WO2021246263A1 - Sponge roller - Google Patents

Sponge roller Download PDF

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Publication number
WO2021246263A1
WO2021246263A1 PCT/JP2021/020036 JP2021020036W WO2021246263A1 WO 2021246263 A1 WO2021246263 A1 WO 2021246263A1 JP 2021020036 W JP2021020036 W JP 2021020036W WO 2021246263 A1 WO2021246263 A1 WO 2021246263A1
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WO
WIPO (PCT)
Prior art keywords
elastic layer
foamed elastic
group
composition
shaft body
Prior art date
Application number
PCT/JP2021/020036
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French (fr)
Japanese (ja)
Inventor
秀隆 大柴
Original Assignee
信越ポリマー株式会社
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Publication date
Application filed by 信越ポリマー株式会社 filed Critical 信越ポリマー株式会社
Priority to CN202180033993.0A priority Critical patent/CN115552338A/en
Publication of WO2021246263A1 publication Critical patent/WO2021246263A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • G03G15/20—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat

Definitions

  • the present invention relates to a sponge roller.
  • An image forming apparatus using an electrophotographic method has a shaft body and an elastic layer formed on the outer peripheral surface thereof, for example, a cleaning roller, a charging roller, a developing roller, a transfer roller, a pressure roller, a paper feed transfer roller, and the like. It is equipped with various printing sponge rollers such as fixing rollers.
  • a thermal roller fixing method As the fixing means in the above image forming apparatus, for example, a thermal roller fixing method is adopted.
  • a heating roller (fixing roller) and a pressure roller are used as a pair of basic configurations, and a recorded material (transfer material sheet, fax paper, printing) on which a toner image is carried on a pressure welding nip portion of the roller pair is used. It is common to heat-press fix the toner image on the material to be recorded by introducing paper, etc.).
  • a foamed elastic layer (sponge layer) is used in the fixing roller or the pressure roller used for the fixing means in order to adjust the nip pressure to an appropriate level.
  • the foamed elastic layer is generally formed by vulcanizing and foaming a spontaneous silicone rubber containing an organopolysiloxane and a filler.
  • a fixing or pressurizing roller having a foamed elastic layer is mounted in a pressure contact state and exerts its function by continuously or intermittently rotating. Therefore, it is easily loaded by heat or friction, and the foamed elastic layer becomes Since the hardness decreases, high durability is required.
  • a silicone rubber composition capable of forming a rubber member for paper feeding having high wear resistance even after repeated use for example, in Patent Document 1, a vinyl group-containing silicone raw rubber is used as a rubber compound for forming a rubber member for paper feeding.
  • a silicone rubber composition added, wherein the loss coefficient tan ⁇ after smelting the rubber compound is 0 ⁇ tan ⁇ ⁇ 1 has been proposed.
  • the fixing roller or the pressure roller is required to have further improved durability.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sponge roller having high durability.
  • the present invention is a sponge roller including a shaft body and a foamed elastic layer formed on the outer periphery of the shaft body, wherein the foamed elastic layer is a mirable type silicone rubber composition, a vinyl group-containing silicone raw rubber, a foaming agent, and the like.
  • the loss coefficient tan ⁇ of the cured rubber composition obtained by foaming and vulcanizing the foamed elastic layer composition containing the foaming elastic layer and removing the foaming agent from the foamed elastic layer composition under the following measurement conditions. It is a sponge roller of 0.035 or less.
  • ⁇ Measurement conditions> Frequency 8Hz, temperature 100 °C, strain control 5 ⁇ m
  • the Asker C hardness of the foamed elastic layer is 15 degrees or more and 40 degrees or less.
  • the sponge of the present invention is preferably a pressure roller.
  • a highly durable sponge roller can be obtained.
  • the sponge roller 1 of the present invention is a sponge roller 1 provided with a shaft body 2 and a foamed elastic layer 3 formed on the outer periphery of the shaft body 2 in this order.
  • the details of the sponge roller 1 of the present invention will be described with reference to FIG.
  • the shaft body 2 preferably, a shaft body having conductivity and used for a conventionally known developing roller can be used.
  • the shaft body 2 is preferably made of at least one metal selected from the group consisting of, for example, iron, aluminum, stainless steel, and brass.
  • the shaft body 2 made of such a metal is also generally known by the name of "core metal".
  • the shaft body 2 may contain an insulating resin.
  • the insulating resin may be, for example, a thermoplastic resin or a thermosetting resin.
  • the shaft body 2 may include, for example, a core body made of an insulating resin and a plating layer provided on the core body. Such a shaft body 2 can be obtained, for example, by plating a core body made of an insulating resin to make it conductive.
  • the shaft body 2 is preferably a core metal in order to obtain good conductivity.
  • the shape of the shaft body 2 is preferably, for example, a rod shape, a tubular shape, or the like.
  • the cross-sectional shape of the shaft body 2 may be, for example, a circular shape, an elliptical shape, or a non-circular shape such as a polygon.
  • the outer peripheral surface of the shaft body 2 may be subjected to a treatment such as a cleaning treatment, a degreasing treatment, and a primer treatment in order to improve the adhesiveness with the foamed elastic layer 3.
  • the length of the shaft body 2 in the axial direction is not particularly limited, and may be appropriately adjusted according to the form of the image forming apparatus to be installed.
  • the length of the shaft body 2 in the axial direction is preferably 250 mm or more and 320 mm or less, and more preferably 260 mm or more and 310 mm or less.
  • the diameter of the shaft body 2 (diameter of the circumscribed circle) is not particularly limited, and may be appropriately adjusted according to the form of the image forming apparatus to be installed.
  • the outer diameter (diameter of the circumscribed circle) of the shaft body 2 is preferably 4 mm or more and 14 mm or less, and more preferably 6 mm or more and 10 mm or less.
  • the foamed elastic layer 3 is formed by foaming and vulcanizing a composition for a foamed elastic layer containing (A) a mirable type silicone rubber composition, (B) a vinyl group-containing silicone raw rubber, (C) a foaming agent and (D) a cross-linking agent. It is something that is made to.
  • the foamed elastic layer 3 has a loss coefficient tan ⁇ measured at a frequency of 8 Hz, a temperature of 100 ° C., and a strain control of 5 ⁇ m in the dynamic viscoelasticity measurement of 0.035 or less, preferably 0.025 or less.
  • the loss coefficient tan ⁇ is a rubber containing (A) a mirable type silicone rubber composition, (B) a vinyl group-containing silicone raw rubber, and (D) a cross-linking agent obtained by removing (C) a foaming agent from the composition for a foamed elastic layer. It is the measurement of the cured product of the composition.
  • the addition-curing type mirable type silicone rubber composition preferably contains, for example, at least (a) an organopolysiloxane and (b) a filler.
  • Organopolysiloxane (a) The organopolysiloxane is represented by the following average composition formula (1).
  • R is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon atoms of 1 to 12, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • A is 1.5. It is a positive number in the range of 2.8, preferably 1.8 to 2.5, more preferably 1.95 to 2.05, and even more preferably 1.98 to 2.01.)
  • n represents a positive number of 1.95 or more and 2.05 or less.
  • R 1 indicates a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different.
  • the number of carbon atoms of the hydrocarbon group is preferably 1 or more and 12 or less, and more preferably 1 or more and 8 or less.
  • R 1 examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, a butenyl group and a hexenyl group.
  • alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group
  • a cycloalkyl group such as a cyclohexyl group
  • vinyl group an allyl group
  • a butenyl group and a hexenyl group examples include an aryl group such as an alkenyl group, a phenyl group and a trill group, and an aralkyl group such as a
  • R 1 may be a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are substituted with a substituent.
  • the substituent may be, for example, a halogen atom, a cyano group, or the like.
  • Examples of the hydrocarbon group having a substituent include a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like.
  • the organopolysiloxane has a molecular chain terminal such as a trialkylsilyl group such as a trimethylsilyl group, a dialkylaralkylsilyl group such as a dimethylvinylsilyl group, a dialkylhydroxysilyl group such as a dimethylhydroxysilyl group, or a trivinylsilyl group. It is preferably sealed with a trialal kill silyl group or the like.
  • the organopolysiloxane preferably has two or more alkenyl groups in the molecule.
  • organopolysiloxane 0.001 mol% or more of R 1 5 mol% or less (more preferably at least 0.01 mol% 0.5 mol%) preferably has an alkenyl group.
