JP3692790B2 - Electrophotographic photoreceptor - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は静電潜像を形成させるための電子写真感光体に関する。詳しくは、耐環境性が良好で、かつ残留電位が小さく繰り返し使用しても安定した電位特性を有する耐久性に優れた電子写真感光体に関するものである。
【０００２】
【従来の技術】
従来、電子写真感光体としては、セレン、酸化亜鉛、硫化カドミウム、シリコン等の無機光導電性化合物を主成分とする感光層を有する無機感光体が、広く用いられてきた。しかし、これらは感度、熱安定性、耐湿性、耐久性等において必ずしも満足し得るものではなく、また一部の無機感光体では感光体中に人体に有害な物質を含むため、廃棄に際しての問題がある。
【０００３】
これら無機感光体の持つ欠点を克服する目的で様々な有機光導電性化合物を主成分とする感光層を有する有機感光体の研究・開発が近年盛んに行われている。とくにキャリア発生機能とキャリア輸送機能とを異なる物質にそれぞれ分担させた機能分離型の感光体は、それぞれの材料を広い範囲から選択することができ、任意の性能を有する感光体を比較的容易に作成し得ることから多くの研究がなされており、一部実用に供されているものがある。
【０００４】
このような有機感光体の表面層には、コロナ帯電、トナー現像、紙への転写及びクリーニング処理等の電気的、機械的外力が加えられるため、それらに対する耐久性が要求される。また実際に複写機、プリンター内で感光体を使用した場合、感光体は帯電極で発生したオゾン、窒素酸化物（ＮＯｘ）等の放電生成物や露光時の紫外線等により表面劣化を受けるため、これらに対する耐性（対環境性）も要求される。
【０００５】
このような感光体劣化に対する一つの技術的対策として感光体に種々の劣化防止・安定剤を添加することが提案されている。例えば紫外線吸収剤として知られるベンゾトリアゾール化合物を添加する方法が特開昭５８−１２０２６０号に、またパラフェニレンジアミン化合物を添加する方法が特開昭６３−５２１４６号に、またジヒドロキノリン化合物をオゾン劣化防止剤として添加する方法が特開昭６３−５８４５５号に、またスピロインダン、スピロクロマン、ヒンダートアミン、ヒンダートフェノールを酸化防止剤として添加する方法が特開昭６３−７１８５６号、同６３−７１８５７号、同６３−１８３５５号、同６３−７３２５５号に、またα−ケト酸、アリールケトン化合物を添加する方法が特開昭６３−１３２２２４号、同６３−１５３５５３号、同６３−１５３５５４号に記載されている。
【０００６】
しかしながら、上述のような添加剤では紫外線、オゾン、ＮＯｘ等の影響は低減されるが、感度、残留電位は悪化してしまうことがあること、また近年、感光体の高感度化に伴い、より高速で高耐刷の複写機、プリンターへの搭載が要求されるようになったこと、また複写機、プリンターの小型化が進み、放電生成物の感光体周辺からの除去が難しくなったことなどにより、従来の感光体では耐久性が不十分となっている。
【０００７】
【発明が解決しようとする課題】
本発明の目的は上記問題点を鑑み、繰り返し使用しても帯電電位、感度、残留電位等の電気特性が変化せず、また文字太り、画像ボケ等の画像特性も安定した耐久性の優れた電子写真感光体を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者等は以上の目的を達成すべく鋭意研究を重ねた結果、導電性支持体上に少なくともキャリア発生物質とキャリア輸送物質を主要成分とする感光層を設けた電子写真感光体において、前記感光層中に下記一般式（Ａ）で示される化合物を含有する電子写真感光体を用いることにより達成することができる。
【０００９】
【化５】
式中、Ｒ1は、上記一般式（Ｂ）で示される残基を表し、Ｒ2は上記一般式（Ｂ）で示される残基、水素原子または炭素数１〜９のアルキル基を表す。但し一般式（Ｂ）中、Ｒは炭素数１〜９のアルキル基を表す。
【００１１】
一般式（Ａ）中、Ｒ2の炭素数１〜９のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基等をあげることができる。
【００１２】
一般式（Ｂ）中、Ｒの炭素数１〜９のアルキル基の具体例としては、メチル基、エチル基、イソプロピル基、ｔ−ブチル基等をあげることができるが、特にｔ−ブチル基が好ましい。
【００１３】
次に、一般式（Ａ）の本発明化合物の具体例について述べるがこれによって本発明の化合物が限定されるものではない。
【００１４】
【化６】
【化７】
