatus main body.
- “supported integrally” means that the process cartridge can be attached or detached as one lump in the unit of the process cartridge when the process cartridge is attached or detached.
- the endless belt-shaped intermediate transfer body unit 7 has an endless belt-shaped intermediate transfer body 70 as a second image carrier having a semiconductive endless belt shape that is wound around a plurality of rollers and is rotatably supported.
- Each color image formed by the image forming units 10Y, 10M, 10C, and 10Bk is sequentially transferred onto a rotating endless belt-shaped intermediate transfer body 70 by primary transfer rollers 5Y, 5M, 5C, and 5Bk as primary transfer means.
- the transfer paper P as a transfer material (support for supporting the final fixed image: for example, plain paper, transparent sheet, etc.) housed in the paper feed cassette 20 is fed by the paper feed means 21 and is a plurality of intermediates.
- the transfer paper P onto which the color image has been transferred is fixed by the fixing means 24, is sandwiched between the paper discharge rollers 25, and is placed on a paper discharge tray 26 outside the apparatus.
- a transfer support for a toner image formed on a photosensitive member such as an intermediate transfer member or a transfer material is collectively referred to as a transfer medium.
- the residual toner is removed by the cleaning means 6b from the endless belt-shaped intermediate transfer body 70 from which the transfer paper P is separated by curvature.
- the primary transfer roller 5Bk is always in contact with the photoreceptor 1Bk.
- the other primary transfer rollers 5Y, 5M, and 5C are in contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.
- the secondary transfer roller 5b contacts the endless belt-shaped intermediate transfer body 70 only when the transfer paper P passes through the secondary transfer roller 5b and the secondary transfer is performed.
- the casing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R.
- the housing 8 includes image forming units 10Y, 10M, 10C, and 10Bk and an endless belt-shaped intermediate transfer body unit 7.
- the image forming units 10Y, 10M, 10C, and 10Bk are arranged in tandem in the vertical direction.
- An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1Bk in the drawing.
- the endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 that can be rotated by winding rollers 71, 72, 73, 74, primary transfer rollers 5Y, 5M, 5C, 5Bk, and cleaning means 6b. Consists of.
- FIG. 3 shows a color image forming apparatus using the organic photoreceptor of the present invention (a copying machine having at least a charging means, an exposure means, a plurality of developing means, a transfer means, a cleaning means, and an intermediate transfer body around the organic photoreceptor.
- a copying machine having at least a charging means, an exposure means, a plurality of developing means, a transfer means, a cleaning means, and an intermediate transfer body around the organic photoreceptor.
- 1 is a cross-sectional view of a configuration of a laser beam printer).
- the belt-shaped intermediate transfer body 70 uses an elastic body having a medium resistance.
- 1 is a rotating drum type photoreceptor that is repeatedly used as an image forming member, and is driven to rotate in a counterclockwise direction indicated by an arrow at a predetermined peripheral speed.
- the photoreceptor 1 is uniformly charged to a predetermined polarity and potential by a charging means (charging process) 2, and then time-series electric digital of image information by an image exposure means (image exposure process) 3 (not shown).
- An electrostatic latent image corresponding to the yellow (Y) color component image (color information) of the target color image is formed by receiving image exposure by scanning exposure light or the like by a laser beam modulated in accordance with the pixel signal.
- the electrostatic latent image is developed with yellow toner which is the first color by yellow (Y) developing means: developing step (yellow color developing device) 4Y.
- developing step yellow color developing device
- the second to fourth developing means magenta developer, cyan developer, black developer
- 4M, 4C, and 4Bk are not activated and do not act on the photoreceptor 1.
- the yellow toner image of the first color is not affected by the second to fourth developing devices.
- the intermediate transfer member 70 is stretched by rollers 79a, 79b, 79c, 79d, and 79e, and is driven to rotate in the clockwise direction at the same peripheral speed as the photosensitive member 1.
- the yellow toner image of the first color formed and supported on the photosensitive member 1 is applied to the intermediate transfer member 70 from the primary transfer roller 5a in the process of passing through the nip portion between the photosensitive member 1 and the intermediate transfer member 70.
