JP3834003B2 - Dispersion preparation method, electrophotographic photosensitive member, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

式中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基、Ｒ_５、Ｒ_６は置換もしくは無置換のアリール基、ｏ、ｐ、ｑはそれぞれ独立して０〜４の整数、ｋ、ｊは組成を表し、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記一般式で表される２価基を表す。
【化２】

Ｒ_１０１、Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）または、
【化３】

（ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換または無置換のアルキル基又はアリール基を表す）を表す。ここで、Ｒ_１０１とＲ_１０２、Ｒ_１０３とＲ_１０４は、それぞれ同一でも異なってもよい。
【０１０９】
【化４】

式中、Ｒ_７、Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１、Ａｒ_２、Ａｒ_３は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１０】
【化５】

式中、Ｒ_９、Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４、Ａｒ_５、Ａｒ_６は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１１】
【化６】

式中、Ｒ_１１、Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７、Ａｒ_８、Ａｒ_９は同一又は異なるアリレン基、ｐは１〜５の整数を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１２】
【化７】

式中、Ｒ_１３、Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０、Ａｒ_１１、Ａｒ_１２は同一又は異なるアリレン基、Ｘ_１、Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１３】
【化８】

式中、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６は同一又は異なるアリレン基、Ｙ_１、Ｙ_２、Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１４】
【化９】

式中、Ｒ_１９、Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表し、Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７、Ａｒ_１８、Ａｒ_１９は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１５】
【化１０】

式中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０、Ａｒ_２１、Ａｒ_２２、Ａｒ_２３は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１６】
【化１１】

式中、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４、Ａｒ_２５、Ａｒ_２６、Ａｒ_２７、Ａｒ_２８は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１７】
【化１２】

式中、Ｒ_２６、Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９、Ａｒ_{３ ０}、Ａｒ_３１は同一又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、（１）式の場合と同じである。
【０１１８】
また、電荷輸送層に使用される高分子電荷輸送物質として、上述の高分子電荷輸送物質の他に、電荷輸送層の成膜時には電子供与性基を有するモノマーあるいはオリゴマーの状態で、成膜後に硬化反応あるいは架橋反応をさせることで、最終的に２次元あるいは３次元の架橋構造を有する重合体も含むものである。
【０１１９】
これら電子供与性基を有する重合体から構成される電荷輸送層、あるいは架橋構造を有する重合体は耐摩耗性に優れたものである。通常、電子写真プロセスにおいては、帯電電位（未露光部電位）は一定であるため、繰り返し使用により感光体の表面層が摩耗すると、その分だけ感光体にかかる電界強度が高くなってしまう。この電界強度の上昇に伴い、地汚れの発生頻度が高くなるため、感光体の耐摩耗性が高いことは、地汚れに対して有利である。これら電子供与性基を有する重合体から構成される電荷輸送層は、自身が高分子化合物であるため成膜性に優れ、低分子分散型高分子からなる電荷輸送層に比べ、電荷輸送部位を高密度に構成することが可能で電荷輸送能に優れたものである。このため、高分子電荷輸送物質を用いた電荷輸送層を有する感光体には高速応答性が期待できる。
【０１２０】
その他の電子供与性基を有する重合体としては、公知単量体の共重合体や、ブロック重合体、グラフト重合体、スターポリマーや、また、例えば特開平３−１０９４０６号公報、特開２０００−２０６７２３号公報、特開２００１−３４００１号公報等に開示されているような電子供与性基を有する架橋重合体などを用いることも可能である。この場合にも、先の移動度を満足できるような材料が有効に使用出来る。
【０１２１】
本発明において電荷輸送層３７中に可塑剤やレベリング剤を添加してもよい。可塑剤としては、ジブチルフタレート、ジオクチルフタレートなど一般の樹脂の可塑剤として使用されているものがそのまま使用でき、その使用量は、結着樹脂に対して０〜３０重量％程度が適当である。
レベリング剤としては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイルなどのシリコーンオイル類や、側鎖にパーフルオロアルキル基を有するポリマーあるいは、オリゴマーが使用され、その使用量は結着樹脂に対して、０〜１重量％が適当である。
【０１２２】
結着樹脂としては、先に電荷輸送層３７で挙げた結着樹脂をそのまま用いるほかに、分散液の作製方法のところで挙げた結着樹脂を混合して用いてもよい。もちろん、先に挙げた高分子電荷輸送物質も良好に使用できる。結着樹脂１００重量部に対する電荷発生物質の量は５〜４０重量部が好ましく、結着樹脂１００重量部に対する電荷輸送物質の量は１〜１９０重量部が好ましく、さらに好ましくは５０〜１５０重量部である。
【０１２３】
単層感光層は、電荷発生物質、結着樹脂を必要ならば電荷輸送物質とともにテトラヒドロフラン、ジオキサン、ジクロロエタン、シクロヘキサン等の溶媒を用いて分散機等で分散した塗工液を、浸漬塗工法やスプレーコート、ビードコートなどで塗工して形成できる。単層感光層の膜厚は、５〜１００μｍ程度が適当である。
【０１２４】
本発明の電子写真感光体には、導電性支持体３１と感光層との間に下引き層を設けることができる。下引き層は一般には樹脂を主成分とするが、これらの樹脂はその上に感光層を溶剤で塗布することを考えると、一般の有機溶剤に対して耐溶剤性の高い樹脂であることが望ましい。このような樹脂としては、ポリビニルアルコール、カゼイン、ポリアクリル酸ナトリウム等の水溶性樹脂、共重合ナイロン、メトキシメチル化ナイロン等のアルコール可溶性樹脂、ポリウレタン、メラミン樹脂、フェノール樹脂、アルキッド−メラミン樹脂、エポキシ樹脂等、三次元網目構造を形成する硬化型樹脂等が挙げられる。
また、下引き層にはモアレ防止、残留電位の低減等のために酸化チタン、シリカ、アルミナ、酸化ジルコニウム、酸化スズ、酸化インジウム等で例示できる金属酸化物の微粉末顔料を加えてもよい。
【０１２５】
これらの下引き層は前述の感光層の如く適当な溶媒、塗工法を用いて形成することができる。更に本発明の下引き層として、シランカップリング剤、チタンカップリング剤、クロムカップリング剤等を使用することもできる。この他、本発明の下引き層には、Ａｌ_２Ｏ_３を陽極酸化にて設けたものや、ポリパラキシリレン（パリレン）等の有機物やＳｉＯ_２、ＳｎＯ_２、ＴｉＯ_２、ＩＴＯ、ＣｅＯ_２等の無機物を真空薄膜作成法にて設けたものも良好に使用できる。このほかにも公知のものを用いることができる。下引き層の膜厚は０〜５μｍが適当である。
【０１２６】
本発明の電子写真感光体には、感光層保護の目的で、保護層が感光層の上に設けられることもある。近年、日常的にコンピュータの使用が行なわれるようになり、プリンタによる高速出力とともに、装置の小型化も望まれている。したがって、保護層を設け、耐久性を向上させることによって、本発明の高感度で異常欠陥のない感光体を有用に用いることができる。
【０１２７】
保護層に使用される材料としてはＡＢＳ樹脂、ＡＣＳ樹脂、オレフィン−ビニルモノマー共重合体、塩素化ポリエーテル、アリル樹脂、フェノール樹脂、ポリアセタール、ポリアミド、ポリアミドイミド、ポリアクリレート、ポリアリルスルホン、ポリブチレン、ポリブチレンテレフタレート、ポリカーボネート、ポリアリレート、ポリエーテルスルホン、ポリエチレン、ポリエチレンテレフタレート、ポリイミド、アクリル樹脂、ポリメチルベンテン、ポリプロピレン、ポリフェニレンオキシド、ポリスルホン、ポリスチレン、ＡＳ樹脂、ブタジエン−スチレン共重合体、ポリウレタン、ポリ塩化ビニル、ポリ塩化ビニリデン、エポキシ樹脂等の樹脂が挙げられる。中でも、ポリカーボネートもしくはポリアリレートが最も良好に使用できる。
【０１２８】
保護層にはその他、耐摩耗性を向上する目的でポリテトラフルオロエチレンのような弗素樹脂、シリコーン樹脂、及びこれらの樹脂に酸化チタン、酸化錫、チタン酸カリウム、シリカ等の無機フィラー、また有機フィラーを分散したもの等を添加することができる。
【０１２９】
また、感光体の保護層に用いられるフィラー材料のうち有機性フィラー材料としては、ポリテトラフルオロエチレンのようなフッ素樹脂粉末、シリコーン樹脂粉末、ａ−カーボン粉末等が挙げられ、無機性フィラー材料としては、銅、スズ、アルミニウム、インジウムなどの金属粉末、シリカ、酸化錫、酸化亜鉛、酸化チタン、酸化インジウム、酸化アンチモン、酸化ビスマス、アンチモンをドープした酸化錫、錫をドープした酸化インジウム等の金属酸化物、チタン酸カリウムなどの無機材料が挙げられる。特に、フィラーの硬度の点からは、この中でも無機材料を用いることが有利である。特に、シリカ、酸化チタン、アルミナが有効に使用できる。
【０１３０】
保護層中のフィラー濃度は使用するフィラー種により、また感光体を使用する電子写真プロセス条件によっても異なるが、保護層の最表層側において全固形分に対するフィラーの比で５重量％以上、好ましくは１０重量％以上、５０重量％以下、より好ましくは３０重量％以下程度が良好である。
【０１３１】
また、使用するフィラーの体積平均粒径は、０．１μｍ〜２μｍの範囲が良好に使用され、好ましくは０．３μｍ〜１μｍの範囲である。この場合、平均粒径が小さすぎると耐摩耗性が充分に発揮されず、大きすぎると塗膜の表面性が悪くなったり、塗膜そのものが形成できなかったりするからである。
【０１３２】
なお、本発明におけるフィラーの平均粒径とは、特別な記載のない限り体積平均粒径であり、超遠心式自動粒度分布測定装置：ＣＡＰＡ−７００（堀場製作所製）により求めたものである。この際、累積分布の５０％に相当する粒子径（Ｍｅｄｉａｎ系）として算出されたものである。また、同時に測定される各々の粒子の標準偏差が１μｍ以下であることが重要である。これ以上の標準偏差の値である場合には、粒度分布が広すぎて、本発明の効果が顕著に得られなくなってしまう場合がある。
【０１３３】
また、本発明で使用するフィラーのｐＨも解像度やフィラーの分散性に大きく影響する。
その理由の一つとしては、フィラー、特に金属酸化物は製造時に塩酸等が残存することが考えられる。その残存量が多い場合には、画像ボケの発生は避けられず、またそれは残存量によってはフィラーの分散性にも影響を及ぼす場合がある。
【０１３４】
もう一つの理由としては、フィラー、特に金属酸化物の表面における帯電性の違いによるものである。通常、液体中に分散している粒子はプラスあるいはマイナスに帯電しており、それを電気的に中性に保とうとして反対の電荷を持つイオンが集まり、そこで電気二重層が形成されることによって粒子の分散状態を安定化している。粒子から遠ざかるに従いその電位（ゼータ電位）は徐々に低くなり、粒子から充分に離れて電気的に中性である領域の電位はゼロとなる。したがって、ゼータ電位の絶対値の増加によって、粒子の反発力が高くなることによって安定性は高くなり、ゼロに近づくに従い凝集しやすく不安定になる。一方、系のｐＨ値によってゼータ電位は大きく変動し、あるｐＨ値において電位はゼロとなり等電点を持つことになる。したがって、系の等電点からできるだけ遠ざけて、ゼータ電位の絶対値を高めることによって分散系の安定化が図られることになる。
【０１３５】
本発明の構成においては、フィラーとしては前述の等電点におけるｐＨが、少なくとも５以上を示すものが画像ボケ抑制の点から好ましく、より塩基性を示すフィラーであるほどその効果が高くなる傾向があることが確認された。等電点におけるｐＨが高い塩基性を示すフィラーは、系が酸性であった方がゼータ電位はより高くなることにより、分散性及びその安定性は向上することになる。
ここで、本発明におけるフィラーのｐＨは、ゼータ電位から等電点におけるｐＨ値を記載した。この際、ゼータ電位の測定は、大塚電子製のレーザーゼータ電位計にて測定した。
【０１３６】
更に、画像ボケが発生しにくいフィラーとしては、電気絶縁性が高いフィラー（比抵抗が１０^１０Ω・ｃｍ以上）が好ましく、フィラーのｐＨが５以上を示すものやフィラーの誘電率が５以上を示すものが特に有効に使用できる。また、ｐＨが５以上のフィラーあるいは誘電率が５以上のフィラーを単独で使用することはもちろん、ｐＨが５以下のフィラーとｐＨが５以上のフィラーとを２種類以上を混合したり、誘電率が５以下のフィラーと誘電率が５以上のフィラーとを２種類以上混合したりして用いることも可能である。また、これらのフィラーの中でも高い絶縁性を有し、熱安定性が高い上に、耐摩耗性が高い六方細密構造であるα型アルミナは、画像ボケの抑制や耐摩耗性の向上の点から特に有用である。
【０１３７】
本発明において使用するフィラーの比抵抗は以下のように定義される。フィラーのような粉体は、充填率によりその比抵抗値が異なるので、一定の条件下で測定する必要がある。本発明においては、特開平５−９４０４９号公報の図１、特開平５−１１３６８８号公報の図１等に示された測定装置と同様の構成の装置を用いて、フィラーの比抵抗値を測定し、この値を用いた。測定装置において、電極面積は４．０ｃｍ^２である。測定前に片側の電極に４ｋｇの荷重を１分間かけ、電極間距離が４ｍｍになるように試料量を調節する。測定の際は、上部電極の重量（１ｋｇ）の荷重状態で測定を行ない、印加電圧は１００Ｖにて測定する。１０^６Ω・ｃｍ以上の領域は、ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲ（横河ヒューレットパッカード）、それ以下の領域についてはデジタルマルチメーター（フルーク）により測定した。これにより得られた比抵抗値を本発明の云うところの比抵抗値と定義するものである。
【０１３８】
フィラーの誘電率は以下のように測定した。上述のような比抵抗の測定と同様なセルを用い、荷重をかけた後に、静電容量を測定し、これより誘電率を求めた。静電容量の測定は、誘電体損測定器（安藤電気製）を使用した。
【０１３９】
更に、これらのフィラーは少なくとも一種の表面処理剤で表面処理させることが可能であり、そうすることがフィラーの分散性の面から好ましい。フィラーの分散性の低下は残留電位の上昇だけでなく、塗膜の透明性の低下や塗膜欠陥の発生、さらには耐摩耗性の低下をも引き起こすため、高耐久化あるいは高画質化を妨げる大きな問題に発展する可能性がある。
【０１４０】
表面処理剤としては、従来用いられている表面処理剤すべてを使用することができるが、フィラーの絶縁性を維持できる表面処理剤が好ましい。例えば、チタネート系カップリング剤、アルミニウム系カップリング剤、ジルコアルミネート系カップリング剤、高級脂肪酸等、あるいはこれらとシランカップリング剤との混合処理や、Ａｌ_２Ｏ_３、ＴｉＯ_２、ＺｒＯ_２、シリコーン、ステアリン酸アルミニウム等、あるいはそれらの混合処理がフィラーの分散性及び画像ボケの点からより好ましい。シランカップリング剤による処理は、画像ボケの影響が強くなるが、上記の表面処理剤とシランカップリング剤との混合処理を施すことによりその影響を抑制できる場合がある。
【０１４１】
表面処理量については、用いるフィラーの平均一次粒径によって異なるが、３〜３０ｗｔ％が適しており、５〜２０ｗｔ％がより好ましい。表面処理量がこれよりも少ないとフィラーの分散効果が得られず、また多すぎると残留電位の著しい上昇を引き起こす。
【０１４２】
これらフィラー材料は単独もしくは２種類以上混合して用いられる。フィラーの表面処理量に関しては、上述のようにフィラー量に対する使用する表面処理剤の重量比で定義される。
これらフィラー材料は、適当な分散機を用いることにより分散できる。また、保護層の透過率の点から使用するフィラーは１次粒子レベルまで分散され、凝集体が少ない方が好ましい。
【０１４３】
また、保護層には残留電位低減、応答性改良のため、電荷輸送物質を含有しても良い。電荷輸送物質は、電荷輸送層の説明のところに記載した材料を用いることができる。電荷輸送物質として、低分子電荷輸送物質を用いる場合には、保護層中における濃度傾斜を設けても構わない。耐摩耗性向上のため、表面側を低濃度にすることは有効な手段である。
ここでいう濃度とは、保護層を構成する全材料の総重量に対する低分子電荷輸送物質の重量の比を表わし、濃度傾斜とは上記重量比において表面側において濃度が低くなるような傾斜を設けることを示す。
また、高分子電荷輸送物質を用いることは、感光体の耐久性を高める点で非常に有利である。
【０１４４】
保護層の形成法としては通常の塗布法が採用される。なお保護層の厚さは０．１〜１０μｍ程度が適当である。また、以上のほかに真空薄膜作成法にて形成したａ−Ｃ、ａ−ＳｉＣなど公知の材料を保護層として用いることができる。
【０１４５】
上述したように、感光層（電荷輸送層）に高分子電荷輸送物質を使用したり、あるいは感光体の表面に保護層を設けることは、各々の感光体の耐久性（耐摩耗性）を高めるだけでなく、後述のようなタンデム型フルカラー画像形成装置中で使用される場合には、モノクロ画像形成装置にはない新たな効果をも生み出すものである。
【０１４６】
フルカラーの画像の場合、様々な形態の画像が入力されるが、逆に定型的な画像も入力される場合がある。例えば、日本語の文書等における検印の存在などである。検印のようなものは通常、画像領域の端の方に位置され、また使用される色も限定される。ランダムな画像が常に書き込まれているような状態においては、画像形成要素中の感光体には、平均的に画像書き込み、現像、転写が行なわれることになるが、上述のように特定の部分に数多くの画像形成が繰り返されたり、特定の画像形成要素ばかり使用された場合には、その耐久性のバランスを欠くことにつながる。
このような状態で表面の耐久性（物理的・化学的・機械的）の小さな感光体が使用された場合には、この差が顕著になり、画像上の問題になりやすい。一方、感光体を高耐久化した場合には、このような局所的な変化量が小さく、結果的に画像上の欠陥として現われにくくなるため、高耐久化を実現すると共に、出力画像の安定性をも増すことになり、非常に有効である。
【０１４７】
本発明の電子写真感光体においては、感光層と保護層との間に中間層を設けることも可能である中間層には、一般にバインダー樹脂を主成分として用いる。これら樹脂としては、ポリアミド、アルコール可溶性ナイロン、水溶性ポリビニルブチラール、ポリビニルブチラール、ポリビニルアルコールなどが挙げられる。中間層の形成法としては、前述のごとく通常の塗布法が採用される。なお、中間層の厚さは０．０５〜２μｍ程度が適当である。
【０１４８】
次に図面を用いて本発明の画像形成装置を詳しく説明する。
図５は、本発明の画像形成プロセス及び画像形成装置を説明するための概略図であり、下記するような変形例も本発明の範疇に属するものである。
図５において、感光体１は導電性支持体上に特定の分散条件により分散されたチタニルフタロシアニン結晶を含有する電荷発生層と、電荷輸送層が設けられてなる。帯電部材３、転写前チャージャー７、転写チャージャー１０、分離チャージャー１１、クリーニング前チャージャー１３には、コロトロン、スコロトロン、固体帯電器（ソリッド・ステート・チャージャー）、帯電ローラーを始めとする公知の手段が用いられる。
【０１４９】
帯電部材は、感光体１に対し接触もしくは近接配置したものが良好に用いられる。また、帯電部材により感光体に帯電を施す際、帯電部材に直流成分に交流成分を重畳した電界により感光体に帯電を与えることにより、帯電ムラを低減することが可能で効果的である。
【０１５０】
ここでいう接触方式の帯電部材とは、感光体表面に帯電部材の表面が接触するタイプのものであり、帯電ローラー、帯電ブレード、帯電ブラシの形状がある。中でも帯電ローラーや帯電ブラシが良好に使用される。
【０１５１】
また、近接配置した帯電部材とは、感光体表面と帯電部材表面の間に１０μｍ以上２００μｍ以下の空隙（ギャップ）を有するように非接触状態で近接配置したタイプのものである。空隙の距離から、コロトロン、スコロトロンに代表される公知の帯電器とは区別されるものである。
【０１５２】
本発明において使用される近接配置された帯電部材は、感光体表面との空隙を適切に制御できる機構のものであればいかなる形状のものでも良い。例えば、感光体の回転軸と帯電部材の回転軸を機械的に固定して、適正ギャップを有するような配置にすればよい。中でも、帯電ローラーの形状の帯電部材を用い、帯電部材の非画像形成部両端にギャップ形成部材を配置して、この部分のみを感光体表面に当接させ、画像形成領域を非接触配置させる、あるいは感光体非画像形成部両端ギャップ形成部材を配置して、この部分のみを帯電部材表面に当接させ、画像形成領域を非接触配置させる様な方法が、簡便な方法でギャップを安定して維持できる方法である。特に特開２００２−１４８９０４号公報、特開２００２−１４８９０５号公報に記載された方法は良好に使用できる。帯電部材側にギャップ形成部材を配置した近接帯電機構の一例を図６に示す。
【０１５３】
転写手段には、一般に上記の帯電器が使用できるが、図５に示されるように転写チャージャー１０と分離チャージャー１１を併用したものが効果的である。
【０１５４】
また、画像露光部５の光源にはＬＤもしくはＬＥＤが用いられる。除電ランプ２等の光源には、蛍光灯、タングステンランプ、ハロゲンランプ、水銀灯、ナトリウム灯、発光ダイオード（ＬＥＤ）、半導体レーザー（ＬＤ）、エレクトロルミネッセンス（ＥＬ）などの発光物全般を用いることができる。そして、所望の波長域の光のみを照射するために、シャープカットフィルター、バンドパスフィルター、近赤外カットフィルター、ダイクロイックフィルター、干渉フィルター、色温度変換フィルターなどの各種フィルターを用いることもできる。
【０１５５】
かかる光源等は、図５に示される工程の他に光照射を併用した転写工程、除電工程、クリーニング工程、あるいは前露光などの工程を設けることにより、感光体に光が照射される。
【０１５６】
現像ユニット６により感光体１上に現像されたトナーは、転写紙９に転写されるが、全部が転写されるわけではなく、感光体１上に残存するトナーも生ずる。このようなトナーは、ファーブラシ１４およびブレード１５により、感光体より除去される。クリーニングは、クリーニングブラシだけで行なわれることもあり、クリーニングブラシにはファーブラシ、マグファーブラシを始めとする公知のものが用いられる。
【０１５７】
電子写真感光体に正（負）帯電を施し、画像露光を行なうと、感光体表面上には正（負）の静電潜像が形成される。これを負（正）極性のトナー（検電微粒子）で現像すれば、ポジ画像が得られるし、また正（負）極性のトナーで現像すれば、ネガ画像が得られる。
かかる現像手段には、公知の方法が適用されるし、また、除電手段にも公知の方法が用いられる。
【０１５８】
図７には、本発明による画像形成プロセスの別の例を示す。感光体２１は導電性支持体上に、特定の分散条件により分散されたチタニルフタロシアニン結晶を含有する電荷発生層と電荷輸送層が設けられてなる。駆動ローラー２２ａ、２２ｂにより駆動され、帯電器２３による帯電、光源２４による像露光、現像（図示せず）、帯電器２５を用いる転写、光源２６によるクリーニング前露光、ブラシ２７によるクリーニング、光源２８による除電が繰返し行なわれる。図７においては、感光体２１（勿論支持体が透光性である）に支持体側より画像露光の光照射が行なわれる。また、画像露光源２４は、ＬＤもしくはＬＥＤが好ましく用いられる。
【０１５９】
以上の図示した画像形成プロセスは、本発明における実施形態を例示するものであって、もちろん他の実施形態も可能である。例えば、図５において感光層側よりクリーニング前露光を行っているが、これは透光性支持体側から行ってもよいし、また、除電光の照射を支持体側から行ってもよい。
一方、光照射工程は、像露光、クリーニング前露光、除電露光が図示されているが、他に転写前露光、像露光のプレ露光、およびその他公知の光照射工程を設けて、感光体に光照射を行なうこともできる。
【０１６０】
以上に示すような画像形成手段は、複写装置、ファクシミリ、プリンター内に固定して組み込まれていてもよいが、プロセスカートリッジの形でそれら装置内に組み込まれてもよい。プロセスカートリッジとは、感光体を内蔵し、他に帯電手段、露光手段、現像手段、転写手段、クリーニング手段、除電手段の少なくとも一つを含んだ装置（部品）である。
プロセスカートリッジの形状等は多く挙げられるが、一般的な例として、図８に示すものが挙げられる。感光体１は導電性支持体上に特定の分散条件により分散されたチタニルフタロシアニン結晶を含有する電荷発生層と電荷輸送層が設けられてなる。
【０１６１】
図９は、本発明のタンデム方式のフルカラー画像形成装置を説明するための概略図であり、下記するような変形例も本発明の範疇に属するものである。
図９において、符号１Ｃ、１Ｍ、１Ｙ、１Ｋはドラム状の感光体であり、この感光体１Ｃ、１Ｍ、１Ｙ、１Ｋは図中の矢印方向に回転し、その周りに少なくとも回転順に帯電部材２Ｃ、２Ｍ、２Ｙ、２Ｋ、現像部材４Ｃ、４Ｍ、４Ｙ、４Ｋ、クリーニング部材５Ｃ、５Ｍ、５Ｙ、５Ｋが配置されている。
【０１６２】
帯電部材２Ｃ、２Ｍ、２Ｙ、２Ｋは、感光体表面を均一に帯電するための帯電装置を構成する帯電部材である。この帯電部材２Ｃ、２Ｍ、２Ｙ、２Ｋと現像部材４Ｃ、４Ｍ、４Ｙ、４Ｋの間の感光体裏面側より、図示しない露光部材からのレーザー光３Ｃ、３Ｍ、３Ｙ、３Ｋが照射され、感光体１Ｃ、１Ｍ、１Ｙ、１Ｋに静電潜像が形成されるようになっている。
【０１６３】
そして、このような感光体１Ｃ、１Ｍ、１Ｙ、１Ｋを中心とした４つの画像形成要素６Ｃ、６Ｍ、６Ｙ、６Ｋが、転写材搬送手段である転写搬送ベルト１０に沿って並置されている。転写搬送ベルト１０は各画像形成ユニット６Ｃ、６Ｍ、６Ｙ、６Ｋの現像部材４Ｃ、４Ｍ、４Ｙ、４Ｋとクリーニング部材５Ｃ、５Ｍ、５Ｙ、５Ｋの間で感光体１Ｃ、１Ｍ、１Ｙ、１Ｋに当接しており、転写搬送ベルト１０の感光体側の裏側に当たる面（裏面）には転写バイアスを印加するための転写ブラシ１１Ｃ、１１Ｍ、１１Ｙ、１１Ｋが配置されている。
各画像形成要素６Ｃ、６Ｍ、６Ｙ、６Ｋは現像装置内部のトナーの色が異なることであり、その他は全て同様の構成となっている。
【０１６４】
図９に示す構成のカラー画像形成装置において、画像形成動作は次のようにして行われる。
まず、各画像形成要素６Ｃ、６Ｍ、６Ｙ、６Ｋにおいて、感光体１Ｃ、１Ｍ、１Ｙ、１Ｋが矢印方向（感光体と連れ周り方向）に回転する帯電部材２Ｃ、２Ｍ、２Ｙ、２Ｋにより帯電され、次に感光体の内側に配置された露光部（図示しない）でレーザー光３Ｃ、３Ｍ、３Ｙ、３Ｋにより、作成する各色の画像に対応した静電潜像が形成される。
【０１６５】
次に現像部材４Ｃ、４Ｍ、４Ｙ、４Ｋにより潜像を現像してトナー像が形成される。現像部材４Ｃ、４Ｍ、４Ｙ、４Ｋは、それぞれＣ（シアン）、Ｍ（マゼンタ）、Ｙ（イエロー）、Ｋ（ブラック）のトナーで現像を行う現像部材で、４つの感光体１Ｃ、１Ｍ、１Ｙ、１Ｋ上で作られた各色のトナー像は転写紙上で重ねられる。
【０１６６】
転写紙７は給紙コロ８によりトレイから送り出され、一対のレジストローラ９で一旦停止し、上記感光体上への画像形成とタイミングを合わせて転写搬送ベルト１０に送られる。転写搬送ベルト１０上に保持された転写紙７は搬送されて、各感光体１Ｃ、１Ｍ、１Ｙ、１Ｋとの当接位置（転写部）で各色トナー像の転写が行われる。感光体上のトナー像は、転写ブラシ１１Ｃ、１１Ｍ、１１Ｙ、１１Ｋに印加された転写バイアスと感光体１Ｃ、１Ｍ、１Ｙ、１Ｋとの電位差から形成される電界により、転写紙７上に転写される。
【０１６７】
そして４つの転写部を通過して４色のトナー像が重ねられた記録紙７は定着装置１２に搬送され、トナーが定着されて、図示しない排紙部に排紙される。また、転写部で転写されずに各感光体１Ｃ、１Ｍ、１Ｙ、１Ｋ上に残った残留トナーは、クリーニング装置５Ｃ、５Ｍ、５Ｙ、５Ｋで回収される。
【０１６８】
なお、図９の例では画像形成要素は転写紙搬送方向上流側から下流側に向けて、Ｃ（シアン）、Ｍ（マゼンタ）、Ｙ（イエロー）、Ｋ（ブラック）の色の順で並んでいるが、この順番に限るものでは無く、色順は任意に設定されるものである。また、黒色のみの原稿を作成する際には、黒色以外の画像形成要素（６Ｃ、６Ｍ、６Ｙ）が停止するような機構を設けることは本発明に特に有効に利用できる。更に、図９において帯電部材は感光体と当接しているが、両者の間に適当なギャップ（１０〜２００μｍ程度）を設けてやることにより、両者の摩耗量が低減できると共に、帯電部材へのトナーフィルミングが少なくて済み良好に使用できる。
【０１６９】
以上に示すような画像形成手段は、複写装置、ファクシミリ、プリンター内に固定して組み込まれていてもよいが、各々の電子写真要素はプロセスカートリッジの形でそれら装置内に組み込まれてもよい。プロセスカートリッジとは、感光体を内蔵し、他に帯電手段、露光手段、現像手段、転写手段、クリーニング手段、除電手段等を含んだ１つの装置（部品）である。
【０１７０】
【実施例】
以下、本発明を実施例を挙げて説明するが、本発明が実施例により制約を受けるものではない。なお、部はすべて重量部である。
まず、ブラッグ角２θの最大回折ピークが２７．２°±０．２°にある結晶型のチタニルフタロシアニン顔料の具体的な合成例を述べる。
【０１７１】
（顔料作製例１）
１，３−ジイミノイソインドリン２９２部とスルホラン１８００部を混合し、窒素気流下でチタニウムテトラブトキシド２０４部を滴下する。滴下終了後、徐々に１８０℃まで昇温し、反応温度を１７０℃〜１８０℃の間に保ちながら５時間撹拌して反応を行った。反応終了後、放冷した後析出物を濾過し、クロロホルムで粉体が青色になるまで洗浄し、つぎにメタノールで数回洗浄し、さらに８０℃の熱水で数回洗浄した後乾燥し、粗チタニルフタロシアニンを得た。
【０１７２】
得られた熱水洗浄処理した粗チタニルフタロシアニン顔料のうち６０部を９６％硫酸１０００部に３〜５℃下撹拌、溶解し、濾過した。得られた硫酸溶液を氷水３５０００部中に撹拌しながら滴下し、析出した結晶を濾過、ついで洗浄液が中性になるまで水洗を繰り返し、チタニルフタロシアニン顔料の水ペーストを得た。
【０１７３】
この水ペーストにテトラヒドロフラン１５００部を加え、室温下で撹拌し、ペーストの濃紺色の色が淡い青色に変化したら、撹拌を停止し、直ちに減圧濾過を行った。濾過装置上で得られた結晶をテトラヒドロフランで洗浄し、顔料のウェットケーキ９８部を得た。これを減圧下（５ｍｍＨｇ）、７０℃で２日間乾燥して、チタニルフタロシアニン結晶７８部を得た。これを顔料１とする。
【０１７４】
顔料作製例１で得られた水ペーストの一部を８０℃の減圧下（５ｍｍＨｇ）で、２日間乾燥して、低結晶性チタニルフタロシアニン粉末を得た。
【０１７５】
上述のように得られた水ペーストの乾燥粉末と、顔料作製例１で得られたチタニルフタロシアニン結晶（顔料１）についてのＸ線回折スペクトルを以下に示す条件で測定した。
Ｘ線管球：Ｃｕ、 電圧 ：４０ｋＶ 電流 ：２０ｍＡ
走査速度：１°／分 走査範囲：３°〜４０° 時定数：２秒
【０１７６】
水ペーストの乾燥粉末のＸ線回折スペクトルを図１０に、顔料１のＸ線回折スペクトルを図１１に示す。
【０１７７】
図１１より、顔料１は、２７．２゜に最大回折ピークを有し、更に９．４゜、９．６゜、２４．０゜に主要なピークを有し、かつ最も低角側の回折ピークとして７．３゜にピークを有し、７．４°以上９．４゜未満の範囲にピークを有さず、また２６．３゜にピークを有さない結晶型を有するチタニルフタロシアニン結晶であることが分かる。
【０１７８】
（比較例１）
下記組成の分散液を下に示す条件のビーズミリングにより作製した（これを分散液１とする）。
顔料作製例１で作製したチタニルフタロシアニン結晶（顔料１）２４０部
ポリビニルブチラール（積水化学製：ＢＸ−１） １６０部
２−ブタノン ３６００部
市販のビーズミル分散機（ＶＭＡ−ＧＥＴＺＭＡＮＮ ＧＭＢＨ製：ＤＩＳＰＥＲＭＡＴ ＳＬ、ローターの直径は５０ｍｍ、分散室容量は１２５ｍｌ）に直径０．５ｍｍのジルコニアボールを用い、ポリビニルブチラールを溶解した２−ブタノンおよび顔料を全て投入し、ローター回転数３０００ｒ．ｐ．ｍ．にて、３００分間分散を行った。
送液用のモーター回転数を目盛り５にセットした際の流量は１リッター／分であるが、上記条件の分散初期状態では、およそ８分間の間、０．３リッター／分に低下した。このままの状態でローター回転数を変えずに、３００分間分散を行った。
分散終了後、ビーズミル分散機よりミルベースを払い出し、更に１０３００部の２−ブタノンを投入し、希釈と同時に分散機に残ったミルベースをすべて払い出し、分散液を作製した。
【０１７９】
（実施例１）
比較例１において、循環流量が低下している間、ローター回転数１０００ｒ．ｐ．ｍ．に落として分散を行い、循環流量が０．９リッター／分以上になったら、所定回転数（３０００ｒ．ｐ．ｍ．）に戻して分散を行った以外は、比較例１と同様に分散を行ない、分散液を作製した（これを分散液２とする）。この際、循環流量が所定流量の９０％未満に低下している時間は１３分間である。
【０１８０】
（実施例２）
比較例１において、循環流量が低下している間、ローター回転数２３００ｒ．ｐ．ｍ．に落として分散を行い、循環流量が０．９リッター／分以上になったら、所定回転数（３０００ｒ．ｐ．ｍ．）に戻して分散を行った以外は、比較例１と同様に分散を行ない、分散液を作製した（これを分散液３とする）。この際、循環流量が所定流量の９０％未満に低下している時間は１０分間である。
【０１８１】
（実施例３）
比較例１において、循環流量が低下している間、ローター回転数５００ｒ．ｐ．ｍ．に落として分散を行い、循環流量が０．９リッター／分以上になったら、所定回転数（３０００ｒ．ｐ．ｍ．）に戻して分散を行った以外は、比較例１と同様に分散を行ない、分散液を作製した（これを分散液４とする）。この際、循環流量が所定流量の９０％未満に低下している時間が２０分かかった。この際、循環流量が所定流量の９０％未満に低下している時間は９分間である。
【０１８２】
（実施例４）
比較例１において、循環流量が低下している間、ローター回転数２５００ｒ．ｐ．ｍ．に落として分散を行い、循環流量が０．９リッター／分以上になったら、所定回転数（３０００ｒ．ｐ．ｍ．）に戻して分散を行った以外は、比較例１と同様に分散を行ない、分散液を作製した（これを分散液５とする）。
【０１８３】
（実施例５）
実施例１において、分散メディアを直径０．８ｍｍのジルコニアボールに変更した以外は、実施例１と同様に分散を行ない、分散液を作製した（これを分散液６とする）。
【０１８４】
（比較例２）
実施例１において、分散メディアを直径１．５ｍｍのジルコニアボールに変更した以外は、実施例１と同様に分散を行ない、分散液を作製した（これを分散液７とする）。
【０１８５】
以上のように作製した分散液１〜７は、以下の評価を行った。結果を表１に示す。なお、表中の回転数とは、循環流量が低下している（分散初期状態における）際のローター回転数である（以下同じ）。
・平均粒径：
堀場製作所：ＣＡＰＡ７００にて体積平均粒径を評価した。
・粗大粒子の観察：
分散液をスライドガラスに塗布し、観察用のサンプルを作製した。続いて、市販の光学顕微鏡（５０〜１００倍）にて、塗膜の観察を行ない、粗大粒子の有無を観察した。
・Ｘ線回折スペクトル：
分散液を乾固し、粉末にしたものを前述と同様にＸ線回折スペクトルを測定した。
・成膜性の評価：
分散液を洗浄したアルミ板に浸漬塗工法により成膜して、塗膜の状態を観察した。
【０１８６】
【表１】

