JPH07113050A - Semi-conducting high polymer elastic member - Google Patents
Semi-conducting high polymer elastic memberInfo
- Publication number
- JPH07113050A JPH07113050A JP16427194A JP16427194A JPH07113050A JP H07113050 A JPH07113050 A JP H07113050A JP 16427194 A JP16427194 A JP 16427194A JP 16427194 A JP16427194 A JP 16427194A JP H07113050 A JPH07113050 A JP H07113050A
- Authority
- JP
- Japan
- Prior art keywords
- electric resistance
- resistance
- roller
- polymer elastic
- elastic member
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Rolls And Other Rotary Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dry Development In Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、帯電防止機能を有する
包装部材や衝撃吸収部材、電子写真プロセス等で利用す
る半導電性高分子弾性部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material having an antistatic function, a shock absorbing material, a semiconductive polymer elastic material used in an electrophotographic process and the like.
【従来の技術】近年、電子技術の進歩に伴い電子部品を
保護するため包装材及び衝撃吸収材の帯電防止技術に対
する要求が高まっている。又、電子写真技術の進歩に伴
い乾式電子写真装置の転写材、トナーに対する接触帯電
部材として半導電性弾性ローラが注目されており、現像
ローラ、転写ローラ等に用いられている。半導電性弾性
ローラは、従来より用いられているコロトロン帯電器と
比較して、転写材等に対して低い電源電圧で必要な帯電
量が与えられるという利点がある。これらの目的に用い
られる弾性ローラには、通常ゴム・ウレタン等の高分子
エラストマーや高分子フォーム材料が用いられ、これに
カーボンブラック等の導電材を配合して所望の導電性を
付与したものが使用されていた。2. Description of the Related Art In recent years, with the progress of electronic technology, there is an increasing demand for antistatic technology for packaging materials and shock absorbing materials in order to protect electronic parts. Further, with the progress of electrophotographic technology, a semi-conductive elastic roller has been attracting attention as a transfer charging member for a dry electrophotographic apparatus and a contact charging member for toner, and is used as a developing roller, a transfer roller or the like. The semiconductive elastic roller has an advantage that a necessary charge amount can be given to a transfer material or the like at a low power supply voltage, as compared with a conventionally used corotron charger. For the elastic roller used for these purposes, a polymer elastomer such as rubber or urethane or a polymer foam material is usually used, and a material to which a conductive material such as carbon black is added to give a desired conductivity is used. Had been used.
【０００２】このような用途に用いられる半導電性部材
は所定の電気抵抗値であるのみならず、電気抵抗の位置
ばらつきが少なく、かつ電気抵抗の印加電圧依存性が少
なく、かつ連続して通電した際の電気抵抗の変動幅が少
ないことが必要である。The semiconductive member used for such an application not only has a predetermined electric resistance value, but also has a small variation in the position of the electric resistance, a small dependence of the electric resistance on the applied voltage, and a continuous electric current. It is necessary that the fluctuation range of the electric resistance at the time of performing is small.
【０００３】[0003]
【発明が解決しようとする課題】カーボンブラック等の
混入により電子写真プロセスに必要な１×１０5 〜１×
１０10［Ωｃｍ］という中抵抗領域で抵抗値を一定に製
造することは困難であり、又、金属や金属酸化物の粉末
やウイスカー及び／又はカーボンブラック等のフィラー
を混入することにより所定の抵抗値に調整した高分子エ
ラストマーや高分子フォーム等の高分子部材は、電気抵
抗の位置ばらつきが大きく、電気抵抗の測定電圧依存性
が大きいという問題点があった。Problems to be Solved by the Invention 1 × 10 5 to 1 × required for an electrophotographic process due to inclusion of carbon black or the like
It is difficult to produce a constant resistance value in the medium resistance region of 10 10 [Ωcm], and a predetermined resistance can be obtained by mixing a powder of metal or metal oxide, whiskers and / or filler such as carbon black. A polymer member such as a polymer elastomer or polymer foam adjusted to a value has a problem in that the electric resistance has a large variation in position and the electric resistance has a large dependence on the measured voltage.
【０００４】そこで、過塩素酸ナトリウム等の如きイオ
ン導電性物質を混入することにより中抵抗領域で抵抗一
定のローラを製造している。ところが、このようなロー
ラを長時間通電状態で運転し続けると漸次抵抗が増大し
ていき、電子写真用途に用いた場合は画像不良を引き起
こすという問題点があった。従って、本発明はかかる従
来の半導電性弾性材料の欠点を解決し、上述した諸特性
を兼備した半導電性弾性部材を提供することを目的とす
る。Therefore, a roller having a constant resistance in the medium resistance region is manufactured by mixing an ion conductive material such as sodium perchlorate. However, when such a roller is continuously operated for a long time in an energized state, the resistance gradually increases, and when used for electrophotography, there is a problem that an image defect occurs. Therefore, an object of the present invention is to solve the drawbacks of the conventional semiconductive elastic material and to provide a semiconductive elastic member having the above-mentioned various properties.
【０００５】[0005]
【課題を解決するするための手段】本発明者等は、上記
目的を達成するために鋭意検討を重ねた結果、電気抵抗
が温度１５〜２８℃、相対湿度１０〜８５％において測
定電圧１０〜５０００Ｖの範囲で１×１０5 〜１×１０
10［Ωｃｍ］であり、上記電気抵抗の位置ばらつきが±
２０％以下であり、かつ連続通電した時の電気抵抗が初
期抵抗の５倍未満であることを特徴とする半導電性高分
子弾性部材として得られることを見出し本発明をなすに
至った。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, have found that the electric resistance is 15 to 28 ° C. and the relative voltage is 10 to 85%. 1 × 10 5 to 1 × 10 in the range of 5000 V
10 [Ωcm], and the positional variation of the electric resistance is ±
The present invention was found to be obtained as a semiconductive polymer elastic member characterized by having an electric resistance of 20% or less and being less than 5 times the initial resistance when continuously energized.
【０００６】従って、本発明は、電気抵抗が測定電圧１
０〜５０００Ｖの範囲で１×１０5〜１×１０10［Ωｃ
ｍ］であり、かつ電気抵抗の位置ばらつきが±２０％以
下であり、かつ電気抵抗の測定電圧依存性が測定電圧１
０〜５０００の範囲で±２０％以下であり、かつ連続通
電時の電気抵抗が初期抵抗の５倍未満であることを特徴
とする半導電性高分子部材を提供する。Therefore, according to the present invention, the electric resistance is 1
1 × 10 5 to 1 × 10 10 [Ωc in the range of 0 to 5000 V
m], the positional variation of the electric resistance is ± 20% or less, and the measured voltage dependence of the electric resistance is the measured voltage 1
Provided is a semiconductive polymer member characterized in that it is ± 20% or less in the range of 0 to 5,000, and the electric resistance during continuous energization is less than 5 times the initial resistance.