  • the vinyl group is particularly preferable as the alkenyl group contained in the organopolysiloxane.
  • the organopolysiloxane is obtained by, for example, co-hydrolyzing and condensing one or more of organohalosilanes, or ring-opening polymerization of a cyclic polysiloxane such as a trimer or tetramer of siloxane.
  • a cyclic polysiloxane such as a trimer or tetramer of siloxane.
  • the organopolysiloxane may be basically a linear diorganopolysiloxane, and may be partially branched. Further, (A) organopolysiloxane may be a mixture of two or more kinds having different molecular structures.
  • the kinematic viscosity of (A) organopolysiloxane at 25 ° C. is preferably 100 cSt or more, and more preferably 100,000 cSt or more and 10,000,000 cSt or less. Further, the degree of polymerization of (A) organopolysiloxane is preferably, for example, 100 or more, and more preferably 3000 or more and 10000 or less.
  • filler examples include silica-based fillers. Examples of the silica-based filler include fumes silica, precipitated silica and the like.
  • a surface-treated silica-based filler surface-treated with the silane coupling agent represented by R 2 Si (OR 3 ) 3 can be preferably used.
  • R 2 may be a group having a vinyl group or an amino group, and may be, for example, a glycidyl group, a vinyl group, an aminopropyl group, a methacrylate group, an N-phenylaminopropyl group, a mercapto group or the like.
  • R 3 may be an alkyl group, for example, a methyl group, an ethyl group, or the like.
  • the silane coupling agent can be easily obtained, for example, under the trade names "KBM1003" and "KBE402" manufactured by Shin-Etsu Chemical Co., Ltd.
  • the surface-treated silica-based filler can be obtained by treating the surface of the silica-based filler with a silane coupling agent according to a conventional method.
  • a commercially available product may be used, for example, J.A. M. Examples thereof include the product name "Zeothix 95" manufactured by HUBER Co., Ltd.
  • the blending amount of the silica-based filler is preferably 11 parts by mass or more and 39 parts by mass or less, and more preferably 15 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of (A) organopolysiloxane.
  • the average particle size of the silica-based filler is preferably 1 ⁇ m or more and 80 ⁇ m or less, and more preferably 2 ⁇ m or more and 40 ⁇ m or less.
  • the average particle size of the silica-based filler can be measured as the median diameter using a particle size distribution measuring device by a laser light diffraction method.
  • the spontaneous silicone rubber in the present invention is, for example, KE-571-U, KE-1571-U, KE-951-U, KE-541-U, KE-551-U, KE manufactured by Shin-Etsu Chemical Co., Ltd. -561-U, KE-961T-U, KE-1541-U, KE-1551-U, KE-941-U, KE-971T-U and the like can be used. Further, as the mirable type silicone rubber containing the conductivity-imparting agent, KE-87C-40PU or the like can be used.
  • Vinyl group-containing silicone raw rubber contains at least one vinyl group in one molecule, and even if one molecule contains two vinyl groups. good.
  • Examples of the vinyl group-containing silicone raw rubber include vinyl methyl silicone raw rubber, phenylmethyl silicone raw rubber, and fluorosilicone raw rubber.
  • the blending amount ratio of (A) the addition-curing type mirable type silicone rubber composition and (B) the vinyl group-containing raw silicone rubber is preferably in the range of 50:50 to 80:20, and is preferably in the range of 60:40 to 70:20. It is more preferably in the range of 30.
  • (C) Foaming Agent As the foaming agent, a known foaming agent used for forming the foaming elastic layer 3 can be used.
  • chemical foaming agents and unexpanded microballoons can be used.
  • examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate and the like
  • examples of the organic foaming agent include organic azo compounds such as a diazoamino derivative, an azonitrile derivative and an azodicarboxylic acid derivative.
  • organic azo compounds azodicarboxylic acid amide, azobis-isobutyronitrile and the like are preferably used.
  • azobis-isobutyronitrile can be preferably used.
  • a resin microballoon can be mentioned.
  • the resin microballoon one using a thermoplastic resin for the outer shell is preferably used.
  • the thermoplastic resin constituting the outer shell include vinylidene chloride / acrylonitrile copolymer, methyl methacrylate / acrylonitrile copolymer, and metaacrylonitrile / acrylonitrile copolymer.
  • the softening temperature of the resin to be the outer shell is within an appropriate range according to the curing temperature of the silicone rubber.
  • examples of the contained evaporative substance include hydrocarbons such as butane and isobutane.
  • the average particle size of the unexpanded microballoon is preferably 5 ⁇ m or more and 50 ⁇ m or less, and more preferably 5 ⁇ m or more and 25 ⁇ m or less.
  • An unexpanded microballoon can also be used as the foaming agent.
  • the uninflated microballoons suitable for the present invention are commercially available as "Matsumoto Microsphere F Series” (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), "Expansel Series” (manufactured by Expansel Co., Ltd.) and the like.
  • the unexpanded resin microballoon suitable for the present invention is selected from resin microballoons having a function of expanding at a temperature higher than the decomposition temperature of the chemical foaming agent used to form the elastic layer.
  • the blending amount of the foaming agent shall be 0.5% by mass or more and 6% by mass or less from the viewpoint of obtaining a cell having a uniform size while having a low specific gravity with respect to 100 parts by mass of the composition for an elastic foam layer. Is preferable.
  • cross-linking agent examples include an addition reaction cross-linking agent and an organic peroxide cross-linking agent.
  • addition reaction cross-linking agent for example, organohydrogenpolysiloxane known as an addition reaction type cross-linking agent having two or more SiH groups (SiH bonds) in one molecule is preferably mentioned.
  • the addition reaction cross-linking agent can be used alone or in combination of two or more.
  • the blending amount of the addition reaction cross-linking agent is usually 0.1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the composition for foam elastic layer.
  • the organic peroxide cross-linking agent can be used alone to cross-link the faux silicone rubber, but when used in combination as an auxiliary cross-linking agent for the addition reaction cross-linking agent, a toner supply roller obtained can be obtained. Physical properties such as strength and strain can be further improved.
  • the organic peroxide cross-linking agent include benzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis. Examples thereof include (t-butylperoxy) hexane.
  • the blending amount of the organic peroxide cross-linking agent is usually 0.1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the composition for foam elastic layer.
  • the organic peroxide cross-linking agent may be used alone or in combination of two or more.
  • the addition reaction cross-linking agent is preferably used in combination with an addition reaction catalyst.
  • Addition reaction catalysts are platinum black, secondary platinum chloride, platinum chloride acid, reaction products of platinum chloride acid and monohydric alcohol, complexes of platinum chloride acid and olefins, platinum bisacetoacetate, palladium-based catalysts, rhodium-based catalysts. And so on.
  • the blending amount of this addition reaction catalyst can be the amount of the catalyst.
  • composition for the foamed elastic layer may further contain additives in addition to the above.
  • Additives include, for example, conductive materials, auxiliaries (chain extenders, cross-linking agents, etc.), catalysts, dispersants, antioxidants, antioxidants, pigments, colorants, processing aids, softeners, plasticizers, etc. Examples thereof include emulsifiers, heat resistance improvers, flame retardancy improvers, acid receiving agents, heat conductivity improvers, mold release agents, solvents and the like.
  • the foamed elastic layer 3 is formed on the outer peripheral surface of the shaft body 2 by performing heat curing and molding simultaneously or continuously by a known molding method.
  • the method for curing the rubber composition may be any method as long as the heat required for curing the rubber composition can be applied.
  • the molding method of the foamed elastic layer 3 is not particularly limited, such as continuous vulcanization by extrusion molding, pressing, and mold molding by injection. For example, extrusion molding or the like can be selected.
  • the foamed elastic layer 3 formed on the shaft body 2 may be ground or polished.
  • the heating temperature for vulcanizing the foamed elastic layer composition is preferably 100 ° C. or higher and 500 ° C. or lower, and more preferably 120 ° C. or higher and 300 ° C. or lower.
  • the heating time is preferably several seconds or more and 1 hour or less, and more preferably 10 seconds or more and 35 minutes or less. Further, if necessary, secondary vulcanization may be carried out. Further, the rubber composition can be easily foamed and cured by a known method to easily form the foamed elastic layer 3 having bubbles.
  • the hardness of the foamed elastic layer 3 is preferably 15 degrees or more and 40 degrees or less. In such a low hardness foam elastic layer, it is effective to use a rubber material exhibiting tan ⁇ as described above.
