JP3960215B2 - Semiconductive composition for electrophotographic equipment member and electrophotographic equipment member using the same - Google Patents

Description

【００１７】
【化４】

【００１８】
一般式（１）において、好ましいＲ¹ としては、炭素数２〜１２のアルキル基等があげられる。また、Ｒ² 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。
【００１９】
また、一般式（２）において、好ましいＲ³ およびＲ⁴ 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。
【００２０】
上記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。
【００２１】
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。
【００２２】
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。
【００２３】
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。
【００２４】
導電性ポリマーの原料モノマーと、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。
【００２５】
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。
【００２６】
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、例えば、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。
【００２７】
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があげられる。
【００２８】
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。
【００２９】
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があげられる。
【００３０】
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）、ウレタンイミド、シリコーンイミド等があげられる。
【００３１】
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があげられる。
【００３２】
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、例えば、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があげられる。
【００３３】
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）、エチレンプロピレンジエンポリマー（ＥＰＤＭ）、ブチルゴム（ＩＩＲ）、フッ素ゴム、アクリルゴム（ＡＣＭ）等があげられる。
【００３４】
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。
【００３５】
このような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。
【００３６】
上記バインダーポリマー（Ｂ成分）と、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、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。
【００３７】
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。
【００３８】
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。
【００３９】
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、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。
【００４０】
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−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。
【００４１】
この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、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。
【００４２】
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。
【００４３】
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、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。
【００４４】
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。
【００４５】
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。
【００４６】
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、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。
【００４７】
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。
【００４８】
ここで、本発明の電子写真機器部材用半導電性組成物における、特定の導電性ポリマー（Ａ成分）は、トルエンまたはメチルエチルケトンに対する溶解度が２０％以上で、かつ、水に対する溶解度が３％未満でなければならず、特に、トルエンまたはメチルエチルケトンに対する溶解度が３０〜３００％の範囲内で、かつ、水に対する溶解度が１％未満であることが好ましい。すなわち、トルエンまたはメチルエチルケトンに対する溶解度が２０％未満であると、バインダーポリマー溶液との混合時に凝集が発生し、電気特性が悪化するからであり、また、水に対する溶解度が３％以上であると、水との親和性が上がり、電子導電性が水分により阻害されるために、湿熱での電気抵抗経時上昇が発生するからである。
【００４９】
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１０⁶ 〜１０¹¹Ω・ｃｍの範囲内であることが好ましく、特に好ましくは１０⁷ 〜１０¹⁰Ω・ｃｍの範囲内である。すなち、電気抵抗が１０⁶ 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１０¹¹Ω・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。
【００５０】
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。
【００５１】
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。
【００５２】
つぎに、実施例について比較例と併せて説明する。
【００５３】
まず、本発明に係る組成物を、以下のようにして作製した。
【００５４】
【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（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、ポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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。
【００５５】
【組成物２】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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。
【００５６】
【組成物３】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）であるＰＭＭＡ（住友化学工業社製、ＬＧ６Ａ、Ｍｎ：２０，０００）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（ジノニルナフタレンスルホン酸）〔スルホン酸基当量：４６０〕０．５ｍｏｌ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、ポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）であるエピクロルヒドリンゴム（大阪曹達社製、エピクロマーＣＧ）８０部と、受酸剤（酸化亜鉛）８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）２．４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）２００部に溶解した後、上記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。
【００５８】
【組成物５】
組成物４と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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）９０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。
【００５９】
【組成物６】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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）７０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。
【００６０】
【組成物７】
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、ポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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）５５０部および溶剤（トルエン）１００部に溶解した後、上記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。
【００６１】
【組成物８】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）である、ポリアミドイミド（東洋紡績社製、バイロマックスＨＲ１６ＮＮ）８０部を、溶剤（ＮＭＰ）５００部に溶解した後、上記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９】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）である、ＥＰＤＭ（住友化学工業社製、エスプレン５０５）８０部と、酸化亜鉛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）２部と、チウラム系架橋促進剤（大内新興化学工業社製、ノクセラーＴＲＡ）１部と、硫黄２部とを、２本ロールを用いて混練し、これらを溶剤（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。
【００６３】
【組成物１０】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）である、アクリルゴム（電気化学工業社製、デンカＥＲ７３００ｔ）８０部と、酸化マグネシウム４部と、アミン系架橋剤（デュポンダウエラストマー社製、ダイアック♯１）１部と、グアニジン系架橋促進剤（住友化学社製、ソクシノールＤＴ）２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。
【００６４】
【組成物１１】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）である、ブタジエンゴム（ＪＳＲ社製、ＢＲ１２２０ＮＭ）８０部と、酸化亜鉛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）２部と、チウラム系架橋促進剤（大内新興化学工業社製、ノクセラーＴＲＡ）１部と、硫黄２部とを、２本ロールを用いて混練し、これらを溶剤（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１２】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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（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）１００部および溶剤（トルエン）５００部に溶解した後、上記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。
【００６６】
【組成物１３】
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（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、ポリピロール（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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。
【００６７】
【組成物１４】
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（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を滴下して酸化重合させ、ポリチオフェン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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。
【００６８】
【組成物１５】
組成物１と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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）７０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１６】
組成物４と同様にして、同様のポリアニリン（Ａ成分）を得た。つぎに、ポリエーテルポリオール（三洋化成社製、ＦＡ７１８）９０部と、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、シリコーン系整泡剤（日本ユニカー社製、Ｌ−５３０９）２部と、上記ポリアニリンの有効成分（不揮発分）２０部のトルエン溶液４０部（５０％溶液）とを、３本ロールを用いて混練した。つぎに、溶剤を揮発させた後、発泡剤（水）２部を添加し、混練を行った。そして、これにクルード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部とを加え、注型機を用いて混合し、８０℃に加熱した型に注型発泡させた後、８０℃で３０分間熱処理して、５倍発泡シート（３００ｍｍ×３００ｍｍ、厚み１０ｍｍ）を作製した。
【００７０】
【組成物１７】
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、Ｒ¹ ＝ブチル基、Ｒ² ＝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、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、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部とを、溶剤（ＭＥＫ）４００部および溶剤（トルエン）２００部に溶解した後、上記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。
【００７１】
【組成物１８】
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（９−アントラセンスルホン酸）〔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、ポリアニリン（Ａ成分）を得た。つぎに、バインダーポリマー（Ｂ成分）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】
エピクロルヒドリンゴム（大阪曹達社製、エピクロマーＣＧ）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、受酸剤（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、２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】
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）１００部を、溶剤（ＭＥＫ）２００部および溶剤（トルエン）４００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（電気化学工業社製、デンカブラックＨＳ１００）の配合量を２０部に変更した。それ以外は、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、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２００２−８９５４３号公報に記載の実施例７に準じて、導電性塗膜を作製した。すなわち、ポリアニリンスルホン酸（三菱レーヨン社製）の１０％水溶液と、ウレンタン系樹脂（武田薬品工業社製、タケラックＷ−６３５）と、メラミン系架橋剤（住友化学工業社製、スミテックスレジンＭ−３）とを、固形分組成比（重量比）が、それぞれ２０：１００：１０となるように配合し、室温攪拌にて均一な組成物を調製した。このようにして得られた組成物を用いて、アルミニウム容器にてキャストコーティングし、８０℃で予備乾燥して溶媒を揮発させた後、さらに架橋反応を進行させるため、１３０℃で１５分間加熱処理し、厚み１００μｍの導電性塗膜を作製した。
【００７９】
【組成物Ｇ】
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。
【００８０】
【組成物Ｈ】
ポリエーテルポリオール（三洋化成社製、ＦＡ７１８）９０部と、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、ケッチェンブラック３部とを配合し、３本ロールを用いて混練した。そして、これにクルード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部とを加え注型機を用いて混合し、８０℃にした型に注型発泡させた後、８０℃で３０分間熱処理して、５倍発泡シート（３００ｍｍ×３００ｍｍ、厚み１０ｍｍ）を作製した。
【００８１】
【組成物Ｉ】
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、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。
【００８２】
このようにして得られた導電性塗膜等を用いて、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。
【００８３】
〔溶解度〕
各組成物に用いられる導電性ポリマーの、トルエンまたはメチルエチルケトン（ＭＥＫ）に対する溶解度、および水に対する溶解度を測定した。
【００８４】
〔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。
【００８５】
〔電気抵抗、電気抵抗の電圧依存性〕
各導電性塗膜等について、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。
【００８６】
〔電気抵抗の環境依存性〕
各導電性塗膜等について、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。
【００８７】
〔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。
【００８８】
【表１】

