JP3554126B2 - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and electrophotographic apparatus - Google Patents

Description

構造式（２）
【化４】

。
【００１３】
【発明の実施の形態】
本発明において用いる導電性支持体は導電性を有するものであれば、何れのものでもよく、例えばアルミニウム、クロム、ニッケル、ステンレス、銅及び亜鉛等の金属や合金、アルミニウムや銅等の金属箔をプラスチックフィルムにラミネ−トしたもの、アルミニウム、酸化インジウム及び酸化スズ等をプラスチックフィルムに蒸着したもの、あるいは、導電性物質を単独または適当な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。
【００１４】
この導電層に用いられる導電性物質としては、アルミニウム、銅、ニッケル及び銀等の金属粉体、金属箔及び金属繊維、酸化アンチモン、酸化インジウム及び酸化スズ等の導電性金属酸化物、ポリピロ−ル、ポリアニリン及び高分子電解質等の高分子導電材料、カ−ボンブラック、グラファイト粉体及び有機もしくは無機の電解質またはこれらの導電性物質で表面を被覆した導電性粉体等が挙げられる。
【００１５】
導電性支持体の形状としては、ドラム状、シ−ト状及びベルト状等が挙げられるが、適用される電子写真装置に最も適した任意の形状であることが好ましい。
【００１６】
導電性支持体と感光層との間に下引き層を設けてもよい。下引き層は、感光層との界面での電荷注入制御をするバリヤ−層や接着層として機能する。下引き層は主に結着樹脂からなるが、前記金属や合金、またはそれらの酸化物、塩類及び界面活性剤を含んでもよい。
【００１７】
下引き層を形成する結着樹脂としては、ポリエステル、ポリウレタン、ポリアクリレ−ト、ポリエチレン、ポリスチレン、ポリブタジエン、ポリカ−ボネ−ト、ポリアミド、ポリプロピレン、ポリイミド、フェノ−ル樹脂、アクリル樹脂、シリコ−ン樹脂、エポキシ樹脂、ユリア樹脂、アリル樹脂、アルキド樹脂、ポリアミドイミド、ポリサルホン、ポリアリルエ−テル、ポリアセタ−ル及びブチラ−ル樹脂等が挙げられる。下引き層の膜厚は、好ましくは０．０５〜７μｍ、より好ましくは０．１〜２μｍである。
【００１８】
本発明の電子写真感光体の感光層の構成は、電荷発生物質と電荷輸送物質を同一の層に含有する単層型、あるいは電荷輸送物質を含有する電荷輸送層と電荷発生物質を含有する電荷発生層に機能分離された積層型のいずれでもよい。
【００１９】
以下、積層型の感光層について説明する。積層型の感光層の構成としては、電荷発生層上に電荷輸送層を積層するものと、電荷輸送層上に電荷発生層を積層するものがある。
【００２０】
本発明における電荷発生層は、電荷発生物質を蒸着、スパッタ−等の方法で成膜した均一な層として形成される、あるいは電荷発生物質を結着樹脂に分散した分散液を塗布乾燥することにより形成される。
【００２１】
電荷発生物質としては、例えば特開平３−２１７４６２号公報に記載されるような、ＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）が９．５°、２４．１°及び２７．３°に強いピ−クを有するオキシチタニウムフタロシアニン（図１）または、例えば特開昭６２−６７０９４号公報に記載されるような、ＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）が９．３°、１０．６°、１３．２°、１５．１°、１５．７°、１６．１°、２０．８°、２３．３°、２６．３°及び２７．１°に強いピ−クを有するオキシチタニウムフタロシアニン（図２）を用いる。
【００２２】
結着樹脂としては、従来用いられる電荷発生層用の樹脂を用いることができ、例えば、ポリビニルブチラ−ル、ポリビニルホルマ−ル等のポリビニルアセタ−ル樹脂、ポリスチレン、アクリル樹脂、セルロ−スエステル、セルロ−スエ−テル、ポリエステル、ポリカ−ボネ−ト、フェノキシ樹脂、ウレタン樹脂及びエポキシ樹脂等が挙げられる。
【００２３】
また、電荷発生層には、例えば２，４，７−トリニトロフルオレノン、テトラシアノキノジメタン等の電子受容性物質、カルバゾ−ル、インド−ル、イミダゾ−ル、オキサゾ−ル、ピラゾ−ル、オキサジアゾ−ル、ピラゾリン、チアジアゾ−ル等の複素環化合物、アニリン誘導体、ヒドラゾン化合物、芳香族アミン誘導体、スチルベン誘導体あるいはこれらの化合物からなる基を主鎖もしくは側鎖に有する重合体等の電子供与性物質が添加されていてもよい。電荷発生層の膜厚は１０μｍ以下であることが好ましく、特には０．０５〜２μｍであることが好ましい。
【００２４】
本発明における電荷輸送層は、電荷輸送物質を成膜性を有する樹脂に適当な溶剤を用いて溶解した塗工液を塗布、乾燥することによって形成される。電荷輸送物質としては、例えばカルバゾ−ル、インド−ル、イミダゾ−ル、チアゾ−ル、オキサジアゾ−ル、ピラゾ−ル、ピラゾリン等の複素環を有する化合物、フェニルアミン、ジフェニルアミン、トリフェニルアミン等のアニリン誘導体、ヒドラゾン誘導体、スチルベン誘導体及びこれらの化合物からなる基を主鎖あるいは側鎖に有する重合体等の電子供与性物質が挙げられる。結着樹脂としては、従来用いられる電荷輸送層用の樹脂を用いることができ、例えば、ポリカ−ボネ−ト、ポリエステル、ポリアリレ−ト、アクリル樹脂、スチレン樹脂及びシリコ−ン樹脂等の熱可塑性樹脂や硬化性の樹脂が挙げられる。電荷輸送層の膜厚は５〜４０μｍが好ましく、特には１０〜３０μｍが好ましい。
【００２５】
次に、単層型の電子写真感光体における感光層について説明する。単層型感光層は、電荷発生物質及び電荷輸送物質を前記樹脂に溶解、分散した液を塗布、乾燥することによって形成される。単層型感光層の膜厚は５〜４０μｍ、特には１０〜３０μｍが好ましい。
【００２６】
本発明の電子写真感光体における表面保護層は、熱または光で硬化させることにより得られる樹脂を主成分とする。樹脂としては、例えばポリビニルアセタ−ル、ポリスチレン、アクリル樹脂、セルロ−スエステル、セルロ−スエ−テル、ポリエステル、ポリカ−ボネ−ト、フェノキシ樹脂、ウレタン樹脂、エポキシ樹脂、ポリアリレ−ト、スチレン樹脂及びシリコ−ン樹脂等の熱可塑性樹脂や硬化性の樹脂が挙げられる。より高い硬度及び優れた耐摩耗性を得るためには、光でモノマ−またはオリゴマ−を硬化させることが好ましく、また、更にモノマ−やオリゴマ−としてはアクリロイル基やメタクリロイル基を有するものが好ましい。モノマ−またはオリゴマ−を硬化させる際には光開始剤を用いてもよい。光開始剤の添加量はモノマ−またはオリゴマ−の全重量に対し、０．１〜１５０重量％が好ましく、特には０．５〜１００重量％であることが好ましい。
【００２７】
本発明の電子写真感光体の表面保護層は、表面保護層の抵抗を調節するという観点から、金属酸化物粒子等の導電性粒子を分散含有することが好ましい。導電性金属酸化物としては、酸化亜鉛、酸化チタン、酸化スズ、酸化アンチモン、酸化インジウム、酸化ビスマス、インジウムをド−プした酸化スズ、アンチモンをド−プした酸化スズ及び酸化ジルコニウム等の粒子が挙げられる。これらの金属酸化物は一種類もしくは二種類以上を混合して用いる。二種類以上を混合した場合には固溶体または融着の形をとってもよい。金属酸化物粒子の含有量は表面保護層の全重量に対し、５〜９０重量％が好ましい。５重量％未満では表面保護層としての抵抗値が高くなりすぎることがあり、９０重量％より多いと感光体表面層として低抵抗となり易く、帯電能の低下やピンホ−ルの原因となることがある。
