JP4011791B2 - Method for producing electrophotographic photosensitive member - Google Patents

Description

【００２０】
上記中、Ｒは置換基を有してもよいメチル基、エチル基及びプロピル基等のアルキル基、置換基を有してもよいベンジル基及びフェネチル基等のアラルキル基及び置換基を有してもよいフェニル基、ナフチル基及びアンスリル基等のアリール基または水素原子等を示す。
【００２１】
開環重合とは、炭素環、オクソ環及び窒素ヘテロ環等のひずみを有した不安定な環状構造が、触媒の作用で活性化され開環すると同時に重合を繰り返し鎖状高分子物を生成する反応であるが、この場合基本的にはイオンが活性種として作用するものが大部分である。開環重合官能基の具体例を以下に示すが、これらに限定されるものではない。
【００２２】
【外１０】

【００２３】
上記中、Ｒ′は置換基を有してもよいメチル基、エチル基及びプロピル基等のアルキル基、置換基を有してもよいベンジル基及びフェネチル基等のアラルキル基及び置換基を有してもよいフェニル基、ナフチル基及びアンスリル基等のアリール基または水素原子等を示す。
【００２４】
上記で説明したような本発明に係る連鎖重合性官能基の中でも、下記の一般式（５）〜（７）で示されるものが好ましい。
【００２５】
【外１１】

【００２６】
式（５）中、Ｅは水素原子、フッ素、塩素及び臭素等のハロゲン原子、置換基を有してもよいメチル基、エチル基、プロピル基及びブチル基等のアルキル基、置換基を有してもよいベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等のアラルキル基、置換基を有してもよいフェニル基、ナフチル基、アンスリル基、ピレニル基、チオフェニル基及びフリル基等のアリール基、ＣＮ基、ニトロ基、メトキシ基、エトキシ基及びプロポキシ基等のアルコキシ基、−ＣＯＯＲ^７及びＣＯＮＲ^８Ｒ^９を示す。
【００２７】
Ｗは置換基を有してもよい２価のフェニレン、ナフチレン及びアントラセニレン等のアリーレン基、置換基を有してもよいメチレン、エチレン及びブチレン等の２価のアルキレン基、−ＣＯＯ−、−ＣＨ_２−、−Ｏ−、−ＯＯ−、−Ｓ−またはＣＯＮＲ^１０−で示される。
【００２８】
Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は水素原子、フッ素、塩素及び臭素等のハロゲン原子、置換基を有してもよいメチル基、エチル基及びプロピル基等のアルキル基、置換基を有してもよいベンジル基及びフェネチル基等のアラルキル基及び置換基を有してもよいフェニル基、ナフチル基及びアンスリル基等のアリール基を示し、Ｒ^８とＲ^９は互いに同一であっても異なってもよい。
【００２９】
また、ｆは０または１を示す。
【００３０】
Ｅ及びＷが有してもよい置換基としては、フッ素、塩素、臭素及びヨウ素等のハロゲン原子、ニトロ基、シアノ基、水酸基、メチル基、エチル基、プロピル基及びブチル基等のアルキル基、メトキシ基、エトキシ基及びプロポキシ基等のアルコキシ基、フェノキシ基及びナフトキシ基等のアリールオキシ基、ベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等のアラルキル基、フェニル基、ナフチル基、アンスリル基及びピレニル基等のアリール基等が挙げられる。
【００３１】
【外１２】

【００３２】
式（６）中、Ｒ^１１及びＲ^１２は水素原子、置換基を有してもよいメチル基、エチル基、プロピル基及びブチル基等のアルキル基、置換基を有してもよいベンジル基及びフェネチル基等のアラルキル基及び置換基を有してもよいフェニル基及びナフチル基等のアリール基を示し、ｇは１〜１０の整数を示す。
【００３３】
【外１３】

【００３４】
式（７）中、Ｒ^１３及びＲ^１４は水素原子、置換基を有してもよいメチル基、エチル基、プロピル基及びブチル基等のアルキル基、置換基を有してもよいベンジル基及びフェネチル基等のアラルキル基及び置換基を有してもよいフェニル基及びナフチル基等のアリール基を示し、ｈは０〜１０の整数を示す。
【００３５】
上記一般式の（６）及び（７）のＲ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４が有してもよい置換基としては、フッ素、塩素、臭素及びヨウ素等のハロゲン原子、メチル基、エチル基、プロピル基及びブチル基等のアルキル基、メトキシ基、エトキシ基及びプロポキシ基等のアルコキシ基、フェノキシ基及びナフトキシ基等のアリールオキシ基、ベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等のアラルキル基及びフェニル基、ナフチル基、アンスリル基及びピレニル基等のアリール基等が挙げられる。
【００３６】
また、上記一般式（５）〜（７）の中でも、更に特に好ましい連鎖重合性官能基としては、下記一般式（８）〜（１４）で示されるものが挙げられる。
【００３７】
【外１４】

【００３８】
更に、上記式（８）〜（１４）の中でも、（８）のアクリロイルオキシ基及び（９）のメタクリロイルオキシ基が、重合特性等の点から特に好ましい。
【００３９】
本発明における「同一分子内に二つ以上の連鎖重合性官能基を有する正孔輸送性化合物」とは、上記で説明した連鎖重合性官能基が正孔輸送性化合物に官能基として少なくとも二つ以上化学結合している化合物である。二つ以上の連鎖重合性官能基は、全て同一でも異なったものであってもよい。
【００４０】
連鎖重合性官能基を二つ以上有する正孔輸送性化合物は、下記の一般式（１）で示されることが好ましい。
【００４１】
【外１５】

【００４２】
Ｐ^１及びＰ^２は連鎖重合性官能基を示し、Ｐ^１とＰ^２は同一でも異なってもよい。Ｚは置換基を有してもよい有機残基を示し、Ｙは水素原子を示す。ａ、ｂ及びｄは、０または１以上の整数を示す。但し、ａ＝０の場合はｂ＋ｄは３以上の整数、ｂまたはｄが０の場合はａは２以上の整数、その他の場合はａ＋ｂ＋ｄは３以上の整数を示す。また、ａが２以上の場合Ｐ^１は同一でも異なってもよく、ｄが２以上の場合Ｐ^２は同一でも異なってもよく、またｂが２以上の場合、Ｚは同一でも異なってもよい。
【００４３】
ここで、「ａが２以上の場合Ｐ^１は同一でも異なってもよく」とは、それぞれ異なるｎ種類の連鎖重合性官能基をＰ^１１、Ｐ^１２、Ｐ^１３、Ｐ^１４、Ｐ^１５…ｐ^ｌｎと示した場合、例えばａ＝３の時に正孔輸送性化合物Ａに直接結合する連鎖重合性官能基Ｐ^１は３つとも同じものでも、二つ同じで一つは違うもの（例えば、Ｐ^１１とＰ^１１とＰ^１２とか）でも、それぞれ３つとも異なるもの（例えば、Ｐ^１２とＰ^１５とＰ^１７とか）でもよいということを意味するものである（「ｄが２以上の場合Ｐ^２は同一でも異なってもよく」というのも、「ｂが２以上の場合、Ｚは同一でも異なってもよい」というのもこれを同様なことを意味するものである。）。
【００４４】
上記一般式（１）のＡは正孔輸送性基を示し、正孔輸送性を示すものであればいずれのものでもよく、Ｐ^１やＺを水素原子に置き換えた水素付加化合物（正孔輸送性化合物）として示せば、例えばオキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、トリフェニルアミン等のトリアリールアミン誘導体、９−（ｐ−ジエチルアミノスチリル）アントラセン、１，１−ビス−（４−ジベンジルアミノフェニル）プロパン、スチリルアントラセン、スチリルピラゾリン、フェニルヒドラゾン類、チアゾール誘導体、トリアゾール誘導体、フェナジン誘導体、アクリジン誘導体、ベンゾフラン誘導体、ベンズイミダゾール誘導体、チオフェン誘導体及びＮ−フェニルカルバゾール誘導体等が挙げられる。
【００４５】
更に、上記正孔輸送性化合物の中でも、下記一般式（４）で示されるものが好ましい。
【００４６】
【外１６】

【００４７】
式（４）中、Ｒ^４、Ｒ^５及びＲ^６は置換基を有してもよいメチル基、エチル基、プロピル基及びブチル基等のＣ_１〜Ｃ_１０のアルキル基、置換基を有してもよいベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等のアラルキル基及び置換基を有してもよいフェニル基、ナフチル基、アンスリル基、フェナンスリル基、ピレニル基、チオフェニル基、フリル基、ピリジル基、キノリル基、ベンゾキノリル基、ガルバゾリル基、フェノチアジニル基、ベンゾフリル基、ベンゾチオフェニル基、ジベンゾフリル基及びジベンゾチオフェニル基等のアリール基を示す。
【００４８】
但し、Ｒ^４、Ｒ^５及びＲ^６のうち少なくとも二つはアリール基を示し、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ同一であっても異なっていてもよい。更に、その中でもＲ^４、Ｒ^５及びＲ^６のすべてがアリール基であるものが特に好ましい。また、上記一般式（４）のＲ^４、Ｒ^５及びＲ^６のうちの任意の二つは、それぞれ直接もしくは結合基を介して結合してもよく、その結合基としてはメチル基、エチル基及びプロピレン基等のアルキレン基、酸素原子及び硫黄原子等のヘテロ原子及びＣＨ＝ＣＨ基等が挙げられる。
【００４９】
また、上記一般式（１）中のＺは、置換基を有してもよいアルキレン基、置換基を有してもよいアリーレン基、ＣＲ^１＝ＣＲ^２（Ｒ^１及びＲ^２はアルキル基、アリール基及び水素原子を示し、Ｒ^１及びＲ^２は同一でも異なってもよい。）、Ｃ＝Ｏ、Ｓ＝Ｏ、ＳＯ_２、酸素原子及び硫黄原子より選ばれる一つあるいはこれらを任意に組み合わせた有機残基を示す。その中でも下記一般式（２）で示されるものが好ましく、下記一般式（３）で示されるものが特に好ましい。
【００５０】
【外１７】

