JP3584565B2 - Electronic device and image forming apparatus - Google Patents
Electronic device and image forming apparatus Download PDFInfo
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- JP3584565B2 JP3584565B2 JP24514795A JP24514795A JP3584565B2 JP 3584565 B2 JP3584565 B2 JP 3584565B2 JP 24514795 A JP24514795 A JP 24514795A JP 24514795 A JP24514795 A JP 24514795A JP 3584565 B2 JP3584565 B2 JP 3584565B2
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photoreceptors In Electrophotography (AREA)
- Electroluminescent Light Sources (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、電荷輸送性高分子化合物を用いた電子デバイス、特に電子写真感光体、およびそれを用いた画像形成装置に関するものである。
【０００２】
【従来の技術】
ポリビニルカルバゾール（ＰＶＫ）に代表される半導体性を電荷輸送性高分子化合物は、電子写真感光体の光導電材料或いは第３６回応用物理学関係連合後援会予稿集３１ｐ−Ｋ−１２（１９９０）等に記載されたような、有機電界発光素子材料として有望なものである。これらは共に層を形成させ、電荷輸送層として使用するが、電荷輸送層を形成する材料としては、ＰＶＫに代表される電荷輸送性高分子と、電荷輸送性の低分子化合物をポリマー中に分散した低分子分散系のものがよく知られている。また、有機電界発光素子では、低分子の電荷輸送材料を蒸着して用いるのが一般的である。これらのうち、低分子分散系のものが、材料の多様性があり、高機能のものが得られやすいことから、特に電子写真感光体では主流になっている。
ところで、プリンター等の高速化によって電子写真感光体に要求される耐久性は年々厳しいものとなっており、繰り返し使用による表面層の摩擦、表面へのトナー等の異物の付着に対する耐性の向上は、耐久性向上に必須な技術として検討が続けられている。その点に関して、現在の主流である低分子分散系の電荷輸送層が最表面層となる積層型感光体では、電気的な特性に関しては、十分に満足できる性能のものが得られつつあるが、低分子化合物をポリマー中に分散して用いるため、機械的な摩耗に対しては本質的に弱いという欠点を有している。特に、オゾンフリーな帯電方式として注目されている接触帯電方式を用いた画像形成装置では、帯電部材が直接接触するために感光層の摩耗が著しく増加し、また、表面に汚れなどの異物付着が発生しやすいという問題を有している。また、有機電界発光素子の場合には、発生するジュール熱により、低分子の電荷輸送材料が溶融し、結晶化等による膜のモルホロジー変化が起こりやすいという欠点があった。
【０００３】
これに対し、電荷輸送性高分子化合物は、この欠点を大きく改善できる可能性があるため、現在盛んに研究されている。例えば、米国特許第４，８０６，４４３号明細書には、特定のジヒドロキシアリールアミンとビスクロロホルメートとの重合によるポリカーボネートが開示されており、米国特許第４，８０６，４４４号明細書には、特定のジヒドロキシアリールアミンとホスゲンとの重合によるポリカーボネートが開示されている。また、米国特許第４，８０１，５１７号明細書には、ビスヒドロキシアルキルアリールアミンとビスクロロホルメート或いはホスゲンとの重合によるポリカーボネートが開示されており、米国特許第４，９３７，１６５号明細書および同第４，９５９，２８８号明細書には、特定のジヒドロキシアリールアミン或いはビスヒドロキシアルキルアリールアミンとの重合によるポリカーボネート、或いはビスアシルハライドとの重合によるポリエステルが開示されている。さらに、米国特許第５，０３４，２９６号明細書には、特定のフルオレノン骨格を有するアリールアミンのポリカーボネート或いはポリエステルが、また米国特許第４，９８３，４８２号明細書には、ポリウレタンが開示されている。さらにまた、特公昭５３−８７２２６号公報および特公昭５９−２８９０３号公報には、特定のビススチリルビスアリールアミンを主鎖としたポリエステルが開示されている。また、特開昭６１−２０９５３号公報、特開平１−１３４４５６号公報、特開平１−１３４４５７号公報、特開平１−１３４４６２号公報、特開平４−１３３０６５号公報および特開平４−１３３０６６号公報には、ヒドラゾンやトリアリールアミン等の電荷輸送性の置換基をペンダントとしたポリマーおよびそれを用いた電子写真感光体が提案されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、これまで工業的に大量に生産されている電子デバイスについて、電荷輸送性高分子化合物が実用化された例は非常に少ない。例えば、電子写真感光体にあっては、現在常用されている積層型の感光体で用いられている電荷輸送層は、液体現像用などの特殊用途を除いては、全て低分子の電荷輸送材料を結着樹脂中に分散させたものである。
これには様々な原因が考えられるものの、電荷輸送性高分子化合物を用いた電子デバイスの電気的な特性が、往々にして大きくばらついてしまうということが一因となっており、これは無視し得ない問題である。
【０００５】
電子デバイスで用いられる半導体材料では、純度或いは特定の不純物の濃度管理が重要であることはよく知られた事実であるが、電荷輸送性高分子化合物では、低分子の電荷輸送材料において一般的に用いられる再結晶、蒸留等の、低コストで高純度が得られる精製法を用いることができない。そのため、原料の純度、重合時の僅かな条件の変化による不純物や夾雑物の種類や濃度が時によって異なり、そのため、電荷輸送性高分子化合物を用いた電子デバイスの電気的な特性も変化することが明らかになった。
初期的な特性のばらつきについては、短時間の試験でその特性を知り、製品を選別することも可能であるが、長期間の繰り返し使用に関わる特性について、長期間の試験を行うことが必要であり、この点が、最終的な製品のコストを著しく引き上げたり、或いは工業的実用化を阻害する決定的な要因となる。
【０００６】
したがって、本発明の目的は、良好な電気特性を維持し、かつ低コストで安定して供給できる電荷輸送性高分子化合物を用いた電子デバイスを提供することにある。本発明の他の目的は、良好な電気的特性と強靱な機械的特性を併せ持つ電荷輸送性高分子化合物を用いた電子写真感光体およびそれを用いた画像形成方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、これらの問題を解決するために、鋭意検討した結果、電荷輸送性高分子化合物に含有される金属が電気的な特性に大きな影響を与えることを見出した。特に、金属の単体、金属の炭酸塩、酢酸塩若しくは酸化物、または有機金属化合物であって、エステル交換反応または重縮合反応における触媒作用を有するもの、なかでも、Ａｌ、Ｃａ、Ｓｂ、Ｇａ、Ｇｅ、Ｍｇ、Ｍｎ、Ｔｉ、ＺｎおよびＺｒの含有量が大きく影響することが明らかになり、その濃度を５０ｐｐｍ以下に抑えることによって、良好な電気的特性が得られることを見出し、本発明を完成するに至った。
【０００８】
本発明の電子デバイスは、電荷輸送性高分子化合物を構成要素の一つとして含有するものであって、その電荷輸送性高分子化合物が、単量体の重合反応に際し、或いはグラフト反応による改質時に、金属を含有する触媒を用いて作製されたものであって、下記一般式（Ｉ−１）または（Ｉ−２）で示される部分構造の少なくとも１種を含有する繰り返し構造単位を含み、かつ、金属の含有量が５０ｐｐｍ以下であることを特徴とする。
【化６】
また、本発明の電子写真感光体は、導電性支持体上に上記の電荷輸送性高分子化合物を構成要素として含有する感光層を設けてなることを特徴とする。
本発明において、金属の含有量が５０ｐｐｍ以下であると、良好な電気特性が得られる理由は明らかではないが、金属原子が電荷輸送性高分子化合物と相互作用して配位し、トラップを形成するために電気特性が変化するためと考えられ、特に、エステル交換反応または重縮合反応に活発な金属原子は、電荷輸送性高分子化合物との相互作用が強いため、影響が大きいと考えられ、したがって、その金属の含有量を低下させることによって、電気特性が改善されると推測される。
【０００９】
【発明の実施の形態】
以下に本発明について詳細に説明する。
本発明の電荷輸送性高分子化合物を用いる電子デバイスにおいては、電荷輸送性高分子化合物は、単量体の重合反応に際して、或いはグラフト反応による改質時に、金属を含有する触媒を用いて作製されたものであって、前記一般式（Ｉ−１）または（Ｉ−２）で示される部分構造の少なくとも１種を含有する繰り返し構造単位を含むものであり、かつ、金属の含有量が５０ｐｐｍ以下であるものが使用される。なかでも、金属単体、金属の炭酸塩、酢酸塩若しくは酸化物、または有機金属化合物であって、エステル交換反応または重縮合反応における触媒作用を有するもの、そのなかでも、Ａｌ、Ｃａ、Ｓｂ、Ｇａ、Ｇｅ、Ｍｇ、Ｍｎ、Ｔｉ、ＺｎおよびＺｒより選択された１種または複数の組み合わせであるものの含有量が、金属として５０ｐｐｍ以下である電荷輸送性高分子化合物が好ましく使用される。
【００１１】
本発明の電子デバイスとしては、特に電子写真感光体が好適ものである。その場合、電荷輸送性高分子化合物は、感光層に用いられるが、感光層は単層構造であっても、機能分離された積層構造のものであってもよい。図１ないし図５は、本発明の電子写真感光体の断面を示す模式図である。図１および図２は、感光層が単層構造の場合を示すものであって、導電性支持体１１上に、光導電層１２が設けられており、図２においては、さらに下引き層１３が設けられている。図３ないし図５は、感光層が積層構造の場合を示すものであって、図３は導電性支持体１１上に電荷発生層１４および電荷輸送層１５が順次設けられている。図４においては、さらに、導電性支持体１１上に下引き層１３が設けられており、また、図５においては、電荷輸送層１５の上に保護層１６が設けられている。
【００１２】
本発明において、電子写真感光体としては、電荷輸送性高分子化合物が最表面層として用いられるのが好ましい。
また、感光層は、上記電荷輸送性高分子化合物と、下記式（ＶＩ−１）ないし（ＶＩ−８）から選択された少なくとも１種の繰り返し構造単位を有するポリカーボネートまたはポリカーボネート−ポリシロキサン共重合体とを混合して使用するのが好ましい。
【００１３】
【化７】
【化９】
を表し、ｓおよびｔは１〜３００の整数であって、ｓ／（ｓ＋ｔ）＝０．１〜０．９の範囲にあり、ｕは１〜２００の整数を表す。〕