【０１８７】
なお、結晶の一部が結晶転移してしまった場合（比較例２）のＸ線回折スペクトルを図１２に示す。図中の矢印が、図１１の結晶には認められない新たなピーク（２６．３゜）である。
【０１８８】
（実施例６）
実施例１の分散液に使用した溶媒を、２−ブタノンからｎ−酢酸ブチルに変更した以外は、実施例１と同様に分散液を作製した（これを分散液８とする）。
【０１８９】
（実施例７）
実施例１の分散液に使用した溶媒を、２−ブタノンからｎ−ブタノールに変更した以外は、実施例１と同様に分散液を作製した（これを分散液９とする）。
【０１９０】
（実施例８）
実施例１の分散液の組成を下記組成のものに変更した以外は、実施例１と同様に分散液を作製した（これを分散液１０とする）。
顔料作製例１で作製したチタニルフタロシアニン結晶（顔料１）２４０部
ポリビニルブチラール（積水化学製：ＢＸ−１） １６０部
テトラヒドロフラン ３６００部
イオン交換水 ３６部
【０１９１】
（実施例９）
実施例８の分散液より、イオン交換水を除いた以外は、実施例８と同様に分散液を作製した（これを分散液１１とする）。
【０１９２】
（実施例１０）
実施例１の分散液より、ポリビニルブチラールを除いた以外は、実施例１と同様に分散液を作製した（これを分散液１２とする）。
【０１９３】
以上のように作製した分散液８〜１２を、分散液１〜７の場合と同様に評価を行った。実施例１の結果と併せて表２に示す。
【０１９４】
【表２】

【０１９５】
表２から分かるように、分散溶媒として２−ブタノン（ケトン系溶媒）、ｎ−酢酸ブチル（エステル系溶媒）、テトラヒドロフラン（エーテル系溶媒）を用いた場合には良好な特性を有する分散液が得られたが、その他の溶媒であるｎ−ブタノール（アルコール系溶媒）を用いた場合には、やや分散安定性に劣る結果となった。
また、イオン交換水を添加しない場合や、バインダー樹脂を添加しない場合においては、結晶安定性に劣る場合が認められた。
【０１９６】
（顔料作製例２）
特開平１−２９９８７４号（特許第２５１２０８１号）公報の「実施例１」に記載の方法に準じて、顔料を作製した。すなわち、先の顔料作製例１で作製したウェットケーキを乾燥し、乾燥物２００ｇをポリエチレングリコール１０００ｇに加え、２００００ｇのガラスビーズと共に、サンドミルを行なった。結晶転移後、希硫酸、水酸化アンモニウム水溶液で順次洗浄し、乾燥して顔料を得た（これを顔料２とする）。
【０１９７】
（顔料作製例３）
特開平３−２６９０６４号（特許第２５８４６８２号）公報の「製造例１」に記載の方法に準じて、顔料を作製した。すなわち、先の顔料作製例１で作製したウェットケーキを乾燥し、乾燥物２００ｇをイオン交換水２０００ｇとモノクロルベンゼン２００ｇの混合溶媒中で１時間撹拌（５０℃）した後、メタノールとイオン交換水で洗浄し、乾燥して顔料を得た（これを顔料３とする）。
【０１９８】
（顔料作製例４）
特開平２−８２５６号（特公平７−９１４８６号）公報の「製造例」に記載の方法に準じて、顔料を作製した。すなわち、フタロジニトリル１９６ｇと１−クロロナフタレン１５００ｍｌを撹拌混合し、窒素気流下で四塩化チタン４４ｍｌを滴下する。滴下終了後、徐々に２００℃まで昇温し、反応温度を２００℃〜２２０℃の間に保ちながら３時間撹拌して反応を行なった。反応終了後、放冷し１３０℃になったところ熱時濾過し、次いで１−クロロナフタレンで粉体が青色になるまで洗浄、次にメタノールで数回洗浄し、更に８０℃の熱水で数回洗浄した後、乾燥し顔料を得た（これを顔料４とする）。
【０１９９】
（顔料作製例５）
特開昭６４−１７０６６号（特公平７−９７２２１号）公報の「合成例１」に記載の方法に準じて、顔料を作製した。すなわち、α型ＴｉＯＰｃ２００部を食塩４００ｇおよびアセトフェノン２００ｇと共にサンドグラインダーにて１００℃にて１０時間結晶変換処理を行なった。これをイオン交換水及びメタノールで洗浄し、希硫酸水溶液で精製し、イオン交換水で酸分がなくなるまで洗浄した後、乾燥して顔料を得た（これを顔料５とする）。
【０２００】
（顔料作製例６）
特開平１１−５９１９号（特許第３００３６６４号）公報の「実施例１」に記載の方法に準じて、顔料を作製した。すなわち、Ｏ−フタロジニトリル２０４部、四塩化チタン部７６部をキノリン５００部中で２００℃にて２時間加熱反応後、水蒸気蒸留で溶媒を除き、２％塩化水溶液、続いて２％水酸化ナトリウム水溶液で精製し、メタノール、Ｎ，Ｎ−ジメチルホルムアミドで洗浄後、乾燥し、チタニルフタロシアニンを得た。このチタニルフタロシアニン２００部を５℃の９８％硫酸４０部の中に少しずつ溶解し、その混合物を約１時間、５℃以下の温度を保ちながら攪拌する。続いて硫酸溶液を高速攪拌した８０００部の氷水中に、ゆっくりと注入し、析出した結晶を濾過する。結晶を酸が残量しなくなるまで蒸留水で洗浄し、ウエットケーキを得る。そのケーキをＴＨＦ１００００部中で約５時間攪拌を行ない、濾過、ＴＨＦによる洗浄を行ない乾燥後、顔料を得た（これを顔料６とする）。
【０２０１】
（顔料作製例７）
特開平３−２５５４５６号（特許第３００５０５２号）公報の「合成例２」に記載の方法に準じて、顔料を作製した。すなわち、先の顔料作製例１で作製したウェットケーキ４００部を塩化ナトリウム６００部とジエチレングリコール２８０部に混合し、８０℃の加熱下で自動乳鉢により６０時間ミリング処理を行なった。次に、この処理品に含まれる塩化ナトリウムとジエチレングリコールを完全に除去するために充分な水洗を行なった。これを減圧乾燥した後にシクロヘキサノン８０００部と直径１ｍｍのガラスビーズを加えて、３０分間サンドミルにより処理を行ない、顔料を得た（これを顔料７とする）。
【０２０２】
以上の顔料作製例２〜７で作製した顔料２〜７は、前記と同様の方法でＸ線回折スペクトルを測定し、それぞれの公報に記載のスペクトルと同様であることを確認した。表３にそれぞれのＸ線回折スペクトルと顔料作製例１で得られた顔料のＸ線回折スペクトルのピーク位置の特徴を示す。
【０２０３】
【表３】