【００５１】
上記一般式（２）中、Ｘ^１〜Ｘ^３は置換基を有してもよいメチレン基、エチレン基及びプロピレン基等のＣ_１〜Ｃ_２０のアルキレン基、（ＣＲ^１＝ＣＲ^２）ｍ、Ｃ＝Ｏ、Ｓ＝Ｏ、ＳＯ_２、酸素原子及び硫黄原子を示し、Ａｒ^１及びＡｒ^２は置換基を有してもよい２価のアリーレン基（フェニレン、ナフタレン、アントラセン、フェナンスレン、ピレン、ベンゾチオフェン、ピリジン、キノリン、ベンゾキノリン、カルバゾール、フェノチアジン、ベンゾフラン、ベンゾチオフェン、ジベンゾフラン及びジベンゾチオフェン等より２個の水素原子をとった基）を示す。
【００５２】
Ｒ^１及びＲ^２は、置換基を有してもよいメチル基、エチル基及びプロピル基等のアルキル基、置換基を有してもよいフェニル基、ナフチル基及びチオフェニル基等のアリール基及び水素原子を示し、Ｒ^１及びＲ^２は同一でも異なってもよい。
【００５３】
ｍは１〜５の整数、ｐ〜ｔは０〜１０の整数を示す（但し、ｐ〜ｔは同時に０であることはない。）。
【００５４】
上記一般式（３）中、Ｘ^４及びＸ^５は（ＣＨ_２）ｍ′、（ＣＨ＝ＣＲ^３）ｎ′、Ｃ＝Ｏ及び酸素原子を示し、Ａｒ^３は置換基を有してもよい２価のアリーレン基（フェニレン、ナフタレン、アントラセン、フェナンスレン、ピレン、ベンゾチオフェン、ピリジン、キノリン、ベンゾキノリン、カルバゾール、フェノチアジン、ベンゾフラン、ベンゾチオフェン、ジベンゾフラン及びジベンゾチオフェン等より２個の水素原子をとった基）を示す。
【００５５】
Ｒ^３は置換基を有してもよいメチル基、エチル基及びプロピル基等のアルキル基、置換基を有してもよいフェニル基、ナフチル基及びチオフェニル基等のアリール基及び水素原子を示す。ｍ′は１〜１０の整数、ｎ′は１〜５の整数、ｕ〜ｗは０〜１０の整数を示す（ｕ〜ｗは０〜５の整数であることが特に好ましい。但し、ｕ〜ｗは同時に０であることはない。）。
【００５６】
上記一般式（１）〜（４）のＲ^１〜Ｒ^６、Ａｒ^１〜Ａｒ^３、Ｘ^１〜Ｘ^５及びＺがそれぞれ有してもよい置換基としては、フッ素、塩素、臭素及びヨウ素等のハロゲン原子、ニトロ基、シアノ基、水酸基、メチル基、エチル基、プロピル基及びブチル基等のアルキル基、メトキシ基、エトキシ基及びプロポキシ基等のアルコキシ基、フェノキシ基、ナフトキシ基等のアリールオキシ基、ベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等のアラルキル基、フェニル基、ナフチル基、アンスリル基及びピレニル基等のアリール基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基、ジフェニルアミノ基及びジ（ｐ−トリル）アミノ基等の置換アミノ基及びスチリル基及びナフチルビニル基等のアリールビニル基等が挙げられる。
【００５７】
本発明における同一分子内に二つ以上の連鎖重合性官能基を有する正孔輸送性化合物は、酸化電位が１．２（Ｖ）以下であることが好ましく、特には０．４〜１．２（Ｖ）であることが好ましい。
【００５８】
酸化電位が１．２（Ｖ）を超えると電荷発生材料よりの電荷（正孔）の注入が起こり難くく、残留電位の上昇や感度悪化及び繰り返し使用時の電位変動が大きくなる等の問題が生じ易くなる。また、酸化電位が０．４（Ｖ）未満では、帯電能の低下等の問題の他に、化合物自体が容易に酸化されるために劣化し易く、それに起因した感度悪化、画像ボケ及び繰り返し使用時の電位変動が大きくなる等の問題が生じ易くなる。なお、酸化電位は、以下の方法によって測定される。
【００５９】
（酸化電位の測定法）
飽和カロメル電極を参照電極とし、電解液に０．１Ｎ（ｎ−Ｂｕ）_４Ｎ^＋ＣｌＯ_４ ⁻アセトニトリル溶液を用い、ポテンシャルスイーパによって作用電極（白金）に印加する電位をスイープし、得られた電流−電位曲線がピークを示した時の電位を酸化電位とした。
【００６０】
詳しくは、サンプルを０．１Ｎ（ｎ−Ｂｕ）_４Ｎ^＋ＣｌＯ_４ ⁻アセトニトリル溶液に５〜１０ｍｍｏｌ％程度の濃度になるように溶解する。そして、このサンプル溶液に作用電極によって電圧を加え、電圧を低電位（０Ｖ）から高電位（＋１．５Ｖ）に直線的に変化させた時の電流変化を測定し、電流−電位曲線を得る。この電流−電位曲線において電流値がピーク（ピークが複数ある場合には最初のピーク）を示した時の電位を酸化電位とした。
【００６１】
以下に二つ以上の連鎖重合性官能基を有する正孔輸送性化合物の好ましい例を挙げるが、これらに限定されるものではない。
【００６２】
【表１】

【００６３】
【表２】

【００６４】
【表３】

【００６５】
【表４】

【００６６】
【表５】

【００６７】
【表６】

【００６８】
【表７】

【００６９】
【表８】

【００７０】
【表９】

【００７１】
【表１０】

【００７２】
【表１１】

【００７３】
【表１２】

【００７４】
【表１３】

【００７５】
【表１４】

【００７６】
【表１５】

【００７７】
【表１６】

【００７８】
【表１７】

【００７９】
【表１８】

【００８０】
【表１９】

【００８１】
本発明に用いられる連鎖重合性官能基を有する正孔輸送性化合物の代表的な合成例を以下に示す。
【００８２】
（合成例１：化合物Ｎｏ．６の合成）
以下のルートに従い合成した。
【００８３】
【外１８】

【００８４】
１（５０ｇ：０．４７ｍｏｌ）、２（４０６ｇ：１．４ｍｏｌ）、無水炭酸カリウム（１９３ｇ）及び銅粉（４４５ｇ）を１，２−ジクロロベンゼン１．２ｋｇと共に１８０〜１９０℃で１５時間加熱撹拌した。反応液を濾過後、減圧下で溶媒を除去し、残留物をシリカゲルカラムを用いカラム精製を行い３を１３２ｇを得た。
【００８５】
３（１２０ｇ：０．２８ｍｏｌ）をメチルセルソルブ１．５ｋｇに加え室温で撹拌しながらナトリウムメチラート（１５０ｇ）をゆっくり添加した。添加終了後そのまま室温で１時間撹拌後、更に７０〜８０℃で１０時間加熱撹拌を行った。反応液を水にあけ希塩酸で中和後、酢酸エチルで抽出し、有機層を無水硫酸ナトリウムで乾燥後、減圧下で溶媒を除去した。残留物をシリカゲルカラムを用いカラム精製を行い４を７８ｇ得た。
【００８６】
４（７０ｇ：０．２ｍｏｌ）及びトリエチルアミン（４０ｇ：０．４ｍｏｌ）を、乾燥テトラヒドロフラン（ＴＨＦ）４００ｍｌに加え０〜５℃に冷却後、塩化アクリロイル（５５ｇ：０．６ｍｏｌ）をゆっくり滴下した。滴下終了後ゆっくり室温に戻し、室温でそのまま４時間撹拌を行った。反応液を水にあけ中和後、酢酸エチルで抽出し、有機層を無水硫酸ナトリウムで乾燥後、溶媒を除去した。残留物をシリカゲルカラムを用いカラム精製を行い５（化合物Ｎｏ．６）を４２ｇ得た（酸化電位：０．８３Ｖ）。
【００８７】
（合成例２：化合物Ｎｏ．７１の合成）
上記合成例１で得られた４（１０ｇ：２９ｍｍｏｌ）を乾燥ＴＨＦ５０ｍｌに加え０〜５℃に冷却後、油性水素化ナトリウム（約６０％）３．５ｇをゆっくり添加した。添加終了後に室温に戻し１時間撹拌後、再び０〜５℃に冷却しアリルブロマイド（１７．５ｇ：１４５ｍｍｏｌ）をゆっくり滴下した。滴下終了後そのまま１時間撹拌後、室温に戻し更に５時間撹拌を行った。反応液を水にあけ中和後、トルエンで抽出し有機層を無水硫酸ナトリウムで乾燥後溶媒を除去した。残留物をシリカゲルカラムを用いカラム精製を行い、目的化合物（化合物Ｎｏ．７１）を５．６ｇ得た（酸化電位：０．８１Ｖ）。
【００８８】
（合成例３：化合物Ｎｏ．５５の合成）
上記合成例２で得られた化合物Ｎｏ．７１ ３．０ｇをジクロロメタン２０ｍｌに溶解後０〜５℃に冷却し、ｍ−クロロ過安息香酸（〜７０％）５．２ｇをゆっくり添加しそのまま１時間撹拌後、室温に戻し１２時間撹拌を行った。反応液を水にあけジクロロメタンで抽出を行った。有機層を無水硫酸ナトリウムで乾燥後、溶媒を除去し、残留物をシリカゲルカラムを用いカラム精製を行い、目的化合物（化合物Ｎｏ．５５）を２．１ｇ得た（酸化電位：０．８１Ｖ）。
【００８９】
（合成例４：化合物Ｎｏ．３１の合成）
以下のルートに従い合成した。
【００９０】
【外１９】

