JP3618962B2 - Electrophotographic photosensitive member, electrophotographic apparatus and process cartridge using the electrophotographic photosensitive member - Google Patents

Description

【００８６】
次いで、下記の構造式を有するトリアリールアミン化合物５部と合成例１の樹脂２．５部及びポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５部をテトラハイドロフラン７０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後１２μｍの膜厚に塗工した。
【００８７】
【化２】

【００８８】
−７００Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−３５０Ｖまで帯電電位が減少する露光量）＝１．２μＪ／ｃｍ^２ 、残留電位４８Ｖと良好であった。
【００８９】
本電子写真感光体をキヤノン製デジタル複写機ＧＰ５５（ローラー帯電方式）を前述の照射スポット径となるように改造した評価機にて初期帯電−４００Ｖにて画像評価を行ったところ、初期及び５０００枚耐久試験後も、均一性の優れた画像出力が得られ、階調再現性も４００ｄｐｉにて２５６階調ときわめて良好であり、感光体の摩耗量も１０００枚の耐久試験あたり０．４μｍと少なかった。
【００９０】
また、感光体の表面の水の接触角を測定すると初期が１０４ｄｅｇに対して５０００枚耐久試験後も９８ｄｅｇと良好であった。
【００９１】
実施例５
合成例１の樹脂、４−［２−（トリエトキシシリル）エチル］トリフェニルアミン及びポリカーボネート樹脂（商品名 Ｚ−２００、三菱瓦斯化学（株）製）を固形分としてそれぞれ２０重量％、４０重量％、４０重量％となるようにＴＨＦに溶解した。
【００９２】
これを５０μｍ厚のアルミニウム板にバーコートを用いて塗布し、１２０度で１時間乾燥した。乾燥後、２０μｍの透明で均一な膜が得られた。顕微鏡で観察したところ均一フィルムが形成されたことが判明した。
【００９３】
更に、このサンプルに導電性ゴムローラを当接させてアルミニウム板をアースとして導電性ゴムローラに−６００Ｖを印加して、更に、ピーク間１５００Ｖ、１５００Ｈｚの交流を重畳させることにより帯電による劣化試験を１時間行った。劣化試験により導電性ゴムローラが前記シートに当接している部分の近傍に放電による凹みが生じ、その凹みの深さを耐放電性の評価として測定した。その結果本実施例のシートにおける凹みは０．１μｍときわめて小さいものであった。
【００９４】
実施例６
鏡面加工により作成した外径８０ｍｍのアルミニウムシリンダーに陽極酸化によりアルマイトを形成したものを用いて電荷発生層及び電荷輸送層は実施例４と同じ条件で感光体を作成した。
【００９５】
本電子写真感光体をキヤノン製デジタルカラー複写機ＣＬＣ５００（コロナ帯電方式）を前述の照射スポット径となるように改造した評価機にて初期帯電−４００Ｖにて画像評価を行ったところ、初期及び５０００枚耐久試験後も、均一性の優れた画像出力が得られ、階調再現性も４００ｄｐｉにて２５６階調ときわめて良好であり、感光体の摩耗量も１０００枚の耐久試験あたり０．２μｍと少なかった。
【００９６】
また、感光体の表面の水の接触角を測定すると初期が１０４ｄｅｇに対して５０００枚耐久試験後も９４ｄｅｇと良好であった。
【００９７】
実施例７
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【００９８】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【００９９】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【０１００】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１０１】
次いで、合成例２で用いたフッ素変成有機ケイ素樹脂２７．５部と実施例４で用いたトリアリールアミン化合物５５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５５部をテトラハイドロフラン７０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後１０μｍの膜厚に塗工した。
【０１０２】
水の接触角は１０５度であった。
【０１０３】
−７００Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−３５０Ｖまで帯電電位が減少する露光量）＝０．１μＪ／ｃｍ^２ 、残留電位４５Ｖと良好であった。
【０１０４】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（前述の照射スポット条件に改造、ＡＣローラー帯電器使用）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は２μｍ以下ときわめて少なく、耐久後の水の接触角も１００度と良好で、画像の劣化もなく、６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性も十分であった。
【０１０５】
実施例８
実施例７と同様に引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１０μｍとなるように塗工した。この導電性支持体に実施例６と同様に１μｍの下引き層、０．２μｍの電荷発生層を形成した。
【０１０６】
次に、実施例４において用いたトリアリールアミン化合物５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５部をクロロベンゼン７０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後８μｍの膜厚に塗工した。
【０１０７】
前記電荷輸送層の上に実施例２で作成した樹脂溶液をスプレーコーティング法により乾燥後４μｍとなるように塗布した。
【０１０８】
１１０℃にて２時間乾燥、熱硬化して本発明の感光体を作成した。
【０１０９】
水の接触角は１０９度であった。
【０１１０】
−７００Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−３５０Ｖまで帯電電位が減少する露光量）＝０．１４μＪ／ｃｍ^２ 、残留電位３９Ｖと良好であった。
【０１１１】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（７８０ｎｍ、１００ｍＷの半導体レーザーを用いてレーザースポット径６０×２０μｍ^２ に光学系を変更）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は２．５μｍときわめて少なく、水の接触角は９８度と良好で黒ポチ等の電荷注入及び干渉縞による画像の劣化もなく、６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性も十分であった。
【０１１２】
実施例９
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【０１１３】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１１４】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【０１１５】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１１６】
次いで、合成例２で用いたフッ素変成有機ケイ素樹脂２７．５部と実施例４で用いたトリアリールアミン化合物５５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５５部をテトラハイドロフラン７０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後２０μｍの膜厚に塗工した。
【０１１７】
水の接触角は１０５度であった。
【０１１８】
−７００Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−３５０Ｖまで帯電電位が減少する露光量）＝０．１１μＪ／ｃｍ^２ 、残留電位５１Ｖと良好であった。
【０１１９】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（前述の照射スポット条件に改造、ＡＣローラー帯電器使用）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は２μｍ以下ときわめて少なく、耐久後の水の接触角も１００度と良好で、画像の劣化もなかったが６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性がやや不十分であった。
【０１２０】
実施例１０
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【０１２１】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１２２】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【０１２３】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１２４】
次いで、合成例３で用いたフッ素変成有機ケイ素樹脂４７．０部と実施例４で用いたトリアリールアミン化合物５５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５５部をテトラハイドロフラン１５０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後１２μｍの膜厚に塗工した。
【０１２５】
水の接触角は１０２度であった。
【０１２６】
−５５０Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−２７５Ｖまで帯電電位が減少する露光量）＝０．１６μＪ／ｃｍ^２ 、残留電位３０Ｖと良好であった。
【０１２７】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（前述の照射スポット条件に改造、ＡＣローラー帯電器使用）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は２μｍ以下ときわめて少なく、耐久後の水の接触角も９０度と良好で、画像の劣化もなかった。
【０１２８】
実施例１１
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【０１２９】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１３０】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【０１３１】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１３２】
次いで、合成例４で用いたフッ素変成有機ケイ素樹脂７０部と実施例４で用いたトリアリールアミン化合物５５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５５部をテトラハイドロフラン１５０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後１５μｍの膜厚に塗工した。
【０１３３】
水の接触角は１１２度であった。
【０１３４】
−７００Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−３５０Ｖまで帯電電位が減少する露光量）＝０．２０μＪ／ｃｍ^２ 、残留電位４０Ｖと良好であった。
【０１３５】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（前述の照射スポット条件に改造、ＡＣローラー帯電器使用）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は３μｍ以下ときわめて少なく、耐久後の水の接触角も１００度と良好で、画像の劣化もなかった。
【０１３６】
実施例１２
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【０１３７】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１３８】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【０１３９】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１４０】
次いで、合成例５で用いたフッ素変成有機ケイ素樹脂２０部と実施例４で用いたトリアリールアミン化合物５５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５５部をテトラハイドロフラン１５０部に溶解した電荷輸送層用の液を前記の電荷発生層の上に浸漬コーティング法により乾燥後１２μｍの膜厚に塗工した。
【０１４１】
水の接触角は１０８度であった。
【０１４２】
−５５０Ｖに帯電して波長６８０ｎｍで電子写真特性を測定したところ、Ｅ１／２ （−２７５Ｖまで帯電電位が減少する露光量）＝０．１９μＪ／ｃｍ^２ 、残留電位２８Ｖと良好であった。
【０１４３】
本電子写真感光体をキヤノン製レーザービームプリンタＰ２７０の改造機（前述の照射スポット条件に改造、ＡＣローラー帯電器使用）にて初期帯電−５００Ｖにて画像評価を行ったところ、４０００枚の耐久試験後の感光体の摩耗量は３μｍ以下ときわめて少なく、耐久後の水の接触角も９３度と良好で、画像の劣化もなかった。
【０１４４】
比較例１
テフロン微粒子（タイキン工業（株）製、ルブロンＬＤ−１、粒子径 約０．２μｍ）、４−［２−（トリエトキシシリル）エチル］トリフェニルアミン及びポリカーボネート樹脂（商品名 Ｚ−２００、三菱瓦斯化学（株）製）を固形分としてそれぞれ５重量％、４７．５重量％、４７．５重量％となるようにＴＨＦに溶解した。
