JPH10219037A - Elastomer composition of medium electroconductivity and electrifying member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject stable composition, remaining economically unchanged in electrical resistance under temperature and/or humidity ambient conditions, and useful for electrifying members, by comparatively blending CHR (epichlorohydrin) rubber as the major ingredient with various lubber elastomers. SOLUTION: This composition comprises CHR rubber as the major ingredient, which is comparatively blended with various rubber elastics, so as to keep its electrical resistance as one of its properties controllable within one order in a medium electroconductivity region (10<2> Ωcm or higher) under an ambient condition (LL, RR or HH). It is preferable that the composition contains 5 to 80 pts.wt. of the rubber elastomers (RP) per 100 pts.wt. of the CHR rubber, and has properties, e.g. a raw rubber Mooney viscosity of 70 or higher [ML1+4 (100 deg.C)] for the whole composition of RP and CHR rubber. Such a composition can be provided with a desired electroconductivity essentially without damaging the inherent properties of the rubber elastomers, and secure good image quality continuously for a number of copies.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は特性として電気抵抗
の中電導性弾性体組成物及びそれを用いた帯電部材に関
し、特には転写用，感光体帯電用或いは搬送や給排紙用
の電子写真用帯電部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medium-conductive elastic composition having a characteristic of electric resistance and a charging member using the same, and more particularly, to an electrophotography for transfer, charging of a photoreceptor, or for conveyance and paper supply / discharge. The present invention relates to a charging member for use.

【０００２】[0002]

【従来の技術】従来、公知の導電性弾性体組成物として
は非導電性の弾性体にポリスチレンスルホン酸，ポリビ
ニ−ルピリジンの金属塩，溶剤中にビニ−ル化合物と置
換させた錯体などの高分子解質のポリエチレングリコ−
ルを主成分とする帯電防止剤を配合したもの及びカ−ボ
ン繊維，カ−ボンブラック粉末，チタンブラック，銀，
銅などの導電性無機粒子，金属粉を配合混合練したもの
が知られている。一方、繊維を用いた導電性組成物につ
いては金属繊維，金属メッキ繊維等特殊な繊維を除いて
通常の天然繊維や合成繊維は上記導電性物質に代るほど
の導電性を有するものはなく、未だ知られていない。そ
して金属繊維や金属メッキ繊維はその比重が大きく、剛
直であること及び耐溶剤性が悪く、且つ高価であるため
に導電性物質として不適当である。又、電子写真用帯電
部材においてその電気抵抗に関する問題がしばしば提起
されている。近年広く普及している小型のレザ−ビ−ム
プリンタ−等の電子写真プリンタ−を例に取ると多くの
場合、感光体として有機光導電体（以下OPCと言う）を
用い、像，露光部を現像する反転現像方法が多く採用さ
れている。この種のプリンタ−用転写装置は装置の小型
化，低電圧の印加で転写が可能でコロナ放電生成物のオ
ゾン発生が少ないこと、紙等の転写材の搬送の安定性が
良いことなどの点から接触式ロ−ラ−転写装置やベルト
転写装置の転写材の搬送の安定性が良いことなどの点か
ら接触式ロ−ラ−転写装置やベルト転写装置が用いられ
ている。2. Description of the Related Art Heretofore, as a known conductive elastic composition, there have been known high-conductivity elastomers such as polystyrene sulfonic acid, a metal salt of polyvinyl pyridine on a non-conductive elastic substance, and a complex in which a vinyl compound is substituted in a solvent. Polyethylene Glyco with molecular degradation
And carbon fiber, carbon black powder, titanium black, silver,
What kneaded and mixed conductive inorganic particles, such as copper, and metal powder is known. On the other hand, as for the conductive composition using fibers, there are no ordinary natural fibers or synthetic fibers except for special fibers such as metal fibers and metal-plated fibers, which have conductivity as much as the conductive material described above. Not yet known. Metal fibers and metal plated fibers have high specific gravity, are rigid, have poor solvent resistance, and are expensive, and are therefore unsuitable as conductive substances. In addition, problems regarding the electrical resistance of the charging member for electrophotography are often raised. Taking an example of an electrophotographic printer such as a small-sized laser beam printer widely used in recent years, in many cases, an organic photoconductor (hereinafter referred to as OPC) is used as a photoconductor, and an image and an exposure unit are used. Are often adopted. This type of transfer device for a printer has the following advantages: the size of the device can be reduced, the transfer can be performed by applying a low voltage, the generation of ozone as a corona discharge product is small, and the transfer stability of a transfer material such as paper is good. A contact roller transfer device and a belt transfer device are used from the viewpoint that the transfer stability of the transfer material of the contact roller transfer device and the belt transfer device is good.

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、前記非
導電性の弾性体に配合混合練したものは、周知の如く中
電導領域では導電フィラ−の添加量に対して抵抗が急に
変化するため導電フィラ−混合時の導電フィラ−の外部
への飛散による損失や分散度合等のわずかの差異が電気
抵抗値の変化として現れる。従って再現性に欠け、量産
安定性に対し問題を抱えている。また可塑剤や低分子量
液体ゴム，界面活性剤等の添加によって中電導性領域で
の安定化が考えられるが、これらの添加剤を使用した場
合、可塑剤や低分子液体状ゴム．．．等が帯電部材の表
面に溢れ出して、それが帯電部材に接触して配置された
感光体に移行し、感光体を汚染してしまう。遂には画像
不良を引き起こすという問題が生じる。又、にじみ出し
により粘着性が著しく増大し、その結果、トナ−や紙粉
が吸着付着し、帯電部材の機能を老化させるという問題
があった。また前記接触型の転写装置において転写材上
に像担持体のトナ−像を良好に転写する時と転写材が非
常に高抵抗である場合（例えば紙，ポリエステルフィル
ム，トランスヘランシ−紙等）強い転写電流が必要であ
る。このような強い転写電界が直接像担持体に印加され
た場合、像担持体には過度の電流が流れ像担持体にダメ
−ジを与え、この現象は、特に小サイズの紙を通紙する
時に顕著になる。これらの問題を解決するために、転写
用帯電部材の抵抗値として中電導性領域（体積固有抵抗
値10²〜10¹⁰Ωcm）が求められている。同様に感光体帯
電接触式帯電装置において導電性の一次帯電部材を用い
た場合の問題点として感光体に流れる電流値が大きく感
光体の寿命が短くなること、感光体上のピンホ−ルが存
在した場合、放電を引き起こし、画像不良を生じること
が知られている。従って転写帯電部材と同様に上記問題
解決するため、一次帯電部材の電気抵抗を中電導性領域
（体積固有抵抗値10²〜10¹⁰Ωcm）とし感光体への流入
電流を制限することによって解決が可能となると考えら
れる。この中電導性領域の抵抗値を持つ材質を得る方法
とし、従来より知られている方法は、先ず導電カ−ボン
のカ−ボンブラック，チタンブラックやグラハイト，金
属粉の銀や銅などの導電フィラ−をゴムや樹脂マトレッ
クスなどの弾性体中に分散させて抵抗を調節する方法が
一般であるが、周知の如く中電導性領域では導電フィラ
−の添加量に対して抵抗が急に変化するため導電フィラ
−混合時の導電フィラ−の外部への飛散による損失や分
散度合等のわずかの差異が電気抵抗値の変化として現れ
る。従って再現性に欠け、量産安定性に対し問題を抱え
ている。また可塑剤や低分子量液体ゴム，界面活性剤等
の添加による中電導性領域での安定化が考えられるが、
これらの添加剤を使用した場合、可塑剤や低分子液体状
ゴム．．．等が帯電部材の表面に溢れ出して、それが帯
電部材に接触して配置された感光体に移行し、感光体を
汚染してしまう。遂には画像不良を引き起こすという問
題が生じる。又、にじみ出しにより粘着性が著しく増大
し、その結果、トナ−や紙粉が吸着付着し、帯電部材の
機能を老化させるという問題があった。However, as is well known, in the medium conductive region, the resistance suddenly changes with respect to the amount of the conductive filler added. A slight difference in loss and dispersion degree due to scattering of the conductive filler to the outside during filler mixing appears as a change in electric resistance value. Therefore, it lacks reproducibility and has a problem with respect to mass production stability. The addition of a plasticizer, a low-molecular-weight liquid rubber, a surfactant or the like can be considered to stabilize the medium-conductivity region. However, when these additives are used, a plasticizer or a low-molecular-weight liquid rubber can be obtained. . . And the like overflows onto the surface of the charging member, and migrates to the photoconductor arranged in contact with the charging member, thereby contaminating the photoconductor. At last, a problem of causing an image defect occurs. In addition, the bleeding significantly increases the tackiness, and as a result, there is a problem that toner and paper dust are adsorbed and adhered to, and the function of the charging member is aged. In the contact type transfer device, when the toner image of the image carrier is transferred well onto the transfer material and when the transfer material has a very high resistance (for example, paper, polyester film, transherency paper, etc.). A strong transfer current is required. When such a strong transfer electric field is directly applied to the image carrier, an excessive current flows through the image carrier and damages the image carrier, and this phenomenon is caused particularly when small-sized paper is passed. Sometimes noticeable. In order to solve these problems, a medium conductive region (a volume specific resistance value of 10 ² to 10 ¹⁰ Ωcm) is required as a resistance value of the transfer charging member. Similarly, when a conductive primary charging member is used in a photoconductor charging contact type charging device, the current flowing through the photoconductor is large, the life of the photoconductor is shortened, and the pinhole on the photoconductor is present. In such a case, it is known that a discharge is caused to cause an image defect. Therefore, similarly to the transfer charging member, the above-mentioned problem can be solved by setting the electric resistance of the primary charging member to a medium conductive region (volume resistivity of 10 ² to 10 ¹⁰ Ωcm) and limiting the inflow current to the photoconductor. It is considered possible. As a method of obtaining a material having a resistance value in the medium conductive region, a conventionally known method is to first use a conductive carbon such as carbon black, titanium black or graphite, or metal powder silver or copper. Generally, the resistance is adjusted by dispersing the filler in an elastic material such as rubber or resin matrix, but as is well known, the resistance suddenly changes in the medium conductive region with respect to the amount of conductive filler added. Therefore, a slight difference such as a loss and a degree of dispersion due to scattering of the conductive filler to the outside when the conductive filler is mixed appears as a change in the electric resistance value. Therefore, it lacks reproducibility and has a problem with respect to mass production stability. In addition, stabilization in the mid-conductivity region can be considered by adding a plasticizer, a low molecular weight liquid rubber, and a surfactant.
When these additives are used, a plasticizer or a low molecular liquid rubber is used. . . And the like overflows onto the surface of the charging member, and migrates to the photoconductor arranged in contact with the charging member, thereby contaminating the photoconductor. At last, a problem of causing an image defect occurs. In addition, the bleeding significantly increases the tackiness, and as a result, there is a problem that toner and paper dust are adsorbed and adhered to, and the function of the charging member is aged.