【０００７】ここで、連続通電の条件に制限はないが、
通常の実験では温度２８℃、相対湿度８５％の環境で＋
１０００Ｖの電圧を８時間連続して印加した後、実験前
の抵抗と実験後の抵抗を比較評価する方法や、同様の環
境下で２μＡの電流を８時間連続して印加した後、実験
前の抵抗と実験後の抵抗を比較評価する方法が用いられ
る。Here, there is no limitation on the condition of continuous energization,
In a normal experiment, the temperature is 28 ° C and the relative humidity is 85%.
After applying a voltage of 1000 V for 8 hours continuously, a method of comparing and evaluating the resistance before the experiment and the resistance after the experiment, or after applying a current of 2 μA for 8 hours continuously under the same environment, A method of comparing and evaluating the resistance and the resistance after the experiment is used.
【０００８】以下、本発明について更に詳しく説明す
る。本発明似係る半導電性高分子弾性部材は、電気抵抗
が 測定電圧１０〜５０００Ｖの範囲において１×１０
5 〜１×１０10［Ωｃｍ］以下であり、かつ電気抵抗の
位置ばらつきが±２０％以下、好ましくは±１０％以下
であり、かつ電気抵抗の測定電圧依存性が測定電圧１０
〜５０００Ｖの範囲で±２０％以下であり、かつ連続通
電時の電気抵抗が初期抵抗の５倍未満、好ましくは４倍
以下であるものである。The present invention will be described in more detail below. The semiconductive polymer elastic member according to the present invention has an electric resistance of 1 × 10 in the range of measurement voltage of 10 to 5000V.
5 to 1 × 10 10 [Ωcm] or less, the positional variation of the electric resistance is ± 20% or less, preferably ± 10% or less, and the measured voltage dependence of the electric resistance is the measured voltage 10.
It is ± 20% or less in the range of up to 5000 V, and the electric resistance during continuous energization is less than 5 times the initial resistance, preferably 4 times or less.
【０００９】本発明で使用される高分子物質としては、
ポリヒドロキシル化合物とポリイソシアネート化合物と
を混合して加熱硬化させる一般的な方法により得ること
ができる。この場合、ポリヒドロキシル化合物として
は、一般の軟質ポリウレタンフォームやエラストマーの
製造に用いられるポリオール、即ち末端にポリヒドロキ
シル基を有するポリエーテルポリオール、ポリエステル
ポリオール、及び両者の共重合物であるポリエーテルポ
リオール等が挙げられるほか、ポリオール中にエチレン
性不飽和単量体を重合させて得られる所謂ポリマーポリ
オール等の一般的なポリオールが使用できる。The polymeric substance used in the present invention includes:
It can be obtained by a general method in which a polyhydroxyl compound and a polyisocyanate compound are mixed and heat-cured. In this case, as the polyhydroxyl compound, a polyol used in the production of general flexible polyurethane foams and elastomers, that is, a polyether polyol having a polyhydroxyl group at the terminal, a polyester polyol, and a polyether polyol which is a copolymer of the both, etc. In addition to the above, general polyols such as so-called polymer polyols obtained by polymerizing an ethylenically unsaturated monomer in the polyol can be used.
【００１０】上記ポリエーテルポリオール、ポリエステ
ルポリオール、ポリテトラメチレンエーテルグリコール
等の親水性ポリオールを構成成分として含む親水性ウレ
タン基材を主として用いることが好ましい。ここでポリ
イソプレン・ポリオールやポリブタジエン・ポリオー
ル、水素添加ポリブタジエン・ポリオールの如き疎水性
ポリオールを主体として用いると、要求を満足するよう
な導電性を付与することが困難である。It is preferable to mainly use a hydrophilic urethane base material containing a hydrophilic polyol such as the above polyether polyol, polyester polyol or polytetramethylene ether glycol as a constituent component. If a hydrophobic polyol such as polyisoprene polyol, polybutadiene polyol, or hydrogenated polybutadiene polyol is used as the main component, it is difficult to impart conductivity that satisfies the requirements.
【００１１】ポリイソシアネート化合物としては、同様
に一般的な軟質ポリウレタンフォームやエラストマーの
製造に用いられるポリイソシアネート、即ちトリレンジ
イソシアネート（ＴＤＩ）、粗製ＴＤＩ、４，４−ジフ
ェニルメタンジイソシアネート（ＭＤＩ）、粗製ＭＤ
Ｉ、炭素数２〜１８の脂肪族ポリイソシアネート、炭素
数４〜１５の脂環式ポリイソシアネート、及びこれらポ
リイソシアネートの混合物や変性物、例えば部分的にポ
リオール類と反応させて得られるプレポリマー等が用い
られる。As the polyisocyanate compound, similarly, polyisocyanates used for producing general flexible polyurethane foams and elastomers, that is, tolylene diisocyanate (TDI), crude TDI, 4,4-diphenylmethane diisocyanate (MDI) and crude MD are used.
I, aliphatic polyisocyanate having 2 to 18 carbon atoms, alicyclic polyisocyanate having 4 to 15 carbon atoms, and mixtures and modified products of these polyisocyanates, for example, prepolymers obtained by partially reacting with polyols, etc. Is used.
【００１２】また、上記導電剤として用いられる有機イ
オン性物質については、具体的には陽イオン性界面活性
剤として、ラウリルトリメチルアンモニウムクロライ
ド、ステアリルトリメチルアンモニウムクロライド、オ
クタデシルトリメチルアンモニウムクロライド、ドデシ
ルトリメチルアンモニウムクロライド、ヘキサデシルト
リメチルアンモニウムクロライド、変性脂肪族ジメチル
エチルアンモニウムエトサルフェート等が、両性イオン
界面活性剤として、ラウリルベタイン、ステアリルベタ
イン、ジメチルアルキルラウリルベタイン等、そして、
過塩素酸テトラエチルアンモニウム、過塩素酸テトラブ
チルアンモニウム、ホウフッ化テトラブチルアンモニウ
ム、ホウフッ化テトラエチルアンモニウム、塩化テトラ
ブチルアンモニウム等の第４級アンモニウム塩が例示さ
れる。なお、これらの中では、ラウリルトリメチルアン
モニウムクロライド、ステアリルトリメチルアンモニウ
ムクロライド、オクタデシルトリメチルアンモニウムク
ロライド、ドデシルトリメチルアンモニウムクロライ
ド、ヘキサデシルトリメチルアンモニウムクロライド、
変性脂肪族ジメチルエチルアンモニウムエトサルフェー
ト等の陽イオン性界面活性剤、過塩素酸テトラブチルア
ンモニウム、ホウフッ化テトラブチルアンモニウム等の
第４級アンモニウム塩が特に好ましく用いられる。Regarding the organic ionic substance used as the conductive agent, specifically, as the cationic surfactant, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, Hexadecyltrimethylammonium chloride, modified aliphatic dimethylethylammonium ethosulfate, etc., as a zwitterionic surfactant, lauryl betaine, stearyl betaine, dimethylalkyl lauryl betaine, etc., and,
Examples thereof include quaternary ammonium salts such as tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetrabutylammonium borofluoride, tetraethylammonium borofluoride and tetrabutylammonium chloride. Among these, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride,
A cationic surfactant such as modified aliphatic dimethylethylammonium ethosulfate and a quaternary ammonium salt such as tetrabutylammonium perchlorate and tetrabutylammonium borofluoride are particularly preferably used.