【０１４５】
これをガラス板にバーコートを用いて塗布し、１２０度で１時間乾燥したところ、乾燥後、１０μｍの白濁した膜が得られた。顕微鏡で観察したところ凝集したテフロン粒子が観測された。
【０１４６】
更に、このサンプルを分光光度計にて６００ｎｍの波長における吸収を測定したところ膜厚１μｍあたりの吸光度として０．０２２が得られ、かなりの光が散乱していることが確認された。
【０１４７】
また、水の接触角を測定したところ８６ｄｅｇと低表面エネルギー化は不十分であった。
【０１４８】
比較例２
メチルポリシロキサン樹脂を主成分とする樹脂溶液の調整
メチルシロキサン単位８０モル％、ジメチルシロキサン単位２０モル％からなる１重量％のシラノール基を含むシリコーン樹脂１０ｇをトルエン１０ｇに溶解し、均一な溶液にした。
【０１４９】
電荷輸送層への相溶性試験
上記メチルポリシロキサン樹脂溶液、４−［２−（トリエトキシシリル）エチル］トリフェニルアミン及びポリカーボネート樹脂（商品名 Ｚ−２００、三菱瓦斯化学（株）製）を固形分としてそれぞれ５重量％、４７．５重量％、４７．５重量％となるようにＴＨＦに溶解した。
【０１５０】
これをガラス板にバーコートを用いて塗布し、１２０度で１時間乾燥したところ、乾燥後、１０μｍの白濁した凹凸のある膜が得られた。顕微鏡で観察したところ凝集した不均一な部分が観測された。
【０１５１】
更に、このサンプルを分光光度計にて６００ｎｍの波長における吸収を測定したところ膜厚１μｍあたりの吸光度として０．０５が得られ、かなりの光が散乱していることが確認された。
【０１５２】
また、水の接触角を測定したところ１０３ｄｅｇと低表面エネルギー化されており良好であった。
【０１５３】
比較例３
フェニルポリシロキサン樹脂を主成分とする樹脂溶液の調製
フェニルシロキサン単位４０モル％、ジフェニルシロキサン単位２０モル％、メチルシロキサン単位２０モル％、ジメチルシロキサン単位２０％からなる１重量％のシラノール基を含むシロキサン樹脂１２ｇをトルエン１０ｇに溶解し、均一な溶液にした。
【０１５４】
電荷輸送層への相溶性試験
上記メチルポリフェニルシロキ樹脂溶液、４−［２−（トリエトキシシリル）エチル］トリフェニルアミン及びポリカーボネート樹脂（商品名 Ｚ−２００、三菱瓦斯化学（株）製）を固形分としてそれぞれ２０重量％、４０重量％、４０重量％となるようにＴＨＦに溶解した。
【０１５５】
これをガラス板にバーコートを用いて塗布し、１２０度で１時間乾燥したところ、乾燥後、１０μｍの白濁した膜が得られた。
【０１５６】
更に、このサンプルを分光光度計にて６００ｎｍの波長における吸収を測定したところ膜厚１μｍあたりの吸光度として０．０１２が得られ、かなりの光が散乱していることが確認された。
【０１５７】
また、水の接触角を測定したところ８８ｄｅｇと低表面エネルギー化は十分ではなかった。
【０１５８】
比較例４
４−［２−（トリエトキシシリル）エチル］トリフェニルアミン及びポリカーボネート樹脂（商品名 Ｚ−２００、三菱瓦斯化学（株）製）を固形分としてそれぞれ５０重量％、５０重量％となるようにＴＨＦに溶解した。
【０１５９】
これを５０μｍ厚のアルミニウム板にバーコートを用いて塗布し、１２０度で１時間乾燥したところ、乾燥後、２０μｍの透明で均一な膜が得られた。顕微鏡で観察したところ均一フィルムが形成されたことが判明した。
【０１６０】
更に、このサンプルに導電性ゴムローラを当接させてアルミニウム板をアースとして導電性ゴムローラに−６００Ｖを印加して、更に、ピーク間１５００Ｖ、１５００Ｈｚの交流を重畳させることにより帯電による劣化試験を１時間行った。劣化試験により導電性ゴムローラが前記シートに当接している部分の近傍に放電による凹みが生じ、その凹みの深さを耐放電性の評価として測定した。
【０１６１】
その結果上記のシートにおける凹みは１μｍとかなり大きいものであった。
【０１６２】
比較例５
実施例４において用いたトリアリールアミン化合物５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５部をクロロベンゼン７０部に溶解した電荷輸送層用の液を前記電荷発生層の上に浸漬コーティング法により乾燥後１２μｍの膜厚に塗工して実施例４と同じキヤノン製レーザービームプリンタにて画像評価を行ったところ、４０００枚の耐久試験後は干渉縞及び黒ポチが認められ、摩耗量が５μｍと大きく、水の接触角も７２度と小さいために不良であり、６００ｄｐｉでのハイライト部の１画素再現も不十分でムラがあった。
【０１６３】
比較例６
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダーを用いて導電層としてフェノール樹脂（商品名 プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸漬コーティング法により、乾燥後の膜厚が１５μｍとなるように塗工した。
【０１６４】
下引き層としてアルコール可溶性共重合ナイロン（商品名 アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸漬コーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１６５】
次に、電荷発生層としてＩ型オキシチタニウムフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸漬コーティング法で塗工した。
【０１６６】
前記電荷発生層の上に実施例４において用いたトリアリールアミン化合物５部とポリカーボネート樹脂（商品名 Ｚ−４００、三菱瓦斯化学（株）製）５部及びテフロン微粒子０．５部をクロロベンゼン７０部に分散、溶解した電荷輸送層用の液を浸漬コーティング法により乾燥後１２μｍの膜厚に塗工して実施例４と同じキヤノン製レーザービームプリンタにて画像評価を行ったところ、４０００枚の耐久試験後は摩耗量が４μｍ程度であり、水の接触角も８９度とやや低表面エネルギーであったが、６００ｄｐｉでのハイライト部の１画素再現は耐久初期から不十分でムラがあった。
【０１６７】
【発明の効果】
本発明の電子写真感光体は、特定のフッ素変性有機ケイ素樹脂を表面層に用いているため、耐摩耗性に優れ、かつ表面エネルギーが小さいことから汚染が少なく、クリーニング性に優れる。しかも残留電位等の電気特性に優れる。更に、該電子写真感光体は光散乱も少ないことからこれを用いた電子写真画像形成装置は耐久性が優れているのみでなく、耐久後も良好な画像を提供する。
【図面の簡単な説明】
【図１】本発明の電子写真装置の一例を示す正面図である。
【図２】本発明の電子写真装置の他の例を示す正面図である。
【図３】本発明の電子写真装置の他の例を示す正面図である。
【図４】照射光ビームの強度分布とスポット面積の関係を示す図である。
【図５】本発明の電子写真装置の他の例を示す正面図である。
【図６】本発明の電子写真装置の他の例を示す正面図である。
【符号の説明】
１ 電子写真感光体
２ 帯電手段
４ 現像手段
５ 転写手段
６ クリーニング手段
７ 前露光手段
９ 記録材
１０ 直接帯電部材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member widely used in a copying machine, a printer, a plate making system, and the like, an electrophotographic apparatus using the electrophotographic photosensitive member, and a process cartridge.
[0002]
[Prior art]
Conventionally, electrophotographic photosensitive members are directly subjected to electrical or mechanical influences by charging processes such as corona charging and roller charging, development processes, transfer processes, and cleaning processes. Required.
[0003]
Specifically, durability against abrasion or scratches on the surface of the photoreceptor due to rubbing or electrical deterioration is required. In particular, in a charging method using a discharge phenomenon such as a roller charging method, durability against high-energy arc discharge is required.
[0004]
In addition, there is a problem of toner adhesion to the surface of the photoreceptor due to repeated development and cleaning with the toner. In response to this problem, improvement in the cleaning property of the photoreceptor surface is required.
[0005]
In order to satisfy the various characteristics required for the surface of the photoreceptor as described above, attempts have been made to provide a surface protective layer mainly composed of various resins on the photosensitive layer. For example, JP-A-57-30843 proposes a protective layer in which resistance is controlled by adding metal oxide particles as conductive particles.
[0006]
It has also been studied to improve the physical properties of the photoreceptor surface by adding various substances not only to the protective layer but also to the charge transport layer. For example, the following has been reported as an additive focusing on the low surface energy of silicone resin.
[0007]
Silicone oil (Japanese Patent Laid-Open No. 61-132594),
Polydimethylsiloxane,
Silicone resin powder (JP-A-4-324454),
Cross-linked silicone resin,
Poly (carbonate-silicone) block copolymer,
Silicone modified polyurethane,
Silicone modified polyester,
[0008]
A typical polymer having a low surface energy is a fluorine-based polymer, and the following can be added to the photosensitive layer as the fluorine-based polymer.
[0009]
Polytetrafluoroethylene powder,
Carbon fluoride powder,
[0010]
[Problems to be solved by the invention]
However, although a surface protective layer containing a metal oxide or the like can be obtained having a considerable hardness, there is a problem in cleaning properties and the like because the surface energy tends to increase. Silicone-based resins are excellent in that they have a small surface energy, but they do not exhibit sufficient compatibility with other resins. In order to precipitate, there existed problems, such as not showing the stable characteristic. In addition, fluoropolymers typified by polytetrafluoroethylene (PTFE), which is a low surface energy polymer, are generally insoluble in solvents and have poor dispersibility, so that a smooth photoreceptor surface can be obtained. It is difficult and the refractive index is small, so that light scattering is likely to occur, thereby causing a problem that the latent image is deteriorated.
