WO2015040660A1 - 帯電部材とその製造方法、プロセスカートリッジ及び電子写真装置 - Google Patents

帯電部材とその製造方法、プロセスカートリッジ及び電子写真装置 Download PDF

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Publication number
WO2015040660A1
WO2015040660A1 PCT/JP2013/005822 JP2013005822W WO2015040660A1 WO 2015040660 A1 WO2015040660 A1 WO 2015040660A1 JP 2013005822 W JP2013005822 W JP 2013005822W WO 2015040660 A1 WO2015040660 A1 WO 2015040660A1
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WIPO (PCT)
Prior art keywords
conductive
charging member
resin particles
resin
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2013/005822
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English (en)
French (fr)
Japanese (ja)
Inventor
太一 佐藤
谷口　智士
雄彦 青山
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Canon Inc
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Canon Inc
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Application filed by Canon Inc filed Critical Canon Inc
Priority to EP13893893.1A priority Critical patent/EP3048489B1/en
Priority to CN201380079702.7A priority patent/CN105556397B/zh
Priority to US14/338,107 priority patent/US9645517B2/en
Publication of WO2015040660A1 publication Critical patent/WO2015040660A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
    • G03G15/0208—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus
    • G03G15/0216—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus by bringing a charging member into contact with the member to be charged, e.g. roller, brush chargers
    • G03G15/0233—Structure, details of the charging member, e.g. chemical composition, surface properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G21/00—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge
    • G03G21/16—Mechanical means for facilitating the maintenance of the apparatus, e.g. modular arrangements
    • G03G21/18—Mechanical means for facilitating the maintenance of the apparatus, e.g. modular arrangements using a processing cartridge, whereby the process cartridge comprises at least two image processing means in a single unit

Definitions

  • the present invention relates to a charging member, a manufacturing method thereof, a process cartridge, and an electrophotographic apparatus.
  • the convex portion having a low height is a contact portion (nip) with a photosensitive member that is a charged member of the contact charging method, and does not come into contact with the photosensitive member.
  • Hard to do when used for a long period of time, dirt may adhere to the low protrusions, and the low protrusions are difficult to contact with the electrophotographic photosensitive member, so that the attached dirt is difficult to peel off. , Dirt tends to accumulate.
  • the present inventors have found that the function of the low convex portion as a discharge point is lowered and stable charging performance may not be exhibited.
  • the present inventors have found that in order to further stabilize the charging performance of the charging member, it is necessary to develop a new technology for making it difficult for dirt to adhere to the convex portion itself of the charging member. Recognized.
  • an object of the present invention is to provide a charging member and a method for manufacturing the same that can hardly exhibit dirt on a convex portion even when used for a long period of time, and as a result, can exhibit stable charging performance over a long period of time. There is to do.
  • Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus that contribute to the formation of high-quality electrophotographic images.
  • a charging member having a conductive substrate and a conductive surface layer,
  • the surface layer includes a matrix containing a binder resin and conductive fine particles, and resin particles dispersed in the matrix,
  • the charging member has convex portions derived from the resin particles on the surface,
  • the resin particle includes a plurality of conductive domains inside,
  • a manufacturing method of the above charging member Forming a coating film of a coating solution for forming a surface layer containing a binder resin, conductive fine particles, core-shell type porous resin particles having pores and a solvent on the conductive substrate;
  • the average pore size of the shell portion of the porous resin particle is larger than the average pore size of the core portion, and the average particle size of the conductive fine particles is larger than the average pore size of the core portion,
  • a method for producing a charging member smaller than the average pore diameter is provided.
  • a process cartridge comprising the above charging member and an electrophotographic photosensitive member disposed in contact with the charging member and having a structure that can be attached to and detached from the main body of the electrophotographic apparatus.
  • an electrophotographic apparatus having the above charging member and an electrophotographic photosensitive member disposed in contact with the charging member.
  • the present invention it is possible to obtain a charging member that exhibits stable charging performance and a method for manufacturing the same even when used for a long period of time. Further, according to the present invention, it is possible to obtain a process cartridge and an electrophotographic apparatus that can form high-quality electrophotographic images over a long period of time.
  • 1 is a cross-sectional view of a charging member according to the present invention, which is an example in which a surface layer 3 is provided on a conductive substrate 1.
  • 1 is a cross-sectional view of a charging member according to the present invention, and is an example in which a conductive elastic layer 2 is provided between a conductive substrate 1 and a surface layer 3.
  • 1 is a cross-sectional view of a charging member according to the present invention, and is an example in which a conductive elastic layer 2 is provided between a conductive substrate 1 and a surface layer 3. It is a fragmentary sectional view of the surface of the charging member of the present invention. It is an expanded sectional view of the vertex of the convex part of the charging member of the present invention.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of an electrophotographic apparatus according to the present invention. It is a schematic sectional drawing of one form of the process cartridge concerning this invention.
  • FIG. 3 is a schematic explanatory diagram illustrating a contact state between a charging roller and an electrophotographic photosensitive member.
  • the present inventors have examined the contamination when using a charging member.
  • an insulating toner external additive adheres to the surface of the charging member as the AC voltage is increased. It was confirmed that it would become easier to do. From this, it was estimated that one of the causes of contamination on the surface of the charging member is that the insulating external toner additive is electrostatically adsorbed on the surface of the charging member.
  • roller-shaped charging member hereinafter also referred to as “charging roller”
  • electrophotographic charging member for the purpose of providing a charge. This is not limited to a charging roller.
  • FIG. 1A shows a cross-sectional view of an example of a charging member according to the present invention.
  • the charging member 5 has a roller shape, and includes a conductive substrate 1 and a conductive surface layer 3 covering its peripheral surface.
  • Become. 1B and 1C show an example in which one or more conductive elastic layers 2 are provided between the conductive substrate 1 and the conductive surface layer 3, and
  • FIG. 1B shows a single conductive elastic layer 2.
  • FIG. 1C is an example in which the conductive elastic layer 2 includes two layers 21 and 22.
  • An adhesive layer may be provided between the conductive substrate 1 and a layer laminated thereon (for example, the conductive surface layer 3 in FIG. 1A, the conductive elastic layer 2 in FIG. 1B, and the conductive elastic layer 21 in FIG. 1C).
  • An adhesive layer may be provided between the conductive adhesive layer.
  • a conductive adhesive containing a known conductive agent can be used.
  • a conductive adhesive layer may be provided between the conductive elastic layer 2 (22) and the conductive surface layer 3 and between the conductive elastic layers 21 and 22.
  • FIG. 2 shows the vicinity of the surface of the charging member in which the laminated portion of the conductive substrate (hereinafter sometimes simply referred to as “substrate”) and the conductive surface layer (hereinafter also simply referred to as “surface layer”) is enlarged.
  • the substrate 101 is covered with a surface layer 3, and the surface layer 3 includes a conductive matrix 103 made of a binder resin and conductive fine particles (not shown) and resin particles 104. A plurality of convex portions 105 derived from the resin particles 104 are formed on the surface.
  • FIG. 3 is an enlarged cross-sectional view near the apex of the convex portion.
  • the resin particles 104 in the surface layer 3 include a plurality of conductive domains 201 inside, and the conductive domains 201 are unevenly distributed near the surface of the resin particles 104.
  • the fact that the conductive domain 201 is unevenly distributed near the surface of the resin particle 104 is defined as follows. That is, when the resin particles are solid (hereinafter also referred to as “solid resin particles”), a circle having an area equal to the area of the cross section passing through the center of gravity of the solid resin particles is concentric with the circle. Then, the area of the donut-shaped portion between the circle having a diameter 0.8 times the diameter of the circle is obtained. Next, in the cross section passing through the center of gravity of the solid resin particles, the surface of the solid resin particles and a line of equal distance from the surface (dotted line 222 in FIG. 3) so as to be equal to the area of the donut-shaped portion. Set the area surrounded by. When the region includes more than 50% (number basis) of the conductive domains 201 appearing in the cross section, the conductive domain 201 is defined as being unevenly distributed near the surface of the resin particle 104. To do.