【０２０４】
（実施例１１）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料２を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１３とする）。
【０２０５】
（実施例１２）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料３を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１４とする）。
【０２０６】
（実施例１３）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料４を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１５とする）。
【０２０７】
（実施例１４）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料５を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１６とする）。
【０２０８】
（実施例１５）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料６を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１７とする）。
【０２０９】
（実施例１６）
実施例１で使用したチタニルフタロシアニン結晶（顔料１）の代わりに、それぞれ顔料７を用いた以外は、実施例１と同様に分散液を作製した（これらを分散液１８とする）。
【０２１０】
以上のように作製した分散液１３〜１８は、実施例１の場合と同様に評価し、実施例１の結果と併せて表４に示す。
【０２１１】
【表４】

【０２１２】
表４から分かるように、顔料１とは結晶型の異なるチタニルフタロシアニン結晶を用いた場合においても、分散初期状態において循環流量が適正領域に到達するまでの間、ローター回転数を制御する分散を行うことにより、結晶転移を起こさず、粗大粒子のない分散安定性の高い分散液を作製することが出来た。
【０２１３】
（感光体の作製）
感光体作製例１：
直径６０ｍｍのアルミニウムシリンダー（ＪＩＳ１０５０）に、下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、１９μｍの電荷輸送層を形成し、積層感光体を作製した（これを感光体１とする）。
【０２１４】
（下引き層塗工液）
酸化チタン（ＣＲ−ＥＬ：石原産業社製） ７０部
アルキッド樹脂（ベッコライトＭ６４０１−５０−Ｓ
（固形分５０％）、大日本インキ化学工業製） １５部
メラミン樹脂（スーパーベッカミンＬ−１２１−６０
（固形分６０％）、大日本インキ化学工業製） １０部
２−ブタノン １００部
【０２１５】
（電荷発生層塗工液）
前記の分散液１を用いた。
【０２１６】
（電荷輸送層塗工液）
ポリカーボネート（ユーピロンＺ３００：三菱ガス化学社製） １０部
下記構造式の電荷輸送物質 ７部
【化１３】

テトラヒドロフラン ８０部
【０２１７】
感光体作製例２：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液２を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体２とする）。
【０２１８】
感光体作製例３：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液３を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体３とする）。
【０２１９】
感光体作製例４：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液４を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体４とする）。
【０２２０】
感光体作製例５：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液５を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体５とする）。
【０２２１】
感光体作製例６：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液６を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体６とする）。
【０２２２】
感光体作製例７：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液７を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体７とする）。
【０２２３】
感光体作製例８：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液８を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体８とする）。
【０２２４】
感光体作製例９：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液９を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体９とする）。
【０２２５】
感光体作製例１０：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１０を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１０とする）。
【０２２６】
感光体作製例１１：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１１を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１１とする）。
【０２２７】
感光体作製例１２：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１２を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１２とする）。
【０２２８】
感光体作製例１３：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１３を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１３とする）。
【０２２９】
感光体作製例１４：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１４を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１４とする）。
【０２３０】
感光体作製例１５：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１５を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１５とする）。
【０２３１】
感光体作製例１６：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１６を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１６とする）。
【０２３２】
感光体作製例１７：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１７を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１７とする）。
【０２３３】
感光体作製例１８：
感光体作製例１における電荷発生層塗工液として、分散液１の代わりに分散液１８を用いた以外は、感光体作製例１と同様に感光体を作製した（これを感光体１８とする）。
【０２３４】
（実施例１７〜３２および比較例３〜４）
以上のように作製した感光体１〜１８を市販の普通紙複写機（リコー製：ｉｍａｇｉｏＭＦ４５５０）に搭載した。ＡＣ電源として複写機本体外に別の電源を用意した。
画像露光光源は７８０ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）とした。
帯電部材としては、第６図に示すような非接触近接配置方式の帯電ローラー（両端の非画像部には、厚さ５０μｍの絶縁テープを巻き付け、感光体表面と帯電ローラー表面の間に、５０μｍの空隙を有するように配置した）を用い、下記の帯電条件で画像を出力した。
帯電条件：
ＤＣバイアス：−９００Ｖ
ＡＣバイアス：２．３ｋＶ（ｐｅａｋｔｏｐｅａｋ）、周波数２ｋＨｚ
【０２３５】
書き込み率６％のチャートを用い、連続して５０００枚の印刷を行い、初期及び５０００枚後の画像を評価した。画像評価は、初期及び５０００枚後に白ベタ画像を出力し、地肌汚れの評価を行った（下記ランクで評価した）。また、４隅および中央に直径１ｃｍの黒丸（黒ベタ）を含むハーフトーン画像を初期及び５０００枚後に出力し画像評価を行った。
結果を表５に示す。
【０２３６】
【表５】

地汚れランク：
５：地汚れほとんど無し、４：わずかにあり、３：実使用限界レベル、２以下：実使用には耐えないレベル
【０２３７】
感光体作製例１９：
感光体作製例２における電荷輸送層塗工液を下記組成のものに変更した以外は、感光体作製例２と同様に感光体を作製した（これを感光体１９とする）。
【０２３８】
（電荷輸送層塗工液）
下記組成の高分子電荷輸送物質
（重量平均分子量：約１４００００） １０部
【化１４】

下記構造の添加剤 ０．５部
【化１５】

テトラヒドロフラン １００部
【０２３９】
感光体作製例２０：
感光体作製例２における電荷輸送層の膜厚を１７μｍとし、電荷輸送層上に下記組成の保護層塗工液を塗布乾燥し、２μｍの保護層を設けた以外は感光体作製例２と同様に感光体を作製した（これを感光体２０とする）。
【０２４０】
（保護層塗工液）
ポリカーボネート（ユーピロンＺ３００：三菱ガス化学社製） １０部
下記構造式の電荷輸送物質 ７部
【化１６】

アルミナ微粒子（比抵抗：２．５×１０^１２Ω・ｃｍ、
平均一次粒径：０．４μｍ） ４部
シクロヘキサノン ５００部
テトラヒドロフラン １５０部
【０２４１】
感光体作製例２１：
感光体作製例２における電荷輸送層の膜厚を１７μｍとし、電荷輸送層上に下記組成の保護層塗工液を塗布乾燥し、２μｍの保護層を設けた以外は感光体作製例２と同様に感光体を作製した（これを感光体２１とする）。
【０２４２】
（保護層塗工液）
下記構造式の高分子電荷輸送物質
（重量平均分子量：約１４００００） １７部
【化１７】

アルミナ微粒子（比抵抗：２．５×１０^１２Ω・ｃｍ、
平均一次粒径：０．４μｍ） ４部
シクロヘキサノン ５００部
テトラヒドロフラン １５０部
【０２４３】
感光体作製例２２：
感光体作製例２１における保護層塗工液中のアルミナ微粒子を以下のものに変更した以外は、感光体作製例２１と同様に感光体を作製した（これを感光体２２とする）。
酸化チタン微粒子（比抵抗：１．５×１０^１０Ω・ｃｍ、
平均一次粒径：０．５μｍ） ４部
【０２４４】
感光体作製例２３：
感光体作製例２１における保護層塗工液中のアルミナ微粒子を以下のものに変更した以外は、感光体作製例２１と同様に感光体を作製した（これを感光体２３とする）。
酸化錫−酸化アンチモン粉末（比抵抗：１０^６Ω・ｃｍ、
平均１次粒径０．４μｍ） ４部
【０２４５】
感光体作製例２４：
感光体作製例２における電荷輸送層塗工液を下記組成のものに変更した以外は、感光体作製例２と同様に感光体を作製した（これを感光体２４とする）。
【０２４６】
（電荷輸送層塗工液）
ポリカーボネート（ユーピロンＺ３００：
三菱ガス化学社製） １０部
下記構造式の電荷輸送物質 ７部
【化１８】

トルエン ８０部
【０２４７】
感光体作製例２５：
感光体作製例２における電荷輸送層塗工液を下記組成のものに変更した以外は、感光体作製例２と同様に感光体を作製した（これを感光体２５とする）。
【０２４８】
（電荷輸送層塗工液）
ポリカーボネート（ユーピロンＺ３００：
三菱ガス化学社製） １０部
下記構造式の電荷輸送物質 ７部
【化１９】

塩化メチレン ８０部
【０２４９】
感光体作製例２６：
感光体作製例２におけるアルミニウムシリンダー（ＪＩＳ１０５０）を以下の陽極酸化皮膜処理を行ない、次いで下引き層を設けずに、感光体作製例２と同様に電荷発生層、電荷輸送層を設け、感光体を作製した（これを感光体２６とする）。
【０２５０】
（陽極酸化皮膜処理）
支持体表面の鏡面研磨仕上げを行ない、脱脂洗浄、水洗浄を行なった後、液温２０゜Ｃ、硫酸１５ｖｏｌ％の電解浴に浸し、電解電圧１５Ｖにて３０分間陽極酸化皮膜処理を行なった。更に、水洗浄を行なった後、７％の酢酸ニッケル水溶液（５０゜Ｃ）にて封孔処理を行なった。その後純水による洗浄を経て、７μｍの陽極酸化皮膜が形成された支持体を得た。
【０２５１】
（実施例３３〜４１）
以上のように作製した感光体２、１９〜２６を市販の普通紙複写機（リコー製：ｉｍａｇｉｏＭＦ４５５０）に搭載した。ＡＣ電源として複写機（ポリゴン・ミラーによる画像書き込み）とした。
帯電部材としては、図６に示すような非接触近接配置方式の帯電ローラー（両端の非画像部には、厚さ５０μｍの絶縁テープを巻き付け、感光体表面と帯電ローラー表面の間に、５０μｍの空隙を有するように配置した）を用い、下記の帯電条件で画像を出力した。
帯電条件：
ＤＣバイアス：−９００Ｖ
ＡＣバイアス：２．３ｋＶ（ｐｅａｋｔｏｐｅａｋ）、周波数２ｋＨｚ
【０２５２】
書き込み率６％のチャートを用い、連続して１００００枚の印刷を行い、初期及び１００００枚後の画像を評価した。画像評価は、初期及び１００００枚後に白ベタ画像を出力し、地肌汚れの評価を行った（下記ランクで評価した）。また、４隅および中央に直径１ｃｍの黒丸（黒ベタ）を含むハーフトーン画像を初期及び１００００枚後に出力し画像評価を行った。
結果を表６に示す。
【０２５３】
【表６】

地汚れランク：
５：地汚れほとんど無し、４：わずかにあり、３：実使用限界レベル、２以下：実使用には耐えないレベル
【０２５４】
（実施例４２）
実施例３３の評価において、帯電条件を以下の条件に変更した以外は、実施例３３と同様に評価を行った。結果を表７に示す。
帯電条件：
ＤＣバイアス：−１７００Ｖ（感光体表面の未露光部電位が−９００Ｖになるように設定）
【０２５５】
（実施例４３）
実施例４２の評価において、使用する帯電ローラーを接触方式（ローラー材質等は同じであり、両端の絶縁テープを巻き付けない）に変更し、下記の帯電条件で画像を出力した。結果を表７に示す。
帯電条件：
ＤＣバイアス：−１６５０Ｖ（感光体表面の未露光部電位が−９００Ｖになるように設定）
【０２５６】
（実施例４４）
実施例４２の評価において、使用する帯電ローラーを接触方式（ローラー材質等は同じであり、両端の絶縁テープを巻き付けない）に変更し、下記の帯電条件で画像を出力した。結果を表７に示す。
帯電条件：
ＤＣバイアス：−９００Ｖ
ＡＣバイアス：２．３ｋＶ（ｐｅａｋｔｏｐｅａｋ）、周波数２ｋＨｚ
【０２５７】
（実施例４５）
実施例３３の評価において、絶縁テープの厚みを変えて、空隙を１５０μｍに変更した以外は実施例３３と同様に評価を行った。結果を表７に示す。
【０２５８】
（実施例４６）
実施例３３の評価において、絶縁テープの厚みを変えて、空隙を２５０μｍに変更した以外は実施例３３と同様に評価を行った。結果を表７に示す。
【０２５９】
（実施例４７）
実施例３３の評価において、使用する帯電部材としてスコロトロンチャージャーを用い、評価を行った。結果を表７に示す。この際、試験に用いる複写機はスコロトロンチャージャーを搭載できるように改造を施した。
帯電条件：
ＤＣバイアス：−６．５ｋＶ
【０２６０】
【表７】

地汚れランク：
５：地汚れほとんど無し、４：わずかにあり、３：実使用限界レベル、２以下：実使用には耐えないレベル
【０２６１】
感光体作製例２７：
感光体作製例１において使用した支持体を、直径３０ｍｍのアルミニウムシリンダー（ＪＩＳ１０５０）に変更した以外は感光体作製例１と同様に感光体を作製した（これを感光体２７とする）。
【０２６２】
感光体作製例２８：
感光体作製例２７において、使用した分散液１の代わりに分散液２を用いた以外は、感光体作製例２７と同様に感光体を作製した（これを感光体２８とする）。
【０２６３】
感光体作製例２９：
感光体作製例２７において、使用した分散液１の代わりに分散液７を用いた以外は、感光体作製例２７と同様に感光体を作製した（これを感光体２９とする）。
【０２６４】
（実施例４８および比較例５、６）
以上のように作製した感光体２７〜２９を、図８に示すような画像形成装置用カートリッジに装着し、図９に示すようなタンデム方式のフルカラー画像形成装置に搭載し（すべての画像形成要素に同じ感光体を搭載した）、画像露光光源を７８０ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、帯電部材として図６に示すような帯電ローラーの両端部に厚さ５０μｍの絶縁テープを巻き付けた近接配置用の帯電部材（感光体と帯電部材表面間の空隙が５０μｍ）を用い、下記の帯電条件で画像を出力した。
帯電条件：
ＤＣバイアス：−８００Ｖ
ＡＣバイアス：２．２ｋＶ（ｐｅａｋ ｔｏ ｐｅａｋ）、周波数：１．５ｋＨｚ
【０２６５】
書き込み率６％のフルカラーチャートを用い、連続して５０００枚の印刷を行い、初期及び５０００枚後の画像を評価した。画像評価は、初期及び５０００枚後に白ベタ画像を出力し、地肌汚れの評価を行った。また、色再現性を評価するチャートにて、５０００枚後の色再現性を評価した。結果を表８に示す。
【０２６６】
【表８】