【００８９】
【表２】

【００９０】
【表３】

【００９１】
【表４】

【００９２】
【表５】

【００９３】
上記表の結果から、組成物１〜１８は、水への親和性が悪く、溶剤への溶解性に優れた導電性ポリマーを用いているため、バインダーポリマーとの相溶性が良好で、凝集物の発生を抑制でき、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。
【００９４】
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、組成物Ｂ，Ｃ，Ｄは、電子導電剤を分散して用いているため、電気抵抗の電圧依存性が劣っていた。組成物Ｅは、導電性ポリマーとしてポリアニリンを用いているが、ナイロンと粒子（１μｍレベル）として混合されているため、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、水との親和性が良好な導電性ポリマーを用いているため、電気抵抗の環境依存性が劣り、環境による電気抵抗変動が大きかった。組成物Ｇは、ポリアニリンが、フッ化処理カーボンブラックやポリアミック酸との相溶性が悪く、凝集物が多量に発生するため、電気抵抗の電圧依存性が大きかった。組成物Ｈは、導電性カーボンの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Ｉは、水への親和性に優れ、溶剤への溶解性が悪い導電性ポリマーを用いているため、バインダーポリマーとの相溶性が若干劣って凝集物が発生し、環境による電気抵抗変動があった。
【００９５】
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。
【００９６】
【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。
【００９７】
【実施例２〜１９、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。
【００９８】
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。
【００９９】
〔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。
【０１００】
〔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。
【０１０１】
〔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。
【０１０２】
〔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。
【０１０３】
〔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。
【０１０４】
（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。
【０１０５】
〔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。
【０１０６】
【実施例２０〜２３、比較例６〜９】
〔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。
【０１０７】
【実施例２４、比較例１０】
〔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。
【０１０８】
【実施例２５，２６、比較例１１】
〔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。
【０１０９】
【実施例２７、比較例１２】
〔トナー供給ロールの作製〕
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１４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。
【０１１０】
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、トナー供給ロールを用いて、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１４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。
【０１１１】
【表６】