  • the sponge roller of the present invention is suitable for a pressure roller or a fixing roller of various image forming devices using an electrophotographic method.
  • Example 1 preparation of composition for foamed elastic layer
  • a composition for a foamed elastic layer was prepared with the following materials.
  • D Cross-linking agent 3 parts by mass
  • the shaft body (made by SUM22, diameter 10 mm, length 275 mm) subjected to electroless nickel plating is washed with ethanol, and a silicone-based primer (trade name "Primer No. 16", manufactured by Shin-Etsu Chemical Co., Ltd.) is used on the surface thereof. ) was applied.
  • the primer-treated shaft was fired at a temperature of 150 ° C. for 10 minutes using a gear oven, and then cooled at room temperature for 30 minutes or more to form a primer layer on the outer peripheral surface of the shaft.
  • the shaft body on which the primer layer was formed and the composition for the foamed elastic layer were integrally separated by an extrusion molding machine, and the above mixture was heated at 250 ° C. for 20 minutes using an infrared heating furnace (IR furnace).
  • the foam roller original body was prepared by secondary vulcanization and then secondary vulcanization at 210 ° C. for 10 hours in a hot air drying oven.
  • the circumferential surface of the foam roller original body was polished at high speed with a metal grindstone by a polishing machine manufactured by Mizuguchi Seisakusho Co., Ltd. to produce a sponge roller roller having an outer diameter of 32 mm.
  • Examples 2 and 3 and Comparative Examples 1 to 3 It was produced in the same manner as in Example 1 except that the type and composition of the vinyl group-containing silicone raw rubber were changed as shown in Table 1.
  • the hardness before the start of measurement (0 hours) is set to 0, and the hardness after 100 hours of rotation and after 200 hours of rotation is measured with an ASKER rubber hardness tester C type (manufactured by Polymer Meter Co., Ltd.) at a measurement load of 9.8 N. did.
  • the amount of change in hardness with time is shown in Table 2, and the graph is shown in FIG.
  • the sponge roller of the present invention has a tan ⁇ of 0.035 or less and a hardness of 0.035 or less by incorporating a silicone raw rubber having a vinyl group in the side chain in the composition for a foamed elastic layer.
  • the amount of change (degree) can be suppressed to within -3.
  • Comparative Example 3 in which the side chain contains a silicone raw rubber containing no vinyl group, the tan ⁇ and the amount of change in hardness are larger than those in the examples, and Comparative Example 1 and Comparative Example 1 in which only the mirable type silicone composition contains no other silicone raw rubber. It can be seen that in No. 2, the tan ⁇ and the amount of change in hardness are large.

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Abstract

Provided is a sponge roller having high durability.　The present invention is a sponge roller 1 comprising a shaft body 2 and a foamed elastic layer 3 formed on the outer circumference of the shaft body 2, wherein: the foamed elastic layer 3 is formed by foaming and vulcanizing a composition which is for a foamed elastic layer and contains a millable-type silicone rubber composition, a vinyl group-containing silicone crude rubber, a foaming agent, and a crosslinking agent; and the loss factor tanδ of a cured product of a rubber composition, which is obtained by removing the foaming agent from the composition for a foamed elastic layer, is at most 0.035 under the following measurement conditions. <Measurement conditions> Frequency of 8 Hz, temperature of 100ºC, and strain control of 5 μm

Description

スポンジローラSponge roller
　本発明は、スポンジローラに関する。 The present invention relates to a sponge roller.
　レーザープリンタ、複写機、ビデオプリンタ、ファクシミリ、これらの複合機等には、電子写真方式を利用した各種の画像形成装置が採用されている。電子写真方式を利用した画像形成装置は、軸体とその外周面に形成された弾性層とを有する、例えば、クリーニングローラ、帯電ローラ、現像ローラ、転写ローラ、加圧ローラ、紙送り搬送ローラ、定着ローラ等の各種印刷用スポンジローラを備えている。 Various image forming devices using an electrophotographic method are used in laser printers, copiers, video printers, facsimiles, and multifunction devices thereof. An image forming apparatus using an electrophotographic method has a shaft body and an elastic layer formed on the outer peripheral surface thereof, for example, a cleaning roller, a charging roller, a developing roller, a transfer roller, a pressure roller, a paper feed transfer roller, and the like. It is equipped with various printing sponge rollers such as fixing rollers.
　上記の画像形成装置における定着手段としては、例えば、熱ローラ定着方式が採用されている。熱ローラ定着方式では、加熱ローラ（定着ローラ）と加圧ローラとを一対の基本構成とし、ローラ対の圧接ニップ部に、トナー画像が担持された被記録材（転写材シート、ファックス紙、印字用用紙等）を導入することで、被記録材にトナー画像を熱圧定着させることが一般的である。定着手段に用いる定着ローラ又は加圧ローラには、適度なニップ圧に調整するために、発泡弾性層（スポンジ層）が用いられている。 As the fixing means in the above image forming apparatus, for example, a thermal roller fixing method is adopted. In the thermal roller fixing method, a heating roller (fixing roller) and a pressure roller are used as a pair of basic configurations, and a recorded material (transfer material sheet, fax paper, printing) on which a toner image is carried on a pressure welding nip portion of the roller pair is used. It is common to heat-press fix the toner image on the material to be recorded by introducing paper, etc.). A foamed elastic layer (sponge layer) is used in the fixing roller or the pressure roller used for the fixing means in order to adjust the nip pressure to an appropriate level.
　発泡弾性層は、一般に、オルガノポリシロキサン及び充填剤を含有するミラブル型シリコーンゴムを加硫及び発泡させて形成される。発泡弾性層を有する定着又は加圧ローラは、圧接状態に装着されて、連続的又は断続的に回転することで機能を発揮するため、熱や摩擦による負荷がかかりやすく、経時で発泡弾性層の硬度が低下するため、耐久性が高いことが求められる。
　繰り返し使用しても高い耐摩耗性を有する紙送り用ゴム部材を形成しうるシリコーンゴム組成物として、例えば、特許文献１に、紙送り用ゴム部材を形成するゴムコンパウンドにビニル基含有シリコーン生ゴムを加えたシリコーンゴム組成物であって、ゴムコンパウンドを加硫させた後の損失係数ｔａｎδが０＜ｔａｎδ≦１であるシリコーンゴム組成物が提案されている。 The foamed elastic layer is generally formed by vulcanizing and foaming a miraculous silicone rubber containing an organopolysiloxane and a filler. A fixing or pressurizing roller having a foamed elastic layer is mounted in a pressure contact state and exerts its function by continuously or intermittently rotating. Therefore, it is easily loaded by heat or friction, and the foamed elastic layer becomes Since the hardness decreases, high durability is required.
As a silicone rubber composition capable of forming a rubber member for paper feeding having high wear resistance even after repeated use, for example, in Patent Document 1, a vinyl group-containing silicone raw rubber is used as a rubber compound for forming a rubber member for paper feeding. A silicone rubber composition added, wherein the loss coefficient tan δ after smelting the rubber compound is 0 <tan δ ≦ 1 has been proposed.
特開平１０－１８２９７７号公報Japanese Unexamined Patent Publication No. 10-182977
　しかしながら、近年の高速、高精細、かつ高品質な画像形成装置を提供するという要望に応えるため、定着ローラ又は加圧ローラには、更なる耐久性の向上が求められている。
　本発明は、上記事情に鑑みてなされたものであり、耐久性が高いスポンジローラを提供することを目的とする。 However, in order to meet the recent demand for providing a high-speed, high-definition, high-quality image forming apparatus, the fixing roller or the pressure roller is required to have further improved durability.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sponge roller having high durability.
　本発明は、軸体と、軸体の外周に形成された発泡弾性層とを備えたスポンジローラであって、発泡弾性層が、ミラブル型シリコーンゴム組成物、ビニル基含有シリコーン生ゴム、発泡剤、及び架橋剤を含有する発泡弾性層用組成物を発泡及び加硫させてなり、発泡弾性層用組成物から発泡剤を除いたゴム組成物の硬化物の、下記測定条件での損失係数ｔａｎδが０．０３５以下であるスポンジローラである。
＜測定条件＞
　周波数８Ｈｚ、温度１００℃、歪み制御５μｍ The present invention is a sponge roller including a shaft body and a foamed elastic layer formed on the outer periphery of the shaft body, wherein the foamed elastic layer is a mirable type silicone rubber composition, a vinyl group-containing silicone raw rubber, a foaming agent, and the like. The loss coefficient tan δ of the cured rubber composition obtained by foaming and vulcanizing the foamed elastic layer composition containing the foaming elastic layer and removing the foaming agent from the foamed elastic layer composition under the following measurement conditions. It is a sponge roller of 0.035 or less.