本発明の化合物は、下記合成法及び公知の文献、例えばＧｅｒ Ｏｆｆｅｎ２４，５６，８６４、Ｇｅｒ Ｏｆｆｅｎ２６，５４，０５８及びＨＥＬＶＥＴＩＣＡ ＣＨＩＭＩＣＡ ＡＣＴＡ ５９（２）５２２〜５３２（１９７６）等により合成できる。
【００１７】
（合成例１ 例示化合物１の合成）
２，２−ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）マロン酸ビス（２，２，６，６−テトラメチルピペリジン−４−イル）エステル（２０．５ｇ；０．０２５モル）を無水酢酸（１００ｍｌ）に加え、１３０〜１４０℃に加熱攪拌して２時間反応させる。
【００１８】
反応後、反応液を氷水８００ｍｌに注いで析出した結晶を濾取し、さらに５００ｍｌの水にて２回攪拌洗浄し、濾取乾燥後、粗結晶をトルエン／ヘキサンにて再結晶して、目的物である例示化合物１を得る。収量１７．８ｇ（ｙ．７９％）本発明の化合物を添加した電子写真感光体は優れた電子写真特性を有し、コロナ帯電等で発生する放電生成物の影響を抑制し、繰り返し使用しても安定した電位特性及び画質を提供する耐久性の高い感光体である。
【００１９】
本発明の感光体の層構成はキャリア発生物質とキャリア輸送物質とがバインダー樹脂中に分散された単層構成でもよく、またキャリア発生物質を含むキャリア発生層とキャリア輸送物質を含むキャリア輸送層が積層された構成でもよい。また必要に応じて導電性支持体と感光層との間に中間層を設けてもよく、感光層の上に保護層を設けても良い。
【００２０】
本化合物の添加量は、その層内の重量比で０．１〜２０重量％、より好ましくは１〜１０重量％添加される。
【００２１】
本発明の感光体に用いられるキャリア輸送物質としては公知のどのようなものでも使用できるが、例えばトリアリールアミン化合物、トリアリールアミンスチリル化合物、ヒドラゾン化合物、ピラゾリン化合物が使用できる。
【００２２】
特に、下記一般式（Ｃ）で示されるトリフェニルアミン化合物が好ましい。
【００２３】
【化８】
式中、Ｒ3、Ｒ4、Ｒ5は各々独立に、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基を表すが、特にはメチル基、メトキシ基が好ましい。
【００２５】
またｎ，ｍ，ｌは各々独立に０〜３の整数を表す。
【００２６】
またＡｒは水素原子または置換、未置換のフェニル基を表し、好ましくはフェニル基であり、置換基として好ましくは、メチル基、エチル基等の炭素数１〜５のアルキル基、メトキシ基、エトキシ基等の炭素数１〜５のアルコキシ基が挙げられ、特に好ましくは未置換のフェニル基である。
【００２７】
次に、一般式（Ｃ）の化合物の具体例について述べるが、これによって本発明の化合物が限定されるわけではない。
【００２８】
【化９】
【化１０】
また本発明の感光体に用いられるキャリア発生物質としては公知のどのようなものでも使用できるが、例えば種々のフタロシアニン化合物、アゾ化合物、ピリリウム化合物、ペリレン系化合物、シアニン系化合物、スクアリウム化合物、多環キノン化合物が使用できる。
【００３１】
フタロシアニン化合物の中ではチタニルフタロシアニンが好ましく、特には特定の結晶系を有するＸ線回折におけるブラッグ角２θが９．５°、２４．１°、２７．２°にピークを有するチタニルフタロシアニンが好ましい。
【００３２】
またアゾ化合物の中では下記構造式のビスアゾ化合物が好ましい。
【００３３】
【化１１】
またペリレン化合物の中では下記構造式のペリレン化合物の異性体混合物が好ましい。
【００３５】
【化１２】
また本発明の感光体に用いられるバインダー樹脂としては、例えばポリカーボネート樹脂、ポリスチレン樹脂、ポリアクリル樹脂、ポリビニルブチラール樹脂、エポキシ樹脂、ポリウレタン樹脂、フェノール樹脂、ポリエステル樹脂、アルキッド樹脂、シリコン樹脂、メラミン樹脂ならびに、これらの樹脂の繰り返し単位のうちの２つ以上を含む共重合体樹脂等が挙げられる。またこれらの絶縁性樹脂の他、ポリ−Ｎ−ビニルカルバゾール等の高分子有機半導体が挙げられる。
【００３７】
本発明の中間層に用いられる樹脂としては、例えばポリアミド樹脂、塩化ビニル樹脂、酢酸ビニル樹脂ならびに、これらの樹脂の繰り返し単位のうちの２つ以上を含む共重合体樹脂が挙げられる。またシランカップリング剤、チタンカップリング剤などの有機金属化合物を熱硬化させた硬化性金属樹脂化合物が挙げられる。
【００３８】