【００１４】
上記の電子写真感光体を用いた本発明の画像形成装置について、その概略の構成を図６に示す。画像形成装置は、導電性支持体１１上に感光層１０を有する感光体１の周囲に、帯電装置２、露光装置３、現像装置４、転写装置５およびクリーニング装置６が配設されている。この図の場合、帯電装置２は、感光体表面に当接したロール帯電器よりなり、ロール表面の導電性部材２１に電源２２より電圧が印加されるようになっている。なお、７は転写紙、４１は現像ロール、４２は層規制部材である。
【００１５】
次に、本発明において使用される上記一般式（Ｉ−１）または（Ｉ−２）で示される部分構造の少なくとも１種を含有する繰り返し構造単位を含む電荷輸送性高分子化合物について説明する。この電荷輸送性高分子化合物としては、下記一般式（II）〜（Ｖ）で示されるものが好適である。
【００１６】
【化１０】
【００１７】
上記一般式（Ｉ−１）または（Ｉ−２）で示される部分構造におけるＸとしては、下記の基（１）〜（７）から選択されたものがあげられる。
【化１１】
【化１２】
【００１８】
また、ＹおよびＺとしては、下記の基（１８）〜（２４）から選択されたものがあげられる。
【化１３】
【００１９】
このうち、特にＸが下記構造式（ＶＩＩ ）および（ＶＩＩＩ）で示されるビフェニル構造を有する電荷輸送性高分子化合物は、“Ｔｈｅ Ｓｉｘｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｇｒｅｓｓ ｏｎ Ａｄｖａｎｃｅｓ ｉｎ Ｎｏｎ−ｉｍｐａｃｔ Ｐｒｉｎｔｉｎｇ Ｔｅｃｈｎｏｌｏｇｉｅｓ，３０６、（１９９０）”にも報告されているようにモビリティーが高く、実用性の高いものである。
【化１４】
上記一般式（Ｉ−１）または（Ｉ−２）で示される部分構造の少なくとも１種を含む繰り返し構造単位におけるＴは、炭素数１〜１０の枝分れしてもよい２価の炭化水素基を示し、具体的には、以下に示すものが例示される。
【化１５】
【化１６】
本発明において使用される電荷輸送性高分子化合物について具体例を示す。以下の表１〜５に上記一般式（Ｉ−１）示される部分構造の具体例を示し、表６〜表１０に一般式（Ｉ−２）で示される部分構造の具体例を示す。また、表１１〜表１２に上記一般式（ＩＩ）で示される電荷輸送性高分子化合物の具体例を示し、表１３に上記一般式（ＩＩＩ ）で示される電荷輸送性高分子化合物の具体例を示し、表１４に一般式（ＩＶ）で示される電荷輸送性高分子化合物の具体例を示し、表１５に一般式（Ｖ）で示される電荷輸送性高分子化合物の具体例を示す。
なお、アリールアミン骨格はどちらの側と結合してもよいが、例えば、Ｔ−５ｒと記すと構造Ｔ−５の右側に、Ｔ−５ｌと記すと構造Ｔ−５の左側にテトラアリールベンジジン骨格が結合していることを示すものとする。
【００２３】
上記一般式（Ｉ−１）示される構造の例
【表１】
【表２】
【表３】
【表４】
【表５】
一般式（Ｉ−２）で示される構造の例
【表６】
【表７】
【表８】
【表９】
【表１０】
一般式（ＩＩ）で示される電荷輸送性高分子化合物の例
【表１１】
【表１２】
一般式（ＩＩＩ ）で示される電荷輸送性高分子化合物の例
【表１３】
一般式（ＩＶ）で示される電荷輸送性高分子化合物の例
【表１４】
一般式（Ｖ）で示される電荷輸送性高分子化合物の例
【表１５】
以下、本発明の電子デバイスを、機能分離型積層構造の電子写真感光体を中心に詳細に説明する。
導電性支持体としては、アルミニウム、ニッケル、クロム、ステンレス鋼等の金属類、およびアルミニウム、チタニウム、ニッケル、クロム、ステンレス鋼、金、バナジウム、酸化錫、酸化インジウム、ＩＴＯ等の薄膜を設けたプラスチック等、あるいは導電性付与剤を塗布または含浸させた紙、およびプラスチックフィルム等があげられる。これらの導電性支持体は、ドラム状、シート状、プレート状、適宜の形状のものとして使用されるが、これらに限定されるものではない。さらに必要に応じて導電性支持体の表面は、画質に影響のない範囲で各種の処理を行うことができる。例えば、表面の酸化処理や薬品処理、および着色処理等、または砂目立て等の乱反射処理等を行うことができる。
【００３９】
また、導電性支持体と電荷発生層の間にさらに下引き層を設けてもよい。この下引き層は積層構造からなる感光層の帯電時において、導電性支持体から感光層への電荷の注入を阻止すると共に、感光層を導電性支持体に対して一体的に接着保持せしめる接着層としての作用、或いは場合によっては導電性支持体に対して一体的に接着保持せしめる接着層としての作用、或いは場合によっては導電性支持体の光の反射防止作用等を示す。
【００４０】
下引き層に用いる結着樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、アクリル樹脂、メタクリル樹脂、ポリアミド樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリイミド樹脂、塩化ビニリデン樹脂、ポリビニルアセタール樹脂、塩化ビニル−酢酸ビニル共重合体、ポリビニルアルコール樹脂、水溶性ポリエステル樹脂、ニトロセルロース、カゼイン、ゼラチン、ポリグルタミン酸、澱粉、スターチアセテート、アミノ澱粉、ポリアクリル酸、ポリアクリルアミド化合物、ジルコニウムキレート化合物、チタニウムキレート化合物、チタニウムアルコキシド化合物、有機チタニウム化合物、シランカップリング剤等の公知の材料をあげることができる。これらの材料は単独または２種以上混合して用いることができる。
また、これらの材料は、酸化チタン、シリカ、酸化ジルコニウム、チタン酸バリウム、シリコーン樹脂等の微粒子を混合して用いることもできる。下引き層の膜厚は０．０１〜１０μｍ、好ましくは０．０５〜２μｍの範囲である。さらにこの下引き層を設ける際に用いる塗布方法としては、ブレードコーティング法、ワイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を採用することができる。
【００４１】
電荷発生層には、電荷発生材料として、非晶質セレン、結晶性セレン−テルル合金、セレン−ひ素合金、その他のセレン化合物およびセレン合金、酸化亜鉛、酸化チタン等の無機光導電性材料、フタロシアニン系、スクエアリウム系、アントアントロン系、ペリレン系、アゾ系、アントラキノン系、ピレン系、ピリリウム系、チアピリリウム系等の有機顔料および染料が用いられるが、ハロゲン化錫フタロシアニン結晶、ハロゲン化ガリウムフタロシアニン結晶、ヒドロキシガリウムフタロシアニン結晶、チタニルフタロシアニン結晶等が好ましい。
電荷発生層に用いる結着樹脂としては、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、部分変性ポリビニルアセタール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ポリビニルアセテート樹脂、塩化ビニル−酢酸ビニル共重合体、シリコーン樹脂、フェノール樹脂、ポリ−Ｎ−ビニルカルバゾール樹脂等をあげることができるが、これらに限定されるものではない。これらの結着樹脂は単独または２種以上混合して用いることができる。
【００４２】
電荷発生材料と結着樹脂との配合比（重量比）は、１０：１〜１：１０の範囲が好ましい。電荷発生層の膜厚は、一般には０．１〜５μｍ、好ましくは０．２〜２．０μｍの範囲に設定される。塗布方法としては、ブレードコーティング法、ワイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を用いることができる。
さらに、電荷発生層を設けるときに用いる溶剤としては、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール、ベンジルアルコール、メチルセロソルブ、エチルセロソルブ、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸メチル、酢酸ｎ−ブチル、ジオキサン、テトラヒドロフラン、メチレンクロライド、クロロホルム等の通常の有機溶剤をあげることができ、これらは単独または２種以上混合して用いることができる。
【００４３】
本発明において、電荷輸送層には、全金属含有量が５０ｐｐｍ以下、好ましくは１０ｐｐｍ以下、より好ましくは１ｐｐｍ以下の電荷輸送性高分子化合物が用いられる。
電荷輸送性高分子化合物中に含まれる全ての金属の含有量を同時に測定するには、灰分量からの推定が簡便であるが、定量値の信頼性が低く、また必要とする試料も大量に必要となる。したがって、電気的な特性に大きな影響を与える金属種、すなわち、金属単体、金属の炭酸塩、酢酸塩、酸化物或いは有機金属化合物のいずれかの状態であり、エステル交換反応または重縮合反応の触媒作用を有するもの、中でも、Ａｌ、Ｃａ、Ｓｂ、Ｇａ、Ｇｅ、Ｍｇ、Ｍｎ、Ｔｌ、Ｚｎ、Ｚｒに着目して分析を行うのが好ましい。そのための分析方法として、誘導プラズマ発光分析法、原子吸光法、蛍光Ｘ線法等を用いることが、正確さと経済性を両立させる上で望ましく、とりわけ誘導プラズマ発光分析法は、同時に多種類の金属種の定量が可能であり、感度、定量性等の点から好適な分析手法である。
【００４４】
本発明において、電荷輸送性高分子化合物としては、前記式（Ｉ−１）または（Ｉ−２）で示される部分構造を主鎖に含むポリカーボネート、ポリエステルおよびポリウレタン等が用いられるが、特に前記した式（II）〜（Ｖ）で示される電荷輸送性高分子化合物を用いることによって、電気特性、機械的特性に優れた電子写真感光体を得ることができる。
【００４５】
電荷輸送性の置換基をペンダントとした電荷輸送性高分子化合物の場合、重合法としてラジカル重合を用いて形成することができ、本質的には金属元素による汚染が起きにくいという長所を有している。しかし、リビングアニオン重合等に見られる金属塩を用いる重合法においては、重合反応条件はもちろん、原材料に含まれる不純物、各工程で用いられる各種溶剤、容器、配管等からの汚染にも最大の注意が必要である。電気特性、機械的強度の点では、主鎖に電荷輸送性の機能を有するもの、なかでもポリカーボネートおよびポリエステルが優れており、本発明の電子デバイス、特に電子写真感光体に好適に使用される。
電荷輸送性高分子化合物がポリカーボネートまたはポリエステルの場合、例えば、ホスゲンを用いて重合してポリカーボネートを得る方法は、本質的に金属元素による汚染が起きにくい方法であるが、安全性、経済性の観点から、工業的にはエステル交換反応による方法が用いられることが多い。したがって、触媒の残留による汚染は不可避であるので、汚染が生じないようにして製造することが必要である。
【００４６】
本発明において、上記の電荷輸送性高分子化合物は、それ単独或いは２種以上混合して使用することもできるが、上記式（ＶＩ−１）〜（ＶＩ−８）で示される繰り返し構造単位を有するポリカーボネートまたはポリカーボネート樹脂−ポリシロキサン共重合体を混合し使用すると、電荷輸送性高分子化合物が有していない特性、例えば、高度な表面潤滑性を与える等の利点があるので好ましい。その場合の配合比は、重量比で５：１〜１：１の範囲が好ましい。
