JP3563916B2 - Electrophotographic photoreceptor, electrophotographic apparatus and process cartridge using the electrophotographic photoreceptor - Google Patents

Description

【００１３】
上記式（１）中、Ｒ_１ 、Ｒ_２ 及びＲ_３ は水素原子またはアルキル基を示す。ｎは４−８の整数を示す。
【００１４】
上記アルキル基としては、メチル基、エチル基又はプロピル基が好ましい。
【００１６】
Ａｒ−（Ｎ_２ ・Ｘ）_ｍ （２）
【００１７】
上記式（２）中、Ａｒは置換基を有してもよい芳香族炭化水素環、置換基を有してもよい複素環、複数の芳香族炭化水素環を結合したものあるいは複数の複素環を結合したものを示す。ＸはＢＦ_４ 、ＺｎＣｌ_２ 又はハロゲン原子を示す。ｍは２−４の整数を示す。
【００１８】
上記芳香族炭化水素環または複素環としては、ベンゼン、ナフタレン、フルオレン、フェナンスレン、アンスラセン、フルオランテン、ピレン等の炭化水素系芳香環、あるいはフラン、チオフェン、ピリジン、インドール、ベンゾチアゾール、カルバゾール、ベンゾカルバゾール、アクリドン、ジベンゾチオフェン、ベンゾオキサゾール、ベンゾトリアゾール、オキサチアゾール、チアゾール、フェナジン、シンノリン、ベンゾシンノリン等の芳香族性の複素環が好ましい。また、Ａｒは複数の芳香族炭化水素環または複数の複素環を、芳香族性あるいは非芳香族性の結合基で、または直接に結合したものでもよい。このようなＡｒとしては、例えばトリフェニルアミン、ジフェニルアミン、Ｎ−メチルジフェニルアミン、ビフェニル、ターフェニル、ビナフチル、フルオレノン、フェナンスレンキノン、アンスラキノン、ベンズアントロン、ジフェニルオキサゾール、フェニルベンズオキサゾール、ジフェニルメタン、ジフェニルスルホン、ジフェニルエーテル、ベンゾフェノン、スチルベン、ジスチリルベンゼン、テトラフェニル−ｐ−フェニレンジアミン、テトラフェニルベンジジン等が挙げられる。
【００１９】
Ａｒの置換基としては、例えば、メチル、エチル、プロピル、ブチル等のアルキル基、メトキシ、エトキシ等のアルコキシ基、ジメチルアミノ、ジエチルアミノ等のジアルキルアミノ基、フッ素原子、塩素原子、臭素原子等のハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基、ハロメチル基等が挙げられる。
【００２０】
Ｘで表わされるハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
【００２１】
本発明の電子写真感光体に含有するアゾ化カリックス〔ｎ〕アレーン化合物は、上記一般式（１）のカリックス〔ｎ〕アレーン化合物と、上記一般式（２）のアゾニウム化合物とのカップリング生成物である。更にアゾ化カリックス〔ｎ〕アレーン化合物としては、下記一般式（３）で示されるものが好ましい。
【００２２】
【外４】

【００２３】
上記式（３）中、Ｒ_１ −Ｒ_３ 及びｎは一般式（１）のＲ_１ −Ｒ_３ 及びｎと同じ意味を持つものである。またＲ_４ −Ｒ_６ は水素原子またはアルキル基を示し、アルキル基としてはメチル基、エチル基又はプロピル基が好ましい。
【００２４】
以下、本発明で使用するアゾ化カリックス〔ｎ〕アレーン化合物の好ましい例を記載する。尚、以下の例示のうち、例示化合物（１）−（１５）は上記一般式（３）に属する化合物であり、Ａｒ，Ｒ_１ −Ｒ_６ ，ｎのみで表わした。
【００２５】
【外５】

【００２６】
【外６】

【００２７】
【外７】

【００２８】
【外８】

【００２９】
【外９】

【００３０】
【外１０】

【００３１】
【外１１】

【００３２】
本発明で用いるアゾ化カリックス〔ｎ〕アレーン化合物は、アミンを常法によりテトラゾ化し、アルカリの存在下カリックス〔ｎ〕アレーンと水系でカップリングするか、アゾニウム塩をホウフッ化塩や塩化亜鉛複塩等に変換した後、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシドあるいはテトラヒドロフラン等の有機溶剤中で酢酸ソーダ、トリエチルアミン、ピリジン、Ｎ−メチルモルホリン等の塩基の存在下、カリックス〔ｎ〕アレーンとカップリングすることによって容易に合成できる。
【００３３】
合成例（例示化合物（１）の合成）
３００ミリリットルのビーカーに、水７５ミリリットル、濃塩酸１５ミリリットル及び２，７−ジアミノフルオレノン１０．５ｇ（０．０５モル）を入れ、０℃まで冷却した。この溶液の中へ、亜硝酸ソーダ７．６ｇ（０．１１モル）を水１７ｇに溶かした液を液温５℃以下に保ちながら１０分間で滴下した。２０分間撹拌した後、カーボンろ過し、この溶液の中へホウフッ化ソーダ１９．８ｇ（０．１８モル）を水６０ミリリットルに溶かした液を撹拌下滴下し、析出したホウフッ化塩をろ取し、冷水で洗浄した後、冷アセトニトリル−イソプロピリエーテルで洗浄し、室温で減圧乾燥した。収量１８．３ｇ、収率９０．０％であった。
【００３４】
次に、１０００ミリリットルのビーカーにＮ，Ｎ−ジメチルホルムアミド８００ミリリットルとカリックス〔ｎ〕アレーン４．２４ｇ（０．０１モル）を入れ、０℃まで冷却し、この溶液の中へ先に得たホウフッ化塩２．０４ｇ（０．００５モル）を加え、次いでＮ−メチルモルホリン４．５ｇをゆっくり加えた。液温を５℃以下に保ちながら２時間撹拌した後、室温で更に１時間撹拌した。析出物をろ取、Ｎ，Ｎ−ジメチルホルムアミドで精製後、水洗浄し、室温で減圧乾燥した。収量４．７１ｇ、収率５３．０％であった。
【００３５】
こうして得た例示化合物（１）について、元素分析装置（ＣＡＲＬＯ ＥＲＢＡ ＩＮＳＴＲＵＭＥＮＴＳ社製ＥＡ−１１０８）を用いて元素分析を行なった。結果を以下に示した。
【００３６】

