JP3717320B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptor Download PDFInfo
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- JP3717320B2 JP3717320B2 JP33971498A JP33971498A JP3717320B2 JP 3717320 B2 JP3717320 B2 JP 3717320B2 JP 33971498 A JP33971498 A JP 33971498A JP 33971498 A JP33971498 A JP 33971498A JP 3717320 B2 JP3717320 B2 JP 3717320B2
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Description
【0001】
【発明の属する技術分野】
本発明は、電子写真用感光体に関し、詳しくは、導電性基体上に有機材料を含む感光層を設けた、電子写真方式のプリンタ、複写機などに用いられる電子写真用感光体に関する。
【0002】
【従来の技術】
従来は、電子写真方式のプリンタ、ファクシミリ、各種複写機等に用いられる電子写真用感光体として、セレンまたはセレン合金などの無機光導電性物質、酸化亜鉛もしくは硫化カドミウムなどの無機光導電性物質を樹脂バインダー中に分散させたものが用いられてきた。近年では、有機光導電性物質を用いた電子写真用感光体の研究も進み、感度や耐久性などが改善されて実用化されているものもある。
【0003】
また、感光体には、暗所で表面電荷を保持する機能、光を受容して電荷を発生する機能、同じく光を受容して電荷を輸送する機能とが必要であるが、一つの層でこれらの機能を合わせ持った、所謂単層型感光体と、主として電荷発生に寄与する層と、暗所での表面電荷の保持と光受容時の電荷輸送に寄与する層とに機能分離した層を積層した、所謂積層型感光体がある。
【0004】
これらの感光体を用いた電子写真法による画像形成には、例えば、カールソンプロセスが適用される。この方法での画像形成は、暗所での感光体へのコロナ放電による帯電、帯電された感光体表面上への露光による原稿の文字や絵などの静電潜像の形成、形成された静電潜像のトナーによる現像、現像されたトナー像の紙などの支持体への定着により行われ、トナー像転写後の感光体は除電、残留トナーの除去、光除電などを行った後、再使用に供される。
【0005】
実用化されている有機感光体は、無機感光体に比べ、可とう性、膜形成性、低コスト、安全性などの利点があり、材料の多様性からさらに感度、耐久性などの改善が進められている。
【0006】
有機感光体のほとんどは、電荷発生層と電荷輸送層とに機能を分離した積層型の感光体である。一般に、積層型有機感光体は、導電性基体上に、顔料、染料などの電荷発生物質からなる電荷発生層と、ヒドラゾン、トリフェニルアミンなどの電荷輸送物質からなる電荷輸送層とを順に形成したもので、電子供与性である電荷輸送物質の性質上、正孔移動型となり、感光体表面を負帯電したときに感度を有する。ところが負帯電では、正帯電に比べ帯電時に用いるコロナ放電が不安定であり、またオゾンや窒素酸化物などを発生し、これが感光体表面に吸着して物理的、化学的劣化を引きおこしやすく、さらに環境を悪化するという問題がある。このような点から、感光体としては、負帯電型感光体よりも使用条件の自由度の大きい正帯電型感光体の方が、その適用範囲は広く有利である。
【0007】
そこで、正帯電で使用するための感光体が種々提案されている。例えば、電荷発生物質と電荷輸送物質を同時に樹脂バインダーに分散させて、単層の感光層として使用する方法が提案され、一部実用化されている。しかし、単層型感光体は高速機に適用するには感度が十分ではなく、また繰り返し特性などの点からもさらに改良が必要である。また、高感度化を目的として機能分離型の積層構造とするため、電荷輸送層上に電荷発生層を積層して感光体を形成し、正帯電で使用する方法が考えられる。
【0008】
しかし、この方式では電荷発生層が表面に形成されるため、コロナ放電、光照射、機械的摩耗などにより、繰り返し使用時での安定性などに問題がある。この場合、電荷発生層の上にさらに保護層を設けることも提案されているが、機械的摩耗は改善されるものの、感度など電気特性の低下を招くなどの問題がある。
【0009】
さらに、電荷発生層上に電子輸送性の電荷輸送層を積層して感光体を形成する方法も提案されている。電子輸送性物質として、2,4,7−トリニトロ−9−フルオレノンなどが知られているが、この物質は発ガン性があり、安全上問題がある。その他、シアノ化合物、キノン系化合物などが特開昭50−131941号公報、特開平6−59483号公報、特開平6−123986号公報、特開平9−190003号公報などにより提案されているが、実用化に十分な電子輸送能を有する化合物が得られていないのが実情であった。
【0010】
【発明が解決しようとする課題】
そこで、本発明の目的は、上述の問題点を解決するため、感光層に電荷輸送物質として今まで用いられたことのない新しい有機材料を用いることにより、高速度な複写機用およびプリンタ用正帯電型電子写真用感光体を提供することにある。
【0011】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために各種有機材料について鋭意検討するなかで、数多くの実験を行った結果、その技術的解明はまだ十分なされてはいないものの、後述の一般式(I)又は(II)で表される特定の化合物を電荷輸送物質として使用することが、電子写真特性の向上に極めて有効であり、正帯電で使用可能な高感度感光体を得ることができることを見出し、本発明を完成するに至った。
【0012】
即ち、本発明の電子写真用感光体は、導電性基体上に電荷発生物質および電荷輸送物質を含有する感光層を設けた電子写真用感光体において、該感光層に、下記一般式(I)、