<Measurement conditions>
Frequency 8Hz, temperature 100 ℃, strain control 5μm
　発泡弾性層のアスカーＣ硬度が、１５度以上４０度以下であることが好ましい。 It is preferable that the Asker C hardness of the foamed elastic layer is 15 degrees or more and 40 degrees or less.
　本発明のスポンジは、加圧ローラであることが好ましい。 The sponge of the present invention is preferably a pressure roller.
　本発明によれば、耐久性が高いスポンジローラを得ることができる。 According to the present invention, a highly durable sponge roller can be obtained.
本発明のスポンジローラを示す斜視図である。It is a perspective view which shows the sponge roller of this invention. 実施例及び比較例のスポンジローラの硬度変化量を示すグラフである。It is a graph which shows the hardness change amount of the sponge roller of an Example and a comparative example.
　以下、本発明の実施形態について詳細に説明するが、以下の実施形態は例示の目的で提示するものであり、本発明は、以下に示す実施形態に何ら限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail, but the following embodiments are presented for purposes of illustration, and the present invention is not limited to the embodiments shown below.
［スポンジローラ］
　本発明のスポンジローラ１は、図１に示すように、軸体２と、軸体２の外周に形成された発泡弾性層３をこの順に備えたスポンジローラ１である。
　以下、本発明のスポンジローラ１の詳細について図１を参照しながら説明する。 [Sponge roller]
As shown in FIG. 1, the sponge roller 1 of the present invention is a sponge roller 1 provided with a shaft body 2 and a foamed elastic layer 3 formed on the outer periphery of the shaft body 2 in this order.
Hereinafter, the details of the sponge roller 1 of the present invention will be described with reference to FIG.
（軸体）
　軸体２は、好ましくは、導電性を有する、従来公知の現像ローラに用いられる軸体を用いることができる。軸体２は、例えば、鉄、アルミニウム、ステンレス鋼、及び真鍮からなる群より選択される少なくとも１種の金属で構成されていることが好ましい。このような金属で構成される軸体２は、一般に、「芯金」の名称でも知られている。 (Axis body)
As the shaft body 2, preferably, a shaft body having conductivity and used for a conventionally known developing roller can be used. The shaft body 2 is preferably made of at least one metal selected from the group consisting of, for example, iron, aluminum, stainless steel, and brass. The shaft body 2 made of such a metal is also generally known by the name of "core metal".
　軸体２は、絶縁性樹脂を含むものであってもよい。絶縁性樹脂は、例えば、熱可塑性樹脂であってもよく、熱硬化性樹脂であってもよい。軸体２は、例えば、絶縁性樹脂からなる芯体と、この芯体上に設けられたメッキ層と、を備えるものであってよい。このような軸体２は、例えば、絶縁性樹脂からなる芯体にメッキを施して導電化することにより得ることができる。
　軸体２は、良好な導電性を得るために、芯金であることが好ましい。 The shaft body 2 may contain an insulating resin. The insulating resin may be, for example, a thermoplastic resin or a thermosetting resin. The shaft body 2 may include, for example, a core body made of an insulating resin and a plating layer provided on the core body. Such a shaft body 2 can be obtained, for example, by plating a core body made of an insulating resin to make it conductive.
The shaft body 2 is preferably a core metal in order to obtain good conductivity.
　軸体２の形状は、例えば、棒状、管状等であることが好ましい。軸体２の断面形状は、例えば、円形、楕円形であってもよく、多角形等の非円形であってもよい。軸体２の外周面には、発泡弾性層３との接着性を向上させるため、洗浄処理、脱脂処理、プライマー処理等の処理が施されていてもよい。 The shape of the shaft body 2 is preferably, for example, a rod shape, a tubular shape, or the like. The cross-sectional shape of the shaft body 2 may be, for example, a circular shape, an elliptical shape, or a non-circular shape such as a polygon. The outer peripheral surface of the shaft body 2 may be subjected to a treatment such as a cleaning treatment, a degreasing treatment, and a primer treatment in order to improve the adhesiveness with the foamed elastic layer 3.
　軸体２の軸線方向の長さは特に限定されず、設置される画像形成装置の形態に応じて適宜調整してもよい。例えば、印字対象がＡ４サイズである場合、軸体２の軸線方向の長さは２５０ｍｍ以上３２０ｍｍ以下であることが好ましく、２６０ｍｍ以上３１０ｍｍ以下であることがより好ましい。また、軸体２の直径（外接円の直径）も特に限定されず、設置される画像形成装置の形態に応じて適宜調整すればよい。例えば、軸体２の外径（外接円の直径）は、４ｍｍ以上１４ｍｍ以下であることが好ましく、６ｍｍ以上１０ｍｍ以下であることがより好ましい。 The length of the shaft body 2 in the axial direction is not particularly limited, and may be appropriately adjusted according to the form of the image forming apparatus to be installed. For example, when the printing target is A4 size, the length of the shaft body 2 in the axial direction is preferably 250 mm or more and 320 mm or less, and more preferably 260 mm or more and 310 mm or less. Further, the diameter of the shaft body 2 (diameter of the circumscribed circle) is not particularly limited, and may be appropriately adjusted according to the form of the image forming apparatus to be installed. For example, the outer diameter (diameter of the circumscribed circle) of the shaft body 2 is preferably 4 mm or more and 14 mm or less, and more preferably 6 mm or more and 10 mm or less.
（発泡弾性層）
　発泡弾性層３は、（Ａ）ミラブル型シリコーンゴム組成物、（Ｂ）ビニル基含有シリコーン生ゴム、（Ｃ）発泡剤及び（Ｄ）架橋剤を含有する発泡弾性層用組成物を発泡及び加硫させてなるものである。 (Foam elastic layer)
The foamed elastic layer 3 is formed by foaming and vulcanizing a composition for a foamed elastic layer containing (A) a mirable type silicone rubber composition, (B) a vinyl group-containing silicone raw rubber, (C) a foaming agent and (D) a cross-linking agent. It is something that is made to.
　発泡弾性層３は、動的粘弾性測定において、周波数８Ｈｚ、温度１００℃、歪み制御５μｍで測定した損失係数ｔａｎδが、０．０３５以下であり、好ましくは、０．０２５以下である。
　損失係数ｔａｎδは、上記発泡弾性層用組成物から（Ｃ）発泡剤を除いた、（Ａ）ミラブル型シリコーンゴム組成物、（Ｂ）ビニル基含有シリコーン生ゴム及び（Ｄ）架橋剤を含有するゴム組成物の硬化物を測定したものである。すなわち、硬化物のｔａｎδが０．０３５以下のゴム組成物を発泡弾性層のゴム材料として用いることによって、疲労劣化しにくい発泡弾性層を得ることができ、結果的に耐久性の高いスポンジローラを得ることができる。
　以下、発泡弾性層用組成物の成分について説明する。 The foamed elastic layer 3 has a loss coefficient tan δ measured at a frequency of 8 Hz, a temperature of 100 ° C., and a strain control of 5 μm in the dynamic viscoelasticity measurement of 0.035 or less, preferably 0.025 or less.
The loss coefficient tan δ is a rubber containing (A) a mirable type silicone rubber composition, (B) a vinyl group-containing silicone raw rubber, and (D) a cross-linking agent obtained by removing (C) a foaming agent from the composition for a foamed elastic layer. It is the measurement of the cured product of the composition. That is, by using a rubber composition having a tan δ of 0.035 or less as the rubber material of the foamed elastic layer, a foamed elastic layer that does not easily deteriorate due to fatigue can be obtained, and as a result, a highly durable sponge roller can be obtained. Obtainable.
Hereinafter, the components of the composition for the foamed elastic layer will be described.
（Ａ）ミラブル型シリコーンゴム組成物
　ミラブル型シリコーンゴム組成物としては、付加硬化型のミラブル型シリコーンゴム組成物が好ましい。付加硬化型のミラブル型シリコーンゴム組成物は、例えば、少なくとも（ａ）オルガノポリシロキサン及び（ｂ）充填剤を含有するものが好ましい。 (A) Mirable Type Silicone Rubber Composition As the mirable type silicone rubber composition, an addition-curing type mirable type silicone rubber composition is preferable. The addition-curing type miraculous silicone rubber composition preferably contains, for example, at least (a) an organopolysiloxane and (b) a filler.
