JP4170186B2 - Charging member, process cartridge, and image forming apparatus - Google Patents
Charging member, process cartridge, and image forming apparatus Download PDFInfo
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- JP4170186B2 JP4170186B2 JP2003328963A JP2003328963A JP4170186B2 JP 4170186 B2 JP4170186 B2 JP 4170186B2 JP 2003328963 A JP2003328963 A JP 2003328963A JP 2003328963 A JP2003328963 A JP 2003328963A JP 4170186 B2 JP4170186 B2 JP 4170186B2
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Description
本発明は、複写機、レーザービームプリンタ、ファクシミリ等の電子写真方式の画像形成装置等に用いられる帯電部材と、この帯電部材を有するプロセスカートリッジ及び画像形成装置に関する。 The present invention relates to a charging member used for an electrophotographic image forming apparatus such as a copying machine, a laser beam printer, and a facsimile, and a process cartridge and an image forming apparatus having the charging member.
従来、複写機、レーザービームプリンタ、ファクシミリ等の電子写真方式の画像形成装置において、被帯電体（感光体）に対して帯電処理を行う帯電部材としては、帯電ローラが一般的に用いられている。図１１は、このような帯電ローラ方式の画像形成装置を模式的に示す。 Conventionally, in an electrophotographic image forming apparatus such as a copying machine, a laser beam printer, or a facsimile, a charging roller is generally used as a charging member that performs a charging process on a member to be charged (photosensitive member). . FIG. 11 schematically shows such a charging roller type image forming apparatus.
この画像形成装置１１１は、静電潜像が形成される感光体ドラム１０１と、感光体ドラム１０１に接触又は近接して帯電処理を行う帯電ローラ１０２と、レーザー光等の露光装置１０３と、感光体ドラム１０１の静電潜像にトナーを付着させる現像ローラ１０４と、帯電ローラ１０２に所定電圧を印加するためのパワーパック１０５と、感光体ドラム１０１上のトナー像を記録紙１０６に転写処理する転写ローラ１０７と、転写処理後の感光体ドラム１０１をクリーニングするためのクリーニング装置１０８と、感光体ドラム１０１の表面電位を測定する表面電位計１０９とを備える。この画像形成装置１１１においては、感光体ドラム１０１、帯電ローラ１０２、現像ローラ１０４及びクリーニング装置１０８の４つのプロセス機器がプロセスカートリッジ１１０として設けられ、それらのプロセス機器が画像形成装置１１１の本体（図示せず）に対して一括して着脱自在となっており、プロセスカートリッジ１１０が画像形成装置１１１の本体部に装着されると、プロセスカートリッジ側の駆動系及び電気系と本体側の駆動系及び電気系とが接続状態となる。 The image forming apparatus 111 includes a photosensitive drum 101 on which an electrostatic latent image is formed, a charging roller 102 that performs charging processing in contact with or in proximity to the photosensitive drum 101, an exposure device 103 such as a laser beam, and a photosensitive member. A developing roller 104 for attaching toner to the electrostatic latent image on the photosensitive drum 101, a power pack 105 for applying a predetermined voltage to the charging roller 102, and a toner image on the photosensitive drum 101 are transferred to a recording paper 106. A transfer roller 107, a cleaning device 108 for cleaning the photosensitive drum 101 after the transfer process, and a surface potential meter 109 for measuring the surface potential of the photosensitive drum 101 are provided. In this image forming apparatus 111, four process devices including a photosensitive drum 101, a charging roller 102, a developing roller 104, and a cleaning device 108 are provided as a process cartridge 110, and these process devices are the main body of the image forming apparatus 111 (see FIG. When the process cartridge 110 is mounted on the main body of the image forming apparatus 111, the process cartridge side drive system and electric system and the main body side drive system and electric The system is connected.
なお、プロセスカートリッジは必ずしも上記４つのプロセス機器を備える必要はなく、少なくとも感光体ドラム１０１と帯電ローラ１０２とを備えていればよい。また、図１１では、帯電ローラ１０２の処理との関連が少ない他の電子写真プロセスにおいて通常必要な機能ユニットは省略してある。 Note that the process cartridge is not necessarily provided with the above four process devices, but may be provided with at least the photosensitive drum 101 and the charging roller 102. Also, in FIG. 11, functional units that are normally required in other electrophotographic processes that are less related to the processing of the charging roller 102 are omitted.
画像形成装置１１１における基本的な作像動作について説明すると、まず感光体ドラム１０１に接触した帯電ローラ１０２に対してパワーパック１０５から所定電圧が給電されることにより、感光体ドラム１０１の表面が一様に高電位に帯電する。続いて、画像光が感光体ドラム１０１の表面に露光装置１０３により照射され、感光体ドラム１０１の照射された部分の電位が低下する。画像光は画像の白／黒に応じた光量の分布であるので、画像光が照射されると感光体ドラム１０１の面に記録画像に対応する電位分布、すなわち、静電潜像が形成される。 The basic image forming operation in the image forming apparatus 111 will be described. First, a predetermined voltage is supplied from the power pack 105 to the charging roller 102 that is in contact with the photosensitive drum 101, so that the surface of the photosensitive drum 101 becomes uniform. In this way, it is charged at a high potential. Subsequently, image light is irradiated onto the surface of the photosensitive drum 101 by the exposure device 103, and the potential of the irradiated portion of the photosensitive drum 101 is lowered. Since the image light has a light amount distribution corresponding to white / black of the image, a potential distribution corresponding to the recorded image, that is, an electrostatic latent image is formed on the surface of the photosensitive drum 101 when the image light is irradiated. .
静電潜像が形成された感光体ドラム１０１の部分が現像ローラ１０４を通過すると、感光体ドラム１０１の表面にはその電位の高低に応じてトナーが付着し、静電画像が顕像化（可視像化）されてトナー像が形成される。このトナー像が形成された感光体ドラム１０１の部分に、記録紙１０６が所定のタイミングでレジストローラ（図示せず）により搬送され、トナー像が転写ローラ１０７によって記録紙１０６に転写される。トナー像が転写された記録紙１０６は感光体ドラム１０１から分離して搬送経路を通って搬送され、図示を略す定着装置によりトナーが加熱されてトナー像が定着した後に、画像形成装置１１１の機外へ排出される。記録紙１０６へのトナー像の転写が完了すると、感光体ドラム１０１は表面がクリーニング装置１０８によりクリーニングされ、クエンチングランプ（図示せず）により残留電荷が除去されて次回の作像処理に備える。 When the portion of the photosensitive drum 101 on which the electrostatic latent image is formed passes through the developing roller 104, toner adheres to the surface of the photosensitive drum 101 according to the level of the potential, and the electrostatic image is visualized ( A visible image) to form a toner image. The recording paper 106 is conveyed to a portion of the photosensitive drum 101 where the toner image is formed by a registration roller (not shown) at a predetermined timing, and the toner image is transferred to the recording paper 106 by the transfer roller 107. The recording paper 106 onto which the toner image has been transferred is separated from the photosensitive drum 101 and conveyed through a conveyance path. After the toner is heated by a fixing device (not shown) and the toner image is fixed, the recording paper 106 is used. It is discharged outside. When the transfer of the toner image onto the recording paper 106 is completed, the surface of the photosensitive drum 101 is cleaned by the cleaning device 108, and residual charges are removed by a quenching lamp (not shown) to prepare for the next image forming process.