【００４７】
電荷輸送層は、上記に電荷輸送性高分子化合物、またはそれと上記式（ＶＩ−１）〜（ＶＩ−８）で示される繰り返し構造単位を有するポリカーボネートまたはポリカーボネート樹脂−ポリシロキサン共重合体との混合物を適当な溶剤に溶解して塗布し、乾燥することによって形成することができる。電荷輸送層の形成に使用される溶剤としては、ベンゼン、トルエン、キシレン、クロルベンゼン等の芳香族炭化水素類、アセトン、２−ブタノン等のケトン類、塩化メチレン、クロロホルム、塩化エチレン等のハロゲン化脂肪族炭化水素類、テトラヒドロフラン、ジオキサン、エチレングリコールジエチルエーテル等の環状または直鎖状のエーテル類、或いはこれらの混合溶剤を用いることができる。
【００４８】
この電荷輸送層を設ける場合に用いる塗布方法としては、ブレードコーティング法、ワイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を採用することができる。電荷輸送層の膜厚は、２〜１００μｍの範囲であり、好ましくは１０〜４０μｍの範囲に設定される。
【００４９】
また、光、熱等による感光体の劣化を防止することを目的として、電荷輸送層中に、酸化防止剤、光安定剤等の添加剤を加えることができる。酸化防止剤としては、例えば、ヒンダードフェノール類、ヒンダードアミン類、パラフェニレンジアミン誘導体、アリールアルカン類、ハイドロキノン誘導体、有機硫黄化合物、有機リン化合物等があげられる。光安定剤としては、例えば、ベンゾフェノン、ベンゾトリアゾール、ジチオカルバメート、テトラメチルピペリジン等の誘導体があげられる。これらの添加剤を単独、或いは混合して用いるが、電荷輸送性高分子化合物の重量の０．０１〜２０重量％、好ましくは０．１〜１０重量％の範囲で添加される。
【００５０】
また、良好な表面性を得ることを主たる目的として、塗料用の改質剤として知られている添加剤を加えることもできる。例えば、ジメチル系ポリシロキサン（ジメチルシリコーンオイル）やメチルフェニル系ポリシロキサン（メチルフェニルシリコーンオイル）等は好ましい例である。また、これらポリシロキサンの一部を変性したアルキル変性、アルコキシ変性、アルキルアリル変性、グリコール変性、アルコール変性、エポキシ変性、メチルスチリル変性、高級脂肪酸変性、高級アルコキシ変性、ポリエーテル変性等の変性シリコーンオイルも好ましい例であり、電荷輸送層の固形分に対して、１〜１０，０００ｐｐｍ、好ましくは５〜２，０００ｐｐｍの範囲で添加される。
また、感度の向上、残留電位の低減、繰り返し使用時の疲労低減等を目的として、少なくとも１種の電子受容性物質を含有させることができる。例えば、無水コハク酸、無水マレイン酸、ジブロム無水マレイン酸、無水フタル酸、テトラブロム無水フタル酸、テトラシアノエチレン、テトラシアノキノジメタン、ｏ−ジニトロベンゼン、ｍ−ジニトロベンゼン、クロラニル、ジニトロアントラキノン、トリニトロフルオレノン、ピクリン酸、ｏ−ニトロ安息香酸、ｐ−ニトロ安息香酸、フタル酸等を用いることができる。
本発明における上記の電荷輸送層は、他の低分子の電荷輸送材料を含有する電荷輸送層の上に設けて、保護層としての作用をもたせることもできる。
【００５１】
その場合の下層の電荷輸送層に用いる低分子の電荷輸送材料としては、２，５−ビス（ｐ−ジエチルアミノフェニル）−１，３，４−オキサジアゾール等のオキサジアゾール誘導体、１，３，５−トリフェニルピラゾリン等のピラゾリン誘導体、トリフェニルアミン等の芳香族３級アミノ化合物、Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（３−メチルフェニル）−［１，１′−ビフェニル］−４，４′−ジアミン等の芳香族３級ジアミノ化合物、３−（４′−ジエチルアミノフェニル）−５，６−ジ（４′−メトキシフェニル）−１，２，４−トリアジン等の１，２，４−トリアジン誘導体、４−ジエチルアミノベンズアルデヒド−１，１′−ジフェニルヒドラゾン等のヒドラゾン誘導体、２−フェニル−４−スチリルキナゾリン等のキナゾリン誘導体、６−ヒドロキシ−２，３−ジ（ｐ−メトキシフェニル）ベンゾフラン等のベンゾフラン誘導体、ｐ−（２，２′−ジフェニルビニル）−Ｎ，Ｎ−ジフェニルアニリン等のα−スチルベン誘導体等があげられる。
また、結着樹脂としては、（変性）ポリカーボネート樹脂、ポリエステル樹脂、メタクリル樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリスチレン樹脂、ポリ酢酸ビニル樹脂、スチレン−ブタジエン共重合体、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、シリコン樹脂、シリコーン−アルキッド樹脂、フェノール−ホルムアルデヒド樹脂、スチレン−アルキッド樹脂等を使用することができる。
【００５２】
この電荷輸送層は、上記電荷輸送性高分子化合物またはそれと上記ポリカーボネート樹脂またはポリカーボネート−ポリシロキサン共重合体との混合物を用いた場合と同様にして設けることができるが、その際の電荷輸送材料と結着樹脂の割合は、重量比で１０：１〜１：５の範囲が好ましく、その膜厚は、一般的には５〜５０μｍ、好ましくは１０〜３０μｍの範囲に設定される。
上記の電荷輸送層を設けた場合において、その上に設ける上記電荷輸送性高分子化合物を用いて形成される保護層の膜厚は、電荷輸送層の膜厚の１〜２００％、好ましくは５〜１００％の範囲に設定される。
【００５３】
次に、本発明の接触帯電方式を用いた画像形成装置について説明する。本発明の画像形成装置は、感光体として上記の電子写真感光体が用いられるが、接触帯電を行うために感光体表面に接触するように導電性部材が設けられる。導電性部材の形状は、ブラシ状、ブレード状、ピン電極状、およびローラー状等、いずれの形状を有するのもでもよいが、なかでもローラー状の導電部材を用いるのが好ましい。通常、ローラー状部材は、外側から抵抗層とそれらを支持する弾性層と芯材から構成される。さらに必要に応じて、抵抗層の外側に保護層を設けることもできる。
【００５４】
芯材の材質としては、導電性を有するもので、一般には、鉄、銅、真鍮、ステンレス鋼、アルミニウム、ニッケル等が用いられる。また、その他の導電性微粒子等を分散した樹脂成形品等を用いることができる。弾性層の材質としては、導電性或いは半導電性を有するもので、一般にはゴム材に導電性粒子或いは半導電性粒子を分散したものが用いられる。ゴム材としては、ＥＰＤＭ、ポリブタジエン、天然ゴム、ポリイソブチレン、ＳＢＲ、ＣＲ、ＮＢＲ、シリコーンゴム、ウレタンゴム、エピクロルヒドリンゴム、ＳＢＳ、熱可塑性エラストマー、ノルボルネンゴム、フロロシリコーンゴム、エチレンオキシドゴム等があげられ、導電性粒子または半導電性粒子としては、カーボンブラック、亜鉛、アルミニウム、銅、鉄、ニッケル、クロム、チタン等の金属、ＺｎＯ−Ａｌ２ Ｏ３ 、ＳｎＯ２ −Ｓｂ２ Ｏ３ 、Ｉｎ２ Ｏ３ −ＳｎＯ２ 、ＺｎＯ−ＴｉＯ２ 、ＭｇＯ−Ａｌ２ Ｏ３ 、ＦｅＯ−ＴｉＯ２ 、ＴｉＯ２ 、ＳｎＯ２ 、Ｓｂ２ Ｏ３ 、Ｉｎ２ Ｏ３ 、ＺｎＯ、ＭｇＯ等の金属酸化物を用いることができる。これらの材料は単独或いは２種以上混合して用いてもよく、２種以上の場合は、一方が微粒子状であってもよく、微粒子としてフッ素系樹脂の微粒子を用いることもできる。
【００５５】
抵抗層および保護層の材質としては、結着樹脂中に導電性粒子または半導電性粒子を分散し、その抵抗を制御したもので、抵抗率としては、１０３ 〜１０１４Ωｃｍ、好ましくは１０５ 〜１０１２Ωｃｍ、さらに好ましくは１０７ 〜１０１２Ωｃｍの範囲が採用される。また、膜厚としては、０．０１〜１０００μｍ、好ましくは０．１〜５００μｍ、さらに好ましくは０．５〜１００μｍの範囲が採用される。
結着樹脂としては、アクリル樹脂、セルロース樹脂、ポリアミド樹脂、メトキシメチル化ナイロン、エトキシメチル化ナイロン、ポリウレタン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、ポリアリレート樹脂、ポリチオフェン樹脂、ポリエチレンテトラフタレート等のポリエステル樹脂、ポリオレフィン樹脂、スチレン−ブタジエン樹脂等があげられる。
【００５６】
導電性粒子または半導電性粒子としては、弾性層の場合と同様のカーボンブラック、金属、金属酸化物等が用いられる。
また、必要に応じて、ヒンダードフェノール、ヒンダードアミン等の酸化防止剤、クレー、カオリン等の充填剤、シリコーンオイル等の潤滑剤を添加することができる。これらの層を形成する手段としては、ブレードコーティング法、ワイヤ−コーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法、真空蒸着法、プラズマコーティング法等を用いることができる。
【００５７】
これらの導電性部材を用いて感光体を帯電させる場合、導電性部材に電圧を印加するが、印加電圧は直流電圧に交流電圧を重畳したものが好ましく、直流電圧のみでは均一な帯電を得ることが難しい。
電圧の範囲としては、直流電圧は正または負の５０〜２０００Ｖの範囲が好ましく、特に１００〜１５００Ｖの範囲が好ましい。重畳する交流電圧としては、ピーク間電圧が４００〜１８００Ｖ、好ましくは８００〜１６００Ｖ、さらに好ましくは１２００〜１８００Ｖの範囲が採用される。このピーク間電圧が１８００Ｖを越えると、交流電圧を重畳しない場合より均一な帯電が得られなくなる。交流電圧の周波数は１００〜２０００Ｈｚの範囲が望ましい。
【００５８】
【実施例】
以下、本発明を実施例によって説明する。なお、「部」は、「重量部」を意味する。
合成例１（例示化合物（７）の合成）
３，３′−ジメチル−Ｎ，Ｎ′−ビス（３，４−ジメチルフェニル）−Ｎ，Ｎ′−ビス［４−（２−メトキシカルボニルエチル）フェニル］−［１，１′−ビフェニル］−４，４′−ジアミン２０ｇ、エチレングリコール４０ｇ、テトラブトキシチタン３．０ｇを５００ｍｌのフラスコに入れ、窒素気流下で３時間加熱還流した。３，３′−ジメチル−Ｎ，Ｎ′−ビス（３，４−ジメチルフェニル）−Ｎ，Ｎ′−ビス［４−（２−メトキシカルボニルエチル）フェニル］−［１，１′−ビフェニル］−４，４′−ジアミンが消費されたことを確認した後、０．５ｍｍＨｇに減圧し、エチレングリコールを留去しながら２３０℃に加熱し、４時間反応を続けた。その後、室温まで冷却し、塩化メチレン５００ｍｌに溶解し、不溶物をろ過し、ろ液をエタノール２５００ｍｌを撹拌している中に滴下し、ポリマーを析出させた。得られたポリマーをろ過し、十分にエタノールで洗浄した後、乾燥させ、１８ｇのポリマーを得た。分子量をＧＰＣにて測定したところ、Ｍｗ＝１．６×１０５ （スチレン換算）であり、モノマーから求めた重合度ｐは、約２１５であった。
