JP5415783B2 - Charging member, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a charging member, more specifically, a charging member for applying a voltage to charge the surface of an electrophotographic photosensitive member to be charged to a predetermined potential, a process cartridge and an electrophotographic image forming apparatus using the charging member. (Hereinafter referred to as “electrophotographic apparatus”).

  An electrophotographic apparatus adopting an electrophotographic system includes an electrophotographic photosensitive member, a charging device, an exposure device, a developing device, a transfer device, and a fixing device. The charging device applies a voltage (a voltage of only a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage) to a charging member placed in contact with or close to the surface of the electrophotographic photosensitive member to thereby apply the surface of the electrophotographic photosensitive member. Many charging methods are used. From the viewpoint of low cost and low ozone, a contact-type charging method is preferably used. Further, from the viewpoint of low cost and downsizing of the apparatus, a method of applying only a DC voltage as the applied voltage to the charging member (hereinafter referred to as “DC charging method”) is preferably used.

  However, the DC charging method does not have a discharge current leveling effect as in the method of applying a voltage in which an AC voltage is superimposed on a DC voltage. For this reason, discharge unevenness due to minute resistance unevenness of the charging member occurs, and as a result, a streak-like image may occur. Therefore, there is a method for improving the generation of streak-like images by incorporating particles in the surface layer of the charging member used in the DC charging method and forming irregularities on the surface of the charging member, such as Patent Documents 1 and 2. It is disclosed.

  In the method in which particles are included in the surface layer of the charging member and irregularities are formed on the surface of the surface layer of the charging member as in the above-mentioned Patent Document 1 and Patent Document 2, the generation of streak-like images is certainly in the initial stage of use. Sometimes it will be improved. However, even in the above charging member, the charging performance of the charging member deteriorates with use, and a streak-like image may occur in the latter half of the service life. Therefore, as disclosed in Patent Document 3, by making the surface irregularity forming particles conductive, a method capable of maintaining a charging performance even in the latter half of the service life and providing a good image without streak-like images. Is disclosed. However, in recent years, there has been a further demand for longer life of process cartridges and compatibility with various temperature / humidity environments, and accordingly, the life of charging members has been further increased and further under various temperature / humidity environments. Charge stability is required.

JP 2007-178599 A JP 09-258523 A JP 2007-127777 A

  It is an object of the present invention to suppress the generation of streak-like images due to minute resistance unevenness and a decrease in charging performance, and to exhibit stable charging performance even in various temperature and humidity environments and to provide a good image. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus.

The charging member according to the present invention is a charging member having a conductive substrate and a conductive surface layer, and the surface layer includes a binder resin and composite particles dispersed in the binder resin. The surface of the member has convex portions derived from the composite particles, the composite particles have an average particle diameter of 1 μm or more and 30 μm or less, and the core portion is coated with a conductive material, The core portion includes a polymer including units derived from ethylene oxide, and the content of the units derived from ethylene oxide is 20% by mass or more and 100% by mass or less with respect to the polymer. And at least one selected from the group consisting of carbon black, conductive polymer, metal oxide, and metal.
In addition, a process cartridge according to the present invention includes the above-described charging member and a photoconductor, and the charging member and the photoconductor are in a nip with the photoconductor by a convex portion on a surface of the charging member. It is arranged so as to generate a gap and is configured to be detachable from the main body of the electrophotographic apparatus.
Furthermore, an electrophotographic apparatus according to the present invention includes the above-described charging member and a photoconductor, and the charging member and the photoconductor are in a nip with the photoconductor by a convex portion on the surface of the charging member. It arrange | positions so that a space | gap may be produced in.

  The charging member of the present invention suppresses the generation of streak-like images due to minute resistance unevenness and a decrease in charging performance, and exhibits stable charging performance in various temperature and humidity environments. Can be provided.

Sectional drawing of the charging member (roller shape) of this invention is shown. Sectional drawing of the charging member (plate shape) of this invention is shown. Sectional drawing of the charging member (belt shape) of this invention is shown. In the apparatus used for the measurement of the electrical resistance value of the charging roller of the present invention, FIG. (A) Schematic diagram representing the cross section viewed from the axial direction, (b) Schematic diagram representing the cross section viewed from the direction perpendicular to the axial direction, the measurement location of the surface roughness and surface layer thickness of the roller of the present invention, Indicates. 1 is a schematic view showing a cross section of one embodiment of an electrophotographic apparatus of the present invention. 1 is a schematic diagram showing a cross section of one embodiment of a process cartridge of the present invention. FIG.

(Charging member)
Examples of the shape of the charging member of the present invention include various shapes such as a roller shape, a flat plate shape, and a belt shape. FIG. 1 shows a roller-shaped charging member (charging roller), FIG. 2 shows a flat plate-shaped charging member, and FIG. 3 shows a schematic cross-sectional view of the belt-shaped charging member.
The structure of the charging roller includes a conductive support and a surface layer, a conductive support, a conductive elastic layer and a surface layer, a conductive support, a conductive elastic layer and a surface layer, and The thing which has an intermediate | middle layer is mentioned. FIG. 1A shows a charging roller having a conductive support 1 and a surface layer 3, and FIG. 1B shows a charging roller having an elastic layer 2 between the conductive support 1 and the surface layer 3. A charging roller having intermediate layers 21 and 22 between the elastic layer 2 and the surface layer 3 is shown as 1C and 1D, respectively. Hereinafter, a charging roller including a surface layer, a conductive elastic layer, and a conductive support will be described.

(Surface layer)
The surface layer includes a binder resin, a conductive agent, and composite particles dispersed in the binder resin.

(Composite particles)
The composite particles are for forming convex portions on the surface of the charging member. The composite particle includes a polymer including a unit derived from ethylene oxide in the core, and the content of the unit derived from ethylene oxide is 20% by mass or more and 100% by mass or less with respect to the polymer. And the conductive material which coat | covers this core part contains at least 1 sort (s) selected from the group which consists of carbon black, a conductive polymer, a metal oxide, and a metal. As described above, even in a charging member in which particles are contained in the surface layer, the charging performance of the charging member is lowered with use, and a streak-like image may be generated in the latter half of the service life. Therefore, the present inventors decided to use composite particles using an ion conductive material for the core and an electronic conductive material for the covering as the particles to be included in the surface layer. Furthermore, a polymer containing a certain amount of units derived from ethylene oxide was used as the ion conductive material of the core. A charging member made using a material containing a certain amount of units derived from ethylene oxide, such as epichlorohydrin rubber, so-called ionic conductive material, has an electrical resistance increase caused by electrification. It is known to be smaller than the member. Therefore, if an ion conductive material is used, good charging characteristics can be obtained even in the latter half of the endurance life.

  On the other hand, a charging member made using a so-called electronic conductive material such as carbon black, conductive polymer, metal oxide, or metal has a variation in electric resistance in different use environments, for example, a high temperature and high humidity environment and a low temperature and low humidity environment. Is known to be small. From the above, it is considered that when the composite particles according to the present invention are used, deterioration of charging performance due to energization can be prevented and the generation of streak-like images can be suppressed as compared with the case where only an electronic conductive material is used. It is done. Furthermore, by protecting the ion conductive material from the influence of temperature and humidity, it is considered that stable charging performance is exhibited in different temperature and humidity environments and a good image can be provided.

