JP2004184512A - Semiconductive composition for electrophotographic equipment member, and electrophotographic equipment member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductive composition for an electrophotographic equipment member having small increase of electric resistance at a high voltage region, and having both excellent characteristics of voltage dependency of the electric resistance and environment dependency of the electric resistance. <P>SOLUTION: The semiconductive composition for the electrophotographic equipment member makes the following (A) and (B) essential components. In the semiconductive composition, a surfactant used for forming a surfactant structure of (A) has a sulfonic acid group in a molecular structure, and a binder polymer of (B) has at least one of the sulfonic acid group and a sulfonic acid metal salt structure in the molecular structure. Here, (A) is the conductive polymer having the surfactant structure, and (B) is the binder polymer. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１８】
【化４】

【００１９】
一般式（１）において、好ましいＲ^１ としては、炭素数２〜１２のアルキル基等があげられる。また、Ｒ^２ としては、水素、アルキル基、アルコキシ基、アルキルチオ基、アルキルチオアルキル基、アリール基、アルキルスルフィニル基、アルコキシアルキル基、アルコキシカルボニル基、カルボキシル基、ニトリル基、ヒドロキシ基が好ましく、さらに好ましくは、水素、アルコキシ基、アルキルチオ基、アルキルチオアルキル基、アルキルスルフィニル基、アルコキシアルキル基、アルコキシカルボニル基、カルボキシル基、ニトリル基、ヒドロキシ基である。また、ｎは２〜４の整数が好ましい。
【００２０】
また、一般式（２）において、好ましいＲ^３ およびＲ^４ としては、水素、アルキル基、アルコキシ基、アルキルチオ基、アルキルチオアルキル基、アルキルスルフィニル基、アルコキシアルキル基、アリールオキシアルキル基、アルキルスルホニル基、アルコキシカルボニル基、カルボキシル基、ニトリル基、ヒドロキシ基、ニトロ基またはハロゲンがあげられる。一般式（２）における好ましいＭとしては、ナトリウムイオン、カリウムイオン、アンモニウムイオンがあげられる。
【００２１】
特に、上記特定の界面活性剤としては、分子構造中にスルホン酸基を有し、かつ、ナフタレン構造およびアントラセン構造の少なくとも一方を有するものが特に好ましい。
【００２２】
また、ナフタレン構造およびアントラセン構造は、１〜９個のうちの任意の数の置換基を有するものが好ましい。この置換基としては、例えば、水素、アルキル基、アルケニル基、アルコキシ基、アルキルチオ基、アルキルチオアルキル基、アリール基、アルキルアリール基、アリールアルキル基、アルキルスルフィニル基、アルコキシアルキル基、アリールオキシアルキル基、ナフチル基、ナフチルアルキル基、アルキルスルホニル基、アルコキシカルボニル基、カルボキシル基、ニトリル基、ヒドロキシ基、ニトロ基、ハロゲン等があげられる。これら置換基は、単独で置換されていてもよいし、２種以上が置換されていてもよい。
【００２３】
このような特定の界面活性剤中のスルホン酸基当量は、３４０〜６００の範囲内が好ましく、特に好ましくは３８０〜５５０の範囲内である。すなわち、スルホン酸基当量が３４０未満であると、バインダーポリマー（Ｂ成分）との相溶性が悪くなる傾向がみられ、逆に６００を超えると、ドーパントとしての効果が減少する傾向がみられるからである。このスルホン酸基当量は、水酸化ナトリウムの滴定や熱重量分析法（ＴＧＡ）に従って求められる。
【００２４】
前記の化学酸化重合法に用いる酸化剤としては、特に限定はないが、例えば、過硫酸アンモニウム（ＡＰＳ）、過酸化水素水、塩化第二鉄等があげられる。
【００２５】
導電性ポリマーの原料モノマーと、特定の界面活性剤との混合比は、モル比で、原料モノマー／界面活性剤＝１／０．０３〜１／３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＝１／０．０５〜１／２の範囲内である。すなわち、界面活性剤のモル比が低くなると、バインダーポリマー（Ｂ成分）との相溶性や分散性が低下する傾向がみられ、逆に界面活性剤のモル比が高くなると、界面活性剤の、イオン導電性への寄与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傾向がみられるからである。
【００２６】
このようにして得られる特定の導電性ポリマー（Ａ成分）の数平均分子量（Ｍｎ）は、１，０００〜１００，０００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。
【００２７】
つぎに、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、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方を有するものであれば特に限定はない。このスルホン酸金属塩構造としては、例えば、スルホン酸ナトリウム塩構造、スルホン酸アンモニウム塩構造、スルホン酸カリウム塩構造等があげられる。
【００２８】
このような、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方を有するバインダーポリマー（Ｂ成分）としては、例えば、そのような構造を有する、アクリル系樹脂、ウレタン系樹脂、フッ素系樹脂、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、熱可塑性エラストマー等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、特定の導電性ポリマー（Ａ成分）との相溶性に優れる点で、アクリル系樹脂、ウレタン系樹脂、ゴム系ポリマー、熱可塑性エラストマーが好適に用いられる。
【００２９】
また、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、ポリブチルアクリレート、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、公知のアクリルモノマーを共重合したもの等であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。バインダーポリマーへのスルホン酸基導入の方法は、スルホン酸基またはスルホン酸金属塩基を有するビニルモノマーと、ラジカル，アニオン，カチオン共重合する方法や、スルホン酸基を有するジオールモノマーを、ウレタン反応，エステル交換反応で導入する方法がある。
【００３０】
また、ウレタン系樹脂としては、分子構造中にウレタン結合を有する樹脂であれば特に限定はなく、例えば、エーテル系，エステル系，アクリル系，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またはフッ素系ポリオールを共重合させたもの等であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。なお、ウレタン系樹脂は、分子構造中にウレア結合またはイミド結合を有するものであってもよい。
【００３１】
また、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であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。
【００３２】
また、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であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。
【００３３】
また、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、エポキシノボラック樹脂、臭素化型エポキシ樹脂、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、シリコー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であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。
【００３４】
また、ウレア系樹脂としては、分子構造中にウレア結合を有する樹脂であれば特に限定はなく、ウレタンウレアエラストマー、メラミン樹脂、尿素ホルムアルデヒド樹脂等であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。
【００３５】
また、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）、塩素化ポリエチレン（Ｃｌ−ＰＥ）、エピクロロヒドリンゴム（ＥＣＯ，ＣＯ）、ブチルゴム（ＩＩＲ）、エチレンプロピレンジエンポリマー（ＥＰＤＭ）、フッ素ゴム等であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。
【００３６】
また、熱可塑性エラストマーとしては、例えば、スチレン−ブタジエンブロック共重合体（ＳＢＳ），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）等のスチレン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー（ＴＰＵ）、オレフィン系熱可塑性エラストマー（ＴＰＯ）、ポリエステル系熱可塑性エラストマー（ＴＰＥＥ）、ポリアミド系熱可塑性エラストマー、フッ素系熱可塑性エラストマー、塩ビ系熱可塑性エラストマー等であって、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方が導入されているものがあげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、合成プロセスの簡便さ、溶剤との溶解性の点で、ＴＰＵが好適に用いられる。
【００３７】
このバインダーポリマー（Ｂ成分）中における、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方の含有量（スルホン酸基量）は、０．００１〜１ｍｍｏｌ／ｇの範囲内が好ましく、特に好ましくは０．０１〜０．２ｍｍｏｌ／ｇの範囲内である。すなわち、このスルホン酸基量が０．００１ｍｍｏｌ／ｇ未満であると、特定の導電性ポリマー（Ａ成分）との相溶性が悪くなる傾向がみられ、逆に１ｍｍｏｌ／ｇを超えると、含水による物性の低下やイオン導電性の発現がみられるからである。
【００３８】
このような特定のバインダーポリマー（Ｂ成分）の数平均分子量（Ｍｎ）は、５００〜２，０００，０００の範囲内が好ましく、特に好ましくは２，０００〜８００，０００の範囲内である。
【００３９】
上記特定のバインダーポリマー（Ｂ成分）と、特定の導電性ポリマー（Ａ成分）とは、後記のようにして混合され半導電性組成物化されるが、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＝１／９９〜４０／６０の範囲が好ましく、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なる傾向がみられ、逆にＡ成分の原料の重量比が４０を超えると、得られる組成物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傾向がみられるからである。
【００４０】
なお、本発明の電子写真機器部材用半導電性組成物には、特定の導電性ポリマー（Ａ成分）および特定のバインダーポリマー（Ｂ成分）に加え、場合によって、イオン導電剤、電子導電剤、架橋剤等を適宜配合しても差し支えない。
【００４１】
このイオン導電剤としては、例えば、過塩素酸リチウム、第四級アンモニウム塩、ホウ酸塩等のポリマー中でイオン解離する化合物があげられる。これらは単独でもしくは２種以上併せて用いられる。
【００４２】
このようなイオン導電剤の配合割合は、物性や電気特性の点から、特定の導電性ポリマー（Ａ成分）の原料（原料モノマーと、界面活性剤との合計量）と、特定のバインダーポリマー（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。
【００４３】
また、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−ＴｉＯ_２ （導電性酸化チタン）、ｃ−ＳｎＯ_２ （導電性酸化錫）、グラファイト等があげられる。
【００４４】
このような電子導電剤の配合割合は、物性や電気特性の点から、特定の導電性ポリマー（Ａ成分）の原料（原料モノマーと界面活性剤との合計量）と、特定のバインダーポリマー（Ｂ成分）との合計１００部に対して、５〜３０部の範囲内が好ましく、特に好ましくは８〜２０部の範囲内である。
【００４５】
また、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、パーオキサイド等があげられる。
【００４６】
このような架橋剤の配合割合は、物性、粘着、液保管性の点から、特定の導電性ポリマー（Ａ成分）の原料（原料モノマーと界面活性剤との合計量）と、特定のバインダーポリマー（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。
【００４７】
なお、本発明の電子写真機器部材用半導電性組成物には、前記各成分に加えて、架橋促進剤、老化防止剤等を必要に応じて配合しても差し支えない。
【００４８】
この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等があげられる。
【００４９】
本発明の電子写真機器部材用半導電性組成物は、例えば、つぎのようにして調製することができる。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）に、特定のバインダーポリマー（Ｂ成分）を配合するとともに、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、目的とする半導電性組成物を得ることができる。ここで、上記特定の導電性ポリマー（Ａ成分）は、溶剤に溶解した状態のものが用いられる。また、バインダーポリマー（Ｂ成分）は、溶剤に溶解した状態で用いられる。
【００５０】
この溶剤としては、例えば、ｍ−クレゾール、メタノール、メチルエチルケトン（ＭＥＫ）、トルエン、テトラヒドロフラン（ＴＨＦ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等の有機溶剤等があげられる。
【００５１】
本発明の電子写真機器部材用半導電性組成物は、２５℃×５０％ＲＨの環境下、１０Ｖの電圧を印加した時の電気抵抗が１０^６ 〜１０^１１Ω・ｃｍの範囲内であることが好ましく、特に好ましくは１０^７ 〜１０^１０Ω・ｃｍの範囲内である。すなわち、電気抵抗が１０^６ Ω・ｃｍ未満であると、電気抵抗が低すぎるため、トナーへの電荷供給や感光体への帯電性等の点で、電子写真機器部材として画像への利点が少なくなる傾向がみられ、逆に１０^１１Ω・ｃｍを超えると、電気抵抗が高すぎるため、チャージアップが起こり、電子写真機器部材としての制御が困難になる傾向がみられるからである。
【００５２】
本発明の電子写真機器部材用半導電性組成物を用いて塗膜を形成した場合、バインダーポリマー（Ｂ成分）中に存在する特定の導電性ポリマー（Ａ成分）の凝集物（１μｍ以上）が、塗膜全体の面積の３％未満であることが好ましく、特に好ましくは０．５％未満である。すなわち、この凝集物が、塗膜全体の面積の３％を超えると、電圧に対する電気抵抗の変動が大きくなる傾向がみられるからである。
【００５３】