【０００４】尚、近年電子写真技術に用いたパ−ソナル
ユ−スのプリンタ−，複写機，ファクシミリ−，ATM等
のOA機器に使用されるプラテンロ−ラ−，搬送ロ−ラ−
特に感光体の帯電，現像，転写，給排紙に弾性ゴムロ−
ラ−やベルトを接触帯電法装置内に従来のコロナ帯電法
の装置部品に代って実用化されつつあり、更に公害環境
問題が問われる昨今、オゾンフリ−な帯電，現像，転写
方法として接触帯電法が注目を浴びている。この接触帯
電法はコロナ帯電法の欠点をカバ−する帯電に高圧電源
を必要としない構造でオゾンの発生も微量という特徴を
有することから実用化の検討が活発でロ−ラ−やベルト
など帯電に用いる方法及び帯電ロ−ラ−やベルトの帯電
構造が注目されている。またレザ−ビ−ムプリンタ−，
複写機，ファクシミリ−，ATM等のOA事務機器のロ−ラ
−やベルト機構に使用される帯電部材として表面粗さ，
耐摩耗性，静電気による紙汚れ，紙粉付着の少ない耐オ
ゾン性の優れた非環境汚染性を持つ帯電部材が望まれて
いる。In recent years, platen rollers and transport rollers used in OA equipment such as personal use printers, copiers, facsimile machines, ATMs, etc. used in electrophotographic technology in recent years.
In particular, elastic rubber rollers are used for charging, developing, transferring, and feeding and discharging the photoconductor.
Rollers and belts are being put into practical use instead of the conventional corona charging method parts in the contact charging method apparatus. Furthermore, in recent years when pollution and environmental problems are required, contact charging is used as an ozone-free charging, developing and transferring method. The law is in the spotlight. This contact charging method is a structure that does not require a high-voltage power supply for charging, which covers the drawbacks of the corona charging method, and has the characteristic of generating only a small amount of ozone. And the charging structure of a charging roller and a belt. In addition, a laser beam printer,
As a charging member used for rollers and belt mechanisms of OA office equipment such as copiers, facsimile machines, ATMs, etc.
There is a demand for a non-environmentally polluting charging member that is excellent in abrasion resistance, paper stains due to static electricity, and ozone resistance with little adhesion of paper powder.

【０００５】本発明の目的は上記欠点のない中電導性弾
性体組成物、特に温度湿度環境条件下で電気抵抗値の経
済的に変化しない安定な中電導性弾性体組成物を提供す
ることにあり、他の目的はゴム弾性固有の特徴を実質的
に損なうことなく、該弾性体組成物に導電性を付与せし
め、それを用いて良好な画質の多数枚連続してコピ−が
形成できる帯電部材を提供することを他の目的とする。An object of the present invention is to provide a medium-conductive elastic composition which does not have the above-mentioned disadvantages, and in particular, a stable medium-conductive elastic composition whose electric resistance value does not economically change under temperature and humidity environment conditions. The other purpose is to impart conductivity to the elastic composition without substantially impairing the inherent characteristics of rubber elasticity, and to use the composition to form a continuous copy with good image quality. It is another object to provide a member.

【０００６】[0006]

【課題を解決するための手段】本発明はCHRゴムを主成
分として種々のゴム弾性体を対比ブレンドし、特性とし
て電気抵抗の中電導性領域10²Ωcm以上で環境条件（LL,
RR,HH）下１オ−ダ−コントロ−ルでき、ゴム硬度JISA
70HS以下で普通紙に対する摩擦係数がμ＝0.6以下のOA
事務機器のロ−ラ−やベルト機構に使用される帯電部材
として表面粗さ，耐摩耗性，静電気による紙汚れや紙粉
付着の少ない耐オゾン性の優れた非環境汚染性を持つ中
電導性弾性体組成物及びそれを用いた帯電部材を得る。According to the present invention, various rubber elastomers containing CHR rubber as a main component are contrast-blended, and as a characteristic, a medium resistance region of electric resistance of at least 10 ² Ωcm and environmental conditions (LL,
RR, HH) 1 order control below, rubber hardness JISA
OA with a friction coefficient μ = 0.6 or less against plain paper at 70HS or less
Medium conductivity with excellent surface roughness, abrasion resistance, ozone resistance with little paper stains and paper powder adhesion due to static electricity, and non-environmental pollution as a charging member used in rollers and belt mechanisms of office equipment An elastic body composition and a charging member using the same are obtained.

【０００７】[0007]