[0011]
In addition, polymer compounds such as polycarbonate, polyacrylic ester, polyester, and polytetrafluoroethylene generally have poor arc discharge resistance, and easily deteriorate because the polymer main chain is cut by discharge. was there.
[0012]
An object of the present invention is to provide a high-resolution electrophotographic photosensitive member that is free from light scattering and bleed and achieves low surface energy and excellent mechanical and electrical durability, and an electrophotographic apparatus and a process cartridge having the photosensitive member. Is to provide.
[0013]
[Means for Solving the Problems]
That is, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer on a support, and the surface layer of the photoreceptor is represented by the following average unit formula (I):The weight average molecular weight is 1000 to 100,000Fluoro-modified organosilicon resinAnd a binder resin,It contains.
{F (CF₂)_a1-Q₁ -R_1m1 SiO_{(3-m1) / 2}}_x1{F (CF₂)_a2-Q₂ -R_2m2 SiO_{(3-m2) / 2}}_x2... {F (CF₂)_ap-Q_p -R_pmp SiO_{(3-mp) / 2}}_xp{R '_1n1SiO_{(4-n1) / 2}}_y1{R '_2n2SiO_{(4-n2) / 2}}_y2... {R '_qnqSiO_{(4-nq) / 2}}_yq (I)
(Wherein R₁ , ..., R_p , R '₁, ..., R '_qIs an alkyl group or an aryl group, and Q is₁ , ..., Q_p Is an alkylene group. m₁ , ..., m_p Is an integer from 0 to 2 and n₁ , ..., n_q Is an integer from 0 to 3 and a₁ , ..., a_p Is an integer and x₁ And y₁ Is a number greater than 0 and x₂ , ..., x_p , Y₂ , ..., y_q Is a number greater than or equal to zero. )
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The electrophotographic photoreceptor of the present invention has a photosensitive layer on a support, and is represented by the following average unit formula (I) on the surface layer of the photoreceptor.The weight average molecular weight is 1000 to 100,000Fluoro-modified organosilicon resinAnd a binder resin,It contains.
Average unit formula (I)
{F (CF₂)_a1-Q₁ -R_1m1 SiO_{(3-m1) / 2}}_x1{F (CF₂)_a2-Q₂ -R_2m2 SiO_{(3-m2) / 2}}_x2... {F (CF₂)_ap-Q_p -R_pmp SiO_{(3-mp) / 2}}_xp{R '_1n1SiO_{(4-n1) / 2}}_y1{R '_2n2SiO_{(4-n2) / 2}}_y2... {R '_qnqSiO_{(4-nq) / 2}}_yq (I)
(Wherein R₁ , ..., R_p , R '₁, ..., R '_qIs an alkyl group or an aryl group, and Q is₁ , ..., Q_p Is an alkylene group. m₁ , ..., m_p Is an integer from 0 to 2 and n₁ , ..., n_q Is an integer from 0 to 3 and a₁ , ..., a_p Is an integer and x₁ And y₁ Is a number greater than 0 and x₂ , ..., x_p , Y₂ , ..., y_q Is a number greater than or equal to zero. )
[0015]
In the present invention, the surface layer means a protective layer when the photosensitive layer has a protective layer. When there is no protective layer, it means a photosensitive layer. In the case where the photosensitive layer does not have a protective layer and is composed of multiple layers, it refers to the layer farthest from the support among the layers constituting the photosensitive layer.
[0016]
R in the above formula (I)₁  , ..., R_p  , R '₁, ..., R '_qIs preferably an alkyl group having 1 to 12 carbon atoms or an aryl group.
[0017]
The alkyl group may be linear, branched, or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group. A decyl group, an undecyl group, a dodecyl group, and the like are preferable. Alkyl groups having a large number of carbon atoms are not preferred because the mechanical strength decreases when a surface layer is formed. As the aryl group, a phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group and the like are preferably used. An aryl group having a large number of carbon atoms is not preferred because the arc discharge resistance is reduced when a surface layer is formed.
[0018]
Q₁  , ..., Q_p  Is preferably an alkylene group having 2 to 6 carbon atoms, such as an ethylene group and a propylene group. m₁  , ..., m_p  Is an integer from 0 to 2 and n₁  , ..., n_q  Is an integer from 0 to 3 and a₁  , ..., a_p  Is an integer and x₁  And y₁  Is a number greater than 0 and x₂  , ..., x_p  , Y₂  , ..., y_q  Is a number greater than or equal to zero. However, (x₁  + X₂  + ... + x_p  ) :( y₁  + Y₂  + ... + y_q  ) = 1: 20-1: 5 is preferable.
[0019]
The fluorine-modified organosilicon resin in the present invention preferably has a softening point of 30 ° C. or higher, and in order to have a softening point of 30 ° C. or higher, R₁ , ..., R_p , R '₁, ..., R '_qIs preferably an aryl group such as a phenyl group. Moreover, this resin may contain some residual silanol groups or alkoxy groups. R₁ , ..., R_p , R '₁, ..., R '_qThe proportion of the aryl group in the total is preferably 20 mol% or more. The weight average molecular weight of the fluorine-modified organosilicon resin used in the present invention is 1000 to 100,000.Is. If the weight average molecular weight is small, the mechanical strength of the surface layer may not be sufficient. Conversely, if the weight average molecular weight is too large, the compatibility with the binder resin tends to be poor, and white turbidity or a decrease in charge transport ability may occur. In the present invention, the weight average molecular weight is a value measured by GPC (gel permeation chromatography).
[0020]
Examples of the fluorine-modified organosilicon resin in the present invention include those represented by the following average unit formula.
[0021]
{F (CF₂)₄C₂H₄SiO_3/2}_0.1{(CH₃)₃SiO_1/2}_0.9(SiO_4/2)_1.0
{F (CF₂)₄C₂H₄(CH₃) SiO_2/2}_0.1{(CH₃)₃SiO_1/2}_0.9(SiO_4/2)_1.0
{F (CF₂)₈C₂H₄(CH₃) SiO_2/2}₁{(C₆H₅)₂SiO_2/2}₁₀
{F (CF₂)₈C₂H₄SiO_3/2}₁{(CH₃)₂SiO_2/2}₁₈{(C₆H₅) SiO_3/2}₂
{F (CF₂)₄C₂H₄SiO_3/2}₁{(CH₃) SiO_3/2}₉
{F (CF₂)₄C₂H₄SiO_3/2}₁{(C₆H₅) SiO_3/2}₉
{F (CF₂)₄C₂H₄SiO_3/2}₁{(CH₃)₃SiO_1/2}_1.2{SiO_4/2}_1.0
{(C₆H₅) SiO_3/2}₉
{F (CF₂)₄C₂H₄SiO_3/2}₁{(C₆H₅)₂SiO_2/2}₉
{F (CF₂)₈C₂H₄(CH₃) SiO_2/2}₁{(C₆H₅)₂SiO_2/2}₈{(C₆H₅) SiO_3/2}₁
{F (CF₂)₈C₂H₄SiO_3/2}₁{(CH₃)₃SiO_1/2}_0.7{SiO_4/2}_1.0
{(C₆H₅)₂SiO_2/2}₁₀
{F (CF₂)₈C₂H₄(CH₃) SiO_2/2}₁{(CH₃)₃SiO_1/2}_0.7{SiO_4/2}_1.0
{(C₆H₅)₂SiO_2/2}₈
{F (CF₂)₈C₂H₄SiO_3/2}₁{(C₆H₅) SiO_3/2}₉
{F (CF₂)₈C₂H₄SiO_3/2}₁{(C₆H₅)₂SiO_2/2}₉
{F (CF₂)₈C₂H₄SiO_3/2}₁{(C₆H₅)₂SiO_2/2}₅{(C₆H₅) SiO_3/2}₅
{F (CF₂)₄C₂H₄SiO_3/2  }₁{(CH₃)₂SiO_2/2}₁  {(C₆H₅) SiO_3/2}₆
{(CF₃) C₂H₄SiO_3/2  }₁{F (CH₂)₈C₂H₄SiO_3/2  }₁  {(CH₃)₃SiO_1/2}₃
{(C₆H₅)₂SiO_2/2}₁₃
{F (CF₂)₈C₂H₄SiO_3/2  }₁{(CH₃)₃SiO_1/2}₅  {(C₆H₅)₂SiO_2/2  }₆  {SiO_4/2}₆
{(CF₃) C₂H₄SiO_3/2  }₃  {(CH₃)₃SiO_1/2}₄  {(C₆H₅) SiO_3/2}₄  {SiO_4/2}₁₀
{(CF₃) C₂H₄SiO_3/2  }₃  {F (CF₂)₄C₂H₄SiO_3/2  }₁  {(C₆H₅) SiO_3/2}₁₀{SiO_4/2}₄
{(CF₃) C₂H₄SiO_3/2  }₃  {F (CH₂)₈C₂H₄SiO_3/2  }₁  {(CH₃)₃SiO_1/2}₁₀
{(C₆H₅)₂SiO_2/2}₁₀
{(CF₃C₂H₄)₂SiO_2/2}₂  {(CH₃)₃SiO_1/2}₈  {(C₆H₅)₂SiO_2/2  }₈  {SiO_4/2}₂
{F (CF₂)₈C₂H₄SiO_3/2  }₁{(CH₃)₃SiO_1/2}₈  {(C₆H₅)₂SiO_3/2  }₈  {SiO_4/2}₄
{(CF₃) C₂H₄SiO_3/2  }₂  {F (CF₂)₄C₂H₄SiO_3/2  }₁  {F (CF₂)₈C₂H₄SiO_3/2  }₁  {(CH₃)₃SiO_1/2}₅  {(C₆H₅)₂SiO_2/2  }₁₅
[0022]
The fluorine-modified organosilicon resin used in the present invention can be produced by a general organopolysiloxane production method.