本発明の電子写真機器部材用半導電性組成物は、電子写真機器部材の少なくとも一部（全部もしくは一部）に用いられる。この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，トナー供給ロール等の導電性ロール、中間転写ベルト，紙送りベルト等の導電性ベルト等があげられ、これらの構成層の少なくとも一部に用いられる。すなわち、本発明の電子写真機器部材用半導電性組成物を、電子写真機器部材の構成層の少なくとも一部に用いると、この半導電性組成物を用いて形成した構成層の電気抵抗の電圧依存性および環境依存性が小さくなる。その結果、他の構成層においても、電気抵抗の電圧依存性および環境依存性の影響を受けにくくなるため、電子写真機器部材全体としての電気抵抗の電圧依存性および環境依存性が小さくなる。
【００５４】
つぎに、実施例について比較例と併せて説明する。
【００５５】
まず、本発明に係る組成物を、以下のようにして作製した。
【００５６】
【組成物１】
アニリン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（ドデシルベンゼンスルホン酸）〔スルホン酸基当量：３２６〕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、界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部を、溶剤（ＭＥＫ）２００部および溶剤（トルエン）３００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００５７】
【組成物２】
アニリン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（ペンタデシルベンゼンスルホン酸）〔スルホン酸基当量：３６８〕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、界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部を、溶剤（ＭＥＫ）１００部および溶剤（トルエン）５００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００５８】
【組成物３】
アニリン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（ジノニルナフタレンスルホン酸）〔スルホン酸基当量：４６０〕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、界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部を、溶剤（ＭＥＫ）３００部および溶剤（トルエン）３００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００５９】
【組成物４】
アニリン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（２，２′−ジナフチルメタン−６−スルホン酸ナトリウム−６′−スルホン酸）〔スルホン酸基当量：４５０〕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、界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部を、溶剤（ＭＥＫ）１００部および溶剤（トルエン）５００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６０】
【組成物５】
アニリン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（一般式（１）において、Ｒ^１ ＝ブチル基、Ｒ^２ ＝水素、ｎ＝２、ｍ＝３で表される化合物）〔スルホン酸基当量：５３４〕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、界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部とを、溶剤（ＭＥＫ）１００部および溶剤（トルエン）５００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布した後、１５０℃にて３０分間加熱架橋して、厚み１００μｍの導電性塗膜を作製した。
【００６１】
【組成物６】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６２】
【組成物７】
ピロール１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（ペンタデシルベンゼンスルホン酸）〔スルホン酸基当量：３６８〕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、界面活性剤構造を有するポリピロール（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリピロールの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６３】
【組成物８】
チオフェン１ｍｏｌと、分子構造中にスルホン酸基を有する界面活性剤（ペンタデシルベンゼンスルホン酸）〔スルホン酸基当量：３６８〕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、界面活性剤構造を有するポリチオフェン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリチオフェンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６４】
【組成物９】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸基を有するバインダーポリマー（Ｂ成分）である、スチレンスルホン酸の存在下で溶液重合することで合成したスルホン化ＮＢＲ（スルホン酸基量：０．１ｍｍｏｌ／ｇ、Ｍｎ：１００，０００）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、２本ロールを用いて混練し、これらを溶剤（ＭＥＫ）３００部および溶剤（トルエン）３００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布した後、１５０℃にて３０分間加熱架橋して、厚み１００μｍの導電性塗膜を作製した。
【００６５】
【組成物１０】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸基を有するバインダーポリマー（Ｂ成分）である、スルホン化ウレタンシリコーン（スルホン酸基量：０．１ｍｍｏｌ／ｇ、Ｍｎ：５０，０００）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。なお、スルホン化ウレタンシリコーンは、ポリブチレンアジペートジオール（Ｍｎ：２，０００）と、シリコーンジオール（Ｍｎ：２，０００）とを、８：２の割合で混合したものに、鎖延長剤として、１，４−ブタンジオールおよび１，４−ブタンジオール−２−スルホン酸ナトリウムを加え、４，４′−ジフェニルメタンジイソシアネート（ＭＤＩ）と等モルで反応させることにより作製した。
【００６６】
【組成物１１】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸基を有するバインダーポリマー（Ｂ成分）である、スルホン化アクリルフッ素（スルホン酸基量：０．１ｍｍｏｌ／ｇ、Ｍｎ：３０，０００）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６７】
【組成物１２】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸基を有するバインダーポリマー（Ｂ成分）である、組成物１０においてスルホン酸基を増量して作製したスルホン化ウレタンシリコーン（スルホン酸基量：１ｍｍｏｌ／ｇ、Ｍｎ：５０，０００）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６８】
【組成物１３】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸基を有するバインダーポリマー（Ｂ成分）である、組成物１０においてスルホン酸基を減量して作製したスルホン化ウレタンシリコーン（スルホン酸基量：０．００１ｍｍｏｌ／ｇ、Ｍｎ：５０，０００）８０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００６９】
【組成物１４】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）９０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）１０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００７０】
【組成物１５】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）７０部と、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）３０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００７１】
【組成物１６】
組成物２と同様にして、同様の界面活性剤構造を有するポリアニリン（Ａ成分）を得た。つぎに、分子構造中にスルホン酸Ｎａ基を有するバインダーポリマー（Ｂ成分）である、ＴＰＵ（日本ポリウレタン工業社製、ニッポラン３３１２、スルホン酸Ｎａ基量：０．０５ｍｍｏｌ／ｇ）８０部と、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、ブロックイソシアネート（大日本インキ化学工業社製、バーノックＤＢ９８０Ｋ）５部とを、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリンの有効成分（不揮発分）２０部を加え、１０分間攪拌し、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００７２】
つぎに、本発明において、比較例となるべき組成物を、以下のようにして作製した。
【００７３】
【組成物Ａ】
分子構造中にスルホン酸基を有しない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、イオン導電剤であるホウ酸塩（日本カーリット社製、ＬＲ１４７）２部と、架橋剤（酸化亜鉛）１０部と、チオウレア系架橋促進剤（三新化学社製、サンセラー２２Ｃ）３部とを配合し、３本ロールを用いて混練した後、これらを溶剤（ＭＥＫ）３００部および溶剤（トルエン）１５０部に溶解して、組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布した後、１５０℃にて３０分間加熱架橋して、厚み１００μｍの導電性塗膜を作製した。
【００７４】
【組成物Ｂ】
分子構造中にスルホン酸基を有しないバインダーポリマーである、カーボネート系ＴＰＵ（日本ミラクトラン社製、Ｅ９８０）１００部を、溶剤（ＭＥＫ）２００部および溶剤（テトラヒドロフラン）３００部に溶解させた後、これに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）７部を配合し、３本ロールを用いて混練して組成物を調製した。そして、これを１５０℃にて３０分間加熱架橋して、ＳＵＳ３０４板上に厚み１００μｍの導電性塗膜を作製した。
【００７５】
【組成物Ｃ】
アセチレンブラックの配合割合を２０部に変更する以外は、組成物Ｂと同様にして、導電性塗膜を作製した。
【００７６】
【組成物Ｄ】
カーボンブラックを分散させたシリコーン（信越化学工業社製、ＫＥ１３５０ＡＢ）をＳＵＳ３０４板上にプレス成型（１５０℃×１０分）して、厚み１００μｍの導電性塗膜を作製した。
【００７７】
【組成物Ｅ】
特開平５−８８５０６号公報に記載の実施例１に準じて、導電性塗膜を作製した。すなわち、アニリン０．４ｍｏｌ／ｌと、硫酸１．０ｍｏｌ／ｌと、過硫酸アンモニウム０．５ｍｏｌ／ｌとを含む水溶液を調製し、化学酸化重合法によりポリアニリンを重合した。得られたポリアニリンを水酸化ナトリウムで中性に調整した後、水洗し、乾燥して、粒子径約１μｍのポリニリン粉末を得た。つぎに、分子構造中にスルホン酸基を有しないバインダーポリマーである、可溶性ナイロン５０部を、溶剤（メタノール）５００部に溶解させ、これに上記ポリアニリン粉末５０部を添加し、レッドデビルで混合して組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布した後、１５０℃にて３０分間加熱架橋して、厚み１００μｍの導電性塗膜を作製した。
【００７８】
【組成物Ｆ】
特開２００１−３２４８８２号公報に記載の実施例１に準じて、導電性塗膜を作製した。すなわち、乾燥したフッ化処理カーボンブラック（ＡＬＬＩＥＤ社製、ＡＣＣＵＦＬＶＯＲ２０２８）を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）中に所定量配合し、ボールミルを用いて室温で６時間混合した。ついで、このカーボンブラック分散ＮＭＰ液に、３，３′，４，４′−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）２９４．２ｇと、ｐ−フェニレンジアミン（ＰＤＡ）１０８．２ｇとを溶解し、窒素雰囲気において、室温で４時間攪拌しながら反応させ、フッ化処理カーボンブラック入りポリアミド酸溶液を得た。また、ＮＭＰ２００ｇに、ポリアニリン粉末２０ｇを添加し、オートホモミキサーを用いて５０００ｒｐｍで１時間攪拌して溶解させ、１０重量％濃度の脱ドープ状態のポリアニリン溶液を得た。ついで、上記フッ化処理カーボンブラック入りポリアミド酸溶液に、所定量のポリアニリン溶液を添加した後、攪拌羽根を用いて室温で１時間攪拌し、所望配合量のフッ化処理カーボンブラック、ポリアニリン入りポリアミド酸溶液（樹脂：ポリアニリン：フッ化処理カーボンブラック＝７４重量％：１５重量％：１１重量％）を得た。そして、この溶液をＳＵＳ３０４板上に塗布した後、１５０℃にて３０分間加熱架橋して２００℃まで２℃／分の昇温温度で昇温し、さらに２００℃で３０分加熱して、厚み１００μｍの導電性塗膜を作製した。
【００７９】
【組成物Ｇ】
特開２００２−１６７５１９号公報に記載の実施例に準じて、導電性塗膜を作製した。すなわち、アニリン１ｍｏｌと、界面活性剤（ドデシルベンゼンスルホン酸）〔スルホン酸基当量：３２６〕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、界面活性剤構造を有するポリアニリンを得た。つぎに、分子構造中にスルホン酸基を有しないバインダーポリマーである、ポリエステル（アジペート）系ＴＰＵ（三井武田ケミカル社製、エラストラン１０４０）８０部を、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００部に溶解した後、上記界面活性剤構造を有するポリアニリン２０部を加え、３本ロールを用いて混練し、導電性組成物（コーティング液）を調製した。そして、この組成物（コーティング液）をＳＵＳ３０４板上に塗布して、厚み１００μｍの導電性塗膜を作製した。
【００８０】
このようにして得られた導電性塗膜を用いて、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１〜表５に併せて示した。
【００８１】
〔凝集物の面積〕
各導電性塗膜の、バインダーポリマー中に存在する導電性ポリマーの粒径（メジアン径）を、５〜８μｍの膜厚のフィルムを３０００倍に拡大観察（光学顕微鏡）して測定した。そして、粒径が１μｍ以上の凝集物が、塗膜全体に占める割合（面積）を測定した。
【００８２】
〔電気抵抗、電気抵抗の電圧依存性〕
各導電性塗膜について、２５℃×５０％ＲＨの環境下、１Ｖの電圧を印加した時の電気抵抗（Ｒｖ＝１Ｖ）と、１３３Ｖの電圧を印加した時の電気抵抗（Ｒｖ＝１３３Ｖ）を、ＳＲＩＳ ２３０４に準じてそれぞれ測定した。そして、Ｌｏｇ（Ｒｖ＝１Ｖ／Ｒｖ＝１３３Ｖ）により、電気抵抗の電圧依存性を変動桁数で表示した。
【００８３】
〔電気抵抗の環境依存性〕
各導電性塗膜について、印加電圧１０Ｖの条件下、低温低湿（１５℃×１０％ＲＨ）時の電気抵抗（Ｒｖ＝１５℃×１０％ＲＨ）と、高温高湿（３５℃×８５％ＲＨ）時の電気抵抗（Ｒｖ＝３５℃×８５％ＲＨ）を、ＳＲＩＳ ２３０４に準じてそれぞれ測定した。そして、Ｌｏｇ（Ｒｖ＝１５℃×１０％ＲＨ／Ｒｖ＝３５℃×８５％ＲＨ）により、電気抵抗の環境依存性を変動桁数で表示した。
【００８４】
〔環境による電気抵抗変動〕
各導電性塗膜について、５０℃×９５％ＲＨの環境下で３０日間放置後の電気抵抗を、ＳＲＩＳ ２３０４に準じて、２５℃×５０％ＲＨの環境下で、１０Ｖ印加で測定した（Ｒｖ＝３０日）。そして、Ｌｏｇ（Ｒｖ＝３０日／Ｒｖ＝０日）により、環境による電気抵抗変動を変動桁数で表示した。
【００８５】
〔高電圧領域での電気抵抗変動（チャージアップ）〕
各導電性塗膜について、２５℃×５０％ＲＨの環境下、３００Ｖの電圧を印加した時の電気抵抗（Ｒｖ＝３００Ｖ）を、ＳＲＩＳ ２３０４に準じて測定した。そして、Ｌｏｇ（Ｒｖ＝３０Ｖ／Ｒｖ＝３００Ｖ）により、高電圧領域での電気抵抗変動を変動桁数で表示した。
【００８６】
【表１】

