JP2007086498A - Rubber member for electrophotographic image formation and electrophotographic image forming apparatus - Google Patents

Rubber member for electrophotographic image formation and electrophotographic image forming apparatus Download PDF

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JP2007086498A
JP2007086498A JP2005276153A JP2005276153A JP2007086498A JP 2007086498 A JP2007086498 A JP 2007086498A JP 2005276153 A JP2005276153 A JP 2005276153A JP 2005276153 A JP2005276153 A JP 2005276153A JP 2007086498 A JP2007086498 A JP 2007086498A
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rubber
filler
electrophotographic image
silicone rubber
roll
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Satao Hirabayashi
佐太央 平林
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Priority to JP2005276153A priority Critical patent/JP2007086498A/en
Priority to KR1020060091551A priority patent/KR20070033903A/en
Publication of JP2007086498A publication Critical patent/JP2007086498A/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • G03G15/2003—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat
    • G03G15/2014—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
    • G03G15/2053—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating
    • G03G15/2057—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating relating to the chemical composition of the heat element and layers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber member for image formation used in office equipment, in which a large number of concavities are formed in the surface of rubber and its surface roughness is improved. <P>SOLUTION: The rubber member for electophotographic image formation having a large number of concavities is formed from: (A) organopolysiloxane represented by formula (1) R<SB>n</SB>SiO<SB>(4-n)/2</SB>(wherein R is a monovalent hydrocarbon group and n is 1.95-2.05); (B) a filler with a new Mohs hardness of 4 or below and an average particle diameter of 2 to 200μm; and (C) silicone rubber obtained by hardening a silicone rubber composition containing a hardener. The large number of concavities are formed in the surface of the rubber by polishing or wearing the rubber surface or subjecting the surface to friction in use environment so that the (B) component, namely the filler, is pulverized or caused to fall. In addition, if the surface roughness after the formation of the concavities in the silicone rubber is denoted by (X) and the surface roughness of the silicone rubber obtained by hardening the composition in which the (B) component is removed from the silicone rubber composition is denoted by (Y), Rz ratio (X/Y) is 1.2 or greater. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、硬化したシリコーンゴム表面を研磨又は面摩耗、あるいは使用環境にて面摩擦されることによって、配合された充填材が粉砕あるいは脱落することにより、ゴム表面に多数の凹穴が付与された電子写真式画像形成用ゴム部材に関する。特に、現像ロールに使用した場合は表面粗さが粗くなり、トナーの物理的搬送力の増加が期待でき、また面摩耗の可能性があるトナーブレードや紙送りロール等のゴム部材は連続使用によっても表面状態の変化が少なく、初期の特性が持続可能で、長期の使用に耐え得る電子写真式画像形成用ゴム部材及びそれを用いた電子写真式画像形成装置に関する。   In the present invention, the surface of the cured silicone rubber is polished, surface worn, or surface-rubbed in the environment of use, so that the blended filler is crushed or dropped to give a large number of concave holes on the rubber surface. The present invention also relates to a rubber member for electrophotographic image formation. In particular, when used for a developing roll, the surface roughness becomes rough, and an increase in the physical conveyance force of the toner can be expected, and rubber members such as a toner blade and a paper feed roll that may be subjected to surface wear can be used continuously. In particular, the present invention relates to a rubber member for electrophotographic image forming that has little change in surface state, can sustain initial characteristics, and can withstand long-term use, and an electrophotographic image forming apparatus using the same.

シリコーンゴムの表面に凹凸を付与する方法として、粒子径の大きい充填材を添加して凹凸をつける方法は様々に用いられている。例えば、粉砕石英、球状溶融シリカ、焼成珪藻土、球状ガラス、アルミナなどを添加し、研磨やゴム面を摩耗させることで表面粗さを粗くしたり、つや消し性や押し出し特性を向上させる方法である。通常、このような表面粗さを粗くするために添加する充填材としては、２〜５００μｍ程度の粒子径をもつ充填材の添加が必要である。このような粒子径の大きい充填材の添加によるゴム表面は、添加した充填材がゴム表面に残って凸面となり、ゴム面から充填材の粒子が突出している状態となる。従って、相手側基材に充填材が接触することになるため、ゴムに接する相手側の基材を傷付けたり、削ったりする場合があり、プラスチック等の樹脂などを傷付ける等の危険があった。   As a method for providing irregularities on the surface of the silicone rubber, various methods for adding irregularities by adding a filler having a large particle diameter are used. For example, crushed quartz, spherical fused silica, calcined diatomaceous earth, spherical glass, alumina or the like is added, and the surface roughness is increased by polishing or abrasion of the rubber surface, and the matteness and extrusion characteristics are improved. Usually, as a filler added in order to roughen such surface roughness, it is necessary to add a filler having a particle diameter of about 2 to 500 μm. The rubber surface resulting from the addition of the filler having such a large particle diameter is in a state where the added filler remains on the rubber surface and becomes a convex surface, and the filler particles protrude from the rubber surface. Therefore, since the filler comes into contact with the mating base material, the mating base material in contact with the rubber may be damaged or scraped, and there is a risk of damaging a resin such as plastic.

そこで、現像ロール用途で相手側（ＯＰＣドラム）を傷付けずにゴム表面に凹凸を付与し、トナー搬送力を増加させる方法として、特開平６−２２１３２１号公報（特許文献１）にあるように、シリコーンゴムパウダーなどを添加して上記の特性を満たす材料が提案されている。   Therefore, as a method for imparting irregularities to the rubber surface without damaging the other side (OPC drum) for developing roll use and increasing the toner conveying force, as disclosed in JP-A-6-221321 (Patent Document 1), A material that satisfies the above-described characteristics by adding silicone rubber powder or the like has been proposed.

しかしながら、シリコーンゴムパウダーが添加されているゴム材料は表面の凹凸を形成するためには有効な手段であるが、耐摩耗性に対しては殆ど効果はなく、摩擦状態を継続すると凹凸がなくなってしまったり、また添加しているシリコーンゴムパウダーの粒度分布がブロードであると表面凹凸の均一性が失われてしまい、現像ロール等の表面粗さが大きくなってしまい、近年のプリンターの高解像度化には対応できなくなる場合がある。   However, the rubber material to which silicone rubber powder is added is an effective means for forming surface irregularities, but has little effect on wear resistance, and the unevenness disappears when the friction state is continued. If the particle size distribution of the added silicone rubber powder is broad, the uniformity of the surface irregularities will be lost and the surface roughness of the developing roll will increase, resulting in higher resolution in recent printers. May not be available.

また、現像ロールの研磨性、摩耗性向上を目的とする方法として、特開２００２−３３８８０８号公報（特許文献２）のように、モース硬度２〜８の充填材を添加してロール耐久性を付与させたロール材料が提案されている。   In addition, as a method for improving the abrasiveness and abrasion of the developing roll, as shown in JP-A-2002-338808 (Patent Document 2), a filler having a Mohs hardness of 2 to 8 is added to improve roll durability. Proposed roll materials have been proposed.

しかし、これらのシリコーン材料に関してはロールの表面粗さを付与する目的ではなく、また充填材の添加によって表面粗さが付与された記述をしていない。   However, these silicone materials are not intended to impart the surface roughness of the roll, and do not describe the addition of the surface roughness due to the addition of a filler.

特開平６−２２１３２１号公報JP-A-6-221321 特開２００２−３３８８０８号公報JP 2002-338808 A

本発明は、上記事情に鑑みなされたもので、ゴム表面に均一な多数の凹穴を付与することによって表面粗さを向上させ、（ｉ）凹穴による物理的な粉体等の搬送又は付着力の向上、（ｉｉ）凹穴による滑り性の付与、安定的な接触面の確保、（ｉｉｉ）凹穴による水膜や油膜の除去、拭き取り性向上等の性能が期待できる、表面に多数の凹穴をもつ電子写真式画像形成用ゴム部材及びそれを用いた電子写真式画像形成装置を提供することを目的とする。   The present invention has been made in view of the above circumstances, and improves the surface roughness by providing a large number of uniform concave holes on the rubber surface, and (i) transports or attaches physical powder or the like through the concave holes. Performance of improvement in adhesion, (ii) imparting slipperiness by recessed holes, securing a stable contact surface, (iii) removing water film and oil film by recessed holes, improving wiping performance, etc. An object of the present invention is to provide an electrophotographic image forming rubber member having a concave hole and an electrophotographic image forming apparatus using the same.

本発明者らは、上記目的を達成するため鋭意検討を行った結果、新モース硬度が５．０以下で平均粒子径２〜２００μｍの充填材を配合し、硬化したゴム表面が研磨又は面摩耗、あるいは使用環境にて面摩擦されることによって、配合された充填材が粉砕あるいは脱落し、ゴム表面に多数の凹穴が付与され、電子写真式画像形成用ゴム部材として、各種ロール、特に現像ロール材料等に有用であることを知見し、本発明をなすに至った。   As a result of intensive studies to achieve the above object, the present inventors have blended a filler having a new Mohs hardness of 5.0 or less and an average particle diameter of 2 to 200 μm, and the cured rubber surface is polished or surface worn. In addition, the compounded filler is pulverized or dropped by surface friction in the use environment, and a large number of concave holes are provided on the rubber surface. As a rubber member for electrophotographic image formation, various rolls, particularly development It has been found useful for roll materials and the like, and has led to the present invention.