【００２８】
また、導電性金属酸化物の吸水性を下げ表面保護層の抵抗の環境変動を抑えるという観点から、金属酸化物表面を撥水処理することが好ましい。撥水処理に用いられる処理剤としてはチタネ−ト系カップリング剤、フッ素含有シランカップリング剤、フッ素変性シリコ−ンオイル、フッ素系界面活性剤及びアセトアルコキシアルミニウムジイソプロピレ−ト等の化合物が挙げられる。
【００２９】
表面保護層に導電性粒子を分散する場合、分散粒子による入射光の散乱を防ぐためには、粒子系が入射光の波長よりも小さいことが好ましく、一般には数平均粒径で０．３μｍ以下が好ましい。
【００３０】
また、残留トナ−を除去するためのクリ−ニングプロセスの中で、最も一般的なブレ−ドクリ−ニング方式はブレ−ド反転の問題が常につきまとう。これは感光体表面とブレ−ドの間の摩擦力が非常に高いため生じる問題であり、ある閾値を越えた時にブレ−ド反転が生じる。そこで、本発明における表面保護層において、感光体表面の摩擦力を下げるために表面保護層にフッ素原子含有樹脂微粒子のような潤滑剤を含有させることが好ましい。
【００３１】
かかるフッ素原子含有樹脂としては、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリジクロロジフルオロエチレン、テトラフルオロエチレン−パ−フルオロアルキルビニルエ−テル共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−エチレン共重合体及びテチラフルオロエチレン−ヘキサフルオロプロピレン−パ−フルオロアルキルビニルエ−テル共重合体からなる群から選ばれた一種類または二種類以上から構成されている樹脂が挙げられる。市販のフッ素原子含有樹脂微粒子をそのまま用いることも可能である。分子量は０．３万〜５００万であることが好ましい。粒径は０．０１〜１０μｍであることが好ましく、特には０．０５〜２．０μｍであることが好ましい。
【００３２】
また、本発明においては、分散性、接着性及び耐環境性等も更に向上させるため、表面保護層に各種カップリング剤や酸化防止剤を添加してもよい。
【００３３】
本発明における表面保護層の膜厚は０．１〜１０μｍが好ましく、特には５〜７μｍであることが好ましい。
【００３４】
上記の各種層は、蒸着や塗布により形成することができる。特に塗布による方法は、薄膜から厚膜まで広い範囲で、しかも、様々な組成の膜の形成が可能であるので好ましい。塗布方法としては、浸漬コ−ティング法、スプレ−コ−ティング法、ビ−ムコ−ティング法、バ−コ−ティング法、ブレ−ドコ−ティング法及びロ−ラコ−ティング法等が挙げられる。
【００３５】
また、本発明は前記本発明の電子写真感光体、及び帯電手段、現像手段及びクリ−ニング手段からなる群より選ばれる少なくとも一つの手段を一体に支持し、電子写真装置本体に着脱自在であることを特徴とするプロセスカ−トリッジから構成される。
【００３６】
また、本発明は、前記本発明の電子写真感光体、帯電手段、像露光手段、現像手段及び転写手段を有することを特徴とする電子写真装置から構成される。
【００３７】
図３に本発明の電子写真感光体を有するプロセスカ−トリッジを有する電子写真装置の概略構成を示す。図において、１はドラム状の本発明の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−ザ−ビ−ム走査露光等の像露光手段（不図示）からの画像露光光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いく。
【００３８】
形成された静電潜像は、次いで現像手段５によりトナ−現像され、現像されたトナ−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の回転と同期取りされて給送された転写材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−）として装置外へプリントアウトされる。像転写後の感光体１の表面は、クリ−ニング手段９によって転写残りトナ−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により除電処理がされた後、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−ラ−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。
【００３９】
本発明においては、上述の感光体１、一次帯電手段３、現像手段５及びクリ−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−トリッジとして一体に結合して構成し、このプロセスカ−トリッジを複写機やレ−ザ−ビ−ムプリンタ−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−ニング手段９の少なくとも１つを感光体１と共に一体に支持してカ−トリッジ化し、装置本体のレ−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−トリッジ１１とすることができる。また、画像露光光４は、電子写真装置が複写機やプリンタ−である場合には、原稿からの反射光や透過光を用いる、あるいは、センサ−で原稿を読み取り、信号化し、この信号に従って行われるレ−ザ−ビ−ムの走査、ＬＥＤアレイの駆動及び液晶シャッタ−アレイの駆動等により照射される光である。
【００４０】
【実施例】
実施例１
３０φ、２５４ｍｍのアルミニウムシリンダ−に平均膜厚１０μｍの陽極酸化被膜を形成した後、封孔処理を行い水洗、乾燥した。
【００４１】
次に、ＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）９．５°、２４．１°及び２７．３°に強いピ−クを有するオキシチタニウムフタロシアニン１０部にｎ−プロパノ−ル２００部を加え粉砕、微粒化分散処理を行った。次いで、ポリビニルブチラ−ル（商品名デンカブチラ−ル＃−６０００、電気化学工業（株）製）を５部含む１０％ｎ−プロパノ−ル溶液と混合し、電荷発生層用塗工液を調製した。この塗工液を前記アルミニウムシリンダ−上に浸漬コ−ティング法で塗布、乾燥し、膜厚０．２μｍの電荷発生層を形成した。
【００４２】
次に、下記構造式（１）で示される化合物７０重量部と下記構造式（２）で示される化合物２０重量部、下記構造式（３）で示される化合物１．７重量部及び下記構造式（４）（繰り返し構造単位のモル比率ｐ／ｑ＝１／１，粘度平均分子量３１０００）で示されるポリカ−ボネ−ト樹脂１００重量部を１，４−ジオキサン１０００重量部に溶解させ、電荷輸送層用塗工液を調製した。塗工液を前記電荷発生層上に浸漬コ−ティング法で塗布、乾燥し、膜厚２０μｍの電荷輸送層を形成した。
【００４３】
構造式（１）
【化１】

