JP4630806B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents
Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus Download PDFInfo
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- JP4630806B2 JP4630806B2 JP2005356220A JP2005356220A JP4630806B2 JP 4630806 B2 JP4630806 B2 JP 4630806B2 JP 2005356220 A JP2005356220 A JP 2005356220A JP 2005356220 A JP2005356220 A JP 2005356220A JP 4630806 B2 JP4630806 B2 JP 4630806B2
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- Prior art keywords
- photosensitive member
- electrophotographic photosensitive
- compound
- electrophotographic
- layer
- Prior art date
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Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
本発明は、電子写真感光体並びにこの電子写真感光体を有するプロセスカートリッジ及び電子写真装置に関する。特に、感光層中に、特定の正孔輸送性化合物とアリーレンエーテル基を有する特定の化合物とを重合した化合物を含有する電子写真感光体並びにこの電子写真感光体を有する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 an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. In particular, the present invention relates to an electrophotographic photosensitive member containing a compound obtained by polymerizing a specific hole transporting compound and a specific compound having an arylene ether group in a photosensitive layer, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. .
従来、電子写真感光体に用いられる光導電材料としては、セレン、硫化カドミウム及び酸化亜鉛等の無機材料が知られていた。他方、有機材料であるポリビニルカルバゾール、フタロシアニン及びアゾ顔料等は、無機材料と比較して光導電特性や耐久性等の点で劣る傾向にあるものの、高生産性や無公害性等の利点が注目され、広く用いられるようになってきた。これらの電子写真感光体は、電気的及び機械的特性の双方を満足するために電荷発生層と電荷輸送層とを積層した機能分離型の電子写真感光体として利用される場合が多い。 Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. On the other hand, polyvinylcarbazole, phthalocyanine and azo pigments, which are organic materials, tend to be inferior in terms of photoconductive properties and durability compared to inorganic materials, but attention is paid to advantages such as high productivity and non-pollution properties. Has been widely used. These electrophotographic photoreceptors are often used as function-separated electrophotographic photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical properties.
一方、当然のことながら電子写真感光体は、適用される電子写真プロセスに応じた感度、電気的特性、そして光学的特性を備えていることが要求される。また、特に繰り返し使用される電子写真感光体にあっては、電子写真感光体の表面は、帯電、画像露光、トナー現像、紙への転写、クリーニング処理といった電気的、機械的外力が直接加えられるため、それらに対する耐久性や安定性が要求される。具体的には、摺擦による表面の磨耗や傷の発生に対する耐久性、帯電時のオゾンや窒素酸化物に対する耐表面劣化性等が要求される。 On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, in an electrophotographic photosensitive member that is repeatedly used, the surface of the electrophotographic photosensitive member is directly subjected to electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning treatment. Therefore, durability and stability against them are required. Specifically, durability against the occurrence of surface wear and scratches due to rubbing, surface degradation resistance against ozone and nitrogen oxides during charging, and the like are required.
一般に、電子写真感光体の表面は、薄い樹脂層であり、樹脂の特性が非常に重要である。上述の諸条件をある程度満足する樹脂として、近年、アクリル樹脂やポリカーボネート樹脂等が選択され、電荷輸送材料を混合させた電荷輸送層として広く実用化されている。 In general, the surface of the electrophotographic photosensitive member is a thin resin layer, and the characteristics of the resin are very important. In recent years, an acrylic resin, a polycarbonate resin, or the like has been selected as a resin that satisfies the above-described conditions to some extent, and has been widely put into practical use as a charge transport layer mixed with a charge transport material.
しかしながら、上述したような表面層は、熱可塑性のポリマーであるために、機械的強度に限界がある。また、電気的特性を満たす目的で低分子の電荷輸送材料を多量に含有するために、耐磨耗性という面で十分ではなく、これらを克服するため、種々の検討がなされている。 However, since the surface layer as described above is a thermoplastic polymer, its mechanical strength is limited. In addition, since a large amount of a low-molecular charge transport material is contained for the purpose of satisfying the electrical characteristics, it is not sufficient in terms of wear resistance, and various studies have been made to overcome these problems.
その一例として、硬化性の樹脂を表面保護層として用いることが有効である（例えば特許文献１、２参照）。紫外線硬化性樹脂及び熱硬化性樹脂を用いた表面層が開示され、耐久性の向上が示されている。なかでも、硬化性のアクリル樹脂は、反応性が高く硬化速度が高いために、各種ハードコートとして使用されており、これを電子写真感光体の表面層に用いた場合にも十分な耐久性が得られることが示されている（例えば特許文献３参照）。 As an example, it is effective to use a curable resin as a surface protective layer (see, for example, Patent Documents 1 and 2). A surface layer using an ultraviolet curable resin and a thermosetting resin is disclosed, which shows improved durability. Among them, curable acrylic resins are used as various hard coats because of their high reactivity and high curing speed, and they have sufficient durability even when they are used for the surface layer of an electrophotographic photoreceptor. It is shown that it can be obtained (for example, refer to Patent Document 3).
また、硬化性の樹脂を電荷輸送層用の樹脂として用いる試みがある（例えば特許文献４参照）。この文献で示すように、電荷輸送層用の樹脂に硬化性の樹脂を用い電荷輸送層を硬化・架橋することによって、機械的強度が増し、繰り返し使用時の耐削れ性及び耐傷性が向上する。 There is an attempt to use a curable resin as a resin for the charge transport layer (see, for example, Patent Document 4). As shown in this document, by hardening and crosslinking the charge transport layer using a curable resin as the resin for the charge transport layer, the mechanical strength is increased, and the abrasion resistance and scratch resistance during repeated use are improved. .
また、特許文献５及び６は、炭素−炭素二重結合を有する電荷輸送材を熱又は光のエネルギーで反応させ、電荷輸送マトリックスに化学的に結合させて、電子写真感光体の表面層の機械的強度を向上させる方法を開示する。さらに、特許文献７は、熱可塑性高分子鎖中に電荷輸送能を有する基を導入したりすることで、電子写真感光体の表面層の機械的強度を向上させる方法を開示する。 In Patent Documents 5 and 6, a charge transport material having a carbon-carbon double bond is reacted with heat or light energy to be chemically bonded to a charge transport matrix, whereby the surface layer of the electrophotographic photosensitive member is mechanically bonded. Disclosed is a method for improving the mechanical strength. Furthermore, Patent Document 7 discloses a method for improving the mechanical strength of the surface layer of an electrophotographic photosensitive member by introducing a group having a charge transporting ability into a thermoplastic polymer chain.
しかしながら、電子写真感光体の表面層の機械的強度が増し、繰り返し使用時の耐削れ性が向上すると、電子写真感光体を帯電する時に生じる帯電生成物の付着等による高湿下での画像流れが発生しやすくなる。この画像流れを防止するために、特許文献８は、電子写真感光体に酸化防止剤を添加する方法を開示する。また、画像形成装置を連続使用の後、数時間放置し、さらにその後使用すると帯電手段である帯電器位置にあった電子写真感光体の一部分に相当する箇所の画像が周りに比べて黒くなるという黒帯という現象が発生する。特に、この現象は、帯電機がコロナ帯電を利用するコロトロンやスコロトロンのようなコロナ帯電器の場合、特に顕著に起こる。この帯電器下黒帯を防止するために、特許文献９及び１０は、電子写真感光体に酸化防止剤を添加するという方法を開示する。 However, when the mechanical strength of the surface layer of the electrophotographic photosensitive member is increased and the abrasion resistance during repeated use is improved, the image flow under high humidity is caused by adhesion of charged products generated when the electrophotographic photosensitive member is charged. Is likely to occur. In order to prevent this image flow, Patent Document 8 discloses a method of adding an antioxidant to an electrophotographic photosensitive member. In addition, if the image forming apparatus is left for several hours after continuous use and then used further, the image of the portion corresponding to a part of the electrophotographic photosensitive member at the position of the charger as the charging means becomes darker than the surroundings. A phenomenon called black belt occurs. In particular, this phenomenon is particularly noticeable when the charging machine is a corona charger such as a corotron or scorotron that uses corona charging. In order to prevent the black belt under the charger, Patent Documents 9 and 10 disclose a method of adding an antioxidant to the electrophotographic photosensitive member.
