WO2011108548A1 - Conductive roller and manufacturing method therefor - Google Patents

Conductive roller and manufacturing method therefor Download PDF

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Publication number
WO2011108548A1
WO2011108548A1 PCT/JP2011/054650 JP2011054650W WO2011108548A1 WO 2011108548 A1 WO2011108548 A1 WO 2011108548A1 JP 2011054650 W JP2011054650 W JP 2011054650W WO 2011108548 A1 WO2011108548 A1 WO 2011108548A1
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WIPO (PCT)
Prior art keywords
elastic layer
roller
conductive roller
layer
shaft
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PCT/JP2011/054650
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French (fr)
Japanese (ja)
Inventor
純一 高野
いづみ 吉村
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株式会社ブリヂストン
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Publication of WO2011108548A1 publication Critical patent/WO2011108548A1/en

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    • 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
    • G03G21/0005—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge for removing solid developer or debris from the electrographic recording medium
    • G03G21/0058—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge for removing solid developer or debris from the electrographic recording medium using a roller or a polygonal rotating cleaning member; Details thereof, e.g. surface structure
    • 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
    • G03G15/06—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to a conductive roller and a manufacturing method thereof (hereinafter also simply referred to as “roller” and “manufacturing method”), and more specifically, a conductive roller used in an image forming apparatus using an electrophotographic method and a manufacturing method thereof. Regarding the method.
  • a transfer roller In general, in an image forming apparatus using an electrophotographic system such as a copying machine, a printer, and a facsimile machine, a transfer roller, a developing roller, a toner supply roller, a charging roller, a cleaning roller, an intermediate transfer roller, and a belt are used in each image forming process.
  • roller member As such a roller member, a conventional structure in which an elastic layer made of rubber, a polymer elastomer, a polymer foam or the like provided with conductivity by blending a conductive agent on the outer periphery of a shaft is used as a basic structure. In order to obtain surface roughness, conductivity, hardness, and the like, those having a single-layer or multiple-layer coating on the outer periphery thereof are used.
  • Patent Document 1 discloses that a layered silica is coated at a predetermined ratio on a water-based electrophotographic apparatus coating material mainly containing an aqueous polyurethane resin and containing a fluororesin dispersion.
  • a technique for containing an acid salt is disclosed, and it is also described that a wetting agent such as a silicone compound can be contained in the coating agent for an electrophotographic apparatus member.
  • a solid (non-foamed) layer is usually provided on the outer periphery of the elastic layer made of a foam body for the purpose of adjusting resistance and ensuring elasticity. It is important that the pore diameter is small. This is because if the pore diameter on the surface of the elastic layer is large, the solid layer paint may permeate into the pores and cause undulation on the surface of the solid layer. Therefore, in a conductive roller having an elastic layer made of a foam body, in addition to low variation in the specific gravity of the elastic layer-forming coating material, it is important to increase the image accuracy that the bubbles in the foam are fine. Become. However, in the method by free foaming using a mixer or the like, it is difficult to adjust the specific gravity of the elastic layer forming coating material made of foam and the pore diameter of the elastic layer surface as desired. .
  • an object of the present invention is to provide a conductive roller that solves the above-described problems, has a small variation in specific gravity of the elastic layer-forming coating material, and has fine pores on the elastic layer surface, and a method for manufacturing the same. .
  • the present inventor has found that the above problem can be solved by blending a wetting agent in the composition of the foam body constituting the elastic layer, and has completed the present invention.
  • the conductive roller of the present invention is a conductive roller comprising a shaft and an elastic layer formed on the outer periphery of the shaft.
  • the elastic layer is made of a polyurethane foam containing a polyurethane resin and a wetting agent.
  • a silicone surfactant can be suitably used as the wetting agent.
  • the polyurethane foam preferably contains the wetting agent in an amount of 0.1 to 4 parts by mass with respect to 100 parts by mass of the polyurethane resin.
  • a surface layer is formed on the outer periphery of the elastic layer.
  • the conductive roller of the present invention can be suitably used as a charging roller.
  • the manufacturing method of the conductive roller of the present invention is a method of manufacturing the conductive roller of the present invention,
  • the compounding material containing the polyurethane resin and the wetting agent is foamed by mechanical stirring, and then the foamed compounding material is dipped on the shaft, and the elastic layer is formed on the outer periphery of the shaft. It is characterized by forming.
  • the inclusion of a wetting agent during the blending of the polyurethane foam constituting the elastic layer reduces the variation in specific gravity of the elastic layer-forming coating material, and the elastic layer surface has fine pores. It has become possible to realize a roller and its manufacturing method.
  • FIG. 3 is a photograph showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 1.
  • FIG. 6 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 2.
  • FIG. 10 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 3.
  • FIG. 10 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 4.
  • 6 is a photographic view showing a state of pores in a cross section of an elastic layer of a conductive roller of Comparative Example 1.
  • FIG. 3 is a photograph showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 1.
  • FIG. 6 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 2.
  • FIG. 1 is a longitudinal sectional view showing an example of the conductive roller of the present invention.
  • the conductive roller 10 of the present invention includes at least a shaft 1 and an elastic layer 2 sequentially formed on the outer periphery thereof.
  • a solid (non-foamed) surface layer 3 is further formed on the outer periphery of the elastic layer 2.
  • the present invention is characterized in that the elastic layer 2 is made of a polyurethane foam containing a polyurethane resin and a wetting agent.
  • a wetting agent to the polyurethane foam composing the elastic layer 2
  • the foaming specific gravity of the paint when freely foamed is controlled more precisely, and the variation in specific gravity is within 0.1 g / ml. It is possible to suppress the foam cell to become coarse, and the pores on the surface of the elastic layer can be reduced to an average pore diameter of about 130 ⁇ m or less, thereby improving the surface property of the roller. It became possible. Further, according to the present invention, a leveling effect can be obtained, that is, dripping of the surface during drying when the elastic layer is applied and formed by dipping can be suppressed.
  • a silicone-based surfactant such as polyether-modified silicone
  • the polyether-modified silicone has a structure in which a part of the alkyl group of poly (dialkylsiloxane) is replaced with a substituent having a polyoxyalkylene group.
  • examples of such polyether-modified silicones include dimethylpolysiloxane polyoxyalkylene copolymers.
  • the foamed cells that have become coarser tend to break As the wetting agent composed of such a silicone surfactant, for example, SN wet 125 manufactured by San Nopco Co., Ltd. can be suitably used.
  • the amount of the wetting agent is preferably 0.1 to 4 parts by mass, particularly 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the blending amount of the wetting agent is too large, gelation of the paint tends to occur. On the other hand, if the blending amount is too small, the desired effect of the present invention may not be obtained sufficiently, which is not preferable.
  • the point that the wetting agent is contained in the polyurethane foam constituting the elastic layer 2 of the conductive roller is important, and other points can be appropriately configured according to a conventional method. It is not limited.
  • the polyurethane resin used for the polyurethane foam a conventionally known material can be appropriately selected and used, and is not particularly limited.
  • the foaming ratio of the polyurethane foam is not particularly limited, but is preferably 1.2 to 50 times, particularly preferably about 1.5 to 10 times, and the foam density is 0.1 to 0.7 g / About cm 3 is preferable.
  • a conductive agent can be added to the elastic layer 2, whereby conductivity can be imparted or adjusted to a predetermined resistance value.
  • the conductive agent is not particularly limited, and lauryltrimethylammonium, stearylmethylammonium, octadodecyltrimethylammonium, hexadecyltrimethylammonium, modified fatty acid / dimethylethylammonium perchlorate, chlorate, borofluoride , Cationic surfactants such as quaternary ammonium salts such as halogenated benzyl salts such as sulfates, etosulphate salts, benzyl bromide salts, benzyl chloride salts, aliphatic sulfonates, higher alcohol sulfates, Anionic surfactants such as higher alcohol ethylene oxide addition sulfate, higher alcohol phosphate, higher alcohol ethylene oxide addition phosphate, higher alcohol ethylene oxide, polyethylene glycol fatty
  • Electrolytes such as Group 1 metal salts or NH 4 + salts, conductive carbons such as ketjen black and acetylene black, rubber carbons such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, and MT Oxidized carbon for color (ink), pyrolytic carbon, natural graphite, artificial graphite, antimony-doped tin oxide, titanium oxide, zinc oxide, nickel, copper, silver, germanium and other metals and metal oxides, Examples thereof include conductive polymers such as polyaniline, polypyrrole, and polyacetylene. These conductive agents may be used alone or in combination of two or more. The blending amount of these conductive agents is appropriately selected according to the type of the composition. Usually, the volume resistivity of the elastic layer 2 is 10 0 to 10 8 ⁇ ⁇ cm, preferably 10 2 to 10 6 ⁇ ⁇ cm. It is adjusted to become.
  • the elastic layer 2 may include a water resistance agent, a foaming agent, a foam stabilizer, a curing agent, a thickener, an antifoaming agent, a leveling agent, a dispersing agent, if necessary.
  • a known additive such as a thixotropic property-imparting agent, an anti-blocking agent, a crosslinking agent, or a film-forming auxiliary agent can be blended.
  • a water-resistant agent for example, ammonium zirconium carbonate can be suitably used.
  • the surface property of the roller can be improved by miniaturization.
  • the blending amount of the water-resistant agent is preferably 0.5 to 20 parts by mass, particularly 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the amount of the water-resistant agent is too large, the viscosity tends to be too high and the pot life tends to decrease. On the other hand, if the amount of the water-resistant agent is too small, the desired effect may not be obtained sufficiently. However, neither is preferable.
  • the thickness of the elastic layer 2 is preferably 0.6 to 5.0 mm, and more preferably 1.0 to 3.0 mm. By setting the thickness of the elastic layer 2 in such a range, spark discharge can be prevented.
  • a metal or plastic hollow cylindrical body or solid cylindrical body can be used, and preferably a metal hollow cylindrical body or solid cylindrical body. More preferably, it is a metal hollow cylinder. Thereby, cost efficiency can be improved.