【００８７】
【表２】

【００８８】
【表３】

【００８９】
【表４】

【００９０】
【表５】

【００９１】
上記表の結果から、組成物１〜１６は、分子構造中にスルホン酸基を有する界面活性剤を用いて形成した特定の導電性ポリマーと、分子構造中にスルホン酸基を有するバインダーポリマーとを併用しているため、両者の相溶性が良好で、凝集物の発生を抑制でき、高電圧領域での電気抵抗の上昇（チャージアップ）が非常に小さかった。また、電気抵抗の電圧依存性および電気抵抗の環境依存性の双方の特性に優れ、環境による電気抵抗変動も小さかった。
【００９２】
これに対して、組成物Ａは、イオン導電剤を用いているため、電気抵抗の環境依存性が劣り、高電圧領域での電気抵抗の上昇が大きかった。組成物Ｂ，Ｃ，Ｄは、電子導電剤を用いているため、電気抵抗の電圧依存性が劣っていた。組成物Ｅは、ポリアニリンとナイロンの相溶性が悪く、凝集物が多く発生するとともに、電気抵抗の電圧依存性に劣っていた。組成物Ｆは、ポリアニリンと、フッ化処理カーボンブラックとの相溶性が悪く、凝集物が多量に発生するため、高電圧領域での電気抵抗変動が大きかった。組成物Ｇは、分子構造中にスルホン酸基を有しないバインダーポリマーを用いているため、界面活性剤構造を有する導電性ポリマーとの相溶性が劣り、凝集物が発生し、高電圧領域での電気抵抗の上昇傾向がみられた。
【００９３】
つぎに、本発明に係る電子写真機器部材の実施例について、比較例と併せて説明する。
【００９４】
【実施例１】
〔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、カーボンブラックを分散させたシリコーン（信越化学工業社製、ＫＥ１３５０ＡＢ）〔組成物Ｄ〕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層を形成した。そして、このベース層の表面をコロナ放電処理（条件：０．３ｋＷ×２０秒）した。ついで、前記で調製した組成物Ｃを上記ベース層の外周面に塗布して、中間層を形成した。さらに、上記中間層の表面に、前記で調製した組成物１からなる表層を形成し、軸体の外周面にベース層が形成され、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。
【００９５】
【実施例２〜１８、比較例１〜５】
ベース層用材料、中間層用材料および表層用材料として、後記の表６〜表９に示す組成物を用いる以外は、実施例１と同様にして、現像ロールを作製した。なお、ベース層、中間層もしくは表層を形成していないものについては、「−」と表示した。
【００９６】
このようにして得られた実施例品および比較例品の現像ロールを用いて、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６〜表９に併せて示した。
【００９７】
〔電気抵抗、電気抵抗の電圧依存性〕
現像ロールの表面をＳＵＳ板に押し当てた状態で、現像ロールの両端に各１ｋｇの荷重をかけ、現像ロールの芯金と、ＳＵＳ板に押し当てた現像ロール表面との間の電気抵抗を、ＳＲＩＳ ２３０４に準じて測定した。なお、電気抵抗は、２５℃×５０％ＲＨの環境下、１Ｖの電圧を印加した時の電気抵抗（Ｒｖ＝１Ｖ）と、１３３Ｖの電圧を印加した時の電気抵抗（Ｒｖ＝１３３Ｖ）をそれぞれ測定した。そして、Ｌｏｇ（Ｒｖ＝１Ｖ／Ｒｖ＝１３３Ｖ）により、電気抵抗の電圧依存性を変動桁数で表示した。
【００９８】
〔電気抵抗の環境依存性〕
上記電気抵抗の評価に準じて、印加電圧１０Ｖの条件下、低温低湿（１５℃×１０％ＲＨ）の時の電気抵抗（Ｒｖ＝１５℃×１０％ＲＨ）と、高温高湿（３５℃×８５％ＲＨ）の時の電気抵抗（Ｒｖ＝３５℃×８５％ＲＨ）を、ＳＲＩＳ ２３０４に準じてそれぞれ測定した。そして、Ｌｏｇ（Ｒｖ＝１５℃×１０％ＲＨ／Ｒｖ＝３５℃×８５％ＲＨ）により、電気抵抗の環境依存性を変動桁数で表示した。
【００９９】
〔硬度（ＪＩＳ Ａ）〕
各現像ロールの最表面の硬度を、ＪＩＳ Ｋ ６２５３に準じて測定した。
【０１００】
〔圧縮永久歪み〕
各現像ロールの圧縮永久歪みを、温度７０℃、試験時間２２時間、圧縮率２５％の条件下、ＪＩＳ Ｋ ６２６２に準じて測定した。
【０１０１】
〔現像ロール特性〕
（画像ムラ）
各現像ロールを市販のカラープリンターに組み込み、２０℃×５０％ＲＨの環境下において画像出しを行った。評価は、ハーフトーン画像での濃度ムラがなく、細線のとぎれや色ムラがなかったものを○、濃度ムラが生じたものを×とした。
【０１０２】
（環境による画質の変動）
各現像ロールを市販のカラープリンターに組み込み、１５℃×１０％ＲＨの環境下において画像出しを行った時と、３５℃×８５％ＲＨの環境下において画像出しを行った時の、環境による画質の変動の評価を行った。評価は、べた黒画像を印刷し、マクベス濃度計で変化が０．１以下の時を○、０．１を超える時を×とした。
【０１０３】
〔チャージアップによる濃度変動〕
各現像ロールを市販のカラープリンターに組み込み、２５℃×５０％ＲＨの環境下、３００Ｖの電圧を印加して画像出しを行った。評価は、ハーフトーン画像での濃度ムラがなく、細線のとぎれや色ムラがなかったものを○、濃度ムラが生じたものを×とした。
【０１０４】
〔環境による電気抵抗経時変化〕
上記電気抵抗の評価に準じて、５０℃×９５％ＲＨの環境下で３０日間放置後の電気抵抗を、ＳＲＩＳ ２３０４に準じて、２５℃×５０％ＲＨの環境下で１０Ｖ印加で測定した（Ｒｖ＝３０日）。そして、Ｌｏｇ（Ｒｖ＝３０日／Ｒｖ＝０日）により、環境による電気抵抗経時変化を変動桁数で表示した。
【０１０５】
【実施例１９〜２２、比較例６〜８】
〔帯電ロールの作製〕
ベース層用材料、中間層用材料もしくは表層用材料として、後記の表１０および表１１に示す組成物を用いる以外は、実施例１の現像ロールの製法に準じて、帯電ロールを作製した。なお、ベース層、中間層もしくは表層を形成していないものについては、「−」と表示した。
【０１０６】
【実施例２３、比較例９】
〔転写ロールの作製〕
ベース層用材料、中間層用材料もしくは表層用材料として、後記の表１２に示す組成物を用いる以外は、実施例１の現像ロールの製法に準じて、転写ロールを作製した。なお、ベース層、中間層もしくは表層を形成していないものについては、「−」と表示した。
【０１０７】
【実施例２４，２５、比較例１０】
〔転写ベルトの作製〕
ベース層用材料、中間層用材料もしくは表層用材料として、後記の表１３に示す組成物を用いる以外は、実施例１の現像ロールの製法に準じて、単層もしくは多層構造の中間転写ベルト（無端ベルト）を作製した。なお、ベース層、中間層もしくは表層を形成していないものについては、「−」と表示した。
【０１０８】
このようにして得られた実施例品および比較例品の帯電ロール、転写ロール、転写ベルトを用いて、前記現像ロールの特性評価の基準に準じて、各特性の評価を行った。これらの結果を、後記の表１０〜表１３に併せて示した。なお、転写ベルトの電気抵抗は、転写ベルトの内部に直径１０ｍｍ、重さ１ｋｇのＳＵＳ棒を載せ、このＳＵＳ棒に接する部分と、ＳＵＳ板との間の電気抵抗を、ＳＲＩＳ
２３０４に準じて測定した。
【０１０９】
【表６】