（ａ）オルガノポリシロキサン
　（ａ）オルガノポリシロキサンは、下記平均組成式（１）で示される。
ＲａＳｉＯ（４－ａ）／２ （１）
（式中、Ｒは互いに同一又は異種の炭素数１～１２、好ましくは炭素数１～１０、より好ましくは１～８の非置換又は置換の一価炭化水素基である。ａは１．５～２．８、好ましくは１．８～２．５、より好ましくは１．９５～２．０５、さらに好ましくは１．９８～２．０１の範囲の正数である。）
　　Ｒ１ ｎＳｉＯ（４－ｎ）／２　　…（１）
　式（１）中、ｎは１．９５以上２．０５以下の正数を示す。また、Ｒ１は、同一又は異なっていてよい、置換又は非置換の一価の炭化水素基を示す。炭化水素基の炭素原子数は、好ましくは１以上１２以下であり、より好ましくは１以上８以下である。 (A) Organopolysiloxane (a) The organopolysiloxane is represented by the following average composition formula (1).
R a SiO (4-a) / 2 (1)
(In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon atoms of 1 to 12, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. A is 1.5. It is a positive number in the range of 2.8, preferably 1.8 to 2.5, more preferably 1.95 to 2.05, and even more preferably 1.98 to 2.01.)
R 1 n SiO (4-n) / 2 ... (1)
In the formula (1), n represents a positive number of 1.95 or more and 2.05 or less. Further, R 1 indicates a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different. The number of carbon atoms of the hydrocarbon group is preferably 1 or more and 12 or less, and more preferably 1 or more and 8 or less.
　Ｒ１としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基及びドデシル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、ブテニル基及びヘキセニル基等のアルケニル基、フェニル基及びトリル基等のアリール基、β－フェニルプロピル基等のアラルキル基等が挙げられる。また、Ｒ１は、これらの炭化水素基が有する水素原子の一部又は全部が置換基で置換された基であってもよい。置換基は、例えばハロゲン原子、シアノ基等であってよい。置換基を有する炭化水素基としては、例えば、クロロメチル基、トリフルオロプロピル基、シアノエチル基等が挙げられる。 Examples of R 1 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, a butenyl group and a hexenyl group. Examples thereof include an aryl group such as an alkenyl group, a phenyl group and a trill group, and an aralkyl group such as a β-phenylpropyl group. Further, R 1 may be a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are substituted with a substituent. The substituent may be, for example, a halogen atom, a cyano group, or the like. Examples of the hydrocarbon group having a substituent include a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like.
　（Ａ）オルガノポリシロキサンは、分子鎖末端が、トリメチルシリル基等のトリアルキルシリル基、ジメチルビニルシリル基等のジアルキルアラルキルシリル基、ジメチルヒドロキシシリル基等のジアルキルヒドロキシシリル基、トリビニルシリル基等のトリアラルキルシリル基等で封鎖されていることが好ましい。 (A) The organopolysiloxane has a molecular chain terminal such as a trialkylsilyl group such as a trimethylsilyl group, a dialkylaralkylsilyl group such as a dimethylvinylsilyl group, a dialkylhydroxysilyl group such as a dimethylhydroxysilyl group, or a trivinylsilyl group. It is preferably sealed with a trialal kill silyl group or the like.
　（Ａ）オルガノポリシロキサンは、分子中に２つ以上のアルケニル基を有することが好ましい。（Ａ）オルガノポリシロキサンは、Ｒ１のうち０．００１モル％以上５モル％以下（より好ましくは０．０１モル％以上０．５モル％以下）のアルケニル基を有することが好ましい。（Ａ）オルガノポリシロキサンが有するアルケニル基としてはビニル基が特に好ましい。 (A) The organopolysiloxane preferably has two or more alkenyl groups in the molecule. (A) organopolysiloxane, 0.001 mol% or more of R 1 5 mol% or less (more preferably at least 0.01 mol% 0.5 mol%) preferably has an alkenyl group. (A) The vinyl group is particularly preferable as the alkenyl group contained in the organopolysiloxane.
　（Ａ）オルガノポリシロキサンは、例えば、オルガノハロシランの１種若しくは２種以上を共加水分解縮合することによって、又は、シロキサンの３量体若しくは４量体等の環状ポリシロキサンを開環重合することによって得ることができる。（Ａ）オルガノポリシロキサンは、基本的には直鎖状のジオルガノポリシロキサンであってよく、一部分岐していてもよい。また、（Ａ）オルガノポリシロキサンは、分子構造の異なる２種又はそれ以上の混合物であってもよい。 (A) The organopolysiloxane is obtained by, for example, co-hydrolyzing and condensing one or more of organohalosilanes, or ring-opening polymerization of a cyclic polysiloxane such as a trimer or tetramer of siloxane. Can be obtained by (A) The organopolysiloxane may be basically a linear diorganopolysiloxane, and may be partially branched. Further, (A) organopolysiloxane may be a mixture of two or more kinds having different molecular structures.
　（Ａ）オルガノポリシロキサンは、２５℃における動粘度が１００ｃＳｔ以上であることが好ましく、１０００００ｃＳｔ以上１０００００００ｃＳｔ以下であることがより好ましい。
　また、（Ａ）オルガノポリシロキサンの重合度は、例えば１００以上であることが好ましく、３０００以上１００００以下であることがより好ましい。 The kinematic viscosity of (A) organopolysiloxane at 25 ° C. is preferably 100 cSt or more, and more preferably 100,000 cSt or more and 10,000,000 cSt or less.
Further, the degree of polymerization of (A) organopolysiloxane is preferably, for example, 100 or more, and more preferably 3000 or more and 10000 or less.
（ｂ）充填剤
　（ｂ）充填材としては、例えばシリカ系充填材が挙げられる。シリカ系充填材としては、例えば、煙霧質シリカ、沈降性シリカ等が挙げられる。 (B) Filler (b) Examples of the filler include silica-based fillers. Examples of the silica-based filler include fumes silica, precipitated silica and the like.
　シリカ系充填材としては、Ｒ２Ｓｉ（ＯＲ３）３で示されるシランカップリング剤で表面処理された、表面処理シリカ系充填材を好適に用いることができる。ここで、Ｒ２は、ビニル基又はアミノ基を有する基であってよく、例えば、グリシジル基、ビニル基、アミノプロピル基、メタクリロキシ基、Ｎ－フェニルアミノプロピル基、メルカプト基等であってよい。Ｒ３はアルキル基であってよく、例えばメチル基、エチル基等であってよい。シランカップリング剤は、例えば信越化学工業株式会社製の商品名「ＫＢＭ１００３」、「ＫＢＥ４０２」等として、容易に入手できる。表面処理シリカ系充填材は、定法に従って、シリカ系充填材の表面をシランカップリング剤で処理することにより得ることができる。表面処理シリカ系充填材としては、市販品を用いてもよく、例えば、Ｊ．Ｍ．ＨＵＢＥＲ株式会社製の商品名「Ｚｅｏｔｈｉｘ　９５」等が挙げられる。 As the silica-based filler, a surface-treated silica-based filler surface-treated with the silane coupling agent represented by R 2 Si (OR 3 ) 3 can be preferably used. Here, R 2 may be a group having a vinyl group or an amino group, and may be, for example, a glycidyl group, a vinyl group, an aminopropyl group, a methacrylate group, an N-phenylaminopropyl group, a mercapto group or the like. R 3 may be an alkyl group, for example, a methyl group, an ethyl group, or the like. The silane coupling agent can be easily obtained, for example, under the trade names "KBM1003" and "KBE402" manufactured by Shin-Etsu Chemical Co., Ltd. The surface-treated silica-based filler can be obtained by treating the surface of the silica-based filler with a silane coupling agent according to a conventional method. As the surface-treated silica-based filler, a commercially available product may be used, for example, J.A. M. Examples thereof include the product name "Zeothix 95" manufactured by HUBER Co., Ltd.