即ち、本発明は、下記の表面に凹穴をもつ電子写真式画像形成用ゴム部材及びそれを用いた電子写真式画像形成装置を提供する。
［１］（Ａ）下記平均組成式（１）
ＲnＳｉＯ(4-n)/2 （１）
（但し、Ｒは置換又は非置換の一価炭化水素基であり、ｎは１．９５〜２．０５の正数である。）
で示されるオルガノポリシロキサン：１００質量部、
（Ｂ）新モース硬度が５．０以下の平均粒子径２〜２００μｍの充填材：５〜２００質量部、及び
（Ｃ）硬化剤：硬化有効量
を含有するシリコーンゴム組成物を硬化することによって得られたシリコーンゴムからなり、該ゴム表面が研磨もしくは面摩耗又は使用環境にて面摩擦されて上記（Ｂ）成分の充填材が粉砕又は脱落することにより、上記ゴム表面に多数の凹穴が形成され、かつ上記シリコーンゴムの凹穴が形成された後の表面粗さ（Ｘ）と上記シリコーンゴム組成物より（Ｂ）成分を除去した組成物を硬化することによって得られたシリコーンゴムの表面粗さ（Ｙ）とのＲｚ比（Ｘ／Ｙ）が１．２以上であることを特徴とする表面に多数の凹穴をもつ電子写真式画像形成用ゴム部材。
［２］電子顕微鏡写真において測定した場合、ゴム表面の凹穴部分の合計面積がゴム表面全体の面積の１５％以上である［１］記載の電子写真式画像形成用ゴム部材。
［３］（Ｂ）成分が、レーザー回折散乱で測定した充填材の平均粒子径に対して５倍以上の粒子径をもつ充填材の割合が２．３質量％以下になるように調整された粒度分布をもつ充填材であることを特徴とする［１］又は［２］記載の電子写真式画像形成用ゴム部材。
［４］充填材が、炭酸カルシウム、塩化ナトリウム又は水酸化アルミニウムであり、平均粒子径が２〜７０μｍである［１］〜［３］のいずれかに記載の電子写真式画像形成用ゴム部材。
［５］シリコーンゴム組成物が、更に（Ｄ）導電材を含み、導電性を付与したゴム材料である［１］〜［４］のいずれかに記載の電子写真式画像形成用ゴム部材。
［６］トナーブレード、現像ロール、トナー搬送ロール、紙送りロール、中間転写ロール、定着ロール、現像ベルト、中間転写ベルト又は定着ベルト用である［１］〜［５］のいずれかに記載の電子写真式画像形成用ゴム部材。
［７］［６］記載の電子写真式画像形成用ゴム部材を有する電子写真式画像形成装置。 That is, the present invention provides an electrophotographic image forming rubber member having a concave hole on the following surface and an electrophotographic image forming apparatus using the same.
[1] (A) The following average composition formula (1)
R n SiO (4-n) / 2 (1)
(However, R is a substituted or unsubstituted monovalent hydrocarbon group, and n is a positive number of 1.95 to 2.05.)
An organopolysiloxane represented by: 100 parts by mass,
(B) By curing a silicone rubber composition containing a filler having an average particle size of 2 to 200 μm having a new Mohs hardness of 5.0 or less: 5 to 200 parts by mass, and (C) a curing agent: an effective amount for curing. It is made of the obtained silicone rubber, and the rubber surface is ground or surface worn or is subjected to surface friction in the use environment, and the filler of the component (B) is crushed or dropped, whereby a large number of concave holes are formed on the rubber surface. The surface of the silicone rubber obtained by curing the composition obtained by removing the component (B) from the surface roughness (X) and the silicone rubber composition after the formation of the concave holes of the silicone rubber. An electrophotographic image forming rubber member having a number of concave holes on a surface thereof, wherein an Rz ratio (X / Y) to roughness (Y) is 1.2 or more.
[2] The electrophotographic image forming rubber member according to [1], wherein the total area of the recessed holes on the rubber surface is 15% or more of the total area of the rubber surface when measured in an electron micrograph.
[3] The component (B) was adjusted so that the proportion of the filler having a particle size of 5 times or more with respect to the average particle size of the filler measured by laser diffraction scattering was 2.3% by mass or less. The electrophotographic image forming rubber member according to [1] or [2], wherein the rubber member is a filler having a particle size distribution.
[4] The electrophotographic image-forming rubber member according to any one of [1] to [3], wherein the filler is calcium carbonate, sodium chloride, or aluminum hydroxide, and the average particle diameter is 2 to 70 μm.
[5] The electrophotographic image forming rubber member according to any one of [1] to [4], wherein the silicone rubber composition further comprises (D) a conductive material and is a rubber material imparted with conductivity.
[6] The electron according to any one of [1] to [5], which is for a toner blade, a developing roll, a toner conveying roll, a paper feed roll, an intermediate transfer roll, a fixing roll, a developing belt, an intermediate transfer belt, or a fixing belt. Rubber member for photographic image formation.
[7] An electrophotographic image forming apparatus having the electrophotographic image forming rubber member according to [6].

本発明によれば、硬化したシリコーンゴム表面が研磨又は面摩耗、あるいは使用環境にて面摩擦されることによって、配合された充填材が粉砕あるいは脱落することにより、ゴム表面に多数の凹穴が付与された電子写真式画像形成用ゴム部材を提供することができ、該ゴム部材は、現像ロールに使用した場合は表面粗さが粗くなり、トナーの物理的搬送力の増加が期待でき、トナーブレードに使用した場合はゴム部材や他樹脂を傷付けることなく安定した掻き落とし能力が可能である。また、面摩耗の可能性があるゴム部材やロール、ベルト等は、連続使用によっても表面状態の変化が少なく、初期の特性が持続可能で、長期の使用に耐え得るもので、本発明のゴム部材は、特に現像ロール、トナー搬送ロール、給紙ロール、中間転写ロール、定着ロール、トナーブレード、現像ベルト、中間転写ベルト及び定着ベルト等の事務機用部材に有用である。   According to the present invention, the surface of the cured silicone rubber is polished or surface worn, or is subjected to surface friction in the environment of use, so that the blended filler is crushed or dropped, resulting in a large number of concave holes on the rubber surface. The applied rubber member for electrophotographic image formation can be provided, and when the rubber member is used for a developing roll, the surface roughness becomes rough, and an increase in the physical conveyance force of the toner can be expected. When used for blades, stable scraping ability is possible without damaging rubber members or other resins. In addition, rubber members, rolls, belts, etc. that have the possibility of surface wear have little change in surface condition even with continuous use, can maintain initial characteristics, and can withstand long-term use. The member is particularly useful for office machine members such as a developing roll, a toner conveying roll, a paper feeding roll, an intermediate transfer roll, a fixing roll, a toner blade, a developing belt, an intermediate transfer belt, and a fixing belt.

本発明において、（Ａ）成分のオルガノポリシロキサンは、下記平均組成式（１）
ＲnＳｉＯ(4-n)/2 （１）
（但し、Ｒは置換又は非置換の一価炭化水素基であり、ｎは１．９５〜２．０５の正数である。）
で示されるものである。 In the present invention, the organopolysiloxane of the component (A) has the following average composition formula (1)
R n SiO (4-n) / 2 (1)
(However, R is a substituted or unsubstituted monovalent hydrocarbon group, and n is a positive number of 1.95 to 2.05.)
It is shown by.

上記平均組成式（１）において、Ｒは置換又は非置換の一価炭化水素基であり、炭素数１〜１２、特に１〜８のものが好ましく、Ｒで示される一価炭化水素基としては、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、ドデシル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、ビニル基、アリル基、ブテニル基、ヘキセニル基などのアルケニル基、フェニル基、トリル基などのアリール基、β−フェニルプロピル基などのアラルキル基、又はこれらの基の炭素原子に結合した水素原子の一部又は全部をハロゲン原子、シアノ基などで置換したクロロメチル基、トリフルオロプロピル基、シアノエチル基などが挙げられる。また、ｎは１．９５〜２．０５の正数である。この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、ジメチルビニルシリル基、ジメチルヒドロキシシリル基、トリビニルシリル基などで封鎖されていることが好ましい。   In the above average composition formula (1), R is a substituted or unsubstituted monovalent hydrocarbon group, preferably having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, and the monovalent hydrocarbon group represented by R is For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, a butenyl group or a hexenyl group, a phenyl group Group, aryl group such as tolyl group, aralkyl group such as β-phenylpropyl group, or chloromethyl group in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atom, cyano group or the like, Examples thereof include a trifluoropropyl group and a cyanoethyl group. N is a positive number from 1.95 to 2.05. In this organopolysiloxane, the molecular chain end is preferably blocked with a trimethylsilyl group, a dimethylvinylsilyl group, a dimethylhydroxysilyl group, a trivinylsilyl group, or the like.

