WO2012132315A1 - 導電性部材 - Google Patents

導電性部材 Download PDF

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Publication number
WO2012132315A1
WO2012132315A1 PCT/JP2012/001915 JP2012001915W WO2012132315A1 WO 2012132315 A1 WO2012132315 A1 WO 2012132315A1 JP 2012001915 W JP2012001915 W JP 2012001915W WO 2012132315 A1 WO2012132315 A1 WO 2012132315A1
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WO
WIPO (PCT)
Prior art keywords
conductive
epichlorohydrin rubber
conductive layer
charging roller
rubber
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
Application number
PCT/JP2012/001915
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English (en)
French (fr)
Japanese (ja)
Inventor
則文 村中
山田　聡
一浩 山内
都留　誠司
由夏 村中
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Canon Inc
Original Assignee
Canon Inc
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=46930103&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012132315(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Canon Inc filed Critical Canon Inc
Priority to KR1020137027619A priority Critical patent/KR101587705B1/ko
Priority to CN201280016672.0A priority patent/CN103492956B/zh
Priority to EP12765709.6A priority patent/EP2693274B1/en
Priority to US13/523,763 priority patent/US20120251171A1/en
Publication of WO2012132315A1 publication Critical patent/WO2012132315A1/ja
Anticipated expiration legal-status Critical
Priority to US14/931,791 priority patent/US9811021B2/en
Priority to US15/722,464 priority patent/US10996581B2/en
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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C08L71/03—Polyepihalohydrins
    • 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
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • 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
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
    • G03G15/0808—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the developer supplying means, e.g. structure of developer supply roller
    • 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
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
    • G03G15/0818—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the structure of the donor member, e.g. 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
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
    • 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
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
    • G03G15/1665—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat
    • G03G15/167—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat at least one of the recording member or the transfer member being rotatable during the transfer
    • G03G15/1685—Structure, details of the transfer member, e.g. chemical composition

Definitions

  • the present invention relates to a conductive member used in an electrophotographic image forming apparatus.
  • a conductive member having a conductive layer formed by adjusting an electrical resistance value by adding an ionic conductive agent to a polar polymer such as hydrin rubber has been proposed.
  • the ionic conductive agent may be unevenly distributed in the conductive layer due to long-term use. This is because the ion exchange group of the ionic conductive agent is ionically dissociated by the application of a DC voltage to the conductive member during use for a long time, and the conductive layer is subjected to repeated stress, and the anion and cation are separated. It is thought that this is caused by moving in the conductive layer and being unevenly distributed. In particular, the uneven distribution of ion exchange groups in the conductive layer increases the electrical resistance value of the conductive member.
  • a long-term application of a direct current potential to the conductive member and repeated application of stress to the conductive layer promote bleed-out of the low molecular weight component in the conductive member to the surface of the conductive layer.
  • the bleed-out of low molecular weight components on the surface of the conductive layer causes contamination of the surface of the photoreceptor.
  • Patent Document 1 a specific quaternary ammonium salt capable of lowering the electric resistance value with a low addition amount is used as an ionic conductive agent.
  • Patent Document 2 the use of a quaternary ammonium salt having an OH group suppresses bleeding and bloom of the ionic conductive agent.
  • an object of the present invention is to provide a conductive member whose electric resistance value hardly changes even after long-term use.
  • a conductive member having a conductive support and a conductive layer Provided is a conductive member comprising a modified epichlorohydrin rubber having a unit represented by the following formula (1) and an anion:
  • R 1, R 2 and R 3 each independently represents hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms].
  • a process cartridge detachably attached to the main body of an electrophotographic apparatus wherein the conductive member is at least one selected from a charging member and a developing member.
  • a process cartridge provided as a member is provided.
  • an electrophotographic apparatus comprising the conductive member as at least one member selected from a charging member and a developing member.
  • a conductive member that can reduce the change in electric resistance value caused by long-term use as much as possible.
  • FIG. 1 is a schematic configuration diagram of a conductive member according to the present invention.
  • a conductive layer 12 is provided on the outer periphery of the conductive support 11.
  • the conductive layer 12 may have a multilayer structure of two or more layers.
  • the conductive member according to the present invention is used as a conveying member such as a charging member (charging roller), a developing member (developing roller), a transfer member (transfer roller), a charge eliminating member, and a sheet feeding roller in an electrophotographic image forming apparatus. It can be used. Further, it is suitable for a conductive member that constantly energizes, such as a charging blade or a transfer pad.