本発明の感光層は本化合物を適当な溶媒にバインダ樹脂、必要に応じてキャリア輸送物質、キャリア発生物質と共に溶解または分散させた分散液をアプリケーター、バーコーター、ディップコーター、円形スライドホッパー等を用いて塗布、乾燥して形成することができる。分散液の調製に使用される溶媒としては、例えばトルエン、キシレン等の炭化水素類；メチレンクロライド、１，２−ジクロルエタン等のハロゲン化炭化水素；メチルエチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル等のエステル類；メタノール、エタノール、プロパノール、ブタノール、メチルセルソルブ、エチルセルソルブ等のアルコール類及びこの誘導体；テトラヒドロフラン、１，４−ジオキサン、１，３−ジオキソラン等のエーテル類；ピリジンやジエチルアミン等のアミン類；Ｎ，Ｎ−ジメチルホルムアミド等のアミド類等の窒素化合物；その他脂肪酸及びフェノール類；二硫化炭素や燐酸トリエチル等の硫黄、燐化合物等の１種又は２種以上を用いることができる。
【００３９】
次に前記感光層を支持する導電性支持体としては、アルミニウム、ニッケルなどの金属板・金属ドラム、またはアルミニウム、酸化錫、酸化インジュウムなどを蒸着したプラスチックフィルム、または導電性物質を塗布した紙・プラスチックフィルム・ドラムを使用することができる。
【００４０】
また本発明の感光体には、その他、感色性補正の染料を添加してもよい。また他の酸化防止剤等の添加剤を併用して添加しても良い。
【００４１】
【実施例】
以下に実施例を用いて本発明を具体的に示すが、本発明はこれらに限定されるものではない。
【００４２】
実施例１
コンパックス加工を施した円筒形アルミドラム上に、チタンカップリング剤「ＴＣ７５０」（松本製薬社製）３０部とシランカップリング剤「ＫＢＭ５０３」（信越化学社製）１７部とをイソプロパノール １５０部に溶解した中間層液を浸漬塗布し、１０５℃にて２５分間加熱硬化させて、厚さ１．０μｍの中間層を設けた。
【００４３】
その上に、キャリア発生物質として、Ｘ線回折におけるブラッグ角２θが９．５°、２４．１°、２７．２°にピークを有するチタニルフタロシアニン １０部、シリコン樹脂「ＫＲ−５２４０」（信越化学社製）１０部、酢酸ｔ−ブチル１０００部をサンドグラインダーを用いて分散した液を円形スライドホッパーにて塗布して、膜厚 ０．３μｍのキャリア発生層を形成した。
【００４４】
次いでキャリア輸送物質（Ｐ−６） １２０部、本発明の例示化合物Ｎｏ．１６部、ポリカーボネート樹脂「ユーピロンＺ−３００」（三菱瓦斯化学社製）１６０部をエチレンクロライド１０００部に溶解した液を、キャリア発生層上に円形スライドホッパーにて塗布して膜厚２０μｍのキャリア輸送層を形成した。
【００４５】
次いでキャリア輸送物質（Ｐ−６） １２０部、本発明の例示化合物Ｎｏ．１６部、ポリカーボネート樹脂「ユーピロンＺ−８００」（三菱瓦斯化学社製）１６０部をエチレンクロライド１０００部に溶解した液を、キャリア輸送層上に円形スライドホッパーにて塗布して膜厚８μｍの保護層を形成し、乾燥温度１１０℃にて、８０分間加熱乾燥して実施例感光体１を作製した。
【００４６】
実施例２
実施例１における例示化合物Ｎｏ．１をＮｏ．２に変えて、キャリア輸送物質（Ｐ−６）を（Ｐ−７）に変えた他は、実施例１と同様にして実施例感光体２を作製した。
【００４７】
比較例１
実施例１における例示化合物Ｎｏ．１を除いた他は、実施例１と同様にして比較例感光体１を作製した。
【００４８】
比較例２
実施例１における例示化合物Ｎｏ．１を比較化合物（Ｈ−１）に変えた他は、実施例１と同様にして比較例感光体２を作製した。
【００４９】
比較例３
実施例１における例示化合物Ｎｏ．１を比較化合物（Ｈ−２）に変えた他は、実施例１と同様にして比較例感光体３を作製した。
【００５０】
尚、比較化合物を下記に示す。
【００５１】
【化１３】
評価１
各実施例、比較例で得られた感光体を電位安定性の耐久テストとしてコニカ（株）社製デジタルコピー機「Ｋｏｎｉｃａ７０５０」に装着し、高温高湿環境下（３３℃；８０％）にて１万回の帯電→露光→除電の空回し試験を行い、初期及び１万回繰り返し後の帯電電位Ｖｈ・中間電位Ｖｇ・残留電位Ｖｒ（ｖ）を測定した。
【００５３】
また各実施例、比較例で得られた感光体を耐環境性の強制劣化テストとして発煙硝酸を用いたＮＯｘ暴露槽（ＮＯ2濃度約５ｐｐｍ前後）に放置暴露した。暴露後、２０分間順応させた後にコニカ（株）社製デジタルコピー機「Ｋｏｎｉｃａ７０５０」に装着して標準チャートの複写を行い、得られた画像の画像特性（画像ボケ）を比較例１を基準にして下記の４段階目視評価を行った。
【００５４】
（画像ボケの目視評価基準）
１：画像ボケ大
２：画像ボケ有り
３：画像ボケ軽微
４：画像ボケ無し
結果を表１に示す。
【００５５】
【表１】
実施例３
円筒形アルミドラム上に、ポリアミド樹脂「ＣＭ８０００」（東レ社製）１５部をメタノール：ｎ−ブタノール＝９：１の混合溶媒 １００部に溶解した中間層液を浸漬塗布し、厚さ０．５μｍの中間層を設けた。
【００５７】
