WO2019187764A1 - 電子写真機器用導電性ロールおよび電子写真機器用導電性ロールの製造方法 - Google Patents

電子写真機器用導電性ロールおよび電子写真機器用導電性ロールの製造方法 Download PDF

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Publication number
WO2019187764A1
WO2019187764A1 PCT/JP2019/005752 JP2019005752W WO2019187764A1 WO 2019187764 A1 WO2019187764 A1 WO 2019187764A1 JP 2019005752 W JP2019005752 W JP 2019005752W WO 2019187764 A1 WO2019187764 A1 WO 2019187764A1
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Prior art keywords
resin
catalyst
conductive roll
meth
silicone rubber
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PCT/JP2019/005752
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English (en)
French (fr)
Japanese (ja)
Inventor
浩介 峰松
穣 葛島
安紀 二村
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Sumitomo Riko Co Ltd
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Sumitomo Riko Co Ltd
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Priority to CN201980008555.1A priority Critical patent/CN111615670B/zh
Publication of WO2019187764A1 publication Critical patent/WO2019187764A1/ja
Priority to US16/987,361 priority patent/US11029621B2/en
Anticipated expiration legal-status Critical
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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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor
    • 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
    • G03G15/1605—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 using at least one intermediate support
    • G03G15/162—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 using at least one intermediate support details of the the intermediate support, e.g. chemical composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/10—Bases for charge-receiving or other layers
    • G03G5/104—Bases for charge-receiving or other layers comprising inorganic material other than metals, e.g. salts, oxides, carbon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/10—Bases for charge-receiving or other layers
    • G03G5/105—Bases for charge-receiving or other layers comprising electroconductive macromolecular compounds

Definitions

  • the present invention relates to a conductive roll for electrophotographic equipment and a method for producing a conductive roll for electrophotographic equipment that are suitably used in electrophotographic equipment such as copying machines, printers, and facsimiles that employ an electrophotographic system.
  • conductive rolls such as a charging roll, a developing roll, a transfer roll, and a toner supply roll are used.
  • the conductive roll of the electrophotographic apparatus has a conductive elastic layer on the outer periphery of the shaft body. Silicone rubber may be used as the base material for the elastic layer.
  • the molding temperature of the elastic body layer is lowered to reduce the difference between the material temperature during curing and the temperature during use, and the thermal shrinkage of the material It is necessary to reduce the amount.
  • Patent Document 1 describes a technique for performing low-temperature molding in emulsion foaming of silicone rubber.
  • a crosslinking catalyst for silicone rubber it is described that a microcapsule catalyst composed of resin fine particles enclosing a crosslinking catalyst is used. . Thereby, the molding temperature can be set below the boiling point where water does not evaporate.
  • the resin covering the cross-linking catalyst of the microcapsule catalyst is preferably a resin having low compatibility with the silicone rubber so that the cross-linking catalyst does not diffuse into the silicone rubber during storage before use. If it does so, in a silicone rubber composition, the dispersibility of a microcapsule type
  • mold catalyst may become low, and there exists a possibility that the hardness after hardening may arise.
  • a conductive roll for electrophotographic equipment includes a shaft body and a non-foamed elastic body layer formed on the outer periphery of the shaft body, and the elastic body layer includes the following: (A) to (d) comprising a crosslinked product of a silicone rubber composition, wherein the secondary particle diameter of the following (d) in the elastic layer is in the range of 100 to 500 nm.
  • Conductive roll for electrophotographic equipment (A) Organopolysiloxane (b) Crosslinking agent (c) Microcapsule catalyst comprising resin fine particles containing a crosslinking catalyst with a resin other than silicone resin (d) Silica having a BET specific surface area of 70 to 350 m 2 / g
  • the resin (c) is preferably a thermosetting resin.
  • the resin (c) is preferably at least one of polyvinyl butyral resin, epoxy resin, and acrylic resin.
  • the (d) preferably has a dimethylsilyl group or a trimethylsilyl group on the surface.
  • the content of (d) is preferably in the range of 3.0 to 35 parts by mass with respect to 100 parts by mass of (a).
  • the molding temperature for molding the crosslinked body of the silicone rubber composition is in the range of 80 to 130 ° C., and the molding time is 5 to 100 seconds.
  • the gist is within the range.