このように帯電ローラを用いた画像形成装置では、感光体に帯電ローラを接触させる接触帯電方式が一般に採られているが、この接触帯電方式には以下のような問題があった。
（ａ）帯電ローラを構成している物質が帯電ローラから染み出し、これが感光体の表面に
付着移行して帯電ローラ跡を残すこと
（ｂ）帯電ローラに交流電圧を印加したときに、感光体に接触している帯電ローラが振動
するので、帯電音が発生すること
（ｃ）感光体上のトナーが帯電ローラに付着するので、帯電ローラの帯電性能が低下する
こと（特に、上述の染み出しによって、トナーの付着が一層起こりやすくなる。）
（ｄ）帯電ローラを構成している物質が感光体へ付着すること
（ｅ）感光体を長期間停止したときに、帯電ローラが永久変形すること
このような問題を解決する技術として、帯電ローラを感光体に接触させずに近接させる近接帯電方式が提案されている（特許文献１参照）。この近接帯電方式は、帯電ローラを感光体に最近接距離（０．００５〜０．３ｍｍ）となるように対向させて帯電ローラに所定電圧を印加することにより、感光体の帯電を行う帯電方式である。近接帯電方式では、帯電ローラと感光体とが接触していないので接触帯電方式において問題となる上記（ｄ），（ｅ）（帯電ローラを構成している物質が感光体へ付着すること、感光体を長期間停止したときに、帯電ローラが永久変形すること）は問題とならない。また、近接帯電方式では帯電ローラに付着するトナーの量が少なくなるので、上記（ｃ）（感光体上のトナーが帯電ローラに付着するので、帯電ローラの帯電性能が低下すること）についても接触帯電方式より優れている。
As described above, in an image forming apparatus using a charging roller, a contact charging method in which a charging roller is brought into contact with a photosensitive member is generally employed. However, this contact charging method has the following problems.
(A) The substance constituting the charging roller oozes out from the charging roller and adheres to the surface of the photoconductor to leave a mark on the charging roller. (B) When the AC voltage is applied to the charging roller, the photoconductor. The charging roller in contact with the vibrator vibrates, so that a charging noise is generated. (This makes toner adhesion more likely to occur.)
(D) The substance constituting the charging roller adheres to the photoconductor. (E) The charging roller is permanently deformed when the photoconductor is stopped for a long time. A proximity charging method has been proposed in which the toner is brought close to the photosensitive member without contacting it (see Patent Document 1). This proximity charging method is a charging method in which the photosensitive member is charged by applying a predetermined voltage to the charging roller with the charging roller facing the photosensitive member at a closest distance (0.005 to 0.3 mm). It is. In the proximity charging method, since the charging roller and the photosensitive member are not in contact with each other, (d) and (e) (substances constituting the charging roller adhere to the photosensitive member, When the body is stopped for a long time, the charging roller is permanently deformed). In addition, since the amount of toner adhering to the charging roller is reduced in the proximity charging method, contact with the above (c) (the charging performance of the charging roller is lowered because the toner on the photosensitive member adheres to the charging roller). It is superior to the charging method.
近接帯電方式に使用される帯電ローラの要求特性は、接触帯電方式に使用される帯電ローラのそれとは異なる。接触帯電方式で一般的に用いられてきた帯電ローラは、感光体を均一に帯電させるために感光体に対して均一に接触することが必要であるので、芯金の周囲に加硫ゴム等の弾性体が被覆された構造となっている。ところが、その加硫ゴム等の弾性体で形成された帯電ローラを近接帯電方式において使用すると、以下のような不具合が生じる。
（ｆ）感光体と帯電ローラとの間に一定の空隙を確保するために、帯電ローラの軸方向両
端の非画像領域（画像形成に関与しない領域）にスペーサ等の空隙確保部材を介在
させなければならないが、弾性体で形成された帯電ローラでは弾性体の変形により
空隙確保部材も動いて空隙を均一にすることが困難であり、帯電電位変動やそれに
起因する画像ムラが発生してしまう。
（ｇ）弾性体を構成する加硫ゴム材料は経時によるへたりや変形が生じやすいので、空隙
も経時的に変動する。
The required characteristics of the charging roller used in the proximity charging method are different from those of the charging roller used in the contact charging method. The charging roller that has been generally used in the contact charging method needs to be in uniform contact with the photoconductor in order to uniformly charge the photoconductor. The structure is covered with an elastic body. However, when the charging roller formed of an elastic body such as vulcanized rubber is used in the proximity charging system, the following problems occur.
(F) In order to ensure a certain gap between the photoconductor and the charging roller, a gap ensuring member such as a spacer is interposed in the non-image area (area not involved in image formation) at both ends in the axial direction of the charging roller. However, with a charging roller formed of an elastic body, it is difficult to make the gap uniform by moving the gap securing member due to deformation of the elastic body, resulting in charging potential fluctuations and resulting image unevenness. .
(G) Since the vulcanized rubber material constituting the elastic body tends to sag and deform over time, the voids also change over time.
このような不具合を解消するために、帯電ローラに非弾性体である熱可塑性樹脂を用いることが考えられ、これにより感光体と帯電ローラとの間の空隙を均一にすることが可能となる。 In order to solve such a problem, it is conceivable to use a thermoplastic resin which is an inelastic material for the charging roller, which makes it possible to make the gap between the photosensitive member and the charging roller uniform.
ところで、帯電ローラによる感光体ドラム表面の帯電メカニズムは、帯電ローラと感光体ドラムとの間の微小放電におけるパッシェンの法則に従った放電であることが知られている。そして、感光体ドラムを所定の帯電電位に保持する機能を得るためには、その熱可塑性樹脂の電気抵抗値を半導電性領域（１０6〜１０9Ωｃｍ程度）に制御することが必要となる。 By the way, it is known that the charging mechanism on the surface of the photosensitive drum by the charging roller is a discharge according to Paschen's law in the minute discharge between the charging roller and the photosensitive drum. In order to obtain a function of holding the photosensitive drum at a predetermined charging potential, it is necessary to control the electric resistance value of the thermoplastic resin to a semiconductive region (about 10 6 to 10 9 Ωcm). .