  • the surface layer 3 provided on the elastic layer 2 is preferably formed using a water-based paint.
  • a water-based paint used for the surface layer 3
  • a known rubber or resin can be used as a material for a roller or the like.
  • the resin include a urethane-modified acrylic resin, a polyurethane resin, an acrylic resin, an acrylic silicone resin, a polyamide resin, a fluororesin, and the like, and one or more of these can be used in combination.
  • a rubber-based water-based paint natural rubber (NR), chloroprene rubber (CR), nitrile rubber (NBR), latex such as styrene-butadiene rubber (SBR), etc.
  • a polyurethane resin-based water-based paint ether-based, Ester and other emulsions and dispersions
  • acrylic resin-based water-based paints, acrylic and acrylic styrene emulsions, and fluororesin-based water-based paints include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Polymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, polyvinylidene fluoride, polyvinyl fluoride Etc.
  • NR natural rubber
  • CR chlor
  • a water-based acrylic resin can be suitably used as the water-based paint.
  • an aqueous acrylic resin those containing acrylonitrile and n-butyl acrylate as essential components and optionally containing other monomers are preferable.
  • examples of other monomers include ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid, Examples include methacrylic acid.
  • acrylonitrile and n-butyl acrylate are essential components is that they contribute to the improvement of elasticity (setting property). From this viewpoint, the amount of n-butyl acrylate is increased as much as possible, and other components It is preferable to reduce the monomer ratio of other monomer components other than the essential components.
  • the monomer ratio of acrylonitrile, which is an essential component, and n-butyl acrylate is preferably in the range of 1 to 25:99 to 75, particularly 5 to 20:95 to 80 in terms of molar ratio.
  • the water-based acrylic resin contains a group having active hydrogen in the molecule.
  • the group having active hydrogen include a carboxyl group, a hydroxyl group, and an amino group, and a carboxyl group is preferable.
  • the ratio of the monomer containing the group having active hydrogen is preferably in the range of 3 to 6% of the total monomer amount.
  • a water-based acrylic resin having a surface acid value adjusted to 10 mg / g or more, for example, 10 to 20 mg / g is suitably obtained by setting the ratio of the monomer containing a group having active hydrogen within this range. Can be used.
  • the water-based paint forming the surface layer 3 is not particularly limited, but the conductivity (electric resistance) of the surface layer 3 can be imparted or adjusted by adding a conductive agent.
  • a conductive agent There is no restriction
  • the thing similar to being used for the elastic layer 2 can be used suitably by 1 type or in mixture of 2 or more types.
  • the blending amount of these conductive agents is appropriately selected according to the type of the composition.
  • the volume resistivity of the surface layer 2 is 1 ⁇ 10 4 to 1 ⁇ 10 12 ⁇ ⁇ cm, preferably 1 ⁇ 10 6 to It is adjusted to be 1 ⁇ 10 8 ⁇ ⁇ cm.
  • additives such as a cross-linking agent, a thickener, a thixotropy imparting agent, and a structural viscosity imparting agent can be added as necessary.
  • the thickness of the surface layer 3 is not particularly limited, but can usually be 1 to 30 ⁇ m, particularly 1 to 20 ⁇ m. When the thickness of the surface layer 3 is less than 1 ⁇ m, the durability of the roller may be inferior. On the other hand, when the thickness exceeds 30 ⁇ m, the charging property is adversely affected and the surface is wrinkled. May not be obtained.
  • the conductive roller 10 of the present invention includes at least an elastic layer 2 on the outer periphery of the shaft 1, and preferably further includes a surface layer 3. If necessary, between the elastic layer 2 and the surface layer 3, The resistance adjustment layer 5 can be provided as an intermediate layer, and the adhesive layer 4 can be further interposed between the elastic layer 2 and the resistance adjustment layer 5. Furthermore, prior to forming the elastic layer 2 on the outer periphery of the shaft 1, an adhesive layer 4 can be provided to improve the adhesion between the shaft 1 and the elastic layer 2.
  • FIG. 2 is a longitudinal sectional view showing another configuration example of the conductive roller of the present invention.
  • the illustrated conductive roller 20 includes a shaft 1 and an adhesive layer 4, an elastic layer 2, a resistance adjusting layer 5, and a surface layer 3 that are sequentially formed on the outer periphery thereof.
  • the resistance adjusting layer 5 can be formed of a resin composition obtained by adding a conductive agent to a resin.
  • the resin constituting the resin composition is not particularly limited, but specifically, for example, urethane resin, acrylic urethane resin, acrylic resin, ester resin, nylon resin, phenol resin, epoxy resin, fluororesin , Silicone resins, and the like, and one or a mixture of two or more of these can be used.
  • water-based paints such as urethane resins, acrylic urethane resins, and acrylic resins are preferably used.
  • the conductive agent added to the water-based paint the same conductive agent as that used for the elastic layer 2 can be used.
  • the resistance adjustment layer 5 is arbitrarily provided to adjust the electrical resistance value of the conductive roller.
  • the resistance value of the resistance adjustment layer 5 is the resistance value of the elastic layer 2 or the resistance required of the roller. Although it is set as appropriate depending on the value, it can usually be in the range of 1 ⁇ 10 3 to 1 ⁇ 10 8 ⁇ ⁇ cm, particularly 1 ⁇ 10 5 to 1 ⁇ 10 7 ⁇ ⁇ cm.
  • the blending amount of the conductive agent can be an appropriate amount that achieves this resistance value, but is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the base resin of the water-based paint. In particular, it is preferably 1 to 10 parts by mass.
  • various additives can be blended into the resistance adjusting layer 5 without departing from the object of the present invention.
  • oxazoline-based, epoxy-based, melamine-based, guanamine-based, isocyanate-based, phenol-based cross-linking agents can be blended in appropriate amounts according to the base resin used. You may mix
  • the thickness of the resistance adjusting layer 5 is appropriately selected according to the thickness of the elastic layer 2 and the form of the conductive roller, and is not particularly limited, but is usually 10 to 500 ⁇ m, particularly 50 to 300 ⁇ m. Is preferred. When the thickness of the resistance adjusting layer 5 is less than 50 ⁇ m, it may be difficult to adjust the resistance value sufficiently. On the other hand, when the thickness exceeds 300 ⁇ m, the thickness of the elastic layer becomes relatively thin, and the roller In some cases, the hardness (member hardness) becomes high, or the cost becomes higher than necessary.
  • the adhesive layer 4 can be provided as desired in order to firmly adhere between the shaft 1 and the elastic layer 2 or between the elastic layer 2 and the resistance adjusting layer 5.
  • the thickness can be about 1 to 100 ⁇ m.
  • the adhesive layer 4 can be formed using, for example, a resin material such as an acrylic resin, a urethane resin, an acrylic urethane resin, a polyester resin, a polyamide resin, and a conductive agent and other additives are added as necessary. You can also.
  • FIG. 3 is a longitudinal sectional view showing still another example of the conductive roller of the present invention.
  • a conductive roller When a conductive roller is used as a charging roller or the like, it is important to form a uniform contact surface in the length direction when pressed by the photosensitive drum. It has a crown shape having a diameter larger than that of the end portion in the central portion in the longitudinal direction.
  • the crown amount representing the degree of protrusion at the center in the length direction in the cross section in the longitudinal direction of the roller is preferably 50 to 300 ⁇ m, thereby further improving the normal image. Can be made. If the crown amount is less than 50 ⁇ m, the contact pressure in the central portion in the roller length direction becomes low. On the other hand, if the crown amount exceeds 300 ⁇ m, the central portion in the roller length direction is too strongly contacted. There is a risk of causing problems such as uneven charge amount.
  • the crown amount of the conductive roller can be measured using a high precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation.
  • the outer diameter is measured at the center of the roller and at a position of 90 mm from the center to the end, and the difference between the outer diameter of the center and the average value of the outer diameter at the positions of 90 mm in both end directions is calculated.
  • the deflection (film thickness accuracy) is 70 ⁇ m or less in the entire region in the roller length direction.
  • the deflection film thickness accuracy
  • the deflection is 70 ⁇ m or less in the entire region in the roller length direction.
  • the deflection of the conductive roller can be measured using a high-precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation. With this measuring machine, the outer diameter is measured for each of the five points in the roller length direction, and the average value of the difference between the maximum value and the minimum value of the outer diameter measured for each point is taken as the shake.
  • the conductive roller of the present invention can be particularly suitably used as a charging roller.
  • the conductive roller of the present invention can be manufactured as follows. That is, first, a wetting agent and other optional additives are added to the polyurethane resin constituting the elastic layer 2, and the resulting blended material is mechanically stirred using a stirrer such as a hand mixer. To make it foam. Then, the elastic layer 2 can be formed on the outer periphery of the shaft 1 by dipping the foamed compounding material onto the shaft 1. By forming the elastic layer 2 by directly applying a paint to the shaft 1, the manufacturing process can be simplified and the cost can be reduced.
  • the adhesive layer 4 is applied and formed using a paint in which the above-described constituent materials are dispersed or dissolved.
  • a coating method a known method such as a dipping method, a spray method, a roll coater method, a die coating method, a ring coating method or the like can be used as appropriate, and the adhesive layer 4 is formed by drying and solidifying after applying the paint.
  • a dipping method as a coating method.
  • the same method as described above may be used when the adhesive layer 4 is provided between the shaft 1 and the elastic layer 2.
  • the resistance adjustment layer 5 can also be applied and formed in the same manner as the adhesive layer 4 if desired.
  • the conductive layer of the present invention is formed by coating the surface layer 3 on the elastic layer 2 or the resistance adjusting layer 5 formed on the elastic layer 2 in the same manner as the adhesive layer 4. Can be obtained.
  • the pore diameter on the surface of the elastic layer 2 is miniaturized, the paint does not enter the pores when the surface layer 3 or the like is applied and formed on the elastic layer 2, and the finally obtained conductivity is obtained. The effect of not impairing the surface property of the roller is obtained.