その上に、キャリア発生物質として、「化１１」で示されるビスアゾ化合物 １２部、ポリビニルブチラール樹脂「エスレックＢＸ−Ｌ」（積水化学社製）４部、メトチルエチルケトン：シクロヘキサノン＝１９：１ ５００部をサンドグラインダーを用いて分散した液を浸漬塗布して、膜厚０．８μｍの電荷発生層を形成した。
【００５８】
次いでキャリア輸送物質（Ｐ−１１） １２０部、本発明の例示化合物Ｎｏ．３ ６部、ポリカーボネート樹脂「ユーピロンＺ−３００」（三菱瓦斯化学社製）１６０部をエチレンクロライド１０００部に溶解した液を、キャリア発生層上に浸漬塗布して膜厚２５μｍの電荷輸送層を形成し、乾燥温度１０５℃にて８０分間加熱乾燥して実施例感光体３を作製した。
【００５９】
実施例４
実施例３における例示化合物Ｎｏ．３をＮｏ．４に変えた他は、実施例１と同様にして実施例感光体４を作製した。
【００６０】
比較例４
実施例３における例示化合物Ｎｏ．３を除いた他は、実施例３と同様にして比較例感光体４を作製した。
【００６１】
比較例５
実施例３における例示化合物Ｎｏ．３を比較化合物（Ｈ−３）に変えた他は、実施例３と同様にして比較例感光体５を作製した。
【００６２】
評価２
各実施例、比較例で得られた感光体を電位安定性の耐久テストとしてコニカ（株）社製コピー機「Ｋｏｎｉｃａ４０４５」に装着した以外は実施例１と同様にして評価を行った。
【００６３】
結果を表２に示す。
【００６４】
【表２】
実施例５
円筒形アルミドラム上に、ポリアミド樹脂「ＣＭ８０００」（東レ社製）１５部をメタノール：ｎ−ブタノール＝９：１の混合溶媒 １００部に溶解した中間層液を浸漬塗布し、厚さ０．３μｍの中間層を設けた。
【００６６】
その上に、キャリア発生物質として、「化１２」で示されるペリレン化合物の異性体混合物５部、ポリビニルブチラール樹脂「エスレックＢＬ−Ｓ」（積水化学社製）１部、メトチルエチルケトン：シクロヘキサノン＝８：２ １２５部をサンドグラインダーを用いて分散した液を浸漬塗布して、膜厚０．２μｍの電荷発生層を形成した。
【００６７】
次いでキャリア輸送物質（Ｐ−７）１００部、本発明の例示化合物Ｎｏ．５ ５部、ポリカーボネート樹脂「ユーピロンＺ−３００」（三菱瓦斯化学社製）１５０部をメチレンクロライド１０００部に溶解した液を、キャリア発生層上に浸漬塗布して膜厚２５μｍのキャリア輸送層を形成した。
【００６８】
次いでキャリア輸送物質（Ｐ−７）１００部、本発明の例示化合物Ｎｏ．５ ５部、ポリカーボネート樹脂「ＴＳ−２０５０」（帝人化成社製）１５０部をエチレンクロライド１０００部に溶解した液を、キャリア輸送層上に円形スライドホッパーにて塗布して膜厚２μｍの保護層を形成し、乾燥温度１１０℃にて６０分間加熱乾燥して実施例感光体５を作製した。
【００６９】
実施例６
実施例５における例示化合物Ｎｏ．５をＮｏ．８に変えて、キャリア輸送物質（Ｐ−７）を（Ｐ−１２）に変えた他は実施例５と同様にして実施例感光体６を作製した。
【００７０】
比較例６
実施例５における例示化合物Ｎｏ．５を除いた他は、実施例５と同様にして比較例感光体６を作製した。
【００７１】
比較例７
実施例５における例示化合物Ｎｏ．５を比較化合物（Ｈ−３）に変えた他は実施例５と同様にして比較例感光体７を作製した。
【００７２】
評価３
各実施例、比較例で得られた感光体を電位安定性の耐久テストとしてコニカ（株）社製コピー機「Ｋｏｎｉｃａ４３５５」に装着した以外は実施例１と同様に評価した。
【００７３】
結果を表３に示す。
【００７４】
【表３】
以上のように、本発明の添加剤を用いた電子写真感光体は、繰り返し使用しても安定した電気特性、画像特性を示し、耐久性に優れた電子写真感光体であることが分かる。
【００７６】
【発明の効果】
本発明の添加剤を用いることにより、繰り返し使用しても帯電電位、感度、残留電位等の電気特性が変化せず、また文字太り、画像ボケ等の画像特性も安定した耐久性の優れた電子写真感光体を得ることができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member for forming an electrostatic latent image. More specifically, the present invention relates to an electrophotographic photoreceptor excellent in durability, having good environmental resistance, having a small residual potential, and having stable potential characteristics even when used repeatedly.