電気抵抗値を制御する方法としては、熱可塑性樹脂中にカーボンブラック等の導電性顔料を分散させる方法が一般的である。しかし、導電性顔料を用いて帯電ローラの電気抵抗調整層（抵抗調整層）を半導電性領域に設定しようとすると、電気抵抗値のばらつきが大きくなり、部分的に帯電不良等が起こって画像欠陥を発生させるという問題があった。 As a method of controlling the electric resistance value, a method of dispersing a conductive pigment such as carbon black in a thermoplastic resin is generally used. However, if the electric resistance adjustment layer (resistance adjustment layer) of the charging roller is set to a semiconductive region using a conductive pigment, the electric resistance value varies greatly, causing a partial charge failure or the like. There was a problem of generating defects.
一方、電気抵抗値を制御するための別の方法として、イオン導電性材料、すなわち、Ｌｉ塩等の電解質塩を用いることが考えられる。イオン導電性材料は、マトリックス樹脂中に分子レベルで分散するので、導電性顔料が分散する場合に比べて電気抵抗値のばらつきが小さく、部分的な帯電不良は画像品質的に問題とならない。ところが、電解質塩は低分子量であるので、マトリックス樹脂の表面にブリードアウトしやすい性質があり、それが帯電ローラの表面にブリードアウトした場合にトナーの固着を発生させ、画像不良を引き起こすという問題があった。 On the other hand, as another method for controlling the electric resistance value, it is conceivable to use an ion conductive material, that is, an electrolyte salt such as a Li salt. Since the ion conductive material is dispersed at the molecular level in the matrix resin, the variation in electric resistance value is small compared to the case where the conductive pigment is dispersed, and partial charging failure does not cause a problem in image quality. However, since the electrolyte salt has a low molecular weight, it tends to bleed out on the surface of the matrix resin, and when it bleeds out on the surface of the charging roller, it causes toner sticking and causes image defects. there were.
そこで、イオン導電性材料のブリードアウトを避けるために、高分子型のイオン導電性材料を使用することが考えられる。この場合、イオン導電性材料はマトリックス樹脂とともに混練樹脂中に海島状に分散固定化され、表面へのブリードアウトが起こり難い。経時によるブリードアウトが少ない帯電部材としては、四級アンモニウム塩基を有する高分子量のイオン導電性材料を使用したものが提案されている（特許文献２参照）。 Therefore, in order to avoid bleeding out of the ion conductive material, it is conceivable to use a polymer type ion conductive material. In this case, the ion conductive material is dispersed and fixed in a sea-island shape in the kneaded resin together with the matrix resin, and bleeding out to the surface hardly occurs. As a charging member with little bleed-out over time, a charging member using a high molecular weight ion conductive material having a quaternary ammonium base has been proposed (see Patent Document 2).
しかしながら、四級アンモニウム塩含有型の高分子型導電剤の場合には、電気抵抗値の温湿度環境依存性が大きく、その添加割合や温湿度環境によっては低電気抵抗化に伴う異常放電や高電気抵抗化に伴う帯電不良等問題が発生する可能性が高いので、処方が難しいという問題がある。 However, in the case of a polymer-type conductive agent containing a quaternary ammonium salt, the electrical resistance value is highly dependent on the temperature and humidity environment. Since there is a high possibility that problems such as charging failure accompanying electrical resistance will occur, there is a problem that prescription is difficult.
また、このような高分子型導電剤分散系において高分子型イオン導電材料が海島状分散の島成分となった場合には、電流が絶縁性のマトリックス樹脂に妨げられるため、抵抗調整層が所望の抵抗値まで低下しなかったり、抵抗値の電圧依存症が大きくなるという問題がある。加えて、海島状分散の分散粒径が大である場合には、射出成形時に顕著なウェルドが発生し、そのウェルド部分の強度が低下したり、抵抗値が変動するという問題もある。ウェルド部分の強度低下は、使用時の電気的・機械的ストレスや経時・環境による体積変動によって抵抗調整層にクラックの発生を招き、ウェルド部分の抵抗変動は部分的画像不良を来すことになる。
本発明は、上記の問題に鑑みて為されたもので、電気抵抗値のばらつき等を抑制して帯電不良を防止することができるとともに、環境安定性や強度、耐久性に優れる帯電部材と、この帯電部材を有するプロセスカートリッジ及び画像形成装置を提供することを課題としている。 The present invention has been made in view of the above-mentioned problems, and it is possible to prevent a charging failure by suppressing variations in electric resistance value and the like, and a charging member excellent in environmental stability, strength, and durability, It is an object of the present invention to provide a process cartridge and an image forming apparatus having the charging member.
上記課題を解決するため、請求項１に係る発明は、導電性支持体上に形成された抵抗調整層と、該抵抗調整層の表面を被覆する保護層とを有する帯電部材であって、前記抵抗調整層が、高分子型イオン導電材料と、熱可塑性樹脂組成物と、前記高分子型イオン導電材料及び前記熱可塑性樹脂組成物の双方に親和性を有するグラフトコポリマーとを含む樹脂組成物からなり、前記高分子型イオン導電材料を海、前記熱可塑性樹脂組成物を島とする海島構造を有することを特徴とする。 In order to solve the above problems, an invention according to claim 1 is a charging member having a resistance adjustment layer formed on a conductive support and a protective layer covering the surface of the resistance adjustment layer, From the resin composition in which the resistance adjusting layer includes a polymer ion conductive material, a thermoplastic resin composition, and a graft copolymer having affinity for both the polymer ion conductive material and the thermoplastic resin composition. It has a sea-island structure in which the polymer ion conductive material is the sea and the thermoplastic resin composition is the island.
請求項１に係る発明によれば、抵抗調整層が高分子型イオン導電材料と、熱可塑性樹脂組成物と、その高分子型イオン導電材料及び熱可塑性樹脂組成物の双方に親和性を有するグラフトコポリマーとを含む樹脂組成物からなり、高分子型イオン導電材料を海、前記熱可塑性樹脂組成物を島とする海島構造を有することにより、電気抵抗値のばらつき等を抑制して帯電不良を防止することができるとともに、帯電部材が環境安定性や強度、耐久性に優れる。さらに、ブリードアウトに伴う帯電不良やトナーの付着も防止することができるので、帯電部材が画像形成装置に搭載されたときに画像品質を高めることができる。 According to the invention of claim 1, the resistance adjusting layer has a polymer type ion conductive material, a thermoplastic resin composition, and a graft having affinity for both the polymer type ion conductive material and the thermoplastic resin composition. It has a sea-island structure consisting of a resin composition containing a copolymer and the polymer type ion conductive material as the sea, and the thermoplastic resin composition as an island, thereby preventing variation in electrical resistance and preventing poor charging. The charging member is excellent in environmental stability, strength, and durability. Furthermore, since charging failure and toner adhesion due to bleed-out can be prevented, image quality can be improved when the charging member is mounted on the image forming apparatus.