【００９１】
６（４０ｇ：０．２４ｍｏｌ）、７（７７ｇ：０．３５ｍｏｌ）、無水炭酸カリウム（４８．８ｇ）及び銅粉（７５ｇ）を１，２−ジクロロベンゼン２５０ｇと共に１８０〜１９０℃で１０時間加熱撹拌した。反応液を濾過後、減圧下で溶媒を除去し、残留物をシリカゲルカラムを用いカラム精製を行い８を４９ｇ得た。
【００９２】
ジメチルホルムアミド（ＤＭＦ）２４２．３ｇを０〜５℃に冷却後、オキシ塩化リン８４．８ｇを１０℃を超えないようにゆっくり滴下した。滴下終了後１５分そのまま撹拌後、８（２４ｇ：０．０９３ｍｏｌ）／ＤＭＦ（１３５ｇ）溶液をゆっくり滴下した。滴下終了後そのまま３０分撹拌後、室温に戻し２時間撹拌し、更に８０〜８５℃に加熱し６時間撹拌を行った。反応液を約１５％の酢酸ナトリウム水溶液２ｋｇにあけ１２時間撹拌を行った。それを中和後、トルエンを用い抽出し、有機層を無水硫酸ナトリウムで乾燥後溶媒を除去し、残留物をシリカゲルカラムを用いカラム精製を行い９を１６ｇ得た。
【００９３】
乾燥ＴＨＦ１００ｍｌに水素化リチウムアルミニウム１．８５ｇを加え室温で撹拌しているところへ、９（１５ｇ：０．４８ｍｏｌ）／乾燥ＴＨＦ（１００ｍｌ）溶液をゆっくり滴下した。滴下終了後室温で４時間撹拌後、５％塩酸水溶液４００ｍｌをゆっくり滴下した。滴下終了後トルエンで抽出し、有機層を無水硫酸ナトリウムで乾燥後溶媒を除去し、残留物をシリカゲルカラムを用いカラム精製を行い１０を１３ｇ得た。
【００９４】
１０（１０ｇ：０．０３ｍｏｌ）及びトリエチルアミン（１２ｇ：０．１２ｍｏｌ）を、乾燥ＴＨＦ１５０ｍｌに加え０〜５℃に冷却後、塩化アクリロイル（８．５ｇ：０．０９ｍｏｌ）をゆっくり滴下した。滴下終了後ゆっくり室温に戻し、室温でそのまま４時間撹拌を行った。反応液を水にあけ中和後、酢酸エチルで抽出し、有機層を無水硫酸ナトリウムで乾燥後溶媒を除去した。残留物をシリカゲルカラムを用いカラム精製を行い１１（化合物Ｎｏ．３１）を５．６ｇ得た（酸化電位：０．９３Ｖ）。
【００９５】
本発明においては、前記同一分子内に二つ以上の連鎖重合性官能基を有する正孔輸送性化合物を重合、架橋させることで、その感光層中において、正孔輸送能を有する化合物は少なくとも二つ以上の架橋点をもって３次元架橋構造の中に共有結合を介して取り込まれる。前記正孔輸送性化合物は、それのみを重合、架橋させる、あるいは他の連鎖重合性官能基を有する化合物と混合させることのいずれもが可能であり、その種類／比率は全て任意である。ここでいう他の連鎖重合性官能基を有する化合物とは、連鎖重合性官能基を有する単量体、オリゴマー及びポリマーのいずれもが含まれる。
【００９６】
正孔輸送性化合物の官能基とその他の連鎖重合性化合物の官能基が、同一の基あるいは互いに重合可能な基である場合には、両者は共有結合を介した共重合３次元架橋構造をとることが可能である。両者の官能基が互いに重合しない官能基である場合には、感光層は少なくとも二つ以上の３次元硬化物の混合物あるいは主成分の３次元硬化物中に他の連鎖重合性化合物単量体、あるいはその硬化物を含んだものとして構成されるが、その配合比率／製膜方法をうまくコントロールすることで、ＩＰＮ（Ｉｎｔｅｒ Ｐｅｎｅｔｒａｔｉｎｇ Ｎｅｔｗｏｒｋ）、即ち、相互進入網目構造を形成することも可能である。
【００９７】
また、前記正孔輸送性化合物と連鎖重合性官能基を有しない単量体、オリゴマー及びポリマーや連鎖重合性以外の重合性官能基を有する単量体、オリゴマー及びポリマー等から感光層を形成してもよい。更に、場合によっては、３次元架橋構造に化学結合的に組み込まれない。即ち、連鎖重合性官能基を有しない正孔輸送性化合物を含有することも可能である。また、その他の各種添加剤、例えばフッ素原子含有樹脂微粒子等の滑剤等を含有してもよい。
【００９８】
本発明の製造方法で製造される電子写真感光体は、支持体上に感光層として電荷発生物質を含有する電荷発生層及び電荷輸送物質を含有する電荷輸送層を、この順に積層した構成あるいは逆に積層した構成、また電荷発生物質と電荷輸送物質を同一層中に分散した単層からなる構成のいずれの構成をとることも可能である。前者の積層型においては電荷輸送層が二層以上の構成、また後者の単層型においては電荷発生物質と電荷輸送物質を同一に含有する感光層上に更に電荷輸送層を構成してもよく、更には電荷発生層あるいは電荷輸送層上に保護層を形成することも可能である。
【００９９】
これらいずれの場合においても、先の連鎖重合性官能基を有する正孔輸送性化合物及び／あるいは前正孔輸送性化合物を重合、架橋したものを感光層が含有していればよい。但し、電子写真感光体としての特性、特に残留電位等の電気的特性及び耐久性の点より、電荷発生層及び電荷輸送層をこの順に積層した機能分離型感光体構成が好ましく、本発明の利点も電荷輸送能を低下させることなく表面層の高耐久化が可能になった点にある。
【０１００】
電子写真感光体が有する支持体は、導電性を有するものであればよい。例えばアルミニウム、銅、クロム、ニッケル、亜鉛及びステンレス等の金属や合金をドラム状またはシート状に成形したもの、アルミニウム及び銅等の金属泊をプラスチックフィルムにラミネートしたもの、アルミニウム、酸化インジウム及び酸化錫等をプラスチックフィルムに蒸着したもの、導電性物質を単独または結着樹脂と共に塗布して導電層を設けた金属、プラスチックフィルム及び紙等が挙げられる。
【０１０１】
本発明においては、支持体と感光層の間にバリアー機能と接着機能をもつ下引き層を設けることができる。下引き層は感光層の接着性改良、塗工性改良、支持体の保護、支持体の欠陥の被覆、支持体からの電荷注入性改良、また感光層の電気的破壊に対する保護等のために形成される。
【０１０２】
下引き層の材料としては、ポリビニルアルコール、ポリ−Ｎ−ビニルイミダゾール、ポリエチレンオキシド、エチルセルロース、エチレン−アクリル酸共重合体、カゼイン、ポリアミド、Ｎ−メトキシメチル化６ナイロン、共重合ナイロン、にかわ及びゼラチン等が挙げられる。下引き層は、これらの材料をそれぞれに適した溶剤に溶解した溶液を支持体上に塗布し、乾燥することによって形成される。膜厚は、０．１〜２μｍであることが好ましい。
【０１０３】
上述のように、積層型の感光層は、電荷発生層及び電荷輸送層を有する。
【０１０４】
電荷発生物質としては、セレン−テルル、ピリリウム、チアピリリウム系染料、また各種の中心金属及び結晶系、具体的には例えば、α、β、γ、ε及びＸ型等の結晶型を有するフタロシアニン化合物、アントアントロン顔料、ジベンズピレンキノン顔料、ピラントロン顔料、トリスアゾ顔料、ジスアゾ顔料、モノアゾ顔料、インジゴ顔料、キナクリドン顔料、非対称キノシアニン顔料、キノシアニン及び特開昭５４−１４３６４５号公報に記載のアモルファスシリコン等が挙げられる。
【０１０５】
電荷発生層は、前記電荷発生物質を０．３〜４倍量の結着樹脂及び溶剤と共にホモジナイザー、超音波分散、ボールミル、振動ボールミル、サンドミル、アドライダー及びロールミル等の方法でよく分散し、得られた分散液を塗布し、乾燥することによって形成されるか、前記電荷発生物質の蒸着膜等、単独組成の膜として形成される。その膜厚は５μｍ以下であることが好ましく、特には０．１〜２μｍであることが好ましい。
【０１０６】
結着樹脂としては、スチレン、酢酸ビニル、塩化ビニル、アクリル酸エステル、メタクリル酸エステル、フッ化ビニリデン、トリフルオロエチレン等のビニル化合物の重合体及び共重合体、ポリビニルアルコール、ポリビニルアセタール、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイド、ポリウレタン、セルロース樹脂、フェノール樹脂、メラミン樹脂、ケイ素樹脂及びエポキシ樹脂等が挙げられる。
【０１０７】
本発明における連鎖重合性官能基を有する正孔輸送性化合物は、前述した電荷発生層上に電荷輸送層として、もしくは電荷発生層上に電荷輸送物質と結着樹脂からなる電荷輸送層を形成した後に正孔輸送能力を有する表面保護層として用いることができる。この表面保護層は正孔輸送能力を有するので、感光層の定義の範囲内に含める。
【０１０８】
いずれの場合も、前記正孔輸送性化合物を含有する溶液を塗布後、重合／架橋反応させるのが好ましいが、前もって正孔輸送性化合物を含む溶液を反応させて硬化物を得た後に、再度溶剤中に分散あるいは溶解させたもの等を用いて、表面層を形成することも可能である。
【０１０９】
連鎖重合性官能基を有する正孔輸送性化合物を電荷輸送層として用いた場合の正孔輸送性化合物の量は、硬化後の電荷輸送層の全重量に対して、正孔輸送性基（例えば一般式（１）中のＡ）の水素付加物が２０重量％以上、好ましくは４０重量％以上含有されていることが好ましい。２０重量％に満たないと電荷輸送能が低下し、感度の低下及び残留電位の上昇等の問題点が生じ易くなる。電荷輸送層の膜厚は、１〜５０μｍであることが好ましく、特には３〜３０μｍであることが好ましい。
【０１１０】
正孔輸送性化合物を電荷発生層／電荷輸送層上の表面保護層として用いた場合、その下層に当たる電荷輸送層は適当な電荷輸送物質、例えばポリ−Ｎ−ビニルカルバゾール及びポリスチリルアントラセン等の複素環や縮合多環芳香族を有する高分子化合物や、ピラゾリン、イミダゾール、オキサゾール、トリアゾール及びカルバゾール等の複素環化合物、トリフェニルメタン等のトリアリールアルカン誘導体、トリフェニルアミン等のトリアリールアミン誘導体、フェニレンジアミン誘導体、Ｎ−フェニルカルバゾール誘導体、スチルベン誘導体及びヒドラジン誘導体等の低分子化合物等を適当な結着樹脂（前述の電荷発生層用樹脂の中から選択できる。）と共に溶剤に分散／溶解した溶液を塗布し、乾燥することによって形成することができる。
【０１１１】
この場合の電荷輸送物質と結着樹脂の比率は、両者の全重量を１００とした場合に電荷輸送物質の重量が３０〜１００であることが好ましく、特には５０〜１００であることが好ましい。電荷輸送物質の量が３０に満たないと、電荷輸送能が低下し、感度の低下及び残留電位の上昇等の問題点が生じ易くなる。電荷輸送層の膜厚は、上層の表面保護層と合わせた総膜厚が１〜５０μｍとなることが好ましく、特には５〜３０μｍであることが好ましい。
【０１１２】
本発明においては上述のいずれの場合においても、連鎖重合性官能基を有する正孔輸送性化合物の硬化物を含有する感光層に、前記電荷輸送物質を含有することが可能である。
【０１１３】
単層型感光層の場合は、正孔輸送性化合物と電荷発生物質の両方を含有する溶液を重合／架橋することによって形成するか、電荷発生物質及び電荷輸送物質を含有する単層型感光層上に正孔輸送性化合物を含有する溶液を塗布後、重合／架橋することによって形成する。
【０１１４】
本発明における感光層には、各種添加剤を添加することができる。添加剤とは酸化防止剤及び紫外線吸収剤等の劣化防止剤や、フッ素原子含有樹脂微粒子等の潤滑剤その他である。
【０１１５】
上記各層用の溶液を塗布する方法としては、例えば浸漬コーティング法、スプレーコーティング法、カーテンコーティング法及びスピンコーティング法等が挙げられるが、効率性／生産性の点からは浸漬コーティング法が好ましい。また、蒸着、プラズマ、その他の公知の製膜方法が適宜選択できる。
【０１１６】
本発明においては、連鎖重合性官能基を有する正孔輸送性化合物の重合／架橋を放射線により行う。
【０１１７】
放射線による重合の最大の利点は、重合開始剤を必要としない点であり、これにより非常に高純度な三次元感光層マトリックスの作製が可能となり、良好な電子写真特性を確保することができる。また、短時間で、かつ効率的な重合反応であるがゆえに生産性も高い。更に、放射線は透過性に優れるので、添加剤等の遮蔽物質が層中に存在したり厚い層を形成する際の硬化阻害の影響が非常に小さいこと等も挙げられる。
【０１１８】
但し、連鎖重合性官能基の種類や中心骨格の種類によっては重合反応が進行しにくい場合があり、その際には影響のない範囲内で重合開始剤を添加することは可能である。
【０１１９】
使用する放射線としては、電子線及びγ線が挙げられるが、効率の点では電子線が好ましい。電子線照射をする場合、加速器としてはスキャニング型、エレクトロカーテン型、ブロードビーム型、パルス型及びラミナー型等いずれの形式も使用することができる。また、電子線を照射する場合に、本発明においては、電気特性及び耐久性能を発現させる上で照射条件が非常に重要である。加速電圧は３００ｋＶ以下が好ましく、最適には１５０ｋＶ以下である。また、線量は好ましくは１Ｍｒａｄ〜１０Ｍｒａｄの範囲、より好ましくは３Ｍｒａｄ〜５０Ｍｒａｄの範囲である。加速電圧が３００ｋＶを超えると感光体特性に対する電子線照射のダメージが増加する傾向にある。また、線量が１Ｍｒａｄよりも少ない場合には架橋が不十分となり易く、１００Ｍｒａｄを超えると感光体の劣化が起こり易いので注意が必要である。
【０１２０】
図１に本発明の製造方法で製造される電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成を示す。図１において、１はドラム状の本発明の製造方法で製造される電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。感光体１は、回転過程において、一次帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いでスリット露光やレーザービーム走査露光等の露光手段（不図示）からの露光光４を受ける。こうして感光体１の周面に静電潜像が順次形成されて行く。
【０１２１】
形成された静電潜像は、次いで現像手段５によりトナー現像され、現像されたトナー現像像は、不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。像転写を受けた転写材７は、感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装置外へプリントアウトされる。
【０１２２】
像転写後の感光体１の表面は、クリーニング手段９によって転写残りトナーの除去を受けて清浄面化され、更に前露光手段（不図示）からの前露光光１０により除電処理された後、繰り返し画像形成に使用される。なお、一次帯電手段３が帯電ローラー等を用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。
【０１２３】
本発明においては、上述の電子写真感光体１、一次帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち、複数のものをプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンター等の電子写真装置本体に対して着脱可能に構成してもよい。例えば、一次帯電手段３、現像手段５及びクリーニング手段９の少なくとも一つを感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２等の案内手段を用いて装置本体に着脱可能なプロセスカートリッジ１１とすることができる。
【０１２４】
また、露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいはセンサーで原稿を読取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動及び液晶シャッターアレイの駆動等により照射される光である。
【０１２５】
本発明の製造方法で製造される電子写真感光体は電子写真複写機に利用するのみならず、レーザービームプリンター、ＣＲＴプリンター、ＬＥＤプリンター、液晶プリンター及びレーザー製版等の電子写真応用分野にも広く用いることができる。
【０１２６】
【実施例】
以下、実施例に従って説明する。実施例中、「部」は重量部を表す。
【０１２７】
（実施例１）
まず、導電層用の塗料を以下の手順で調製した。１０％の酸化アンチモンを含有する酸化スズで被覆した導電性酸化チタン粉体５０部、フェノール樹脂２５部、メチルセロソルブ２０部、メタノール５部及びシリコーンオイル（ポリジメチルシロキサンポリオキシアルキレン共重合体、平均分子量３０００）０．００２部をφ１ｍｍガラスビーズを用いたサンドミル装置で２時間分散して調製した。この塗料をφ３０ｍｍのアルミニウムシリンダー上に浸漬塗布方法で塗布し、１４０℃で３０分乾燥して、膜厚２０μｍの導電層を形成した。
【０１２８】
次に、Ｎ−メトキシメチル化ナイロン５部をメタノール９５部中に溶解し、中間層用塗料を調製した。この塗料を前記の導電層上に浸漬コーティング法によって塗布し、１００℃で２０分間乾燥して、０．６μｍの中間層を形成した。
【０１２９】
次に下記構造式（Ａ）のビスアゾ顔料５部、ポリビニルブチラール樹脂２部及びシクロヘキサノン６０部を、φ１ｍｍガラスビーズを用いたサンドミル装置で２４時間分散し、更にテトラヒドロフラン６０部を加えて電荷発生層用塗料とした。この塗料を前記の中間層の上に浸漬コーティング法で塗布して、１００℃で１５分間乾燥して、膜厚０．２μｍの電荷発生層を形成した。
【０１３０】
【外２０】