Examples of the conductive material used for covering the core part include carbon black, conductive polymer, metal oxide, and metal.
Examples of the carbon black include carbon powder such as furnace black, thermal black, acetylene black, PAN (polyacrylonitrile) -based carbon, and pitch-based carbon. As furnace black, for example, SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, I-ISAF-HS, HAF-HS, HAF, HAF-LS, T-HS, T-NS, MAF, FEF, There are GPF, SRF-HS-HM, SRF-LM, ECF, FEF-HS and the like. Thermal black includes FT, MT, and the like.
As a conductive polymer, as a host polymer, polyacetylene, poly (p-phenylene), polypyrrole, polythiophenine, poly (p-phenylene oxide), poly (p-phenylene sulfide), poly (p-ferene vinylene), poly (2,6-dimethylphenylene oxide, poly (bisphenol A carbonate), polyvinylcarbazole, polydiacetylene, poly (N-methyl-4-vinylpyridine), polyaniline, polyquinoline, poly (phenylene ether sulfone), etc. the _{material, AsF 5, I 2, Br} 2, SO 3, Na, K, ClO 4, FeCl 3, F, Cl, Br, I, Kr, Li, TCNQ (7,7,8,8- tetracyanoquinodimethane Dimethane) and the like may be mentioned.
Examples of the metal oxide include tin oxide, zinc oxide, indium oxide, titanium oxide, gallium oxide, bismuth oxide, and tin oxide-indium oxide solid solution oxide.
Examples of the metal include aluminum, tin, copper, stainless steel, nickel, silver, cobalt, gold, palladium, and platinum. These conductive materials may be used alone or in combination of two or more, and the coating may have a multilayer structure. Moreover, you may contain another material in the range which does not impair the effect of this invention.

  The following are mentioned as a material used for the core part of the composite particle contained in the surface layer of this invention. Polymers containing units derived from ethylene oxide include poly (ethylene glycol acrylate), poly (ethylene glycol) methyl ether, poly (ethylene glycol) and polyethylene block copolymers, poly (ethylene glycol) and poly (propylene glycol). ) Block copolymer, poly (ethylene glycol) and poly (tetramethylene glycol) block copolymer, and the like. Examples of the copolymer in which the polymer including the unit derived from ethylene oxide further includes an amide bond include polyether amide and polyether amide imide.

  The polyether amide is a copolymer obtained, for example, by reacting a terminal of a polyglycol component with a diamine and a dicarboxylic acid component. The polyether amide can be usually produced according to a known production method.

  The diamine component is illustrated. Examples of the diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine, and phenylene diamine. Further, as the diamine component, it is also possible to use a polyethylene glycol diamine in which both ends are modified to amino groups by reacting acrylonitrile with polyglycol and further carrying out a hydrogenation reaction.

  These diamines use salts formed with the dicarboxylic acid component described above, and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, and hexamethylenediamine-isophthalate. You can also.

  The dicarboxylic acid component is illustrated. Of terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid and 5-sodiumsulfoisophthalic acid Aromatic dicarboxylic acids such as: 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-dicarboxymethylcyclohexane, 1, Alicyclic dicarboxylic acids such as 4-dicarboxymethylcyclohexane and dicyclohexyl-4,4′-dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid), etc. Or a mixture of them.

  Lactam, α, ω-aminocarboxylic acid can also be used as a raw material having the same effect as that of obtaining a polyamide obtained from diamine and dicarboxylic acid. Specifically, aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; Lactams such as caprolactam, enantolactam, capryllactam and laurolactam.

  Polyether amide imide is a copolymer obtained by reacting, for example, a polyamide imide component having an imide ring and a polyglycol component. Polyether amide imide can be normally manufactured in accordance with a well-known manufacturing method. For example, it can be produced by reacting a polyamide composed of lactam, aminocarboxylic acid, diamine, or dicarboxylic acid with an aromatic polycarboxylic acid to form a polyamideimide, and then adding a polyglycol component and polymerizing under high temperature and reduced pressure.

  The polyamideimide component includes a polymer composed of a lactam and a trivalent or tetravalent aromatic polycarboxylic acid or an anhydride thereof capable of forming at least one imide ring. Alternatively, there is a polymer composed of an aminocarboxylic acid and the above aromatic polycarboxylic acid or an anhydride thereof. Alternatively, there is a polymer composed of polyamide composed of diamine or dicarboxylic acid and the above aromatic polycarboxylic acid or its anhydride. And mixtures thereof.

  The aromatic polycarboxylic acid or anhydride thereof is exemplified below. Examples of the trivalent aromatic polycarboxylic acid or its anhydride include the following. 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, diphenylether-3,3′4-tricarboxylic acid Acids, benzophenone-3,3 ', 4-tricarboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid and anhydrides thereof. Examples of the tetravalent aromatic polycarboxylic acid or its anhydride include the following. Pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, diphenylether-2,2', 3,3'-tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic Acids, diphenylsulfone-2,2 ', 3,3'-tetracarboxylic acid and their anhydrides.

  Examples of the copolymer in which the polymer including the unit derived from ethylene oxide further includes an ester bond include polyether ester. The polyether ester is a copolymer obtained by reacting, for example, a polyglycol component, a dicarboxylic acid component, and a diol component. The polyether ester can be usually produced according to a known production method. For example, it can be produced by a method of directly esterifying the three of polyglycol, dicarboxylic acid and aliphatic diol, or a method of transesterifying dicarboxylic acid and aliphatic diol and then polycondensating with polyglycol.

  The diol component is illustrated. An aliphatic group having 2 to 12 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, neoventyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, or Alicyclic diols; bisphenols such as bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) methane, bis (p-hydroxyphenyl) propane; and mixtures thereof.

  Examples of the copolymer in which the polymer including the unit derived from ethylene oxide further includes a urethane bond include polyether urethane. Polyether urethane is a copolymer obtained, for example, by reacting a polyglycol component, an alkylene diisocyanate component, and an alkylene glycol component. Regarding the production method of polyether urethane, it can be produced according to a generally known production method. For example, the method of making it react with alkylene glycol after superposing | polymerizing a urethane prepolymer from polyoxyalkylene glycol is mentioned. An alkylene diisocyanate component is illustrated. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate.

  Examples of the copolymer in which the polymer containing the unit derived from ethylene oxide includes both an amide bond and an ester bond include polyether ester amide. The polyether ester amide is, for example, a copolymer obtained by reacting the polyglycol component, the diamine component, and the dicarboxylic acid component. Regarding the method for producing the polyetheresteramide, it can be usually produced according to a known production method. For example, it is produced by polycondensation using a polyamide-forming monomer, a hydroxyl-terminated polyether and a dicarboxylic acid as starting materials.

  The polymer containing the unit derived from ethylene oxide used for these core parts may use 1 type, or may use 2 or more types together. Moreover, you may make a core part contain another material in the range which does not impair the effect of this invention. These polymers are preferably polymers containing 40% by mass or more of units derived from ethylene oxide and further containing an ester bond or a urethane bond. By adopting such a configuration, it is possible to effectively prevent the charging performance of the charging member from decreasing and the generation of streak-like images in the latter half of the service life. These polymers are preferably synthesized using polyethylene oxide having a number average molecular weight of 1000 or more and 30000 or less. By setting the number average molecular weight within this range, the conductivity of the core portion can be further exhibited. Moreover, it is preferable that the number average molecular weights of these polymers are 5000 or more and 50000 or less. By setting the number average molecular weight within this range, molding stability during granulation can be improved.

(Measurement of mass% of units derived from ethylene oxide)
The mass% of units derived from ethylene oxide in the above-mentioned polymers can be measured using a nuclear magnetic resonance spectrum (hereinafter referred to as “NMR”).

(Measurement of number average molecular weight)
The number average molecular weight of the polymers listed above can be measured using gel permeation chromatography (hereinafter referred to as “GPC”).

(Conductive material coating method)
As a method for coating the core portion with a conductive material, a known method such as a dry method or a wet method can be used. As a dry method, there is a method in which particles forming the core portion are coated with a conductive material using an edge runner, multi mill, conner mill, wet pan mill, high speed mixer, Henschel mixer, planetary mixer or the like. Examples of the wet method include a method in which particles forming the core portion are coated with a conductive material in a solvent. For example, as a method for coating the conductive polymer, particles forming the core portion are added to a solvent composed of one or more of water, acetonitrile, or alcohol such as methanol and ethanol. Thereafter, the particles forming the core portion are stirred in the presence of the conductive polymer or derivative thereof, the oxidizing agent, and the dopant at a temperature of −30 ° C. to 40 ° C. so that the oxidized polymer of the conductive polymer or derivative thereof is formed. Conductive particles coated with can be obtained. Examples of the metal coating method include an electroless plating method. Specifically, it is treated with a metal salt such as palladium chloride, and a metal colloid is deposited on the particles forming the core part to obtain metal colloid-coated particles. Thereafter, the metal layer is deposited on the surface of the particles by treating with an electroless plating solution, whereby the particles forming the core portion can be coated with the metal.