請求項２に係る発明は、請求項１に記載の帯電部材において、前記海島構造における島の径が２０μｍ以下であることを特徴とする。 According to a second aspect of the present invention, in the charging member according to the first aspect, an island diameter of the sea-island structure is 20 μm or less.
請求項２に係る発明によれば、海島構造の島成分の径が２０μｍ以下を満たすことにより、請求項１に係る発明の効果を確実に得ることができる。 According to the invention according to claim 2, the effect of the invention according to claim 1 can be reliably obtained when the diameter of the island component of the sea-island structure satisfies 20 μm or less.
請求項３に係る発明は、請求項１又は請求項２に記載の帯電部材において、前記高分子型イオン導電材料が、ポリエーテルエステルアミドを含有する化合物であることを特徴とする。 According to a third aspect of the present invention, in the charging member according to the first or second aspect, the polymer ion conductive material is a compound containing a polyether ester amide.
請求項３に係る発明によれば、高分子型イオン導電材料がポリエーテルエステルアミドを含有する化合物であることにより、抵抗調整層に要求される抵抗値を容易に実現することができる。また、導電性顔料が分散した樹脂組成物にみられるような分散不良に伴う電気抵抗値のばらつきや、ブリードアウトを効果的に防止することができる。 According to the third aspect of the invention, the polymer ion conductive material is a compound containing polyether ester amide, whereby the resistance value required for the resistance adjustment layer can be easily realized. In addition, it is possible to effectively prevent variation in electrical resistance value due to poor dispersion and bleeding out as seen in a resin composition in which conductive pigments are dispersed.
請求項４に係る発明は、請求項１乃至請求項３のいずれかに記載の帯電部材において、前記熱可塑性樹脂組成物が、スチレン系熱可塑性樹脂であることを特徴とする。 The invention according to claim 4 is the charging member according to any one of claims 1 to 3, wherein the thermoplastic resin composition is a styrene-based thermoplastic resin.
請求項４に係る発明によれば、前記熱可塑性樹脂組成物がスチレン系熱可塑性樹脂であることにより、抵抗調整層に要求される強度及び抵抗値を容易に実現することができる。 According to the invention which concerns on Claim 4, the intensity | strength and resistance value which are required for a resistance adjustment layer can be easily implement | achieved because the said thermoplastic resin composition is a styrene-type thermoplastic resin.
請求項５に係る発明は、請求項１乃至請求項４のいずれかに記載の帯電部材において、前記グラフトコポリマーが、主鎖にポリカーボネート樹脂を有して側鎖にアクリロニトリル−スチレン−グリシジルメタクリレート共重合体を有するグラフトコポリマーであることを特徴とする。 The invention according to claim 5 is the charging member according to any one of claims 1 to 4, wherein the graft copolymer has a polycarbonate resin in the main chain and an acrylonitrile-styrene-glycidyl methacrylate copolymer in the side chain. It is a graft copolymer having a coalescence.
請求項５に係る発明によれば、グラフトコポリマーが主鎖にポリカーボネート樹脂を有して側鎖にアクリロニトリル−スチレン−グリシジルメタクリレート共重合体を有することにより、要求される分散粒径、すなわち、島成分の所望の径を容易に得ることができる。 According to the invention of claim 5, when the graft copolymer has a polycarbonate resin in the main chain and an acrylonitrile-styrene-glycidyl methacrylate copolymer in the side chain, a required dispersion particle size, that is, an island component The desired diameter can be easily obtained.
請求項６に係る発明は、請求項１乃至請求項５のいずれかに記載の帯電部材において、前記抵抗調整層をなす樹脂組成物が、前記高分子型イオン導電材料、前記熱可塑性樹脂組成物及び前記グラフトコポリマーを溶融混練してなることを特徴とする。 According to a sixth aspect of the present invention, in the charging member according to any one of the first to fifth aspects, the resin composition forming the resistance adjusting layer is the polymer ion conductive material or the thermoplastic resin composition. And the graft copolymer is melt-kneaded.
請求項６に係る発明によれば、抵抗調整層をなす樹脂組成物が高分子型イオン導電材料、熱可塑性樹脂組成物及びグラフトコポリマーを溶融混練してなるので、グラフトコポリマーを高分子型イオン導電材料及び熱可塑性樹脂組成物に対して相溶剤として作用させ、使用時の電気的・機械的ストレスや経時又は環境変化に伴う体積変動によりウェルド部分に発生するクラックを効果的に抑制することができる。 According to the invention of claim 6, since the resin composition forming the resistance adjusting layer is obtained by melt-kneading the polymer ion conductive material, the thermoplastic resin composition, and the graft copolymer, the graft copolymer is converted into the polymer ion conductive material. It can act as a compatibilizer for materials and thermoplastic resin compositions, and can effectively suppress cracks that occur in the weld due to electrical and mechanical stress during use and volume fluctuations with time or environmental changes. .
請求項７に係る発明は、請求項１乃至請求項６のいずれかに記載の帯電部材において、前記抵抗調整層をなす樹脂組成物における前記高分子型イオン導電材料及び前記熱可塑性樹脂組成物の配合比がそれぞれ５０〜７０重量％及び５０〜３０重量％であり、かつ、前記グラフトコポリマーの配合量が前記高分子型イオン導電材料及び前記熱可塑性樹脂組成物の合計１００重量部に対して１〜１５重量部であることを特徴とする。 According to a seventh aspect of the present invention, in the charging member according to any one of the first to sixth aspects, the polymeric ion conductive material and the thermoplastic resin composition in the resin composition forming the resistance adjusting layer. The blending ratio is 50 to 70% by weight and 50 to 30% by weight, respectively, and the blending amount of the graft copolymer is 1 with respect to 100 parts by weight in total of the polymer ion conductive material and the thermoplastic resin composition. It is -15 weight part, It is characterized by the above-mentioned.