- the intermediate transfer (primary transfer) is sequentially performed on the outer peripheral surface of the intermediate transfer body 70 by the electric field formed by the primary transfer bias.
- the surface of the photoreceptor 1 after the transfer of the first color yellow toner image corresponding to the intermediate transfer body 70 is cleaned by the cleaning device 6a.
- the second color magenta toner image, the third color cyan toner image, and the fourth color black (black) toner image are sequentially superimposed and transferred onto the intermediate transfer body 70 to correspond to the target color image.
- a superimposed color toner image is formed.
- the secondary transfer roller 5b is supported in parallel with the secondary transfer counter roller 79b so as to be separated from the lower surface of the intermediate transfer body 70.
- the primary transfer bias for sequentially superimposing and transferring the first to fourth color toner images from the photosensitive member 1 to the intermediate transfer member 70 has a polarity opposite to that of the toner and is applied from a bias power source.
- the applied voltage is, for example, in the range of +100 V to +2 kV.
- the secondary transfer roller 5b and the intermediate transfer member cleaning means 6b can be separated from the intermediate transfer member 70.
- the secondary transfer roller 5b When the superimposed color toner image transferred onto the belt-shaped intermediate transfer member 70 is transferred onto the transfer paper P as the second image carrier, the secondary transfer roller 5b is brought into contact with the belt of the intermediate transfer member 70. At the same time, the transfer paper P is fed from the pair of paper feeding registration rollers 23 through the transfer paper guide to the belt of the intermediate transfer body 70 to the contact nip with the secondary transfer roller 5b at a predetermined timing.
- a secondary transfer bias is applied to the secondary transfer roller 5b from a bias power source. By this secondary transfer bias, the superimposed color toner image is transferred (secondary transfer) from the intermediate transfer body 70 to the transfer sheet P as the second image carrier.
- the transfer paper P that has received the transfer of the toner image is introduced into the fixing means 24 and fixed by heating.
- the image forming apparatus of the present invention is generally applicable to electrophotographic apparatuses such as an electrophotographic copying machine, a laser printer, an LED printer, and a liquid crystal shutter type printer, and further displays, recordings, light printing, plate making, and facsimiles using electrophotographic technology.
- electrophotographic apparatuses such as an electrophotographic copying machine, a laser printer, an LED printer, and a liquid crystal shutter type printer, and further displays, recordings, light printing, plate making, and facsimiles using electrophotographic technology.
- the present invention can be widely applied to such devices.
- part means “part by mass”.
- Photoreceptor 1 was produced as follows.
- An intermediate layer coating solution having the following composition was prepared.
- Polyamide resin X1010 manufactured by Daicel Degussa Co., Ltd.
- Titanium oxide SMT500SAS manufactured by Teika
- Dispersion was carried out for 10 hours in a batch manner using a sand mill as a disperser.
- coating was performed on the support by a dip coating method so that the film thickness after drying at 110 ° C. for 20 minutes was 2 ⁇ m.
- CTM Charge transport material
- One part of silicon oil KF-54: manufactured by Shin-Etsu Chemical Co., Ltd. was mixed and dissolved to prepare a charge transport layer coating solution. The coating liquid was dried on the charge generation layer by dip coating at 110 ° C. for 60 minutes to form a charge transport layer having a thickness of 20 ⁇ m.
- ⁇ Protective layer> Alumina particles having a reactive group (alumina particles having a number average primary particle size of 6 nm surface-treated with the same mass of methacryloxypropyltrimethoxysilane (surface treatment agent)) 100 parts Curing compound (Exemplary Compound No. 31) 100 parts Isopropyl alcohol 500 parts After dispersing the above components for 10 hours using a sand mill, 30 parts of polymerization initiator 1-6 was added and dissolved by mixing and stirring under light shielding to prepare a protective layer coating solution (light-shielding during storage). A protective layer was applied using a circular slide hopper applicator on the photoreceptor on which the coating solution had been prepared up to the charge transport layer.
- a metal halide lamp 500 W is used for irradiation for 1 minute while rotating the photoreceptor at a position of 100 mm (ultraviolet curing process), and a protective layer having a thickness of 3 ⁇ m.