【０１３１】
次いで、化合物例Ｎｏ．６の正孔輸送性化合物６０部をモノクロロベンゼン３０部／ジクロロメタン３０部の混合溶媒中に溶解し、電荷輸送層用塗料を調製した。この塗料を前記の電荷発生層上にコーティングし、加速電圧１５０ｋＶ、線量３０Ｍｒａｄの条件で電子線を照射し樹脂を硬化し、膜厚１５μｍの電荷輸送層を形成し、電子写真感光体を得た。
【０１３２】
作製した電子写真感光体について、経時析出性、電子写真特性及び耐久性を評価した。経時析出性については、複写機用のウレタンゴム製のクリーニングブレードを感光体表面に圧接し、７５℃で保存し析出性に対する加速試験を行った。評価は１４日後に感光体表面を顕微鏡により観察し析出の有無を判定した。析出のない場合は、更に３０日後まで試験を継続した。
【０１３３】
電子写真特性及び耐久性は、この感光体をキヤノン（株）製ＬＢＰ−ＳＸに装着して評価した。初期の感光体特性〔暗部電位Ｖｄ、光減衰感度（暗部電位−７００Ｖ設定で−１５０Ｖに光減衰させるために必要な光量）及び残留電位Ｖｓ１（光減衰感度の光量の３倍の光量を照射した時の電位）〕を測定し、更に１００００枚の通紙耐久試験を行い、目視による画像欠陥の発生の有無の観察、感光体の削れ量及び耐久後の前記感光体特性を測定し、各々の変化値ΔＶｄ、ΔＶｌ（初期のＶｌと、初期にＶｌを−１５０Ｖにするのに必要な光量と同量の光量を耐久後に照射した時のＶｌとの差）及びΔＶｓｌを求めた。
【０１３４】
結果を第１表に示すが、本発明の製造方法で製造される電子写真感光体では析出は発生せず、また感光体特性が良好であり、耐久での削れ量が少なく、かつ耐久においても感光体特性にはほとんど変化が見られないというように、非常に安定した良好な特性を示している。
【０１３５】
（実施例２〜２５）
正孔輸送性化合物Ｎｏ．６を下表に示した化合物に代えた以外は、実施例１と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１３６】
【表２０】

【０１３７】
（実施例２６）
正孔輸送性化合物Ｎｏ．６の量を４８部とし、更に下記構造式（Ｂ）の構造を有するアクリルモノマーを１２部添加した以外は、実施例１と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１３８】
【外２１】

【０１３９】
（実施例２７）
正孔輸送性化合物Ｎｏ．１１の量を４８部とし、更に下記構造式（Ｃ）の構造を有するアクリレートモノマーを１２部添加した以外は、実施例７と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１４０】
【外２２】

【０１４１】
（実施例２８）
正孔輸送性化合物Ｎｏ．６の量を４８部とし、更に下記構造式（Ｄ）の構造を有するアクリルオリゴマー（数平均分子量２，０００）を１２部添加した以外は、実施例１と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１４２】
【外２３】

【０１４３】
（実施例２９〜３３）
電子線の照射条件を下表に示したように変えた以外は、実施例１と同様にして電子写真感光体を作製し、評価した。結果、削れ量、耐久画像は良好であったが、線量を上げることで初期の電子写真特性において、若干の感度低下や残留電位の上昇が見られた。結果を第１表に示す。
【０１４４】
【表２１】

【０１４５】
（実施例３４）
実施例１と同様にして電荷発生層まで形成した。
【０１４６】
次いで、下記構造式（Ｅ）のスチリル化合物２０部、
【０１４７】
【外２４】

及び下記構造式（Ｆ）の繰り返し単位を有するポリカーボネート樹脂（数平均分子量２０，０００）１０部
【０１４８】
【外２５】

をモノクロロベンゼン５０部／ジクロロメタン２０部の混合溶媒中に溶解して調製した電荷輸送層用塗料を用いて、前記電荷発生層上に電荷輸送層を形成した。この時の電荷輸送層の膜厚は１０μｍであった。
【０１４９】
次いで、正孔輸送性化合物Ｎｏ．６の６０部をモノクロロベンゼン５０部／ジクロロメタン５０部の混合溶媒中に溶解し、表面保護層用塗料を調製した。この塗料をスプレーコーティング法により先の電荷輸送層上に塗布し、加速電圧１５０ｋＶ、線量３０Ｍｒａｄの条件で電子線を照射し樹脂を硬化し、膜厚５μｍの表面保護層を形成し、電子写真感光体を得た。この感光体を実施例１と同様にして評価した。結果を第１表に示す。
【０１５０】
（実施例３５）
正孔輸送性化合物Ｎｏ．６を正孔輸送性化合物Ｎｏ．７に変えた以外は、実施例３４と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１５１】
（実施例３６）
正孔輸送性化合物Ｎｏ．６の量を３０部とし、実施例２６で用いた構造式（Ｂ）のアクリルモノマー３０部を添加した以外は、実施例３４と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１５２】
（実施例３７）
正孔輸送性化合物Ｎｏ．６の量を３０部とし、実施例２８で用いた構造式（Ｄ）のアクリルオリゴマー３０部を添加した以外は、実施例３４と同様にして電子写真感光体を作製し、評価した。結果を第１表に示す。
【０１５３】
【表２２】

【０１５４】
（比較例１）
実施例１と同様にして電荷発生層まで形成した。
【０１５５】
次いで、構造式（Ｅ）のスチリル化合物１５部及び下記構造式（Ｇ）の繰り返し単位を有するポリメチルメタクリレート樹脂（数平均分子量４００００）１５部をモノクロロベンゼン５０部／ジクロロメタン２０部の混合溶媒中に溶解して調製した電荷輸送層用塗料を用いて、前記電荷発生層上に電荷輸送層を形成した。この時の電荷輸送層の膜厚は１５μｍであった。
【０１５６】
【外２６】

【０１５７】
この電子写真感光体を実施例１と同様にして評価した結果、１４日後に析出が見られた。一方、初期の電子写真特性は良好であったが、耐久での表面層の削れ量が多く、かぶり、傷等の画像欠陥が発生している。更に８０００枚以降は削れによって電荷輸送層の膜厚が薄くなり、帯電不良が発生し、画像形成が不可能となった。結果を第２表に示す。
【０１５８】
（比較例２）
構造式（Ｇ）で示されるポリメチルメタクリレート樹脂のかわりに構造式（Ｆ）で示されるポリカーボネート樹脂（数平均分子量２００００）を用いた以外は、比較例１と同様にして電子写真感光体を作製し、評価した。その結果、３０日後に析出が観察された。また、ポリメチルメタクリレート樹脂の場合に比べて、耐久性は若干向上したものの十分ではなく、やはり耐久後の画像欠陥は発生した。結果を第２表に示す。
【０１５９】
（比較例３）
構造式（Ｅ）のスチリル化合物を１０部、構造式（Ｆ）のポリカーボネート樹脂を１５部とした以外は、比較例２と同様にして電子写真感光体を作製し、評価した。その結果、比較例２に比べて耐久性は向上したものの、電荷輸送物質間の距離が広がったことによって電荷輸送能が低下し、感度低下及び残留電位の上昇が見られた。その結果、画像においてはゴーストの発生が見られた。結果を第２表に示す。
【０１６０】
（比較例４）
実施例３４と同様にして電荷輸送層まで形成した。
【０１６１】
次いで、構造式（Ｅ）で示されるスチリル化合物１０部及び構造式（Ｆ）で示されるポリカーボネート樹脂１５部をモノクロロベンゼン５０部／ジクロロメタン３０部の混合溶媒中に溶解し、表面保護層用塗料を調製した。この塗料をスプレーコーティング法により先の電荷輸送層上に塗布し、１２０℃で１時間乾燥し、５μｍの表面保護層を形成した。
【０１６２】
この感光体を実施例３４と同様にして評価した結果、電荷輸送能の高い電荷輸送層が下層にあるために感度低下、残留電位上昇は見られず画像ゴーストの発生もなかったが、耐久後の画像にはまだ傷／かぶりが発生しており、十分な耐久性は確保できなかった。結果を第２表に示す。
【０１６３】
（比較例５）
正孔輸送性化合物Ｎｏ．６の代りに、特開平５−２１６２４９号公報に開示されている下記構造式（Ｈ）の化合物を用いた以外は、実施例１と同様にして電子写真感光体を作製し、評価した。その結果、初期の電子写真特性は良好であったが、実施例１に比較して耐久性が大幅に低下した。結果を第２表に示す。
【０１６４】
【外２７】

【０１６５】
（比較例６）
正孔輸送性化合物Ｎｏ．６のかわりに、構造式（Ｈ）の化合物を用いた以外は、実施例２６と同様にして電子写真感光体を作製し、評価した。その結果、初期の電子写真特性は良好であったが、実施例２６と比較して耐久性が大幅に低下した。結果を第２表に示す。
【０１６６】
（比較例７）
実施例１と同様にして電荷発生層まで形成した。
【０１６７】
次いで、特開平８−２４８６４９号公報のＰ１０〜１１に記載されている製造法に従って合成した下記構造式（Ｉ）のポリカーボネート樹脂（数平均分子量２００００）２０部をテトラヒドロフラン８０部に溶解して調製した電荷輸送層用塗料を用いて、前記電荷発生層上に電荷輸送層を形成した。
【０１６８】
この電荷輸送層の膜厚は１５μｍであった。この電子写真感光体を実施例１と同様に評価した結果、比較例１及び２に比較して機械的強度は向上したものの、十分な耐久性が確保できなかった。結果を第２表に示す。
【０１６９】
【外２８】