  • the elastic body layer is composed of a crosslinked body of the silicone rubber composition containing the above (a) to (d), and the above (a) to (d) In the silicone rubber composition to be contained, since (d) has a specific BET specific surface area and (d) has a specific secondary particle diameter in the elastic body layer, the product end portion swells and the product hardness varies And is excellent in fluidity and storage stability of the material before curing.
  • the resin (c) is a thermosetting resin
  • a decrease in compression set of the elastic body layer due to the resin (c) is suppressed, and the settling resistance is improved.
  • the resin of said (c) is at least 1 sort (s) of polyvinyl butyral resin, an epoxy resin, and an acrylic resin
  • the above (d) has a dimethylsilyl group or a trimethylsilyl group on the surface, the compatibility between the silicone rubber and the above (d) is improved, and the dispersibility of the microcapsule catalyst in the silicone rubber composition is improved. Variation in product hardness is further suppressed.
  • content of said (d) is a specific range, it is excellent in the balance of the effect which suppresses the dispersion
  • the molding temperature for molding the crosslinked body of the silicone rubber composition is in the range of 80 to 130 ° C., and the molding time is 5 to 100. Since it is within the range of seconds, the swelling of the end of the product and the variation in product hardness are suppressed, and the fluidity and storage stability of the material before curing are excellent.
  • FIG. 1A is a schematic external view of a conductive roll for electrophotographic equipment according to an embodiment of the present invention.
  • the electroconductive roll for electrophotographic equipment according to the present invention (hereinafter sometimes simply referred to as a conductive roll) will be described in detail.
  • the conductive roll 10 includes a shaft body 12 and an elastic body layer 14 formed on the outer periphery of the shaft body 12.
  • the elastic body layer 14 is a layer (base layer) serving as a base of the conductive roll 10.
  • the elastic layer 14 is made of a non-foamed elastic body (solid elastic body).
  • the conductive roll 10 can be suitably used as a conductive roll such as a charging roll, a developing roll, a transfer roll, and a toner supply roll in an electrophotographic apparatus such as a copying machine, a printer, or a facsimile that employs an electrophotographic system.
  • the elastic body layer 14 is made of a crosslinked body of a silicone rubber composition containing the following (a) to (d).
  • the secondary particle diameter (d) below in the elastic layer 14 is in the range of 100 to 500 nm.
  • (A) Organopolysiloxane (b) Crosslinking agent (c) Microcapsule catalyst comprising resin fine particles containing a crosslinking catalyst with a resin other than silicone resin (d) Silica having a BET specific surface area of 70 to 350 m 2 / g
  • Organopolysiloxane is (b) an organopolysiloxane having at least two functional groups crosslinked in one molecule by a crosslinking agent.
  • the functional group-containing organopolysiloxane includes alkenyl group-containing organopolysiloxane, hydroxyl group-containing organopolysiloxane, (meth) acryl group-containing organopolysiloxane, isocyanate-containing organopolysiloxane, amino group-containing organopolysiloxane, and epoxy group-containing organopolysiloxane. Examples thereof include siloxane. Of these, alkenyl group-containing organopolysiloxane is preferred.
  • the alkenyl group-containing organopolysiloxane is used as a main raw material of, for example, an addition-curable silicone rubber composition.
  • the alkenyl group-containing organopolysiloxane is crosslinked by a hydrosilyl crosslinking agent by an addition reaction with the hydrosilyl crosslinking agent.
  • Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • Organopolysiloxane has an organic group in addition to the above functional group.
  • the organic group is a monovalent substituted or unsubstituted hydrocarbon group.
  • unsubstituted hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, alkyl groups such as dodecyl groups, aryl groups such as phenyl groups, ⁇ -phenylethyl groups, ⁇ -phenylpropyl groups, etc. And an aralkyl group.
  • Examples of the substituted hydrocarbon group include a chloromethyl group and a 3,3,3-trifluoropropyl group.
  • organopolysiloxanes having a methyl group as an organic group are frequently used for ease of synthesis.
  • the organopolysiloxane is preferably linear, but may be branched or cyclic.
  • the cross-linking agent is a cross-linking agent that cross-links (a) organopolysiloxane.
  • the crosslinking agent include hydrosilyl crosslinking agents and peroxide crosslinking agents. Of these, hydrosilyl crosslinking agents are preferred.
  • the hydrosilyl cross-linking agent is used as a cross-linking agent for addition-curable silicone rubber compositions.
  • the hydrosilyl crosslinking agent has a hydrosilyl group (SiH group) in its molecular structure.