地汚れランク：
５：地汚れほとんど無し、４：わずかにあり、３：実使用限界レベル、２以下：実使用には耐えないレベル
【０２６７】
続いて、本発明で使用するチタニルフタロシアニン結晶の特徴であるブラッグ角θの最低角ピークである７．３°について、公知材料の最低角７．５°と同一であるか否かについて検証する。
【０２６８】
（顔料作製例８）
顔料作製例１における結晶変換溶媒を塩化メチレンから２−ブタノンに変更した以外は、合成例１と同様に処理を行ない、チタニルフタロシアニン結晶を得た。
【０２６９】
図１１の場合と同様に、顔料作製例８で作製したチタニルフタロシアニン結晶のＸＤスペクトルを測定した。これを図１３に示す。図１３より、顔料作製例８で作製されたチタニルフタロシアニン結晶のＸＤスペクトルにおける最低角は、合成例１で作製されたチタニルフタロシアニンの最低角（７．３°）とは異なり、７．５°に存在することが判る。
【０２７０】
（測定例１）
顔料作製例１で得られた顔料（最低角７．３°）に特開昭６１−２３９２４８号公報に記載の顔料（最大回折ピークを７．５°に有する）と同様に作製したものを３重量％添加し、乳鉢で混合して、先程と同様にＸ線回折スペクトルを測定した。測定例１のＸ線回折スペクトルを図１４に示す。
【０２７１】
（測定例２）
顔料作製例８で得られた顔料（最低角７．５°）に特開昭６１−２３９２４８号公報に記載の顔料（最大回折ピークを７．５°に有する）と同様に作製したものを３重量％添加し、乳鉢で混合して、先程と同様にＸ線回折スペクトルを測定した。測定例２のＸ線回折スペクトルを図１５に示す。
【０２７２】
図１４のスペクトルにおいては、低角側に７．３°と７．５°の２つの独立したピークが存在し、少なくとも７．３°と７．５°のピークは異なるものであることが判る。一方、図１５のスペクトルにおいては、低角側のピークは７．５°のみに存在し、図１４のスペクトルとは明らかに異なっている。
以上のことから、本願発明のチタニルフタロシアニン結晶における最低角ピークである７．３°は、公知のチタニルフタロシアニン結晶における７．５°のピークとは異なるものであることが判る。
【０２７３】
【発明の効果】
本発明に依れば、結晶安定性が低く、微粒子化が困難であるチタニルフタロシアニン結晶の分散に鑑み、循環方式のビーズミル分散装置を用い、循環分散初期の分散室出口側の顔料目詰まりが起こる際に、分散室のローター回転数を落とし、特定の条件化で分散を行うことにより、結晶安定性と微粒子化のトレード・オフの関係を解消することが出来た。この結果、結晶安定性が高く（結晶転移の少ない）、粒子サイズの小さなチタニルフタロシアニン結晶を含む分散液の製造方法が提供される。この分散液は、保存安定性にも富み、成膜性が良好であるだけでなく、チタニルフタロシアニン結晶特有の特性を維持したままの状態で微粒子化が施される。このため、この分散液を用いて作製される感光体は、高感度を失うことなく、繰り返し使用によっても帯電性の低下と残留電位の上昇を生じない安定な電子写真感光体である。また、繰り返し使用によっても異常画像の発生の少ない電子写真感光体が提供される。
更に、高速プリントが可能で、異常画像の発生の少ない、安定な画像形成装置および画像形成装置用プロセスカートリッジが提供される。
【図面の簡単な説明】
【図１】本発明の分散液作製に用いられるビーズミル分散装置の概略図。
【図２】図１に示すビーズミル分散装置の分散室２の内部を示す図。
【図３】本発明の電子写真感光体の一例の構成例を示す図。
【図４】本発明の電子写真感光体の別の構成例を示す図。
【図５】本発明の画像形成プロセスを説明するための図。
【図６】画像形成装置の帯電部剤側にギャップ形成部材を配置した近接帯電機構の一例を示す図。
【図７】本発明の画像形成プロセスの別の例を説明するための図。
【図８】画像形成装置用プロセスカートリッジの１例を示す図。
【図９】カラー画像形成装置を説明するための概略図。
【図１０】顔料作成例一で得られた水ペーストの乾燥粉末のＸ線回析スペクトル。
【図１１】顔料１のＸ線回析スペクトル。
【図１２】比較例２（結晶の一部が結晶転移している）のＸ線回析スペクトル。
【図１３】顔料作製例８で作製したチタニルフタロシアニン結晶のＸ線回析スペクトル。
【図１４】実施例１のＸ線回析スペクトル。
【図１５】実施例２のＸ線回析スペクトル。
【符号の説明】
（図１および図２において）
１ モーター
２ 分散室
３ 流量計
４ 循環タンク
５ 循環ポンプ
６ 配管
７ 分散室固定台
１０ 分散メディア
１１ スリット
１２ 循環出口側配管
１３ 分散室の壁
１４ ローター
１５ 循環入り口側配管
１６ モーター
（図３および図４において）
３１ 導電性支持体
３５ 電荷発生層
３７ 電荷輸送層
３９ 保護層
（図６において）
２９ 感光体
３０ 帯電ローラー
３１ ギャップ形成部材
３２ 金属シャフト
３３ 画像形成領域
３４ 非画像形成領域
（図９において）
１Ｃ、１Ｍ、１Ｙ、１Ｋ 感光体
２Ｃ、２Ｍ、２Ｙ、２Ｋ 帯電部材
３Ｃ、３Ｍ、３Ｙ、３Ｋ レーザー光
４Ｃ、４Ｍ、４Ｙ、４Ｋ 現像部材
５Ｃ、５Ｍ、５Ｙ、５Ｋ クリーニング部材
６Ｃ、６Ｍ、６Ｙ、６Ｋ 画像形成要素
１０ 転写搬送ベルト
１１Ｃ、１１Ｍ、１１Ｙ、１１Ｋ 転写ブラシ
１２ 定着装置[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a dispersion using titanyl phthalocyanine crystals. The present invention also relates to an electrophotographic photosensitive member manufactured using the dispersion liquid prepared as described above, an image forming apparatus using the electrophotographic photosensitive member, and a process cartridge for the image forming apparatus.
Specifically, the method of preparing a dispersion containing titanyl phthalocyanine crystals having excellent dispersibility and crystal stability, and excellent handling properties, as well as excellent charging potential stability even after repeated use, and almost no increase in residual potential. The present invention relates to an electrophotographic photosensitive member with less occurrence of abnormal images such as dirt, an image forming apparatus using the electrophotographic photosensitive member, and a process cartridge for the image forming apparatus.
[0002]
[Prior art]
Organic pigments have been used as fillers for paints for a relatively long time. In particular, the richness of the color is an advantage not found in inorganic pigments. In recent years, as an application example of organic pigments, various materials have been produced since they have been spotlighted as materials for organic photoelectric conversion devices.
An electrophotographic photoreceptor containing an organic pigment is generally formed by a wet method. In particular, the dip coating method suitable for mass production is the majority of the method for producing a drum-shaped photoreceptor. The dip coating method is most suitable for mass-product manufacturing because the apparatus and method are simple. However, even when a small number of coatings are applied, the minimum amount of coating solution is required. This minimum required amount is extremely large as compared with other coating methods such as spraying method and nozzle coating method.
[0003]
Various methods for dispersing organic pigments have been proposed, but some limitations arise when producing a large amount of dispersion. That is, in a ball mill, a vibration mill, etc., the pot capacity determines the amount that can be produced. From such a viewpoint, as a dispersion system capable of producing a large amount of dispersion in one batch, a dispersion system having a part having dispersion ability (dispersion chamber) in the circulation system has been proposed [for example, JP 2000- No. 181104 (Patent Document 1)]. The term “dispersion” as used herein refers to a state where the pigment leaks sufficiently to the vehicle and reaches an equilibrium state while repeating aggregation and redispersion.
[0004]
Such a system is generally designed to have a small capacity of the dispersion chamber with respect to a large-capacity stock tank. This is for the purpose of compacting the system, saving energy, and reducing the number of distributed media used in the distributed room.
In such a dispersion system, in order to make the pigment particle diameter after dispersion fine, a bead mill type dispersion system using small-diameter beads in the dispersion chamber is often used.
[0005]
The smaller the diameter of the beads used here, the smaller the reached particle diameter of the dispersed pigment. Therefore, those having a diameter of 1 mm or less are generally used, and those having a diameter of 0.5 mm or less are preferably used [ JP, 2001-290292, A (patent documents 2)]. However, if it is too small, the wear of the beads becomes large, or the pigment particles before dispersion need to be made small, or the handling at the time of maintenance becomes worse. Beads (dispersion media) are used.
[0006]
In the preparation of the dispersion liquid, such small-diameter beads are present in the dispersion chamber, and the pigment particles are dispersed by the rotation of the rotor. At the same time, the liquid containing the pigment needs to pass through the dispersion chamber. In a dispersion method that is not a circulation method, the dispersion medium does not flow out of a dispersion chamber (for example, a pot of a ball mill). However, in a circulation method dispersion device (bead mill) as used in the present invention, a liquid containing a pigment is used. As the medium circulates, the dispersion media may flow out of the dispersion chamber. In order to prevent such a flow of the dispersion medium, a filter, a mesh or the like smaller than the diameter of the dispersion medium is installed on the outlet side of the dispersion chamber.
[0007]
The pore diameter of this filter or the like is set to about half of the minimum bead diameter to be used in consideration of the bead size distribution and the like. In the case of using a dispersion medium having a diameter exceeding 1 mm, there is not much problem because the hole diameter is about 500 μm, but when the bead diameter is smaller than about 1 mm (preferably 0.5 mm). In the initial stage of dispersion, the coarsely pulverized pigment particles may be clogged. Except in extreme cases, the clogged pigment gradually becomes finer in the dispersion chamber and eventually becomes smaller than the filter pore size and is discharged from the dispersion chamber. However, since the pigment clogged at the outlet side remains in the dispersion chamber for a time longer than a predetermined time corresponding to the flow rate, it gives a larger energy than the target dispersion energy. This results in excessive stress.
[0008]
Even in such a case, if an organic pigment having a very stable crystal form is used, the particle size is only reduced, and the particle size of the entire pigment is finally averaged (uniform) by further dispersion. ). However, when an organic pigment that does not have a very high crystal form stability is used, the crystal form changes to a stable form, and the desired crystal form is not maintained. As a result, the color of the pigment in the paint, or Various properties of the pigment are changed.
[0009]
Even if organic pigments are represented by the same structural formula, there are pigments having many crystal forms (crystal polymorphs). Such pigments have different molecular arrangements in crystals as an aggregate of molecules even if they have the same chemical structural formula at the molecular level. In such a case, the pigment color (absorption spectrum), particle morphology, and physical properties (characteristics) often change extremely depending on the crystal form.
When the absorption spectrum and particle morphology change in this way, for example, when used as a paint, the color changes and a coating film having a desired color cannot be formed. Further, when an organic pigment is used as a functional material, if a physical property value is different, an element using the same may not exhibit a desired function.
[0010]
The titanyl phthalocyanine crystal used in the present invention is a typical polymorphic organic pigment. Among them, there are cases in which specific characteristics are exhibited only when a specific crystal form is exhibited (when it is used as a charge generation material of a photoreceptor, it exhibits a highly sensitive photocarrier generation ability). A dispersion method and conditions that maintain the mold are necessary, but there are not many examples examined. In particular, a titanyl phthalocyanine crystal having a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα is an electrophotographic photoreceptor. As a charge generation material, it exhibits extremely high photocarrier generation efficiency, but since it is in a metastable state as a crystal state, it is easily transferred to another crystal type.
[0011]
When an excessive stress is applied to this crystal, the crystal transitions easily to a titanyl phthalocyanine crystal having a maximum diffraction peak at 26.3 ° as a diffraction peak with a Bragg angle 2θ, and this crystal has a carrier generation efficiency much higher than that of the previous crystal. Therefore, even if only a part of the crystal is transferred, if it is used as a charge generation material for a photoreceptor, problems such as a decrease in photosensitivity and an increase in residual potential during repeated use occur.
[0012]
Such a problem is attributed to the problem of crystal transition caused by clogging of the pigment on the circulation outlet side of the dispersion chamber. However, a circulation type bead mill disperser was used and a small diameter dispersion medium was used. In some cases, this is an unavoidable problem.
[0013]
In relation to such a point, Japanese Patent Application Laid-Open No. 2000-126638 (Patent Document 3) discloses a technique in which pigment particles used for wet dispersion are previously set to 1/2 or less of the diameter of a dispersion medium. In this method, since a pigment finer than the dispersion medium diameter is used, there is a possibility that the clogging of the pigment on the outlet side of the dispersion chamber is reduced. However, if the pigment stays in the dispersion chamber for a predetermined time or longer, there is still a possibility of causing crystal transition. In addition, it is necessary to dry-disperse the pigment particles in advance or to make the particle size uniform by using a sieve, etc., in order to cause loss of pigment, increase in cost due to an increase in processes, or to use fine pigments It is not necessarily suitable for mass production because the handleability deteriorates.
[0014]
In this way, when carrying out circulating bead mill dispersion using a small-diameter dispersion medium, it is easy to achieve both stable crystal form and finer particles in a short time without substantially reducing the dispersion efficiency. There was no means to solve the problem.
[0015]
On the other hand, in Example 1 of JP-A-11-249324 (Patent Document 4), in the preparation of a dispersion using a bead mill dispersion device, the rotor of the dispersion chamber is rotated before the circulation pump is operated, and then the circulation pump is turned on. An example is described in which the rotor speed is increased after operation. However, in this example, the rotational speed of the rotor is increased simultaneously with the operation of the circulation pump, and does not particularly mention clogging or crystal transition of titanyl phthalocyanine, and is related to the circulation flow rate. Is not described. Therefore, the rotational speed of the rotor is not reduced before the circulating flow rate reaches the predetermined amount as in the present invention, and the effect of the present invention is not obtained.
[0016]
[Patent Document 1]
JP 2000-181104 A
[Patent Document 2]
JP 2001-290292 A
[Patent Document 3]
JP 2000-126638 A
[Patent Document 4]
Japanese Patent Laid-Open No. 11-249324
[0017]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a dispersion containing titanyl phthalocyanine crystals having high crystal stability (small crystal transition) and small particle size. Specifically, a simple method is used to efficiently produce a large amount of dispersion by a simple method using a compact apparatus.
Another object of the present invention is to provide a stable electrophotographic photosensitive member that does not cause a decrease in chargeability and an increase in residual potential even after repeated use without losing high sensitivity. Another object of the present invention is to provide an electrophotographic photosensitive member that is less likely to cause abnormal images even when used repeatedly.
Furthermore, another object of the present invention is to provide an image forming apparatus and a process cartridge for the image forming apparatus that can perform high-speed printing, generate less abnormal images, and perform stable image formation.
[0018]
[Means for Solving the Problems]
As a result of examining the problems of the prior art, the present inventor has found that the outlet of the dispersion chamber as described above is used in order to prevent the crystal transition that occurs as a result of the pigment staying in the dispersion chamber longer than a predetermined time being given excessive dispersion energy. It has been found that it is important to eliminate the clogging in the above, or to make a condition that does not cause crystal transition even if clogging occurs to some extent.
[0019]
In the former method, it is necessary that all the pigment particles are smaller than the pore diameter of the filter or the like at the outlet of the dispersion chamber, pre-dispersion by a dry method as described in JP-A-2000-126638, Sorting with a sieve or the like is required, which is not preferable in the process. From this, the present inventor selected the latter method and searched for a method for realizing it.
[0020]
As a result, when clogging occurs at the outlet of the dispersion chamber, the required flow rate cannot be obtained even if liquid is fed by a pump or the like to flow a constant flow rate. Was found to be secured. It was also confirmed that the pigment particles that once passed through the filter at the outlet of the dispersion chamber never clogged. Although it varies depending on the size of the pigment used for dispersion, the amount of pigment used, etc., the time for the flow rate to drop is generally between a few minutes and a few tens of minutes. During this time, the pigment staying in the dispersion chamber will continue to give dispersion stress, which is considered to promote the crystal transition, and in order to reduce the dispersion stress during this time, the rotational speed of the rotor is reduced. It has been found that the crystal transition can be prevented by the treatment. Furthermore, when the rotational speed of the rotor is extremely low (about 500 rpm), the flow rate is reduced to about 20 minutes.
[0021]
Continuing dispersion at a rotational speed that does not cause crystal transition does not cause a problem when there is no time constraint, but it is not preferable because it leads to a decrease in dispersion efficiency when manufacturing is considered. Therefore, when the flow rate falls within a certain range, it is preferable to set the rotation speed quickly and to continue the circulation dispersion.
In order to make the above-mentioned method concrete, the present inventor has eliminated the drawbacks of the circulation and dispersion system generally used in recent years, found a stable dispersion preparation method, and completed the present invention.
[0022]
Further, the present invention was made for the purpose of improving the problems in producing a dispersion using a circulation type bead mill disperser capable of producing a large amount of dispersion with a compact dispersion apparatus. . Specifically, it solves the problems that occur when a dispersion medium having a smaller diameter is used in order to make the pigment particles contained in the dispersed liquid finer.
[0023]
By the way, in an electrophotographic photoreceptor using an organic pigment as a charge generation material, various characteristics are affected by the size of the charge generation material particles in the photosensitive layer. For example, in the photocarrier generation process, if the charge generation material particle size is large before the photocarrier generated by the charge generation material is transferred to the charge transport material, the probability of deactivation inside the particle increases. In addition, when the photocarrier is transferred to the charge transport material, if the pigment particles are large, the surface area is inevitably reduced, the contact amount between them is reduced, and the carrier injection efficiency is lowered. Furthermore, if the charge generation material particle size is large, the probability of coating film defects in the photosensitive layer (charge generation layer) is increased, and image defects based on this are likely to occur.
[0024]
For this reason, it is desired to reduce the particle size of the charge generation material in the photosensitive layer (charge generation layer) as much as possible. Since the photosensitive layer (charge generation layer) is usually formed by a wet coating method, in order to reduce the particle size of the charge generation material in the photosensitive layer, the particles of the charge generation material in the coating dispersion forming the photosensitive layer. It is necessary to reduce the size.
[0025]
Various dispersion methods have been proposed to reduce the particle size of the charge generation material in the dispersion for coating the photosensitive layer (charge generation layer) as described above. A major issue is how to pulverize and disperse secondary particles, which are structures, into primary particles. In these methods, by increasing the dispersion energy, extending the dispersion time, etc., it has been devised to make it as close as possible to the primary particles, but this primary particle size is determined at the stage of charge generation material synthesis, In a normal method, it is difficult to make the particles smaller than the primary particle size.
[0026]
On the other hand, a dispersion method capable of giving stronger dispersion energy than a method such as ball milling that has been used for a long time has been proposed, and a method for further breaking up primary particles has been developed in recent years. In such a case, even if the primary particles are somewhat large, the crystal itself is pulverized by enormous dispersion energy, thereby reducing the particle size of the charge generation material. Such a system can be said to be very suitable for a material having high crystal stability of the charge generation material to be used.
[0027]
However, in the case of an organic charge generating material, there are many cases where only a specific crystal form exhibits a specific function even if it is a material represented by the same chemical structural formula. Such a specific crystal type may easily change due to simple physical / mechanical stress in addition to chemical stress. When using such a material, as described above, giving excessive dispersion energy that pulverizes the primary particles themselves changes the crystal form prior to the action of pulverizing the particles. Will happen. As a result, there are many cases in which a material that exhibits a specific function is changed to a material that does not exhibit its function sufficiently.
[0028]
The titanyl phthalocyanine crystal used in the present invention is a polymorphic material, and the crystal form with particularly high photocarrier generation efficiency is a diffraction peak (±±) of Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 波長) of CuKα. 0.2 °), which is only a crystal having a maximum diffraction peak at 27.2 °, and other crystal-type materials have a function as a charge generating material, but a high speed required by the current electrophotographic process. However, it does not have characteristics that satisfy the requirements of high stability, reduction in diameter of the photoreceptor, and high stability during repeated use. Therefore, it can be said that the crystal form is a specific crystal form.
[0029]
However, this titanyl phthalocyanine crystal having a maximum diffraction peak at least 27.2 ° is a metastable state as a titanyl phthalocyanine crystal and is a material having low crystal stability. Therefore, excessive application of mechanical and physical stress as described above causes the crystal to be transferred to another crystal type which is a stable crystal type. In this way, it is a titanyl phthalocyanine crystal that has a high function as a charge generation material. However, when it is applied to an electrophotographic photosensitive member, there is a trade-off relationship between particle miniaturization and crystal stability. There was no way to solve this easily.
[0030]
In order to solve the problems as described above, the present inventor tried to analyze the pulverization / dispersion process of the titanyl phthalocyanine crystal and obtained the following knowledge.
[0031]
(1) Excessive dispersion energy causes crystal transition to proceed
That is, in the dispersion process of the titanyl phthalocyanine crystal, when dispersing to the target particle size, it is necessary to pulverize and disperse larger particles, but if excessive dispersion energy is given, Excessive energy becomes the energy of crystal transition.
[0032]
(2) The temperature rise at the time of dispersion is to advance the crystal transition.
The titanyl phthalocyanine crystal undergoes a crystal transition depending on the temperature. In addition, when the crystal transition is caused by excessive dispersion energy as in the above (1), the higher the temperature, the more the crystal transition is promoted. That is, in the step of dispersing the titanyl phthalocyanine crystal, partial temperature rise causes crystal transition or promotes crystal transition. Accordingly, a sufficient cooling mechanism is required in the portion where the dispersion energy is applied to the titanyl phthalocyanine crystal in the dispersion apparatus when the temperature rise is expected.
[0033]
Considering the above two points, in the method of dispersing by dispersing the dispersion liquid described in JP-A-4-372955 and the like in two directions, it is possible to suppress application of excessive energy. The temperature of the dispersion is inevitable even if the entire apparatus is cooled. This shows that this method is disadvantageous. Also, when using a high-pressure homogenizer as described in Japanese Patent Laid-Open No. 5-188614, it is difficult to suppress the temperature rise of the dispersion as in the case of the previous dispersion apparatus, and this method is not a good idea. Furthermore, since conventionally used ball mill type dispersion devices rotate the pot directly, it is basically difficult to provide a cooling mechanism. Therefore, this method is also not an advantageous method.
[0034]
On the other hand, the bead mill method used in the present invention can cool the dispersion chamber itself, and it is also possible to prevent the dispersion liquid from being heated at all by controlling the size and rotation speed of the dispersion chamber. Further, by using a circulation type bead mill dispersing device as will be described later, it is possible to suppress a slight increase in temperature by performing sufficient cooling in the circulation tank section. In addition, the scale can be made relatively large by this method.
From the above points, it can be said that the bead mill method is the most appropriate dispersion method as the dispersion method.
[0035]
Furthermore, the present inventor tried to analyze the pulverization / dispersion process of the titanyl phthalocyanine crystal when using the bead mill method, and obtained the following knowledge.
[0036]
(1) The final particle size after dispersion is determined by the size of the dispersion media diameter.
That is, the larger the dispersion media diameter used for dispersion, the higher the ability to grind coarse particles of titanyl phthalocyanine crystals (aggregates of primary particles). However, since a dispersion method such as a bead mill is a method having a high pulverizing ability from the beginning, it does not necessarily require the aid of the size (ie, weight) of the dispersion medium. Rather, it is important how much dispersive media can be packed per predetermined volume (how small the porosity is). It was found that the smaller the porosity, the smaller the titanyl phthalocyanine particle size after dispersion. Practically, if the dispersion media diameter is 1 mm or less (preferably 0.5 mm or less), it can be used sufficiently. However, the smaller the size is, the more the wear of the dispersion medium becomes, and the handling at the time of cleaning becomes very complicated. For this reason, there is a lower limit, and dispersion media of less than 0.1 mm should not be used.
[0037]
(2) When using small-diameter media, pigment clogging at the outlet side of the dispersion chamber is large.
In the case of carrying out circulation type dispersion, the loss is prevented by providing a filter or mesh of an appropriate size so that the dispersion medium does not flow out of the dispersion chamber. However, the smaller the dispersion media, the smaller the pore size, and the higher the probability that undispersed pigment particles will get caught in the filter and cause clogging. In the case of clogging, if a liquid is circulated by applying a constant pressure by a circulation pump or the like, pressure loss occurs and the circulation flow rate decreases (if it is severe, circulation becomes impossible). As a result, the pigment particles that cannot escape from the dispersion chamber remain in the dispersion chamber for a time longer than the passage time of the dispersion chamber according to the circulation flow rate, and thus receive excessive dispersion stress. As a result, a pigment having low crystal stability may cause crystal transition.
[0038]
(3) The crystal transition depends on the rotation speed of the rotor installed in the dispersion chamber.
Assuming that the dispersion chamber is clogged, an experiment was carried out to disperse under non-circulating conditions. It was found to cause metastasis. Also, from experiments in which the pigment concentration in the dispersion chamber was changed, this decrease was more pronounced as the concentration was higher, and as a result of clogging, the pigments that were sent to the dispersion chamber one after another caused the pigment in the dispersion chamber from a steady state. It was found that the crystal transition was promoted by increasing the concentration. In experiments where the number of rotations was changed, the dependence of the crystal transition on the rotor rotation speed was high, and the crystal transition speed could be suppressed even by slightly reducing the rotation, but by reducing it to 80% or less of the predetermined rotation speed. A certain effect was obtained. In addition, at a rotation speed of 30% or less, the pulverization ability is surely reduced, the circulation flow rate reduction time becomes long, and not only the dispersion efficiency is lowered, but also the possibility of crystal transition is increased. I understood.
As for the circulation flow rate, when 90% or more of the predetermined flow rate is reached when the liquid is fed by a circulation pump or the like, it is confirmed that most of the clogged pigment flows out without convection, I understood that clogging can be grasped by monitoring the flow rate.
[0039]
However, according to the present invention, the above-described problems are achieved by the following (1) to (22).
[0040]
(1) In a method of preparing a dispersion containing titanyl phthalocyanine crystals by a circulation type bead mill dispersion device using a dispersion medium having a diameter of 1 mm or less, dispersion is performed while measuring the circulation flow rate, and the circulation flow rate starts to be dispersed. A method for producing a dispersion characterized in that the rotational speed of a rotor installed in the dispersion chamber is lower than the rotational speed in a steady state of dispersion until reaching 90% or more of a predetermined amount.
[0041]
(2) From the start of dispersion until the circulating flow rate reaches 90% or more of a predetermined amount, the rotational speed of the rotor is set to 30 to 80% of the rotational speed in a steady state of dispersion. 1) A method for producing the dispersion described above.
[0042]
(3) The titanyl phthalocyanine crystal has a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα characteristic X-rays (wavelength 1.542 mm). The method for producing a dispersion according to (1) or (2).
[0043]
(4) The titanyl phthalocyanine crystal further has a Bragg angle 2θ diffraction peak (± 0.2 °) with respect to CuKα characteristic X-ray (wavelength 1.542Å), and further 9.4 °, 9.6 °, 24.0. Characterized by having a major peak at °, a peak at 7.3 ° as the lowest angled diffraction peak, and no peak in the range of 7.4 ° to less than 9.4 °. The method for producing a dispersion according to (3) above.
[0044]
(5) The method for producing a dispersion according to (3) or 4, wherein the titanyl phthalocyanine further has no peak at 26.3 °.
[0045]
(6) In any one of the above (1) to (5), in the method for preparing the dispersion, at least one selected from a ketone solvent, an ester solvent, and an ether solvent is used as a dispersion solvent. A method for producing the dispersion described in 1.
[0046]
(7) The method for producing a dispersion according to any one of (1) to (6) above, wherein a binder resin is used in combination with the dispersion of the titanyl phthalocyanine crystal in the method for producing the dispersion.
[0047]