【００１３】前記の基材に上記の各種の有機イオン性物
質を混合することにより、体積固有抵抗を１×１０5 〜
１×１０10［Ωｃｍ］という中抵抗領域に調整すること
が可能となる。また、これらをフォーム状に発泡体とす
ることも好ましい。発泡させる場合の発泡方法に制限は
ないが、発泡剤を混入使用する方法や機械的な撹拌によ
り気泡を混入する方法が好ましく用いられる。By mixing the above-mentioned various organic ionic substances with the above-mentioned substrate, the volume resistivity is 1 × 10 5 to
It becomes possible to adjust to a medium resistance region of 1 × 10 10 [Ωcm]. It is also preferable to make these into foams. The foaming method for foaming is not limited, but a method of mixing and using a foaming agent or a method of mixing bubbles by mechanical stirring is preferably used.
【００１４】ウレタンの製造方法に制限はないが、ポリ
エーテルポリオール、ポリエステルポリオール、ポリテ
トレメチレンエーテルグリコール、グリセリンにポリエ
チレンオキサイドやポリプロピレンオキサイドを付加重
合したポリオール、エチレングリコール、プロパンジオ
ール、ブタンジオール等の親水性鎖延長剤とトリレンジ
イソシアネート（ＴＤＩ）、ジフェニルメタンジイソシ
アネート（ＭＤＩ）、粗製ジフェニルメタンジイソシア
ネート（クルードＭＤＩ）、ウレトンイミン変性ＭＤ
Ｉ、イソホロンジイソシアネート等の架橋剤を、導電性
付与のために、本発明において必須として添加する第４
級アンモニウム塩、及び必要に応じてカーボンブラック
等の補強剤、架橋反応触媒等と共に混合した後、加熱硬
化させる方法が好ましく用いられる。There is no limitation on the method for producing urethane, but hydrophilic properties such as polyether polyol, polyester polyol, polytetremethylene ether glycol, polyol obtained by addition-polymerizing polyethylene oxide or polypropylene oxide to glycerin, ethylene glycol, propanediol, butanediol, etc. Chain extender and tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate (crude MDI), uretonimine modified MD
I, a cross-linking agent such as isophorone diisocyanate is added as an essential component in the present invention in order to impart conductivity.
A method of mixing with a secondary ammonium salt and, if necessary, a reinforcing agent such as carbon black, a crosslinking reaction catalyst and the like and then heating and curing is preferably used.
【００１５】本発明の主な利用分野である電子写真用導
電性ローラは、現像、転写等の各ローラーとして好適に
用いられるが、これらの用途に限定されるものではな
く、帯電／除電操作を行なうための部材であればいずれ
のものにも適用できる。また、その形態も、図１に示し
たローラ状に限定されるものではなく、例えば、ブラシ
状、プレート状、ブロック状その他の形態であっても良
い。通常、鉄にメッキを施した、或はステンレス等の芯
金を本発明の導電性材料で被覆したものであり、用途に
より更にその外側を導電性及び／又は半導電性及び／又
は絶縁性の塗料により塗装しても良く、要は用途の応じ
て導電性ローラー層の表面に保護皮膜を形成したり、該
ローラー層を複数層に形成することも出来る。いずれに
しても電子写真用導電性ローラーに使用される半導電性
弾性部材は、通常、１×１０5 〜１×１０10［Ωｃｍ］
という中抵抗領域で安定な抵抗値を示すものである。The electrophotographic conductive roller, which is the main field of application of the present invention, is suitably used as each roller for development, transfer, etc., but is not limited to these applications, and charging / discharging operations can be performed. Any member can be applied as long as it is a member for performing. Further, the form thereof is not limited to the roller form shown in FIG. 1, and may be, for example, a brush form, a plate form, a block form or the like. Usually, iron is plated, or a cored bar of stainless steel or the like is coated with the conductive material of the present invention, and the outer side of the cored bar is made conductive and / or semiconductive and / or insulating depending on the application. It may be coated with a paint, and in short, a protective film may be formed on the surface of the conductive roller layer, or a plurality of roller layers may be formed depending on the application. In any case, the semiconductive elastic member used for the electrophotographic conductive roller is usually 1 × 10 5 to 1 × 10 10 [Ωcm].
That is, it shows a stable resistance value in the medium resistance region.
【００１６】本導電性ローラを用いた転写装置の一例を
説明すると、芯金（図示せず）を具備したローラ状基体
（導電性ローラ）１を、感光体ドラム等の被帯電体２に
紙等の転写材４を介して当接させ、この転写部材１と被
帯電体２との間に電源３により電圧を印加し、被帯電体
と転写部材間に電界を発生させることによって、被帯電
体２上のトナー等の現像剤を転写材に転写するものであ
る。本半導電性部材を複写機等の電子写真装置に組み込
む場合は、静電画像現像部、トナー又は現像材転写部等
に応用される。ここで、従来より用いられていたイオン
導電性物質として過塩素酸リチウム、過塩素酸ナトリウ
ム、過塩素酸カルシウムの如き無機塩を添加したウレタ
ン製導電性ローラに、所定の電圧が電源３によって印加
されるが、連続的に同極性電位に保たれたまま運転を継
続した場合、導電性ローラの抵抗が上昇し、所定の電流
を通電せしめる場合に相当の高電位を印加しなくてはな
らなくなり、しいては所定電流量が確保できない状況に
陥る場合があった。An example of a transfer device using the present conductive roller will be described. A roller-shaped substrate (conductive roller) 1 provided with a cored bar (not shown) is applied to a charged body 2 such as a photosensitive drum. And the like, and a voltage is applied between the transfer member 1 and the member 2 to be charged by a power source 3 to generate an electric field between the member to be charged and the member to be charged, thereby charging the member to be charged. A developer such as toner on the body 2 is transferred to a transfer material. When the semiconductive member is incorporated in an electrophotographic apparatus such as a copying machine, it is applied to an electrostatic image developing section, a toner or developer transfer section, or the like. Here, a predetermined voltage is applied by a power source 3 to a urethane conductive roller to which an inorganic salt such as lithium perchlorate, sodium perchlorate, or calcium perchlorate has been added as an ion conductive substance that has been conventionally used. However, if the operation is continued while the potential of the same polarity is continuously maintained, the resistance of the conductive roller rises, and it is necessary to apply a considerably high potential when energizing a predetermined current. However, in some cases, the predetermined current amount could not be secured.