構造式（２）
【化２】

構造式（３）
【化３】

構造式（４）
【化４】

【００４４】
次に表面保護層用塗工液を下記の手順により調製した。平均粒径０．０２μｍのアンチモン含有酸化スズ微粒子（商品名Ｔ−１、三菱マテリアル（株）製）１００重量部、（３，３，３−トリフルオロプロピル）トリメトキシシラン（信越化学（株）製）３０重量部、９５％エタノ−ル５％水溶液３００重量部をミリング装置で１時間ミリング処理した溶液をろ過しエタノ−ルで洗浄後、乾燥し、１２０℃１時間の加熱処理をすることにより、微粒子の表面処理を行った。
【００４５】
次に結着樹脂として下記構造式（５）で示されるアクリルモノマ−を２５部、構造式（５）
【化５】

光重合開始剤としての２−メチルチオキサントン０．５重量部、前記表面処理を行ったアンチモン含有酸化スズ粒子３５重量部及びエタノ−ル３００重量部を混合してサンドミル装置で９６時間分散した分散液に四フッ化エチレン樹脂粒子（商品名ルブロンＬ−２、ダイキン工業（株）製）２５重量部を混合してサンドミル装置で８時間分散することにより表面保護層用塗工液を調製した。この塗工液を前記電荷輸送層上に浸漬コ−ティング法で塗布して成膜し、乾燥後高圧水銀灯にて８００ｍＷ／ｃｍ^２ の光強度で１５秒間紫外線照射して、膜厚３μｍの保護層を形成し、電子写真感光体を作成した。
【００４６】
作成した電子写真感光体を２３．５℃、５２％ＲＨ下で一晩放置後、レ−ザ−ビ−ムプリンタ−（商品名ＬＢＰ−ＥＸ、キヤノン（株）製）に装着し、残留電位を測定した。測定は、現像器、クリ−ナ−を外したカ−トリッジを用意し、暗部電位が−７００Ｖになるように帯電設定を行い、明部電位が−１５０Ｖになるようにレ−ザ−光量を調整して、明部電位を５枚プリント相当流し、５枚目の電位をＶ１とし、その後レ−ザ−を照射したまま一次帯電を切り、５回転目の電位を残留電位とした。
【００４７】
次に１００００枚通紙耐久を行い、上記と同様の方法で耐久直後の残留電位
Ｖ１を測定した。
【００４８】
また、上記耐久前後での画像評価も行った。評価画像は５ｍｍ×５ｍｍの塗りつぶしの四角形を縦横１ｃｍの間隔で画像上に均一になるように電子写真感光体の一周分形成した後、１ドット１スペ−スのドット密度の画像を形成したものをサンプリングした。そしてこの画像の１ドット１スペ−スのドット密度の画像の部分が均一であるかどうか、即ち、前のプロセスで５ｍｍ×５ｍｍの塗りつぶしの四角形の潜像を形成された部分の白抜け（ゴ−スト現象）の有無で判断した。評価結果を表１に示す。ただし、表中のゴ−スト結果において、○はゴ−スト無し、×はゴ−スト有りを表わす。
【００４９】
実施例２
電荷発生物質としてＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）９．３°、１０．６°、１３．２°、１５．１°、１５．７°、１６．１°、２０．８°、２３．３°、２６．３°及び２７．１°に強いピ−クを有するオキシチタニウムフタロシアニンを用いた他は、実施例１と同様にして、電荷発生層までを形成した。
【００５０】
次に、構造式（４）で示されるポリカ−ボネ−ト樹脂を下記構造式（６）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例１と同様にして電荷輸送層用塗工液を調製し、塗工液を前記電荷発生層上に浸漬コ−ティング法で塗布、乾燥し、膜厚２０μｍの電荷輸送層を形成した。
構造式（６）
【化６】