【０１１０】
【表７】

【０１１１】
【表８】

【０１１２】
【表９】

【０１１３】
【表１０】

【０１１４】
【表１１】

【０１１５】
【表１２】

【０１１６】
【表１３】

【０１１７】
上記結果から、すべての実施例品は、電子写真機器部材の構成層の少なくとも一部に、本発明の半導電性組成物（組成物１〜１６）を用いているため、現像ロール特性、帯電ロール特性、転写ロール特性、転写ベルト特性に優れていた。
【０１１８】
これに対して、比較例品は、電気抵抗の電圧依存性や電気抵抗の環境依存性に劣る組成物（組成物Ａ〜Ｇのいずれか）のみを用いているため、現像ロール特性、帯電ロール特性、転写ロール特性、転写ベルト特性に劣っていた。
【０１１９】
【発明の効果】
以上のように、本発明の電子写真機器部材用半導電性組成物は、分子構造中にスルホン酸基を有する界面活性剤を用いて、界面活性剤構造を有する導電性ポリマーを形成し、この導電性ポリマー（Ａ成分）とともに、分子構造中に、スルホン酸基およびスルホン酸金属塩構造の少なくとも一方を有するバインダーポリマー（Ｂ成分）を併用するものである。そのため、両者の相溶性が良好となり、凝集物の発生を抑制でき、高電圧領域での電気抵抗の上昇が小さくなるとともに、電気抵抗の電圧依存性および電気抵抗の環境依存性の双方の特性に優れるという効果を奏する。
【０１２０】
また、バインダーポリマー（Ｂ成分）として、アクリル系樹脂等の特定のポリマーを用いたり、もしくはバインダーポリマー（Ｂ成分）中における、スルホン酸基量を特定の範囲に設定すると、Ａ成分とＢ成分との相溶性がさらに向上するようになる。
【０１２１】
また、Ａ成分の界面活性剤構造を形成するために用いられる界面活性剤が、分子構造中にスルホン酸基を有し、かつ、ナフタレン構造およびアントラセン構造の少なくとも一方を有するか、もしくはこれらが特定の置換基を備えているか、Ａ成分の界面活性剤構造を形成するために用いられる界面活性剤が、前記の一般式（１）で表されるものであると、Ａ成分とＢ成分との相溶性がさらに向上するようになる。しかも、Ａ成分の界面活性剤構造を形成するために用いられる界面活性剤中のスルホン酸基当量が、特定の範囲内に設定されていると、Ａ成分とＢ成分との相溶性がより一層向上するようになる。
【０１２２】
また、本発明の電子写真機器部材用半導電性組成物を、電子写真機器部材の少なくとも一部に用いると、この半導電性組成物に特有な効果を備えた電子写真機器部材を得ることができる。すなわち、本発明の半導電性組成物を、電子写真機器部材の構成層の少なくとも一部に用いると、先で述べたような、高電圧領域での電気抵抗の上昇が小さくなり、電気抵抗の電圧依存性および電気抵抗の環境依存性の双方の特性に優れるという、本発明の半導電性組成物の効果が、この半導電性組成物を用いていない他の構成層にも及ぶようになる。その結果、電子写真機器部材全体として、湿熱環境での電気抵抗変動が小さくなるため、良好な画像が得られるという効果を奏する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a semiconductive composition for an electrophotographic device member and an electrophotographic device member using the same, and more particularly, to a semiconductive composition used for an electrophotographic device member such as a developing roll, and a use thereof. Related to electrophotographic equipment members.
[0002]
[Prior art]
Generally, for a conductive composition used for a member of an electrophotographic apparatus such as a developing roll, control of electric resistance is indispensable to use it suitably. Therefore, conventionally, the electrical resistance has been controlled by blending an ion conductive agent such as a quaternary ammonium salt or an electronic conductive agent such as carbon black with a binder polymer such as a resin or rubber.
[0003]
Among the above-mentioned conductive agents, the ionic conductive agent is dissolved in the binder polymer, so that the dispersion of the conductivity is small, and the fluctuation of the electric resistance when the voltage is changed is small, and the voltage dependence of the electric resistance is excellent. There are advantages. However, ionic conductive agents are susceptible to the effects of moisture and the like, and their electrical resistance fluctuates by more than two orders of magnitude under high-temperature, high-humidity and low-temperature, low-humidity conditions. Has many restrictions. On the other hand, an electronic conductive agent such as carbon black is less susceptible to moisture and the like, and has a small variation in electrical resistance under high-temperature, high-humidity, and low-temperature, low-humidity conditions, and thus has the advantage of being excellent in the environmental dependence of electrical resistance. There is. However, since the electronic conductive agent generally has a strong cohesive property, it is difficult to uniformly disperse it in the binder polymer, and therefore, the electric resistance has a large variation, and it is difficult to control the conductivity. In addition, even when the voltage is changed even when the voltage is changed, even if the particles are relatively uniformly dispersed, the mechanism of manifesting conductivity is a tunnel effect or a hopping phenomenon in which electrons are transmitted by a high voltage between carbons in the binder polymer. Of the electric resistance is large, and the electric resistance is poor in voltage dependency.
[0004]
In order to solve these problems, conventionally, a roll-shaped charging member in which a composite of polyaniline and nylon is fixed on a polyurethane roll surface (see Patent Document 1), a π-electron conjugated conductive polymer, a resin component, and a solvent There has been proposed a composition for forming an antistatic film (see Patent Document 2). Further, an intermediate transfer member (see Patent Document 3) containing a conductive agent for imparting electronic conductivity and a conductive polymer such as polyaniline in a composition material, a water-soluble polyaniline having an acidic group, A semiconductive member containing a molecular compound or a water-based polymer compound comprising a water-based emulsion-forming polymer compound has been proposed (see Patent Document 4). However, in Patent Document 1, since the compatibility between polyaniline, which is a conductive polymer, and nylon is poor and the composition is agglomerated as particles of 1 μm or more, the initial characteristics of electrical resistance and the voltage dependence of electrical resistance are reduced. In Patent Document 2, since the compatibility between the π-electron conjugated conductive polymer and the resin component is poor, the voltage dependence of the electric resistance is poor. Further, in Patent Document 3, when a conductive polymer such as polyaniline is blended with a conductive agent that imparts electronic conductivity, undoping is indispensable, and in such a case, a special solvent called N-methyl-2-pyrrolidone (NMP) is used. Therefore, it is very difficult to blend a conductive agent imparting electronic conductivity with a conductive polymer. Further, an oxidation treatment is required after the formation of the coating film, so that uniform control is difficult and the process is complicated. In Patent Document 4, since water-soluble polyaniline having an acidic group is water-soluble, repelling and uneven coating occur at the time of application to a product, and the time-dependent change when left under moist heat conditions is large. There are great restrictions on the use of.
[0005]
In order to solve these problems, the present inventors have already applied for a patent for a conductive composition containing a conductive polymer having a surfactant structure and a binder polymer as essential components (Patent Document 5). reference).
[0006]
[Patent Document 1]
JP-A-5-88506
[Patent Document 2]
JP-A-9-48921
[Patent Document 3]
JP 2001-324882 A
[Patent Document 4]
JP-A-2002-89543
[Patent Document 5]
JP-A-2002-167519
[0007]
[Problems to be solved by the invention]
However, the present inventors have further studied the conductive composition described in Patent Literature 5, and as a result, this composition has good affinity for water, but poor solubility in a solvent. It has been found that the compatibility between the conductive polymer having the activator structure and the binder polymer is slightly inferior to form aggregates, and thus the electrical resistance tends to increase in a high voltage region.
[0008]
The present invention has been made in view of such circumstances, and an electronic resistance which is small in the rise of electric resistance in a high voltage region and excellent in both voltage dependence of electric resistance and environment dependence of electric resistance. An object of the present invention is to provide a semiconductive composition for a photographic device member and an electrophotographic device member using the same.
[0009]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present invention provides a semiconductive composition for an electrophotographic device member comprising the following (A) and (B) as essential components, and forms the surfactant structure of (A). The surfactant used for the electrophotography has a sulfonic acid group in the molecular structure, and the binder polymer (B) has at least one of a sulfonic acid group and a metal sulfonic acid salt structure in the molecular structure. A first aspect of the present invention is a semiconductive composition for an apparatus member, and a second aspect of the present invention is an electrophotographic apparatus member using the semiconductive composition for an electrophotographic apparatus member in at least a part of the electrophotographic apparatus member. .
(A) A conductive polymer having a surfactant structure.
(B) a binder polymer.
[0010]
That is, the present inventors have aimed to obtain a semiconductive composition in which the increase in electrical resistance in a high voltage region is small, and the electrical resistance is excellent in both the voltage dependence of the electrical resistance and the environmental dependence of the electrical resistance. , Earnestly studied. As a result, a conductive polymer having a surfactant structure is formed using a surfactant having a sulfonic acid group in the molecular structure, and a sulfonic acid group and a metal sulfonic acid are formed in the molecular structure together with the conductive polymer. When a binder polymer having at least one of the salt structures is used in combination, the compatibility between the two becomes good and the generation of aggregates can be suppressed, so that the increase in electric resistance in a high voltage region is reduced, and the intended purpose is achieved. They found what they could do and arrived at the present invention.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, an embodiment of the present invention will be described.
[0012]
The semiconductive composition for an electrophotographic device member of the present invention can be obtained by using a conductive polymer having a surfactant structure (A component) and a binder polymer (B component).
[0013]
In the present invention, the surfactant used for forming the surfactant structure of the conductive polymer having the surfactant structure (component A) includes a sulfonic acid group (—SO 2) in the molecular structure. ₃ H), and the binder polymer (component B) has at least one of a sulfonic acid group and a metal sulfonic acid salt structure in its molecular structure, which is the greatest feature.
[0014]
The conductive polymer having the surfactant structure (A component) is, for example, chemically oxidized by subjecting a raw material monomer of the conductive polymer and a specific surfactant to oxidative polymerization in water in the presence of an oxidizing agent. It can be produced by a polymerization method or the like.
[0015]
The raw material monomer of such a conductive polymer is not particularly limited as long as the polymer has conductivity by doping, and examples thereof include aniline (in addition to aniline derivatives, aniline salts such as aniline hydrochloride), Pyrrole, thiophene, alkylthiophene, ethylenedioxythiophene, isonaphthothiophene, 3-thiophene-β-ethanesulfonic acid, dichenothiophene, acetylene, paraphenylene, pheninvinylene, furan, selenophene, tellurophen, isothianaphthene, Examples include paraphenylene sulfide, paraphenylene oxide, and vinylene sulfide.
[0016]
The specific surfactant is not particularly limited as long as it has a sulfonic acid group in the molecular structure, and examples thereof include those represented by the following general formula (1) or (2).
[0017]
Embedded image

