JP5147274B2 - Novel imide compound and electrophotographic photosensitive member, process cartridge and electrophotographic apparatus using the same - Google Patents
Novel imide compound and electrophotographic photosensitive member, process cartridge and electrophotographic apparatus using the same Download PDFInfo
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- JP5147274B2 JP5147274B2 JP2007092758A JP2007092758A JP5147274B2 JP 5147274 B2 JP5147274 B2 JP 5147274B2 JP 2007092758 A JP2007092758 A JP 2007092758A JP 2007092758 A JP2007092758 A JP 2007092758A JP 5147274 B2 JP5147274 B2 JP 5147274B2
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- Prior art keywords
- photosensitive member
- electrophotographic photosensitive
- electrophotographic
- resin
- layer
- Prior art date
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- -1 imide compound Chemical class 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 39
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Landscapes
- Photoreceptors In Electrophotography (AREA)
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Description
本発明は、新規なイミド化合物及びそれを用いた電子写真感光体、プロセスカートリッジ及び電子写真装置に関し、詳しくは中間層に新規なイミド化合物を有する電子写真感光体、該電子写真感光体を備えたプロセスカートリッジ及び電子写真装置に関する。 The present invention relates to a novel imide compound, an electrophotographic photoreceptor using the same, a process cartridge, and an electrophotographic apparatus, and more specifically, an electrophotographic photoreceptor having a novel imide compound in an intermediate layer, and the electrophotographic photoreceptor. The present invention relates to a process cartridge and an electrophotographic apparatus.
電子写真用感光体材料としては、正孔を輸送する正孔輸送材料、電子を輸送する電子輸送材料、電荷を発生する電荷発生材料、それらを成形し機械／電気的強度等を付与するバインダー樹脂、その他各種特性を付与する各種添加剤等が知られている。 Electrophotographic photoreceptor materials include hole transport materials that transport holes, electron transport materials that transport electrons, charge generation materials that generate charges, and binder resins that form them to give mechanical / electrical strength, etc. In addition, various additives that impart various other properties are known.
その中でも電子輸送材料は、有機太陽電池や有機発光素子などの各種エレクトロデバイスを作成する上も求められているが、溶解性や安定性等様々な難点があることが多く、実用化されている例は正孔輸送材料よりも少ないのが現状である。 Among them, electron transport materials are also required for making various electro devices such as organic solar cells and organic light-emitting elements, but are often put into practical use because they have various difficulties such as solubility and stability. There are fewer examples than hole transport materials.
その中でも、２−ニトロ−９−フルオレノン、２，７−ジニトロ−９−フルオレノン、２，４，７−トリニトロ−９−フルオレノン、２，４，５，７−テトラニトロ−９−フルオレノン、２−ニトロベンゾチオフエンなどが知られている。また、２，４，８−トリニトロチオキサントン、ジニトロアントラセン、ジニトロアクリジン、ジニトロアントラキノン、ナフトキノン類、３，５−ジメチル−３’，５’−ジｔ−ブチルジフェノキノンなどが知られている。その中で、ナフタレンテトラカルボン酸ジイミド骨格を有するイミド化合物は、有機発光デバイス（例えば特許文献１）や、エレクトロクロミック素子（例えば特許文献２）等、有機エレクトロニクス材料として知られている。また、ナフタレンテトラカルボン酸ジイミド骨格を有するイミド化合物は、電子輸送材料としても有望なものの一つであり、電子写真用材料としても広く知られている（例えば特許文献３及び特許文献４）。 Among them, 2-nitro-9-fluorenone, 2,7-dinitro-9-fluorenone, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2-nitro Benzothiophene and the like are known. Further, 2,4,8-trinitrothioxanthone, dinitroanthracene, dinitroacridine, dinitroanthraquinone, naphthoquinones, 3,5-dimethyl-3 ', 5'-di-t-butyldiphenoquinone and the like are known. Among them, an imide compound having a naphthalenetetracarboxylic acid diimide skeleton is known as an organic electronic material such as an organic light emitting device (for example, Patent Document 1) and an electrochromic element (for example, Patent Document 2). In addition, an imide compound having a naphthalenetetracarboxylic acid diimide skeleton is one of promising electron transport materials, and is widely known as an electrophotographic material (for example, Patent Document 3 and Patent Document 4).
電子写真感光体は、適用される電子写真プロセスに応じた感度、電気特性、光学特性及び画像欠陥がない高品位な画質が要求され、また、低温低湿から高温高湿のいずれの環境においてもその特性が十分に発揮されるような環境安定性を有していることが要求される。 An electrophotographic photosensitive member is required to have high image quality without sensitivity, electrical characteristics, optical characteristics and image defects according to the applied electrophotographic process, and in any environment of low temperature and low humidity to high temperature and high humidity. It is required to have environmental stability so that the characteristics are sufficiently exhibited.
画像欠陥の代表的なものとしては、画像スジ、白地部分の黒点、黒字部分の白点、白地部分の地カブリ等が挙げられる。更にはデジタル複写機やレーザービームプリンター等のレーザーダイオードを光源として露光を行う場合には、支持体の表面形状や感光体の膜厚ムラ等の要因によって発生する干渉縞等が挙げられる。 Typical image defects include image streaks, black spots on white portions, white spots on black portions, ground fog on white portions, and the like. Furthermore, when exposure is performed using a laser diode such as a digital copying machine or a laser beam printer as a light source, there may be interference fringes generated due to factors such as the surface shape of the support and the film thickness unevenness of the photoreceptor.
前記の画像欠陥を防止する方法として必要に応じて中間層が用いられる。中間層は、電子写真感光体に電圧を印加したとき支持体から電荷注入が起こらないように電気的ブロッキング機能が要求される。これは支持体から電荷注入があると、帯電能の低下、画像コントラストの低下や反転現像方式の場合は白地に黒点や地カブリの原因になり画質を著しく低下させる。 An intermediate layer is used as necessary as a method for preventing the image defects. The intermediate layer is required to have an electrical blocking function so that charge injection does not occur from the support when a voltage is applied to the electrophotographic photosensitive member. If there is charge injection from the support, the chargeability, image contrast, and reversal development method cause black spots and fogging on a white background, resulting in a significant decrease in image quality.
一方、中間層の電気的抵抗が高すぎると感光層で発生した電荷が感光層内部に滞留し、結果として残留電位の上昇や繰り返し使用による電位変動の原因になる。従って、電気的ブロッキング機能以外にも中間層の電気的抵抗値をある程度小さくする必要があり、前記ブロッキング機能や電気的抵抗特性が低温低湿から高温高湿のいずれの環境下においても大きく変化してはならない。 On the other hand, if the electrical resistance of the intermediate layer is too high, the charge generated in the photosensitive layer stays inside the photosensitive layer, resulting in an increase in residual potential and potential fluctuation due to repeated use. Therefore, in addition to the electrical blocking function, it is necessary to reduce the electrical resistance value of the intermediate layer to some extent, and the blocking function and electrical resistance characteristics change greatly in any environment from low temperature to low humidity to high temperature and high humidity. Must not.
中間層を形成する材料として例えばポリアミド（特許文献５、特許文献６及び特許文献７）、ポリエステル（特許文献８及び特許文献９）、ポリウレタン（特許文献１０及び特許文献１１）、カゼイン（特許文献１２）などが知られている。また、ポリペブチド（特許文献１３）、ポリビニルアルコール（特許文献１４）、ポリビニルピロリドン（特許文献１５）、酢酸ビニル−エチレン共重合体（特許文献１６）、無水マレイン酸エステル重合体（特許文献１７）などが知られている。また、ポリビニルブチラール（特許文献１８及び特許文献１９）、第四級アンモニウム塩含有重合体（特許文献２０及び特許文献２１）などが知られている。 Examples of the material for forming the intermediate layer include polyamide (Patent Literature 5, Patent Literature 6 and Patent Literature 7), polyester (Patent Literature 8 and Patent Literature 9), polyurethane (Patent Literature 10 and Patent Literature 11), and casein (Patent Literature 12). ) Etc. are known. Polypeptide (patent document 13), polyvinyl alcohol (patent document 14), polyvinylpyrrolidone (patent document 15), vinyl acetate-ethylene copolymer (patent document 16), maleic anhydride ester polymer (patent document 17), etc. It has been known. Also known are polyvinyl butyral (Patent Literature 18 and Patent Literature 19), quaternary ammonium salt-containing polymers (Patent Literature 20 and Patent Literature 21), and the like.
しかし、これら樹脂は多くの場合吸湿性が高く、外界の湿度により抵抗値も大きく変化し、樹脂単独で中間層を形成した場合、残留電位の増加や低温低湿下、高温高湿下の環境における感光体の電気特性の変動が生じ、画像欠陥の改善も十分でなかった。 However, these resins often have high hygroscopicity, and the resistance value changes greatly depending on the humidity of the outside world. When an intermediate layer is formed of the resin alone, the residual potential increases, in low temperature / low humidity, high temperature / high humidity environments. Variations in the electrical characteristics of the photoreceptor occurred, and image defects were not sufficiently improved.
そこで、抵抗値が環境変化に依存しにくい樹脂として、架橋性の樹脂を中間層に用いる提案もなされている。 Therefore, a proposal has been made to use a crosslinkable resin for the intermediate layer as a resin whose resistance value is less dependent on environmental changes.