  • the conductive domain 201 is present in the resin particles having convex portions formed on the surface, and the concentration of the conductive fine particles is higher than the concentration of the conductive fine particles in the matrix 103 of the surface layer. It is an area.
  • the resin particles 104 are contained in a matrix 103 including a binder resin and conductive fine particles dispersed in the binder resin.
  • the conductive domain 201 is electrically connected to the matrix 103, as shown in FIG. 3, the conductive domain 201 is in a state as if it is isolated. Therefore, the conductive domain 201 is in a state where it is easy to retain electric charges.
  • the inventors of the present invention have inferred the reason why the adhesion of dirt to the convex portion is suppressed according to the charging member of the present invention as follows.
  • the charging member used for contact charging is generally 1.0, for example, in an environment of a temperature of 23 ° C. and a relative humidity of 50% so as not to leak even when a charged body such as an electrophotographic photosensitive member has a pinhole.
  • a surface layer having a volume resistivity of about ⁇ 10 3 to 1.0 ⁇ 10 13 ⁇ ⁇ cm is provided. Therefore, when charging the object to be charged, the charge is released from the surface of the charging member by discharge, but at that moment, the surface of the charging member has a polarity opposite to the polarity applied at the time of discharge. Charge accumulates. This will be described with reference to FIGS. 4A and 4B. 4A and 4B are explanatory diagrams of the state of charge in the vicinity of the top of the convex portion 105.
  • FIG. 4A and 4B are explanatory diagrams of the state of charge in the vicinity of the top of the convex portion 105.
  • FIG. 4A shows a state in which negative charges are accumulated on the surface of the charging member when a DC voltage and an AC voltage are applied in a superimposed manner between the charging member 5 and a member to be charged (not shown). . At this time, negative charges are still accumulated on the surface of the conductive domain 201.
  • the charge density on the surface of the charging member becomes positive ( FIG. 4B).
  • the surface layer of the charging member used for contact charging has an electric resistance of about 1.0 ⁇ 10 3 to 1.0 ⁇ 10 13 ⁇ ⁇ cm in terms of volume resistivity as described above. This is because a certain amount of time is required to replenish the charge on the surface of the charging member after the negative charge is released.
  • the charge accumulated on the surface of the top of the convex portion of the charging member and the charge accumulated in the conductive domain 201 are reversed. That is, a reverse electric field is formed in the vicinity of the vertex of the convex portion of the charging member.
  • the dirt that is electrostatically adsorbed to the convex part on the surface of the charging member is subjected to a force in the direction of peeling from the convex part due to the formation of this reverse electric field, and the dirt on the vertex of the convex part of the charging member Will be suppressed.
  • the conductive domain 201 needs to be unevenly distributed near the surface of the resin particle.
  • the charge that can be held by the resin particle is diffused throughout the resin particle.
  • the strength of the reverse electric field formed immediately after the discharge described above becomes weak on the convex surface of the charging member.
  • the effect of removing dirt that electrostatically adheres to the convex portion is reduced.
  • the conductive domains that are unevenly distributed on the surface of the resin particles are preferably present from the surface of the resin particles to a region of about 10% of the particle size of the resin particles.
  • the thickness of the region 220 where the conductive domains unevenly distributed on the surface of the resin particles exist is referred to as a conductive domain region width.
  • the volume average particle diameter of the resin particles contained in the surface layer of the charging member is 5 to 60 ⁇ m, and more preferably 15 to 40 ⁇ m. By setting it within this range, the convex portions formed by the resin particles formed on the surface layer have an appropriate height, which is a good discharge point.
  • the electric field is increased by increasing the reverse electric field, that is, the electric charge is concentrated in the vicinity of the surface of the resin particle on the convex part apex side of the charging member serving as the discharge point. It is preferable to hold.
  • the conductive domain is preferably formed in the resin particle so that the interface 202 between the insulating portion 104a near the surface and the conductive domain 201 intersects the direction of the electric field.
  • the conductive domain diameter in the cross section of the resin particle is preferably 5 to 50% of the width of the conductive domain region described later.
  • the occupation ratio of the conductive domains included in the conductive domain region is preferably 10 to 50% with respect to the area of the conductive domain region. If it is within this range, there can be a sufficient interface where charges accumulate. In addition, a state in which charges are likely to accumulate at the interface, that is, a state in which the conductive domain easily retains charges during discharge as described above is likely to occur.
  • the thickness of the matrix covering the resin particles affects the strength of the reverse electric field. Specifically, the smaller the distance, the stronger the reverse electric field, and the greater the effect of suppressing the adhesion of dirt to the convex portion. On the other hand, if the thickness of the matrix is too thin, it is difficult to accumulate charges on the surface of the convex portion of the charging member. Therefore, in order to ensure that the convex portion functions as a discharge point, the thickness of the matrix covering the resin particles should be 0.1 to 2.0 ⁇ m, particularly 0.4 to 1.0 ⁇ m. preferable.
  • the conductive surface layer according to the present invention includes a binder resin and a matrix containing conductive fine particles dispersed in the binder resin, and resin particles dispersed in the matrix. And on the surface of the surface layer, it has the convex part derived from this resin particle. Furthermore, the resin particles enclose conductive domains therein, and the conductive domains are unevenly distributed near the surface of the resin particles.
  • each component will be described.
  • Binder resin As the binder resin used for the surface layer, a known binder resin used for manufacturing a charging member can be employed. For example, a thermosetting resin or a thermoplastic resin can be used. Of these, fluorine resin, polyamide resin, acrylic resin, polyurethane resin, acrylic urethane resin, silicone resin, and butyral resin are preferable. These may be used alone or in combination of two or more. Moreover, the raw material monomers of these resins may be copolymerized and used as a copolymer.
  • the surface layer has a volume resistivity of about 1.0 ⁇ 10 3 to 1.0 ⁇ 10 13 ⁇ ⁇ cm in an environment of a temperature of 23 ° C. and a relative humidity of 50%.
  • conductive fine particles include aluminum, palladium, iron, copper, silver; -Fine particles of metal oxides such as titanium oxide, tin oxide, zinc oxide; -Carbon black and carbon-based fine particles.
  • composite fine particles obtained by subjecting the surface of metal fine particles or metal oxides to surface treatment by electrolytic treatment, spray coating or mixed vibration can be used as conductive fine particles.
  • conductive fine particles can be used alone or in combination of two or more.
  • the conductive fine particles are carbon black
  • conductive composite fine particles in which a metal oxide is coated with carbon black may be used.
  • the conductive fine particles are also a component that condenses in the porous resin particles to form conductive domains in the resin particles.
  • the average primary particle size (volume average particle size or arithmetic average particle size) of the conductive fine particles is preferably 10 to 100 nm, and more preferably 12 to 50 nm.
  • resin particles The resin particles according to the present invention cause convex portions to be formed on the surface layer.
  • acrylic resin acrylic resin, styrene resin, acrylonitrile resin, vinylidene chloride resin, vinyl chloride resin and the like can be used. These resins can be used alone or in combination of two or more. Furthermore, a copolymer obtained by appropriately selecting a raw material monomer of these resins and copolymerizing them may be used. Further, these resins may be the main component, and other known resins may be included as necessary.
  • Resin particles that are present in the surface layer of the charging member according to the present invention and have convex portions formed on the surface of the charging member include a plurality of conductive domains therein, and the conductive domains are formed of resin particles. It is unevenly distributed near the surface.
  • porous resin particles are resin particles having pores penetrating the surface (hereinafter also referred to as “through holes”).
