JP4082222B2 - Conductive composition for electrophotographic equipment member, electrophotographic equipment member using the same, and production method thereof - Google Patents

Description

【００２０】
【化３】

【００２１】
【化４】

【００２２】
【化５】

【００２３】
【化６】

【００２４】
上記導電性ポリマーの原料モノマーと、界面活性剤（ａ）との混合比は、重量比で、原料モノマー／界面活性剤（ａ）＝９６／４〜３０／７０の範囲内が好ましく、特に好ましくは原料モノマー／界面活性剤（ａ）＝８０／２０〜４０／６０の範囲内である。すなわち、界面活性剤（ａ）の重量比が４未満であると、バインダーポリマーとの相溶性や分散性が低下し、逆に界面活性剤（ａ）の重量比が７０を超えると、界面活性剤のイオン導電性への効果が強くなりすぎ、導電性ポリマーの電子導電性を減らすこととなるからである。
【００２５】
上記特定の導電性ポリマー（Ａ成分）の数平均分子量（Ｍｎ）は、５００〜１００，０００の範囲内が好ましく、特に好ましくは１，０００〜２０，０００の範囲内である。
【００２６】
上記特定の導電性ポリマー（Ａ成分）とともに用いられるバインダーポリマー（Ｂ成分）としては、アクリル系樹脂、ウレタン系樹脂、フッ素系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、エポキシ系樹脂、ウレア系樹脂、ゴム系ポリマーおよび熱可塑性エラストマーからなる群から選ばれた少なくとも一つからなる溶剤可溶性のものが用いられる。これらのなかでも、Ａ成分との相溶性に優れる点で、溶剤可溶性のアクリル系樹脂、溶剤可溶性のエポキシ系樹脂が好ましい。
【００２７】
なお、本発明において、溶剤可溶性とは、溶剤に完全に溶解するか、もしくは懸濁状態（サスペンション）にある場合をいう。
【００２８】
上記溶剤可溶性のアクリル系樹脂としては、例えば、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチルメタクリレート、ポリメチルアクリレート、ポリエチルアクリレート、ポリヒドロキシメタクリレート、アクリルシリコーン系樹脂、アクリルフッ素系樹脂等があげられる。
【００２９】
上記溶剤可溶性のウレタン系樹脂としては、例えば、エーテル系，エステル系，脂肪族系等のウレタンや、それにシリコーン系ポリオール、フッ素系ポリオールを共重合させたもの等があげられる。
【００３０】
上記溶剤可溶性のフッ素系樹脂としては、例えば、ポリビニリデンフルオライド（ＰＶＤＦ）、フッ化ビニリデン−四フッ化エチレン共重合体、フッ化ビニリデン−四フッ化エチレン−六フッ化プロピレン共重合体等があげられる。
【００３１】
上記溶剤可溶性のポリアミド系樹脂としては、例えば、アルコール可溶性メトキシメチル化ナイロン等があげられる。
【００３２】
上記溶剤可溶性のポリイミド系樹脂としては、例えば、ポリアミドイミド（ＰＡＩ）、ポリアミック酸、シリコーンイミド等があげられる。
【００３３】
上記溶剤可溶性のエポキシ系樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、臭素化エポキシ樹脂、ポリグリコール型エポキシ樹脂、ポリアミド併用型エポキシ樹脂、シリコン変性エポキシ樹脂、アミノ樹脂併用型エポキシ樹脂、アルキッド樹脂併用型エポキシ樹脂等があげられる。
【００３４】
上記溶剤可溶性のゴム系ポリマーとしては、例えば、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、水素添加ＮＢＲ（Ｈ−ＮＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）、ウレタンゴム、クロロプレンゴム（ＣＲ）、エピクロロヒドリンゴム（ＥＣＯ）、エチレン−プロピレン−ジエンポリマー（ＥＰＤＭ）、アクリルゴム（ＡＣＭ）、クロロスルホン化ポリエチレン（ＣＳＭ）、多硫化ゴム、フッ素ゴム等があげられる。
【００３５】
上記溶剤可溶性の熱可塑性エラストマーとしては、例えば、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、スチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）、スチレン−エチレン・ブチレン−スチレンブロック共重合体（ＳＥＢＳ）、スチレン−エチレン・プロピレン−スチレンブロック共重合体（ＳＥＰＳ）等があげられる。
【００３６】
上記特定のバインダーポリマー（Ｂ成分）の数平均分子量（Ｍｎ）は、５，０００〜２，０００，０００の範囲内が好ましく、特に好ましくは２０，０００〜８００，０００の範囲内である。
【００３７】
上記特定の導電性ポリマー（Ａ成分）の原料（導電性ポリマーの原料モノマーと界面活性剤（ａ）との合計量）と、特定のバインダーポリマー（Ｂ成分）との混合比は、重量比で、Ａ成分の原料／Ｂ成分＝１／９９〜５０／５０の範囲内が好ましく、特に好ましくはＡ成分の原料／Ｂ成分＝４／９６〜３５／６５の範囲内である。すなわち、Ａ成分の原料の重量比が１未満であると、導電性への効果が少なく、逆にＡ成分の原料の重量比が５０を超えると、導電性ポリマーが固くて脆くなりやすく、組成物としての物性が低下するからである。
【００３８】
なお、本発明の導電性組成物には、上記Ａ成分およびＢ成分に加えて、イオン導電剤、電子導電剤、架橋剤等を配合しても差し支えない。
【００３９】
上記イオン導電剤としては、例えば、第四級アンモニウム塩、ホウ酸塩、界面活性剤〔上記界面活性剤（ａ）以外のもの〕等があげられる。これらは単独でもしくは２種以上併せて用いられる。
【００４０】
また、上記イオン導電剤の配合割合は、物性や電気特性の点から、Ａ成分の原料（原料モノマーと界面活性剤（ａ）との合計量）とＢ成分との合計１００重量部（以下「部」と略す）に対して、０．０１〜５部の範囲内が好ましく、特に好ましくは０．５〜２部の範囲内である。
【００４１】
上記電子導電剤としては、例えば、カーボンブラック、ｃ−ＺｎＯ（導電性酸化亜鉛）、ｃ−ＴｉＯ₂ （導電性酸化チタン）、ｃ−ＳｎＯ₂ （導電性酸化錫）、グラファイト等があげられる。
【００４２】
また、上記電子導電剤の配合割合は、物性や電気特性の点から、Ａ成分の原料（原料モノマーと界面活性剤（ａ）との合計量）とＢ成分との合計１００部に対して、１〜３０部の範囲内が好ましく、特に好ましくは５〜２０部の範囲内である。
【００４３】
上記架橋剤としては、例えば、硫黄、イソシアネート、ブロックイソシアネート、メラミン等の尿素樹脂、エポキシ硬化剤、ポリアミン硬化剤、ヒドロシリル架橋剤、パーオキサイド等があげられる。
【００４４】
また、上記架橋剤の配合割合は、物性、粘着性、液保管性の点から、Ａ成分の原料（原料モノマーと界面活性剤（ａ）との合計量）とＢ成分との合計１００部に対して、１〜３０部の範囲内が好ましく、特に好ましくは３〜１０部の範囲内である。
【００４５】
なお、上記導電性組成物には、前記各成分に加えて、架橋促進剤、触媒、老化防止剤、ドーパント等を必要に応じて配合しても差し支えない。
【００４６】
上記架橋促進剤としては、例えば、スルフェンアミド系架橋促進剤、ジチオカルバミン酸塩系架橋促進剤、アミン類、有機錫系触媒等があげられる。
【００４７】
本発明の導電性組成物は、例えば、つぎのようにして製造することができる。すなわち、まず、前述の方法に従い、特定の導電性ポリマー（Ａ成分）を作製する。つぎに、この特定の導電性ポリマー（Ａ成分）を、特定のバインダーポリマー（Ｂ成分）に配合するとともに、必要に応じて、イオン導電剤、電子導電剤、架橋剤等を配合する。そして、これらをロール，ニーダー，バンバリーミキサー等の混練機を用いて混練することにより、目的とする導電性組成物を得ることができる。また、ロール等で混練した後に、水や溶剤等に溶解または分散させて、導電性組成物（コーティング液）としても差し支えない。
【００４８】
なお、前述の方法に従い、特定の導電性ポリマー（Ａ成分）を作製するとともに、この特定の導電性ポリマー（Ａ成分）を高剪断分散機を用いて特定のバインダーポリマー（Ｂ成分）中に分散させてもよい。このように高剪断分散機を用いると、特定の導電性ポリマー（Ａ成分）の粒径がより小さくなり、特定のバインダーポリマー（Ｂ成分）中に均一に微分散するようになるため好ましい。特定の導電性ポリマー（Ａ成分）の粒径（メジアン径）は、分散性の点から、１μｍ以下が好ましい。
【００４９】
上記高剪断分散機としては、例えば、ガラス，ジルコニア等のセラミックビーズを利用した高速ビーズミルや、サンドミル、ボールミル、３本ロール、加圧ニーダー、すりつぶし力を利用したコロイドミル等が用いられる。
【００５０】
上記溶剤としては、例えば、ｍ−クレゾール、メチルエチルケトン（ＭＥＫ）、トルエン等の有機溶剤等があげられる。
【００５１】
本発明の導電性組成物は、例えば、現像ロール，帯電ロール，転写ロール，定着ロール，トナー供給ロール，除電ロール，給紙ロール，搬送ロール，クリーニングロール等のロール部材、現像ブレード，帯電ブレード，クリーニングブレード等のブレード部材、転写ベルト，紙送りベルト等のベルト部材等の電子写真機器部材、もしくはこれらの電気特性を利用したセンサー，静電防止材，アクチュエーター等の電子部材に用いられる。
【００５２】
本発明の導電性組成物を用いた電子写真機器部材としては、例えば、現像ロール，帯電ロール，転写ロール，定着ロール，トナー供給ロール，除電ロール，給紙ロール，搬送ロール，クリーニングロール等のロール部材、現像ブレード，帯電ブレード，クリーニングブレード等のブレード部材、転写ベルト，紙送りベルト等のベルト部材等があげられる。そして、本発明の電子写真機器部材においては、中間層および表層の少なくとも一方が、本発明の導電性組成物を用いて形成されていることが好ましい。
【００５３】
つぎに、実施例について比較例と併せて説明する。
【００５４】
【実施例１】
アニリン１ｍｏｌと、界面活性剤である前記式（２）で表されるポリオキシアルキレンアルキルエーテルリン酸エステル（第一工業製薬社製、プライサーフ２１５Ｃ）１ｍｏｌとを、酸化剤（過硫酸アンモニウム）１ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分をトルエンに置換し、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるポリメチルメタクリレート（住友化学社製、スミペックスＬＧ６Ａ、Ｍｎ：２００００）８０部を、溶剤（トルエン）５００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で２０部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００５５】
【実施例２】
界面活性剤として、前記式（４）で表されるジアルキルスルホコハク酸エステルナトリウム塩（第一工業製薬社製、ネオコールＳＷ−Ｃ）を用いる以外は、実施例１と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。そして、この特定の導電性ポリマー（ポリアニリン）を用いて、実施例１と同様にして、導電性組成物を調製した。
【００５６】
【実施例３】
界面活性剤として、前記式（５）で表されるポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）を用いる以外は、実施例１と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。そして、この特定の導電性ポリマー（ポリアニリン）を用いて、実施例１と同様にして、導電性組成物を調製した。
【００５７】
【実施例４】
界面活性剤として、前記式（６）で表されるアミドエーテルスルホン酸ナトリウム（日本油脂社製、サンアミドＣＦ３）を用いる以外は、実施例１と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。そして、この特定の導電性ポリマー（ポリアニリン）を用いて、実施例１と同様にして、導電性組成物を調製した。
【００５８】
【実施例５】
アニリン１ｍｏｌと、界面活性剤であるポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーである可溶性ナイロン（帝国化学社製、トレジンＥＦ３０Ｔ）８０部を、メタノール４００部と水１００部とに溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で２０部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００５９】
【実施例６】
アニリン１ｍｏｌと、界面活性剤であるポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をしてメチルエチルケトン（ＭＥＫ）と置換し、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるポリウレタン（日本ミラクトラン社製、ＴＰＵ）９２部を、メチルエチルケトン（ＭＥＫ）５００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で８部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６０】
【実施例７】
アニリン１ｍｏｌと、界面活性剤であるポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分と未反応物を溶媒〔ＭＥＫ／トルエン＝２／３（重量比）〕で置換し、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるアクリルフッ素系樹脂（大日本インキ化学工業社製、ディフェンサＴＲ２３０Ｋ）８０部を、メチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で２０部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６１】
【実施例８】
実施例７と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）を８０部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で２０部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６２】
【実施例９】
実施例７と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるアクリルフッ素系樹脂（大日本インキ化学工業社製、ディフェンサＴＲ２３０Ｋ）を固形分で８０部と、導電剤であるアセチレンブラック（電気化学工業社製、デンカブラックＨＳ１００）５部とを、メチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で１５部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６３】
【実施例１０】
アニリン１ｍｏｌと、界面活性剤であるポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．３ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分を溶媒〔ＭＥＫ／トルエン＝２／３（重量比）〕で置換し、特定の導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）８０部と、導電剤である第四級アンモニウム塩（テトラブチルアンモニウムハイドロゲンサルフェート：ＴＢＡＨＳ）１部と、導電剤であるホウ酸カリウム塩（日本カーリット社製、ＬＲ１４７）１部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリアニリン）を固形分で１８部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６４】
【実施例１１】
ピロール１ｍｏｌと、界面活性剤として、ポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分を溶媒〔ＭＥＫ／トルエン＝２／３（重量比）〕で置換し、特定の導電性ポリマー（ポリピロール）を得た。つぎに、バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）８０部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリピロール）を固形分で２０部加え、導電性組成物を調製した。
【００６５】
【実施例１２】
チオフェン１ｍｏｌと、界面活性剤として、ポリオキシアルキレンアルキルフェニルエーテルサルフェートアンモニウム塩（第一工業製薬社製、ハイテノールＮＯ８）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分を溶媒〔ＭＥＫ／トルエン＝２／３（重量比）〕で置換し、特定の導電性ポリマー（ポリチオフェン）を得た。つぎに、バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）８０部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記特定の導電性ポリマー（ポリチオフェン）を固形分で２０部加え、導電性組成物を調製した。
【００６６】
【参考例１】
アニリン１ｍｏｌと、前記一般式（１）で表される界面活性剤（式中、Ｒ¹ ＝ブチル基、Ｒ² ＝水素、ｎ＝２、ｍ＝３）１ｍｏｌとを、水溶液化した酸化剤（過硫酸アンモニウム）１ｍｏｌを滴下しながら酸化重合させ、導電性ポリマー（ポリアニリン）を得た。つぎに、バインダーポリマーであるポリアミドイミドのＮＭＰ（Ｎ−メチル−２−ピロリドン）１５％溶液（東洋紡績社製、バイロマックスＨＲ１６ＮＮ）の有効成分（不揮発分）７５部に、上記導電性ポリマー（ポリアニリン）の有効成分（不揮発分）２５部を加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６７】
【比較例１】
アニリン１ｍｏｌと、界面活性剤として、下記の式（７）で表されるオレイルザルコシン酸（日本油脂社製、オレイルザルコシン２２１Ｐ）０．８ｍｏｌとを、酸化剤（過硫酸アンモニウム）０．５ｍｏｌの存在下に酸化重合させた後、メタノールで未反応物を取り除き、濾過をして水分を除去し、導電性ポリマー（ポリアニリン）を作製した。つぎに、バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）８０部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、上記導電性ポリマー（ポリアニリン）を固形分で２０部加え、３本ロールを用いて混練し、導電性組成物を調製した。
【００６８】
【化７】