連鎖重合官能基を有する正孔輸送性化合物を重合した化合物等を有する高硬度な表面層は、機械的強度が高い。しかしながら、一定期間の使用の後に発生する削れ量も少ないため、連鎖重合官能基を有する正孔輸送性化合物を重合した化合物からなる高硬度表面層を有する電子写真感光体は、前述のように画像流れや帯電器下黒帯の問題を潜在的に有する。画像流れや帯電器下黒帯等の問題を防止する手段として、従来のような酸化防止剤を添加するという方法では、重合を阻害するため、硬化度が低下し、耐久性、寿命の点で、問題がある。また、画像流れがさらに悪化するという現象が起こり、問題が解決できなかった。
本発明は、上述の問題に鑑みてなされたものであり、高耐久、高寿命でありながら、高湿下での画像流れや、帯電器下黒帯の問題の発生しない、優れた電子写真感光体、プロセスカートリッジ及び電子写真装置を提供することを目的とする。 The present invention has been made in view of the above-described problems, and has excellent durability and long life, and does not cause problems such as image flow under high humidity and black belt under a charger. It is an object to provide a body, a process cartridge, and an electrophotographic apparatus.
本発明は、支持体と、該支持体上に設けられた感光層とを有する電子写真感光体であって、該電子写真感光体の最表面層が、下記化合物（Ａ）と下記化合物（Ｂ）とを重合して得られる重合体を含有する層であることを特徴とする電子写真感光体：
化合物（Ａ）：同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送性化合物；
化合物（Ｂ）：下記構造式（４）で示される化合物
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule;
Compound (B): Compound represented by the following structural formula (4)
また、本発明によるプロセスカートリッジ及び電子写真装置は、上述の電子写真感光体と、該電子写真感光体の表面を帯電させる帯電手段、該電子写真感光体の表面に形成された静電潜像をトナーで現像して該電子写真感光体の表面にトナー像を形成する現像手段、及び、該電子写真感光体の表面の転写残りトナーを除去するクリーニング手段からなる群より選ばれた少なくとも１つの手段とを一体に支持し、電子写真装置本体に着脱可能であることを特徴とするプロセスカートリッジである。
また、本発明は、上述の電子写真感光体、該電子写真感光体を帯電させる帯電手段、帯電した電子写真感光体の表面に対して露光を行って該電子写真感光体の表面に静電潜像を形成する露光手段、該電子写真感光体の表面に形成された静電潜像をトナーで現像して該電子写真感光体の表面にトナー像を形成する現像手段、及び、電子写真感光体の表面に形成されたトナー像を転写材に転写する転写手段を備えることを特徴とする電子写真装置である。
The process cartridge and the electrophotographic apparatus according to the present invention include the above-described electrophotographic photosensitive member , charging means for charging the surface of the electrophotographic photosensitive member, and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member. At least one means selected from the group consisting of developing means for developing with toner to form a toner image on the surface of the electrophotographic photosensitive member, and cleaning means for removing transfer residual toner on the surface of the electrophotographic photosensitive member Is a process cartridge that can be attached to and detached from the main body of the electrophotographic apparatus .
The present invention also provides an electrostatic latent image on the surface of the electrophotographic photosensitive member by exposing the surface of the electrophotographic photosensitive member to the above-described electrophotographic photosensitive member, charging means for charging the electrophotographic photosensitive member, and the surface of the charged electrophotographic photosensitive member. Exposure means for forming an image, developing means for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner to form a toner image on the surface of the electrophotographic photosensitive member, and electrophotographic photosensitive member An electrophotographic apparatus comprising transfer means for transferring a toner image formed on the surface of the toner image onto a transfer material.
本発明によれば、高硬化性の高耐久、高寿命表面層を有する電子写真感光体において、硬化度を損なわず、画像流れや帯電器下黒帯の発生の問題がなく、高耐久、高寿命の優れた電子写真感光体を提供することができる。 According to the present invention, in an electrophotographic photosensitive member having a highly curable, highly durable and long-life surface layer, the degree of curing is not impaired, and there is no problem of image flow or occurrence of a black belt under a charger, and it is highly durable and highly durable. An electrophotographic photosensitive member having an excellent lifetime can be provided.
本発明による電子写真感光体は、導電性支持体上に、感光層として電荷発生材料を含有する電荷発生層と電荷輸送材料を含有する電荷輸送層とをこの順に積層した構成、又は電荷発生層と電荷輸送層とを逆に積層した構成であってもよい。また、本発明による電子写真感光体は、電荷発生材料と電荷輸送材料とを同一層中に分散した単層からなる構成であってもよい。前者の積層型においては、電荷輸送層が二層以上の構成であってもよい。また、後者の単層型においては、電荷発生材料と電荷輸送材料とを同一層に含有する感光層上に更に電荷輸送層を構成してもよく、更には電荷発生層又は電荷輸送層上に保護層を形成させてもよい。 The electrophotographic photoreceptor according to the present invention has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated in this order on a conductive support, or a charge generation layer. The charge transport layer may be reversely laminated. Further, the electrophotographic photoreceptor according to the present invention may have a single layer structure in which a charge generation material and a charge transport material are dispersed in the same layer. In the former stacked type, the charge transporting layer may be composed of two or more layers. In the latter single layer type, a charge transport layer may be further formed on the photosensitive layer containing the charge generation material and the charge transport material in the same layer, and further on the charge generation layer or the charge transport layer. A protective layer may be formed.
いずれの構成をとった場合でも、本発明による電子写真感光体の最表面層は、以下の化合物（Ａ）と化合物（Ｂ）とを重合して得られる重合体を含有する層であることを特徴とする。 Even when taking any configuration, the outermost layer of the electrophotographic photosensitive member according to the present invention is a layer having containing a polymer obtained by polymerizing the following compounds (A) and (B) Features.
化合物（Ａ）：同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送性化合物
化合物（Ｂ）：連鎖重合性官能基とアリーレンエーテル基を有し、水酸基を有さず、連鎖重合性官能基とアリーレンエーテル基の間に少なくとも下記構造式（１）で示される官能基を有し、かつ正孔輸送機能を有さない化合物
なお、化合物（Ａ）と化合物（Ｂ）の詳細については、後述する。
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule Compound (B): having a chain polymerizable functional group and an arylene ether group, having no hydroxyl group and having a chain at least it has a functional group represented by the following structural formula (1), and compounds having no hole transporting function between the polymerizable functional group and arylene ether groups
Details of the compound (A) and the compound (B) will be described later.
（構造式（１）中、ｖ及びｗは、０〜５の整数を示す。ただし、ｖとｗとの和は、２〜５である。）(In structural formula (1), v and w represent integers of 0 to 5. However, the sum of v and w is 2 to 5.)
（支持体）
本発明による電子写真感光体において、支持体は、導電性を有するものであればよい。例えばアルミニウム、銅、クロム、ニッケル、亜鉛及びステンレス等の金属や合金をドラム状又はシート状に成形したもの、アルミニウム及び銅等の金属箔をプラスチックフィルムにラミネートしたものであってもよい。また、アルミニウム、酸化インジウム及び酸化錫等をプラスチックフィルムに蒸着したもの、導電性材料を単独又は結着樹脂と共に塗布して導電層を設けた金属、プラスチックフィルム及び紙等が挙げられる。
(Support)
In the electrophotographic photoreceptor according to the present invention, the support may be any one having conductivity. For example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc, and stainless steel formed into a drum shape or a sheet shape, or a metal foil such as aluminum and copper laminated on a plastic film may be used. In addition, examples include aluminum, indium oxide, tin oxide, and the like deposited on a plastic film, a metal, a plastic film, paper, and the like provided with a conductive layer by applying a conductive material alone or with a binder resin.