【発明の実施の形態】本発明の中電導性弾性体組成物及
びそれを用いた帯電部材はCHRゴムを主成分とし、種々
のゴム弾性体を対比ブレンドし、特性として電気抵抗の
中電導性領域10²Ωcm以上環境条件（LL,RR,HH）下１オ
−ダ−コントロ−ルを特徴とし、更に以下の要件を満た
すことが望ましい。第１には、主成分となるCHRゴムに
種々のゴム弾性体とのRP／CHRで表すブレンド組成比割
合が、5／100〜80／100Wt％範囲であるゴム弾性体組成
物であること。第２には、前記RP／CHRの総和に対して
生ゴムム−ニ−粘度が70以上（ＭＬ1+4 100℃）である
か、或いは可塑剤50Wt％精錬した際、ム−ニ−粘度が60
±１５範囲（ＭＬ1+4 100℃）であるゴム弾性体組成物
であること。第３には、前記RP／CHRの総和に対して２
種以上の酸化物からなる高次化合物で２種以上の金属が
共存してなる金属化合物である複酸化物から選ばれた少
なくとも１種以上の複酸化物を２倍以下精錬配合される
中電導性弾性体組成物であること。第４には、補強材と
してカ−ボンブラックの配合が弾性体RP／CHRの総和に
対して5／100〜50／100Wt％精錬配合される中電導性弾
性体組成物であること。第５には、中電導性弾性体組成
物の体積固有抵抗値10²〜10¹⁰Ωcm以下及びそれを加硫
した帯電部材の表面固有抵抗値10⁶〜10¹²Ωであるこ
と。第６には、帯電部材が電子写真装置や静電記録装置
内の電子写真感光体を均一に帯電させる位置に配置して
感光体転写，帯電，現像，搬送，給排紙の電子写真装置
機構のベルトやロ−ラ−に使用される帯電部材であるこ
と。BEST MODE FOR CARRYING OUT THE INVENTION The medium conductive elastic composition of the present invention and a charging member using the same have a CHR rubber as a main component and various rubber elastic bodies are contrasted and blended. It is characterized by one-order control under an environmental condition (LL, RR, HH) of 10 ² Ωcm or more, and it is desirable to further satisfy the following requirements. First, a rubber elastic body composition in which a blend composition ratio of RP / CHR with various rubber elastic bodies to CHR rubber as a main component is in the range of 5/100 to 80/100 Wt%. Second, the raw rubber has a viscosity of 70 or more (ML1 + 4 100 ° C.) with respect to the sum of RP / CHR, or a viscosity of 60 wt.
A rubber elastic composition having a range of ± 15 (ML1 + 4 100 ° C.). Third, the sum of RP / CHR is 2
Medium conductivity in which at least one or more complex oxides selected from a complex oxide which is a metal compound in which two or more metals coexist in a higher order compound composed of at least two kinds of oxides is refined twice or less. Elastic composite. Fourth, a medium-conductive elastic material composition in which carbon black is blended as a reinforcing material in a ratio of 5/100 to 50/100 Wt% based on the total amount of the elastic materials RP / CHR. Fifth, the volume specific resistance of the medium conductive elastic composition should be 10 ² to 10 ¹⁰ Ωcm or less, and the surface specific resistance of the charging member obtained by vulcanizing the same should be 10 ⁶ to 10 ¹² Ω. Sixth, an electrophotographic apparatus mechanism for transferring, charging, developing, transporting, and feeding / discharging a photoconductor by arranging a charging member at a position for uniformly charging an electrophotographic photoconductor in an electrophotographic apparatus or an electrostatic recording apparatus. Charging member used for a belt or a roller.

【０００８】本発明に使用されるゴム弾性体としてはCH
R（エピクロヒドリンゴム）を主原料として、EPDM（エ
チレンピロピレンジエンポリマ−），BR（ポリブタジエ
ンゴム），NR（天然ゴム），IIR（ポリイソプレンゴ
ム），SBR（スチレンブタジエンゴム），CR（クロロプ
レンゴム），NBR（ニトリルブタジエンゴム），SI（シ
リコンゴム），U（ウレタンゴム）．．．等のゴムやRB
（ブタジエン樹脂），SBR（スチレンブタジエンエラス
トマ−）．．．等のポリスチレン系，ポリオレフィン
系，ポリエステル系，PVC．．．等の熱可塑エラストマ
−やポリウレタン，ポリスチレン，PE（ポリエチレ
ン），PP（ポリプロピレン），PVA（ポリ塩化ビニ−
ル），アクリル系樹脂，スチレン酢酸ビニ−ル共重合
体，ブタジエンアクリルニトリル共重合体等の高分子材
料などを用いることが出来る。また上記弾性体を必要に
応じて5／100〜80／100Wt％の組成比割合で発泡体或い
はソリットゴムとして適用可能である。更に必要に応じ
て炭酸カルシウム，各種クレ−，タルクなど或いはそれ
らのブレンドしたもの，また含水ケイ酸，無水ケイ酸及
びそれぞれの塩等のシリカ系充填剤など一般ゴムに使用
される配合物を添加してもよい。尚、組成比割合が5／1
00Wt％以下になると、電気特性が不安定になり、80／10
0Wt％以上になると、混合物の特性になってしまう。The rubber elastic material used in the present invention is CH
Using R (epichlorohydrin rubber) as a main raw material, EPDM (ethylene pyropyrene diene polymer), BR (polybutadiene rubber), NR (natural rubber), IIR (polyisoprene rubber), SBR (styrene butadiene rubber), CR ( (Chloroprene rubber), NBR (nitrile butadiene rubber), SI (silicone rubber), U (urethane rubber). . . Rubber and RB etc.
(Butadiene resin), SBR (styrene butadiene elastomer). . . Such as polystyrene, polyolefin, polyester, PVC. . . Thermoplastic elastomer such as polyurethane, polystyrene, PE (polyethylene), PP (polypropylene), PVA (polyvinyl chloride)
), An acrylic resin, a polymer material such as styrene vinyl acetate copolymer, butadiene acrylonitrile copolymer, or the like. The elastic body can be applied as a foam or a solit rubber at a composition ratio of 5/100 to 80/100 Wt% as required. Further, if necessary, calcium carbonate, various clays, talc and the like or blends thereof, and compounds used for general rubbers such as silica-based fillers such as hydrous silicic acid, silicic anhydride and respective salts are added. May be. The composition ratio is 5/1
When the content is less than 00 Wt%, the electrical characteristics become unstable,
If it exceeds 0 Wt%, the properties of the mixture will be obtained.

【０００９】以上の他、この種ロ−ラ−が電子写真法の
帯電，現像，転写に使用される場合に現像剤のトナ−離
れを良くするために図１に示すように帯電部材ロ−ラ−
やベルトの外周面に離型剤の良い、例えばテフロン層，
シリコン層，紫外線処理層，化学薬品処理層などを形成
し、外周摩擦係数μ＝0.2〜0.6以内とし、これによりト
ナ−のオフセットを防止することなど可能となる。更に
本発明に係る中電導性領域組成物に発泡剤配合すること
によって電子写真法の帯電，現象，転写に使用される低
硬度性（JISA 20HS〜55HS以下），耐オゾン性，耐候
性，耐熱性，耐寒性に優れ、機械的強度である耐摩耗性
が改善でき、搬送や給排紙パ−ツとしても要求される特
性を全て満足する普通紙に対して高摩擦係数（μ＝1.4
〜2.2処理層無）で耐久性に優れ、且つ紙汚れ，紙粉付
着の少ない安価な中電導性領域の発泡体帯電部材を提供
することも可能となる。発泡剤を用いた場合、発泡剤と
してはA.D.C.A（アゾジカルボナミド）系，D.P.T（ジニ
トロソペンタメチレンテトラミン）系，O.B.S.H（4.4オ
キシビスベンゼンサルフオニルヒドラジド）系，T.S.H
（Pトルエンサルフオニルヒドラジド）系，A.I.B.N（ア
ゾビスイソブチロニトリル）系．．．等を使用すること
ができ、特にA.D.C.A系，O.B.S.H系，ブレンド系では微
細な発泡体で且つ加硫のタイト（架橋密度が高い）な発
泡体が得られる。In addition to the above, when this type of roller is used for charging, developing, and transferring in electrophotography, the charging member roller as shown in FIG. Lar
Or a good release agent on the outer surface of the belt, such as a Teflon layer,
A silicon layer, an ultraviolet treatment layer, a chemical treatment layer, and the like are formed, and the outer peripheral friction coefficient μ is set to 0.2 to 0.6 or less, whereby it is possible to prevent toner offset. Further, by blending a foaming agent with the composition of the middle conductive region according to the present invention, low hardness (JISA 20HS to 55HS or less) used for electrophotography charging, phenomenon and transfer, ozone resistance, weather resistance, heat resistance High friction coefficient (μ = 1.4) for plain paper that has excellent properties and abrasion resistance, which is excellent in heat resistance, cold resistance, and mechanical strength, and satisfies all the characteristics required for conveyance and paper supply / discharge parts.
It is also possible to provide an inexpensive foam charging member in the middle conductive region, which is excellent in durability and has little paper stain and adhesion of paper powder, with no 2.2 treatment layer. When a blowing agent is used, ADCA (azodicarbonamide), DPT (dinitrosopentamethylenetetramine), OBSH (4.4 oxybisbenzenesulfonyl hydrazide), TSH
(P-toluenesulfonylhydrazide), AIBN (azobisisobutyronitrile). . . In particular, ADCA-based, OBSH-based and blend-based foams provide fine foams and vulcanized tight (high crosslink density) foams.