このオルガノポリシロキサンは、分子中に少なくとも２個のアルケニル基を有することが好ましく、Ｒのうち０．００１〜５モル％、特に０．０１〜０．５モル％がアルケニル基、特にビニル基であることが好ましい。特に後述する硬化剤として白金系触媒とオルガノハイドロジェンポリシロキサンとの組み合わせを使用する場合には、このようなアルケニル基を含有するオルガノポリシロキサンを常用使用する。   The organopolysiloxane preferably has at least two alkenyl groups in the molecule, and 0.001 to 5 mol%, particularly 0.01 to 0.5 mol% of R is an alkenyl group, particularly a vinyl group. Preferably there is. In particular, when a combination of a platinum catalyst and an organohydrogenpolysiloxane is used as a curing agent to be described later, such an organopolysiloxane containing an alkenyl group is commonly used.

また、このオルガノポリシロキサンは、通常選択されたオルガノハロゲノシランの１種又は２種以上を共加水分解縮合することによって、あるいは環状ポリシロキサン（シロキサンの３量体あるいは４量体など）をアルカリ性又は酸性の触媒を用いて開環重合することによって得ることができるもので、このものは基本的には直鎖状のジオルガノポリシロキサンであるが、一部分岐していてもよい。また、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。更に、このオルガノポリシロキサンの粘度は、ＪＩＳ Ｋ ６２４９による２５℃における粘度が１００ｍＰａ・ｓ以上のものが好ましい。より好ましくは１００，０００〜１０，０００，０００ｍＰａ・ｓである。重合度では１００以上、特に３，０００以上が好ましく、その上限は好ましくは１００，０００であり、更に好ましくは１０，０００である。   In addition, this organopolysiloxane can be obtained by cohydrolyzing and condensing one or more selected organohalogenosilanes, or by converting a cyclic polysiloxane (such as a siloxane trimer or tetramer) to be alkaline or It can be obtained by ring-opening polymerization using an acidic catalyst. This is basically a linear diorganopolysiloxane, but may be partially branched. Further, it may be a mixture of two or more different molecular structures. Further, the viscosity of this organopolysiloxane is preferably 100 mPa · s or more at 25 ° C. according to JIS K 6249. More preferably, it is 100,000-10,000,000 mPa * s. The degree of polymerization is preferably 100 or more, particularly preferably 3,000 or more, and the upper limit thereof is preferably 100,000, more preferably 10,000.

次に、（Ｂ）成分の充填材について説明する。
本発明の充填材は、一般的に補強性シリカ等の補強性充填材とは異なり、ロール表面に均一な凹穴を付与する目的で添加され、新モース硬度（硬さのレベルによって１〜１５に分別）が５．０以下の充填材を（Ａ）成分に添加、混合する。 Next, the filler of the component (B) will be described.
Unlike the reinforcing filler such as reinforcing silica, the filler of the present invention is generally added for the purpose of providing a uniform concave hole on the roll surface, and has a new Mohs hardness (1 to 15 depending on the hardness level). To the component (A) is added and mixed.

本発明は、（Ｂ）成分の充填材が添加されたシリコーンゴム組成物を硬化した後、ゴム表面を研磨又は面摩耗、あるいは使用環境にて面摩擦される状態とすることによって充填材を粉砕あるいは脱落することでゴム表面に多数の凹穴を付与することが可能となる。従って、充填材がシリコーンゴムと分離、脱落し易く、また研磨や摩耗により充填材が粉砕するものがより好まれる。（Ｂ）成分の充填材の形状、性質等は特に規定されるものではないが、本発明において好適に使用される充填材としては、球状あるいは粉砕状、四面体以上の結晶状、角柱の粒子が好ましい。具体的には水酸化アルミニウム、炭酸カルシウム（方解石）、塩化ナトリウム、粉末蛍石、岩塩粉末、石膏粉末等の金属酸化物、不定形グラファイト、球状グラファイト、金属アルミニウム粉等が挙げられるが、より好ましくは研磨あるいは表面摩耗によって粒子が粉砕可能な物質が好ましく、炭酸カルシウム、塩化ナトリウム、水酸化アルミニウムが好適である。金属等に特有の展性をもつ物質はあまり好ましくない。また導電性充填材（金属微粒子、導電性酸化金属微粒子、グラファイト等）も使用可能である。   In the present invention, after the silicone rubber composition to which the filler of the component (B) is added is cured, the filler is pulverized by polishing, surface abrasion, or surface friction in a use environment. Or it becomes possible to give many concave holes to the rubber surface by dropping off. Therefore, it is more preferable that the filler is easily separated and removed from the silicone rubber and the filler is pulverized by polishing or abrasion. The shape, properties, etc. of the filler of the component (B) are not particularly specified, but the filler suitably used in the present invention is spherical or pulverized, crystalline tetrahedral or more, prismatic particles Is preferred. Specific examples include metal oxides such as aluminum hydroxide, calcium carbonate (calcite), sodium chloride, powder fluorite, rock salt powder, gypsum powder, amorphous graphite, spherical graphite, metal aluminum powder, and the like. Is preferably a substance whose particles can be pulverized by polishing or surface abrasion, and calcium carbonate, sodium chloride and aluminum hydroxide are preferred. Substances having malleability specific to metals and the like are not preferred. Also, conductive fillers (metal fine particles, conductive metal oxide fine particles, graphite, etc.) can be used.

また、充填材自身の硬さは新モース硬度が５．０以下であることがよく、より好ましくは３以下である。充填材が硬すぎると研磨等によって粉体が脱落、粉砕しずらく、また表面に充填材が凸状となって残り、シリコーンゴムが接触する相手材料を傷付けたりする場合がある。   The filler itself has a new Mohs hardness of 5.0 or less, more preferably 3 or less. If the filler is too hard, the powder may not easily fall off or be pulverized by polishing or the like, and the filler may remain convex on the surface, which may damage the mating material with which the silicone rubber comes into contact.

ここで使用される充填材の平均粒子径はＪＩＳ Ｒ ６００２に基づいてレーザー回折散乱で測定した２〜２００μｍの大きさであり、好ましくは２〜１００μｍ、より好ましくは２〜７０μｍ、特に５〜７０μｍの大きさである。   The average particle size of the filler used here is 2 to 200 μm, preferably 2 to 100 μm, more preferably 2 to 70 μm, particularly 5 to 70 μm, measured by laser diffraction scattering based on JIS R 6002. Is the size of

また、均一な凹穴をもたせるために充填材は粒度分布の狭いものを使用することが好ましく、平均粒子径に対して５倍以上の粒子径をもつ充填材の割合が２．３質量％以下、より好ましくは１質量％以下になるように調整された粒度分布をもつ充填材であることが望ましい。狭い粒度分布をもつ充填材の添加により、少ない充填材の添加で、より表面に沢山の凹穴を作ることが可能である。   In order to provide a uniform concave hole, it is preferable to use a filler having a narrow particle size distribution, and the ratio of the filler having a particle size of 5 times or more with respect to the average particle size is 2.3% by mass or less. It is desirable that the filler has a particle size distribution adjusted to be 1% by mass or less. By adding a filler having a narrow particle size distribution, it is possible to make many concave holes on the surface with a small amount of filler.

特に充填材の粒度分布を正規分布Ｎ（μ，σ2）と見立てた場合、Ｎ（μ，２μ2）の正規分布範囲に上記充填材の９５．４質量％以上の粒子が含まれる分散状態をもつ粉体が好ましく、より好ましくはσが平均粒子径の一倍値以内であるシャープな正規分布をもつ粉体であることが望ましい［但し、μは充填材の平均粒子径であり、その正規分布の標準偏差σは平均粒子径μの二倍値あるいは一倍値以内とする。］。 In particular, when assuming that the particle size distribution of the filler is a normal distribution N (μ, σ 2 ), a dispersion state in which particles of 95.4 mass% or more of the filler are included in the normal distribution range of N (μ, 2 μ 2 ). It is desirable that the powder has a sharp normal distribution in which σ is within the average value of the average particle diameter [wherein μ is the average particle diameter of the filler, The standard deviation σ of the normal distribution is set to be twice or less than the average particle diameter μ. ].