【００３７】
本発明の電子写真感光体は、導電性支持体上にアゾ化カリックス〔ｎ〕アレーン化合物を含有する感光層を有する。感光層は単一層でもかまわないが、アゾ化カリックス〔ｎ〕アレーン化合物を含有する層を電荷発生層とし、これに電荷輸送物質を含有する電荷輸送層を積層した機能分離型の感光層が好ましい。
【００３８】
電荷発生層は、前記のアゾ化カリックス〔ｎ〕アレーン化合物を適当な溶剤中でバインダー樹脂と共に分散した塗布液を、導電性支持体上に公知の方法によって塗布することによって形成することができる。電荷発生層の膜厚は５μｍ以下、好ましくは０．１〜１μｍとすることが望ましい。アゾ化カリックス〔ｎ〕アレーン化合物の含有量は、アゾ化カリックス〔ｎ〕アレーン化合物の含有する層に対して４０−８５重量％更には５０−８０重量％が好ましい。
【００３９】
電荷発生層に用いるバインダー樹脂は、広範な絶縁性樹脂あるいは有機光導電性ポリマーから選択されるが、例えば置換または無置換のポリビニルブチラール、ポリビニルベンザール、ポリアリレート、ポリカーボネート、ポリエステル、フェノキシ樹脂、セルロース樹脂、アクリル樹脂、ポリウレタン等が好ましく、置換基としてはハロゲン原子、アルキル基、アルコキシ基、ニトロ基、トリフルオロメチル基、シアノ基等が好ましい。
【００４０】
また、使用する溶剤は、前記のバインダー樹脂を溶解し、後述の電荷輸送層や下引き層を溶解しない溶剤を選択することが好ましい。例えばテトラヒドロフラン、１，４−ジオキサン等のエーテル類、シクロヘキサノン、メチルエチルケトン等のケトン類、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、酢酸メチル、酢酸エチル等のエステル類、トルエン、キシレン、クロロベンゼン等の芳香族炭化水素化合物、メタノール、エタノール、２−プロパノール等のアルコール類、クロロホルム、塩化メチレン等の脂肪族炭化水素化合物等が挙げられる。
【００４１】
電荷輸送層は電荷発生層の上または下に積層される。電荷輸送層は電荷輸送物質を必要に応じて適当なバインダー樹脂と共に溶剤中に溶解した塗布液を塗布することによって形成される。電荷発生層の膜厚は５〜４０μｍ、好ましくは１０〜３０μｍである。
【００４２】
電荷輸送物質には電子輸送物質と正孔輸送物質があり、電子輸送物質としては、例えば２，４，７−トリニトロフロオレノン、２，４，５，７−テトラニトロフルオレノン、クロラニル、テトラシアノキノジメタン等の電子吸引性物質やこれ等電子吸引性物質を高分子化したもの等が挙げられる。また、正孔輸送物質としては、例えばピレン、アントラセン等の多環芳香族化合物、カルバゾール、インドール、イミダゾール、オキサゾール、チアゾール、オキサジアゾール、ピラゾール、ピラゾリン、チアジアゾール、トリアゾール系化合物等の複素環化合物、ｐ−ジエチルアミドベンズアルデヒド−Ｎ，Ｎ−ジフェニルヒドラゾン、Ｎ，Ｎ−ジフェニルヒドラジノ−３−メチリデン−９−エチルカルバゾール等のヒドラゾン系化合物、α−フェニル−４′−Ｎ，Ｎ−ジフェニルアミノスチルベン、５−〔４−（ジ−ｐ−トリルアミノ）ベンジリデン〕−５Ｈ−ジベンゾ〔ａ，ｂ〕シクロヘプテン等のスチリル系化合物、ベンジジン系化合物、トリアリールメタン系化合物、トリ（ｐ−トリル）アミン、２−〔ジ（ｐ−トリル）〕−アミノビフェニル、１−〔ジ−（ｐ−トリル）〕−アミノピレン等のトリアリールアミン系化合物あるいはこれ等の化合物からなる基を主鎖または側鎖に有するポリマー（例えばポリ−Ｎ−ビニルカルバゾール、ポリビニルアントランセン等）が挙げられる。
【００４３】
これ等の有機電荷輸送物質の他にセレン、セレン−テルル、アモルファスシリコン、硫化カドミウム等の無機材料も用いることができる。また、これ等の電荷輸送物質は１種または２種以上を組み合わせて用いることができる。電荷輸送物質の含有率は、電荷輸送層に対して３０〜７０重量％が好ましい。
【００４４】
電荷輸送物質に用いるバインダー樹脂としては、例えばアクリル樹脂、ポリアリレート、ポリカーボネート、ポリエステル、ポリスチレン、アクリロニトリル−スチレンコポリマー、ポリアクリルアミド、ポリアミド、塩素化ゴム等の絶縁性樹脂あるいはポリ−Ｎ−ビニルカルバゾール、ポリビニルアントラセン等の有機光導電性ポリマーなどが挙げられる。
【００４５】
感光層が単一層の場合、感光層の厚みは５〜４０μｍ、更には１０〜３０μｍが好ましい。
【００４６】
感光層が単一層の場合、前記アゾ化カリックス〔ｎ〕アレーン化合物と電荷輸送物質を適当な樹脂溶液中に分散させた液を導電性支持体上に塗布乾燥して作成することができる。
【００４７】
各層を塗工するコーティング法としては、一般的なものが使用でき、例えば、浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ローラーコーティング法、マイヤーバーコーティング法、ブレードコーティング法などのコーティング法が使用できる。
【００４８】
感光層が形成される導電性支持体の材料としては、例えばアルミニウム、アルミニウム合金、銅、亜鉛、ステンレス、バナジウム、モリブデン、クロム、チタン、ニッケル、インジウム、金や白金等が用いられる。またこれ等の金属または合金を真空蒸着したプラスチック（例えばポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリエチレンテレフタレート、アクリル樹脂等）や導電性粒子（例えばカーボンブラック、銀粒子等）を適当なバインダー樹脂と共にプラスチックまたは金属基板上に被覆した支持体、更には導電性粒子をプラスチックや紙に含浸させた支持体等を用いることができる。
【００４９】
導電性支持体と感光層の中間にバリヤー機能と接着機能を有する下引き層を設けることもできる。下引き層はカゼイン、ポリビニルアルコール、ニトロセルロース、ポリアミド（ナイロン６、ナイロン６６、ナイロン６１０、共重合ナイロン、アルコキシメチル化ナイロン等）、ポリウレタン、酸化アルミニウム等によって形成できる。その膜厚は５μｍ以下、好ましくは０．１〜３μｍが適当である。
【００５０】
本発明で使用するアゾ化カリックス〔ｎ〕アレーン化合物の結晶形は非晶質であっても結晶質であってもよく、また必要に応じて前記アゾ化カリックス〔ｎ〕アレーン化合物を２種以上組み合わせたり、公知の電荷発生物質、例えばフタロシアニン系顔料、アゾ系顔料、ペリレン系顔料等と組み合わせて使用することも可能である。
【００５１】
本発明の電子写真感光体は電子写真複写機及びファクシミリのプリンター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、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。
【００５２】
感光層上には、必要に応じて保護層を設けてもよい。保護層は、ポリビニルブチラール，ポリエステル、ポリカーボネート（ポリカーボネートＺ、変性ポリカーボネート等）、ナイロン、ポリイミド、ポリアリレート、ポリウレタン、スチレン−ブタジエンコポリマー、スチレン−アクリル酸コポリマー、スチレン−アクリロニトリルコポリマーなどの樹脂を適当な有機溶剤によって溶解し、感光層の上に塗布、乾燥して形成できる。保護層の膜厚は、０．０５〜２０μｍが好ましい。また、保護層中に導電性粒子や紫外線吸収剤などを含ませてもよい。導電性粒子としては、例えば酸化錫粒子等の金属酸化物が好ましい。
【００５３】
次に、本発明の電子写真感光体を用いた電子写真装置について説明する。
【００５４】
図１において、１は本発明のドラム型感光体であり軸１ａを中心に矢印方向に所定の周速度で回転駆動する。該感光体１はその回転過程で帯電手段２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、次いで露光部３にて不図示の像露光手段により光像露光Ｌ（スリット露光あるいはレーザービーム走査露光など）を受ける。これにより感光体周面に露光像に対応した静電潜像が順次形成されていく。その静電潜像は、次いで現像手段４でトナー現像され、そのトナー現像像がコロナ転写手段５により不図示の給紙部から感光体１と転写手段５との間に感光体１の回転と同期取りされて給送された記録材９の面に順次転写されていく。像転写を受けた記録材９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て複写物（コピー）として機外へプリントアウトされる。像転写後の感光体１の表面はクリーニング手段６にて転写残りトナーの除去を受けて清浄面化され、前露光手段７により除電処理がされて繰り返して像形成に使用される。
【００５５】
また、図２に示す装置では、少なくとも感光体１、帯電手段２及び現像手段４を容器２０に納めてプロセスカートリッジとし、このプロセスカートリッジを装置本体のレールなどの案内手段１２を用いて着脱自在に構成している。クリーニング手段６は容器２０内に配置しても配置しなくてもよい。
【００５６】
また、図３及び図４に示すように、帯電手段として直接帯電部材１０を用い、電圧印加された直接帯電部材１０を感光体１に接触させることにより感光体１の帯電を行なってもよい（この帯電方法を、以下直接帯電という）。図３及び図４に示す装置では感光体１上のトナー像も直接帯電部材２３で記録材９に転写される。即ち、電圧印加された直接帯電部材２３を記録材９に接触させることにより感光体１上のトナー像を記録材９に転写させる。
【００５７】
更に図４に示す装置では、少なくとも感光体１及び直接帯電部材１０を第１の容器２１に納めて第１のプロセスカートリッジとし、少なくとも現像手段４を第２の容器２２に納めて第２のプロセスカートリッジとし、これら第１のプロセスカートリッジと、第２のプロセスカートリッジとを着脱自在に構成している。クリーニング手段６は容器２１内に配置しても配置しなくてもよい。
【００５８】
光像露光Ｌは、電子写真装置を複写機やプリンターとして使用する場合には、原稿からの反射光や透過光を用いる、あるいは、原稿を読み取り信号化に従って、この信号によりレーザービームの走査、発光ダイオードアレイの駆動、または液晶シャッターアレイの駆動などを行なうことにより行なわれる。
【００５９】
本発明の電子写真感光体は、高い感度を有し、繰り返し使用しても安定して優れた電位特性を有するという顕著な効果を奏する。また、プロセスカー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。
【００６０】
【実施例】
実施例１〜８
シート状のアルミニウム支持体上にメトキシメチル化ナイロン（重量平均分子量３２０００）５ｇとアルコール可溶性共重合ナイロン（重量平均分子量２９０００）１０ｇをメタノール９５ｇに溶解した液をマイヤーバーで塗布し、乾燥後の膜厚が１μｍの下引き層を形成した。
【００６１】
次に、前記例示化合物（１）６ｇを、シクロヘキサノン９５ｇにブチラール樹脂（ブチラール化度６３モル％）２ｇを溶解した液に加え、サンドミルで２０時間分散した。この分散液を上記下引き層の上に乾燥後の膜厚が０．２μｍとなるようにマイヤーバーで塗布し、電荷発生層を形成した。
【００６２】
次に、下記構造式を有するヒドラゾン化合物５ｇ
【００６３】
【外１２】