得られたポリマー中に残存するＴｉ量を、以下の方法で定量した。すなわち、試料２５０ｍｇを２５ｍｌのメスフラスコに計り採り、クロロホルムで溶解して３線まで薄めた溶液を作った。この溶液中のＴｉ量を、高周波誘導結合プラズマ発光分析装置（ＳＰＳ１２００ＶＲ型、セイコー電子工業社製）を用い、オルトチタン酸テトラ−ｎ−ブチル（Ｔｉ含有率１３．９５％）のクロロホルム溶液を標準溶液として測定し、元のポリマー中のＴｉ量を求めた。結果は、ポリマー１ｇにつき、２６０μｇ（２６０ｐｐｍ）であった。
【００５９】
合成例２
合成例１における、エタノール２５００ｍｌに滴下して、ポリマーを析出させた後、さらにポリマーをＴＨＦ５００ｍｌに溶解し、蒸溜水２５００ｍｌに滴下する工程を加えた以外は、合成例１と同様にしてポリマーを得た。Ｔｉ量は１８０ｐｐｍであった。
合成例３
合成例１における、テトラブトキシチタン３．０ｇを、０．５ｇに変更した以外は、合成例１と同様にしてポリマーを得た。Ｔｉ量は６６ｐｐｍであった。
合成例４
合成例２において、テトラブトキシチタン３．０ｇを、０．５ｇに変更した以外は、合成例２と同様にしてポリマーを得た。Ｔｉ量は４５ｐｐｍであった。
合成例５
合成例１における、テトラブトキシチタン３．０ｇを、０．１ｇに変更した以外は、合成例１と同様にしてポリマーを得た。Ｔｉ量は６．８ｐｐｍであった。
合成例６
合成例５において、塩化メチレン５００ｍｌの溶液を、１Ｎの水酸化ナトリウム水溶液５００ｍｌと混合撹拌し、静置した後、水溶液を取り去り、さらに１Ｎの希塩酸５００ｍｌと混合撹拌し、静置した後、水溶液を取り去り、さらに蒸溜水５００ｍｌと混合撹拌し、静置した後、水溶液を取り去ったものを、２５００ｍｌのエタノールに滴下してポリマーを析出させる工程を加えた以外は、合成例５と同様にしてポリマーを得た。Ｔｉ量は０．６ｐｐｍであった。
【００６０】
合成例７（例示化合物（３９）の合成）
３，３′−ジメチル−Ｎ，Ｎ′−ビス（３，４−ジメチルフェニル）−Ｎ，Ｎ′−ビス［４−（２−メトキシカルボニルエチル）フェニル］−［１，１′−ビフェニル］−４，４′−ジアミン１５ｇ、セバシン酸ジメチル３．０ｇ，エチレングリコール３０ｇ、トリメトキシガリウム１．０ｇを２００ｍｌのフラスコに入れ、窒素気流下で３時間加熱還流した。３，３′−ジメチル−Ｎ，Ｎ′−ビス（３，４−ジメチルフェニル）−Ｎ，Ｎ′−ビス［４−（２−メトキシカルボニルエチル）フェニル］−［１，１′−ビフェニル］−４，４′−ジアミンが消費されたことを確認した後、０．５ｍｍＨｇに減圧し、エチレングリコールを留去しながら２３０℃に加熱し、４時間反応を続けた。その後、室温まで冷却し、塩化メチレン１００ｍｌに溶解し、不溶物をろ過し、ろ液をアセトン１５００ｍｌを撹拌している中に滴下し、ポリマーを析出させた。得られたポリマーをろ過し、十分にエタノールで洗浄した後、乾燥させ、１７．５ｇのポリマーを得た。分子量をＧＰＣにて測定したところ、Ｍｗ＝１．１×１０５ （スチレン換算）であった。（重合度ｐ＝約１２０、ｒ＝約９０）
また、誘導プラズマ発光分析装置（ＩＣＰ）で測定したＧａ量は、ポリマー１ｇにつき８０μｇ（８０ｐｐｍ）であった。
【００６１】
合成例８
合成例７において、塩化メチレン１００ｍｌの溶液を、１Ｎの水酸化ナトリウム水溶液１００ｍｌと混合撹拌し、静置した後、水溶液を取り去り、さらに１Ｎの希塩酸１００ｍｌと混合撹拌し、静置した後、水溶液を取り去り、さらに蒸溜水１００ｍｌと混合撹拌し、静置した後、水溶液を取り去ったものを、２５００ｍｌのエタノールに滴下してポリマーを析出させる工程を加えた以外は、合成例７と同様にしてポリマーを得た。Ｇａ量はポリマー１ｇにつき２．５ｐｐｍであった。
【００６２】
比較例１
アルムニウムパイプ上に、ジルコニウム化合物（オルガッチクスＺＣ５４０、マツモト製薬社製）１０部およびシラン化合物（Ａ１１１０、日本ユニカー社製）１部とｉ−プロパノール４０部およびブタノール２０部からなる溶液を浸漬コーティング法で塗布し、１５０℃において１０分間加熱乾燥し、膜厚０．１μｍの下引き層を形成した。次に、ｘ型無金属フタロシアニン結晶１部を、ポリビニルブチラール樹脂（エスレックＢＭ−Ｓ、積水化学社製）１部およびシクロヘキサノン１００部と混合し、ガラスビーズとともにサンドミルで１時間処理して分散した後、得られた塗布液を上記下引き層上に浸漬コーティング法で塗布し、１００℃において１０分間加熱乾燥して、膜厚０．１５μｍの電荷発生層を形成した。次に合成例１で得た電荷輸送性高分子化合物（例示化合物（７））７部を、モノクロルベンゼン１５部とテトラヒドロフラン１５部の混合溶剤に溶解し、得られた塗布液を、上記の電荷発生層上に浸漬コーティング法で塗布し、１１５℃において１時間加熱乾燥、膜厚２０μｍの電荷輸送層を形成した。
【００６３】
次に、芯材として、直径６ｍｍのステンレス鋼棒を用い、弾性層として抵抗１０６ Ωｃｍの導電性ＥＰＤＭゴムを用い、抵抗層として抵抗１０９ Ωｃｍのエピクロルヒドリンゴムを用いて、直径１２ｍｍの導電性ロールを形成した。
上記のようにして得られた電子写真感光体と導電性ロールを、レーザービームプリンターの現像機位置に表面電位計（Ｔｒｅｋ社製）を装着した試験装置（ＸＰ−１１改造機、富士ゼロックス社製）に装着して、導電性ロールにＤＣ：５００Ｖ、ＡＣ：１５００Ｖ（ピーク間電圧）を印加して、現像機位置での黒ベタの画像に対応する表面電位を測定した。
その後、表面電位計と現像機を交換して画像を採取し、さらにプリントを５万回繰り返してから画像を採取して、その画質を評価し、現像機と表面電位計を交換して現像機位置での黒ベタの画像に対応する表面電位を測定した。その結果を表１６に示す。
さらに別の電子写真感光体を通常のスコロトロンによる帯電方法を持つレーザープリンター（ＸＰ−１１、富士ゼロックス社製）を改造した前記したと同様の試験装置に装着し、同様の評価を行った。その結果を表１７に示す。
【００６４】
比較例２
電荷輸送層に合成例２で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
比較例３
電荷輸送層に合成例３で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
実施例１
電荷輸送層に合成例４で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
実施例２
電荷輸送層に合成例５で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
実施例３
電荷輸送層に合成例６で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
比較例４
電荷輸送層に合成例７で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
実施例４
電荷輸送層に合成例８で得たポリマーを用いた以外は、比較例１と同様にして、電子写真感光体を作製し、同様に測定を行った。
【００６５】
比較例５
下記のベンジジン化合物を２部、前記構造式（ＶＩ−２）で示される繰り返し構造単位からなるポリカーボネート樹脂（粘度平均分子量Ｍｖ＝４．０×１０４ ）３部を、モノクロルベンゼン１０部およびテトラヒドロフラン１０部の混合液に溶解して得た塗布液を塗布し、乾燥して電荷輸送層を形成した以外は、比較例１と同様にして電子写真感光体を作成し、同様に評価を行った。
【化１７】
比較例６
比較例１において、下記のヒドラゾン化合物を３部、前記構造式（ＶＩ−３）で示される繰り返し構造単位からなるポリカーボネート樹脂（粘度平均分子量Ｍｖ＝５．０×１０４ ）３部を用いた以外は、比較例１と同様にして電子写真感光体を作成し、同様に評価を行った。
【化１８】
実施例５
比較例１の電荷輸送層の上に、Ｔｉ含有量が０．８ｐｐｍの例示化合物３０（Ｍｗ＝１．４×１０５ ）２部と、前記構造式（ＶＩ−２）で示される繰り返し構造単位からなるポリカーボネート樹脂（粘度平均分子量Ｍｖ＝４．０×１０４ ）１部からなる保護層を形成した以外は、比較例１と同様にして電子写真感光体を作成し、同様に評価した。
【００６８】
【表１６】
【表１７】
【発明の効果】
本発明の電子デバイスは、上記の構成を有することにより、良好かつ安定した電気特性と優れた機械的特性を併せ持ち、従来問題となっていた電気的特性の不安定さを著しく減少することができる。また、本発明の電子写真感光体は、従来の電荷輸送材料を結着樹脂中に分散させた層を用いたものに比べ、感光層の摩耗と異物付着による画像欠陥の発生を低減させることができ、寿命と信頼性の改善された接触帯電方式を用いた画像形成装置が作製される。
【図面の簡単な説明】
【図１】本発明の電子写真感光体の一例の模式的断面図である。
【図２】本発明の電子写真感光体の他の一例の模式的断面図である。
【図３】本発明の電子写真感光体の他の一例の模式的断面図である。
【図４】本発明の電子写真感光体の他の一例の模式的断面図である。
【図５】本発明の電子写真感光体の他の一例の模式的断面図である。
【図６】本発明の画像形成装置の概略構成図である。
【符号の説明】
１…感光体、２…帯電装置、３…露光装置、４…現像装置、５…転写装置、６…クリーニング装置、７…転写紙、１０…感光層、１１…導電性支持体、１２…光導電層、１３…下引き層、１４…電荷発生層、１５…電荷輸送層、１６…保護層、２１…導電性部材、２２…電源、４１…現像ロール、４２…層規制部材。[0001]
[Industrial applications]
The present invention relates to an electronic device using a charge transporting polymer compound, particularly an electrophotographic photoreceptor, and an image forming apparatus using the same.
[0002]
[Prior art]
The semiconductive and charge transporting polymer compound represented by polyvinyl carbazole (PVK) is a photoconductive material for an electrophotographic photoreceptor or the 36th Applied Physics Association Supporters Association Proceedings 31p-K-12 (1990). As described above, the organic electroluminescent device material is promising. These form a layer together and are used as a charge transport layer. As a material for forming the charge transport layer, a charge transport polymer represented by PVK and a low molecular compound having a charge transport property are dispersed in the polymer. The low-molecular-weight dispersion system is well known. Further, in an organic electroluminescent device, it is common to deposit and use a low-molecular charge transport material. Of these, low-molecular dispersion systems have become mainstream, particularly in electrophotographic photoreceptors, because they have a variety of materials and are easy to obtain high-performance ones.