【０１７０】
【表２３】

【０１７１】
【発明の効果】
以上のように、本発明の製造方法で製造される電子写真感光体は耐析出性、耐摩耗性及び耐傷性に優れた効果を有する。更に、感度や残留電位等の電子写真特性も非常に良好であり、また繰り返し使用時にも安定した性能を発揮することができる。
【０１７２】
【図面の簡単な説明】
【図１】 本発明の製造方法で製造される電子写真感光体を有するプロセスカートリッジを備えた電子写真装置の概略構成の例を示す図である。[0001]
BACKGROUND OF THE INVENTION
  The present invention,More particularly, the electrophotographic photosensitive member having a photosensitive layer containing a specific compound.the body'sIt relates to a manufacturing method.
[0002]
[Prior art]
  Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. On the other hand, polyvinylcarbazole, phthalocyanine, and azo pigments, which are organic materials, are attracting attention for advantages such as high productivity and non-pollution, and tend to be inferior in terms of photoconductive properties and durability compared to inorganic materials. , Has come to be widely used.
[0003]
  These electrophotographic photoreceptors are often used as function-separated photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical properties. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, since various electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning are directly applied to the surface of the photoreceptor to be used repeatedly, durability against them is required.
[0004]
  Specifically, durability against the occurrence of surface wear and scratches due to rubbing, surface deterioration due to charging, for example, transfer efficiency and slipperiness decrease, and durability against deterioration of electrical characteristics such as sensitivity reduction and potential decrease. Required.
[0005]
  In general, the surface layer of an electrophotographic photoreceptor using an organic photoconductive material is a thin resin layer, and the characteristics of the resin are very important. In recent years, acrylic resins and polycarbonate resins have been put to practical use as resins that satisfy the above-mentioned various conditions. However, not all of the above-mentioned characteristics are satisfied with these resins, and it is difficult to say that the hardness of the resin is sufficiently high particularly for further enhancement of durability. Even when these resins are used as the resin for the surface layer, the surface layer may be worn or scratched with repeated use.
[0006]
  In addition, due to the recent demand for higher sensitivity, low molecular weight compounds such as charge transport materials are often added in relatively large amounts. In this case, the film strength is significantly reduced due to the plasticizer action of these low molecular weight materials. Therefore, wear and scratches on the surface layer during repeated use have become a more prominent problem. In addition, a problem that the low molecular weight compound precipitates during storage of the electrophotographic photosensitive member is likely to occur.
[0007]
  As means for solving these problems, the use of a curable resin as a resin for a charge transport layer is disclosed in, for example, JP-A-2-127852. In this case, a curable resin is used as the resin for the charge transport layer, and the charge transport layer is cured and crosslinked to greatly improve the abrasion resistance and scratch resistance during repeated use.
[0008]
  However, even when a curable resin is used, since the low molecular weight compound acts as a plasticizer in the binder resin, the problem of precipitation as described above has not been fundamentally solved. In the charge transport layer composed of the organic charge transport material and the binder resin, the charge transport ability largely depends on the resin. For example, in a curable resin having a sufficiently high hardness, the charge transport ability is not easily lowered. Both the hardness and the electrophotographic characteristics have not been fully satisfied, for example, the residual potential tends to increase during repeated use.
[0009]
  In JP-A-5-216249 and JP-A-7-72640, etc., the charge transport layer contains a monomer having a carbon-carbon double bond, and the carbon-carbon double bond of the charge transport material is heated. Alternatively, an electrophotographic photoreceptor in which a charge transport layer is formed by reacting with light energy is disclosed. However, the charge transport material is only immobilized in a pendant form on the main skeleton of the polymer, and the mechanical strength is not sufficient because the above plastic action cannot be sufficiently eliminated. Further, if the concentration of the charge transport material is increased to improve the charge transport capability, the crosslink density is lowered and sufficient mechanical strength cannot be ensured. Furthermore, there is a concern about the influence of the initiators required during polymerization on the electrophotographic characteristics.
[0010]
  As another solution, for example, JP-A-8-248649 discloses an electrophotographic photosensitive member having a charge transport layer containing a thermoplastic polymer into which a group having a charge transport ability is introduced in the main chain. Compared to conventional molecular dispersion type charge transport layers, it has an effect on precipitation and improves mechanical strength, but it is a thermoplastic resin, and its mechanical strength is limited. Also, it is difficult to say that the handling and productivity including the solubility of the resin are sufficient.
[0011]
  As described above, it has been studied to achieve both mechanical strength and charge transport capability at a higher level.
[0012]
[Problems to be solved by the invention]
  The object of the present invention is to solve the problems of the conventional electrophotographic photosensitive member, to improve the abrasion resistance and scratch resistance by increasing the film strength, and to have good precipitation resistance. BodyHow to makeIt is to provide.
[0013]
  Another object of the present invention is to provide an electrophotographic photoreceptor capable of exhibiting stable performance even during repeated use, with very little change and deterioration in photoreceptor properties such as an increase in residual potential during repeated use.How to makeIt is to provide.
[0014]
[Means for Solving the Problems]
  That is, the present inventionIn the method for producing an electrophotographic photosensitive member for forming a photosensitive layer on a support,
In the formation of the photosensitive layer, a step of curing the hole transporting compound by performing polymerization or crosslinking of the hole transporting compound having two or more chain polymerizable functional groups in the same molecule by using radiation. A process for producing an electrophotographic photosensitive member comprisingIt is.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
  Details of the present invention will be described below.
[0016]
  The chain polymerization in the present invention refers to the former polymerization reaction form when the polymer formation reaction is largely divided into chain polymerization and sequential polymerization. For details, see, for example, “Basic Chemistry Resin Chemistry” by Giho Tadahiro Miho. (New Edition) ”July 25, 1995 (1 edition, 8 prints) As described in FIG. 24, the form mainly refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization, etc. in which the reaction proceeds via an intermediate such as a radical or ion.
[0017]
  The chain polymerizable functional group means a functional group capable of the above-described reaction form, and here, a specific example of an unsaturated polymerization or ring-opening polymerizable functional group that occupies most of the functional group and has a wide application range will be shown.
[0018]
  Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, and C≡N are polymerized by radicals and ions. It is. Specific examples of the unsaturated polymerizable functional group are shown below, but are not limited thereto.
[0019]
[Outside 9]

[0020]
  In the above, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group and an anthryl group, or a hydrogen atom may be used.
[0021]
  Ring-opening polymerization is an unstable cyclic structure with distortions such as carbocycles, oxo rings and nitrogen heterocycles activated by the action of a catalyst, and at the same time, the polymerization is repeated to produce a chain polymer. In this case, most of the reactions basically have ions acting as active species. Specific examples of the ring-opening polymerization functional group are shown below, but are not limited thereto.
[0022]
[Outside 10]

[0023]
  In the above, R ′ has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group, and an anthryl group, a hydrogen atom, or the like may be used.
[0024]
  Among the chain polymerizable functional groups according to the present invention as described above, those represented by the following general formulas (5) to (7) are preferable.
[0025]
[Outside 11]

[0026]
  formula(5)E is a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an alkyl group such as a methyl group, ethyl group, propyl group and butyl group which may have a substituent, or a benzyl which may have a substituent. Group, aralkyl group such as phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, aryl group such as phenyl group, naphthyl group, anthryl group, pyrenyl group, thiophenyl group and furyl group which may have a substituent, CN Group, alkoxy group such as nitro group, methoxy group, ethoxy group and propoxy group, -COOR⁷And CONR⁸R⁹Indicates.
[0027]
  W is an arylene group such as divalent phenylene, naphthylene and anthracenylene which may have a substituent, a divalent alkylene group such as methylene, ethylene and butylene which may have a substituent, -COO-, -CH₂-, -O-, -OO-, -S- or CONR¹⁰Indicated by −.
[0028]
  R⁷, R⁸, R⁹And R¹⁰Is a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an alkyl group such as an optionally substituted methyl group, an ethyl group and a propyl group, an optionally substituted benzyl group and a phenethyl group An aryl group such as an aralkyl group and an optionally substituted phenyl group, naphthyl group and anthryl group;⁸And R⁹May be the same or different.
[0029]
  F represents 0 or 1.
[0030]
  Examples of the substituent that E and W may have include halogen atoms such as fluorine, chlorine, bromine and iodine, alkyl groups such as nitro group, cyano group, hydroxyl group, methyl group, ethyl group, propyl group and butyl group, Alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, phenyl group, naphthyl group, Examples include aryl groups such as anthryl group and pyrenyl group.
[0031]
[Outside 12]

[0032]
  formula(6)Medium, R¹¹And R¹²Has a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an aralkyl group such as an optionally substituted benzyl group and a phenethyl group, and a substituent. And an aryl group such as a phenyl group and a naphthyl group, and g represents an integer of 1 to 10.
[0033]
[Outside 13]

[0034]
  formula(7)Medium, R¹³And R¹⁴Has a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an aralkyl group such as an optionally substituted benzyl group and a phenethyl group, and a substituent. And an aryl group such as a phenyl group and a naphthyl group, and h represents an integer of 0 to 10.
[0035]
  R in the above general formulas (6) and (7)¹¹, R¹², R¹³And R¹⁴Substituents that may have include halogen atoms such as fluorine, chlorine, bromine and iodine, alkyl groups such as methyl, ethyl, propyl and butyl, alkoxy such as methoxy, ethoxy and propoxy Group, aryloxy groups such as phenoxy group and naphthoxy group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, and aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group, etc. Can be mentioned.
[0036]
  Among the general formulas (5) to (7), more particularly preferable chain polymerizable functional groups include those represented by the following general formulas (8) to (14).
[0037]
[Outside 14]

[0038]
  Furthermore, among the above formulas (8) to (14), the acryloyloxy group of (8) and the methacryloyloxy group of (9) are particularly preferable from the viewpoint of polymerization characteristics and the like.
[0039]
  In the present invention, “a hole transporting compound having two or more chain polymerizable functional groups in the same molecule” means the chain polymerizable property described above.SensualityIt is a compound in which at least two groups are chemically bonded to a hole transporting compound as a functional group. Two or more chain polymerizable functional groups may be the same or different.
[0040]
  The hole transporting compound having two or more chain polymerizable functional groups is preferably represented by the following general formula (1).
[0041]
[Outside 15]

[0042]
  P¹And P²Represents a chain polymerizable functional group, P¹And P²May be the same or different. Z represents an organic residue which may have a substituent, and Y represents a hydrogen atom. a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. If a is 2 or more, P¹May be the same or different, and when d is 2 or more, P²May be the same or different, and when b is 2 or more, Z may be the same or different.
[0043]
  Here, “a is 2 or more P¹May be the same or different ”means that each of n different types of chain polymerizable functional groups is represented by P¹¹, P¹², P¹³, P¹⁴, P¹⁵... p^lnFor example, when a = 3, the chain polymerizable functional group P directly bonded to the hole transporting compound A¹May be the same for all three, but the same for two but different for one (for example, P¹¹And P¹¹And P¹²However, each of the three is different (for example, P¹²And P¹⁵And P¹⁷Or the like) (If “d is 2 or more, P²"May be the same or different" and "when b is 2 or more, Z may be the same or different" means the same thing..).
[0044]
  A in the general formula (1) represents a hole transporting group, and any group may be used as long as it exhibits hole transportability.¹And a hydrogenation compound (hole transporting compound) in which Z is replaced with a hydrogen atom, for example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylamino) Styryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, Examples include thiophene derivatives and N-phenylcarbazole derivatives.
[0045]
  Further, among the hole transporting compounds, those represented by the following general formula (4) are preferable.
[0046]
[Outside 16]