【００１７】この抵抗上昇に関するメカニズムは必ずし
も明確ではないが、本ローラは過塩素酸リチウム、過塩
素酸ナトリウム、過塩素酸カルシウム、ホウフッ化リチ
ウムの如き塩の添加により導電性を発現させており、同
極性連続印加がなされると、このイオン性物質の解離・
分極が起こり、電流が流れにくくなるために抵抗が上昇
するものと考えられる。Although the mechanism relating to this increase in resistance is not always clear, this roller develops conductivity by the addition of salts such as lithium perchlorate, sodium perchlorate, calcium perchlorate and lithium borofluoride. When the same polarity is continuously applied, this ionic substance dissociates and
It is considered that the resistance rises because polarization occurs and the current hardly flows.
【００１８】実際、後述する実験例に示すように、過塩
素酸ナトリウムを導電材として用いた導電性ローラに一
定極性の電圧を印加し、抵抗値が上昇したローラの内側
部分と外側部分のナトリウム量及び過塩素酸量を定量し
たところ、電圧を印加していない標準試料に比較して、
内側部分ではナトリウムが減少していると共に過塩素酸
が増加しており、一方外側部分では逆にナトリウムが増
加していた。このことから、電圧印加による過塩素酸ナ
トリウムの電気泳動分極が認められた。Actually, as shown in an experimental example described later, when a voltage having a constant polarity is applied to a conductive roller using sodium perchlorate as a conductive material, sodium in the inner portion and the outer portion of the roller whose resistance value is increased. When the amount and the amount of perchloric acid were quantified, compared with a standard sample to which no voltage was applied,
Sodium was decreasing and perchloric acid was increasing in the inner part, while sodium was conversely increasing in the outer part. From this, the electrophoretic polarization of sodium perchlorate by voltage application was recognized.
【００１９】イオン導電性物質として過塩素酸リチウ
ム、過塩素酸ナトリウム、過塩素酸カルシウムの如き無
機塩に代えて、有機イオン性物質である、ラウリルトリ
メチルアンモニウムクロライド、ステアリルトリメチル
アンモニウムクロライド、オクタデシルトリメチルアン
モニウムクロライド、ドデシルトリメチルアンモニウム
クロライド、ヘキサデシルトリメチルアンモニウムクロ
ライド、変成脂肪酸・ジメチルエチルアンモニウムエト
サルフェート、過塩素酸テトラエチルアンモニウム、過
塩素酸テトラブチルアンモニウム、ホウフッ化テトラブ
チルアンモニウム、ホウフッ化テトラエチルアンモニウ
ム、塩化テトラブチルアンモニウムの如き第４級アンモ
ニウム塩からなる群より選ばれる１種又は２種以上を、
ウレタンの０．００１〜２０重量部、より好ましくは
０．０１〜３重量部添加することによって、体積固有抵
抗１×１０5 〜１×１０10［Ω・ｃｍ］で長時間通電時
にも抵抗が安定であるウレタン材料が得られることを知
見した。Instead of an inorganic salt such as lithium perchlorate, sodium perchlorate or calcium perchlorate as an ion conductive substance, an organic ionic substance such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride or octadecyl trimethyl ammonium is used. Chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, modified fatty acid dimethylethylammonium ethosulfate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetrabutylammonium borofluoride, tetraethylammonium borofluoride, tetrabutylammonium chloride One or more selected from the group consisting of quaternary ammonium salts such as
By adding 0.001 to 20 parts by weight, and more preferably 0.01 to 3 parts by weight of urethane, the volume resistivity is 1 × 10 5 to 1 × 10 10 [Ω · cm], and the resistance is long-time energization. It was found that a stable urethane material can be obtained.
【００２０】この際、上記第４級アンモニウム塩の分子
量は１４０以上、より好ましくは２００〜６００の範囲
が特に好ましい。なお、この場合抵抗の通電長期安定性
には上記の第４級アンモニウム塩を添加したことが本質
的に重要であるが、本発明の効能を損なわない範囲で、
従来より用いられている過塩素酸リチウム、過塩素酸ナ
トリウム、又は過塩素酸カルシウムの如き無機塩やカー
ボンブラックを併用しても良い。本発明に用いるポリウ
レタンは、親水性であるため導電性を添加しない状態で
温度１５℃、相対湿度１０％における抵抗値が、温度２
８℃、相対湿度８５％における抵抗値の１００倍以上で
あり、第４級アンモニウム塩を添加してもなお２０倍以
上の抵抗値があるので、過塩素酸リチウムの如き無期イ
オンやカーボンブラックを併用すると、低温低湿時と高
温高湿時の抵抗変動を少なくすることが出来る。又、第
４級アンモニウム塩を各種エーテル、アルコール等の溶
媒に溶解して用いることも好ましい。At this time, the molecular weight of the quaternary ammonium salt is preferably 140 or more, more preferably 200 to 600. In this case, it is essentially important to add the above quaternary ammonium salt to the long-term stability of resistance, but within a range that does not impair the effects of the present invention.
Conventionally used inorganic salts such as lithium perchlorate, sodium perchlorate, or calcium perchlorate, and carbon black may be used in combination. Since the polyurethane used in the present invention is hydrophilic, the resistance value at a temperature of 15 ° C. and a relative humidity of 10% is 2
Since it has a resistance value of 100 times or more at 8 ° C and 85% relative humidity, and still has a resistance value of 20 times or more even if a quaternary ammonium salt is added, indefinite ions such as lithium perchlorate and carbon black are used. When used together, it is possible to reduce resistance fluctuations at low temperature and low humidity and at high temperature and high humidity. It is also preferable to dissolve the quaternary ammonium salt in a solvent such as various ethers or alcohols before use.
【００２１】第４級アンモニウム塩を形成する負けイオ
ン種に制限はないが、通常Ｃｌ- 、Ｆ- 、Ｂｒ- 、Ｉ
- 、ＣｌＯ4 -、ＢＦ4 -、ＳＯ4 -- 、Ｃ2 Ｈ5-ＳＯ4 -が用
いられ、特に親水性ウレタンに対する溶解性の点でＣｌ
Ｏ4 -、ＢＦ4 -、Ｃ2 Ｈ5-ＳＯ4 -が好ましく用いられる。There is no limitation on the negative ion species forming the quaternary ammonium salt, but it is usually Cl − , F − , Br − , I.
-, ClO 4 -, BF 4 -, SO 4 -, C 2 H 5 -SO 4 - it is used, in particular Cl in terms of solubility in the hydrophilic urethane
O 4 − , BF 4 − and C 2 H 5 —SO 4 − are preferably used.