【００６９】
【比較例２】
バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）９２部と、導電剤であるアセチレンブラック（電気化学工業社製、デンカブラックＨＳ１００）８部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【００７０】
【比較例３】
バインダーポリマーであるアクリルフッ素系樹脂（大日本インキ化学工業社製、ディフェンサＴＲ２３０Ｋ）９８部と、導電剤である第四級アンモニウム塩（テトラブチルアンモニウムハイドロゲンサルフェート：ＴＢＡＨＳ）１部と、導電剤であるホウ酸カリウム塩（日本カーリット社製、ＬＲ１４７）１部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【００７１】
【比較例４】
界面活性剤として、高級アルコール硫酸エステルナトリウム塩（第一工業製薬社製、モノゲンＹ５００）を用いる以外は、実施例１と同様にして、導電性ポリマー（ポリアニリン）を作製した。そして、この導電性ポリマー（ポリアニリン）を用いて、実施例１と同様にして、導電性組成物を調製した。
【００７２】
【比較例５】
バインダーポリマーであるポリメチルメタクリレート（住友化学社製、スミペックスＬＧ６Ａ、Ｍｎ：２００００）９２部と、導電剤であるアセチレンブラック（電気化学工業社製、デンカブラックＨＳ１００）８部をロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【００７３】
このようにして得られた実施例品、参考例品および比較例品について、下記の基準に従い、各特性の評価を行った。これらの結果を、後記の表１〜表３に併せて示した。
【００７４】
〔溶解性〕
特定の導電性ポリマーに用いられる界面活性剤の、メチルエチルケトン（ＭＥＫ）およびトルエンに対する溶解性をそれぞれ評価した。評価は、ＭＥＫ等に溶解した界面活性剤の濃度が３重量％以上のものを○、３重量％未満のものを×とした。
【００７５】
〔溶解性〕
導電性ポリマーに用いられる界面活性剤の、水に対する溶解性を評価した。評価は、界面活性剤が水に３％以上の溶解性を示すか、もしくは水中でミセル分散状態を１０時間以上保持するものを○、界面活性剤の水に対する溶解性が３％未満であるか、もしくは水中でのミセル分散状態の保持時間が１０時間未満のものを×とした。
【００７６】
〔安定性〕
導電性組成物のバインダーポリマー中での、導電性ポリマーの１０時間後の安定性を目視評価した。評価は、溶媒に溶かしたバインダーポリマー中での導電性ポリマーの安定性が悪く、分離したり、５０μｍ以上の凝集をするものを×、バインダーポリマー中での導電性ポリマーの安定性が良く、５０μｍ以上の凝集をしないものを○とした。なお、凝集の評価は、つぶゲージ法（ＪＩＳ Ｋ５４４０）に準じて行った。
【００７７】
〔初期および経時の電気抵抗〕
導電性組成物をガラス板上に塗布して、厚み２０μｍの導電性塗膜を作製した。そして、５０℃×９５％ＲＨの環境下において、１０Ｖの電圧を印加した時の導電性塗膜の初期の電気抵抗、および３０日後の経時の電気抵抗を、ＳＲＩＳ ２３０４に準じてそれぞれ測定した。
【００７８】
〔環境依存性〕
上記電気抵抗の評価に準じて、導電性塗膜（厚み２０μｍ）の低温低湿（１５℃×１０％ＲＨ）時の電気抵抗と、高温高湿（３５℃×８５％ＲＨ）時の電気抵抗をそれぞれ測定し、電気抵抗の差を変動桁数で示した。なお、この時の印加電圧は１０Ｖである。
【００７９】
〔電圧依存性〕
上記電気抵抗の評価に準じて、２５℃×５０％ＲＨの環境下、導電性塗膜（厚み２０μｍ）の０．１Ｖ電圧印加時の電気抵抗と、１００Ｖ電圧印加時の電気抵抗をそれぞれ測定し、電気抵抗の差を変動桁数で示した。
【００８０】
【表１】