【０１１２】
【表７】

【０１１３】
【表８】

【０１１４】
【表９】

【０１１５】
【表１０】

【０１１６】
【表１１】

【０１１７】
【表１２】

【０１１８】
【表１３】

【０１１９】
【表１４】

【０１２０】
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１〜１８）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、トナー供給ロール特性に優れていた。
【０１２１】
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〜Ｉ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、トナー供給ロール特性に劣っていた。
【０１２２】
【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、特定の導電性ポリマー（Ａ成分）と、バインダーポリマー（Ｂ成分）とを必須成分とし、特定の導電性ポリマー（Ａ成分）が、トルエンまたはメチルエチルケトンに対する溶解度が２０％以上で、かつ、水に対する溶解度が３％未満であるものである。そのため、特定の導電性ポリマー（Ａ成分）が、水との親和性が低下し、溶剤への溶解性が適正に向上するため、バインダーポリマー（Ｂ成分）との相溶性が良好となって凝集物の発生を抑制でき、その結果、本発明の電子写真機器部材用半導電性組成物は、湿熱環境での電気抵抗の変動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。
【０１２３】
また、Ａ成分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。
【０１２４】
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、湿熱環境での電気抵抗変動が小さくなり、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]
BACKGROUND OF THE INVENTION
The present invention relates to a semiconductive composition for an electrophotographic apparatus member and an electrophotographic apparatus member using the same, and more specifically, to a semiconductive composition used for an electrophotographic apparatus member such as a developing roll and the like. The present invention relates to an electrophotographic apparatus member.
[0002]
[Prior art]
In general, in order to use a conductive composition used for an electrophotographic apparatus member such as a developing roll, it is essential to control electric resistance. Therefore, conventionally, the electrical resistance is controlled by blending an ion conductive agent such as a quaternary ammonium salt or an electronic conductive agent such as carbon black into a binder polymer such as resin or rubber.
[0003]
Among the above conductive agents, the ionic conductive agent dissolves in the binder polymer, so there is little variation in conductivity, and there is little variation in electrical resistance when the voltage is changed, and the electrical resistance is excellent in voltage dependency. There is. However, ionic conductive agents are easily affected by moisture, etc., and electrical resistance fluctuates by two orders of magnitude under conditions of high temperature and high humidity and low temperature and low humidity. There are many restrictions. On the other hand, electronic conductive agents such as carbon black are not easily affected by moisture, etc., and have a small variation in electrical resistance under conditions of high temperature and high humidity and low temperature and low humidity. There is. However, since the electronic conductive agent is generally highly cohesive, it is difficult to uniformly disperse it in the binder polymer. Therefore, variation in electric resistance is large and it is difficult to control the conductivity. In addition, even when dispersed relatively uniformly, the mechanism of conductivity development is due to the tunnel effect or hopping phenomenon in which electrons are transmitted between the carbons in the binder polymer by a high voltage. The electrical resistance fluctuates greatly, and the voltage dependence of the electrical resistance is inferior.
[0004]
In order to solve these problems, conventionally, a roll-shaped charging member (see Patent Document 1) in which a composite of polyaniline and nylon is fixed on the surface of a polyurethane roll, a π-electron conjugated conductive polymer, a resin component, and a solvent There has been proposed an antistatic film-forming composition (see Patent Document 2). In addition, an intermediate transfer member (see Patent Document 3) containing a conductive agent imparting electronic conductivity and a conductive polymer such as polyaniline in the composition material, a water-soluble polyaniline having an acidic group, A semiconductive member containing a molecular compound or an aqueous polymer compound comprising an aqueous emulsion-forming polymer compound has been proposed (see Patent Document 4). However, in Patent Document 1, since the composition of polyaniline, which is a conductive polymer, is not compatible with nylon and is agglomerated as particles of 1 μm or more, the initial characteristics of electrical resistance and the voltage dependence of electrical resistance are improved. Inferior, in Patent Document 2, since the compatibility between the π-electron conjugated conductive polymer and the resin component is poor, the voltage dependency of electrical resistance is poor. Further, in Patent Document 3, a conductive polymer such as polyaniline is required to be undoped when blended with a conductive agent imparting electronic conductivity, and in that case, a special solvent called N-methyl-2-pyrrolidone (NMP) is also used. Therefore, it is very difficult to blend a conductive agent imparting electronic conductivity with a conductive polymer. Moreover, an oxidation process is required after coating film formation, uniform control is difficult, and a process is also complicated. In Patent Document 4, since the water-soluble polyaniline having an acidic group is water-soluble, repelling or uneven coating occurs during application to a product, or the change with time when left under wet heat conditions is large, and as an electrophotographic apparatus member There are significant restrictions on the use of.
[0005]
In order to solve these problems, the present inventors have already filed a patent application 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]
Japanese Patent Laid-Open No. 9-48821
[Patent Document 3]
JP 2001-324882 A
[Patent Document 4]
JP 2002-89543 A
[Patent Document 5]
JP 2002-167519 A
[0007]
[Problems to be solved by the invention]
However, as a result of further investigations on the conductive composition described in Patent Document 5, the present inventors have found that the compatibility between the conductive polymer having a surfactant structure and the binder polymer is slightly higher. It was inferior, and when it left to stand for a long time in wet heat conditions, it discovered that the tendency for electroconductivity to fall a little was seen.
[0008]
The present invention has been made in view of such circumstances, and is an electrophotographic device that has a small variation in electrical resistance in a moist heat environment, and that is excellent in both the voltage dependence of electrical resistance and the environmental dependence of electrical resistance. The object is to provide a semiconductive composition for an apparatus member and an electrophotographic apparatus member using the same.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a semiconductive composition for an electrophotographic apparatus member comprising the following components (A) and (B) as essential components: Guidance An electroconductive polymer having a solubility in toluene or methyl ethyl ketone of 20% or more and a solubility in water of less than 3% is defined as a first gist, and for this electrophotographic apparatus member An electrophotographic apparatus member using the semiconductive composition as at least a part of the electrophotographic apparatus member is a second gist.
(A) Raw material monomer and Surfactant Obtained by oxidative polymerization in the presence of an oxidizing agent. Conductive polymer.
(B) Binder polymer.
[0010]
That is, as a result of further earnest research on the conductive composition described in Patent Document 5 filed by the present inventors, the present inventors formed a conductive polymer having a surfactant structure. Since the surfactant used in is good in affinity with water and poor in solubility in a solvent, it is easily dissociated by moisture and cannot play a role as a dopant when energized. Therefore, it was found that the compatibility between the conductive polymer having a surfactant structure and the binder polymer is slightly inferior, and aggregates are generated, whereby the electric resistance in a moist heat environment tends to fluctuate. And after further research, Raw material monomer and Surfactant Obtained by oxidative polymerization in the presence of an oxidizing agent. When a conductive polymer having a solubility in toluene or methyl ethyl ketone of 20% or more and a solubility in water of less than 3% is used, the affinity with water is lowered and the solubility in a solvent is properly adjusted. As a result, the compatibility with the binder polymer is improved and the generation of aggregates can be suppressed. As a result, the obtained semiconductive composition has a small variation in electric resistance in a moist heat environment, and the expected The inventors have found that the object can be achieved and have reached the present invention.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the present invention will be described.
[0012]
The semiconductive composition for an electrophotographic apparatus member of the present invention is specific It can be obtained using a conductive polymer (component A) and a binder polymer (component B).
[0013]
this specific Conductive polymer (component A) , Guidance Chemical oxidative polymerization, such as oxidative polymerization in water of raw material monomer and surfactant in the presence of oxidizing agent To the law Therefore, it can be manufactured.
[0014]
The raw material monomer of such a conductive polymer is not particularly limited as long as the polymer has conductivity by doping. For example, aniline (including aniline salts such as aniline hydrochloride in addition to aniline derivatives), Pyrrole, thiophene, alkylthiophene, ethylenedioxythiophene, isonaphthothiophene, 3-thiophene-β-ethanesulfonic acid, dichenothiophene, acetylene, paraphenylene, phenynevinylene, furan, selenophene, tellurophene, isothianaphthene, Paraphenylene sulfide, paraphenylene oxide, vinylene sulfide and the like can be mentioned.
[0015]
The surfactant is not particularly limited, but a sulfonic acid group (-SO _Three What has H) is preferable, for example, what is represented by the following general formula (1) or (2) is mention | raise | lifted.
[0016]
[Chemical 3]

[0017]
[Formula 4]