  • a charging roller charging roller
  • developing roller developing roller
  • transfer roller transfer roller
  • charge eliminating member a charge eliminating member
  • sheet feeding roller in an electrophotographic image forming apparatus. It can be used. Further, it is suitable for a conductive member that constantly energizes, such as a charging blade or a transfer pad.
  • the present invention will be described using a charging roller, a developing roller, and the like, which are representative examples of conductive members.
  • the conductive support has conductivity in order to supply power to the surface of the charging roller through the support.
  • the conductive support is, for example, a cylinder having a nickel plating with a thickness of about 5 ⁇ m on the surface of a carbon steel alloy.
  • Examples of other materials constituting the conductive support include metals such as iron, aluminum, titanium, copper and nickel; alloys such as stainless steel, duralumin, brass and bronze containing these metals; carbon black and carbon fibers made of plastic
  • the composite material hardened with can be mentioned.
  • a known material that is rigid and exhibits conductivity can also be used.
  • a shape it can also be set as the cylindrical shape which made the center part the cavity other than column shape.
  • the conductive layer contains a modified epichlorohydrin rubber having a unit represented by the following formula (1) and an anion.
  • R1, R2 and R3 each independently represent hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms.
  • epichlorohydrin rubber which is a raw material of the modified epichlorohydrin rubber according to the present invention, is a generic term for rubbers having units derived from epichlorohydrin represented by the following formula (2).
  • An allyl glycidyl ether terpolymer is exemplified.
  • n an integer of 1 to 3.
  • the terpolymer having units represented by the above formulas (2), (3) and (4) has a vulcanization rate due to the presence of a double bond in the unit derived from allyl glycidyl ether. Since it is easy to adjust the vulcanization density, it is suitably used as the modified epichlorohydrin rubber according to the present invention.
  • the epichlorohydrin rubber having units represented by the formulas (2) to (4) can control the degree of fluctuation of the electric resistance value and the electric resistance value due to the temperature and humidity environment by the molar ratio of each unit.
  • the unit derived from epichlorohydrin is 19 mol% to 75 mol%
  • the unit derived from ethylene oxide is 24 mol% to 80 mol%
  • the unit derived from allyl glycidyl ether is used. The thing made into 1 mol% or more and 15 mol% or less is mentioned.
  • More preferable molar ratios are 19 mol% to 45 mol% of units derived from epichlorohydrin, 50 mol% to 80 mol% of units derived from ethylene oxide, and 1 mol% to 10 mol% of units derived from allyl glycidyl ether. It is what. By setting it as such a molar ratio, an electrical resistance value can be made low and the fluctuation
  • the modified epichlorohydrin rubber according to the present invention is a unit in which at least one of the units derived from epichlorohydrin in the above-described epichlorohydrin rubber is a unit represented by the formula (1). That is, in the modified epichlorohydrin rubber according to the present invention, quaternary ammonium ions are chemically bonded in the molecule.
  • the conductive layer expresses ionic conductivity as anions as carrier molecules present in the conductive layer move in the conductive layer, but in the conductive layer according to the present invention, quaternary ammonium ions as cations are present.
  • the conductive member according to the present invention Since it is chemically bonded to the modified epichlorohydrin rubber that is the binder of the conductive layer, excessive movement of the anion that is the carrier ion in the conductive layer is suppressed. As a result, in the conductive member according to the present invention, bleeding (bleeding) of the ion conductive component from the inside of the conductive layer to the surface is suppressed. In addition, even when a high DC voltage is applied between the charging member and the photoconductor in a state where the electroconductive member according to the present invention is used as a charging member and disposed in contact with the photoconductor, the conductive layer Increase in electrical resistance is unlikely to occur.
  • R1, R2 and R3 are each independently hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, particularly a saturated hydrocarbon group having 1 to 8 carbon atoms. Is preferred. If the saturated hydrocarbon group has too many carbon atoms, the ion exchange capacity of the amine compound per unit mass decreases due to the increase in molecular weight accompanying the increase in carbon number, and as a result, it is difficult to obtain the conductivity required for the conductive layer. Become.