(式中、R1およびR2はそれぞれ独立にハロゲン原子、置換基を有してもよい炭素数1〜8のアルキル基若しくはアルコキシ基、アリールアルキル基、置換基を有してもよいアリール基、又は環を形成するための残基、R3は水素原子、炭素数1〜8のアルキル基あるいは置換基を有していてもよいアリール基、A1は酸素原子、又は=CR4R5(但し、R4およびR5はそれぞれシアノ基又はアルコキシカルボニル基)、mは0〜4の整数、nは0〜5の整数を表し、mおよびnが2以上の場合の、2個以上あるR1およびR2もそれぞれ同一でも異なっていてもよい。)で示される電子輸送性化合物の少なくとも1種を電荷輸送物質として含有することを特徴とするものである。
【0013】
また、本発明の他の電子写真用感光体は、導電性基体上に電荷発生物質および電荷輸送物質を含有する感光層を設けた電子写真用感光体において、該感光層に、下記一般式(II)、
(式中、R6、R7、R8およびR9はそれぞれ独立にハロゲン原子、置換基を有してもよい炭素数1〜8のアルキル基、R11およびR12はそれぞれ水素原子、炭素数1〜8のアルキル基、置換基を有してもよいアリール基、R10およびR13はそれぞれ独立に水素原子、炭素数1〜8のアルキル基あるいは置換基を有していてもよいアリール基、B1およびB2はそれぞれ酸素原子、又は=CR14R15(但し、R14およびR15はそれぞれシアノ基又はアルコキシカルボニル基)、o、p、qおよびrは0〜4の整数を表し、o、p、qおよびrが2以上の場合の、2個以上あるR6、R7、R8およびR9もそれぞれ同一でも異なっていてもよい。)で示される電子輸送性化合物の少なくとも1種を電荷輸送物質として含有することを特徴とするものである。
【0014】
【発明の実施の形態】
前記一般式(I)および(II)で示される化合物の具体例を、それぞれ下記の化合物No.I−1〜I−32およびNo.II−1〜II−16で表される構造式にて示す。
【0015】
【0016】
【0017】
【0018】
【0019】
【0020】
【0021】
前記一般式(I)および(II)で示される化合物は、通常の方法により合成することができる。例えば、化合物No.I−1、化合物No.II−2、化合物No.I−20あるいは化合物No.II−10で示される化合物は、下記構造式(III)、(IV)、(V)あるいは(VI)で示される化合物を適当な酸化剤(例えば、過マンガン酸カリウムなど)を用いて有機溶媒(例えば、クロロホルムなど)中で酸化することにより、それぞれ容易に合成することができる。
【0022】
以下、本発明の感光体の好適例の具体的構成について図面を参照しながら説明する。図1および図2は、感光体の各種構成例を示す模式的断面図である。
【0023】
図1は、所謂単層型感光体の一構成例を示し、導電性基体1の上に、電荷発生物質と電荷輸送物質とを樹脂バインダー(結着剤)中に分散させた単層の感光層2が設けられ、さらに必要に応じて被覆層(保護層)6が積層されてなる。この感光体は、電荷発生物質を電荷輸送物質および樹脂バインダーを溶解した溶液中に分散せしめ、この分散液を導電性基体上に塗布することによって作製することができる。さらに、必要な場合は被覆層を塗布形成することができる。
【0024】
図2は、所謂積層型感光体の一構成例を示し、導電性基体1の上に電荷発生物質を主体とする電荷発生層3と、電荷輸送物質を含有する電荷輸送層4とが順次積層された感光層5が設けられてなる。この感光体は、導電性基体上に電荷発生物質を真空蒸着するか、あるいは電荷発生物質の粒子を溶剤または樹脂バインダー中に分散させて得た分散液を塗布、乾燥し、その上に電荷輸送物質を樹脂バインダー中に溶解又は分散させて得た分散液を塗布、乾燥することにより作製することができる。
【0025】
なお、本発明のいずれのタイプの感光体も、前記電荷輸送物質として前記一般式(I)または(II)で表される電子輸送性化合物を含有する。
【0026】
以下、本発明の好適な実施の形態を図2に示す積層型感光体について説明するが、本発明は以下の具体例に限定されるものではない。
導電性基体1は、感光体の電極としての役目と同時に他の各層の支持体となっており、円筒状、板状、フィルム状のいずれでもよく、材質的にはアルミニウム、ステンレス鋼、ニッケルなどの金属、あるいはガラス、樹脂などの上に導電処理を施したものを用いることができる。
【0027】
電荷発生層3は、前記のように電荷発生物質の粒子を樹脂バインダー中に分散させた材料を塗布するか、あるいは真空蒸着などの方法により形成され、光を受容して電荷を発生する。また、その電荷発生効率が高いことと同時に発生した電荷の電荷輸送層4への注入性が重要で、電場依存性が少なく低電場でも注入の良いことが望ましい。電荷発生物質としては、無金属フタロシアニン、チタニルフタロシアニンなどのフタロシアニン化合物、各種アゾ、キノン、インジゴ、シアニン、スクアリリウム、アズレニウム、ピリリウム化合物などの顔料あるいは染料や、セレン又はセレン化合物などが用いられ、画像形成に使用される露光光源の光波長領域に応じて好適な物質を選ぶことができる。電荷発生層は電荷発生機能を有すればよいので、その膜厚は電荷発生物質の光吸収係数より決まり、一般的には5μm以下であり、好適には2μm以下である。電荷発生層は電荷発生物質を主体としてこれに電荷輸送物質などを添加して使用することも可能である。
【0028】
電荷発生層用の樹脂バインダーとしては、ポリカーボネート、ポリエステル、ポリアミド、ポリウレタン、塩化ビニル樹脂、フェノキシ樹脂、ポリビニルブチラール、ジアクリルフタレート樹脂、メタクリル酸エステルの重合体およびこれらの共重合体などを適宜組み合わせて使用することが可能である。
【0029】
電荷輸送層4は、樹脂バインダー中に電荷輸送物質として前記一般式(I)または(II)で表される電子輸送性化合物を分散させた塗膜であり、暗所では絶縁体層として感光体の電荷を保持し、光受容時には電荷発生層から注入される電荷を輸送する機能を発揮する。
【0030】
電荷輸送層用の樹脂バインダーとしては、各種ポリカーボネートをはじめ、ポリエステル、ポリスチレン、メタクリル酸エステルの重合体および共重合体等を用いることができる。
【0031】
また、感光体を使用する際に使用上障害となるオゾン劣化などを防止する目的で、電荷輸送層4にアミン系、フェノール系、硫黄系、亜リン酸エステル系、リン系などの酸化防止剤を含有させることも可能である。
【0032】