（下引き層）
本発明による電子写真感光体において、支持体と感光層との間にバリアー機能と接着機能とを有する下引き層を設けてもよい。下引き層は、感光層の接着性改良、塗工性改良、支持体の保護、支持体の欠陥の被覆、支持体からの電荷注入性改良、また感光層の電気的破壊に対する保護等のために形成される。
(Underlayer)
In the electrophotographic photoreceptor according to the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the support and the photosensitive layer. The undercoat layer is used to improve the adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the support, and protect against electrical breakdown of the photosensitive layer. Formed.
下引き層の材料としては、ポリビニルアルコール、ポリ−Ｎ−ビニルイミダゾール、ポリエチレンオキシド、エチルセルロース、エチレン−アクリル酸共重合体、カゼイン、ポリアミド、Ｎ−メトキシメチル化６ナイロン、共重合ナイロンなどが挙げられる。また、にかわ及びゼラチン等が挙げられる。下引き層は、これらの材料をそれぞれに適した溶剤に溶解した溶液を支持体上に塗布し、乾燥することによって形成される。膜厚は、０．１〜２μｍであることが好ましい。 Examples of the material for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, and copolymer nylon. . In addition, glue and gelatin are listed. The undercoat layer is formed by applying a solution prepared by dissolving these materials in a solvent suitable for each of the materials onto a support and drying it. The film thickness is preferably 0.1 to 2 μm.
（電荷発生材料、電荷発生層）
本発明による電子写真感光体において、積層型の感光層を有する場合、その電荷発生層は、少なくとも電荷発生材料と結着樹脂とからなる。電荷発生材料としては、セレン−テルル、ピリリウム、チアピリリウム系染料、また各種の中心金属及び結晶系が挙げられる。具体的には例えば、α、β、γ、ε及びＸ型等の結晶型を有するフタロシアニン化合物が挙げられる。また、アントアントロン顔料、ジベンズピレンキノン顔料、ピラントロン顔料、トリスアゾ顔料、ジスアゾ顔料、モノアゾ顔料、インジゴ顔料、キナクリドン顔料、非対称キノシアニン顔料、キノシアニンなどが挙げられる。さらに、特許文献１１に記載のアモルファスシリコン等が挙げられる。
(Charge generation material, charge generation layer)
When the electrophotographic photoreceptor according to the present invention has a laminated photosensitive layer, the charge generation layer is composed of at least a charge generation material and a binder resin. Examples of the charge generating material include selenium-tellurium, pyrylium, thiapyrylium dyes, and various central metals and crystal systems. Specific examples include phthalocyanine compounds having crystal types such as α, β, γ, ε, and X type. Moreover, anthanthrone pigment, dibenzpyrenequinone pigment, pyranthrone pigment, trisazo pigment, disazo pigment, monoazo pigment, indigo pigment, quinacridone pigment, asymmetric quinocyanine pigment, quinocyanine and the like can be mentioned. Furthermore, the amorphous silicon etc. of patent document 11 are mentioned.
結着樹脂としては、スチレン、酢酸ビニル、塩化ビニル、アクリル酸エステル、メタクリル酸エステル、フッ化ビニリデン、トリフルオロエチレン等のビニル化合物の重合体及び共重合体が挙げられる。また、ポリビニルアルコール、ポリビニルアセタール、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイド、ポリウレタン、セルロース樹脂、フェノール樹脂、メラミン樹脂、ケイ素樹脂及びエポキシ樹脂等が挙げられる。 Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene. In addition, examples include polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.
電荷発生層の製造方法としては、まず、上述の電荷発生材料を０．３〜４倍量の結着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、アドライダー及びロールミル等の方法でよく分散する。得た分散液を塗布し、乾燥することによって形成するか、電荷発生材料の蒸着膜等、単独組成の膜として形成する。その膜厚は５μｍ以下であることが好ましく、特には０．１〜２μｍであることが好ましい。 As a method for producing the charge generation layer, first, the charge generation material described above, such as a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an adrider, and a roll mill, together with 0.3 to 4 times the amount of binder resin and solvent are used. Disperse well by method. The obtained dispersion is applied and dried, or formed as a single composition film such as a vapor-deposited film of a charge generating material. The film thickness is preferably 5 μm or less, and particularly preferably 0.1 to 2 μm.
（電荷輸送材料、電荷輸送層）
本発明による電子写真感光体において、積層型の感光層を構成する電荷輸送層又は単層型の感光層に含まれる電荷輸送材料は、上述の化合物（Ａ）や適当な電荷輸送材料を用いることができる。この適当な電荷輸送材料としては、例えば、ポリ−Ｎ−ビニルカルバゾール及びポリスチリルアントラセン等の複素環や縮合多環芳香族を有する高分子化合物が挙げられる。また、ピラゾリン、イミダゾール、オキサゾール、トリアゾール及びカルバゾール等の複素環化合物、トリフェニルメタン等のトリアリールアルカン誘導体、トリフェニルアミン等のトリアリールアミン誘導体が挙げられる。さらに、フェニレンジアミン誘導体、Ｎ−フェニルカルバゾール誘導体、スチルベン誘導体及びヒドラジン誘導体等の低分子化合物等が挙げられる。電荷輸送層は、これら電荷輸送材料と結着樹脂とからなる。
(Charge transport material, charge transport layer)
In the electrophotographic photoreceptor according to the present invention, the above-mentioned compound (A) or an appropriate charge transporting material is used as the charge transporting material contained in the charge transporting layer constituting the laminated photosensitive layer or the single-layered photosensitive layer. Can do. Examples of suitable charge transporting materials include polymer compounds having a heterocyclic ring or condensed polycyclic aromatics such as poly-N-vinylcarbazole and polystyrylanthracene. In addition, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, and triarylamine derivatives such as triphenylamine can be given. Furthermore, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazine derivatives are exemplified. The charge transport layer is composed of these charge transport materials and a binder resin.
結着樹脂は、上述の電荷発生層で言及した結着樹脂を使用し得る。電荷発生材料と電荷輸送材料とを同一層中に分散した単層の場合、電荷輸送材料、電荷発生材料及び結着樹脂からなる。 As the binder resin, the binder resin mentioned in the above charge generation layer can be used. In the case of a single layer in which the charge generation material and the charge transport material are dispersed in the same layer, the charge generation material and the charge generation material are composed of a charge transport material, a charge generation material, and a binder resin.
上述のように、本発明による電子写真感光体は、この電子写真感光体を構成する感光層が積層型であっても単層型であっても、最表面層が、以下の化合物（Ａ）と化合物（Ｂ）とを重合して得られる重合体を含有する層であることを特徴とする。 As described above, the electrophotographic photosensitive member according to the present invention has the following compound (A) as the outermost surface layer, regardless of whether the photosensitive layer constituting the electrophotographic photosensitive member is a multilayer type or a single layer type. and wherein the compound (B) and the polymerization to obtain the polymer is a layer having free.
化合物（Ａ）：同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送性化合物
化合物（Ｂ）：連鎖重合性官能基とアリーレンエーテル基を有し、水酸基を有さず、連鎖重合性官能基とアリーレンエーテル基の間に少なくとも下記構造式（１）で示される官能基を有し、かつ正孔輸送機能を有さない化合物
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule Compound (B): having a chain polymerizable functional group and an arylene ether group, having no hydroxyl group and having a chain at least it has a functional group represented by the following structural formula (1), and compounds having no hole transporting function between the polymerizable functional group and arylene ether groups
（構造式（１）中、ｖ及びｗは、０〜５の整数を示す。ただし、ｖとｗとの和は、２〜５である。）(In structural formula (1), v and w represent integers of 0 to 5. However, the sum of v and w is 2 to 5.)