【００５１】
次に、実施例１と同様にして表面保護層を形成し、電子写真感光体を作成し、同様に評価を行った。結果を表１に示す。
【００５２】
実施例３
実施例１において、電荷輸送層用塗工液の調製に用いた構造式（４）で示されるポリカ−ボネ−ト樹脂を構造式（６）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００５３】
実施例４
実施例２において、電荷輸送層用塗工液の調製に用いた構造式（６）で示されるポリカ−ボネ−ト樹脂を構造式（４）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例２と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００５４】
実施例５
実施例１において、電荷輸送層用塗工液の調製に用いた構造式（４）で示されるポリカ−ボネ−ト樹脂を下記構造式（７）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
構造式（７）
【化７】

【００５５】
実施例６
実施例２において、電荷輸送層用塗工液の調製に用いた構造式（６）で示されるポリカ−ボネ−ト樹脂を下記構造式（７）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例２と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００５６】
実施例７
実施例１において、電荷輸送層用塗工液の調製に用いた構造式（４）で示されるポリカ−ボネ−ト樹脂を下記構造式（８）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
構造式（８）
【化８】

【００５７】
実施例８
実施例２において、電荷輸送層用塗工液の調製に用いた構造式（６）で示されるポリカ−ボネ−ト樹脂を下記構造式（８）で示されるポリカ−ボネ−ト樹脂に代えた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００５８】
比較例１
電荷発生物質としてＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）が７．６°、１０．２°、２２．５°、２５．３°及び２８．６°に強いピ−クを有するオキシチタニウムフタロシアニンを用いた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００５９】
比較例２
電荷発生物質としてＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）が７．６°、１０．２°、２２．５°、２５．３°及び２８．６°に強いピ−クを有するオキシチタニウムフタロシアニンを用いた他は、実施例２と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００６０】
比較例３
電荷発生物質としてＣｕＫα特性Ｘ線回折における回折角（２θ±０．２°）が７．１°、１０．４°、２４．８°及び２７．４°に強いピ−クを有するオキシチタニウムフタロシアニンを用いた他は、実施例１と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００６１】
比較例４
電荷発生物質としてＸ型無金属フタロシアニンを用いた他は、実施例２と同様にして電子写真感光体を作成し、評価を行った。結果を表１に示す。
【００６２】
【表１】

【００６３】
【発明の効果】
本発明の電子写真感光体は、感光層に特定のオキシチタニウムフタロシアニンを含有することにより、高湿下においてもボケ、流れがなく、高精細な画像が得られ、耐摩耗性の低下や残留電位増大によるトナ−被り等の画像欠陥がなく、また繰り返し使用時の残留電位の蓄積が低減された、高耐久、かつ、初期から繰り返し使用後までゴ−スト等の画像欠陥が生じず、高品位を保つことができるという顕著な効果を奏する。また、該電子写真感光体はカ−トリッジ及び電子写真装置に装着して同様に優れた効果を奏する。
【図面の簡単な説明】
【図１】本発明に用いられるオキシチタニウムフタロシアニンのＣｕＫα特性Ｘ線回折図。
【図２】本発明に用いられるオキシチタニウムフタロシアニンのＣｕＫα特性Ｘ線回折図。
【図３】本発明の電子写真感光体を有するプロセスカ−トリッジを有する電子写真装置の概略構成を示す図。
【符号の説明】
１ 本発明の電子写真感光体
２ 軸
３ 一次帯電手段
４ 画像露光光
５ 現像手段
６ 転写手段
７ 転写材
８ 像定着手段
９ クリ−ニング手段
１０ 前露光光
１１ プロセスカ−トリッジ
１２ レ−ル[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, a process cartridge including the electrophotographic photosensitive member, and an electrophotographic apparatus.
[0002]
[Prior art]
The electrophotographic photoreceptor is naturally required to have required sensitivity, electrical characteristics and optical characteristics according to the applied electrophotographic process. Particularly, in the case of a photoreceptor that is repeatedly used, the surface of the photoreceptor is directly applied with an electrical or mechanical external force such as charging, image exposure, toner development, transfer to paper, and cleaning. Durability against them is required. Specifically, the durability of the photoreceptor and the potential characteristics of the photoreceptor and potential characteristics due to ozone and charge products generated at the time of electrification, and the like, are reduced. Required. Furthermore, there is a problem that toner adheres to the surface of the photoreceptor due to repetition of toner development and cleaning, and good cleaning properties are also required.
[0003]
Attempts have been made to provide a surface protective layer containing a resin as a main component on the photosensitive layer in order to satisfy the characteristics required for the photosensitive member as described above. For example, JP-A-56-42863 and JP-A-53-103741 propose to improve the hardness and abrasion resistance by providing a surface protective layer containing a curable resin as a main component. Have been.
[0004]
In order to obtain a better image, the surface protective layer of the photoreceptor is required to have not only characteristics such as high hardness and excellent abrasion resistance, but also an appropriate resistance of the surface protective layer itself. . If the resistance is too low, the electrostatic latent image flows in the surface protective layer in the plane direction, and problems such as blurring and blurring of the image occur. However, if the resistance of the surface protective layer is too high, the charge is accumulated in the surface protective layer by repeating an electrophotographic process such as charging and exposure, that is, a so-called increase in residual potential occurs. Is not stable, so that the image quality is also unstable. In order to solve this problem, for example, Japanese Patent Application Laid-Open No. 57-30843 proposes controlling the resistance of a surface protective layer by adding a metal oxide as conductive fine particles to the surface protective layer.
[0005]
In addition, the water absorption of the metal oxide surface is high, and the resistance of the surface protective layer changes depending on the degree of the water absorption. Therefore, the resistance depends on the environment. It was difficult to suppress the resistance in an appropriate environment. To solve this problem, for example, Japanese Patent Application Laid-Open No. 62-295066 discloses a surface protection method in which a metal fine powder or a metal oxide fine powder having a water-repellent treatment and improved dispersibility and moisture resistance is dispersed in a binder resin. It has been proposed to control the resistance of the layer by providing the layer.
[0006]
Inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide have been conventionally used as photoconductive materials for electrophotographic photoreceptors, but they have disadvantages such as easy deterioration of characteristics and large restrictions on handling.
[0007]
On the other hand, organic photoconductive materials such as polyvinyl carbazole, oxadiazol, and phthalocyanine have advantages such as non-pollution and high productivity compared to inorganic photoconductive materials. Oxytitanium phthalocyanine has high sensitivity particularly to long-wavelength light, and many crystal forms are known as in metal-free phthalocyanine and copper phthalocyanine. For example, JP-A-59-49544 (US Pat. No. 4,444,861), JP-A-59-166959, JP-A-61-239248 (US Pat. No. 4,728,592), and JP-A-62-67094. JP-A-63-366, JP-A-63-116158, JP-A-63-198067 and JP-A-64-17066 disclose different crystal forms. Oxytitanium phthalocyanine has been reported.
[0008]
However, in the case of using an electrophotographic photosensitive member having a surface protective layer provided on a photosensitive layer using oxytitanium phthalocyanine as a photoconductive material, there are the following problems. That is, it is a phenomenon caused by a change in the light portion potential and the residual potential during continuous printing. For example, when used in a developing process (reversal development system) in which a dark portion potential portion, which is often used in a printer at present, is a non-developing portion and a bright portion potential is a developing portion, the portion exposed to light at the time of previous printing is used. When a full-length black image or a halftone image is taken at the next print after the history is left, a so-called ghost phenomenon in which a portion irradiated with light at the previous print appears black or becomes white appears. there were.
[0009]
With the recent increase in image quality and durability, electrophotographic photoreceptors having more excellent durability and capable of stably providing excellent images are being studied.
[0010]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotograph which is highly durable, has no accumulation of residual potential in a repetitive electrophotographic process, and can maintain high quality image quality free from image defects such as image bleeding, blurring and ghosting. It is another object of the present invention to provide a photoreceptor, and to provide a process cartridge and an electrophotographic apparatus to which the electrophotographic photoreceptor is applied.
[0011]
[Means for Solving the Problems]
The present invention provides an electrophotographic photoreceptor in which a photosensitive layer and a surface protective layer are laminated in this order on an anodic oxide film of an aluminum cylinder having an anodic oxide film formed on a surface thereof.
The oxytitanium phthalocyanine in which the photosensitive layer has a strong peak at a diffraction angle (2θ ± 0.2 °) of 9.5 °, 24.1 ° and 27.3 ° in CuKα characteristic X-ray diffraction as a charge generating substance. Or 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, 20.8 °, 23.3 °, 26.3 ° and 27.1 ° Containing an oxytitanium phthalocyanine having a strong peak,
It comprises a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2) as a charge transporting substance, and the surface protective layer further includes conductive particles and a resin. The electrophotographic photoreceptor consists of :
Structural formula (1)
Embedded image