By the way, the durability required for the electrophotographic photoreceptor has been becoming severer year by year due to the speeding up of printers and the like. It is being studied as a technology essential for improving durability. In that regard, in the laminated photoreceptor in which the charge transport layer of the low molecular dispersion system, which is the current mainstream, is the outermost surface layer, with regard to the electrical characteristics, a sufficiently satisfactory performance is being obtained, Since a low-molecular compound is used by dispersing it in a polymer, it has a disadvantage that it is essentially weak against mechanical wear. In particular, in an image forming apparatus using a contact charging method, which has been attracting attention as an ozone-free charging method, wear of the photosensitive layer significantly increases due to direct contact of the charging member, and foreign matter such as dirt adheres to the surface. There is a problem that it easily occurs. Further, in the case of the organic electroluminescent device, there is a disadvantage that the low-molecular charge transporting material is melted by the generated Joule heat, and the morphology of the film is easily changed by crystallization or the like.
[0003]
On the other hand, charge-transporting polymer compounds are being actively studied at present because there is a possibility that this disadvantage can be greatly improved. For example, U.S. Pat. No. 4,806,443 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate, and U.S. Pat. No. 4,806,444 discloses a polycarbonate. Discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and phosgene. U.S. Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerizing a bishydroxyalkylarylamine with bischloroformate or phosgene, and is disclosed in U.S. Pat. No. 4,937,165. No. 4,959,288 discloses a polycarbonate obtained by polymerization with a specific dihydroxyarylamine or bishydroxyalkylarylamine, or a polyester obtained by polymerization with a bisacyl halide. Further, U.S. Pat. No. 5,034,296 discloses polycarbonate or polyester of arylamine having a specific fluorenone skeleton, and U.S. Pat. No. 4,983,482 discloses polyurethane. I have. JP-B-53-87226 and JP-B-59-28903 disclose polyesters having a specific bisstyrylbisarylamine as a main chain. Also, JP-A-61-20953, JP-A-1-134456, JP-A-1-134457, JP-A-1-134462, JP-A-4-1330065 and JP-A-4-133066. Has proposed a polymer in which a charge-transporting substituent such as hydrazone or triarylamine is pendant, and an electrophotographic photoreceptor using the same.
[0004]
[Problems to be solved by the invention]
However, with respect to electronic devices that have been industrially mass-produced, very few examples of charge transport polymer compounds have been put to practical use. For example, in the case of electrophotographic photoreceptors, the charge transport layer used in currently commonly used laminated photoreceptors is a low-molecular charge transport material except for special applications such as liquid development. Is dispersed in a binder resin.
Although there are various possible causes for this, one of the causes is that the electrical characteristics of electronic devices using charge-transporting polymer compounds often fluctuate greatly. It is a problem that cannot be obtained.
[0005]
It is a well-known fact that it is important to control purity or the concentration of specific impurities in semiconductor materials used in electronic devices. It is not possible to use a purification method such as recrystallization and distillation that can be used to obtain high purity at low cost. Therefore, the purity and purity of raw materials and the types and concentrations of impurities and contaminants due to slight changes in polymerization conditions vary depending on the time, and the electrical characteristics of electronic devices using charge-transporting polymer compounds may also change. Was revealed.
It is possible to know the characteristics of the initial characteristics by short-term tests and select products, but it is necessary to conduct long-term tests for characteristics related to long-term repeated use. Yes, this is a decisive factor that significantly increases the cost of the final product or hinders industrial practical use.