例えばメラミン樹脂を用いる例（特許文献２２、特許文献２３及び特許文献２４）、フェノール樹脂を用いる例（特許文献２５）、エポキシ樹脂を用いる例（特開昭５２−１２１３２５号公報）などが知られている。しかし、筆者等の検討によれば、これらの方法も抵抗値の環境依存性は比較的小さいが絶対値が高く残留電位上昇の原因となったり、繰り返し使用の際に環境依存性が大きくなっていくなどの問題が生じる。 For example, an example using a melamine resin (Patent Literature 22, Patent Literature 23 and Patent Literature 24), an example using a phenol resin (Patent Literature 25), an example using an epoxy resin (Japanese Patent Laid-Open No. 52-121325), and the like are known. ing. However, according to the authors' study, these methods also have a relatively small resistance dependency on the environment, but the absolute value is high, causing a rise in residual potential, and the environment dependency becomes large during repeated use. Problems occur.
また、ポリナフチルイミド樹脂を有する中間層が提案されており（例えば特許文献２７）、低温低湿下から高温高湿下まで安定した電位特性が得られている。また、カルボン酸エステルを含有するナフタレンテトラカルボン酸ジイミドを含む中間層が提案されており（例えば特許文献２８）、非加水分解性重合基を持つ電子輸送材料を重合させた中間層が提案されている（例えば特許文献２９）。 In addition, an intermediate layer having a polynaphthylimide resin has been proposed (for example, Patent Document 27), and stable potential characteristics are obtained from low temperature and low humidity to high temperature and high humidity. An intermediate layer containing naphthalenetetracarboxylic acid diimide containing a carboxylic acid ester has been proposed (for example, Patent Document 28), and an intermediate layer obtained by polymerizing an electron transport material having a non-hydrolyzable polymerizable group has been proposed. (For example, Patent Document 29).
しかしながら、今日の電子写真技術の発展は著しく、電子写真感光体に求められる特性に対しても非常に高度な技術が要求されている。例えば、プロセススピードは年々速くなり、帯電特性、感度や耐久安定性などが求められるようになってきている。特に、近年ではカラー化に代表されるように高画質化がさけばれ、白黒画像が文字中心の画像だったものが、カラー化により、写真に代表されるハーフトーン画像やベタ画像が多くなっており、それらの画像品質は年々高まる一方である。また複数枚以上の連続印刷の頻度が増していることで、各印刷画像が高品質であるだけでなく、全ての画像の均一性も重要となっている。近年の高画質化、高耐久化に伴い、より優れた電位写真感光体を提供するためには様様な環境下における電位変動及び画像欠陥の問題をぜひ解決する必要があった。 However, the development of today's electrophotographic technology is remarkable, and very advanced technology is required for the characteristics required for electrophotographic photoreceptors. For example, process speeds are increasing year by year, and charging characteristics, sensitivity, durability stability, and the like have been demanded. In particular, in recent years, high-quality images have been avoided as represented by colorization, and black-and-white images that have been character-centered have become more and more halftone images and solid images represented by photographs. Their image quality is increasing year by year. Further, since the frequency of continuous printing of a plurality of sheets is increasing, not only the quality of each print image is high, but also the uniformity of all images is important. With the recent improvement in image quality and durability, it has been necessary to solve the problems of potential fluctuations and image defects under various environments in order to provide a more excellent electrophotographic photosensitive member.
現在、電子写真感光体に接触配置した帯電部材に直接電圧を印加し、電子写真感光体を帯電する接触帯電方式を採用した電子写真装置が広く普及している。 At present, an electrophotographic apparatus that employs a contact charging method in which a voltage is directly applied to a charging member arranged in contact with the electrophotographic photosensitive member to charge the electrophotographic photosensitive member is widely used.
特に帯電部材としてローラ形状の帯電部材を電子写真感光体表面に接触させ、直流電圧と交流電圧の重畳電圧を印加、あるいは、直流電圧のみを印加することにより電子写真感光体の帯電を行う方式が主流となっている。直流電圧と交流電圧を重畳させる場合、直流電源と交流電源が必要となり装置自体のコストアップを招くこと、直流電圧のみに比べ装置サイズが大きくなること、交流電流を多量に消費することにより帯電部材及び感光体の耐久性が低下する等のデメリットがある。従って、装置コスト削減、装置小型化及び高耐久性を考慮すると、直流電圧のみを印加する方式（ＤＣ帯電方式）がより好ましいと言える。しかしながら、ＤＣ帯電方式を用いた電子写真装置にあっては、直流電圧と交流電圧を重畳させる場合に比べて、帯電時の電子写真感光体表面電位の帯電均一性が劣る。このため、ハーフトーン画像等で帯電ムラに起因する電子写真感光体の長手方向のスジムラ状の不良画像（帯電スジ）が問題となっている。
本発明の目的は、感光層のはじき、ムラを生じず、帯電スジ及び低温低湿下における電位変動を抑制し、優れた画像を継続して形成し得る電子写真感光体を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member that does not cause repelling or unevenness of a photosensitive layer, can suppress charging stripes and potential variation under low temperature and low humidity, and can continuously form excellent images.
また、本発明のさらに他の目的は、上記電子写真感光体を備えたプロセスカートリッジ及び電子写真装置を提供することにある。 Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus provided with the electrophotographic photosensitive member.
本発明者は、塗工性及び帯電スジと電位変動の両者の改善を高いレベルで両立させることが可能な化合物の検討を行った結果、以下に説明する新規なイミド化合物の合成に成功し、このイミド化合物は、上記の特性を有することを見出した。 As a result of investigating a compound capable of achieving both improvement in coating properties and both charging stripes and potential fluctuations at a high level, the present inventors have succeeded in synthesizing a novel imide compound described below. It has been found that this imide compound has the above characteristics.
すなわち、本発明は、下記式（１）−１または（１）−３で示されるイミド化合物である。 That is, the present invention has the following formula (1) -1 or (1) - imide compound represented by 3.
また、本発明は、導電性支持体と、該導電性支持体上の中間層と、該中間層上の感光層とを有する電子写真感光体において、該中間層が、上記式（１）−１または（１）−３で示されるイミド化合物を含むことを特徴とする電子写真感光体である。 The present invention also provides an electrophotographic photosensitive member having a conductive support, an intermediate layer on the conductive support, and a photosensitive layer on the intermediate layer, wherein the intermediate layer has the formula (1)- 1. An electrophotographic photosensitive member comprising an imide compound represented by 1 or (1) -3 .
また、本発明は、上記電子写真感光体を備えたプロセスカートリッジ及び電子写真装置である。 The present invention also provides a process cartridge and an electrophotographic apparatus provided with the electrophotographic photosensitive member.
本発明のイミド化合物を含有する感光体がこのような優れた特性を有する理由は、明らかではないが、種々のイミド化合物の中で本発明の構造が特に優れた特性を示すことから、次のことが予想される。置換基の配置が重要と考えられ、イミド化合物とバインダー樹脂との相互作用、界面で接する電荷発生層との何らかの相互作用の結果である。 The reason why the photoreceptor containing the imide compound of the present invention has such excellent characteristics is not clear, but the structure of the present invention exhibits particularly excellent characteristics among various imide compounds. It is expected that. The arrangement of substituents is considered important and is the result of some interaction between the imide compound and the binder resin and the charge generation layer in contact with the interface.
イミド化された２つの置換基の構造が大きく異なる非対称体が優れた特性を示し、特に、一方がイミドに対する２つのｏ位がアルキル置換されたフェニルであり、もう一方が水酸基を持つアルキルであるイミド化合物が優れた特性を示した。 Asymmetries with greatly different structures of the two imidized substituents show excellent properties, in particular, one is an alkyl-substituted phenyl at the two o positions relative to the imide and the other is an alkyl with a hydroxyl group. The imide compound showed excellent properties.
本発明の新規なイミド化合物は、感光層のはじき、ムラを生じず、帯電スジ及び低温低湿下における電位変動を抑制し、優れた画像を継続して形成し得る電子写真感光体を可能にした。また、本発明は、上記電子写真感光体を備えたプロセスカートリッジ及び電子写真装置を可能にした。 The novel imide compound of the present invention enables an electrophotographic photoreceptor capable of continuously forming excellent images without causing repelling or unevenness of the photosensitive layer, suppressing charging stripes and potential fluctuations under low temperature and low humidity. . The present invention also enables a process cartridge and an electrophotographic apparatus provided with the electrophotographic photosensitive member.
以下、本発明の電子写真感光体について詳細に説明する。 Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail.
本発明に用いられる導電性支持体としては、アルミニウム、ニッケル、銅、金、鉄等の金属または合金、ポリエステル、ポリカーボネート、ポリイミド等が例示できる。また、ガラス等の絶縁性支持体上にアルミニウム、銀、金等の金属あるいは酸化インジウム、酸化スズ等の導電材料の薄膜を形成したもの、カーボンや導電性フィラーを樹脂中に分散し導電性を付与したもの等が例示できる。これらの支持体表面は、電気的特性改善あるいは密着性改善のために、陽極酸化等の電気化学的な処理を行った支持体を用いることもできる。また、導電性支持体表面をアルカリリン酸塩あるいはリン酸やタンニン酸を主成分とする酸性水溶液に金属塩の化合物またはフッ素化合物の金属塩を溶解してなる溶液で化学処理を施したものを用いることもできる。 Examples of the conductive support used in the present invention include metals or alloys such as aluminum, nickel, copper, gold, and iron, polyester, polycarbonate, and polyimide. In addition, a thin film of a conductive material such as indium oxide or tin oxide formed on a metal such as aluminum, silver or gold on an insulating support such as glass, carbon or conductive filler is dispersed in the resin to make it conductive. Examples can be given. For the surface of these supports, a support that has been subjected to an electrochemical treatment such as anodization can be used in order to improve electrical characteristics or adhesion. Also, the surface of the conductive support is chemically treated with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution mainly composed of alkali phosphate or phosphoric acid or tannic acid. It can also be used.