[0018]
In general formula (1), preferred R ¹ Examples thereof include an alkyl group having 2 to 12 carbon atoms. R ² Are preferably hydrogen, alkyl group, alkoxy group, alkylthio group, alkylthioalkyl group, aryl group, alkylsulfinyl group, alkoxyalkyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, more preferably 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. N is preferably an integer of 2 to 4.
[0019]
Moreover, in General formula (2), preferable R ^Three And R ^Four 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 a halogen is mention | raise | lifted. Preferable M in the general formula (2) includes sodium ion, potassium ion and ammonium ion.
[0020]
As the 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.
[0021]
The naphthalene structure and the anthracene structure preferably have an arbitrary number of substituents of 1 to 9. Examples of the substituent include hydrogen, alkyl group, alkenyl group, alkoxy group, alkylthio group, alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, Examples include naphthyl group, naphthylalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, nitro group, halogen and the like. These substituents may be substituted alone or in combination of two or more.
[0022]
The sulfonic acid group equivalent in such a specific surfactant is preferably in the range of 340 to 600, 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 poor, and conversely if it exceeds 600, the effect as a dopant tends to decrease. It is. This sulfonic acid group equivalent is determined according to titration of sodium hydroxide or thermogravimetric analysis (TGA).
[0023]
The oxidizing agent used in the chemical oxidative polymerization method is not particularly limited, and examples thereof include ammonium persulfate (APS), hydrogen peroxide solution, and ferric chloride.
[0024]
The mixing ratio of the raw material monomer of the conductive polymer and the surfactant is preferably in the range of raw material monomer / surfactant = 1 / 0.03 to 1/3, particularly preferably raw material monomer / interface. Active agent = 1 / 0.05 to 1/2. That is, when the molar ratio of the surfactant is decreased, the compatibility and dispersibility with the binder polymer (component B) tend to be reduced. Conversely, when the molar ratio of the surfactant is increased, 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.
[0025]
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.
[0026]
Next, examples of the binder polymer (component B) used together with the specific conductive polymer (component A) include acrylic resins, urethane resins, fluorine resins, polyimide resins, epoxy resins, and 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 in terms of excellent compatibility with a specific conductive polymer (component A).
[0027]
Examples of the acrylic resin include polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and known acrylic resin. Examples include those obtained by copolymerizing monomers.
[0028]
The urethane resin is not particularly limited as long as the resin has a urethane bond in the molecular structure. For example, ether-based, ester-based, acrylic-based, aliphatic-based urethane, silicone-based polyol or fluorine Examples thereof include those obtained by copolymerizing a system polyol. The urethane-based resin may have a urea bond or an imide bond in the molecular structure.
[0029]
Examples of the fluororesin include polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, and the like. .
[0030]
Examples of the polyimide resin include polyamide imide (PAI), urethane imide, and silicone imide.
[0031]
Examples of the epoxy resin include bisphenol A type epoxy resin, epoxy novolac resin, brominated epoxy resin, polyglycol type epoxy resin, polyamide combined type epoxy resin, silicone modified epoxy resin, amino resin combined type epoxy resin, Examples include alkyd resin combined type epoxy resins.
[0032]
The urea resin is not particularly limited as long as it has a urea bond in the molecular structure, and examples thereof include a urethane urea elastomer, a melamine resin, and a urea formaldehyde resin.
[0033]
Examples of the rubber 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), ethylene propylene diene polymer (EPDM), butyl rubber (IIR), fluoro rubber, acrylic rubber (ACM) Etc.
[0034]
Examples of the thermoplastic elastomer include styrene thermoplastic elastomers such as styrene-butadiene block copolymer (SBS) and styrene-ethylene-butylene-styrene block copolymer (SEBS), and urethane thermoplastic elastomer (TPU). ), Olefin-based thermoplastic elastomer (TPO), polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and the like. These may be used alone or in combination of two or more. Among these, TPU is preferably used in terms of simplicity of the synthesis process and solubility in a solvent.
[0035]
The number average molecular weight (Mn) of such a binder polymer (component B) is preferably in the range of 500 to 2,000,000, particularly preferably in the range of 2,000 to 800,000.
[0036]
The binder polymer (component B) and the conductive polymer (component A) are mixed and made into a semiconductive composition as described later, but the raw material of the conductive polymer (component A) (conductive polymer) The mixing ratio of the raw material monomer and the surfactant) and the binder polymer (component B) is preferably a weight ratio in the range of component A raw material / component B = 1/99 to 40/60, Particularly preferably, the raw material of component A / component B = 4/96 to 35/65. That is, when the weight ratio of the component A raw material is less than 1, the effect on the conductivity tends to be reduced. Conversely, when the weight ratio of the component A raw material exceeds 40, the resulting composition is hard. This is because the composition tends to be brittle and the physical properties of the composition tend to decrease.
[0037]
In addition to the specific conductive polymer (component A) and binder polymer (component B), the semiconductive composition for electrophotographic equipment members of the present invention may optionally include an ionic conductive agent, an electronic conductive agent, and a crosslinking agent. Etc. may be blended appropriately.
[0038]
Examples of the ionic conductive agent include compounds that ionically dissociate in polymers such as lithium perchlorate, quaternary ammonium salts, and borate salts. These may be used alone or in combination of two or more.
[0039]
The blending ratio of such an ionic conductive agent is determined from the viewpoints of physical properties and electrical characteristics. The raw material of the specific conductive polymer (component A) (total amount of raw material monomers and surfactant) and the binder polymer (component B) ) And a total of 100 parts by weight (hereinafter abbreviated as “parts”) is preferably in the range of 0.01 to 5 parts, particularly preferably in the range of 0.5 to 2 parts.
[0040]
Examples of the electronic 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.
[0041]
The blending ratio of the electronic conductive agent is determined from the physical properties and electrical characteristics of the raw material of the specific conductive polymer (component A) (total amount of raw material monomer and surfactant) and the binder polymer (component B). It is preferably within a range of 5 to 30 parts, particularly preferably within a range of 8 to 20 parts, with respect to a total of 100 parts.
[0042]
Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, blocked isocyanate, and melamine, epoxy curing agents, polyamine curing agents, and peroxides.
[0043]
The blending ratio of such a crosslinking agent is determined from the viewpoints of physical properties, adhesion, and liquid storage properties. The raw material of the specific conductive polymer (component A) (total amount of raw material monomers and surfactant) and the binder polymer (B The amount is preferably in the range of 1 to 30 parts, particularly preferably in the range of 3 to 10 parts, relative to 100 parts in total with the component.
[0044]
The semiconductive composition for electrophotographic apparatus members of the present invention may contain a crosslinking accelerator, an anti-aging agent, etc., if necessary, in addition to the above components.
[0045]
Examples of the crosslinking accelerator include a sulfenamide-based crosslinking accelerator and a dithiocarbamate-based crosslinking accelerator.
[0046]
The semiconductive composition for an electrophotographic apparatus member of the present invention can be prepared, for example, as follows. That is, first, a specific conductive polymer (component A) is produced according to the method described above. Next, a binder polymer (component B) is blended with the specific conductive polymer (component A), and an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like are blended as necessary. And these can be knead | mixed using kneading machines, such as a roll, a kneader, a Banbury mixer, and the target semiconductive composition can be obtained. Here, the specific conductive polymer (component A) is in a state dissolved in a solvent. Moreover, a binder polymer (B component) is used in the state melt | dissolved in the solvent.
[0047]
Examples of this solvent include organic solvents such as m-cresol, methanol, methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), and N-methyl-2-pyrrolidone (NMP).
[0048]
Here, the specific conductive polymer (component A) in the semiconductive composition for an electrophotographic apparatus member of the present invention has a solubility in toluene or methyl ethyl ketone of 20% or more and a solubility in water of less than 3%. In particular, the solubility in toluene or methyl ethyl ketone is preferably in the range of 30 to 300%, and the solubility in water is preferably less than 1%. That is, if the solubility in toluene or methyl ethyl ketone is less than 20%, aggregation occurs when mixed with the binder polymer solution and the electrical characteristics deteriorate, and if the solubility in water is 3% or more, This is because the electrical resistance is increased with time and the electrical conductivity is hindered by moisture, so that the electrical resistance is increased with time.
[0049]