図1に示す被覆層6は、暗所ではコロナ放電の電荷を受容して保持する機能を有しており、かつ感光層が感応する光を透過する性能を有し、露光時に光を透過して感光層に到達させ、発生した電荷の注入を受けて表面電荷を中和消滅させることが必要である。被覆層の材料としては、ポリエステル、ポリアミドなどの有機絶縁性皮膜形成材料を適用することができる。また、これら有機材料とガラス、SiO2などの無機材料、さらには金属、金属酸化物などの電気抵抗を低減せしめる材料とを混合して用いることができる。被覆層の材料は前述の通り電荷発生物質の光の吸収極大の波長領域においてできるだけ透明であることが望ましい。
【0033】
被覆層自体の膜厚は被覆層の配合組成にも依存するが、繰り返し連続使用したとき残留電位が増大するなどの悪影響が出ない範囲で任意に設定できる。
【0034】
【実施例】
以下、本発明を実施例に基づき具体的に説明する。
実施例1
x型無金属フタロシアニン(H2Pc)20重量部と、前記化合物No.I−1で示される化合物100重量部とをポリエステル樹脂(商品名バイロン200:東洋紡(株)製)100重量部とテトラヒドロフラン(THF)溶剤とともに3時間混合機により混練して塗布液を調製し、導電性基体である外径30mm、長さ260mmのアルミニウム製ドラム上に塗布して、乾燥後の膜厚が12μmになるように感光体を作製した。
【0035】
実施例2
x型無金属フタロシアニン(H2Pc)2重量部と、前記化合物No.I−2で示される化合物40重量部と、下記式、
で表されるベンジジン誘導体60重量部と、ポリカーボネート樹脂(PCZ−200、三菱ガス化学(株)製)100重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に乾燥後の膜厚が約20μmになるように感光体を作製した。
【0036】
実施例3
チタニルフタロシアニン(TiOPc)2重量部と、前記化合物No.I−3で示される化合物40重量部と、下記式、
で表されるベンジジン誘導体60重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に乾燥後の膜厚が約20μmになるように感光体を作製した。
【0037】
実施例4
実施例3において、チタニルフタロシアニンに代えて下記式、
で表されるスクアリリウム化合物を用い、また化合物No.I−3に代えて化合物No.II−1の化合物を用いた以外は実施例3と同様にして感光体を作製した。
【0038】
実施例5
チタニルフタロシアニン(TiOPc)70重量部と、塩化ビニル共重合体(商品名MR−110、日本ゼオン(株)製)30重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に約1μmになるように塗布し、電荷発生層を形成した。次に、化合物No.II−2で示される化合物100重量部と、ポリカーボネート樹脂(PCZ−200、三菱ガス化学(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、前記電荷発生層の上に約10μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0039】
実施例6
実施例5において、チタニルフタロシアニンに代えて下記式、
で示されるビスアゾ顔料を用いた以外は実施例5と同様にして電荷発生層を形成した。次に、化合物No.II−1の化合物100重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、電荷発生層の上に約10μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0040】
実施例7
実施例5において、電荷発生物質に下記式、
で示されるビスアゾ顔料を用いた以外は実施例5と同様にして電荷発生層を形成した。次に、化合物No.II−2の化合物100重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、電荷発生層の上に約10μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0041】
実施例8
x型無金属フタロシアニン(H2Pc)20重量部と、前記化合物No.I−18で示される化合物100重量部とをポリエステル樹脂(商品名バイロン200:東洋紡(株)製)100重量部とテトラヒドロフラン(THF)溶剤とともに3時間混合機により混練して塗布液を調製し、導電性基体である外径30mm、長さ260mmのアルミニウム製ドラム上に塗布して、乾燥後の膜厚が12μmになるように感光体を作製した。
【0042】
実施例9
x型無金属フタロシアニン(H2Pc)2重量部と、前記化合物No.I−19で示される化合物40重量部と、下記式、
で表されるベンジジン誘導体60重量部と、ポリカーボネート樹脂(PCZ−200、三菱ガス化学(株)製)100重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に乾燥後の膜厚が約20μmになるように感光体を作製した。
【0043】
実施例10
チタニルフタロシアニン(TiOPc)2重量部と、前記化合物No.I−20で示される化合物40重量部と、下記式、
で表されるベンジジン誘導体60重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に乾燥後の膜厚が約20μmになるように感光体を作製した。
【0044】
実施例11
実施例10において、チタニルフタロシアニンに代えて下記式、
で表されるスクアリリウム化合物を用い、また化合物No.I−20に代えて化合物No.II−10の化合物を用いた以外は実施例10と同様にして感光体を作製した。
【0045】
実施例12
チタニルフタロシアニン(TiOPc)70重量部と、塩化ビニル共重合体(商品名MR−110、日本ゼオン(株)製)30重量部とを塩化メチレンとともに3時間混合機により混練して塗布液を調製し、アルミニウム支持体上に約1μmになるように塗布し、電荷発生層を形成した。次に、化合物No.II−11で示される化合物100重量部と、ポリカーボネート樹脂(PCZ−200、三菱ガス化学(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、前記電荷発生層の上に約7μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0046】