  • through holes are resin particles having pores penetrating the surface.
  • porous resin particles porous resin particles having through-holes in both the core part and the shell part, and the pore diameter of the core part is relatively smaller than the pore diameter of the shell part are used. Is effective.
  • the porous resin particles according to the present invention are prepared by a suspension polymerization method, an interfacial polymerization method, an interfacial precipitation method, a submerged drying method, or a method for precipitation by adding a solute or solvent that lowers the solubility of the resin to the resin solution. Can be produced.
  • a porous agent is dissolved in the polymerizable monomer in the presence of the crosslinkable monomer to prepare an oily mixed solution.
  • aqueous suspension polymerization is performed in an aqueous medium containing a surfactant and a dispersion stabilizer.
  • washing and drying steps are performed to remove water and the porosifying agent.
  • Resin particles can be obtained.
  • a compound having a reactive group that reacts with the functional group of the polymerizable monomer or an organic filler can also be added.
  • polymerizable monomer examples include the following. Styrene monomers such as styrene, p-methylstyrene, p-tert-butylstyrene; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, methacryl Ethyl acetate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, hydrofurfuryl methacrylate, lauryl methacrylate (Meth) acrylic acid ester monomers such as These polymerizable monomers may be used alone or in combination of two or
  • the crosslinkable monomer is not particularly limited as long as it has a plurality of vinyl groups, and the following can be exemplified.
  • the crosslinkable monomer is preferably used in an amount of 5 to 90% by mass in the monomer. By setting it within this range, it becomes possible to reliably form pores inside the particles.
  • a non-polymerizable solvent a mixture of a linear polymer and a non-polymerizable solvent dissolved in a mixture of polymerizable monomers, or a cellulose resin
  • the non-polymerizable solvent include toluene, benzene, ethyl acetate, butyl acetate, normal hexane, normal octane, normal dodecane, and the like.
  • Ethyl cellulose can be mentioned.
  • the addition amount of the porosifying agent can be appropriately selected according to the purpose of use, but it is 20 to 90 in 100 parts by mass of the oil phase comprising the polymerizable monomer, the crosslinkable monomer and the porosifying agent. It is preferable to use in the range of parts by mass. By setting it within this range, the porous resin particles are not easily fragile and can function as a discharge point for a long period of time without deformation or loss even in the nip between the charging member and the electrophotographic photosensitive member.
  • the polymerization initiator is not particularly limited, but is preferably soluble in the polymerizable monomer.
  • Known peroxide initiators and azo initiators can be used.
  • the following can be shown as an azo initiator. 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexane 1-carbonitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and 2,2'-azobis -2,4-Dimethylvaleronitrile.
  • surfactants include the following.
  • Anionic surfactants such as sodium lauryl sulfate, polyoxyethylene (degree of polymerization 1 to 100), triethanolamine lauryl sulfate; stearyltrimethylammonium chloride, diethylaminoethylamide stearate lactate, dilaurylamine hydrochloride, oleylamine lactate
  • Nonionic surfactants such as adipic acid diethanolamine condensate, lauryl dimethylamine oxide, glyceryl monostearate, sorbitan monolaurate, diethylaminoethylamide stearate; palm oil fatty acid amidopropyl dimethylamino Amphoteric surfactants of betaine acetate, lauryl hydroxysulfobetaine, sodium ⁇ -laurylaminopropionate; polyvinyl alcohol, starch, and carboxy Polymer dispersant such as chill cellulose.
  • Organic fine particles such as polystyrene fine particles, polymethyl methacrylate fine particles, polyacrylic acid fine particles, and polyepoxide fine particles; silica such as colloidal silica; calcium carbonate, calcium phosphate, aluminum hydroxide, barium carbonate, and magnesium hydroxide.
  • Suspension polymerization is preferably carried out in a sealed manner using a pressure vessel, and the raw material components may be suspended in a disperser or the like before polymerization and then transferred to the pressure vessel for suspension polymerization. It may be suspended.
  • the polymerization temperature is more preferably 50 to 120 ° C.
  • the polymerization may be carried out under atmospheric pressure, but is preferably carried out under pressure (under a pressure obtained by adding 0.1 to 1 MPa to atmospheric pressure) so as not to make the porous agent gaseous. After completion of the polymerization, solid-liquid separation and washing may be performed by centrifugation or filtration.
  • drying or pulverization may be performed at a temperature lower than the softening temperature of the resin constituting the porous resin particles. Drying and pulverization can be performed by a known method, and an air dryer, a normal air dryer, and a Nauta mixer can be used. Further, drying and pulverization can be simultaneously performed by a pulverization dryer or the like. Surfactants and dispersion stabilizers can be removed by repeating washing filtration after production.
  • the particle size of the porous resin particles is determined based on the mixing conditions of the oil-based liquid mixture composed of a polymerizable monomer or a porosizing agent and an aqueous medium containing a surfactant or a dispersion stabilizer, the addition amount of a dispersion stabilizer, It can be adjusted by stirring and dispersing conditions. By increasing the addition amount of the dispersion stabilizer, the average particle diameter can be lowered. In addition, the average particle diameter of the porous resin particles can be lowered by increasing the stirring speed under the stirring and dispersing conditions.
  • the volume average particle size of the porous resin particles as the raw material for the resin particles according to the present invention is preferably in the range of 5 to 60 ⁇ m, particularly 15 to 45 ⁇ m. By setting it within this range, a convex portion that can function stably as a discharge point can be formed on the surface of the charging member.
  • the pore diameter and internal pore diameter of the porous resin particles, and the ratio of the region containing air can be adjusted by the addition amount of the crosslinkable monomer, the kind and addition amount of the porous agent.
  • the pore diameter can be adjusted by increasing or decreasing the amount of the porous agent added to the polymerization monomer. Moreover, it can also adjust by increase / decrease in the addition amount of a crosslinkable monomer.
  • the direction of increasing the amount of the porous agent and decreasing the addition amount of the crosslinkable monomer is the direction of increasing the pore diameter.
  • it can achieve by using a cellulose resin as a porosification agent.
  • the porous resin particles having a core-shell structure having a shell portion with a pore diameter larger than the core portion pore diameter described above are composed of two kinds of porous agents, in particular, a solubility parameter (hereinafter referred to as “SP value”). It can be produced by using two kinds of porosifying agents having a difference in the above.
  • SP value solubility parameter
  • the case where normal hexane and ethyl acetate are used as the porosifying agent will be described below as an example.
  • porosifying agents when an oily mixture obtained by mixing a polymerizable monomer and a porosifying agent is added to an aqueous medium, water used as the medium and ethyl acetate having an SP value close to that, A large amount will be present on the aqueous medium side, that is, outside the suspension droplets.
  • the outside pore diameter is larger than the inside pore diameter.
  • Large porous resin particles can be produced.
  • the pore diameter in the outer portion of the droplet that becomes the shell portion can be adjusted by the SP value of the porous agent that comes outside the droplet.
  • the thickness of the shell part of the completed porous resin particle can be adjusted with the ratio of two types of porosifying agents used.
  • the porous agent used in the above means, for example, ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, butyl acetate, acetone, methyl ethyl ketone and the like are preferable.
  • the porosifying agent having a high solubility of the polymerizable monomer and having an SP value far from water, the pore diameter inside the porous resin particles is reduced, and the pores The rate can be reduced.
  • the conductive material is provided near the apex of the convex portion formed on the surface of the charging member.
  • the above particles are used for the purpose of concentrating the sex domains.
  • the porosifying agent having an SP value closer to that of water is preferably 50 parts by mass or less with respect to 100 parts by mass of the entire porosizing agent. More preferably, it is 15 to 25 parts by mass.
  • the resin particles contained in the coating solution for forming the surface layer have a core-shell structure, and pores ( It is preferable that the resin particles have a through hole) and the average pore diameter of the core portion is smaller than the average pore diameter of the shell portion.