The semiconductive composition for an electrophotographic apparatus 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 ^Ten It is in the range of Ω · cm. That is, electric resistance is 10 ⁶ If it is less than Ω · cm, the electrical resistance is too low, so that there is a tendency that the advantage to the image as an electrophotographic apparatus member tends to be reduced in terms of charge supply to the toner and chargeability to the photoreceptor. 10 ¹¹ This is because if it exceeds Ω · cm, the electric resistance is too high, so that charge-up occurs and control as an electrophotographic apparatus member tends to be difficult.
[0050]
When a coating film is formed using the semiconductive composition for electrophotographic apparatus members 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 present. It is preferably less than 3% of the total area of the coating film, particularly preferably less than 0.5%. That is, if this aggregate exceeds 3% of the total area of the coating film, the variation in electrical resistance with respect to voltage tends to increase.
[0051]
The semiconductive composition for an electrophotographic apparatus member of the present invention is used for at least a part (all or a part) of an electrophotographic apparatus member. Examples of the electrophotographic apparatus member include a conductive roll such as a developing roll, a charging roll, a transfer roll, and a toner supply roll, a conductive belt such as an intermediate transfer belt and a paper feed belt, and the like. Used at least in part. That is, when the semiconductive composition for an electrophotographic apparatus member of the present invention is used for at least part of the constituent layer of the electrophotographic apparatus member, the voltage of the electrical resistance of the constituent layer formed using this semiconductive composition Dependency and environment dependency are reduced. As a result, the other constituent layers are less susceptible to the voltage dependency and the environment dependency of the electric resistance, so that the voltage dependency and the environment dependency of the electric resistance as a whole of the electrophotographic apparatus member are reduced.
[0052]
Next, examples will be described together with comparative examples.
[0053]
First, the composition according to the present invention was produced as follows.
[0054]
[Composition 1]
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 oxidizing agent (ammonium persulfate) in an aqueous solution. Polymerize The Rianiline (component A) was obtained. Next, 80 parts of polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040), which is a binder polymer (component B), is dissolved in 200 parts of solvent (MEK) and 400 parts of solvent (toluene). ,Up Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0055]
[Composition 2]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of a polyester (adipate) TPU (manufactured by Mitsui Takeda Chemical Co., Elastollan 1040) which is a binder polymer (component B), and 5 parts of blocked isocyanate (manufactured by Dainippon Ink & Chemicals, Inc., Bernock DB980K) Is dissolved in 200 parts of solvent (MEK) and 400 parts of solvent (toluene). Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0056]
[Composition 3]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of PMMA (manufactured by Sumitomo Chemical Co., Ltd., LG6A, Mn: 20,000), which is a binder polymer (component B), is dissolved in 100 parts of a solvent (MEK) and 500 parts of a solvent (toluene). Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0057]
[Composition 4]
1 mol of aniline and a surfactant having a sulfonic acid group in its molecular structure (dinonylnaphthalenesulfonic acid) [sulfonic acid group equivalent: 460] 0.5 mol were added dropwise in an aqueous solution of 1 mol of oxidizing agent (ammonium persulfate). Oxidative polymerization while The Rianiline (component A) was obtained. Next, 80 parts of epichlorohydrin rubber (Epichromer CG, manufactured by Osaka Soda Co., Ltd.) which is a binder polymer (component B), 8 parts of an acid acceptor (zinc oxide), and a thiourea-based crosslinking accelerator (manufactured by Sanshin Chemical Co., Ltd., Sunseller) 22C) 2.4 parts are kneaded using two rolls, and these are dissolved in 300 parts of solvent (MEK) and 200 parts of solvent (toluene). Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0058]
[Composition 5]
Same as composition 4, similar Of the Rianiline (component A) was obtained. Next, after dissolving 90 parts of a polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040), which is a binder polymer (component B), in 200 parts of solvent (MEK) and 400 parts of solvent (toluene) ,Up Note 10 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0059]
[Composition 6]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, after dissolving 70 parts of a polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040), which is a binder polymer (component B), in 200 parts of solvent (MEK) and 400 parts of solvent (toluene) ,Up Note 30 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0060]
[Composition 7]
1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (2,2'-dinaphthylmethane-6-sodium sulfonate-6'-sulfonic acid, sulfonic acid group equivalent: 450) in an aqueous solution Oxidative polymerization while dropping 1 mol of oxidized oxidizer (ammonium persulfate) The Rianiline (component A) was obtained. Next, 80 parts of an acrylic fluororesin (Dainippon Ink Chemical Co., Ltd., Defensa TR230K), which is a binder polymer (component B), and 5 parts of blocked isocyanate (Dainippon Ink Chemical Co., Ltd., Bernock DB980K) are used. After dissolving in 550 parts of solvent (MEK) and 100 parts of solvent (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0061]
[Composition 8]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, after dissolving 80 parts of polyamideimide (manufactured by Toyobo Co., Ltd., Bilomax HR16NN), which is a binder polymer (component B), in 500 parts of solvent (NMP), Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0062]
[Composition 9]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of EPDM (Esprene 505, manufactured by Sumitomo Chemical Co., Ltd.) which is a binder polymer (component B), 5 parts of zinc oxide, and a dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller) 2 parts of BZ), 1 part of thiuram crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller TRA) and 2 parts of sulfur are kneaded using two rolls, and these are 100 parts of solvent (MEK). And after dissolving in 500 parts of solvent (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0063]
[Composition 10]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of acrylic rubber (Denka ER7300t, manufactured by Denki Kagaku Kogyo Co., Ltd.), 4 parts of magnesium oxide, and amine-based cross-linking agent (Du Pont Dow Elastomer Co., Diac # 1) 1 are binder polymers (component B). Part and guanidine-based crosslinking accelerator (Sumitomo Chemical Co., Ltd., Soxinol DT) 2 parts are kneaded using two rolls and dissolved in 300 parts of solvent (MEK) and 300 parts of solvent (toluene). ,Up Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0064]
[Composition 11]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of butadiene rubber (BR1220NM, manufactured by JSR Co., Ltd.), 5 parts of zinc oxide, and a dithiocarbamate-based crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller BZ) which is a binder polymer (component B) 2 parts, 1 part of a thiuram crosslinking accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller TRA) and 2 parts of sulfur are kneaded using two rolls, and these are mixed with 100 parts of a solvent (MEK) and a solvent. After dissolving in 500 parts (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0065]
[Composition 12]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 80 parts of H-NBR (Zeon Pole 0020, manufactured by Nippon Zeon Co., Ltd.), 1 part of a cross-linking agent (sulfur), and a sulfenamide-based cross-linking accelerator (Ouchi Emerging Chemical) Kneading 0.5 parts of NOXELLA CZ, manufactured by Kogyo Co., Ltd. and 0.5 parts of dithiocarbamate-based crosslinking accelerator (NOCELLER BZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) using two rolls, After dissolving in 100 parts of solvent (MEK) and 500 parts of solvent (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0066]
[Composition 13]
1 mol of pyrrole 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 oxidizing agent (ammonium persulfate) in an aqueous solution. Polymerize The Ripyrrole (component A) was obtained. Next, 80 parts of a polyester (adipate) TPU (manufactured by Mitsui Takeda Chemical Co., Elastollan 1040) which is a binder polymer (component B), and 5 parts of blocked isocyanate (manufactured by Dainippon Ink & Chemicals, Inc., Bernock DB980K) Is dissolved in 200 parts of solvent (MEK) and 400 parts of solvent (toluene). Note 20 parts of an active ingredient (nonvolatile content) of ripirole was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0067]
[Composition 14]
1 mol of thiophene and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (dinonylnaphthalenesulfonic acid) [sulfonic acid group equivalent: 460] are added dropwise to form 1 mol of an oxidizing agent (ammonium persulfate) in an aqueous solution. Polymerize The Lithiophene (component A) was obtained. Next, 80 parts of a polyester (adipate) TPU (manufactured by Mitsui Takeda Chemical Co., Elastollan 1040) which is a binder polymer (component B), and 5 parts of blocked isocyanate (manufactured by Dainippon Ink & Chemicals, Inc., Bernock DB980K) Is dissolved in 200 parts of solvent (MEK) and 400 parts of solvent (toluene). Note 20 parts of an active ingredient (non-volatile content) of lithiophene was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0068]
[Composition 15]
Same as Composition 1, same Of the Rianiline (component A) was obtained. Next, 70 parts of a polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040) which is a binder polymer (component B), 5 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo), After dissolving 5 parts of blocked isocyanate (Dainippon Ink & Chemicals, Bernock DB980K) in 200 parts of solvent (MEK) and 400 parts of solvent (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0069]