実施例13
実施例12において、チタニルフタロシアニンに代えて下記式、
で示されるビスアゾ顔料を用いた以外は実施例12と同様にして電荷発生層を形成した。次に、化合物No.I−20の化合物100重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、電荷発生層の上に約10μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0047】
実施例14
実施例12において、電荷発生物質に下記式、
で示されるビスアゾ顔料を用いた以外は実施例12と同様にして電荷発生層を形成した。次に、化合物No.II−10の化合物100重量部と、ポリカーボネート樹脂(BP−PC、出光興産(株)製)100重量部と、シリコーンオイル0.1重量部とを塩化メチレンと混合し、電荷発生層の上に約8μmの膜厚となるように塗布し、電荷輸送層を形成して、感光体を作製した。
【0048】
感光体の評価
上述の実施例で作製した感光体の電子写真特性を下記の方法で評価した。
感光体に暗所で+4.5kVのコロナ放電を行って感光体表面を正帯電せしめたときの初期の表面電位をVs(V)とし、続いてコロナ放電を中止した状態で5秒間暗所に保持したときの表面電位Vd(V)を測定し、さらに続いて感光体表面に照度100ルックス(lx)の白色光を照射して表面電位Vdが半分になるまでの時間(秒)を求め、感度E1/2 (lx・s)とした。
【0049】
また、照度100ルックスの白色光を10秒間照射したときの表面電位を残留電位Vr(V)とした。また、実施例1〜5および8〜12については、長波長での高感度が期待できるので、波長780nmの単色光を用いたときの電子写真特性も同時に測定した。すなわち、Vdまでは同様に測定し、次に白色光の替わりに1μWの単色光(780nm)を照射して半減衰露光量(μJ/cm2)を求め、また、この光を10秒間感光体表面に照射したときの残留電位Vr(V)を測定した。測定の結果を下記の表1に示す。
【0050】
【表1】
【0051】
【発明の効果】
本発明によれば、導電性基体上に設けた感光層に電荷輸送物質として前記一般式(I)または(II)で示される電子輸送性化合物を用いたことにより、正帯電において高感度で電気特性の優れた感光体を得ることができる。また、電荷発生物質は露光光源の種類に対応して好適な物質を選ぶことができ、フタロシアニン化合物、スクアリリウム化合物、ビスアゾ化合物などを用いることにより、半導体レーザプリンタや複写機に使用可能な感光体を得ることができる。さらに、必要に応じて表面に被覆層を設けて耐久性の向上を図ることが可能である。
【図面の簡単な説明】
【図1】本発明に係る単層型電子写真用感光体の模式的構造断面図である。
【図2】本発明に係る積層型電子写真用感光体の模式的構造断面図である。
【符号の説明】
1 導電性基体
2 感光層
3 電荷発生層
4 電荷輸送層
5 感光層(積層)
6 被覆層(保護層)[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor used in an electrophotographic printer, a copying machine, or the like, in which a photosensitive layer containing an organic material is provided on a conductive substrate.
[0002]
[Prior art]
Conventionally, as an electrophotographic photoreceptor used in electrophotographic printers, facsimiles, various copying machines, etc., an inorganic photoconductive material such as selenium or a selenium alloy, or an inorganic photoconductive material such as zinc oxide or cadmium sulfide is used. Those dispersed in a resin binder have been used. In recent years, research on electrophotographic photoreceptors using organic photoconductive materials has progressed, and some have been put into practical use with improved sensitivity and durability.
[0003]
In addition, the photoreceptor needs to have a function of holding a surface charge in a dark place, a function of receiving light to generate a charge, and a function of receiving light to transport a charge. A layer that is separated into a so-called single-layer type photoreceptor having these functions, a layer that mainly contributes to charge generation, and a layer that contributes to retention of surface charges in the dark and charge transport during light reception. There is a so-called multi-layer photoreceptor in which the above are laminated.