  • a conductive roller having a configuration in which an elastic layer 2 and a surface layer 3 are sequentially formed on the outer periphery of the shaft 1 as shown in FIG. 1 was produced as follows according to the formulation shown in the table below.
  • Epocros emulsion of oxazoline group-containing styrene-acrylic copolymer
  • water-based paint aqueous emulsion of acrylonitrile-alkyl acrylate-methacrylic acid-glycidyl methacrylate copolymer
  • dispersed carbon 7.5 parts by weight of fine seal X-12 (hydrophilic silica)
  • SN deformer 777 antifoaming agent
  • 1 part by weight of SN wet 970 wetting agent
  • UH420 thickening agent
  • the water-based paint containing each component was filtered through a mesh to remove aggregates.
  • the shaft 1 was dipped on this water-based paint and thermally dried to form an adhesive layer 4 having a thickness of 100 ⁇ m on the outer periphery of the shaft 1.
  • the elastic layer compounding materials shown in the table below were put into a container and stirred for 30 minutes using a wing. Thereafter, the mixture was stirred for 6 minutes using a commercially available hand mixer and foamed to obtain a foamed urethane water dispersion.
  • CS-12 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (CS-12, Chisso Corporation) with respect to 100 parts by mass of water-based paint (acrylic silicone resin, EX102SI, manufactured by Nippon Shokubai Co., Ltd.) )) 70 parts by mass, water-based silicone graft acrylic polymer (Cymac US-450, manufactured by Toagosei Co., Ltd.), polyether modified polydimethylsiloxane (BYK-333, manufactured by BYK Japan Japan) 27 parts by mass Parts, 2 parts by mass of fluorine-containing nonionic surfactant (Furgent 215M, manufactured by Neos Co., Ltd.), 10 parts by mass of silica (Fine Seal X-12, manufactured by Tokuyama Co., Ltd.), nylon particles (Gantz Pearl GPA-550) , Manufactured by Ganz Kasei Co., Ltd.) 15 parts by mass, an aqueous dispersion of
  • Urethane resin Adekabon titer HUX-950 (manufactured by ADEKA) * 2) Foaming agent: Nopco DC-100-A (manufactured by San Nopco) * 3) Wetting agent: SN wet 125 (manufactured by San Nopco) * 4) Conductive agent: BSYD14971 (manufactured by Gokoku Color Co., Ltd.) * 5) Foam stabilizer: Neogen S-20D (Daiichi Kogyo Seiyaku Co., Ltd.) * 6) Curing agent: Adekabon titer HUX-SW (manufactured by ADEKA Corporation) * 7) Water-resistant agent: AZ coat 5800MT (manufactured by San Nopco)

Abstract

Disclosed are a conductive roller and a manufacturing method therefor. The surface of an elastic layer in said roller has tiny air pores, and variations in the specific gravity of a coating used to form the elastic layer are minimized. The disclosed conductive roller comprises a shaft (1) and an elastic layer (2) formed on the outer surface of the shaft. The elastic layer (2) comprises a polyurethane foam containing a polyurethane resin and a moisturizing agent. To manufacture the disclosed conductive roller, a blended material containing a polyurethane resin and a moisturizing agent is foamed via mechanical agitation, and a shaft (1) is dipped in the foamed blended material, thereby forming an elastic layer (2) on the outer surface of the shaft (1).

Description

導電性ローラおよびその製造方法Conductive roller and manufacturing method thereof
　本発明は、導電性ローラおよびその製造方法（以下、単に「ローラ」および「製造方法」とも称する）に関し、詳しくは、電子写真方式を用いた画像形成装置において使用される導電性ローラおよびその製造方法に関する。 The present invention relates to a conductive roller and a manufacturing method thereof (hereinafter also simply referred to as “roller” and “manufacturing method”), and more specifically, a conductive roller used in an image forming apparatus using an electrophotographic method and a manufacturing method thereof. Regarding the method.
　一般に、複写機やプリンタ、ファクシミリ等の電子写真方式を用いた画像形成装置においては、画像形成の各工程で、転写ローラ、現像ローラ、トナー供給ローラ、帯電ローラ、クリーニングローラ、中間転写ローラ、ベルト駆動ローラ等の、導電性を付与したローラが用いられている。 In general, in an image forming apparatus using an electrophotographic system such as a copying machine, a printer, and a facsimile machine, a transfer roller, a developing roller, a toner supply roller, a charging roller, a cleaning roller, an intermediate transfer roller, and a belt are used in each image forming process. A roller having conductivity, such as a driving roller, is used.
　かかるローラ部材としては、従来、軸の外周に、導電剤を配合することにより導電性を付与したゴムや高分子エラストマー、高分子フォーム等からなる弾性層を形成した構造を基本構造として、所望の表面粗さや導電性、硬度などを得るために、その外周に一層または複数層の塗膜を設けたものが使用されている。 As such a roller member, a conventional structure in which an elastic layer made of rubber, a polymer elastomer, a polymer foam or the like provided with conductivity by blending a conductive agent on the outer periphery of a shaft is used as a basic structure. In order to obtain surface roughness, conductivity, hardness, and the like, those having a single-layer or multiple-layer coating on the outer periphery thereof are used.
　導電性ローラの改良に係る技術としては、例えば、特許文献１に、水系ポリウレタン樹脂を主成分とし、フッ素樹脂ディスパージョンを含有する水系の電子写真装置部材用コーティング剤に、所定の割合で層状ケイ酸塩を含有させる技術が開示されており、この電子写真装置部材用コーティング剤にはシリコーン系化合物等の湿潤剤を含有させることができることも記載されている。 As a technique related to the improvement of the conductive roller, for example, Patent Document 1 discloses that a layered silica is coated at a predetermined ratio on a water-based electrophotographic apparatus coating material mainly containing an aqueous polyurethane resin and containing a fluororesin dispersion. A technique for containing an acid salt is disclosed, and it is also described that a wetting agent such as a silicone compound can be contained in the coating agent for an electrophotographic apparatus member.
特開２００４－１１７６７４号公報（特許請求の範囲，段落［００２２］等）Japanese Unexamined Patent Application Publication No. 2004-117664 (Claims, paragraph [0022], etc.)
　上述のように、フォーム体からなる弾性層の外周には、通常、抵抗調整や弾性確保の目的でソリッド（非発泡）の層が設けられるが、これら目的の達成のためには、弾性層表面の気孔径が小さいことが重要である。これは、弾性層表面の気孔径が大きいと、ソリッド層の塗料が気孔内に浸み込んでしまい、ソリッド層表面にうねりを生ずる場合があるためである。したがって、フォーム体からなる弾性層を備える導電性ローラにおいては、弾性層形成用塗料の比重のバラツキが低いことに加え、フォーム内の気泡が微細であることが、画像精度を高める上で重要となる。しかしながら、ミキサー等を用いた自由発泡による手法では、フォーム体からなる弾性層形成用塗料の比重や、弾性層表面の気孔径を所望に調整することは困難であるため、改良が求められていた。 As described above, a solid (non-foamed) layer is usually provided on the outer periphery of the elastic layer made of a foam body for the purpose of adjusting resistance and ensuring elasticity. It is important that the pore diameter is small. This is because if the pore diameter on the surface of the elastic layer is large, the solid layer paint may permeate into the pores and cause undulation on the surface of the solid layer. Therefore, in a conductive roller having an elastic layer made of a foam body, in addition to low variation in the specific gravity of the elastic layer-forming coating material, it is important to increase the image accuracy that the bubbles in the foam are fine. Become. However, in the method by free foaming using a mixer or the like, it is difficult to adjust the specific gravity of the elastic layer forming coating material made of foam and the pore diameter of the elastic layer surface as desired. .
　そこで本発明の目的は、上記問題を解消して、弾性層形成用塗料の比重のバラツキが小さく、かつ、弾性層表面が微細な気孔を有する導電性ローラおよびその製造方法を提供することにある。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a conductive roller that solves the above-described problems, has a small variation in specific gravity of the elastic layer-forming coating material, and has fine pores on the elastic layer surface, and a method for manufacturing the same. .
　本発明者は鋭意検討した結果、弾性層を構成するフォーム体の組成中に湿潤剤を配合することにより、上記問題を解消できることを見出して、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found that the above problem can be solved by blending a wetting agent in the composition of the foam body constituting the elastic layer, and has completed the present invention.
　すなわち、本発明の導電性ローラは、シャフトと、該シャフトの外周に形成された弾性層と、を備える導電性ローラにおいて、
　前記弾性層が、ポリウレタン樹脂と湿潤剤とを含有するポリウレタンフォームからなることを特徴とするものである。 That is, the conductive roller of the present invention is a conductive roller comprising a shaft and an elastic layer formed on the outer periphery of the shaft.
The elastic layer is made of a polyurethane foam containing a polyurethane resin and a wetting agent.
　本発明において、前記湿潤剤としては、シリコーン系界面活性剤を好適に用いることができる。また、前記ポリウレタンフォームには、前記湿潤剤を前記ポリウレタン樹脂１００質量部に対し０．１～４質量部にて含有させることが好ましい。さらに、本発明のローラにおいては、前記弾性層の外周に、表層が形成されていることが好ましい。本発明の導電性ローラは、帯電ローラとして好適に用いることができる。 In the present invention, a silicone surfactant can be suitably used as the wetting agent. The polyurethane foam preferably contains the wetting agent in an amount of 0.1 to 4 parts by mass with respect to 100 parts by mass of the polyurethane resin. Furthermore, in the roller of the present invention, it is preferable that a surface layer is formed on the outer periphery of the elastic layer. The conductive roller of the present invention can be suitably used as a charging roller.
　また、本発明の導電性ローラの製造方法は、上記本発明の導電性ローラを製造する方法であって、
　前記ポリウレタン樹脂と湿潤剤とを含有する配合材料を、機械的に攪拌することにより発泡させた後、発泡した該配合材料を、前記シャフトにディッピング塗布して、該シャフトの外周に前記弾性層を形成することを特徴とするものである。 Moreover, the manufacturing method of the conductive roller of the present invention is a method of manufacturing the conductive roller of the present invention,
The compounding material containing the polyurethane resin and the wetting agent is foamed by mechanical stirring, and then the foamed compounding material is dipped on the shaft, and the elastic layer is formed on the outer periphery of the shaft. It is characterized by forming.