(8) The method for producing a dispersion according to any one of the above (1) to (6), wherein water is used in combination for the dispersion of the titanyl phthalocyanine crystal in the method for producing the dispersion.
[0048]
(9) In an electrophotographic photosensitive member in which at least a charge generation layer and a charge transport layer are laminated on a conductive support, the charge generation layer is formed by the method according to any one of (1) to (8). An electrophotographic photosensitive member formed using the produced dispersion.
[0049]
(10) The electrophotographic photosensitive member according to (9), wherein the charge transport layer contains a polycarbonate having at least a triarylamine structure in the main chain and / or side chain.
[0050]
(11) The electrophotographic photosensitive member according to (9) or (10), wherein a protective layer is laminated on the charge transport layer in the electrophotographic photosensitive member.
[0051]
(12) The protective layer has a specific resistance of 10¹⁰The electrophotographic photosensitive member according to (11) above, which contains an inorganic pigment or metal oxide of Ω · cm or more.
[0052]
(13) The electrophotographic photosensitive member according to any one of (9) to (12), wherein the charge transport layer of the photosensitive member is formed using a non-halogen solvent.
[0053]
(14) The electrophotographic photoreceptor as described in (13) above, wherein at least one selected from cyclic ethers or aromatic hydrocarbons is used as the non-halogen solvent.
[0054]
(15) The electrophotographic photosensitive member according to any one of (9) to (14), wherein the surface of the conductive support of the electrophotographic photosensitive member is anodized.
[0055]
(16) In an image forming apparatus comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member, the electrophotographic photosensitive member according to any one of (9) to (15) An image forming apparatus which is a photoconductor.
[0056]
(17) In an image forming apparatus in which a plurality of image forming elements comprising at least a charging unit, an exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member are arranged, the electrophotographic photosensitive member according to the above (9) to (15) An image forming apparatus comprising the electrophotographic photosensitive member according to any one of the above.
[0057]
(18) The image forming apparatus according to (16) or (17), wherein a contact charging method is used for the charging unit.
[0058]
(19) The image forming apparatus according to (16) or (17), wherein a non-contact proximity arrangement method is used for the charging unit.
[0059]
(20) The image forming apparatus according to (19), wherein a gap between the charging member used for the charging unit and the electrophotographic photosensitive member is 10 μm or more and 200 μm or less.
[0060]
(21) The image forming apparatus according to any one of (16) to (20), wherein a voltage obtained by superimposing an AC voltage on a DC voltage is applied to the charging unit.
[0061]
(22) A process cartridge for an image forming apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (9) to (15). A process cartridge for an image forming apparatus.
[0062]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
First, a method for synthesizing a crude product of titanyl phthalocyanine crystal will be described.
Methods for synthesizing phthalocyanines have been known for a long time, and are described in “Phthacyanine Compounds” (1963), “The Phthalocyanines” (1983), JP-A-6-293769, etc. by Moser et al.
[0063]
For example, as a first method, a mixture of phthalic anhydrides, metals or metal halides and urea is heated in the presence or absence of a high boiling point solvent. In this case, a catalyst such as ammonium molybdate is used in combination as necessary.
[0064]
As a second method, phthalonitriles and metal halides are heated in the presence or absence of a high boiling point solvent. This method is used for phthalocyanines that cannot be produced by the first method, such as aluminum phthalocyanines, indium phthalocyanines, oxovanadium phthalocyanines, oxotitanium phthalocyanines, zirconium phthalocyanines, and the like.
[0065]
As a third method, phthalic anhydride or phthalonitrile and ammonia are first reacted to produce an intermediate such as 1,3-diiminoisoindoline, and then in a metal halide and a high boiling point solvent. This is a reaction method.
[0066]
As a fourth method, a phthalonitrile and a metal alkoxide are reacted in the presence of urea or the like. In particular, the fourth method does not cause chlorination (halogenation) to the benzene ring, and is a very useful method as a method for synthesizing an electrophotographic material.
[0067]
Next, a method for synthesizing amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) will be described.
This method is a method in which phthalocyanines are dissolved in sulfuric acid, diluted with water and reprecipitated, and what is called an acid paste method or an acid slurry method can be used.
[0068]
As a specific method, the above-mentioned synthetic crude product is dissolved in 10 to 50 times the amount of concentrated sulfuric acid, and if necessary, insoluble matter is removed by filtration or the like, and this is sufficiently cooled to 10 to 50 times the amount of sulfuric acid. Slowly throw it into water or ice water to reprecipitate titanyl phthalocyanine. The precipitated titanyl phthalocyanine is filtered, washed with ion-exchanged water and filtered, and this operation is sufficiently repeated until the filtrate becomes neutral. Finally, after washing with clean ion-exchanged water, filtration is performed to obtain a water paste having a solid content concentration of about 5 to 15 wt%.
[0069]
What was produced in this way was the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) used in the present invention. In this case, the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) is at least 7.0 to 7 as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.514Å) of CuKα. It is preferable to have a maximum diffraction peak at 5 °. In particular, the half width of the diffraction peak is more preferably 1 ° or more. Further, the major axis of the primary particles being 0.1 μm or less is important in forming finer primary particles in the subsequent crystal conversion step.
[0070]
Next, a crystal conversion method will be described.
Crystal transformation is carried out using at least the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) as a diffraction peak (± 0.2 °) at a Bragg angle 2θ with respect to a desired crystal form (characteristic X-ray of CuKα (wavelength 1.542 mm)). And a crystal form having a maximum diffraction peak at 27.2 °. In particular, among the crystal types, there are further main peaks at 9.4 °, 9.6 °, 24.0 °, and the lowest diffraction angle has a peak at 7.3 °, A titanyl phthalocyanine crystal having no peak in the range of 7.4 ° or more and less than 9.4 ° is preferably used, and a titanyl phthalocyanine crystal having no peak at 26.3 ° is particularly preferably used.
[0071]
As a specific method, the amorphous form of the titanyl phthalocyanine (low crystalline titanyl phthalocyanine) is mixed and stirred with an organic solvent in the presence of water without drying, thereby obtaining the crystal form.
In this case, any organic solvent can be used as long as the desired crystal form can be obtained, but tetrahydrofuran, toluene, methylene chloride, carbon disulfide, orthodichlorobenzene, 1,1, Good results are obtained when one selected from 2-trichloroethane is selected. These organic solvents are preferably used alone, but two or more of these organic solvents may be mixed or used in combination with other solvents.
[0072]
Subsequently, the crystallized titanyl phthalocyanine crystal is immediately filtered to be separated from the crystal conversion solvent. This filtration is performed by using a filter of an appropriate size. In this case, it is most appropriate to use vacuum filtration.
Thereafter, the separated titanyl phthalocyanine crystal is heat-dried as necessary. Any known dryer can be used for heat drying, but a blower-type dryer is preferred when the drying is performed in the atmosphere. Furthermore, drying under reduced pressure is a very effective means in order to increase the drying speed and to exhibit the effects of the present invention more remarkably. In particular, it is an effective means for a material that decomposes at a high temperature or changes its crystal form. In particular, it is effective to dry in a state where the degree of vacuum is higher than 10 mmHg.
[0073]
Here, the organic pigment having a high photocarrier generating ability as used in the present invention generally has a very strong cohesive force. When the crystals are filtered and fractionated and then dried as described above, the primary particles are aggregated to form secondary particles. This can be dispersed up to the primary particles by a normal dispersing apparatus, but it may not be dried if the crystal conversion solvent and the dispersion solvent of the dispersion subsequently used are the same. In that case, the wet cake of titanyl phthalocyanine crystals after filtration may be directly put into a dispersion solvent in which a binder resin is dissolved, if necessary, to carry out dispersion. This method makes it unnecessary to disperse a large lump of secondary particles, making the effect of the present invention even more remarkable.
[0074]
The titanyl phthalocyanine crystal thus obtained is extremely useful as a charge generating material for an electrophotographic photoreceptor. In particular, a crystal type having a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα has an extremely high photocarrier generation efficiency. It is what has. Among them, the diffraction peak (± 0.2 °) of Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα further has major peaks at 9.4 °, 9.6 °, and 24.0 °. The titanyl phthalocyanine crystal having a peak at 7.3 ° as the diffraction peak on the lowest angle side and having no peak in the range of 7.4 ° to less than 9.4 ° is extremely sensitive and repeats It is a good material with little decrease in chargeability in use. Further, the titanyl phthalocyanine crystal is more preferably one having no peak at 26.3 °, which makes it a better material as an electrophotographic photosensitive member.
[0075]
Next, a bead mill dispersing apparatus used for preparing the dispersion of the present invention will be described. The bead mill disperser is generally used in the production of paints and the like. As an example, the bead mill disperser can be exemplified as shown in FIG. Here, 1 is a motor, 2 is a dispersion chamber, 3 is a flow meter, 4 is a circulation tank, 5 is a circulation pump, 6 is piping, and 7 is a table for fixing the dispersion chamber. Although not shown, it is very effective in the present invention to provide a cooling jacket around the dispersion chamber 2 and the circulation tank 4 in FIG. The flow meter 3 in FIG. 1 may be installed anywhere in the circulation pipe, but it is desirable to install it near the circulation outlet side so as to detect clogging at an early stage.
[0076]
FIG. 2 shows the inside of the dispersion chamber 2 in FIG. Here, 10 is a dispersion medium, 11 is a slit for preventing the dispersion medium from flowing out, 12 is a pipe on the circulation outlet side, 13 is a wall of the dispersion chamber, 14 is a rotor, 15 is a pipe on the circulation inlet side, 16 is A shaft connected to a motor.
The capacity of the dispersion chamber 2 is a portion excluding the volume occupied by the shaft 16 and the rotor 14 in the volume of the dispersion chamber wall excluding the piping portion shown in FIG.
[0077]
The larger the rotor diameter shown in FIG. 2, the stronger the dispersion energy can be generated. It is also possible to change the dispersion energy by the rotational speed. However, as described above, the titanyl phthalocyanine crystal used in the present invention is a material that easily undergoes a crystal transition. However, if the rotor diameter is too large, it is necessary to reduce the number of rotations. There is a limit to the torque of the motor, and making the rotor diameter larger than necessary will cause uneven rotation and the operation of the disperser itself becomes unstable. For this reason, a suitable rotor diameter is 100 mm or less (preferably 50 mm or less), and 10 mm or more is suitable.
In addition, examples of the material constituting the rotor include various metals (for example, stainless steel) and various ceramics (for example, alumina and sirconia). However, in consideration of repeated wear resistance and contamination contamination in the dispersion liquid. Zirconia or partially stabilized zirconia in which a part of the composition is modified with yttrium or the like is preferably used.
[0078]
Regarding the dispersion medium, the outer diameter is desirably 1.0 mm or less, more preferably 0.5 mm or less. Moreover, since a specific surface area will become large when too small and problems, such as being easy to grind | polish, will arise, it is preferable that it is 0.1 mm or more. Examples of the material constituting the dispersion medium include the same material as that of the rotor, but zirconia or partially stabilized zirconia obtained by modifying a part of the composition with yttrium or the like is preferably used in the dispersion medium.
[0079]
The rotational speed of the rotor is not particularly limited. However, if the rotational speed is high, the amount of dispersed energy naturally increases, so that excess energy is given to the titanyl phthalocyanine crystal. Accordingly, in the case of a rotor having a diameter of 50 mm, approximately 3000 revolutions (r.p.m.) or less is appropriate.
[0080]
The dispersion time is inevitably selected from the pigment dispersion state. When the dispersion time is too short, although the pulverization of the particles proceeds, the dispersion stability may be inferior. The minimum time that an equilibrium state of dispersion and re-aggregation can be created should be ensured.
[0081]
Next, a method for producing a dispersion in the present invention will be described.
The pigment used is a titanyl phthalocyanine crystal as described above, preferably at least 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα. It is a titanyl phthalocyanine crystal having a crystal type having a maximum diffraction peak. More preferably, it has a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα, and further 9.4 °, 9 It has a major peak at .6 ° and 24.0 °, and a peak at 7.3 ° as the lowest diffraction peak, and a peak in the range from 7.4 ° to less than 9.4 °. It has no titanyl phthalocyanine crystal. In addition, titanyl phthalocyanine crystals having no peak at 26.3 ° are most suitable. These titanyl phthalocyanine crystals are put together with an organic solvent into the aforementioned bead mill dispersing device and dispersed to prepare a dispersion.
[0082]
The amount of dispersion solvent used, which determines the scale of the entire dispersion. The ratio can be arbitrarily set by enlarging the circulation tank. According to the study of the present inventor, the amount of dispersion energy relative to the weight of the titanyl phthalocyanine crystal (in other words, the dispersion force per unit time determined by the rotational speed of the rotor, the dispersion media diameter, etc., and the dispersion time) When the product) is in a proportional relationship, it was found that the dispersed state (attainable particle size, dispersion stability, etc.) is almost the same. Therefore, the weight of the titanyl phthalocyanine crystal used and the dispersion time are basically proportional. For this reason, when the scale is increased, the dispersion time should be increased accordingly.
However, there arises a problem that the dispersion time becomes too long and the apparatus becomes so large. Furthermore, it is preferable to provide a stirring device in the circulation tank. When the capacity of the circulation tank is increased, the stirring capacity must be increased accordingly, and the energy (electric power, etc.) used is increased. End up.
From the above, the ratio of the amount of use (volume) of the dispersion solvent to the capacity of the dispersion chamber is in a suitable range of about 5: 1 to 50: 1. More preferably, it is in the range of 10: 1 to 50: 1.
[0083]
As a dispersion solvent to be used, any commonly used organic solvent can be used as long as it can disperse titanyl phthalocyanine crystals. Examples include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin and the like. Among them, good results can be obtained by using one kind selected from a ketone solvent, an ester solvent, and an ether solvent. These organic solvents may be used alone or in combination.
[0084]
In addition, a binder resin is used in combination when necessary. The combined use of the binder resin is a very effective means because it significantly reduces the crystal transition rate of the titanyl phthalocyanine crystal. Usable binder resins include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N-vinylcarbazole, polyacrylamide, and polyvinyl benzal. Polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, and the like. In particular, polyvinyl butyral can be used most effectively.
The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of titanyl phthalocyanine crystal.
[0085]
Further, water is used in combination as needed when dispersing. The combined use of water is a very effective means because the crystal transition rate of the titanyl phthalocyanine crystal is remarkably lowered as in the case of the binder resin. When used, distilled water or ion-exchanged water from which impurities are sufficiently removed is preferably used. If it is used in a large amount, problems such as dispersibility decrease, separation from an organic solvent, and precipitation of a binder resin occur. For this reason, depending on the type of organic solvent used, in the case of a hydrophobic solvent, the upper limit of the water solubility of the organic solvent, and in the case of a hydrophilic solvent, 2 to 3 wt% with respect to the weight of the organic solvent The degree is the upper limit.
[0086]
As a dispersion procedure, an appropriate amount of an organic solvent, titanyl phthalocyanine crystal, a binder resin and water as necessary are put into a circulation tank 4 of an apparatus as shown in FIG. 1 and sufficiently stirred. When a binder resin or water is used in combination, it is desirable that the binder resin or water is mixed and dissolved in advance with an organic solvent in another apparatus. By stirring in the circulation tank 4, the titanyl phthalocyanine crystals are thoroughly mixed in the vehicle. When sufficiently mixed, the circulation pump 5 is operated to supply the dispersion liquid from the circulation tank 4 to the dispersion chamber 2. At this time, before mixing the organic solvent and the titanyl phthalocyanine crystal, the organic solvent is supplied to the dispersion chamber 2 in advance, and filling the dispersion chamber has an effect of preventing clogging at the outlet of the dispersion chamber. Big and effective means. In addition, rotating the rotor of the dispersion chamber before feeding the dispersion is also an effective and effective means for preventing clogging at the exit of the dispersion chamber.
[0087]
Next, although the titanyl phthalocyanine crystal contained in the dispersion supplied to the dispersion chamber 2 is dispersed, there is a time during which the predetermined flow rate cannot be obtained for the liquid feeding by a pump or the like in the initial state of dispersion. Therefore, in this specification, the “initial state of dispersion” means a state from the start of dispersion until the circulating flow rate reaches 90% or more of a predetermined amount. If dispersion is performed at a normal rotation speed during this time period, excessive dispersion energy is given to the titanyl phthalocyanine crystal, which causes crystal transition.
[0088]
The above time is considered to be until all of the titanyl phthalocyanine crystals subjected to dispersion pass once through the dispersion chamber, but the change in flow rate depending on clogging may vary from dispersion to dispersion. It is important to measure the flow rate at any time and perform dispersion with the rotor rotation speed reduced until the time when a flow rate of 90% or more of the predetermined flow rate flows. At this time, if the rotational speed is 80% or more of the steady state, the effect is small, and there is a possibility of causing crystal transition, and if it is 30% or less, the dispersion efficiency is extremely lowered and the residence time is increased. Resulting in. Therefore, in the initial state of dispersion, the rotational speed of the rotor is suitably in the range of 30 to 80% of the rotational speed in the steady state of dispersion. The steady state of dispersion refers to a state in which the flow rate obtained by pumping or the like maintains a range of about ± 10% of a predetermined amount, and indicates a state in which continuous operation of circulation dispersion is possible. is there.
[0089]
The end of the dispersion is carried out under predetermined conditions and managed according to the dispersion time, but it is preferable to carry out while confirming the state of the dispersion. For example, measurement of the particle diameter or formation of a thin film and observation of the state of the coating film with a microscope can be mentioned. In the former case, a minute amount of coarse particles may not be measured, and this is not an optimal method when used as a dispersion for forming a thin film such as a charge generation layer of a photoreceptor. Therefore, it is desirable to confirm with a sample equivalent to the actual use state.
[0090]
When such a predetermined dispersion time is completed, the dispersion liquid is then discharged. Generally, although there is of course an upper limit due to various restrictions, the higher the pigment concentration, the higher the dispersion efficiency. This can be explained by the high probability of contact with the distributed media. In general, the dispersion is performed in the range of about 5 to 15% as the pigment concentration. At such a high pigment concentration, a considerable loss occurs during removal of the dispersion. This problem is particularly noticeable when the circulation system is long. Usually, the concentration of the dispersion is different from the concentration of the dispersion, and the former is a higher concentration. Therefore, there is at least a dilution step before use. In circulation dispersion, performing dilution together with dispensing can increase the dispensing efficiency (recovery efficiency), and at the same time enables the dispersion device to be cleaned, which is very efficient. For simplicity, after the dispersion is completed, the dispersion liquid (raw solution) is dispensed with a feed pump or the like, and the dispenser with the pump is stopped, or the solvent for dilution is put into the circulation tank immediately before that, and the pump is again dispensed with the pump. . At this time, it is important not to circulate as much as possible. By discharging before returning to the circulation tank, the circulation system becomes clean and the efficiency of the discharge is increased.
As described above, a dispersion containing a titanyl phthalocyanine crystal is produced.
[0091]
Next, the electrophotographic photosensitive member of the present invention will be described with reference to the drawings.
FIG. 3 is a cross-sectional view showing the electrophotographic photosensitive member of the present invention. On the conductive support 31, a charge generation layer 35 mainly composed of a charge generation material and a charge transport layer mainly composed of a charge transport material. 37 is provided.
FIG. 4 is a cross-sectional view showing another structural example of the electrophotographic photosensitive member of the present invention, in which a protective layer 39 is laminated on the charge generation layer 35 and the charge transport layer 37.
[0092]
The conductive support 31 has a volume resistance of 10¹⁰Films having conductivity of Ω · cm or less, for example, metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, metal oxide such as tin oxide, indium oxide, etc. are deposited or sputtered. Or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. and surface after cutting, superfinishing, polishing, etc. after extruding and drawing them out Treated tubes and the like can be used. Further, an endless nickel belt or an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can also be used as the conductive support 31.
[0093]
Of these, a cylindrical support made of aluminum, which can be easily subjected to the anodic oxide film treatment, can be most preferably used. As used herein, aluminum includes both pure aluminum and aluminum alloys. Specifically, JIS A1000 series, 3000 series, and 6000 series aluminum or aluminum alloy is most suitable. The anodized film is obtained by anodizing various metals and various alloys in an electrolyte solution. Among them, a film called alumite obtained by anodizing aluminum or an aluminum alloy in an electrolyte solution is used in the present invention. Is most suitable for. In particular, it is excellent in preventing point defects (black spots, background stains) that occur when used in reversal development (negative / positive development).
[0094]
The anodizing treatment is performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, sulfamic acid. Of these, treatment with a sulfuric acid bath is most suitable. For example, sulfuric acid concentration: 10-20%, bath temperature: 5-25 ° C., current density: 1-4 A / dm²The treatment is carried out in the range of electrolytic voltage: 5 to 30 V, treatment time: about 5 to 60 minutes, but is not limited thereto. Since the anodic oxide film thus produced is porous and has high insulation, the surface is very unstable. For this reason, there is a change with time after fabrication, and the physical property value of the anodized film is likely to change. In order to avoid this, it is desirable to further seal the anodized film.
[0095]
Examples of the sealing treatment include a method of immersing the anodized film in an aqueous solution containing nickel fluoride and nickel acetate, a method of immersing the anodized film in boiling water, and a method of treating with pressurized steam. Among these, the method of immersing in the aqueous solution containing nickel acetate is the most preferable.
[0096]
Subsequent to the sealing treatment, the anodic oxide film is washed. The main purpose of this is to remove excess metal salts and the like attached by the sealing treatment. If this remains excessively on the surface of the support (anodized film), it not only adversely affects the quality of the coating film formed on this surface, but also generally low resistance components remain, resulting in the occurrence of soiling. It can also be a cause. The cleaning may be performed once with pure water, but is usually performed at another stage. At this time, it is preferable that the final cleaning liquid is as clean (deionized) as possible. Moreover, it is desirable to perform physical rubbing cleaning with a contact member in one of the other cleaning processes.
[0097]
The film thickness of the anodized film formed as described above is preferably about 5 to 15 μm. If it is too thin, the effect of the barrier property as an anodic oxide film is not sufficient, and if it is thicker than this, the time constant as an electrode becomes too large, resulting in the generation of residual potential and the response of the photoreceptor. There is a case.
[0098]
In addition, the conductive support 31 of the present invention can be used in which conductive powder is dispersed in a suitable binder resin and coated on the support. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
[0099]
Furthermore, it is made conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon (R) on a suitable cylindrical substrate. What provided the layer can also be used suitably as the electroconductive support body 31 of this invention.
[0100]
Next, the photosensitive layer will be described.
The charge generation layer 35 is a layer formed using the dispersion liquid mainly composed of the titanyl phthalocyanine crystal described above. Preferably, a crystalline titanyl phthalocyanine crystal having a maximum diffraction peak at 27.2 ° is used as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα. . In particular, among the crystal types, there are further major peaks at 9.4 °, 9.6 °, 24.0 °, and the lowest diffraction angle peak at 7.3 °, A titanyl phthalocyanine crystal having no peak in the range of 7.4 ° or more and less than 9.4 ° is preferably used, and a titanyl phthalocyanine crystal having no peak at 26.3 ° is particularly preferably used.
As the coating method of the dispersion, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used. The thickness of the charge generation layer 35 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.
[0101]
The charge transport layer 37 can be formed by dissolving or dispersing a charge transport material and a binder resin in a suitable solvent, and applying and drying the solution on the charge generation layer. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.
[0102]
Charge transport materials include hole transport materials and electron transport materials.
Examples of the charge transport material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
[0103]
Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.
[0104]
The binder resin is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, poly Vinylidene chloride, polyarate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin And thermoplastic or thermosetting resins such as alkyd resins.
[0105]
The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer is preferably about 5 to 100 μm. As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. Of these, non-halogen solvents such as cyclic ethers such as tetrohydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene are preferably used.
[0106]
When these non-halogen solvents are used as a coating solvent for the charge transport layer and titanyl phthalocyanine crystals are used as the charge generation material, there are cases where the desired photosensitivity cannot be obtained. When it is formed, this does not happen. The reason for this is presumed to be that micronization is progressing and crystal transition is small.
[0107]
In addition, a polymer charge transport material having a function as a charge transport material and a function of a binder resin is also preferably used for the charge transport layer. The charge transport layer composed of these polymer charge transport materials is excellent in wear resistance. As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, the polymer charge transport materials represented by the formulas (1) to (10) are favorably used, and these are exemplified below and specific examples are shown.
[0108]
[Chemical 1]