[0047]
  formula(4)Medium, R⁴, R⁵And R⁶Is an optionally substituted C such as methyl, ethyl, propyl and butyl groups.₁~ C₁₀An alkyl group, an optionally substituted benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group and a thienyl group, and an optionally substituted phenyl group, naphthyl group, anthryl group, phenanthryl An aryl group such as a group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, galvazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group and dibenzothiophenyl group;
[0048]
  However, R⁴, R⁵And R⁶At least two of them represent an aryl group, and R⁴, R⁵And R⁶May be the same or different. Furthermore, among them, R⁴, R⁵And R⁶Particularly preferred are those in which all are aryl groups. In addition, R in the general formula (4)⁴, R⁵And R⁶Any two of them may be bonded directly or via a bonding group, such as an alkylene group such as a methyl group, an ethyl group and a propylene group, or a hetero atom such as an oxygen atom and a sulfur atom. And CH = CH group and the like.
[0049]
  Z in the general formula (1) is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR¹= CR²(R¹And R²Represents an alkyl group, an aryl group and a hydrogen atom, and R¹And R²May be the same or different.), C = O, S = O, SO₂, One selected from oxygen atoms and sulfur atoms, or any combination thereofWowThe organic residue is shown. Among them, those represented by the following general formula (2) are preferable, and those represented by the following general formula (3) are particularly preferable.
[0050]
[Outside 17]

[0051]
  In the general formula (2), X¹~ X³Is a C such as methylene group, ethylene group and propylene group which may have a substituent.₁~ C₂₀An alkylene group of (CR¹= CR²) M, C = O, S = O, SO₂Represents an oxygen atom and a sulfur atom, Ar¹And Ar²Is an optionally substituted divalent arylene group (from phenylene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. A group having two hydrogen atoms).
[0052]
  R¹And R²Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and a thiophenyl group which may have a substituent, and a hydrogen atom;¹And R²May be the same or different.
[0053]
  m represents an integer of 1 to 5, and p to t represent an integer of 0 to 10 (provided that p to t are not 0 at the same time).).
[0054]
  In the general formula (3), X⁴And X⁵Is (CH₂) M ′, (CH = CR³) Represents n ′, C═O and an oxygen atom, Ar³Is an optionally substituted divalent arylene group (from phenylene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. A group having two hydrogen atoms).
[0055]
  R³Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and a thiophenyl group which may have a substituent, and a hydrogen atom. m ′ is an integer of 1 to 10, n ′ is an integer of 1 to 5, u to w are integers of 0 to 10 (u to w are particularly preferably integers of 0 to 5, provided that u to w is never 0 at the same time.).
[0056]
  R in the general formulas (1) to (4)¹~ R⁶, Ar¹~ Ar³, X¹~ X⁵And Z may have a substituent each having a halogen atom such as fluorine, chlorine, bromine and iodine, an alkyl group such as a nitro group, a cyano group, a hydroxyl group, a methyl group, an ethyl group, a propyl group and a butyl group, Alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, phenyl group, naphthyl group, Aryl groups such as anthryl group and pyrenyl group, substituted amino groups such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group and di (p-tolyl) amino group, and arylvinyl groups such as styryl group and naphthylvinyl group Groups and the like.
[0057]
  The hole transporting compound having two or more chain polymerizable functional groups in the same molecule in the present invention preferably has an oxidation potential of 1.2 (V) or less, particularly 0.4 to 1.2. (V) is preferred.
[0058]
  When the oxidation potential exceeds 1.2 (V), injection of charges (holes) from the charge generating material is difficult to occur, and there are problems such as increase in residual potential, deterioration in sensitivity, and increase in potential fluctuation during repeated use. It tends to occur. In addition, when the oxidation potential is less than 0.4 (V), in addition to problems such as a decrease in charging ability, the compound itself is easily oxidized and thus easily deteriorates, resulting in sensitivity deterioration, image blurring and repeated use. Problems such as increased potential fluctuations are likely to occur. The oxidation potential is measured by the following method.
[0059]
  (Measurement method of oxidation potential)
  Saturated calomel electrode as reference electrode and 0.1N (n-Bu) as electrolyte₄N⁺ClO₄ ⁻Using an acetonitrile solution, the potential applied to the working electrode (platinum) was swept by a potential sweeper, and the potential when the obtained current-potential curve showed a peak was taken as the oxidation potential.
[0060]
  Specifically, the sample is 0.1N (n-Bu)₄N⁺ClO₄ ⁻Dissolve in acetonitrile solution to a concentration of about 5-10 mmol%. Then, a voltage is applied to the sample solution with a working electrode, and a current change when the voltage is linearly changed from a low potential (0 V) to a high potential (+1.5 V) is measured to obtain a current-potential curve. In this current-potential curve, the potential when the current value showed a peak (or the first peak when there were a plurality of peaks) was defined as the oxidation potential.
[0061]
  Preferred examples of the hole transporting compound having two or more chain polymerizable functional groups are listed below, but are not limited thereto.
[0062]
[Table 1]

[0063]
[Table 2]

[0064]
[Table 3]

[0065]
[Table 4]

[0066]
[Table 5]

[0067]
[Table 6]

[0068]
[Table 7]

[0069]
[Table 8]

[0070]
[Table 9]

[0071]
[Table 10]

[0072]
[Table 11]

[0073]
[Table 12]

[0074]
[Table 13]

[0075]
[Table 14]

[0076]
[Table 15]

[0077]
[Table 16]

[0078]
[Table 17]

[0079]
[Table 18]

[0080]
[Table 19]

[0081]
  A typical synthesis example of a hole transporting compound having a chain polymerizable functional group used in the present invention is shown below.
[0082]
  (Synthesis Example 1: Synthesis of Compound No. 6)
  Synthesized according to the following route.
[0083]
[Outside 18]

[0084]
  1 (50 g: 0.47 mol), 2 (406 g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) together with 1.2 kg of 1,2-dichlorobenzene and stirred at 180-190 ° C. for 15 hours did. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 132 g of 3.
[0085]
  3 (120 g: 0.28 mol) was added to 1.5 kg of methyl cellosolve, and sodium methylate (150 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred at 70 to 80 ° C. for 10 hours. The reaction solution was poured into water, neutralized with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 78 g of 4.
[0086]
  4 (70 g: 0.2 mol) and triethylamine (40 g: 0.4 mol) were added to 400 ml of dry tetrahydrofuran (THF), cooled to 0-5 ° C., and then acryloyl chloride (55 g: 0.6 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 42 g of 5 (Compound No. 6) (oxidation potential: 0.83 V).
[0087]
  (Synthesis Example 2: Synthesis of Compound No. 71)
  4 (10 g: 29 mmol) obtained in Synthesis Example 1 was added to 50 ml of dry THF and cooled to 0 to 5 ° C., and then 3.5 g of oily sodium hydride (about 60%) was slowly added. After completion of the addition, the mixture was returned to room temperature, stirred for 1 hour, cooled again to 0 to 5 ° C., and allyl bromide (17.5 g: 145 mmol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour, returned to room temperature, and further stirred for 5 hours. The reaction solution was poured into water, neutralized, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 5.6 g of the target compound (Compound No. 71) (oxidation potential: 0.81 V).
[0088]
  (Synthesis Example 3: Synthesis of Compound No. 55)
  Compound No. obtained in Synthesis Example 2 above. 71 3.0 g dissolved in 20 ml dichloromethane, cooled to 0-5 ° C., slowly added 5.2 g m-chloroperbenzoic acid (˜70%), stirred for 1 hour, then returned to room temperature and stirred for 12 hours It was. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified using a silica gel column to obtain 2.1 g of the target compound (Compound No. 55) (oxidation potential: 0.81 V).
[0089]
  (Synthesis Example 4: Synthesis of Compound No. 31)
  Synthesized according to the following route.
[0090]
[Outside 19]