[0004]
For example, a Carlson process is applied to image formation by electrophotography using these photoreceptors. Image formation by this method is performed by charging a photoconductor in the dark by corona discharge, forming an electrostatic latent image such as a character or a picture of an original by exposure on the surface of the charged photoconductor, The electrostatic latent image is developed by toner, and the developed toner image is fixed on a support such as paper. After the toner image is transferred, the photosensitive member is subjected to charge removal, residual toner removal, light charge removal, etc. Provided for use.
[0005]
Organic photoreceptors in practical use have advantages such as flexibility, film formation, low cost and safety compared to inorganic photoreceptors, and further improvements in sensitivity and durability are made possible due to the variety of materials. It has been.
[0006]
Most of the organic photoreceptors are multi-layer photoreceptors in which functions are separated into a charge generation layer and a charge transport layer. In general, in the multilayer organic photoreceptor, a charge generation layer made of a charge generation material such as a pigment or a dye and a charge transport layer made of a charge transport material such as hydrazone or triphenylamine are sequentially formed on a conductive substrate. In view of the nature of the electron transporting charge transport material, it is a hole transfer type and has sensitivity when the surface of the photoreceptor is negatively charged. However, in negative charging, corona discharge used during charging is unstable compared to positive charging, and ozone and nitrogen oxides are generated, which are easily adsorbed on the surface of the photoconductor and cause physical and chemical degradation. There is also a problem of worsening the environment. From this point of view, the positively charged type photoconductor having a greater degree of freedom of use conditions than the negatively charged type photoconductor has a wider application range and is advantageous.
[0007]
Therefore, various photoreceptors for use with positive charging have been proposed. For example, a method in which a charge generation material and a charge transport material are simultaneously dispersed in a resin binder and used as a single photosensitive layer has been proposed and partially put into practical use. However, the single-layer type photoreceptor is not sufficiently sensitive to be applied to a high-speed machine, and further improvement is required from the viewpoint of repeatability. In order to achieve a function-separated layered structure for the purpose of increasing sensitivity, a method of forming a photoconductor by laminating a charge generation layer on a charge transport layer and using it in a positive charge can be considered.
[0008]
However, in this method, since the charge generation layer is formed on the surface, there is a problem in stability during repeated use due to corona discharge, light irradiation, mechanical wear, and the like. In this case, it has been proposed to further provide a protective layer on the charge generation layer. However, although mechanical wear is improved, there are problems such as a reduction in electrical characteristics such as sensitivity.
[0009]
Furthermore, a method of forming a photoconductor by laminating an electron transporting charge transport layer on a charge generation layer has also been proposed. 2,4,7-trinitro-9-fluorenone is known as an electron transporting substance, but this substance is carcinogenic and has a safety problem. In addition, cyano compounds, quinone compounds, and the like have been proposed in JP-A-50-131941, JP-A-6-59483, JP-A-6-123986, JP-A-9-190003, and the like. In fact, a compound having an electron transporting ability sufficient for practical use has not been obtained.
[0010]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to solve the above-mentioned problems by using a new organic material that has never been used as a charge transport material in the photosensitive layer, thereby enabling high speed copying machines and printers. An object of the present invention is to provide a chargeable electrophotographic photoreceptor.
[0011]
[Means for Solving the Problems]
The inventors of the present invention have conducted extensive studies on various organic materials in order to achieve the above-mentioned object. As a result, although the technical clarification has not yet been sufficiently performed, the following general formula (I ) Or (II) is used as a charge transport material, it is extremely effective in improving electrophotographic characteristics, and a high-sensitivity photoconductor usable with positive charge can be obtained. The present invention has been completed.
[0012]
That is, the electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member in which a photosensitive layer containing a charge generating material and a charge transporting material is provided on a conductive substrate, and the photosensitive layer has the following general formula (I): ,
Wherein R 1 and R 2 are each independently a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an alkoxy group, an arylalkyl group, and an optionally substituted aryl group. Or a residue for forming a ring, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, A 1 is an oxygen atom, or ═CR 4 R 5 (Wherein R 4 and R 5 are each a cyano group or an alkoxycarbonyl group), m represents an integer of 0 to 4, n represents an integer of 0 to 5, and when m and n are 2 or more, there are 2 or more. R 1 and R 2 may be the same or different from each other. At least one of the electron transport compounds represented by the formula (1) is contained as a charge transport material.
[0013]
Another electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance is provided on a conductive substrate, and the photosensitive layer has the following general formula ( II),
(In the formula, R 6 , R 7 , R 8 and R 9 are each independently a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, R 11 and R 12 are a hydrogen atom and a carbon atom, respectively. An alkyl group having 1 to 8 atoms, an aryl group which may have a substituent, R 10 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl which may have a substituent; Group, B 1 and B 2 are each an oxygen atom, or ═CR 14 R 15 (where R 14 and R 15 are each a cyano group or an alkoxycarbonyl group), o, p, q and r are integers of 0 to 4 In the case where o, p, q and r are 2 or more, two or more R 6 , R 7 , R 8 and R 9 may be the same or different. At least one type of charge transfer It is characterized in that it contains as substance.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Specific examples of the compounds represented by the general formulas (I) and (II) are the following compound Nos. I-1 to I-32 and No.1. It is shown by the structural formula represented by II-1 to II-16.