(Average particle diameter of composite particles)
The average particle size of the composite particles is 1 μm or more and 30 μm or less. More preferably, they are 2 micrometers or more and 20 micrometers or less. When the average particle diameter is less than 1 μm, the above-described streak-like image may not be sufficiently suppressed. On the other hand, when the average particle size is larger than 30 μm, an image or a smear image due to overdischarge may occur. The average particle size of the composite particles is calculated as follows. An arbitrary point on the surface layer is cut out with a focused ion beam “FB-2000C” (trade name, manufactured by Hitachi, Ltd.) every 20 nm over 500 μm, and a cross-sectional image thereof is taken. And the image which image | photographed the same particle | grains is combined by 20 nm space | interval, and a three-dimensional particle shape is created. This operation is performed at an arbitrary 100 points. For the average particle diameter of the particles, the projected area is calculated from the three-dimensional particle shape obtained above, and the equivalent circle diameter of the obtained area is calculated. The volume average particle diameter is obtained from the equivalent circle diameter, and the value is defined as the average particle diameter. In addition, the said measuring method is applicable also to the measurement of particle diameters, such as a electrically conductive agent and insulating particles.

(binder)
As the binder used for the surface layer of the present invention, a known binder can be employed. For example, a binder resin, natural rubber, a vulcanized product thereof, rubber such as synthetic rubber, and the like can be used. As the binder resin, a resin such as a thermosetting resin or a thermoplastic resin can be used. Of these, fluorine resin, polyamide resin, acrylic resin, polyurethane resin, silicone resin, butyral resin, and the like are more preferable. The following are mentioned as a synthetic rubber. Ethylene-propylene-diene copolymer (EPDM), styrene-butadiene copolymer rubber (SBR), silicone rubber, urethane rubber, isoprene rubber (IR), butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR ), Acrylic rubber and epichlorohydrin rubber. These may use 1 type, may use 2 or more types together, and may be a copolymer.

(Conductive agent)
The surface layer can be made conductive by containing a conductive agent such as an ionic conductive agent or an electronic conductive agent. The following are mentioned as an ionic conductive agent. Inorganic ionic substances such as lithium perchlorate, sodium perchlorate, calcium perchlorate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, trioctylpropylammonium Cationic surfactants such as bromide, modified aliphatic dimethylethylammonium ethosulphate, zwitterionic surfactants such as lauryl betaine, stearyl betaine, dimethylalkyl lauryl betaine, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, Quaternary ammonium salts such as trimethyloctadecyl ammonium perchlorate, trifluoro Organic acid lithium salts such as lithium methanesulfonate or the like. These can be used alone or in combination of two or more.

  Examples of the electronic conductive agent include metal fine particles, metal oxide fine particles, and carbon powder. Examples of the metal fine particles include aluminum, palladium, iron, copper, silver and the like. Examples of the metal oxide fine particles include titanium oxide, tin oxide, and zinc oxide. Examples of the carbon powder include furnace black, thermal black, acetylene black, PAN (polyacrylonitrile) -based carbon, pitch-based carbon, and the like. Examples of furnace black include the following. For example, SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, I-ISAF-HS, HAF-HS, HAF, HAF-LS, T-HS, T-NS, MAF, FEF, GPF, SRF-HS -HM, SRF-LM, ECF, FEF-HS, etc. Examples of the thermal black include FT and MT.

  Moreover, these electrically conductive agents can be used individually or in combination of 2 or more types. The conductive agent has an average particle diameter of more preferably 0.01 μm to 0.9 μm, and still more preferably 0.01 μm to 0.5 μm. Within this range, the volume resistivity of the surface layer can be easily controlled. The amount of these conductive agents added to the surface layer is suitably in the range of 2 to 80 parts by weight, preferably 20 to 60 parts by weight with respect to 100 parts by weight of the binder resin.

  The surface of the conductive agent may be treated. As the surface treating agent, organosilicon compounds such as alkoxysilanes, fluoroalkylsilanes, polysiloxanes, various titanate-based, aluminate-based and zirconate-based coupling agents, oligomers or polymer compounds can be used. These may be used alone or in combination of two or more. Preferred are organosilicon compounds such as alkoxysilane and polysiloxane, and various coupling agents of titanate, aluminate or zirconate.

  When carbon black is used as a conductive agent, it is preferably used as composite conductive fine particles in which metal oxide fine particles are coated with carbon black. Since carbon black forms a structure, it tends to be difficult for the carbon black to exist uniformly with respect to the binder. When carbon black is used as composite conductive fine particles coated with a metal oxide, the conductive agent can be uniformly present in the binder, and the volume resistivity can be controlled more easily. Examples of the metal oxide fine particles used for this purpose include metal oxides and composite metal oxides. Specifically, examples of the metal oxide include zinc oxide, tin oxide, indium oxide, titanium oxide (such as titanium dioxide and titanium monoxide), iron oxide, silica, alumina, magnesium oxide, and zirconium oxide. Examples of the composite metal oxide include strontium titanate, calcium titanate, magnesium titanate, barium titanate, and calcium zirconate. The metal oxide fine particles are preferably surface-treated. As the surface treatment, organosilicon compounds such as alkoxysilane, fluoroalkylsilane and polysiloxane, titanate-based, aluminate-based and zirconate-based coupling agents, oligomers or polymer compounds can be used. These may use 1 type or may use 2 or more types together.

(Other ingredients)
The surface layer can contain other materials as long as the effects of the present invention are not impaired. Examples of other materials include insulating particles made of a polymer compound and a release agent. Examples of the insulating particles made of a polymer compound include the following. Polyamide resin, silicone resin, fluororesin, (meth) acrylic resin, styrene resin, phenol resin, polyester resin, melamine resin, urethane resin, olefin resin, epoxy resin, resins such as copolymers, modified products, and derivatives, Ethylene-propylene-diene copolymer (EPDM), styrene-butadiene copolymer rubber (SBR), silicone rubber, urethane rubber, isoprene rubber (IR), butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR ), Rubber such as epichlorohydrin rubber, polyolefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, polystyrene-based thermoplastic elastomer, fluororubber-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide Thermoplastic elastomers, polybutadiene type thermoplastic elastomers, ethylene vinyl acetate type thermoplastic elastomers, polyvinyl chloride thermoplastic elastomer, and thermoplastic elastomers such as chlorinated polyethylene based thermoplastic elastomer. In particular, (meth) acrylic resin, styrene resin, urethane resin, fluororesin, and silicone resin are preferable.
Further, the surface layer may contain a release agent in order to improve the release property of the surface. By including a release agent in the surface layer, it is possible to prevent dirt from adhering to the surface of the charging member. Further, the relative movement between the charging member and the photosensitive member becomes smooth, and the occurrence of an irregular movement state such as stick-slip is reduced. As a result, the occurrence of irregular wear on the surface of the charging member, the generation of abnormal noise, and the like are suppressed. When the release agent is a liquid, it also acts as a leveling agent when forming the surface layer.

  As such a release agent, those having low surface energy, those having slidability, and the like can be used, and those having solid and liquid properties can be used. Specifically, it is a metal oxide such as graphite, graphite fluoride, molybdenum disulfide, tungsten disulfide, boron nitride, lead monoxide. In addition, oil- or solid-state (release resin or powder thereof, a part of the polymer into which a part having release property is introduced) silicon or fluorine-containing compound, wax, higher fatty acid, salt thereof , Esters and other derivatives can also be used.