　シリカ系充填材の配合量は、（Ａ）オルガノポリシロキサン１００質量部に対して１１質量部以上３９質量部以下であることが好ましく、１５質量部以上３５質量部以下であることがより好ましい。また、シリカ系充填材の平均粒子径は、１μｍ以上８０μｍ以下であることが好ましく、２μｍ以上４０μｍ以下であることがより好ましい。なお、シリカ系充填材の平均粒子径は、レーザー光回折法による粒度分布測定装置を用いて、メジアン径として測定できる。 The blending amount of the silica-based filler is preferably 11 parts by mass or more and 39 parts by mass or less, and more preferably 15 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of (A) organopolysiloxane. The average particle size of the silica-based filler is preferably 1 μm or more and 80 μm or less, and more preferably 2 μm or more and 40 μm or less. The average particle size of the silica-based filler can be measured as the median diameter using a particle size distribution measuring device by a laser light diffraction method.
　本発明におけるミラブル型シリコーンゴムは、例として、信越化学工業株式会社製のＫＥ－５７１－Ｕ、ＫＥ－１５７１－Ｕ、ＫＥ－９５１－Ｕ、ＫＥ－５４１－Ｕ、ＫＥ－５５１－Ｕ、ＫＥ－５６１－Ｕ、ＫＥ－９６１Ｔ－Ｕ、ＫＥ－１５４１－Ｕ、ＫＥ－１５５１－Ｕ、ＫＥ－９４１－Ｕ、ＫＥ－９７１Ｔ－Ｕ等を使用することができる。また、導電性付与剤を含有しているミラブル型シリコーンゴムとしては、ＫＥ－８７Ｃ－４０ＰＵ等を使用することができる。 The miraculous silicone rubber in the present invention is, for example, KE-571-U, KE-1571-U, KE-951-U, KE-541-U, KE-551-U, KE manufactured by Shin-Etsu Chemical Co., Ltd. -561-U, KE-961T-U, KE-1541-U, KE-1551-U, KE-941-U, KE-971T-U and the like can be used. Further, as the mirable type silicone rubber containing the conductivity-imparting agent, KE-87C-40PU or the like can be used.
（Ｂ）ビニル基含有シリコーン生ゴム
　（Ｂ）ビニル基含有シリコーン生ゴムとしては、１分子中にビニル基を少なくとも１つ含有するものであり、ビニル基は１分子中に２つ含有するものあってもよい。
　ビニル基含有シリコーン生ゴムとしては、ビニルメチルシリコーン生ゴム、フェニルメチルシリコーン生ゴム、フロロシリコーン生ゴム等が挙げられる。 (B) Vinyl group-containing silicone raw rubber (B) The vinyl group-containing silicone raw rubber contains at least one vinyl group in one molecule, and even if one molecule contains two vinyl groups. good.
Examples of the vinyl group-containing silicone raw rubber include vinyl methyl silicone raw rubber, phenylmethyl silicone raw rubber, and fluorosilicone raw rubber.
　（Ａ）付加硬化型のミラブル型シリコーンゴム組成物と（Ｂ）ビニル基含有シリコーン生ゴムとの配合量比は、５０：５０から８０：２０の範囲であることが好ましく、６０：４０から７０：３０の範囲であることがより好ましい。 The blending amount ratio of (A) the addition-curing type mirable type silicone rubber composition and (B) the vinyl group-containing raw silicone rubber is preferably in the range of 50:50 to 80:20, and is preferably in the range of 60:40 to 70:20. It is more preferably in the range of 30.
（Ｃ）発泡剤
　発泡剤としては、発泡弾性層３の形成に用いられる既知の発泡剤を用いることができる。例えば、化学発泡剤、未膨張マイクロバルーンを用いることができる。化学発泡剤であれば、無機系発泡剤として、重炭酸ソーダ、炭酸アンモニウム等が挙げられ、有機系発泡剤として、ジアゾアミノ誘導体、アゾニトリル誘導体、アゾジカルボン酸誘導体等の有機アゾ化合物等が挙げられる。有機アゾ化合物の中でも、アゾジカルボン酸アミド、アゾビス－イソブチロニトリル等が好適に使用される。特に、アゾビス－イソブチロニトリルが好適に使用できる。 (C) Foaming Agent As the foaming agent, a known foaming agent used for forming the foaming elastic layer 3 can be used. For example, chemical foaming agents and unexpanded microballoons can be used. In the case of a chemical foaming agent, examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate and the like, and examples of the organic foaming agent include organic azo compounds such as a diazoamino derivative, an azonitrile derivative and an azodicarboxylic acid derivative. Among the organic azo compounds, azodicarboxylic acid amide, azobis-isobutyronitrile and the like are preferably used. In particular, azobis-isobutyronitrile can be preferably used.
　未膨張マイクロバルーンとして、樹脂マイクロバルーンを挙げることができる。樹脂マイクロバルーンとしては、外殻に熱可塑性樹脂を用いたものが好ましく用いられる。外殻を構成する熱可塑性樹脂としては、塩化ビニリデン／アクリロニトリル共重合体、メチルメタクリレート／アクリロニトリル共重合体、メタアクリロニトリル／アクリロニトリル共重合体等を挙げることができる。シリコーンゴムの硬化温度に合わせて、外殻となる樹脂の軟化温度が適当な範囲内にある樹脂マイクロバルーンを用いることが好ましい。また、内包される蒸発性物質としては、ブタン、イソブタン等の炭化水素を挙げることができる。
　未膨張マイクロバルーンの平均粒子径は、５μｍ以上５０μｍ以下であることが好ましく、５μｍ以上２５μｍ以下であることがより好ましい。 As the unexpanded microballoon, a resin microballoon can be mentioned. As the resin microballoon, one using a thermoplastic resin for the outer shell is preferably used. Examples of the thermoplastic resin constituting the outer shell include vinylidene chloride / acrylonitrile copolymer, methyl methacrylate / acrylonitrile copolymer, and metaacrylonitrile / acrylonitrile copolymer. It is preferable to use a resin microballoon in which the softening temperature of the resin to be the outer shell is within an appropriate range according to the curing temperature of the silicone rubber. Further, examples of the contained evaporative substance include hydrocarbons such as butane and isobutane.
The average particle size of the unexpanded microballoon is preferably 5 μm or more and 50 μm or less, and more preferably 5 μm or more and 25 μm or less.
　発泡剤として未膨張マイクロバルーンを用いることもできる。本発明に好適な未膨張マイクロバルーンは、「マツモトマイクロスフェアーＦシリーズ」（松本油脂製薬株式会社製）、「エクスパンセルシリーズ」（エクスパンセル社製）等として市販されている。この発明に好適な未膨張の樹脂マイクロバルーンは、弾性層を形成するのに使用される化学発泡剤の分解温度よりも高い温度で膨張する機能を有する樹脂マイクロバルーンから選択される。
　発泡剤の配合量は、発泡弾性層用組成物１００質量部に対しての低比重でありながら、大きさが均一なセルを得る観点から、０．５質量％以上６質量％以下であることが好ましい。 An unexpanded microballoon can also be used as the foaming agent. The uninflated microballoons suitable for the present invention are commercially available as "Matsumoto Microsphere F Series" (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), "Expansel Series" (manufactured by Expansel Co., Ltd.) and the like. The unexpanded resin microballoon suitable for the present invention is selected from resin microballoons having a function of expanding at a temperature higher than the decomposition temperature of the chemical foaming agent used to form the elastic layer.
The blending amount of the foaming agent shall be 0.5% by mass or more and 6% by mass or less from the viewpoint of obtaining a cell having a uniform size while having a low specific gravity with respect to 100 parts by mass of the composition for an elastic foam layer. Is preferable.
（Ｄ）架橋剤
　架橋剤としては、付加反応架橋剤、有機過酸化物架橋剤等を挙げることができる。
　上記付加反応架橋剤として、例えば、一分子中に二個以上のＳｉＨ基（ＳｉＨ結合）を有する付加反応型の架橋剤として公知のオルガノハイドロジェンポリシロキサンが好適に挙げられる。付加反応架橋剤は一種単独で又は二種以上を混合して用いることができる。
　付加反応架橋剤の配合量は、通常、発泡弾性層用組成物１００質量部に対して０．１質量部以上７質量部以下である。 (D) Cross-linking agent Examples of the cross-linking agent include an addition reaction cross-linking agent and an organic peroxide cross-linking agent.
As the addition reaction cross-linking agent, for example, organohydrogenpolysiloxane known as an addition reaction type cross-linking agent having two or more SiH groups (SiH bonds) in one molecule is preferably mentioned. The addition reaction cross-linking agent can be used alone or in combination of two or more.