【００１０】本発明のゴム弾性体組成物中に複酸化物を
含有する帯電部材によれば、従来安定しなかった中電導
性領域で安定して且つ再現性良く製造でき、また補強材
や軟化剤をゴム弾性体組成物中に添加することによって
中電導性領域において任意の抵抗値の材料が安定して得
られること、ともに補強性や柔軟性もゴム弾性体に付与
させることができ感光体の帯電に適用した場合には、感
光体に対し粘着性のない充分な接触面、ニップ幅が得ら
れ、良好な帯電特性が得られる。本発明に用いる複酸化
物とは、２種以上の酸化物から成る高次化合物（分子間
結合によって生じた化合物）であって２種以上の金属が
共存している金属酸化物である。複酸化物の製造方法の
一例を挙げると、金属酸化物結晶格子中に１種又は２種
以上異種の金属イオンを分散させて還元領域中で焼成す
る。例えば酸化亜鉛と酸化アルミニウムとの複酸化物の
場合には、酸化亜鉛とアルミニウム塩をアンモニウム塩
水溶液中で処理し脱水処理窒素雰囲気中で焼成して得る
（特公昭62−41171号公報参照）。従って単なる金属酸
化物とは異なる。このような複酸化物としては、例えば
酸化亜鉛（ZnO）と酸化アルミニウム（Al₂O₃）との固溶
体の化合物，酸化錫（SnO₂）と酸化アンチモン（Sb
₂O₃）との固溶体の化合物及び酸化インジウム（In₂O₃）
との固溶体の化合物，酸化マグネシウム（MgO）と酸化
アルミニウム（Al₂O₃）との固溶体の化合物及び酸化鉄
（FeO）と酸化チタン（TiO₂）との固溶体の化合物など
が挙げられる。According to the charging member containing a double oxide in the rubber elastic composition of the present invention, it can be manufactured stably and with good reproducibility in the middle conductive region, which has not been conventionally stable, and can be used as a reinforcing material or a softening material. By adding an agent to the rubber elastic composition, a material having an arbitrary resistance value can be stably obtained in the medium conductive region, and both the reinforcing property and the flexibility can be imparted to the rubber elastic body. When applied to the charging of the photosensitive member, a sufficient contact surface and nip width having no sticking to the photoreceptor can be obtained, and good charging characteristics can be obtained. The double oxide used in the present invention is a higher-order compound (compound generated by intermolecular bonding) composed of two or more kinds of oxides, and is a metal oxide in which two or more kinds of metals coexist. To give an example of a method for producing a double oxide, one or two or more different metal ions are dispersed in a metal oxide crystal lattice and fired in a reduction region. For example, in the case of a double oxide of zinc oxide and aluminum oxide, it can be obtained by treating zinc oxide and aluminum salt in an aqueous solution of ammonium salt and firing in a nitrogen atmosphere for dehydration treatment (see Japanese Patent Publication No. 41171/1987). Therefore, it is different from a mere metal oxide. Examples of such a complex oxide include a solid solution compound of zinc oxide (ZnO) and aluminum oxide (Al ₂ O ₃ ), tin oxide (SnO ₂ ) and antimony oxide (Sb
Compound in solid solution with ₂ O ₃ ) and indium oxide (In ₂ O ₃ )
And a solid solution compound of magnesium oxide (MgO) and aluminum oxide (Al ₂ O ₃ ) and a solid solution compound of iron oxide (FeO) and titanium oxide (TiO ₂ ).

【００１１】このような複酸化物の特徴はそれぞれ金属
原子半径が近く、置換型固溶体を成していること及びそ
れぞれの原子価数が異なることにより各々単独の金属酸
化物では得られない導電性が得られ、これらの複酸化物
の比抵抗値は10¹〜10³Ωcmであり、導電性カ−ボンブラ
ック又はTiO₂や酸化ルチニウムなど（10²〜10⁰Ωcm）よ
り高く、又酸化亜鉛，酸化アルミニウム，酸化アンチモ
ン，酸化インジウム，四三酸化鉄及び酸化錫など（10⁴
Ωcm以上）より低い。即ち本発明の複酸化物の10¹〜10³
Ωcmのフィラ−を使用した場合、物性に問題を生じさせ
ない添加量で安定した中電導性が得られ、再現性及び量
産安定性に優れている。これに対して高分子カ−ボン，
金属等の分散媒に分散させる従来のフィラ−はその比抵
抗が10¹Ωcm未満の場合、先に述べたようにフィラ−の
添加量に対して抵抗値が急変する領域に相当するため再
現性，量産安定性に欠ける。又、10²Ωcmより高い場合
は逆に中電導性を実現させるには、かなり多量の添加量
が必要となり、分散加工が困難になる。仮に分散できた
としても物性は著しく劣り実用レベルに至らない。又硬
度もかなり高くなり感光体等に対して安定した圧接状態
が得られないなどの問題が生じる。又上記複酸化物の中
でも特にZn，Al₂O₃又はSnO₂，Sb₂O₃が優れている。この
理由としてはこのフィラ−の比抵抗が10²〜10³Ωcmと中
電導性領域での抵抗安定性に対して最も理想的な抵抗値
であること、ゴムや樹脂マトレックス等の高分子分散媒
に対して分散が容易であり加工性に優れていること、コ
ストが安価であること、Sb₂O₃のド−ブ量によって適宜
な抵抗値が達成できることなどが挙げられる。ゴム弾性
体組成物中の複酸化物の含有量はRP／CHR弾性体組成物
の総和に対して２倍以下精錬配合させる。特に20Wt％〜
80Wt％が好ましい。The characteristics of such double oxides are that they have a metal atom radius close to each other, form a substitution type solid solution, and have different valence numbers, so that they cannot be obtained by a single metal oxide. is obtained, the resistivity of these composite oxide is 10 ¹ to 10 ³ [Omega] cm, conductive mosquitoes - such as carbon black or TiO ₂ or oxide Ruchiniumu (10 ² ~10 ⁰ Ωcm) higher than, and zinc oxide , Aluminum oxide, antimony oxide, indium oxide, triiron tetroxide and tin oxide (10 ⁴
Ωcm or more). That is, 10 ¹ to 10 ³ of the double oxide of the present invention
When a filler of Ωcm is used, stable medium conductivity can be obtained with an addition amount that does not cause a problem in physical properties, and the reproducibility and mass production stability are excellent. On the other hand, polymer carbon,
Conventional fillers dispersed in a dispersion medium such as metal have a reproducibility when the specific resistance is less than 10 ¹ Ωcm, which corresponds to the area where the resistance value changes abruptly with the amount of filler added as described above. , Lack of mass production stability. On the other hand, if it is higher than 10 ² Ωcm, a considerably large amount of addition is required to realize medium conductivity, and dispersion processing becomes difficult. Even if dispersed, the physical properties are remarkably inferior to the practical level. Further, the hardness becomes considerably high, and there arises a problem that a stable pressure contact state cannot be obtained with respect to the photoreceptor or the like. Among the above-mentioned complex oxides, Zn, Al ₂ O ₃ or SnO ₂ , Sb ₂ O ₃ is particularly excellent. The reason for this is that the specific resistance of this filler is 10 ² to 10 ³ Ωcm, which is the most ideal resistance value for resistance stability in the medium conductive region, and the dispersion of polymers such as rubber and resin matrex It is easy to disperse in a medium and is excellent in workability, the cost is low, and an appropriate resistance value can be achieved by the amount of Sb ₂ O ₃ drive. The content of the double oxide in the rubber elastic body composition is not more than twice as much as the total amount of the RP / CHR elastic body composition. Especially 20Wt% ~
80 Wt% is preferred.