上記の粒度分布をもつ粉体（充填材）の製造方法は特に規定するものではないが、粉砕及び分級工程を経た充填材、エマルジョンを出発原料として得られる充填材、金属や樹脂等を高温溶融させて微粉化する方法、化学合成による結晶成長による方法等が挙げられるが、特に粉体粒度分布を狭い範囲で管理可能な化学合成品、粗粒子や微粉をカットした粉砕品が好適に使用される。   The method for producing the powder (filler) having the above particle size distribution is not particularly specified, but the filler obtained through the pulverization and classification process, the filler obtained from the emulsion as a starting material, the metal, the resin, etc. are melted at high temperature. The method of finely pulverizing, the method of crystal growth by chemical synthesis, etc. are mentioned, but in particular, a chemically synthesized product capable of managing the powder particle size distribution in a narrow range, a pulverized product obtained by cutting coarse particles and fine powder is preferably used. The

上記のような充填材として特に好ましく用いられるのは、炭酸カルシウム、水酸化アルミニウム、塩化ナトリウム等の粉体である。   Particularly preferably used as the filler as described above are powders such as calcium carbonate, aluminum hydroxide, and sodium chloride.

（Ｂ）成分の添加量は、（Ａ）成分１００質量部に対して５〜２００質量部、特に５〜１００質量部とすることが望ましい。より好ましくは１０〜７０質量部であることが望ましい。５質量部未満では、十分な凹穴が得られず、２００質量部を超えるとゴム物性の低下が著しいばかりか、配合すること自体も困難である。   Component (B) is added in an amount of 5 to 200 parts by weight, particularly 5 to 100 parts by weight, per 100 parts by weight of component (A). More preferably, it is 10 to 70 parts by mass. If it is less than 5 parts by mass, sufficient concave holes cannot be obtained. If it exceeds 200 parts by mass, not only the physical properties of the rubber are remarkably deteriorated, but also blending itself is difficult.

また、上記の充填材は、硬化したシリコーンゴムからより脱落し易くすることを目的として充填材をシラン、シリコーンオイルや炭化水素系オイル、ワックスなどで表面処理することも可能である。   In addition, the filler can be surface-treated with silane, silicone oil, hydrocarbon oil, wax or the like for the purpose of facilitating removal from the cured silicone rubber.

本発明においては、（Ｃ）成分として硬化剤を硬化有効量配合する。（Ｃ）成分の硬化剤としては既知の白金系触媒とオルガノハイドロジェンポリシロキサンとの組合せ又は有機過酸化物触媒を使用し得る。白金系触媒としては公知のものが使用でき、具体的には白金元素単体、白金化合物、白金複合体、塩化白金酸、塩化白金酸のアルコール化合物、アルデヒド化合物、エーテル化合物、各種オレフィン類とのコンプレックスなどが例示される。白金系触媒の添加量は、（Ａ）成分のオルガノポリシロキサンに対して白金原子として１〜２，０００ｐｐｍの範囲とすることが望ましい。   In the present invention, an effective amount of curing agent is blended as the component (C). As the curing agent for the component (C), a combination of a known platinum catalyst and an organohydrogenpolysiloxane or an organic peroxide catalyst can be used. Known platinum-based catalysts can be used. Specifically, platinum elements alone, platinum compounds, platinum complexes, chloroplatinic acid, chloroplatinic acid alcohol compounds, aldehyde compounds, ether compounds, and complexes with various olefins Etc. are exemplified. The addition amount of the platinum-based catalyst is preferably in the range of 1 to 2,000 ppm as platinum atoms with respect to the organopolysiloxane of component (A).

白金系触媒と組合せて使用するオルガノハイドロジェンポリシロキサンとしては、直鎖状、分岐鎖状、環状のいずれであってもよいが、重合度が３００以下のものが好ましく、ジメチルハイドロジェンシリル基で末端が封鎖されたジオルガノポリシロキサン、ジメチルシロキサン単位とメチルハイドロジェンシロキサン単位及び末端トリメチルシロキシ単位との共重合体、ジメチルハイドロジェンシロキサン単位（Ｈ（ＣＨ3）2ＳｉＯ0.5単位）とＳｉＯ2単位とからなる低粘度流体、１，３，５，７−テトラハイドロジェン−１，３，５，７−テトラメチルシクロテトラシロキサン、１−プロピル−３，５，７−トリハイドロジェン−１，３，５，７−テトラメチルシクロテトラシロキサン、１，５−ジハイドロジェン−３，７−ジヘキシル−１，３，５，７−テトラメチルシクロテトラシロキサンなどが例示される。この硬化剤としてのオルガノハイドロジェンポリシロキサンの添加量は、（Ａ）成分のオルガノポリシロキサンのアルケニル基に対して、ケイ素原子に直結した水素原子（ＳｉＨ基）が５０〜５００モル％となる割合で用いられることが望ましい。 The organohydrogenpolysiloxane used in combination with the platinum-based catalyst may be linear, branched or cyclic, but preferably has a degree of polymerization of 300 or less, and is a dimethylhydrogensilyl group. End-blocked diorganopolysiloxane, copolymer of dimethylsiloxane unit and methylhydrogensiloxane unit and terminal trimethylsiloxy unit, dimethylhydrogensiloxane unit (H (CH 3 ) 2 SiO 0.5 unit) and SiO 2 unit 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3 , 5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl 1,3,5,7-tetramethyl cyclotetrasiloxane and the like. The addition amount of the organohydrogenpolysiloxane as the curing agent is such that the hydrogen atom (SiH group) directly bonded to the silicon atom is 50 to 500 mol% with respect to the alkenyl group of the organopolysiloxane of the component (A). It is desirable to be used in.

有機過酸化物触媒としては、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン等のアルキル過酸化物、ジクミルパーオキサイド等のアラルキル過酸化物等の有機過酸化物が挙げられる。   Examples of organic peroxide catalysts include di-t-butyl peroxide, alkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and aralkyl peroxides such as dicumyl peroxide. Organic peroxides such as oxides can be mentioned.

有機過酸化物の使用量は、上記（Ａ）成分１００質量部に対し０．１〜１０質量部とすることが好ましい。   It is preferable that the usage-amount of an organic peroxide shall be 0.1-10 mass parts with respect to 100 mass parts of said (A) component.

なお、付加架橋と有機過酸化物架橋を併用してもよい。液状材料の硬化剤としては付加架橋が推奨される。   Note that addition crosslinking and organic peroxide crosslinking may be used in combination. Addition crosslinking is recommended as a curing agent for liquid materials.

更に、（Ｄ）成分として導電性物質を添加して導電性ゴム組成物とすることは任意である。導電性物質は、その種類、配合量は制限されないが、導電性カーボンブラック、導電性酸化金属系粒子、例えば、導電性亜鉛華、導電性酸化チタンなどが使用でき、また導電性物質は１種又は２種以上を併用してもよい。   Furthermore, it is optional to add a conductive material as component (D) to obtain a conductive rubber composition. The type and amount of the conductive material are not limited, but conductive carbon black, conductive metal oxide particles such as conductive zinc oxide, conductive titanium oxide, etc. can be used, and there is only one conductive material. Or you may use 2 or more types together.

カーボンブラックとしては、通常導電性ゴム組成物に常用されているものが使用し得、例えば、アセチレンブラック、コンダクティブファーネスブラック（ＣＦ）、スーパーコンダクティブファーネスブラック（ＳＣＦ）、エクストラコンダクティブファーネスブラック（ＸＣＦ）、コンダクティブチャンネルブラック（ＣＣ）、１，５００〜３，０００℃程度の高温で熱処理されたファーネスブラックやチャンネルブラック等を挙げることができる。具体的には、アセチレンブラックとしてはデンカブラック（電気化学工業社製）、シャウニガンアセチレンブラック（シャウニガンケミカル社製）等が、コンダクティブファーネスブラックとしてはコンチネックスＣＦ（コンチネンタルカーボン社製）、バルカンＣ（キャボット社製）等が、スーパーコンダクティブファーネスブラックとしてはコンチネックスＳＣＦ（コンチネンタルカーボン社製）、バルカンＳＣ（キャボット社製）等が、エクストラコンダクティブファーネスブラックとしては旭ＨＳ−５００（旭カーボン社製）、バルカンＸＣ−７２（キャボット社製）等が、コンダクティブチャンネルブラックとしてはコウラックスＬ（デグッサ社製）等が例示され、また、ファーネスブラックの一種であるケッチェンブラックＥＣ及びケッチェンブラックＥＣ−６００ＪＤ（ケッチェンブラックインターナショナル社製）を用いることもできる。ファーネスブラックは不純物、特に硫黄や硫黄化合物の量が硫黄元素の濃度で６，０００ｐｐｍ以下、より好ましくは３，０００ｐｐｍ以下が望ましい．なお、これらのうちでは、アセチレンブラックは不純物含有率が少ない上、発達した２次ストラクチャー構造を有することから導電性に優れており、本発明において特に好適に用いられる。なおまた、その卓越した比表面積から低充填量でも優れた導電性を示すケッチェンブラックＥＣやケッチェンブラックＥＣ−６００ＪＤ等も好ましく使用できる。   As carbon black, those commonly used in conductive rubber compositions can be used, such as acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), extra conductive furnace black (XCF), Examples thereof include conductive channel black (CC), furnace black and channel black heat-treated at a high temperature of about 1,500 to 3,000 ° C. Specifically, as acetylene black, Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.), Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.), etc., as conductive furnace black Continex CF (manufactured by Continental Carbon Co.), Vulcan C (manufactured by Cabot Corp.) etc., Superconductive Furnace Black as Connexex SCF (Continental Carbon Corp.), Vulcan SC (Cabot Corp.), etc. As Extra Conductive Furnace Black Asahi HS-500 (Asahi Carbon Corp.) ), Vulcan XC-72 (manufactured by Cabot Corporation), etc., and as a conductive channel black, Kourax L (manufactured by Degussa) and the like are exemplified, and Ketjen Black EC which is a kind of furnace black It is also possible to use a fine-Ketchen black EC-600JD (manufactured by Ketchen Black International Co., Ltd.). In furnace black, the amount of impurities, particularly sulfur and sulfur compounds, is preferably 6,000 ppm or less, more preferably 3,000 ppm or less in terms of the concentration of elemental sulfur. Among these, acetylene black has a low impurity content and has a developed secondary structure structure, so that it has excellent conductivity and is particularly preferably used in the present invention. In addition, ketjen black EC, ketjen black EC-600JD, etc., which exhibit excellent conductivity even at a low filling amount due to their excellent specific surface area, can be preferably used.