とポリメチルメタクリレート（数平均分子量１０００００）５ｇをクロロベンゼン４０ｇに溶解した液を上記電荷発生層の上にマイヤーバーで塗布し、乾燥して、膜厚１６μｍの電荷感光層を形成し、本発明の電子写真感光体を作成した。
【００６４】
例示化合物（１）に代えて、表１に示した例示化合物を用いた他は、実施例１と全く同様にして実施例２〜８の電子写真感光体を作成した。
【００６５】
この様にして作成した電子写真感光体を静電複写紙試験装置（ＳＰ−４２８、川口電機（株）製）を用いて−５ＫＶのコロナ放電で負に帯電し、１秒間暗所放置した後、ハロゲンランプを用いて照度１０ルックスで露光し、帯電特性を評価した。帯電特性としては帯電直後の表面電位Ｖ_０ と、１秒間の暗所放置後の表面電位を１／２に減衰するに必要な露光料をＥ_１／２ を測定した。結果を表１に示した。
【００６６】
【表１】

【００６７】
比較例１及び２
実施例１で用いた例示化合物（１）に代えて、下記の比較顔料１及び２を用いた他は、実施例１と全く同様にして電子写真感光体を作成し、それぞれの感光体について実施例１と同様にして帯電特性を評価した。結果を表２に示した。
【００６８】
比較顔料１
【００６９】
【外１３】

【００７０】
比較顔料２
【００７１】
【外１４】

【００７２】
【表２】

【００７３】
この結果から、本発明の電子写真感光体はいずれも十分な帯電能と改善された優れた感度特性を有することが知られる。
【００７４】
実施例９〜１３
実施例１で作成した電子写真感光体を、図２の電子写真複写機のシリンダーに貼り付けた。コロナ帯電器には−７．０ｋＶの電圧をかけた。初期の暗部電位Ｖ_Ｄ と明部電位Ｖ_Ｌ がそれぞれ−７００Ｖ付近，−２００Ｖ付近になるように設定した後、帯電，露光，除電のサイクルを５０００回繰り返し使用し、初期と繰り返し使用後での暗部電位の変動量ΔＶ_Ｄ と明部電位の変動量ΔＶ_Ｌ を測定することにより耐久特性を評価した。結果を表３に示した。なお、電位変動における負符号は電位の絶対値が減少したことを表わし、正符号は電位の絶対値が増加したことを表わす。
【００７５】
実施例２、３、５及び８で作成した電子写真感光体についても同様に評価を行なった。結果を表３に示した。
【００７６】
【表３】