また、単一波長のレーザー光等を用いたプリンターに本電子写真感光体を用いる場合には、干渉縞を抑制するために導電性支持体はその表面を適度に粗しておくことが必要である。具体的には、上記支持体表面をホーニング、ブラスト、切削、電界研磨等の処理をした支持体もしくはアルミニウム及びアルミニウム合金上に導電性金属酸化物及びバインダー樹脂からなる導電性皮膜を有する支持体を用いることが必要である。 In addition, when the electrophotographic photosensitive member is used in a printer using a single wavelength laser beam or the like, the surface of the conductive support needs to be appropriately roughened in order to suppress interference fringes. is there. Specifically, a support having a surface of the support subjected to honing, blasting, cutting, electropolishing, or the like, or a support having a conductive film made of a conductive metal oxide and a binder resin on aluminum and an aluminum alloy is provided. It is necessary to use it.
ホーニング処理としては、乾式及び湿式での処理方法があるがいずれを用いてもよい。湿式ホーニング処理は、水等の液体に粉末状の研磨剤を懸濁させ、高速度で支持体表面に吹き付けて粗面化する方法であり、表面粗さは吹き付け圧力、速度、研磨剤の量、種類、形状、大きさ、硬度、比重及び懸濁温度等により制御することができる。同様に、乾式ホーニング処理は、研磨剤をエアーにより、高速度で導電性支持体表面に吹き付けて粗面化する方法であり、湿式ホーニング処理と同じように表面粗さを制御することができる。これら湿式または乾式ホーニング処理に用いる研磨剤としては、炭化ケイ素、アルミナ、鉄及びガラスビーズ等の粒子が挙げられる。 As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing process is a method in which a powdered abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity, suspension temperature and the like. Similarly, the dry honing process is a method in which an abrasive is sprayed onto the surface of the conductive support with air at a high speed to roughen the surface, and the surface roughness can be controlled in the same manner as the wet honing process. Examples of the abrasive used in these wet or dry honing processes include particles such as silicon carbide, alumina, iron and glass beads.
導電性金属酸化物及びバインダー樹脂からなる導電性皮膜をアルミニウムやアルミニウム合金の支持体に塗布し導電性支持体とする方法では、導電性皮膜中にはフィラーとして、導電性微粒子からなる粉体を含有する。この方法では、微粒子を皮膜中に分散させることでレーザー光を乱反射させ干渉縞を防ぐと共に塗布前の支持体の傷や突起等を隠蔽する効果もある。微粒子には酸化チタンや硫酸バリウム等が用いられ、必要によってはこの微粒子に酸化錫等で導電性被覆層を設けることにより、フィラーとして適切な比抵抗としている。導電性微粒子粉体の比抵抗は０．１Ω・ｃｍ以上１０００Ω・ｃｍ以下が好ましく、更には１Ω・ｃｍ以上１０００Ω・ｃｍ以下が好ましい。粉体比抵抗は三菱化学社製の抵抗測定装置ロレスタＡＰ（Loresta Ap）を用いて測定した。測定対象の粉体は、４９ＭＰａ（５００ｋｇ／ｃｍ２）の圧力で固めてコイン状のサンプルとして上記測定装置に装着した。微粒子の平均粒径は０．０５μｍ以上１．０μｍ以下が好ましく、更には０．０７μｍ以上０．７μｍ以下が好ましい。微粒子の平均粒径は遠心沈降法により測定した値である。フィラーの含有量は、導電性皮膜層に対して１．０質量％以上９０質量％以下が好ましく、更には５．０質量％以上８０質量％以下が好ましい。被覆層には、必要に応じてフッ素あるいはアンチモンを含有してもよい。 In the method of applying a conductive film made of a conductive metal oxide and a binder resin to an aluminum or aluminum alloy support to make a conductive support, a powder made of conductive fine particles is used as a filler in the conductive film. contains. This method has the effect of dispersing the fine particles in the film to diffusely reflect the laser beam to prevent interference fringes and conceal the scratches and protrusions of the support before coating. Titanium oxide, barium sulfate, or the like is used for the fine particles. If necessary, a conductive coating layer is provided on the fine particles with tin oxide or the like, so that a specific resistance suitable as a filler is obtained. The specific resistance of the conductive fine particle powder is preferably 0.1 Ω · cm to 1000 Ω · cm, more preferably 1 Ω · cm to 1000 Ω · cm. The specific resistance of the powder was measured using a resistance measuring device Loresta AP manufactured by Mitsubishi Chemical Corporation. The powder to be measured was hardened at a pressure of 49 MPa (500 kg / cm 2 ) and mounted as a coin-shaped sample on the measuring device. The average particle size of the fine particles is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.07 μm or more and 0.7 μm or less. The average particle diameter of the fine particles is a value measured by a centrifugal sedimentation method. The content of the filler is preferably 1.0% by mass or more and 90% by mass or less, and more preferably 5.0% by mass or more and 80% by mass or less with respect to the conductive film layer. The coating layer may contain fluorine or antimony as necessary.
導電性皮膜に用いられるバインダー樹脂としては、例えば、フェノール樹脂、ポリウレタン、ポリアミド、ポリイミド、ポリアミドイミド、ポリアミド酸、ポリビニールアセタール、エポキシ樹脂、アクリル樹脂、メラミン樹脂あるいはポリエステル等が好ましい。これらの樹脂は単独でも、二種以上を組み合わせて用いてもよい。これらの樹脂は、支持体に対する接着性が良好であると共に、使用するフィラーの分散性を向上させ、かつ成膜後の耐溶剤性が良好である。上記樹脂の中でも特にフェノール樹脂、ポリウレタン及びポリアミド酸が好ましい。 As the binder resin used for the conductive film, for example, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, or polyester is preferable. These resins may be used alone or in combination of two or more. These resins have good adhesion to the support, improve the dispersibility of the filler used, and have good solvent resistance after film formation. Among the above resins, phenol resin, polyurethane and polyamic acid are particularly preferable.
導電性皮膜は、例えば浸漬あるいはマイヤーバー等による溶剤塗布で形成することができる。導電性皮膜の厚みは０．１μｍ以上３０μｍ以下が好ましく、更には０．５μｍ以上２０μｍ以下が好ましい。また、導電性皮膜の体積抵抗率は１０１３Ω・ｃｍ以下が好ましく、更には１０１２Ω・ｃｍ以下１０５Ω・ｃｍ以上が好ましい。本発明において、体積抵抗率はアルミニウム板上に測定対象の導電性皮膜を塗布し、更にこの皮膜上に金の薄膜を形成して、アルミニウム板と金薄膜の両電極間を流れる電流値をｐＡメーターで測定して求めた。導電性皮膜には、被覆層を有する硫酸バリウム微粒子からなる粉体以外に、酸化亜鉛や酸化チタン等の粉体からなるフィラーを含有してもよい。更に、表面性を高めるためにレベリング剤を添加してもよい。 The conductive film can be formed, for example, by dipping or solvent application with a Meyer bar or the like. The thickness of the conductive film is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 20 μm or less. The volume resistivity of the conductive film is preferably 10 13 Ω · cm or less, more preferably 10 12 Ω · cm or less and 10 5 Ω · cm or more. In the present invention, the volume resistivity is obtained by applying a conductive film to be measured on an aluminum plate, further forming a gold thin film on the film, and calculating the current value flowing between both electrodes of the aluminum plate and the gold thin film as pA. It was determined by measuring with a meter. The conductive film may contain a filler made of powder such as zinc oxide or titanium oxide in addition to the powder made of barium sulfate fine particles having a coating layer. Furthermore, a leveling agent may be added to enhance the surface property.
導電性支持体の形状は、特に制約はなく必要に応じて板状、ドラム状またはベルト状のものが用いられる。 The shape of the conductive support is not particularly limited, and a plate shape, a drum shape or a belt shape is used as necessary.
本発明に用いられる中間層は必要に応じて、接着機能及びバリアー機能を有するバインダー樹脂を含有させてもよい。バインダー樹脂としてはポリアミド、ポリビニルアルコール、ポリエチレンオキシド、エチルセルロース、カゼイン、ポリウレタン及びポリエーテルウレタンなどの熱可塑性樹脂が挙げられる。また、メラミン樹脂、フェノール樹脂、アルキド樹脂、エポキシ樹脂やシランカップリング剤、有機金属錯体などの熱硬化性の材料が挙げられる。 The intermediate layer used in the present invention may contain a binder resin having an adhesive function and a barrier function, if necessary. Examples of the binder resin include thermoplastic resins such as polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. Moreover, thermosetting materials, such as a melamine resin, a phenol resin, an alkyd resin, an epoxy resin, a silane coupling agent, and an organometallic complex, are mentioned.