請求項７に係る発明によれば、高分子型イオン導電材料及び熱可塑性樹脂組成物の配合比がそれぞれ５０〜７０重量％及び５０〜３０重量％であり、かつ、グラフトコポリマーの配合量が高分子型イオン導電材料及び熱可塑性樹脂組成物の合計１００重量部に対して１〜１５重量部であることにより、抵抗調整層に要求される強度及び抵抗値を容易に実現することができる。 According to the invention which concerns on Claim 7, the compounding ratio of a polymeric ion conductive material and a thermoplastic resin composition is 50 to 70 weight% and 50 to 30 weight%, respectively, and the compounding quantity of a graft copolymer is high. By being 1-15 weight part with respect to a total of 100 weight part of a molecular type ion conductive material and a thermoplastic resin composition, the intensity | strength and resistance value which are required for a resistance adjusting layer are easily realizable.
請求項８に係る発明は、請求項１乃至請求項７のいずれかに記載の帯電部材において、前記保護層が、導電剤が分散した樹脂組成物からなることを特徴とする。 The invention according to claim 8 is the charging member according to any one of claims 1 to 7, wherein the protective layer is made of a resin composition in which a conductive agent is dispersed.
請求項８に係る発明によれば、保護層が導電剤が分散した樹脂組成物からなることにより、保護層に要求される抵抗値を容易に得ることができる。 According to the invention which concerns on Claim 8, the resistance value requested | required of a protective layer can be obtained easily because a protective layer consists of a resin composition in which the electrically conductive agent was disperse | distributed.
請求項９に係る発明は、請求項１乃至請求項８のいずれかに記載の帯電部材において、前記保護層が、アクリル樹脂、アクリルシリコン樹脂、ポリウレタン樹脂、フッ素樹脂、ポリエステル樹脂、ポリアミド樹脂及びポリビニルブチラール樹脂のいずれかを含む樹脂組成物からなることを特徴とする。 The invention according to claim 9 is the charging member according to any one of claims 1 to 8, wherein the protective layer is an acrylic resin, an acrylic silicon resin, a polyurethane resin, a fluororesin, a polyester resin, a polyamide resin, and a polyvinyl resin. It consists of a resin composition containing either butyral resin.
請求項９に係る発明によれば、保護層がアクリル樹脂、アクリルシリコン樹脂、ポリウレタン樹脂、フッ素樹脂、ポリエステル樹脂、ポリアミド樹脂及びポリビニルブチラール樹脂のいずれかを含む樹脂組成物からなることにより、保護層の非粘着性を容易に確保することができる。 According to the invention which concerns on Claim 9, when a protective layer consists of a resin composition containing either an acrylic resin, an acrylic silicon resin, a polyurethane resin, a fluororesin, a polyester resin, a polyamide resin, and a polyvinyl butyral resin, a protective layer The non-adhesiveness can be easily ensured.
請求項１０に係る発明は、請求項１乃至請求項９のいずれかに記載の帯電部材と、該帯電部材により帯電する被帯電体とを有し、前記帯電部材が前記被帯電体を帯電させた後に該被帯電体が露光されることにより該被帯電体上に静電潜像が形成され、該静電潜像が前記被帯電体に付着するトナーにより顕像化されてトナー像が形成され、該トナー像が記録体に転写される画像形成装置を特徴とする。 An invention according to a tenth aspect includes the charging member according to any one of the first to ninth aspects, and a member to be charged that is charged by the charging member, and the charging member charges the member to be charged. After that, the charged object is exposed to form an electrostatic latent image on the charged object, and the electrostatic latent image is visualized by toner adhering to the charged object to form a toner image. And an image forming apparatus in which the toner image is transferred to a recording medium.
請求項１０に係る発明によれば、請求項１乃至請求項９のいずれかに記載の帯電部材を有するので、上記請求項１乃至請求項９のいずれかに記載の帯電部材の効果を画像形成装置において得ることができる。 Since the charging member according to any one of claims 1 to 9 is provided, the effect of the charging member according to any one of claims 1 to 9 is formed as an image. Can be obtained in the apparatus.
請求項１１に係る発明は、請求項１乃至請求項９のいずれかに記載の帯電部材と該帯電部材により帯電する被帯電体とを有するとともに、画像形成装置の本体部に対して着脱自在に取り付けられ、前記画像形成装置において前記帯電部材が前記被帯電体を帯電させた後に該被帯電体が露光されることにより、該被帯電体上に静電潜像が形成されるプロセスカートリッジを特徴とする。 An eleventh aspect of the invention includes the charging member according to any one of the first to ninth aspects and a member to be charged that is charged by the charging member, and is detachable from the main body of the image forming apparatus. A process cartridge is mounted, and in the image forming apparatus, an electrostatic latent image is formed on the charged body by exposing the charged body after the charging member charges the charged body. And
請求項１１に係る発明によれば、請求項１乃至請求項９のいずれかに記載の帯電部材を有するので、上記請求項１乃至請求項９のいずれかに記載の帯電部材の効果をプロセスカートリッジにおいて得ることができる。 According to the eleventh aspect of the present invention, since the charging member according to any one of the first to ninth aspects is provided, the effect of the charging member according to any one of the first to ninth aspects is obtained by the process cartridge. Can be obtained in
請求項１２に係る発明は、請求項１１に記載のプロセスカートリッジを有する画像形成装置を特徴とする。 According to a twelfth aspect of the invention, there is provided an image forming apparatus having the process cartridge according to the eleventh aspect.
請求項１２に係る発明によれば、請求項１１に記載のプロセスカートリッジ、すなわち、請求項１乃至請求項９のいずれかに記載の帯電部材を有するので、上記請求項１乃至請求項９のいずれかに記載の帯電部材の効果を画像形成装置において得ることができる。 According to the twelfth aspect of the present invention, the process cartridge according to the eleventh aspect, that is, the charging member according to any one of the first to ninth aspects, is included. The effect of the charging member described above can be obtained in the image forming apparatus.
本発明を実施するための最良の形態を図面に基づいて説明する。 The best mode for carrying out the present invention will be described with reference to the drawings.
図１は、本形態に係る画像形成装置としての複写機を示す。この複写機１は、複写対象となる原稿を読み取る原稿読取部２と、印刷用の用紙がストックされる給紙部３と、給紙部３から供給される用紙に原稿読取部２からの画像信号に基づいてトナー像を形成する画像形成部４と、そのトナー像を用紙に定着させる定着部５と、トナー像定着後の用紙を機外に排出するための排紙部６とを有する。 FIG. 1 shows a copying machine as an image forming apparatus according to the present embodiment. The copying machine 1 includes a document reading unit 2 that reads a document to be copied, a sheet feeding unit 3 that stocks printing paper, and an image from the document reading unit 2 on a sheet supplied from the sheet feeding unit 3. An image forming unit 4 that forms a toner image based on a signal, a fixing unit 5 that fixes the toner image on a sheet, and a sheet discharge unit 6 that discharges the sheet after the toner image is fixed to the outside of the apparatus.