上記導電性物質の添加量は、導電性シリコーンゴム組成物のゴムが導電となる抵抗値、即ち体積抵抗率が１０14Ω・ｍ以下となる量であればよいが、上述した（Ａ）成分１００質量部に対して１〜１００質量部、特に５〜５０質量部とすることが好ましい。添加量が１質量部未満では所望の導電性を得ることができない場合があり、１００質量部を超えると物理的混合が難しくなったり機械的強度が低下したりする可能性があり、目的とするゴム弾性を得られないことがある。 The conductive material may be added in any amount as long as the resistance of the conductive silicone rubber composition becomes conductive, that is, the volume resistivity is 10 14 Ω · m or less. It is preferable to set it as 1-100 mass parts with respect to 100 mass parts, especially 5-50 mass parts. If the addition amount is less than 1 part by mass, the desired conductivity may not be obtained. If the addition amount exceeds 100 parts by mass, physical mixing may be difficult or the mechanical strength may be lowered. Rubber elasticity may not be obtained.

本発明のゴム組成物には、必要に応じて補強性シリカ微粉末を添加することが好ましい。シリカ微粉末は、機械的強度の優れたゴム組成物を得るために必要であるが、この目的のためには比表面積が１０ｍ2／ｇ以上、好ましくは５０〜４００ｍ2／ｇである。このシリカ微粉末としては煙霧質シリカ（乾式シリカ）、沈殿シリカ（湿式シリカ）が例示され、煙霧質シリカ（乾式シリカ）が好ましい。これらの使用可能な補強性シリカを市販品で例示すると、エアロジル１３０，２００，３００，３８０（日本アエロジル社製商品名）、Ｃａｂ−Ｏ−ｓｉｌ ＭＳ−５，ＭＳ−７，ＨＳ−５，ＨＳ−７（キャボット社製商品名）、Ｓａｎｔｏｃｅｌ ＦＲＣ，ＣＳ（モンサント社製商品名）、ニップシルＶＮ−３（日本シリカ工業社製商品名）などである。また、これらの表面をオルガノポリシロキサン、オルガノポリシラザン、クロロシラン、アルコキシシラン等で疎水化処理してもよい。これらのシリカは単独でも２種以上併用してもよい。なお、このシリカ微粉末の添加量は、厳密なものではないが、好ましくはオルガノポリシロキサン１００質量部当たり５〜２００質量部の範囲である。５質量部未満では少なすぎて十分な補強効果が得られず、２００質量部より多くすると加工性が悪くなり、好ましくは５〜１００質量部、より好ましくは５〜９０質量部、特に好ましくは１０〜５０質量部である。 It is preferable to add reinforcing silica fine powder to the rubber composition of the present invention as necessary. Silica fine powder, it is necessary to obtain good rubber composition in mechanical strength, specific surface area for this purpose 10 m 2 / g or more, preferably 50 to 400 m 2 / g. Examples of the silica fine powder include fumed silica (dry silica) and precipitated silica (wet silica), and fumed silica (dry silica) is preferable. Examples of commercially available reinforcing silicas include Aerosil 130, 200, 300, 380 (trade name, manufactured by Nippon Aerosil Co., Ltd.), Cab-O-sil MS-5, MS-7, HS-5, HS. -7 (trade name, manufactured by Cabot Corporation), Santocel FRC, CS (trade name, manufactured by Monsanto Corporation), Nipsil VN-3 (trade name, manufactured by Nippon Silica Industry Co., Ltd.), and the like. Further, these surfaces may be hydrophobized with organopolysiloxane, organopolysilazane, chlorosilane, alkoxysilane, or the like. These silicas may be used alone or in combination of two or more. The amount of silica fine powder added is not critical, but is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of the organopolysiloxane. If it is less than 5 parts by mass, it is too small to obtain a sufficient reinforcing effect, and if it exceeds 200 parts by mass, the workability deteriorates, preferably 5 to 100 parts by mass, more preferably 5 to 90 parts by mass, and particularly preferably 10 parts. -50 mass parts.

また、新モース硬度が５．０を超える（Ｂ）成分の充填材よりも粒径が小さい増量材としての充填材、例えば、粉砕結晶性シリカや珪藻土微粉末を添加することは任意である。   Further, it is optional to add a filler as an extender having a particle size smaller than that of the component (B) having a new Mohs hardness exceeding 5.0, for example, pulverized crystalline silica or diatomaceous earth fine powder.

その他の添加剤としては、必要に応じて着色剤、オクチル酸鉄等の耐熱向上剤、難燃性を付与させるハロゲン化合物、受酸剤、酸化鉄、酸化セリウム、熱伝導向上剤等の添加剤や離型剤、アルコキシシラン、重合度が（Ａ）成分よりも低いジメチルシロキサンオイル、シラノール、例えばジフェニルシランジオール等の両末端シラノール封鎖低分子シロキサン等の分散剤、接着性や成形加工性を向上させるための各種カーボンファンクショナルシラン、シリコーンの架橋などを阻害しない硬化、未硬化の各種オレフィン系エラストマー等を混合、添加してもよいが、添加するものが粒子状である場合は（Ｂ）成分の充填材よりも粒径が小さいことが望ましい。   Other additives include colorants, heat resistance improvers such as iron octylate, halogen compounds that impart flame retardancy, acid acceptors, iron oxide, cerium oxide, heat conductivity improvers, etc. as necessary. Dispersing agents such as siloxane siloxane oil, silanol, low-molecular-weight silanols of both ends such as diphenylsilane diol, adhesiveness and molding processability are improved. Various carbon functional silanes for curing and curing and uncured various olefin elastomers that do not inhibit crosslinking of silicone may be mixed and added, but if the added is in the form of particles, component (B) It is desirable that the particle size be smaller than that of the filler.

本発明のゴム組成物は、上記した成分を２本ロール、バンバリミキサー、ドゥーミキサー（ニーダー）、品川ミキサー、プラネタリミキサーなどのポリマーと粉体の混合器を用いて均一に混合することにより得ることができる。このようにして調製されたゴム組成物は既知の方法で加熱硬化させることにより容易にシリコーンゴムを得ることができる。また、硬化方法はゴムの架橋に必要な熱をかけられる方法であればよく、そ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など、特に制限されるものではない。この場合、加熱温度は７０〜５００℃、特に１２０〜３００℃、時間は数秒〜１時間、特に１０秒〜３０分間であることが好ましい。また、必要に応じて１００〜２００℃で１〜２０時間程度２次加硫してもよい。   The rubber composition of the present invention is obtained by uniformly mixing the above-described components using a polymer and powder mixer such as two rolls, a Banbury mixer, a dough mixer (kneader), a Shinagawa mixer, and a planetary mixer. Can do. Silicone rubber can be easily obtained by heat-curing the rubber composition thus prepared by a known method. The curing method may be any method that can apply heat necessary for crosslinking of the rubber, and the molding method is not particularly limited, such as continuous vulcanization by extrusion molding, pressing, or molding by injection. In this case, it is preferable that the heating temperature is 70 to 500 ° C., particularly 120 to 300 ° C., and the time is several seconds to 1 hour, particularly 10 seconds to 30 minutes. Moreover, you may carry out secondary vulcanization at 100-200 degreeC for about 1 to 20 hours as needed.

本発明のゴム部材は、上記シリコーンゴム組成物を硬化してシリコーンゴムを得た後、このシリコーンゴム表面を研磨もしくは面摩耗し、あるいは使用環境にて面摩擦し、上記シリコーンゴム組成物中の（Ｂ）成分の充填材を粉砕あるいは脱落させて、シリコーンゴム表面に多数の凹穴を形成するものである。この場合、表面は平滑であって、突起物がなく、この平滑表面に多数の凹穴を有する状態となることが有効である。   In the rubber member of the present invention, after the silicone rubber composition is cured to obtain a silicone rubber, the surface of the silicone rubber is polished or subjected to surface abrasion, or surface friction is caused in a use environment. The filler of component (B) is pulverized or dropped to form a number of concave holes on the silicone rubber surface. In this case, it is effective that the surface is smooth, has no protrusions, and has a number of concave holes on the smooth surface.