【００７７】
比較例３及び４
比較例１及び２で作成した電子写真感光体について、実施例９と同様の方法で繰り返し使用時の電位変動量を測定した。結果を表４に示した。
【００７８】
【表４】

【００７９】
実施例９〜１３、比較例３及び４の結果から、本発明の電子写真感光体は繰り返し使用時の電位変動が少ないことがわかる。
【００８０】
実施例１４
シート状のアルミニウム支持体上に、膜厚０．５μｍのポリビニルアルコールの下引き層を形成した。
【００８１】
下引き層の上に、実施例７において用いたと同じ例示化合物（１８）の分散液をマイヤーバーで塗布し、乾燥することによって、膜厚が０．２μｍの電荷発生層を形成した。
【００８２】
次に、下記構造式を有する化合物５ｇ
【００８３】
【外１５】

とポリカーボネート（重量平均分子量５５０００）５ｇをテトラヒドロフラン４０ｇに溶解した液を電荷発生層の上に塗布乾燥して、膜厚１６μｍの電荷輸送層を形成し、本発明の電子写真感光体を作成した。
【００８４】
この電子写真感光体について、以下のようにして感度を測定した。
【００８５】
作成した電子写真感光体を、直接帯電で帯電を行なうレーザービームプリンター（商品名ＬＢＰ−ＳＸ，キヤノン（株）製）のシリンダーに貼り付けて暗部電位が−７００Ｖになるように帯電した。その後波長８０２ｎｍのレーザー光を電子写真感光体に照射して−７００Ｖの電位を−１５０Ｖまで下げるのに必要な光量を測定して感度とした。
【００８６】
次に、暗部電位−７００Ｖ、明部電位−１５０Ｖに設定した状態で連続４０００枚の通紙耐久試験を行なって暗部電位変動量ΔＶ_Ｄ と明部電位変動量ΔＶ_Ｌ を測定した。感度と電位変動量の測定結果を以下に示した。
【００８７】
感 度：１．２５μＪ／ｃｍ^２
ΔＶ_Ｄ ：０Ｖ
ΔＶ_Ｌ ：＋５Ｖ
【００８８】
実施例１５
シート状のアルミニウム支持体上に、膜厚０．５μｍの膜厚を有するポリビニルアルコールの下引き層を形成した。
【００８９】
下引き層の上に実施例５において用いたと同じ例示化合物（１４）の分散液をマイヤーバーで塗布乾燥して、膜厚０．２μｍの電荷発生層を形成した。
【００９０】
次に、下記構造式を有する化合物５ｇ
【００９１】
【外１６】

とポリカーボネート（重量平均分子量５５０００）５ｇをテトラヒドロフラン４０ｇに溶解した液を電荷発生層の上に塗布乾燥して、膜厚１７μｍの電荷輸送層を形成し、本発明の電子写真感光体を作成した。
【００９２】
この電子写真感光体の感度と、耐久試験による電位変動量とを実施例１４と同様にして測定した。測定結果を以下に示した。
【００９３】
感 度：１．１０μＪ／ｃｍ^２
ΔＶ_Ｄ ：０Ｖ
ΔＶ_Ｌ ：＋５Ｖ
【００９４】
実施例１６
実施例５で作成した電子写真感光体の電荷発生層と電荷輸送層を逆の順番で積層した本発明の電子写真感光体を作成し、実施例１と同様の方法で帯電特性を評価した。ただし、帯電は正帯電とした。結果を以下に示した。
【００９５】
Ｖ_０ ：＋６２０Ｖ
Ｅ_１／２ ：２．７５ルックス・秒
【００９６】
実施例１７
実施例５におけると同様にして電荷発生層までを形成した。その上に２，４，７−トリニトロ−９−フルオレノン５ｇとポリ−４，４−ジオキシジフェニル−２，２−プロパンカーボネート（重量平均分子量３０００００）５ｇをテトラヒドロフラン５０ｇに溶解した液をマイヤーバーで塗布乾燥して、膜厚が１６μｍの電荷輸送層を形成し、電子写真感光体を作成した。実施例１と同様の方法で帯電特性を評価した。ただし、帯電は正帯電とした。結果を以下に示した。
【００９７】
Ｖ_０ ：＋６５０Ｖ
Ｅ_１／２ ：２．５０ルックス・秒
【００９８】
実施例１８
０．５ｇの例示化合物（２）をシクロヘキサノン９．５ｇに加え、ペイントシェイカーで５時間分散した。この分散液に実施例１で用いたと同じ電荷輸送物質５ｇとポリカーボネート５ｇをテトラヒドロフラン４０ｇに溶解した溶液を加え、更に１時間振とうした。調製した塗布液をアルミニウム基板上にマイヤーバーで塗布乾燥して膜厚２０μｍの感光層を形成し、本発明の電子写真感光体を作成した。この電子写真感光体について実施例１と同様の方法で帯電特性を評価した。ただし、帯電は正帯電とした。結果を以下に示した。
【００９９】
Ｖ_０ ：＋６４０Ｖ
Ｅ_１／２ ：２．２０ルックス・秒
【０１００】
【発明の効果】
本発明の電子写真感光体は、高い感度を有し、繰り返し使用しても安定して優れた電位特性を有するという顕著な効果を奏する。また、プロセスカー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】本発明の電子写真装置の一例を示す図である。
【図２】本発明の電子写真装置の他の例を示す図である。
【図３】本発明の電子写真装置の他の例を示す図である。
【図４】本発明の電子写真装置の他の例を示す図である。
【符号の説明】
１ 電子写真感光体
２ 帯電手段
４ 現像手段
５ 転写手段
６ クリーニング手段
７ 前露光手段
９ 記録材
１０ 直接帯電部材[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, an electrophotographic apparatus including the electrophotographic photosensitive member, and a process cartridge.
[0002]
[Prior art]
Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide, and zinc oxide have been widely used for electrophotographic photoreceptors. On the other hand, as an electrophotographic photoreceptor using an organic photoconductive substance, a photoconductive polymer represented by poly-N-vinylcalibazole or 2,5-bis (p-diethylaminophenyl) -1,3,4- Known are those using a low-molecular organic photoconductive substance such as oxadiazole, and those combining such an organic photoconductive substance with various dyes and pigments.
[0003]
An electrophotographic photosensitive member using an organic photoconductive substance has good film-forming properties and can be produced by coating, and thus has an advantage of providing an inexpensive electrophotographic photosensitive member with extremely high productivity. In addition, there is an advantage that the photosensitive wavelength range can be freely controlled by selecting a dye or a pigment to be used, and wide studies have been made so far. In particular, recently, the development of a function-separated photoconductor in which a charge generation layer containing an organic photoconductive dye or pigment and a charge transport layer containing a photoconductive polymer or a low-molecular organic photoconductive substance are laminated, Significant improvements have been made in the sensitivity and durability, which have been regarded as disadvantages of the organic electrophotographic photoreceptor.
[0004]
There is an azo pigment as an organic photoconductive substance.Since azo pigments show excellent photoconductivity and compounds with various properties can be easily obtained by combining azo components and coupler components, Numerous compounds have been proposed, for example, JP-A-54-22834, JP-A-58-177555, JP-A-58-194035, JP-A-61-215556, and JP-A-61-215556. And Japanese Patent Application Laid-Open No. Sho 63-17456.
[0005]
[Problems to be solved by the invention]
However, electrophotographic photoreceptors using conventional azo pigments are not always sufficient in terms of sensitivity and potential stability during repeated use, and only a few materials have been put to practical use. is there.
[0006]
An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity characteristics and a stable potential characteristic when repeatedly used, and an electrophotographic apparatus and a process cartridge using the electrophotographic photosensitive member.
[0007]
[Means for Solving the Problems]
The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having at least a photosensitive layer on a support, wherein the photosensitive layer is formed by coupling a calix [n] arene compound with an azonium compound having at least two azos. Containing the azotized calix [n] arene compound.
[0008]
Further, the electrophotographic apparatus of the present invention includes the above electrophotographic photosensitive member, a charging unit for charging the electrophotographic photosensitive member, and an image for forming an electrostatic latent image by performing image exposure on the charged electrophotographic photosensitive member. An exposure unit; and a developing unit for developing the electrophotographic photosensitive member, on which the electrostatic latent image is formed, with toner.
[0009]
Further, a process cartridge of the present invention includes the above-described electrophotographic photosensitive member, and a charging member for charging the electrophotographic photosensitive member.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The electrophotographic photoreceptor of the present invention has at least a photosensitive layer on a support, and the photosensitive layerRepresented by the following general formula (1)A calix [n] arene compound,Represented by the following general formula (2)An azide calix [n] arene compound generated by coupling with at least two azo-containing azonium compounds is contained as a charge generating substance.
[0012]
[Outside 3]