原稿読取部２は、原稿を走査するために矢印Ｌ方向に走行するランプ７及びミラー８ａ，８ｂと、その原稿からの反射光を受光するＣＣＤ９とを備える。給紙部３は複数のトレイ１０ａ，１０ｂ，…を備え、各トレイにはそれぞれ異なるサイズの用紙がストックされている。 The document reading unit 2 includes a lamp 7 and mirrors 8a and 8b that run in the direction of arrow L to scan the document, and a CCD 9 that receives reflected light from the document. The paper feed unit 3 includes a plurality of trays 10a, 10b,..., And sheets of different sizes are stocked in each tray.
画像形成部４は、矢印Ｒ方向に回転する感光体ドラム１１と、感光体ドラム１１の表面を一様に帯電させる帯電ローラ１２と、この一様に帯電した感光体ドラム１１の表面にＣＣＤ９の受光結果に基づいて静電潜像を形成するレーザー光源１３と、感光体ドラム１１の表面にトナーを供給して静電潜像をトナー像として顕像化する現像ローラ１４と、感光体ドラム１１の表面に形成されたトナー像を給紙部３からの用紙に転写する転写ローラ１５と、転写後の感光体ドラム１１の表面を清掃するクリーニング機構１６とを備える。感光体ドラム１１、帯電ローラ１２、現像ローラ１４及びクリーニング機構１６は、ケース１７に収容されてプロセスカートリッジ１８を構成し、このプロセスカートリッジ１８は複写機１の筐体１９に対して着脱自在に取り付けられている。 The image forming unit 4 includes a photosensitive drum 11 that rotates in the direction of arrow R, a charging roller 12 that uniformly charges the surface of the photosensitive drum 11, and a surface of the uniformly charged photosensitive drum 11. A laser light source 13 that forms an electrostatic latent image based on the light reception result, a developing roller 14 that visualizes the electrostatic latent image as a toner image by supplying toner to the surface of the photosensitive drum 11, and the photosensitive drum 11 A transfer roller 15 for transferring the toner image formed on the surface of the photosensitive drum 11 to a sheet from the paper supply unit 3 and a cleaning mechanism 16 for cleaning the surface of the photosensitive drum 11 after the transfer. The photosensitive drum 11, the charging roller 12, the developing roller 14, and the cleaning mechanism 16 are accommodated in a case 17 to form a process cartridge 18, and the process cartridge 18 is detachably attached to the casing 19 of the copying machine 1. It has been.
定着部５は、画像形成部４から搬送された用紙上の未定着のトナー像を加熱して定着させる加熱定着ローラ２０と、加熱定着ローラ２０の内部に設けられてこれを加熱するハロゲンランプ２１と、加熱定着ローラ２０に当接して用紙を加熱定着ローラ２０に密着させる加圧ローラ２２と、トナー像の定着後に用紙が加熱定着ローラ２０に付着して生じる紙詰まりを防止するために、加熱定着ローラ２０に当接してこれに付着した用紙を分離させる分離爪２３とを備える。また、排紙部６は、筐体１９の内外を連通する排紙口２４と、排出された用紙を受けるトレイ２５とを備え、定着部５からの用紙は排紙口２４を通過してトレイ２５上に排出される。 The fixing unit 5 heats and fixes an unfixed toner image on the sheet conveyed from the image forming unit 4 and a halogen lamp 21 provided inside the heat fixing roller 20 to heat the toner image. And a pressure roller 22 that comes into contact with the heat-fixing roller 20 to make contact with the heat-fixing roller 20, and a heat roller to prevent paper jamming caused by the paper adhering to the heat-fixing roller 20 after the toner image is fixed. A separation claw 23 is provided for separating the paper adhered to and contacting the fixing roller 20. The paper discharge unit 6 includes a paper discharge port 24 that communicates with the inside and outside of the housing 19 and a tray 25 that receives the discharged paper. The paper from the fixing unit 5 passes through the paper discharge port 24 and passes through the tray. 25 is discharged.
帯電ローラ１２は、図２に示すように、ケース１７に回転自在に軸支された導電性の芯軸２６と、芯軸２６の周囲に形成された抵抗調整層２７と、抵抗調整層２７の表面を被覆する保護層２８とを備えている。抵抗調整層２７は円筒状を呈し、その軸方向両端部は、図３に示すように、リング状のスペーサ２９に挿入されて接着されている。なお、スペーサ２９は感光体ドラム１１との空隙を一定に保つためのものであるから、空隙を確保することができるのであれば、スペーサ２９を用いる代わりに抵抗調整層２７にテープを貼着したり、熱収縮性のフィルムを被覆したりしてもよい。 As shown in FIG. 2, the charging roller 12 includes a conductive core shaft 26 rotatably supported by the case 17, a resistance adjustment layer 27 formed around the core shaft 26, and a resistance adjustment layer 27. And a protective layer 28 covering the surface. The resistance adjusting layer 27 has a cylindrical shape, and both end portions in the axial direction are inserted and bonded to a ring-shaped spacer 29 as shown in FIG. Since the spacer 29 is for keeping the gap with the photosensitive drum 11 constant, if the gap can be secured, a tape is attached to the resistance adjustment layer 27 instead of using the spacer 29. Or a heat-shrinkable film may be coated.
抵抗調整層２７は、高分子型イオン導電剤と、熱可塑性組成物と、これら双方に親和性を持つグラフトコポリマーとを含む樹脂組成物からなり、高分子型イオン導電剤を海、熱可塑性樹脂組成物を島とする海島構造を有する（以下、説明の便宜のために、高分子型イオン導電剤、熱可塑性組成物、グラフトコポリマーのそれぞれに（Ａ）、（Ｂ）、（Ｃ）を付すこともある。）。 The resistance adjusting layer 27 is made of a resin composition including a polymer type ion conductive agent, a thermoplastic composition, and a graft copolymer having affinity for both, and the polymer type ion conductive agent is used as a sea, thermoplastic resin. It has a sea-island structure with the composition as an island (hereinafter, for convenience of explanation, (A), (B), and (C) are attached to the polymer type ionic conductive agent, the thermoplastic composition, and the graft copolymer, respectively. Sometimes.).
高分子型イオン導電剤（Ａ）としては、ここではポリエーテルエステルアミド含有化合物が用いられている。ポリエーテルエステルアミドは、次式 As the polymer type ion conductive agent (A), a polyetheresteramide-containing compound is used here. Polyetheresteramide has the following formula
熱可塑性樹脂組成物（Ｂ）としては、スチレン系熱可塑性樹脂が用いられている。ここで、スチレン系熱可塑性樹脂とはスチレン重合体又は共重合体をいい、具体的にはポリスチレン（ＰＳ）、スチレン−ブタジエン共重合体（ＨＩ−ＰＳ）、スチレン−アクリロニトリル共重合体（ＡＳ）、スチレン−ブタジエン−アクリロニトリル共重合体（ＡＢＳ）等が該当する。 Styrenic thermoplastic resins are used as the thermoplastic resin composition (B). Here, the styrenic thermoplastic resin means a styrene polymer or copolymer, and specifically, polystyrene (PS), styrene-butadiene copolymer (HI-PS), styrene-acrylonitrile copolymer (AS). And styrene-butadiene-acrylonitrile copolymer (ABS).