[0002]
[Prior art]
Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, and silicon has been widely used. However, these are not always satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc., and some inorganic photoreceptors contain substances harmful to the human body. There is.
[0003]
In order to overcome the drawbacks of these inorganic photoreceptors, research and development of organic photoreceptors having a photosensitive layer mainly composed of various organic photoconductive compounds have been actively conducted in recent years. In particular, the function-separated type photoconductor in which the carrier generation function and the carrier transport function are respectively assigned to different substances can be selected from a wide range of materials, and a photoconductor having an arbitrary performance can be relatively easily obtained. Much research has been done since it can be created, and some have been put into practical use.
[0004]
The surface layer of the organic photoreceptor is required to have durability against electric and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning. In addition, when a photoconductor is actually used in a copying machine or printer, the photoconductor is subject to surface degradation due to discharge products such as ozone and nitrogen oxide (NOx) generated at the strip electrode and ultraviolet rays during exposure. Resistance to these (environmental resistance) is also required.
[0005]
As a technical countermeasure against such photoreceptor deterioration, it has been proposed to add various deterioration prevention / stabilizers to the photoreceptor. For example, a method of adding a benzotriazole compound known as an ultraviolet absorber is disclosed in JP-A-58-120260, a method of adding a paraphenylenediamine compound is disclosed in JP-A-63-52146, and a dihydroquinoline compound is deteriorated by ozone. A method of adding as an inhibitor is disclosed in JP-A-63-58455, and a method of adding spiroindane, spirochroman, hindered amine and hindered phenol as an antioxidant is disclosed in JP-A-63-71856 and 63-71857. 63-185355 and 63-73255, and methods for adding α-keto acids and aryl ketone compounds are described in JP-A-63-132224, 63-153553, and 63-153554. ing.
[0006]
However, although the effects of ultraviolet rays, ozone, NOx, etc. are reduced with the additives as described above, the sensitivity and residual potential may be deteriorated. High-speed, high-life-proof copying machines and printers are now required to be installed, and copying machines and printers have become more compact, making it difficult to remove discharge products from the periphery of the photoreceptor. Therefore, the durability of the conventional photoreceptor is insufficient.
[0007]
[Problems to be solved by the invention]
In view of the above problems, the object of the present invention is that the electrical characteristics such as charging potential, sensitivity, and residual potential do not change even when used repeatedly, and the image characteristics such as character thickening and image blur are stable and excellent in durability. The object is to provide an electrophotographic photoreceptor.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have obtained an electrophotographic photosensitive member in which a photosensitive layer comprising at least a carrier generating substance and a carrier transporting substance as main components is provided on a conductive support. This can be achieved by using an electrophotographic photosensitive member containing a compound represented by the following general formula (A) in the photosensitive layer.
[0009]
[Chemical formula 5]
In the formula, R 1 represents a residue represented by the general formula (B), and R 2 represents a residue represented by the general formula (B), a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms. However, in general formula (B), R represents a C1-C9 alkyl group.
[0011]
In the general formula (A), specific examples of the alkyl group having 1 to 9 carbon atoms of R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
[0012]
In the general formula (B), specific examples of the alkyl group having 1 to 9 carbon atoms of R include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and the like. preferable.
[0013]
Next, although the specific example of this invention compound of general formula (A) is described, the compound of this invention is not limited by this.
[0014]
[Chemical 6]
[Chemical 7]
The compound of the present invention can be synthesized by the following synthesis method and known literatures such as Ger Offen 24, 56, 864, Ger Offe 26, 54, 058, and HELVETICA CHIMICA ACTA 59 (2) 522-532 (1976).
[0017]
(Synthesis Example 1 Synthesis of Exemplary Compound 1)
2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonic acid bis (2,2,6,6-tetramethylpiperidin-4-yl) ester (20.5 g; 0.025 Mol) is added to acetic anhydride (100 ml) and heated to 130-140 ° C. with stirring for 2 hours.