【００２２】以下、本発明の半導電性弾性部材の実施例
である導電性ローラについて述べるが、本発明は下記実
施例に制限されるものではない。なお、実施例、比較例
に先立ち、電圧印加による導電性部材の抵抗上昇メカニ
ズムについての実験例を記す。 ［実験例］イオンクロマトグラフ法により、イオン物質
の分極移動を定量した。用いた試料は、ＴＤＩ−１００
（住友バイエルウレタン社製、スミジュールＴ−１０
０）２０重量部、グリセリンにプロピレンオキサイドと
エチレンオキサイドを付加して分子量５０００としたポ
リエーテルポリオール（旭硝子社製、エキセノール８２
８）１００重量部、１、４−ブタンジオール６．３重量
部、シリコーン系界面活性剤（日本ユニカ社製、ＳＦ２
９３５Ｆ）４重量部、ジブチルチンジラウレート０．０
３重量部、過塩素酸ナトリウムの３３％ジエチレングリ
コールモノメチルエステル溶液０．０２重量部を、Ｍｏ
ｎｄｏｍｉｘ社製泡立注入機で泡立て、その混合物をロ
ーラ芯金を中央部に配置したモールドに注入し８０℃
で、１２時間キュアーした。キュアー後、所定の寸法に
バフし導電性ローラを得た。導電性ローラの直径は１
６．５ｍｍであった。A conductive roller which is an example of the semiconductive elastic member of the present invention will be described below, but the present invention is not limited to the following example. Prior to the examples and comparative examples, experimental examples of the mechanism of increasing the resistance of the conductive member due to voltage application will be described. [Experimental Example] The polarization transfer of an ionic substance was quantified by an ion chromatography method. The sample used is TDI-100.
(Sumitur Bayer Urethane Co., Sumidur T-10
0) 20 parts by weight, propylene oxide and ethylene oxide were added to glycerin to give a polyether polyol having a molecular weight of 5000 (exenol 82 manufactured by Asahi Glass Co., Ltd.).
8) 100 parts by weight, 6.3 parts by weight of 1,4-butanediol, silicone-based surfactant (SF2, manufactured by Nippon Unica Co., Ltd.)
935F) 4 parts by weight, dibutyltin dilaurate 0.0
3 parts by weight, 0.02 parts by weight of a 33% solution of sodium perchlorate in diethylene glycol monomethyl ester was added to Mo.
Foam with a foaming machine manufactured by Ndomix, and pour the mixture into a mold having a roller cored bar at the center, and the temperature is 80 ° C.
Then I cured for 12 hours. After curing, it was buffed to a predetermined size to obtain a conductive roller. The diameter of the conductive roller is 1
It was 6.5 mm.
【００２３】次いで、直径３０ｍｍのアルミドラムを対
向電極として、Ｔｒｅｃｋ社製Ｍｏｄｅｌ ６１０Ｃ電
源を用いて、導電性ローラの芯金に＋１０００Ｖの電圧
を８時間印加した。電圧印加時の環境は、温度２８℃、
湿度８５％であった。初期抵抗は約２×１０7 Ωであっ
たものが電圧印加と共に上昇し、８時間後には約１×１
０8 Ω程度まで抵抗値が上昇した。このローラの芯金よ
りの部分を２ｍｍの厚さに切り取った試料（以下内側と
呼ぶ）０．５ｇとローラの表面部分を２ｍｍの厚さに切
り取った試料（以下外側と呼ぶ）０．５ｇ、及び電圧を
印加しなかった標準試料０．５ｇを各々１．４ｍｌの蒸
留水に２４時間浸漬抽出し、イオンクロマトグラフ法に
より定量した。用いた装置は、東洋曹達ＣＣＰＤポン
プ、ウオータースＵ−６Ｋインジェクター、Ｗｅｓｃａ
ｎ電気伝導度検出器、島津ＩＣ−Ａ１（アニオン分析
用）又はＩＣ−Ｇ１（カチオン分析用）カラムで、流速
は３ｍｌ／分とした。移動相はアニオン分析にはフタル
酸緩衝液（４ｍＭ，Ｐｈ６．２）、カチオン分析には硝
酸水溶液（２ｍＭ）を用いた。分析結果は表１に示す通
りであり、この結果からイオン物質の分極による抵抗上
昇という仮説が支持される。Next, a +1000 V voltage was applied to the core of the conductive roller for 8 hours by using a Model 610C power source manufactured by Trek Co., using an aluminum drum having a diameter of 30 mm as a counter electrode. The environment at the time of voltage application is 28 ° C,
The humidity was 85%. The initial resistance was about 2 × 10 7 Ω, but it increased with the voltage application, and after 8 hours it was about 1 × 1.
Up to about 0 8 Ω resistance value has increased. 0.5 g of a sample (hereinafter referred to as the inner side) having a thickness of 2 mm cut out from the cored bar of the roller and 0.5 g of a sample having a thickness of 2 mm cut from the surface portion of the roller (hereinafter referred to as the outer side). And 0.5 g of a standard sample to which no voltage was applied were each immersed in 1.4 ml of distilled water for 24 hours for extraction and quantified by ion chromatography. The equipment used was Toyo Soda CCPD pump, Waters U-6K injector, Wesca
The flow rate was 3 ml / min using an n conductivity detector, Shimadzu IC-A1 (for anion analysis) or IC-G1 (for cation analysis) column. As a mobile phase, a phthalate buffer solution (4 mM, Ph6.2) was used for anion analysis, and a nitric acid aqueous solution (2 mM) was used for cation analysis. The results of the analysis are shown in Table 1, and this result supports the hypothesis that the resistance increases due to the polarization of the ionic substance.