  • FIG. 5 shows a schematic cross-sectional view of the porous resin particles.
  • the porous resin particle 210 includes a core part 110 having relatively small holes and a shell part 111 having relatively large holes near the surface of the particles. That is, the porous resin particles used for forming the convex portion on the surface layer in the present invention are particles in which the pores of the shell portion 111 near the surface of the particles are larger than the pores of the core portion 110 near the particle central portion. Means.
  • the average pore diameters of the core part and the shell part are suitably 10 to 50 nm and 40 to 500 nm, respectively, and the maximum pore diameter is 5% or less with respect to the volume average particle diameter of the porous resin particles. Is preferred. Further, it is preferably 15 nm or more and 40 nm or less and 50 to 200 nm, respectively, and the maximum pore diameter is more preferably 1% or less with respect to the volume average particle diameter of the porous resin particles. By setting it within this range, the resin particles are not lost even in the nip portion between the charging member and the electrophotographic photosensitive member, and the functionality as a discharge point can be stably exhibited even after long-term use.
  • the determination method of a core part and a shell part is as follows.
  • porous resin particles are made of a photocurable resin such as “visible light curable embedding resin D-800” (trade name, manufactured by Nissin EM Co., Ltd.), “Epok812 set” (trade name, Oken Shoji Co., Ltd.). Embedded).
  • a photocurable resin such as “visible light curable embedding resin D-800” (trade name, manufactured by Nissin EM Co., Ltd.), “Epok812 set” (trade name, Oken Shoji Co., Ltd.). Embedded).
  • a diamond knife “DiATOME CRYO DRY” trade name, manufactured by DIATOME
  • the cut sections were stained using any of osmium tetroxide, ruthenium tetroxide, and phosphotungstic acid stains, and transferred to a transmission electron microscope “H-7100FA” (trade name, manufactured by Hitachi, Ltd.). Then, a cross-sectional image of 100 porous resin particles is taken. At this time, the resin portion is white, and the hole portion into which the embedding resin has entered is observed black.
  • the resin and the dyeing agent to be embedded are appropriately selected in combination with which the pores of the porous resin particles can be clearly confirmed depending on the material of the porous resin particles. For example, in the porous resin particle A1 produced in Production Example A1 to be described later, the pores can be clearly confirmed by using “visible light curable embedding resin D-800” (trade name) and ruthenium tetroxide. Can do.
  • reference numeral 301 denotes the center of gravity when the area of the region including the pore portion of the porous resin particles is calculated and the porous resin particles are assumed to be solid particles.
  • a circle 302 having an area equivalent to that of the region centered on the center of gravity 301 is defined.
  • a circle 303 whose diameter is 1 ⁇ 2 of the diameter of the circle 302 with the center of gravity 301 as the center is defined, and the inside of the circle 303 is defined as an internal region 304.
  • the ratio of the total area of the vacancies in the internal region to the total area of the region including the vacancies in the internal region 304 is calculated, and this is used as the central porosity.
  • the radius of the first circle is a radius 305
  • the radius of the outer circle is a radius 306
  • a region surrounded by the radius 305 and the radius 306 is defined as an outer shell region 307.
  • the ratio of the total area of the void portion of the outer shell region to the total area of the region including the void portion of the outer shell region 307 is defined as the outer shell region porosity.
  • the outer shell region porosity is sequentially calculated for each circle having a radius of 100 nm larger toward the outside of the circle 303, and when the outer shell region porosity is 1.2 times or more than the central portion porosity for the first time.
  • the inside of the radius 305 is defined as a core portion, and the outside thereof is defined as a shell portion.
  • the conductive surface layer according to the present invention may contain insulating particles in addition to the conductive fine particles.
  • the insulating particles include the following. Zinc oxide, tin oxide, indium oxide, titanium oxide (titanium dioxide, titanium monoxide, etc.), iron oxide, silica, alumina, magnesium oxide, zirconium oxide, strontium titanate, calcium titanate, magnesium titanate, barium titanate, Calcium zirconate, barium sulfate, molybdenum disulfide, calcium carbonate, magnesium carbonate, dolomite, talc, kaolin clay, mica, aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, diatomaceous earth, glass beads, bentonite, montmorillonite, hollow Particles such as glass spheres, organometallic compounds and organometallic salts.
  • iron oxides such as ferrite, magnetite and hematite and activated carbon can also be used.
  • the conductive surface layer may further contain a release agent in order to improve the releasability.
  • a release agent in the conductive surface layer, adhesion of dirt to the surface of the charging member can be prevented, and the durability of the charging member can be improved.
  • the release agent is a liquid, it acts as a leveling agent when forming the conductive surface layer.
  • the conductive surface layer may be subjected to a surface processing treatment using UV or electron beam, or a surface modification treatment for adhering and / or impregnating a compound on the surface.
  • the conductive surface layer according to the present invention can be formed by an electrostatic spray coating method, a dipping coating method, a brush coating method, or the like. Moreover, it can also form by adhere
  • the solvent used in the coating solution may be any solvent that can dissolve the binder resin. Specifically, the following can be mentioned. 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, di Ethers such as butyl ether and ethylene glycol dimethyl ether; cellosolves such as ethylene glycol monomethyl ether; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatic compounds such as toluene, xylene, chlorobenzene and dichlorobenzene.
  • Alcohols such as methanol, ethanol, isopropanol, ketones such as acetone, methyl ethy
  • dispersing means such as a ball mill, a sand mill, a paint shaker, a dyno mill, and a pearl mill can be used.
  • the binder resin and conductive fine particles enter the pores of the porous resin particles in the coating solution for forming the surface layer.
  • the pore diameter of the core portion of the porous resin particles is smaller than the pore diameter of the pores of the shell portion. Therefore, although the binder resin can easily penetrate into the pores of the core portion, the conductive fine particles are difficult to penetrate.
  • the coating liquid for forming the surface layer containing the binder resin and the conductive fine particles has a core portion in which the conductive fine particles are removed in the pores of the shell portion in the process of entering the pores in the porous resin particles.
  • the binder resin hardly penetrates into the core part, and the binder resin penetrates into the core part.
  • the pores in the shell portion of the porous resin particles are filled with the conductive fine particles in a rich state.
  • the pores of the porous resin particles produced by the above method have a very complicated shape, but the conductive fine particles pass through the pores communicating with the surface of the porous resin particles. Go inside. For this reason, the region in which the conductive fine particles are taken in the particles and the conductive fine particles are condensed, that is, the conductive domains are not electrically isolated in the resin particles. That is, the conductive domain is electrically connected to the matrix. However, as shown in FIG. 3, the conductive domains are as if they are isolated in any cross-section through the center of the particle. Therefore, the conductive domain is in a state where it is easy to retain electric charge.
  • the conductive domain (the region where the conductive fine particles that have entered into the pores of the porous resin particles are condensed) is formed on the surface of the resin particles. A state of uneven distribution on the side can be easily achieved.
  • the average pore diameter of the shell portion of the porous resin particles is preferably larger than the volume average particle diameter of the conductive fine particles. Preferably, it is at least twice the average particle size of the conductive fine particles. By setting it as this range, the permeation
  • the average porosity of the shell part is preferably 10% by volume or more and 50% by volume or less. More preferably, they are 20 volume% or more and 40 volume% or less. By being in this range, it becomes easy to form the conductive domain which tends to hold
  • the average pore diameter of the core part of the porous resin particles is preferably smaller than the average particle diameter of the conductive fine particles, and more preferably 1/2 or less of the average particle diameter of the conductive fine particles.
  • the average pore diameter of the core part is small, the flow of the binder resin penetrates into the core part.
  • the conductive fine particles having a large particle size block the holes at the hole inlets of the core part.