本発明において、化合物（Ａ）とは、正孔輸送機能を有する化合物であり、かつ同一分子内に２つ以上の連鎖重合性官能基を有する化合物を意味する。化合物（Ａ）は、正孔輸送機能を有する点で、トリアリールアミン構造を有することが好ましい。正孔輸送機能を発現する構造としては各種あるが、本発明の効果を最も得るためにはトリアリールアミン構造が最も好ましい。特に、無置換または水酸基以外の置換基で置換されたトリフェニルアミン構造が好ましい。 In the present invention, the compound (A) means a compound having a hole transport function and having two or more chain polymerizable functional groups in the same molecule. The compound (A) preferably has a triarylamine structure in that it has a hole transport function. There are various structures exhibiting a hole transport function, but a triarylamine structure is most preferable in order to obtain the best effects of the present invention. In particular, a triphenylamine structure which is unsubstituted or substituted with a substituent other than a hydroxyl group is preferable.
一方、連鎖重合性官能基としては、一般的な付加反応、縮合反応、脱水反応、重合反応、架橋反応等が可能な官能基群から最適なものを選択すればよい。特に、反応効率等の点から、重合又は架橋性反応基が好ましい。重合又は架橋性反応基の例としては、ラジカル重合又はイオン重合等の連鎖重合性官能基、付加縮合、重縮合、重付加等の逐次重合性官能基等が挙げられる。特に、反応効率の点から、連鎖重合性官能基が好ましい。ここで、連鎖重合性官能基について詳しく説明する。 On the other hand, as the chain-polymerizable functional group, an optimal group may be selected from a functional group group capable of general addition reaction, condensation reaction, dehydration reaction, polymerization reaction, crosslinking reaction and the like. In particular, from the viewpoint of reaction efficiency and the like, a polymerization or crosslinkable reactive group is preferable. Examples of the polymerization or crosslinkable reactive group include chain polymerizable functional groups such as radical polymerization or ionic polymerization, sequential polymerizable functional groups such as addition condensation, polycondensation, and polyaddition. In particular, a chain polymerizable functional group is preferable from the viewpoint of reaction efficiency. Here, the chain polymerizable functional group will be described in detail.
高分子物の生成反応を大きく連鎖重合と逐次重合に分けた場合、本発明において、連鎖重合とは、前者の重合反応形態を言う。詳しくは、例えば、非特許文献１に説明されているように、その形態が主にラジカル又はイオン等の中間体を経由して反応が進行する不飽和重合、開環重合及び異性化重合等のことをいう。ここでは、その大半を占め応用範囲の広い不飽和重合又は開環重合性官能基の具体例を示す。 When the polymer formation reaction is largely divided into chain polymerization and sequential polymerization, in the present invention, chain polymerization refers to the former polymerization reaction mode. Specifically, for example, as described in Non-Patent Document 1, such as unsaturated polymerization, ring-opening polymerization and isomerization polymerization in which the reaction proceeds mainly via an intermediate such as a radical or an ion. That means. Here, specific examples of unsaturated polymerization or ring-opening polymerizable functional groups that occupy most of them and have a wide application range are shown.
不飽和重合とは、ラジカル、イオン等によって不飽和基、例えばＣ＝Ｃ、Ｃ≡Ｃ、Ｃ＝Ｏ、Ｃ＝Ｎ、Ｃ≡Ｎ等が重合する反応であるが、主にはＣ＝Ｃ同士の反応である。不飽和重合性官能基の具体例を表１に示すがこれらに限定されるものではない。 Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, and C≡N are polymerized by radicals, ions, etc., but mainly C═C. It is a reaction between each other. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.
不飽和重合性官能基の具体例
Specific examples of unsaturated polymerizable functional groups
表中、Ｒは、置換若しくは無置換の、アルキル基、アラルキル基若しくはアリール基又は水素原子を示す。置換若しくは無置換のアルキル基としては、メチル基、エチル基、プロピル基及びブチル基等の置換若しくは無置換体が挙げられる。置換若しくは無置換のアラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、フルフリル基及びチエニル基等の置換若しくは無置換体が挙げられる。置換若しくは無置換のアリール基としては、フェニル基、ナフチル基及びアンスリル基等の置換若しくは無置換体が挙げられる。 In the table, R represents a substituted or unsubstituted alkyl group, aralkyl group, aryl group, or hydrogen atom. Examples of the substituted or unsubstituted alkyl group include substituted or unsubstituted products such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the substituted or unsubstituted aralkyl group include substituted or unsubstituted products such as a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. Examples of the substituted or unsubstituted aryl group include substituted or unsubstituted compounds such as a phenyl group, a naphthyl group, and an anthryl group.
開環重合とは、炭素環、オキソ環及び窒素ヘテロ環等のひずみを有する不安定な環状構造が触媒の作用で活性化され、開環すると同時に重合を繰り返し鎖状高分子物を生成する反応を言う。この場合、基本的にはイオンが活性種として作用するものが大部分である。開環重合性官能基の具体例を表２に示すがこれらに限定されるものではない。 Ring-opening polymerization is a reaction in which unstable cyclic structures with distortions such as carbocycles, oxo rings, and nitrogen heterocycles are activated by the action of a catalyst, and at the same time, the polymerization is repeated to produce a chain polymer. Say. In this case, basically, most of the ions act as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.
開環重合性官能基の具体例
Specific examples of ring-opening polymerizable functional groups
なお、表中のＲは、上述の不飽和重合性官能基で定義した通りである。 In the table, R is as defined in the unsaturated polymerizable functional group described above.
本発明において、上述の化合物（Ａ）は、水酸基を有さないことが好ましい。化合物（Ａ）が水酸基を有する場合、電子写真感光体の雰囲気中の水分を吸着する傾向があると考えられ、本発明の効果が小さい。 In the present invention, the above compound (A) preferably has no hydroxyl group. When the compound (A) has a hydroxyl group, it is considered that there is a tendency to adsorb moisture in the atmosphere of the electrophotographic photosensitive member, and the effect of the present invention is small.
また、化合物（Ａ）は、アリーレンエーテル基を有さないことが好ましい。 Moreover, it is preferable that a compound (A) does not have an arylene ether group.
一方、本発明において、上述の化合物（Ｂ）は、連鎖重合性官能基とアリーレンエーテル基とを有し、水酸基を有さず、連鎖重合性官能基とアリーレンエーテル基との間に少なくとも下記構造式（１）で示される官能基を有し、かつ正孔輸送機能を有さない化合物である。 On the other hand, in the present invention, the above-mentioned compound (B) has a chain polymerizable functional group and an arylene ether group, has no hydroxyl group, and at least the following structure between the chain polymerizable functional group and the arylene ether group: having a functional group represented by the formula (1), and a compound having no hole transporting function.
（構造式（１）中、ｖ及びｗは、０〜５の整数を示す。ただし、ｖとｗとの和は、２〜５である。）
(In structural formula (1), v and w represent an integer of 0 to 5. However, the sum of v and w is 2 to 5. )
化合物（Ｂ）は、アリーレンエーテル基を２個以上４個以下有することが好ましい。２個未満であると、構造式（１）の部分が切れにくくなると考えられる理由で本発明の効果が小さくなる。また、４個を越えると、化合物（Ａ）に対する化合物（Ｂ）の立体構造が大きくなり、その結果、正孔輸送機能が小さくなるため、感度が低下するという弊害が現れる。 The compound (B) preferably has 2 to 4 arylene ether groups. When the number is less than 2, the effect of the present invention is reduced for the reason that the part of the structural formula (1) is considered to be difficult to cut. On the other hand, when the number exceeds four, the three-dimensional structure of the compound (B) with respect to the compound (A) becomes large, and as a result, the hole transport function becomes small, resulting in a detrimental effect that the sensitivity is lowered.
化合物（Ｂ）は、下記構造式（２）で示される化合物であることが好ましい。 Compound (B) is preferably a Ru of compound represented by the following structural formula (2).