[0018]
Embedded image

[0019]
In the general formula (1), preferred R ¹ Examples thereof include an alkyl group having 2 to 12 carbon atoms. Also, R ² As hydrogen, an alkyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an aryl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, and a hydroxy group are preferable, and hydrogen, An alkoxy group, an alkylthio group, an alkylthioalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, and a hydroxy group. Further, n is preferably an integer of 2 to 4.
[0020]
In the general formula (2), preferred R ³ And R ⁴ As hydrogen, alkyl group, alkoxy group, alkylthio group, alkylthioalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, nitro group Or halogen. Preferred M in the general formula (2) includes a sodium ion, a potassium ion and an ammonium ion.
[0021]
In particular, as the specific surfactant, those having a sulfonic acid group in the molecular structure and at least one of a naphthalene structure and an anthracene structure are particularly preferable.
[0022]
Further, the naphthalene structure and the anthracene structure preferably have an arbitrary number of substituents among 1 to 9. Examples of the substituent include hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an aryloxyalkyl group. Examples include a naphthyl group, a naphthylalkyl group, an alkylsulfonyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, a hydroxy group, a nitro group, and a halogen. These substituents may be substituted alone, or two or more of them may be substituted.
[0023]
The sulfonic acid group equivalent in such a specific surfactant is preferably in the range of 340 to 600, and particularly preferably in the range of 380 to 550. That is, if the sulfonic acid group equivalent is less than 340, the compatibility with the binder polymer (component B) tends to be deteriorated, and if it exceeds 600, the effect as a dopant tends to decrease. It is. The sulfonic acid group equivalent is determined according to sodium hydroxide titration or thermogravimetric analysis (TGA).
[0024]
The oxidizing agent used in the chemical oxidative polymerization is not particularly limited, and examples thereof include ammonium persulfate (APS), aqueous hydrogen peroxide, and ferric chloride.
[0025]
The mixing ratio between the raw material monomer of the conductive polymer and the specific surfactant is preferably in a molar ratio of raw material monomer / surfactant = 1 / 0.03 to 1/3, and particularly preferably raw material monomer. /Surfactant=1/0.05 to 1/2. That is, when the molar ratio of the surfactant decreases, the compatibility and dispersibility with the binder polymer (component B) tend to decrease. Conversely, when the molar ratio of the surfactant increases, the This is because the effect of contributing to ionic conductivity becomes too strong, and there is a tendency to reduce the electronic conductivity of the conductive polymer.
[0026]
The number average molecular weight (Mn) of the specific conductive polymer (component A) thus obtained is preferably in the range of 1,000 to 100,000, particularly preferably in the range of 1,000 to 20,000. It is.
[0027]
Next, the binder polymer (component B) used together with the specific conductive polymer (component A) is not particularly limited as long as it has at least one of a sulfonic acid group and a sulfonic acid metal salt structure in a molecular structure. There is no. Examples of the sulfonic acid metal salt structure include a sodium sulfonic acid structure, an ammonium sulfonic acid salt structure, and a potassium sulfonic acid salt structure.
[0028]
Examples of the binder polymer (component B) having at least one of a sulfonic acid group and a sulfonic acid metal salt structure in its molecular structure include, for example, an acrylic resin, a urethane resin, and fluorine having such a structure. Resins, polyimide resins, epoxy resins, urea resins, rubber polymers, thermoplastic elastomers and the like. These may be used alone or in combination of two or more. Among these, acrylic resins, urethane resins, rubber polymers, and thermoplastic elastomers are preferably used because of their excellent compatibility with a specific conductive polymer (component A).
[0029]
Examples of the acrylic resin include, for example, polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and known acrylic resin. Examples thereof include copolymers of monomers and the like, in which at least one of a sulfonic acid group and a metal sulfonic acid salt structure is introduced into a molecular structure. The method of introducing a sulfonic acid group into a binder polymer includes a method of copolymerizing a vinyl monomer having a sulfonic acid group or a sulfonic acid metal base with a radical, an anion or a cation, or a method of subjecting a diol monomer having a sulfonic acid group to urethane reaction, esterification. There is a method of introducing by an exchange reaction.
[0030]
The urethane-based resin is not particularly limited as long as it has a urethane bond in its molecular structure. Examples thereof include urethanes such as ether-based, ester-based, acryl-based, and aliphatic-based resins, and silicone-based polyols or fluorine-based resins. Examples thereof include those obtained by copolymerizing a system polyol, wherein at least one of a sulfonic acid group and a metal sulfonic acid salt structure is introduced into the molecular structure. The urethane resin may have a urea bond or an imide bond in the molecular structure.
[0031]
Examples of the fluorine-based resin include polyvinylidene fluoride (PVDF), vinylidene fluoride-ethylene tetrafluoride copolymer, vinylidene fluoride-ethylene tetrafluoride-ethylene hexafluoropropylene copolymer, and the like. And those having at least one of a sulfonic acid group and a sulfonic acid metal salt structure introduced into the molecular structure.
[0032]
Examples of the polyimide resin include polyamide imide (PAI), polyamic acid, and silicone imide in which at least one of a sulfonic acid group and a sulfonic acid metal salt structure is introduced into a molecular structure. can give.
[0033]
As the epoxy resin, for example, bisphenol A type epoxy resin, epoxy novolak resin, brominated type epoxy resin, polyglycol type epoxy resin, polyamide combined type epoxy resin, silicone modified epoxy resin, amino resin combined type epoxy resin, Epoxy resins used in combination with alkyd resins, in which at least one of a sulfonic acid group and a metal sulfonic acid salt structure is introduced into the molecular structure, may be mentioned.
[0034]
The urea-based resin is not particularly limited as long as it has a urea bond in the molecular structure, and may be a urethane urea elastomer, a melamine resin, a urea formaldehyde resin, or the like. Examples include those into which at least one of the acid metal salt structures has been introduced.
[0035]
Examples of the rubber-based polymer include natural rubber (NR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), hydrogenated NBR (H-NBR), styrene butadiene rubber (SBR), and isoprene rubber (IR). , Urethane rubber, chloroprene rubber (CR), chlorinated polyethylene (Cl-PE), epichlorohydrin rubber (ECO, CO), butyl rubber (IIR), ethylene propylene diene polymer (EPDM), fluorine rubber, etc. Examples include those in which at least one of a sulfonic acid group and a sulfonic acid metal salt structure is introduced into the structure.
[0036]
Examples of the thermoplastic elastomer include styrene-based thermoplastic elastomers such as styrene-butadiene block copolymer (SBS) and styrene-ethylene-butylene-styrene block copolymer (SEBS), and urethane-based thermoplastic elastomers (TPU). ), Olefin-based thermoplastic elastomers (TPO), polyester-based thermoplastic elastomers (TPEE), polyamide-based thermoplastic elastomers, fluorine-based thermoplastic elastomers, PVC-based thermoplastic elastomers, and the like. And those into which at least one of a sulfonic acid metal salt structure is introduced. These may be used alone or in combination of two or more. Among them, TPU is preferably used in view of simplicity of the synthesis process and solubility in a solvent.
[0037]
The content (the amount of the sulfonic acid group) of at least one of the sulfonic acid group and the sulfonic acid metal salt structure in the binder polymer (component B) is preferably in the range of 0.001 to 1 mmol / g, and particularly preferably 0. It is in the range of 0.01 to 0.2 mmol / g. That is, if the amount of the sulfonic acid group is less than 0.001 mmol / g, the compatibility with the specific conductive polymer (component A) tends to be deteriorated. This is because physical properties and ionic conductivity are observed.
[0038]
The number average molecular weight (Mn) of such a specific binder polymer (component B) is preferably in the range of 500 to 2,000,000, and particularly preferably in the range of 2,000 to 800,000.
[0039]
The specific binder polymer (component B) and the specific conductive polymer (component A) are mixed and formed into a semiconductive composition as described below. The mixing ratio of the raw material (the total amount of the raw material monomer of the conductive polymer and the surfactant) and the specific binder polymer (B component) is expressed as a weight ratio of the raw material of the A component / the B component = 1/99 to The range of 40/60 is preferable, and the ratio of the raw material of the component A / the component B = 4/96 to 35/65 is particularly preferable. That is, if the weight ratio of the component A raw material is less than 1, the effect on conductivity tends to be reduced. Conversely, if the weight ratio of the component A raw material exceeds 40, the resulting composition becomes hard. This is because the composition tends to be brittle and the physical properties of the composition tend to decrease.
[0040]
In addition, in addition to a specific conductive polymer (A component) and a specific binder polymer (B component), an ionic conductive agent, an electronic conductive agent, A crosslinking agent or the like may be appropriately compounded.
[0041]
Examples of the ionic conductive agent include compounds that dissociate ions in polymers such as lithium perchlorate, quaternary ammonium salts and borates. These may be used alone or in combination of two or more.
[0042]
From the viewpoint of physical properties and electrical properties, the mixing ratio of such an ionic conductive agent is determined based on the raw material (the total amount of the raw material monomer and the surfactant) of the specific conductive polymer (A component) and the specific binder polymer ( The amount is preferably in the range of 0.01 to 5 parts, more preferably 0.5 to 2 parts, based on 100 parts by weight (hereinafter, abbreviated as “parts”) of the total amount of component (B).
[0043]
Examples of the electron conductive agent include carbon black, c-ZnO (conductive zinc oxide), and c-TiO. ₂ (Conductive titanium oxide), c-SnO ₂ (Conductive tin oxide), graphite and the like.
[0044]
From the viewpoint of physical properties and electrical properties, the mixing ratio of such an electronic conductive agent is determined based on the raw material (total amount of the raw material monomer and the surfactant) of the specific conductive polymer (A component) and the specific binder polymer (B The amount is preferably in the range of 5 to 30 parts, more preferably in the range of 8 to 20 parts, based on 100 parts in total.
[0045]
Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, blocked isocyanate, and melamine, epoxy curing agents, polyamine curing agents, and peroxides.
[0046]
The mixing ratio of such a cross-linking agent is determined based on the physical properties, adhesion, and liquid storage properties of the raw material of the specific conductive polymer (A component) (the total amount of the raw material monomer and the surfactant) and the specific binder polymer. It is preferably in the range of 1 to 30 parts, more preferably 3 to 10 parts, based on 100 parts in total with (B component).