[0018]
After the reaction, the reaction solution was poured into 800 ml of ice water, and the precipitated crystals were collected by filtration, further washed with stirring twice with 500 ml of water, filtered and dried, and then the crude crystals were recrystallized with toluene / hexane. Example compound 1 which is a thing is obtained. Yield 17.8 g (y. 79%) The electrophotographic photosensitive member to which the compound of the present invention is added has excellent electrophotographic characteristics, suppresses the influence of discharge products generated by corona charging, and is used repeatedly. Is a highly durable photoconductor that provides stable potential characteristics and image quality.
[0019]
The layer structure of the photoconductor of the present invention may be a single layer structure in which a carrier generating material and a carrier transporting material are dispersed in a binder resin, or a carrier generating layer containing a carrier generating material and a carrier transporting layer containing a carrier transporting material. A stacked configuration may be used. If necessary, an intermediate layer may be provided between the conductive support and the photosensitive layer, and a protective layer may be provided on the photosensitive layer.
[0020]
The addition amount of this compound is 0.1-20 weight% by weight ratio in the layer, More preferably, 1-10 weight% is added.
[0021]
Any known carrier transporting material used in the photoreceptor of the present invention can be used. For example, a triarylamine compound, a triarylamine styryl compound, a hydrazone compound, and a pyrazoline compound can be used.
[0022]
In particular, a triphenylamine compound represented by the following general formula (C) is preferable.
[0023]
[Chemical 8]
In the formula, R 3 , R 4 , and R 5 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and particularly preferably a methyl group or a methoxy group.
[0025]
N, m and l each independently represents an integer of 0 to 3.
[0026]
Ar represents a hydrogen atom or a substituted or unsubstituted phenyl group, preferably a phenyl group, and the substituent is preferably an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group, a methoxy group, or an ethoxy group. C1-C5 alkoxy groups, such as these, are mentioned, Especially preferably, it is an unsubstituted phenyl group.
[0027]
Next, specific examples of the compound of the general formula (C) will be described, but the compound of the present invention is not limited thereto.
[0028]
[Chemical 9]
[Chemical Formula 10]
Any known carrier generating material used in the photoreceptor of the present invention can be used. For example, various phthalocyanine compounds, azo compounds, pyrylium compounds, perylene compounds, cyanine compounds, squalium compounds, polycyclic compounds, and the like. Quinone compounds can be used.
[0031]
Among the phthalocyanine compounds, titanyl phthalocyanine is preferable, and in particular, titanyl phthalocyanine having a Bragg angle 2θ in X-ray diffraction having a specific crystal system and peaks at 9.5 °, 24.1 °, and 27.2 ° is preferable.
[0032]
Of the azo compounds, bisazo compounds having the following structural formula are preferred.
[0033]
Embedded image
Among the perylene compounds, an isomer mixture of perylene compounds having the following structural formula is preferable.
[0035]
Embedded image
Examples of the binder resin used in the photoreceptor of the present invention include polycarbonate resin, polystyrene resin, polyacrylic resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, silicon resin, melamine resin and And a copolymer resin containing two or more of these resin repeating units. In addition to these insulating resins, polymer organic semiconductors such as poly-N-vinylcarbazole can be used.
[0037]
Examples of the resin used for the intermediate layer of the present invention include a polyamide resin, a vinyl chloride resin, a vinyl acetate resin, and a copolymer resin containing two or more repeating units of these resins. Moreover, the curable metal resin compound which heat-cured organometallic compounds, such as a silane coupling agent and a titanium coupling agent, is mentioned.
[0038]
The photosensitive layer of the present invention uses an applicator, a bar coater, a dip coater, a circular slide hopper, etc. with a dispersion obtained by dissolving or dispersing this compound in a suitable solvent with a binder resin, and if necessary, a carrier transporting material and a carrier generating material. Can be formed by coating and drying. Examples of the solvent used for preparing the dispersion include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ketones such as methyl ethyl ketone and cyclohexanone; ethyl acetate and butyl acetate. Esters such as: alcohols such as methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve and their derivatives; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane; pyridine, diethylamine, etc. Amines such as: Nitrogen compounds such as amides such as N, N-dimethylformamide; Other fatty acids and phenols; One or more of sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate can be used. .
[0039]
Next, as the conductive support for supporting the photosensitive layer, a metal plate / metal drum such as aluminum or nickel, or a plastic film deposited with aluminum, tin oxide, indium oxide, or the like, or paper coated with a conductive substance, Plastic film drums can be used.
[0040]
In addition, a dye for color sensitivity correction may be added to the photoreceptor of the present invention. Further, other additives such as antioxidants may be used in combination.