- Photoconductors 2 to 27 were produced in the same manner except that the materials used for the protective layer of photoconductor 1 and the curing conditions were changed as shown in the list of Table 1.
- Photoconductor 28 (without protective layer) In the production of the photoreceptor 1, a laminated photoreceptor including an intermediate layer, a charge generation layer, and a charge transport layer is formed in the same manner until the charge transport layer is formed. However, no protective layer is installed.
- Photoconductor 29 (alumina surface treatment without reactive organic groups) In the same manner as the photoreceptor 1, a laminated photoreceptor having an intermediate layer, a charge generation layer, and a charge transport layer was formed.
- a protective layer was installed in the same manner as in Example 1 except that alumina particles having a primary particle size of 6 nm surface-treated with the same mass of isobutyltrimethoxysilane were used instead of the alumina particles having a reactive group.
- Photoreceptor 30 (sol-gel formed glass film) In the same manner as the photoreceptor 1, a laminated photoreceptor having an intermediate layer, a charge generation layer, and a charge transport layer was formed. A coating solution in which the following materials were mixed and dissolved on the charge transport layer was coated using a circular slide hopper coating machine, dried by heating at 140 ° C. for 30 minutes, and a 3 ⁇ m protective layer was installed.
- a protective layer was installed in the same manner as in Example 1 except that the alumina particles having reactive groups were removed.
- Photoconductor 32 (silica having no reactive organic group + curable compound) In the same manner as the photoreceptor 1, a laminated photoreceptor having an intermediate layer, a charge generation layer, and a charge transport layer was formed.
- a protective layer was installed in the same manner as in Example 1 except that silica particles having a primary particle diameter of 10 nm that had been surface-treated with the same mass of isobutyltrimethoxysilane were used in place of the alumina particles having reactive groups.
- silica particles having a primary particle diameter of 10 nm that had been surface-treated with the same mass of isobutyltrimethoxysilane were used in place of the alumina particles having reactive groups.
- the photoconductor was modified so that the bizhub PRO C6500 (laser exposure / reverse development / intermediate transfer tandem color multi-function machine) manufactured by Konica Minolta Business Technologies, Inc. was mounted on an evaluation machine with optimized exposure ( At 20 ° C. and 50% RH), the surface state of the photoreceptor was observed before and after printing 1 million sheets of A4 images with a YMCBk color printing rate of 2.5% on neutral paper, and the state of scratches was evaluated.
- the evaluation photoconductor is installed in the cyan position.
- the film thickness measuring device is an eddy current film thickness measuring device EDDY560C (manufactured by HELMUT FISCHER GMBTE CO), and the difference in the photosensitive layer thickness before and after the actual shooting test is defined as the film thickness depletion amount.
- A The amount of wear is 1 ⁇ m or less (good)
- ⁇ Amount of wear is 1 ⁇ m to 3 ⁇ m (no problem in practical use)
- X The amount of wear is larger than 3 ⁇ m (there is a problem in practical use).