（構造式（２）中、Ｐは、連鎖重合性反応基を示す。Ｘは、ｎ価（ｎは２〜４の整数）の有機残基を示す。Ｒ２０１〜Ｒ２０４は、それぞれ独立に、水素原子、又は、１価の水酸基でない有機残基を示す。ｖ及びｗは、０〜５の整数を示す。ただし、ｖとｗとの和は、２〜５である。）
(In the structural formula (2), P is shows the chain polymerizable reactive group. X is n-valent (n is shows the organic residue of an integer of 2 to 4). R 201 ~R 204, respectively independently, hydrogen atom, or, shows the monovalent hydroxyl group such have organic residues. v and w, is the sum of the. Here, v and w represent an integer of 0 to 5, at 2-5 Yes. )
また、化合物（Ｂ）は、下記構造式（３）で示される化合物であることが好ましい。 The compound (B) is preferably a Ru of compound represented by the following structural formula (3).
（構造式（３）中、Ｐは、連鎖重合性反応基を示す。Ｒ３０１〜Ｒ３１０は、それぞれ独立に、水素原子、又は、１価の水酸基でない有機残基を示す。ｐ、ｑ、ｒ及びｓは、０〜５の整数を示す。ただし、ｐとｑとの和及びｒとｓとの和は、２〜５である。）
(In the structural formula (3), P is shows the chain polymerizable reactive group. R 301 to R 310 are independently a hydrogen atom, or, shows the monovalent hydroxyl group such have an organic residue . p, q, r and s represents an integer of 0 to 5. However, the sum of the sum and r and s of p and q is 2-5.)
さらに、化合物（Ｂ）は、下記構造式（４）で示される化合物であることが好ましい。 Further, the compound (B) is preferably a Ru of compound represented by the following structural formula (4).
（構造式（４）中、Ｐは、連鎖重合性反応基を示す。Ｒ４０１及びＲ４０２は、それぞれ独立に、１価の水酸基でない有機残基を示し、ｐ、ｑ、ｒ及びｓは、０〜５の整数を示す。ただし、ｐとｑとの和及びｒとｓとの和は、２〜５である。）
(In the structural formula (4), P is shows the chain polymerizable reactive group. R 401 and R 402 are each independently a have organic residues in a monovalent hydroxyl, p, q, r and s represents an integer of 0 to 5. However, the sum of p and q and the sum of r and s are 2 to 5. )
なお、上述の構造式（２）乃至（４）で示される化合物の置換基Ｘに定義した有機残基としては、特に限定されないが、アルカンまたはシクロアルカンから水素原子をｎ個除いたものが好ましい。また、上述の構造式（２）乃至（４）で示される化合物の置換基Ｒ４０１及びＲ４０２並びにＲ３０１〜Ｒ３１０に定義した有機残基としては、特に限定されないが、アルキル基が好ましく、メチル基がより好ましい。さらに、上述のアリーレンエーテル基は、無置換又は水酸基以外の置換基で置換されたフェニレンエーテル基であることが好ましい。 Incidentally, those examples of the organic residue as defined substituent X of shows the compounds by the above structural formula (2) to (4), is not particularly limited, except the n hydrogen atoms from an alkane or cycloalkane preferable. The organic residue as defined substituents R 401 and R 402 and R 301 to R 310 of shown the compounds by the above structural formula (2) to (4), is not particularly limited, an alkyl group is preferable A methyl group is more preferable. Furthermore, the above-mentioned arylene ether group is preferably a phenylene ether group which is unsubstituted or substituted with a substituent other than a hydroxyl group.
いずれの場合も、本発明による電子写真感光体の最表面層は、上述の化合物（Ａ）及び化合物（Ｂ）を含有する溶液を塗布後、重合／架橋反応させるのが好ましい。特に、前もって化合物（Ａ）及び化合物（Ｂ）を含む溶液を反応させて硬化物を得た後に、再度溶剤中に分散ないし溶解させた混合物等を用いて、表面層を形成することも可能である。 In any case, the outermost surface layer of the electrophotographic photosensitive member according to the present invention is preferably subjected to polymerization / crosslinking reaction after applying the solution containing the compound (A) and the compound (B). In particular, it is also possible to form a surface layer using a mixture or the like that is dispersed or dissolved in a solvent again after reacting a solution containing the compound (A) and the compound (B) in advance to obtain a cured product. is there.
本発明による電子写真感光体において、この電子写真感光体の最表面層に対応する層が電荷輸送層である場合、電荷輸送材料として用いる化合物（Ａ）の量は、硬化後の電荷輸送層の全質量に対して、正孔輸送性基が２０質量％以上含有されていることが好ましい。特に、４０質量％以上含有されていることがより好ましい。なお、この正孔輸送性基とは、化合物（Ａ）を構成する置換基を全て水素に置き換えて得た化合物に対応するものを言う。例えば、トリアリールアミンを化合物（Ａ）として用いる場合、その置換基をすべて水素に置き換えたものを言う。正孔輸送性基が２０質量％未満であると、電荷輸送能が低下し、感度の低下及び残留電位の上昇等の問題点が生じ易くなる。電荷輸送層の膜厚は、１〜５０μｍであることが好ましく、特には３〜３０μｍであることがより好ましい。 In the electrophotographic photoreceptor according to the present invention, when the layer corresponding to the outermost surface layer of the electrophotographic photoreceptor is a charge transport layer, the amount of the compound (A) used as the charge transport material is the amount of the cured charge transport layer. It is preferable that the hole transporting group is contained in an amount of 20% by mass or more based on the total mass. In particular, the content is more preferably 40% by mass or more. In addition, this positive hole transportable group means the thing corresponding to the compound obtained by substituting all the substituents which comprise a compound (A) with hydrogen. For example, when triarylamine is used as the compound (A), it means that all the substituents are replaced with hydrogen. When the hole transporting group is less than 20% by mass, the charge transporting ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur. The thickness of the charge transport layer is preferably 1 to 50 μm, and more preferably 3 to 30 μm.
この場合、両者の全質量に対し、化合物（Ａ）の質量が２０〜７０質量％であることが好ましく、２５〜６０質量％であることがより好ましい。化合物（Ａ）の量が２０質量％未満であると、電荷輸送能が低下し、感度の低下及び残留電位の上昇等の問題点が生じ易くなる。また、化合物（Ａ）の量が７０質量％を越えると、相対的に化合物（Ｂ）の量が少なくなり、高湿下での画像流れや帯電器下黒帯等の問題が生じやすくなる。電荷輸送層の膜厚は、上層の表面保護層と合わせた総膜厚が１〜５０μｍとなることが好ましく、特には５〜３０μｍであることが好ましい。 In this case, it is preferable that the mass of a compound (A) is 20-70 mass% with respect to both total mass, and it is more preferable that it is 25-60 mass%. When the amount of the compound (A) is less than 20% by mass, the charge transport ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur. On the other hand, when the amount of the compound (A) exceeds 70% by mass, the amount of the compound (B) is relatively small, and problems such as image flow under high humidity and a black belt under a charger are likely to occur. The total thickness of the charge transport layer combined with the upper surface protective layer is preferably 1 to 50 μm, and particularly preferably 5 to 30 μm.
また、本発明において、上述のいずれの場合にも、化合物（Ａ）と化合物（Ｂ）とを重合して得られた重合体を含有する感光層に、この化合物（Ａ）以外の電荷輸送材料を含有させてもよい。 Further, in the present invention, in the case of any of the above are also compounds (A) and (B) and a photosensitive layer having containing the resulting polymer by polymerizing a charge transport material other than the compound (A) May be included.
本発明による電子写真感光体を構成する感光層が単層型感光層である場合、化合物（Ａ）、電荷発生材料及び化合物（Ｂ）を含有する溶液を重合／架橋することによって形成してもよい。また、電荷発生材料及び電荷輸送材料を有する単層型感光層上に化合物（Ａ）と化合物（Ｂ）とを含有する溶液を塗布後、重合／架橋することによって形成してもよい。 When the photosensitive layer constituting the electrophotographic photoreceptor according to the present invention is a monolayer type photosensitive layer, it may be formed by polymerizing / crosslinking a solution containing the compound (A), the charge generating material and the compound (B). Good. Alternatively, it may be formed by applying a solution containing the compound (A) and the compound (B) on a monolayer type photosensitive layer having a charge generation material and a charge transport material, and then polymerizing / crosslinking.