[0006]
Therefore, an object of the present invention is to provide an electronic device using a charge transporting polymer compound that can maintain good electrical characteristics and can be stably supplied at low cost. Another object of the present invention is to provide an electrophotographic photoreceptor using a charge transporting polymer compound having both good electrical properties and tough mechanical properties, and an image forming method using the same.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve these problems, and as a result, have found that a metal contained in the charge-transporting polymer compound has a large effect on electrical characteristics. In particular, simple metals, metal carbonates, acetates or oxides, or organometallic compounds having a catalytic action in a transesterification reaction or a polycondensation reaction, among which Al, Ca, Sb, Ga, It has been clarified that the contents of Ge, Mg, Mn, Ti, Zn, and Zr have a great effect, and it has been found that good electrical characteristics can be obtained by suppressing the concentration to 50 ppm or less, and the present invention has been completed. I came to.
[0008]
The electronic device of the present invention contains a charge-transporting polymer compound as one of the constituent elements, and the charge-transporting polymer compound is modified during polymerization of a monomer or by a graft reaction. Occasionally, it is made using a metal-containing catalyst.A repeating structural unit containing at least one of the partial structures represented by the following general formula (I-1) or (I-2);In addition, the metal content is 50 ppm or less.
Embedded image
Further, the electrophotographic photoreceptor of the present invention is characterized in that a photosensitive layer containing the above-mentioned charge transporting polymer compound as a component is provided on a conductive support.
In the present invention, when the content of the metal is 50 ppm or less, it is not clear why good electrical properties are obtained. However, the metal atom interacts with the charge transporting polymer compound to coordinate to form a trap. In particular, it is considered that the metal atoms active in the transesterification reaction or the polycondensation reaction have a strong influence due to strong interaction with the charge transporting polymer compound, Therefore, it is presumed that the electrical characteristics are improved by reducing the content of the metal.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
In the electronic device using the charge-transporting polymer compound of the present invention, the charge-transporting polymer compound is produced by using a metal-containing catalyst during a polymerization reaction of a monomer or during a modification by a graft reaction. ThatIt contains a repeating structural unit containing at least one of the partial structures represented by the general formula (I-1) or (I-2), andThose having a metal content of 50 ppm or less are used. Among them, simple metals, metal carbonates, acetates or oxides, or organometallic compounds having a catalytic action in a transesterification reaction or a polycondensation reaction, among which, Al, Ca, Sb, Ga , Ge, Mg, Mn, Ti, Zn and Zr, a charge transporting polymer compound in which the content of one or a combination of a plurality thereof is 50 ppm or less as a metal is preferably used.
[0011]
As the electronic device of the present invention, an electrophotographic photosensitive member is particularly suitable. In this case, the charge transporting polymer compound is used for the photosensitive layer. The photosensitive layer may have a single-layer structure or a laminated structure with separated functions. 1 to 5 are schematic views showing a cross section of the electrophotographic photosensitive member of the present invention. FIGS. 1 and 2 show a case where the photosensitive layer has a single-layer structure, in which a
[0012]
In the present invention, as the electrophotographic photoreceptor, a charge transporting polymer compound is preferably used as the outermost surface layer.
Further, the photosensitive layer is a polycarbonate or a polycarbonate-polysiloxane copolymer having the charge transporting polymer compound and at least one repeating structural unit selected from the following formulas (VI-1) to (VI-8). Are preferably used in combination.
[0013]
Embedded image
Embedded image
Wherein s and t are integers of 1 to 300, s / (s + t) = 0.1 to 0.9, and u represents an integer of 1 to 200. ]
[0014]
FIG. 6 shows a schematic configuration of the image forming apparatus of the present invention using the above electrophotographic photosensitive member. In the image forming apparatus, a charging device 2, an
[0015]
Next, a repeating structural unit containing at least one of the partial structures represented by the general formula (I-1) or (I-2) used in the present invention is described below.IncludingThe charge transporting polymer compound will be described. As the charge transporting polymer compound, compounds represented by the following general formulas (II) to (V) are preferable.
[0016]
Embedded image
[0017]
Examples of X in the partial structure represented by the general formula (I-1) or (I-2) include those selected from the following groups (1) to (7).
Embedded image
Embedded image
[0018]
Examples of Y and Z include those selected from the following groups (18) to (24).
Embedded image
[0019]
Among them, particularly, the charge transporting polymer compound having a biphenyl structure represented by the following structural formulas (VII) and (VIII) is described in "The Sixth International Congress on Advances in Non-impact Printing Technologies, 306, (1990). It has high mobility and practicality as reported in
Embedded image
T in the repeating structural unit containing at least one of the partial structures represented by the general formula (I-1) or (I-2) is a divalent hydrocarbon having 1 to 10 carbon atoms which may be branched. And the following groups are specifically exemplified.
Embedded image
Embedded image
Specific examples of the charge transporting polymer compound used in the present invention will be shown. The following Tables 1 to 5 show specific examples of the partial structure represented by the general formula (I-1), and Tables 6 to 10 show specific examples of the partial structure represented by the general formula (I-2). Tables 11 to 12 show specific examples of the charge transporting polymer compound represented by the general formula (II). Table 13 shows specific examples of the charge transporting polymer compound represented by the general formula (III). Table 14 shows specific examples of the charge transporting polymer compound represented by the general formula (IV), and Table 15 shows specific examples of the charge transporting polymer compound represented by the general formula (V).
The arylamine skeleton may be bonded to either side. Are bound to each other.
[0023]
Examples of the structure represented by the general formula (I-1)
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
Example of structure represented by general formula (I-2)
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
Examples of the charge transporting polymer compound represented by the general formula (II)
[Table 11]
[Table 12]
Examples of the charge transporting polymer compound represented by the general formula (III)
[Table 13]
Examples of the charge transporting polymer compound represented by the general formula (IV)
[Table 14]
Examples of the charge transporting polymer compound represented by the general formula (V)
[Table 15]
Hereinafter, the electronic device of the present invention will be described in detail focusing on an electrophotographic photosensitive member having a function-separated type laminated structure.
Examples of the conductive support include metals such as aluminum, nickel, chromium, and stainless steel, and plastics provided with thin films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, and ITO. Or a paper coated with or impregnated with a conductivity-imparting agent, and a plastic film. These conductive supports are used in the form of a drum, a sheet, a plate, or an appropriate shape, but are not limited thereto. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment, chemical treatment, coloring treatment, or the like, or irregular reflection treatment such as graining can be performed.
[0039]
Further, an undercoat layer may be further provided between the conductive support and the charge generation layer. The undercoating layer prevents the injection of electric charge from the conductive support to the photosensitive layer when the photosensitive layer having the laminated structure is charged, and also bonds the photosensitive layer integrally to the conductive support. It acts as a layer, or in some cases, as an adhesive layer that is integrally adhered to and held on the conductive support, or in some cases, acts to prevent light reflection from the conductive support.
[0040]
As the binder resin used for the undercoat layer, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, Polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide compound, zirconium chelate Known materials such as compounds, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents can be used. These materials can be used alone or in combination of two or more.
In addition, these materials can be used by mixing fine particles such as titanium oxide, silica, zirconium oxide, barium titanate, and silicone resin. The thickness of the undercoat layer is in the range of 0.01 to 10 μm, preferably 0.05 to 2 μm. Further, as an application method used for providing the undercoat layer, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc. Can be adopted.
[0041]
In the charge generation layer, inorganic photoconductive materials such as amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide and titanium oxide, and phthalocyanine Organic pigments and dyes such as a system, a squarium system, an anthrone system, a perylene system, an azo system, an anthraquinone system, a pyrene system, a pyrylium system, and a thiapyrylium system are used. Hydroxygallium phthalocyanine crystal, titanyl phthalocyanine crystal and the like are preferable.
Examples of the binder resin used for the charge generation layer include polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polycarbonate resin, polyester resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, and vinyl chloride-acetic acid. Examples include, but are not limited to, vinyl copolymers, silicone resins, phenol resins, poly-N-vinyl carbazole resins, and the like. These binder resins can be used alone or in combination of two or more.
[0042]
The compounding ratio (weight ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10. The thickness of the charge generation layer is generally set in the range of 0.1 to 5 μm, preferably 0.2 to 2.0 μm. As a coating method, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used.
Further, as a solvent used when providing the charge generation layer, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane And ordinary organic solvents such as tetrahydrofuran, methylene chloride and chloroform, and these can be used alone or as a mixture of two or more.
[0043]
In the present invention, a charge transporting polymer compound having a total metal content of 50 ppm or less, preferably 10 ppm or less, more preferably 1 ppm or less is used for the charge transport layer.
Estimation from the ash content is easy to measure simultaneously the contents of all metals contained in the charge transporting polymer compound, but the reliability of the quantitative value is low and the required sample is large. Required. Therefore, it is a metal species that greatly affects the electrical properties, that is, a metal simple substance, a metal carbonate, an acetate, an oxide or an organometallic compound, and is a catalyst for a transesterification reaction or a polycondensation reaction. It is preferable that the analysis is performed focusing on Al, Ca, Sb, Ga, Ge, Mg, Mn, Tl, Zn, and Zr, which have an action. As an analysis method therefor, it is desirable to use an induction plasma emission analysis method, an atomic absorption method, an X-ray fluorescence method, or the like in order to achieve both accuracy and economy. In particular, the induction plasma emission analysis method uses a variety of metals simultaneously. Species can be quantified, and it is a suitable analysis method in terms of sensitivity, quantification, and the like.
[0044]
In the present invention, as the charge transporting polymer compoundIs mainly a partial structure represented by the formula (I-1) or (I-2).Polycarbonates, polyesters, polyurethanes, and the like containing in the chain are used. In particular, by using the charge-transporting polymer compound represented by the above formulas (II) to (V), electrophotography having excellent electrical and mechanical properties is obtained. A photoreceptor can be obtained.