[Composition 16]
Same as composition 4, similar Of the Rianiline (component A) was obtained. Next, 90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and tertiary amine catalyst (manufactured by Kao Co., Ltd., Kaulizer No. 31) 0 5 parts, 0.05 part of tertiary amine catalyst (Tosoh Corporation, Toyocat HX-35), 2 parts of silicone foam stabilizer (Nihon Unicar Co., Ltd., L-5309), Note 40 parts of a toluene solution (50% solution) of 20 parts of an active ingredient (non-volatile content) of reaniline was kneaded using three rolls. Next, after volatilizing the solvent, 2 parts of a foaming agent (water) was added and kneaded. Then, 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Sumidur 44V20) and 20.5 parts of tolylene diisocyanate (Mitsui Chemicals Co., TDI-80) are added thereto, and a casting machine is used. After mixing and casting into a mold heated to 80 ° C., heat treatment was performed at 80 ° C. for 30 minutes to prepare a 5-fold expanded sheet (300 mm × 300 mm, thickness 10 mm).
[0070]
[Composition 17]
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 is oxidatively polymerized while dropping 1 mol of an aqueous oxidizing agent (ammonium persulfate). The Rianiline (component A) was obtained. Next, 80 parts of a polyester (adipate) -based TPU (manufactured by Mitsui Takeda Chemical Co., Elastollan 1040), which is a binder polymer (component B) having a sulfonic acid Na group in the molecular structure, and 400 parts of a solvent (MEK) And after dissolving in 200 parts of solvent (toluene) Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0071]
[Composition 18]
1 mol of aniline and 1 mol of a surfactant having a sulfonic acid group in its molecular structure (9-anthracenesulfonic acid) [sulfonic acid group equivalent: 460] are oxidized while dropping 1 mol of an oxidizing agent (ammonium persulfate) in aqueous solution. Polymerize The Rianiline (component A) was obtained. Next, 80 parts of polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040), which is a binder polymer (component B), is dissolved in 200 parts of solvent (MEK) and 400 parts of solvent (toluene). ,Up Note 20 parts of an active ingredient (non-volatile content) of reaniline was added and stirred for 10 minutes to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0072]
Next, in the present invention, a composition to be a comparative example was prepared as follows.
[0073]
[Composition A]
100 parts of epichlorohydrin rubber (Osaka Soda Co., Ltd., Epichromer CG), 2 parts of borate salt (made by Nippon Carlit Co., Ltd., LR147), 10 parts of acid acceptor (zinc oxide), and thiourea-based crosslinking promotion 3 parts of an agent (manufactured by Sanshin Chemical Co., Ltd., Sunseller 22C), kneaded using two rolls, and then dissolved in 300 parts of solvent (MEK) and 150 parts of solvent (toluene) (Coating solution) was prepared. And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0074]
[Composition B]
100 parts of a polyester (adipate) TPU (manufactured by Mitsui Takeda Chemical Co., Elastollan 1040) was dissolved in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene), and then acetylene black (electric 7 parts by chemical industry, Denka Black HS100) were blended and kneaded using three rolls to prepare a composition. And this was heat-crosslinked at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm on a SUS304 plate.
[0075]
[Composition C]
The amount of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) was changed to 20 parts. Other than that was carried out similarly to the composition B, and produced the electroconductive coating film.
[0076]
[Composition D]
Silicone in which carbon black was dispersed (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) was press-molded (150 ° C. × 10 minutes) on a SUS304 plate to prepare 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 aniline 0.4 mol / l, sulfuric acid 1.0 mol / l, and ammonium persulfate 0.5 mol / l was prepared, and polyaniline was polymerized by a chemical oxidative polymerization method. The obtained polyaniline was adjusted to neutral with sodium hydroxide, then washed with water and dried to obtain a polyniline powder having a particle size of about 1 μm. Next, 50 parts of soluble nylon was dissolved in 500 parts of a solvent (methanol), 50 parts of the polyaniline powder was added thereto, and mixed with red devil to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.
[0078]
[Composition F]
A conductive coating film was prepared according to Example 7 described in JP-A-2002-89543. That is, a 10% aqueous solution of polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd.), a urethane resin (Takeda Pharmaceutical Co., Ltd., Takelac W-635), and a melamine cross-linking agent (Sumitomo Chemical Co., Ltd., Smithex Resin M-) 3) was blended so that the solid composition ratio (weight ratio) was 20: 100: 10, respectively, and a uniform composition was prepared by stirring at room temperature. The composition thus obtained was cast coated in an aluminum container, preliminarily dried at 80 ° C. to volatilize the solvent, and then further heated at 130 ° C. for 15 minutes in order to advance the crosslinking reaction. Then, a conductive coating film having a thickness of 100 μm was produced.
[0079]
[Composition G]
A conductive coating film was prepared according to Example 1 described in JP-A No. 2001-324882. That is, a predetermined amount of dried fluorinated carbon black (manufactured by ALLIED, ACCUFLVOR2028) was mixed in N-methyl-2-pyrrolidone (NMP) and mixed at room temperature for 6 hours using a ball mill. Next, 294.2 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 liquid. The reaction was carried out in a nitrogen atmosphere with stirring for 4 hours at room temperature to obtain a polyamic acid solution containing fluorinated carbon black. Further, 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 wt% concentration dedope polyaniline solution. Next, after adding a predetermined amount of polyaniline solution to the above-mentioned fluorinated carbon black-containing polyamic acid solution, the mixture is stirred for 1 hour at room temperature using a stirring blade, and a desired blending amount of fluorinated carbon black and polyaniline-containing polyamic acid is added. A solution (resin: polyaniline: fluorinated carbon black = 74% by weight: 15% by weight: 11% by weight) was obtained. And after apply | coating this solution on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minutes, heated up to 200 degreeC at the temperature increase temperature of 2 degree-C / min, and also heated at 200 degreeC for 30 minutes, and thickness A 100 μm conductive coating film was prepared.
[0080]
[Composition H]
90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and 0.5 part of tertiary amine catalyst (manufactured by Kao Corporation, Kaulizer No. 31) And 0.05 parts of a tertiary amine catalyst (Toyocat HX-35, manufactured by Tosoh Corporation), 2 parts of a foaming agent (water), and 2 parts of a silicone foam stabilizer (manufactured by Nihon Unicar Company, Ltd., L-5309) And 3 parts of ketjen black were mixed and kneaded using three rolls. Then, 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Sumidur 44V20) and 20.5 parts of tolylene diisocyanate (Mitsui Chemicals, TDI-80) are added and mixed using a casting machine. Then, it was cast and foamed in a mold set at 80 ° C. and then heat-treated at 80 ° C. for 30 minutes to prepare a 5-fold foamed sheet (300 mm × 300 mm, thickness 10 mm).
[0081]
[Composition I]
A conductive coating film was produced according to the examples described in JP-A No. 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 dropping 1 mol of an oxidizing agent (ammonium persulfate) in an aqueous solution. The Reaniline was obtained. Next, 80 parts of a polyester (adipate) TPU (Mitsui Takeda Chemicals, Elastollan 1040), which is a binder polymer, is dissolved in 200 parts of a solvent (MEK) and 400 parts of a solvent (toluene). Note 20 parts of reaniline was added and kneaded using three rolls to prepare a conductive composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.
[0082]
Using the conductive coating film thus obtained, each characteristic was evaluated according to the following criteria. These results are also shown in Tables 1 to 5 below.
[0083]
〔solubility〕
The solubility of the conductive polymer used in each composition in toluene or methyl ethyl ketone (MEK) and in water was measured.
[0084]
[Aggregate area]
The particle size (median diameter) of the conductive polymer present in the binder polymer of each conductive coating film was measured by magnifying (optical microscope) 3000 times a film having a thickness of 5 to 8 μm. And the ratio (area) which the aggregate with a particle size of 1 micrometer or more occupied to the whole coating film was measured.
[0085]
[Electrical resistance, voltage dependence of electrical resistance]
For each conductive coating, etc., an electrical resistance when a voltage of 1V is applied (Rv = 1V) in an environment of 25 ° C. × 50% RH and an electrical resistance when a voltage of 133V is applied (Rv = 133V) Were measured according to SRIS 2304, respectively. Then, the voltage dependence of the electrical resistance is displayed in the number of fluctuation digits by Log (Rv = 1V / Rv = 133V).
[0086]
[Environmental dependence of electrical resistance]
For each conductive coating, etc., electrical resistance (Rv = 15 ° C. × 10% RH) at low temperature and low humidity (15 ° C. × 10% RH) and high temperature and high humidity (35 ° C. × 85%) under the condition of applied voltage of 10V RH), the electrical resistance (Rv = 35 ° C. × 85% RH) was measured according to SRIS 2304. Then, the environmental dependency of the electrical resistance was displayed by the number of fluctuation digits by Log (Rv = 15 ° C. × 10% RH / Rv = 35 ° C. × 85% RH).
[0087]
[Electric resistance fluctuation due to environment]
For each conductive coating film, the electrical resistance after standing for 30 days in an environment of 50 ° C. × 95% RH was measured according to SRIS 2304 under an environment of 25 ° C. × 50% RH by applying 10 V (Rv = 30 days). Then, the electrical resistance fluctuation due to the environment was displayed in the number of fluctuation digits by Log (Rv = 30 days / Rv = 0 day).
[0088]
[Table 1]