ここで、研磨は、ロール等の研磨に用いられる円筒研削盤、アンギュラ型円筒研磨盤、円形ディスク板研磨装置、ロールフィルム研磨装置、スーパーフィニッシャー研磨装置を用いる等の方法が採用し得る。面摩耗は、研磨テープやシート等によるラップ研磨、ポリッシングパット、ベルト研磨、バレル研磨等の方法が採用し得る。
また、使用環境にて面摩擦するとは、金属面やプラスチック面等の平坦面とゴム部材が常時あるいは定期的に動きながら接している状態で、その結果ゴム接触面が摩耗することをいう。 Here, for polishing, a method such as using a cylindrical grinding machine, an angular cylindrical polishing machine, a circular disk plate polishing apparatus, a roll film polishing apparatus, or a super finisher polishing apparatus used for polishing a roll or the like can be employed. For surface wear, methods such as lapping with a polishing tape or sheet, polishing pad, belt polishing, barrel polishing, etc. can be employed.
Further, the surface friction in the use environment means that the rubber contact surface is worn as a result of the rubber member being in contact with a flat surface such as a metal surface or a plastic surface constantly or periodically.

なお、凹穴はゴム表面に均一に形成されるが、この場合、電子顕微鏡写真（好ましくは倍率５０〜５，０００倍、特に１００〜１，０００倍）において、ゴム表面の凹穴部分の合計面積が表面全体の面積の１５％以上、より好ましくは３０〜８０％、更に好ましくは５０〜７０％であることが望ましい。なお、上記面積比は３箇所の測定値の平均である。   The concave holes are uniformly formed on the rubber surface. In this case, in the electron micrograph (preferably 50 to 5,000 times, particularly 100 to 1,000 times), the total number of the concave holes on the rubber surface. It is desirable that the area is 15% or more of the entire surface area, more preferably 30 to 80%, and still more preferably 50 to 70%. In addition, the said area ratio is an average of the measured value of three places.

更に、上記凹穴が形成されたシリコーンゴム表面の粗さＲｚをＪＩＳ Ｂ ０６０１−１９９４に準じて１０点平均粗さとして測定した場合の測定値をＸ、またこのシリコーンゴムを得るためのシリコーンゴム組成物より（Ｂ）成分の充填材を除いた組成物を上記シリコーンゴムを得る場合と同条件で硬化することにより得られたシリコーンゴム表面の粗さＲｚを上記と同様に測定した場合の測定値をＹとした場合、ＸとＹとの比［Ｒｚ比＝Ｘ／Ｙ］が１．２以上、好ましくは１．４以上、更に好ましくは２．０以上であることが必要である。Ｘ／Ｙが１．２より小さいと、穴が十分にあいていない状態となる。   Further, when the roughness Rz of the surface of the silicone rubber having the concave hole is measured as an average roughness of 10 points according to JIS B 0601-1994, the measured value is X, and the silicone rubber for obtaining this silicone rubber Measurement when the surface roughness Rz of the silicone rubber obtained by curing the composition obtained by removing the filler of the component (B) from the composition under the same conditions as in the case of obtaining the silicone rubber is measured in the same manner as described above. When the value is Y, the ratio of X to Y [Rz ratio = X / Y] needs to be 1.2 or more, preferably 1.4 or more, and more preferably 2.0 or more. When X / Y is smaller than 1.2, the hole is not sufficiently formed.

また、本発明によって得られたゴム部材の凹穴を有する表面に各種の樹脂、エラストマー、モノマー等で表面処理あるいは表面コートを行うことも有用である。コート厚み数μｍ以下の薄い膜厚コートの場合は、ゴム部材の凹穴を残した表層となり、部材の表面粗さの特徴を残し、またコート厚み数十μｍ以上の膜厚コートの場合でも凹穴のアンカー効果及び接着表面積の増大効果により、強固に接着、密着したコート面を形成することが可能となる。
本発明の電子写真式画像形成用ゴム部材は、トナーブレード、現像ロール、トナー搬送ロール、紙送りロール、中間転写ロール、定着ロール、現像ベルト、中間転写ベルト、定着ベルト用等として好適に用いられる。 It is also useful to perform surface treatment or surface coating with various resins, elastomers, monomers, etc. on the surface of the rubber member obtained by the present invention having a concave hole. In the case of a thin film coat with a coating thickness of several μm or less, it becomes a surface layer with a concave hole in the rubber member, leaving the characteristics of the surface roughness of the member. Due to the anchor effect of the holes and the effect of increasing the adhesion surface area, it is possible to form a coated surface that is firmly adhered and closely adhered.
The rubber member for electrophotographic image formation of the present invention is suitably used for toner blades, developing rolls, toner transport rolls, paper feed rolls, intermediate transfer rolls, fixing rolls, developing belts, intermediate transfer belts, fixing belts, and the like. .

以下、実施例と比較例を示して本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。実施例と比較例において示す部はいずれも質量部を示し、平均粒子径はＪＩＳ Ｒ ６００２に基づいてレーザー回折散乱で測定し、粘度はＪＩＳ Ｋ ６２４９に基づいて測定した２５℃における粘度である。   EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. The parts shown in Examples and Comparative Examples all indicate parts by mass, the average particle diameter is measured by laser diffraction scattering based on JIS R 6002, and the viscosity is a viscosity at 25 ° C. measured based on JIS K 6249.

［実施例１］
ジメチルシロキサン単位９９．８２５モル％及びメチルビニルシロキサン単位０．１５モル％とからなり、分子鎖両末端がジメチルビニルシリル基０．０２５モル％で封鎖された粘度が１×１０7ｍＰａ・ｓのオルガノポリシロキサン１００部、アセチレンブラックであるデンカブラック（４０ｎｍ、電気化学工業（株）製商品名）１２部及び比表面積が２００ｍ2／ｇであるヒュームドシリカ（エアロジル２００、日本アエロジル（株）製）１０部、分散剤として平均重合度３〜１０の両末端シラノールジメチルポリシロキサン重合体２部、充填材として平均粒子径１０μｍ、新モース硬度３．０の粉砕重質炭酸カルシウムＡ（粉体Ａ）４０部を加圧ニーダーを用いて混練した後、このベースコンパウンド１００部に対し硬化剤として２，５−ジメチル−ビス−（２，５−ｔ−ブチルパーオキシ）ヘキサンの２５質量％シリコーンペースト２部を加えてシリコーンゴム組成物を調製した。 [Example 1]
It has a viscosity of 1 × 10 7 mPa · s, comprising 99.825 mol% of dimethylsiloxane units and 0.15 mol% of methylvinylsiloxane units, and having both ends of the molecular chain blocked with 0.025 mol% of dimethylvinylsilyl groups. 100 parts of organopolysiloxane, 12 parts of acetylene black, Denka Black (40 nm, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) and fumed silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) with a specific surface area of 200 m 2 / g ) 10 parts, 2 parts of both-end silanol dimethylpolysiloxane polymer having an average degree of polymerization of 3 to 10 as a dispersant, pulverized heavy calcium carbonate A (powder A) having an average particle diameter of 10 μm and a new Mohs hardness of 3.0 as a filler ) After kneading 40 parts using a pressure kneader, 100 parts of this base compound is 2,5 as a curing agent. A silicone rubber composition was prepared by adding 2 parts of 25% by weight silicone paste of dimethyl-bis- (2,5-t-butylperoxy) hexane.

次に、この組成物を用いて、直径６ｍｍの芯金の周囲に肉厚６ｍｍ、即ち直径１８ｍｍの太さ、長さ５０ｍｍのロール形状と２ｍｍ厚さのシート状に成形した。なお、このときの成形条件はプレスキュアー１７０℃／１５分間、ポストキュアー２００℃／４時間であった。ロールは表面粗さがごく少なくなるようロール研磨機にて５００μｍずつ３回、２５０μｍずつ２回、合計５回に分け、直径が１６ｍｍになるように研磨を行い、その後＃５０００の耐水ペーパーでロールを回転させながら均一に押し付けるようにして表面処理を行い、表面が平滑で、多数の凹穴を有するロールを得た。   Next, this composition was used to form a 6 mm thick metal core around a 6 mm diameter metal core, that is, a 18 mm diameter, 50 mm long roll and a 2 mm thick sheet. The molding conditions at this time were a press cure of 170 ° C./15 minutes and a post cure of 200 ° C./4 hours. The roll is divided into 5 times, 3 times each by 500 μm and 2 times by 250 μm, so that the surface roughness is extremely small, and polished to a diameter of 16 mm, and then rolled with # 5000 water-resistant paper. The surface treatment was performed so as to press evenly while rotating to obtain a roll having a smooth surface and a large number of concave holes.