  • the hydrosilyl crosslinking agent is a hydrosilyl group-containing organopolysiloxane (organohydrogenpolysiloxane).
  • the number of hydrosilyl groups in the molecular structure is not particularly limited, but is preferably in the range of 2 to 50 from the viewpoints of excellent curing speed and excellent stability. When the molecular structure has two or more hydrosilyl groups, the hydrosilyl groups are preferably present in different Si.
  • the polysiloxane may be a chain or a cyclic one.
  • the hydrosilyl group-containing organopolysiloxane preferably has at least two hydrosilyl groups in one molecule.
  • the hydrosilyl crosslinking agent preferably has a number average molecular weight in the range of 200 to 30000 from the viewpoint of excellent handleability.
  • hydrosilyl group-containing organopolysiloxanes include trimethylsiloxy group-blocked methylhydrogenpolysiloxanes at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymers at both ends, Terminal dimethylhydrogensiloxy-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethyl Siloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, (CH 3 ) 2 HSiO1 / 2 unit and SiO 4
  • a copolymer include trimethylsiloxy group-blocked methylhydrogenpoly
  • the blending amount of the hydrosilyl crosslinking agent is not particularly limited, but is usually in the range of 0.1 to 40 parts by mass with respect to 100 parts by mass of the alkenyl group-containing organopolysiloxane.
  • organic peroxides examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, dicumyl peroxide, cumyl-t-butyl peroxide, and 2,5-dimethyl-2. , 5-di-t-butylperoxyhexane, di-t-butylperoxide and the like. Of these, dicumyl peroxide, cumyl-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, di-t-butyl peroxide are provided because they give particularly low compression set. Is preferred.
  • the amount of the organic peroxide added is not particularly limited, but is usually in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the alkenyl group-containing organopolysiloxane.
  • the crosslinking catalyst is a catalyst that promotes the crosslinking reaction of (a) organopolysiloxane by (b) a crosslinking agent.
  • the crosslinking catalyst (c) include a platinum catalyst, a ruthenium catalyst, and a rhodium catalyst as hydrosilylation catalysts.
  • the platinum catalyst include fine-particle platinum, platinum black, platinum-supported activated carbon, platinum-supported silica, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, and the like. These may be used alone or in combination of two or more.
  • the crosslinking catalyst is microencapsulated using a resin.
  • the microcapsule type catalyst (microencapsulated catalyst) is composed of resin fine particles enclosing a crosslinking catalyst.
  • the resin fine particles encapsulating the crosslinking catalyst are solid at least at room temperature and have an average particle size of 30 ⁇ m or less.
  • the average particle diameter is measured with a laser microscope.
  • the average particle diameter of the resin fine particles encapsulating the crosslinking catalyst is preferably 10 ⁇ m or less from the viewpoint of enhancing the dispersibility of the crosslinking catalyst. More preferably, it is 7.0 ⁇ m or less. Moreover, it is preferable that it is 0.1 micrometer or more from a viewpoint of raising the fine particle collection rate at the time of preparation. More preferably, it is 2.0 ⁇ m or more.
  • the resin (coating resin) of the microcapsule type catalyst is made of a resin other than silicone resin. This is because, during storage (storage) before use, in the silicone rubber composition, the resin of the microcapsule type catalyst swells, and the encapsulated crosslinking catalyst diffuses into the silicone rubber composition. This is to prevent the siloxane crosslinking reaction from proceeding. From this point of view, it is preferable to use (a) a resin having low compatibility with the organopolysiloxane as the resin of the microcapsule catalyst. Specifically, (a) a solubility parameter that greatly deviates from the solubility parameter of the organopolysiloxane is preferable.
  • the solubility parameter (SP value) of the resin of the microcapsule type catalyst is preferably 7.9 or more. More preferably, it is 8.3 or more, More preferably, it is 9.0 or more.
  • the upper limit value of the solubility parameter of the resin of the microcapsule type catalyst is not particularly limited, and may be, for example, 20 or less.
  • the solubility parameter can be calculated from the molecular structure by the Small calculation method.
  • the resin of the microcapsule type catalyst may be either a thermoplastic resin or a thermosetting resin.
  • the resin of the microcapsule catalyst is more preferably a thermosetting resin from the viewpoint of being able to suppress a decrease in compression set by being crosslinked.