バインダー樹脂としては、ポリアミド樹脂、アルキレン主鎖及び側鎖にイソシアネート基を持つ繰り返し単位ユニットを有する樹脂が特に好ましい。該繰り返し単位ユニットを有する樹脂としては、下記式（Ａ）で示される繰り返し単位ユニットを有し、スチレン、メチルメタクリレート、ベンジルメタクリレートなどのビニルモノマーとの共重合体であることが好ましい。 As the binder resin, a polyamide resin and a resin having a repeating unit unit having an isocyanate group in the alkylene main chain and side chain are particularly preferable. The resin having the repeating unit is preferably a copolymer having a repeating unit represented by the following formula (A) and a vinyl monomer such as styrene, methyl methacrylate or benzyl methacrylate.
（式（Ａ）中、Ｒ２１は水素原子または置換基を有してもよいアルキル基もしくはアリール基を示す。Ｒ２２は炭素数１以上のエーテル基で中断されていてもよいアルキル基、エーテル基で中断されていてもよいアルケニル基、複素環基を示す。またはＲ２２はアルキル基もしくはアルケニル基もしくはニトロ基もしくはハロゲン基もしくはハロゲン置換アルキル基を有してもよいアリール基を示す。またはＲ２２はアルキル基もしくはアルケニル基もしくはニトロ基もしくはハロゲン基もしくはハロゲン置換アルキル基を有してもよいアラルキル基を示す。） (In the formula (A), R 21 represents a hydrogen atom or an optionally substituted alkyl group or aryl group. R 22 represents an alkyl group or ether optionally interrupted by an ether group having 1 or more carbon atoms. R 22 represents an alkyl group, an alkenyl group, a nitro group, a halogen group, or an aryl group which may have a halogen-substituted alkyl group, or R which may be interrupted by a group, or R. 22 represents an aralkyl group which may have an alkyl group, an alkenyl group, a nitro group, a halogen group or a halogen-substituted alkyl group.
この式（Ａ）で示される繰り返し単位ユニットを有する樹脂における、該繰り返し単位ユニットの樹脂全体に対する比は１０モル％以上９０モル％以下が好ましく、樹脂の分子量は１０００以上２０００００以下であることが好ましい。 In the resin having the repeating unit represented by the formula (A), the ratio of the repeating unit to the whole resin is preferably 10 mol% or more and 90 mol% or less, and the molecular weight of the resin is preferably 1000 or more and 200000 or less. .
本発明のイミド化合物は、下記式（１）−１または（１）−３で示される非対称イミド化合物である。 The imide compound of the present invention is an asymmetric imide compound represented by the following formula (1) -1 or (1) -3 .
本発明において中間層には、上記イミド化合物及びその重合物の一方または両方が含まれる。イミド化合物及びその重合物は中間層全体に対して５質量％以上９５質量％以下が好ましく、より好ましくは１０質量％以上８０質量％以下の範囲、更に好ましくは３０質量％以上７０質量％以下である。 In the present invention, the intermediate layer contains one or both of the imide compound and a polymer thereof. The imide compound and the polymer thereof are preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less with respect to the entire intermediate layer. is there.
上記材料は、適当な溶剤に溶解して塗布され、中間層の膜厚は０．０５μｍ以上５μｍ以下が好ましく、特には０．３μｍ以上３μｍ以下が好ましい。 The above material is applied after being dissolved in a suitable solvent, and the film thickness of the intermediate layer is preferably 0.05 μm or more and 5 μm or less, and particularly preferably 0.3 μm or more and 3 μm or less.
次に、イミド化合物の例を挙げる。Next, the example of an imide compound is given.
本発明に用いられる電荷発生材料として、ピリリウム系染料、チオピリリウム系染料、フタロシアニン系顔料、アントアントロン系顔料、ジベンズピレンキノン系顔料、ピラトロン系顔料、アゾ系顔料、インジゴ系顔料、キナクリドン系顔料等が挙げられる。また、キノシアニン系染料等が挙げられる。フタロシアニン系顔料としては、無金属フタロシアニンや、オキシチタニウムフタロシアニン、ヒドロキシフタロシアニン、及びクロロガリウム等のハロゲン化ガリウムフタロシアニン等が挙げられる。特に、金属フタロシアニン顔料が好ましく、その中でも、オキシチタニウムフタロシアニン結晶、クロロガリウムフタロシアニン結晶、ジクロロスズ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が好ましい。更に、ヒドロキシガリウムフタロシアニン結晶が特に好ましい。オキシチタニウムフタロシアニン結晶としては、ＣｕＫαを線源とするＸ線回折において、ブラッグ角度（２θ±0.2°）の9.0°、14.2°、23.9°及び27.1°に強いピークを有するオキシチタニウムフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の9.5°、9.7°、11.7°、15.0°、23.5°、24.1°及び27.3°に強いピークを有するオキシチタニウムフタロシアニン結晶が好ましい。クロロガリウムフタロシアニン結晶としては、ＣｕＫαを線源とするＸ線回折において、ブラッグ角度（２θ±0.2°）の7.4°、16.6°、25.5及び28.2°に強い回折ピークを有するクロロガリウムフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の6.8°、17.3°、23.6°及び26.9°に強い回折ピークを有するクロロガリウムフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の8.7〜9.2°、17.6°、24.0°、27.4°及び28.8°に強い回折ピークを有するクロロガリウムフタロシアニン結晶が好ましい。ジクロロスズフタロシアニン結晶としては、ＣｕＫαを線源とするＸ線回折において、ブラッグ角度（２θ±0.2°）の8.3°、12.2°、13.7°、15.9°、18.9°及び28.2°に強い回折ピークを有するジクロロスズフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の8.5、11.2°、14.5°及び27.2°に強い回折ピークを有するジクロロスズフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の8.7°、9.9°、10.9°、13.1°、15.2°、16.3°、17.4°、21.9°及び25.5°に強い回折ピークを有するジクロロスズフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の9.2°、12.2°、13.4°、14.6°、17.0°及び25.3°に強い回折ピークを有するジクロロスズフタロシアニン結晶が好ましい。ヒドロキシガリウムフタロシアニン結晶としては、ＣｕＫαを線源とするＸ線回折において、ブラッグ角度（２θ±0.2°）の7.3°、24.9°及び28.1°に強い回折ピークを有するヒドロキシガリウムフタロシアニン結晶が好ましい。また、ブラッグ角度（２θ±0.2°）の7.5°、9.9°、12.5°、16.3°、18.6°、25.1°及び28.3°に強い回折ピークを有するヒドロキシガリウムフタロシアニン結晶が好ましい。 Examples of charge generating materials used in the present invention include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyratron pigments, azo pigments, indigo pigments, quinacridone pigments, etc. Is mentioned. Further, quinocyanine dyes and the like can be mentioned. Examples of the phthalocyanine pigment include metal-free phthalocyanine, oxytitanium phthalocyanine, hydroxyphthalocyanine, and gallium halide phthalocyanine such as chlorogallium. In particular, metal phthalocyanine pigments are preferable, and among them, oxytitanium phthalocyanine crystal, chlorogallium phthalocyanine crystal, dichlorotin phthalocyanine crystal, and hydroxygallium phthalocyanine crystal are preferable. Furthermore, hydroxygallium phthalocyanine crystals are particularly preferred. The oxytitanium phthalocyanine crystal is preferably an oxytitanium phthalocyanine crystal having strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° of the Bragg angles (2θ ± 0.2 °) in X-ray diffraction using CuKα as a radiation source. Further, oxytitanium phthalocyanine crystals having strong peaks at Bragg angles (2θ ± 0.2 °) of 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° are preferable. The chlorogallium phthalocyanine crystal is preferably a chlorogallium phthalocyanine crystal having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 and 28.2 ° in X-ray diffraction using CuKα as a radiation source. Further, chlorogallium phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 6.8 °, 17.3 °, 23.6 ° and 26.9 ° are preferable. Further, chlorogallium phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 8.7 to 9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 ° are preferable. The dichlorotin phthalocyanine crystal has strong diffraction peaks at 8.3 °, 12.2 °, 13.7 °, 15.9 °, 18.9 ° and 28.2 ° Bragg angles (2θ ± 0.2 °) in X-ray diffraction using CuKα as a radiation source. Dichlorotin phthalocyanine crystals are preferred. Further, dichlorotin phthalocyanine crystals having strong diffraction peaks at 8.5, 11.2 °, 14.5 °, and 27.2 ° of the Bragg angle (2θ ± 0.2 °) are preferable. Further, dichlorotin phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, 16.3 °, 17.4 °, 21.9 °, and 25.5 ° are preferable. Further, dichlorotin phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 9.2 °, 12.2 °, 13.4 °, 14.6 °, 17.0 °, and 25.3 ° are preferable. The hydroxygallium phthalocyanine crystal is preferably a hydroxygallium phthalocyanine crystal having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.3 °, 24.9 °, and 28.1 ° in X-ray diffraction using CuKα as a radiation source. Further, hydroxygallium phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, and 28.3 ° are preferable.
上記電荷発生層には、フタロシアニン化合物以外の電荷発生材料を、全電荷発生材料に対して５０質量％まで含有させることも可能である。例えば、セレン−テルル、ピリリウム、チアピリリウム系染料、アントアントロン、ジベンズピレンキノン、トリスアゾ、シアニン、ジスアゾ、モノアゾ、インジゴ、キナクリドン及び非対称キノシアニン系の各顔料等が挙げられる。 The charge generation layer may contain a charge generation material other than the phthalocyanine compound up to 50% by mass with respect to the total charge generation material. Examples thereof include selenium-tellurium, pyrylium, thiapyrylium dyes, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments.