[0015]
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
The compounds represented by the general formulas (I) and (II) can be synthesized by an ordinary method. For example, Compound No. I-1, Compound No. II-2, Compound No. I-20 or Compound No. The compound represented by II-10 is an organic solvent prepared by using a compound represented by the following structural formula (III), (IV), (V) or (VI) with an appropriate oxidizing agent (for example, potassium permanganate). Each can be easily synthesized by oxidation in chloroform (for example, chloroform).
[0022]
Hereinafter, a specific configuration of a preferred example of the photoreceptor of the present invention will be described with reference to the drawings. 1 and 2 are schematic cross-sectional views showing various configuration examples of the photoreceptor.
[0023]
FIG. 1 shows an example of the structure of a so-called single-layer type photoconductor, in which a single-layer photoconductor in which a charge generating substance and a charge transporting substance are dispersed in a resin binder (binder) on a
[0024]
FIG. 2 shows an example of the configuration of a so-called multilayer photoreceptor, in which a
[0025]
Note that any type of photoreceptor of the present invention contains the electron transporting compound represented by the general formula (I) or (II) as the charge transporting substance.
[0026]
Hereinafter, a preferred embodiment of the present invention will be described with respect to a multilayer photoreceptor shown in FIG. 2, but the present invention is not limited to the following specific examples.
The
[0027]
The
[0028]
As the resin binder for the charge generation layer, polycarbonate, polyester, polyamide, polyurethane, vinyl chloride resin, phenoxy resin, polyvinyl butyral, diacryl phthalate resin, methacrylate polymer, and copolymers thereof may be appropriately combined. It is possible to use.
[0029]
The charge transport layer 4 is a coating film in which the electron transport compound represented by the above general formula (I) or (II) is dispersed as a charge transport material in a resin binder. The function of transporting the charge injected from the charge generation layer when receiving light is exhibited.
[0030]
As the resin binder for the charge transport layer, various polycarbonates, polyesters, polystyrenes, polymers and copolymers of methacrylic acid esters, and the like can be used.
[0031]
Further, for the purpose of preventing ozone deterioration, which is an obstacle to use when using a photoreceptor, an antioxidant such as amine, phenol, sulfur, phosphite, or phosphorus is added to the charge transport layer 4. It is also possible to contain.
[0032]
The coating layer 6 shown in FIG. 1 has a function of receiving and holding a corona discharge charge in a dark place, and has a capability of transmitting light sensitive to the photosensitive layer, and transmits light during exposure. It is necessary to neutralize and extinguish the surface charge by receiving the generated charge and reaching the photosensitive layer. As a material for the covering layer, organic insulating film forming materials such as polyester and polyamide can be applied. Furthermore, can be used as a mixture thereof organic materials and glass, inorganic material such as SiO 2, further metals, and a material capable of reducing the electric resistance, such as metal oxides. As described above, the material of the coating layer is desirably as transparent as possible in the wavelength region of the light absorption maximum of the charge generation material.
[0033]
Although the film thickness of the coating layer itself depends on the composition of the coating layer, it can be arbitrarily set within a range where no adverse effect such as an increase in residual potential occurs when repeatedly used.
[0034]
【Example】
Hereinafter, the present invention will be specifically described based on examples.
Example 1
20 parts by weight of x-type metal-free phthalocyanine (H 2 Pc); A coating solution was prepared by kneading 100 parts by weight of the compound represented by I-1 with 100 parts by weight of a polyester resin (trade name Byron 200: manufactured by Toyobo Co., Ltd.) and a tetrahydrofuran (THF) solvent for 3 hours using a mixer. It was applied onto an aluminum drum having an outer diameter of 30 mm and a length of 260 mm, which was a conductive substrate, to prepare a photoreceptor so that the film thickness after drying was 12 μm.
[0035]
Example 2
2 parts by weight of x-type metal-free phthalocyanine (H 2 Pc); 40 parts by weight of the compound represented by I-2,
A coating solution was prepared by kneading 60 parts by weight of a benzidine derivative represented by the following formula and 100 parts by weight of a polycarbonate resin (PCZ-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with methylene chloride for 3 hours using a mixer. A photoconductor was prepared on the body so that the film thickness after drying was about 20 μm.
[0036]
Example 3
2 parts by weight of titanyl phthalocyanine (TiOPc); 40 parts by weight of the compound represented by I-3,
60 parts by weight of a benzidine derivative represented by the formula (1) and 100 parts by weight of a polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.) were kneaded with a methylene chloride for 3 hours to prepare a coating solution, and an aluminum support. A photoconductor was prepared so that the film thickness after drying was about 20 μm.
[0037]
Example 4
In Example 3, instead of titanyl phthalocyanine, the following formula:
The squarylium compound represented by the formula In place of compound I-3, compound no. A photoconductor was prepared in the same manner as in Example 3 except that the compound of II-1 was used.