　本発明によれば、弾性層を構成するポリウレタンフォームの配合中に湿潤剤を含有させたことで、弾性層形成用塗料の比重のバラツキが小さく、かつ、弾性層表面が微細な気孔を有する導電性ローラおよびその製造方法を実現することが可能となった。 According to the present invention, the inclusion of a wetting agent during the blending of the polyurethane foam constituting the elastic layer reduces the variation in specific gravity of the elastic layer-forming coating material, and the elastic layer surface has fine pores. It has become possible to realize a roller and its manufacturing method.
本発明の導電性ローラの一例を示す長手方向断面図である。It is longitudinal direction sectional drawing which shows an example of the electroconductive roller of this invention. 本発明の導電性ローラの他の例を示す長手方向断面図である。It is longitudinal direction sectional drawing which shows the other example of the electroconductive roller of this invention. 本発明の導電性ローラのさらに他の例を示す長手方向断面図である。It is longitudinal direction sectional drawing which shows the other example of the electroconductive roller of this invention. 実施例１の導電性ローラの弾性層の断面における気孔の状態を示す写真図である。FIG. 3 is a photograph showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 1. 実施例２の導電性ローラの弾性層の断面における気孔の状態を示す写真図である。FIG. 6 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 2. 実施例３の導電性ローラの弾性層の断面における気孔の状態を示す写真図である。FIG. 10 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 3. 実施例４の導電性ローラの弾性層の断面における気孔の状態を示す写真図である。FIG. 10 is a photographic diagram showing the state of pores in the cross section of the elastic layer of the conductive roller of Example 4. 比較例１の導電性ローラの弾性層の断面における気孔の状態を示す写真図である。6 is a photographic view showing a state of pores in a cross section of an elastic layer of a conductive roller of Comparative Example 1. FIG.
　以下、本発明の実施の形態について、図面を参照しつつ詳細に説明する。
　図１は、本発明の導電性ローラの一例を示す長手方向断面図である。図示するように、本発明の導電性ローラ１０は、シャフト１と、その外周に順次形成された弾性層２とを少なくとも備えるものである。好適には図示するように、弾性層２の外周に、さらにソリッド（非発泡）の表層３が形成されている。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a longitudinal sectional view showing an example of the conductive roller of the present invention. As shown in the figure, the conductive roller 10 of the present invention includes at least a shaft 1 and an elastic layer 2 sequentially formed on the outer periphery thereof. As shown in the figure, a solid (non-foamed) surface layer 3 is further formed on the outer periphery of the elastic layer 2.
　本発明においては、弾性層２が、ポリウレタン樹脂と、湿潤剤とを含有するポリウレタンフォームからなる点に特徴がある。弾性層２を構成するポリウレタンフォームの配合中に、湿潤剤を含有させたことで、自由発泡させた際の塗料の発泡比重をより精密に制御して、比重のバラツキを０．１ｇ／ｍｌ以内程度に小さく抑えることができるとともに、発泡セルの粗大化を抑制して、弾性層表面の気孔を平均気孔径で１３０μｍ以下程度にまで微細化することができ、これによりローラの表面性を向上することが可能となった。また、本発明によれば、レベリング効果も得ることができ、すなわち、弾性層をディッピングにより塗布形成した際における乾燥時の表面の液ダレを抑制することができる。 The present invention is characterized in that the elastic layer 2 is made of a polyurethane foam containing a polyurethane resin and a wetting agent. By adding a wetting agent to the polyurethane foam composing the elastic layer 2, the foaming specific gravity of the paint when freely foamed is controlled more precisely, and the variation in specific gravity is within 0.1 g / ml. It is possible to suppress the foam cell to become coarse, and the pores on the surface of the elastic layer can be reduced to an average pore diameter of about 130 μm or less, thereby improving the surface property of the roller. It became possible. Further, according to the present invention, a leveling effect can be obtained, that is, dripping of the surface during drying when the elastic layer is applied and formed by dipping can be suppressed.
　本発明において、かかる湿潤剤としては、例えば、ポリエーテル変性シリコーン等のシリコーン系界面活性剤を好適に使用することができる。ポリエーテル変性シリコーンは、ポリ（ジアルキルシロキサン）のアルキル基の一部を、ポリオキシアルキレン基を持つ置換基に置き換えた構造を有する。かかるポリエーテル変性シリコーンとしては、例えば、ジメチルポリシロキサンポリオキシアルキレン共重合体が挙げられる。本発明において、弾性層２中に、かかる湿潤剤を配合することで上記効果が得られる理由としては、湿潤剤が低起泡作用を有するために、塗料がある程度まで発泡するとそれ以上発泡しにくくなること、および、粗大化した発泡セルが破泡しやすくなることによるものと考えられる。かかるシリコーン系界面活性剤からなる湿潤剤としては、例えば、サンノプコ（株）製のＳＮウェット１２５等を好適に用いることができる。 In the present invention, as the wetting agent, for example, a silicone-based surfactant such as polyether-modified silicone can be suitably used. The polyether-modified silicone has a structure in which a part of the alkyl group of poly (dialkylsiloxane) is replaced with a substituent having a polyoxyalkylene group. Examples of such polyether-modified silicones include dimethylpolysiloxane polyoxyalkylene copolymers. In the present invention, the above-mentioned effect can be obtained by blending such a wetting agent in the elastic layer 2 because the wetting agent has a low foaming action, so that it is difficult to foam further when the paint is foamed to a certain extent. This is considered to be due to the fact that the foamed cells that have become coarser tend to break. As the wetting agent composed of such a silicone surfactant, for example, SN wet 125 manufactured by San Nopco Co., Ltd. can be suitably used.
　弾性層２を構成するポリウレタンフォームにおいて、湿潤剤の配合量は、ポリウレタン樹脂１００質量部に対し、０．１～４質量部、特には０．１～２質量部とすることが好ましい。湿潤剤の配合量が多すぎると、塗料のゲル化が生じやすくなり、一方、少なすぎると、本発明の所期の効果を十分に得られないおそれがあり、いずれも好ましくない。 In the polyurethane foam constituting the elastic layer 2, the amount of the wetting agent is preferably 0.1 to 4 parts by mass, particularly 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the blending amount of the wetting agent is too large, gelation of the paint tends to occur. On the other hand, if the blending amount is too small, the desired effect of the present invention may not be obtained sufficiently, which is not preferable.
　本発明においては、導電性ローラの弾性層２を構成するポリウレタンフォーム中に湿潤剤を含有させた点のみが重要であり、それ以外の点については、常法に従い適宜構成することができ、特に制限されるものではない。例えば、上記ポリウレタンフォームに用いるポリウレタン樹脂としては、従来公知の材料を適宜選択して用いることができ、特に制限されるものではない。また、ポリウレタンフォームの発泡倍率としては、特に制限されるものではないが、１．２～５０倍、特には１．５～１０倍程度が好ましく、フォーム密度は、０．１～０．７ｇ／ｃｍ３程度が好ましい。 In the present invention, only the point that the wetting agent is contained in the polyurethane foam constituting the elastic layer 2 of the conductive roller is important, and other points can be appropriately configured according to a conventional method. It is not limited. For example, as the polyurethane resin used for the polyurethane foam, a conventionally known material can be appropriately selected and used, and is not particularly limited. The foaming ratio of the polyurethane foam is not particularly limited, but is preferably 1.2 to 50 times, particularly preferably about 1.5 to 10 times, and the foam density is 0.1 to 0.7 g / About cm 3 is preferable.
　弾性層２には導電剤を添加することができ、これにより、導電性を付与し、または調整して、所定の抵抗値とすることができる。かかる導電剤としては、特に限定されず、ラウリルトリメチルアンモニウム、ステアリルメチルアンモニウム、オクタドデシルトリメチルアンモニウム、ヘキサデシルトリメチルアンモニウム、変性脂肪酸・ジメチルエチルアンモニウムの過塩素酸塩、塩素酸塩、ホウフッ化水素酸塩、硫酸塩、エトサルフェート塩、臭化ベンジル塩、塩化ベンジル塩等のハロゲン化ベンジル塩等の第四級アンモニウム塩などの陽イオン性界面活性剤、脂肪族スルホン酸塩、高級アルコール硫酸エステル塩、高級アルコールエチレンオキサイド付加硫酸エステル塩、高級アルコール燐酸エステル塩、高級アルコールエチレンオキサイド付加燐酸エステル塩などの陰イオン界面活性剤、高級アルコールエチレンオキサイド、ポリエチレングリコール脂肪酸エステル、多価アルコール脂肪酸エステル等の非イオン性帯電防止剤などの帯電防止剤、ＮａＣｌＯ４、ＬｉＡｓＦ６、ＬｉＢＦ４、ＮａＳＣＮ、ＫＳＣＮ、ＮａＣｌ等のＬｉ＋、Ｎａ＋、Ｋ＋等の周期律表第１族の金属塩、あるいはＮＨ４ ＋の塩などの電解質、また、ケッチェンブラック、アセチレンブラック等の導電性カーボン、ＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＦ、ＳＲＦ、ＦＴ、ＭＴ等のゴム用カーボン、酸化処理を施したカラー（インク）用カーボン、熱分解カーボン、天然グラファイト、人造グラファイト、アンチモンドープの酸化錫、酸化チタン、酸化亜鉛、ニッケル、銅、銀、ゲルマニウム等の金属および金属酸化物、ポリアニリン、ポリピロール、ポリアセチレン等の導電性ポリマー等が挙げられる。これらの導電剤は単独で用いてもよく、２種以上を混合して用いてもよい。また、これら導電剤の配合量は、組成物の種類に応じて適宜選定され、通常、弾性層２の体積抵抗率が１００～１０８Ω・ｃｍ、好ましくは１０２～１０６Ω・ｃｍとなるように調整される。 A conductive agent can be added to the elastic layer 2, whereby conductivity can be imparted or adjusted to a predetermined resistance value. The conductive agent is not particularly limited, and lauryltrimethylammonium, stearylmethylammonium, octadodecyltrimethylammonium, hexadecyltrimethylammonium, modified fatty acid / dimethylethylammonium perchlorate, chlorate, borofluoride , Cationic surfactants such as quaternary ammonium salts such as halogenated benzyl salts such as sulfates, etosulphate salts, benzyl bromide salts, benzyl chloride salts, aliphatic sulfonates, higher alcohol sulfates, Anionic surfactants such as higher alcohol ethylene oxide addition sulfate, higher alcohol phosphate, higher alcohol ethylene oxide addition phosphate, higher alcohol ethylene oxide, polyethylene glycol fatty acid ester , Antistatic agents such as polyhydric alcohol fatty acid nonionic antistatic agents such as esters, NaClO 4, LiAsF 6, LiBF 4, NaSCN, KSCN, such as NaCl Li +, Na +, the Periodic Table of K +, etc. Electrolytes such as Group 1 metal salts or NH 4 + salts, conductive carbons such as ketjen black and acetylene black, rubber carbons such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, and MT Oxidized carbon for color (ink), pyrolytic carbon, natural graphite, artificial graphite, antimony-doped tin oxide, titanium oxide, zinc oxide, nickel, copper, silver, germanium and other metals and metal oxides, Examples thereof include conductive polymers such as polyaniline, polypyrrole, and polyacetylene. These conductive agents may be used alone or in combination of two or more. The blending amount of these conductive agents is appropriately selected according to the type of the composition. Usually, the volume resistivity of the elastic layer 2 is 10 0 to 10 8 Ω · cm, preferably 10 2 to 10 6 Ω · cm. It is adjusted to become.