電荷発生層は、前記電荷発生材料を質量比で０．３倍量以上４倍量以下のバインダー樹脂及び溶剤と共にホモジナイザー、超音波分散、ボールミル、振動ボールミル、サンドミル、アトライター、ロールミルまたは液衝突型高速分散機等を使用して十分分散させる。その後分散液中に電子搬送性化合物を添加した溶液を塗布、乾燥させて形成される。 The charge generation layer comprises a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, or a liquid collision type together with a binder resin and a solvent having a mass ratio of 0.3 to 4 times by weight. Disperse sufficiently using a high-speed disperser. Thereafter, a solution obtained by adding an electron transporting compound to the dispersion is applied and dried.
バインダー樹脂としては、ブチラール樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリスチレン樹脂、ポリビニルメタクリレート樹脂、ポリビニルアクリレート樹脂、ポリ酢酸ビニル樹脂、ポリ塩化ビニル樹脂等が挙げられる。また、ポリアミド樹脂、ポリウレタン樹脂、シリコーン樹脂、アルキッド樹脂、エポキシ樹脂、セルロース樹脂及びメラミン樹脂等が挙げられるが、これらに限定されるものではない。特に、ブチラール樹脂が好ましい。電荷発生層の膜厚は５μｍ以下が好ましく、特には０．１μｍ以上２μｍ以下が好ましい。 Examples of the binder resin include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, and polyvinyl chloride resin. Moreover, although a polyamide resin, a polyurethane resin, a silicone resin, an alkyd resin, an epoxy resin, a cellulose resin, a melamine resin, etc. are mentioned, it is not limited to these. In particular, a butyral resin is preferred. The film thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.1 μm or more and 2 μm or less.
電荷発生層の上には電荷輸送層が形成される。電荷輸送層は主として、ホール輸送能を持つ電荷輸送材料（正孔輸送材料）とバインダー樹脂とを溶剤中に溶解させた塗料を塗布、乾燥して形成する。用いられる電荷輸送材料としては、トリアリールアミン系化合物、ヒドラゾン化合物、スチルベン化合物、ピラゾリン系化合物、オキサゾール系化合物、トリアリルメタン系化合物及びチアゾール系化合物等が挙げられる。 A charge transport layer is formed on the charge generation layer. The charge transport layer is mainly formed by applying and drying a paint in which a charge transport material (hole transport material) having a hole transport ability and a binder resin are dissolved in a solvent. Examples of the charge transport material used include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds, and thiazole compounds.
バインダー樹脂としては、ポリエステル樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリスチレン樹脂、ポリビニルメタクリレート樹脂、ポリビニルアクリレート樹脂、ポリアミド樹脂、ポリウレタン樹脂、シリコーン樹脂等が挙げられる。また、アルキッド樹脂、エポキシ樹脂、セルロース樹脂及びメラミン樹脂等が挙げられるが、下記式（Ｂ）で示される構造単位を有するポリアリレート樹脂を用いた場合に特に好ましい電位変動抑制効果が得られた。 Examples of the binder resin include polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyamide resin, polyurethane resin, and silicone resin. Moreover, although an alkyd resin, an epoxy resin, a cellulose resin, a melamine resin, etc. are mentioned, when the polyarylate resin which has a structural unit shown by following formula (B) was used, the especially preferable electrical potential fluctuation inhibitory effect was acquired.
下記式（Ｂ）で示される構造単位を有するポリアリレート樹脂は、単独であるいはポリカーボネート樹脂、ポリエステル樹脂、ポリメタクリル酸エステル、ポリスチレン樹脂、アクリル樹脂、ポリアミド樹脂等の樹脂と混合して用いることが好ましい。また、ポリ−Ｎ−ビニルカルバゾールやポリビニルアントラセンのような有機光導電性ポリマー等と混合して用いることが好ましい。 The polyarylate resin having a structural unit represented by the following formula (B) is preferably used alone or mixed with a resin such as a polycarbonate resin, a polyester resin, a polymethacrylic acid ester, a polystyrene resin, an acrylic resin, or a polyamide resin. . Further, it is preferable to use a mixture with an organic photoconductive polymer such as poly-N-vinylcarbazole or polyvinylanthracene.
（式中、Ｘ４０は炭素原子または単結合（この際のＲ１５及びＲ１６はなし）を示し、Ｒ１１からＲ１４は水素原子、ハロゲン原子、置換されてもよいアルキル基またはアリール基を示す。また、Ｒ１５及びＲ１６は水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基またはＲ１５とＲ１６が結合することによって形成されるアルキリデン基を示す。また、Ｒ１７からＲ２０は水素原子、ハロゲン原子、置換されてもよいアルキル基またはアリール基を示す。） (In the formula, X 40 represents a carbon atom or a single bond (in which R 15 and R 16 are absent), and R 11 to R 14 represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group. R 15 and R 16 represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an aryl group, or an alkylidene group formed by combining R 15 and R 16 , and R 17 to R 20 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group.)
バインダー樹脂の重量平均分子量は、５万以上２０万以下が好ましく、更には１０万以上１８万以下が好ましい。重量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー（東ソー（株）製「ＨＬＣ−８１２０」）を用いて分子量分布を測定し、ポリスチレン換算で計算した。 The weight average molecular weight of the binder resin is preferably 50,000 to 200,000, more preferably 100,000 to 180,000. The weight average molecular weight was determined by measuring the molecular weight distribution using gel permeation chromatography (“HLC-8120” manufactured by Tosoh Corporation) and calculating the polystyrene equivalent.
測定は、展開溶媒としてテトラヒドロフラン（ＴＨＦ）を用い、樹脂試料の０．１質量％溶液について、カラムとして排除限界分子量（ポリスチレン換算）４×１０６のカラム（東ソー（株）製「ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｎ」）を用いて行った。また、検出器としてＲＩを用いて、カラム温度４０℃、インジェクション量２０μｌ、流速１．０ｍｌ／分の条件で行った。 For the measurement, tetrahydrofuran (THF) was used as a developing solvent, and a 0.1 mass% solution of a resin sample was used as a column with an exclusion limit molecular weight (polystyrene conversion) 4 × 10 6 column (“TSKgel SuperHM-N” manufactured by Tosoh Corporation). )). Further, RI was used as a detector under the conditions of a column temperature of 40 ° C., an injection amount of 20 μl, and a flow rate of 1.0 ml / min.
電荷輸送材料は質量比で０．５倍量以上２倍量以下のバインダー樹脂と組み合わされ、塗布、乾燥して電荷輸送層を形成する。電荷輸送層の膜厚は、５μｍ以上３０μｍ以下が好ましく、更には８μｍ以上１９μｍ以下が好ましい。 The charge transport material is combined with a binder resin having a mass ratio of 0.5 to 2 times, and is applied and dried to form a charge transport layer. The film thickness of the charge transport layer is preferably 5 μm or more and 30 μm or less, and more preferably 8 μm or more and 19 μm or less.
電荷輸送層には、その他、ヒンダードフェノール類やヒンダードアミン類等の酸化防止剤、シリコーンオイル、シリコーンオイル粒子及びフッ素原子含有樹脂粒子等の潤滑性材料、シリコーン玉等の膜強度補強材等を添加してもよい。これらを含有した塗工液を電荷発生層上に塗布し、乾燥して、電荷輸送層が得られる。 In addition to the charge transport layer, antioxidants such as hindered phenols and hindered amines, lubricating materials such as silicone oil, silicone oil particles and fluorine atom-containing resin particles, and film strength reinforcing materials such as silicone balls are added. May be. A coating liquid containing these is applied onto the charge generation layer and dried to obtain a charge transport layer.
また、本発明においては、電荷輸送層上に保護層を設けてもよい。保護層を構成する材料としては、ポリエステル、ポリアクリレート、ポリエチレン、ポリスチレン、ポリブタジエン、ポリカーボネート、ポリアミド、ポリプロピレン、ポリイミド、ポリアミドイミド、ポリサルホン、ポリアクリルエーテル等が挙げられる。また、ポリアセタール、フェノール、アクリル、シリコーン、エポキシ、ユリア、アリル、アルキッド、ブチラール、フェノキシ、ホスファゼン、アクリル変性エポキシ、アクリル変性ウレタン及びアクリル変性ポリエステル樹脂等が挙げられる。保護層の膜厚は、０．２μｍ以上１０μｍ以下であることが好ましい。 In the present invention, a protective layer may be provided on the charge transport layer. Examples of the material constituting the protective layer include polyester, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, and polyacryl ether. Moreover, polyacetal, phenol, acrylic, silicone, epoxy, urea, allyl, alkyd, butyral, phenoxy, phosphazene, acrylic modified epoxy, acrylic modified urethane, acrylic modified polyester resin, and the like can be given. The thickness of the protective layer is preferably 0.2 μm or more and 10 μm or less.