[0038]
Example 5
A coating solution was prepared by kneading 70 parts by weight of titanyl phthalocyanine (TiOPc) and 30 parts by weight of a vinyl chloride copolymer (trade name MR-110, manufactured by Nippon Zeon Co., Ltd.) with methylene chloride using a mixer for 3 hours. Then, it was applied on an aluminum support so as to have a thickness of about 1 μm to form a charge generation layer. Next, Compound No. 100 parts by weight of the compound represented by II-2, 100 parts by weight of a polycarbonate resin (PCZ-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.1 part by weight of silicone oil are mixed with methylene chloride, and the charge generation is performed. A photoconductor was prepared by coating the layer so as to have a thickness of about 10 μm and forming a charge transport layer.
[0039]
Example 6
In Example 5, instead of titanyl phthalocyanine, the following formula:
A charge generation layer was formed in the same manner as in Example 5 except that the bisazo pigment represented by Next, Compound No. 100 parts by weight of the compound of II-1, 100 parts by weight of polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.) and 0.1 parts by weight of silicone oil are mixed with methylene chloride, and the mixture is formed on the charge generation layer. The photosensitive member was prepared by coating to a thickness of about 10 μm and forming a charge transport layer.
[0040]
Example 7
In Example 5, the charge generation material is represented by the following formula:
A charge generation layer was formed in the same manner as in Example 5 except that the bisazo pigment represented by Next, Compound No. 100 parts by weight of II-2 compound, 100 parts by weight of polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.) and 0.1 part by weight of silicone oil are mixed with methylene chloride, and the mixture is formed on the charge generation layer. The photosensitive member was prepared by coating to a thickness of about 10 μm and forming a charge transport layer.
[0041]
Example 8
20 parts by weight of x-type metal-free phthalocyanine (H 2 Pc); A coating solution was prepared by kneading 100 parts by weight of the compound represented by I-18 together with 100 parts by weight of a polyester resin (trade name Byron 200: manufactured by Toyobo Co., Ltd.) and a tetrahydrofuran (THF) solvent with a mixer for 3 hours. It was applied onto an aluminum drum having an outer diameter of 30 mm and a length of 260 mm, which was a conductive substrate, to prepare a photoreceptor so that the film thickness after drying was 12 μm.
[0042]
Example 9
2 parts by weight of x-type metal-free phthalocyanine (H 2 Pc); 40 parts by weight of a compound represented by I-19,
A coating solution was prepared by kneading 60 parts by weight of a benzidine derivative represented by the formula and 100 parts by weight of a polycarbonate resin (PCZ-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with methylene chloride for 3 hours using a mixer. A photoconductor was prepared on the body so that the film thickness after drying was about 20 μm.
[0043]
Example 10
2 parts by weight of titanyl phthalocyanine (TiOPc); 40 parts by weight of a compound represented by I-20, the following formula:
60 parts by weight of a benzidine derivative represented by the formula (1) and 100 parts by weight of a polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.) were kneaded with a methylene chloride for 3 hours to prepare a coating solution, and an aluminum support. A photoconductor was prepared so that the film thickness after drying was about 20 μm.
[0044]
Example 11
In Example 10, instead of titanyl phthalocyanine, the following formula:
The squarylium compound represented by the formula In place of I-20, Compound No. A photoconductor was prepared in the same manner as in Example 10 except that the compound of II-10 was used.
[0045]
Example 12
A coating solution was prepared by kneading 70 parts by weight of titanyl phthalocyanine (TiOPc) and 30 parts by weight of a vinyl chloride copolymer (trade name MR-110, manufactured by Nippon Zeon Co., Ltd.) with methylene chloride using a mixer for 3 hours. Then, it was applied on an aluminum support so as to have a thickness of about 1 μm to form a charge generation layer. Next, Compound No. 100 parts by weight of the compound represented by II-11, 100 parts by weight of a polycarbonate resin (PCZ-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 0.1 parts by weight of silicone oil are mixed with methylene chloride to generate the charge. A photoconductor was produced by applying a film having a thickness of about 7 μm on the layer to form a charge transport layer.
[0046]
Example 13
In Example 12, instead of titanyl phthalocyanine, the following formula:
A charge generation layer was formed in the same manner as in Example 12 except that the bisazo pigment represented by Next, Compound No. 100 parts by weight of a compound of I-20, 100 parts by weight of a polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.) and 0.1 parts by weight of silicone oil are mixed with methylene chloride, and the mixture is formed on the charge generation layer. The photosensitive member was prepared by coating to a thickness of about 10 μm and forming a charge transport layer.
[0047]
Example 14
In Example 12, the charge generation material is represented by the following formula:
A charge generation layer was formed in the same manner as in Example 12 except that the bisazo pigment represented by Next, Compound No. 100 parts by weight of a compound of II-10, 100 parts by weight of a polycarbonate resin (BP-PC, manufactured by Idemitsu Kosan Co., Ltd.), and 0.1 parts by weight of silicone oil are mixed with methylene chloride. The photosensitive member was prepared by coating the film so as to have a film thickness of about 8 μm and forming a charge transport layer.
[0048]
Evaluation of photoreceptors The electrophotographic characteristics of the photoreceptors prepared in the above-described examples were evaluated by the following methods.
The initial surface potential when the photoconductor surface is positively charged by performing +4.5 kV corona discharge in the dark is Vs (V), and then the corona discharge is stopped for 5 seconds in the dark. The surface potential Vd (V) when held is measured, and then the time (second) until the surface potential Vd is halved by irradiating the photoreceptor surface with white light with an illuminance of 100 lux (lx) is obtained. The sensitivity was E 1/2 (lx · s).