  • the modified epichlorohydrin rubber having a unit represented by the formula (1) can be obtained by dechlorinating a chlorine atom at an alkylene chloride site in a unit of an unmodified epichlorohydrin rubber by a nucleophilic substitution reaction of an amine compound. . That is, a quaternary ammonium group having an ionic conductivity by utilizing a polymer reaction with respect to epichlorohydrin rubber having excellent electrical and mechanical properties, contained as a binder polymer in the elastic layer of the charging member. Is introduced.
  • the method for substitution with an amine compound is not particularly limited as long as the nucleophilic substitution reaction between the chlorine atom of the alkylene chloride moiety of the epichlorohydrin rubber and the amine compound proceeds.
  • epichlorohydrin rubber is dissolved in an organic solvent such as dimethylformamide (DMF) and then an amine compound is added, or an amine compound is added at the rubber kneading stage of epichlorohydrin rubber.
  • DMF dimethylformamide
  • the chlorine atom of the alkylene chloride part of the unit derived from epichlorohydrin may be substituted with a primary amine using a delepine reaction, a Gabriel reaction, or the like.
  • a vulcanization accelerator is added simultaneously with the amine compound, the amine compound and the vulcanization accelerator react, and a nucleophilic substitution reaction with the chlorine atom of the alkylene chloride portion of the unit derived from epichlorohydrin. It is preferable to replace the amine compound before vulcanization.
  • any amine compound of primary amine, secondary amine, and tertiary amine can be used.
  • the boiling point of the amine compound is preferably 200 ° C. or less, more preferably 160 ° C. or less, which facilitates removal by heating.
  • R1, R2 and R3 in the amine compound are desirably saturated hydrocarbon groups having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms.
  • Anions contained in the conductive layer function as carrier molecules that cause the conductive layer to exhibit ionic conductivity by moving through the conductive layer. It does not specifically limit as a kind of anion, For example, a chlorine ion, a perchlorate ion, a bis (trifluoromethanesulfonyl) imide ion etc. are mentioned. The structure of bis (trifluoromethanesulfonyl) imide ion is shown in the following formula (5).
  • a method for introducing a desired anion into the conductive layer for example, there is a method in which a desired anion is reacted as a counter anion with respect to a quaternary ammonium ion of the modified epichlorohydrin rubber according to the present invention. That is, a modified epichlorohydrin rubber in which a quaternary ammonium base composed of a desired counter anion and a quaternary ammonium ion to be contained in the conductive layer is introduced into the epichlorohydrin rubber is contained in the conductive layer.
  • the quaternary ammonium salt is ion-dissociated in the conductive layer, the counter anion is liberated, and the desired anion can be present in the conductive layer.
  • the epichlorohydrin rubber when the synthesis of the modified epichlorohydrin rubber according to the present invention is performed by nucleophilic substitution of an amine compound at the chlorine atom of the alkylene chloride portion of the epichlorohydrin rubber, the epichlorohydrin rubber has a quaternary having a chlorine ion as a counter ion. An ammonium base is introduced.
  • the quaternary ammonium base is ionically dissociated, whereby chlorine ions as counter ions are liberated, and chlorine ions as anions exist in the conductive layer. it can.
  • a method of allowing perchlorate ions or bis (trifluoromethanesulfonyl) imide ions represented by the above formula (5) to exist in the conductive layer a method in which a desired anion is introduced as a counter ion as a binder in the conductive layer.
  • Examples include a method using a modified epichlorohydrin rubber modified with a quaternary ammonium base.
  • a modified epichlorohydrin rubber modified with a quaternary ammonium base in which a desired anion is introduced as a counter ion can be prepared by the following method.
  • a modified epichlorohydrin rubber into which a quaternary ammonium base having chlorine ions as counter ions is introduced is prepared.
  • the chloride ion of the quaternary ammonium base of the modified epichlorohydrin rubber is converted into a desired anion using an ion exchange reaction.
  • a modified epichlorohydrin rubber modified with a quaternary ammonium base having a desired anion introduced as a counter ion can be obtained.
  • the presence and quantification of the carrier molecule anion in the conductive layer can be verified by extracting the anion using an ion exchange reaction.
  • the modified epichlorohydrin rubber is stirred in a dilute aqueous solution of hydrochloric acid or sodium hydroxide, and the anion in the modified epichlorohydrin rubber is extracted into the aqueous solution.
  • the aqueous solution after extraction is dried, the extract is collected, and mass spectrometry is performed by a time-of-flight mass spectrometer (TOF-MS), whereby anion can be identified and quantified. Even when the molecular weight of the anion is high, it can be analyzed without decomposing the anion in the TOF-MS measurement.