【００８１】
【表２】

【００８２】
【表３】

【００８３】
上記結果から、全実施例品は、特定の導電性ポリマーと、特定のバインダーポリマーとを組み合わせて用いているため、環境依存性および電圧依存性の双方の特性に優れ、しかも電気抵抗が小さいことがわかる。しかも、全実施例品は、特定の溶解性を示す界面活性剤を用いているため、安定性に優れ、経時の電気抵抗も良好であることがわかる。
【００８４】
これに対して、比較例１，４品は、導電性ポリマーと、バインダーポリマーとを組み合わせて用いているため、環境依存性および電圧依存性の双方の特性に優れ、しかも電気抵抗が小さい。しかし、導電性ポリマーを形成するために用いられる界面活性剤が、所定の溶解性を示すものではない。特に、比較例４品は、バインダーポリマー中で、導電性ポリマーが凝集して安定性が悪いため、電気抵抗の電圧依存性が悪い。また、比較例１品は、界面活性剤がカルボン酸であり、イオン結合力が弱いため、保管後経時とともに電気抵抗が大きくなることがわかる。また、比較例２，５品は、電子導電剤を用いているため、環境依存性に優れているが、バインダーポリマー中に分散している電子導電剤の粒径が大きく、電子導電剤がバインダーポリマー中で均一に分散していないため、電圧依存性に劣ることがわかる。比較例３品は、イオン導電剤を用いているため、電圧依存性に優れているが、環境依存性に劣ることがわかる。
【００８５】
【実施例１３】
実施例１０と同様にして、特定の導電性ポリマー（ポリアニリン）を作製した。ついで、このポリアニリンの固形分５部を、ポリエーテルポリオール（三洋化成社製、ＦＡ７１８）９０部に混合し、水分と溶剤分を揮発させた後、ポリマーポリオール（三井化学社製、ＰＯＰ３１−２８）１０部と、第三級アミン触媒（花王社製、カオライザーＮｏ．３１）０．５部と、第三級アミン触媒（東ソー社製、トヨキャットＨＸ−３５）０．０５部と、発泡剤（水）２部と、シリコーン系整泡剤（日本ユニカー社製、Ｌ−５３０９）２部と、クルードＭＤＩ（住友バイエルウレタン社製、スミジュール４４Ｖ２０）８．８部と、トリレンジイソシアネート（三井化学社製、ＴＤＩ−８０）２０．５部と、ホウ酸カリウム塩（日本カーリット社製、ＬＲ１４７）１部とを配合して、ポリウレタン原料を調製した。つぎに、予め準備した成形型（円筒型）内に、軸体となる芯金（直径５ｍｍ、ＳＵＳ３０４製）をセットした後、成形キャビティ内に上記ポリウレタン原料を注入し、これを発泡硬化させた。その後、脱型して、軸体の外周面に沿ってウレタンフォーム層（厚み４ｍｍ）が形成されてなるトナー供給ロールを作製した。
【００８６】
【実施例１４】
〔ベース層用材料の調製〕
（シリカ処理済みカーボンブラックの作製）
カーボンブラック（三菱化学社製、ダイアブラック♯３０３０）を５００部計り取り、メタノールと水の混合溶液〔メタノール：水＝１：９（重量比）〕１０００部で湿潤させ、さらに４０００部の水を加え、スチールボールを充填したアトライターで均一で粘稠なスラリーになるまで充分に分散させた。つぎに、スラリーを篩を通してスチールボールと分離し、水１０，０００部に相当する容量まで希釈した。そして、スラリーを９０℃に加熱した後、水酸化ナトリウム溶液の添加により、ｐＨを１０．０に調節した。つぎに２種類の溶液を別個に調製した。
（イ）３号けい酸ナトリウム溶液８３．３部を水１０００部に相当する容量まで水で希釈した。
（ロ）２．５０％硫酸溶液を５００部
その後、上記ｐＨを１０．０に調節したスラリーに、（イ）の希釈けい酸ナトリウム溶液５０部を３０秒以内で加え、スラリーのｐＨを１１．０に調節した。このｐＨに保ったまま１０分間攪拌を続けた後、（ロ）の硫酸溶液５０部を３０秒以内で加え、スラリーのｐＨを８．５に調節した。この添加方法を２０回繰り返し、（イ）、（ロ）の両液を添加し終えた。さらに１時間攪拌を続け、希硫酸を加えｐＨを６．５〜７．０に調節した。スラリーを濾過し、可溶性塩がなくなるまで洗浄し乾燥することにより、目的とするシリカ処理済みカーボンブラック（Ｓｉ含有量５．０重量％）を得た。
【００８７】
つぎに、両末端にビニル基を有するポリジメチルシロキサン（アヅマックス社製、ＤＭＳ−Ｖ３１）〔粘度：１０００ｍＰａ・Ｓ／２５℃〕１００部と、上記のシリカ処理済みカーボンブラック１０部と、ヒドロシリル硬化剤（東芝シリコーン社製、ＴＳＦ４８４）５部と、ヒドロシリル化触媒〔白金カルボニル錯体（アヅマックス社製、ＳＩＰ ６８２９．０）〕３０ｐｐｍと、アセチレンアルコール〔３，５−ジメチル−１−ヘキシン−３−オール（ＤＭＨＯ）〕０．０５部を、ロールを用いて混練して、液状ポリマー組成物を調製した。
【００８８】
〔中間層用材料の調製〕
実施例１２と同様にして、導電性組成物を調製した。
【００８９】
〔表層用材料の調製〕
実施例１と同様にして、導電性組成物を調製した。
【００９０】
〔現像ロールの作製〕
軸体である芯金（直径１０ｍｍ、ＳＵＳ３０４製）をセットした射出成形用金型内に、上記ベースゴム層用材料を注型し、１５０℃×４５分の条件で加熱した後、脱型して、軸体の外周面に沿ってベースゴム層（厚み５ｍｍ）を形成した。ついで、上記中間層用材料を上記ベースゴム層の外周面に塗布して、厚み５０μｍの中間層を形成した。さらに、上記表層用材料を上記中間層の表面に塗布して表層（厚み２０μｍ）を形成し、軸体の外周面にベースゴム層が形成され、その外周面に中間層が形成され、さらにその外周面に表層が形成されてなる現像ロールを作製した。
【００９１】
【実施例１５】
〔ベース層用材料の調製〕
実施例１４のベース層用材料と同様にして、液状ポリマー組成物を調製した。
【００９２】
〔中間層用材料の調製〕
バインダーポリマーであるＨ−ＮＢＲ（日本ゼオン社製、ゼットポール００２０）１００部と、実施例１４のベース層用材料で用いたシリカ処理済みカーボンブラック３５部と、架橋剤である硫黄１部と、スルフェンアミド系架橋促進剤（大内新興化学工業社製、ノクセラーＣＺ）０．５部と、ジチオカルバミン酸塩系架橋促進剤（大内新興化学工業社製、ノクセラーＢＺ）０．５部とをロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）２００部とトルエン３００部に溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【００９３】
〔表層用材料の調製〕
実施例９と同様にして、導電性組成物を調製した。
【００９４】
〔帯電ロールの作製〕
軸体である芯金（直径１０ｍｍ、ＳＵＳ３０４製）をセットした射出成形用金型内に、上記ベースゴム層用材料を注型し、１５０℃×４５分の条件で加熱した後、脱型して、軸体の外周面に沿ってベースゴム層（厚み３ｍｍ）を形成した。ついで、上記中間層用材料を上記ベースゴム層の外周面に塗布して、厚み３０μｍの中間層を形成した。さらに、上記表層用材料を上記中間層の表面に塗布して表層（厚み１０μｍ）を形成し、軸体の外周面にベースゴム層が形成され、その外周面に中間層が形成され、さらにその外周面に表層が形成されてなる帯電ロールを作製した。
【００９５】
【実施例１６】
実施例６と同様にして、導電性組成物を調製した。そして、この導電性組成物を、円筒状軸体が配設されたロール成形用金型に注型して、単層構造の給紙ロール（厚み４ｍｍ）を作製した。
【００９６】
【実施例１７】
〔ベース層用材料の調製〕
実施例６と同様にして、導電性組成物を調製した。
【００９７】
〔中間層用材料の調製〕
実施例５と同様にして、導電性組成物を調製した。
【００９８】
〔表層用材料の調製〕
実施例７と同様にして、導電性組成物を調製した。
【００９９】
〔中間転写ベルトの作製〕
上記各材料を用いて、厚み２００μｍのベース層と、厚み５０μｍの中間層と、厚み５０μｍの表層とからなる、３層構造の中間転写ベルト（無端ベルト）を作製した。
【０１００】
【実施例１８】
〔ベース層用材料の調製〕
実施例６と同様にして、導電性組成物を調製した。
【０１０１】
〔中間層用材料の調製〕
参考例１と同様にして、導電性組成物を調製した。
【０１０２】
〔表層用材料の調製〕
実施例７と同様にして、導電性組成物を調製した。
【０１０３】
〔中間転写ベルトの作製〕
上記各材料を用いて、厚み５０μｍのベース層と、厚み２００μｍの中間層と、厚み２０μｍの表層とからなる、３層構造の中間転写ベルト（無端ベルト）を作製した。
【０１０４】
【比較例６】
〔中間層用材料の調製〕
比較例２と同様にして、導電性組成物を調製した。
【０１０５】
〔表層用材料の調製〕
比較例５と同様にして、導電性組成物を調製した。
【０１０６】
〔現像ロールの作製〕
上記中間層用材料および表層用材料を、それぞれ上記のように変更する以外は、実施例１４と同様にして、現像ロールを作製した。
【０１０７】
【比較例７】
〔中間層用材料の調製〕
比較例２と同様にして、導電性組成物を調製した。
【０１０８】
〔表層用材料の調製〕
比較例３と同様にして、導電性組成物を調製した。
【０１０９】
〔帯電ロールの作製〕
上記中間層用材料および表層用材料を、それぞれ上記のように変更する以外は、実施例１５と同様にして、帯電ロールを作製した。
【０１１０】
【比較例８】
導電性ポリマー（ポリアニリン）を配合しない以外は、実施例１３と同様にして、トナー供給ロールを作製した。
【０１１１】
【比較例９】
〔ベース層用材料の調製〕
バインダーポリマーであるポリウレタン（日本ミラクトラン社製、ＴＰＵ）９５部と、導電剤であるアセチレンブラック（電気化学工業社製、デンカブラックＨＳ１００）５部をロールを用いて混練し、これらをメチルエチルケトン（ＭＥＫ）５００部に溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【０１１２】
〔中間層用材料の調製〕
バインダーポリマーである可溶性ナイロン（帝国化学社製、トレジンＥＦ３０Ｔ）９５部と、導電剤であるアセチレンブラック（電気化学工業社製、デンカブラックＨＳ１００）５部を、メタノール４００部と水１００部とに溶解した後、３本ロールを用いて混練し、導電性組成物を調製した。
【０１１３】
〔表層用材料の調製〕
比較例３と同様にして、導電性組成物を調製した。
【０１１４】
〔中間転写ベルトの作製〕
上記各材料を用いる以外は、実施例１７と同様にして、３層構造の中間転写ベルト（無端ベルト）を作製した。
【０１１５】
このようにして得られた実施例品および比較例品の各ロールを用いて、下記の基準に従い、各特性の評価を行った。これらの結果を、後記の表４および表５に併せて示した。
【０１１６】
〔電気抵抗〕
金属ロール電極法により、電気抵抗を測定した。すなわち、ステンレス製の金属ロール上に、各ロールを接触させ、各ロールの両端を荷重７００ｇで押圧し、この状態で上記各ロールの一端に１００Ｖの電圧を印加してロールの電気抵抗を測定した。なお、中間転写ベルトについては、中間転写ベルトの内側および外側にステンレス製の金属ロールを、それぞれ荷重７００ｇで押圧し、上記ロールと同様にして、電気抵抗を測定した。
【０１１７】
〔環境依存性〕
上記電気抵抗の評価に準じて、低温低湿（１５℃×１０％ＲＨ）時の電気抵抗と、高温高湿（３５℃×８５％ＲＨ）時の電気抵抗をそれぞれ測定し、電気抵抗の差を変動桁数で示した。なお、この時の印加電圧は１０Ｖである。
【０１１８】
〔電圧依存性〕
上記電気抵抗の評価に準じて、２５℃×５０％ＲＨの環境下、０．１Ｖ電圧印加時の電気抵抗と、１００Ｖ電圧印加時の電気抵抗をそれぞれ測定し、電気抵抗の差を変動桁数で示した。
【０１１９】
〔トナー供給耐久性〕
トナー供給ロールを市販のプリンターに組み込み、５０００枚プリントした後のトナー供給ロールの状態を観察した。そして、トナーの詰まりがなく、画像への影響がないものを○、トナーの詰まりがあり、べた黒画像の濃度がマクベス濃度で１．２５以下になったものを×として評価した。
【０１２０】
〔現像特性〕
現像ロールを市販のプリンター（キャノン社製、ＬＢＰ２８１０）に組み込み１週間放置した後、低温低湿（１５℃×１０％ＲＨ）、常温常湿（２５℃×５０％ＲＨ）、高温高湿（３５℃×８５％ＲＨ）下で文字画像をプリントして、画像を目視評価した。そして、細線の途切れがなく、画像のかすれが見られないものを○、細線の途切れがあり、画像のかすれが見られるものを×として評価した。
【０１２１】
〔帯電特性〕
上記現像特性に準じて、ハーフトーンの画像を目視評価した。そして、画像にすじ、黒斑点、白ぬけがあるものを×、ないものを○として評価した。
【０１２２】
〔給紙特性〕
給紙ロールを市販のプリンター（キャノン社製、ＬＢＰ２８１０）に組み込み、帯電した紙粉による付着で摩擦係数が３０％以上低下したものを×、摩擦係数の変化量が３０％未満のものを○とした。
【０１２３】
〔転写特性〕
中間転写ベルト（無端ベルト）を市販のフルカラー複写機に組み込み、８０ｇ／ｍ² 紙にベタ画像の画出しを行った。画出しをする環境は、１０℃×２０％ＲＨ、２５℃×５０％ＲＨ、３５℃×８５％ＲＨの３環境で行った。評価は、３環境とも濃度むらがなく、均一な画像が得られたものを○、いずれかの環境で濃度むらが発生するものを×とした。
【０１２４】
【表４】