[0023]
General methods for producing organopolysiloxanes include those described in Japanese Patent Publication Nos. 26-2696 and 28-6297, Chemistry and Technology of Silicones, Chapter 5, p. 191- (Walter Noll, Academic Press, Inc. 1968).
[0024]
For example, it is synthesized by dissolving organoalkoxysilane or organohalogenosilane in an organic solvent, polymerizing by hydrolysis and condensation in the presence of an acid or base, and then removing the solvent.
[0025]
Hereinafter, the present invention will be described by taking an electrophotographic photosensitive member having a charge transport layer containing a fluorine-modified organosilicon resin as an example.
[0026]
As the support of the electrophotographic photosensitive member, the support itself has conductivity, such as aluminum, aluminum alloy, copper, zinc, stainless steel, chromium, titanium, nickel, magnesium, indium, gold, platinum, silver and iron Can be used. In addition, aluminum, indium oxide, tin oxide, gold, or the like is formed on a dielectric support such as plastic by vapor deposition or the like to form a conductive layer, or conductive fine particles mixed with plastic or paper are used. Can do. These conductive supports are required to have uniform conductivity and a smooth surface is important. Since the smoothness of the surface greatly affects the uniformity of the undercoat layer, the charge generation layer and the charge transport layer formed thereon, the surface roughness is preferably 0.3 μm or less.
[0027]
In particular, a support coated with a conductive layer obtained by dispersing and coating conductive fine particles in a polymer binder is easy to form and preferably used because it has a homogeneous surface. The primary particle size of the conductive fine particles used at this time is 100 nm or less, more preferably 50 nm or less. As the conductive fine particles, conductive zinc oxide, conductive titanium oxide, Al, Au, Cu, Ag, Co, Ni, Fe, carbon black, lTO, tin oxide, indium oxide, indium, and the like are used. The surface of the insulating fine particles may be coated. The conductive fine particle content is used so that the volume resistance of the conductive layer is sufficiently low, and preferably 1 × 10.¹⁰It is added so as to have a resistance of Ωcm or less. More preferably 1 × 10⁸Used at Ωcm or less.
[0028]
When exposure is performed using a coherent light source such as a laser, irregularities can be formed on the surface of the conductive support in order to prevent image degradation due to interference. At this time, in order to make it difficult for defects such as charge injection and unevenness of the residual potential to occur, unevenness of about 1 / 2λ of the wavelength used is dispersed with an insulator such as silica beads having a diameter of several μm or less at a cycle of 10 μm or less. It can be formed and used.
[0029]
An undercoat layer having an injection preventing function and an adhesive function can be provided between the conductive support and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, polyamide, polyurethane, gelatin, and the like. The thickness of the undercoat layer is preferably from 0.1 to 10 μm, more preferably from 0.3 to 3 μm.
[0030]
The photosensitive layer may be a single layer, but is preferably constructed by laminating a charge generation layer and a charge transport layer in order from the support side. Moreover, you may laminate | stack a charge transport layer and a charge generation layer in an order from the support body side.
[0031]
When the photosensitive layer is a single layer, the photosensitive layer is prepared by mixing a charge generating material, a charge transporting material, the fluorine-modified organosilicon resin represented by the above formula (I), and a binder resin with a solvent. A film is formed by a coating method.
[0032]
When the photosensitive layer is composed of a charge generation layer and a charge transport layer, the charge generation layer is formed by mixing at least a charge generation material and a binder resin with a solvent and forming a film by a normal coating method. The charge transport layer is formed by mixing at least a charge transport material and a binder resin with a solvent and forming a film by a normal coating method. Further, in the present invention, the fluorine-modified organosilicon resin represented by the above formula (I) is contained in the layer far from the support.
[0033]
Examples of charge generating materials include selenium tellurium, pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, azo pigments, Indigo pigments, quinacridone pigments, cyanine pigments, and the like can be used.
[0034]
Charge transport materials are roughly classified into electron transport compounds and hole transport compounds.
[0035]
Examples of electron transporting compounds include electron accepting compounds such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil, tetracyanoquinodimethane, and alkyl-substituted diphenoquinone, and the like. And those obtained by polymerizing these electron-accepting compounds. Examples of the hole transporting compound include polycyclic aromatic compounds such as pyrene and anthracene, heterocyclic compounds such as carbazole, indole, oxazole, thiazole, oxathiazole, pyrazole, pyrazoline, thiadiazole and triazole, p-diethylaminobenzaldehyde Hydrazone compounds such as N, N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, α-phenyl-4′-N, N-diphenylaminostilbene and 5- (4- ( Di-p-tolylamino) benzylidene) -5H-dibenzo (a, d) styryl compounds such as cycloheptene, benzidine compounds and triarylamine compounds, or polymers having groups consisting of these compounds in the main chain or side chain Compound( Li -N- vinylcarbazole, polyvinyl anthracene and the like).
[0036]
As the binder resin used for each layer, for example, a polymer or copolymer of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride and trifluoroethylene, further polyvinyl alcohol, Examples include polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, organosilicon resin, and epoxy resin.
[0037]
When the photosensitive layer is a single layer, the content of the fluorine-modified organosilicon resin is preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the solid content of the photosensitive layer. If the content of the fluorine-modified organosilicon resin is too small, problems such as insufficient reduction in surface energy and a decrease in electrical durability may occur. On the other hand, if the content of the fluorine-modified organosilicon resin is too large, the mechanical strength and charge transport capability of the photosensitive layer may be lowered. The content of the charge generating material is preferably 3 to 30% by weight with respect to the solid content of the photosensitive layer. The content of the charge transport material is preferably 20 to 70% by weight based on the solid content of the photosensitive layer.
[0038]
When the photosensitive layer is composed of a charge generation layer and a charge transport layer, the content of the fluorine-modified organosilicon resin is preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the solid content of the surface layer. If the content of the fluorine-modified organosilicon resin is too small, the effect of the present invention cannot be sufficiently obtained. Conversely, if the content of the fluorine-modified organosilicon resin is too large, the mechanical strength of the surface layer may not be sufficiently obtained. is there. The content of the charge generation material is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the solid content of the charge generation layer. The content of the charge transport material is preferably 20 to 70% by weight with respect to the solid content of the charge transport layer.
[0039]
In the case of a single layer, the thickness of the photosensitive layer is preferably 3 to 40 μm. The thickness of the charge generation layer is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. The thickness of the charge transport layer is preferably 1 to 30 μm, more preferably 3 to 20 μm.
[0040]
A protective layer may be provided on the photosensitive layer as necessary. When a protective layer is provided on the photosensitive layer, the protective layer contains the fluorine-modified organosilicon resin of the average unit formula (I). In this case, the content of the fluorine-modified organosilicon resin is preferably 10 to 80% by weight, more preferably 20 to 60% by weight, based on the solid content of the protective layer. If the content of the fluorine-modified organosilicon resin is too small, the effect of the present invention cannot be obtained sufficiently, and conversely if too large, the mechanical strength of the protective layer may not be sufficiently obtained.
[0041]
The protective layer is a fluorine-modified organosilicon resin and polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer. Such a resin can be dissolved in a suitable organic solvent, applied onto the photosensitive layer and dried. The thickness of the protective layer is preferably 0.05 to 20 μm. Moreover, you may contain electroconductive particle, a ultraviolet absorber, etc. in a protective layer. As the conductive particles, metal oxides such as tin oxide particles are preferable.
[0042]
Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.
[0043]
In FIG. 1, reference numeral 1 denotes a drum type photoconductor of the present invention, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about a shaft 1a. The photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 2 during the rotation process, and then the optical image exposure L (slit exposure or laser exposure) is performed at the exposure unit 3 by an image exposure unit (not shown). Beam scanning exposure). As a result, electrostatic latent images corresponding to image exposure are sequentially formed on the circumferential surface of the photoreceptor. The electrostatic latent image is then developed with toner by the developing unit 4, and the toner developed image is rotated by the corona transfer unit 5 between the photosensitive unit 1 and the transfer unit 5 from a sheet feeding unit (not shown). The images are sequentially transferred onto the surface of the recording material 9 taken out in synchronization. The recording material 9 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, and printed out as a copy (copy). After the image transfer, the surface of the photoreceptor 1 is cleaned by the transfer unit 6 after removal of the transfer residual toner, is subjected to a charge removal process by the pre-exposure unit 7 and repeatedly used for image formation. As the uniform charging means 2 for the photoreceptor 1, a corona charging device is generally widely used.