[0089]
[Table 2]

[0090]
[Table 3]

[0091]
[Table 4]

[0092]
[Table 5]

[0093]
From the result of the said table | surface, since the composition 1-18 uses the electroconductive polymer with the bad affinity to water, and was excellent in the solubility to a solvent, compatibility with a binder polymer is favorable, and it is an aggregate. Generation was suppressed, the electrical resistance was excellent in both voltage dependence and electrical resistance environmental dependence, and the electrical resistance variation due to the environment was small.
[0094]
On the other hand, since composition A uses an ionic conductive agent, the electrical resistance is inferior to the environment, and compositions B, C, and D use an electronic conductive agent dispersedly. The voltage dependency of the resistance was inferior. In composition E, polyaniline was used as the conductive polymer. However, since it was mixed as nylon and particles (1 μm level), many agglomerates were generated and the voltage dependence of electrical resistance was inferior. Since the composition F uses a conductive polymer having a good affinity for water, the electrical dependency of the electrical resistance is inferior, and the electrical resistance varies greatly depending on the environment. In composition G, polyaniline has poor compatibility with fluorinated carbon black and polyamic acid, and a large amount of aggregates are generated, so that the electrical resistance has a large voltage dependency. The composition H had many conductive carbon aggregates and was inferior in voltage dependency of electrical resistance. Composition I uses a conductive polymer that has an excellent affinity for water and poor solubility in a solvent. Therefore, the compatibility with the binder polymer is slightly inferior and aggregates are generated, resulting in fluctuations in electrical resistance due to the environment. was there.
[0095]
Next, examples of the electrophotographic apparatus member according to the present invention will be described together with comparative examples.
[0096]
[Example 1]
[Preparation of developing roll]
Into a mold for injection molding in which a cored bar (diameter 10 mm, made of SUS304) as a shaft body is set, silicone in which carbon black is dispersed (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) [Composition D] is cast, 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. The surface of the base layer was subjected to corona discharge treatment (condition: 0.3 kW × 20 seconds). Subsequently, the composition C prepared above was applied to the outer peripheral surface of the base layer to form an intermediate layer. Furthermore, a surface layer made of the composition 1 prepared above is formed on the surface of the intermediate layer, a base layer is formed on the outer peripheral surface of the shaft body, 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 was prepared.
[0097]
Examples 2 to 19 and Comparative Examples 1 to 5
A developing roll was produced 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, "-" was displayed about the thing which has not formed the base layer, the intermediate | middle layer, or the surface layer.
[0098]
Each characteristic was evaluated according to the following reference | standard using the developing roll of the Example goods and comparative example goods which were obtained in this way. These results are shown in Tables 6 to 9 below.
[0099]
[Electrical resistance, voltage dependence of electrical resistance]
With the surface of the developing roll pressed against the SUS plate, a load of 1 kg is applied to both ends of the developing roll, and the electrical resistance between the core of the developing roll and the surface of the developing roll pressed against the SUS plate is Measured according to SRIS 2304. The electrical resistance is the electrical resistance when a voltage of 1V is applied (Rv = 1V) and the electrical resistance when a voltage of 133V is applied (Rv = 133V) in an environment of 25 ° C. × 50% RH, respectively. It was measured. Then, the voltage dependence of the electrical resistance is displayed in the number of fluctuation digits by Log (Rv = 1V / Rv = 133V).
[0100]
[Environmental dependence of electrical resistance]
According to the evaluation of the electrical resistance, the electrical resistance (Rv = 15 ° C. × 10% RH) at the low temperature and low humidity (15 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × 35 ° C.) The electrical resistance (Rv = 35 ° C. × 85% RH) at 85% RH was measured according to SRIS 2304. Then, the environmental dependency of the electrical resistance was displayed by the number of fluctuation digits by Log (Rv = 15 ° C. × 10% RH / Rv = 35 ° C. × 85% RH).
[0101]
[Hardness (JIS A)]
The hardness of the outermost surface of each developing roll was measured according to JIS K 6253.
[0102]
(Compression set)
The compression set of each developing roll was measured according to JIS K 6262 under conditions of a temperature of 70 ° C., a test time of 22 hours, and a compression rate of 25%.
[0103]
(Development roll characteristics)
(Image unevenness)
Each developing roll was incorporated into a commercially available color printer, and images were taken out in an environment of 20 ° C. × 50% RH. In the evaluation, a case where there was no density unevenness in a halftone image and there was no break in fine lines or color unevenness was indicated as ◯, and a case where density unevenness occurred was indicated as x.
[0104]
(Changes in image quality due to the environment)
Image quality depending on the environment when each developing roll is incorporated in a commercially available color printer and images are output in an environment of 15 ° C. × 10% RH and when images are output in an environment of 35 ° C. × 85% RH We evaluated the fluctuations. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.
[0105]
[Change in electrical resistance over time due to the environment]
According to the evaluation of the electrical resistance, the electrical resistance after being left for 30 days in an environment of 50 ° C. × 95% RH was measured by applying 10 V under an environment of 25 ° C. × 50% RH in accordance with SRIS 2304 ( Rv = 30 days). The change in electrical resistance over time due to the environment was displayed as the number of fluctuation digits using Log (Rv = 30 days / Rv = 0 day).
[0106]
Examples 20-23, Comparative Examples 6-9
[Preparation of charging roll]
A charging roll was prepared in accordance with the developing roll manufacturing method of Example 1 except that the compositions shown in Table 10 and Table 11 below were used as the base layer material, intermediate layer material, or surface layer material. In addition, "-" was displayed about the thing which has not formed the base layer, the intermediate | middle layer, or the surface layer.
[0107]
Example 24, Comparative Example 10
[Preparation of transfer roll]
A transfer roll was produced in accordance with the developing roll production method of Example 1 except that the composition shown in Table 12 below was used as the base layer material, intermediate layer material, or surface layer material. In addition, "-" was displayed about the thing which has not formed the base layer, the intermediate | middle layer, or the surface layer.
[0108]
Examples 25 and 26, Comparative Example 11
[Production of transfer belt]
An intermediate transfer belt having a single-layer or multi-layer structure according to the developing roll manufacturing method of Example 1 except that the composition shown in Table 13 below is used as the base layer material, intermediate layer material, or surface layer material. An endless belt) was produced. In addition, "-" was displayed about the thing which has not formed the base layer, the intermediate | middle layer, or the surface layer.
[0109]
Example 27, Comparative Example 12
[Production of toner supply roll]
An intermediate transfer belt having a single-layer or multi-layer structure according to the developing roll manufacturing method of Example 1 except that the composition shown in Table 14 below is used as the base layer material, intermediate layer material, or surface layer material. An endless belt) was produced. In addition, "-" was displayed about the thing which has not formed the base layer, the intermediate | middle layer, or the surface layer.
[0110]
Using the charging roll, transfer roll, transfer belt, and toner supply roll of the example product and the comparative product thus obtained, each property was evaluated according to the criteria for property evaluation of the developing roll. . These results are shown in Tables 10 to 14 below. The electrical resistance of the transfer belt was measured by measuring the electrical resistance between the portion contacting the SUS rod and the SUS plate in accordance with SRIS 2304 by placing a 10 mm diameter SUS rod inside the transfer belt. did.
[0111]
[Table 6]