本発明における化合物（Ａ）の例を以下に示すが、これらに限定されるものではない。 Although the example of the compound (A) in this invention is shown below, it is not limited to these.
また、本発明における化合物（Ｂ）の例を以下に示すが、これらに限定されるものではない。 Moreover, although the example of the compound (B) in this invention is shown below, it is not limited to these.
（添加剤）
本発明による電子写真感光体を構成する感光層は、目的に応じて、各種添加剤を有していてもよい。
(Additive)
The photosensitive layer constituting the electrophotographic photoreceptor according to the present invention may have various additives depending on the purpose.
上述の最表面層の他、本発明による電子写真感光体の各層用の塗布液を塗布する方法としては、例えば浸漬コーティング法、スプレーコーティング法、カーテンコーティング法及びスピンコーティング法等が挙げられる。なかでも、効率性／生産性の点から、浸漬コーティング法が好ましい。また、蒸着、プラズマ、その他の公知の製膜方法が適宜選択できる。 In addition to the outermost surface layer described above, examples of the method for applying the coating solution for each layer of the electrophotographic photoreceptor according to the present invention include a dip coating method, a spray coating method, a curtain coating method, and a spin coating method. Of these, the dip coating method is preferable from the viewpoint of efficiency / productivity. Also, vapor deposition, plasma, and other known film forming methods can be appropriately selected.
（重合）
本発明において、上述の添加剤を重合させる手法としては、熱、紫外線、γ線、電子線のような高エネルギー放射線を利用するのが好ましく、場合によっては重合開始剤を併用してもよい。但し、開始剤類は、電子写真特性に悪影響を及ぼすことのないよう、適宜選択すればよい。特に、開始剤を必要としない点と、重合効率が高い点とから、電子線等の高エネルギー線を利用することが好ましい。
(polymerization)
In the present invention, as a method for polymerizing the above-mentioned additives, it is preferable to use high energy radiation such as heat, ultraviolet rays, γ rays, and electron beams, and a polymerization initiator may be used in some cases. However, the initiators may be appropriately selected so as not to adversely affect the electrophotographic characteristics. In particular, it is preferable to use a high energy beam such as an electron beam because it does not require an initiator and has a high polymerization efficiency.
（熱重合）
熱により重合反応を行う際、熱エネルギーのみで重合反応が進行する場合と重合開始剤が必要となる場合とがあるが、より低い温度で効率よく反応を進行させるためには、開始剤を添加することが好ましい。
(Thermal polymerization)
When carrying out the polymerization reaction with heat, there are cases where the polymerization reaction proceeds only with thermal energy and there are cases where a polymerization initiator is required, but in order to advance the reaction efficiently at a lower temperature, an initiator is added. It is preferable to do.
この場合に用いられる重合開始剤としては、室温以上で半減期を有するものであればよい。具体例には、過硫酸アンモン、ジクミルパーオキサイド、ベンゾイルパーオキサイド、シクロヘキサンパーオキサイド、ｔ−ブチルハイドロパーオキサイド及びジ−ｔ−ブチルパーオキサイド等の過酸化物やアゾビスブチロニトリル等のアゾ系化合物等である。重合開始剤の添加量は、連鎖重合性官能基を有する化合物１００質量部に対して０．０１〜１０質量部程度であり、反応系の温度は、開始剤に応じて、室温〜２００℃の間で適宜選択してもよい。 The polymerization initiator used in this case may be any one having a half-life at room temperature or higher. Specific examples include peroxides such as ammonium persulfate, dicumyl peroxide, benzoyl peroxide, cyclohexane peroxide, t-butyl hydroperoxide and di-t-butyl peroxide, and azo such as azobisbutyronitrile. Compounds. The addition amount of the polymerization initiator is about 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable functional group, and the temperature of the reaction system is from room temperature to 200 ° C. depending on the initiator. You may select suitably between.
（光（紫外光）重合）
紫外線により重合反応を行う際には、光エネルギーのみで反応を進行させてもよいが、一般には光重合開始剤が併用される。
(Light (ultraviolet light) polymerization)
When the polymerization reaction is performed with ultraviolet rays, the reaction may proceed only with light energy, but generally a photopolymerization initiator is used in combination.
この場合の重合開始剤とは、主には波長４００ｎｍ以下の紫外線を吸収してラジカルやイオン等の活性種を生成し、重合を開始させるものを言う。具体的には、アセトフェノン、ベンゾイン、ベンゾフェノン及びチオキサンソン系等のラジカル重合開始剤、ジアゾニウム化合物、スルフォニウム化合物、ヨードニウム化合物及び金属錯体化合物等のイオン重合開始剤等である。近年、波長４００ｎｍ以上で赤外／可視領域の光を吸収して先の活性種を生成する重合開始剤が発表されており、それらを利用して、赤外／可視領域の光による重合反応を行ってもよい。開始剤の添加量は、連鎖重合性官能基を有する化合物１００質量部に対して、０．０１〜５０質量部程度である。なお、本発明において、上述した熱及び光重合開始剤を併用してもよい。 In this case, the polymerization initiator mainly refers to an agent that absorbs ultraviolet rays having a wavelength of 400 nm or less to generate active species such as radicals and ions and starts polymerization. Specific examples include radical polymerization initiators such as acetophenone, benzoin, benzophenone, and thioxanthone, and ion polymerization initiators such as diazonium compounds, sulfonium compounds, iodonium compounds, and metal complex compounds. In recent years, a polymerization initiator that absorbs light in the infrared / visible region at a wavelength of 400 nm or more to generate the previous active species has been announced, and the polymerization reaction by light in the infrared / visible region is utilized using them. You may go. The addition amount of the initiator is about 0.01 to 50 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable functional group. In the present invention, the above-described heat and photopolymerization initiator may be used in combination.
（プロセスカートリッジ及び電子写真装置）
次に、本発明による上述の電子写真感光体を有するプロセスカートリッジ及び電子写真装置について説明する。図１は、本発明による電子写真感光体を有するプロセスカートリッジを用いる電子写真装置の概略構成の例を示す。図１において、１はドラム状の本発明による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又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等の露光手段（図示せず）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る。帯電手段３としてスコロトロンやコロトロンのようなコロナ帯電器を用いた場合、上述の課題に挙げた問題点が発生しやすい。従って、本発明の効果は帯電手段３がコロナ帯電器の場合に特に顕著に得られる。
(Process cartridge and electrophotographic apparatus)
Next, a process cartridge and an electrophotographic apparatus having the above-described electrophotographic photoreceptor according to the present invention will be described. FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus using a process cartridge having an electrophotographic photosensitive member according to the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member according to the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. The electrophotographic photosensitive member 1, in the rotation process, positive or on the peripheral surface thereof by a static-unit 3 receives the uniform charging of a predetermined negative potential, then the slit exposure or laser beam scanning exposure or the like of an exposure unit (not shown) The exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1 . When using a static-unit 3 as a scorotron or the corona charger such as a corotron, problems mentioned of the above-described problems are likely to occur. Therefore, the effect of the present invention is a band conductor means 3 obtained particularly pronounced in the case of the corona charger.
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る。その後、現像されたトナー像は、給紙部（図示せず）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の回転と同期して給紙された転写材７に、転写手段６により順次転写されていく。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て、複写物（コピー）として装置外へプリントアウトされる。 The electrostatic latent image thus formed is then developed with toner by the developing means 5. Thereafter, toner over image is generated, the paper feeding unit transferred has been fed in synchronism with the rotation of the electrophotographic photosensitive member 1 between the (not shown) between the electrophotographic photosensitive member 1 and the transfer means 6 material 7 Then, the images are sequentially transferred by the transfer means 6. 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, and printed out as a copy (copy).