【０１２５】
【表５】

【０１２６】
上記結果から、実施例品は、トナー供給耐久性、現像特性、帯電特性、給紙特性、転写特性が優れていることがわかる。
【０１２７】
これに対して、比較例６品は現像特性が劣り、比較例７品は帯電特性が劣り、比較例８品はトナー供給耐久性が劣り、比較例９品は転写特性が劣ることがわかる。
【０１２８】
【発明の効果】
以上のように、本発明の導電性組成物は、特定の導電性ポリマーと、特定のバインダーポリマーとを含有するものである。そのため、特定の導電性ポリマーが、特定のバインダーポリマー中に分散または溶解して特定の導電性ポリマーと特定のバインダーポリマーとの複合体からなるポリマーアロイを形成し、電気抵抗の電圧依存性に優れるというイオン導電剤の利点と、電気抵抗の環境依存性に優れるという電子導電剤の利点との双方の特性を備え、しかも電気抵抗のばらつきが小さく、低電気抵抗化が可能であるという優れた効果を奏する。そのうえ、上記特定の導電性ポリマーを形成するために用いられる界面活性剤が、所定の溶解性を示すものであるため、特定のバインダーポリマー中で、特定の界面導電性ポリマーが、凝集することなく安定に存在し、経時の電気抵抗も良好になる。
【０１２９】
また、上記界面活性剤が、分子構造中に、スルホン酸基またはリン酸エステル構造を有するものであると、導電性ポリマーのドーパントとしての役割を果たし、導電性がさらに良好となる。さらにまた、上記界面活性剤が、分子構造中に、エーテル構造とともに、スルホン酸基またはリン酸エステル構造を有するものであると、電気的な安定性がより一層良好となる。
【０１３０】
さらに、上記界面活性剤が、分子構造中に、アルキレンエーテルの繰り返し構造を有するものであると、特定の導電性ポリマーと、特定のバインダーポリマーとの相溶性が向上し、導電性組成物の調製が容易となる。
【０１３１】
さらにまた、上記アルキレンエーテルの繰り返し構造（ｎ）が特定の範囲内のものであると、特定の導電性ポリマーと、溶剤や特定のバインダーポリマーとの相溶性がさらに向上し、導電性組成物の調製がさらに容易となる。
【０１３２】
そして、本発明の導電性組成物を電子写真機器部材、例えば、現像ロールの電極層、表層等として用いた場合、画質が良好で、環境の変化が大きい場合でも画質への影響が少なく、品質の安定性に優れている。また、軸体（芯金）に導電性組成物をコーティングして電極層や表層を形成する場合、従来の電子導電剤を用いた場合のように膜厚を制御する必要がなく、しかも本発明の導電性組成物は安定なため、膜厚の製品特性への影響が少なくなる。また、本発明の導電性組成物は、印加電圧による電気抵抗を一定に制御できるため、例えば、現像ロールではトナー層形成性、帯電性を安定化することができ、帯電部材では感光体との間での電流制御を安定化でき、転写部材でも感光体上のトナーの転写は電圧の制御により行われることから転写性能を安定化できる。 [0001]
BACKGROUND OF THE INVENTION
  The present inventionFor electrophotographic equipmentConductive composition and electrophotographic apparatus using the sameVesselMaterial, Its manufacturing methodSpecifically, an electrophotographic machine such as a developing roll, a charging roll, a transfer roll, a toner supply roll, a static elimination roll, a paper feeding roll, a transport roll, a cleaning roll, a developing blade, a charging blade, a cleaning blade, a transfer belt, etc.VesselUsed for materials,For electrophotographic equipmentConductive composition and electrophotographic apparatus using the sameVesselMaterial, Its manufacturing methodIt is about.
[0002]
[Prior art]
  Generally, in order to control conductivity, an ion conductive agent or an electronic conductive agent is blended in the binder polymer. Since the ionic conductive agent is dissolved in the binder polymer, there is an advantage that the variation in conductivity is small, the variation in electric resistance when the voltage is changed is small, and the voltage dependency of the electric resistance is excellent. However, the ionic conductive agent has an electric resistance of 1 × 10 6 because the mechanism of conductivity development is due to ionic conduction.⁸If it is Ω · cm or more, the conduction of ions in the binder polymer is good and the conductivity can be controlled, but the electrical resistance is 1 × 10⁸If it is less than Ω · cm, ion conduction is less likely to occur, and control of conductivity becomes difficult. In addition, since the ionic conductive agent is easily affected by moisture and the like, and the electric resistance fluctuates by two or more digits under the conditions of high temperature and high humidity and low temperature and low humidity, the electric resistance is inferior to the environment and the electrophotographic machineVesselThere are many restrictions on the use as a material (OA member).
[0003]
  On the other hand, electronic conductive agents such as carbon black are not easily affected by moisture, etc., have small fluctuations in electrical resistance under conditions of high temperature and high humidity and low temperature and low humidity, and are excellent in environmental dependence and can have low electric resistance. Because it is an electrophotographic machineVesselIt is used as a material (OA member). However, since the above-mentioned electronic conductive agent is difficult to uniformly disperse in the binder polymer, variation in electric resistance is large and it is difficult to control conductivity. In addition, even when they are relatively uniformly dispersed, the electrical conductivity changes due to the tunnel effect in which electrons are transmitted between the carbons in the binder polymer by a high voltage, so that the electrical resistance fluctuates when the voltage is changed. Large and inferior in voltage dependency of electrical resistance. For this reason, at the time of use as an OA member, current and voltage must be controlled to a high degree, and there is a limit to simplification (cost reduction) of the OA member.
[0004]
  As described above, each of the ionic conductive agent and the electronic conductive agent has drawbacks, and the conductive composition having the respective advantages, that is, the ionic conductivity that the electrical resistance is small and the voltage dependence of the electrical resistance is excellent. Development of a conductive composition having both the advantages of the agent and the advantages of the electronic conductive agent that can reduce the electrical resistance and is excellent in the environmental dependency of the electrical resistance is awaited.
[0005]
  Therefore, the present inventor has conducted research to solve these problems, and applied for a patent on a conductive composition containing a conductive polymer having a surfactant structure and a binder polymer as essential components (see Patent Document 1). ) When the conductive composition described in Patent Document 1 was used, significant improvement in electrical characteristics could be achieved.
[0006]
[Patent Document 1]
          JP 2002-167519 A
[0007]
[Problems to be solved by the invention]
  However, as a result of further research on the conductive composition described in Patent Document 1, the inventor found that the conductive composition had a slightly poor stability of the conductive polymer in the binder polymer, and was agglomerated. Therefore, it was found that the initial electric resistance was good, but the electric resistance tended to increase with time.
[0008]
  The present invention has been made in view of such circumstances, and is excellent in voltage dependence and environmental dependence of electrical resistance, has small variations in electrical resistance, can be reduced in electrical resistance, and can be stored with time during storage of the composition. Excellent electrical resistanceFor electrophotographic equipmentConductive composition and electrophotographic apparatus using the sameVesselMaterial, Its manufacturing methodThe purpose is to provide
[0009]
[Means for Solving the Problems]
  In order to achieve the above object, the present invention comprises the following (A) and (B) as essential components:For electrophotographic equipmentA conductive composition comprising:belowSurfactant(A)Has a solubility of 3% or more in toluene or methyl ethyl ketone and a solubility of 3% or more in water, or maintains a micelle dispersion state in water for 10 hours or more.For electrophotographic equipmentThe conductive composition is the first gist. The present invention also provides the aboveFor electrophotographic equipmentElectrophotographic machine using conductive compositionVesselMaterial 2nd summaryAnd the manufacturing method of the electrophotographic apparatus member is the third gist.And
(A)The raw material monomer of the conductive polymer and the following surfactant (a) are chemically oxidatively polymerized with an oxidizing agent.Conductive polymer.
  (A) At least one surfactant selected from the group consisting of polyoxyalkylene alkyl ether phosphate esters, dialkyl sulfosuccinate sodium salts, polyoxyalkylene alkyl phenyl ether sulfate ammonium salts, and sodium amide ether sulfonates.
(B)Solvent-soluble, consisting of at least one selected from the group consisting of acrylic resins, urethane resins, fluorine resins, polyamide resins, polyimide resins, epoxy resins, urea resins, rubber polymers and thermoplastic elastomersBinder polymer.
[0010]
  That is, this inventor is excellent in the stability of the conductive polymer in the binder polymer and also has good electrical resistance over time.For electrophotographic equipmentFurther research and development were conducted to obtain a conductive composition. AndChemical oxidative polymerization of the raw material monomer of the conductive polymer and surfactant with an oxidizing agentOf conductive polymerThe worldFocusing on surfactants, research was repeated focusing on the solubility of surfactants. As a result, the surfactant used has a solubility of 3% or more in toluene or methyl ethyl ketone and a solubility of 3% or more in water, or maintains a micelle dispersion state in water for 10 hours or more. If there isspecificIn the binder polymer,specificThe present inventors have found that the conductive polymer exists stably without agglomeration and that the electric resistance with time is good, and the present invention has been achieved.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  Next, an embodiment of the present invention will be described.
[0012]
  Of the present inventionFor electrophotographic equipmentConductive composition(Hereafter, abbreviated as “conductive composition”)IsThe raw material monomer of the conductive polymer and the following surfactant (a) are chemically oxidatively polymerized with an oxidizing agent.A conductive polymer (component A),specificIt can be obtained using a binder polymer (component B). In the present invention,WorldSurfactant(A)However, the greatest feature is that it exhibits a solubility of 3% or more in toluene or methyl ethyl ketone and a solubility of 3% or more in water, or maintains a micelle dispersion state in water for 10 hours or more. is there.
  (A) At least one surfactant selected from the group consisting of polyoxyalkylene alkyl ether phosphate esters, dialkyl sulfosuccinate sodium salts, polyoxyalkylene alkyl phenyl ether sulfate ammonium salts, and sodium amide ether sulfonates.
[0013]
  the abovespecificConductive polymer (component A), GuidanceA raw material monomer for the electropolymer;the aboveSurfactant(A)Is chemically oxidatively polymerized with an oxidizing agent such as ammonium persulfate, hydrogen peroxide, ferric chloride, etc.thingCan be manufactured by.
[0014]
  The raw material monomer of the conductive polymer is not particularly limited as long as it has conductivity. For example, aniline (including aniline derivatives as well as aniline salts such as aniline hydrochloride), pyrrole, thiophene, acetylene, para Examples thereof include phenylene, phenylene vinylene, furan, selenophene, isothianaphthene, paraphenylene sulfide, paraphenylene oxide, and vinylene sulfide.
[0015]
  The above surfactant(A)It is necessary to use one that exhibits a solubility of 3% or more in toluene or methyl ethyl ketone and a solubility of 3% or more in water, or that maintains a micelle dispersion state in water for 10 hours or more. That is, the above surfactant(A)However, if the solubility in toluene or methyl ethyl ketone is less than 3%, the compatibility with the binder polymer becomes poor. In addition, the above surfactant(A)However, if the solubility in water is less than 3%, or the retention time of the micelle dispersion state in water is less than 10 hours, the reactivity during synthesis and the uniformity of the polymer are deteriorated.
[0016]
  In the present invention, water is intended to use pure water (distilled water), and toluene and methyl ethyl ketone are intended to use special grades, respectively. Further, in the present invention, the solubility of 3% or more means that the solution is completely dissolved at least 3% or is in a suspended state (suspension).
[0017]
  The above surfactant(A) inThe repeating structure (n) of the alkylene ether is preferably in the range of n = 1-30, particularly preferably in the range of n = 3-15.
[0018]
  The above surfactant(A)Specifically, polyoxyalkylene alkyl ether phosphate represented by the following formula (2) or formula (3), dialkylsulfosuccinate sodium salt represented by the following formula (4), And polyoxyalkylene alkylphenyl ether sulfate ammonium salt represented by the formula (5), sodium amide ether sulfonate represented by the following formula (6), and the like. The sulfonic acid or phosphoric acid may be a salt or an acid obtained by ion exchange.
[0019]
[Chemical formula 2]