  • the resin of the microcapsule type catalyst is not particularly limited, but preferably has a glass transition temperature (Tg) of 40 to 145 ° C.
  • the glass transition temperature (Tg) of the thermosetting resin is a value before thermosetting.
  • the resin melting start time is shortened and the crosslinking reactivity is improved by increasing the diffusion amount of the crosslinking catalyst. Therefore, the cross-linking reactivity at low temperature is also excellent.
  • the glass transition temperature is preferably 40 ° C. or higher so that the resin softens and melts at room temperature and does not impair the storage stability. More preferably, the glass transition temperature is 45 ° C. or higher, or 50 ° C. or higher.
  • the glass transition temperature can be measured by DSC (differential scanning calorimetry).
  • the resin of the microcapsule type catalyst is not particularly limited, but preferably has a thermal conductivity of 0.16 W / m ⁇ K or more.
  • A By making it higher than the thermal conductivity of the organopolysiloxane, the melting rate of the resin during heating (during reaction) can be increased, and the crosslinking reactivity can be improved by improving the diffusibility of the crosslinking catalyst. .
  • the thermal conductivity can be measured according to ASTM C177.
  • the resin of the microcapsule type catalyst includes epoxy resin, acrylic resin, polyvinyl butyral resin, styrene polymer, polycarbonate resin, unsaturated polyester resin, alkyd resin, urea resin, melamine resin, vinyl chloride resin, polyurethane resin, polyether
  • examples include sulfone resins, polysulfone resins, polyphenylene sulfide resins, phenol resins, diallyl phthalate resins, polyvinyl alcohol resins, and hydrogenated terpene resins. These may be used individually by 1 type as resin of a microcapsule type catalyst, and may be used in combination of 2 or more type.
  • thermosetting resin examples include polyvinyl butyral resin, epoxy resin, unsaturated polyester resin, phenol resin, resol resin, alkyd resin, urea resin, melamine resin, polyurethane resin, diallyl phthalate resin, and acrylic resin.
  • the resin of the microcapsule catalyst it is more preferable that the resin composition does not contain a nitrogen compound such as amine or amide, or a compound such as phosphorus or sulfur from the viewpoint of not inhibiting the reactivity of the crosslinking catalyst. Since each resin includes those having different solubility parameters and different glass transition temperatures in the same kind of material, even when any one of the resins is used alone as a resin for the microcapsule type catalyst, the materials having different physical property values are used.
  • the acrylic resin includes both a polymer containing acrylate as a monomer and a polymer containing methacrylate as a monomer. Also included are polymers containing acrylate and methacrylate as monomers. Among these, from the viewpoint of maintaining a solid state at room temperature, a polymer containing acrylate and methacrylate as monomers, and a polymer containing only methacrylate as monomers are more preferable.
  • the acrylic resin may be a homopolymer synthesized from a single monomer, or may be a copolymer synthesized from two or more monomers.
  • the acrylic resin is preferably a copolymer from the viewpoint of easily adjusting the glass transition temperature to a low temperature of 100 ° C. or lower or 85 ° C. or lower. Among acrylic resins, a copolymer of ethyl methacrylate and methyl methacrylate is particularly preferable from the viewpoint that the glass transition temperature can be lowered to 85 ° C. or lower.
  • alkyl (meth) acrylate As acrylic monomers and methacrylic monomers, alkyl (meth) acrylate, cycloalkyl (meth) acrylate, halogenated alkyl (meth) acrylate, hydroxyl-containing (meth) acrylate, alkoxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate And alkoxyalkylene glycol (meth) acrylate.
  • alkyldiol di (meth) acrylate such as 1,9-nonanediol di (meth) acrylate
  • polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate
  • polypropylene such as dipropylene glycol di (meth) acrylate Glycol di (meth) acrylate
  • trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate
  • glycerol tri (meth) acrylate ethylene glycol diglycidyl ether and unsaturated carboxylic acid Multivalent (meth) acrylates and glycidyl (meth) acrylates obtained by addition reaction of compounds with ethylenically unsaturated bonds such as unsaturated alcohols and active hydrogen
  • Polyvalent (meth) acrylamides such as polyvalent (
  • the styrene polymer may be a homopolymer synthesized from a single monomer or a copolymer synthesized from two or more monomers.
  • the styrenic polymer is preferably a copolymer.