  • element analysis is performed by inductively coupled plasma (ICP) emission analysis of the extract and combined with the results of mass spectrometry, it becomes easier to identify and quantify the anion as a carrier molecule.
  • ICP inductively coupled plasma
  • Examples of the method for forming the conductive layer include a method in which the rubber composition as the raw material for the conductive layer is molded by a known method such as extrusion molding, injection molding, or compression molding.
  • the conductive layer may be formed directly on the conductive support, or may be formed by covering the conductive support with a conductive layer previously formed into a tube shape. Note that it is also preferable that the surface of the conductive layer is polished to form a shape after the conductive layer is formed.
  • FIG. 2 is an explanatory diagram of a conductive layer forming step around the conductive support by extrusion molding using a crosshead.
  • the conductive support 11 sequentially taken out from the conductive support holding container (not shown) is conveyed without a gap vertically by a plurality of pairs of feed rollers 23 that feed the conductive support 11 and introduced into the crosshead 22. Is done.
  • the unvulcanized rubber composition is supplied to the crosshead 22 from the direction perpendicular to the conveying direction of the conductive support 11 by the extruder 21, and the crosshead is formed as a coating layer covering the periphery of the conductive support 11 here. 22 is pushed out. Thereafter, the coating layer is cut by a cutting / removing machine 25 and divided for each conductive support to obtain an unvulcanized rubber roller 26.
  • the conductive layer is preferably formed in a crown shape that is thickest at the center and narrows toward both ends in order to ensure adhesion between the charging roller and the electrophotographic photosensitive member.
  • the charging roller generally used is brought into contact with the electrophotographic photosensitive member by applying a predetermined pressing force to both ends of the support. That is, the pressing force at the central portion is small and increases at both end portions. Therefore, there is no problem if the straightness of the charging roller is sufficient, but if it is not sufficient, density unevenness may occur in the images corresponding to the central portion and both end portions.
  • the crown shape is formed to prevent this.
  • the outer diameter fluctuation of the charging roller is small.
  • FIG. 4 is a schematic view of an electrophotographic apparatus using the conductive member according to the present invention as a charging roller.
  • the electrophotographic apparatus includes a charging roller 302 that charges the electrophotographic photosensitive member 301, a latent image forming device 308 that performs exposure, a developing device 303 that develops the toner image, a transfer device 305 that transfers the transfer material 304, and an electrophotographic photosensitive member.
  • a cleaning device 307 for collecting the transfer toner on the upper side, a fixing device 306 for fixing the toner image, and the like are included.
  • the electrophotographic photoreceptor 301 is a rotary drum type having a photosensitive layer on a conductive substrate.
  • the electrophotographic photosensitive member 301 is rotationally driven in the direction of the arrow at a predetermined peripheral speed (process speed).
  • the charging roller 302 is placed in contact with the electrophotographic photosensitive member 301 by being pressed with a predetermined force.
  • the charging roller 302 is driven to rotate in accordance with the rotation of the electrophotographic photosensitive member 301, and applies a predetermined DC voltage from the charging power source 313 to charge the electrophotographic photosensitive member 301 to a predetermined potential.
  • An electrostatic latent image is formed on the uniformly charged electrophotographic photosensitive member 301 by irradiating light 308 corresponding to image information.
  • the developer 315 in the developer container 309 is supplied to the surface of the developing roller 303 disposed in contact with the electrophotographic photosensitive member 301 by the developer supply roller 311. Thereafter, a developer layer charged to the same polarity as the charging potential of the electrophotographic photosensitive member is formed on the surface of the developing roller 303 by the developer amount regulating member 310. Using this developer, the electrostatic latent image formed on the electrophotographic photosensitive member is developed by reversal development.
  • the transfer device 305 has a contact-type transfer roller. The toner image is transferred from the electrophotographic photosensitive member 301 to a transfer material 304 such as plain paper. The transfer material 304 is transported by a paper feed system having a transport member.
  • the cleaning device 307 includes a blade-type cleaning member and a collection container. After the transfer, the transfer residual toner remaining on the electrophotographic photosensitive member 301 is mechanically scraped and collected. Here, it is possible to omit the cleaning device 307 by adopting a development simultaneous cleaning system in which the developing device 303 collects the transfer residual toner.
  • the fixing device 306 is configured by a heated roll or the like, fixes the transferred toner image on the transfer material 304, and discharges the toner image outside the apparatus.