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Abstract
Description
5.前記アルミナ粒子の数平均一次粒径が、1~300nmであることを特徴とする前記4に記載の有機感光体。
7.前記保護層が、前記反応性有機基を有するアルミナ粒子と硬化性化合物との反応により、形成された保護層であることを特徴とする前記6に記載の有機感光体。
11.前記反応性有機基が、重合性官能基であることを特徴とする前記1に記載の有機感光体。
S-2 CH2=CHSi(OCH3)3
S-3 CH2=CHSiCl3
S-4 CH2=CHCOO(CH2)2Si(CH3)(OCH3)2
S-5 CH2=CHCOO(CH2)2Si(OCH3)3
S-6 CH2=CHCOO(CH2)2Si(OC2H5)(OCH3)2
S-7 CH2=CHCOO(CH2)3Si(OCH3)3
S-8 CH2=CHCOO(CH2)2Si(CH3)Cl2
S-9 CH2=CHCOO(CH2)2SiCl3
S-10 CH2=CHCOO(CH2)3Si(CH3)Cl2
S-11 CH2=CHCOO(CH2)3SiCl3
S-12 CH2=C(CH3)COO(CH2)2Si(CH3)(OCH3)2
S-13 CH2=C(CH3)COO(CH2)2Si(OCH3)3
S-14 CH2=C(CH3)COO(CH2)3Si(CH3)(OCH3)2
S-15 CH2=C(CH3)COO(CH2)3Si(OCH3)3
S-16 CH2=C(CH3)COO(CH2)2Si(CH3)Cl2
S-17 CH2=C(CH3)COO(CH2)2SiCl3
S-18 CH2=C(CH3)COO(CH2)3Si(CH3)Cl2
S-19 CH2=C(CH3)COO(CH2)3SiCl3
S-20 CH2=CHSi(C2H5)(OCH3)2
S-21 CH2=C(CH3)Si(OCH3)3
S-22 CH2=C(CH3)Si(OC2H5)3
S-23 CH2=CHSi(OCH3)3
S-24 CH2=C(CH3)Si(CH3)(OCH3)2
S-25 CH2=CHSi(CH3)Cl2
S-26 CH2=CHCOOSi(OCH3)3
S-27 CH2=CHCOOSi(OC2H5)3
S-28 CH2=C(CH3)COOSi(OCH3)3
S-29 CH2=C(CH3)COOSi(OC2H5)3
S-30 CH2=C(CH3)COO(CH2)3Si(OC2H5)3
S-S1 CH2=CHCOO(CH2)2Si(CH3)2(OCH3)
S-S2 CH2=CHCOO(CH2)2Si(CH3)(OCOCH3)2
S-S3 CH2=CHCOO(CH2)2Si(CH3)(ONHCH3)2
S-S4 CH2=CHCOO(CH2)2Si(CH3)(OC6H5)2
S-S5 CH2=CHCOO(CH2)2Si(C10H21)(OCH3)2
S-S6 CH2=CHCOO(CH2)2Si(CH2C6H5)(OCH3)2
又、前記一般式(1)の化合物以外でも、下記のようなラジカル重合可能な反応性有機基を有するシラン化合物を用いてもよい。
本発明に係わる反応性有機基を有するアルミナ粒子は、アルミナ粒子を前記した一般式(1)等で表されるシラン化合物を用いて表面処理することにより、得ることが出来る。該表面被覆処理するに際し、アルミナ粒子100質量部に対し、シラン化合物を表面処理剤として0.1~100質量部、溶媒50~5000質量部を用いて湿式メディア分散型装置を使用して処理することが好ましい。
本発明においては、硬化性反応基当量の異なる2種類以上の硬化性化合物を混合して使用してもよい。
本発明で用いられるアルミナ粒子は、アルミニウムの酸化物であれば、特に制限されないが、広く工業的に生産されている、ボーキサイトから精製、焼結されたアルミナ粒子を用いることが好ましい。
α-アミノアセトフェノン系の例
本発明で用いる支持体は導電性を有するものであればいずれのものでもよく、例えば、アルミニウム、銅、クロム、ニッケル、亜鉛及びステンレスなどの金属をドラムまたはシート状に成形したもの、アルミニウムや銅などの金属箔をプラスチックフィルムにラミネートしたもの、アルミニウム、酸化インジウム及び酸化スズなどをプラスチックフィルムに蒸着したもの、導電性物質を単独またはバインダー樹脂と共に塗布して導電層を設けた金属、プラスチックフィルム及び紙などが挙げられる。
本発明においては、導電層と感光層の中間にバリアー機能と接着機能をもつ中間層を設けることもできる。