[0020]
[Chemical Formula 3]

[0021]
[Formula 4]

[0022]
[Chemical formula 5]

[0023]
[Chemical 6]

[0024]
  Raw material monomers for the conductive polymer and surfactant(A)Is the weight ratio of raw material monomer / surfactant(A)= Preferably within the range of 96/4 to 30/70, particularly preferably raw material monomer / surfactant(A)= Within the range of 80/20 to 40/60. That is, surfactant(A)If the weight ratio is less than 4, the compatibility and dispersibility with the binder polymer will decrease, and conversely the surfactant.(A)If the weight ratio exceeds 70, the effect of the surfactant on the ionic conductivity becomes too strong, and the electronic conductivity of the conductive polymer is reduced.
[0025]
  the abovespecificThe number average molecular weight (Mn) of the conductive polymer (component A) is preferably in the range of 500 to 100,000, particularly preferably in the range of 1,000 to 20,000.
[0026]
  the abovespecificAs binder polymer (component B) used with conductive polymer (component A)AKuryl resin, urethane resin, fluorine resin, polyamide resin, polyimide resin, epoxy resin, urea resin, rubber polymerandThermoplastic elastomerSolvent-soluble one consisting of at least one selected from the group consisting ofBe. ThisAmong these, in terms of excellent compatibility with the component A,Solvent solubleAcrylic resin,Solvent solubleEpoxy resins are preferred.
[0027]
  In the present invention, the term “solvent soluble” refers to a case where the solvent is completely dissolved in the solvent or is in a suspended state (suspension).
[0028]
  the aboveSolvent solubleExamples of the acrylic resin include polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and the like.
[0029]
  the aboveSolvent solubleExamples of the urethane-based resin include ether-based, ester-based, aliphatic-based urethane, and those obtained by copolymerizing silicone-based polyol and fluorine-based polyol.
[0030]
  the aboveSolvent solubleExamples of the fluorine-based resin include polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, and the like.
[0031]
  the aboveSolvent solubleExamples of the polyamide-based resin include alcohol-soluble methoxymethylated nylon.
[0032]
  the aboveSolvent solubleExamples of the polyimide resin include polyamide imide (PAI), polyamic acid, and silicone imide.
[0033]
  the aboveSolvent solubleExamples of the epoxy resin include bisphenol A type epoxy resin, novolak type epoxy resin, brominated epoxy resin, polyglycol type epoxy resin, polyamide combined type epoxy resin, silicon modified epoxy resin, amino resin combined type epoxy resin, and alkyd resin. Combination type epoxy resin and the like can be mentioned.
[0034]
  the aboveSolvent solubleExamples of the rubber polymer include natural rubber (NR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (H-NBR), styrene butadiene rubber (SBR), isoprene rubber (IR), Urethane rubber, chloroprene rubber (CR), epichlorohydrin rubber (ECO), ethylene-propylene-diene polymer (EPDM), acrylic rubber (ACM), chlorosulfonated polyethylene (CSM), polysulfide rubber, fluoro rubber, etc. It is done.
[0035]
  the aboveSolvent solubleExamples of the thermoplastic elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and styrene. -Ethylene / propylene / styrene block copolymer (SEPS) and the like.
[0036]
  the abovespecificThe number average molecular weight (Mn) of the binder polymer (component B) is preferably in the range of 5,000 to 2,000,000, particularly preferably in the range of 20,000 to 800,000.
[0037]
  the abovespecificConductive polymer (component A) raw material (conductive polymer raw material monomer and surfactant)(A)And the total amount)specificThe mixing ratio with the binder polymer (component B) is preferably within the range of A component raw material / B component = 1/99 to 50/50, particularly preferably A component raw material / B component = 4 / It is in the range of 96 to 35/65. That is, if the weight ratio of the component A raw material is less than 1, the effect on conductivity is small. Conversely, if the weight ratio of the component A raw material exceeds 50, the conductive polymer tends to be hard and brittle. This is because the physical properties as physical properties are lowered.
[0038]
  In addition to the A component and the B component, an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like may be added to the conductive composition of the present invention.
[0039]
  Examples of the ionic conductive agent include a quaternary ammonium salt, a borate, a surfactant [the surfactant(A)Etc.]. These may be used alone or in combination of two or more.
[0040]
  In addition, the blending ratio of the ionic conductive agent is determined from the viewpoint of physical properties and electrical characteristics.(A)In the range of 0.01 to 5 parts, particularly preferably in the range of 0.5 to 2 parts, based on 100 parts by weight (hereinafter abbreviated as “parts”) of the total of component B and component B. It is.
[0041]
  Examples of the electronic conductive agent include carbon black, c-ZnO (conductive zinc oxide), and c-TiO.₂(Conductive titanium oxide), c-SnO₂(Conductive tin oxide), graphite and the like.
[0042]
  In addition, the blending ratio of the electronic conductive agent is determined from the viewpoint of physical properties and electrical characteristics.(A)Is preferably in the range of 1 to 30 parts, particularly preferably in the range of 5 to 20 parts.
[0043]
  Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, block isocyanate, and melamine, epoxy curing agents, polyamine curing agents, hydrosilyl crosslinking agents, and peroxides.
[0044]
  In addition, the blending ratio of the crosslinking agent is determined from the viewpoint of physical properties, adhesiveness, and liquid storage properties.(A)Is preferably in the range of 1 to 30 parts, particularly preferably in the range of 3 to 10 parts, with respect to 100 parts in total of the B component and the total of 100 parts.
[0045]
  In addition to the above components, the conductive composition may contain a crosslinking accelerator, a catalyst, an anti-aging agent, a dopant and the like as necessary.
[0046]
  Examples of the crosslinking accelerator include sulfenamide-based crosslinking accelerators, dithiocarbamate-based crosslinking accelerators, amines, and organic tin-based catalysts.
[0047]
  The conductive composition of the present invention can be produced, for example, as follows. That is, first, according to the method described above,specificA conductive polymer (component A) is prepared. Then thisspecificConductive polymer (component A)specificWhile blended with the binder polymer (component B), an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like are blended as necessary. And the target electrically conductive composition can be obtained by knead | mixing these using kneading machines, such as a roll, a kneader, a Banbury mixer. Further, after kneading with a roll or the like, it may be dissolved or dispersed in water or a solvent to form a conductive composition (coating liquid).
[0048]
  According to the above method,specificWhile producing conductive polymer (component A), thisspecificConductive polymer (component A) using a high shear disperserspecificYou may make it disperse | distribute in a binder polymer (B component). When using a high shear disperser like this,specificThe particle size of the conductive polymer (component A) becomes smaller,specificThis is preferable because it is finely dispersed uniformly in the binder polymer (component B).specificThe particle size (median diameter) of the conductive polymer (component A) is preferably 1 μm or less from the viewpoint of dispersibility.
[0049]
  As the high shear disperser, for example, a high speed bead mill using ceramic beads such as glass and zirconia, a sand mill, a ball mill, a three roll, a pressure kneader, a colloid mill using a grinding force, and the like are used.
[0050]
  Examples of the solvent include m-cresol., MeExamples thereof include organic solvents such as tilethyl ketone (MEK) and toluene.
[0051]
  The conductive composition of the present invention includes, for example, a developing roll, a charging roll, a transfer roll, a fixing roll, a toner supply roll, a static elimination roll, a roll member such as a paper feeding roll, a transport roll, and a cleaning roll, a developing blade, a charging blade, Electrophotographic machines such as blade members such as cleaning blades, belt members such as transfer belts and paper feed beltsVesselUsed for electronic materials such as materials, sensors utilizing these electrical characteristics, antistatic materials, actuators and the like.
[0052]
  Electrophotographic machine using the conductive composition of the present inventionVesselExamples of the material include developing rolls, charging rolls, transfer rolls, fixing rolls, toner supply rolls, static elimination rolls, paper feed rolls, transport rolls, cleaning rolls and other roll members, developing blades, charging blades, cleaning blades and other blades. Examples thereof include belt members such as members, transfer belts, and paper feed belts. And the electrophotographic machine of the present inventionVesselIn the material, at least one of the intermediate layer and the surface layer is preferably formed using the conductive composition of the present invention.
[0053]
  Next, examples will be described together with comparative examples.
[0054]
[Example 1]
  1 mol of aniline and 1 mol of polyoxyalkylene alkyl ether phosphate ester (Price Surf 215C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) represented by the above formula (2) which is a surfactant, After oxidative polymerization in the presence, remove unreacted material with methanol, filter and replace the moisture with toluene,Specific conductive polymer (Polyaniline)Was made. Next, after dissolving 80 parts of polymethyl methacrylate (Sumitomo Chemical Co., Ltd., Sumipex LG6A, Mn: 20000) as a binder polymer in 500 parts of a solvent (toluene), the above-mentionedSpecific conductive polymer (Polyaniline)20 parts in solid content was added and kneaded using a three roll to prepare a conductive composition.
[0055]
[Example 2]
  As surfactant, except using dialkyl sulfosuccinate ester sodium salt (Daiichi Kogyo Seiyaku Co., Ltd., Neocor SW-C) represented by the formula (4),Specific conductive polymer (Polyaniline)Was made. And thisSpecific conductive polymer (Polyaniline)Was used in the same manner as in Example 1 to prepare a conductive composition.
[0056]
[Example 3]
  Except using polyoxyalkylene alkyl phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) represented by the formula (5) as the surfactant, the same as in Example 1,Specific conductive polymer (Polyaniline)Was made. And thisSpecific conductive polymer (Polyaniline)Was used in the same manner as in Example 1 to prepare a conductive composition.
[0057]
[Example 4]
  Except using sodium amide ether sulfonate represented by the formula (6) (manufactured by NOF Corporation, Sanamide CF3) as a surfactant,Specific conductive polymer (Polyaniline)Was made. And thisSpecific conductive polymer (Polyaniline)Was used in the same manner as in Example 1 to prepare a conductive composition.
[0058]
[Example 5]
  1 mol of aniline and 0.8 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After polymerization, remove unreacted material with methanol,Specific conductive polymer (Polyaniline)Was made. Next, 80 parts of soluble nylon (Torresin EF30T manufactured by Teikoku Chemical Co., Ltd.), which is a binder polymer, is dissolved in 400 parts of methanol and 100 parts of water.Specific conductive polymer (Polyaniline)20 parts in solid content was added and kneaded using a three roll to prepare a conductive composition.
[0059]
[Example 6]
  1 mol of aniline and 0.8 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After polymerization, unreacted substances are removed with methanol, and filtered to replace methyl ethyl ketone (MEK).Specific conductive polymer (Polyaniline)Was made. Next, 92 parts of polyurethane (manufactured by Nippon Milactolan, TPU), which is a binder polymer, is dissolved in 500 parts of methyl ethyl ketone (MEK).Specific conductive polymer (Polyaniline)8 parts of solid content was added and kneaded using three rolls to prepare a conductive composition.
[0060]
[Example 7]
  1 mol of aniline and 0.8 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After polymerization, unreacted substances are removed with methanol, and filtration is performed to replace moisture and unreacted substances with a solvent [MEK / toluene = 2/3 (weight ratio)].Specific conductive polymer (Polyaniline)Was made. Next, 80 parts of an acrylic fluororesin (Dainippon Ink and Chemicals, Defensor TR230K) as a binder polymer is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, and then the above.Specific conductive polymer (Polyaniline)20 parts in solid content was added and kneaded using a three roll to prepare a conductive composition.
[0061]
[Example 8]
  As in Example 7,Specific conductive polymer (Polyaniline)Was made. Next, 80 parts of H-NBR (Nippon Zeon Corporation, Zetpol 0020) as a binder polymer, 1 part of sulfur as a crosslinking agent, and a sulfenamide-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller CZ) 0.5 part and dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) 0.5 part are kneaded using a roll, and these are 200 parts of methyl ethyl ketone (MEK). After dissolving in 300 parts of toluene, the aboveSpecific conductive polymer (Polyaniline)20 parts in solid content was added and kneaded using a three roll to prepare a conductive composition.
[0062]
[Example 9]
  As in Example 7,Specific conductive polymer (Polyaniline)Was made. Next, 80 parts in solid content of acrylic fluorine-based resin (Dainippon Ink & Chemicals, manufactured by Dainippon Ink & Chemicals, Inc.) as a binder polymer, and 5 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku & Co.) as a conductive agent. Are dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene,Specific conductive polymer (Polyaniline)Was added in a solid content of 15 parts and kneaded using three rolls to prepare a conductive composition.
[0063]
[Example 10]
  1 mol of aniline and 0.3 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After the polymerization, unreacted substances were removed with methanol, filtered, and water was replaced with a solvent [MEK / toluene = 2/3 (weight ratio)].Specific conductive polymer (Polyaniline)Was made. Next, 80 parts of binder polymer H-NBR (manufactured by Zeon Corporation, Zetpol 0020), 1 part of quaternary ammonium salt (tetrabutylammonium hydrogen sulfate: TBAHS) as a conductive agent, and conductive agent. 1 part of potassium borate (manufactured by Nippon Carlit Co., LR147), 1 part of sulfur as a crosslinking agent, 0.5 part of a sulfenamide-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ), After kneading 0.5 part of dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller BZ) using a roll and dissolving them in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, the aboveSpecific conductive polymer (Polyaniline)18 parts in solid content was added and kneaded using three rolls to prepare a conductive composition.
[0064]
Example 11
  1 mol of pyrrole and 0.8 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Hightenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After the polymerization, unreacted substances were removed with methanol, filtered, and water was replaced with a solvent [MEK / toluene = 2/3 (weight ratio)].Specific conductive polymer (Polypyrrole)Got. Next, 80 parts of H-NBR as a binder polymer (Zeppol 0020 manufactured by Nippon Zeon Co., Ltd.), 1 part of sulfur as a cross-linking agent, and a sulfenamide-based cross-linking accelerator (manufactured by Ouchi Shinsei Chemical Industries, Noxeller) CZ) 0.5 part and 0.5 part of a dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) are kneaded using a roll, and these are kneaded with 200 parts of methyl ethyl ketone (MEK) and toluene. After dissolving in 300 parts,Specific conductive polymer (Polypyrrole)Was added in a solid content of 20 parts to prepare a conductive composition.
[0065]
Example 12
  1 mol of thiophene and 0.8 mol of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku, Hytenol NO8) as a surfactant are oxidized in the presence of 0.5 mol of an oxidizing agent (ammonium persulfate). After the polymerization, unreacted substances were removed with methanol, filtered, and water was replaced with a solvent [MEK / toluene = 2/3 (weight ratio)].Specific conductive polymer (Polythiophene)Got. Next, 80 parts of H-NBR as a binder polymer (Zeppol 0020 manufactured by Nippon Zeon Co., Ltd.), 1 part of sulfur as a cross-linking agent, and a sulfenamide-based cross-linking accelerator (manufactured by Ouchi Shinsei Chemical Industries, Noxeller) CZ) 0.5 part and 0.5 part of a dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) are kneaded using a roll, and these are kneaded with 200 parts of methyl ethyl ketone (MEK) and toluene. After dissolving in 300 parts,Specific conductive polymer (Polythiophene)Was added in a solid content of 20 parts to prepare a conductive composition.
[0066]
[Reference example 1]
  1 mol of aniline and a surfactant represented by the general formula (1) (wherein R¹= Butyl group, R²= Hydrogen, n = 2, m = 3) 1 mol of the oxidizer (ammonium persulfate) 1 mol in an aqueous solution was dropped and subjected to oxidative polymerization,Conductive polymer (Polyaniline)Got. Next, 75 parts of an active ingredient (nonvolatile content) of NMP (N-methyl-2-pyrrolidone) 15% solution (manufactured by Toyobo Co., Ltd., Viromax HR16NN) of polyamideimide as a binder polymer is added to the above.Conductive polymer (Polyaniline)The active ingredient (nonvolatile content) of 25 parts was added and kneaded using three rolls to prepare a conductive composition.
[0067]
[Comparative Example 1]
  1 mol of aniline and 0.8 mol of oleyl sarcosine acid represented by the following formula (7) (manufactured by NOF Corporation, oleyl sarcosine 221P) as a surfactant, 0.5 mol of an oxidizing agent (ammonium persulfate) After oxidative polymerization in the presence, remove unreacted material with methanol, filter to remove moisture,Conductive polymer (Polyaniline)Was made. Next, 80 parts of H-NBR as a binder polymer (Zeppol 0020 manufactured by Nippon Zeon Co., Ltd.), 1 part of sulfur as a cross-linking agent, and a sulfenamide-based cross-linking accelerator (manufactured by Ouchi Shinsei Chemical Industries, Noxeller) CZ) 0.5 part and 0.5 part of a dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) are kneaded using a roll, and these are kneaded with 200 parts of methyl ethyl ketone (MEK) and toluene. After dissolving in 300 parts,Conductive polymer (Polyaniline)20 parts in solid content was added and kneaded using a three roll to prepare a conductive composition.
[0068]
[Chemical 7]