[0047]
The semiconductive composition for an electrophotographic device member of the present invention may contain a crosslinking accelerator, an antioxidant, and the like, if necessary, in addition to the above components.
[0048]
Examples of the crosslinking accelerator include a sulfenamide-based crosslinking accelerator, a dithiocarbamate-based crosslinking accelerator, and the like.
[0049]
The semiconductive composition for an electrophotographic device member of the present invention can be prepared, for example, as follows. That is, first, a specific conductive polymer (component A) is prepared according to the method described above. Next, a specific binder polymer (component B) is added to the specific conductive polymer (component A), and an ionic conductive agent, an electronic conductive agent, a cross-linking agent, and the like are added as necessary. And these are kneaded using a kneading machine such as a roll, a kneader, a Banbury mixer or the like, whereby a desired semiconductive composition can be obtained. Here, the specific conductive polymer (component A) is used in a state of being dissolved in a solvent. The binder polymer (component B) is used in a state of being dissolved in a solvent.
[0050]
Examples of the solvent include organic solvents such as m-cresol, methanol, methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), and N-methyl-2-pyrrolidone (NMP).
[0051]
The semiconductive composition for an electrophotographic device member of the present invention has an electric resistance of 10 when a voltage of 10 V is applied in an environment of 25 ° C. × 50% RH. ⁶ -10 ¹¹ It is preferably within the range of Ω · cm, particularly preferably 10 ⁷ -10 ¹⁰ Within the range of Ω · cm. That is, the electric resistance is 10 ⁶ If it is less than Ω · cm, the electrical resistance is too low, and there is a tendency that the advantage of the electrophotographic device member to the image decreases in terms of charge supply to the toner and charging property to the photoreceptor. To 10 ¹¹ If the resistance exceeds Ω · cm, the electrical resistance is too high, so that a charge-up occurs and the control as an electrophotographic device member tends to be difficult.
[0052]
When a coating film is formed using the semiconductive composition for an electrophotographic device member of the present invention, an aggregate (1 μm or more) of a specific conductive polymer (A component) present in the binder polymer (B component) is formed. It is preferably less than 3% of the total area of the coating film, particularly preferably less than 0.5%. That is, when this aggregate exceeds 3% of the area of the entire coating film, the fluctuation of the electric resistance with respect to the voltage tends to increase.
[0053]
The semiconductive composition for an electrophotographic device member of the present invention is used for at least a part (all or a part) of an electrophotographic device member. Examples of the electrophotographic device members include conductive rolls such as a developing roll, a charging roll, a transfer roll, and a toner supply roll, and conductive belts such as an intermediate transfer belt and a paper feed belt. Used at least in part. That is, when the semiconductive composition for an electrophotographic device member of the present invention is used for at least a part of the constituent layer of the electrophotographic device member, the voltage of the electric resistance of the constituent layer formed using the semiconductive composition is reduced. Dependencies and environmental dependencies are reduced. As a result, the other constituent layers are less susceptible to the voltage dependence and the environment dependence of the electric resistance, so that the voltage dependence and the environment dependence of the electric resistance of the entire electrophotographic apparatus member are reduced.
[0054]
Next, examples will be described together with comparative examples.
[0055]
First, the composition according to the present invention was prepared as follows.
[0056]
[Composition 1]
Oxidative polymerization of 1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (dodecylbenzenesulfonic acid) [equivalent of sulfonic acid group: 326], while dropping 1 mol of an oxidizing agent (ammonium persulfate) in an aqueous solution. As a result, a polyaniline (A component) having a surfactant structure was obtained. Then, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, was dissolved in a solvent. After dissolving in 200 parts of (MEK) and 300 parts of a solvent (toluene), 20 parts of an active ingredient (non-volatile content) of the above polyaniline having a surfactant structure is added and stirred for 10 minutes to prepare a composition (coating liquid). did. Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0057]
[Composition 2]
1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in the molecular structure (pentadecylbenzenesulfonic acid) [sulfonic acid group equivalent: 368] are oxidized while dropping 1 mol of an aqueous oxidizing agent (ammonium persulfate). Polymerization was carried out to obtain polyaniline (A component) having a surfactant structure. Then, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, was dissolved in a solvent. After dissolving in 100 parts of (MEK) and 500 parts of a solvent (toluene), 20 parts of an active ingredient (non-volatile content) of the above polyaniline having a surfactant structure is added, and the mixture is stirred for 10 minutes to prepare a composition (coating liquid). did. Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0058]
[Composition 3]
1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (dinonylnaphthalenesulfonic acid) [sulfonic acid group equivalent: 460] are oxidized while dropping 1 mol of an aqueous oxidizing agent (ammonium persulfate). Polymerization was carried out to obtain polyaniline (A component) having a surfactant structure. Then, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, was dissolved in a solvent. After dissolving in 300 parts of (MEK) and 300 parts of a solvent (toluene), 20 parts of an active ingredient (non-volatile content) of the above polyaniline having a surfactant structure is added and stirred for 10 minutes to prepare a composition (coating liquid). did. Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0059]
[Composition 4]
1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in the molecular structure (sodium 2,2′-dinaphthylmethane-6-sulfonate-6′-sulfonic acid) [sulfonic acid group equivalent: 450] Oxidative polymerization was carried out while dropwise adding 1 mol of an aqueous oxidizing agent (ammonium persulfate) to obtain polyaniline (A component) having a surfactant structure. Then, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, was dissolved in a solvent. After dissolving in 100 parts of (MEK) and 500 parts of a solvent (toluene), 20 parts of an active ingredient (non-volatile content) of the above polyaniline having a surfactant structure is added, and the mixture is stirred for 10 minutes to prepare a composition (coating liquid). did. Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0060]
[Composition 5]
1 mol of aniline and a surfactant having a sulfonic acid group in the molecular structure (in the general formula (1), R ¹ = Butyl group, R ² = Hydrogen, compound represented by n = 2, m = 3) [sulfonic acid group equivalent: 534] 1 mol and oxidative polymerization of 1 mol of an oxidizing agent (ammonium persulfate) in the form of an aqueous solution to form a surfactant structure (A component) having the following formula: Next, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, After dissolving in 100 parts of a solvent (MEK) and 500 parts of a solvent (toluene), 20 parts of an active ingredient (non-volatile content) of the above polyaniline having a surfactant structure is added, and the mixture is stirred for 10 minutes to prepare a composition (coating liquid). Prepared. Then, after applying this composition (coating liquid) on a SUS304 plate, it was crosslinked by heating at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm.
[0061]
[Composition 6]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and a block After dissolving 5 parts of an isocyanate (manufactured by Dainippon Ink and Chemicals, Inc., Vernock DB980K) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient of the polyaniline having the above surfactant structure (nonvolatile content) ) Was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0062]
[Composition 7]
1 mol of pyrrole and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (pentadecylbenzenesulfonic acid) [sulfonic acid group equivalent: 368] are oxidized while dropping 1 mol of an aqueous oxidizing agent (ammonium persulfate). Polymerization was performed to obtain polypyrrole (A component) having a surfactant structure. Next, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and a block 5 parts of an isocyanate (manufactured by Dainippon Ink and Chemicals, Inc., Vernock DB980K) are dissolved in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), and then the active ingredient (non-volatile ) Was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0063]
[Composition 8]
1 mol of thiophene and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (pentadecylbenzenesulfonic acid) [sulfonic acid group equivalent: 368] are oxidized while dropping 1 mol of an aqueous oxidizing agent (ammonium persulfate). Polymerization was performed to obtain a polythiophene having a surfactant structure (A component). Next, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and a block After dissolving 5 parts of an isocyanate (manufactured by Dainippon Ink and Chemicals, Inc., Barnock DB980K) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient of the polythiophene having the surfactant structure (nonvolatile content) ) Was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0064]
[Composition 9]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, a sulfonated NBR synthesized by solution polymerization in the presence of styrene sulfonic acid, which is a binder polymer (component B) having a sulfonic acid group in the molecular structure (sulfonic acid group content: 0.1 mmol / g, (Mn: 100,000) 80 parts, 1 part of sulfur as a cross-linking agent, 0.5 part of a sulfenamide-based cross-linking accelerator (Noxeller CZ, manufactured by Ouchi Shinko Chemical Co., Ltd.), and dithiocarbamate-based cross-linking promotion And 0.5 parts of an agent (NOCSELA BZ, manufactured by Ouchi Shinko Chemical Co., Ltd.) using a two-roll mill and dissolving them in 300 parts of a solvent (MEK) and 300 parts of a solvent (toluene). 20 parts of an active ingredient (nonvolatile content) of polyaniline having a surfactant structure was added, and the mixture was stirred for 10 minutes to prepare a composition (coating liquid). Then, after applying this composition (coating liquid) on a SUS304 plate, it was crosslinked by heating at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm.
[0065]
[Composition 10]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 80 parts of a sulfonated urethane silicone (sulfonic acid group content: 0.1 mmol / g, Mn: 50,000), which is a binder polymer having a sulfonic acid group in the molecular structure (component B), and a blocked isocyanate ( After dissolving 5 parts of Vernock DB980K (manufactured by Dainippon Ink and Chemicals, Inc.) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient (nonvolatile matter) of polyaniline having the surfactant structure 20 Was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm. The sulfonated urethane silicone was prepared by mixing polybutylene adipate diol (Mn: 2,000) and silicone diol (Mn: 2,000) at a ratio of 8: 2, and adding 1% as a chain extender. It was prepared by adding 1,4-butanediol and sodium 1,4-butanediol-2-sulfonate and reacting with 4,4'-diphenylmethane diisocyanate (MDI) in an equimolar amount.