【００１２】補強材としてはカ−ボンブラック，カ−ボ
ン繊維，金属繊維，金属メッキ繊維，ウイスカ−繊維な
ど例えばISAS(intermediate super abrasion furnac
e），SAF（super abrasion furnace），HAF（ハイアブ
レ−ション.ファネスブラック），HAF（fast extrusion
furnace），SRF（semi reinforcing furnace），FT（f
ine thermol），EPC（easy processing channel），MPC
（medium processing channel）などやウイスカ−シリ
カなど適宜用いることができる。カ−ボンブラックを用
いる場合については我々が検討した結果、比抵抗として
は10⁰Ωcm以上、添加量としては5Wt％〜50Wt％、好まし
くは10Wt％〜30Wt％範囲において補強性が優れ、且つ抵
抗が安定することを見出した。即ち比抵抗が10⁰Ωcm未
満であると導電能力が大きく少量の添加でも電位ムラを
引き起こしやすい。又50Wt％を越える添加量になると抵
抗値に対して複酸化物よりカ−ボンブラックによる依存
度が大きく複酸化物添加の意味がなくなる傾向にある。
尚、本発明における粉体の比抵抗は負荷加重100kg/cm²
で25℃×60Rh％温度湿度下で一般的な粉体抵抗値測定法
（JIS）により測定した。また完成したロ−ラ−形状の
帯電部材（１）の寸法は外径Φ16mm×芯金Φ6mm×ゴム
長230mmであった。この時のロ−ラ−電気抵抗値を図５
に示す方法即ち帯電ロ−ラ−基層上に幅10mm箔（２）を
巻き芯金（11）と該アルミ箔（２）間に電源（３）によ
り直流1kwを印加し電流を測定し、芯金（11）とアルミ
箔（２）の抵抗値を計る方法で測定した。Examples of the reinforcing material include carbon black, carbon fiber, metal fiber, metal plated fiber, whisker fiber and the like, for example, ISAS (intermediate super abrasion furnac).
e), SAF (super abrasion furnace), HAF (high abrasion. furnace black), HAF (fast extrusion)
furnace), SRF (semi reinforcing furnace), FT (f
ine thermol), EPC (easy processing channel), MPC
(Medium processing channel) or whisker-silica can be used as appropriate. Ca - the case of using the carbon black results we have examined, specific examples of the resistor 10 ⁰ [Omega] cm or more, 5 wt% 50 wt% The amount added is preferably excellent in reinforcing at 10 Wt% 30 wt% range, and resistance Was found to be stable. That the resistivity is likely to cause a 10 ⁰ potential non-uniformity in small amount larger conductive capacity is less than [Omega] cm. On the other hand, if the addition amount exceeds 50 Wt%, the resistance value is more dependent on carbon black than on the composite oxide, and there is a tendency that the addition of the composite oxide becomes meaningless.
The specific resistance of the powder in the present invention is 100 kg / cm ^{2 under} load.
At 25 ° C. × 60 Rh% temperature and humidity by a general powder resistance value measuring method (JIS). The dimensions of the completed roller-shaped charging member (1) were 16 mm in outer diameter, 6 mm in core metal, and 230 mm in rubber length. The roller electric resistance at this time is shown in FIG.
In other words, a 10 mm wide foil (2) was wound on the charging roller base layer, and a current of 1 kW was applied between the core metal (11) and the aluminum foil (2) by a power source (3) to measure the current. The resistance was measured by measuring the resistance values of gold (11) and aluminum foil (2).

【００１３】図１は本発明の帯電部材の実施例を示す斜
視図、図２は本実施例で使用する電子写真装置の要部構
造を示す説明図、図３は本実施例による電子写真装置を
プリンタ−としてファクシミリ−の要部構成を示すブロ
ック図であり、図４は添加剤の添加量と帯電部材の抵抗
の関係を示したグラフ、図５はロ−ル形状の帯電部材の
抵抗測定を示す説明図である。以下、本発明を実施例に
よって説明するが、本発明はこれにより制約を受けるも
のではない。尚、実施例中の「部」は「重量部」を表
す。FIG. 1 is a perspective view showing an embodiment of a charging member according to the present invention, FIG. 2 is an explanatory view showing a main structure of an electrophotographic apparatus used in the present embodiment, and FIG. 3 is an electrophotographic apparatus according to the present embodiment. FIG. 4 is a block diagram showing a main part of a facsimile as a printer, FIG. 4 is a graph showing the relationship between the amount of additive added and the resistance of the charging member, and FIG. FIG. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited by the examples. In the examples, “parts” represents “parts by weight”.

【００１４】[0014]

【実施例１】以下、本発明を発泡体帯電部材の実施例に
よって説明する。CHR（エピクロマ−HG ダイソ−K.K.
製） 75部とNBR（ニッポ−ルDN101 日本ゼオンK.K.製）
25部を分散ポリマ−として、亜鉛華１号 10部，ステア
リン酸 2部，促進剤BZ（ノクセラ−BZ 大内新興化学K.
K.製） 1部，イオウ 2部，発泡剤（セルマイクC 三協化
成K.K.製） 5部，発泡助剤（セルトンNP 三協化成K.K.
製） 5部，更に補強材と絶縁オイル及びその他表１に基
づくそれぞれの配合組成にて配合し、２本ロ−ルを用い
て均一に分散混合練し、プライマ−を付けた芯金にゴム
押出機にて填入60℃×100kgf/cm²にてベントクロス押出
成型し、これを蒸気加硫缶（160℃×90分）にて加硫
し、放置冷却後、研磨加工することによってロ−ラ−形
状の帯電部材（１）を作製した。そして表１に基づく配
合組成によって作られたものをそれぞれ試作品Ａ〜Ｅと
した。この寸法は芯金Φ6mm×ゴム外径Φ16mm×ゴム長2
30mmであった。尚、抵抗値測定はAL板の上に両端1kg負
荷を加え、芯金とAL板との間の抵抗値を試作品Ａ〜Ｅに
ついて測定した（23℃×65RH％環境室測定）。Embodiment 1 Hereinafter, the present invention will be described with reference to an embodiment of a foam charging member. CHR (Epichroma-HG Daiso-KK
75 parts and NBR (Nippol DN101 made by Nippon Zeon KK)
25 parts of a dispersion polymer, 10 parts of Zinc Hua No. 1, 2 parts of stearic acid, accelerator BZ (Noxera-BZ Ouchi Shinko Chemical K.
K.) 1 part, sulfur 2 parts, foaming agent (Celmic C Sankyo Kasei KK) 5 parts, foaming aid (Celton NP Sankyo Chemical KK)
5 parts, reinforcing material, insulating oil, and other components according to the respective composition shown in Table 1, and uniformly mixed and kneaded using two rolls. Rubber was added to the cored bar with primer. b by extruder vent cross extruded at HamaIri 60 ℃ × 100kgf / cm ² at which the vulcanized by steam vulcanizer (160 ° C. × 90 minutes), allowed to stand cooling, polished A charging member (1) having a labyrinth shape was prepared. And the thing made by the compounding composition based on Table 1 was set as prototype A-E, respectively. This dimension is core metal Φ6mm × rubber outer diameter Φ16mm × rubber length 2
30 mm. The resistance was measured by applying a load of 1 kg to both ends of the AL plate and measuring the resistance value between the core metal and the AL plate for the prototypes A to E (23 ° C. × 65 RH% environment chamber measurement).

【００１５】[0015]

【表１】 帯電部材の試作品 配 合 物 Ａ Ｂ Ｃ Ｄ Ｅ 補強材 HAF カ−ボン #70 (東海カ−ボン製) ４５ ５０ ４５ 補強材 FHF カ−ボン #60 (旭カ−ボン製) ２０ ３０ 絶縁オイル パラフィンオイル 1.0×10¹⁰Ωcm ７０ ６０ ６５ ５５ ４０ ケッチェンブラックEC （ライオン．アクゾ製） 0.1Ωcm 変量 S nO₂，Sb₂O₃複酸化物 （ 石原産業製 4×10²Ωcm） 変量 変量 変量 ZnO ，Al₂O₃（2×10⁶Ωcm） (白水化学製) 変量 [Table 1]Prototype of charging member Compound ABCDDE Reinforcement material HAF carbon # 70 (Tokai Carbon) 45 50 45 Reinforcing material FHF carbon # 60 (Made by Asahi Carbon) 20 30 Insulating oil Paraffin oil1.0 × 10 ¹⁰ Ωcm 70 60 65 55 40 Ketchen Black EC (Lion. Akzo) 0.1Ωcm variableS nO_Two, Sb_TwoO_ThreeDouble oxide( Ishihara Sangyo 4 × 10 ² Ωcm) Variable Variable Variable ZnO, Al_TwoO_Three(2x10⁶Ωcm)(Manufactured by Hakusui Chemical)