Where R₁, R₂, R₃Each independently represents a substituted or unsubstituted alkyl group or a halogen atom, R₄Is a hydrogen atom or a substituted or unsubstituted alkyl group, R₅, R₆Is a substituted or unsubstituted aryl group, o, p, q are each independently an integer of 0-4, k, j are compositions, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n Represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.
[Chemical 2]

R₁₀₁, R₁₀₂Each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO₂-, -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group) or
[Chemical Formula 3]

(A is an integer from 1 to 20, b is an integer from 1 to 2000, R₁₀₃, R₁₀₄Represents a substituted or unsubstituted alkyl group or aryl group. Where R₁₀₁And R₁₀₂, R₁₀₃And R₁₀₄May be the same or different.
[0109]
[Formula 4]

Where R₇, R₈Is a substituted or unsubstituted aryl group, Ar₁, Ar₂, Ar₃Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0110]
[Chemical formula 5]

Where R₉, R₁₀Is a substituted or unsubstituted aryl group, Ar₄, Ar₅, Ar₆Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0111]
[Chemical 6]

Where R₁₁, R₁₂Is a substituted or unsubstituted aryl group, Ar₇, Ar₈, Ar₉Are the same or different arylene groups, and p represents an integer of 1 to 5. X, k, j, and n are the same as in the case of equation (1).
[0112]
[Chemical 7]

Where R₁₃, R₁₄Is a substituted or unsubstituted aryl group, Ar₁₀, Ar₁₁, Ar₁₂Are the same or different arylene groups, X₁, X₂Represents a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j, and n are the same as in the case of equation (1).
[0113]
[Chemical 8]

Where R₁₅, R₁₆, R₁₇, R₁₈Is a substituted or unsubstituted aryl group, Ar₁₃, Ar₁₄, Ar₁₅, Ar₁₆Are the same or different arylene groups, Y₁, Y₂, Y₃Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. X, k, j, and n are the same as in the case of equation (1).
[0114]
[Chemical 9]

Where R₁₉, R₂₀Represents a hydrogen atom, a substituted or unsubstituted aryl group, and R₁₉And R₂₀May form a ring. Ar₁₇, Ar₁₈, Ar₁₉Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0115]
[Chemical Formula 10]

Where R₂₁Is a substituted or unsubstituted aryl group, Ar₂₀, Ar₂₁, Ar₂₂, Ar₂₃Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0116]
Embedded image

Where R₂₂, R₂₃, R₂₄, R₂₅Is a substituted or unsubstituted aryl group, Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇, Ar₂₈Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0117]
Embedded image

Where R₂₆, R₂₇Is a substituted or unsubstituted aryl group, Ar₂₉, Ar_{3 0}, Ar₃₁Represent the same or different arylene groups. X, k, j, and n are the same as in the case of equation (1).
[0118]
Further, as the polymer charge transport material used in the charge transport layer, in addition to the polymer charge transport material described above, in the state of the monomer or oligomer having an electron donating group at the time of film formation of the charge transport layer, A polymer having a two-dimensional or three-dimensional crosslinked structure is finally included by carrying out a curing reaction or a crosslinking reaction.
[0119]
A charge transport layer composed of a polymer having these electron donating groups or a polymer having a crosslinked structure is excellent in wear resistance. Usually, in the electrophotographic process, since the charging potential (unexposed portion potential) is constant, if the surface layer of the photoreceptor is worn by repeated use, the electric field strength applied to the photoreceptor increases accordingly. As the electric field strength increases, the occurrence frequency of scumming increases. Therefore, the high wear resistance of the photosensitive member is advantageous for scumming. The charge transport layer composed of a polymer having these electron donating groups is a polymer compound, so it has excellent film-forming properties and has a charge transport site compared to a charge transport layer composed of a low molecular weight dispersed polymer. It can be configured with high density and has excellent charge transport capability. For this reason, a photoreceptor having a charge transport layer using a polymer charge transport material can be expected to have a high speed response.
[0120]
Examples of the other polymer having an electron donating group include a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, and, for example, JP-A-3-109406 and JP-A-2000- It is also possible to use a crosslinked polymer having an electron-donating group as disclosed in JP-A-206723, JP-A No. 2001-34001, and the like. Also in this case, a material that can satisfy the above mobility can be used effectively.
[0121]
In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 37. As the plasticizer, those used as general plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30% by weight based on the binder resin.
As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount used is 0 to 0 with respect to the binder resin. 1% by weight is suitable.
[0122]
As the binder resin, the binder resin previously mentioned in the charge transport layer 37 may be used as it is, or the binder resin mentioned in the method for preparing the dispersion may be mixed and used. Of course, the polymer charge transport materials mentioned above can also be used favorably. The amount of the charge generation material with respect to 100 parts by weight of the binder resin is preferably 5 to 40 parts by weight, the amount of the charge transport material with respect to 100 parts by weight of the binder resin is preferably 1 to 190 parts by weight, and more preferably 50 to 150 parts by weight. It is.
[0123]
A single-layer photosensitive layer is formed by dip coating or spraying with a coating solution dispersed with a disperser using a solvent such as tetrahydrofuran, dioxane, dichloroethane, or cyclohexane together with a charge transport material, if necessary, with a charge generating material and a binder resin. It can be formed by coating with a coat or bead coat. The thickness of the single photosensitive layer is suitably about 5 to 100 μm.
[0124]
In the electrophotographic photosensitive member of the present invention, an undercoat layer can be provided between the conductive support 31 and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin.
Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
[0125]
These undercoat layers can be formed using an appropriate solvent and coating method as in the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, the undercoat layer of the present invention includes Al.₂O₃Anodic oxidation, organic materials such as polyparaxylylene (parylene), and SiO₂, SnO₂TiO₂, ITO, CeO₂A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.
[0126]
In the electrophotographic photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. In recent years, computers have been used on a daily basis, and there has been a demand for downsizing of the apparatus as well as high-speed output by a printer. Therefore, by providing a protective layer and improving the durability, it is possible to use the photosensitive member of the present invention with high sensitivity and no abnormal defects.
[0127]
Materials used for the protective layer include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, Polybutylene terephthalate, polycarbonate, polyarylate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polychlorinated Examples thereof include resins such as vinyl, polyvinylidene chloride, and epoxy resin. Of these, polycarbonate or polyarylate can be most preferably used.
[0128]
Other protective layers include fluorine resins such as polytetrafluoroethylene, silicone resins, and inorganic fillers such as titanium oxide, tin oxide, potassium titanate, and silica for the purpose of improving wear resistance. What disperse | distributed the filler etc. can be added.
[0129]
Among the filler materials used for the protective layer of the photoreceptor, examples of the organic filler material include fluororesin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder, and the like. Metals such as copper, tin, aluminum, indium, etc., metals such as silica, tin oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, antimony-doped tin oxide, tin-doped indium oxide Inorganic materials such as oxide and potassium titanate can be mentioned. In particular, it is advantageous to use an inorganic material among them from the viewpoint of the hardness of the filler. In particular, silica, titanium oxide, and alumina can be used effectively.
[0130]
The filler concentration in the protective layer varies depending on the type of filler used and also on the electrophotographic process conditions using the photoconductor, but the ratio of filler to the total solid content on the outermost layer side of the protective layer is preferably 5% by weight or more, preferably 10% by weight or more and 50% by weight or less, more preferably about 30% by weight or less is good.
[0131]
Moreover, the volume average particle diameter of the filler to be used is preferably in the range of 0.1 μm to 2 μm, and preferably in the range of 0.3 μm to 1 μm. In this case, if the average particle size is too small, the wear resistance is not sufficiently exhibited, and if it is too large, the surface property of the coating film is deteriorated or the coating film itself cannot be formed.
[0132]
In addition, unless otherwise indicated, the average particle diameter of the filler in this invention is a volume average particle diameter, and is calculated | required with the ultracentrifugal automatic particle size distribution measuring apparatus: CAPA-700 (made by Horiba Seisakusho). At this time, the particle size (Median system) corresponding to 50% of the cumulative distribution was calculated. In addition, it is important that the standard deviation of each particle measured simultaneously is 1 μm or less. If the standard deviation is larger than this, the particle size distribution may be too wide, and the effects of the present invention may not be obtained remarkably.
[0133]
Further, the pH of the filler used in the present invention greatly affects the resolution and the dispersibility of the filler.
One possible reason is that hydrochloric acid or the like remains in the filler, particularly the metal oxide, during production. When the remaining amount is large, the occurrence of image blur is unavoidable, and depending on the remaining amount, the dispersibility of the filler may be affected.
[0134]
Another reason is due to the difference in chargeability on the surface of the filler, particularly the metal oxide. Usually, particles dispersed in a liquid are charged positively or negatively, and ions having opposite charges gather to try to keep it electrically neutral, and an electric double layer is formed there. The dispersed state of particles is stabilized. The potential (zeta potential) gradually decreases with increasing distance from the particle, and the potential in a region that is sufficiently away from the particle and electrically neutral is zero. Therefore, as the absolute value of the zeta potential increases, the repulsive force of the particles increases, so that the stability increases, and as it approaches zero, it tends to aggregate and become unstable. On the other hand, the zeta potential varies greatly depending on the pH value of the system, and at a certain pH value, the potential becomes zero and has an isoelectric point. Therefore, the dispersion system is stabilized by increasing the absolute value of the zeta potential as far as possible from the isoelectric point of the system.
[0135]
In the configuration of the present invention, the filler having a pH at the isoelectric point of at least 5 is preferably from the viewpoint of image blur suppression, and the more basic the filler, the higher the effect. It was confirmed that there was. The filler having a high basic pH at the isoelectric point has a higher zeta potential when the system is acidic, so that dispersibility and stability thereof are improved.
Here, the pH of the filler in the present invention is the pH value at the isoelectric point from the zeta potential. At this time, the zeta potential was measured with a laser zeta potentiometer manufactured by Otsuka Electronics.
[0136]
Furthermore, as a filler that hardly causes image blur, a filler having high electrical insulation (specific resistance is 10%).¹⁰(Ω · cm or more) is preferable, and those having a filler pH of 5 or more and those having a dielectric constant of 5 or more can be used particularly effectively. In addition, a filler having a pH of 5 or more or a filler having a dielectric constant of 5 or more can be used alone, or two or more fillers having a pH of 5 or less and a filler having a pH of 5 or more can be mixed. It is also possible to use a mixture of two or more fillers having a dielectric constant of 5 or less and a filler having a dielectric constant of 5 or more. Among these fillers, α-type alumina, which has high insulation properties, high thermal stability, and high wear resistance, is a hexagonal close-packed structure, from the viewpoint of suppressing image blur and improving wear resistance. It is particularly useful.
[0137]
The specific resistance of the filler used in the present invention is defined as follows. Since the specific resistance value of a powder such as a filler varies depending on the filling rate, it is necessary to measure under certain conditions. In the present invention, the specific resistance value of the filler is measured using an apparatus having the same configuration as the measuring apparatus shown in FIG. 1 of JP-A-5-94049, FIG. 1 of JP-A-5-113688, and the like. This value was used. In the measuring device, the electrode area is 4.0 cm.²It is. Prior to the measurement, a load of 4 kg is applied to the electrode on one side for 1 minute, and the sample amount is adjusted so that the distance between the electrodes is 4 mm. At the time of measurement, the measurement is performed with the weight of the upper electrode (1 kg) loaded, and the applied voltage is measured at 100V. 10⁶The region above Ω · cm was measured with HIGH RESISTING METER (Yokogawa Hewlett Packard), and the region below it was measured with a digital multimeter (Fluk). The specific resistance value thus obtained is defined as the specific resistance value of the present invention.
[0138]
The dielectric constant of the filler was measured as follows. Using a cell similar to the measurement of the specific resistance as described above, after applying a load, the capacitance was measured, and the dielectric constant was determined from this. The capacitance was measured using a dielectric loss measuring device (manufactured by Ando Electric).
[0139]
Further, these fillers can be surface-treated with at least one kind of surface treatment agent, and it is preferable from the viewpoint of dispersibility of the fillers. Decreasing the dispersibility of the filler not only increases the residual potential, but also decreases the transparency of the coating, causes defects in the coating, and decreases the wear resistance. It can develop into a big problem.
[0140]
As the surface treatment agent, all conventionally used surface treatment agents can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler is preferable. For example, titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, higher fatty acids, etc., or mixed treatment of these with silane coupling agents, Al₂O₃TiO₂, ZrO₂, Silicone, aluminum stearate, etc., or a mixture thereof is more preferable from the viewpoint of filler dispersibility and image blur. The treatment with the silane coupling agent is strongly influenced by image blur, but the influence may be suppressed by performing a mixing treatment of the surface treatment agent and the silane coupling agent.
[0141]
The surface treatment amount varies depending on the average primary particle size of the filler used, but is preferably 3 to 30 wt%, more preferably 5 to 20 wt%. If the surface treatment amount is less than this, the filler dispersion effect cannot be obtained, and if it is too much, the residual potential is significantly increased.
[0142]
These filler materials may be used alone or in combination of two or more. The surface treatment amount of the filler is defined by the weight ratio of the surface treatment agent to be used with respect to the filler amount as described above.
These filler materials can be dispersed by using an appropriate disperser. Further, from the viewpoint of the transmittance of the protective layer, it is preferable that the filler used is dispersed to the primary particle level and has less aggregates.
[0143]
Further, the protective layer may contain a charge transport material for reducing residual potential and improving responsiveness. As the charge transport material, the materials described in the description of the charge transport layer can be used. When a low molecular charge transport material is used as the charge transport material, a concentration gradient in the protective layer may be provided. In order to improve wear resistance, it is an effective means to reduce the concentration of the surface side.
The concentration here refers to the ratio of the weight of the low molecular charge transporting material to the total weight of all the materials constituting the protective layer, and the concentration gradient is a gradient that lowers the concentration on the surface side in the above weight ratio. It shows that.
The use of a polymer charge transport material is very advantageous in terms of enhancing the durability of the photoreceptor.
[0144]
As a method for forming the protective layer, a normal coating method is employed. In addition, about 0.1-10 micrometers is suitable for the thickness of a protective layer. In addition to the above, a known material such as a-C or a-SiC formed by a vacuum thin film forming method can be used as the protective layer.
[0145]
As described above, the use of a polymer charge transport material for the photosensitive layer (charge transport layer) or the provision of a protective layer on the surface of the photoreceptor increases the durability (wear resistance) of each photoreceptor. In addition, when used in a tandem type full-color image forming apparatus as described later, a new effect not found in the monochrome image forming apparatus is also produced.
[0146]
In the case of a full-color image, various types of images are input, but on the contrary, a typical image may also be input. For example, the presence of a seal in a Japanese document or the like. Things like indicia are usually located towards the edge of the image area and the colors used are also limited. In a state in which a random image is always written, image writing, development, and transfer are performed on the photoconductor in the image forming element on average. When many image formations are repeated or only a specific image forming element is used, the durability balance is lost.
When a photoconductor having a low surface durability (physical / chemical / mechanical) is used in such a state, this difference becomes prominent and easily causes an image problem. On the other hand, when the photoconductor is made highly durable, the amount of such local change is small, and as a result, it becomes difficult to appear as a defect on the image, so that high durability is achieved and the stability of the output image is improved. This is very effective.
[0147]
In the electrophotographic photoreceptor of the present invention, a binder resin is generally used as a main component in the intermediate layer in which an intermediate layer can be provided between the photosensitive layer and the protective layer. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a normal coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.
[0148]
Next, the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 5 is a schematic diagram for explaining the image forming process and the image forming apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 5, the photoreceptor 1 is provided with a charge generation layer containing titanyl phthalocyanine crystals dispersed under a specific dispersion condition on a conductive support and a charge transport layer. For the charging member 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13, known means such as a corotron, a scorotron, a solid charger (solid state charger), and a charging roller are used. It is done.
[0149]
As the charging member, one that is in contact with or close to the photoreceptor 1 is preferably used. In addition, when charging the photosensitive member with the charging member, charging unevenness can be effectively reduced by charging the photosensitive member with an electric field in which an AC component is superimposed on a DC component on the charging member.
[0150]
The contact-type charging member here is a type in which the surface of the charging member is in contact with the surface of the photosensitive member, and includes a charging roller, a charging blade, and a charging brush. Among them, a charging roller and a charging brush are used favorably.
[0151]
Further, the charging member disposed in the vicinity is a type in which the charging member is disposed in a non-contact state so as to have a gap (gap) of 10 μm or more and 200 μm or less between the surface of the photosensitive member and the surface of the charging member. It is distinguished from known chargers typified by corotron and scorotron from the distance of the gap.
[0152]
The adjacently arranged charging member used in the present invention may have any shape as long as it has a mechanism capable of appropriately controlling the gap with the surface of the photoreceptor. For example, the rotation shaft of the photosensitive member and the rotation shaft of the charging member may be mechanically fixed so as to have an appropriate gap. Among them, using a charging member in the shape of a charging roller, a gap forming member is disposed at both ends of the non-image forming portion of the charging member, and only this portion is brought into contact with the surface of the photoreceptor, and the image forming region is disposed in a non-contact manner. Alternatively, the gap forming member at both ends of the non-photosensitive portion of the photoconductor is disposed, and only this portion is brought into contact with the surface of the charging member, and the image forming region is disposed in a non-contact manner, so that the gap can be stably stabilized. It is a method that can be maintained. In particular, the methods described in JP-A Nos. 2002-148904 and 2002-148905 can be used satisfactorily. An example of the proximity charging mechanism in which the gap forming member is arranged on the charging member side is shown in FIG.
[0153]
As the transfer means, the above charger can be generally used, but a combination of the transfer charger 10 and the separation charger 11 as shown in FIG. 5 is effective.
[0154]
An LD or LED is used as the light source of the image exposure unit 5. As a light source such as the static elimination lamp 2, general light emitting materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. . Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
[0155]
Such a light source or the like irradiates the photosensitive member with light by providing a transfer process, a static elimination process, a cleaning process, or a pre-exposure process using light irradiation in addition to the process shown in FIG.
[0156]
The toner developed on the photoreceptor 1 by the developing unit 6 is transferred to the transfer paper 9, but not all is transferred, and some toner remains on the photoreceptor 1. Such toner is removed from the photoreceptor by the fur brush 14 and the blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.
[0157]
When the electrophotographic photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.
[0158]
FIG. 7 shows another example of the image forming process according to the present invention. The photoreceptor 21 is formed by providing a charge generation layer containing a titanyl phthalocyanine crystal dispersed under a specific dispersion condition and a charge transport layer on a conductive support. Driven by driving rollers 22a and 22b, charging by charger 23, image exposure by light source 24, development (not shown), transfer using charger 25, exposure before cleaning by light source 26, cleaning by brush 27, by light source 28 Static elimination is repeated. In FIG. 7, light exposure for image exposure is performed on the photoreceptor 21 (of course, the support is translucent) from the support side. The image exposure source 24 is preferably an LD or an LED.
[0159]
The above-described image forming process illustrated exemplifies an embodiment of the present invention, and other embodiments are of course possible. For example, in FIG. 5, the pre-cleaning exposure is performed from the photosensitive layer side, but this may be performed from the translucent support side, or irradiation with static elimination light may be performed from the support side.
On the other hand, in the light irradiation process, image exposure, pre-cleaning exposure, and static elimination exposure are illustrated. In addition, pre-exposure exposure, pre-exposure of image exposure, and other known light irradiation processes are provided to light the photosensitive member. Irradiation can also be performed.
[0160]
The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. The process cartridge is an apparatus (part) that contains a photosensitive member and includes at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit.
There are many shapes and the like of the process cartridge, but a general example is shown in FIG. The photoreceptor 1 is provided with a charge generation layer containing a titanyl phthalocyanine crystal dispersed under a specific dispersion condition on a conductive support and a charge transport layer.
[0161]
FIG. 9 is a schematic diagram for explaining the tandem-type full-color image forming apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 9, reference numerals 1C, 1M, 1Y, and 1K denote drum-shaped photoconductors. The photoconductors 1C, 1M, 1Y, and 1K rotate in the direction of the arrow in the figure, and at least around the charging member 2C in the order of rotation. 2M, 2Y, 2K, developing members 4C, 4M, 4Y, 4K, and cleaning members 5C, 5M, 5Y, 5K are arranged.
[0162]
The charging members 2C, 2M, 2Y, and 2K are charging members that constitute a charging device for uniformly charging the surface of the photoreceptor. Laser beams 3C, 3M, 3Y, and 3K from an exposure member (not shown) are irradiated from the back side of the photoreceptor between the charging members 2C, 2M, 2Y, and 2K and the developing members 4C, 4M, 4Y, and 4K. Electrostatic latent images are formed at 1C, 1M, 1Y, and 1K.
[0163]
The four image forming elements 6C, 6M, 6Y, and 6K centering on the photoreceptors 1C, 1M, 1Y, and 1K are juxtaposed along the transfer conveyance belt 10 that is a transfer material conveyance unit. The transfer / conveying belt 10 contacts the photoreceptors 1C, 1M, 1Y, and 1K between the developing members 4C, 4M, 4Y, and 4K of the image forming units 6C, 6M, 6Y, and 6K and the cleaning members 5C, 5M, 5Y, and 5K. Transfer brushes 11 </ b> C, 11 </ b> M, 11 </ b> Y, and 11 </ b> K for applying a transfer bias are disposed on a surface (back surface) that is in contact with the back side of the transfer conveyance belt 10 on the photoconductor side.
Each of the image forming elements 6C, 6M, 6Y, and 6K is different in the color of the toner inside the developing device, and the others are the same in configuration.
[0164]
In the color image forming apparatus having the configuration shown in FIG. 9, the image forming operation is performed as follows.
First, in each of the image forming elements 6C, 6M, 6Y, and 6K, the photoreceptors 1C, 1M, 1Y, and 1K are charged by charging members 2C, 2M, 2Y, and 2K that rotate in the direction of the arrow (the direction along with the photoreceptor). Next, an electrostatic latent image corresponding to each color image to be created is formed by laser light 3C, 3M, 3Y, and 3K in an exposure unit (not shown) disposed inside the photoconductor.
[0165]
Next, the latent image is developed by the developing members 4C, 4M, 4Y, and 4K to form a toner image. The developing members 4C, 4M, 4Y, and 4K are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively, and the four photosensitive members 1C, 1M, and 1Y. The toner images of each color created on 1K are superimposed on the transfer paper.
[0166]
The transfer paper 7 is sent out from the tray by a paper feed roller 8, temporarily stopped by a pair of registration rollers 9, and sent to the transfer conveyance belt 10 in synchronism with the image formation on the photosensitive member. The transfer paper 7 held on the transfer conveyance belt 10 is conveyed, and the color toner images are transferred at the contact positions (transfer portions) with the photoconductors 1C, 1M, 1Y, and 1K. The toner image on the photoconductor is transferred onto the transfer paper 7 by an electric field formed from a potential difference between the transfer bias applied to the transfer brushes 11C, 11M, 11Y, and 11K and the photoconductors 1C, 1M, 1Y, and 1K. The
[0167]
Then, the recording paper 7 on which the four color toner images are passed through the four transfer portions is conveyed to the fixing device 12, where the toner is fixed, and is discharged to a paper discharge portion (not shown). In addition, the residual toner that is not transferred by the transfer unit and remains on the photosensitive members 1C, 1M, 1Y, and 1K is collected by the cleaning devices 5C, 5M, 5Y, and 5K.
[0168]
In the example of FIG. 9, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer sheet conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (6C, 6M, 6Y) other than black. Further, in FIG. 9, the charging member is in contact with the photosensitive member, but by providing an appropriate gap (about 10 to 200 μm) between them, the wear amount of both can be reduced and the charging member Less toner filming and good use.
[0169]
The image forming means as described above may be fixedly incorporated in a copying apparatus, facsimile, or printer, but each electrophotographic element may be incorporated in the apparatus in the form of a process cartridge. A process cartridge is a single device (part) that contains a photoconductor and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a neutralizing unit, and the like.
[0170]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight.
First, a specific synthesis example of a crystalline titanyl phthalocyanine pigment having a maximum diffraction peak with a Bragg angle 2θ of 27.2 ° ± 0.2 ° will be described.
[0171]
(Pigment production example 1)
292 parts of 1,3-diiminoisoindoline and 1800 parts of sulfolane are mixed, and 204 parts of titanium tetrabutoxide are added dropwise under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature between 170 ° C. and 180 ° C. After the completion of the reaction, the mixture was allowed to cool, and then the precipitate was filtered, washed with chloroform until the powder turned blue, then washed several times with methanol, further washed several times with hot water at 80 ° C., and dried. Crude titanyl phthalocyanine was obtained.
[0172]
60 parts of the obtained crude titanyl phthalocyanine pigment washed with hot water was stirred and dissolved in 1000 parts of 96% sulfuric acid at 3 to 5 ° C. and filtered. The obtained sulfuric acid solution was added dropwise to 35000 parts of ice water with stirring, the precipitated crystals were filtered, and then washed with water until the washing solution became neutral to obtain an aqueous paste of titanyl phthalocyanine pigment.
[0173]
To this water paste, 1500 parts of tetrahydrofuran was added and stirred at room temperature. When the dark blue color of the paste changed to light blue, the stirring was stopped and immediately filtered under reduced pressure. The crystals obtained on the filter were washed with tetrahydrofuran to obtain 98 parts of a pigment wet cake. This was dried under reduced pressure (5 mmHg) at 70 ° C. for 2 days to obtain 78 parts of titanyl phthalocyanine crystals. This is designated as Pigment 1.
[0174]
Part of the water paste obtained in Pigment Preparation Example 1 was dried at 80 ° C. under reduced pressure (5 mmHg) for 2 days to obtain a low crystalline titanyl phthalocyanine powder.
[0175]
X-ray diffraction spectra of the dry powder of the water paste obtained as described above and the titanyl phthalocyanine crystal (pigment 1) obtained in Pigment Preparation Example 1 were measured under the following conditions.
X-ray tube: Cu, voltage: 40 kV, current: 20 mA
Scanning speed: 1 ° / min Scanning range: 3 ° -40 ° Time constant: 2 seconds
[0176]
The X-ray diffraction spectrum of the dry powder of water paste is shown in FIG. 10, and the X-ray diffraction spectrum of Pigment 1 is shown in FIG.
[0177]
From FIG. 11, Pigment 1 has a maximum diffraction peak at 27.2 °, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °, and the diffraction at the lowest angle side. A titanyl phthalocyanine crystal having a crystal form having a peak at 7.3 °, no peak in the range of 7.4 ° to less than 9.4 °, and no peak at 26.3 °. I understand that there is.
[0178]
(Comparative Example 1)
A dispersion having the following composition was prepared by bead milling under the conditions shown below (this is referred to as Dispersion 1).
240 parts of titanyl phthalocyanine crystal (Pigment 1) prepared in Pigment Preparation Example 1
160 parts of polyvinyl butyral (manufactured by Sekisui Chemical: BX-1)
2-butanone 3600 parts
Using commercially available bead mill disperser (VMA-GETZMANN GMBH: DISPERMAT SL, rotor diameter 50 mm, dispersion chamber capacity 125 ml) zirconia balls 0.5 mm in diameter, all 2-butanone and pigment dissolved polyvinyl butyral The rotor rotation speed is 3000r. p. m. And dispersion for 300 minutes.
The flow rate when the number of revolutions of the liquid feeding motor was set to the scale 5 was 1 liter / min. However, in the initial dispersion state under the above conditions, the flow rate decreased to 0.3 liter / min for approximately 8 minutes. In this state, dispersion was performed for 300 minutes without changing the rotor rotational speed.
After the dispersion was completed, the mill base was discharged from the bead mill disperser, and further 10300 parts of 2-butanone was added, and all the mill base remaining in the disperser was discharged simultaneously with the dilution to prepare a dispersion.
[0179]
(Example 1)
In Comparative Example 1, while the circulating flow rate is decreasing, the rotor rotational speed is 1000 r. p. m. The dispersion was performed in the same manner as in Comparative Example 1 except that when the circulating flow rate became 0.9 liters / minute or more, the dispersion was returned to the predetermined number of revolutions (3000 rpm). Then, a dispersion liquid was prepared (this liquid dispersion is designated as dispersion liquid 2). At this time, the time during which the circulating flow rate is reduced to less than 90% of the predetermined flow rate is 13 minutes.
[0180]
(Example 2)
In Comparative Example 1, the rotor rotational speed 2300 r. p. m. The dispersion was performed in the same manner as in Comparative Example 1 except that when the circulating flow rate became 0.9 liters / minute or more, the dispersion was returned to the predetermined number of revolutions (3000 rpm). Then, a dispersion liquid was prepared (this liquid dispersion is referred to as dispersion liquid 3). At this time, the time during which the circulating flow rate is reduced to less than 90% of the predetermined flow rate is 10 minutes.
[0181]
(Example 3)
In Comparative Example 1, while the circulating flow rate is decreasing, the rotor rotational speed is 500 r. p. m. The dispersion was performed in the same manner as in Comparative Example 1 except that when the circulating flow rate became 0.9 liters / minute or more, the dispersion was returned to the predetermined number of revolutions (3000 rpm). Then, a dispersion liquid was prepared (this liquid dispersion is referred to as dispersion liquid 4). At this time, it took 20 minutes for the circulating flow rate to drop to less than 90% of the predetermined flow rate. At this time, the time during which the circulating flow rate is reduced to less than 90% of the predetermined flow rate is 9 minutes.
[0182]
(Example 4)
In Comparative Example 1, while the circulating flow rate is decreasing, the rotor rotational speed is 2500 r. p. m. The dispersion was performed in the same manner as in Comparative Example 1 except that when the circulating flow rate became 0.9 liters / minute or more, the dispersion was returned to the predetermined number of revolutions (3000 rpm). Then, a dispersion liquid was prepared (this liquid dispersion is designated as dispersion liquid 5).
[0183]
(Example 5)
In Example 1, except that the dispersion medium was changed to zirconia balls having a diameter of 0.8 mm, dispersion was performed in the same manner as in Example 1 to prepare a dispersion (this is referred to as Dispersion 6).
[0184]
(Comparative Example 2)
In Example 1, except that the dispersion medium was changed to a zirconia ball having a diameter of 1.5 mm, dispersion was performed in the same manner as in Example 1 to prepare a dispersion (this is referred to as Dispersion 7).
[0185]
Dispersions 1 to 7 produced as described above were evaluated as follows. The results are shown in Table 1. In addition, the rotation speed in a table | surface is a rotor rotation speed when the circulating flow volume is falling (in a dispersion | distribution initial state) (hereinafter the same).
・ Average particle size:
HORIBA, Ltd .: Volume average particle diameter was evaluated by CAPA700.
・ Observation of coarse particles:
The dispersion was applied to a slide glass to prepare a sample for observation. Subsequently, the coating film was observed with a commercially available optical microscope (50 to 100 times), and the presence or absence of coarse particles was observed.
X-ray diffraction spectrum:
The dispersion was dried and powdered, and the X-ray diffraction spectrum was measured in the same manner as described above.
・ Evaluation of film formability:
A film was formed on the cleaned aluminum plate by dip coating, and the state of the coating film was observed.
[0186]
[Table 1]