[0066]
[Composition 11]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 80 parts of sulfonated acrylic fluorine (sulfonic acid group content: 0.1 mmol / g, Mn: 30,000), which is a binder polymer (component B) having a sulfonic acid group in the molecular structure, and blocked isocyanate ( After dissolving 5 parts of Vernock DB980K (manufactured by Dainippon Ink and Chemicals, Inc.) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient (nonvolatile matter) of polyaniline having the surfactant structure 20 Was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0067]
[Composition 12]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, a sulfonated urethane silicone (amount of sulfonic acid group: 1 mmol / g, Mn :), which is a binder polymer having a sulfonic acid group in the molecular structure (component B) and prepared by increasing the number of sulfonic acid groups in the composition 10. 50,000) and 5 parts of a blocked isocyanate (Dai Nippon Ink and Chemicals, Inc., Vernock DB980K) were dissolved in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene). Then, 20 parts of an active ingredient (non-volatile component) of polyaniline having the formula (1) was added and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0068]
[Composition 13]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, a sulfonated urethane silicone (a sulfonic acid group content: 0.001 mmol / g, which is a binder polymer having a sulfonic acid group in the molecular structure (component B)) produced by reducing the amount of the sulfonic acid group in the composition 10 After dissolving 80 parts of Mn (50,000) and 5 parts of blocked isocyanate (Vanok DB980K, manufactured by Dainippon Ink and Chemicals, Inc.) in 200 parts of solvent (MEK) and 400 parts of solvent (toluene), 20 parts of an active ingredient (nonvolatile content) of polyaniline having an agent structure was added and stirred for 10 minutes to prepare a composition (coating liquid). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0069]
[Composition 14]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 90 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., Nippon Polyurethane Industry Co., Ltd., amount of sodium sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and a block After dissolving 5 parts of an isocyanate (manufactured by Dainippon Ink and Chemicals, Inc., Vernock DB980K) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient of the polyaniline having the above surfactant structure (nonvolatile content) 10), and stirred for 10 minutes to prepare a composition (coating solution). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0070]
[Composition 15]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 70 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and a block After dissolving 5 parts of isocyanate (manufactured by Dainippon Ink and Chemicals, Inc., Vernock DB980K) in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), the active ingredient of the polyaniline having the above surfactant structure (nonvolatile content) ) 30 parts was added and stirred for 10 minutes to prepare a composition (coating liquid). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0071]
[Composition 16]
In the same manner as in composition 2, polyaniline (component A) having the same surfactant structure was obtained. Next, 80 parts of TPU (Nipporan 3312, manufactured by Nippon Polyurethane Industry Co., Ltd., amount of Na sulfonate group: 0.05 mmol / g), which is a binder polymer (component B) having a sodium sulfonate group in the molecular structure, and acetylene 5 parts of black (Denka Black HS100, manufactured by Denki Kagaku Kogyo) and 5 parts of blocked isocyanate (Bernock DB980K, manufactured by Dainippon Ink and Chemicals, Inc.) are dissolved in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene). After that, 20 parts of an active ingredient (nonvolatile content) of the above-mentioned polyaniline having a surfactant structure was added, and the mixture was stirred for 10 minutes to prepare a composition (coating liquid). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0072]
Next, in the present invention, a composition to be a comparative example was prepared as follows.
[0073]
[Composition A]
100 parts of H-NBR (Zetpol 0020, manufactured by Zeon Corporation), which is a binder polymer having no sulfonic acid group in the molecular structure, and 2 parts of borate (LR147, manufactured by Nippon Carrit Company) which is an ion conductive agent And 10 parts of a cross-linking agent (zinc oxide) and 3 parts of a thiourea-based cross-linking accelerator (Suncellar 22C, manufactured by Sanshin Chemical Co., Ltd.), kneaded using a three-roll mill, and then kneaded them with a solvent (MEK). It was dissolved in 300 parts and 150 parts of a solvent (toluene) to prepare a composition (coating liquid). Then, after applying this composition (coating liquid) on a SUS304 plate, it was crosslinked by heating at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm.
[0074]
[Composition B]
After dissolving 100 parts of a carbonate-based TPU (E980, manufactured by Nippon Miractran Co.), which is a binder polymer having no sulfonic acid group in the molecular structure, in 200 parts of a solvent (MEK) and 300 parts of a solvent (tetrahydrofuran), Was mixed with 7 parts of acetylene black (DENKA BLACK HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and kneaded using a three-roll mill to prepare a composition. Then, this was heated and crosslinked at 150 ° C. for 30 minutes to produce a 100 μm-thick conductive coating film on a SUS304 plate.
[0075]
[Composition C]
Except having changed the compounding ratio of acetylene black into 20 parts, it carried out similarly to composition B, and produced the conductive coating film.
[0076]
[Composition D]
Silicone in which carbon black was dispersed (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) was press-molded (150 ° C. × 10 minutes) on a SUS304 plate to form a conductive coating film having a thickness of 100 μm.
[0077]
[Composition E]
A conductive coating film was prepared according to Example 1 described in JP-A-5-88506. That is, an aqueous solution containing 0.4 mol / l of aniline, 1.0 mol / l of sulfuric acid, and 0.5 mol / l of ammonium persulfate was prepared, and polyaniline was polymerized by a chemical oxidation polymerization method. The obtained polyaniline was adjusted to neutrality with sodium hydroxide, washed with water, and dried to obtain a polyaniline powder having a particle diameter of about 1 μm. Next, 50 parts of soluble nylon, which is a binder polymer having no sulfonic acid group in the molecular structure, is dissolved in 500 parts of a solvent (methanol), and 50 parts of the above polyaniline powder is added thereto, and mixed with Red Devil. Thus, a composition (coating solution) was prepared. Then, after applying this composition (coating liquid) on a SUS304 plate, it was crosslinked by heating at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm.
[0078]
[Composition F]
A conductive coating film was produced according to Example 1 described in JP-A-2001-324882. That is, a predetermined amount of dried fluorinated carbon black (ACCUFLVOR2028, manufactured by ALLIED) was blended in N-methyl-2-pyrrolidone (NMP), and mixed at room temperature for 6 hours using a ball mill. Next, 293.2 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 108.2 g of p-phenylenediamine (PDA) were dissolved in the carbon black-dispersed NMP solution. The reaction was carried out while stirring at room temperature for 4 hours in a nitrogen atmosphere to obtain a polyamic acid solution containing fluorinated carbon black. In addition, 20 g of polyaniline powder was added to 200 g of NMP, and the mixture was stirred and dissolved at 5000 rpm for 1 hour using an auto-homomixer to obtain a 10% by weight undoped polyaniline solution. Next, a predetermined amount of the polyaniline solution is added to the fluorinated carbon black-containing polyamic acid solution, and the mixture is stirred at room temperature for 1 hour using a stirring blade to obtain a desired blended amount of the fluorinated carbon black and the polyaniline-containing polyamic acid. A solution (resin: polyaniline: fluorinated carbon black = 74% by weight: 15% by weight: 11% by weight) was obtained. Then, after applying this solution on a SUS304 plate, heat-crosslinking is performed at 150 ° C. for 30 minutes, and the temperature is raised to 200 ° C. at a temperature increase rate of 2 ° C./min. A 100 μm conductive coating was produced.
[0079]
[Composition G]
A conductive coating film was produced according to the examples described in JP-A-2002-167519. That is, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) [sulfonic acid group equivalent: 326] are oxidatively polymerized while 1 mol of an aqueous oxidizing agent (ammonium persulfate) is added dropwise to form a surfactant structure. To obtain polyaniline. Next, 80 parts of a polyester (adipate) -based TPU (Elastolane 1040, manufactured by Mitsui Takeda Chemical Co., Ltd.), which is a binder polymer having no sulfonic acid group in the molecular structure, is mixed with 200 parts of a solvent (MEK) and a solvent (toluene). After dissolving in 400 parts, 20 parts of the above polyaniline having a surfactant structure was added and kneaded using a three-roll mill to prepare a conductive composition (coating liquid). Then, this composition (coating liquid) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.
[0080]
Using the conductive coating film thus obtained, each characteristic was evaluated according to the following criteria. The results are shown in Tables 1 to 5 below.
[0081]
(Aggregate area)
The particle size (median diameter) of the conductive polymer present in the binder polymer of each conductive coating film was measured by observing a film having a thickness of 5 to 8 μm at 3000 times magnification (optical microscope). Then, the ratio (area) of aggregates having a particle size of 1 μm or more to the entire coating film was measured.
[0082]
[Electric resistance, voltage dependence of electric resistance]
For each conductive coating film, the electric resistance (Rv = 1 V) when a voltage of 1 V was applied and the electric resistance (Rv = 133 V) when a voltage of 133 V was applied under an environment of 25 ° C. × 50% RH. And SRIS 2304. Then, the voltage dependence of the electric resistance was represented by the number of digits of variation by Log (Rv = 1 V / Rv = 133 V).
[0083]
[Environmental dependence of electrical resistance]
For each conductive coating film, the electric resistance (Rv = 15 ° C. × 10% RH) at low temperature and low humidity (15 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × 85% RH) under the condition of an applied voltage of 10 V )) (Rv = 35 ° C. × 85% RH) was measured according to SRIS 2304, respectively. Then, the logarithm (Rv = 15 ° C. × 10% RH / Rv = 35 ° C. × 85% RH) was used to indicate the environmental dependence of the electric resistance in a variable digit.
[0084]
[Electric resistance fluctuation due to environment]
The electric resistance of each conductive coating film after being left for 30 days in an environment of 50 ° C. × 95% RH was measured according to SRIS 2304 in an environment of 25 ° C. × 50% RH by applying 10 V (Rv = 30 days). And, by Log (Rv = 30 days / Rv = 0 days), the electric resistance fluctuation due to the environment was displayed by the number of digits of the fluctuation.
[0085]
[Electrical resistance fluctuation in high voltage range (charge up)]
The electrical resistance (Rv = 300 V) of each conductive coating film when a voltage of 300 V was applied in an environment of 25 ° C. × 50% RH was measured according to SRIS 2304. Then, the electrical resistance variation in the high voltage region was indicated by the number of digits of variation by Log (Rv = 30V / Rv = 300V).
[0086]
[Table 1]