像転写後の電子写真感光体１の表面は、クリーニング手段９によって転写残りトナーの除去を受けて清浄面化され、更に前露光手段（図示せず）からの前露光光１０により除電処理された後、繰り返し画像形成に使用される。なお、帯電手段３が帯電ローラー等を用いた接触帯電手段である場合、前露光は、必ずしも必要ではない。 The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown). After that, it is repeatedly used for image formation. Incidentally, when the strip conductor means 3 is a contact charging means using a charging roller or the like, pre-exposure is not necessarily required.
本発明によるプロセスカートリッジは、上述の電子写真感光体１と、帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち１以上の構成要素とをプロセスカートリッジとして一体に結合して構成すればよい。このプロセスカートリッジは、複写機やレーザービームプリンター等の電子写真装置本体に対して着脱可能に構成してもよい。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、電子写真装置本体のレール等の案内手段１２を用いて装置本体に着脱可能なプロセスカートリッジ容器１１とすることができる。 The process cartridge according to the present invention, the electrophotographic photosensitive member 1 described above, strip conductor means 3, and integrally coupled to the one or more components of the components such as the developing means 5 and cleaning means 9 as a process cartridge structure do it. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, strip conductor means 3, and a cartridge integrally supported to form at least one with the electrophotographic photosensitive member 1 of the developing means 5 and cleaning means 9, the apparatus main body by using a guiding means 12 such as a rail of the electrophotographic apparatus body The process cartridge container 11 can be attached and detached.
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であってもよい。また、露光光４は、センサーで原稿を読取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動及び液晶シャッターアレイの駆動等により照射される光であってもよい。 The exposure light 4 may be reflected light or transmitted light from an original when the electrophotographic apparatus is a copying machine or a printer. The exposure light 4 may be light emitted by reading a document with a sensor, converting it into a signal, scanning with a laser beam performed according to this signal, driving an LED array, driving a liquid crystal shutter array, and the like.
本発明により電子写真感光体は、電子写真複写機に利用するのみならず、レーザービームプリンター、ＣＲＴプリンター、ＬＥＤプリンター、液晶プリンター及びレーザー製版等の電子写真応用分野にも広く用いることができる。 The electrophotographic photosensitive member according to the present invention can be used not only for electrophotographic copying machines but also widely for electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
以下に、本発明に従った実施例を例示するが、本発明は、これらに限定されるものではない。なお、「部」は「質量部」を意味する。 Examples according to the present invention are illustrated below, but the present invention is not limited thereto. “Part” means “part by mass”.
（参考例１）
導電層用の塗料を以下の手順で調製した。まず、以下の成分をφ１ｍｍガラスビーズを用いたサンドミル装置で２時間分散して、塗料を調製した。
( Reference Example 1)
A paint for the conductive layer was prepared by the following procedure. First, the following components were dispersed for 2 hours in a sand mill apparatus using φ1 mm glass beads to prepare a paint.
１０％の酸化アンチモンを含有する酸化スズで被覆した導電性酸化チタン粉体
５０部
フェノール樹脂 ２５部
メチルセロソルブ ２０部
メタノール ５部
シリコーンオイル
（ポリジメチルシロキサンポリオキシアルキレン共重合体、重量平均分子量３０００）
０．００２部
この塗料をφ３０ｍｍのアルミニウムシリンダー上に浸漬塗布方法で塗布し、１４０℃で３０分間乾燥して、膜厚１６μｍの導電層を形成した。
Conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide
50 parts phenol resin 25 parts methyl cellosolve 20 parts methanol 5 parts silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, weight average molecular weight 3000)
0.002 parts This coating material was applied on a φ30 mm aluminum cylinder by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 16 μm.
次に、Ｎ−メトキシメチル化ナイロン５部をメタノール９５部中に溶解し、下引き層用塗料を調製した。この塗料を上述の導電層上に浸漬コーティング法によって塗布し、１００℃で２０分間乾燥して、０．５μｍの下引き層を形成した。 Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an undercoat layer coating material. This paint was applied onto the above-mentioned conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form a 0.5 μm undercoat layer.
次に、下記（５）５部、ポリビニルブチラール樹脂２部及びシクロヘキサノン６０部を、φ１ｍｍガラスビーズを用いたサンドミル装置で２４時間分散した。これに、テトラヒドロフラン６０部を加えて電荷発生層用塗料とした。この塗料を上述の下引き層の上に浸漬コーティング法で塗布して、１００℃で１５分間乾燥して、膜厚０．２５μｍの電荷発生層を形成した。 Next, 5 parts of the following (5), 2 parts of polyvinyl butyral resin, and 60 parts of cyclohexanone were dispersed for 24 hours in a sand mill apparatus using φ1 mm glass beads. To this, 60 parts of tetrahydrofuran was added to obtain a charge generation layer coating material. This paint was applied on the undercoat layer by the dip coating method and dried at 100 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.25 μm.
ついで、テトラフルオロエチレン樹脂粒子（ルブロンＬ−２、ダイキン工業製）６部及びモノクロロベンゼン５０部をガラスビーズを用いたサンドミル装置で分散した。このテトラフルオロエチレン樹脂粒子分散液に化合物（Ａ）の化合物例Ｎｏ．２５３の化合物３０部、化合物（Ｂ）の化合物例Ｎｏ．７の化合物３０部を加えて溶解した。これに、ジクロロメタン３０部を加えて電荷輸送層用塗料を調製した。 Subsequently, 6 parts of tetrafluoroethylene resin particles (Lublon L-2, manufactured by Daikin Industries) and 50 parts of monochlorobenzene were dispersed in a sand mill apparatus using glass beads. In this tetrafluoroethylene resin particle dispersion, Compound Example No. 30 parts of Compound No. 253, Compound Example No. 30 parts of compound 7 were added and dissolved. 30 parts of dichloromethane was added thereto to prepare a charge transport layer coating material.
この塗料を上述の電荷発生層上に浸漬コーティング法によってコーティングし、加速電圧１５０ｋＶ、線量２４Ｍｒａｄの条件で電子線を照射し樹脂を硬化させ、膜厚１５μｍの電荷輸送層を形成して、電子写真感光体を得た。 This paint is coated on the above-described charge generation layer by dip coating, and the resin is cured by irradiating with an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 24 Mrad to form a charge transport layer having a film thickness of 15 μm. A photoreceptor was obtained.
作製した電子写真感光体について、初期の電子写真特性、繰り返し使用時の画像及び繰り返し使用後一定期間放置した後の画像を評価した。初期の電子写真特性及び耐久性は、この感光体をキヤノン（株）製ＬＢＰ−ＳＸに装着して評価した。初期の感光体特性［暗部電位Ｖｄ、明部電位Ｖｌ及び残留電位Ｖｓｌ（露光光量の４．５倍の光量を照射したときの電位）］を３３℃／８７％の環境で測定した。さらに、この環境において、一日当たり１５００枚通紙耐久し、１５時間以上置いて次の日に一日当たり１５００枚通紙耐久し、これを繰り返して延べ１５０００枚となるまで、通紙耐久試験を行った。その後１５時間放置した後、画像を出力し、下述の＜画像流れ＞及び＜帯電器下黒帯＞の基準に従って、目視による画像欠陥（画像流れ、帯電器下黒帯）の発生の有無を観察した。また、感光体の削れ量を測定した。その結果を表９６に示す。本発明による電子写真感光体は、感光体特性、画像共に良好であり、耐久での削れ量が少なく、かつ耐久を通じて画像流れも帯電器下黒帯も発生せず、良好であった。なお、削れ量は、渦電流式膜厚測定器（ＦＩＳＣＨＥＲ社製、ＰＥＲＭＡＳＣＯＰＥ ＴＹＰＥ Ｅ１１１）を用いて測定した。以下同様に測定した。 The produced electrophotographic photoreceptor was evaluated for initial electrophotographic characteristics, images during repeated use, and images after standing for a certain period after repeated use. The initial electrophotographic characteristics and durability were evaluated by attaching this photoreceptor to Canon Inc. LBP-SX. The initial photoreceptor characteristics [dark part potential Vd, bright part potential Vl and residual potential Vsl (potential when a light amount 4.5 times the amount of exposure light was irradiated)] were measured in an environment of 33 ° C./87%. Further, in this environment, 1500 sheets per day were durable, and after 15 hours or more, 1500 sheets per day were durable on the next day, and this was repeated until a total of 15000 sheets was tested. It was. After leaving it for 15 hours, output an image and check for the occurrence of visual image defects (image flow, black under charger) according to the criteria of <image flow> and <black under charger> described below. Observed. Further, the amount of photoconductor scraping was measured. The results are shown in Table 96. The electrophotographic photosensitive member according to the present invention was good in both the characteristics of the photosensitive member and the image, the amount of shaving during durability was small, and the image flow and the black belt under the charger were not generated throughout the durability. In addition, the amount of chipping was measured using an eddy current film thickness measuring device (manufactured by FISCHER, PERMASCOPE TYPE E111). Thereafter, the same measurement was performed.