  The surface layer of the present invention preferably has a thickness of 0.1 μm or more and 100 μm or less. More preferably, they are 1 micrometer or more and 50 micrometers or less. The film thickness of the surface layer can be measured by cutting the roller cross section with a sharp blade at the position shown in FIGS. 5A and 5B and observing it with an optical microscope or an electron microscope.

  The surface layer may be subjected to a surface treatment. Examples of the surface treatment include a surface processing treatment using UV or electron beam, and a surface modification treatment for adhering and / or impregnating a compound or the like on the surface.

  The surface layer can be formed by a coating method such as electrostatic spray coating or dipping coating. Or it can also form by adhere | attaching or coat | covering the sheet-shaped or tube-shaped layer beforehand formed into a predetermined film thickness. Alternatively, a method of curing and molding the material into a predetermined shape in the mold can also be used. Among these, it is preferable to apply a paint by a coating method to form a coating film.

  When the layer is formed by a coating method, the solvent used in the coating solution may be any solvent that can dissolve the binder. Specific examples include the following. Alcohols such as methanol, ethanol, isopropanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran, dioxane, ethylene Ethers such as glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aromatic compounds such as xylene, ligroin, chlorobenzene and dichlorobenzene. As a method for dispersing the binder, conductive agent, particles, and the like in the coating solution, known solution dispersing means such as a ball mill, a sand mill, a paint shaker, a dyno mill, and a pearl mill can be used.

The volume resistivity of the surface layer is preferably 1 × 10 ³ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less in a 23 ° C./50% RH environment. By setting the volume resistivity of the surface layer within the above range, even when a pinhole is generated in the photoconductor, the entire longitudinal direction of the pinhole portion becomes a strip-like charging defect and hardly appears in an image. Further, the photoconductor can be charged to a predetermined potential, and the image can have a desired density. The volume resistivity of the surface layer can be measured, for example, by the following method. First, the surface layer is peeled off from the roller state and cut into strips of about 5 mm × 5 mm. Metal is vapor-deposited on both surfaces to produce an electrode and a guard electrode, and a measurement sample is obtained. Alternatively, it is applied on an aluminum sheet to form a surface layer coating film, and a metal for vapor deposition is deposited on the coating film surface to obtain a measurement sample. A voltage of 200 V is applied to the obtained measurement sample using a microammeter (trade name: ADVANTEST R8340A ULTRA HIGH RESISTANCE METER, manufactured by Advantest Corporation). Then, the current after 30 seconds is measured and calculated from the thickness of the sample and the electrode area. In addition, the said measuring method is applicable also to the measurement of the volume resistivity of a conductive elastic layer. In addition, the ten-point average roughness (Rzjis) of the surface layer, that is, the surface of the charging member, is preferably 3 μm or more and 20 μm or less in order to exhibit stable charging performance.

(Conductive elastic layer)
Since the charging roller of the present invention is used in contact with the electrophotographic photosensitive member, it is more preferable to have elasticity. In the present invention, preferably, the conductive elastic layer 2 is formed on the outer periphery of the conductive support 1. The conductive elastic layer 2 is made of a conductive elastic body. The conductive elastic body is formed, for example, by dispersing a conductive agent in a polymer elastic body. As the conductive agent, the above-described ionic conductive agent or electronic conductive agent can be used. The amount of the conductive agent is such that the volume resistivity of the conductive elastic body is a low temperature and low humidity environment (15 ° C./10% RH), a normal temperature and normal humidity environment (23 ° C./50% RH), and a high temperature high humidity environment (30 ° C. / 80% RH) and the volume resistivity is preferably 1 × 10 ³ Ω · cm or more and 1 × 10 ⁹ Ω · cm or less. By setting the volume resistivity of the conductive elastic layer within the above range, it is possible to suppress the occurrence of a band-like image defect on the image even when there is a pinhole in the photosensitive member as the member to be charged. Further, it is not necessary to apply a high voltage in order to obtain a desired charging potential.

  Examples of the polymer elastic body include the following. For example, synthetic rubbers such as epichlorohydrin rubber, acrylonitrile-butadiene rubber, chloroprene rubber, urethane rubber, and silicone rubber. Alternatively, thermoplastic elastomers such as styrene / butadiene / styrene block copolymers and styrene / ethylene butylene / styrene block copolymers may be used. As the polymer elastic body, epichlorohydrin rubber is particularly preferably used. In the epichlorohydrin rubber, the polymer itself has conductivity in the middle resistance region, and good conductivity is exhibited even if the addition amount of the conductive agent is small. Moreover, since the variation in electric resistance depending on the position can be reduced, it is suitably used as a polymer elastic body. Examples of the epichlorohydrin rubber include an epichlorohydrin homopolymer, an epichlorohydrin-ethylene oxide copolymer, an epichlorohydrin-allyl glycidyl ether copolymer, and an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Of these, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is particularly preferably used since it exhibits stable conductivity in a medium resistance region. The epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer can control conductivity and workability by arbitrarily adjusting the degree of polymerization and composition ratio.

  In addition, plasticizers, fillers, vulcanizing agents, vulcanization accelerators, anti-aging agents, scorch preventing agents, dispersants and release agents may be added to the conductive elastic body as necessary. You can also.

  The conductive elastic layer is preferably formed by a known method such as extrusion molding, injection molding, or compression molding after mixing the raw materials of the conductive elastic body with a closed mixer. The conductive elastic layer may be produced by directly forming a conductive elastic body on a conductive support. Alternatively, a conductive elastic body previously formed into a tube shape may be formed on the conductive support. Note that the surface may be polished and the shape may be adjusted after the production of the conductive elastic layer.

  The hardness of the conductive elastic layer is preferably 70 ° or less, more preferably 60 ° or less in terms of micro hardness (MD-1 type). By setting the micro hardness (MD-1 type) within the above range, the nip width between the charging member and the photosensitive member can be appropriately adjusted, and the contact pressure can be prevented from becoming excessively large. In addition, "micro hardness (MD-1 type)" is the hardness of the charging member measured using Asker micro rubber hardness meter MD-1 type (trade name, manufactured by Kobunshi Keiki Co., Ltd.). Specifically, the hardness meter is a value measured in a peak hold mode of 10 N with respect to a charging member left for 12 hours or more in an environment of normal temperature and normal humidity (23 ° C./55% RH).

The charging roller of the present invention usually has a volume resistivity of 1 × 10 ⁴ Ω · cm or more and 1 × 10 ¹⁰ Ω in a 23 ° C./50% RH environment in order to improve the charging of the photoreceptor. -It is preferable that it is cm or less. As an example, FIG. 4 shows a method for measuring the electrical resistance of the charging roller. Both ends of the conductive support 1 are brought into contact with a cylindrical metal 32 having the same curvature as that of the photosensitive member by a bearing 33 under load so as to be parallel to each other. In this state, the cylindrical metal 32 is rotated by a motor (not shown), and the charging roller 5 abutted thereby is driven to rotate. Then, a DC voltage of −200 V is applied from the stabilized power supply 34. The current flowing at this time is measured by an ammeter 35, and the resistance of the charging roller is calculated. Here, the load is 4.9 N, the metal cylinder has a diameter of 30 mm, and the rotation of the metal cylinder has a peripheral speed of 45 mm / sec. The charging roller of the present invention preferably has a so-called crown shape in which the central portion in the longitudinal direction is the thickest and narrows toward both ends in the longitudinal direction from the viewpoint of making the longitudinal nip width uniform with respect to the photoreceptor. . The crown amount is preferably such that the difference between the outer diameter at the center and the outer diameter at a position 90 mm away from the center is not less than 30 μm and not more than 200 μm.
A method for measuring the ten-point average roughness Rzjis on the surface of the charging roller and the average unevenness Sm on the surface is shown below. Measured based on JIS B0601 (1994) and performed using a surface roughness measuring instrument “SE-3400” (trade name, manufactured by Kosaka Laboratory Ltd.). Here, the measurement conditions were cut-off value: 0.8 mm, filter: Gaussian, preliminary length: cut-off × 2, leveling: straight line (entire area), evaluation length: 8 mm. Note that Rzjis is obtained by randomly measuring six charging members, and taking the average value of the values obtained at each point as the Rzjis of the charging member. Similarly, Sm is measured at six random locations on the charging member, and the average value of the values obtained at each location is taken as Sm of the charging member.