グラフトコポリマー（Ｃ）としては、主鎖にポリカーボネート樹脂を、側鎖にアクリロニトリル−スチレン−グリシジルメタクリレート共重合体を有するグラフトコポリマーが用いられている。このグラフトコポリマーにおける主鎖のポリカーボネート樹脂は、有極性基及びジオキシ基を持つ分子鎖を有しているので、分子間引力が非常に強い。このため、力学的強度やクリープ特性等に優れ、特に衝撃強度は他のプラスチックと比較して著しく優れている。また、このグラフトコポリマーは比較的吸水性が低いので、吸水変動に伴う体積変動が少ない。これらの特性により、グラフトコポリマーの主鎖としてポリカーボネート樹脂を使用した系では、使用時の電気的・機械的ストレスや経時又は環境変化に伴う体積変動によるクラックが生じ難くなる。 As the graft copolymer (C), a graft copolymer having a polycarbonate resin in the main chain and an acrylonitrile-styrene-glycidyl methacrylate copolymer in the side chain is used. Since the main chain polycarbonate resin in this graft copolymer has a molecular chain having a polar group and a dioxy group, the intermolecular attractive force is very strong. For this reason, it is excellent in mechanical strength, creep characteristics, etc., and especially impact strength is remarkably excellent compared with other plastics. In addition, since this graft copolymer has a relatively low water absorption, there is little volume fluctuation due to water absorption fluctuation. Due to these characteristics, in a system using a polycarbonate resin as the main chain of the graft copolymer, it is difficult for cracks due to electrical and mechanical stress during use and volume fluctuations with time or environmental changes.
また、上記グラフトコポリマーの側鎖に含まれるアクリロニトリル−スチレン−グリシジルメタクリレート共重合体は、アクリロニトリル成分と、スチレン成分と、反応基であるグリシジルメタクリレート成分とからなる。反応基のグリシジルメタクリレートは、加熱によりエポキシ基がポリエーテルエステルアミド含有化合物のエステル基やアミノ基と反応し、ポリエーテルエステルアミド含有化合物と強固に化学的結合をする。さらに、アクリロニトリル成分及びスチレン成分は、スチレン系熱可塑性樹脂との相溶性が良好である。このため、上記グラフトコポリマーは、本来親和性の低い高分子型イオン導電剤とスチレン系熱可塑性樹脂との間の相溶化剤として機能し、高分子型イオン導電剤とスチレン系熱可塑性樹脂との分散状態を均一かつ緻密化する。換言すれば、側鎖のアクリロニトリル−スチレン−グリシジルメタクリレート共重合体は、高分子型イオン導電剤及びスチレン系熱可塑性樹脂の分散不良に伴うウェルド部分の抵抗値の変動や、使用時の電気的・機械的ストレスや経時又は環境変化に伴う体積変動によりウェルド部分に発生するクラックを抑制することができ、上記主鎖のポリカーボネート樹脂と相俟って強度的に優れた混練系の樹脂組成物を構成する。 The acrylonitrile-styrene-glycidyl methacrylate copolymer contained in the side chain of the graft copolymer comprises an acrylonitrile component, a styrene component, and a glycidyl methacrylate component that is a reactive group. In the glycidyl methacrylate reactive group, the epoxy group reacts with the ester group or amino group of the polyether ester amide-containing compound by heating to form a strong chemical bond with the polyether ester amide-containing compound. Furthermore, the acrylonitrile component and the styrene component have good compatibility with the styrenic thermoplastic resin. For this reason, the graft copolymer functions as a compatibilizer between the polymer type ionic conductive agent and the styrenic thermoplastic resin, which originally has a low affinity. Uniform and dense dispersion. In other words, the acrylonitrile-styrene-glycidyl methacrylate copolymer in the side chain is a variation in the resistance value of the weld portion due to poor dispersion of the polymer type ion conductive agent and the styrenic thermoplastic resin. Can suppress cracks that occur in the weld due to mechanical stress and volume fluctuations with time or environmental changes, and constitutes a kneading resin composition that is excellent in strength in combination with the polycarbonate resin of the main chain. To do.
図４及び図５は、このグラフトコポリマーの添加の有無による樹脂組成物の強度の違いを示す。図４は、イオン導電剤と高耐久性を有するＡＢＳ樹脂とが混練されてなる樹脂組成物を射出成形して得たテストピースの拡大写真であり、その樹脂組成物にグラフトコポリマーは添加されていない。このテストピースには符号３０で表すウェルドが明確にみられ、このテストピースを強度試験に供するとウェルド３０の部分にクラック３１が発生した。一方、図５は、イオン導電剤と高耐久性を有するＡＢＳ樹脂とが混練されてなる樹脂組成物を射出成形して得たテストピースの拡大写真であり、その樹脂組成物にグラフトコポリマーが添加されている。このテストピースには符号３２で表すウェルドが一応視認することができる程度にみられ、このテストピースを上記強度試験と同様の試験に供してもクラックは発生しなかった。 4 and 5 show the difference in strength of the resin composition depending on whether or not this graft copolymer is added. FIG. 4 is an enlarged photograph of a test piece obtained by injection molding a resin composition obtained by kneading an ionic conductive agent and a highly durable ABS resin. A graft copolymer is added to the resin composition. Absent. A weld indicated by reference numeral 30 was clearly seen in this test piece, and when this test piece was subjected to a strength test, a crack 31 occurred in the weld 30 portion. On the other hand, FIG. 5 is an enlarged photograph of a test piece obtained by injection molding a resin composition obtained by kneading an ionic conductive agent and a highly durable ABS resin. A graft copolymer is added to the resin composition. Has been. In this test piece, the weld represented by reference numeral 32 was seen to the extent that it could be visually recognized. No crack was generated even when this test piece was subjected to the same test as the above-described strength test.