【００１６】図４に示す帯電部材である試作品Ａ〜Ｅの
各抵抗値と各フィラ−の添加部数との関係から明らかな
ように、所定の中電導性領域においてSnO₂，Sb₂O₃複酸
化物を添加することによって添加量の変化に対して抵抗
変動が少なく安定していることが判明した。各配合にて
抵抗値の再現性試験を行った結果、導電性カ−ボン（ケ
ッチェンブラックEC）の場合、12PHR添加において10⁹Ω
cmに対してレンジで3オ−ダ−のバラツキ（5×10¹⁰〜5
×10⁸Ωcm）を生じた。これに対してSnO₂，Sb₂O₃複酸化
物の場合、レンジ1/4オ−ダ−（測定値×1.125〜0.87
5）内と測定誤差範囲程度のバラツキであった。又帯電
部材については一般的範囲でZnO，Al₂O₃の添加量を変え
てみても所望の中電導性領域が実現できた。更に補強カ
−ボンと絶縁オイルの比率を変えることによって、より
安定する抵抗値が任意に設定でき、またゴム押出成型の
際、２層（ソリット，スポンジ）上層，下層任意に組合
せることによっても抵抗値の安定が図れることも判明し
た。As is clear from the relationship between the resistance values of the prototypes A to E as charging members shown in FIG. 4 and the number of added parts of each filler, SnO ₂ , Sb ₂ O ₃ in a predetermined medium conductivity region. It was found that by adding the double oxide, the resistance fluctuation was small with respect to the change of the added amount, and it was stable. As a result of resistance value reproducibility test for each formulation, it was found that conductive carbon (Ketjen Black EC) was 10 ⁹ Ω when 12 PHR was added.
3 orders of variation in cm (5 × 10 ^{10 to} 5
× 10 ⁸ Ωcm). On the other hand, in the case of SnO ₂ and Sb ₂ O ₃ double oxide, the range is 1/4 order (measured value × 1.125 to 0.87
5) The variation was within the measurement error range. Also, for the charging member, a desired medium-conductivity region could be realized even if the addition amounts of ZnO and Al ₂ O ₃ were changed within a general range. Further, by changing the ratio between the reinforcing carbon and the insulating oil, a more stable resistance value can be arbitrarily set, and in the case of rubber extrusion molding, it is also possible to arbitrarily combine two layers (solit, sponge) in the upper and lower layers. It was also found that the resistance value could be stabilized.

【００１７】[0017]

【実施例２】本発明の別実施例である発泡体帯電部材に
ついて説明すれば、CHR（ゼクロンCHR 日本ゼオンK.K.
製）65部，EPDM（EPT4045 三井石油化学K.K.製）45部を
分散ポリマ−とし、亜鉛華１号 10部，ステアリン酸 2
部，複酸化物ZnO，Al₂O₃（23K-S 白水化学製） 100部，
促進剤（ノックセラ−M 大内新興化学製） 1部，イオウ
2部，発泡剤（セルマイクC 三協化成製） 5部，発泡助
剤（セルトンNP 三協化成製） 5部，及び補強材であるH
AFカ−ボンブラック 50部，絶縁オイルであるパラフィ
ンオイル 60部の配合組成で前述と同様の製法によりロ
−ラ−形状の帯電部材である試作品No１を作製した。又
HAFカ−ボンブラックを50部，パラフィンオイルを65部
とする以外は試作品No１と同様の配合組成でロ−ラ−形
状の帯電部材である試作品No２を作製した。又HAFカ−
ボンブラックを45部，パラフィンオイル 55部とする以
外は試作品No１と同様の配合組成でロ−ラ−形状の帯電
部材の試作品No３を作製した。又複酸化物ZnO，Al₂O₃ 1
50部，シリコン架橋剤（C8信越化学製） 2部及びAIBM 5
部の配合組成で試作品No１と同様の製法によりロ−ラ−
形状の帯電部材の試作品No４を作製した。また複酸化物
In₂O₃，SnO₂を70部用いる以外は試作品No１と同様にし
てロ−ラ−形状の帯電部材の試作品No５を作製した。又
HAFカ−ボンブラックを20部，パラフィンオイル 70部，
ケッチェンブラックECを20部用いる以外は試作品No１と
同様にしてロ−ラ−形状の帯電部材の試作品No６を作製
した。又複酸化物Al₂O₃を100部用いる以外は試作品No１
と同様にしてロ−ラ−形状の帯電部材の試作品No７を作
製した。このようにして作製したロ−ラ−形状の帯電部
材である試作品No１〜No７の硬度及び電気抵抗値を表２
に示す。[Embodiment 2] A foam charging member according to another embodiment of the present invention will be described with reference to CHR (Zeklon CHR Nippon Zeon KK).
65 parts), EPDM (EPT4045 Mitsui Petrochemical KK) 45 parts as a dispersing polymer, Zinc Hua No. 1 10 parts, stearic acid 2
Parts, double oxide ZnO, Al ₂ O ₃ (23K-S made by Shirasu Chemical) 100 parts,
Accelerator (Knock Cera-M Ouchi Shinko Chemical) 1 part, sulfur
2 parts, 5 parts of foaming agent (Celmic C, manufactured by Sankyo Kasei), 5 parts of foaming aid (Celton NP, manufactured by Sankyo Chemical), and H as a reinforcing material
Prototype No. 1 as a roller-shaped charging member was manufactured by the same manufacturing method as described above with a composition of 50 parts of AF carbon black and 60 parts of paraffin oil as an insulating oil. or
Prototype No. 2 which is a roller-shaped charging member was prepared with the same composition as Prototype No. 1 except that HAF carbon black was 50 parts and paraffin oil was 65 parts. HAF car
Prototype No. 3 of a roller-shaped charging member was produced with the same composition as in Prototype No. 1 except that Bon Black was 45 parts and paraffin oil was 55 parts. Double oxide ZnO, Al ₂ O ₃ 1
50 parts, Silicon crosslinker (C8 Shin-Etsu Chemical) 2 parts and AIBM 5
Roller with the same composition as Prototype No. 1
Prototype No. 4 of a charging member having a shape was produced. Also double oxide
Prototype No. 5 of a roller-shaped charging member was produced in the same manner as in Prototype No. 1 except that 70 parts of In ₂ O ₃ and SnO ₂ were used. or
20 parts HAF carbon black, 70 parts paraffin oil,
Prototype No. 6 of a roller-shaped charging member was produced in the same manner as in Prototype No. 1 except that 20 parts of Ketjen Black EC were used. Prototype No. 1 except for using 100 parts of double oxide Al ₂ O ₃
In the same manner as described above, a prototype No. 7 roller-shaped charging member was produced. Table 2 shows the hardness and electric resistance of the prototypes No. 1 to No. 7, which are roller-shaped charging members produced in this manner.
Shown in

【００１８】[0018]

【表２】 帯電部材の試作品 No１ No２ No３ No４ No５ No６ No７ 硬度アスカ−Ｃ (高分子計器製) ２８ ３０ ３２ ３０ ２８ ３０ ２８ 電気抵抗値 Ω.cm 2×10⁸ 2×10⁸ 4×10⁸ 1×10⁹ 6×10⁸ 1×10⁸ 3×10¹² 画像評価 ◎ ◎ ◎ ○ ○ ×リク ×転写 ◎.耐久１５万通紙後非常に良好画像 ○.良好画像 ×.画像不良[Table 2] Prototype of charging member No1 No2 No3 No4 No5 No6 No7 Hardness Asker C (manufactured by Kobunshi Keiki) 28 30 32 30 28 30 28 Electric resistance Ω.cm 2 × 10 ⁸ 2 × 10 ⁸ 4 × 10 ⁸ 1 × 10 ⁹ 6 × 10 ⁸ 1 × 10 ⁸ 3 × 10 ¹² Image evaluation ◎ ◎ ◎ ○ ○ × Riku × Transfer ◎ Durability Very good image after 150,000 paper passes ○ Good image × Bad image

【００１９】[0019]