(Conductive support)
The conductive support used in the charging member of the present invention is conductive and has a function of supporting a surface layer, an elastic layer, and the like provided on the support. Examples of the material include metals such as iron, copper, stainless steel, aluminum, nickel, and alloys thereof. In addition, for the purpose of imparting scratch resistance to these surfaces, plating treatment or the like may be performed as long as the conductivity is not impaired. Furthermore, as the conductive support, those made of a resin base material coated with a metal or the like to be surface conductive or those manufactured from a conductive resin composition can be used. The conductive support and the conductive elastic layer to be described later, or sequentially laminated layers (for example, the elastic layer and surface layer shown in 1B) may be bonded via an adhesive. In this case, the adhesive is preferably conductive. In order to make it conductive, the adhesive may have a known conductive agent. Examples of the binder of the adhesive include thermosetting resins and thermoplastic resins, and known ones such as urethane, acrylic, polyester, polyether, and epoxy can be used. As a conductive agent for imparting conductivity to the adhesive, it can be appropriately selected from the conductive agents described above, and can be used alone or in combination of two or more.

(Electrophotographic equipment)
FIG. 6 is a schematic configuration diagram of an electrophotographic apparatus according to the present invention. A charging device 5 for charging the photosensitive member 4 as a member to be charged, a latent image forming device 11 for performing exposure, a developing device 6 for developing a toner image, a transfer device 8 for transferring to a transfer material 7, and a transfer toner on the photosensitive member. It comprises a cleaning device 10 for collecting, a fixing device 9 for fixing a toner image, and the like.
The photoreceptor 4 is a rotary drum type having a photosensitive layer on a conductive substrate. The photoreceptor is driven to rotate in the direction of the arrow at a predetermined peripheral speed (process speed).
The charging device 5 includes a contact-type charging roller that is placed in contact with the photosensitive member by being pressed with a predetermined force. The charging roller is a driven rotating roller that rotates in accordance with the rotation of the photosensitive member, and charges the photosensitive member to a predetermined potential by applying a predetermined DC voltage from a charging power source. For example, an exposure apparatus such as a laser beam scanner is used as the latent image forming apparatus 11 that forms an electrostatic latent image on the photosensitive member. An electrostatic latent image is formed by performing exposure corresponding to image information on a uniformly charged photoconductor.
The developing device 6 has a contact-type developing roller disposed close to or in contact with the photoreceptor. The toner electrostatically processed to the same polarity as the photosensitive member charge polarity is developed by reversal development to visualize and develop the electrostatic latent image into a toner image. The transfer device 8 has a contact-type transfer roller. The toner image is transferred from the photosensitive member to a transfer material 7 such as plain paper (the transfer material is conveyed by a paper feed system having a conveying member). The cleaning device 10 has a blade-type cleaning member and a collection container, and after transferring, mechanically scrapes and collects transfer residual toner remaining on the photosensitive member. Here, it is also possible to remove the cleaning device by adopting a development simultaneous cleaning system in which the transfer device collects the transfer residual toner.
The fixing device 9 is composed of a heated roll or the like, fixes the transferred toner image, and discharges the toner image to the outside of the apparatus. It is also possible to use a process cartridge designed such that the photoreceptor 4, the charging device 5, the developing device 6, the cleaning device 10, and the like are integrated and detachable from the image forming apparatus. An example is shown in FIG. This is a process cartridge that is detachably attached to the main body of the image forming apparatus, in which the photosensitive member 4, the charging roller 5, the developing roller 6, the elastic regulation blade 13, the toner supply roller 14, and the cleaning blade 10 are integrally supported. . Further, in the present invention, the charging member is integrated with the member to be charged, and the convex portion on the surface of the charging member creates a gap in the nip portion with the member to be charged, and is detachable from the main body of the electrophotographic apparatus. Process cartridge.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the scope of the present invention is not limited thereto.

(Production of composite particles)
(Production Example 1)
A polymer containing units derived from ethylene oxide was prepared. Put 32 parts by mass of dimethyl terephthalate, 20 parts by mass of ethylene glycol, 0.02 parts by mass of manganese acetate tetrahydrate in a stainless steel autoclave, heat at 200 ° C. for 3 hours, and evaporate the produced methanol while distilling off the generated methanol. An exchange reaction was performed. Next, 49 parts by mass of terminal diamine-modified polyethylene glycol (number average molecular weight 890), 0.03 parts by mass of antimony trioxide, and 0.015 parts by mass of trimethyl phosphate were further added, and the temperature was raised to 260 ° C. Thereafter, the inside of the autoclave was depressurized to 1 torr or less, and the polymerization reaction was carried out for 3 hours while maintaining the pressure at 1 torr or less while distilling off excess ethylene glycol. Thereafter, purification was performed and pulverization was performed after pelletization to obtain a powdery polyetheramide copolymer. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 1.

(Production Example 2)
A stainless steel autoclave was charged with 30.0 parts by mass of ε-caprolactam, 6 parts by mass of trimellitic anhydride, 58 parts by mass of polyethylene glycol (number average molecular weight 980), and 0.3 parts by mass of an antioxidant. Next, dehydration was performed for 30 minutes under reduced pressure of 1 torr or less while stirring at 100 ° C. Next, the temperature was raised to 260 ° C. while flowing nitrogen at a rate of 60 ml per minute, and after carrying out the polymerization reaction for 4 hours, the pressure was reduced and unreacted ε-caprolactam was distilled off at 1 torr or less for 3 hours. Next, 0.4 parts by mass of tetrabutyl titanate was added, and a polymerization reaction was carried out for 8 hours under reduced pressure of 1 Torr or less. Thereafter, purification was performed and pulverization was performed after pelletization to obtain a powdery polyetheramide imide copolymer. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 2.

(Production Example 3)
A powdered polyetheramide copolymer was obtained in the same manner as in Production Example 1 except that the amount of polyethylene glycol charged in Production Example 1 was changed to 20 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 21% by mass. This is designated as Polymer 3.

(Production Example 4)
A powdery polyetheramide copolymer was obtained in the same manner as in Production Example 1 except that the amount of polyethylene glycol charged in Production Example 1 was changed to 4750 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52,000, and the content of ethylene oxide-derived units measured by NMR was 98% by mass. This is designated as Polymer 4.

(Production Example 5)
Put 32 parts by mass of dimethyl terephthalate, 20 parts by mass of ethylene glycol and 0.02 parts by mass of manganese acetate tetrahydrate in a stainless steel autoclave, heat at 200 ° C for 3 hours, and transesterify while distilling off the produced methanol. The reaction was carried out. Next, 49 parts by mass of polyethylene glycol (number average molecular weight 980), 0.03 parts by mass of antimony trioxide, and 0.015 parts by mass of trimethyl phosphate were further added, and the temperature was raised to 260 ° C. Thereafter, the inside of the autoclave was decompressed, and the polymerization reaction was carried out for 3 hours while maintaining the pressure at 1 Torr or less while distilling off excess ethylene glycol. Thereafter, purification was performed and pulverization was performed after pelletization to obtain a powdery polyether ester copolymer. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 5.

(Production Example 6)
50 parts of a prepolymer obtained by reacting 100 parts by mass of polyethylene glycol (number average molecular weight 980) and 150 parts by mass of HDI was kneaded with a twin screw extruder at 200 ° C. and a residence time of 30 seconds. Then, it was taken out into a strand shape and pulverized after pelletizing to obtain a powdery polyetherurethane copolymer. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 6.

(Production Example 7)
A powdery polyether ester copolymer was obtained in the same manner as in Production Example 5 except that the amount of polyethylene glycol charged in Production Example 5 was changed to 33 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of units derived from ethylene oxide measured by NMR was 42% by mass. This is designated as Polymer 7.