  • Styrene polymers include styrene-maleic anhydride copolymer (SMA), styrene-butadiene copolymer (SBS), styrene-isoprene copolymer (SIS), hydrogenated styrene-butadiene copolymer (SEBS).
  • SEPS hydrogenated styrene-isoprene copolymer
  • SAN styrene-acrylonitrile copolymer
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the microcapsule type catalyst can be produced by a conventionally known method. From the viewpoints of productivity, sphericity, etc., suspension polymerization, emulsion polymerization, spray dryer, and submerged drying are preferred.
  • the cross-linking catalyst is used as a solid core material, which is dispersed in an organic solvent that does not dissolve, and the monomer is suspended in this dispersion liquid, such as suspension polymerization method or emulsion polymerization method.
  • the polymer covers the surface of the core material.
  • a microcapsule catalyst in which the crosslinking catalyst is encapsulated in the resin fine particles is obtained.
  • a crosslinking catalyst and a resin to be encapsulated are dissolved in an organic solvent insoluble in water, and this solution is dropped into an aqueous surfactant solution to produce an emulsion. Then, after reducing the pressure and removing the organic solvent, an encapsulated catalyst is obtained by filtration.
  • the metal atom content of the cross-linking catalyst in the microcapsule catalyst is preferably 5% by mass or less from the viewpoint of being sufficiently covered with a resin and ensuring excellent storage stability. More preferably, it is 2 mass% or less. Moreover, it is preferable that it is 0.01 mass% or more from a viewpoint of ensuring the outstanding catalyst activity. More preferably, it is 0.1 mass% or more.
  • the content of the microcapsule-type catalyst in the silicone rubber composition depends on the content of the cross-linking catalyst in the microcapsule-type catalyst, but when the content of the cross-linking catalyst in the microcapsule-type catalyst is within the above predetermined range.
  • (A) It can be in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the organopolysiloxane.
  • the cross-linking catalyst is a metal catalyst, the amount is usually in the range of 1 ppm to 1.0 part by mass in terms of metal amount with respect to 100 parts by mass of (a) organopolysiloxane.
  • silica (d) silica having a BET specific surface area of 70 to 350 m 2 / g is used.
  • the BET specific surface area of the silica to be used is less than 70 m 2 / g and the surface area is too small, (c) the interaction with the microcapsule catalyst is small, and (c) the dispersibility of the microcapsule catalyst is lowered. Thereby, the hardness dispersion
  • the BET specific surface area of the silica to be used exceeds 350 m ⁇ 2 > / g and a surface area is too large, the fluidity
  • the BET specific surface area of the silica used is more preferably 90 m 2 / g or more, and particularly preferably 130 m 2 / g or more.
  • liquidity of the material before hardening More preferably, it is 300 m ⁇ 2 > / g or less.
  • the primary particle diameter of silica (d) is preferably in the range of 7.0 to 20 nm. More preferably, it is in the range of 7.0 to 16 nm.
  • the primary particle diameter of silica can be measured with a laser microscope.
  • the silica content is preferably in the range of 3.0 to 35 parts by mass with respect to 100 parts by mass of (a) organopolysiloxane. More preferably, it is in the range of 5.0 to 30 parts by mass.
  • the content of silica in (d) is 3.0 parts by mass or more with respect to 100 parts by mass of (a) organopolysiloxane, the hardness variation of the elastic layer 14 is easily suppressed.
  • the content of silica in (d) is 35 parts by mass or less with respect to 100 parts by mass of (a) organopolysiloxane, a decrease in fluidity of the material before curing is easily suppressed.
  • Silica may be surface-treated with a surface treatment agent or may not be surface-treated.
  • the surface treatment agent include a silylating agent and dimethylpolysiloxane.
  • the silica in (d) can have a hydrophobic group such as a dimethylsilyl group or a trimethylsilyl group on the surface.
  • the compatibility with (a) organopolysiloxane is improved, and (c) microcapsules are passed through the silica of (d). Dispersibility of the type catalyst is improved. Thereby, the hardness variation of the elastic body layer 14 is suppressed more.
  • the silicone rubber composition can be added with an additive that can be added to the silicone rubber within a range not inhibiting the present invention.
  • Additives include reinforcing materials, conductive agents, fillers, crosslinking accelerators, crosslinking retarders, crosslinking aids, scorch inhibitors, anti-aging agents, softeners, plasticizers, lubricants, thermal stabilizers, flame retardants, flame retardants Examples include a combustion aid, an ultraviolet absorber, and a rust inhibitor.