[0187]
FIG. 12 shows an X-ray diffraction spectrum when a part of the crystal has undergone crystal transition (Comparative Example 2). The arrow in the figure is a new peak (26.3 °) that is not observed in the crystal of FIG.
[0188]
(Example 6)
A dispersion was prepared in the same manner as in Example 1 except that the solvent used in the dispersion of Example 1 was changed from 2-butanone to n-butyl acetate (this is referred to as Dispersion 8).
[0189]
(Example 7)
A dispersion was prepared in the same manner as in Example 1 except that the solvent used in the dispersion of Example 1 was changed from 2-butanone to n-butanol (this is referred to as Dispersion 9).
[0190]
(Example 8)
A dispersion was prepared in the same manner as in Example 1 except that the composition of the dispersion in Example 1 was changed to the following composition (this is referred to as Dispersion 10).
240 parts of titanyl phthalocyanine crystal (Pigment 1) prepared in Pigment Preparation Example 1
160 parts of polyvinyl butyral (manufactured by Sekisui Chemical: BX-1)
Tetrahydrofuran 3600 parts
36 parts of ion exchange water
[0191]
Example 9
A dispersion was prepared in the same manner as in Example 8 except that ion-exchanged water was removed from the dispersion of Example 8 (this is referred to as Dispersion 11).
[0192]
(Example 10)
A dispersion was prepared in the same manner as in Example 1 except that polyvinyl butyral was removed from the dispersion of Example 1 (this is referred to as Dispersion 12).
[0193]
The dispersions 8 to 12 produced as described above were evaluated in the same manner as in the case of the dispersions 1 to 7. The results are shown in Table 2 together with the results of Example 1.
[0194]
[Table 2]

[0195]
As can be seen from Table 2, when 2-butanone (ketone solvent), n-butyl acetate (ester solvent), and tetrahydrofuran (ether solvent) are used as the dispersion solvent, a dispersion having good characteristics is obtained. However, when n-butanol (alcohol solvent), which is another solvent, was used, the dispersion stability was slightly inferior.
Moreover, when ion-exchange water was not added or when binder resin was not added, the case where it was inferior to crystal stability was recognized.
[0196]
(Pigment production example 2)
A pigment was prepared according to the method described in “Example 1” of JP-A-1-299874 (Patent No. 2512081). That is, the wet cake prepared in the previous pigment preparation example 1 was dried, 200 g of the dried product was added to 1000 g of polyethylene glycol, and sand milling was performed together with 20000 g of glass beads. After the crystal transition, the mixture was washed successively with dilute sulfuric acid and an aqueous ammonium hydroxide solution and dried to obtain a pigment (this is referred to as Pigment 2).
[0197]
(Pigment production example 3)
A pigment was prepared according to the method described in “Production Example 1” of JP-A-3-269064 (Patent No. 2854682). That is, after drying the wet cake prepared in Pigment Preparation Example 1, 200 g of the dried product was stirred in a mixed solvent of 2000 g of ion-exchanged water and 200 g of monochlorobenzene for 1 hour (50 ° C.), and then methanol and ion-exchanged water. It was washed and dried to obtain a pigment (this is referred to as Pigment 3).
[0198]
(Pigment production example 4)
A pigment was prepared according to the method described in “Production Example” of JP-A-2-8256 (Japanese Patent Publication No. 7-91486). That is, 196 g of phthalodinitrile and 1500 ml of 1-chloronaphthalene are stirred and mixed, and 44 ml of titanium tetrachloride is added dropwise under a nitrogen stream. After completion of the dropping, the temperature was gradually raised to 200 ° C., and the reaction was carried out by stirring for 3 hours while maintaining the reaction temperature between 200 ° C. and 220 ° C. After completion of the reaction, the mixture was allowed to cool to 130 ° C. and filtered while hot, then washed with 1-chloronaphthalene until the powder turned blue, then washed several times with methanol, and further with hot water at 80 ° C. After washing twice, it was dried to obtain a pigment (this is referred to as Pigment 4).
[0199]
(Pigment preparation example 5)
A pigment was prepared according to the method described in “Synthesis Example 1” in JP-A No. 64-17066 (Japanese Patent Publication No. 7-97221). That is, 200 parts of α-type TiOPc was subjected to crystal conversion treatment at 100 ° C. for 10 hours with a sand grinder together with 400 g of sodium chloride and 200 g of acetophenone. This was washed with ion-exchanged water and methanol, purified with dilute sulfuric acid aqueous solution, washed with ion-exchanged water until the acid content disappeared, and then dried to obtain a pigment (this is referred to as Pigment 5).
[0200]
(Pigment preparation example 6)
A pigment was prepared according to the method described in “Example 1” of JP-A-11-5919 (Japanese Patent No. 3003664). That is, 204 parts of O-phthalodinitrile and 76 parts of titanium tetrachloride were heated and reacted in 500 parts of quinoline at 200 ° C. for 2 hours, the solvent was removed by steam distillation, 2% aqueous chloride solution, followed by 2% hydroxylation. The resulting solution was purified with an aqueous sodium solution, washed with methanol and N, N-dimethylformamide, and then dried to obtain titanyl phthalocyanine. 200 parts of this titanyl phthalocyanine is dissolved little by little in 40 parts of 98% sulfuric acid at 5 ° C., and the mixture is stirred for about 1 hour while maintaining the temperature at 5 ° C. or less. Subsequently, the sulfuric acid solution is slowly poured into 8000 parts of ice water stirred at high speed, and the precipitated crystals are filtered. The crystals are washed with distilled water until no acid remains, and a wet cake is obtained. The cake was stirred in 10000 parts of THF for about 5 hours, filtered, washed with THF and dried to obtain a pigment (this is referred to as Pigment 6).
[0201]
(Pigment preparation example 7)
A pigment was prepared according to the method described in “Synthesis Example 2” of JP-A-3-255456 (Patent No. 3005052). That is, 400 parts of the wet cake prepared in Pigment Preparation Example 1 was mixed with 600 parts of sodium chloride and 280 parts of diethylene glycol, and milled for 60 hours with an automatic mortar under heating at 80 ° C. Next, sufficient washing was performed to completely remove sodium chloride and diethylene glycol contained in the treated product. After drying this under reduced pressure, 8000 parts of cyclohexanone and glass beads having a diameter of 1 mm were added, and the mixture was treated with a sand mill for 30 minutes to obtain a pigment (hereinafter referred to as pigment 7).
[0202]
The pigments 2 to 7 prepared in the above pigment preparation examples 2 to 7 were measured for X-ray diffraction spectra by the same method as described above, and confirmed to be the same as the spectra described in the respective publications. Table 3 shows the characteristics of each X-ray diffraction spectrum and the peak position of the X-ray diffraction spectrum of the pigment obtained in Pigment Preparation Example 1.
[0203]
[Table 3]

[0204]
(Example 11)
A dispersion was prepared in the same manner as in Example 1 except that pigment 2 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 13).
[0205]
(Example 12)
A dispersion was prepared in the same manner as in Example 1 except that pigment 3 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 14).
[0206]
(Example 13)
A dispersion was prepared in the same manner as in Example 1 except that pigment 4 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 15).
[0207]
(Example 14)
A dispersion was prepared in the same manner as in Example 1 except that pigment 5 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 16).
[0208]
(Example 15)
A dispersion was prepared in the same manner as in Example 1 except that pigment 6 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 17).
[0209]
(Example 16)
A dispersion was prepared in the same manner as in Example 1 except that pigment 7 was used instead of the titanyl phthalocyanine crystal (pigment 1) used in Example 1 (these are referred to as dispersion 18).
[0210]
Dispersions 13 to 18 produced as described above were evaluated in the same manner as in Example 1, and are shown in Table 4 together with the results of Example 1.
[0211]
[Table 4]

[0212]
As can be seen from Table 4, even when a titanyl phthalocyanine crystal having a crystal form different from that of the pigment 1 is used, dispersion is performed to control the rotor rotational speed until the circulation flow rate reaches an appropriate region in the initial dispersion state. As a result, it was possible to produce a dispersion having high dispersion stability without causing crystal transition and without coarse particles.
[0213]
(Production of photoconductor)
Photoconductor Preparation Example 1:
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition were sequentially applied and dried on an aluminum cylinder (JIS1050) having a diameter of 60 mm, and an undercoat layer of 3.5 μm, A 0.2 μm charge generation layer and a 19 μm charge transport layer were formed to produce a laminated photoreceptor (this is referred to as “photoreceptor 1”).
[0214]
(Undercoat layer coating solution)
Titanium oxide (CR-EL: Ishihara Sangyo Co., Ltd.) 70 parts
Alkyd resin (Beckolite M6401-50-S
(Solid content 50%), Dainippon Ink & Chemicals) 15 parts
Melamine resin (Super Becamine L-121-60
(Solid content 60%), manufactured by Dainippon Ink & Chemicals) 10 parts
2-butanone 100 parts
[0215]
(Charge generation layer coating solution)
The above dispersion 1 was used.
[0216]
(Charge transport layer coating solution)
Polycarbonate (Iupilon Z300: manufactured by Mitsubishi Gas Chemical Company) 10 parts
7 parts of charge transport material with the following structural formula
Embedded image