[0087]
[Table 2]

[0088]
[Table 3]

[0089]
[Table 4]

[0090]
[Table 5]

[0091]
From the results in the above table, Compositions 1 to 16 are a specific conductive polymer formed using a surfactant having a sulfonic acid group in the molecular structure, and a binder polymer having a sulfonic acid group in the molecular structure. Since they were used in combination, the compatibility of the two was good, the generation of aggregates could be suppressed, and the rise (charge-up) of electric resistance in a high voltage region was very small. Further, both the voltage dependence of the electric resistance and the environment dependence of the electric resistance were excellent, and the electric resistance fluctuation due to the environment was small.
[0092]
On the other hand, since the composition A used the ionic conductive agent, the environmental resistance of the electric resistance was inferior, and the electric resistance in the high voltage region increased significantly. Compositions B, C, and D used the electronic conductive agent, and thus had poor voltage dependence of electrical resistance. Composition E had poor compatibility between polyaniline and nylon, generated many aggregates, and was inferior in voltage dependence of electric resistance. Composition F had poor compatibility between polyaniline and fluorinated carbon black and generated a large amount of aggregates, so that the electrical resistance in the high voltage region varied greatly. Since the composition G uses a binder polymer having no sulfonic acid group in the molecular structure, the compatibility with the conductive polymer having a surfactant structure is inferior, an aggregate is generated, and a high voltage region is generated. There was an upward trend in electrical resistance.
[0093]
Next, examples of the electrophotographic apparatus member according to the present invention will be described together with comparative examples.
[0094]
Embodiment 1
[Production of developing roll]
Injection-molded silicone (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) [composition D] into an injection molding mold in which a core metal (diameter: 10 mm, made of SUS304) as a shaft was set. After heating at 150 ° C. for 45 minutes, the mold was removed and a base layer was formed along the outer peripheral surface of the shaft. Then, the surface of the base layer was subjected to a corona discharge treatment (condition: 0.3 kW × 20 seconds). Next, the composition C prepared above was applied to the outer peripheral surface of the base layer to form an intermediate layer. Further, on the surface of the intermediate layer, a surface layer composed of the composition 1 prepared as described above is formed, a base layer is formed on the outer peripheral surface of the shaft, an intermediate layer is formed on the outer peripheral surface, and further on the outer peripheral surface. A developing roll having a surface layer formed thereon was produced.
[0095]
Examples 2 to 18, Comparative Examples 1 to 5
A developing roll was prepared in the same manner as in Example 1 except that the compositions shown in Tables 6 to 9 below were used as the base layer material, the intermediate layer material, and the surface layer material. In addition, about the thing which does not form a base layer, an intermediate | middle layer, or a surface layer, it displayed with "-".
[0096]
Using the developing rolls of the example product and the comparative example product thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 6 to 9 below.
[0097]
[Electric resistance, voltage dependence of electric resistance]
With the surface of the developing roll pressed against the SUS plate, a load of 1 kg was applied to each end of the developing roll, and the electric resistance between the core of the developing roll and the surface of the developing roll pressed against the SUS plate, It was measured according to SRIS 2304. The electric resistance is the electric resistance (Rv = 1 V) when a voltage of 1 V is applied and the electric resistance (Rv = 133 V) when a voltage of 133 V is applied in an environment of 25 ° C. × 50% RH. It was measured. Then, the voltage dependence of the electric resistance was represented by the number of digits of variation by Log (Rv = 1 V / Rv = 133 V).
[0098]
[Environmental dependence of electrical resistance]
According to the evaluation of the electric resistance, the electric resistance (Rv = 15 ° C. × 10% RH) at low temperature and low humidity (15 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × The electric resistance (Rv = 35 ° C. × 85% RH) at the time of 85% RH was measured in accordance with SRIS 2304, respectively. Then, the logarithm (Rv = 15 ° C. × 10% RH / Rv = 35 ° C. × 85% RH) was used to indicate the environmental dependence of the electric resistance in a variable digit.
[0099]
[Hardness (JIS A)]
The hardness of the outermost surface of each developing roll was measured according to JIS K6253.
[0100]
(Compression set)
The compression set of each developing roll was measured according to JIS K 6262 under the conditions of a temperature of 70 ° C., a test time of 22 hours, and a compression ratio of 25%.
[0101]
[Developing roll characteristics]
(Image unevenness)
Each developing roll was incorporated in a commercially available color printer, and an image was formed in an environment of 20 ° C. × 50% RH. The evaluation was evaluated as "O" when there was no density unevenness in the halftone image and no breaks or color unevenness of the thin line, and "Poor" when the density unevenness occurred.
[0102]
(Variation in image quality due to environment)
Image quality depending on the environment when each developing roll is incorporated into a commercially available color printer and an image is output under an environment of 15 ° C. × 10% RH, and when an image is output under an environment of 35 ° C. × 85% RH. Was evaluated. For evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○ was given, and when it exceeded 0.1, x was given.
[0103]
[Concentration fluctuation due to charge-up]
Each developing roll was incorporated in a commercially available color printer, and a voltage of 300 V was applied under an environment of 25 ° C. × 50% RH to perform image output. The evaluation was evaluated as "O" when there was no density unevenness in the halftone image and no breaks or color unevenness of the thin line, and "Poor" when the density unevenness occurred.
[0104]
[Electrical resistance over time due to environment]
According to the evaluation of the electric resistance, the electric resistance after being left for 30 days in an environment of 50 ° C. × 95% RH was measured in an environment of 25 ° C. × 50% RH according to SRIS 2304 by applying 10 V ( Rv = 30 days). Then, the change with time in the electrical resistance due to the environment was indicated by the number of digits of variation by Log (Rv = 30 days / Rv = 0 days).
[0105]
Examples 19 to 22, Comparative Examples 6 to 8
(Preparation of charging roll)
A charging roll was prepared in accordance with the method of manufacturing the developing roll of Example 1, except that the compositions shown in Tables 10 and 11 below were used as the material for the base layer, the material for the intermediate layer, or the material for the surface layer. In addition, about the thing which does not form a base layer, an intermediate | middle layer, or a surface layer, it displayed with "-".
[0106]
Example 23, Comparative Example 9
[Production of transfer roll]
A transfer roll was prepared according to the method of manufacturing the developing roll of Example 1, except that the composition shown in Table 12 below was used as the material for the base layer, the material for the intermediate layer, or the material for the surface layer. In addition, about the thing which does not form a base layer, an intermediate | middle layer, or a surface layer, it displayed with "-".
[0107]
Examples 24 and 25, Comparative Example 10
[Production of transfer belt]
Except for using the composition shown in Table 13 below as the material for the base layer, the material for the intermediate layer, or the material for the surface layer, an intermediate transfer belt having a single-layer or multilayer structure ( Endless belt). In addition, about the thing which does not form a base layer, an intermediate | middle layer, or a surface layer, it displayed with "-".
[0108]
Using the charging rolls, transfer rolls, and transfer belts of the example product and the comparative example product thus obtained, each characteristic was evaluated in accordance with the standard for evaluating the characteristics of the developing roll. These results are shown in Tables 10 to 13 below. The electric resistance of the transfer belt was determined by placing a SUS rod having a diameter of 10 mm and weighing 1 kg inside the transfer belt, and measuring the electric resistance between the portion in contact with the SUS rod and the SUS plate by SRIS.
It was measured according to 2304.
[0109]
[Table 6]

[0110]
[Table 7]

[0111]
[Table 8]

[0112]
[Table 9]

[0113]
[Table 10]

[0114]
[Table 11]

[0115]
[Table 12]

[0116]
[Table 13]

[0117]
From the above results, all the products of Examples use the semiconductive composition (compositions 1 to 16) of the present invention in at least a part of the constituent layers of the member of the electrophotographic apparatus, so that the characteristics of the developing roll and the charge Excellent roll characteristics, transfer roll characteristics, and transfer belt characteristics.
[0118]
On the other hand, since the comparative example uses only a composition (any one of the compositions A to G) which is inferior in the voltage dependence of the electric resistance and the environment dependence of the electric resistance, the developing roll characteristics, the charging roll The characteristics, transfer roll characteristics and transfer belt characteristics were inferior.
[0119]
【The invention's effect】
As described above, the semiconductive composition for an electrophotographic device member of the present invention uses a surfactant having a sulfonic acid group in a molecular structure to form a conductive polymer having a surfactant structure. A binder polymer (component B) having at least one of a sulfonic acid group and a sulfonic acid metal salt structure in the molecular structure is used together with the conductive polymer (component A). Therefore, the compatibility between the two becomes good, the generation of agglomerates can be suppressed, the rise in electric resistance in a high voltage region is reduced, and both the voltage dependence of electric resistance and the environmental dependence of electric resistance are improved. It has the effect of being superior.
[0120]
When a specific polymer such as an acrylic resin is used as the binder polymer (component B), or when the amount of the sulfonic acid group in the binder polymer (component B) is set to a specific range, the components A and B become Is further improved.
[0121]
Further, the surfactant used for forming the surfactant structure of the component A has a sulfonic acid group in a molecular structure and has at least one of a naphthalene structure and an anthracene structure, or the surfactant has a specific structure. Or the surfactant used for forming the surfactant structure of the component A is a compound represented by the above general formula (1). Compatibility is further improved. Moreover, when the sulfonic acid group equivalent in the surfactant used to form the surfactant structure of the component A is set within a specific range, the compatibility between the component A and the component B is further improved. Be improved.
[0122]
Further, when the semiconductive composition for an electrophotographic device member of the present invention is used for at least a part of an electrophotographic device member, an electrophotographic device member having an effect unique to the semiconductive composition can be obtained. it can. That is, when the semiconductive composition of the present invention is used for at least a part of the constituent layers of the electrophotographic device member, as described above, the increase in electric resistance in a high voltage region is reduced, and the electric resistance is reduced. The effect of the semiconductive composition of the present invention, which is excellent in both the voltage dependency and the environment dependency of electric resistance, extends to other constituent layers not using this semiconductive composition. . As a result, fluctuations in electrical resistance in a moist heat environment are reduced as a whole of the electrophotographic device member, and thus an effect is obtained in that a good image can be obtained.

Claims (9)

A semiconductive composition for an electrophotographic device member comprising the following (A) and (B) as essential components, wherein the surfactant used for forming the surfactant structure of (A) has a molecular structure Wherein the binder polymer (B) has at least one of a sulfonic acid group and a metal sulfonic acid salt structure in its molecular structure. object. (A) A conductive polymer having a surfactant structure.
(B) a binder polymer. (B) the binder polymer is at least one selected from the group consisting of an acrylic resin, a urethane resin, a fluorine resin, a polyimide resin, an epoxy resin, a urea resin, a rubber polymer, and a thermoplastic elastomer. The composition according to claim 1, wherein the composition is: 3. The member for an electrophotographic apparatus according to claim 1, wherein the content of at least one of the sulfonic acid group and the sulfonic acid metal salt structure in the binder polymer (B) is in the range of 0.001 to 1 mmol / g. A semiconductive composition. The surfactant used for forming the surfactant structure of (A) has a sulfonic acid group in a molecular structure and has at least one of a naphthalene structure and an anthracene structure. 4. The semiconductive composition for an electrophotographic device member according to any one of the above items 3. The naphthalene structure or the anthracene structure in the molecular structure of the surfactant has an arbitrary number of substituents among 1 to 9, and the substituent is hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group. Group, alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, naphthyl group, naphthylalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group 5. The semiconductive composition for an electrophotographic device member according to claim 4, wherein the composition is selected from the group consisting of, a hydroxy group, a nitro group and a halogen. The electrophotographic apparatus according to any one of claims 1 to 3, wherein the surfactant used for forming the surfactant structure (A) is represented by the following general formula (1). A semiconductive composition for a member.

The electrophotographic apparatus according to any one of claims 1 to 5, wherein the surfactant used for forming the surfactant structure (A) is represented by the following general formula (2). A semiconductive composition for a member.

The electrophotographic apparatus according to any one of claims 1 to 7, wherein the sulfonic acid group equivalent in the surfactant used to form the surfactant structure (A) is in the range of 340 to 600. A semiconductive composition for a member. An electrophotographic device member, wherein the semiconductive composition for an electrophotographic device member according to any one of claims 1 to 8 is used for at least a part of the electrophotographic device member.