本発明に係る感光層は、電荷発生層および電荷輸送層の少なくとも2層で構成されることが好ましい。
本発明の感光体に用いられる電荷輸送層は、電荷輸送物質とバインダー樹脂を含有し、電荷輸送物質をバインダー樹脂溶液中に溶解、塗布して形成される。
下記の様に感光体1を作製した。
下記組成の中間層塗布液を作製した。
ポリアミド樹脂X1010(ダイセルデグサ株式会社製) 1部
酸化チタンSMT500SAS(テイカ社製) 1.1部
エタノール 20部
分散機としてサンドミルを用いて、バッチ式で10時間の分散を行った。
電荷発生物質:チタニルフタロシアニン顔料(Cu-Kα特性X線回折スペクトル測定で、少なくとも27.3°の位置に最大回折ピークを有するチタニルフタロシアニン顔料)
20部
ポリビニルブチラール樹脂(#6000-C:電気化学工業社製) 10部
酢酸t-ブチル 700部
4-メトキシ-4-メチル-2-ペンタノン 300部
を混合し、サンドミルを用いて10時間分散し、電荷発生層塗布液を調製した。この塗布液を前記中間層の上に浸漬塗布法で塗布し、乾燥膜厚0.3μmの電荷発生層を形成した。
電荷輸送物質:CTM(下記化合物A) 150部
バインダー:ポリカーボネート(Z300:三菱ガス化学社製) 300部
酸化防止剤(Irganox1010:日本チバガイギー社製) 6部
トルエン/テトラヒドロフラン=1/9体積% 2000部
シリコンオイル(KF-54:信越化学社製) 1部
を混合し、溶解して電荷輸送層塗布液を調製した。この塗布液を前記電荷発生層の上に
浸漬塗布法を用いて、110℃で60分乾燥後膜厚20μmの電荷輸送層を形成した。
反応性基を有するアルミナ粒子
(同一質量のメタクリロキシプロピルトリメトキシシラン(表面処理剤)で表面処理した数平均一次粒径6nmのアルミナ粒子) 100部
硬化性化合物(例示化合物No.31) 100部
イソプロピルアルコール 500部
上記成分をサンドミルを用いて10時間分散した後、
重合開始剤1-6 30部
を加え、遮光下で混合攪拌して溶解し保護層塗布液を作製した(保存中は遮光)。該塗布液を先に電荷輸送層まで作製した感光体上に円形スライドホッパー塗布機を用いて、保護層を塗布した。塗布後、室温で20分乾燥後(溶媒乾燥工程)、メタルハライドランプ(500W)を用いて100mmの位置で感光体を回転させながら1分間照射して(紫外線硬化工程)、膜厚3μmの保護層を得た。
感光体1の保護層に使用する材料、硬化条件を表1の一覧表のように変更した以外は、同様にして感光体2~27を作製した。
硬化条件(光):メタルハライドランプ(500W)より100mmの位置で感光体を回転させながら1分間照射して膜厚3μmの保護層を得た。
硬化条件(熱):140℃で30分間加熱し膜厚3μmの保護層を得た。
(比較用感光体の作製)
感光体28(保護層なし)
感光体1の作製において、電荷輸送層の形成までは同様にして中間層、電荷発生層、電荷輸送層の積層感光体を形成する。しかし、保護層を設置しない。
感光体1と同様に中間層、電荷発生層、電荷輸送層の積層感光体を形成した。
感光体1と同様に中間層、電荷発生層、電荷輸送層の積層感光体を形成した。電荷輸送層上に以下の材料を混合溶解した塗布液を円形スライドホッパー塗布機を用いて塗布し140℃で30分加熱乾燥後、3μmの保護層を設置した。
エタノール 100部
感光体31(アルミナなし、硬化性化合物単独)
感光体1と同様に中間層、電荷発生層、電荷輸送層の積層感光体を形成した。
感光体1と同様に中間層、電荷発生層、電荷輸送層の積層感光体を形成した。
〔感光体の評価〕
(表面傷)
作製した各感光体を下記のように評価した。
○:100万枚印字後に表面傷1~10箇所発生(実用上問題なし)
×:100万枚印字後に表面傷11箇所以上発生(実用上問題有り)。
上記評価で100万の画出しを行い、初期膜厚と100万枚後の膜厚さで評価した。感光層の膜厚は均一膜厚部分(感光体の両端は膜厚が不均一になりやすいので、少なくとの両端3cmは除く)をランダムに10ケ所測定し、その平均値を感光層の膜厚とする。膜厚測定器は渦電流方式の膜厚測定器EDDY560C(HELMUT FISCHER GMBTE CO社製)を用いて行い、実写試験前後の感光層膜厚の差を膜厚減耗量とする。
○:減耗量が 1μm~3μm(実用上問題なし)
×:減耗量が 3μmより大きい(実用上問題有り)。