  • Reference numerals 312 and 314 denote DC power supplies.
  • FIG. 5 is a schematic sectional view of a process cartridge in which the conductive member according to the present invention is applied to the charging roller 302.
  • the process cartridge according to the present invention includes an electrophotographic photosensitive member 301, a charging roller 302, a developing device 303, a cleaning device 307, and the like, which are detachable (detachable) from the main body of the electrophotographic device. Possible).
  • Example 1 100 g of epichlorohydrin-ethylene oxide-allyl glycidyl ether (EP / EO / AGE) terpolymer (trade name: Epion 301, manufactured by Daiso Corporation) was dissolved in 1000 ml of N, N-dimethylformamide (DMF). It was. To this solution, 8 g of a 40% by mass aqueous methylamine solution (3.2 g as methylamine) was added, and the mixture was heated to reflux at 50 ° C. for 12 hours in a nitrogen atmosphere.
  • EP / EO / AGE epichlorohydrin-ethylene oxide-allyl glycidyl ether
  • reaction solution was concentrated to dryness to obtain an EP / EO / AGE terpolymer in which quaternary ammonium ions were introduced into the epichlorohydrin unit portion.
  • This was designated as modified epichlorohydrin rubber No. Set to 1.
  • modified epichlorohydrin rubber No. 1 100 parts by mass, the materials shown in Table 1 were added, mixed by an open roll, and unvulcanized rubber composition No. 1 was mixed. 1 was obtained.
  • a stainless steel core bar having a diameter of 6 mm and a length of 258 mm was prepared, and the surface thereof was nickel-plated to a thickness of about 5 ⁇ m to obtain a conductive support.
  • FIG. 3 shows a schematic diagram of the electrical resistance measuring apparatus used in this evaluation.
  • Charging roller No. 1 is rotatably held by bearings 31 attached to both ends thereof, and is pressed against an aluminum cylindrical drum 33 having an outer diameter of 30 mm with a pressing force of 450 gf on one side by a spring 32 attached to the bearing 31. .
  • the cylindrical drum 33 is driven to rotate at a rotational speed of 33 rpm. 1 was driven to rotate.
  • a voltage was applied for 305 seconds in a constant current control mode by an external DC power supply 34 (trade name: Model 610E; manufactured by TReK) so that a DC current of 50 ⁇ A flows through the drum 33 to the charging roller 1.
  • the output voltage at the initial stage (5 seconds after application 2 seconds) and 300 seconds (after 5 seconds after 300 seconds) was measured at a sampling frequency of 100 Hz.
  • the initial value Va and the voltage change rate Vb / Va were measured with the average value of the initial output voltage being Va (V) and the average value of the output voltage after 300 seconds being Vb (V).
  • Va was 25.2 (V), indicating good conductivity.
  • Vb / Va is 1.14, showing that there is almost no change in the electrical resistance value.
  • Charging roller No. 1 is placed on a polyethylene terephthalate (PET) sheet at a temperature of 40 ° C. and a humidity of 95% RH. A load of 550 gf is applied to the exposed portions of the core metal at both ends of the charging roller No. The surface of 1 conductive layer was pressed against a PET sheet. After maintaining this state for one week, the charging roller No. 1 is removed from the PET sheet, and the charging roller No. 1 on the surface of the PET sheet is removed. The portion where 1 was pressed was observed with an optical microscope. The state of adhesion of the bleed material from the conductive layer 1 was observed and evaluated based on the criteria described in Table 3 below.
  • Example 2 The modified epichlorohydrin rubber No. 1 according to Example 1 except that the epichlorohydrin rubber as a raw material, the amine species used for modification and the addition amount of the amine were changed as described in Table 4.
  • the modified epichlorohydrin rubber no. 2 to No. 12 was synthesized.
  • Table 4 the alphabet of the epichlorohydrin rubber type as a raw material indicates the material described in Table 5.
  • the obtained modified epichlorohydrin rubber No. 2 to No. Except for using No. 12, unvulcanized rubber composition no. 2 to No. 12 was prepared, and using this, the charging roller No. 12 was prepared. 2 to No. 12 was produced. These charging rollers were subjected to Evaluations 1 to 3 in Example 1.