【００２４】[0024]
【表１】 [Table 1]
【００２５】［実施例１］上記実験例に示した配合処
方、即ちＴＤＩ−１００を２０重量部、グリセリンにプ
ロピレンオキサイドとエチレンオキサイドを付加して分
子量５０００としたポリエーテルポリオール１００重量
部、１、４−ブタンジオール６．３重量部、シリコーン
系界面活性剤（日本ユニカ社製、ＳＦ２９３５Ｆ）４重
量部、ジブチルチンジラウレート０．０３重量部、そし
て、上記実験例のうち過塩素酸ナトリウムの３３％ジエ
チレンモノメチルエステル溶液０．０２重量部に代えて
変成脂肪族・ジメチルエチルアンモニウムエトサルフェ
ート（Ｈ[ ＣＨ2]4-20Ｃ2 Ｈ5Ｎ [ＣＨ3]2 Ｃ2 Ｈ5 Ｓ
Ｏ4 ，分子量４６６〜５５０）０．５重量部をＭｏｎｄ
ｏｍｉｘ社製泡立て注入機で泡立て、その混合物をロー
ラ芯金を中央部に配置したモールドに注入し８０℃、１
２時間キュアーした。キュアー後、所定の寸法にバフし
て導電性ローラを得た。[Example 1] 20 parts by weight of the compounding formulation shown in the above experimental example, that is, TDI-100, 100 parts by weight of polyether polyol having a molecular weight of 5000 by adding propylene oxide and ethylene oxide to glycerin, 1, 6.3 parts by weight of 4-butanediol, 4 parts by weight of a silicone-based surfactant (SF2935F manufactured by Nippon Unica Co., Ltd.), 0.03 part by weight of dibutyltin dilaurate, and 33% of sodium perchlorate in the above experimental examples. diethylene monomethyl ester solution 0.02 modified aliphatic instead parts by dimethylethyl ammonium ethosulfate (H [CH 2] 4-20 C 2 H 5 N [CH 3] 2 C 2 H 5 S
O 4 , molecular weight 466 to 550) 0.5 part by weight
Lather with a whipping and pouring machine manufactured by Omix, and pour the mixture into a mold in which a roller core metal is placed in the center, and the temperature is 80 ° C., 1
I cured for 2 hours. After curing, the conductive roller was buffed to a predetermined size to obtain a conductive roller.
【００２６】図１の装置において、２の半導電性弾性材
料部材として直径１６．５ｍｍの上記ローラを用い、１
の部分には直径３０ｍｍのアルミドラムを用いて、アル
ミドラムの回転数が１７ｒｐｍとなるように設定した。
次いで、定電流発生電源としてＴｒｅｃｋ社製Ｍｏｄｅ
ｌ ６１０Ｃを用い、２μＡ定電流を印加した。この時
の電圧値を観測して電流値との換算からローラ抵抗を求
め、通電時間に対してプロットしたものが図２である。
これにより導電性ローラ抵抗の上昇はほとんど見られ
ず、良好な連続運転が可能であることが示された。In the apparatus shown in FIG. 1, the above-mentioned rollers having a diameter of 16.5 mm are used as the two semiconductive elastic material members.
An aluminum drum having a diameter of 30 mm was used for the portion of, and the rotation speed of the aluminum drum was set to 17 rpm.
Next, as a constant current generating power source, a Mode manufactured by Treck
1 610C was used and a 2 μA constant current was applied. FIG. 2 shows the roller resistance obtained by observing the voltage value at this time, converting it to the current value, and plotting it against the energization time.
As a result, almost no increase in the resistance of the conductive roller was observed, indicating that good continuous operation was possible.
【００２７】［比較例１］配合するイオン導電性材料を
変成脂肪族ジメチルエチルアンモニウムエトサルフェー
ト０．５重量部に代えて過塩素酸ナトリウム（ＮａＣｌ
Ｏ4 、分子量１２２．５）の３３％ジエチレングリコー
ルモノメチルエステル溶液０．０２重量部とした以外
は、実施例１と同様にして実験を行い、導電性ローラ抵
抗の時間に対する変化を図３に示した。この場合、初期
抵抗が約２×１０7 Ωであったものが電圧印加と共に上
昇し、８時間後には１×１０8 Ω以上まで抵抗値が上昇
してしまった。このことにより初期値と同等の電流量を
確保するためには、初期値の５倍の電圧を印加しなけれ
ばならないことになる。[Comparative Example 1] Sodium perchlorate (NaCl) was used instead of 0.5 parts by weight of modified aliphatic dimethylethylammonium ethosulfate as the ion conductive material to be blended.
An experiment was conducted in the same manner as in Example 1 except that 0.02 part by weight of a 33% diethylene glycol monomethyl ester solution containing O 4 and a molecular weight of 122.5) was used, and the change with time of the conductive roller resistance is shown in FIG. . In this case, what had an initial resistance of about 2 × 10 7 Ω increased with the voltage application, and after 8 hours, the resistance value increased to 1 × 10 8 Ω or more. Therefore, in order to secure a current amount equivalent to the initial value, it is necessary to apply a voltage that is five times the initial value.
【００２８】［実施例２］配合するイオン導電性材料を
変成脂肪族ジメチルエチルアンモニウムエトサルフェー
ト０．５重量部に代えてラウリルトリメチルアンモニウ
ムクロライド（Ｃ12Ｈ25Ｎ[ ＣＨ3 ］3 Ｃｌ、分子量２
４９．５）の２０％イソプロパノール溶液１重量部とし
た以外は実施例１と同様に実験を行い、導電性ローラ抵
抗の時間に対する変化を図４に示した。これにより導電
性ローラ抵抗の上昇はほとんど見られず、良好な連続運
転が可能であることが示された。[Example 2] The ion conductive material to be blended was replaced with 0.5 part by weight of modified aliphatic dimethylethylammonium ethosulfate, and lauryltrimethylammonium chloride (C 12 H 25 N [CH 3 ] 3 Cl, molecular weight 2) was added.
An experiment was conducted in the same manner as in Example 1 except that 19.5 parts by weight of the 49.5) 20% isopropanol solution was used, and the change in the resistance of the conductive roller with time is shown in FIG. As a result, almost no increase in the resistance of the conductive roller was observed, indicating that good continuous operation was possible.
【００２９】［実施例３］配合するイオン導電性材料を
変成脂肪族ジメチルエチルアンモニウムエトサルフェー
ト０．５重量部に代えてホウフッ化テトラブチルアンモ
ニウム０．２重量部とした以外は実施例１と同様に実験
を行い、導電性ローラの時間に対する変化を図５に示し
た。導電性ローラ抵抗の上昇はほとんど見られず、良好
な連続運転が可能であることが示された。[Example 3] The same as Example 1 except that the ion-conductive material to be blended was changed to 0.5 parts by weight of modified aliphatic dimethylethylammonium ethosulfate and 0.2 parts by weight of tetrabutylammonium borofluoride was used. The experiment was conducted and the change with time of the conductive roller is shown in FIG. Almost no increase in the resistance of the conductive roller was observed, indicating that good continuous operation was possible.
【００３０】［比較例２］配合するイオン導電性付与剤
を変成脂肪族ジメチルエチルアンモニウムエトサルフェ
ート０．５重量部に代えてアセチレンブラック２重量部
とした以外は実施例１と同様に実験を行った。図１に示
す装置より４の転写材を除いた装置で３の電源より２μ
Ａの定電流を供給した際の電圧変動を測定したところ、
ローラの回転に伴い、電圧が周期的に５０Ｖから４００
Ｖの間で変動した。このような現象は実施例では観測さ
れない。Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that the ion conductivity imparting agent to be blended was changed to 0.5 parts by weight of modified aliphatic dimethylethylammonium ethosulfate and 2 parts by weight of acetylene black was used. It was 2μ from the power source of 3 in the device shown in FIG.