[0091]
  6 (40 g: 0.24 mol), 7 (77 g: 0.35 mol), anhydrous potassium carbonate (48.8 g) and copper powder (75 g) together with 250 g of 1,2-dichlorobenzene were heated and stirred at 180 to 190 ° C. for 10 hours. did. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 49 g of 8.
[0092]
  After cooling 242.3 g of dimethylformamide (DMF) to 0 to 5 ° C., 84.8 g of phosphorus oxychloride was slowly added dropwise so as not to exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred as it was for 15 minutes, and then an 8 (24 g: 0.093 mol) / DMF (135 g) solution was slowly added dropwise. After completion of dropping, the mixture was stirred as it was for 30 minutes, then returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C. and stirred for 6 hours. The reaction solution was poured into 2 kg of an approximately 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralization, extraction was performed using toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 16 g of 9.
[0093]
  To a place where 1.85 g of lithium aluminum hydride was added to 100 ml of dry THF and stirred at room temperature, a 9 (15 g: 0.48 mol) / dry THF (100 ml) solution was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and 400 ml of 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 13 g of 10.
[0094]
  10 (10 g: 0.03 mol) and triethylamine (12 g: 0.12 mol) were added to 150 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (8.5 g: 0.09 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 5.6 g of 11 (Compound No. 31) (oxidation potential: 0.93 V).
[0095]
  In the present invention, a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is polymerized and crosslinked, so that at least two compounds having a hole transporting ability are contained in the photosensitive layer. It is incorporated into the three-dimensional crosslinked structure through a covalent bond with two or more crosslinking points. The hole transporting compound is polymerized, crosslinked, or other chain polymerizableSensualityAny mixing with a compound having a group is possible, and the type / ratio is arbitrary. Other chain polymerizability hereSensualityA compound having a group is chain polymerizableSensualityAny of monomers, oligomers and polymers having groups is included.
[0096]
  When the functional group of the hole transporting compound and the functional group of the other chain polymerizable compound are the same group or a group that can be polymerized with each other, both have a copolymerized three-dimensional crosslinked structure via a covalent bond. It is possible. When both functional groups are functional groups that do not polymerize with each other, the photosensitive layer is a mixture of at least two or more three-dimensional cured products or other chain polymerizable compound monomers in the main component three-dimensional cured product, Or it is comprised as what contains the hardened | cured material, However, IPN (Inter Penetrating Network), ie, an interpenetrating network structure, can also be formed by controlling the compounding ratio / film forming method well.
[0097]
  In addition, the hole transporting compound and chain polymerizableSensualityMonomers, oligomers and polymers that do not have groups, and polymerizability other than chain polymerizabilitySensualityYou may form a photosensitive layer from the monomer, oligomer, polymer, etc. which have group. Furthermore, in some cases, it is not chemically bonded to the three-dimensional crosslinked structure. That is, it is also possible to contain a hole transporting compound having no chain polymerizable functional group. Moreover, you may contain other various additives, for example, lubricants, such as fluorine atom containing resin fine particles.
[0098]
  Of the present inventionElectrophotography produced by the production methodThe photosensitive member has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated as a photosensitive layer on the support in this order, or vice versa. It is possible to take any configuration consisting of a single layer in which the transport material is dispersed in the same layer. In the former stacked type, the charge transport layer may be composed of two or more layers. In the latter single layer type, a charge transport layer may be further formed on the photosensitive layer containing the same charge generating material and charge transport material. Furthermore, a protective layer can be formed on the charge generation layer or the charge transport layer.
[0099]
  In any of these cases, the chain polymerizationSensualityIt is only necessary that the photosensitive layer contains a polymerized and crosslinked hole transporting compound having a group and / or a previous hole transporting compound. However, from the viewpoint of characteristics as an electrophotographic photoreceptor, particularly electrical characteristics such as residual potential and durability, a function-separated photoreceptor structure in which a charge generation layer and a charge transport layer are laminated in this order is preferable, and the advantages of the present invention However, the surface layer can be made highly durable without deteriorating the charge transport ability.
[0100]
  The support that the electrophotographic photosensitive member has is only required to have conductivity. For example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum shape or a sheet shape, a metal stay such as aluminum and copper laminated on a plastic film, aluminum, indium oxide and tin oxide Or the like deposited on a plastic film, a metal provided with a conductive layer by applying a conductive substance alone or with a binder resin, a plastic film, and paper.
[0101]
  In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided between the support and the photosensitive layer. The undercoat layer is used to improve the adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the support, and protect against electrical breakdown of the photosensitive layer. It is formed.
[0102]
  Materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue and gelatin Etc. The undercoat layer is formed by applying a solution prepared by dissolving these materials in a solvent suitable for each of the materials onto a support and drying it. The film thickness is preferably 0.1 to 2 μm.
[0103]
  As described above, the laminated photosensitive layer has a charge generation layer and a charge transport layer.
[0104]
  Examples of charge generation materials include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals and crystal systems, specifically, phthalocyanine compounds having crystal types such as α, β, γ, ε, and X type, Anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanine, and amorphous silicon described in JP-A No. 54-143645 It is done.
[0105]
  The charge generation layer is obtained by dispersing the charge generation material together with 0.3 to 4 times the amount of binder resin and solvent by a method such as homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, adrider and roll mill. The resulting dispersion is applied and dried, or is formed as a single composition film such as a vapor-deposited film of the charge generation material. The film thickness is preferably 5 μm or less, and particularly preferably 0.1 to 2 μm.
[0106]
  As binder resin, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester , Polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin and epoxy resin.
[0107]
  In the present invention, the hole transporting compound having a chain polymerizable functional group formed a charge transport layer on the charge generation layer described above or a charge transport layer made of a charge transport material and a binder resin on the charge generation layer. It can be used later as a surface protective layer having a hole transport capability. Since this surface protective layer has a hole transport capability, it is included within the definition of the photosensitive layer.
[0108]
  In any case, it is preferable to carry out polymerization / crosslinking reaction after applying the solution containing the hole transporting compound, but after reacting the solution containing the hole transporting compound in advance to obtain a cured product, again, It is also possible to form the surface layer using a material dispersed or dissolved in a solvent.
[0109]
  Chain polymerizationSensualityWhen the hole transporting compound having a group is used as the charge transporting layer, the amount of the hole transporting compound is based on the total weight of the charge transporting layer after curing (for example, the general formula (1 It is preferable that the hydrogen adduct of A) is contained in an amount of 20% by weight or more, preferably 40% by weight or more. If it is less than 20% by weight, the charge transport ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur. The thickness of the charge transport layer is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm.
[0110]
  When the hole transporting compound is used as a surface protective layer on the charge generation layer / charge transport layer, the charge transport layer corresponding to the lower layer is formed of a suitable charge transport material such as a complex such as poly-N-vinylcarbazole and polystyrylanthracene. Polymer compounds having rings and condensed polycyclic aromatics, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylene Low molecular weight compounds such as diamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazine derivatives can be selected from appropriate binder resins (from the above-described resins for charge generation layers)..) And a solution dispersed / dissolved in a solvent, and dried.
[0111]
  In this case, the ratio of the charge transport material to the binder resin is preferably 30 to 100, particularly preferably 50 to 100, when the total weight of both is 100. If the amount of the charge transport material is less than 30, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. The total thickness of the charge transport layer combined with the upper surface protective layer is preferably 1 to 50 μm, and particularly preferably 5 to 30 μm.
[0112]
  In the present invention, in any of the above cases, chain polymerization is possible.SensualityThe charge transport material can be contained in a photosensitive layer containing a cured product of a hole transport compound having a group.
[0113]
  In the case of a single layer type photosensitive layer, it is formed by polymerizing / crosslinking a solution containing both a hole transporting compound and a charge generation material, or a single layer type photosensitive layer containing a charge generation material and a charge transport material It is formed by polymerizing / crosslinking after applying a solution containing a hole transporting compound thereon.
[0114]
  Various additives can be added to the photosensitive layer in the invention. Additives include anti-degradation agents such as antioxidants and ultraviolet absorbers, and lubricants such as fluorine atom-containing resin fine particles.
[0115]
  Examples of the method for applying the solution for each layer include a dip coating method, a spray coating method, a curtain coating method, and a spin coating method. The dip coating method is preferable from the viewpoint of efficiency / productivity. Also, vapor deposition, plasma, and other known film forming methods can be appropriately selected.
[0116]
  In the present invention, chain polymerizabilitySensualityRadiation polymerization / crosslinking of a hole transporting compound having a groupYeah.
[0117]
  The greatest advantage of polymerization by radiation is that a polymerization initiator is not required, which makes it possible to produce a very high-purity three-dimensional photosensitive layer matrix and ensure good electrophotographic characteristics. In addition, the productivity is high because it is a short and efficient polymerization reaction. Furthermore, since radiation is excellent in permeability, it can be mentioned that a blocking substance such as an additive is present in the layer or the influence of curing inhibition when forming a thick layer is very small.
[0118]
  However, chain polymerizableSensualityDepending on the type of group and the type of central skeleton, the polymerization reaction may not proceed easily, and in this case, it is possible to add a polymerization initiator within a range that does not affect the polymerization reaction.
[0119]
  Examples of the radiation to be used include an electron beam and γ-ray, and an electron beam is preferable in terms of efficiency. In the case of electron beam irradiation, any type of accelerator such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used. Moreover, when irradiating an electron beam, in this invention, irradiation conditions are very important in order to express an electrical property and durability performance. Acceleration voltage is 300kV or less is preferred, optimally 150kV or less. The dose is preferably in the range of 1 Mrad to 10 Mrad, more preferably in the range of 3 Mrad to 50 Mrad. Acceleration voltage is 300kIf it exceeds V, the damage of the electron beam irradiation on the characteristics of the photoreceptor tends to increase. In addition, it is necessary to be careful since the crosslinking tends to be insufficient when the dose is less than 1 Mrad, and the photoreceptor is liable to deteriorate when the dose exceeds 100 Mrad.
[0120]
  FIG. 1 shows the present invention.Manufactured by manufacturing method1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member. In FIG. 1, reference numeral 1 denotes a drum-like shapeManufactured by manufacturing methodAn electrophotographic photoreceptor, which is driven to rotate at a predetermined peripheral speed in the direction of the arrow about the shaft 2. In the rotating process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then exposure light from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Receive 4. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1.
[0121]
  The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 that is synchronously taken out and fed. The transfer material 7 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, thereby being printed out as a copy (copy).
[0122]
  After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9 and further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0123]
  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are integrally coupled as a process cartridge. May be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photosensitive member 1 to form a cartridge and can be attached to and detached from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained.
[0124]
  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is a reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal, and scanning of the laser beam performed according to this signal, Light emitted by driving the LED array, driving the liquid crystal shutter array, or the like.
[0125]
  Of the present inventionManufactured by manufacturing methodThe electrophotographic photosensitive member can be used not only for electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
[0126]
【Example】
  Hereinafter, it demonstrates according to an Example. In the examples, “parts” represents parts by weight.
[0127]
  Example 1
  First, the coating material for conductive layers was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average 0.002 part of molecular weight 3000) was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on an aluminum cylinder having a diameter of 30 mm by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0128]
  Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating material. This paint was applied onto the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form a 0.6 μm intermediate layer.
[0129]
  Next, 5 parts of a bisazo pigment of the following structural formula (A), 2 parts of polyvinyl butyral resin, and 60 parts of cyclohexanone are dispersed for 24 hours in a sand mill using φ1 mm glass beads, and 60 parts of tetrahydrofuran is further added to form a charge generation layer. Paint was used. This paint was applied onto the intermediate layer by a dip coating method and dried at 100 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.2 μm.
[0130]
[Outside 20]

[0131]
  Compound Example No. 60 parts of the hole transporting compound No. 6 were dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating material for a charge transport layer. This paint is coated on the charge generation layer, and an acceleration voltage of 150 is applied.kThe resin was cured by irradiating an electron beam under the conditions of V and a dose of 30 Mrad to form a charge transport layer having a thickness of 15 μm to obtain an electrophotographic photosensitive member.
[0132]
  The produced electrophotographic photosensitive member was evaluated for precipitation with time, electrophotographic characteristics, and durability. With respect to precipitation over time, a urethane rubber cleaning blade for a copying machine was pressed against the surface of the photoreceptor, stored at 75 ° C., and an accelerated test for precipitation was performed. In the evaluation, the surface of the photoreceptor was observed with a microscope after 14 days to determine the presence or absence of precipitation. When there was no precipitation, the test was continued until 30 days later.
[0133]
  The electrophotographic characteristics and durability were evaluated by attaching this photoreceptor to a LBP-SX manufactured by Canon Inc. Initial photosensitive member characteristics [dark portion potential Vd, light attenuation sensitivity (light amount necessary for light attenuation to −150 V when dark portion potential −700 V is set) and residual potential Vs1 (light amount three times the light attenuation sensitivity) ), And a 10,000 sheet passing durability test was performed to visually observe the occurrence of image defects, the amount of photoconductor scraping, and the characteristics of the photoconductor after the endurance. Change values ΔVd, ΔVl (difference between initial Vl and Vl when irradiation with the same amount of light as that required to initially set Vl to −150 V after endurance) and ΔVsl were obtained.
[0134]
  The results are shown in Table 1.Electrophotography produced by the production methodPrecipitation does not occur on the photoconductor, the photoconductor characteristics are good, the amount of abrasion is small, and there is almost no change in the photoconductor characteristics even in durability. The characteristic is shown.
[0135]
  (Examples 2 to 25)
  Hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that 6 was replaced with the compounds shown in the table below. The results are shown in Table 1.
[0136]
[Table 20]

[0137]
  (Example 26)
  Hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the amount of 6 was 48 parts and 12 parts of an acrylic monomer having the structure of the following structural formula (B) was further added. The results are shown in Table 1.
[0138]
[Outside 21]

[0139]
  (Example 27)
  Hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 7 except that the amount of 11 was 48 parts and 12 parts of an acrylate monomer having the structure of the following structural formula (C) was added. The results are shown in Table 1.
[0140]
[Outside 22]

[0141]
  (Example 28)
  Hole-transporting compound No. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount of 6 was 48 parts and 12 parts of an acrylic oligomer (number average molecular weight 2,000) having the structure of the following structural formula (D) was added. And evaluated. The results are shown in Table 1.
[0142]
[Outside 23]

[0143]
  (Examples 29 to 33)
  An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the electron beam irradiation conditions were changed as shown in the table below. As a result, the shaving amount and the durable image were good, but the sensitivity was slightly lowered and the residual potential was slightly increased in the initial electrophotographic characteristics by increasing the dose. The results are shown in Table 1.
[0144]
[Table 21]

[0145]
  (Example 34)
  The charge generation layer was formed in the same manner as in Example 1.
[0146]
  Next, 20 parts of a styryl compound of the following structural formula (E),
[0147]
[Outside 24]