80 parts of tetrahydrofuran
[0217]
Photoconductor preparation example 2:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 2 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 2). ).
[0218]
Photoconductor Preparation Example 3:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 3 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 3). ).
[0219]
Photoconductor Preparation Example 4:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 4 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 4). ).
[0220]
Photoconductor Preparation Example 5:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion Liquid 5 was used instead of Dispersion Liquid 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 5). ).
[0221]
Photoconductor Preparation Example 6:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 6 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 6). ).
[0222]
Photoconductor Preparation Example 7:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 7 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 7). ).
[0223]
Photoconductor Preparation Example 8:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 8 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 8). ).
[0224]
Photoconductor Preparation Example 9:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 9 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 9). ).
[0225]
Photoconductor Preparation Example 10:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 10 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 10). ).
[0226]
Photoconductor Preparation Example 11:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 11 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 11). ).
[0227]
Photoconductor Preparation Example 12:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 12 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this photoconductor is referred to as Photoconductor 12). ).
[0228]
Photoconductor Preparation Example 13:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 13 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 13). ).
[0229]
Photoconductor Preparation Example 14:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 14 was used instead of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this photoconductor is referred to as Photoconductor 14). ).
[0230]
Photoconductor Preparation Example 15:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 15 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 15). ).
[0231]
Photoconductor Preparation Example 16:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the dispersion liquid 16 was used instead of the dispersion liquid 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is referred to as Photoconductor 16). ).
[0232]
Photoconductor Preparation Example 17:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that Dispersion 17 was used in place of Dispersion 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is Photoconductor 17). ).
[0233]
Photoconductor Preparation Example 18:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the dispersion liquid 18 was used in place of the dispersion liquid 1 as the charge generation layer coating solution in Photoconductor Preparation Example 1 (this is referred to as Photoconductor 18). ).
[0234]
(Examples 17 to 32 and Comparative Examples 3 to 4)
The photoreceptors 1 to 18 produced as described above were mounted on a commercially available plain paper copying machine (manufactured by Ricoh: imagioMF4550). As an AC power source, another power source was prepared outside the copying machine main body.
The image exposure light source was a 780 nm semiconductor laser (image writing by a polygon mirror).
As the charging member, a non-contact proximity arrangement type charging roller as shown in FIG. 6 (50 μm thick insulating tape is wound around the non-image portions at both ends, and 50 μm between the surface of the photoreceptor and the charging roller surface. The image was output under the following charging conditions.
Charging conditions:
DC bias: -900V
AC bias: 2.3 kV (peak toppeak), frequency 2 kHz
[0235]
Using a chart with a writing rate of 6%, 5000 sheets were continuously printed, and images at the initial stage and after 5000 sheets were evaluated. In the image evaluation, a white solid image was output at the initial stage and after 5000 sheets, and the background stain was evaluated (evaluated by the following rank). In addition, halftone images including black circles (solid black) having a diameter of 1 cm at the four corners and the center were output at the initial stage and after 5000 sheets for image evaluation.
The results are shown in Table 5.
[0236]
[Table 5]

Dirt rank:
5: Almost no dirt, 4: Slightly, 3: Actual use limit level, 2 or less: Level that cannot withstand actual use
[0237]
Photoconductor Preparation Example 19:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the charge transport layer coating solution in Photoconductor Preparation Example 2 was changed to one having the following composition (this is referred to as Photoconductor 19).
[0238]
(Charge transport layer coating solution)
Polymer charge transport material with the following composition
(Weight average molecular weight: about 140000) 10 parts
Embedded image

0.5 parts of additive with the following structure
Embedded image

Tetrahydrofuran 100 parts
[0239]
Photoconductor Preparation Example 20:
Similar to Photoconductor Preparation Example 2, except that the thickness of the charge transport layer in Photoconductor Preparation Example 2 was 17 μm, a protective layer coating solution having the following composition was applied and dried on the charge transport layer, and a protective layer of 2 μm was provided. A photoconductor was prepared (this photoconductor 20).
[0240]
(Protective layer coating solution)
Polycarbonate (Iupilon Z300: manufactured by Mitsubishi Gas Chemical Company) 10 parts
7 parts of charge transport material with the following structural formula
Embedded image

Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm,
(Average primary particle size: 0.4 μm) 4 parts
500 parts of cyclohexanone
150 parts of tetrahydrofuran
[0241]
Photoconductor Preparation Example 21:
Similar to Photoconductor Preparation Example 2, except that the thickness of the charge transport layer in Photoconductor Preparation Example 2 was 17 μm, a protective layer coating solution having the following composition was applied and dried on the charge transport layer, and a protective layer of 2 μm was provided. A photoreceptor was prepared (this is referred to as photoreceptor 21).
[0242]
(Protective layer coating solution)
Polymer charge transport material of the following structural formula
(Weight average molecular weight: about 140000) 17 parts
Embedded image

Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm,
(Average primary particle size: 0.4 μm) 4 parts
500 parts of cyclohexanone
150 parts of tetrahydrofuran
[0243]
Photoconductor Preparation Example 22:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 21 except that the alumina fine particles in the protective layer coating solution in Photoconductor Preparation Example 21 were changed to the following (this is referred to as Photoconductor 22).
Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm,
(Average primary particle size: 0.5 μm) 4 parts
[0244]
Photoconductor Preparation Example 23:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 21 except that the alumina fine particles in the protective layer coating solution in Photoconductor Preparation Example 21 were changed to the following (this is referred to as Photoconductor 23).
Tin oxide-antimony oxide powder (specific resistance: 10⁶Ω · cm,
Average primary particle size 0.4μm) 4 parts
[0245]
Photoconductor Preparation Example 24:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the charge transport layer coating solution in Photoconductor Preparation Example 2 was changed to one having the following composition (this is referred to as Photoconductor 24).
[0246]
(Charge transport layer coating solution)
Polycarbonate (Iupilon Z300:
(Mitsubishi Gas Chemical Co., Ltd.) 10 parts
7 parts of charge transport material with the following structural formula
Embedded image

80 parts of toluene
[0247]
Photoconductor Preparation Example 25:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the charge transport layer coating solution in Photoconductor Preparation Example 2 was changed to one having the following composition (this is referred to as Photoconductor 25).
[0248]
(Charge transport layer coating solution)
Polycarbonate (Iupilon Z300:
(Mitsubishi Gas Chemical Co., Ltd.) 10 parts
7 parts of charge transport material with the following structural formula
Embedded image

80 parts of methylene chloride
[0249]
Photoconductor Preparation Example 26:
The aluminum cylinder (JIS 1050) in photoreceptor preparation example 2 is subjected to the following anodic oxide film treatment, and then a charge generation layer and a charge transport layer are provided in the same manner as in photoreceptor preparation example 2 without providing an undercoat layer. (This is referred to as a photoreceptor 26).
[0250]
(Anodized film treatment)
The surface of the support was mirror-polished, degreased and washed with water, then immersed in an electrolytic bath at a liquid temperature of 20 ° C. and sulfuric acid of 15 vol%, and an anodized film treatment was performed at an electrolysis voltage of 15 V for 30 minutes. Further, after washing with water, sealing treatment was performed with a 7% nickel acetate aqueous solution (50 ° C.). Thereafter, the substrate was washed with pure water to obtain a support on which a 7 μm anodic oxide film was formed.
[0251]
(Examples 33 to 41)
The photoconductors 2 and 19 to 26 produced as described above were mounted on a commercially available plain paper copying machine (manufactured by Ricoh: imagioMF4550). A copying machine (image writing by a polygon mirror) was used as an AC power source.
As the charging member, a charging roller of a non-contact proximity arrangement system as shown in FIG. 6 (50 μm thick insulating tape is wound around the non-image portions at both ends, and a 50 μm thickness is interposed between the surface of the photoreceptor and the charging roller surface. An image was output under the following charging conditions.
Charging conditions:
DC bias: -900V
AC bias: 2.3 kV (peak toppeak), frequency 2 kHz
[0252]
Using a chart with a writing rate of 6%, 10,000 sheets were continuously printed, and images at the initial stage and after 10,000 sheets were evaluated. In the image evaluation, a white solid image was output at the initial stage and after 10,000 sheets, and the background stain was evaluated (evaluated by the following rank). In addition, a halftone image including black circles (solid black) having a diameter of 1 cm at the four corners and the center was output at the initial stage and after 10,000 sheets for image evaluation.
The results are shown in Table 6.
[0253]
[Table 6]

Dirt rank:
5: Almost no dirt, 4: Slightly, 3: Actual use limit level, 2 or less: Level that cannot withstand actual use
[0254]
(Example 42)
In the evaluation of Example 33, the evaluation was performed in the same manner as in Example 33 except that the charging conditions were changed to the following conditions. The results are shown in Table 7.
Charging conditions:
DC bias: -1700 V (set so that the potential of the unexposed area on the surface of the photoreceptor becomes -900 V)
[0255]
(Example 43)
In the evaluation of Example 42, the charging roller to be used was changed to a contact method (the roller material is the same and the insulating tape at both ends is not wound), and an image was output under the following charging conditions. The results are shown in Table 7.
Charging conditions:
DC bias: −1650 V (set so that the potential of the unexposed area on the surface of the photoreceptor becomes −900 V)
[0256]
(Example 44)
In the evaluation of Example 42, the charging roller to be used was changed to a contact method (the roller material is the same and the insulating tape at both ends is not wound), and an image was output under the following charging conditions. The results are shown in Table 7.
Charging conditions:
DC bias: -900V
AC bias: 2.3 kV (peak toppeak), frequency 2 kHz
[0257]
(Example 45)
In the evaluation of Example 33, the evaluation was performed in the same manner as in Example 33 except that the thickness of the insulating tape was changed and the gap was changed to 150 μm. The results are shown in Table 7.
[0258]
(Example 46)
In the evaluation of Example 33, the evaluation was performed in the same manner as in Example 33 except that the thickness of the insulating tape was changed and the gap was changed to 250 μm. The results are shown in Table 7.
[0259]
(Example 47)
In the evaluation of Example 33, a scorotron charger was used as the charging member to be used for evaluation. The results are shown in Table 7. At this time, the copying machine used for the test was modified so that the scorotron charger could be installed.
Charging conditions:
DC bias: -6.5 kV
[0260]
[Table 7]

Dirt rank:
5: Almost no dirt, 4: Slightly, 3: Actual use limit level, 2 or less: Level that cannot withstand actual use
[0261]
Photoconductor Preparation Example 27:
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the support used in Photoconductor Preparation Example 1 was changed to an aluminum cylinder (JIS1050) having a diameter of 30 mm (this is referred to as Photoconductor 27).
[0262]
Photoconductor Preparation Example 28:
In Photoconductor Preparation Example 27, a photoconductor was prepared in the same manner as Photoconductor Preparation Example 27 except that Dispersion 2 was used instead of Dispersion 1 used (this is referred to as Photoconductor 28).
[0263]
Photoconductor Preparation Example 29:
In Photoconductor Preparation Example 27, a photoconductor was prepared in the same manner as Photoconductor Preparation Example 27 except that Dispersion 7 was used instead of Dispersion 1 used (this is referred to as Photoconductor 29).
[0264]
(Example 48 and Comparative Examples 5 and 6)
The photoconductors 27 to 29 produced as described above are mounted on an image forming apparatus cartridge as shown in FIG. 8 and mounted on a tandem type full color image forming apparatus as shown in FIG. 9 (all image forming elements). The same photoconductor is mounted), an image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror), and an insulating tape having a thickness of 50 μm is wound around both ends of a charging roller as shown in FIG. 6 as a charging member. An image was output under the following charging conditions using a charging member for close placement (the gap between the photoreceptor and the charging member surface was 50 μm).
Charging conditions:
DC bias: -800V
AC bias: 2.2 kV (peak to peak), frequency: 1.5 kHz
[0265]
Using a full color chart with a writing rate of 6%, 5000 sheets were continuously printed, and images at the initial stage and after 5000 sheets were evaluated. In the image evaluation, a white solid image was output at the initial stage and after 5000 sheets, and the background stain was evaluated. Further, the color reproducibility after 5000 sheets was evaluated using a chart for evaluating color reproducibility. The results are shown in Table 8.
[0266]
[Table 8]

Dirt rank:
5: Almost no dirt, 4: Slightly, 3: Actual use limit level, 2 or less: Level that cannot withstand actual use
[0267]
Subsequently, it is verified whether 7.3 °, which is the lowest angle peak of the Bragg angle θ, which is a feature of the titanyl phthalocyanine crystal used in the present invention, is the same as the minimum angle 7.5 ° of a known material.
[0268]
(Pigment preparation example 8)
A titanyl phthalocyanine crystal was obtained in the same manner as in Synthesis Example 1 except that the crystal conversion solvent in Pigment Preparation Example 1 was changed from methylene chloride to 2-butanone.
[0269]
As in the case of FIG. 11, the XD spectrum of the titanyl phthalocyanine crystal prepared in Pigment Preparation Example 8 was measured. This is shown in FIG. From FIG. 13, the lowest angle in the XD spectrum of the titanyl phthalocyanine crystal produced in Pigment Production Example 8 is 7.5 °, which is different from the lowest angle (7.3 °) of the titanyl phthalocyanine produced in Synthesis Example 1. It can be seen that it exists.
[0270]
(Measurement Example 1)
A pigment prepared in the same manner as the pigment described in JP-A-61-239248 (having a maximum diffraction peak at 7.5 °) was used as the pigment obtained in Pigment Preparation Example 1 (minimum angle 7.3 °). Weight% was added and mixed in a mortar, and the X-ray diffraction spectrum was measured in the same manner as before. The X-ray diffraction spectrum of Measurement Example 1 is shown in FIG.
[0271]
(Measurement example 2)
A pigment prepared in the same manner as the pigment described in JP-A No. 61-239248 (having a maximum diffraction peak at 7.5 °) was used as the pigment obtained in Pigment Preparation Example 8 (minimum angle 7.5 °). Weight% was added and mixed in a mortar, and the X-ray diffraction spectrum was measured in the same manner as before. The X-ray diffraction spectrum of Measurement Example 2 is shown in FIG.
[0272]
In the spectrum of FIG. 14, it can be seen that there are two independent peaks at 7.3 ° and 7.5 ° on the low angle side, and at least the peaks at 7.3 ° and 7.5 ° are different. . On the other hand, in the spectrum of FIG. 15, the low angle side peak exists only at 7.5 °, which is clearly different from the spectrum of FIG.
From the above, it can be seen that the minimum angle peak of 7.3 ° in the titanyl phthalocyanine crystal of the present invention is different from the 7.5 ° peak in the known titanyl phthalocyanine crystal.
[0273]
【The invention's effect】
According to the present invention, in view of the dispersion of titanyl phthalocyanine crystals, which are low in crystal stability and difficult to be finely divided, pigment clogging occurs at the outlet side of the dispersion chamber at the beginning of circulation dispersion using a circulation type bead mill dispersion device. At the same time, the trade-off relationship between crystal stability and microparticulation could be eliminated by reducing the rotor rotation speed in the dispersion chamber and carrying out dispersion under specific conditions. As a result, a method for producing a dispersion containing titanyl phthalocyanine crystals having high crystal stability (low crystal transition) and small particle size is provided. This dispersion is rich in storage stability and not only has good film formability, but is also microparticulated while maintaining the characteristic properties of titanyl phthalocyanine crystals. For this reason, the photoconductor produced using this dispersion is a stable electrophotographic photoconductor that does not lose high sensitivity and does not cause a decrease in chargeability and an increase in residual potential even after repeated use. In addition, an electrophotographic photosensitive member that is less likely to cause abnormal images even when used repeatedly is provided.
Furthermore, a stable image forming apparatus and a process cartridge for an image forming apparatus that can perform high-speed printing and have few abnormal images are provided.
[Brief description of the drawings]
FIG. 1 is a schematic view of a bead mill dispersing apparatus used for preparing a dispersion according to the present invention.
FIG. 2 is a diagram showing the inside of a dispersion chamber 2 of the bead mill dispersion apparatus shown in FIG.
FIG. 3 is a diagram showing a configuration example of an example of the electrophotographic photosensitive member of the present invention.
FIG. 4 is a view showing another configuration example of the electrophotographic photosensitive member of the present invention.
FIG. 5 is a view for explaining an image forming process of the present invention.
FIG. 6 is a diagram illustrating an example of a proximity charging mechanism in which a gap forming member is disposed on the charging member side of the image forming apparatus.
FIG. 7 is a view for explaining another example of the image forming process of the present invention.
FIG. 8 is a diagram illustrating an example of a process cartridge for an image forming apparatus.
FIG. 9 is a schematic diagram for explaining a color image forming apparatus.
FIG. 10 is an X-ray diffraction spectrum of a dry powder of water paste obtained in Pigment Preparation Example 1.
11 is an X-ray diffraction spectrum of Pigment 1. FIG.
FIG. 12 is an X-ray diffraction spectrum of Comparative Example 2 (a part of the crystal has undergone crystal transition).
13 is an X-ray diffraction spectrum of a titanyl phthalocyanine crystal prepared in Pigment Preparation Example 8. FIG.
14 is an X-ray diffraction spectrum of Example 1. FIG.
15 is an X-ray diffraction spectrum of Example 2. FIG.
[Explanation of symbols]
(In FIGS. 1 and 2)
1 Motor
2 Dispersion room
3 Flow meter
4 Circulation tank
5 Circulation pump
6 Piping
7 Dispersion chamber fixing base
10 Distributed media
11 Slit
12 Circulation outlet side piping
13 Wall of dispersion chamber
14 Rotor
15 Circulation inlet side piping
16 motor
(In FIGS. 3 and 4)
31 Conductive support
35 Charge generation layer
37 Charge transport layer
39 Protective layer
(In FIG. 6)
29 photoconductor
30 Charging roller
31 Gap forming member
32 Metal shaft
33 Image formation area
34 Non-image forming area
(In FIG. 9)
1C, 1M, 1Y, 1K photoconductor
2C, 2M, 2Y, 2K charging member
3C, 3M, 3Y, 3K laser light
4C, 4M, 4Y, 4K development member
5C, 5M, 5Y, 5K Cleaning member
6C, 6M, 6Y, 6K imaging elements
10 Transfer conveyor belt
11C, 11M, 11Y, 11K transfer brush
12 Fixing device

Claims (22)

In a method of producing a dispersion containing titanyl phthalocyanine crystals by a circulation type bead mill dispersion device using a dispersion medium having a diameter of 1 mm or less, dispersion is performed while measuring the circulation flow rate, and the circulation flow rate is a predetermined amount from the start of dispersion. A method for producing a dispersion, wherein the rotational speed of a rotor installed in a dispersion chamber is lower than the rotational speed in a steady state of dispersion until reaching 90% or more. The rotor rotation speed is set to 30 to 80% of the rotation speed in a steady state of dispersion until the circulating flow rate reaches 90% or more of a predetermined amount from the start of the dispersion. A method for producing a dispersion. The titanyl phthalocyanine crystal has a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα characteristic X-rays (wavelength 1.542 mm). Item 3. A method for producing a dispersion according to Item 1 or 2. The titanyl phthalocyanine crystal has a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα, which is further dominant at 9.4 °, 9.6 °, and 24.0 °. And a peak at 7.3 ° as a diffraction peak on the lowest angle side, and no peak in a range of 7.4 ° or more and less than 9.4 °. 3. A method for producing the dispersion liquid according to 3. The method for producing a dispersion according to claim 3 or 4, wherein the titanyl phthalocyanine further has no peak at 26.3 °. 6. The dispersion according to claim 1, wherein at least one selected from a ketone solvent, an ester solvent, and an ether solvent is used as a dispersion solvent in the method for producing the dispersion. Manufacturing method. The method for preparing a dispersion according to any one of claims 1 to 6, wherein a binder resin is used in combination when the titanyl phthalocyanine crystal is dispersed. The method for producing a dispersion according to any one of claims 1 to 6, wherein water is used in combination when the titanyl phthalocyanine crystal is dispersed in the method for producing the dispersion. An electrophotographic photosensitive member in which at least a charge generation layer and a charge transport layer are laminated on a conductive support, wherein the charge generation layer uses a dispersion prepared by the method according to claim 1. An electrophotographic photoreceptor characterized in that the electrophotographic photoreceptor is formed. 10. The electrophotographic photoreceptor according to claim 9, wherein the charge transport layer contains a polycarbonate having at least a triarylamine structure in the main chain and / or side chain. 11. The electrophotographic photoreceptor according to claim 9, wherein a protective layer is laminated on the charge transport layer in the electrophotographic photoreceptor. The electrophotographic photoreceptor according to claim 11, wherein the protective layer contains an inorganic pigment or metal oxide having a specific resistance of 10 ¹⁰ Ω · cm or more. The electrophotographic photosensitive member according to claim 9, wherein the charge transport layer of the photosensitive member is formed using a non-halogen solvent. 14. The electrophotographic photoreceptor according to claim 13, wherein at least one selected from cyclic ethers or aromatic hydrocarbons is used as the non-halogen solvent. The electrophotographic photosensitive member according to claim 9, wherein the surface of the electroconductive support of the electrophotographic photosensitive member is anodized. 16. An image forming apparatus comprising at least a charging unit, an exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 9 to 15. An image forming apparatus. The image forming apparatus in which a plurality of image forming elements including at least a charging unit, an exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member are arranged, wherein the electrophotographic photosensitive member is an electrophotographic device according to any one of claims 9 to 15. An image forming apparatus characterized by being a photographic photoreceptor. 18. The image forming apparatus according to claim 16, wherein a contact charging method is used for the charging unit. The image forming apparatus according to claim 16, wherein a non-contact proximity arrangement method is used for the charging unit. 20. The image forming apparatus according to claim 19, wherein a gap between the charging member used for the charging unit and the electrophotographic photosensitive member is 10 μm or more and 200 μm or less. 21. The image forming apparatus according to claim 16, wherein a voltage obtained by superimposing an AC voltage on a DC voltage is applied to the charging unit. A process cartridge for an image forming apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 9 to 15. Process cartridge for equipment.

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