The blending amount of the addition reaction cross-linking agent is usually 0.1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the composition for foam elastic layer.
　付加反応架橋剤を使用する場合、有機過酸化物架橋剤は、単独でミラブル型シリコーンゴムを架橋させることも可能であるが、付加反応架橋剤の補助架橋剤として併用すると、得られるトナー供給ローラの強度、歪み等の物性をより一層向上させることができる。有機過酸化物架橋剤としては、例えば、ベンゾイルパーオキサイド、ビス－２，４－ジクロロベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン等が挙げられる。
　有機過酸化物架橋剤の配合量は、通常、発泡弾性層用組成物１００質量部に対して０．１質量部以上７質量部以下である。有機過酸化物架橋剤は一種単独で又は二種以上を混合して用いることができる。 When an addition reaction cross-linking agent is used, the organic peroxide cross-linking agent can be used alone to cross-link the miraculous silicone rubber, but when used in combination as an auxiliary cross-linking agent for the addition reaction cross-linking agent, a toner supply roller obtained can be obtained. Physical properties such as strength and strain can be further improved. Examples of the organic peroxide cross-linking agent include benzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis. Examples thereof include (t-butylperoxy) hexane.
The blending amount of the organic peroxide cross-linking agent is usually 0.1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the composition for foam elastic layer. The organic peroxide cross-linking agent may be used alone or in combination of two or more.
　付加反応架橋剤は、付加反応触媒を併用するのが好ましい。付加反応触媒は白金黒、塩化第二白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート、パラジウム系触媒、ロジウム系触媒等が挙げられる。なお、この付加反応触媒の配合量は触媒量とすることができる。 The addition reaction cross-linking agent is preferably used in combination with an addition reaction catalyst. Addition reaction catalysts are platinum black, secondary platinum chloride, platinum chloride acid, reaction products of platinum chloride acid and monohydric alcohol, complexes of platinum chloride acid and olefins, platinum bisacetoacetate, palladium-based catalysts, rhodium-based catalysts. And so on. The blending amount of this addition reaction catalyst can be the amount of the catalyst.
　発泡弾性層用組成物は、上記以外に、添加剤を更に含有してもよい。添加剤としては、例えば、導電材、助剤（鎖延長剤、架橋剤等）、触媒、分散剤、老化防止剤、酸化防止剤、顔料、着色剤、加工助剤、軟化剤、可塑剤、乳化剤、耐熱性向上剤、難燃性向上剤、受酸剤、熱伝導性向上剤、離型剤、溶剤等が挙げられる。 The composition for the foamed elastic layer may further contain additives in addition to the above. Additives include, for example, conductive materials, auxiliaries (chain extenders, cross-linking agents, etc.), catalysts, dispersants, antioxidants, antioxidants, pigments, colorants, processing aids, softeners, plasticizers, etc. Examples thereof include emulsifiers, heat resistance improvers, flame retardancy improvers, acid receiving agents, heat conductivity improvers, mold release agents, solvents and the like.
　発泡弾性層３は、公知の成形方法によって、加熱硬化と成形とを同時に又は連続して行い、軸体２の外周面に形成される。ゴム組成物の硬化方法はゴム組成物の硬化に必要な熱を加えられる方法であればよい。また、発泡弾性層３の成形方法も、押出成形による連続加硫、プレス、インジェクションによる型成形等、特に制限されるものではない。例えば、押出成形等を選択することができる。また、軸体２上に形成された発泡弾性層３を研削又は研磨等してもよい。 The foamed elastic layer 3 is formed on the outer peripheral surface of the shaft body 2 by performing heat curing and molding simultaneously or continuously by a known molding method. The method for curing the rubber composition may be any method as long as the heat required for curing the rubber composition can be applied. Further, the molding method of the foamed elastic layer 3 is not particularly limited, such as continuous vulcanization by extrusion molding, pressing, and mold molding by injection. For example, extrusion molding or the like can be selected. Further, the foamed elastic layer 3 formed on the shaft body 2 may be ground or polished.
　発泡弾性層用組成物を加硫させる際の加熱温度は、１００℃以上５００℃以下が好ましく、１２０℃以上３００℃以下がより好ましい。加熱時間は数秒以上１時間以下が好ましく、１０秒以上３５分以下がより好ましい。また、必要に応じ、二次加硫してもよい。また、ゴム組成物は既知の方法で発泡硬化させることにより、気泡を有する発泡弾性層３を容易に形成することもできる。 The heating temperature for vulcanizing the foamed elastic layer composition is preferably 100 ° C. or higher and 500 ° C. or lower, and more preferably 120 ° C. or higher and 300 ° C. or lower. The heating time is preferably several seconds or more and 1 hour or less, and more preferably 10 seconds or more and 35 minutes or less. Further, if necessary, secondary vulcanization may be carried out. Further, the rubber composition can be easily foamed and cured by a known method to easily form the foamed elastic layer 3 having bubbles.
　発泡弾性層３の硬度（アスカーＣ硬度）は、１５度以上４０度以下であることが好ましい。このような低硬度の発泡弾性層において、上記のようなｔａｎδを示すゴム材料を用いることは効果的である。 The hardness of the foamed elastic layer 3 (ascar C hardness) is preferably 15 degrees or more and 40 degrees or less. In such a low hardness foam elastic layer, it is effective to use a rubber material exhibiting tan δ as described above.
　本発明のスポンジローラは、電子写真方式を利用した各種の画像形成装置の加圧ローラ又は定着ローラに好適である。
　以上、本発明を、実施形態を用いて説明したが、本発明の技術的範囲は上記の実施形態に記載の発明の範囲には限定されないことは言うまでもなく、上記実施形態に、多様な変更又は改良を加えることが可能であることが当業者に明らかである。また、そのような変更又は改良を加えた発明も本発明の技術的範囲に含まれ得ることが、請求の範囲の記載から明らかである。 The sponge roller of the present invention is suitable for a pressure roller or a fixing roller of various image forming devices using an electrophotographic method.
Although the present invention has been described above with reference to the embodiments, it goes without saying that the technical scope of the present invention is not limited to the scope of the invention described in the above embodiments. It will be apparent to those skilled in the art that improvements can be made. It is also clear from the description of the claims that the invention with such changes or improvements may be included in the technical scope of the present invention.
　以下、本発明について、実施例を挙げて詳細に説明する。
［実施例１］
（発泡弾性層用組成物の調製）
　以下の材料で、発泡弾性層用組成物を調製した。
　（Ａ）付加硬化型のミラブル型シリコーンゴム組成物（Ｘ－３０－４０３７Ｕ、信越化学工業株式会社製）　　　　　　　　　　　　　　８０質量部
　（Ｂ）ビニル基含有シリコーン生ゴム（ＫＥ－７７ＶＢ、信越化学工業株式会社製）　　　　　　　　　　　　　　　　　　　　　　　　２０質量部
　（Ｃ）化学発泡剤　　　　　　　　　　　　　　　　　　　　　５質量部
　（Ｄ）架橋剤　　　　　　　　　　　　　　　　　　　　　　　３質量部 Hereinafter, the present invention will be described in detail with reference to examples.
[Example 1]
(Preparation of composition for foamed elastic layer)
A composition for a foamed elastic layer was prepared with the following materials.
(A) Cross-linking curable type silicone rubber composition (X-30-4037U, manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts by mass (B) Vinyl group-containing silicone raw rubber (KE-77VB, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts by mass (C) Chemical foaming agent 5 parts by mass (D) Cross-linking agent 3 parts by mass
（プライマー層の形成）
　無電解ニッケルメッキ処理が施された軸体（ＳＵＭ２２製、直径１０ｍｍ、長さ２７５ｍｍ）をエタノールで洗浄し、その表面にシリコーン系プライマー（商品名「プライマーＮｏ．１６」、信越化学工業株式会社製）を塗布した。プライマー処理した軸体を、ギヤオーブンを用いて、１５０℃の温度にて１０分焼成処理した後、常温にて３０分以上冷却し、軸体の外周面にプライマー層を形成した。 (Formation of primer layer)
The shaft body (made by SUM22, diameter 10 mm, length 275 mm) subjected to electroless nickel plating is washed with ethanol, and a silicone-based primer (trade name "Primer No. 16", manufactured by Shin-Etsu Chemical Co., Ltd.) is used on the surface thereof. ) Was applied. The primer-treated shaft was fired at a temperature of 150 ° C. for 10 minutes using a gear oven, and then cooled at room temperature for 30 minutes or more to form a primer layer on the outer peripheral surface of the shaft.