Structural formula (2)
Embedded image

.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The conductive support used in the present invention may be any as long as it has conductivity, for example, a metal or alloy such as aluminum, chromium, nickel, stainless steel, copper and zinc, and a metal foil such as aluminum or copper. Laminated plastic films, aluminum, indium oxide, tin oxide, etc. deposited on plastic films, or metals or plastics provided with a conductive layer by applying a conductive substance alone or with an appropriate binder resin Examples include films and paper.
[0014]
Examples of the conductive material used for the conductive layer include metal powders such as aluminum, copper, nickel and silver, metal foils and metal fibers, conductive metal oxides such as antimony oxide, indium oxide and tin oxide, and polypyrrol. And polymer conductive materials such as polyaniline and polymer electrolytes, carbon black, graphite powder, and organic or inorganic electrolytes or conductive powders whose surfaces are coated with these conductive substances.
[0015]
Examples of the shape of the conductive support include a drum shape, a sheet shape, a belt shape and the like, and it is preferable that the shape is an arbitrary shape most suitable for the applied electrophotographic apparatus.
[0016]
An undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer functions as a barrier layer or an adhesive layer for controlling charge injection at the interface with the photosensitive layer. The undercoat layer is mainly made of a binder resin, but may contain the above-mentioned metal or alloy, or oxides, salts and surfactants thereof.
[0017]
Examples of the binder resin for forming the undercoat layer include polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, and silicone resin. , Epoxy resins, urea resins, allyl resins, alkyd resins, polyamide imides, polysulfones, polyallyl ethers, polyacetals and butyral resins. The thickness of the undercoat layer is preferably 0.05 to 7 μm, more preferably 0.1 to 2 μm.
[0018]
The structure of the photosensitive layer of the electrophotographic photoreceptor of the present invention may be a single layer containing a charge generating substance and a charge transporting substance in the same layer, or a charge transporting layer containing a charge transporting substance and a charge containing a charge generating substance. Any of a stacked type in which functions are separated into generation layers may be used.
[0019]
Hereinafter, the laminated photosensitive layer will be described. The structure of the laminated photosensitive layer includes a structure in which a charge transport layer is laminated on a charge generation layer and a structure in which a charge generation layer is laminated on a charge transport layer.
[0020]
The charge generating layer in the present invention is formed as a uniform layer formed by depositing a charge generating substance by a method such as evaporation or sputtering, or by applying and drying a dispersion in which the charge generating substance is dispersed in a binder resin. It is formed.
[0021]
Examples of the charge generating substance, for example, as described in JP-A 3-21746 2 JP, diffraction angle in CuKα characteristic X-ray diffraction (2θ ± 0.2 °) is 9.5 °, 24.1 ° and 27 Oxytitanium phthalocyanine having a strong peak at 0.3 ° (FIG. 1) or a diffraction angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction as described in, for example, JP-A-62-67094. ) Are 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, 20.8 °, 23.3 °, 26.3 ° and 27.1. Oxytitanium phthalocyanine (FIG. 2) having a peak at an angle of .ANG. Is used.
[0022]
As the binder resin, conventionally used resins for the charge generation layer can be used. For example, polyvinyl acetal resins such as polyvinyl butyral and polyvinyl formal, polystyrene, acrylic resin, cellulose ester , Cellulose ether, polyester, polycarbonate, phenoxy resin, urethane resin and epoxy resin.
[0023]
The charge generating layer may be formed of an electron-accepting substance such as 2,4,7-trinitrofluorenone or tetracyanoquinodimethane, carbazole, indole, imidazole, oxazole, or pyrazole. Electron donation of heterocyclic compounds such as oxadiazol, pyrazoline and thiadiazole, aniline derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives or polymers having a group consisting of these compounds in the main chain or side chain. Sexual substances may be added. The thickness of the charge generation layer is preferably 10 μm or less, and particularly preferably 0.05 to 2 μm.
[0024]
The charge transport layer in the present invention is formed by applying a coating solution obtained by dissolving a charge transport material in a resin having film forming properties using an appropriate solvent, and drying the coating solution. Examples of the charge transport material include compounds having a heterocyclic ring such as carbazole, indole, imidazole, thiazole, oxadiazol, pyrazol, and pyrazoline; and phenylamine, diphenylamine, triphenylamine and the like. An electron donating substance such as an aniline derivative, a hydrazone derivative, a stilbene derivative, and a polymer having a group consisting of these compounds in a main chain or a side chain is exemplified. As the binder resin, conventionally used resins for the charge transport layer can be used. For example, thermoplastic resins such as polycarbonate, polyester, polyarylate, acrylic resin, styrene resin and silicone resin can be used. And a curable resin. The thickness of the charge transport layer is preferably from 5 to 40 μm, particularly preferably from 10 to 30 μm.
[0025]
Next, the photosensitive layer in the single-layer type electrophotographic photosensitive member will be described. The single-layer type photosensitive layer is formed by applying and drying a solution in which a charge generating substance and a charge transporting substance are dissolved and dispersed in the resin. The thickness of the single-layer type photosensitive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.
[0026]
The surface protective layer in the electrophotographic photoreceptor of the present invention contains, as a main component, a resin obtained by curing with heat or light. Examples of the resin include polyvinyl acetal, polystyrene, acrylic resin, cellulose ester, cellulose ether, polyester, polycarbonate, phenoxy resin, urethane resin, epoxy resin, polyarylate, styrene resin, and the like. Examples thereof include thermoplastic resins such as silicone resins and curable resins. In order to obtain higher hardness and excellent abrasion resistance, it is preferable to cure the monomer or oligomer with light, and the monomer or oligomer preferably has an acryloyl group or a methacryloyl group. When curing the monomer or oligomer, a photoinitiator may be used. The amount of the photoinitiator to be added is preferably from 0.1 to 150% by weight, particularly preferably from 0.5 to 100% by weight, based on the total weight of the monomers or oligomers.
[0027]
The surface protective layer of the electrophotographic photoreceptor of the present invention preferably contains conductive particles such as metal oxide particles dispersedly from the viewpoint of adjusting the resistance of the surface protective layer. Examples of the conductive metal oxide include particles such as zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide doped with indium, tin oxide doped with antimony, and zirconium oxide. No. These metal oxides are used alone or as a mixture of two or more. When two or more kinds are mixed, they may be in the form of solid solution or fusion. The content of the metal oxide particles is preferably from 5 to 90% by weight based on the total weight of the surface protective layer. If it is less than 5% by weight, the resistance value as a surface protective layer may be too high, and if it is more than 90% by weight, the resistance of the photoreceptor surface layer tends to be low, which may cause a decrease in charging ability and pinhole. is there.