[0044]
Further, as shown in FIGS. 2 and 3, the photosensitive member 1 may be charged by using a direct charging member 10 as a charging unit and bringing the direct charging member 10 to which voltage is applied into contact with the photosensitive member 1 ( This charging method is hereinafter referred to as direct charging). 2 and 3, the toner image on the photoreceptor 1 is also directly transferred to the recording material 9 by the charging member 23. That is, the toner image on the photoreceptor 1 is transferred to the recording material 9 by bringing the direct charging member 23 to which voltage is applied into contact with the recording material 9.
[0045]
In the apparatus shown in FIG. 2, at least the photosensitive member 1, the direct charging member 10, and the developing means 4 are accommodated in a container 20 to form one electrophotographic apparatus unit, and this apparatus unit is used as a guide means such as a rail of the apparatus main body. And detachable. The cleaning means 6 may or may not be disposed in the container 20.
[0046]
Further, in the apparatus shown in FIG. 3, at least the photosensitive member 1 and the direct charging member 10 are housed in a first container 21 to form a first electrophotographic apparatus unit, and at least the developing means 4 is housed in a container 22 to form a second electron. The first apparatus unit and the second apparatus unit are detachably configured as a photographic apparatus unit. The cleaning means 6 may or may not be disposed in the container 21.
[0047]
On the other hand, in recent years, the resolution and gradation required for an image forming apparatus using an electrophotographic method are increasing. In consideration of such requirements, in an electrophotographic image forming apparatus in which a latent image is formed by irradiating a light beam, the product of the photosensitive layer thickness and the irradiation spot area and gradation reproducibility are formed. I found a certain relationship between the two. That is, the product of the spot area and the film thickness of the photosensitive layer of the photoreceptor is 20000 μm.³By setting the following, 400 dpi and 256 gradations can be realized.
[0048]
This indicates that the film thickness of the photosensitive layer of the photoreceptor using minute light that can be generally realized, mainly the film thickness of the charge transport layer, is 12 μm or less. As described above, it is desirable that the photosensitive layer is thin. However, a pinhole of 1 μm or more is desirable because pinholes at the same charging potential, a decrease in sensitivity, and the like occur. More desirably, the film thickness is 3 μm or more.
[0049]
As shown in FIG. 4, the spot area of the light beam 30 is 1 / e of the peak intensity.²It is expressed in the part until it decreases. Examples of the light beam used include a scanning optical system using a semiconductor laser, and a solid state scanner such as an LED or a liquid crystal shutter. The light intensity distribution includes a Gaussian distribution and a Lorentz distribution. e²The area up to is the spot area. The light spot generally has an elliptical shape as shown in FIG. M is a spot diameter in the main scanning direction, and S is a spot diameter in the sub-scanning direction.
[0050]
Another example of the electrophotographic apparatus of the present invention will be described with reference to FIGS.
[0051]
In FIG. 5, first, the original G is set on the original table 10 with the surface to be copied facing down. Next, copying is started by pressing the copy button. The unit 109 in which the original irradiation lamp, the short focus lens array, and the CCD sensor are integrated scans the original while irradiating the original, so that the irradiation scanning light is imaged by the short focus lens array and incident on the CCD sensor. The The CCD sensor includes a light receiving unit, a transfer unit, and an output unit. An optical signal is converted into an electrical signal in the CCD light receiving unit, and sequentially transferred to the output unit in synchronization with the clock pulse in the transfer unit, and the charge signal is converted into a voltage signal in the output unit, amplified and reduced in impedance and output. The analog signal obtained in this way is converted into a digital signal, and further converted into a digital signal for output by performing image processing that optimizes the resolution and gradation according to the characteristics of the image, and the printer Sent to the department. When outputting from a computer or the like, the resolution, gradation reproduction method, and the like are selected, processed and converted so as to obtain a desired image, and sent to the printer unit. The printer unit receives the image signal and forms an electrostatic latent image as follows. The photosensitive drum 101 of the present invention is rotationally driven around a central support shaft at a predetermined peripheral speed. During the rotation process, the charger 103 receives a positive or negative uniform charging process at a predetermined voltage. The surface of the photosensitive drum 101 is electrostatic latent image corresponding to the original image by scanning the light of the solid laser element that emits light ON / OFF corresponding to the image signal on the uniformly charged surface with a rotating polygon mirror that rotates at high speed. Images are formed sequentially. 102 is a pre-exposure unit, 103 is a charging unit, 104 is a developing unit, 105 is a cleaning unit, and 106 is a fixing unit.
[0052]
FIG. 6 shows a schematic diagram of the color copying machine of the present invention.
[0053]
In FIG. 6, reference numeral 201 denotes an image scanner unit which reads a document and performs digital signal processing. Reference numeral 200 denotes a printer unit which prints out an image corresponding to the original image read by the image scanner 201 on a sheet in full color.
[0054]
In the image scanner unit 201, reference numeral 202 denotes an original plate, which is used for fixing an original 204 on an original table glass (hereinafter referred to as a platen) 203. The original 204 is irradiated with light from a halogen lamp 205. Reflected light from the original 204 is guided to mirrors 206 and 207, and an image is formed on a three-line sensor (hereinafter referred to as CCD) 210 constituted by three CCD line sensors by a lens 208. The CCD 210 color-separates light information from the document and sends it to the signal processing unit 209 as red (R), green (G), and blue (B) components in the full color information. 205 and 206 are speeds v, 207 is 1 / 2v and mechanically move in a direction (hereinafter referred to as sub-scanning direction) perpendicular to the electrical scanning direction (hereinafter referred to as main scanning direction) of the line sensor. Scan the entire document.
[0055]
Reference numeral 211 denotes a standard white plate, which is used to generate data for correcting read data corresponding to the R, G, and B component line sensors of the sensors 210-2 to 210-4 at the time of shading correction.
[0056]
This standard white plate exhibits almost uniform reflection characteristics with respect to visible light. This standard white plate is used to correct the output data of the R, G, B visible sensors 210-2 to 210-4.
[0057]
The signal processing unit 209 electrically processes the read signal, decomposes it into magenta (M), cyan (C), yellow (Y), and black (BK) components and sends them to the printer unit 200. Further, for one document scan (scan) in the image scanner unit 201, one component of M, C, Y, and BK is sequentially sent to the printer 200, and is scanned once by a total of four document scans. Color image formation is completed.
[0058]
M, C, Y, and BK image signals sent from the image scanner unit 201 are sent to the laser driver 212. The laser driver 212 modulates and drives the semiconductor laser 213 according to the image signal. The laser beam scans on the photosensitive drum 217 via the polygon mirror 214, the f-θ lens 215, and the mirror 216.
[0059]
Reference numerals 219 to 222 denote developing units, which are composed of a magenta developing unit 219, a cyan developing unit 220, a yellow developing unit 221, and a black developing unit 222. The four developing units are alternately in contact with the photosensitive drum, and are arranged on the photosensitive drum 217. The electrostatic latent images of M, C, Y, and BK formed in the above are developed with corresponding toners.
[0060]
A transfer drum 223 winds a sheet fed from the sheet cassette 224 or 225 around the transfer drum 223, and transfers the toner image developed on the photosensitive drum 217 to the sheet. After the four colors M, C, Y, and BK are sequentially transferred in this way, the sheet passes through the fixing unit 226, is fixed, and is discharged.
[Example]
A fluorine-modified organosilicon resin was synthesized as follows.
[0061]
Synthesis example 1
A mixture of 24 g of water and 90 g of toluene is placed in a flask, and the mixture is added to the formula: C while stirring them.₈F₁₇C₂H₄SiCl₃A mixture of 23 g of heptadecafluorodecyltrichlorosilane, 101 g of diphenyldichlorosilane and 120 g of toluene was added dropwise.
[0062]
After completion of dropping, the mixture was mixed for 2 hours. Next, this was allowed to stand to separate the aqueous layer, and the obtained organic solvent layer was washed repeatedly in order of pure water, 10% by weight sodium bicarbonate water, and pure water. After washing, the organic solvent is removed by heating and the following formula:
{F (CF₂)₈C₂H₄SiO_3/2}_X{(C₆H₅)₂SiO_2/2}_y
(Wherein x is 1 on average and y is 10 on average)
87 g of a fluorine-modified organosilicon resin represented by This resin was a white solid having a softening point of 70 ° C. The weight average molecular weight is 8.3 × 10⁴  Met.
[0063]
Synthesis example 2
A mixture of 24 g of water and 70 g of toluene is placed in a flask, and the mixture is stirred while stirring the formula: C₈F₁₇C₂H₄SiCl₃A mixture of 23 g of heptadecafluorodecyltrichlorosilane, 71 g of diphenyldichlorosilane, 25 g of phenyltrichlorosilane and 120 g of toluene was added dropwise.