（発泡弾性層の形成）
　次いで、プライマー層を形成した軸体と発泡弾性層用組成物とを押出成形機にて一体分出し、赤外線加熱炉（ＩＲ炉）を用いて上記混合物を２５０℃で２０分間加熱することにより１次加硫し、その後、熱風乾燥炉において、２１０℃で１０時間にわたって２次加硫することにより発泡ローラ原体を作製した。この発泡ローラ原体の円周面を、株式会社水口製作所製の研磨機により金属砥石による高速研磨を行い、外径３２ｍｍのスポンジローラローラを作製した。 (Formation of foamed elastic layer)
Next, the shaft body on which the primer layer was formed and the composition for the foamed elastic layer were integrally separated by an extrusion molding machine, and the above mixture was heated at 250 ° C. for 20 minutes using an infrared heating furnace (IR furnace). The foam roller original body was prepared by secondary vulcanization and then secondary vulcanization at 210 ° C. for 10 hours in a hot air drying oven. The circumferential surface of the foam roller original body was polished at high speed with a metal grindstone by a polishing machine manufactured by Mizuguchi Seisakusho Co., Ltd. to produce a sponge roller roller having an outer diameter of 32 mm.
［実施例２、３、及び比較例１から３］
　ビニル基含有シリコーン生ゴムの種類及び配合を表１に示すように変えた以外は、実施例１と同様に作製した。 [Examples 2 and 3 and Comparative Examples 1 to 3]
It was produced in the same manner as in Example 1 except that the type and composition of the vinyl group-containing silicone raw rubber were changed as shown in Table 1.
［評価］
　上記実施例及び比較例について、下記の耐久性評価を行った。評価結果を表１に示す。
（硬度変化量）
　耐久性評価として、以下の評価方法により硬度変化量を測定した。
　シャフト径φ２２．０ｍｍを用いて製品径φ３２ｍｍのローラを作製した。そのローラをφ４０．０ｍｍの金属ローラに、ゴム厚の３５％相当を圧縮し固定した。その状態で１８０℃の温度を与えながら、２００時間回転させた。測定開始前（０時間）の硬度を０として、１００時間回転後及び２００時間回転後の硬度を、ＡＳＫＥＲゴム硬度計Ｃ型（高分子計器株式会社製）を用い、測定荷重９．８Ｎで測定した。時間毎の硬度変化量を表２に示し、グラフを図２に示す。 [evaluation]
The following durability evaluations were carried out for the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 1.
(Amount of change in hardness)
As a durability evaluation, the amount of change in hardness was measured by the following evaluation method.
A roller having a product diameter of φ32 mm was manufactured using a shaft diameter of φ22.0 mm. The roller was compressed and fixed to a metal roller having a diameter of 40.0 mm, equivalent to 35% of the rubber thickness. In that state, it was rotated for 200 hours while giving a temperature of 180 ° C. The hardness before the start of measurement (0 hours) is set to 0, and the hardness after 100 hours of rotation and after 200 hours of rotation is measured with an ASKER rubber hardness tester C type (manufactured by Polymer Meter Co., Ltd.) at a measurement load of 9.8 N. did. The amount of change in hardness with time is shown in Table 2, and the graph is shown in FIG.
（損失係数ｔａｎδ）
　次に、上記実施例及び比較例において、発泡剤を添加していない発泡弾性層用組成物を調製し、加硫させて、長さ２０ｍｍ×幅５ｍｍ×厚み２ｍｍの試料を作製し、粘弾性スペクトルメーター（レオロジー株式会社製）で損失係数ｔａｎδを測定した。測定条件は以下のとおりである。
＜測定条件＞
　動的粘弾測定機（商品名「Pheogel-E4000」、株式会社ＵＢＭ）を用い、周波数８Ｈｚ、開始温度３０℃、終了温度１００℃、昇温速度５℃／ｍｉｎ、歪み制御５μｍ、チャック間距離１０ｍｍｍで測定した。 (Loss coefficient tanδ)
Next, in the above Examples and Comparative Examples, a composition for a foamed elastic layer to which a foaming agent was not added was prepared and vulcanized to prepare a sample having a length of 20 mm × a width of 5 mm × a thickness of 2 mm, and viscoelasticity was prepared. The loss coefficient tan δ was measured with a spectrum meter (manufactured by Rheology Co., Ltd.). The measurement conditions are as follows.
<Measurement conditions>
Using a dynamic sticky bullet measuring machine (trade name "Pheogel-E4000", UBM Co., Ltd.), frequency 8 Hz, start temperature 30 ° C, end temperature 100 ° C, temperature rise rate 5 ° C / min, strain control 5 μm, distance between chucks. It was measured at 10 mm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１、２及び図２に示すように、本発明のスポンジローラは、側鎖にビニル基を含有するシリコーン生ゴムを発泡弾性層用組成物に含有させることによって、ｔａｎδを０．０３５以下、硬度変化量（度）を－３以内に抑えることができる。
　一方、側鎖にビニル基を含有しないシリコーン生ゴムを含有させた比較例３は、ｔａｎδ及び硬度変化量が実施例より大きく、ミラブル型シリコーン組成物のみで他のシリコーン生ゴムを含有しない比較例１および２は、更にｔａｎδ及び硬度変化量が大きいことがわかる。 As shown in Tables 1 and 2, the sponge roller of the present invention has a tan δ of 0.035 or less and a hardness of 0.035 or less by incorporating a silicone raw rubber having a vinyl group in the side chain in the composition for a foamed elastic layer. The amount of change (degree) can be suppressed to within -3.
On the other hand, in Comparative Example 3 in which the side chain contains a silicone raw rubber containing no vinyl group, the tan δ and the amount of change in hardness are larger than those in the examples, and Comparative Example 1 and Comparative Example 1 in which only the mirable type silicone composition contains no other silicone raw rubber. It can be seen that in No. 2, the tan δ and the amount of change in hardness are large.
　１　スポンジローラ
　２　軸体
　３　発泡弾性層 1 Sponge roller 2 Shaft body 3 Foam elastic layer

Claims (3)

  1. 　軸体と、該軸体の外周に形成された発泡弾性層とを備えたスポンジローラであって、
    　前記発泡弾性層が、ミラブル型シリコーンゴム組成物、ビニル基含有シリコーン生ゴム、発泡剤、及び架橋剤を含有する発泡弾性層用組成物を発泡及び加硫させてなり、
    　前記発泡弾性層用組成物から前記発泡剤を除いたゴム組成物の硬化物の、下記測定条件での損失係数ｔａｎδが０．０３５以下である
    　スポンジローラ。
    ＜測定条件＞
    　周波数８Ｈｚ、温度１００℃、歪み制御５μｍ     A sponge roller provided with a shaft body and a foamed elastic layer formed on the outer periphery of the shaft body.
    The foamed elastic layer is formed by foaming and vulcanizing a composition for a foamed elastic layer containing a mirable type silicone rubber composition, a vinyl group-containing silicone raw rubber, a foaming agent, and a cross-linking agent.
    A sponge roller having a loss coefficient tan δ of 0.035 or less under the following measurement conditions of a cured product of a rubber composition obtained by removing the foaming agent from the composition for an elastic foam layer.
    <Measurement conditions>
    Frequency 8Hz, temperature 100 ℃, strain control 5μm
  2. 　前記発泡弾性層のアスカーＣ硬度が、１５度以上４０度以下である請求項１記載のスポンジローラ。 The sponge roller according to claim 1, wherein the asker C hardness of the foamed elastic layer is 15 degrees or more and 40 degrees or less.
  3. 　加圧ローラである請求項１又は２記載のスポンジローラ。 The sponge roller according to claim 1 or 2, which is a pressure roller.
PCT/JP2021/020036 2020-06-05 2021-05-26 Sponge roller WO2021246263A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005300591A (en) * 2004-04-06 2005-10-27 Canon Inc Fixing member and fixing device
JP2008070574A (en) * 2006-09-14 2008-03-27 Shin Etsu Polymer Co Ltd Method for manufacturing elastic roller, elastic roller and image forming apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005300591A (en) * 2004-04-06 2005-10-27 Canon Inc Fixing member and fixing device
JP2008070574A (en) * 2006-09-14 2008-03-27 Shin Etsu Polymer Co Ltd Method for manufacturing elastic roller, elastic roller and image forming apparatus

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