この時点でロールの表面粗さＲｚをＪＩＳ Ｂ ０６０１−１９９４に準じて１０点平均粗さとして測定した。更に、凹状態を確認するために電子顕微鏡にて表面状態の観察を行った。取得した電子顕微鏡写真より全体の面積における成型物表面の凹んでいる部分の面積比率（％）を求めた。また、厚さ２ｍｍのシートはＪＩＳ Ｋ ６２４９に従い、シートで硬さ（デュロメータタイプＡ）等の測定に用いた。   At this time, the surface roughness Rz of the roll was measured as a 10-point average roughness according to JIS B 0601-1994. Furthermore, in order to confirm the concave state, the surface state was observed with an electron microscope. From the acquired electron micrograph, the area ratio (%) of the concave portion of the surface of the molded product in the entire area was determined. A sheet having a thickness of 2 mm was used for measuring hardness (durometer type A) or the like according to JIS K 6249.

更に、このロールが平均粒子径８μｍの非磁性一成分系トナーを使用する現像ロール用途であることを想定し、現像ロール上のトナーの均一な層形成の目安として８μｍトナーをこのロールに十分にまぶした後、トナー掻き落としブレードとして厚さ０．２ｍｍのＳＵＳ版の両端に０．２ｋｇ荷重をかけて、このロールに押し付け、３０秒間空回転させた後にこのロール上に残ったトナーをセロハンテープで転写してセロハンテープに付着したトナー質量よりトナー搬送性を調べた。セロハンテープに付着したトナー量が０．１ｇ／ｃｍ2以上を○、０．０５ｇ／ｃｍ2以上０．１ｇ／ｃｍ2未満を△、０．０５ｇ／ｃｍ2未満を×とした。また、トナーの濃淡の評価基準は下記の通りである。
セロハンテープのトナーの付着状態
○：目視で透かして見たときに、均一にトナーが付着していて濃淡がない
△：＜５％（全体の）ムラがあるもの
×：５〜２０％（全体の）ムラがあるもの Further, assuming that this roll is used for a developing roll using a non-magnetic one-component toner having an average particle diameter of 8 μm, 8 μm toner is sufficiently added to this roll as a guide for forming a uniform layer of toner on the developing roll. After coating, 0.2 kg load is applied to both ends of a 0.2 mm thick SUS plate as a toner scraping blade, pressed against this roll, and idled for 30 seconds, and then the toner remaining on this roll is removed with cellophane tape. The toner transportability was examined from the toner mass transferred on the cellophane and adhered to the cellophane tape. ○ The amount toner adhering to the cellophane tape 0.1 g / cm 2 or more, 0.05 g / cm 2 or more 0.1 g / cm 2 less than the △, was × less than 0.05 g / cm 2. In addition, the evaluation criteria of the density of the toner are as follows.
The adhesion state of the toner on the cellophane tape ○: The toner adheres uniformly and there is no shading when viewed through the eyes visually. Δ: <5% (overall) unevenness ×: 5-20% (overall) Of) unevenness

［実施例２］
実施例１記載の粉砕炭酸カルシウムＡの代わりに平均粒子径２０μｍ、新モース硬度３．０の粉砕水酸化アルミニウムＢ（粉体Ｂ）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Example 2]
A sheet as in Example 1 except that instead of the pulverized calcium carbonate A described in Example 1, a pulverized aluminum hydroxide B (powder B) having an average particle diameter of 20 μm and a new Mohs hardness of 3.0 was used, Got a roll.

［実施例３］
実施例１記載の粉砕炭酸カルシウムＡの代わりに平均粒子径５０μｍ、新モース硬度２．５の塩化ナトリウムＣ（粉体Ｃ）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Example 3]
Sheets and rolls were obtained in the same manner as in Example 1 except that sodium chloride C (powder C) having an average particle size of 50 μm and a new Mohs hardness of 2.5 was used instead of the pulverized calcium carbonate A described in Example 1. Obtained.

［実施例４］
実施例１記載の粉砕炭酸カルシウムＡの代わりに平均粒子径５μｍ、新モース硬度３．０である軽質合成炭酸カルシウムＤ（粉体Ｄ）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Example 4]
A sheet as in Example 1 except that light synthetic calcium carbonate D (powder D) having an average particle size of 5 μm and a new Mohs hardness of 3.0 was used instead of the ground calcium carbonate A described in Example 1. Got a roll.

［実施例５］
両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン（重合度３００）１００部、エアロジル２００を１部、平均粒子径５μｍ、新モース硬度３．０である軽質合成炭酸カルシウムＤ（粉体Ｄ）４０部、アセチレンブラック（デンカブラックＨＳ−１００、電気化学工業（株）製）５部をプラネタリーミキサーに入れ、３０分間撹拌を続けた後、３本ロールに１回通した。これをプラネタリーミキサーに戻し、架橋剤として、両末端及び側鎖にＳｉ−Ｈ基を有するメチルハイドロジェンポリシロキサン（重合度１７、Ｓｉ−Ｈ基量０．００６０ｍｏｌ／ｇ）２．１部、反応制御剤としてエチニルシクロヘキサノール０．１部、白金触媒（Ｐｔ濃度１質量％）０．１部を添加し、１５分間撹拌を続けてできあがった組成物をシリコーンゴム組成物（１）とした。なお、この組成物（１）の２５℃における粘度は、７８Ｐａ・ｓであった。 [Example 5]
Light synthetic calcium carbonate D (powder D) having 100 parts of dimethylpolysiloxane (degree of polymerization 300) capped with dimethylvinylsiloxy groups at both ends, 1 part of Aerosil 200, average particle diameter of 5 μm and new Mohs hardness of 3.0 ) 40 parts, 5 parts of acetylene black (Denka Black HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.) were put into a planetary mixer and stirred for 30 minutes, and then passed once through three rolls. This was returned to the planetary mixer, and as a crosslinking agent, 2.1 parts of methyl hydrogen polysiloxane having a Si—H group at both ends and side chains (polymerization degree 17, Si—H group amount 0.0060 mol / g), As a reaction control agent, 0.1 part of ethynylcyclohexanol and 0.1 part of platinum catalyst (Pt concentration: 1% by mass) were added, and a composition obtained by continuing stirring for 15 minutes was designated as a silicone rubber composition (1). In addition, the viscosity in 25 degreeC of this composition (1) was 78 Pa.s.

このシリコーンゴム組成物（１）を撹拌終了後３０分以内に１５０℃で５分間プレス硬化し、更に、２００℃で４時間ポストキュアーし、実施例１と同様にロール及び厚さ２ｍｍのシートを得た。   This silicone rubber composition (1) was press-cured at 150 ° C. for 5 minutes within 30 minutes after the completion of stirring, and further post-cured at 200 ° C. for 4 hours. As in Example 1, a roll and a sheet having a thickness of 2 mm were formed. Obtained.

［実施例６］
実施例１記載の粉砕炭酸カルシウムＡ４０部を減量して５部とした以外は実施例１と同様にシート、ロールを得た。 [Example 6]
A sheet and a roll were obtained in the same manner as in Example 1 except that 40 parts of pulverized calcium carbonate A described in Example 1 was reduced to 5 parts.

［実施例７］
実施例１記載の粉砕炭酸カルシウムＡ４０部を減量して２０部とした以外は実施例１と同様にシート、ロールを得た。 [Example 7]
A sheet and a roll were obtained in the same manner as in Example 1 except that 40 parts of pulverized calcium carbonate A described in Example 1 was reduced to 20 parts.

［実施例８］
実施例１記載の粉砕炭酸カルシウムＡ４０部を増量して１００部とした以外は実施例１と同様にシート、ロールを得た。 [Example 8]
A sheet and roll were obtained in the same manner as in Example 1 except that 40 parts of pulverized calcium carbonate A described in Example 1 was increased to 100 parts.

［比較例１］
実施例１記載の粉砕炭酸カルシウムＡを添加しない代わりにゴム硬さを合わせる目的でエアロジル２００を更に１０部添加した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 1]
A sheet and a roll were obtained in the same manner as in Example 1 except that 10 parts of Aerosil 200 was further added for the purpose of matching the rubber hardness instead of adding the pulverized calcium carbonate A described in Example 1.

［比較例２］
実施例５記載の軽質合成炭酸カルシウムＤを添加しない代わりにゴム硬さを合わせる目的でエアロジル２００を更に１０部添加した以外は実施例５と同様にシート、ロールを得た。 [Comparative Example 2]
A sheet and a roll were obtained in the same manner as in Example 5 except that 10 parts of Aerosil 200 was added for the purpose of matching the rubber hardness instead of adding the light synthetic calcium carbonate D described in Example 5.

［比較例３］
実施例１記載の粉砕重質炭酸カルシウムＡの代わりに平均粒子径５．４μｍ、新モース硬度５．５の焼成珪藻土オプライトＷ３００５Ｓ（粉体Ｅ）（オプライト工業製）に変更した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 3]
Example 1 except that it was changed to calcined diatomite Oplite W3005S (powder E) (manufactured by Oplite Industries) having an average particle size of 5.4 μm and a new Mohs hardness of 5.5 instead of the ground heavy calcium carbonate A described in Example 1. Sheets and rolls were obtained in the same manner as above.