[0064]
After completion of dropping, the mixture was mixed for 2 hours. Next, this was allowed to stand to separate the aqueous layer, and the obtained organic solvent layer was washed repeatedly in order of pure water, 10% by weight sodium bicarbonate water, and pure water. After washing, the organic solvent is removed by heating and the following formula:
{F (CF₂)₈C₂H₄SiO_3/2}_X{(C₆H₅)₂SiO_2/2}_y
{(C₆H₅) SiO_3/2}_z
(Wherein x: y: z is an average of 1: 7: 3)
82 g of a fluorine-modified organosilicon resin represented by This resin was a white solid having a softening point of 30 to 40 ° C. The weight average molecular weight is 1.1 × 10⁴  Met.
[0065]
Synthesis example 3
{F (CF₂)₄  C₂H₄SiO_3/2}_X{(CH₃  )₂SiO_2/2}_y1{(C₆H₅) SiO_3/2  }_y2
A mixture of 10 g of water, 2 g of isopropanol, and 20 g of toluene is placed in a flask, and these are stirred and added to the formula: C₄  F₉  C₂H₄SiCl₃  11.4g, Me₂  SiCl₂    A mixed solution of 2.6 g, 27.5 g of phenyltrichlorosilane and 30 g of toluene was dropped.
[0066]
After completion of dropping, the mixture was mixed for 2 hours. Next, this was allowed to stand to separate the aqueous layer, and the resulting organic solvent layer was washed repeatedly in the order of pure water, 4 wt% sodium bicarbonate water, and pure water. After washing, the organic solvent is removed by heating and the following formula:
{F (CF₂)₄  C₂H₄SiO_3/2}_X{(CH₃  )₂SiO_2/2}_y1{(C₆H₅) SiO_3/2  }_y2
(Wherein x is an average of 1 and y₁  Is 1 on average and y₂  Is an average of 6. )
21 g of a fluorine-modified organosilicon resin represented by This resin was a white solid having a softening point of 50-60 ° C. The weight average molecular weight is 4.9 × 10⁴  Met.
[0067]
Synthesis example 4
{(CF₃) C₂H₄SiO_3/2}_X1{F (CF₂)₈  C₂H₄SiO_3/2}_X2{(CH₃  )₃  SiO_1/2  }_y1{(C₆H₅)₂  SiO_2/2  }_y2
A mixture of 20 g of water and 90 g of toluene is placed in a flask, and these are stirred and added to the formula: (CF₃  ) C₂H₄SiCl₃  4.7 g, C₈  H₁₇C₂  H₄  SiCl₃    11.6g, Me₃  A mixed solution of 5.6 g of SiCl, 75.9 g of diphenyldichlorosilane and 120 g of toluene was added dropwise.
[0068]
After completion of dropping, the mixture was mixed for 2 hours. Next, this was allowed to stand to separate the aqueous layer, and the resulting organic solvent layer was washed repeatedly in the order of pure water, 4 wt% sodium bicarbonate water, and pure water. After washing, the organic solvent is removed by heating and the following formula:
{(CF₃) C₂H₄SiO_3/2}_X1{F (CF₂)₈  C₂H₄SiO_3/2}_X2{(CH₃  )₃  SiO_1/2  }_y1{(C₆H₅)₂  SiO_2/2  }_y2
(Where x₁  Is 1 on average and x₂  Is 1 on average and y₁  Is an average of 3 and y₂  Is an average of 13. )
61 g of a fluorine-modified organosilicon resin represented by This resin was a white solid having a softening point of 60-70 ° C. The weight average molecular weight is 8.4 × 10³  Met.
[0069]
Synthesis example 5
{F (CF₂)₈  C₂H₄SiO_3/2}_X{(CH₃  )₃  SiO_1/2  }_y1{(C₆H₅)₂  SiO_2/2  }_y2{SiO_4/2  }_y3
A mixed liquid of 24 g of 36% by weight hydrochloric acid and 100 g of toluene was put into a flask, and these were stirred and added to the formula: C₈  F₁₇C₂H₄SiCl₃  11.5g, Me₃  SiCl 11.0 g, diphenyldichlorosilane 25.1 g, Si (OC₂  H₅  )₄    A mixed solution of 20.4 g and 100 g of toluene was added dropwise.
[0070]
After completion of dropping, the mixture was mixed for 2 hours. Next, this was allowed to stand to separate the aqueous layer, and the resulting organic solvent layer was washed repeatedly in the order of pure water, 4 wt% sodium bicarbonate water, and pure water. After washing, the organic solvent is removed by heating and the following formula:
{F (CF₂)₈  C₂H₄SiO_3/2}_X{(CH₃  )₃  SiO_1/2  }_y1{(C₆H₅)₂  SiO_2/2  }_y2{SiO_4/2  }_y3
(Wherein x is an average of 1 and y₁  Is an average of 5 and y₂  Is an average of 5 and y₃  Is an average of 6. )
Thus, 37 g of a fluorine-modified organosilicon resin represented by The softening point of this resin was 200 ° C. or higher and was a white solid. Weight average molecular weight is 4.5 × 10³  Met.
[0071]
Example 1
The resin of Synthesis Example 1, 4- [2- (triethoxysilyl) ethyl] triphenylamine, and polycarbonate resin (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids are 20 wt% and 40 wt%, respectively. % And 40% by weight were dissolved in THF.
[0072]
This was applied to a glass plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 10 μm transparent and uniform film was obtained. Observation with a microscope revealed that a uniform film was formed.
[0073]
Furthermore, when this sample was measured for absorption at a wavelength of 600 nm with a spectrophotometer, 0.001 was obtained as the absorbance per 1 μm of film thickness, and the sample was transparent.
[0074]
Further, when the contact angle of water was measured, the surface energy was lowered to 105 deg.
[0075]
Example 2
The resin of Synthesis Example 2, 4- [2- (triethoxysilyl) ethyl] triphenylamine, and polycarbonate resin (trade name Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids are 20 wt% and 40 wt%, respectively. % And 40% by weight were dissolved in THF.
[0076]
This was applied to a glass plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 10 μm transparent and uniform film was obtained. Observation with a microscope revealed that a uniform film was formed.
[0077]
Furthermore, when this sample was measured for absorption at a wavelength of 600 nm with a spectrophotometer, 0.001 was obtained as the absorbance per 1 μm of film thickness, and the sample was transparent.
[0078]
Further, when the contact angle of water was measured, the surface energy was reduced to 107 deg.
[0079]
Example 3
The resin of Synthesis Example 2, 4- [2- (triethoxysilyl) ethyl] triphenylamine, and polycarbonate resin (trade name Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids are 20 wt% and 40 wt%, respectively. % And 40% by weight were dissolved in THF.
[0080]
This was applied to a 50 μm thick aluminum plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 20 μm transparent and uniform film was obtained. Observation with a microscope revealed that a uniform film was formed.
[0081]
Furthermore, a conductive rubber roller is brought into contact with this sample, an aluminum plate is grounded, −600 V is applied to the conductive rubber roller, and further, an alternating current of 1500 V and 1500 Hz between peaks is superimposed, and a deterioration test due to charging is performed for 1 hour. went. As a result of the deterioration test, a dent due to discharge was generated near the portion where the conductive rubber roller was in contact with the sample, and the depth of the dent was measured as an evaluation of the discharge resistance. As a result, the dent in the sheet of this example was as extremely small as 0.3 μm.
[0082]
Example 4
An alumite formed by anodization on an aluminum cylinder having an outer diameter of 60 mm prepared by mirror finishing was used as a conductive support.
[0083]
Next, 5 parts (by weight, the same applies hereinafter) of the following bisazo pigment as a charge generation layer is added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone and dispersed in a sand mill for 20 hours. did.
[0084]
This dispersion was applied onto the conductive support by a dip coating method so that the film thickness after drying was 0.2 μm.
[0085]
[Chemical 1]

[0086]
Next, 5 parts of a triarylamine compound having the following structural formula, 2.5 parts of the resin of Synthesis Example 1 and 5 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) are added to 70 parts of tetrahydrofuran. The solution for the charge transport layer dissolved in was dried on the charge generation layer by a dip coating method and coated to a thickness of 12 μm.
[0087]
[Chemical 2]

[0088]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −700 V, E1 / 2 (exposure amount at which the charging potential decreased to −350 V) = 1.2 μJ / cm²The residual potential was as good as 48V.
[0089]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charging of -400 V using an evaluation machine in which a Canon digital copying machine GP55 (roller charging method) was modified so as to have the aforementioned irradiation spot diameter, the initial and 5000 sheets were evaluated. Even after the durability test, an image output with excellent uniformity was obtained, the gradation reproducibility was very good at 256 gradations at 400 dpi, and the wear amount of the photoconductor was as small as 0.4 μm per 1000 sheets of durability tests. It was.
[0090]
Further, when the contact angle of water on the surface of the photoconductor was measured, the initial value was as good as 98 deg after the endurance test for 5000 sheets with respect to 104 deg.
[0091]
Example 5
The resin of Synthesis Example 1, 4- [2- (triethoxysilyl) ethyl] triphenylamine, and polycarbonate resin (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids are 20 wt% and 40 wt%, respectively. % And 40% by weight were dissolved in THF.
[0092]
This was applied to a 50 μm thick aluminum plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 20 μm transparent and uniform film was obtained. Observation with a microscope revealed that a uniform film was formed.