  • Example 13 100 g of epichlorohydrin rubber J as a raw material and 8.1 g of triethylamine were mixed with an open roll, and modified epichlorohydrin rubber No. 1 was mixed. 13 was obtained. The resulting modified epichlorohydrin rubber No. Except for using No. 13, in the same manner as in Example 1, unvulcanized rubber composition No. 13 was prepared, and using this, charging roller No. 13 was prepared. 13 was created. This charging roller was subjected to Evaluations 1 to 3 in Example 1.
  • Example 14 to 44 The modified epichlorohydrin rubber No. 1 according to Example 1 was changed except that the epichlorohydrin rubber as a raw material, the amine species used for modification and the addition amount of the amine were changed as shown in Table 6.
  • the modified epichlorohydrin rubber no. 14-No. 44 was synthesized. Subsequently, the obtained modified epichlorohydrin rubber No. 14-No.
  • the unvulcanized rubber composition No. 4 was used in the same manner as in Example 1 except that 44 was used. 14-No. No. 44 is prepared, and using this, the charging roller No. 44 is prepared. 14-No. 44 was created. These charging rollers were subjected to Evaluations 1 to 3 in Example 1.
  • Example 45 100 g of epichlorohydrin rubber A as a raw material and 10.3 g of dimethylhexylamine were mixed in an open roll, and modified epichlorohydrin rubber No. 1 was mixed. 45 was obtained. Next, the materials listed in Table 7 below were mixed using an open roll, and unvulcanized rubber composition No. 45 was obtained.
  • a stainless steel core bar having an outer diameter of 6 mm and a length of 258 mm was prepared, and nickel plating with a thickness of about 5 ⁇ m was applied to the surface.
  • This metal core is set at the center of a cylindrical mold having an inner diameter of 8.5 mm, and an unvulcanized rubber composition No. 1 is placed between the conductive support and the mold. 45 was placed.
  • the unvulcanized rubber composition No. 4 was heated in steam at a temperature of 160 ° C. for 40 minutes. 45 was first vulcanized. Subsequently, it heated in the electric oven with a temperature of 150 degreeC for 1 hour, and was set as the rubber layer.
  • Examples 46 to 47 In the same manner as in Example 45 except that the epichlorohydrin rubber A as the raw material in Example 45 was changed to the epichlorohydrin rubber B or epichlorohydrin rubber C shown in Table 5, modified epichlorohydrin rubber No. 46-No. 47 was synthesized. Subsequently, the obtained modified epichlorohydrin rubber No. 46-No. Except that 47 was used, the unvulcanized rubber composition no. 46-No. 47 is prepared, and using this, charging roller No. 47 is prepared. 46-No. 47 was created. These charging rollers were subjected to Evaluations 1 to 3 in Example 1.
  • Example 48 100 g of epichlorohydrin rubber J as a raw material was dissolved in 1000 ml of N, N-dimethylformamide (DMF). To this solution, 31.7 g of potassium phthalimide was added, and the mixture was refluxed for 12 hours at a temperature of 70 ° C. in a nitrogen atmosphere. Methanol was added to the reaction solution to precipitate the reaction product, and unreacted potassium phthalimide was removed. The epichlorohydrin rubber to which phthalimide was added was dissolved again in 1000 ml of N, N-dimethylformamide, 11 ml of hydrazine monohydrate was added, and the mixture was heated to reflux at 70 ° C. for 12 hours.
  • DMF N, N-dimethylformamide
  • Example 49 Modified epichlorohydrin rubber No. 1 in Example 3 3 was dissolved in 100 g of N, N-dimethylformamide (DMF) 1000 ml. Next, 11 g of lithium perchlorate was dissolved in 10 ml of DMF. The two types of DMF solutions obtained were mixed and stirred for 2 hours. After mixing and stirring, the DMF solution was poured into water stirred at room temperature and reprecipitated. Reprecipitation and washing with water were repeated twice, and after drying, an unvulcanized rubber composition No. 4 containing perchlorate ions (ClO 4 ⁇ ) was obtained. 49 was obtained. Next, the obtained unvulcanized rubber No. No. 49 and charging roller No. 49 was produced. This charging roller was subjected to Evaluations 1 to 3 in Example 1.
  • DMF N, N-dimethylformamide
  • Example 50 Unvulcanized rubber containing bis (trifluoromethanesulfonyl) imide ion (TFSI ⁇ ) in the same manner as in Example 49 except that 29 g of bis (trifluoromethanesulfonyl) imide lithium was used instead of lithium perchlorate of Example 49 Composition No. 50 is prepared, and using this, the charging roller No. 50 is prepared. 50 was produced. This charging roller was subjected to Evaluations 1 to 3 in Example 1.