[0069]
[Comparative Example 2]
  92 parts of binder polymer H-NBR (manufactured by Zeon Corporation, Zettopol 0020), 8 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.), 1 part of sulfur as a crosslinking agent, , 0.5 part of a sulfenamide-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ) and 0.5 part of a dithiocarbamate crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) Were kneaded using a roll, dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, and then kneaded using three rolls to prepare a conductive composition.
[0070]
[Comparative Example 3]
  98 parts of an acrylic fluorine-based resin (Dai Nippon Ink Chemical Co., Ltd., Defensor TR230K) as a binder polymer, 1 part of a quaternary ammonium salt (tetrabutylammonium hydrogen sulfate: TBAHS) as a conductive agent, and a conductive agent 1 part of potassium borate (manufactured by Nippon Carlit Co., Ltd., LR147) is kneaded using a roll, dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, kneaded using 3 rolls, and conductive. A sex composition was prepared.
[0071]
[Comparative Example 4]
  Except for using a higher alcohol sulfate sodium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Monogen Y500) as a surfactant,Conductive polymer (Polyaniline)Was made. And thisConductive polymer (Polyaniline)Was used in the same manner as in Example 1 to prepare a conductive composition.
[0072]
[Comparative Example 5]
  92 parts of binder polymer polymethyl methacrylate (Sumitomo Chemical Co., Sumipex LG6A, Mn: 20000) and conductive agent acetylene black (Electrochemical Co., Ltd., Denka Black HS100) are kneaded using a roll. These were dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, and then kneaded using three rolls to prepare a conductive composition.
[0073]
  Example product thus obtained, Reference productThe properties of the comparative example products were evaluated according to the following criteria. These results are shown in Tables 1 to 3 below.
[0074]
[Solubility]
  specificConductive polymerToThe solubility of the surfactant used in methyl ethyl ketone (MEK) and toluene was evaluated. In the evaluation, a surfactant having a concentration of 3% by weight or more dissolved in MEK or the like was evaluated as ◯, and a surfactant having a concentration of less than 3% by weight was evaluated as ×.
[0075]
[Solubility]
  GuidanceElectrical polymerToThe solubility of the surfactant used in water was evaluated. Evaluation is that the surfactant has a solubility of 3% or more in water, or that the micelle dispersion state is maintained in water for 10 hours or more, and the solubility of the surfactant in water is less than 3% Or the thing with the retention time of the micelle dispersion state in water less than 10 hours was set as x.
[0076]
〔Stability〕
  In the binder polymer of the conductive composition, GuidanceThe stability of the electropolymer after 10 hours was visually evaluated. Evaluation is performed in a binder polymer dissolved in a solvent.GuidanceIn the binder polymer, the electropolymer has poor stability and is separated or aggregates of 50 μm or more.GuidanceA polymer having good stability and not agglomerating 50 μm or more was rated as “◯”. In addition, evaluation of aggregation was performed according to the crush gauge method (JIS K5440).
[0077]
[Electric resistance of initial and time]
  The conductive composition was applied on a glass plate to prepare a conductive coating film having a thickness of 20 μm. Then, in an environment of 50 ° C. × 95% RH, the initial electrical resistance of the conductive coating film when a voltage of 10 V was applied and the electrical resistance after 30 days were measured according to SRIS 2304.
[0078]
(Environment dependency)
  According to the evaluation of the electrical resistance, the electrical resistance at the low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at the high temperature and high humidity (35 ° C. × 85% RH) of the conductive coating film (thickness 20 μm) Each was measured, and the difference in electrical resistance was indicated by the number of fluctuation digits. The applied voltage at this time is 10V.
[0079]
(Voltage dependency)
  According to the evaluation of the electrical resistance, the electrical resistance at the time of applying 0.1V voltage and the electrical resistance at the time of applying 100V voltage of the conductive coating film (thickness 20 μm) were measured in an environment of 25 ° C. × 50% RH. The difference in electrical resistance is shown by the number of fluctuation digits.
[0080]
[Table 1]

[0081]
[Table 2]

[0082]
[Table 3]

[0083]
  From the above results, all the examples arespecificA conductive polymer;specificSince the binder polymer is used in combination, it can be seen that both the environmental dependency and the voltage dependency are excellent and the electric resistance is small. In addition, all the examples have a surface activity that exhibits a specific solubility.AgentSince it is used, it is understood that the stability is excellent and the electrical resistance with time is also good.
[0084]
  On the other hand, since Comparative Examples 1 and 4 use a combination of a conductive polymer and a binder polymer, they are excellent in both environmental dependency and voltage dependency characteristics, and have low electrical resistance. However, GuidanceElectrical polymer-The surfactant used for forming does not exhibit a predetermined solubility. In particular, the Comparative Example 4 product is a binder polymer., GuidanceSince the electropolymer aggregates and the stability is poor, the voltage dependency of the electrical resistance is poor. Moreover, since the surfactant is carboxylic acid and the ionic bond strength is weak, it can be seen that the electrical resistance increases with time after storage. In addition, Comparative Examples 2 and 5 are excellent in environmental dependency because they use an electronic conductive agent, but the particle size of the electronic conductive agent dispersed in the binder polymer is large, and the electronic conductive agent is a binder. Since it is not uniformly dispersed in the polymer, it can be seen that the voltage dependency is poor. Since the product of Comparative Example 3 uses an ionic conductive agent, it is excellent in voltage dependency, but is inferior in environmental dependency.
[0085]
【Example13]
  In the same manner as in Example 10,Specific conductive polymer (Polyaniline)Was made. Next, 5 parts of the solid content of this polyaniline was mixed with 90 parts of polyether polyol (manufactured by Sanyo Kasei Co., Ltd., FA718) to evaporate water and solvent, and then polymer polyol (manufactured by Mitsui Chemicals, POP31-28). 10 parts, 0.5 part of a tertiary amine catalyst (Kao Corporation, Kaorizer No. 31), 0.05 part of a tertiary amine catalyst (manufactured by Tosoh Corporation, Toyocat HX-35), and blowing agent ( 2 parts of water), 2 parts of silicone-based foam stabilizer (manufactured by Nihon Unicar Co., Ltd., L-5309), 8.8 parts of Crude MDI (manufactured by Sumitomo Bayer Urethane Co., Sumidur 44V20), and tolylene diisocyanate (Mitsui Chemicals) A polyurethane raw material was prepared by blending 20.5 parts manufactured by TDI-80) and 1 part potassium borate (manufactured by Nippon Carlit Co., Ltd., LR147). Next, after setting a core metal (diameter 5 mm, made of SUS304) as a shaft body in a previously prepared mold (cylindrical mold), the polyurethane raw material was injected into the mold cavity and foamed and cured. . Thereafter, the mold was removed to prepare a toner supply roll in which a urethane foam layer (thickness 4 mm) was formed along the outer peripheral surface of the shaft body.
[0086]
【Example14]
[Preparation of base layer material]
(Production of silica-treated carbon black)
  500 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, Dia Black # 3030) is weighed and wetted with 1000 parts of a mixed solution of methanol and water [methanol: water = 1: 9 (weight ratio)], and 4000 parts of water is further added. In addition, it was sufficiently dispersed with an attritor filled with steel balls until a uniform and viscous slurry was obtained. The slurry was then separated from the steel balls through a sieve and diluted to a volume corresponding to 10,000 parts of water. And after heating a slurry to 90 degreeC, pH was adjusted to 10.0 by the addition of sodium hydroxide solution. Next, two types of solutions were prepared separately.
(A) 83.3 parts of No. 3 sodium silicate solution was diluted with water to a volume corresponding to 1000 parts of water.
(B) 500 parts of a 2.50% sulfuric acid solution
  Thereafter, 50 parts of the diluted sodium silicate solution (i) was added within 30 seconds to the slurry whose pH was adjusted to 10.0, and the pH of the slurry was adjusted to 11.0. Stirring was continued for 10 minutes while maintaining this pH, and then 50 parts of the sulfuric acid solution of (b) was added within 30 seconds to adjust the pH of the slurry to 8.5. This addition method was repeated 20 times, and the addition of both solutions (a) and (b) was completed. Stirring was further continued for 1 hour, and diluted sulfuric acid was added to adjust the pH to 6.5 to 7.0. The slurry was filtered, washed until it was free of soluble salts, and dried to obtain the target silica-treated carbon black (Si content: 5.0% by weight).
[0087]
  Next, 100 parts of polydimethylsiloxane having vinyl groups at both ends (manufactured by AMAX Co., DMS-V31) [viscosity: 1000 mPa · S / 25 ° C.], 10 parts of the above silica-treated carbon black, and hydrosilyl curing agent (Toshiba Silicone, TSF484) 5 parts, hydrosilylation catalyst [platinum carbonyl complex (manufactured by AMAX, SIP 6829.0)] 30 ppm, acetylene alcohol [3,5-dimethyl-1-hexyn-3-ol ( DMHO)] was kneaded using a roll to prepare a liquid polymer composition.
[0088]
[Preparation of intermediate layer material]
  A conductive composition was prepared in the same manner as in Example 12.