[0013]
In the above formula (1), R₁  , R₂  And R₃  Represents a hydrogen atom or an alkyl group. n shows the integer of 4-8.
[0014]
The alkyl group is preferably a methyl group, an ethyl group or a propyl group.
[0016]
Ar- (N₂  ・ X)_m                                    (2)
[0017]
In the above formula (2), Ar is an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent, one in which a plurality of aromatic hydrocarbon rings are bonded, or a plurality of heterocycles Are combined. X is BF₄  , ZnCl₂  Or a halogen atom. m shows the integer of 2-4.
[0018]
Examples of the aromatic hydrocarbon ring or heterocyclic ring, benzene, naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, hydrocarbon aromatic ring such as pyrene, or furan, thiophene, pyridine, indole, benzothiazole, carbazole, benzocarbazole, Preferred are aromatic heterocycles such as acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, phenazine, cinnoline, and benzocinnoline. Ar may be one in which a plurality of aromatic hydrocarbon rings or a plurality of heterocycles are bonded with an aromatic or non-aromatic bonding group or directly. Examples of such Ar include, for example, triphenylamine, diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone , Diphenyl ether, benzophenone, stilbene, distyrylbenzene, tetraphenyl-p-phenylenediamine, tetraphenylbenzidine and the like.
[0019]
Examples of the substituent for Ar include an alkyl group such as methyl, ethyl, propyl, and butyl; an alkoxy group such as methoxy and ethoxy; a dialkylamino group such as dimethylamino and diethylamino; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom. Examples include an atom, a hydroxy group, a nitro group, a cyano group, and a halomethyl group.
[0020]
Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0021]
The azoxy calix [n] arene compound contained in the electrophotographic photoreceptor of the present invention is a coupling product of the calix [n] arene compound of the above general formula (1) and the azonium compound of the above general formula (2).It is.Further, as the azotized calix [n] arene compound, a compound represented by the following general formula (3) is preferable.
[0022]
[Outside 4]

[0023]
In the above formula (3), R₁  -R₃  And n are R of the general formula (1)₁  -R₃  And n have the same meaning. Also R₄  -R₆  Represents a hydrogen atom or an alkyl group, and the alkyl group is preferably a methyl group, an ethyl group or a propyl group.
[0024]
Hereinafter, preferred examples of the azoxy calix [n] arene compound used in the present invention will be described. In addition, in the following examples, the exemplified compounds (1) to (15) are compounds belonging to the general formula (3), and Ar, R₁  -R₆  , N only.
[0025]
[Outside 5]

[0026]
[Outside 6]

[0027]
[Outside 7]

[0028]
[Outside 8]

[0029]
[Outside 9]

[0030]
[Outside 10]

[0031]
[Outside 11]

[0032]
The azylated calix [n] arene compound used in the present invention is obtained by subjecting an amine to tetrazotization by an ordinary method and coupling the calix [n] arene with an aqueous system in the presence of an alkali, or converting an azonium salt into a borofluoride or a zinc chloride double salt. And then coupled with calix [n] arene in an organic solvent such as N, N-dimethylformamide, dimethylsulfoxide or tetrahydrofuran in the presence of a base such as sodium acetate, triethylamine, pyridine or N-methylmorpholine. Can be easily synthesized.
[0033]
Synthesis Example (Synthesis of Exemplified Compound (1))
A 300 ml beaker was charged with 75 ml of water, 15 ml of concentrated hydrochloric acid and 10.5 g (0.05 mol) of 2,7-diaminofluorenone, and cooled to 0 ° C. A solution prepared by dissolving 7.6 g (0.11 mol) of sodium nitrite in 17 g of water was dropped into this solution over 10 minutes while maintaining the temperature at 5 ° C. or lower. After stirring for 20 minutes, the mixture was filtered with carbon, and a solution prepared by dissolving 19.8 g (0.18 mol) of sodium borofluoride in 60 ml of water was dropped into this solution with stirring, and the precipitated borofluoride was collected by filtration. After washing with cold water, the mixture was washed with cold acetonitrile-isopropylether and dried at room temperature under reduced pressure. The yield was 18.3 g and the yield was 90.0%.
[0034]
Next, 800 ml of N, N-dimethylformamide and 4.24 g (0.01 mol) of calix [n] arene were placed in a 1000 ml beaker, cooled to 0 ° C., and the previously obtained fluorinated solution was poured into the solution. 2.04 g (0.005 mol) of the chlorinated salt was added, and then 4.5 g of N-methylmorpholine was slowly added. After stirring for 2 hours while maintaining the liquid temperature at 5 ° C. or lower, the mixture was further stirred at room temperature for 1 hour. The precipitate was collected by filtration, purified with N, N-dimethylformamide, washed with water, and dried at room temperature under reduced pressure. The yield was 4.71 g, and the yield was 53.0%.
[0035]
The exemplary compound (1) thus obtained was subjected to elemental analysis using an elemental analyzer (EA-1108 manufactured by CARLO ERBA INSTRUMENTS). The results are shown below.
[0036]