  • the conductive agent include an electronic conductive agent (carbon black, graphite, c-TiO 2 , c-ZnO, c-SnO 2 (c- means conductivity)), an ionic conductive agent (quaternary ammonium salt). , Quaternary phosphonium salts, borates, surfactants, and the like).
  • the elastic layer 14 can be produced, for example, as follows. First, the shaft body 12 is coaxially installed in the hollow part of the roll molding die, injected with an uncrosslinked conductive silicone rubber composition, heated and cured (crosslinked), and then demolded, Alternatively, the elastic body layer 14 can be formed on the outer periphery of the shaft body 12 by extruding an uncrosslinked conductive silicone rubber composition on the surface of the shaft body 12.
  • the molding temperature for molding the crosslinked body of the silicone rubber composition is preferably in the range of 80 to 130 ° C.
  • the molding time is preferably in the range of 5 to 100 seconds.
  • the secondary particle diameter (d) is in the range of 100 to 500 nm. Preferably, it is in the range of 150 to 400 nm. When the secondary particle size of (d) is less than 100 nm, the fluidity of the material is lowered. On the other hand, when the secondary particle diameter of (d) is more than 500 nm, the hardness variation of the product occurs.
  • the secondary particle size (d) in the elastic layer 14 can be adjusted by the primary particle size, content, dispersion conditions, and the like.
  • the secondary particle diameter (d) in the elastic body layer 14 can be measured by observing a cross section of the elastic body layer 14. Specifically, it can be measured with a transmission electron microscope.
  • the elastic body layer 14 can be adjusted to a predetermined volume resistivity.
  • the volume resistivity of the elastic layer 14 may be set as appropriate in the range of 10 2 to 10 10 ⁇ ⁇ cm according to the application.
  • the thickness of the elastic layer 14 is not particularly limited, and may be set as appropriate within a range of 0.1 to 10 mm according to the application.
  • the shaft body 12 is not particularly limited as long as it has conductivity. Specific examples include solid bodies made of metal such as iron, stainless steel, and aluminum, and a cored bar made of a hollow body. You may apply
  • the crosslinking catalyst of the silicone rubber composition forming the elastic layer 14 is a microcapsule type catalyst, low-temperature molding can be performed in a short time, and the end of the product Swelling is suppressed. Moreover, it is excellent also in the storage stability of the material before hardening. And in a silicone rubber composition, the dispersibility of the microcapsule type
  • the conductive roll according to the present invention may be composed of only the shaft body 12 and one elastic body layer 14, or other layers other than the one elastic body layer 14 may be used. Furthermore, the structure which it has may be sufficient. Examples of other layers include a surface layer and an intermediate layer.
  • the surface layer is a layer that appears on the surface of the conductive roll, and is provided for the purpose of protecting the surface of the conductive roll and imparting surface characteristics.
  • One or more intermediate layers are provided between the shaft body 12 and one elastic body layer 14 or between one elastic body layer 14 and the surface layer.
  • the intermediate layer is provided for the purpose of improving adhesion and preventing diffusion of components to other parts.
  • the same function as that in the case of providing the surface layer may be imparted by performing a surface modification treatment for modifying the surface of the elastic body layer 14.
  • Organopolysiloxane (silicone rubber): “DMS-V31” manufactured by Gelest ⁇
  • Crosslinking agent Hydrosilyl crosslinking agent (“HMS-501” manufactured by Gelest)
  • Microcapsule type catalyst synthetic product below ⁇ Silica ⁇ 1>: “AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd., surface treatment with hexamethyldisilazane ⁇ Silica ⁇ 2>: “AEROSIL 90” manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL 300 surface treatment with hexamethyldisilazane, silica ⁇ 4>: Nippon Aerosil Co., Ltd.
  • AEROSIL 200 dimethyldichloro Surface treatment with silazane, silica ⁇ 5>: “AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd.
  • Silica ⁇ 6> “AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd., surface treated with silicone oil.
  • AEROSIL 380 surface treatment with hexamethyldisilazane: Additive: Conductive agent (Denka “Denka Black HS-100”)
  • microcapsule type catalyst A 20 mass% xylene solution of a platinum catalyst, each coating resin used for encapsulation, and acetone are mixed in a ratio (mass ratio) of 0.6: 5: 95, and this solution is placed in a spray dryer tank at 70 ° C. in a nitrogen atmosphere. To obtain fine particles containing a coating resin and a platinum catalyst. Thereby, a microcapsule type catalyst having a predetermined average particle diameter was produced. The average particle size of the microcapsule catalyst was measured with a laser microscope.