[0089]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Example 1.
[0090]
[Preparation of developing roll]
  The base rubber layer material is poured into an injection mold having a shaft core (diameter 10 mm, made of SUS304), heated at 150 ° C. for 45 minutes, and then removed from the mold. Then, a base rubber layer (thickness 5 mm) was formed along the outer peripheral surface of the shaft body. Subsequently, the intermediate layer material was applied to the outer peripheral surface of the base rubber layer to form an intermediate layer having a thickness of 50 μm. Furthermore, the surface layer material is applied to the surface of the intermediate layer to form a surface layer (thickness 20 μm), a base rubber layer is formed on the outer peripheral surface of the shaft body, an intermediate layer is formed on the outer peripheral surface, and A developing roll having a surface layer formed on the outer peripheral surface was produced.
[0091]
【Example15]
[Preparation of base layer material]
  Example14A liquid polymer composition was prepared in the same manner as the base layer material.
[0092]
[Preparation of intermediate layer material]
  100 parts of H-NBR (Nippon Zeon Corporation, Zettopol 0020), which is a binder polymer, and Examples1435 parts of silica-treated carbon black used in the base layer material, 1 part of sulfur as a cross-linking agent, and 0.5 part of a sulfenamide-based cross-linking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ) , 0.5 parts of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) were kneaded using a roll, and after dissolving them in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene, A conductive composition was prepared by kneading using three rolls.
[0093]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Example 9.
[0094]
[Preparation of charging roll]
  The base rubber layer material is poured into an injection mold having a shaft core (diameter 10 mm, made of SUS304), heated at 150 ° C. for 45 minutes, and then removed from the mold. Then, a base rubber layer (thickness 3 mm) was formed along the outer peripheral surface of the shaft body. Subsequently, the intermediate layer material was applied to the outer peripheral surface of the base rubber layer to form an intermediate layer having a thickness of 30 μm. Further, the surface layer material is applied to the surface of the intermediate layer to form a surface layer (thickness 10 μm), a base rubber layer is formed on the outer peripheral surface of the shaft body, an intermediate layer is formed on the outer peripheral surface, A charging roll having a surface layer formed on the outer peripheral surface was produced.
[0095]
【Example16]
  A conductive composition was prepared in the same manner as in Example 6. Then, this conductive composition was cast into a roll molding die provided with a cylindrical shaft body to produce a single-layer paper feed roll (thickness 4 mm).
[0096]
【Example17]
[Preparation of base layer material]
  A conductive composition was prepared in the same manner as in Example 6.
[0097]
[Preparation of intermediate layer material]
  A conductive composition was prepared in the same manner as in Example 5.
[0098]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Example 7.
[0099]
[Preparation of intermediate transfer belt]
  Using each of the above materials, an intermediate transfer belt (endless belt) having a three-layer structure including a base layer having a thickness of 200 μm, an intermediate layer having a thickness of 50 μm, and a surface layer having a thickness of 50 μm was produced.
[0100]
【Example18]
[Preparation of base layer material]
  A conductive composition was prepared in the same manner as in Example 6.
[0101]
[Preparation of intermediate layer material]
  Reference example 1In the same manner, a conductive composition was prepared.
[0102]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Example 7.
[0103]
[Preparation of intermediate transfer belt]
  Using each of the above materials, an intermediate transfer belt (endless belt) having a three-layer structure including a base layer having a thickness of 50 μm, an intermediate layer having a thickness of 200 μm, and a surface layer having a thickness of 20 μm was produced.
[0104]
[Comparative Example 6]
[Preparation of intermediate layer material]
  A conductive composition was prepared in the same manner as in Comparative Example 2.
[0105]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Comparative Example 5.
[0106]
[Preparation of developing roll]
  Example except that the intermediate layer material and the surface layer material were changed as described above.14A developing roll was produced in the same manner as described above.
[0107]
[Comparative Example 7]
[Preparation of intermediate layer material]
  A conductive composition was prepared in the same manner as in Comparative Example 2.
[0108]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Comparative Example 3.
[0109]
[Preparation of charging roll]
  Example except that the intermediate layer material and the surface layer material were changed as described above.15In the same manner as above, a charging roll was produced.
[0110]
[Comparative Example 8]
  Conductive polymer (Polyaniline)Except for not containing13In the same manner, a toner supply roll was produced.
[0111]
[Comparative Example 9]
[Preparation of base layer material]
  95 parts of polyurethane (TPU), which is a binder polymer, and 5 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.), a conductive agent, are kneaded using a roll, and these are methyl ethyl ketone (MEK). After dissolving in 500 parts, a conductive composition was prepared by kneading using three rolls.
[0112]
[Preparation of intermediate layer material]
  95 parts of soluble nylon (Torresin EF30T manufactured by Teikoku Chemical Co., Ltd.) as a binder polymer and 5 parts of acetylene black (Denka Black HS100 manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive agent are dissolved in 400 parts of methanol and 100 parts of water. After that, the mixture was kneaded using three rolls to prepare a conductive composition.
[0113]
(Preparation of surface layer material)
  A conductive composition was prepared in the same manner as in Comparative Example 3.
[0114]
[Preparation of intermediate transfer belt]
  Except for using the above materials, Examples17In the same manner, an intermediate transfer belt (endless belt) having a three-layer structure was produced.
[0115]
  Using the rolls of the example product and the comparative product obtained as described above, each property was evaluated according to the following criteria. These results are shown in Table 4 and Table 5 below.
[0116]
[Electric resistance]
  The electrical resistance was measured by the metal roll electrode method. That is, each roll was brought into contact with a metal roll made of stainless steel, both ends of each roll were pressed with a load of 700 g, and a voltage of 100 V was applied to one end of each roll in this state to measure the electrical resistance of the roll. . For the intermediate transfer belt, stainless steel metal rolls were pressed on the inside and outside of the intermediate transfer belt with a load of 700 g, respectively, and the electrical resistance was measured in the same manner as the above rolls.
[0117]
(Environment dependency)
  According to the evaluation of the electrical resistance, the electrical resistance at low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at high temperature and high humidity (35 ° C. × 85% RH) are measured, and the difference in electrical resistance is determined. It is shown by the number of variable digits. The applied voltage at this time is 10V.
[0118]
(Voltage dependency)
  In accordance with the evaluation of the electrical resistance, the electrical resistance when 0.1V voltage is applied and the electrical resistance when 100V voltage is applied are measured in an environment of 25 ° C. × 50% RH. It showed in.
[0119]
[Toner supply durability]
  The toner supply roll was incorporated into a commercially available printer, and the state of the toner supply roll after printing 5000 sheets was observed. Evaluation was made as ◯ when there was no toner clogging and no influence on the image, and x when there was toner clogging and the density of the solid black image was 1.25 or less in Macbeth density.
[0120]
(Development characteristics)
  The developing roll was installed in a commercially available printer (Canon, LBP2810) and allowed to stand for 1 week, then low temperature and low humidity (15 ° C. × 10% RH), normal temperature and normal humidity (25 ° C. × 50% RH), high temperature and high humidity (35 ° C.) A character image was printed under (x85% RH), and the image was visually evaluated. Then, evaluation was made as ◯ when there was no thin line break and no blurring of the image, and x when there was a fine line break and blurring of the image.
[0121]
(Charging characteristics)
  The halftone image was visually evaluated according to the above development characteristics. Then, an image having a streak, a black spot, or a white spot was evaluated as “x”, and an image having no stripe was evaluated as “◯”.
[0122]
(Paper feed characteristics)
  A feed roll is incorporated into a commercially available printer (Canon, LBP2810), and x indicates that the friction coefficient has decreased by 30% or more due to adhesion by charged paper dust, and x indicates that the change in friction coefficient is less than 30%. did.
[0123]
(Transfer characteristics)
  An intermediate transfer belt (endless belt) is incorporated into a commercially available full-color copying machine, 80 g / m²A solid image was drawn on paper. Images were drawn in three environments of 10 ° C. × 20% RH, 25 ° C. × 50% RH, and 35 ° C. × 85% RH. The evaluation was evaluated as ◯ when there was no density unevenness in all three environments and a uniform image was obtained, and x when density unevenness occurred in any of the environments.
[0124]
[Table 4]