When the voltage fluctuation when the constant current of A was supplied was measured,
The voltage periodically changes from 50V to 400 with the rotation of the roller.
Fluctuated between V. Such a phenomenon is not observed in the examples.
【００３１】［実施例４］配合するイオン導電性付与剤
を変成脂肪族ジメチルエチルアンモニウムエトサルフェ
ート０．５重量部に加え更に過塩素酸ナトリウム（Ｎａ
ＣｌＯ4 、分子量１２２．５）の３３％ジエチレングリ
コールモノメチルエステル溶液０．０１５重量部とした
以外は実施例１と同様に実験を行った。図１に示す装置
より４の転写材を除いた装置で３の電源より２μＡの定
電流を供給した際の電圧変動を測定したところ、ローラ
の回転に伴い電圧が周期的に変動する現象は観測され
ず、連続通電時の抵抗安定性も良好であった。Example 4 The ionic conductivity-imparting agent to be blended was added to 0.5 parts by weight of modified aliphatic dimethylethylammonium ethosulfate, and sodium perchlorate (Na) was added.
An experiment was conducted in the same manner as in Example 1 except that 0.015 parts by weight of a 33% diethylene glycol monomethyl ester solution having ClO 4 and a molecular weight of 122.5) was used. When the voltage fluctuation was measured when a constant current of 2 μA was supplied from the power supply 3 in the device shown in FIG. 1 except the transfer material 4 was observed, it was observed that the voltage periodically fluctuated with the rotation of the roller. However, resistance stability during continuous energization was also good.
【００３２】［実施例５］配合するイオン導電性材料を
変成脂肪族ジメチルエチルアンモニウムエトサルフェー
ト０．５重量部に加え更にオイルファーネス・カーボン
ブラック（ＨＡＦ級）４重量部とした以外は実施例１と
同様に実験を行った。図１に示す装置より４の転写材を
除いた装置で３の電源より２μＡの定電流を供給した際
の電圧変動を測定したところ、ローラの回転に伴い電圧
が周期的に変動する現象は観測されず、連続通電時の抵
抗安定性も良好であった。[Example 5] Example 1 except that the ion conductive material to be blended was added to 0.5 parts by weight of modified aliphatic dimethylethylammonium ethosulfate and 4 parts by weight of oil furnace carbon black (HAF grade) was further added. An experiment was conducted in the same manner as in. When the voltage fluctuation was measured when a constant current of 2 μA was supplied from the power supply 3 in the device shown in FIG. 1 except the transfer material 4 was observed, it was observed that the voltage periodically fluctuated with the rotation of the roller. However, resistance stability during continuous energization was also good.
【００３３】［比較例３］2,4-トリレンジイソシアネー
ト１８．２重量部と水素添加1、2-ポリブタジエンポリオ
ール（分子量２０００）１００重量部、1、4-ブタンジオ
ール６．３重量部、シリコーン系界面活性剤( 日本ユニ
カ社製、ＳＦ２９３５Ｆ）４重量部、ジブチルチンジラ
ウレート０．０１重量部、変成脂肪族・ジメチルエチル
アンモニウムエトサルフェート（Ｈ[ ＣＨ2 ]14-20Ｃ2
Ｈ5 Ｎ [ＣＨ3]2 Ｃ2 Ｈ5 ＳＯ4 、分子量４６６〜５５
０）０．５重量部をＭｏｎｄｏｍｉｘ社製泡立て注入機
で泡立て、その混合物をローラ芯金を中央部に配置した
モールドに注入し８０℃、１２時間キュアーした。キュ
アー後、所定の寸法にバフし弾性ローラを得た。このロ
ーラの抵抗は２×１０12Ωであり、導電性を付与できな
かった。Comparative Example 3 18.2 parts by weight of 2,4-tolylene diisocyanate and 100 parts by weight of hydrogenated 1,2-polybutadiene polyol (molecular weight 2000), 6.3 parts by weight of 1,4-butanediol, silicone 4 parts by weight of a surface-active agent (SF2935F manufactured by Nippon Unica Co., Ltd.), 0.01 part by weight of dibutyltin dilaurate, modified aliphatic dimethylethylammonium ethosulfate (H [CH 2 ] 14-20 C 2
H 5 N [CH 3] 2 C 2 H 5 SO 4, molecular weight from 466 to 55
0) 0.5 parts by weight of the mixture was bubbled with a whipping and pouring machine manufactured by Mondmix Co., and the mixture was poured into a mold having a roller cored bar in the center and cured at 80 ° C. for 12 hours. After curing, it was buffed to a predetermined size to obtain an elastic roller. The resistance of this roller was 2 × 10 12 Ω, and conductivity could not be imparted.
【００３４】［実施例６］有機イオン性導電剤として、
変性脂肪族ジメチルエチルアンモニウムエトサルフェー
ト０．５重量部に代えてラウリルトリメチルアンモニウ
ムクロライド（Ｃ12Ｈ25Ｎ［ＣＨ3 ］3 Ｃｌ、分子量２
４９．５）の２０％イソプロパノール溶液１重量部とし
た以外は実施例６と同様にして導電性ローラを製造し、
実施例３と同様に実験を行って、導電性ローラ抵抗の時
間に対する変化を調べた。Example 6 As an organic ionic conductive agent,
Instead of 0.5 part by weight of modified aliphatic dimethylethylammonium ethosulfate, lauryltrimethylammonium chloride (C 12 H 25 N [CH 3 ] 3 Cl, molecular weight 2
49.5) A conductive roller was produced in the same manner as in Example 6 except that 1 part by weight of a 20% isopropanol solution of 49.5) was used.
An experiment was conducted in the same manner as in Example 3 to examine the change with time of the conductive roller resistance.
【００３５】その結果、初期抵抗が約２．８×１０7 Ω
であったものが、８時間後には約４．３×１０7 の抵抗
値であった。これにより、導電性ローラ抵抗の上昇はほ
とんど見られず、良好な連続運転が可能であることが確
認された。As a result, the initial resistance is about 2.8 × 10 7 Ω.
However, the resistance value was about 4.3 × 10 7 after 8 hours. From this, it was confirmed that the resistance of the conductive roller was hardly increased, and good continuous operation was possible.
【００３６】[0036]
【発明の効果】以上説明したように、本発明の材料を用
いた導電性ローラによれば、連続使用しても抵抗の上昇
のないものが得られ、これを電子写真プロセスに適用す
れば、長時間使用においても安定して良好な画像が得ら
れるものである。As described above, according to the conductive roller using the material of the present invention, it is possible to obtain a roller which does not increase in resistance even if it is continuously used. If this is applied to an electrophotographic process, Even when used for a long time, a good image can be stably obtained.