[0093]
Furthermore, a conductive rubber roller is brought into contact with this sample, an aluminum plate is grounded, −600 V is applied to the conductive rubber roller, and further, an alternating current of 1500 V and 1500 Hz between peaks is superimposed, and a deterioration test due to charging is performed for 1 hour. went. As a result of the deterioration test, a dent due to discharge was generated near the portion where the conductive rubber roller was in contact with the sheet, and the depth of the dent was measured as an evaluation of the discharge resistance. As a result, the dent in the sheet of this example was as small as 0.1 μm.
[0094]
Example 6
A photoconductor was prepared under the same conditions as in Example 4 for the charge generation layer and the charge transport layer using an anodized aluminum cylinder having an outer diameter of 80 mm prepared by mirror finishing.
[0095]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charging of −400 V using an evaluation machine in which a Canon digital color copier CLC500 (corona charging method) was modified so as to have the above-mentioned irradiation spot diameter, the initial and 5000 Even after the sheet durability test, an image output with excellent uniformity was obtained, the gradation reproducibility was very good at 256 gradations at 400 dpi, and the wear amount of the photosensitive member was 0.2 μm per 1000 sheet durability tests. There were few.
[0096]
Further, when the contact angle of water on the surface of the photoreceptor was measured, the initial value was as good as 94 deg after the endurance test for 5000 sheets with respect to 104 deg.
[0097]
Example 7
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0098]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0099]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours.
[0100]
This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0101]
Next, 27.5 parts of the fluorine-modified organosilicon resin used in Synthesis Example 2, 55 parts of the triarylamine compound used in Example 4, and 55 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) A solution for charge transport layer in which 70 parts of tetrahydrofuran was dissolved was coated on the charge generation layer by a dip coating method to a thickness of 10 μm.
[0102]
The contact angle of water was 105 degrees.
[0103]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −700 V, E1 / 2 (exposure amount at which the charging potential decreased to −350 V) = 0.1 μJ / cm²The residual potential was as good as 45V.
[0104]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charge of −500 V using a modified laser beam printer P270 manufactured by Canon (modified to the above-mentioned irradiation spot condition and using an AC roller charger), a durability test of 4000 sheets was performed. The wear amount of the subsequent photoreceptor is very small, 2 μm or less, the contact angle of water after durability is 100 degrees, the image is not deteriorated, and the one-pixel reproducibility of the highlight portion in the input signal equivalent to 600 dpi is also achieved. It was enough.
[0105]
Example 8
In the same manner as in Example 7, 167 parts of phenol resin (trade name: PRIOFEN, manufactured by Dainippon Ink & Chemicals, Inc.) as a conductive layer using 100 mm of an aluminum cylinder having an outer diameter of 30 mm obtained by drawing is used as 100 parts of methyl cellosolve. A solution obtained by dispersing 200 parts of conductive barium sulfate ultrafine particles (primary particle size 50 nm) into the dissolved material was applied by a dip coating method so that the film thickness after drying was 10 μm. A 1 μm undercoat layer and a 0.2 μm charge generation layer were formed on the conductive support in the same manner as in Example 6.
[0106]
Next, a solution for a charge transport layer in which 5 parts of a triarylamine compound and 5 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) used in Example 4 were dissolved in 70 parts of chlorobenzene was prepared as described above. On the charge generation layer, the film was dried by a dip coating method and coated to a film thickness of 8 μm.
[0107]
On the charge transport layer, the resin solution prepared in Example 2 was applied by a spray coating method so as to be 4 μm after drying.
[0108]
The photoreceptor of the present invention was prepared by drying at 110 ° C. for 2 hours and thermosetting.
[0109]
The contact angle of water was 109 degrees.
[0110]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −700 V, E1 / 2 (exposure amount at which the charging potential decreased to −350 V) = 0.14 μJ / cm²The residual potential was as good as 39V.
[0111]
This electrophotographic photosensitive member is converted from a laser beam printer P270 manufactured by Canon (a laser spot diameter of 60 × 20 μm using a semiconductor laser of 780 nm and 100 mW).²When the image was evaluated at an initial charge of −500 V, the wear amount of the photoreceptor after the durability test of 4000 sheets was extremely small at 2.5 μm, and the contact angle of water was as good as 98 degrees. Thus, there was no deterioration of the image due to charge injection such as black spots and interference fringes, and the one-pixel reproducibility of the highlight portion with an input signal equivalent to 600 dpi was sufficient.
[0112]
Example 9
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0113]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0114]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours.
[0115]
This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0116]
Next, 27.5 parts of the fluorine-modified organosilicon resin used in Synthesis Example 2, 55 parts of the triarylamine compound used in Example 4, and 55 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) A solution for a charge transport layer in which 70 parts of tetrahydrofuran was dissolved was coated on the charge generation layer by a dip coating method to a thickness of 20 μm.
[0117]
The contact angle of water was 105 degrees.
[0118]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −700 V, E1 / 2 (exposure amount at which the charging potential decreased to −350 V) = 0.11 μJ / cm²The residual potential was as good as 51V.
[0119]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charge of −500 V using a modified laser beam printer P270 manufactured by Canon (modified to the above-mentioned irradiation spot condition and using an AC roller charger), a durability test of 4000 sheets was performed. The amount of wear of the subsequent photoconductor is very small, 2 μm or less, the contact angle of water after durability is as good as 100 degrees, and there is no image degradation, but the one pixel reproducibility of the highlight portion in the input signal equivalent to 600 dpi However, it was somewhat insufficient.
[0120]
Example 10
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0121]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0122]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours.
[0123]
This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0124]
Next, 47.0 parts of the fluorine-modified organosilicon resin used in Synthesis Example 3, 55 parts of the triarylamine compound used in Example 4, and 55 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) A solution for a charge transport layer in which 150 parts of tetrahydrofuran was dissolved was coated on the charge generation layer by a dip coating method to a thickness of 12 μm.
[0125]
The contact angle of water was 102 degrees.
[0126]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −550 V, E1 / 2 (exposure amount at which the charging potential decreased to −275 V) = 0.16 μJ / cm²The residual potential was as good as 30V.
[0127]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charge of −500 V using a modified laser beam printer P270 manufactured by Canon (modified to the above-mentioned irradiation spot condition and using an AC roller charger), a durability test of 4000 sheets was performed. The amount of wear of the subsequent photoreceptor was very small, 2 μm or less, the contact angle of water after durability was as good as 90 degrees, and there was no image deterioration.
[0128]
Example 11
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0129]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0130]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours.
[0131]
This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0132]
Next, 70 parts of the fluorine-modified organosilicon resin used in Synthesis Example 4, 55 parts of the triarylamine compound used in Example 4 and 55 parts of polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) The charge transport layer solution dissolved in 150 parts of hydrofuran was coated on the charge generation layer by a dip coating method to a film thickness of 15 μm.
[0133]
The contact angle of water was 112 degrees.
[0134]
When the electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −700 V, E1 / 2 (exposure amount at which the charging potential decreased to −350 V) = 0.20 μJ / cm²The residual potential was as good as 40V.
[0135]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charge of −500 V using a modified laser beam printer P270 manufactured by Canon (modified to the above-mentioned irradiation spot condition and using an AC roller charger), a durability test of 4000 sheets was performed. The amount of wear of the subsequent photoreceptor was very small, 3 μm or less, the contact angle of water after durability was 100 °, and the image was not deteriorated.
[0136]
Example 12
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0137]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0138]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours.
[0139]
This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0140]
Next, 20 parts of the fluorine-modified organosilicon resin used in Synthesis Example 5, 55 parts of the triarylamine compound used in Example 4 and 55 parts of polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) A liquid for a charge transport layer dissolved in 150 parts of hydrofuran was coated on the charge generation layer by a dip coating method to a film thickness of 12 μm.
[0141]
The contact angle of water was 108 degrees.
[0142]
When electrophotographic characteristics were measured at a wavelength of 680 nm after charging to −550 V, E1 / 2 (exposure amount at which the charging potential decreased to −275 V) = 0.19 μJ / cm²The residual potential was as good as 28V.
[0143]
When this electrophotographic photosensitive member was subjected to image evaluation at an initial charging of −500 V using a modified laser beam printer P270 manufactured by Canon (modified to the above-mentioned irradiation spot condition and using an AC roller charger), a durability test of 4000 sheets was performed. The amount of wear of the subsequent photoreceptor was very small, 3 μm or less, the contact angle of water after durability was as good as 93 degrees, and there was no image deterioration.
[0144]
Comparative Example 1
Teflon fine particles (manufactured by Taikin Kogyo Co., Ltd., Lubron LD-1, particle size of about 0.2 μm), 4- [2- (triethoxysilyl) ethyl] triphenylamine and polycarbonate resin (trade name Z-200, Mitsubishi Gas) Chemical Co., Ltd.) was dissolved in THF so as to be 5 wt%, 47.5 wt%, and 47.5 wt%, respectively, as a solid content.
[0145]
This was applied to a glass plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 10 μm cloudy film was obtained. When observed with a microscope, aggregated Teflon particles were observed.
[0146]
Furthermore, when this sample was measured for absorption at a wavelength of 600 nm with a spectrophotometer, 0.022 was obtained as the absorbance per 1 μm of film thickness, and it was confirmed that considerable light was scattered.
[0147]
Further, when the contact angle of water was measured, the surface energy was not sufficiently reduced to 86 deg.