　また、この弾性層２には、上記導電剤の他にも、必要に応じて、耐水化剤、発泡剤、整泡剤、硬化剤、増粘剤、消泡剤、レベリング剤、分散剤、チクソトロピー性付与剤、ブロッキング防止剤、架橋剤、成膜助剤等の公知の添加剤を適量配合することができる。このうち耐水化剤としては、例えば、炭酸アンモニウムジルコニウムを好適に使用することができる。弾性層２に耐水化剤を含有させることで、ローラ抵抗の環境依存性を改善して、環境変化に伴う抵抗の変動を抑制することができるとともに、弾性層２の表面に形成される気孔を微細化して、ローラの表面性を向上することができる。かかる耐水化剤の配合量は、ポリウレタン樹脂１００質量部に対し、０．５～２０質量部、特には０．５～５質量部とすることが好ましい。耐水化剤の配合量が多すぎると、粘度が高くなりすぎてポットライフが低下する傾向があり、一方、耐水化剤の配合量が少なすぎると、所期の効果を十分に得られないおそれがあり、いずれも好ましくない。 In addition to the conductive agent, the elastic layer 2 may include a water resistance agent, a foaming agent, a foam stabilizer, a curing agent, a thickener, an antifoaming agent, a leveling agent, a dispersing agent, if necessary. An appropriate amount of a known additive such as a thixotropic property-imparting agent, an anti-blocking agent, a crosslinking agent, or a film-forming auxiliary agent can be blended. Among these, as a water-resistant agent, for example, ammonium zirconium carbonate can be suitably used. By adding a water-proofing agent to the elastic layer 2, it is possible to improve the environmental dependency of the roller resistance and to suppress fluctuations in resistance due to environmental changes, and to form pores formed on the surface of the elastic layer 2. The surface property of the roller can be improved by miniaturization. The blending amount of the water-resistant agent is preferably 0.5 to 20 parts by mass, particularly 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the amount of the water-resistant agent is too large, the viscosity tends to be too high and the pot life tends to decrease. On the other hand, if the amount of the water-resistant agent is too small, the desired effect may not be obtained sufficiently. However, neither is preferable.
　弾性層２の厚みとしては、０．６～５．０ｍｍであることが好ましく、１．０～３．０ｍｍであることがより好ましい。弾性層２の厚みをかかる範囲とすることで、スパーク放電を防止することができる。 The thickness of the elastic layer 2 is preferably 0.6 to 5.0 mm, and more preferably 1.0 to 3.0 mm. By setting the thickness of the elastic layer 2 in such a range, spark discharge can be prevented.
　本発明のローラに用いるシャフト１としては、金属製またはプラスチック製の、中空円筒体または中実円柱体を使用することができるが、好ましくは、金属製の中空円筒体または中実円柱体であり、より好ましくは、金属製の中空円筒体である。これにより、コスト性を向上することができる。 As the shaft 1 used for the roller of the present invention, a metal or plastic hollow cylindrical body or solid cylindrical body can be used, and preferably a metal hollow cylindrical body or solid cylindrical body. More preferably, it is a metal hollow cylinder. Thereby, cost efficiency can be improved.
　また、本発明において弾性層２上に設ける表層３は、好適には、水系塗料を用いて形成する。かかる表層３に用いる水系塗料には、ローラ等の材料として公知のゴムや樹脂を用いることができる。樹脂としては、例えば、ウレタン変性アクリル樹脂、ポリウレタン樹脂、アクリル樹脂、アクリルシリコーン樹脂、ポリアミド樹脂、フッ素樹脂等が挙げられ、これらの１種または２種以上を混合して用いることができる。また、ゴム系の水系塗料としては、天然ゴム（ＮＲ）、クロロプレンゴム（ＣＲ）、ニトリルゴム（ＮＢＲ）、スチレンブタジエンゴム（ＳＢＲ）等のラテックス、ポリウレタン樹脂系の水系塗料としては、エーテル系、エステル系等のエマルションやディスパージョン、アクリル樹脂系の水系塗料としては、アクリル、アクリルスチレン等のエマルション、フッ素樹脂系の水系塗料としては、ポリテトラフルオロエチレン、テトラフルオロエチレン‐パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン‐エチレン共重合体、ポリクロロトリフルオロエチレン、クロロトリフルオロエチレン‐エチレン共重合体、テトラフルオロエチレン‐ビニリデンフルオライド共重合体、ポリビニリデンフルオライド、ポリビニルフルオライド等を好適に用いることができる。 In the present invention, the surface layer 3 provided on the elastic layer 2 is preferably formed using a water-based paint. For the water-based paint used for the surface layer 3, a known rubber or resin can be used as a material for a roller or the like. Examples of the resin include a urethane-modified acrylic resin, a polyurethane resin, an acrylic resin, an acrylic silicone resin, a polyamide resin, a fluororesin, and the like, and one or more of these can be used in combination. In addition, as a rubber-based water-based paint, natural rubber (NR), chloroprene rubber (CR), nitrile rubber (NBR), latex such as styrene-butadiene rubber (SBR), etc., as a polyurethane resin-based water-based paint, ether-based, Ester and other emulsions and dispersions, acrylic resin-based water-based paints, acrylic and acrylic styrene emulsions, and fluororesin-based water-based paints include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Polymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, polyvinylidene fluoride, polyvinyl fluoride Etc. can be suitably used Oraido.
　本発明においては、上記の中でも、水系塗料として、水系アクリル樹脂を好適に用いることができる。かかる水系アクリル樹脂としては、アクリロニトリルとｎ－ブチルアクリレートとを必須成分とし、任意にその他のモノマーを含むものが好ましく、その他のモノマーとしては、エチルアクリレート、アクリル酸２‐エチルへキシル、アクリル酸、メタクリル酸等が挙げられる。アクリロニトリルおよびｎ‐ブチルアクリレートを必須成分とするのは、これらが弾性（セット性）の向上に寄与するためであり、かかる観点からは、可能な限りｎ‐ブチルアクリレート量を増量し、他の成分を減量するとともに、必須成分以外のその他のモノマー成分のモノマー比率を減らすことが好ましい。一方、アクリロニトリルの比率を高めすぎると、形成された層が硬くなってしまうため好ましくない。したがって、必須成分であるアクリロニトリルとｎ－ブチルアクリレートとのモノマー比率は、モル比で１～２５：９９～７５、特には５～２０：９５～８０の範囲内とすることが好ましい。 In the present invention, among the above, a water-based acrylic resin can be suitably used as the water-based paint. As such an aqueous acrylic resin, those containing acrylonitrile and n-butyl acrylate as essential components and optionally containing other monomers are preferable. Examples of other monomers include ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid, Examples include methacrylic acid. The reason why acrylonitrile and n-butyl acrylate are essential components is that they contribute to the improvement of elasticity (setting property). From this viewpoint, the amount of n-butyl acrylate is increased as much as possible, and other components It is preferable to reduce the monomer ratio of other monomer components other than the essential components. On the other hand, if the ratio of acrylonitrile is too high, the formed layer becomes hard, which is not preferable. Therefore, the monomer ratio of acrylonitrile, which is an essential component, and n-butyl acrylate is preferably in the range of 1 to 25:99 to 75, particularly 5 to 20:95 to 80 in terms of molar ratio.
　また、上記水系アクリル樹脂は、分子中に活性水素を有する基を含んでいることが好ましい。活性水素を有する基としては、カルボキシル基、水酸基、アミノ基等が挙げられ、好適にはカルボキシル基である。本発明において、かかる活性水素を有する基を含むモノマーの比率は、全モノマー量の３～６％の範囲内とすることが好ましい。本発明においては、活性水素を有する基を含むモノマーの比率をこの範囲内とすることで、表面酸価が１０ｍｇ／ｇ以上、例えば、１０～２０ｍｇ／ｇに調整された水系アクリル樹脂を好適に用いることができる。 Moreover, it is preferable that the water-based acrylic resin contains a group having active hydrogen in the molecule. Examples of the group having active hydrogen include a carboxyl group, a hydroxyl group, and an amino group, and a carboxyl group is preferable. In the present invention, the ratio of the monomer containing the group having active hydrogen is preferably in the range of 3 to 6% of the total monomer amount. In the present invention, a water-based acrylic resin having a surface acid value adjusted to 10 mg / g or more, for example, 10 to 20 mg / g is suitably obtained by setting the ratio of the monomer containing a group having active hydrogen within this range. Can be used.