[0045]
In the case of a charge-transporting polymer compound in which a charge-transporting substituent is pendant, it can be formed by radical polymerization as a polymerization method, and has an advantage that contamination by a metal element hardly occurs. I have. However, in the polymerization method using metal salts found in living anionic polymerization, etc., the greatest attention must be paid not only to polymerization reaction conditions, but also to impurities from raw materials, various solvents used in each step, contamination from containers, piping, etc. is necessary. In terms of electrical properties and mechanical strength, those having a charge transporting function in the main chain, among which polycarbonate and polyester are excellent, are suitably used for the electronic device of the present invention, particularly, the electrophotographic photoreceptor.
When the charge-transporting polymer compound is a polycarbonate or a polyester, for example, a method of polymerizing with phosgene to obtain a polycarbonate is a method in which contamination by a metal element is essentially unlikely to occur, but from the viewpoint of safety and economy. Therefore, a method based on a transesterification reaction is often used industrially. Therefore, contamination due to residual catalyst is inevitable, and it is necessary to manufacture the catalyst without causing contamination.
[0046]
In the present invention, the above-mentioned charge transporting polymer compound may be used alone or in combination of two or more kinds. However, the repeating structural units represented by the above formulas (VI-1) to (VI-8) may be used. It is preferable to use a mixture of a polycarbonate or a polycarbonate resin-polysiloxane copolymer having properties that the charge transporting polymer compound does not have, such as high surface lubricity. In this case, the compounding ratio is preferably in the range of 5: 1 to 1: 1 by weight.
[0047]
The charge-transporting layer is a mixture of the charge-transporting polymer compound described above or a polycarbonate or a polycarbonate resin-polysiloxane copolymer having the repeating structural units represented by the above formulas (VI-1) to (VI-8). Is dissolved in an appropriate solvent, applied, and dried. Examples of the solvent used for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenated compounds such as methylene chloride, chloroform and ethylene chloride. Aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran, dioxane, and ethylene glycol diethyl ether, or a mixed solvent thereof can be used.
[0048]
As a coating method used for providing the charge transport layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like is employed. can do. The thickness of the charge transport layer is in the range of 2 to 100 μm, and preferably in the range of 10 to 40 μm.
[0049]
Further, additives such as an antioxidant and a light stabilizer can be added to the charge transport layer for the purpose of preventing the photoreceptor from deteriorating due to light, heat and the like. Examples of the antioxidant include hindered phenols, hindered amines, paraphenylenediamine derivatives, arylalkanes, hydroquinone derivatives, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. These additives may be used alone or as a mixture, but may be added in the range of 0.01 to 20% by weight, preferably 0.1 to 10% by weight based on the weight of the charge transporting polymer compound.
[0050]
In addition, for the main purpose of obtaining good surface properties, additives known as modifiers for paints can be added. For example, dimethyl-based polysiloxane (dimethylsilicone oil), methylphenyl-based polysiloxane (methylphenylsilicone oil) and the like are preferable examples. In addition, modified silicone oils such as alkyl-modified, alkoxy-modified, alkylallyl-modified, glycol-modified, alcohol-modified, epoxy-modified, methylstyryl-modified, higher fatty acid-modified, higher alkoxy-modified, polyether-modified, etc., which are obtained by partially modifying these polysiloxanes Is also a preferred example, and is added in the range of 1 to 10,000 ppm, preferably 5 to 2,000 ppm, based on the solid content of the charge transport layer.
Further, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue when repeatedly used, and the like. For example, succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, tri Nitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like can be used.
The above-mentioned charge transport layer in the present invention can be provided on the charge transport layer containing another low-molecular charge transport material, and can also function as a protective layer.
[0051]
In this case, the low-molecular-weight charge transporting material used for the lower charge transporting layer includes oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, Derivatives, such as 1,5-triphenylpyrazoline, aromatic tertiary amino compounds such as triphenylamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'- Aromatic tertiary diamino compounds such as biphenyl] -4,4'-diamine; 3- (4'-diethylaminophenyl) -5,6-di (4'-methoxyphenyl) -1,2,4-triazine; 1,2,4-triazine derivatives, hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1'-diphenylhydrazone, quinazos such as 2-phenyl-4-styrylquinazoline Derivatives, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran, α-stilbene derivatives such as p- (2,2′-diphenylvinyl) -N, N-diphenylaniline, etc. can give.
Examples of the binder resin include (modified) polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and vinyl chloride. -Vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin and the like can be used.
[0052]
This charge transporting layer can be provided in the same manner as in the case of using the charge transporting polymer compound or a mixture thereof with the polycarbonate resin or the polycarbonate-polysiloxane copolymer. The ratio of the binder resin is preferably in the range of 10: 1 to 1: 5 by weight, and the thickness thereof is generally set in the range of 5 to 50 μm, preferably 10 to 30 μm.
In the case where the charge transport layer is provided, the thickness of the protective layer formed using the charge transport polymer compound provided thereon is 1 to 200% of the thickness of the charge transport layer, preferably 5 to 200%. It is set in the range of １００100%.
[0053]
Next, an image forming apparatus using the contact charging system of the present invention will be described. In the image forming apparatus of the present invention, the above-described electrophotographic photoreceptor is used as a photoreceptor, but a conductive member is provided so as to be in contact with the surface of the photoreceptor for performing contact charging. The conductive member may have any shape such as a brush shape, a blade shape, a pin electrode shape, and a roller shape, but among them, a roller-shaped conductive member is preferably used. Usually, the roller-shaped member is composed of a resistance layer, an elastic layer supporting them and a core material from the outside. If necessary, a protective layer can be provided outside the resistance layer.
[0054]
The material of the core material has conductivity, and generally, iron, copper, brass, stainless steel, aluminum, nickel or the like is used. Further, a resin molded product or the like in which other conductive fine particles or the like are dispersed can be used. The elastic layer is made of a material having conductivity or semi-conductivity. Generally, a material in which conductive particles or semi-conductive particles are dispersed in a rubber material is used. Examples of the rubber material include EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, and ethylene oxide rubber. Examples of the conductive particles or semiconductive particles include metals such as carbon black, zinc, aluminum, copper, iron, nickel, chromium, and titanium, and ZnO-Al2O3, SnO2-Sb2O3, In2O3-SnO2, ZnO-TiO2, MgO-Al2O3, FeO-TiO2, TiO2, SnO2, Sb2O3, In2O3, ZnO, MgO, and other metal oxides can be used. These materials may be used alone or as a mixture of two or more kinds. In the case of two or more kinds, one of them may be fine particles, and the fine particles of a fluororesin may be used as the fine particles.
[0055]
The material of the resistance layer and the protective layer is a material in which conductive particles or semiconductive particles are dispersed in a binder resin and the resistance thereof is controlled.3-1014Ωcm, preferably 105-1012Ωcm, more preferably 107-1012A range of Ωcm is employed. The thickness is in the range of 0.01 to 1000 μm, preferably 0.1 to 500 μm, and more preferably 0.5 to 100 μm.
As the binder resin, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl chloride resin, polyarylate resin, polythiophene resin, polyethylene Examples thereof include polyester resins such as tetraphthalate, polyolefin resins, and styrene-butadiene resins.
[0056]
As the conductive particles or semiconductive particles, the same carbon black, metal, metal oxide, and the like as in the case of the elastic layer are used.
If necessary, antioxidants such as hindered phenol and hindered amine, fillers such as clay and kaolin, and lubricants such as silicone oil can be added. As means for forming these layers, a blade coating method, a wire coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, a vacuum deposition method, a plasma coating method, or the like is used. be able to.
[0057]
When charging the photoreceptor using these conductive members, a voltage is applied to the conductive members. Preferably, the applied voltage is obtained by superimposing an AC voltage on a DC voltage. Is difficult.
As for the range of the voltage, the DC voltage is preferably in the range of 50 to 2000 V, positive or negative, and more preferably in the range of 100 to 1500 V. As a superimposed AC voltage, a peak-to-peak voltage in a range of 400 to 1800 V, preferably 800 to 1600 V, and more preferably 1200 to 1800 V is employed. When the peak-to-peak voltage exceeds 1800 V, uniform charging cannot be obtained as compared with a case where no AC voltage is superimposed. The frequency of the AC voltage is preferably in the range of 100 to 2000 Hz.
[0058]
【Example】
Hereinafter, the present invention will be described with reference to examples. “Parts” means “parts by weight”.
Synthesis Example 1 (Synthesis of Exemplified Compound (7))
3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl]- 20 g of 4,4'-diamine, 40 g of ethylene glycol, and 3.0 g of tetrabutoxytitanium were put in a 500 ml flask, and heated and refluxed for 3 hours under a nitrogen stream. 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl]- After confirming that 4,4′-diamine was consumed, the pressure was reduced to 0.5 mmHg, and the mixture was heated to 230 ° C. while distilling off ethylene glycol, and the reaction was continued for 4 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 500 ml of methylene chloride, insolubles were filtered, and the filtrate was dropped into 2500 ml of ethanol while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with ethanol, and then dried to obtain 18 g of a polymer. When the molecular weight was measured by GPC, Mw = 1.6 × 105(In terms of styrene), and the degree of polymerization p determined from the monomer was about 215.
The amount of Ti remaining in the obtained polymer was quantified by the following method. That is, 250 mg of a sample was weighed and placed in a 25 ml volumetric flask, and dissolved in chloroform to prepare a solution diluted to three lines. The amount of Ti in this solution was measured using a high-frequency inductively coupled plasma emission spectrometer (SPS1200VR type, manufactured by Seiko Instruments Inc.) using a chloroform solution of tetra-n-butyl orthotitanate (Ti content 13.95%) as a standard. It was measured as a solution, and the amount of Ti in the original polymer was determined. The result was 260 μg (260 ppm) per 1 g of the polymer.