(Production Example 8)
In Production Example 5, a powdery polyether ester copolymer was obtained in the same manner as in Production Example 5 except that the amount of polyethylene glycol charged was changed to 1600 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52,000, and the content of ethylene oxide-derived units measured by NMR was 98% by mass. This is designated as Polymer 8.

(Production Example 9)
In Production Example 5, a powdery polyetherester copolymer was obtained in the same manner as in Production Example 5 except that the amount of polyethylene glycol charged was changed to 40 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of units derived from ethylene oxide measured by NMR was 38% by mass. This is designated as Polymer 9.

(Production Example 10)
Put 83.5 parts by mass of ε-caprolactam, 16.5 parts by mass of adipic acid, 0.3 parts by mass of antioxidant, and 6 parts by mass of water in a stainless steel autoclave. After replacing the inside of the autoclave with nitrogen, pressurize at 220 ° C. The mixture was heated and stirred for 4 hours in a sealed state to react. Thereafter, the pressure was reduced and unreacted ε-caprolactam was distilled off at 1 torr or less for 3 hours to obtain polyamide. Next, 160 parts by mass of polyethylene glycol (number average molecular weight 980) and 0.5 parts by mass of zirconyl acetate were further added, and a polymerization reaction was carried out at 245 ° C. under reduced pressure of 1 torr or less for 5 hours. Thereafter, purification was performed and pulverization was performed after pelletization to obtain a powdery polyetheresteramide copolymer. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 10.

(Production Example 11)
In Production Example 10, a powdery polyetheresteramide copolymer was obtained in the same manner as in Production Example 10, except that the amount of polyethylene glycol charged was changed to 65 parts by mass. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 52000, and the content of units derived from ethylene oxide measured by NMR was 38% by mass. This is designated as Polymer 11.

(Production Example 12)
A powdery polyetherester copolymer was obtained in the same manner as in Production Example 5 except that polyethylene glycol having a number average molecular weight of 5000 was used in Production Example 5. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 65,000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 12.

(Production Example 13)
In Production Example 12, a powdery polyether ester copolymer was obtained in the same manner as in Production Example 12 except that the polymerization time was changed to 1.5 hours. The average particle size of this powder was 10 μm, the number average molecular weight measured by GPC was 35000, and the content of units derived from ethylene oxide measured by NMR was 60% by mass. This is designated as Polymer 13.

(Production Example 14)
A powdered polyetheramide copolymer was obtained in the same manner as in Production Example 1 except that terminal diamine-modified polyethylene glycol having a number average molecular weight of 5000 was used in Production Example 1. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 65,000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 14.

(Production Example 15)
A powdered polyetheramide copolymer was obtained in the same manner as in Production Example 14 except that the polymerization time was changed to 1.5 hours in Production Example 14. The average particle size of this powder was 10 μm, the number average molecular weight measured by GPC was 35000, and the content of units derived from ethylene oxide measured by NMR was 60% by mass. This is designated as Polymer 15.

(Production Example 16)
In Production Example 10, a powdery polyetheresteramide copolymer was obtained in the same manner as in Production Example 10 except that polyethylene glycol having a number average molecular weight of 5000 was used. The average particle diameter of this powder was 10 μm, the number average molecular weight measured by GPC was 65,000, and the content of ethylene oxide-derived units measured by NMR was 60% by mass. This is designated as Polymer 16.

(Production Example 17)
A powdery polyetheresteramide copolymer was obtained in the same manner as in Production Example 16 except that the polymerization time was changed to 1.5 hours in Production Example 16. The average particle size of this powder was 10 μm, the number average molecular weight measured by GPC was 35000, and the content of units derived from ethylene oxide measured by NMR was 60% by mass. This is designated as Polymer 17.

(Production Example 18)
A polyethylene oxide-polyethylene copolymer powder was prepared as a polymer containing units derived from ethylene oxide. The average particle size of this powder is 10 μm, the number average molecular weight measured by GPC is 3950, the number average molecular weight measured by GPC of polyethylene glycol used for polymerization is 910, and the content of ethylene oxide-derived units measured by NMR is It was 55% by mass. This is designated as Polymer 18.

(Production Example 19)
A polyethylene oxide-polyethylene copolymer powder was prepared as a polymer containing units derived from ethylene oxide. The average particle size of this powder is 10 μm, the number average molecular weight measured by GPC is 3950, the number average molecular weight measured by GPC of polyethylene glycol used for polymerization is 910, and the content of ethylene oxide-derived units measured by NMR is It was 21% by mass. This is designated as Polymer 19.

(Production Example 20)
A polyethylene oxide-polyethylene copolymer powder was prepared as a polymer containing units derived from ethylene oxide. The average particle size of this powder is 10 μm, the number average molecular weight measured by GPC is 3950, the number average molecular weight measured by GPC of polyethylene glycol used for polymerization is 910, and the content of ethylene oxide-derived units measured by NMR is It was 98 mass%. This is designated as Polymer 20.

(Production Example 21)
A polyethylene oxide polymer powder was prepared as a polymer containing units derived from ethylene oxide. The average particle size of this powder was 10 μm, and the number average molecular weight measured by GPC was 52,000. This is designated as Polymer 21.

(Production Example 22)
A polyethylene oxide-polyethylene copolymer powder was prepared as a polymer containing units derived from ethylene oxide. The average particle size of this powder is 10 μm, the number average molecular weight measured by GPC is 3950, the number average molecular weight measured by GPC of polyethylene glycol used for polymerization is 910, and the content of ethylene oxide-derived units measured by NMR is It was 18 mass%. This is designated as Polymer 22.

  Next, an example of producing composite particles having the polymers 1 to 22 as a core part is shown.

(Production Example 23)
5.0 kg of the polymer 1 powder and 5.0 kg of carbon black particles (particle diameter 20 nm) are added to the running edge runner over 10 minutes, and a line of 588 N / cm (60 kg / cm) is added. The mixture was stirred for 60 minutes under load. Thereafter, the composite particles 1 were obtained by drying at room temperature for 60 minutes.

(Production Example 24)
17 g of ferric chloride hexahydrate was dissolved in 250 ml of acetonitrile, 30 g of the polymer 1 powder was added thereto, and the mixture was stirred and dispersed while cooling to 0 ° C. Next, while maintaining the liquid temperature at 0 to 5 ° C., 40 ml of acetonitrile solution containing 1.7 g of pyrrole was added and stirred for 1 hour. Then, the composite particles 2 were obtained by filtering, washing with water and methanol, and drying.

(Production Example 25)
A composite particle 3 was obtained in the same manner as in Production Example 23, except that the carbon black particles were replaced with tin oxide (particle diameter 40 nm) in Production Example 23.

(Production Example 26)
A plating solution consisting of 50 g of powder of polymer 1, 32 g of copper chloride, 400 g of 25% ammonia water, 68 g of disodium ethylenediaminetetraacetate, 5.8 g of hydrazine, and 600 g of ion-exchanged water. Electrolytic plating was performed to form a coating layer. Thereafter, centrifugal dehydration, washing with water and drying were performed to obtain composite particles 4.

(Production Example 27)
The powder of the polymer 1 was subjected to classification treatment, and the particle size was prepared by collecting the fine powder side. Otherwise in the same manner as in Production Example 23, composite particles 5 were obtained.

(Production Example 28)
The powder of the polymer 1 was subjected to a classification treatment, and the particle diameter was prepared by collecting the coarse powder side. Otherwise in the same manner as in Production Example 23, composite particles 6 were obtained.

(Production Examples 29 to 49)
Instead of the polymer 1 powder, polymers 2 to 20 were used. Otherwise in the same manner as in Production Example 23, composite particles 7 to 27 were obtained.

(Production Example 50)
The powder of the polymer 1 was subjected to classification treatment, and the particle size was prepared by collecting the fine powder side. Otherwise in the same manner as in Production Example 23, composite particles 28 were obtained.