[0037]
The electrophotographic photoreceptor of the present invention has a photosensitive layer containing an azoxy calix [n] arene compound on a conductive support. The photosensitive layer may be a single layer, but a function-separated type photosensitive layer in which a layer containing an azide calix [n] arene compound is used as a charge generation layer and a charge transport layer containing a charge transport substance is laminated thereon is preferred. .
[0038]
The charge generation layer can be formed by applying a coating solution obtained by dispersing the above-described azotized calix [n] arene compound together with a binder resin in an appropriate solvent onto a conductive support by a known method. It is desirable that the thickness of the charge generation layer be 5 μm or less, preferably 0.1 to 1 μm. The content of the azotized calix [n] arene compound is preferably from 40 to 85% by weight, more preferably from 50 to 80% by weight, based on the layer containing the azotized calix [n] arene compound.
[0039]
The binder resin used for the charge generation layer is selected from a wide range of insulating resins or organic photoconductive polymers.For example, substituted or unsubstituted polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose Resins, acrylic resins, polyurethanes and the like are preferred, and the substituents are preferably halogen atoms, alkyl groups, alkoxy groups, nitro groups, trifluoromethyl groups, cyano groups and the like.
[0040]
Further, as the solvent to be used, it is preferable to select a solvent that dissolves the binder resin and does not dissolve the charge transport layer or the undercoat layer described below. For example, ethers such as tetrahydrofuran and 1,4-dioxane, cyclohexanone, methylLeKetones such as ethyl ketone, amides such as N, N-dimethylformamide, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbon compounds such as toluene, xylene and chlorobenzene, alcohols such as methanol, ethanol and 2-propanol And aliphatic hydrocarbon compounds such as chloroform and methylene chloride.
[0041]
The charge transport layer is laminated above or below the charge generation layer. The charge transport layer is formed by applying a coating solution in which a charge transport material is dissolved in a solvent together with an appropriate binder resin as required. The thickness of the charge generation layer is 5 to 40 μm, preferably 10 to 30 μm.
[0042]
The charge transport material includes an electron transport material and a hole transport material. Examples of the electron transport material include 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil, and tetra Examples thereof include an electron-withdrawing substance such as cyanoquinodimethane and a substance obtained by polymerizing such an electron-withdrawing substance. Further, as the hole transporting substance, for example, polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole, heterocyclic compounds such as triazole-based compounds, hydrazone compounds such as p-diethylamidobenzaldehyde-N, N-diphenylhydrazone, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, α-phenyl-4′-N, N-diphenylaminostilbene, 5 Styryl compounds such as-[4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, b] cycloheptene, benzidine compounds, triarylmethane compounds, tri (p-tolyl) amine, 2- [ Di (p-tolyl)]-ami Triarylamine compounds such as biphenyl and 1- [di- (p-tolyl)]-aminopyrene or polymers having a group consisting of these compounds in the main chain or side chain (for example, poly-N-vinylcarbazole, polyvinylanthra And the like).
[0043]
In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon, and cadmium sulfide can also be used. These charge transport materials can be used alone or in combination of two or more. The content of the charge transport material is preferably 30 to 70% by weight based on the charge transport layer.
[0044]
As the binder resin used for the charge transport material, for example, an insulating resin such as acrylic resin, polyarylate, polycarbonate, polyester, polystyrene, acrylonitrile-styrene copolymer, polyacrylamide, polyamide, chlorinated rubber or poly-N-vinylcarbazole, polyvinyl Organic photoconductive polymers such as anthracene are exemplified.
[0045]
When the photosensitive layer is a single layer, the thickness of the photosensitive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.
[0046]
When the photosensitive layer is a single layer, it can be prepared by applying a liquid obtained by dispersing the above-mentioned azoxy calix [n] arene compound and a charge transport material in an appropriate resin solution on a conductive support and drying it.
[0047]
As the coating method for coating each layer, a general method can be used, for example, a coating method such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, or a blade coating method is used. it can.
[0048]
As the material of the conductive support on which the photosensitive layer is formed, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, platinum, and the like are used. In addition, a plastic (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) obtained by vacuum-depositing these metals or alloys or conductive particles (for example, carbon black, silver particles, etc.) together with a suitable binder resin, together with a plastic or A support coated on a metal substrate, a support in which conductive particles are impregnated in plastic or paper, or the like can be used.
[0049]
An undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like. The film thickness is suitably 5 μm or less, preferably 0.1 to 3 μm.
[0050]
The crystal form of the azotized calix [n] arene compound used in the present invention may be amorphous or crystalline, and if necessary, two or more of the azotized calix [n] arene compounds may be used. It is also possible to use in combination with known charge generating substances such as phthalocyanine pigments, azo pigments and perylene pigments.
[0051]
The electrophotographic photoreceptor of the present invention can be widely used not only for electrophotographic copying machines and facsimile printers but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. it can.
[0052]
A protective layer may be provided on the photosensitive layer as needed. The protective layer is made of a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer. It can be formed by dissolving with a solvent, coating and drying the photosensitive layer. The thickness of the protective layer is preferably 0.05 to 20 μm. Further, the protective layer may contain conductive particles, an ultraviolet absorber and the like. As the conductive particles, for example, metal oxides such as tin oxide particles are preferable.
[0053]
Next, an electrophotographic apparatus using the electrophotographic photoreceptor of the present invention will be described.
[0054]
In FIG. 1, reference numeral 1 denotes a drum-type photosensitive member of the present invention, which is driven to rotate around an axis 1a in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by a charging means 2 during the rotation process, and then, in an exposure section 3, a light image exposure L (slit exposure or Laser beam scanning exposure). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor. The electrostatic latent image is then developed with toner by developing means 4, and the developed toner image is transferred by a corona transfer means 5 from a paper feeding unit (not shown) to the photosensitive body 1 between the photosensitive body 1 and the transfer means 5. The recording material 9 is sequentially transferred to the surface of the recording material 9 which is fed synchronously. The recording material 9 to which the image has been transferred is separated from the surface of the photoreceptor, introduced into the image fixing means 8, subjected to image fixing, and printed out of the apparatus as a copy. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by the removal of untransferred toner by the cleaning unit 6, is subjected to a charge removal treatment by the pre-exposure unit 7, and is repeatedly used for image formation.
[0055]
In the apparatus shown in FIG. 2, at least the photosensitive member 1, the charging means 2 and the developing means 4 are housed in a container 20 to form a process cartridge, and this process cartridge is detachably attached to the apparatus body by using a guide means 12 such as a rail. Make up. The cleaning means 6 may or may not be disposed in the container 20.
[0056]
Further, as shown in FIGS. 3 and 4, the charging of the photoconductor 1 may be performed by using the direct charging member 10 as a charging unit and bringing the direct charging member 10 to which the voltage is applied into contact with the photoconductor 1 ( This charging method is hereinafter referred to as direct charging). In the apparatus shown in FIGS. 3 and 4, the toner image on the photoconductor 1 is also directly transferred to the recording material 9 by the charging member 23. That is, the toner image on the photoconductor 1 is transferred to the recording material 9 by bringing the direct charging member 23 to which the voltage is applied into contact with the recording material 9.
[0057]
Further, in the apparatus shown in FIG. 4, at least the photoreceptor 1 and the direct charging member 10 are housed in a first container 21 to form a first process cartridge, and at least the developing means 4 is housed in a second container 22 for a second process. The first process cartridge and the second process cartridge are configured to be detachable. The cleaning means 6 may or may not be disposed in the container 21.
[0058]
In the case where the electrophotographic apparatus is used as a copier or a printer, the light image exposure L uses the reflected light or transmitted light from the original, or scans and emits a laser beam according to the read signal of the original according to a signal. This is performed by driving a diode array or a liquid crystal shutter array.
[0059]
The electrophotographic photoreceptor of the present invention has a remarkable effect that it has high sensitivity and has excellent potential characteristics stably even when used repeatedly. In addition, it can be mounted on a process cartridge and an electrophotographic apparatus to provide the same excellent effects.
[0060]
【Example】
Examples 1 to 8
A solution prepared by dissolving 5 g of methoxymethylated nylon (weight average molecular weight: 32,000) and 10 g of alcohol-soluble copolymerized nylon (weight average molecular weight: 29000) in 95 g of methanol is applied on a sheet-like aluminum support with a Meyer bar, and dried. An undercoat layer having a thickness of 1 μm was formed.
[0061]
Next, 6 g of the exemplified compound (1) was added to a solution prepared by dissolving 2 g of butyral resin (butyralization degree: 63 mol%) in 95 g of cyclohexanone, and dispersed by a sand mill for 20 hours. This dispersion was applied on the undercoat layer with a Meyer bar so that the film thickness after drying was 0.2 μm, to form a charge generation layer.
[0062]
Next, 5 g of a hydrazone compound having the following structural formula
[0063]
[Outside 12]