[0028]
Further, from the viewpoint of reducing the water absorption of the conductive metal oxide and suppressing the environmental fluctuation of the resistance of the surface protective layer, it is preferable to perform a water-repellent treatment on the metal oxide surface. Examples of the treating agent used for the water-repellent treatment include compounds such as a titanate-based coupling agent, a fluorine-containing silane coupling agent, a fluorine-modified silicone oil, a fluorine-based surfactant, and acetoalkoxyaluminum diisopropylate. Can be
[0029]
When the conductive particles are dispersed in the surface protective layer, the particle system is preferably smaller than the wavelength of the incident light in order to prevent scattering of the incident light by the dispersed particles, and the number average particle diameter is generally 0.3 μm or less. preferable.
[0030]
Also, among the cleaning processes for removing residual toner, the most common blade cleaning method always involves the problem of blade reversal. This is a problem caused by a very high frictional force between the photoreceptor surface and the blade. When a certain threshold value is exceeded, blade reversal occurs. Thus, in the surface protective layer of the present invention, it is preferable that the surface protective layer contains a lubricant such as fluorine atom-containing resin fine particles in order to reduce the frictional force on the surface of the photoreceptor.
[0031]
Examples of such a fluorine atom-containing resin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polydichlorodifluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoro Propylene copolymer, tetrafluoroethylene-ethylene copolymer and tetirafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer composed of one or more selected from the group consisting of Resin. Commercially available fluorine atom-containing resin fine particles can be used as they are. It is preferable that the molecular weight is from 30000 to 5,000,000. The particle size is preferably from 0.01 to 10 μm, and particularly preferably from 0.05 to 2.0 μm.
[0032]
Further, in the present invention, various coupling agents and antioxidants may be added to the surface protective layer in order to further improve the dispersibility, adhesiveness, environmental resistance and the like.
[0033]
The thickness of the surface protective layer in the present invention is preferably from 0.1 to 10 μm, and particularly preferably from 5 to 7 μm.
[0034]
The various layers described above can be formed by vapor deposition or coating. In particular, the coating method is preferable because it can form films of various compositions in a wide range from a thin film to a thick film. Examples of the coating method include an immersion coating method, a spray coating method, a beam coating method, a bar coating method, a blade coating method, and a roller coating method.
[0035]
Further, the present invention integrally supports at least one means selected from the group consisting of the electrophotographic photoreceptor of the present invention and a charging means, a developing means and a cleaning means, and is detachable from an electrophotographic apparatus main body. And a process cartridge characterized in that:
[0036]
Further, the present invention comprises an electrophotographic apparatus comprising the electrophotographic photoreceptor of the present invention, a charging unit, an image exposing unit, a developing unit and a transfer unit.
[0037]
FIG. 3 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow. In the rotation process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging means 3, and then the image exposure means (such as slit exposure or laser beam scanning exposure) is used. (See FIG. 1). Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.
[0038]
The formed electrostatic latent image is then toner-developed by the developing unit 5, and the developed toner-developed image is transferred between the photoconductor 1 and the transfer unit 6 from a paper feeding unit (not shown). The image is sequentially transferred by the transfer unit 6 to the transfer material 7 fed in synchronization with the rotation. The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out of the apparatus as a copy (copy). The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning means 9, and is further subjected to a static elimination treatment by pre-exposure light 10 from a pre-exposure means (not shown). After that, it is repeatedly used for image formation. When the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not necessarily required.
[0039]
In the present invention, a plurality of components such as the photoreceptor 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and the apparatus main body is guided by a guide means such as the rail 12 of the apparatus main body. The process cartridge 11 can be detachably mounted on the cartridge. When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal. This is light emitted by scanning of a laser beam, driving of an LED array, driving of a liquid crystal shutter array, and the like.
[0040]
【Example】
Example 1
After forming an anodic oxide film having an average film thickness of 10 μm on an aluminum cylinder having a diameter of 30 mm and a diameter of 254 mm, the film was subjected to sealing treatment, washed with water, and dried.
[0041]
Next, n-propanol was added to 10 parts of oxytitanium phthalocyanine having strong peaks at 9.5 °, 24.1 ° and 27.3 ° in the diffraction angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. And pulverized and atomized and dispersed. Subsequently, a 10% n-propanol solution containing 5 parts of polyvinyl butyral (trade name: Denkabutyral # -6000, manufactured by Denki Kagaku Kogyo KK) was mixed to prepare a coating liquid for a charge generation layer. did. This coating solution was applied on the aluminum cylinder by an immersion coating method and dried to form a charge generation layer having a thickness of 0.2 μm.
[0042]
Next, 70 parts by weight of the compound represented by the following structural formula (1), 20 parts by weight of the compound represented by the following structural formula (2), 1.7 parts by weight of the compound represented by the following structural formula (3), and the following structural formula (4) 100 parts by weight of a polycarbonate resin represented by (molar ratio of repeating structural units p / q = 1/1, viscosity average molecular weight 31,000) is dissolved in 1,000 parts by weight of 1,4-dioxane, and charge transport is performed. A coating solution for a layer was prepared. The coating liquid was applied on the charge generation layer by a dipping coating method and dried to form a charge transport layer having a thickness of 20 μm.
[0043]
Structural formula (1)
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Structural formula (2)
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Structural formula (3)
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Structural formula (4)
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[0044]