  • Comparative Example 2 In Comparative Example 1, an unvulcanized rubber composition No. 1 was prepared in the same manner as Comparative Example 1 except that tetraethylammonium chloride was not blended. C-2 was obtained. Unvulcanized rubber composition No. Except that C-2 was used, the charging roller No. 1 was the same as in Example 1. C-2 was created. This charging roller was subjected to Evaluations 1 to 3 in Example 1.
  • Comparative Example 3 In Comparative Example 2, an unvulcanized rubber composition No. 1 was prepared in the same manner as in Comparative Example 2 except that 18 g of triethylamine was added when mixing with an open roll. C-3 was obtained. Unvulcanized rubber composition No. Except for using C-3, the charging roller no. C-3 was created. This charging roller was subjected to Evaluations 1 to 3 in Example 1. The charging roller No. 1 according to Examples 1 to 50 described above. 1-No. The evaluation results of 50 are shown in Tables 9-1 to 9-2. In addition, the charging roller No. 1 according to Comparative Examples 1 to 3 is used. C-1 to No. The evaluation results of C-3 are shown in Table 9-3.
  • Example 51 The primer layer was baked on the peripheral surface of a stainless steel core bar having a diameter of 6 mm and a length of 279 mm baked with the primer. While this is used for a conductive support, unvulcanized rubber composition No. 13, the conductive roller no. In the same manner as in No. 1, the conductive roller no. 51 was created. However, the thickness of the rubber layer was 3 mm, and the width of the rubber layer was 235 mm.
  • Conductive roller No. 51 was subjected to Evaluation 1, 2 and Evaluation 5 below.
  • Conductive roller No. 51 was incorporated as a developing roller of a laser printer (trade name: LBP5400, manufactured by Canon Inc.), and one cyan solid image and one halftone image were output. These are defined as an evaluation image group a.
  • the conductive roller No. 51 is taken out and the conductive roller No. 51 is used by using the electrical resistance measuring apparatus used in the evaluation 1.
  • a direct current of 400 ⁇ A was passed through 51 for 120 minutes.
  • the conductive roller no. 51 was incorporated as a developing roller of a laser printer (trade name: LBP5400, manufactured by Canon Inc.), and one cyan solid image and one halftone image were output. Let these be the evaluation image group b.
  • the evaluation image group a and the evaluation image group b were visually observed and evaluated according to the following criteria.
  • Example 52 to 54 and [Comparative Example 4] In the same manner as in Example 51 except that the polymer and amine used in the unvulcanized rubber composition were changed to those shown in Table 10, the conductive roller no. 52-No. 54, and no. C-4 was prepared and used for Evaluations 1, 2 and 5. The results are shown in Table 11.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrostatic Charge, Transfer And Separation In Electrography (AREA)
  • Dry Development In Electrophotography (AREA)
  • Electrophotography Configuration And Component (AREA)
  • Rolls And Other Rotary Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)
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JP6346494B2 (ja) * 2014-05-16 2018-06-20 キヤノン株式会社 電子写真用部材、プロセスカートリッジおよび電子写真装置
JP2016028268A (ja) * 2014-07-09 2016-02-25 キヤノン株式会社 電子写真感光体、電子写真感光体の製造方法、プロセスカートリッジおよび電子写真装置
JP6590652B2 (ja) * 2015-11-16 2019-10-16 キヤノン株式会社 現像部材、その製造方法、プロセスカートリッジおよび電子写真画像形成装置
JP6922477B2 (ja) * 2017-06-29 2021-08-18 富士フイルムビジネスイノベーション株式会社 画像形成装置
JP2019012100A (ja) * 2017-06-29 2019-01-24 富士ゼロックス株式会社 導電性部材、帯電装置、転写装置、プロセスカートリッジ、及び画像形成装置
JP2019012101A (ja) * 2017-06-29 2019-01-24 富士ゼロックス株式会社 導電性部材、帯電装置、転写装置、プロセスカートリッジ、及び画像形成装置

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JP6000580B2 (ja) 2016-09-28
CN103492956A (zh) 2014-01-01
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CN105259741A (zh) 2016-01-20
EP2693274A1 (en) 2014-02-05
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KR20140003605A (ko) 2014-01-09
DE202012013607U1 (de) 2018-04-19

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