And a solution prepared by dissolving 5 g of polymethyl methacrylate (number average molecular weight 100,000) in 40 g of chlorobenzene was applied on the above-mentioned charge generating layer with a Meyer bar, and dried to form a charge-sensitive layer having a thickness of 16 μm. An electrophotographic photoreceptor was prepared.
[0064]
The electrophotographic photoreceptors of Examples 2 to 8 were prepared in exactly the same manner as in Example 1 except that the exemplified compounds shown in Table 1 were used instead of the exemplified compound (1).
[0065]
The electrophotographic photoreceptor thus prepared was negatively charged by a corona discharge of -5 KV using an electrostatic copying paper tester (SP-428, manufactured by Kawaguchi Electric Co., Ltd.), and left in a dark place for 1 second. Exposure was performed at an illuminance of 10 lux using a halogen lamp, and the charging characteristics were evaluated. The charging characteristics include the surface potential V immediately after charging.₀  And the exposure charge required to attenuate the surface potential after being left in a dark place for 1 second to Ｅ_1/2  Was measured. The results are shown in Table 1.
[0066]
[Table 1]

[0067]
Comparative Examples 1 and 2
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 1, except that the following comparative pigments 1 and 2 were used in place of the exemplary compound (1) used in Example 1, and each photoreceptor was used. The charging characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0068]
Comparative pigment 1
[0069]
[Outside 13]

[0070]
Comparative pigment 2
[0071]
[Outside 14]

[0072]
[Table 2]

[0073]
From these results, it is known that all of the electrophotographic photoreceptors of the present invention have a sufficient charging ability and improved sensitivity characteristics.
[0074]
Examples 9 to 13
The electrophotographic photosensitive member prepared in Example 1 was attached to the cylinder of the electrophotographic copying machine shown in FIG. A voltage of -7.0 kV was applied to the corona charger. Initial dark area potential V_D  And bright part potential V_L  Are set to around -700 V and around -200 V, respectively, and the cycle of charging, exposure, and charge elimination is repeated 5000 times, and the variation ΔV of the dark portion potential at the initial stage and after the repeated use is obtained._D  And the variation ΔV of the bright portion potential_L  Was measured to evaluate the durability characteristics. The results are shown in Table 3. Note that a negative sign in the potential fluctuation indicates that the absolute value of the potential has decreased, and a positive sign indicates that the absolute value of the potential has increased.
[0075]
The electrophotographic photosensitive members prepared in Examples 2, 3, 5, and 8 were similarly evaluated. The results are shown in Table 3.
[0076]
[Table 3]

[0077]
Comparative Examples 3 and 4
With respect to the electrophotographic photosensitive members prepared in Comparative Examples 1 and 2, the amount of potential fluctuation during repeated use was measured in the same manner as in Example 9. The results are shown in Table 4.
[0078]
[Table 4]

[0079]
From the results of Examples 9 to 13 and Comparative Examples 3 and 4, it can be seen that the electrophotographic photoreceptor of the present invention has little potential fluctuation upon repeated use.
[0080]
Example 14
An undercoat layer of polyvinyl alcohol having a thickness of 0.5 μm was formed on a sheet-like aluminum support.
[0081]
On the undercoat layer, a dispersion liquid of the same exemplified compound (18) as used in Example 7 was applied with a Meyer bar, and dried to form a charge generation layer having a thickness of 0.2 μm.
[0082]
Next, 5 g of a compound having the following structural formula
[0083]
[Outside 15]