(Production Example 51)
The powder of the polymer 1 was subjected to a classification treatment, and the particle diameter was prepared by collecting the coarse powder side. Otherwise, composite particles 29 were obtained in the same manner as in Production Example 23. Table 1 shows the average particle diameters of the composite particles 1 to 29 thus obtained.

(Production Example 52)
(Preparation of conductive fine particles)
To 7.0 kg of silica particles (average particle diameter 15 nm, volume resistivity 1.8 × 10 ¹² Ω · cm), 140 g of methyl hydrogen polysiloxane was added while operating the edge runner, and 588 N / cm (60 kg / cm ) Was mixed and stirred for 30 minutes. The stirring speed at this time was 22 rpm.
Into this, 7.0 kg of carbon black particles (particle diameter 20 nm, volume resistivity 1.0 × 10 ² Ω · cm, pH 6.0) was added over 10 minutes while operating the edge runner, and further 588 N / The mixture was stirred for 60 minutes with a linear load of cm (60 kg / cm). After carbon black was adhered to the surface of the silica particles coated with methylhydrogenpolysiloxane in this manner, drying was performed at 80 ° C. for 60 minutes using a dryer to obtain conductive fine particles. The stirring speed at this time was 22 rpm. The obtained conductive fine particles had an average particle diameter of 15 nm and a volume resistivity of 1.1 × 10 ² Ω · cm.

(Production Example 53)
(Production of surface-treated titanium oxide particles)
1000 g of acicular rutile-type titanium oxide particles (average particle diameter 15 nm, length: width = 3: 1, volume resistivity 2.3 × 10 ¹⁰ Ω · cm), 110 g of isobutyltrimethoxysilane as a surface treatment agent, and toluene as a solvent A slurry was prepared by blending 3000 g.
This slurry was mixed with a stirrer for 30 minutes, and then supplied to Viscomill in which 80% of the effective internal volume was filled with glass beads having an average particle diameter of 0.8 mm, and wet crushing was performed at a temperature of 35 ± 5 ° C. .
Toluene was removed from the slurry obtained by wet pulverization by vacuum distillation (bath temperature: 110 ° C., product temperature: 30-60 ° C., degree of vacuum: about 100 Torr) using a kneader, and the surface was kept at 120 ° C. for 2 hours. The treating agent was baked. The baked particles were cooled to room temperature and then pulverized using a pin mill to obtain surface-treated titanium oxide particles.

Production Example 54 (Production of conductive elastic roller)
Epichlorohydrin rubber 100 parts by mass (epichlorohydrin: ethylene oxide: allyl glycidyl ether = 40 mol%: 56 mol%: 4 mol%)
Tetrabutylammonium perchlorate 1 part by weight Heavy calcium carbonate 60 parts by weight Carbon black (MT thermal) 5 parts by weight Zinc oxide 5 parts by weight Zinc stearate 1 part by weight 2-Mercaptobenzimidazole 0.5 parts by weight Sebacic acid polyester 5 parts by weight Part

The raw materials were kneaded for 10 minutes with a pressure kneader whose temperature was adjusted to 100 ° C. Furthermore, 1 part by mass of tetramethylthiuram monosulfide as a vulcanization accelerator and 2 parts by mass of sulfur as a vulcanizing agent were added and further kneaded for 10 minutes with an open roll adjusted to 25 ° C. to prepare a raw material compound. .
The conductive support used was a steel cylindrical shaft having a diameter of 6 mm and a length of 256 mm, the surface of which was nickel-plated. Thermosetting adhesive containing metal and rubber in a region up to 115 mm on both sides across the center in the axial direction of the cylindrical surface (a region with an axial width of 230 mm) (carbon content 2 mass%, methyl isobutyl ketone content 50 mass) %) Was applied. This was heated at 80 ° C. for 30 minutes and then further heated at 160 ° C. for 30 minutes to obtain a conductive support coated with an adhesive.
The resulting compound is formed into a roller around the conductive support under the condition that the screw rotation speed is 15 rpm, the cylinder temperature and the head temperature are adjusted to 70 ° C. by a rubber extruder (inner diameter 50 mm, L / D 20). Molded as follows. The roller-shaped molding was vulcanized and the adhesive was cured in an electric oven at 160 ° C. for 30 minutes. Next, both ends of the rubber part were removed, and the longitudinal width of the conductive elastic layer part was 232 mm. Thereafter, the rubber portion is polished by a plunge polishing machine (grinding stone GC120, grinding wheel diameter φ300 mm, grinding wheel rotation speed 2500 rpm, roller rotation speed 333 rpm), and a crown-shaped conductive elasticity having an end diameter of 8.3 mm and a central diameter of 8.5 mm. Got Laura.

Example 1
(Preparation of surface layer paint)
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 14% by mass.
The following components were added to 714.3 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.
Conductive fine particles 45 parts by mass Surface-treated titanium oxide particles 20 parts by mass Modified dimethyl silicone oil 0.2 parts by mass Blocked isocyanate mixture (* 1) 80.14 parts by mass At this time, the blocked isocyanate mixture is represented by “NCO / OH = 1.0 ”.
(* 1) A 7: 3 mixture of each butanone oxime block of HDI and isophorone diisocyanate (IPDI).
200 g of the above mixed solution was placed in a glass bottle having an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 18 hours using a paint shaker disperser. After the dispersion, 10 parts by mass of the composite particle 1 produced in Production Example 23 was added. Thereafter, dispersion was performed for 5 minutes, and the glass beads were removed to obtain a surface layer coating material.

(Preparation of charging roller 1)
Using the above surface layer coating material, the conductive elastic roller produced in Production Example 54 was dipped once. After air drying at room temperature for 30 minutes or more, it was dried with a hot air circulating dryer at 80 ° C. for 1 hour and further at 160 ° C. for 1 hour to obtain a charging roller 1 having a surface layer formed on the conductive elastic layer. Here, the dipping coating is as follows. The dipping coating descending speed was 30 mm / s, the dipping time was 9 seconds, the dipping coating lifting speed was the initial speed of 20 mm / s, and the final speed was 2 mm / s, while the speed was changed linearly with respect to time.

(Measurement of physical properties of charging roller)
The ten-point average roughness Rzjis of the obtained charging roller 1 was measured by the method described above. The results are shown in Table 1.

(An endurance test)
As an electrophotographic apparatus having the configuration shown in FIG. 6, a color laser jet printer (Color Laser Jet 3800, trade name, manufactured by Hewlett Packard) is modified to a recording medium output speed of 200 mm / sec (A4 vertical output). It was. The resolution of the image is 600 dpi, and the primary charging output is a DC voltage of −1100V. As the process cartridge having the configuration shown in FIG. 7, the process cartridge for the printer was used (for black). The attached charging roller was removed from the process cartridge, and the charging roller 1 of the present invention was set. Then, the durability test was performed under two kinds of environments: a 23 ° C./50% RH environment (hereinafter referred to as “environment 1”) and a 15 ° C./10% RH environment (hereinafter referred to as “environment 2”). Specifically, an endurance test was performed in which a plurality of images having a printing density of 5% (an image in which a horizontal line having a width of 2 dots and an interval of 50 dots is drawn in the direction perpendicular to the rotation direction of the photosensitive member) are printed. In environment 1 and environment 2, images after output of 6,000 images (hereinafter referred to as “image 1” and “image 2”, respectively), and in environment 1, in addition to image 1, images after output of 12,000 images The streak-like images were evaluated for a total of three types of images (hereinafter referred to as “image 3”). A halftone image (an image in which a horizontal line having a width of 1 dot and an interval of 2 dots is drawn in the direction perpendicular to the rotation direction of the photosensitive member) was output as the evaluation image. The evaluation results are shown in Table 1. Here, the evaluation criteria are as follows.
Rank 5: Generation of streak-like images is not recognized.
Rank 4: Although a very slight streak-like image is recognized, it is a level that can hardly be confirmed.
Rank 3: A streak-like image can be confirmed in part, but the image quality has no practical problem.
Rank 2: A streak-like image is conspicuous and a decrease in image quality is recognized.
Rank 1: A streak-like image occurs in the entire area, and the image quality is remarkably deteriorated.