　また、上記表層３を形成する水系塗料中には、特に制限されるものではないが、導電剤を添加して、表層３の導電性（電気抵抗）を付与または調整することができる。この場合に用いる導電剤としては、特に制限はなく、弾性層２に使用されるのと同様のものを、１種にて、または２種以上を混合して、適宜用いることができる。また、これら導電剤の配合量は、組成物の種類に応じて適宜選定され、通常、表層２の体積抵抗率が１×１０４～１×１０１２Ω・ｃｍ、好ましくは１×１０６～１×１０８Ω・ｃｍとなるように調整される。 In addition, the water-based paint forming the surface layer 3 is not particularly limited, but the conductivity (electric resistance) of the surface layer 3 can be imparted or adjusted by adding a conductive agent. There is no restriction | limiting in particular as a electrically conductive agent used in this case, The thing similar to being used for the elastic layer 2 can be used suitably by 1 type or in mixture of 2 or more types. The blending amount of these conductive agents is appropriately selected according to the type of the composition. Usually, the volume resistivity of the surface layer 2 is 1 × 10 4 to 1 × 10 12 Ω · cm, preferably 1 × 10 6 to It is adjusted to be 1 × 10 8 Ω · cm.
　なお、この表層３を形成する水系塗料中には、架橋剤、増粘剤、チクソトロピー性付与剤、構造粘性付与剤等の添加剤を、必要に応じて添加することができる。 In the water-based paint forming the surface layer 3, additives such as a cross-linking agent, a thickener, a thixotropy imparting agent, and a structural viscosity imparting agent can be added as necessary.
　表層３の厚みは、特に制限されるものではないが、通常１～３０μｍ、特には１～２０μｍとすることができる。表層３の厚みが１μｍ未満であると、ローラの耐久性に劣る場合があり、一方、３０μｍを超えると、帯電特性等に悪影響を与えたり、表面にしわを生じたりするなど、良好な表面性が得られない場合がある。 The thickness of the surface layer 3 is not particularly limited, but can usually be 1 to 30 μm, particularly 1 to 20 μm. When the thickness of the surface layer 3 is less than 1 μm, the durability of the roller may be inferior. On the other hand, when the thickness exceeds 30 μm, the charging property is adversely affected and the surface is wrinkled. May not be obtained.
　本発明の導電性ローラ１０は、シャフト１の外周に少なくとも弾性層２を備え、好適にはさらに表層３を備えるものであるが、必要に応じて、弾性層２と表層３との間に、中間層として抵抗調整層５を設けることができ、また、弾性層２と抵抗調整層５との間に、さらに接着層４を介在させることもできる。さらに、シャフト１の外周に、弾性層２を形成するに先立って、接着層４を設けて、シャフト１と弾性層２との接着性を向上させることもできる。図２は、本発明の導電性ローラの他の構成例を示す長手方向断面図である。図示する導電性ローラ２０は、シャフト１と、その外周に順次形成された接着層４、弾性層２、抵抗調整層５および表層３と、を備えるものである。 The conductive roller 10 of the present invention includes at least an elastic layer 2 on the outer periphery of the shaft 1, and preferably further includes a surface layer 3. If necessary, between the elastic layer 2 and the surface layer 3, The resistance adjustment layer 5 can be provided as an intermediate layer, and the adhesive layer 4 can be further interposed between the elastic layer 2 and the resistance adjustment layer 5. Furthermore, prior to forming the elastic layer 2 on the outer periphery of the shaft 1, an adhesive layer 4 can be provided to improve the adhesion between the shaft 1 and the elastic layer 2. FIG. 2 is a longitudinal sectional view showing another configuration example of the conductive roller of the present invention. The illustrated conductive roller 20 includes a shaft 1 and an adhesive layer 4, an elastic layer 2, a resistance adjusting layer 5, and a surface layer 3 that are sequentially formed on the outer periphery thereof.
　上記抵抗調整層５は、樹脂に導電剤を添加した樹脂組成物により形成することができる。この樹脂組成物を構成する樹脂としては、特に制限されるものではないが、具体的には例えば、ウレタン樹脂、アクリルウレタン樹脂、アクリル樹脂、エステル樹脂、ナイロン樹脂、フェノール樹脂、エポキシ樹脂、フッ素樹脂、シリコーン樹脂等が挙げられ、これらのうちの１種を、または、２種以上を混合して用いることができ、中でも、ウレタン樹脂、アクリルウレタン樹脂、アクリル樹脂等の水系塗料が好ましく用いられる。また、この水系塗料に添加される導電剤としては、上記弾性層２に用いられた導電剤と同じものを使用することができる。 The resistance adjusting layer 5 can be formed of a resin composition obtained by adding a conductive agent to a resin. The resin constituting the resin composition is not particularly limited, but specifically, for example, urethane resin, acrylic urethane resin, acrylic resin, ester resin, nylon resin, phenol resin, epoxy resin, fluororesin , Silicone resins, and the like, and one or a mixture of two or more of these can be used. Among these, water-based paints such as urethane resins, acrylic urethane resins, and acrylic resins are preferably used. In addition, as the conductive agent added to the water-based paint, the same conductive agent as that used for the elastic layer 2 can be used.
　抵抗調整層５は、導電性ローラの電気抵抗値を調整するために任意に設けられるものであり、かかる抵抗調整層５の抵抗値は、上記弾性層２の抵抗値や、ローラに求められる抵抗値に応じて適宜設定されるが、通常は１×１０３～１×１０８Ω・ｃｍ、特には１×１０５～１×１０７Ω・ｃｍの範囲とすることができる。この場合、上記導電剤の配合量は、この抵抗値が達成される適量とすることができるが、通常は、上記水系塗料の基材樹脂１００質量部に対して、０．１～２０質量部、特には１～１０質量部とすることが好ましい。 The resistance adjustment layer 5 is arbitrarily provided to adjust the electrical resistance value of the conductive roller. The resistance value of the resistance adjustment layer 5 is the resistance value of the elastic layer 2 or the resistance required of the roller. Although it is set as appropriate depending on the value, it can usually be in the range of 1 × 10 3 to 1 × 10 8 Ω · cm, particularly 1 × 10 5 to 1 × 10 7 Ω · cm. In this case, the blending amount of the conductive agent can be an appropriate amount that achieves this resistance value, but is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the base resin of the water-based paint. In particular, it is preferably 1 to 10 parts by mass.
　また、上記抵抗調整層５には、導電剤の他に、本発明の目的を逸脱しない範囲で種々の添加剤を配合することができる。例えば、オキサゾリン系、エポキシ系、メラミン系、グアナミン系、イソシアネート系、フェノール系等の架橋剤を、使用する基材樹脂に応じて適量にて配合することができ、その他、造膜助剤、分散剤、増粘剤、レベリング剤、チクソトロピー性付与剤、構造粘性付与剤等の公知の添加剤を適量にて配合してもよい。 In addition to the conductive agent, various additives can be blended into the resistance adjusting layer 5 without departing from the object of the present invention. For example, oxazoline-based, epoxy-based, melamine-based, guanamine-based, isocyanate-based, phenol-based cross-linking agents can be blended in appropriate amounts according to the base resin used. You may mix | blend well-known additives, such as an agent, a thickener, a leveling agent, a thixotropy imparting agent, a structural viscosity imparting agent, in an appropriate amount.
　抵抗調整層５の厚みは、弾性層２の厚みや導電性ローラの形態などに応じて適宜選定され、特に制限されるものではないが、通常は１０～５００μｍ、特には５０～３００μｍとすることが好ましい。抵抗調整層５の厚みが５０μｍ未満であると、十分な抵抗値の調整を行うことが困難になる場合があり、一方、３００μｍを超えると、相対的に弾性層の厚みが薄くなって、ローラ硬度（部材硬度）が高くなってしまったり、必要以上にコスト高となったりする場合がある。 The thickness of the resistance adjusting layer 5 is appropriately selected according to the thickness of the elastic layer 2 and the form of the conductive roller, and is not particularly limited, but is usually 10 to 500 μm, particularly 50 to 300 μm. Is preferred. When the thickness of the resistance adjusting layer 5 is less than 50 μm, it may be difficult to adjust the resistance value sufficiently. On the other hand, when the thickness exceeds 300 μm, the thickness of the elastic layer becomes relatively thin, and the roller In some cases, the hardness (member hardness) becomes high, or the cost becomes higher than necessary.
　また、接着層４は、シャフト１と弾性層２との間、または、弾性層２と抵抗調整層５との間を強固に接着させるために、所望に応じ設けることができるものであり、その厚みは１～１００μｍ程度とすることができる。接着層４は、例えば、アクリル樹脂、ウレタン樹脂、アクリルウレタン樹脂、ポリエステル樹脂、ポリアミド樹脂等の樹脂材料を用いて形成することができ、必要に応じて導電剤や他の添加剤を添加することもできる。 The adhesive layer 4 can be provided as desired in order to firmly adhere between the shaft 1 and the elastic layer 2 or between the elastic layer 2 and the resistance adjusting layer 5. The thickness can be about 1 to 100 μm. The adhesive layer 4 can be formed using, for example, a resin material such as an acrylic resin, a urethane resin, an acrylic urethane resin, a polyester resin, a polyamide resin, and a conductive agent and other additives are added as necessary. You can also.
　図３は、本発明の導電性ローラのさらに他の例を示す長手方向断面図である。導電性ローラを帯電ローラ等として用いる場合には、感光ドラムに押圧される際に長さ方向に均一な当たり面を形成することが重要であるため、図示する好適例の導電性ローラ３０は、長手方向中央部において端部よりも径が大きくなっているクラウン形状を有している。 FIG. 3 is a longitudinal sectional view showing still another example of the conductive roller of the present invention. When a conductive roller is used as a charging roller or the like, it is important to form a uniform contact surface in the length direction when pressed by the photosensitive drum. It has a crown shape having a diameter larger than that of the end portion in the central portion in the longitudinal direction.