Next, a coating solution for a surface protective layer was prepared by the following procedure. 100 parts by weight of antimony-containing tin oxide fine particles having an average particle size of 0.02 μm (trade name: T-1, manufactured by Mitsubishi Materials Corporation), (3,3,3-trifluoropropyl) trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) A solution obtained by milling 30 parts by weight and 300 parts by weight of a 95% ethanol 5% aqueous solution for 1 hour with a milling device is filtered, washed with ethanol, dried, and heated at 120 ° C. for 1 hour. To perform a surface treatment of the fine particles.
[0045]
Next, as a binder resin, 25 parts of an acrylic monomer represented by the following structural formula (5) were used.
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A dispersion prepared by mixing 0.5 parts by weight of 2-methylthioxanthone as a photopolymerization initiator, 35 parts by weight of the surface-treated antimony-containing tin oxide particles, and 300 parts by weight of ethanol and dispersing the mixture in a sand mill for 96 hours. Was mixed with 25 parts by weight of tetrafluoroethylene resin particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) and dispersed by a sand mill for 8 hours to prepare a coating liquid for a surface protective layer. This coating solution is applied on the charge transport layer by immersion coating to form a film. After drying, the coating solution is irradiated with ultraviolet light at a light intensity of 800 mW / cm ² for 15 seconds using a high-pressure mercury lamp to protect the film to a thickness of 3 μm. A layer was formed to prepare an electrophotographic photoreceptor.
[0046]
The prepared electrophotographic photoreceptor was allowed to stand overnight at 23.5 ° C. and 52% RH, and then mounted on a laser beam printer (trade name: LBP-EX, manufactured by Canon Inc.). Was measured. For the measurement, a developing device and a cartridge with the cleaner removed are prepared, charging is set so that the dark portion potential becomes -700 V, and the amount of laser light is set so that the bright portion potential becomes -150 V. After the adjustment, the bright portion potential was flowed for the printing of five sheets, the potential of the fifth sheet was set to V1, then the primary charging was stopped while the laser was irradiated, and the potential at the fifth rotation was set to the residual potential.
[0047]
Next, 10,000 sheets of paper were passed, and the residual potential V1 immediately after the durability was measured by the same method as described above.
[0048]
In addition, image evaluation before and after the above-mentioned durability was also performed. The evaluation image was formed by forming a solid square of 5 mm x 5 mm for one circumference of the electrophotographic photosensitive member so as to be uniform on the image at intervals of 1 cm in length and width, and then forming an image with a dot density of 1 dot and 1 space. Was sampled. Whether or not the image portion of this image having a dot density of 1 dot and 1 space is uniform, that is, the blank portion of the portion where the filled rectangular latent image of 5 mm × 5 mm was formed in the previous process. −strike phenomenon). Table 1 shows the evaluation results. In the ghost results in the table, ○ indicates no ghost and X indicates ghost.
[0049]
Example 2
As a charge generation material, diffraction angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, Except for using oxytitanium phthalocyanine having strong peaks at 20.8 °, 23.3 °, 26.3 °, and 27.1 °, a charge generation layer was formed in the same manner as in Example 1. .
[0050]
Next, a charge transporting layer was formed in the same manner as in Example 1 except that the polycarbonate resin represented by the structural formula (4) was replaced with a polycarbonate resin represented by the following structural formula (6). A coating solution was prepared, and the coating solution was applied on the charge generation layer by a dip coating method and dried to form a charge transport layer having a thickness of 20 μm.
Structural formula (6)
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[0051]
Next, a surface protective layer was formed in the same manner as in Example 1, and an electrophotographic photoreceptor was prepared. Table 1 shows the results.
[0052]
Example 3
In Example 1, the polycarbonate resin represented by the structural formula (4) used in the preparation of the coating solution for the charge transport layer was replaced with the polycarbonate resin represented by the structural formula (6). In the same manner as in Example 1, an electrophotographic photosensitive member was prepared and evaluated. Table 1 shows the results.
[0053]
Example 4
In the same manner as in Example 2, except that the polycarbonate resin represented by the structural formula (6) used for preparing the coating liquid for the charge transport layer was replaced with the polycarbonate resin represented by the structural formula (4) In the same manner as in Example 2, an electrophotographic photosensitive member was prepared and evaluated. Table 1 shows the results.
[0054]
Example 5
In Example 1, the polycarbonate resin represented by the structural formula (4) used for preparing the coating liquid for the charge transport layer was replaced with a polycarbonate resin represented by the following structural formula (7). Otherwise, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.
Structural formula (7)
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[0055]
Example 6
In Example 2, the polycarbonate resin represented by the structural formula (6) used in the preparation of the coating solution for the charge transport layer was replaced with a polycarbonate resin represented by the following structural formula (7). Except for this, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2. Table 1 shows the results.
[0056]
Example 7
In Example 1, the polycarbonate resin represented by the structural formula (4) used in the preparation of the coating solution for the charge transport layer was replaced with a polycarbonate resin represented by the following structural formula (8). Otherwise, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.
Structural formula (8)
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[0057]
Example 8
In Example 2, the polycarbonate resin represented by the structural formula (6) used in the preparation of the coating solution for the charge transport layer was replaced with a polycarbonate resin represented by the following structural formula (8). Otherwise, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.
[0058]
Comparative Example 1
As a charge generating substance, a peak having a strong diffraction angle (2θ ± 0.2 °) in 7.6 °, 10.2 °, 22.5 °, 25.3 ° and 28.6 ° in CuKα characteristic X-ray diffraction. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that oxytitanium phthalocyanine having the following formula was used. Table 1 shows the results.
[0059]
Comparative Example 2
As a charge generating substance, a peak having a strong diffraction angle (2θ ± 0.2 °) in 7.6 °, 10.2 °, 22.5 °, 25.3 ° and 28.6 ° in CuKα characteristic X-ray diffraction. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2 except that oxytitanium phthalocyanine having the following formula was used. Table 1 shows the results.
[0060]
Comparative Example 3
Oxytitanium phthalocyanine having a peak at a diffraction angle (2θ ± 0.2 °) of 7.1 °, 10.4 °, 24.8 ° and 27.4 ° in CuKα characteristic X-ray diffraction as a charge generating substance An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except for using. Table 1 shows the results.
[0061]
Comparative Example 4
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2, except that X-type metal-free phthalocyanine was used as the charge generating substance. Table 1 shows the results.
[0062]
[Table 1]