環境条件を30℃、80%RHに変更した以外は、表面傷の評価条件でA4画像を中性紙に2.5万枚の印刷を行い、印刷終了後60秒で実機の主電源を停止した。停止12時間後に電源を入れ印字可能状態になった後直ちにA3中性紙全面にハーフトーン画像(マクベス濃度計で相対反射濃度0.4)とA3全面の6dot格子画像を印字した。印字画像の状態を観察し以下の評価を行った。
○:ハーフトーン画像のみに感光体長軸方向の薄い帯状濃度低下が認められる(実用上問題なし)
×:画像ボケによる格子画像の欠損もしくは線幅の細りが発生(実用上問題有り)
評価結果を下記表1にまとめた。
1Y、1M、1C、1Bk 感光体
2Y、2M、2C、2Bk 帯電手段
3Y、3M、3C、3Bk 露光手段
4Y、4M、4C、4Bk 現像手段
Claims (16)
- 導電性支持体上に感光層を有し、該感光層上に保護層を有する有機感光体において、該保護層が、少なくとも、反応性有機基を有するアルミナ粒子を用いて、形成された保護層であることを特徴とする有機感光体。
- 前記反応性有機基を有するアルミナ粒子が、反応性有機基を有するシラン化合物とアルミナ粒子とを反応させて製造されたものであることを特徴とする請求項1に記載の有機感光体。
- 前記、反応性有機基を有するシラン化合物、の反応性有機基が、重合性官能基であることを特徴とする請求項2に記載の有機感光体。
- 前記アルミナ粒子の数平均一次粒径が、1~300nmであることを特徴とする請求項4に記載の有機感光体。
- 前記保護層が、前記反応性有機基を有するアルミナ粒子と硬化性化合物とを用いた反応により、形成された保護層であることを特徴とする請求項1から5のいずれか1項に記載の有機感光体
- 前記保護層が、前記反応性有機基を有するアルミナ粒子と硬化性化合物との反応により、形成された保護層であることを特徴とする請求項6に記載の有機感光体。
- 前記硬化性化合物が炭素=炭素二重結合を有する化合物であることを特徴とする請求項7に記載の有機感光体。
- 前記炭素=炭素二重結合を有する化合物がアクリロイル基又はメタクリロイル基を有する化合物であることを特徴とする請求項8に記載の有機感光体。
- 前記アクリロイル基又はメタクリロイル基を有する化合物の分子量Mと該アクリロイル基又はメタクリロイル基数Acの比;Ac/Mが下記の範囲であることを特徴とする請求項9に記載の有機感光体。
0.005< Ac/M <0.012 - 前記反応性有機基が、重合性官能基であることを特徴とする請求項1に記載の有機感光体。
- 前記反応性有機基が炭素=炭素二重結合を有する基であることを特徴とする請求項11に記載の有機感光体。
- 前記重合性官能基が、ラジカル重合性官能基であることを特徴とする請求項12に記載の有機感光体。
- 前記保護層の形成が反応性有機基を有するアルミナ粒子相互間での反応により形成されたことを特徴とする請求項1に記載の有機感光体。
- 有機感光体の周辺に、少なくとも帯電手段、露光手段、現像手段を有し、繰り返し画像形成を行う画像形成装置において、該有機感光体が請求項1に記載の有機感光体であることを特徴とする画像形成装置。
- 請求項15に記載の画像形成装置に用いられるプロセスカートリッジであって、少なくとも請求項1に記載の有機感光体と、帯電手段、像露光手段、現像手段の少なくとも1つとを一体として有しており、該画像形成装置に出し入れ可能に構成されることを特徴とするプロセスカートリッジ。
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US20110217651A1 (en) * | 2010-03-08 | 2011-09-08 | Konica Minolta Business Technologies, Inc. | Image formation method and image formation apparatus |
JP2011221381A (ja) * | 2010-04-13 | 2011-11-04 | Konica Minolta Business Technologies Inc | 有機感光体及び画像形成装置 |
US8354212B2 (en) | 2008-09-26 | 2013-01-15 | Konica Minolta Business Technologies, Inc. | Electrophotographic photoreceptor, image forming apparatus, and method for image formation |
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