　導電性ローラをクラウン形状とする場合に、ローラ長手方向断面における、長さ方向中央の突出の程度を表すクラウン量としては、５０～３００μｍとすることが好ましく、これにより、通常の画像を一層良好なものにすることができる。クラウン量が５０μｍ未満であると、ローラ長さ方向中央部の接触圧が低くなり、一方、クラウン量が３００μｍを超えると、ローラ長さ方向中央部が強く接触しすぎてしまい、いずれの場合も帯電量の不均一等の不具合を招くおそれがある。なお、本発明において導電性ローラのクラウン量の測定は、ミツトヨ（株）製高精度レーザ測定機ＬＳＭ－４３０ｖを用いて行うことができる。この測定機により、ローラ中央部および中央部から端部へ向かう９０ｍｍの位置において外径を測定し、中央部の外径と両端部方向へ各９０ｍｍの位置における外径の平均値との差をローラクラウン量とする。例えば、ローラ長２５０ｍｍの導電性ローラにおいては、一方の端から３５ｍｍ、１２５ｍｍ、２１５ｍｍの３点において外径を測定する。その際、一方の端から３５ｍｍ位置における外径をＡ（ｍｍ）、１２５ｍｍ位置における外径をＢ（ｍｍ）、２１５ｍｍ位置における外径をＣ（ｍｍ）とすると、クラウン量（μｍ）は下記計算式（１）、
クラウン量（μｍ）＝｛Ｂ－（Ａ＋Ｃ）／２｝×１０００　　　（１）
で求めることができる。 When the conductive roller has a crown shape, the crown amount representing the degree of protrusion at the center in the length direction in the cross section in the longitudinal direction of the roller is preferably 50 to 300 μm, thereby further improving the normal image. Can be made. If the crown amount is less than 50 μm, the contact pressure in the central portion in the roller length direction becomes low. On the other hand, if the crown amount exceeds 300 μm, the central portion in the roller length direction is too strongly contacted. There is a risk of causing problems such as uneven charge amount. In the present invention, the crown amount of the conductive roller can be measured using a high precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation. With this measuring machine, the outer diameter is measured at the center of the roller and at a position of 90 mm from the center to the end, and the difference between the outer diameter of the center and the average value of the outer diameter at the positions of 90 mm in both end directions is calculated. The amount of roller crown. For example, in a conductive roller having a roller length of 250 mm, the outer diameter is measured at three points of 35 mm, 125 mm, and 215 mm from one end. At that time, assuming that the outer diameter at the 35 mm position from one end is A (mm), the outer diameter at the 125 mm position is B (mm), and the outer diameter at the 215 mm position is C (mm), the crown amount (μm) is calculated as follows. Formula (1),
Crown amount (μm) = {B− (A + C) / 2} × 1000 (1)
Can be obtained.
　また、本発明の導電性ローラにおいては、振れ（膜厚精度）を、ローラ長さ方向全領域において、７０μｍ以下とすることが好ましい。導電性ローラを帯電ローラとして使用して、感光体と接触させながら回転させた場合、導電性ローラの振れが大きいと、導電性ローラと感光体との間に空隙が生じ、さらに、その空隙距離も様々になってしまう。この場合、感光体上に残留しているトナー粒子および外添剤が、その空隙に侵入しやすくなり、導電性ローラにムラとなって付着する。そのため、ローラ表面がまだらに汚れて、画像不良の原因となってしまう。なお、本発明において導電性ローラの振れの測定は、ミツトヨ（株）製の高精度レーザ測定機ＬＳＭ－４３０ｖを用いて行うことができる。この測定機により、外径を、ローラ長さ方向各５点について測定し、各点について測定した外径の最大値と最小値との差の平均値を振れとする。 Further, in the conductive roller of the present invention, it is preferable that the deflection (film thickness accuracy) is 70 μm or less in the entire region in the roller length direction. When a conductive roller is used as a charging roller and rotated while being in contact with the photosensitive member, if the conductive roller is shaken greatly, a gap is generated between the conductive roller and the photosensitive member, and the gap distance is further increased. Will also vary. In this case, the toner particles and the external additive remaining on the photosensitive member are liable to enter the gap and adhere to the conductive roller as unevenness. As a result, the roller surface becomes mottled and causes image defects. In the present invention, the deflection of the conductive roller can be measured using a high-precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation. With this measuring machine, the outer diameter is measured for each of the five points in the roller length direction, and the average value of the difference between the maximum value and the minimum value of the outer diameter measured for each point is taken as the shake.
　本発明の導電性ローラは、特に、帯電ローラとして好適に用いることができる。 The conductive roller of the present invention can be particularly suitably used as a charging roller.
　本発明の導電性ローラは、以下のようにして製造することができる。すなわち、まず、弾性層２を構成するポリウレタン樹脂に、湿潤剤および他の任意の添加剤を添加して、得られた配合材料を、攪拌機、例えば、ハンドミキサー等を用いて機械的に攪拌することにより発泡させる。その後、発泡した配合材料を、シャフト１にディッピング塗布することにより、シャフト１の外周に弾性層２を形成することができる。弾性層２を、シャフト１に直接塗料を塗布することにより形成することで、製造工程の簡略化が可能となり、コストを低減することができる。 The conductive roller of the present invention can be manufactured as follows. That is, first, a wetting agent and other optional additives are added to the polyurethane resin constituting the elastic layer 2, and the resulting blended material is mechanically stirred using a stirrer such as a hand mixer. To make it foam. Then, the elastic layer 2 can be formed on the outer periphery of the shaft 1 by dipping the foamed compounding material onto the shaft 1. By forming the elastic layer 2 by directly applying a paint to the shaft 1, the manufacturing process can be simplified and the cost can be reduced.
　次いで、所望に応じ、接着層４を、前述した構成材料を分散または溶解させた塗料を用いて、塗布形成する。塗布方法としては、ディッピング法、スプレー法、ロールコーター法、ダイコート法、リング塗装法等の公知の手法を適宜用いることができ、塗料を塗布後、乾燥固化することにより、接着層４が形成される。中でも、塗布方法としては、ディッピング法を用いることが好ましい。なお、シャフト１と弾性層２との間に接着層４を設ける場合にも上記と同様の手法を用いればよい。また、抵抗調整層５についても、所望に応じ、接着層４と同様にして塗布形成することができる。 Next, if desired, the adhesive layer 4 is applied and formed using a paint in which the above-described constituent materials are dispersed or dissolved. As a coating method, a known method such as a dipping method, a spray method, a roll coater method, a die coating method, a ring coating method or the like can be used as appropriate, and the adhesive layer 4 is formed by drying and solidifying after applying the paint. The Among these, it is preferable to use a dipping method as a coating method. The same method as described above may be used when the adhesive layer 4 is provided between the shaft 1 and the elastic layer 2. The resistance adjustment layer 5 can also be applied and formed in the same manner as the adhesive layer 4 if desired.
　さらに、表層３を、上記弾性層２上、または、弾性層２上に形成された抵抗調整層５上に、上記接着層４と同様の手法で塗布形成することにより、本発明の導電性ローラを得ることができる。本発明においては、弾性層２表面の気孔径が微細化されているので、弾性層２上に表層３等を塗布形成する際に塗料が気孔内に入り込むことがなく、最終的に得られる導電性ローラの表面性を損なわないという効果が得られる。 Furthermore, the conductive layer of the present invention is formed by coating the surface layer 3 on the elastic layer 2 or the resistance adjusting layer 5 formed on the elastic layer 2 in the same manner as the adhesive layer 4. Can be obtained. In the present invention, since the pore diameter on the surface of the elastic layer 2 is miniaturized, the paint does not enter the pores when the surface layer 3 or the like is applied and formed on the elastic layer 2, and the finally obtained conductivity is obtained. The effect of not impairing the surface property of the roller is obtained.
　以下、本発明を、実施例を用いてより詳細に説明する。
　図１に示すような、シャフト１の外周に弾性層２および表層３が順次形成された構成を有する導電性ローラを、下記表中に示す配合に従い、以下に示すようにして作製した。 Hereinafter, the present invention will be described in more detail with reference to examples.
A conductive roller having a configuration in which an elastic layer 2 and a surface layer 3 are sequentially formed on the outer periphery of the shaft 1 as shown in FIG. 1 was produced as follows according to the formulation shown in the table below.
　まず、水系塗料（アクリロニトリル－アクリル酸アルキルエステル－メタクリル酸－メタクリル酸グリシジル共重合物の水性エマルション）１００質量部に対し、エポクロス（オキザゾリン基含有スチレン－アクリル共重合物のエマルション）５質量部、水分散カーボン１０質量部、ファインシールＸ－１２（親水性シリカ）７．５質量部、ＳＮデフォーマー７７７（消泡剤）１質量部、ＳＮウェット９７０（湿潤剤）１質量部、ＵＨ４２０（増粘剤）１．６質量％を配合し、撹拌機で撹拌した。各成分を配合した水系塗料をメッシュでろ過し、凝集物を取り除いた。シャフト１を、この水系塗料にディッピング塗布して熱乾燥することにより、シャフト１の外周に、厚み１００μｍの接着層４を形成した。次いで、下記表中にそれぞれ示す弾性層の配合材料を容器内に投入し、羽を用いて３０分撹拌した。その後、市販のハンドミキサーを用いて６分間撹拌し、発泡させて、発泡ウレタン水分散液を得た。 First, 5 parts by weight of Epocros (emulsion of oxazoline group-containing styrene-acrylic copolymer) and 100 parts by weight of water-based paint (aqueous emulsion of acrylonitrile-alkyl acrylate-methacrylic acid-glycidyl methacrylate copolymer), water 10 parts by weight of dispersed carbon, 7.5 parts by weight of fine seal X-12 (hydrophilic silica), 1 part by weight of SN deformer 777 (antifoaming agent), 1 part by weight of SN wet 970 (wetting agent), UH420 (thickening agent) ) 1.6% by mass was mixed and stirred with a stirrer. The water-based paint containing each component was filtered through a mesh to remove aggregates. The shaft 1 was dipped on this water-based paint and thermally dried to form an adhesive layer 4 having a thickness of 100 μm on the outer periphery of the shaft 1. Next, the elastic layer compounding materials shown in the table below were put into a container and stirred for 30 minutes using a wing. Thereafter, the mixture was stirred for 6 minutes using a commercially available hand mixer and foamed to obtain a foamed urethane water dispersion.