  • the fine powder of conductive fine particles there is almost no influence by the fine powder of conductive fine particles.
  • the binder resin easily penetrates into the core portion, and the flow of the binder resin promotes the closing of the pores with the above-described conductive fine particles having a large particle diameter. Therefore, the conductive domain is more restricted to the particle surface, and a more stable antifouling effect can be exhibited.
  • the average porosity of the core part is preferably 5% by volume or more and 50% by volume or less. More preferably, they are 10 volume% or more and 40 volume% or less. By being in this range, the flow of the binder resin into the core portion described above is stable, and even in the nip portion with respect to the photoreceptor, there is no loss, and the convex portion that is the discharge point is stably held.
  • a coating for forming the surface layer including the following (i) to (iv).
  • a dispersion component other than porous resin particles for example, conductive fine particles and a solvent are mixed with a binder resin together with glass beads having a diameter of 0.8 mm, and dispersed using a paint shaker disperser for 5 to 60 hours.
  • porous resin particles are added and dispersed.
  • the dispersion time is preferably 2 minutes or more and 30 minutes or less.
  • the viscosity is adjusted to 3 to 30 mPa ⁇ s, more preferably 3 to 20 mPa ⁇ s to obtain a coating solution for forming the surface layer.
  • a coating film is formed on the conductive substrate or the conductive elastic layer by dipping or the like so that the film thickness of the surface layer is 0.5 to 50 ⁇ m, more preferably 1 to 20 ⁇ m, and particularly preferably 1 to 10 ⁇ m. Form. Next, the coating film is dried and cured to form a surface layer.
  • the film thickness of the surface layer means the thickness of the matrix 103 in a portion where the convex portions due to the resin particles 104 are not formed.
  • the film thickness of the surface layer can be measured by cutting the cross section of the charging member with a sharp blade and observing with an optical microscope or an electron microscope. In the present invention, measurement is performed at a total of nine points in the longitudinal direction of the charging member, that is, three arbitrary points in the longitudinal direction and three in the circumferential direction, and the average value is used as the film thickness.
  • the surface layer is formed by using a coating solution for forming a surface layer containing the above (i) to (iii), and drying the coating film of the coating solution for forming the surface layer, if necessary. Convex portions resulting from the resin particles are formed on the surface of the surface layer formed by curing.
  • the ten-point average surface roughness (Rzjis) of the charging member surface is preferably 8.0 to 100.0 ⁇ m, and more preferably 12.0 to 60.0 ⁇ m.
  • the average unevenness (RSm) on the surface is preferably 20 to 300 ⁇ m, particularly 50 to 200 ⁇ m. By setting it within this range, it becomes easy to form a gap in the nip with the electrophotographic photosensitive member, and stable discharge within the nip can be performed.
  • the 10-point average surface roughness and the uneven average interval were measured in accordance with JIS B0601-1994 surface roughness standards, and a surface roughness measuring instrument “SE-3500” (trade name, manufactured by Kosaka Laboratory Ltd.) To do.
  • the ten-point average surface roughness is an average value obtained by arbitrarily measuring six charging members.
  • the average unevenness interval is calculated as an average value of 6 average values by measuring 10 unevenness intervals at each of the 6 arbitrary points and obtaining an average value thereof. In the measurement, the cut-off value is set to 0.8 mm, and the evaluation length is set to 8 mm.
  • the surface roughness (Rzjis, Rsm) of the charging member having convex portions due to the resin particles on the surface according to the present invention is mainly the particle size of the resin particles as the raw material, the viscosity of the coating liquid for forming the surface layer.
  • the content of the resin particles in the coating liquid for forming the surface layer and the thickness of the surface layer are adjusted. For example, increasing the particle size of the resin particles as the raw material acts to increase Rzjis. Increasing the specific gravity and viscosity of the coating solution for forming the surface layer acts to reduce Rzjis. Further, increasing the thickness of the surface layer acts in the direction of reducing Rzjis.
  • the surface layer when forming a surface layer using resin particles having a core / shell structure and having pores penetrating the surface in the core and shell, the surface layer has a thickness of Even when the volume average particle size of the resin particles is 10 times, convex portions derived from the resin particles can be formed on the surface of the surface layer.
  • the surface layer may be subjected to a surface treatment.
  • the surface treatment include a surface processing treatment using UV or electron beam, and a surface modification treatment for attaching and / or impregnating a compound or the like on the surface.
  • the amount of solvent in the coating solution is 40% by mass or more, preferably 50% by mass or more, and particularly preferably 60% by mass or more.
  • the specific gravity of the coating solution is preferably 0.80 ⁇ 1.20g / cm 3, more preferably 0.85 ⁇ 1.00g / cm 3. By setting it as this range, it becomes easy for the binder resin and the conductive fine particles to permeate into the pores of the porous resin particles.
  • the volume resistivity of the conductive surface layer according to the present invention is preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 13 ⁇ ⁇ cm in a 23 ° C./50% RH environment. By setting this range, it becomes easier to appropriately charge the electrophotographic photosensitive member by discharging.
  • the volume resistivity of the conductive surface layer can be determined as follows. First, a conductive surface layer is cut out from a charging member into a rectangle of 5 mm length ⁇ 5 mm width. A measurement sample is obtained by depositing metal on both sides. If the conductive surface layer is too thin to cut out, apply the coating solution for the conductive surface layer on the aluminum sheet to form a coating film, and use the same conditions as when forming the conductive surface layer. A sample for measurement is obtained by vapor-depositing a metal on the surface of the coating film prepared as described above. 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 the volume resistivity is obtained by calculating from the film thickness and the electrode area. The volume resistivity of the conductive surface layer can be adjusted by the conductive fine particles described above.
  • the conductive fine particles preferably have a volume average particle size of 10 to 900 nm, more preferably 10 to 500 nm as long as the purpose is to control the volume resistivity of the surface layer. Within this range, the volume resistivity of the surface layer can be easily controlled.
  • the conductive substrate is conductive and has a function of supporting an elastic layer or the like provided thereon.
  • the material include metals such as iron, copper, stainless steel, aluminum, and nickel, and alloys thereof. Further, for the purpose of imparting scratch resistance, these surfaces may be subjected to plating treatment or the like as long as the conductivity is not impaired.
  • a resin substrate whose surface is made conductive by coating the surface with a metal or the like, or a substrate manufactured from a conductive resin composition can be used.
  • a conductive elastic layer may be formed between the conductive substrate and the conductive surface layer.
  • the conductive elastic layer is not necessarily a single layer, and may have a laminated structure of two or more layers in consideration of the function.
  • a known rubber can be adopted as the rubber used as the binder in the conductive elastic layer.
  • resin, natural rubber, a vulcanized product thereof, synthetic rubber and the like can be mentioned.
  • thermosetting resin a thermoplastic resin, or the like
  • fluorine resin polyamide resin, acrylic resin, polyurethane resin, silicone resin, butyral resin, and the like are more preferable.
  • the following can be used as synthetic rubber.
  • ethylene propylene diene rubber EPDM
  • SBR styrene butadiene rubber
  • silicone rubber silicone rubber
  • urethane rubber isoprene rubber
  • IR isoprene rubber
  • NBR acrylonitrile butadiene rubber
  • CR chloroprene rubber
  • acrylic rubber epichlorohydrin rubber, etc.
  • a thermoplastic elastomer such as styrene butadiene styrene block copolymer (SBS) or styrene ethylene butylene styrene block copolymer (SEBS) can also be used. These may be used alone or in combination of two or more.
  • polar rubber because the resistance can be easily adjusted.
  • epichlorohydrin rubber and NBR are preferable. These have the advantage that resistance control and hardness control of the conductive elastic layer can be performed more easily.
  • the volume resistivity of the conductive elastic layer is preferably 1.0 ⁇ 10 2 ⁇ ⁇ cm or more and 1.0 ⁇ 10 10 ⁇ ⁇ cm or less as measured in a 23 ° C./50% RH environment.