以上の各層には、クリーニング性や耐摩耗性等の改善のために、ポリ四フッ化エチレン、ポリフッ化ビニリデン、フッ素系グラフトポリマー、シリコーン系グラフトポリマー及びフッ素系ブロックポリマー等の潤滑剤を含有させてもよい。また、シリコーン系ブロックポリマー及びシリコーン系オイル等の潤滑剤を含有させてもよい。更に、耐候性を向上させる目的で、酸化防止剤等の添加物を加えてもよい。 Each of the above layers contains a lubricant such as polytetrafluoroethylene, polyvinylidene fluoride, fluorine-based graft polymer, silicone-based graft polymer, and fluorine-based block polymer in order to improve cleaning properties and abrasion resistance. May be. Further, a lubricant such as a silicone block polymer and a silicone oil may be contained. Furthermore, an additive such as an antioxidant may be added for the purpose of improving the weather resistance.
また、保護層には、抵抗制御の目的で、導電性酸化スズ及び導電性酸化チタニウム等の導電性粉体を分散してもよい。 Further, conductive powder such as conductive tin oxide and conductive titanium oxide may be dispersed in the protective layer for the purpose of resistance control.
図１に本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成を示す。 FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
図１において、１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。電子写真感光体１は、回転過程において、帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いで、スリット露光やレーザービーム走査露光などの露光手段（不図示）からの露光光４を受ける。こうして電子写真感光体１の周面に静電潜像が順次形成されていく。 In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotation process, the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.
形成された静電潜像は、次いで現像手段５によりトナー現像され、現像されたトナー像は、不図示の給紙部から電子写真感光体１と転写手段６との間に電子写真感光体１の回転と同期取り出されて給紙された転写材上に、転写手段６により順次転写されていく。 The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner image is transferred between the electrophotographic photosensitive member 1 and the transfer unit 6 from a paper supply unit (not shown). Then, the image is sequentially transferred by the transfer means 6 onto the transfer material taken out in synchronization with the rotation of the paper and fed.
像転写を受けた転写材７は、電子写真感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装置外へプリントアウトされる。 The transfer material 7 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as a copy (copy).
転写工程後に、クリーニング手段９によって電子写真感光体上に残余するトナーが除去、回収されて電子写真感光体の表面が清浄面化される。さらに前露光手段（不図示）からの前露光光１０により除電処理される場合もある。 After the transfer process, the toner remaining on the electrophotographic photosensitive member is removed and collected by the cleaning means 9 to clean the surface of the electrophotographic photosensitive member. Further, there may be a case where static elimination processing is performed by pre-exposure light 10 from pre-exposure means (not shown).
帯電手段３は、コロナ放電を利用したスコロトロン帯電器やコロトロン帯電器でも良く、ローラ形状、ブレード形状、ブラシ形状など公知の形態が使用される接触型帯電器を用いてもよい。 The charging means 3 may be a scorotron charger or a corotron charger using corona discharge, or a contact type charger using a known form such as a roller shape, a blade shape, or a brush shape.
本発明においては、上述の電子写真感光体１、帯電手段３、現像手段５及びクリーニング手段９などの構成要素のうち、複数のものをプロセスカートリッジとして一体に結合してプロセスカートリッジを構成してもよい。また、このプロセスカートリッジを複写機やレーザービームプリンターなどの電子写真装置本体に対して着脱自在に構成してもよい。 In the present invention, a process cartridge may be configured by integrally combining a plurality of components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 9 as a process cartridge. Good. The process cartridge may be configured to be detachable from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.
例えば、帯電手段３、現像手段５及びクリーニング手段９の少なくとも１つを電子写真感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２などの案内手段を用いて装置本体に着脱自在なプロセスカートリッジ１１とすることができる。 For example, at least one of the charging unit 3, the developing unit 5 and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is detachable from the apparatus main body using guide means such as a rail 12 of the apparatus main body. Process cartridge 11.
また、露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号にしたがって行われるレーザービームの走査により照射される光である。また、この信号にしたがって行われるＬＥＤアレイの駆動及び液晶シャッターアレイの駆動などにより照射される光である。 Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is a reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam performed in accordance with this signal. It is light irradiated by scanning. Further, the light is emitted by driving the LED array, driving the liquid crystal shutter array, or the like performed according to this signal.
本発明の電子写真感光体は、複写機、レーザープリンター、ＬＥＤプリンター、液晶シャッター式プリンターなどの電子写真装置一般に適応し得る。さらに、電子写真技術を応用したディスプレー、記録、軽印刷、製版及びファクシミリなどの装置にも幅広く適用し得るものである。 The electrophotographic photosensitive member of the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers. Furthermore, the present invention can be widely applied to apparatuses such as a display, recording, light printing, plate making and facsimile using the electrophotographic technology.
次に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例により限定されるものではない。なお、実施例中の「部」は質量部を表す。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In addition, "part" in an Example represents a mass part.
（合成例１）
窒素気流下、１，４，５，８−ナフタレンテトラカルボン酸二無水物２０部、イミダゾール１部を混合し、２−メチル−６−エチルアニリン５０部及び２−アミノ−１−ブタノール７．３部を添加し、１７０℃で３ｈ加熱撹拌した。反応終了後、トルエン５００ｍｌを加えシリカゲルカラムクロマトグラフィーで分離精製を行った。得られた褐色液体を加熱、冷却し黄白色の結晶を１０部得た。
(Synthesis Example 1)
Under a nitrogen stream, 1,4,5,8-naphthalenetetracarboxylic dianhydride (20 parts) and imidazole (1 part) were mixed, and 2-methyl-6-ethylaniline (50 parts) and 2-amino-1-butanol (7.3) were mixed. Part was added and stirred with heating at 170 ° C. for 3 h. After completion of the reaction, 500 ml of toluene was added and separation and purification were performed by silica gel column chromatography. The obtained brown liquid was heated and cooled to obtain 10 parts of yellowish white crystals.
（MALDI-TOF MS：ブルカー・ダルトニクス（株）製ultraflex）（加速電圧：２０ｋＶ、モード：Reflector、分子量標準品：フラーレンＣ６０）で、質量分析により分子量を測定した所、ピークトップ値として４５６が得られた。また、図２に示す赤外吸収スペクトル、図３に示すプロトンＮＭＲより、上記式（１）−１で示されるイミド化合物であることを確認した。 (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C60), when molecular weight was measured by mass spectrometry, 456 was obtained as the peak top value. It was. Moreover, it confirmed that it was an imide compound shown by the said Formula (1) -1 from the infrared absorption spectrum shown in FIG. 2, and the proton NMR shown in FIG .
赤外吸収スペクトルは、パーキンエルマージャパン社製フーリエ変換赤外分光光度計（商品名：Paragon1000）によるＫＢｒ錠剤法で分解能：４ｃｍ−１で行い、ＮＭＲは日立製作所社製R-1100を用い、溶媒：ＣＤＣｌ３、濃度１０％、内部標準ＴＭＳで行った。 The infrared absorption spectrum was measured by a KBr tablet method using a Fourier transform infrared spectrophotometer (trade name: Paragon1000) manufactured by PerkinElmer Japan, Inc. at a resolution of 4 cm −1 , and NMR was performed using R-1100 manufactured by Hitachi, Ltd. : CDCl3, concentration 10%, internal standard TMS
（実施例１）
熱間押し出しにより得たＡ３００３の外径φ２９．９２ｍｍ、長さ２６０．５ｍｍのアルミニウム素管（ＥＤ管）を準備した。
Example 1
An aluminum base pipe (ED pipe) of A3003 obtained by hot extrusion and having an outer diameter of 29.92 mm and a length of 260.5 mm was prepared.
以下の材料からなる溶液を約２０時間ボールミルで分散し、導電性粒子樹脂分散層用塗布液を調製した（この塗布液に含有するフィラーの平均粒径は０．２２μｍであった）。酸化スズで形成された被覆層を有する硫酸バリウム微粒子からなる粉体（被覆率５０質量％、粉体比抵抗７００Ω・ｃｍ）１２０部。レゾール型フェノール樹脂（商品名：ブライオーフェンＪ−３２５、大日本インキ化学工業（株）製、固形分７０質量％）７０部。２−メトキシ−１−プロパノール１００部。この塗布液を上記アルミニウム素管上に浸漬コーティング法によって塗布し、１４０℃で３０分間加熱硬化することにより、膜厚が１５μｍの導電性粒子樹脂分散層を形成し、これを導電性支持体とした。 A solution composed of the following materials was dispersed with a ball mill for about 20 hours to prepare a coating solution for conductive particle resin dispersion layer (the average particle size of the filler contained in this coating solution was 0.22 μm). 120 parts of powder composed of fine particles of barium sulfate having a coating layer formed of tin oxide (coverage: 50 mass%, powder specific resistance: 700 Ω · cm). 70 parts of a resol type phenolic resin (trade name: Bryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 70% by mass). 100 parts of 2-methoxy-1-propanol. The coating solution is applied onto the aluminum base tube by a dip coating method and heated and cured at 140 ° C. for 30 minutes to form a conductive particle resin dispersion layer having a thickness of 15 μm. did.
上記導電性支持体上に上記式（１）−１で示されるイミド化合物を３部、ポリアミド樹脂（アミランCM8000、東レ（株）製）７部とをブタノール１２０部、メタノ−ル１００部、ＤＭＦ３０部とに溶解した溶液を浸漬塗布法で塗布した。次いで、９０℃で５分間乾燥し、膜厚が０．７μｍの中間層を形成した。 3 parts of the imide compound represented by the above formula (1) -1 and 7 parts of polyamide resin (Amilan CM8000, manufactured by Toray Industries, Inc.) on the conductive support are 120 parts of butanol, 100 parts of methanol, DMF30. The solution dissolved in the part was applied by a dip coating method. Subsequently, it dried at 90 degreeC for 5 minute (s), and formed the intermediate | middle layer with a film thickness of 0.7 micrometer.