　上記発泡ウレタン水分散液を、接着層４が形成されたシャフト１の外周にディッピング塗布して、熱風オーブンで乾燥・硬化させることにより、それぞれ下記表中に示す厚みを有するポリウレタンフォームからなる弾性層２を形成した。 An elastic layer made of a polyurethane foam having the thickness shown in the following table by dipping the urethane foam aqueous dispersion on the outer periphery of the shaft 1 on which the adhesive layer 4 is formed, and drying and curing in a hot air oven. 2 was formed.
　次いで、水系塗料（アクリルシリコン樹脂，ＥＸ１０２ＳＩ、日本触媒（株）製）１００質量部に対し、２，２，４‐トリメチル‐１，３‐ペンタンジオールモノイソブチレート（ＣＳ‐１２，チッソ（株）製）７０質量部、水系シリコーングラフトアクリルポリマー（サイマックＵＳ‐４５０、東亞合成（株）製）８質量部、ポリエーテル変性ポリジメチルシロキサン（ＢＹＫ‐３３３，ビックケミー・ジャパン（株）製）２７質量部、含フッ素ノニオン系界面活性剤（フタージェント２１５Ｍ，（株）ネオス製）２質量部、シリカ（ファインシールＸ‐１２，（株）トクヤマ製）１０質量部、ナイロン粒子（ガンツパールＧＰＡ‐５５０，ガンツ化成（株）製）１５質量部、黒色有機顔料の水系分散液（ＢＯＮＪＥＴ　ＢＬＡＣＫ　ＣＷ‐３（オリエント化学（株）製）１０質量部を配合し、撹拌機で撹拌した。得られた水系塗料を、上記弾性層２上にディッピング塗布し、室温で３０分間、１１０℃で２０分間乾燥することにより厚み５μｍの表層３を形成して、各導電性ローラを得た。 Next, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (CS-12, Chisso Corporation) with respect to 100 parts by mass of water-based paint (acrylic silicone resin, EX102SI, manufactured by Nippon Shokubai Co., Ltd.) )) 70 parts by mass, water-based silicone graft acrylic polymer (Cymac US-450, manufactured by Toagosei Co., Ltd.), polyether modified polydimethylsiloxane (BYK-333, manufactured by BYK Japan Japan) 27 parts by mass Parts, 2 parts by mass of fluorine-containing nonionic surfactant (Furgent 215M, manufactured by Neos Co., Ltd.), 10 parts by mass of silica (Fine Seal X-12, manufactured by Tokuyama Co., Ltd.), nylon particles (Gantz Pearl GPA-550) , Manufactured by Ganz Kasei Co., Ltd.) 15 parts by mass, an aqueous dispersion of black organic pigment (BONJET BLACK C -3 (manufactured by Orient Chemical Co., Ltd.) was mixed with 10 parts by mass and stirred with a stirrer, and the resulting water-based paint was dipped on the elastic layer 2 for 30 minutes at room temperature and 20 minutes at 110 ° C. By drying, a surface layer 3 having a thickness of 5 μm was formed to obtain each conductive roller.
　各ローラにつき、表層３形成前の弾性層の表面近傍を肉厚３ｍｍ程度にて切り出し、デジタルマイクロスコープ（（株）キーエンス製，ＶＨＸ－１００）を用いて、画面上で大きいものから順に気孔の直径を１０点測定して、平均化した。得られた気孔径の平均値を、塗料の比重を５回測定した際の、比重の平均値、および、（最大値）－（最小値）で表される比重のバラツキの値とともに、下記表中に示す。また、弾性層断面を撮影した写真を、図４～８中に示す。 For each roller, cut out the vicinity of the surface of the elastic layer before forming the surface layer 3 with a thickness of about 3 mm, and use a digital microscope (manufactured by Keyence Corporation, VHX-100) to increase the pore size in order from the largest on the screen. The diameter was measured at 10 points and averaged. The average value of the pore diameters obtained is shown in the following table together with the average value of specific gravity when the specific gravity of the paint was measured 5 times and the variation of specific gravity expressed by (maximum value)-(minimum value). Shown in. Also, photographs taken of the cross section of the elastic layer are shown in FIGS.
Figure JPOXMLDOC01-appb-T000001
 ＊１）ウレタン樹脂：アデカボンタイターＨＵＸ－９５０（（株）ＡＤＥＫＡ製）
＊２）発泡剤：ノプコＤＣ－１００－Ａ（サンノプコ（株）製）
＊３）湿潤剤：ＳＮウェット１２５（サンノプコ（株）製）
＊４）導電剤：ＢＳＹＤ１４９７１（御国色素（株）製）
＊５）整泡剤：ネオゲンＳ－２０Ｄ（第一工業製薬（株）製）
＊６）硬化剤：アデカボンタイターＨＵＸ－ＳＷ（（株）ＡＤＥＫＡ製）
＊７）耐水化剤：ＡＺコート５８００ＭＴ（サンノプコ（株）製）
Figure JPOXMLDOC01-appb-T000001
 * 1) Urethane resin: Adekabon titer HUX-950 (manufactured by ADEKA)
* 2) Foaming agent: Nopco DC-100-A (manufactured by San Nopco)
* 3) Wetting agent: SN wet 125 (manufactured by San Nopco)
* 4) Conductive agent: BSYD14971 (manufactured by Gokoku Color Co., Ltd.)
* 5) Foam stabilizer: Neogen S-20D (Daiichi Kogyo Seiyaku Co., Ltd.)
* 6) Curing agent: Adekabon titer HUX-SW (manufactured by ADEKA Corporation)
* 7) Water-resistant agent: AZ coat 5800MT (manufactured by San Nopco)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表中に示すように、弾性層配合中にポリウレタン樹脂とともに湿潤剤を含有させた各実施例のローラにおいては、湿潤剤を含有させなかった比較例１のローラと比べて、発泡比重をより精密に制御できることが確かめられた。また、上記表および図中に示すように、各実施例のローラにおいては、比較例１のローラと比べて、弾性層表面における気孔径が微細化されていることが確かめられた。 As shown in the above table, in the roller of each example in which the wetting agent was contained together with the polyurethane resin during the elastic layer formulation, the specific gravity of foaming was higher than that of the roller of Comparative Example 1 in which the wetting agent was not contained. It was confirmed that it can be controlled precisely. Further, as shown in the table and the drawings, it was confirmed that the pore diameter on the surface of the elastic layer was made finer in the roller of each example than in the roller of Comparative Example 1.
１　シャフト
２　弾性層
３　表層
４　接着層
５　抵抗調整層
１０，２０，３０　導電性ローラ DESCRIPTION OF SYMBOLS 1 Shaft 2 Elastic layer 3 Surface layer 4 Adhesive layer 5 Resistance adjustment layer 10, 20, 30 Conductive roller

Claims (6)

  1. 　シャフトと、該シャフトの外周に形成された弾性層と、を備える導電性ローラにおいて、
    　前記弾性層が、ポリウレタン樹脂と湿潤剤とを含有するポリウレタンフォームからなることを特徴とする導電性ローラ。     In a conductive roller comprising a shaft and an elastic layer formed on the outer periphery of the shaft,
    The conductive roller, wherein the elastic layer is made of polyurethane foam containing a polyurethane resin and a wetting agent.
  2. 　前記湿潤剤が、シリコーン系界面活性剤である請求項１記載の導電性ローラ。 The conductive roller according to claim 1, wherein the wetting agent is a silicone-based surfactant.
  3. 　前記ポリウレタンフォームが、前記湿潤剤を前記ポリウレタン樹脂１００質量部に対し０．１～４質量部含有する請求項１記載の導電性ローラ。 The conductive roller according to claim 1, wherein the polyurethane foam contains 0.1 to 4 parts by mass of the wetting agent with respect to 100 parts by mass of the polyurethane resin.
  4. 　前記弾性層の外周に、表層が形成されている請求項１記載の導電性ローラ。 The conductive roller according to claim 1, wherein a surface layer is formed on an outer periphery of the elastic layer.
  5. 　帯電ローラである請求項１記載の導電性ローラ。 The conductive roller according to claim 1, which is a charging roller.
  6. 　請求項１記載の導電性ローラを製造する方法であって、
    　前記ポリウレタン樹脂と湿潤剤とを含有する配合材料を、機械的に攪拌することにより発泡させた後、発泡した該配合材料を、前記シャフトにディッピング塗布して、該シャフトの外周に前記弾性層を形成することを特徴とする導電性ローラの製造方法。     A method for producing a conductive roller according to claim 1,
    The compounding material containing the polyurethane resin and the wetting agent is foamed by mechanical stirring, and then the foamed compounding material is dipped on the shaft, and the elastic layer is formed on the outer periphery of the shaft. A method for producing a conductive roller, comprising: forming a conductive roller.
PCT/JP2011/054650 2010-03-01 2011-03-01 Conductive roller and manufacturing method therefor WO2011108548A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363237A (en) * 2001-06-07 2002-12-18 Bridgestone Corp Electroconductive polyurethane foam member
JP2009025418A (en) * 2007-07-17 2009-02-05 Bridgestone Corp Conductive roller

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363237A (en) * 2001-06-07 2002-12-18 Bridgestone Corp Electroconductive polyurethane foam member
JP2009025418A (en) * 2007-07-17 2009-02-05 Bridgestone Corp Conductive roller

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