[0059]
Synthesis Example 2
A polymer was obtained in the same manner as in Synthesis Example 1 except that a polymer was precipitated by dropping into 2500 ml of ethanol and then further dissolved in 500 ml of THF and dropped into 2500 ml of distilled water in Synthesis Example 1. Was. The Ti content was 180 ppm.
Synthesis Example 3
A polymer was obtained in the same manner as in Synthesis Example 1, except that 3.0 g of tetrabutoxytitanium in Synthesis Example 1 was changed to 0.5 g. The Ti content was 66 ppm.
Synthesis Example 4
In Synthesis Example 2, a polymer was obtained in the same manner as in Synthesis Example 2 except that 3.0 g of tetrabutoxytitanium was changed to 0.5 g. The Ti content was 45 ppm.
Synthesis Example 5
A polymer was obtained in the same manner as in Synthesis Example 1, except that 3.0 g of tetrabutoxytitanium in Synthesis Example 1 was changed to 0.1 g. The Ti content was 6.8 ppm.
Synthesis Example 6
In Synthesis Example 5, a solution of 500 ml of methylene chloride was mixed and stirred with 500 ml of a 1N aqueous sodium hydroxide solution, allowed to stand, the aqueous solution was removed, further mixed with 500 ml of 1N dilute hydrochloric acid, stirred, and allowed to stand. Removed, further mixed and stirred with 500 ml of distilled water, allowed to stand, and allowed to stand. After removing the aqueous solution, 2500 ml of ethanol was added dropwise to precipitate a polymer. Obtained. The Ti content was 0.6 ppm.
[0060]
Synthesis Example 7 (Synthesis of Exemplified Compound (39))
3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl]- 15 g of 4,4'-diamine, 3.0 g of dimethyl sebacate, 30 g of ethylene glycol and 1.0 g of trimethoxygallium were placed in a 200 ml flask, and heated under reflux for 3 hours under a nitrogen stream. 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl]- After confirming that 4,4′-diamine was consumed, the pressure was reduced to 0.5 mmHg, and the mixture was heated to 230 ° C. while distilling off ethylene glycol, and the reaction was continued for 4 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 100 ml of methylene chloride, insolubles were filtered, and the filtrate was dropped into 1500 ml of acetone while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with ethanol, and then dried to obtain 17.5 g of a polymer. When the molecular weight was measured by GPC, Mw = 1.1 × 105(Styrene equivalent). (Polymerization degree p = about 120, r = about 90)
The amount of Ga measured by an induction plasma emission spectrometer (ICP) was 80 μg (80 ppm) per 1 g of the polymer.
[0061]
Synthesis Example 8
In Synthesis Example 7, a solution of 100 ml of methylene chloride was mixed and stirred with 100 ml of a 1N aqueous sodium hydroxide solution, allowed to stand, the aqueous solution was removed, and further mixed with 100 ml of 1N diluted hydrochloric acid, stirred, and allowed to stand. Removed, further mixed with 100 ml of distilled water, stirred and allowed to stand. After removing the aqueous solution, the polymer was dropped in 2500 ml of ethanol to add a step of precipitating the polymer. Obtained. The Ga content was 2.5 ppm per 1 g of the polymer.
[0062]
Comparative Example 1
A solution consisting of 10 parts of a zirconium compound (Orgatechx ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 1 part of a silane compound (A1110, manufactured by Nippon Unicar), 40 parts of i-propanol and 20 parts of butanol was coated on the aluminum pipe by dip coating. It was applied and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm. Next, 1 part of the x-type metal-free phthalocyanine crystal was mixed with 1 part of a polyvinyl butyral resin (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone, and dispersed by treating with glass beads for 1 hour using a sand mill. The obtained coating solution was applied onto the undercoat layer by a dip coating method, and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm. Next, 7 parts of the charge transporting polymer compound (exemplified compound (7)) obtained in Synthesis Example 1 was dissolved in a mixed solvent of 15 parts of monochlorobenzene and 15 parts of tetrahydrofuran, and the obtained coating solution was charged with the above-described charge. It was applied on the generating layer by a dip coating method and dried by heating at 115 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.
[0063]
Next, a stainless steel rod having a diameter of 6 mm was used as a core material, and a resistance of 10 mm was used as an elastic layer.6Ωcm conductive EPDM rubber and a resistance of 109A conductive roll having a diameter of 12 mm was formed using epichlorohydrin rubber of Ωcm.
The electrophotographic photoreceptor and the conductive roll obtained as described above were placed in a test apparatus (XP-11 modified machine, manufactured by Fuji Xerox Co., Ltd.) equipped with a surface electrometer (manufactured by Trek) at the developing machine position of a laser beam printer. ), And DC: 500 V, AC: 1500 V (peak-to-peak voltage) was applied to the conductive roll, and the surface potential corresponding to the solid black image at the position of the developing machine was measured.
Then, replace the surface voltmeter and the developing machine to collect the image, repeat printing 50,000 times, collect the image, evaluate the image quality, replace the developing machine and the surface voltmeter, and The surface potential corresponding to the solid black image at the position was measured. Table 16 shows the results.
Further, another electrophotographic photoreceptor was mounted on the same test apparatus as described above, which was modified from a laser printer (XP-11, manufactured by Fuji Xerox Co., Ltd.) having a normal scorotron charging method, and the same evaluation was performed. Table 17 shows the results.
[0064]
Comparative Example 2
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 2 was used for the charge transport layer, and the measurement was performed in the same manner.
Comparative Example 3
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 3 was used for the charge transport layer, and the measurement was performed in the same manner.
Example 1
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 4 was used for the charge transport layer, and the measurement was performed in the same manner.
Example 2
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 5 was used for the charge transport layer, and the measurement was performed in the same manner.
Example 3
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 6 was used for the charge transport layer, and the measurement was performed in the same manner.
Comparative Example 4
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 7 was used for the charge transport layer, and the measurement was performed in the same manner.
Example 4
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 8 was used for the charge transport layer, and the measurement was performed in the same manner.
[0065]
Comparative Example 5
A polycarbonate resin comprising 2 parts of the following benzidine compound and a repeating structural unit represented by the above structural formula (VI-2) (viscosity average molecular weight Mv = 4.0 × 1043) Electrophotography was performed in the same manner as in Comparative Example 1 except that a coating solution obtained by dissolving 3 parts in a mixture of 10 parts of monochlorobenzene and 10 parts of tetrahydrofuran was applied, and dried to form a charge transport layer. A body was prepared and evaluated similarly.
Embedded image
Comparative Example 6
In Comparative Example 1, a polycarbonate resin comprising 3 parts of the following hydrazone compound and a repeating structural unit represented by the above structural formula (VI-3) (viscosity average molecular weight Mv = 5.0 × 1043) An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that three parts were used, and the evaluation was performed in the same manner.
Embedded image
Example 5
On the charge transport layer of Comparative Example 1, Exemplified Compound 30 having a Ti content of 0.8 ppm (Mw = 1.4 × 105A) a polycarbonate resin comprising 2 parts and a repeating structural unit represented by the above structural formula (VI-2) (viscosity average molecular weight Mv = 4.0 × 1041) An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 1 except that a protective layer consisting of 1 part was formed, and evaluated in the same manner.
[0068]
[Table 16]
[Table 17]
【The invention's effect】
The electronic device of the present invention, having the above structure, has both good and stable electric characteristics and excellent mechanical characteristics, and can significantly reduce the instability of the electric characteristics which has been a problem in the past. . Further, the electrophotographic photoreceptor of the present invention can reduce the occurrence of image defects due to abrasion of the photosensitive layer and adhesion of foreign matter, as compared with a conventional one using a layer in which a charge transport material is dispersed in a binder resin. As a result, an image forming apparatus using a contact charging system with improved life and reliability is manufactured.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.
FIG. 2 is a schematic sectional view of another example of the electrophotographic photosensitive member of the present invention.
FIG. 3 is a schematic sectional view of another example of the electrophotographic photosensitive member of the present invention.
FIG. 4 is a schematic sectional view of another example of the electrophotographic photosensitive member of the present invention.
FIG. 5 is a schematic sectional view of another example of the electrophotographic photosensitive member of the present invention.
FIG. 6 is a schematic configuration diagram of an image forming apparatus of the present invention.
[Explanation of symbols]
DESCRIPTION OF
Claims (8)
を表し、ｓおよびｔは１〜３００の整数であって、ｓ／（ｓ＋ｔ）＝０．１〜０．９の範囲にあり、ｕは１〜２００の整数を表す。〕Wherein s and t are integers of 1 to 300, s / (s + t) = 0.1 to 0.9, and u represents an integer of 1 to 200. ]
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24514795A JP3584565B2 (en) | 1995-08-31 | 1995-08-31 | Electronic device and image forming apparatus |
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| Application Number | Priority Date | Filing Date | Title |
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| JP24514795A JP3584565B2 (en) | 1995-08-31 | 1995-08-31 | Electronic device and image forming apparatus |
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| JP3584565B2 true JP3584565B2 (en) | 2004-11-04 |
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| JP3890796B2 (en) * | 1999-01-25 | 2007-03-07 | 住友化学株式会社 | Polymer light emitting device |
| JP3599036B2 (en) * | 2002-03-14 | 2004-12-08 | 富士ゼロックス株式会社 | Charge transporting polymer |
| JP4752355B2 (en) * | 2005-06-27 | 2011-08-17 | 富士ゼロックス株式会社 | Diamine compound polymer having 1,3-phenylene group and charge transport material |
| JP4696928B2 (en) * | 2006-01-23 | 2011-06-08 | 富士ゼロックス株式会社 | Organic photoconductor for electrophotography and image forming apparatus using the same |
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