【実施例３】次に本発明のソリッド帯電部材及び２層帯
電部材の実施例について説明する。CHR（ゼクロンCHR
日本ゼオン製）を主原料とし他ゴム原料を5／100部，25
／75部，45／65部，85／15部を分散ポリマ−として亜鉛
華１号 5部，ステアリン酸 1部，カ−ボンブラックシ−
スト3 20部，促進剤DM 1.5部，T.T 1部，イオウ 1.5
部，その他表３に基づきそれぞれ配合組成とし、２本ロ
−ルを用いて均一に分散精錬し、プライマ−を塗布した
芯金にクロスベント押出成型機填入し、放置冷却後研磨
加工することによりロ−ラ−形状の帯電部材である試作
品Ａ〜Ｄを作製した。このように作製したロ−ラ−形状
の帯電部材（１）の電気抵抗値の測定方法を図５に示
す。この帯電部材（１）の寸法は外径Φ18mm×芯金Φ8m
m×ゴム長230mmであった。電気抵抗は実施例１と同様方
法，条件で測定した。更に補強カ−ボンの比率を変える
ことにより安定する抵抗値が任意に設定でき、又ゴム押
出成型の際、２層の内１層を異なった硬度或いは抵抗値
の異なった組成物を組合せることによって表層抵抗値の
安定が図れることも判明した。Embodiment 3 Next, an embodiment of a solid charging member and a two-layer charging member of the present invention will be described. CHR (Zeklon CHR
5/100 parts, 25/25
/ 75 parts, 45/65 parts, 85/15 parts as dispersing polymer, zinc flower No. 1 5 parts, stearic acid 1 part, carbon black sea
Strike 3 20 parts, accelerator DM 1.5 parts, TT 1 part, sulfur 1.5
Parts, etc. The composition should be based on Table 3 and the mixture should be uniformly dispersed and refined using two rolls, charged into a core metal coated with a primer, cross-vented by an extruder, left to cool, and then polished. As a result, prototypes A to D as roller-shaped charging members were produced. FIG. 5 shows a method of measuring the electric resistance value of the roller-shaped charging member (1) thus manufactured. The dimensions of this charging member (1) are outer diameter Φ18mm x core metal Φ8m
mx rubber length 230 mm. The electric resistance was measured by the same method and conditions as in Example 1. Furthermore, by changing the ratio of the reinforcing carbon, a stable resistance value can be arbitrarily set. In rubber extrusion molding, one of two layers is combined with a composition having different hardness or resistance value. It was also found that the stabilization of the surface layer resistance value could be achieved.

【００２０】[0020]

【表３】 帯電部材の試作品 配 合 物 Ａ Ｂ Ｃ Ｄ RR／CHR 5／100 25／75 45／65 85／15 補強材 FAF カ−ボン (東海カ−ボン製) １５ １５ １５ １５ ケッチェンブラックEC （ライオン．アクゾ製） 変量 変量 変量 Sb₂O₃，SnO₂複酸化物 （白水化学製） 変量 変量 TiO₂，SnO₂複酸化物(白水化学製) 変量 変量 [Table 3] Prototype mixture of charging members A B C D RR / CHR 5/100 25/75 45/65 85/15 Reinforcement FAF carbon (Tokai Carbon ) 15 15 15 15 Ketjen Black EC (Lion, Akzo) Variable Variable Variable Sb ₂ O ₃ , SnO ₂ complex oxide (manufactured by Shisui Chemical) Variable Variable TiO ₂ , SnO ₂ complex oxide (manufactured by Shisui Chemical) Variable Variable

【００２１】このロ−ラ−形状の帯電部材である試作品
Ａ〜Ｄを図２の上方の帯電ロ−ラ−（１）に使用し、ま
た下方の転写ロ−ラ−（１'）には実施例２の帯電部材
である試作品Ｎｏ１のロ−ラ−を使用して、帯電ロ−ラ
−（１）への電圧印加をAC周波数150Hz,ACピ−ク間電圧
2KV，DC電圧700Vとする以外は実施例２と同様にして画
像出し評価を行ったところ耐久15万枚後も初期と同様の
高画質が得られた。又OPCドラム感光体に直径0.5mm程度
のピンホ−ルを作り温度湿度（LL）15℃×10％，温度湿
度（RR）25℃×60％，温度湿度（HH）32℃×85％の各々
環境条件下で同様にして画像評価を行ったところ３環境
条件下共に帯電ロ−ラ−の表面層及び下地弾性層が通電
破壊を起こすこともなく帯電に必要な充分な帯電電位が
得られた。The prototypes A to D, which are roller-shaped charging members, are used for the upper charging roller (1) in FIG. 2 and for the lower transfer roller (1 '). Using the roller of the prototype No. 1 which is the charging member of the second embodiment, applying a voltage to the charging roller (1) at an AC frequency of 150 Hz and a voltage between AC peaks.
An image output evaluation was performed in the same manner as in Example 2 except that the voltage was 2 KV and the DC voltage was 700 V. As a result, the same high image quality as the initial one was obtained even after 150,000 sheets of durability. A pinhole with a diameter of about 0.5mm is made on the OPC drum photoreceptor. Temperature and humidity (LL) 15 ℃ × 10%, temperature and humidity (RR) 25 ℃ × 60%, temperature and humidity (HH) 32 ℃ × 85% When the image evaluation was performed in the same manner under the environmental conditions, the surface layer and the underlying elastic layer of the charging roller did not break down under all three environmental conditions, and a sufficient charging potential required for charging was obtained. .

【００２２】[0022]

【発明の効果】本発明はこのように構成させたことによ
り、下記に記載する効果を有する。The present invention having the above-described structure has the following effects.

【００２３】請求項１のように主成分となるCHRゴムに
種々のゴム弾性体とのRR／CHRで表すブレンド組成比割
合として5／100〜80／100Wt％範囲であるゴム弾性体組
成物と成すことにより、電気抵抗の中電導性領域の表面
固有抵抗値10⁶〜10¹²Ω、体積固有抵抗値10²〜10¹⁰Ωcm
の中電導の電気部材を得ることが可能となる。A rubber elastic composition according to claim 1, wherein the blend composition ratio of CHR rubber as a main component to various rubber elastic bodies is in the range of 5/100 to 80/100 Wt% as RR / CHR. The surface resistivity of the medium conductive region of the electrical resistance is 10 ⁶ to 10 ¹² Ω, and the volume resistivity is 10 ² to 10 ¹⁰ Ωcm.
It is possible to obtain a medium conductive electric member.

【００２４】請求項２のようにCHRゴムを主成分として
種々のゴム弾性体を対比ブレンドし、RR／CHRの総和に
対して生ゴムム−ニ−粘度が70以上（ＭＬ1+4 100℃）
であるか、或いは可塑剤50Wt％精錬した際、ム−ニ−粘
度が60±15範囲（ＭＬ1+4 100℃）であるゴム弾性体組
成物と成すことにより、弾性体組成物の特性が硬度JISA
70HS以下で、且つ普通紙に対する摩擦係数がμ＝0.2〜
0.6範囲の中電導の電気部材を得ることが可能となる。As described in claim 2, various rubber elastic bodies containing CHR rubber as a main component are contrast-blended, and the raw rubber muny viscosity is 70 or more with respect to the sum of RR / CHR (ML1 + 4 100 ° C.).
Or a rubber elastic composition having a Mooney viscosity in the range of 60 ± 15 (ML1 + 4 100 ° C.) when the plasticizer is refined at 50 Wt%, the characteristic of the elastic composition is hardness. JISA
70HS or less and friction coefficient against plain paper μ = 0.2 ~
It is possible to obtain a medium-conducting electric member in the range of 0.6.

【００２５】請求項３に示すようにCHRゴムを主成分と
して種々のゴム弾性体を対比ブレンドし、RR／CHRの総
和に対して２種以上の酸化物からなる高次化合物で２種
以上の金属が共存してなる金属化合物である複酸化物か
ら選ばれた少なくとも１種以上の複酸化物を２倍以下精
錬配合して中電導性弾性体組成物を得ることにより、請
求項２と同様に弾性体組成物の特性が硬度JISA 70HS以
下で、且つ普通紙に対する摩擦係数がμ＝0.2〜0.6範囲
の中電導の電気部材を得ることが可能となる。According to a third aspect of the present invention, various rubber elastomers are contrast-blended with CHR rubber as a main component, and two or more high-order compounds composed of two or more oxides with respect to the sum of RR / CHR. The same as claim 2 by obtaining a medium conductive elastic composition by refining and compounding at least one or more double oxides selected from multiple oxides which are metal compounds coexisting with the metal. In addition, it is possible to obtain a medium-conducting electric member in which the elastic composition has a hardness of JISA 70HS or less and a friction coefficient against plain paper in the range of μ = 0.2 to 0.6.