  • the volume resistivity of the conductive elastic layer is determined in the same manner as in the conductive surface layer. That is, the conductive elastic layer is cut out from the charging member into a 5 mm ⁇ 5 mm rectangle.
  • a measurement sample obtained by vapor-depositing metal on both sides to produce an electrode and a guard electrode was measured using a microammeter 30 seconds after applying a voltage of 200 V, and calculated from the sample thickness and electrode area. To do.
  • a known conductive agent can be appropriately added to the conductive elastic layer.
  • the conductive agent an ionic conductive agent or an electronic conductive agent can be used.
  • the conductive elastic layer may contain additives such as softening oil and plasticizer, and may appropriately contain materials that impart various functions. Examples of these include foaming agents, anti-aging agents, fillers and the like.
  • the composition comprising the above-described various rubber components and other components is mixed with a ribbon blender, Nauter mixer, Henschel mixer, super mixer, Banbury mixer, pressure kneader, etc.
  • An unvulcanized rubber composition for an elastic layer is obtained.
  • a crosshead is an extrusion die that is used to configure a coating layer of an electric wire or a wire and is installed at the tip of a cylinder of an extruder.
  • the unvulcanized rubber roller is vulcanized with a hot air oven or the like, and then the surface of the roller is ground to adjust the shape.
  • the conductive substrate may be bonded to the layer immediately above it via an adhesive.
  • the adhesive is preferably conductive.
  • the adhesive may have a known conductive agent.
  • the adhesive resin for the adhesive examples include thermosetting resins and thermoplastic resins, and known adhesive resins such as urethane, acrylic, polyester, polyether, and epoxy can be used.
  • an ionic conductive agent can be used as the conductive agent for imparting conductivity to the adhesive, and other electronic conductive agents can also be used. These conductive agents can be used alone or in combination of two or more.
  • the conductive elastic layer when the conductive elastic layer is provided, the conductive elastic layer may be bonded to the conductive surface layer, and when the conductive elastic layer is a multilayer, the conductive elastic layers may be bonded via an adhesive.
  • the adhesive is preferably conductive.
  • the electric resistance measured by the following method is 1 in an environment of 23 ° C./50% RH in order to improve the charging of the electrophotographic photosensitive member. It is preferably 0.0 ⁇ 10 3 to 1.0 ⁇ 10 10 ⁇ .
  • FIG. 7 shows an example of a method for measuring the electrical resistance of the charging roller.
  • the charging roller 5 is brought into contact with both ends of the conductive substrate 1 by bearings 33 and 33 to a cylindrical metal 32 having the same curvature as that of the electrophotographic photosensitive member so as to be parallel to each other under a load.
  • the cylindrical metal 32 is rotated by a motor (not shown), and a DC voltage of ⁇ 200 V is applied from the stabilizing power supply 34 while the charging roller 5 that is in contact with the rotation is driven to rotate.
  • the current flowing at this time is measured by an ammeter 35, and the resistance of the charging roller is calculated.
  • the load was 4.9 N each
  • the diameter of the cylindrical metal was 30 mm
  • the rotation of the cylindrical metal was a peripheral speed of 45 mm / sec.
  • the charging roller preferably has a crown shape that is thickest at the center in the longitudinal direction and narrows toward both ends in the longitudinal direction.
  • the crown amount depends on the thickness of the charging roller, the difference between the outer diameter of the central portion and the outer diameter at a position 90 mm away from the central portion is preferably 30 ⁇ m or more and 200 ⁇ m or less.
  • the crown shape is preferably formed simultaneously with the grinding of the conductive elastic layer.
  • the surface hardness of the charging member is preferably 90 ° or less in micro hardness (MD-1 type), and more preferably 40 to 80 °. By setting this range, it is easy to stabilize the contact with the electrophotographic photosensitive member, and more stable in-nip discharge can be performed.
  • the “micro hardness (MD-1 type)” is the hardness of the charging member measured using an 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).
  • FIG. 8 shows a schematic configuration of an example of an electrophotographic apparatus provided with the charging member of the present invention.
  • the electrophotographic apparatus is composed of the following apparatuses.
  • Electrophotographic photosensitive member 4 charging device for charging electrophotographic photosensitive member, latent image forming device 11 for forming a latent image by exposure, developing device for developing the latent image into a toner image, transfer device for transferring the toner image to a transfer material
  • a cleaning device that removes and collects transfer residual toner on the electrophotographic photosensitive member, a fixing device 9 that fixes a toner image on a transfer material, and the like.
  • the electrophotographic photosensitive member 4 is a rotary drum type having a photosensitive layer on a conductive substrate.
  • the electrophotographic photosensitive member 4 is rotationally driven at a predetermined peripheral speed (process speed) in the direction of the arrow.
  • the charging device has a contact-type charging roller 5 that is placed in contact with the electrophotographic photosensitive member 4 by contacting with the electrophotographic photosensitive member 4 with a predetermined pressing force.
  • the charging roller 5 is driven rotation that rotates in accordance with the rotation of the electrophotographic photosensitive member 4, and charges the electrophotographic photosensitive member 4 to a predetermined potential by applying a predetermined DC voltage from the charging power source 19.
  • the charging member of the present invention is used as the charging roller.
  • the latent image forming apparatus 11 that forms an electrostatic latent image on the electrophotographic photosensitive member 4 is, for example, an exposure apparatus such as a laser beam scanner. An electrostatic latent image is formed by exposing the uniformly charged electrophotographic photosensitive member 4 according to image information.
  • the developing device has a developing sleeve or developing roller 6 disposed close to or in contact with the electrophotographic photosensitive member 4 and is reversely developed with toner electrostatically processed to the same polarity as the charging polarity of the electrophotographic photosensitive member.
  • the electrostatic latent image is developed to form a toner image.
  • the transfer device includes a contact-type transfer roller 8 and transfers a toner image from an electrophotographic 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). To do.
  • the cleaning device has a blade-type cleaning member 10 and a collection container 14, and mechanically scrapes and collects transfer residual toner remaining on the electrophotographic photosensitive member 4 after the toner image is transferred. It is possible to omit the cleaning device by adopting a developing simultaneous cleaning system that collects the transfer residual toner.
  • the fixing device 9 is composed of a heated roll or the like, and fixes the transferred toner image to the transfer material 7. Thereafter, the transfer material on which the toner image is fixed is discharged out of the apparatus.
  • a process cartridge in which an electrophotographic photosensitive member and at least one of a charging device, a developing device, and a cleaning device are integrated.
  • the process cartridge shown in FIG. 9 includes an electrophotographic photosensitive member 4 and a charging roller 5 disposed in contact with the electrophotographic photosensitive member 4.
  • the process cartridge further includes a developing device including a developing sleeve 6 and a cleaning device including a cleaning blade 10 and a collection container 14.
  • the process cartridge has a structure that can be attached to and detached from the electrophotographic apparatus main body.
  • average particle diameter means “volume average particle diameter” unless otherwise specified.
  • the porous resin particles are made of a light curable resin, for example, “visible light curable embedding resin D-800” (trade name, manufactured by Nissin EM Co., Ltd.) or “Epok 812 set” (trade name, Oken Corporation) Embedded by company).
  • a diamond knife “DiATOME CRYO DRY” trade name, manufactured by DIATOME
  • a staining treatment is performed using any one of osmium tetroxide, ruthenium tetroxide, and phosphotungstic acid, and a transmission electron microscope “H-7100FA” (trade name, manufactured by Hitachi, Ltd.) is used.
  • H-7100FA transmission electron microscope
  • a cross-sectional image of 100 porous resin particles is taken.
  • the resin portion is observed to be white and the pore portion is observed to be black.