And a solution of 5 g of polycarbonate (weight average molecular weight: 55000) dissolved in 40 g of tetrahydrofuran was applied on the charge generating layer and dried to form a charge transporting layer having a thickness of 16 μm, thereby preparing an electrophotographic photoreceptor of the present invention.
[0084]
The sensitivity of this electrophotographic photosensitive member was measured as follows.
[0085]
The prepared electrophotographic photoreceptor was attached to a cylinder of a laser beam printer (trade name: LBP-SX, manufactured by Canon Inc.) which performs charging by direct charging, and was charged so that the dark portion potential became -700V. Thereafter, a laser beam having a wavelength of 802 nm was irradiated on the electrophotographic photosensitive member to measure the amount of light required to reduce the potential of -700 V to -150 V, and the sensitivity was determined.
[0086]
Next, a continuous paper passing durability test of 4000 sheets was performed with the dark part potential set to −700 V and the light part potential −150 V, and the dark part potential variation ΔV_D  And the bright portion potential variation ΔV_L  Was measured. The measurement results of the sensitivity and the amount of potential fluctuation are shown below.
[0087]
Sensitivity: 1.25 μJ / cm²
ΔV_D  : 0V
ΔV_L  : + 5V
[0088]
Example 15
An undercoat layer of polyvinyl alcohol having a thickness of 0.5 μm was formed on a sheet-like aluminum support.
[0089]
On the undercoat layer, the same dispersion of the exemplified compound (14) as used in Example 5 was applied using a Meyer bar and dried to form a 0.2 μm-thick charge generation layer.
[0090]
Next, 5 g of a compound having the following structural formula
[0091]
[Outside 16]

And a solution of 5 g of polycarbonate (weight average molecular weight: 55000) dissolved in 40 g of tetrahydrofuran was applied on the charge generation layer and dried to form a charge transport layer having a thickness of 17 μm, thereby preparing an electrophotographic photoreceptor of the present invention.
[0092]
The sensitivity of the electrophotographic photoreceptor and the amount of potential fluctuation in the durability test were measured in the same manner as in Example 14. The measurement results are shown below.
[0093]
Sensitivity: 1.10 μJ / cm²
ΔV_D  : 0V
ΔV_L  : + 5V
[0094]
Example 16
An electrophotographic photoreceptor of the present invention was prepared by laminating the charge generation layer and the charge transport layer of the electrophotographic photoreceptor prepared in Example 5 in reverse order, and the charging characteristics were evaluated in the same manner as in Example 1. However, the charging was positive. The results are shown below.
[0095]
V₀    : + 620V
E_1/2  : 2.75 lux seconds
[0096]
Example 17
In the same manner as in Example 5, the layers up to the charge generation layer were formed. A solution prepared by dissolving 5 g of 2,4,7-trinitro-9-fluorenone and 5 g of poly-4,4-dioxydiphenyl-2,2-propanecarbonate (weight average molecular weight: 300,000) in 50 g of tetrahydrofuran was further subjected to a Meyer bar. After coating and drying, a charge transport layer having a thickness of 16 μm was formed, and an electrophotographic photosensitive member was prepared. The charging characteristics were evaluated in the same manner as in Example 1. However, the charging was positive. The results are shown below.
[0097]
V₀      : + 650V
E_1/2  ： 2.50 looks / sec
[0098]
Example 18
0.5 g of Exemplified Compound (2) was added to 9.5 g of cyclohexanone, and dispersed for 5 hours with a paint shaker. To this dispersion, a solution in which 5 g of the same charge transporting substance as used in Example 1 and 5 g of polycarbonate were dissolved in 40 g of tetrahydrofuran was added, and the mixture was further shaken for 1 hour. The prepared coating solution was applied on an aluminum substrate with a Meyer bar and dried to form a photosensitive layer having a thickness of 20 μm, thereby preparing an electrophotographic photosensitive member of the present invention. The charging characteristics of this electrophotographic photosensitive member were evaluated in the same manner as in Example 1. However, the charging was positive. The results are shown below.
[0099]
V₀      : + 640V
E_1/2  ： 2.20 looks / sec
[0100]
【The invention's effect】
The electrophotographic photoreceptor of the present invention has a remarkable effect that it has high sensitivity and has excellent potential characteristics stably even when used repeatedly. In addition, it can be mounted on a process cartridge and an electrophotographic apparatus to provide the same excellent effects.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an example of an electrophotographic apparatus according to the present invention.
FIG. 2 is a diagram illustrating another example of the electrophotographic apparatus of the present invention.
FIG. 3 is a diagram illustrating another example of the electrophotographic apparatus of the present invention.
FIG. 4 is a diagram showing another example of the electrophotographic apparatus of the present invention.
[Explanation of symbols]
1. Electrophotographic photoreceptor
2 Charging means
4 Developing means
5 transfer means
6 Cleaning means
7 Pre-exposure means
9 Recording materials
10 Direct charging member

Claims (10)

In an electrophotographic photosensitive member having at least a photosensitive layer on a support, the photosensitive layer comprises a calix [n] arene compound represented by the following general formula (1) and at least two azo compounds represented by the following general formula (2). An electrophotographic photoreceptor comprising an azoxy calix [n] arene compound formed by coupling with an azonium compound having :
[Outside 1]

(In the formula (1), R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group; n represents an integer of 4-8);
Ar- (N ₂ · X) _m (2)
(In the formula (2), X represents BF ₄ , ZnCl ₂ or a halogen atom, and Ar represents an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent, or a plurality of In which an aromatic hydrocarbon ring or a plurality of heterocyclic rings are combined, and m represents an integer of 2-4) . 2. The electrophotographic photoreceptor according to claim 1, wherein the azolic calix [n] arene compound has the following general formula (3) :
[Outside 2]

(In the above (3), R ₁ -R ₆ represent a hydrogen atom or an alkyl group, and n represents an integer of 4-8 ) . The content of the azo reduction calix [n] arene compound, the azo reduction calix [n] electrophotographic photoreceptor according to claim 1, wherein a 40-85% by weight with respect to the layer containing the arene compound. The electrophotographic photosensitive member according to claim 3 , wherein the content is 50 to 80% by weight. 2. The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer is obtained by laminating at least a charge generation layer and a charge transport layer, and the charge generation layer contains the azide calix [n] arene compound. 2. The electrophotographic photoreceptor according to claim 1, wherein said photosensitive layer is composed of a single layer. 2. An electrophotographic photosensitive member according to claim 1, charging means for charging said electrophotographic photosensitive member, image exposing means for performing image exposure on said charged electrophotographic photosensitive member to form an electrostatic latent image; Developing means for developing the electrophotographic photosensitive member having the latent image formed thereon with toner. The electrophotographic apparatus according to claim 7 , wherein the charging unit is a direct charging member. A process cartridge comprising: the electrophotographic photosensitive member according to claim 1; and a charging member for charging the electrophotographic photosensitive member. The process cartridge according to claim 9, further comprising a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member.

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