In Example 1, the rank of the image 1 is 5, the rank of the image 2 is 4, and the rank of the image 3 is 4, and a good image is obtained.

(Examples 2 to 26)
A charging roller was produced in the same manner as in Example 1 except that the addition amount and type of the composite particles were changed as shown in Table 1. In the manufactured charging roller, the physical property measurement and the streak-like image were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
A charging roller was produced in the same manner as in Example 1 except that the composite particles shown in Table 1 were used.
In the manufactured charging roller, the physical property measurement and the streak-like image were evaluated in the same manner as in Example 1. The results are shown in Table 1.
In Comparative Example 1, a streak-like image was conspicuous in image 1 (rank 2), and a streak-like image occurred in image 2 in all areas (rank 1). And the rank of the image 3 is 1, and the deterioration of the image quality is recognized.

(Comparative Examples 2 to 5)
A charging roller was produced in the same manner as in Example 1 except that the addition amount and type of the composite particles were changed as shown in Table 1. In the manufactured charging roller, the physical property measurement and the streak-like image were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 6)
In Example 1, a charging roller was produced in the same manner as in Example 1 except that crosslinked acrylic particles (average particle size: 9.95 μm) were used instead of the composite particles. In the manufactured charging roller, the physical property measurement and the streak-like image were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Reference Example 1)
A charging roller was produced in the following manner.
First, conductive carbon particles were produced in the following manner.
The phenol resin particles having an average particle size of 12.0 μm were subjected to air classification to obtain particles having an average particle size of 12.0 μm. The obtained particles were heat-stabilized at 300 ° C. for 1 hour in an oxidizing atmosphere, and then calcined at 2200 ° C. for graphitization. The particles after the graphitization treatment were further subjected to an air classification treatment to obtain conductive carbon particles having an average particle diameter of 9.9 μm.

Next, a conductive elastic layer was produced in the following manner.

Epichlorohydrin rubber 100 parts by mass (epichlorohydrin: ethylene oxide: allyl glycidyl ether = 40 mol%: 56 mol%: 4 mol%)
Tetrabutylammonium perchlorate 1 part by weight Heavy calcium carbonate 60 parts by weight Carbon black (MT thermal) 5 parts by weight Zinc oxide 5 parts by weight Zinc stearate 1 part by weight 2-Mercaptobenzimidazole 0.5 parts by weight Sebacic acid polyester 5 parts by weight Part

The raw materials were kneaded for 10 minutes with a pressure kneader whose temperature was adjusted to 100 ° C. Furthermore, 1 part by mass of tetramethylthiuram monosulfide as a vulcanization accelerator and 2 parts by mass of sulfur as a vulcanizing agent were added and further kneaded for 10 minutes with an open roll adjusted to 25 ° C. to prepare a raw material compound. .
The conductive support used was a steel cylindrical shaft having a diameter of 6 mm and a length of 256 mm, the surface of which was nickel-plated. Thermosetting adhesive containing metal and rubber in a region up to 115 mm on both sides across the center in the axial direction of the cylindrical surface (a region with an axial width of 230 mm) (carbon content 2 mass%, methyl isobutyl ketone content 50 mass) %) Was applied. This was heated at 80 ° C. for 30 minutes and then further heated at 160 ° C. for 30 minutes to obtain a conductive support coated with an adhesive.
The resulting compound is formed into a roller around the conductive support under the condition that the screw rotation speed is 15 rpm, the cylinder temperature and the head temperature are adjusted to 70 ° C. by a rubber extruder (inner diameter 50 mm, L / D 20). Molded as follows. The roller-shaped molding was vulcanized and the adhesive was cured in an electric oven at 160 ° C. for 30 minutes. Next, both ends of the rubber part were removed, and the longitudinal width of the conductive elastic layer part was 232 mm. Thereafter, the rubber portion is polished by a plunge polishing machine (grinding stone GC120, grinding wheel diameter φ300 mm, grinding wheel rotation speed 2500 rpm, roller rotation speed 333 rpm), and a crown-shaped conductive elasticity having an end diameter of 8.3 mm and a central diameter of 8.5 mm. Got Laura.

Next, methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 14% by mass.
The following components were added to 714.3 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.
Conductive fine particles 45 parts by mass Surface-treated titanium oxide particles 20 parts by mass Modified dimethyl silicone oil 0.2 parts by mass Blocked isocyanate mixture (* 1) 80.14 parts by mass At this time, the blocked isocyanate mixture is represented by “NCO / OH = 1.0 ”.
(* 1) A 7: 3 mixture of each butanone oxime block of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
200 g of the above mixed solution was placed in a glass bottle having an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 18 hours using a paint shaker disperser.
After the dispersion, 10 parts by mass of the carbon particles were added. Thereafter, dispersion was performed for 5 minutes, and the glass beads were removed to obtain a surface layer coating material.
Using the surface layer coating material, the conductive elastic roller produced above was dipped once. After air drying at room temperature for 30 minutes or more, it was dried at 80 ° C. for 1 hour and further at 160 ° C. for 1 hour with a hot air circulating dryer to obtain a charging roller having a surface layer formed on the conductive elastic layer.
Here, the dipping coating is as follows. The dipping coating descending speed was 30 mm / s, the dipping time was 9 seconds, the dipping coating lifting speed was the initial speed of 20 mm / s, and the final speed was 2 mm / s, while the speed was changed linearly with respect to time.
In the manufactured charging roller, the physical property measurement and the streak-like image were evaluated in the same manner as in Example 1. The results are shown in Table 1.
In the reference example, the rank of image 1 was 4, and the rank of image 2 was 3. The rank of the image 3 is 3, and a streak-like image is partially recognized, but an image having no practical problem was obtained.

  As described above, the charging roller of the present invention can maintain good charging performance for a long period of time and suppress the occurrence of streaky images. In addition, it exhibits stable performance in different temperature and humidity environments, can provide a good image, and is preferably incorporated into an electrophotographic apparatus and a process cartridge.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Conductive elastic layer 3 Surface layer

Claims (8)

A charging member having a conductive substrate and a conductive surface layer,
The surface layer includes a binder resin and composite particles dispersed in the binder resin,
The surface of the charging member has a convex portion derived from the composite particle,
The composite particles are
Having an average particle diameter of 1 μm or more and 30 μm or less ,
Core portion is coated with an electron-conductive material,
The core portion includes a polymer that includes units derived from ethylene oxide, the content of units derived from the ethylene oxide is 20 mass% or more with respect to the polymer, Ru der 100 wt% or less <br/> A charging member. The charging member according to claim 1, wherein the electronically conductive material includes at least one selected from the group consisting of carbon black, metal oxide, and metal. The polymer charging member according to claim 1 or 2 which is a copolymer further having an amide bond. The polymer, wherein comprises units derived from ethylene oxide 40 mass% or more with respect to the polymer, and, in any one of claims 1 to 3 which is a copolymer further containing an ester bond or urethane bond The charging member described. The polymer has a number average molecular weight of 1,000 or more, the charging member according to any one of claims 1-4 is synthesized using a polyethylene oxide of 30,000. Nip and the charging member according to any one of claims 1 to 5, and a photosensitive member, the charging member and the photosensitive member, the convex portion of the surface of the charging member, the photosensitive member A process cartridge, wherein the process cartridge is disposed so as to generate a gap and is detachably attached to the main body of the electrophotographic apparatus. Nip and the charging member according to any one of claims 1 to 5, and a photosensitive member, the charging member and the photosensitive member, the convex portion of the surface of the charging member, the photosensitive member An electrophotographic apparatus, wherein the electrophotographic apparatus is disposed so as to generate a void.   The electrophotographic apparatus according to claim 7, wherein only the direct current voltage is applied to the charging member to charge the member to be charged.

Images