  • the solubility parameter (SP value) and glass transition temperature (Tg) of the coating resin of the microcapsule catalyst were measured by the following methods.
  • SP value Solubility parameter (SP value)
  • Glass transition temperature (Tg) Glass transition temperature (Tg)
  • DSC measurement inspection scanning calorimetry
  • a silicone rubber composition was filled into a mold in which a core metal (diameter 6 mm, made of SUS304) serving as a shaft was set, and then heat-crosslinked under the predetermined conditions (temperature, time) described in the table. Thereafter, the mold was removed, the rubber end portion was cut to a predetermined size, and a roll-shaped elastic body layer (thickness 3 mm) made of conductive silicone rubber was formed along the outer peripheral surface of the shaft body. Thus, a conductive roll was produced.
  • the values of the BET specific surface area and primary particle diameter of the silica used are catalog values.
  • the secondary particle diameter of silica is the secondary particle diameter of silica in the elastic layer and is a measured value.
  • the storage stability, material fluidity, and curability of the prepared silicone rubber composition were evaluated. Moreover, about the produced electroconductive roll, hardness dispersion
  • the prepared silicone rubber composition was mixed until there was no difference in the dispersed state, allowed to stand at room temperature, and judged by whether it was cured by touching with the hand. Especially good when not cured for more than one week “ ⁇ ”, good when not cured for more than 3 days “good”, acceptable when not cured for more than one day “ ⁇ ”, poor when cured immediately It was set as “x”.
  • the surface hardness was measured with an Acker C hardness meter at a position of 10 mm in the axial direction from the end of the elastic layer in the axial direction at a 45 ° pitch in the circumferential direction, and the hardness variation was determined.
  • the case where the average value is within ⁇ 0.5 is particularly good “ ⁇ ”
  • the case where it is within ⁇ 1.0 is good “ ⁇ ”
  • the case where it is less than ⁇ 1.5 is acceptable “ ⁇ ”
  • ⁇ The case where it was 1.5 or more was defined as a defective “x”.
  • the prepared silicone rubber composition was measured with “AR500 rheometer” manufactured by TA Instruments Japan in a 2 cm 2 ° cone / gap distance of 50 ⁇ m / equilibrium flow mode, and the reading was Shear rate 10 (1 / s). . Especially good when it is less than 1000 Pa ⁇ s “ ⁇ ”, good when it is 1000 Pa ⁇ s or more and less than 2000 Pa ⁇ s“ good ”, or good when it is 2000 Pa ⁇ s or more and less than 3000 Pa ⁇ s“ ⁇ ” The case where the pressure was 3000 Pa ⁇ s or higher was defined as a defective “x”.
  • the elastic layer was evaluated by what percentage of the thickness at the 10 mm position the difference in outer diameter between the 0.5 mm position and the 10 mm position in the axial direction from the axial end of the elastic layer. When it is 4.0% or less, particularly good “ ⁇ ”, when it is more than 4.0% and 5.5% or less, it is “good”, when it is more than 5.5% and 6.0% or less Was acceptable “ ⁇ ”, and the case where it was over 6.0% was regarded as “bad”.
  • the crosslinking catalyst is not a microcapsule catalyst. For this reason, low-temperature molding cannot be performed for a short time, and swelling of the end portion of the product cannot be suppressed.
  • the coating resin of the microcapsule type catalyst is a silicone resin. For this reason, storage stability was bad and various evaluation was impossible.
  • silica is not blended in the silicone rubber composition. For this reason, the dispersibility of the microcapsule type catalyst is poor and the hardness variation is large.
  • the BET specific surface area of silica is too small.
  • the silicone rubber composition forming the elastic body layer is made of microparticles composed of (a) an organopolysiloxane, (b) a crosslinking agent, and (c) resin fine particles including a crosslinking catalyst in a resin other than a silicone resin.
  • the capsule-type catalyst (d) contains silica having a BET specific surface area of 70 to 350 m 2 / g, and the secondary particle diameter of (d) in the elastic layer is in the range of 100 to 500 nm. Swelling and variations in product hardness are suppressed, and the fluidity and storage stability of the material before curing are excellent.

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