【図１】本発明の半導電性弾性部材を用いた帯電システ
ムの一例を示す該略図である。FIG. 1 is a schematic view showing an example of a charging system using a semiconductive elastic member of the present invention.
【図２】実施例１にかかる半導電性弾性部材を用いて製
造した導電性ローラの連続使用による抵抗値変化を示す
グラフである。FIG. 2 is a graph showing a resistance value change due to continuous use of a conductive roller manufactured using the semiconductive elastic member according to the first embodiment.
【図３】従来の導電性材料を用いて製造した比較例１の
導電性ローラの連続使用による抵抗値変化を示すグラフ
である。FIG. 3 is a graph showing resistance value changes due to continuous use of the conductive roller of Comparative Example 1 manufactured using a conventional conductive material.
【図４】実施例２にかかる半導電性弾性部材を用いて製
造した導電性ローラの連続使用による抵抗値変化を示す
グラフである。FIG. 4 is a graph showing a resistance value change due to continuous use of a conductive roller manufactured using the semiconductive elastic member according to the second embodiment.
【図５】実施例３にかかる半導電性弾性部材を用いて製
造した導電性ローラの連続使用による抵抗値変化を示す
グラフである。FIG. 5 is a graph showing changes in resistance value due to continuous use of a conductive roller manufactured using the semiconductive elastic member according to the third embodiment.
１ 帯電ローラ（導電部材） １ａ 芯金 １ｂ 導電性ローラ層（主体） ２ 感光体ロール（被帯電体） ３ 電源 1 Charging Roller (Conductive Member) 1a Core Bar 1b Conductive Roller Layer (Main Body) 2 Photosensitive Roll (Charged Object) 3 Power Supply
Claims (8)
１０〜８５％において測定電圧１０〜５０００Ｖの範囲
で１×１０5 〜１×１０10［Ωｃｍ］であり、上記電気
抵抗の位置ばらつきが±２０％以下であり、かつ連続通
電した時の電気抵抗が初期抵抗の５倍未満であることを
特徴とする半導電性高分子弾性部材。1. The electric resistance is 1 × 10 5 to 1 × 10 10 [Ωcm] in a range of a measurement voltage of 10 to 5000 V at a temperature of 15 to 28 ° C. and a relative humidity of 10 to 85%. Is ± 20% or less, and the electric resistance when continuously energized is less than 5 times the initial resistance. A semiconductive polymer elastic member.
性物質を添加してなることを特徴とする請求項１記載の
半導電性高分子弾性部材。2. The semiconductive polymer elastic member according to claim 1, wherein the polymer material is a base material and an organic ionic material is added thereto.
樹脂からなることを特徴とする請求項２記載の半導電性
高分子弾性部材。3. The semiconductive polymer elastic member according to claim 2, wherein the polymer substance is mainly composed of a hydrophilic urethane resin.
／又は両性イオン界面活性剤であることを特徴とする請
求項２記載の半導電性高分子弾性材料。4. The semiconductive polymer elastic material according to claim 2, wherein the organic ionic substance is a cationic and / or zwitterionic surfactant.
第４級アンモニウム塩であることを特徴とする請求項４
記載の半導電性高分子弾性材料。5. The cationic surfactant is at least a quaternary ammonium salt.
The semiconductive polymer elastic material described.
定電圧５０００Ｖにおける電気抵抗の２倍以下であるこ
とを特徴とする請求項１乃至５記載の半導電性高分子弾
性材料。6. The semiconductive polymer elastic material according to claim 1, wherein the electric resistance at a measuring voltage of 10 V is not more than twice the electric resistance at a measuring voltage of 5000 V.
ックを有機イオン物質に加えて高分子物質に添加してな
ることを特徴とする請求項２乃至６記載の半導電性高分
子弾性部材。7. The semiconductive polymer elastic member according to claim 2, wherein an inorganic ionic substance and / or carbon black is added to the polymeric substance in addition to the organic ionic substance.
とを特徴とする請求項１乃至７のいずれかに記載の半導
電性高分子弾性材料。8. The semiconductive polymer elastic material according to claim 1, which is an elastic roller for an electrophotographic process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6164271A JP3018906B2 (en) | 1993-07-19 | 1994-07-15 | Semiconductive polymer elastic member |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20002693 | 1993-07-19 | ||
| JP5-200026 | 1993-08-27 | ||
| JP23580093 | 1993-08-27 | ||
| JP5-235800 | 1993-08-27 | ||
| JP6164271A JP3018906B2 (en) | 1993-07-19 | 1994-07-15 | Semiconductive polymer elastic member |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34589597A Division JP3331936B2 (en) | 1993-07-19 | 1997-12-01 | Semiconductive polymer elastic member |
| JP11283479A Division JP2000154228A (en) | 1993-07-19 | 1999-10-04 | Elastic material of electrically semiconductive polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07113050A true JPH07113050A (en) | 1995-05-02 |
| JP3018906B2 JP3018906B2 (en) | 2000-03-13 |
Family
ID=27322301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6164271A Expired - Lifetime JP3018906B2 (en) | 1993-07-19 | 1994-07-15 | Semiconductive polymer elastic member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3018906B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1288729A2 (en) | 2001-08-28 | 2003-03-05 | Tokai Rubber Industries, Ltd. | Elastic member of semiconductive polymer and OA equipment using the same |
| EP1616217A2 (en) * | 2003-03-27 | 2006-01-18 | E Ink Corporation | Electro-optic assemblies |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50150438A (en) * | 1974-04-26 | 1975-12-02 | ||
| JPH01101375A (en) * | 1987-10-15 | 1989-04-19 | Tokai Rubber Ind Ltd | Semiconductive polymer composition |
-
1994
- 1994-07-15 JP JP6164271A patent/JP3018906B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50150438A (en) * | 1974-04-26 | 1975-12-02 | ||
| JPH01101375A (en) * | 1987-10-15 | 1989-04-19 | Tokai Rubber Ind Ltd | Semiconductive polymer composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1288729A2 (en) | 2001-08-28 | 2003-03-05 | Tokai Rubber Industries, Ltd. | Elastic member of semiconductive polymer and OA equipment using the same |
| EP1288729A3 (en) * | 2001-08-28 | 2010-05-05 | Tokai Rubber Industries, Ltd. | Elastic member of semiconductive polymer and OA equipment using the same |
| EP1616217A2 (en) * | 2003-03-27 | 2006-01-18 | E Ink Corporation | Electro-optic assemblies |
| JP2006521586A (en) * | 2003-03-27 | 2006-09-21 | イー−インク コーポレイション | Electro-optic assembly |
| EP1616217A4 (en) * | 2003-03-27 | 2007-04-11 | E Ink Corp | Electro-optic assemblies |
| EP2273307A1 (en) * | 2003-03-27 | 2011-01-12 | E Ink Corporation | Electro-optic displays |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3018906B2 (en) | 2000-03-13 |
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