  • the resin and the dyeing agent to be embedded are appropriately selected in combination with which the pores of the porous resin particles can be clearly confirmed depending on the material of the porous resin particles.
  • the porous resin particles A1 produced in the following Production Example A1 can clearly confirm the pores by using “visible light curable embedding resin D-800” (trade name) and ruthenium tetroxide. I was able to.
  • reference numeral 301 denotes the center of gravity when the area of the region including the pore portion is calculated and the porous resin particles are assumed to be solid particles.
  • a circle 302 having an area equivalent to that of the region centered on the center of gravity 301 is defined.
  • a circle 303 whose diameter is 1 ⁇ 2 of the diameter of the circle 302 with the center of gravity 301 as the center is defined, and the inside of the circle 303 is defined as an internal region 304.
  • the ratio of the total area of the vacancies in the internal region to the total area of the region including the vacancies in the internal region 304 is calculated, and this is used as the central porosity.
  • the radius of the first circle is a radius 305
  • the radius of the outer circle is a radius 306
  • a region surrounded by the radius 305 and the radius 306 is defined as an outer shell region 307.
  • the ratio of the total area of the void portion of the outer shell region to the total area of the region including the void portion of the outer shell region 307 is defined as the outer shell region porosity.
  • the outer shell region porosity is sequentially calculated for each circle having a radius of 100 nm larger toward the outside of the circle 303, and when the outer shell region porosity is 1.2 times or more than the central portion porosity for the first time.
  • the inside of the radius 305 is a core part, and the outside is a shell part.
  • the ratio of the total area of the hole part to the total area of the region including the hole part is calculated. This operation is performed for 10 arbitrary porous resin particles, and the core portion porosity and shell portion porosity obtained for each particle are averaged, and the average voids of the core portion and shell portion of the porous resin particles are averaged. Determine the porosity.
  • the actual measurement is based on the area standard, but since multiple samples are observed with thin sections with a thickness approximately the same as the hole diameter, it is judged that there is no problem even if it is handled as a volume. Is done.
  • [1-4. (Average pore diameter of core and shell of porous resin particles) Arbitrarily select 10 hole portions observed in black in the core portion and shell portion determined in [1-3] above, and obtain the diameter (equal area diameter) of a circle having the same area as each hole portion. The diameter of the hole portion. The diameters of the pores of the core part and the shell part are averaged to obtain the average pore diameter of the core part and the shell part of the porous resin particle. The average pore diameter is measured for 10 arbitrary porous resin particles, and the obtained average pore diameter is averaged again to obtain the average pore diameter of the core portion and the shell portion of the porous resin particles.
  • Average Porosity of Other Resin Particles Calculate the total volume of the region containing air from the three-dimensional shape of the resin particles obtained in [1-1], and include the region of the resin particles containing air. The ratio of the total volume is calculated. This ratio is calculated for each of 100 resin particles as a raw material, and the arithmetic average value thereof is defined as the “average porosity” of other resin particles.
  • Resin particles contained in the surface layer [2-1. 3D image of 3D particle shape of resin particles contained in the surface layer)
  • a focused ion beam (trade name: FB-2000C, Hitachi, 20 nm from the apex side of the convex part of the charging member over an area of 200 ⁇ m in length and 200 ⁇ m in width that is parallel to the surface of the charging member at any convex part on the surface of the charging member. Cut out by Seisakusho Co., Ltd. and take a cross-sectional image. And the image which image
  • a section having a thickness of 100 nm is prepared by including the center of gravity of the resin particles forming the convex portion or the vicinity thereof, and the section is made of osmium tetroxide and tetraoxide. Stain using ruthenium or phosphotungstic acid, and then photograph the stained section using a transmission electron microscope “H-7100FA” (trade name). White and conductive domains (portions where conductive fine particles are aggregated) are observed as black. Carried out on the convex portion of the place.
  • yen in the cross section of the resin particle is made into an electroconductive domain area
  • the value of the width of the conductive domain region is obtained by subtracting the radius of the second circle from the radius of the first circle.
  • the width value of the conductive domain region obtained for the 100 convex section cross-sectional images is obtained, and the arithmetic average value is set as the value of the conductive domain region width of the resin particles contained in the surface layer of the charging member.
  • This oily mixture was dispersed in an aqueous medium with a homomixer at a rotational speed of 3600 rpm, then charged into a nitrogen-substituted polymerization reaction vessel, and suspended and polymerized at 70 ° C. for 8 hours while stirring at 250 rpm. .
  • hydrochloric acid was added to the resulting suspension to decompose calcium phosphate.
  • the suspension was filtered, and the resulting resin particles were repeatedly washed with water, and then dried at 80 ° C. for 5 hours. Thereafter, the dried resin particles were crushed and classified by a sonic classifier to obtain multi-hollow resin particles A25 having a volume average particle diameter of 20.2 ⁇ m.
  • the multi-hollow resin particle A24 had a plurality of pores of about 300 nm inside.
  • This oily mixture was dispersed in an aqueous medium at a rotation speed of 3800 rpm with a homomixer, and then single hollow resin particles A26 having a volume average particle diameter of 15.2 ⁇ m were obtained in the same manner as in Production Example A25.
  • the single hollow resin particle A26 was a single hollow particle having one hollow portion inside.
  • the hollow portion was recognized as a gray portion.
  • the diameter of a circle having the same area as the area of the hollow part recognized as the gray part was obtained and used as the diameter of the hollow part.
  • the diameter was similarly determined for 100 of the 100 single hollow resin particles A26 in total, and the volume average particle diameter was determined. This value was defined as the volume average particle size of the hollow part of the single hollow particle A26.
  • the volume average particle size of the hollow portion of the single hollow resin particle A26 was 4.2 ⁇ m.
  • 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 surfaced 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.
  • the obtained surface-treated titanium oxide particles had a primary particle volume average particle size of 15 nm and a volume resistivity of 5.2 ⁇ 10 15 ⁇ ⁇ cm.
  • Conductive substrate A stainless steel rod having a diameter of 6 mm and a length of 244 mm was coated with a thermosetting adhesive containing 10% by mass of carbon black and dried.
  • NBR Acrylonitrile butadiene rubber “JSR N230SV” (trade name, manufactured by JSR Corporation).
  • Calcium carbonate Calcium carbonate “Silver W” (trade name, manufactured by Shiroishi Kogyo Co., Ltd.).
  • Adipic acid ester Adipic acid ester plasticizer “Polysizer W305ELS” (trade name, manufactured by DIC Corporation).
  • Zinc stearate Zinc stearate “SZ-2000” (brand name, manufactured by Sakai Chemical Industry Co., Ltd.).
  • MB 2-mercaptobenzimidazole (anti-aging agent).
  • Zinc oxide 2 types of zinc white (manufactured by Sakai Chemical Industry Co., Ltd.).
  • Quaternary ammonium salt LV Antistatic plasticizer “Adekasizer LV70” (trade name, manufactured by ADEKA Corporation).
  • Carbon black A Carbon black “Thermax Flow Foam N990” (trade name, manufactured by Canada, Canada; volume average particle diameter of primary particles: 270 nm).
  • Carbon black B Carbon black “Toka Black # 7360SB” (trade name, manufactured by Tokai Carbon Co., Ltd., arithmetic average particle size of primary particles: 28 nm).
  • Sulfur Sulfur (vulcanizing agent).
  • DM Dibenzothiazyl sulfide (vulcanization accelerator).
  • TS Tetramethylthiuram monosulfide (vulcanization accelerator).
  • TBzTD Tetrabenzylthiuram disulfide “Parcasit TBzTD” (vulcanization accelerator) (trade name, sold by Tesco Corporation).
  • the conductive rubber composition to be coated had a thickness of 1.75 mm.