＜画像流れ＞
文字画像および１ドットを図２に示すように桂馬状に配置したパターンの画像の再現性を１１〜０の１２段階に分け評価した。最も良いものを１１、最も悪いものを０とし、４以下は本発明の効果が得られていないものと考えた。
<Image flow>
The reproducibility of the character image and the image of the pattern in which one dot is arranged in a Keima-like pattern as shown in FIG. The best one was 11, the worst one was 0, and 4 or less considered that the effect of the present invention was not obtained.
＜帯電器下黒帯＞
文字画像、１ｄｏｔ画像の再現性を１１〜０の１２段階に分け評価した。最も良いものを１１、最も悪いものを０とし、４以下は本発明の効果が得られていないものと考えた。
<Black belt under charger>
The reproducibility of the character image and 1 dot image was evaluated in 12 stages of 11 to 0. The best one was 11, the worst one was 0, and 4 or less considered that the effect of the present invention was not obtained.
（参考例２〜５）
参考例１において、化合物（Ｂ）の化合物例Ｎｏ．７の化合物３０部の代わりに、それぞれ、化合物（Ｂ）の化合物例Ｎｏ．５、６、８及び１０の化合物３０部を用いた他は参考例１と同様に電子写真感光体を作製し評価した。その結果を表９６に示す。
( Reference Examples 2-5)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds of 5, 6, 8 and 10 were used. The results are shown in Table 96.
（参考例６〜８）
参考例１において、化合物（Ｂ）の化合物例Ｎｏ．７の化合物３０部の代わりに、それぞれ化合物（Ｂ）の化合物例Ｎｏ．３、９及び１２の化合物３０部を用いた他は参考例１と同様に電子写真感光体を作製し評価した。その結果を表９６に示す。
( Reference Examples 6-8)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1, except that 30 parts of the compounds of 3, 9, and 12 were used. The results are shown in Table 96.
（実施例９〜１０）
参考例１において、化合物（Ｂ）の化合物例Ｎｏ．７の化合物３０部の代わりに、それぞれ化合物（Ｂ）の化合物例Ｎｏ．１３及び１４の化合物３０部を用いた他は参考例１と同様に電子写真感光体を作製し評価した。その結果を表９６に示す。
(Examples 9 to 10)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds 13 and 14 were used. The results are shown in Table 96.
（参考例１１〜１２）
参考例１において、化合物（Ａ）の化合物例Ｎｏ．２５３の化合物３０部の代わりに、それぞれ下記構造式（６）及び（７）の化合物３０部を用いた他は参考例１と同様に電子写真感光体を作製し評価した。その結果を表９６に示す。
( Reference Examples 11-12)
In Reference Example 1, compound example No. of compound (A). An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds of the following structural formulas (6) and (7) were used instead of 30 parts of the compound of 253. The results are shown in Table 96.
（比較例１〜５）
参考例１において、化合物（Ｂ）の化合物例Ｎｏ．７の化合物３０部の代わりに、それぞれ、下記表９５の化合物例Ｎｏ．１〜５の化合物３０部を用いた他は参考例１と同様に電子写真感光体を作製し評価した。その結果を表９７に示す。
(Comparative Examples 1-5)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds 1 to 5 were used. The results are shown in Table 97.
１ 電子写真感光体
２ 軸
３ 帯電手段
４ 露光光
５ 現像手段
６ 転写手段
７ 転写材
８ 定着手段
９ クリーニング手段
１０ 前露光光
１１ プロセスカートリッジ容器
１２ 案内手段
DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge container 12 Guide means
Claims (7)
化合物（Ａ）：同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送性化合物；
化合物（Ｂ）：下記構造式（４）で示される化合物
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule;
Compound (B): Compound represented by the following structural formula (4)
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| JP5049109B2 (en) * | 2006-12-11 | 2012-10-17 | 株式会社リコー | Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus |
| JP5146811B2 (en) * | 2007-01-16 | 2013-02-20 | 株式会社リコー | Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus |
| JP5046678B2 (en) * | 2007-02-22 | 2012-10-10 | 株式会社リコー | Electrophotographic apparatus and process cartridge |
| TW200906869A (en) * | 2007-05-30 | 2009-02-16 | Toagosei Co Ltd | Active energy ray curable composition and optical material |
| JP5057907B2 (en) * | 2007-09-11 | 2012-10-24 | 株式会社リコー | Electrophotographic apparatus and process cartridge |
| JP5504929B2 (en) * | 2010-02-02 | 2014-05-28 | Ｊｓｒ株式会社 | NOVEL COMPOUND, METHOD FOR SYNTHESIZING THE COMPOUND, ANTIOXIDANT, RESIN COMPOSITION, AND RESIN MOLDED BODY CONTAINING THE COMPOUND |
| JP5573187B2 (en) * | 2010-01-19 | 2014-08-20 | Ｊｓｒ株式会社 | NOVEL COMPOUND, METHOD FOR SYNTHESIZING THE COMPOUND, ANTIOXIDANT, RESIN COMPOSITION, AND RESIN MOLDED BODY CONTAINING THE COMPOUND |
| WO2011090008A1 (en) * | 2010-01-19 | 2011-07-28 | Jsr株式会社 | Novel compound; method for synthesizing said compound; and antioxidant, release agent, resin composition, and resin mold product containing said compound |
| JP5521589B2 (en) * | 2010-02-02 | 2014-06-18 | Ｊｓｒ株式会社 | NOVEL COMPOUND, AND RESIN COMPOSITION AND RESIN MOLDED BODY CONTAINING THE COMPOUND |
| JP5644133B2 (en) * | 2010-02-23 | 2014-12-24 | 富士ゼロックス株式会社 | Electrophotographic photosensitive member, process cartridge, image forming apparatus, charge transporting composition, and charge transporting cured film |
| JP5625411B2 (en) | 2010-03-17 | 2014-11-19 | 富士ゼロックス株式会社 | Image forming apparatus and process cartridge |
| JP5732727B2 (en) | 2010-02-23 | 2015-06-10 | 富士ゼロックス株式会社 | Electrophotographic photosensitive member, process cartridge, and image forming apparatus |
| US8816033B2 (en) * | 2011-03-08 | 2014-08-26 | Dic Corporation | Radically curable compound, cured product thereof, and method for producing the compound |
| JP6056256B2 (en) * | 2011-09-02 | 2017-01-11 | 株式会社リコー | Electrophotographic photoreceptor, image forming apparatus having the photoreceptor, image forming method, process cartridge, and electrophotographic photoreceptor surface layer coating solution |
| JP5974559B2 (en) * | 2012-03-14 | 2016-08-23 | 株式会社リコー | Photoconductor and manufacturing method thereof |
| JP5962793B2 (en) * | 2015-02-10 | 2016-08-03 | 富士ゼロックス株式会社 | Cured film |
| GB2545626A (en) * | 2015-10-16 | 2017-06-28 | Lomox Ltd | Cross-linkable charge transport materials |
| KR20190034213A (en) * | 2016-07-21 | 2019-04-01 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | COMPOSITIONS, RESINS, COMPOSITIONS |
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