[0041]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0042]
Example 1
30 parts of titanium coupling agent “TC750” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 17 parts of silane coupling agent “KBM503” (manufactured by Shin-Etsu Chemical Co., Ltd.) on 150 parts of isopropanol on a cylindrical aluminum drum subjected to Compaqs processing The dissolved intermediate layer solution was applied by dip coating and heat cured at 105 ° C. for 25 minutes to provide an intermediate layer having a thickness of 1.0 μm.
[0043]
In addition, 10 parts of titanyl phthalocyanine having peaks at Bragg angles 2θ of 9.5 °, 24.1 °, and 27.2 ° in X-ray diffraction, silicon resin “KR-5240” (Shin-Etsu Chemical) A liquid in which 10 parts and 1000 parts of t-butyl acetate were dispersed using a sand grinder was applied by a circular slide hopper to form a carrier generation layer having a thickness of 0.3 μm.
[0044]
Subsequently, 120 parts of carrier transport material (P-6), Exemplified Compound No. 16 parts, 160 parts of polycarbonate resin “Iupilon Z-300” (manufactured by Mitsubishi Gas Chemical Co., Ltd.) dissolved in 1000 parts of ethylene chloride was applied onto the carrier generation layer with a circular slide hopper, and the carrier transported with a film thickness of 20 μm. A layer was formed.
[0045]
Subsequently, 120 parts of carrier transport material (P-6), Exemplified Compound No. 16 parts of a polycarbonate resin “Iupilon Z-800” (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 160 parts of ethylene chloride was applied onto a carrier transport layer with a circular slide hopper, and a protective layer having a thickness of 8 μm. And dried by heating at a drying temperature of 110 ° C. for 80 minutes to prepare Example Photoreceptor 1.
[0046]
Example 2
Example Compound No. 1 in Example 1 No. 1 Example Photosensitive member 2 was prepared in the same manner as Example 1 except that the carrier transport material (P-6) was changed to (P-7) instead of 2.
[0047]
Comparative Example 1
Example Compound No. 1 in Example 1 A comparative photoreceptor 1 was produced in the same manner as in Example 1 except that 1.
[0048]
Comparative Example 2
Example Compound No. 1 in Example 1 A comparative photoreceptor 2 was produced in the same manner as in Example 1 except that 1 was changed to the comparative compound (H-1).
[0049]
Comparative Example 3
Example Compound No. 1 in Example 1 A comparative photoreceptor 3 was produced in the same manner as in Example 1 except that 1 was changed to the comparative compound (H-2).
[0050]
The comparative compounds are shown below.
[0051]
Embedded image
Evaluation 1
The photoconductors obtained in each Example and Comparative Example were mounted on a digital copier “Konica 7050” manufactured by Konica Corporation as a potential stability durability test, and in a high temperature and high humidity environment (33 ° C .; 80%). A blanking test of 10,000 times charging → exposure → static elimination was performed, and charging potential Vh / intermediate potential Vg / residual potential Vr (v) after initial and 10,000 times repetition were measured.
[0053]
In addition, the photoreceptors obtained in each Example and Comparative Example were left exposed in a NOx exposure tank (NO 2 concentration of about 5 ppm) using fuming nitric acid as a forced deterioration test for environmental resistance. After the exposure, the product was allowed to acclimate for 20 minutes, and then mounted on a digital copy machine “Konica 7050” manufactured by Konica Corporation. A standard chart was copied, and the image characteristics (image blur) of the obtained image were based on Comparative Example 1. The following four-stage visual evaluation was performed.
[0054]
(Visual evaluation standard for image blur)
1: Large image blur 2: Image blur 3: Image blur minor 4: No image blur results are shown in Table 1.
[0055]
[Table 1]
Example 3
An intermediate layer solution in which 15 parts of polyamide resin “CM8000” (manufactured by Toray Industries Inc.) is dissolved in 100 parts of a mixed solvent of methanol: n-butanol = 9: 1 is dip-coated on a cylindrical aluminum drum, and the thickness is 0.5 μm. An intermediate layer was provided.
[0057]
In addition, 12 parts of a bisazo compound represented by “Chemical Formula 11”, 4 parts of a polyvinyl butyral resin “S-REC BX-L” (manufactured by Sekisui Chemical Co., Ltd.), methoyl ethyl ketone: cyclohexanone = 19: 1 500 A liquid in which a part was dispersed using a sand grinder was applied by dip coating to form a charge generation layer having a thickness of 0.8 μm.
[0058]
Subsequently, 120 parts of carrier transport material (P-11), Exemplified Compound No. 36 parts, 160 parts of polycarbonate resin “Iupilon Z-300” (Mitsubishi Gas Chemical Co., Ltd.) dissolved in 1000 parts of ethylene chloride is dip-coated on the carrier generation layer to form a charge transport layer having a thickness of 25 μm. Then, the photosensitive member 3 of Example was produced by heating and drying at a drying temperature of 105 ° C. for 80 minutes.