【００２６】請求項４に示すようゴム弾性体組成物を加
硫した場合、電気抵抗の中電導性領域の表面固有抵抗値
10⁶〜10¹²Ω、体積固有抵抗値10²〜10¹⁰Ωcmとすること
により、安定した中電導性の帯電部材を得ることが可能
となり、特性として、電気抵抗の中電導性領域10²Ωcm
以上で環境条件（LL,RR,HH）下で１オ−ダ−コントロ−
ル出来る帯電部材が得られる。When the rubber elastic composition is vulcanized as described in claim 4, the surface resistivity of the middle conductive region of the electric resistance
By setting the volume resistivity to 10 ⁶ to 10 ¹² Ω and the volume resistivity to 10 ² to 10 ¹⁰ Ωcm, a stable medium-conductive charging member can be obtained.As a characteristic, the medium conductivity region of the electric resistance is 10 ² Ωcm.
As described above, one order control under environmental conditions (LL, RR, HH).
Thus, a charging member that can be used is obtained.

【００２７】請求項５のように弾性体組成物の特性が硬
度JISA 70HS以下で、且つ普通紙に対する摩擦係数がμ
＝0.2〜0.6範囲とすることにより、良好な表面粗さ，耐
摩耗性，静電気による紙汚れや紙粉付着の少ない耐オゾ
ン性の優れた非環境汚染性を持つ帯電部材を得ることが
可能となる。According to a fifth aspect of the present invention, the elastic composition has a hardness of not more than JISA 70HS and a coefficient of friction against plain paper of μ.
By setting the content in the range of 0.2 to 0.6, it is possible to obtain a non-environmentally-contaminated charging member having excellent surface roughness, abrasion resistance, and excellent ozone resistance with less paper stain and paper powder adhesion due to static electricity. Become.

【００２８】請求項６のように弾性体組成物が電子写真
装置や静電記録装置内の電子写真感光体を均一に帯電さ
せる位置に配置して感光体転写，帯電，現像，搬送，給
排紙の電子写真装置機構のベルトやロ−ラ−に使用する
ことにより、安定した中電導性の帯電部材が得られ、特
性として、電気抵抗の中電導性領域10²Ωcm以上で環境
条件（LL,RR,HH）下で１オ−ダ−コントロ−ル出来る帯
電部材が得られる。また良好な表面粗さ，耐摩耗性，静
電気による紙汚れや紙粉付着の少ない耐オゾン性の優れ
た非環境汚染性を持つ帯電部材が得られるのである。According to a sixth aspect of the present invention, the elastic body composition is disposed at a position where the electrophotographic photosensitive member is uniformly charged in the electrophotographic apparatus or the electrostatic recording apparatus, and the photosensitive element is transferred, charged, developed, transported, and discharged. belts and b paper electrophotographic apparatus mechanism - La - by using the stable electrically conductive charging member in the is obtained, the characteristics, environmental conditions in an electric resistance conductive region 10 ² [Omega] cm or more (LL , RR, HH) can be obtained. In addition, a charging member having good non-environmental pollution with excellent surface roughness, abrasion resistance, and excellent ozone resistance with little paper stain or paper powder adhesion due to static electricity can be obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の実施例の帯電部材を示す斜視図であ
る。FIG. 1 is a perspective view showing a charging member according to an embodiment of the present invention.

【図２】本実施例で使用した電子写真装置の要部構造を
示す説明図である。FIG. 2 is an explanatory diagram illustrating a main structure of the electrophotographic apparatus used in the present embodiment.

【図３】本実施例による電子写真装置をプリンタ−とし
てファクシミリ−の要部構成を示すブロック図である。FIG. 3 is a block diagram illustrating a main configuration of a facsimile using the electrophotographic apparatus according to the present embodiment as a printer.

【図４】添加剤の添加量と帯電部材の抵抗の関係を示し
たグラフである。FIG. 4 is a graph showing the relationship between the amount of additive and the resistance of the charging member.

【図５】ロ−ル形状の帯電部材の抵抗測定を示す説明図
である。FIG. 5 is an explanatory diagram showing resistance measurement of a roll-shaped charging member.

【符号の説明】[Explanation of symbols]

１ 帯電部材 11 導電性基本 12 弾性体 1 Charging member 11 Basic conductivity 12 Elastic body

─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成９年２月１４日[Submission date] February 14, 1997

【手続補正１】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００１５[Correction target item name] 0015

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００１５】[0015]

【表１】 [Table 1]

【手続補正２】[Procedure amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００１８[Correction target item name] 0018

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００１８】[0018]

【表２】 ◎.耐久１５万通紙後非常に良好画像 ○.良好画像 ×.画像不良[Table 2] ◎ .Durable very good image after 150,000 passes ○ .Good image × .Poor image

【手続補正３】[Procedure amendment 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００２０[Correction target item name] 0020

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００２０】[0020]

【表３】 [Table 3]

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 主成分となるCHRゴムに種々のゴム弾性
体とのRP／CHRで表すブレンド組成比割合が、5／100〜8
0／100Wt％範囲であるゴム弾性体組成物から成る中電導
性弾性体組成物。1. A blend composition ratio of RP / CHR with various rubber elastic bodies to CHR rubber as a main component is from 5/100 to 8/100.
A medium conductive elastic composition comprising a rubber elastic composition in the range of 0/100 Wt%. 【請求項２】 CHRゴムを主成分として種々のゴム弾性
体を対比ブレンドし、前記RP／CHRの総和に対して生ゴ
ムム−ニ−粘度が70以上（ＭＬ1+4 100℃）であるか、
或いは可塑剤50Wt％精錬した際、ム−ニ−粘度が60±15
範囲（ＭＬ1+4100℃）であるゴム弾性体組成物から成る
中電導性弾性体組成物。2. A rubber blend containing various kinds of rubber as a main component comprising a CHR rubber as a main component, and a raw rubber membrane viscosity of 70 or more (ML1 + 4 100 ° C.) with respect to the sum of the RP / CHR,
Alternatively, when the plasticizer is refined at 50% by weight, the Mooney viscosity is 60 ± 15.
A medium conductive elastic composition comprising a rubber elastic composition having a temperature range (ML1 + 4100 ° C.). 【請求項３】 CHRゴムを主成分として種々のゴム弾性
体を対比ブレンドし、前記RP／CHRの総和に対して２種
以上の酸化物からなる高次化合物で２種以上の金属が共
存してなる金属化合物である複酸化物から選ばれた少な
くとも１種以上の複酸化物を２倍以下精錬配合されて成
る中電導性弾性体組成物。3. A blend of various rubber elastomers containing a CHR rubber as a main component and a high-order compound composed of two or more oxides with respect to the sum of RP / CHR, wherein two or more metals coexist. A medium conductive elastic composition comprising at least one compound oxide selected from compound oxides, which is a metal compound, which is refined and blended twice or less. 【請求項４】 前記ゴム弾性体組成物を加硫した場合、
電気抵抗の中電導性領域の表面固有抵抗値10⁶〜10
¹²Ω、体積固有抵抗値10²〜10¹⁰Ωcmとなる請求項１又
は２記載の中電導性弾性体組成物を用いた帯電部材。4. When the rubber elastic composition is vulcanized,
Surface resistivity of medium conductivity region of electrical resistance 10 ⁶ to 10
¹² Omega, volume resistivity becomes 10 ² to 10 ¹⁰ [Omega] cm claim 1 or 2 charging member using the conductive elastic body composition in the description. 【請求項５】 前記弾性体組成物の特性が硬度JISA 70H
S以下で、且つ普通紙に対する摩擦係数がμ＝0.2〜0.6
範囲である請求項１、２又は３記載の中電導性弾性体組
成物を用いた帯電部材。5. The elastic body composition has a hardness of JISA 70H.
S or less, and the friction coefficient against plain paper is μ = 0.2 to 0.6
The charging member using the medium conductive elastic composition according to claim 1, wherein the charging member is in a range. 【請求項６】 前記弾性体組成物が電子写真装置や静電
記録装置内の電子写真感光体を均一に帯電させる位置に
配置して感光体転写，帯電，現像，搬送，給排紙の電子
写真装置機構のベルトやロ−ラ−に使用される請求項
１、２、３又は４記載の中電導性弾性体組成物を用いた
帯電部材。6. The image forming apparatus according to claim 1, wherein said elastic composition is disposed at a position for uniformly charging an electrophotographic photoreceptor in an electrophotographic apparatus or an electrostatic recording apparatus. The charging member according to claim 1, 2, 3 or 4, which is used for a belt or a roller of a photographic apparatus mechanism.