[0049]
The surface potential when irradiated with white light having an illuminance of 100 lux for 10 seconds was defined as a residual potential Vr (V). Moreover, about Examples 1-5 and 8-12, since the high sensitivity in a long wavelength can be anticipated, the electrophotographic characteristic when using monochromatic light with a wavelength of 780 nm was also measured simultaneously. That is, the same measurement is performed up to Vd, and then a 1 μW monochromatic light (780 nm) is irradiated instead of white light to obtain a half-attenuated exposure (μJ / cm 2 ). A residual potential Vr (V) when the surface was irradiated was measured. The measurement results are shown in Table 1 below.
[0050]
[Table 1]
[0051]
【The invention's effect】
According to the present invention, the electron transporting compound represented by the above general formula (I) or (II) is used as a charge transporting substance in the photosensitive layer provided on the conductive substrate, so that it is highly sensitive and electrically sensitive in positive charging. A photoreceptor having excellent characteristics can be obtained. The charge generation material can be selected according to the type of exposure light source. By using a phthalocyanine compound, a squarylium compound, a bisazo compound, etc., a photoconductor that can be used in a semiconductor laser printer or a copying machine can be obtained. Can be obtained. Furthermore, it is possible to improve durability by providing a coating layer on the surface as necessary.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of a single-layer electrophotographic photoreceptor according to the present invention.
FIG. 2 is a schematic cross-sectional view of a multilayer electrophotographic photoreceptor according to the present invention.
[Explanation of symbols]
DESCRIPTION OF
6 Covering layer (protective layer)
Claims (2)
(式中、R1およびR2はそれぞれ独立にハロゲン原子、置換基を有してもよい炭素数1〜8のアルキル基若しくはアルコキシ基、アリールアルキル基、置換基を有してもよいアリール基、又は環を形成するための残基、R3は水素原子、炭素数1〜8のアルキル基あるいは置換基を有していてもよいアリール基、A1は酸素原子、又は=CR4R5(但し、R4およびR5はそれぞれシアノ基又はアルコキシカルボニル基)、mは0〜4の整数、nは0〜5の整数を表し、mおよびnが2以上の場合の、2個以上あるR1およびR2もそれぞれ同一でも異なっていてもよい。)で示される電子輸送性化合物の少なくとも1種を電荷輸送物質として含有することを特徴とする電子写真用感光体。In the electrophotographic photoreceptor in which a photosensitive layer containing a charge generation material and a charge transport material is provided on a conductive substrate, the photosensitive layer has the following general formula (I),
Wherein R 1 and R 2 are each independently a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an alkoxy group, an arylalkyl group, and an optionally substituted aryl group. Or a residue for forming a ring, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, A 1 is an oxygen atom, or ═CR 4 R 5 (Wherein R 4 and R 5 are each a cyano group or an alkoxycarbonyl group), m represents an integer of 0 to 4, n represents an integer of 0 to 5, and when m and n are 2 or more, there are 2 or more. R 1 and R 2 may be the same or different from each other.) A photosensitive member for electrophotography characterized in that it contains at least one electron transporting compound represented by formula (1) as a charge transporting substance.
(式中、R6、R7、R8およびR9はそれぞれ独立にハロゲン原子、置換基を有してもよい炭素数1〜8のアルキル基、R11およびR12はそれぞれ水素原子、炭素数1〜8のアルキル基、置換基を有してもよいアリール基、R10およびR13はそれぞれ独立に水素原子、炭素数1〜8のアルキル基あるいは置換基を有していてもよいアリール基、B1およびB2はそれぞれ酸素原子、又は=CR14R15(但し、R14およびR15はそれぞれシアノ基又はアルコキシカルボニル基)、o、p、qおよびrは0〜4の整数を表し、o、p、qおよびrが2以上の場合の、2個以上あるR6、R7、R8およびR9もそれぞれ同一でも異なっていてもよい。)で示される電子輸送性化合物の少なくとも1種を電荷輸送物質として含有することを特徴とする電子写真用感光体。In the electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance is provided on a conductive substrate, the photosensitive layer has the following general formula (II),
(In the formula, R 6 , R 7 , R 8 and R 9 are each independently a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, R 11 and R 12 are a hydrogen atom and a carbon atom, respectively. An alkyl group having 1 to 8 atoms, an aryl group which may have a substituent, R 10 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl which may have a substituent; Group, B 1 and B 2 are each an oxygen atom, or ═CR 14 R 15 (where R 14 and R 15 are each a cyano group or an alkoxycarbonyl group), o, p, q and r are integers of 0 to 4 In the case where o, p, q and r are 2 or more, two or more R 6 , R 7 , R 8 and R 9 may be the same or different. At least one type of charge transfer Electrophotographic photoreceptor, characterized in that it contains as substance.
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JP33971498A JP3717320B2 (en) | 1998-10-29 | 1998-11-30 | Electrophotographic photoreceptor |
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JP10-308279 | 1998-10-29 | ||
JP30827998 | 1998-10-29 | ||
JP33971498A JP3717320B2 (en) | 1998-10-29 | 1998-11-30 | Electrophotographic photoreceptor |
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JP3717320B2 true JP3717320B2 (en) | 2005-11-16 |
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