［比較例４］
実施例１記載の粉砕重質炭酸カルシウムＡの代わりに平均粒子径４μｍ、２０μｍ以上の粗粒約１％以下であるクリスタライトＶＸ−Ｓ（粉体Ｆ）（（株）龍森製商品名）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 4]
Crystallite VX-S (powder F) having an average particle size of 4 μm and coarse particles having a diameter of 20 μm or more of about 1% or less instead of the ground heavy calcium carbonate A described in Example 1 (trade name, manufactured by Tatsumori Co., Ltd.) A sheet and a roll were obtained in the same manner as in Example 1 except that the use of was used.

［比較例５］
実施例１記載の粉砕重質炭酸カルシウムＡの代わりに平均粒子径２８μｍ、１４０μｍ以上の粗粒約４％以上であるクリスタライトＡ−２（粉体Ｇ）（（株）龍森製商品名）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 5]
Crystallite A-2 (powder G) having an average particle size of 28 μm and coarse particles of 140 μm or more instead of the ground heavy calcium carbonate A described in Example 1 (trade name, manufactured by Tatsumori Co., Ltd.) A sheet and a roll were obtained in the same manner as in Example 1 except that the use of was used.

［比較例６］
実施例１記載の粉砕重質炭酸カルシウムＡの代わりに平均粒子径１０μｍ、５０μｍ以上の粗粒約３％以上である酸化アルミニウムであるアルミナＡＳ−５０（粉体Ｈ）（（株）龍森製商品名）を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 6]
Instead of the ground heavy calcium carbonate A described in Example 1, alumina AS-50 (powder H), which is aluminum oxide having an average particle size of 10 μm and coarse particles of 50 μm or more of about 3% or more (manufactured by Tatsumori Co., Ltd.) A sheet and a roll were obtained in the same manner as in Example 1 except that the product name was changed to using the product name.

［比較例７］
実施例１記載の粉砕重質炭酸カルシウムＡ４０部の代わりに平均粒子径１３μｍ、６５μｍ以上の粗粒約３％以上であるシリコーンゴムパウダーであるＫＭＰ−５９８（粉体Ｉ）（信越化学工業（株）製）２０部を用いることに変更した以外は実施例１と同様にシート、ロールを得た。 [Comparative Example 7]
KMP-598 (powder I) which is a silicone rubber powder having an average particle size of 13 μm and coarse particles of 65 μm or more of about 3% or more instead of 40 parts of pulverized heavy calcium carbonate A described in Example 1 (Shin-Etsu Chemical Co., Ltd.) ) Made) A sheet and roll were obtained in the same manner as in Example 1 except that 20 parts were used.

上記実施例及び比較例の結果を表１，２に示す。また、実施例及び比較例で使用した充填材の特性を表３にまとめて示す。   The results of the above examples and comparative examples are shown in Tables 1 and 2. Table 3 summarizes the characteristics of the fillers used in the examples and comparative examples.

Figure 2007086498
Figure 2007086498

Figure 2007086498
＊１：充填材の平均粒子径に対して５倍以上の粒子径をもつ粗粒の割合
＊２：ＪＩＳ Ｂ ０６０１−１９９４による１０点平均粗さ
＊３：〔（成型物表面の凹んでいる部分の面積）／（表面全体の面積）〕×１００（％）
Figure 2007086498
 * 1: Ratio of coarse particles having a particle diameter of 5 times or more with respect to the average particle diameter of the filler * 2: 10-point average roughness according to JIS B 0601-1994 * 3: [(dent on the surface of the molded product Area of the part) / (area of the entire surface)] × 100 (%)

Figure 2007086498
Figure 2007086498

充填材の平均粒子径に対して５倍以上の粒子径をもつ粗粒の割合の多い充填材はトナーの濃淡が出やすいことがわかる。   It can be seen that the density of the toner tends to appear in the filler having a large proportion of coarse particles having a particle diameter of 5 times or more with respect to the average particle diameter of the filler.

Claims (7)

（Ａ）下記平均組成式（１）
ＲnＳｉＯ(4-n)/2 （１）
（但し、Ｒは置換又は非置換の一価炭化水素基であり、ｎは１．９５〜２．０５の正数である。）
で示されるオルガノポリシロキサン：１００質量部、
（Ｂ）新モース硬度が５．０以下の平均粒子径２〜２００μｍの充填材：５〜２００質量部、及び
（Ｃ）硬化剤：硬化有効量
を含有するシリコーンゴム組成物を硬化することによって得られたシリコーンゴムからなり、該ゴム表面が研磨もしくは面摩耗又は使用環境にて面摩擦されて上記（Ｂ）成分の充填材が粉砕又は脱落することにより、上記ゴム表面に多数の凹穴が形成され、かつ上記シリコーンゴムの凹穴が形成された後の表面粗さ（Ｘ）と上記シリコーンゴム組成物より（Ｂ）成分を除去した組成物を硬化することによって得られたシリコーンゴムの表面粗さ（Ｙ）とのＲｚ比（Ｘ／Ｙ）が１．２以上であることを特徴とする表面に多数の凹穴をもつ電子写真式画像形成用ゴム部材。 (A) The following average composition formula (1)
R n SiO (4-n) / 2 (1)
(However, R is a substituted or unsubstituted monovalent hydrocarbon group, and n is a positive number of 1.95 to 2.05.)
An organopolysiloxane represented by: 100 parts by mass,
(B) By curing a silicone rubber composition containing a filler having an average particle size of 2 to 200 μm having a new Mohs hardness of 5.0 or less: 5 to 200 parts by mass, and (C) a curing agent: an effective amount for curing. It is made of the obtained silicone rubber, and the rubber surface is ground or surface worn or is subjected to surface friction in the use environment, and the filler of the component (B) is crushed or dropped, whereby a large number of concave holes are formed on the rubber surface. The surface of the silicone rubber obtained by curing the composition obtained by removing the component (B) from the surface roughness (X) and the silicone rubber composition after the formation of the concave holes of the silicone rubber. An electrophotographic image forming rubber member having a number of concave holes on a surface thereof, wherein an Rz ratio (X / Y) to roughness (Y) is 1.2 or more. 電子顕微鏡写真において測定した場合、ゴム表面の凹穴部分の合計面積がゴム表面全体の面積の１５％以上である請求項１記載の電子写真式画像形成用ゴム部材。   2. The electrophotographic image-forming rubber member according to claim 1, wherein the total area of the recessed portions on the rubber surface is 15% or more of the total area of the rubber surface when measured in an electron micrograph. （Ｂ）成分が、レーザー回折散乱で測定した充填材の平均粒子径に対して５倍以上の粒子径をもつ充填材の割合が２．３質量％以下になるように調整された粒度分布をもつ充填材であることを特徴とする請求項１又は２記載の電子写真式画像形成用ゴム部材。   (B) The particle size distribution is adjusted so that the proportion of the filler having a particle diameter of 5 times or more with respect to the average particle diameter of the filler measured by laser diffraction scattering is 2.3% by mass or less. 3. The electrophotographic image forming rubber member according to claim 1, wherein the rubber member is a filler. 充填材が、炭酸カルシウム、塩化ナトリウム又は水酸化アルミニウムであり、平均粒子径が２〜７０μｍである請求項１乃至３のいずれか１項記載の電子写真式画像形成用ゴム部材。   The rubber member for electrophotographic image formation according to any one of claims 1 to 3, wherein the filler is calcium carbonate, sodium chloride or aluminum hydroxide and has an average particle diameter of 2 to 70 µm. シリコーンゴム組成物が、更に（Ｄ）導電材を含み、導電性を付与したゴム材料である請求項１乃至４のいずれか１項記載の電子写真式画像形成用ゴム部材。   The rubber member for electrophotographic image formation according to any one of claims 1 to 4, wherein the silicone rubber composition is a rubber material further including (D) a conductive material and imparting conductivity. トナーブレード、現像ロール、トナー搬送ロール、紙送りロール、中間転写ロール、定着ロール、現像ベルト、中間転写ベルト又は定着ベルト用である請求項１乃至５のいずれか１項記載の電子写真式画像形成用ゴム部材。   6. An electrophotographic image forming apparatus according to claim 1, wherein the image forming apparatus is for a toner blade, a developing roll, a toner conveying roll, a paper feeding roll, an intermediate transfer roll, a fixing roll, a developing belt, an intermediate transfer belt or a fixing belt. Rubber member. 請求項６記載の電子写真式画像形成用ゴム部材を有する電子写真式画像形成装置。
An electrophotographic image forming apparatus comprising the electrophotographic image forming rubber member according to claim 6.
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US11415913B2 (en) 2020-05-28 2022-08-16 Canon Kabushiki Kaisha Electrophotographic member and electrophotographic image forming apparatus

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