次に、電荷発生材料として以下の材料にシクロヘキサノン３５０部を加え、１ｍｍφガラスビーズを用いたサンドミルで３時間分散し、これに酢酸エチル１２００部を加えて希釈した。ＣｕＫαを線源とするＸ線回折において、ブラッグ角度（２θ±0.2°）の7.5°、9.9°、12.5°、16.3°、18.6°、25.1°及び28.3°に強い回折ピークを有するヒドロキシガリウムフタロシアニン結晶２０部。下記式（２）で示される構造を有する化合物０．２部。 Next, 350 parts of cyclohexanone was added to the following materials as a charge generation material, dispersed in a sand mill using 1 mmφ glass beads for 3 hours, and diluted with 1200 parts of ethyl acetate. Hydroxygallium phthalocyanine crystal with strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° in X-ray diffraction using CuKα as a radiation source 20 copies. 0.2 part of a compound having a structure represented by the following formula (2).
ポリビニルブチラール樹脂（商品名：ＢＸ−１、積水化学工業（株）製）１０部。このときの電荷発生材料のＣＡＰＡ−７００（堀場製作所（株）製）による分散粒径は０．１５μｍであった。中間層上に、この電荷発生層用塗工液を浸漬塗布し、１００℃で１０分間乾燥して、膜厚が０．２μｍの電荷発生層を形成した。 10 parts of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.). At this time, the dispersed particle diameter of the charge generation material CAPA-700 (manufactured by Horiba, Ltd.) was 0.15 μm. On the intermediate layer, this charge generation layer coating solution was applied by dip coating and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.
次に、下記構造式の化合物式（Ｃ）を７部、化合物式（Ｄ）を１部、 Next, 7 parts of the compound formula (C) of the following structural formula, 1 part of the compound formula (D),
及び、以下のポリアリレート樹脂１０部をモノクロルベンゼン５０部、ジクロルメタン１０部に溶解し、電荷輸送層用塗料を調製した。下記式（Ｅ）で示される構成単位を有するビスフェノールＣ型ポリアリレート樹脂（分子量Ｍｗ１１００００、エステル基同士がｍ−位及びｐ−位の繰り返し構造単位が５０％ずつである共重合体）。 Then, 10 parts of the following polyarylate resin was dissolved in 50 parts of monochlorobenzene and 10 parts of dichloromethane to prepare a charge transport layer coating material. A bisphenol C-type polyarylate resin having a structural unit represented by the following formula (E) (a copolymer having a molecular weight of Mw 110000 and 50% of repeating structural units each having m-position and p-position between ester groups).
この塗料を電荷発生層上に浸漬塗布法で塗布し、１１０℃で１時間乾燥して、膜厚が１８μｍの電荷輸送層を形成した。こうして電子写真感光体を作成した。 This paint was applied onto the charge generation layer by a dip coating method and dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm. Thus, an electrophotographic photosensitive member was prepared.
作製した電子写真感光体を、常温常湿（２３℃、５０％ＲＨ）、低温低湿（１２℃、１０％ＲＨ）の環境下にて、以下のプリンターに装着して、１５０００枚通紙耐久後の明部電位変動と画像の評価を行った。キヤノン（株）製レーザービームプリンターのＬＢＰ−２５１０（プロセススピードを１８０ｍｍ／ｓｅｃ、前露光を点灯の有無選択可、帯電条件可変、レーザー露光量可変で作動するように改造）。詳しくは以下のとおりである。 The prepared electrophotographic photosensitive member is mounted on the following printer in an environment of normal temperature and normal humidity (23 ° C., 50% RH) and low temperature and low humidity (12 ° C., 10% RH). The image was evaluated for light potential fluctuation and image. Canon's laser beam printer LBP-2510 (process speed is 180mm / sec, pre-exposure can be turned on / off, charging conditions are variable, and laser exposure is variable). Details are as follows.
ＬＢＰ−２５１０のシアン色用のプロセスカートリッジに作製した電子写真感光体を装着して、シアンのプロセスカートリッジのステーションに装着し、画像を出力した。ドラム表面電位は、初期暗部電位が−５００Ｖ、明部電位が−１２０Ｖになるように設定し、１５０００枚通紙耐久後の明部電位を測定した。表面電位の測定は、カートリッジを改造し、現像位置に電位プローブ（model6000B-8：トレック・ジャパン（株）製）を装着し、ドラム中央部の電位を表面電位計（model344：トレック・ジャパン（株）製）を使用して測定した。 The produced electrophotographic photosensitive member was attached to a cyan process cartridge of LBP-2510, and was attached to a cyan process cartridge station, and an image was output. The drum surface potential was set such that the initial dark portion potential was −500 V and the light portion potential was −120 V, and the light portion potential after 15,000 sheets were passed through was measured. Surface potential is measured by remodeling the cartridge, attaching a potential probe (model6000B-8: manufactured by Trek Japan) to the development position, and measuring the potential at the center of the drum with a surface potential meter (model344: Trek Japan, Inc.) )).
通紙時は各色の印字率１％の文字画像をＡ４サイズの普通紙でフルカラープリント操作を行い、前露光を点灯せずに１５０００枚の画像出力を行った。 When the paper was passed, a full color printing operation was performed on a character image with a printing rate of 1% for each color using plain paper of A4 size, and 15000 images were output without turning on the pre-exposure.
帯電スジの評価は１ドット桂馬パターンのハーフトーン画像で行った。 The charging streaks were evaluated with halftone images of 1-dot Keima pattern.
画像の評価の基準は以下のとおりである。 The criteria for image evaluation are as follows.
（帯電スジ）
帯電スジの有無は、１ドット桂馬パターンのハーフトーン画像から、Ａ：帯電スジが全くなし、Ｂ：帯電スジがほとんどなし、Ｃ：帯電スジがわずかに観測される、Ｄ：帯電スジが観測される、Ｅ：帯電スジがはっきりわかる、とした。
(Charging stripe)
Presence / absence of charged streaks, from a halftone image of 1-dot Keima pattern, A: no charged streaks, B: almost no charged streaks, C: slightly charged streaks, D: charged streaks observed E: The charging streaks are clearly understood.
また、感光層のはじき、ムラの評価は電荷発生層作成後の目視で行った。 The evaluation of the repelling and unevenness of the photosensitive layer was performed visually after the charge generation layer was formed.
結果を表２に示す。 The results are shown in Table 2.
（参考例２、実施例３、参考例４〜６）
イミド化合物として表２に記載のイミド化合物を用いた以外は実施例１と同様に電子写真感光体を作成し、評価を行った。
( Reference Example 2 , Example 3, Reference Examples 4 to 6)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the imide compounds listed in Table 2 were used as the imide compounds.
（実施例７）
中間層に添加するポリアミド樹脂を９．５部、イミド化合物を０．５部に変えた以外は実施例１と同様に電子写真感光体を作製し同様な評価を行った。
(Example 7)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the polyamide resin added to the intermediate layer was changed to 9.5 parts and the imide compound was changed to 0.5 parts.
（実施例８）
中間層に添加するポリアミド樹脂を９部、イミド化合物を１部に変えた以外は実施例１と同様に電子写真感光体を作製し同様な評価を行った。
(Example 8)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 9 parts of the polyamide resin added to the intermediate layer and 1 part of the imide compound were changed.
（実施例９）
中間層に添加するポリアミド樹脂を５部、イミド化合物を５部に変えた以外は実施例１と同様に電子写真感光体を作製し同様な評価を行った。
Example 9
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that 5 parts of the polyamide resin added to the intermediate layer and 5 parts of the imide compound were changed.
（実施例１０）
中間層に添加するポリアミド樹脂を３部、イミド化合物を７部に変えた以外は実施例１と同様に電子写真感光体を作製し同様な評価を行った。
(Example 10)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the polyamide resin added to the intermediate layer was changed to 3 parts and the imide compound was changed to 7 parts.
（参考例１１）
中間層に用いる樹脂をポリメチルメタクリレート（分子量Ｍｗ１２００００）に変えた以外は参考例５と同様に電子写真感光体を作製し評価した。
( Reference Example 11)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 5 except that the resin used for the intermediate layer was changed to polymethyl methacrylate (molecular weight Mw 120,000).
（比較例１）
イミド化合物を下記式（Ｆ）の化合物に変えた以外は実施例１と同様に電子写真感光体を作製し評価した。
(Comparative Example 1)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the imide compound was changed to the compound of the following formula (F).
（比較例２）
イミド化合物を用いず実施例１と同様に電子写真感光体を作製し評価した。
(Comparative Example 2)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 without using an imide compound.
以上の結果を表２に示す。 The results are shown in Table 2.
（実施例１２）
中間層に添加するポリアミド樹脂を５部、イミド化合物を５部に変えた以外は実施例１と同様に電子写真感光体を作製した。
(Example 12)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 5 parts of the polyamide resin added to the intermediate layer and 5 parts of the imide compound were changed.
評価は前露光を点灯させた以外は実施例１と同様に評価した。 Evaluation was performed in the same manner as in Example 1 except that the pre-exposure was turned on.
（実施例１３）
中間層を以下のように作成した以外は実施例１２と同様に電子写真感光体を作成し評価した。
(Example 13)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 12 except that the intermediate layer was prepared as follows.