[0112]
[Table 7]

[0113]
[Table 8]

[0114]
[Table 9]

[0115]
[Table 10]

[0116]
[Table 11]

[0117]
[Table 12]

[0118]
[Table 13]

[0119]
[Table 14]

[0120]
From the above results, all of the products of the examples use the semiconductive composition (compositions 1 to 18) of the present invention in at least a part of the constituent layers of the electrophotographic apparatus member. Excellent roll characteristics, transfer roll characteristics, transfer belt characteristics, and toner supply roll characteristics.
[0121]
On the other hand, since the comparative product uses only a composition (any one of Compositions A to I) that is inferior in voltage dependency of electric resistance and environmental dependency of electric resistance, the characteristics of the developing roll, the charging roll Characteristics, transfer roll characteristics, transfer belt characteristics, and toner supply roll characteristics were inferior.
[0122]
【The invention's effect】
As described above, the semiconductive composition for an electrophotographic apparatus member of the present invention is specific Conductive polymer (component A) and binder polymer (component B) are essential components, specific The conductive polymer (component A) has a solubility in toluene or methyl ethyl ketone of 20% or more and a solubility in water of less than 3%. for that reason, specific Since the conductive polymer (component A) has a reduced affinity with water and the solubility in the solvent is appropriately improved, the compatibility with the binder polymer (component B) is improved, and aggregates are generated. As a result, the semiconductive composition for an electrophotographic apparatus member according to the present invention has both small fluctuations in electric resistance in a moist heat environment and both voltage dependence of electric resistance and environmental dependence of electric resistance. The effect is excellent in characteristics.
[0123]
In addition, A In minutes The surfactant used has a sulfonic acid group in the molecular structure and at least one of a naphthalene structure and an anthracene structure, or these have a specific substituent, In minutes When the surfactant used is represented by the general formula (1), the compatibility between the component A and the component B is further improved. Moreover, A In minutes When the sulfonic acid group equivalent in the surfactant to be used is set within a specific range, the compatibility between the component A and the component B is further improved.
[0124]
In addition, when the semiconductive composition for an electrophotographic apparatus member of the present invention is used for at least a part of the electrophotographic apparatus member, an electrophotographic apparatus member having effects specific to the semiconductive composition can be obtained. it can. That is, when the semiconductive composition of the present invention is used in at least a part of the constituent layers of an electrophotographic apparatus member, as described above, the electric resistance variation in a moist heat environment is reduced, and the voltage dependence of the electric resistance is reduced. The effect of the semiconductive composition of the present invention, which is excellent in both the properties of both the electrical properties and the environmental dependency of the electrical resistance, extends to other constituent layers not using this semiconductive composition. As a result, the electrophotographic apparatus member as a whole is less susceptible to fluctuations in electrical resistance in a moist heat environment, so that an excellent image can be obtained.

Claims (9)

A semiconductive composition for an electrophotographic apparatus member comprising the following (A) and (B) as essential components, wherein the conductive polymer (A) has a solubility in toluene or methyl ethyl ketone of 20% or more, and A semiconductive composition for an electrophotographic apparatus member having a solubility in water of less than 3%.
(A) a raw material monomer, a surfactant and a is that the conductive polymer obtained by oxidative polymerization in the presence of an oxidizing agent.
(B) Binder polymer. The semiconductive composition for an electrophotographic apparatus member according to claim 1, wherein the surfactant used in (A) has a sulfonic acid group in the molecular structure. 3. The semiconductive material for electrophotographic apparatus members according to claim 2, wherein the surfactant used in (A) has a sulfonic acid group in the molecular structure and at least one of a naphthalene structure and an anthracene structure. Composition.   The naphthalene structure or anthracene structure in the molecular structure of the surfactant has an arbitrary number of substituents of 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 The semiconductive composition for an electrophotographic apparatus member according to claim 3, wherein the composition is selected from the group consisting of: a hydroxy group, a nitro group, and a halogen. The semiconductive composition for an electrophotographic apparatus member according to claim 1 or 2, wherein the surfactant used in (A) is represented by the following general formula (1).

The surfactant used in (A) is represented by the following general formula (2): The semiconductive composition for an electrophotographic apparatus member according to any one of claims 1 to 4.

The semiconductive composition for an electrophotographic apparatus member according to any one of claims 2 to 6, wherein the sulfonic acid group equivalent in the surfactant used in (A) is in the range of 340 to 600.   The binder polymer (B) is at least one selected from the group consisting of acrylic resins, urethane resins, fluorine resins, polyimide resins, epoxy resins, urea resins, rubber polymers, and thermoplastic elastomers. The semiconductive composition for an electrophotographic apparatus member according to any one of claims 1 to 7.   An electrophotographic apparatus member, wherein the semiconductive composition for an electrophotographic apparatus member according to claim 1 is used for at least a part of the electrophotographic apparatus member.