[0063]
【The invention's effect】
The electrophotographic photoreceptor of the present invention, by containing a specific oxytitanium phthalocyanine in the photosensitive layer, has no blur and no flow even under high humidity, and provides a high-definition image. There is no image defect such as toner fogging due to the increase, and the accumulation of residual potential during repeated use is reduced. High durability, no image defects such as ghost from the beginning to after repeated use, and high quality Has a remarkable effect that it can be maintained. The electrophotographic photoreceptor can be similarly mounted on a cartridge and an electrophotographic apparatus to provide excellent effects.
[Brief description of the drawings]
FIG. 1 is a CuKα characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the present invention.
FIG. 2 is a CuKα characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the present invention.
FIG. 3 is a diagram showing a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
REFERENCE SIGNS LIST 1 electrophotographic photoreceptor 2 shaft 3 primary charging means 4 image exposure light 5 developing means 6 transfer means 7 transfer material 8 image fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge 12 rail

Claims (7)

An electrophotographic photoreceptor in which at least a photosensitive layer and a surface protective layer are laminated in this order on an anodic oxide film of an aluminum cylinder having an anodic oxide film formed on the surface thereof, wherein the photosensitive layer is used as a charge generating substance in CuKα characteristic X-ray diffraction. Oxytitanium phthalocyanine or 9.3 °, 10.6 °, 13.2 ° having strong peaks at diffraction angles (2θ ± 0.2 °) of 9.5 °, 24.1 ° and 27.3 ° Oxytitanium phthalocyanine, which has strong peaks at 15.1 °, 15.7 °, 16.1 °, 20.8 °, 23.3 °, 26.3 ° and 27.1 ° ,
It comprises a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2) as a charge transporting substance, and the surface protective layer further includes conductive particles and a resin. Electrophotographic photoreceptor :
Structural formula (1)

Structural formula (2)

. The electrophotographic photoreceptor of claim 1, wherein the resin as the main ingredient the surface protective layer is cured by heat or light. Claim 1 or 2 electrophotographic photosensitive member according the surface protective layer is further contain a fluorine atom-containing resin particles. The electrophotographic photoreceptor of claim 1, wherein said conductive particles are metal oxide particles. The electrophotographic photosensitive member according to claim 4, wherein the metal oxide particles have been subjected to a water-repellent treatment. An electrophotographic photosensitive member according to claim 1, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported, and are detachably attached to an electrophotographic apparatus main body. Process cartridge. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.

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