式（Ａ）の繰り返し単位ユニットとスチレンの共重合体（式（Ａ）の繰り返し単位ユニット３０モル％、分子量Ｍｗ４２０００）５部と上記式（１）−１で示されるイミド化合物５部とを、ＤＭＦ１００部と、メタノール１００部とに溶解した。この溶液を浸漬塗布法で塗布し、１５０℃で３０分間乾燥し、膜厚が０．７μｍの中間層を形成した。 5 parts of a repeating unit unit of the formula (A) and a copolymer of styrene (30 mol% of the repeating unit unit of the formula (A), molecular weight Mw 42000) and 5 parts of the imide compound represented by the above formula (1) -1 . Dissolved in 100 parts of DMF and 100 parts of methanol. This solution was applied by a dip coating method and dried at 150 ° C. for 30 minutes to form an intermediate layer having a thickness of 0.7 μm.
なお、式（Ａ）単位ユニットとスチレンの共重合体は２−イソシアナトエチルメタクリレート６０．０ｇ、スチレン７２．８ｇ、２、２−アゾビスーイソブチロニトリル（以下ＡＩＢＮ）３ｇをトルエン１００ｇに加え、１２０℃で５時間加熱して得た。式（Ａ）の繰り返し単位ユニットの存在比率は赤外吸収スペクトルより行いイソシアネート基の2200から2300ｃｍ−１付近のピーク、3350ｃｍ−１付近のＮＨ−のピーク、共重合させたスチレンモノマー由来の２５４ｎｍの紫外線吸収スペクトルより算出した。算出された存在比率は仕込み比率とほぼ同等の３０モル％であった。 The copolymer of the unit unit of formula (A) and styrene is 60.0 g of 2-isocyanatoethyl methacrylate, 72.8 g of styrene, 3 g of 2,2-azobis-isobutyronitrile (hereinafter AIBN) added to 100 g of toluene. And heated at 120 ° C. for 5 hours. The abundance ratio of the repeating unit unit of the formula (A) was determined from an infrared absorption spectrum. The peak of the isocyanate group in the vicinity of 2200 to 2300 cm −1 , the peak of NH— near 3350 cm −1 , 254 nm derived from the copolymerized styrene monomer. It was calculated from the ultraviolet absorption spectrum. The calculated abundance ratio was 30 mol%, which was almost equivalent to the charging ratio.
なお、上述の重量平均分子量は、以下の条件で測定して得た値をポリスチレン換算した値である。 In addition, the above-mentioned weight average molecular weight is a value obtained by converting a value obtained by measurement under the following conditions into polystyrene.
測定機器 ：ゲルパーミエーションクロマトグラフィー「ＨＬＣ−８１２０」
（東ソー（株）製）
展開溶媒 ：０．１質量％ＴＨＦ溶液
カラム ：東ソー（株）製「ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｎ」
検出器 ：ＲＩ
カラム温度 ：４０℃
インジェクション量：２０μｌ
流速 ：１．０ｍｌ／分
Measuring instrument: Gel permeation chromatography “HLC-8120”
(Manufactured by Tosoh Corporation)
Developing solvent: 0.1 mass% THF solution Column: “TSKgel SuperHM-N” manufactured by Tosoh Corporation
Detector: RI
Column temperature: 40 ° C
Injection volume: 20 μl
Flow rate: 1.0 ml / min
（実施例１４）
イミド化合物として上記式（１）−３で示されるイミド化合物を用いた以外は実施例１３と同様に電子写真感光体を作製し同様な評価を行った。
(Example 14)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 13 except that the imide compound represented by the above formula (1) -3 was used as the imide compound .
（実施例１５）
共重合樹脂を合成する際のＡＩＢＮ量を８ｇ、トルエン量を１５０ｇとした以外は実施例１３と同様に電子写真感光体を作製し評価した。樹脂の分子量Ｍｗは１０００であった。
(Example 15)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 13 except that the amount of AIBN when synthesizing the copolymer resin was 8 g and the amount of toluene was 150 g. The molecular weight Mw of the resin was 1000.
（実施例１６）
共重合樹脂を合成する際のＡＩＢＮ量を１ｇ、反応時間を８時間とした以外は実施例１３と同様に電子写真感光体を作製し評価した。樹脂の分子量Ｍｗは２０００００であった。
(Example 16)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 13 except that the amount of AIBN when synthesizing the copolymer resin was 1 g and the reaction time was 8 hours. The molecular weight Mw of the resin was 200000.
（実施例１７）
共重合樹脂を合成する際のＡＩＢＮ量を９ｇ、トルエン量を１５０ｇ、反応時間を４時間とした以外は実施例１３と同様に電子写真感光体を作製し評価した。樹脂の分子量Ｍｗは８００であった。
(Example 17)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 13 except that the amount of AIBN when synthesizing the copolymer resin was 9 g, the amount of toluene was 150 g, and the reaction time was 4 hours. The molecular weight Mw of the resin was 800.
（実施例１８）
共重合樹脂を合成する際のＡＩＢＮ量を１ｇ、トルエン量を８０ｇ、反応時間を８時間とした以外は実施例１３と同様に電子写真感光体を作製し評価した。樹脂の分子量Ｍｗは２５００００であった。
(Example 18)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 13 except that the amount of AIBN when synthesizing the copolymer resin was 1 g, the amount of toluene was 80 g, and the reaction time was 8 hours. The molecular weight Mw of the resin was 250,000.
（実施例１９）
中間層に用いる樹脂をブチラール樹脂（エスレックスＢＭ−Ｓ、積水化学社製）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Example 19)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that the resin used for the intermediate layer was changed to butyral resin (Esrex BM-S, manufactured by Sekisui Chemical Co., Ltd.).
（実施例２０）
中間層に用いる樹脂をポリメチルメタクリレート（分子量Ｍｗ１２００００）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Example 20)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 12 except that the resin used for the intermediate layer was changed to polymethyl methacrylate (molecular weight Mw 120,000).
（参考例２１）
イミド化合物として上記式（１）−６で示されるイミド化合物を用いた以外は実施例２０と同様に電子写真感光体を作製し同様な評価を行った。
( Reference Example 21)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 20 except that the imide compound represented by the above formula (1) -6 was used as the imide compound.
（比較例３）
イミド化合物を下記式（Ｆ）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Comparative Example 3)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that the imide compound was changed to the following formula (F).
（比較例４）
イミド化合物を下記式（Ｇ）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Comparative Example 4)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that the imide compound was changed to the following formula (G).
（比較例５）
イミド化合物を下記式（Ｈ）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Comparative Example 5)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that the imide compound was changed to the following formula (H).
（比較例６）
イミド化合物を下記式（Ｉ）に変えた以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Comparative Example 6)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that the imide compound was changed to the following formula (I).
（比較例７）
イミド化合物を用いない以外は実施例１２と同様に電子写真感光体を作製し評価した。
(Comparative Example 7)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 12 except that no imide compound was used.
結果を表３に示す。 The results are shown in Table 3.
１：電子写真感光体
２：回転軸
３：一次帯電器（接触系、非接触系など）
４：像露光（レーザー光など）
５：現像器（接触系、非接触系など）
６：転写帯電器（接触系、非接触系など）
７：紙などの転写材
８：定着器
９：クリーナー（ない場合もある）
１０：前露光（ない場合もある）
１１：カートリッジ枠
１２：カートリッジ挿入ガイド
1: Electrophotographic photosensitive member 2: Rotating shaft 3: Primary charger (contact system, non-contact system, etc.)
4: Image exposure (laser light, etc.)
5: Developer (contact system, non-contact system, etc.)
6: Transfer charger (contact system, non-contact system, etc.)
7: Transfer material such as paper 8: Fixing device 9: Cleaner (may not be present)
10: Pre-exposure (may not be present)
11: Cartridge frame 12: Cartridge insertion guide
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| US10514621B2 (en) | 2018-04-11 | 2019-12-24 | Fuji Xerox Co., Ltd. | Electrophotographic photoreceptor, process cartridge, image forming apparatus, and imide compound |
| EP4310593A1 (en) | 2022-07-20 | 2024-01-24 | FUJIFILM Business Innovation Corp. | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| EP4528382A1 (en) | 2023-09-25 | 2025-03-26 | FUJIFILM Business Innovation Corp. | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
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| JP4859239B2 (en) * | 2007-03-30 | 2012-01-25 | キヤノン株式会社 | Method for producing electrophotographic photosensitive member |
| JP5784074B2 (en) * | 2012-06-29 | 2015-09-24 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP6415274B2 (en) * | 2013-12-26 | 2018-10-31 | キヤノン株式会社 | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus, and imide compound |
| JP6468825B2 (en) * | 2013-12-26 | 2019-02-13 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, electrophotographic apparatus, and imide compound |
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| US10514621B2 (en) | 2018-04-11 | 2019-12-24 | Fuji Xerox Co., Ltd. | Electrophotographic photoreceptor, process cartridge, image forming apparatus, and imide compound |
| US10890854B2 (en) | 2018-04-11 | 2021-01-12 | Fuji Xerox Co.. Ltd. | Electrophotographic photoreceptor, process cartridge, image forming apparatus, and imide compound |
| EP4310593A1 (en) | 2022-07-20 | 2024-01-24 | FUJIFILM Business Innovation Corp. | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| EP4528382A1 (en) | 2023-09-25 | 2025-03-26 | FUJIFILM Business Innovation Corp. | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
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