  • the obtained roller was heated in a hot air oven at 160 ° C. for 1 hour, and then the end of the elastic layer was removed to a length of 224 mm. Further, secondary heating was performed at 160 ° C. for 1 hour to obtain a layer thickness of 1.
  • a roller having a conductive rubber coating layer of 75 mm was produced.
  • the outer peripheral surface of the obtained roller was polished using a plunge cut type cylindrical polishing machine to produce an elastic roller 1.
  • a vitrified wheel was used as the polishing wheel, the abrasive grains were green silicon carbide (GC), and the particle size was 100 mesh.
  • the rotation speed of the roller was 350 rpm, the rotation speed of the polishing wheel was 2050 rpm, and the rotation direction of the roller and the rotation direction of the polishing wheel were the same direction (driven direction). Further, the cutting speed is changed stepwise from 10 mm / min to 0.1 mm / min from when the grindstone contacts the unpolished roller until it is polished to ⁇ 9 mm, and the spark-out time (time to 0 mm cutting) is 5 Set to seconds.
  • the thickness of the elastic layer was 1.5 mm, and the crown amount of this roller (the difference in outer diameter between the center and 90 mm away from the center) was 100 ⁇ m.
  • a conductive surface layer is formed on the surface thereof to produce a charging roller.
  • the raw materials used for creating the surface layer are as follows.
  • Acrylic polyol solution A Caprolactone-modified acrylic polyol solution "Placcel DC2016” (trade name, manufactured by Daicel Corporation) was adjusted with methyl isobutyl ketone to a solid content of 17% by mass.
  • Acrylic polyol solution B Caprolactone-modified acrylic polyol solution “Placcel DC2016” (trade name) prepared with methyl isobutyl ketone so as to have a solid content of 14% by mass.
  • Block isocyanate mixture 7: 3 mixture of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) in a molar ratio of each butanone oxime block.
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Conductive agent Composite conductive fine particles those prepared in the above Production Example B-1.
  • Carbon black C Carbon black “Mitsubishi Carbon Black # 52” (trade name, manufactured by Mitsubishi Chemical Corporation, average particle size 27 nm).
  • -Resin particles for forming convex portions Porous resin particles A1 to A23: those prepared in the above production examples A1 to A23.
  • Other resin particles A24 to A26 those prepared in the above production examples A24 to A26.
  • Other components Silicone oil: Modified dimethyl silicone oil “SH28PA” (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.).
  • Surface-treated titanium oxide particles those produced in Production Example B-2.
  • Example 1 [1. Preparation of coating solution for surface layer formation] The following components were added to 588.24 parts by mass of acrylic polyol solution A (acrylic polyol solid content 100 parts by mass) to prepare a mixed solution.
  • Acrylic polyol solution A acrylic polyol solid content 100 parts by mass
  • Composite conductive fine particles 55 parts by mass
  • Surface-treated titanium oxide particles 35 parts by mass
  • Modified dimethyl silicone oil 0.08 parts by mass
  • Blocked isocyanate mixture 80.14 parts by mass
  • the elastic roller 1 produced in Production Example 1 was immersed in the coating solution with the longitudinal direction thereof being the vertical direction, and was coated by a dipping method.
  • the dipping time was 9 seconds
  • the pulling speed was initially 20 mm / s, and finally 2 mm / s, and during that time, the speed was changed linearly with respect to time.
  • the obtained coated product is air-dried at 23 ° C. for 30 minutes, and then heated in a hot-air circulating drying furnace at a temperature of 100 ° C. for 1 hour and further at a temperature of 160 ° C. for 1 hour to cure the coating film,
  • a charging roller 1 having an elastic layer and a surface layer formed in this order on the outer periphery of the conductive substrate was produced.
  • the film thickness of the surface layer of the obtained charging roller 1 was measured.
  • the film thickness of the surface layer was measured in the location where the resin particle does not exist.
  • the electrophotographic apparatus monochrome laser printer “SATELLA LBP6300” (trade name, manufactured by Canon Inc.) having the configuration shown in FIG. 9 is used to determine the performance of the charging roller and the image of the electrophotographic image formed using the charging roller. This was done by evaluation. Specifically, an AC voltage having a peak peak voltage (Vpp) of 1400 V and a frequency (f) of 1350 Hz and a DC voltage (Vdc) of ⁇ 560 V were applied to the charging member of the printer from the outside. The image resolution was output at 600 dpi. A process cartridge “toner cartridge 519II” (trade name, manufactured by Canon Inc.) for this printer was modified and used.
  • toner extracted from a process cartridge “Toner Cartridge 326” (trade name, manufactured by Canon Inc.) for a monochrome laser printer “Satella LBP6200” (trade name, manufactured by Canon Inc.) was used.
  • the charging roller 1 of the process cartridge is removed, and the manufactured charging roller 1 is pressed against the electrophotographic photosensitive member with a spring pressure of 4.9 N at one end and a total of 9.8 N at both ends as shown in FIG. Touched and set. In this way, three process cartridges for evaluation were prepared.
  • the evaluation process cartridge is 24 hours in a 7.5 ° C./30% RH environment (environment 1), 15 ° C./10% RH environment (environment 2), or 23 ° C./humidity 50% RH environment (environment 3). After the acclimatization, an electrophotographic image was formed as follows in each environment.
  • the halftone image is an image in which a horizontal line having a width of 1 dot and an interval of 2 dots is drawn in a direction perpendicular to the rotation direction of the electrophotographic photosensitive member.
  • image Nos. 1 to 3 were visually observed, and the occurrence of moire images was determined based on the following ranks.
  • the evaluation results are shown in Table 5.
  • Rank 1 No moire image is generated.
  • Rank 2 The moire image can be confirmed in a part of the image, but is slight.
  • Rank 3 A moire image can be confirmed, but there is no practical problem.
  • Rank 4 A moire image is generated in the entire image, and deterioration in image quality is recognized.
  • the moire image is a phenomenon that occurs when charging unevenness due to the period of the AC voltage applied to the charging roller interferes with the horizontal line of the halftone image. While the convex portion formed on the surface of the charging roller functions as a discharge point, the dot-like charging by the discharge point cancels the charging unevenness due to the cycle of the applied voltage, and therefore it does not interfere with the dots of the halftone image. Absent. That is, the decrease in the functionality of the discharge point in the electrophotographic image forming process may generate the moire image, and this image evaluation suppresses the decrease in the functionality as the discharge point of the convex portion caused by the resin particles. The correlation between the effect of the image and the quality of the electrophotographic image can be seen.
  • Examples 2 to 7 Charging rollers 2 to 7 were produced in the same manner as in Example 1 except that the type of porous resin particles for forming the convex portions was changed as shown in Table 3, and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 5.
  • a coating solution for forming the surface layer was prepared as follows.
  • Examples 15 to 21 Except for changing the type of resin particles as shown in Table 3, charging rollers 15 to 21 were prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 5.
  • Example 22 to 24 As in Example 8, except that the elastic roller 2 produced in Production Example 2 was used as the elastic roller, and the coating liquid for forming the surface layer prepared by changing the porous resin particles as shown in Table 3 was used. Then, charging rollers 22 to 24 were respectively produced and evaluated in the same manner as in Example 8. The evaluation results are shown in Tables 3 and 5.
  • Example 25 In Example 1, in the formation of the surface layer, heating for 1 hour at a temperature of 100 ° C. in a hot air circulating drying furnace was set to 80 ° C. for 1 hour, and thereafter, the charging roller 25 was produced and carried out in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 5.

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PCT/JP2013/005822 2013-09-20 2013-09-30 帯電部材とその製造方法、プロセスカートリッジ及び電子写真装置 Ceased WO2015040660A1 (ja)

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CN201380079702.7A CN105556397B (zh) 2013-09-20 2013-09-30 充电构件及其制造方法、处理盒和电子照相设备
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EP3048489A4 (en) 2017-05-31
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