[0059]
Example 4
Exemplified Compound No. 2 in Example 3 No. 3 Example Photosensitive member 4 was produced in the same manner as Example 1 except for changing to 4.
[0060]
Comparative Example 4
Exemplified Compound No. 2 in Example 3 A comparative photoconductor 4 was produced in the same manner as in Example 3 except that 3.
[0061]
Comparative Example 5
Exemplified Compound No. 2 in Example 3 A comparative photoreceptor 5 was produced in the same manner as in Example 3 except that 3 was changed to the comparative compound (H-3).
[0062]
Evaluation 2
Evaluation was performed in the same manner as in Example 1 except that the photoconductors obtained in each Example and Comparative Example were installed in a copy machine “Konica 4045” manufactured by Konica Corporation as a potential stability durability test.
[0063]
The results are shown in Table 2.
[0064]
[Table 2]
Example 5
An intermediate layer solution obtained by dissolving 15 parts of polyamide resin “CM8000” (manufactured by Toray Industries Inc.) in 100 parts of a mixed solvent of methanol: n-butanol = 9: 1 is dip-coated on a cylindrical aluminum drum, and the thickness is 0.3 μm. An intermediate layer was provided.
[0066]
In addition, as a carrier generating substance, 5 parts of an isomer mixture of perylene compounds represented by “Chemical Formula 12”, 1 part of polyvinyl butyral resin “ESREC BL-S” (manufactured by Sekisui Chemical Co., Ltd.), A liquid in which 125 parts of 8: 2 were dispersed using a sand grinder was applied by dip coating to form a charge generation layer having a thickness of 0.2 μm.
[0067]
Subsequently, 100 parts of carrier transport material (P-7), Exemplified Compound No. 5 5 parts, 150 parts of polycarbonate resin “Iupilon Z-300” (manufactured by Mitsubishi Gas Chemical Co., Inc.) dissolved in 1000 parts of methylene chloride is dip-coated on the carrier generation layer to form a carrier transport layer having a thickness of 25 μm. did.
[0068]
Subsequently, 100 parts of carrier transport material (P-7), Exemplified Compound No. 5 5 parts, 150 parts of polycarbonate resin “TS-2050” (manufactured by Teijin Kasei Co., Ltd.) dissolved in 1000 parts of ethylene chloride was applied on a carrier transport layer with a circular slide hopper to form a protective layer with a thickness of 2 μm. The photosensitive body 5 was prepared and dried by heating at a drying temperature of 110 ° C. for 60 minutes.
[0069]
Example 6
Exemplified Compound No. 5 in Example 5 No. 5 Example Photosensitive member 6 was prepared in the same manner as Example 5 except that the carrier transport material (P-7) was changed to (P-12) instead of 8.
[0070]
Comparative Example 6
Exemplified Compound No. 5 in Example 5 A comparative photoconductor 6 was prepared in the same manner as in Example 5 except that 5 was omitted.
[0071]
Comparative Example 7
Exemplified Compound No. 5 in Example 5 A comparative photoreceptor 7 was produced in the same manner as in Example 5 except that 5 was changed to the comparative compound (H-3).
[0072]
Evaluation 3
The photoconductors obtained in each Example and Comparative Example were evaluated in the same manner as in Example 1 except that the photoconductor was mounted on a copy machine “Konica 4355” manufactured by Konica as a potential stability durability test.
[0073]
The results are shown in Table 3.
[0074]
[Table 3]
As described above, it can be seen that the electrophotographic photosensitive member using the additive of the present invention is an electrophotographic photosensitive member that exhibits stable electric characteristics and image characteristics even after repeated use and has excellent durability.
[0076]
【The invention's effect】
By using the additive of the present invention, the electrical characteristics such as charging potential, sensitivity, residual potential, etc. do not change even when used repeatedly, and the electronic properties with excellent durability are stable in image characteristics such as character thickening and image blurring. A photographic photoreceptor could be obtained.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24013998A JP3692790B2 (en) | 1997-08-27 | 1998-08-26 | Electrophotographic photoreceptor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23092497 | 1997-08-27 | ||
| JP9-230924 | 1997-08-27 | ||
| JP24013998A JP3692790B2 (en) | 1997-08-27 | 1998-08-26 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11133637A JPH11133637A (en) | 1999-05-21 |
| JP3692790B2 true JP3692790B2 (en) | 2005-09-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24013998A Expired - Fee Related JP3692790B2 (en) | 1997-08-27 | 1998-08-26 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3692790B2 (en) |
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| Publication number | Publication date |
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| JPH11133637A (en) | 1999-05-21 |
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