[0148]
Comparative Example 2
Preparation of resin solution mainly composed of methylpolysiloxane resin
10 g of a silicone resin containing 1 mol% of silanol groups composed of 80 mol% of methylsiloxane units and 20 mol% of dimethylsiloxane units was dissolved in 10 g of toluene to obtain a uniform solution.
[0149]
Compatibility test for charge transport layer
The above-mentioned methylpolysiloxane resin solution, 4- [2- (triethoxysilyl) ethyl] triphenylamine and polycarbonate resin (trade name Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids are 5% by weight and 47%, respectively. Dissolved in THF to 5 wt% and 47.5 wt%.
[0150]
When this was applied to a glass plate using a bar coat and dried at 120 ° C. for 1 hour, after drying, a 10 μm cloudy and uneven film was obtained. When observed with a microscope, an agglomerated non-uniform portion was observed.
[0151]
Furthermore, when this sample was measured for absorption at a wavelength of 600 nm with a spectrophotometer, 0.05 was obtained as the absorbance per 1 μm of film thickness, and it was confirmed that a considerable amount of light was scattered.
[0152]
Further, when the contact angle of water was measured, the surface energy was lowered to 103 deg.
[0153]
Comparative Example 3
Preparation of resin solution based on phenylpolysiloxane resin
12 g of a siloxane resin containing 1% by weight silanol group consisting of 40 mol% phenylsiloxane units, 20 mol% diphenylsiloxane units, 20 mol% methylsiloxane units and 20% dimethylsiloxane units was dissolved in 10 g of toluene to obtain a uniform solution. did.
[0154]
Compatibility test for charge transport layer
20% by weight of each of the above methylpolyphenylsiloxane resin solution, 4- [2- (triethoxysilyl) ethyl] triphenylamine and polycarbonate resin (trade name Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids, It dissolved in THF so that it might become 40 weight% and 40 weight%.
[0155]
This was applied to a glass plate using a bar coat and dried at 120 ° C. for 1 hour. After drying, a 10 μm cloudy film was obtained.
[0156]
Furthermore, when the absorption of this sample at a wavelength of 600 nm was measured with a spectrophotometer, 0.012 was obtained as an absorbance per 1 μm of film thickness, and it was confirmed that considerable light was scattered.
[0157]
Moreover, when the contact angle of water was measured, 88 deg and surface energy reduction were not enough.
[0158]
Comparative Example 4
4- [2- (triethoxysilyl) ethyl] triphenylamine and polycarbonate resin (trade name Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as solids were adjusted to 50 wt% and 50 wt%, respectively. Dissolved in.
[0159]
When this was applied to a 50 μm thick aluminum plate using a bar coat and dried at 120 ° C. for 1 hour, a 20 μm transparent and uniform film was obtained after drying. Observation with a microscope revealed that a uniform film was formed.
[0160]
Furthermore, a conductive rubber roller is brought into contact with this sample, an aluminum plate is grounded, −600 V is applied to the conductive rubber roller, and further, an alternating current of 1500 V and 1500 Hz between peaks is superimposed, and a deterioration test due to charging is performed for 1 hour. went. As a result of the deterioration test, a dent due to discharge was generated near the portion where the conductive rubber roller was in contact with the sheet, and the depth of the dent was measured as an evaluation of the discharge resistance.
[0161]
As a result, the dent in the above sheet was as large as 1 μm.
[0162]
Comparative Example 5
A solution for a charge transport layer prepared by dissolving 5 parts of a triarylamine compound and 5 parts of a polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) used in Example 4 in 70 parts of chlorobenzene was used as the charge generation layer. After being dried by a dip coating method and coated to a film thickness of 12 μm, and image evaluation was performed with the same Canon laser beam printer as in Example 4, interference fringes and black spots were found after 4000 endurance tests. It was recognized that the amount of wear was as large as 5 μm and the contact angle of water was as small as 72 degrees, which was unsatisfactory, and one pixel reproduction of the highlight portion at 600 dpi was insufficient and uneven.
[0163]
Comparative Example 6
Conductivity of 167 parts phenolic resin (trade name Pryofen, manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve as a conductive layer using an aluminum cylinder with an outer diameter of 30 mm obtained by drawing. A dispersion in which 200 parts of barium sulfate ultrafine particles (primary particle size 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dip coating method so that the film thickness after drying was 15 μm.
[0164]
As an undercoat layer, a solution obtained by dissolving 5 parts of alcohol-soluble copolymer nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. The film was dried at 80 ° C. for 10 minutes to form an undercoat layer having a thickness of 1 μm.
[0165]
Next, 5 parts of a type I oxytitanium phthalocyanine pigment as a charge generation layer was added to a solution obtained by dissolving 2 parts of polyvinyl benzal (benzalization degree: 75% or more) in 95 parts of cyclohexanone, and dispersed in a sand mill for 2 hours. This dispersion was coated on the previously formed undercoat layer by a dip coating method so that the film thickness after drying was 0.2 μm.
[0166]
On the charge generation layer, 5 parts of the triarylamine compound used in Example 4, 5 parts of polycarbonate resin (trade name Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.5 parts of Teflon fine particles were added to 70 parts of chlorobenzene. The solution for the charge transport layer dispersed and dissolved in the sample was dried by a dip coating method and coated to a film thickness of 12 μm, and image evaluation was performed with the same Canon laser beam printer as in Example 4. After the test, the wear amount was about 4 μm and the contact angle of water was 89 degrees, which was slightly low surface energy. However, one pixel reproduction of the highlight portion at 600 dpi was insufficient and uneven from the beginning of the durability.
[0167]
【The invention's effect】
Since the electrophotographic photoreceptor of the present invention uses a specific fluorine-modified organosilicon resin for the surface layer, it is excellent in abrasion resistance and has low surface energy, so it is less contaminated and excellent in cleaning properties. Moreover, it has excellent electrical characteristics such as residual potential. Further, since the electrophotographic photosensitive member has little light scattering, an electrophotographic image forming apparatus using the electrophotographic photosensitive member not only has excellent durability but also provides a good image after durability.
[Brief description of the drawings]
FIG. 1 is a front view showing an example of an electrophotographic apparatus of the present invention.
FIG. 2 is a front view showing another example of the electrophotographic apparatus of the present invention.
FIG. 3 is a front view showing another example of the electrophotographic apparatus of the present invention.
FIG. 4 is a diagram showing a relationship between an intensity distribution of an irradiation light beam and a spot area.
FIG. 5 is a front view showing another example of the electrophotographic apparatus of the present invention.
FIG. 6 is a front view showing another example of the electrophotographic apparatus of the present invention.
[Explanation of symbols]
1 Electrophotographic photoreceptor
2 Charging means
4 Development means
5 Transfer means
6 Cleaning means
7 Pre-exposure means
9 Recording material
10 Direct charging member

Claims (10)

On a conductive support an electrophotographic photosensitive member having a photosensitive layer, a surface layer of the photosensitive body, and fluorine-modified organic silicone resin of weight average molecular weight from 1,000 to 100,000 represented by the following average unit formula (I), the binding an electrophotographic photosensitive member, characterized in that it contains a Chakujushi, a:
_{{F (CF 2) a1 -Q} 1 -R 1m1 SiO (3-m1) / 2} x1 {F (CF 2) a2 -Q 2 -R 2m2 SiO (3-m2) / 2} x2 ··· { _{F (CF 2) ap -Q p} -R pmp SiO (3-mp) / 2} xp {R '1n1 SiO (4-n1) / 2} y1 {R' 2n2 SiO (4-n2) / 2} y2 ... {R ' _qnq SiO _{(4-nq) / 2} } _yq (I)
_{(Wherein, R 1, ..., R p} , R '1, ..., R' q is an alkyl group or an aryl _{group, Q 1, ..., .m 1} Q p is an alkylene group, ..., m _p Is an integer from 0 to 2, n ₁ ,..., N _q are integers from 0 to 3, a ₁ ,..., A _p are integers, x ₁ and y ₁ are numbers greater than 0, x ₂ ,..., x _p , y _{2 ,.} The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a photosensitive layer. The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a charge transport layer. The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a charge generation layer. The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a protective layer. R ₁ ,..., R _p , R ′ ₁ ,..., R ′ _q have 1 to 12 carbon atoms, Q ₁ ,..., Q _p have 2 to 6 carbon atoms, and (x ₁ + x ₂ +. _2. The electrophotographic photosensitive member according to claim _{1, wherein p} ) :( y ₁ + y ₂ +... + y _q ) = 1: 20 to 1: 5. Image forming an electrophotographic photosensitive member according to any one of claims 1 to 6, a charging means for charging said electrophotographic photosensitive member, an electrostatic latent image performs image exposure to the charged the electrophotographic photosensitive member exposing means and an electrophotographic apparatus, characterized in that it comprises a developing means for developing said electrophotographic photosensitive member is formed of an electrostatic latent image with toner, a. The electrophotographic apparatus according to claim 7, wherein the charging means is a direct charging member. A process cartridge comprising at least one of a charging unit, a developing unit, and a cleaning unit, together with the electrophotographic photosensitive member according to any one of claims 1 to 6 . A process cartridge comprising a direct charging member and the electrophotographic photosensitive member according to claim 1 collectively.

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