And 10 parts of a polycarbonate resin having a repeating unit of the following structural formula (F) (number average molecular weight 20,000)
[0148]
[Outside 25]

A charge transport layer was formed on the charge generation layer using a charge transport layer coating material prepared by dissolving in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. At this time, the thickness of the charge transport layer was 10 μm.
[0149]
  Subsequently, the hole transporting compound No. 60 parts of No. 6 were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 50 parts of dichloromethane to prepare a coating material for the surface protective layer. This paint is applied on the charge transport layer by spray coating, and an acceleration voltage of 150kThe resin was cured by irradiating an electron beam under the conditions of V and a dose of 30 Mrad to form a surface protective layer having a thickness of 5 μm to obtain an electrophotographic photosensitive member. This photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0150]
  (Example 35)
  Hole-transporting compound No. 6 is a hole transporting compound no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 34 except that it was changed to 7. The results are shown in Table 1.
[0151]
  (Example 36)
  Hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 34 except that the amount of 6 was 30 parts and 30 parts of the acrylic monomer of the structural formula (B) used in Example 26 was added. The results are shown in Table 1.
[0152]
  (Example 37)
  Hole-transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 34 except that the amount of 6 was 30 parts and 30 parts of the acrylic oligomer of the structural formula (D) used in Example 28 was added. The results are shown in Table 1.
[0153]
[Table 22]

[0154]
  (Comparative Example 1)
  The charge generation layer was formed in the same manner as in Example 1.
[0155]
  Next, 15 parts of a styryl compound of the structural formula (E) and 15 parts of a polymethyl methacrylate resin (number average molecular weight 40000) having a repeating unit of the following structural formula (G) are mixed in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. A charge transport layer was formed on the charge generation layer using a charge transport layer coating prepared by dissolution. The thickness of the charge transport layer at this time was 15 μm.
[0156]
[Outside 26]

[0157]
  As a result of evaluating this electrophotographic photosensitive member in the same manner as in Example 1, precipitation was observed after 14 days. On the other hand, although the initial electrophotographic characteristics were good, the amount of abrasion of the surface layer in durability was large, and image defects such as fogging and scratches occurred. Further, after 8000 sheets, the thickness of the charge transport layer was reduced by scraping, and charging failure occurred, making it impossible to form an image. The results are shown in Table 2.
[0158]
  (Comparative Example 2)
  An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the polycarbonate resin (number average molecular weight 20000) represented by the structural formula (F) was used instead of the polymethyl methacrylate resin represented by the structural formula (G). And evaluated. As a result, precipitation was observed after 30 days. Further, although the durability was slightly improved as compared with the case of the polymethylmethacrylate resin, it was not sufficient, and image defects after durability were generated. The results are shown in Table 2.
[0159]
  (Comparative Example 3)
  An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2 except that 10 parts of the styryl compound of the structural formula (E) and 15 parts of the polycarbonate resin of the structural formula (F) were used. As a result, although the durability was improved as compared with Comparative Example 2, the charge transport ability was lowered and the sensitivity was lowered and the residual potential was increased by increasing the distance between the charge transport materials. As a result, ghost was observed in the image. The results are shown in Table 2.
[0160]
  (Comparative Example 4)
  The charge transport layer was formed in the same manner as in Example 34.
[0161]
  Next, 10 parts of the styryl compound represented by the structural formula (E) and 15 parts of the polycarbonate resin represented by the structural formula (F) are dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to obtain a coating material for the surface protective layer. Prepared. This paint was applied on the charge transport layer by spray coating and dried at 120 ° C. for 1 hour to form a surface protective layer of 5 μm.
[0162]
  As a result of evaluating this photoconductor in the same manner as in Example 34, the charge transporting layer having a high charge transporting capability was present in the lower layer, so that the sensitivity was not decreased, the residual potential was not increased, and no image ghost was generated. The image still had scratches / fogging, and sufficient durability could not be secured. The results are shown in Table 2.
[0163]
  (Comparative Example 5)
  Hole-transporting compound No. Instead of 6, an electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the compound represented by the following structural formula (H) disclosed in JP-A-5-216249 was used. As a result, the initial electrophotographic characteristics were good, but the durability was significantly reduced as compared with Example 1. The results are shown in Table 2.
[0164]
[Outside 27]

[0165]
  (Comparative Example 6)
  Hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 26 except that the compound of the structural formula (H) was used instead of 6. As a result, the initial electrophotographic characteristics were good, but the durability was significantly reduced as compared with Example 26. The results are shown in Table 2.
[0166]
  (Comparative Example 7)
  The charge generation layer was formed in the same manner as in Example 1.
[0167]
  Next, 20 parts of a polycarbonate resin (number average molecular weight 20000) of the following structural formula (I) synthesized according to the production method described in P10 to 11 of JP-A-8-248649 was prepared by dissolving in 80 parts of tetrahydrofuran. A charge transport layer was formed on the charge generation layer using the charge transport layer coating material.
[0168]
  The thickness of this charge transport layer was 15 μm. As a result of evaluating this electrophotographic photosensitive member in the same manner as in Example 1, the mechanical strength was improved as compared with Comparative Examples 1 and 2, but sufficient durability could not be ensured. The results are shown in Table 2.
[0169]
[Outside 28]

[0170]
[Table 23]

[0171]
【The invention's effect】
  As described above, the present inventionManufactured by manufacturing methodThe electrophotographic photoreceptor has an excellent effect in precipitation resistance, abrasion resistance and scratch resistance. Furthermore, electrophotographic characteristics such as sensitivity and residual potential are very good, and stable performance can be exhibited even during repeated use.
[0172]
[Brief description of the drawings]
FIG. 1 of the present inventionManufactured by manufacturing method1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member.

Claims (16)

In the method for producing an electrophotographic photosensitive member for forming a photosensitive layer on a support,
In forming the photosensitive layer, Ru curing the hole transporting compound by carrying out the polymerization or crosslinking of the hole-transporting compound having two or more chain polymerizable functional groups in the same molecule with radiation A process for producing an electrophotographic photoreceptor, comprising a step. The hole transporting compound, process for producing an electrophotographic photosensitive member according to claim 1 which is a compound represented by the following general formula (1).
[Outside 1]

(In formula (1) , A represents a hole transporting group. P ¹ and P ² represent chain polymerizable functional groups. P ¹ and P ² may be the same or different. Z has a substituent. And Y represents a hydrogen atom, a, b and d represent 0 or an integer of 1 or more, provided that when a = 0, b + d is an integer of 3 or more, b or When d is 0, a is an integer of 2 or more, otherwise a + b + d is an integer of 3 or more, and when a is 2 or more, P ¹ may be the same or different, and when d is 2 or more P ² may be the same or different, and when b is 2 or more, Z may be the same or different . Wherein Z is an optionally substituted alkylene group, an optionally substituted arylene ^{group, CR 1 = CR 2 (R} 1 and R ² represents an alkyl group which may have a substituent group, a substituted One group selected from an aryl group which may have a group and a hydrogen atom, and R ¹ and R ² may be the same or different . ), C═O, S═O, SO ₂ , an oxygen atom and The method for producing an electrophotographic photosensitive member according to claim 2, which shows one group selected from sulfur atoms or an organic residue obtained by arbitrarily combining these groups . Wherein Z is The method for producing an electrophotographic photosensitive member according to claim 2 or 3 is a group represented by the following general formula (2).
[Outside 2]

(In the formula ^(2), X 1 ~X ³ is an alkylene group which may have a ^{substituent, (CR 1 = CR 2)} m, C = O, S = O, SO 2, from oxygen atom and a sulfur atom One group selected , Ar ¹ and Ar ² represent an arylene group which may have a substituent, R ¹ and R ² each have an alkyl group which may have a substituent, and a substituent; represents one of the groups also selected from an aryl group and a hydrogen atom, ^{R 1} and ^{R 2} is selected from the same or different .m is an integer from 1 to 5, the p~t an integer of 0. However , P to t are not 0 at the same time . Wherein Z is The method for producing an electrophotographic photosensitive member according to any one of claims 2 to 4 is a group represented by the following general formula (3).
[Outside 3]

(In formula (3) , Ar ³ represents an arylene group which may have a substituent. X ⁴ and X ⁵ are (CH ₂ ) m ′, (CH═CR ³ ) n ′, C═O and oxygen) R ³ represents one group selected from atoms, R ³ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, and one group selected from a hydrogen atom; -10 to n, n 'represents an integer from 1 to 5, u to w represent an integer from 0 to 10. However, u to w are not 0 at the same time . The method for producing an electrophotographic photosensitive member according to any one of claims 2 to 5 , wherein the hydrogen adduct obtained by replacing the bonding site of A with P ¹ and Z with a hydrogen atom is represented by the following general formula (4).
[Outside 4]

(In the formula (4) , R ⁴ , R ⁵ and R ⁶ are selected from an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and an aryl group which may have a substituent. ( However, at least two of them represent aryl groups, and R ⁴ , R ^5, and R ⁶ may be the same or different . ) The method for producing an electrophotographic photosensitive member according to claim 6, wherein all of R ⁴ , R ⁵ and R ⁶ are aryl groups which may have a substituent. At least one of said P ¹ and P ^2, the manufacturing method of the electrophotographic photosensitive member according to any one of claims 2-7 an unsaturated polymerizable functional group represented by the following general formula (5).
[Outside 5]

(In the formula (5) , E represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a cyano group. , A nitro group, an alkoxy group, —COOR ⁷ (R ⁷ may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. One group selected from an aryl group) and CONR ⁸ R ⁹ (R ⁸ and R ⁹ are a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, and a substituent. 1 represents a group selected from aryl groups which may have a group, and may be the same or different from each other . ) 1 represents a group selected from the above , and W may have a substituent. Arylene group, alkylene which may have a substituent Group, —COO—, —C—, —O—, —OO—, —S— and —CONR ¹⁰ — (R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. .f showing one group selected from a group) selected from an aryl group which may have a aralkyl groups and substituents have is 0 or 1.) Wherein at least one of P ¹ and P ^2, the manufacturing method of the electrophotographic photosensitive member according to any one of claims 2 to 7, which is a cyclic ether group represented by the following general formula (6).
[Outside 6]

(In the formula (6), R ¹¹ and R ¹² are a hydrogen atom, an optionally substituted alkyl group, selected from an aryl group which may have a aralkyl group and a substituted group may have a substituent represents one of the groups, g is an integer of 1 to 10.) Wherein at least one of P ¹ and P ^2, the manufacturing method of the electrophotographic photosensitive member according to any one of claims 2 to 7 which is an alicyclic epoxy group represented by the following general formula (7).
[Outside 7]

(In the formula (7), R ¹³ and R ¹⁴ are a hydrogen atom, an optionally substituted alkyl group, also selected from an aryl group having a aralkyl group and a substituted group may have a substituent represents one of the groups, h is an integer of 0.) Wherein at least one of P ¹ and P ^2, the manufacturing method of the electrophotographic photosensitive member according to any one of claims 2 to 7, which is a group represented by any one of the following formulas (8) to (14).
[Outside 8]

The method for producing an electrophotographic photosensitive member according to claim 11 , wherein at least one of P ¹ and P ² is a group represented by any one of the formulas (8) and (9). The method for producing an electrophotographic photosensitive member according to any one of claims 1-12 wherein the radiation is an electron beam. The method for producing an electrophotographic photosensitive member according to claim 13 , wherein the polymerization or crosslinking is performed without using a polymerization initiator. The method for producing an electrophotographic photosensitive member according to claim 13 or 14 accelerating voltage of the electron beam is less than 300 k V. The method for producing an electrophotographic photosensitive member according to any one of claims 13-15 dose of the electron beam is 1～100Mrad.

Images