[0125]
[Table 5]

[0126]
  From the above results, it can be seen that the example products are excellent in toner supply durability, development characteristics, charging characteristics, paper feed characteristics, and transfer characteristics.
[0127]
  In contrast, it can be seen that the product of Comparative Example 6 has poor development characteristics, the product of Comparative Example 7 has poor charging characteristics, the product of Comparative Example 8 has poor toner supply durability, and the product of Comparative Example 9 has poor transfer characteristics.
[0128]
【The invention's effect】
  As described above, the conductive composition of the present invention isspecificA conductive polymer;specificIt contains a binder polymer. Therefore, specialDefiniteConductive polymerspecificDispersed or dissolved in binder polymerDefiniteWith conductive polymerspecificForming a polymer alloy composed of a composite with a binder polymer, the characteristics of both the ionic conductive agent that is excellent in voltage dependence of electrical resistance and the electronic conductive agent that is superior in environmental dependency of electrical resistance In addition, there is an excellent effect that variation in electric resistance is small and low electric resistance can be achieved. In addition, the abovespecificConductive polymer-Since the surfactant used to form the material exhibits a predetermined solubility,specificIn the binder polymer,specificThe interfacial conductive polymer is stably present without agglomeration, and the electrical resistance with time is improved.
[0129]
  In addition, the above surface activityAgentWhen the molecular structure has a sulfonic acid group or a phosphate ester structure, it plays a role as a dopant of the conductive polymer, and the conductivity is further improved. Furthermore, the above surface activityAgentWhen the molecular structure has an ether structure and a sulfonic acid group or a phosphate ester structure, the electrical stability is further improved.
[0130]
  Furthermore, the surface activityAgentIn the molecular structure, having a repeating structure of alkylene ether,specificA conductive polymer;specificThe compatibility with the binder polymer is improved, and the preparation of the conductive composition becomes easy.
[0131]
  Furthermore, when the repeating structure (n) of the alkylene ether is within a specific range,specificConductive polymer and solventspecificThe compatibility with the binder polymer is further improved, and the preparation of the conductive composition is further facilitated.
[0132]
  And the electroconductive composition of the present invention is applied to an electrophotographic machine.VesselWhen used as a material, for example, an electrode layer or a surface layer of a developing roll, the image quality is good, and even when the environmental change is large, there is little influence on the image quality, and the quality is stable. Further, when an electrode layer or surface layer is formed by coating a conductive composition on a shaft body (core metal), it is not necessary to control the film thickness as in the case of using a conventional electronic conductive agent, and the present invention Since the conductive composition is stable, the influence of the film thickness on the product characteristics is reduced. In addition, since the conductive composition of the present invention can control the electric resistance depending on the applied voltage to be constant, for example, the developing layer can stabilize the toner layer forming property and the charging property, and the charging member can be connected to the photoreceptor. Current can be stabilized, and the transfer performance can be stabilized because the toner on the photosensitive member is transferred by voltage control even with the transfer member..

Claims (8)

An electrophotographic apparatus member conductive composition comprising the following (A) and (B) as essential components, wherein the following surfactant (a) exhibits a solubility of 3% or more in toluene or methyl ethyl ketone, In addition, a conductive composition for an electrophotographic apparatus member , which exhibits a solubility of 3% or more in water or maintains a micelle dispersion state in water for 10 hours or more.
(A) and the raw material monomer of the conductive polymer, the following surfactant (a) and the conductive polymer ing by chemical oxidative polymerization with an oxidizing agent.
(A) At least one surfactant selected from the group consisting of polyoxyalkylene alkyl ether phosphate esters, dialkyl sulfosuccinate sodium salts, polyoxyalkylene alkyl phenyl ether sulfate ammonium salts, and sodium amide ether sulfonates.
(B) It consists of at least one selected from the group consisting of acrylic resins, urethane resins, fluorine resins, polyamide resins, polyimide resins, epoxy resins, urea resins, rubber polymers, and thermoplastic elastomers. Solvent-soluble binder polymer. The surfactant (a) alkylene ether repeating structures in (n) is, according to claim 1 an electrophotographic apparatus member for electrically conducting composition described is n = 1 to 30. The surfactant (a) is a polyoxyalkylene alkyl ether phosphate ester represented by the following formula (2), a polyoxyalkylene alkyl ether phosphate ester represented by the following formula (3), and the following formula Dialkylsulfosuccinic acid sodium salt represented by (4), polyoxyalkylene alkylphenyl ether sulfate ammonium salt represented by the following formula (5), and sodium amide ether sulfonate represented by the following formula (6) The electroconductive composition for electrophotographic apparatus members according to claim 1, which is at least one selected from the group consisting of:

The raw material monomer in the above (A) is at least selected from the group consisting of aniline, pyrrole, thiophene, acetylene, paraphenylene, phenylene vinylene, furan, selenophene, isothianaphthene, paraphenylene sulfide, paraphenylene oxide and vinylene sulfide. It is one, The electron as described in any one of Claims 1-3 A conductive composition for photographic equipment members. A conductive composition for electrophotographic equipment member is coated on a glass plate to produce a conductive film having a thickness of 20 μm, and the conductivity when a voltage of 10 V is applied in an environment of 50 ° C. × 95% RH. The initial electrical resistance of the coating is 3.1 × 10 ^Four ~ 8.8 × 10 ⁷ It is in the range of Ω · cm, and the electrical resistance over time after 30 days is 3 × 10 ^Four ~ 8x10 ⁷ It is the range of ohm * cm, The electroconductive composition for electrophotographic equipment members as described in any one of Claims 1-4. Electrophotographic equipment member, characterized in that using the electrophotographic apparatus member for conductive composition according to any one of claims 1-5. Comprising the electrophotographic equipment member is an intermediate layer or a surface layer, at least one of the intermediate layer and surface layer using an electrophotographic apparatus member for conductive composition according to any one of claims 1 to 5 electrophotographic equipment member according to claim 6, wherein formed. An electroconductive composition for an electrophotographic apparatus member according to any one of claims 1 to 5 is dissolved in an organic solvent to form a coating solution, and an intermediate layer or a surface layer comprising a conductive coating film is applied thereto. The manufacturing method of the electrophotographic apparatus member of Claim 7 produced.