なお、抵抗調整層２７を構成する樹脂組成物は、ポリエーテルエステルアミド含有化合物、スチレン系熱可塑性樹脂及び上記グラフトコポリマーを混合させた後、これらを二軸混練機、ニーダー等により溶融混練することによって容易につくられる。その溶融混練時の加熱により、グラフトコポリマーのグリシジル成分がポリエーテルエステルアミド含有化合物のエステル基成分やアミノ基成分と化学的に結合し、かつ、ポリエーテルエステルアミド含有化合物、スチレン系熱可塑性樹脂及び上記グラフトコポリマーの各成分が緻密に分散する。このとき、高分子型イオン導電剤（Ａ）、熱可塑性樹脂組成物（Ｂ）の配合比をそれぞれ５０〜７０重量％、５０〜３０重量％とすることにより、抵抗調整層２７に要求される半導電性領域の抵抗値、及び、高分子型イオン導電剤（Ａ）が海、熱可塑性樹脂組成物（Ｂ）が島となる海島構造を容易に得ることができる。また、グラフトコポリマー（Ｃ）の配合量を高分子型イオン導電剤（Ａ）及び熱可塑性樹脂組成物（Ｂ）の合計１００重量部に対して１〜１５重量部とすることにより、上述したように高分子型イオン導電剤（Ａ）及び熱可塑性樹脂組成物（Ｂ）の間の相溶性を向上させ、要求される分散粒径、すなわち、島成分の所望の径を容易に得ることができる。 The resin composition constituting the resistance adjusting layer 27 is obtained by mixing a polyetheresteramide-containing compound, a styrene thermoplastic resin and the graft copolymer, and then melt-kneading them with a biaxial kneader, a kneader or the like. Easy to make. By heating during the melt-kneading, the glycidyl component of the graft copolymer is chemically bonded to the ester group component or amino group component of the polyether ester amide-containing compound, and the polyether ester amide-containing compound, styrene-based thermoplastic resin, and Each component of the graft copolymer is finely dispersed. At this time, the resistance adjustment layer 27 is required by setting the blending ratio of the polymer type ion conductive agent (A) and the thermoplastic resin composition (B) to 50 to 70% by weight and 50 to 30% by weight, respectively. It is possible to easily obtain a sea-island structure in which the resistance value of the semiconductive region and the polymer-type ion conductive agent (A) are the sea and the thermoplastic resin composition (B) is the island. Moreover, as above-mentioned by making the compounding quantity of a graft copolymer (C) into 1-15 weight part with respect to a total of 100 weight part of a polymeric ion conductive agent (A) and a thermoplastic resin composition (B). The compatibility between the polymer type ion conductive agent (A) and the thermoplastic resin composition (B) can be improved, and the required dispersed particle size, that is, the desired diameter of the island component can be easily obtained. .
保護層２８の組成材料については、製膜性が良好であるという点から樹脂組成物が好適である。このような樹脂組成物に用いられる樹脂材料としては、アクリル樹脂、アクリルシリコン樹脂、ポリウレタン樹脂、フッ素樹脂、ポリエステル樹脂、ポリアミド樹脂及びポリビニルブチラール樹脂が非粘着性に優れ、帯電ローラ１２におけるトナーの付着を有効に防止するので好ましい。その一方、樹脂材料は電気的に絶縁性であるため、単体で保護層２８を形成すると帯電ローラとしての特性が得られない。そこで、上記樹脂材料に対して各種の導電性材料（カーボン、金属酸化物等）を分散させることによって、保護層２８の抵抗値を調整する。この保護層２８の抵抗値は、抵抗調整層２７のそれよりも大きくなるように調整され、これにより感光体ドラム１１の欠陥部への電圧集中、異常放電（リーク）が回避される。ただし、保護層２８の抵抗値を大きくし過ぎると帯電効率が低下するため、保護層２８と抵抗調整層２７との抵抗値の差が１０3Ωｃｍ以下であることが好ましい。 As the composition material of the protective layer 28, a resin composition is preferable from the viewpoint of good film forming properties. As the resin material used in such a resin composition, acrylic resin, acrylic silicon resin, polyurethane resin, fluorine resin, polyester resin, polyamide resin, and polyvinyl butyral resin are excellent in non-adhesiveness, and toner adheres to the charging roller 12. Is preferable because it effectively prevents On the other hand, since the resin material is electrically insulating, if the protective layer 28 is formed alone, the characteristics as a charging roller cannot be obtained. Therefore, the resistance value of the protective layer 28 is adjusted by dispersing various conductive materials (carbon, metal oxide, etc.) in the resin material. The resistance value of the protective layer 28 is adjusted to be larger than that of the resistance adjusting layer 27, thereby avoiding voltage concentration and abnormal discharge (leakage) on the defective portion of the photosensitive drum 11. However, if the resistance value of the protective layer 28 is excessively increased, the charging efficiency is lowered. Therefore, the difference in resistance value between the protective layer 28 and the resistance adjustment layer 27 is preferably 10 3 Ωcm or less.
さらに、上記樹脂組成物には、保護層２８と抵抗調整層２７との接着性を向上させるためにイソシアネート等の反応性硬化剤を分散させてもよく、上記樹脂組成物により保護層２８を形成する際には、樹脂組成物を有機溶媒に分散させて塗料を作製し、この塗料をスプレー塗装やディッピング等によりコーティングすればよい。 Furthermore, in order to improve the adhesiveness between the protective layer 28 and the resistance adjusting layer 27, a reactive curing agent such as isocyanate may be dispersed in the resin composition, and the protective layer 28 is formed by the resin composition. In this case, the resin composition may be dispersed in an organic solvent to prepare a paint, and this paint may be coated by spray painting or dipping.
以下、より具体的な実施例について説明する。 Hereinafter, more specific examples will be described.
〈実施例１〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）５０重量％及びＡＢＳ樹脂（ＧＲ−０５００、電気化学工業株式会社製）５０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面に、アクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
<Example 1>
Polycarbonate-glycidyl methacrylate-styrene-based on 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, manufactured by Ciba Specialty Chemicals) and 50% by weight of ABS resin (GR-0500, manufactured by Denki Kagaku Kogyo Co., Ltd.) A resin composition obtained by adding 4.5 parts by weight of acrylonitrile copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading it at 220 ° C. is injected onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering by molding. Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. And on the surface of the resistance adjustment layer 27, a film thickness of about 3000 mm by a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35 wt% with respect to the total solid content). A protective layer 28 having a thickness of 10 μm was formed, and a charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下（そのほとんどが５〜１０μｍ）であった（図７参照）。なお、島成分の粒径（最大粒径）の計測は、図６に示すように、レーザー顕微鏡の観察画像で観察範囲中最大となる粒子の最長径を求めて行った（図６において符号３３は海を、符号３４は島を表す。）。
〈実施例２〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）６０重量％及びＡＢＳ樹脂（ＧＲ−０５００、電気化学工業株式会社製）４０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面に、アクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less (most of which was 5 to 10 μm) (see FIG. 7). In addition, the particle size (maximum particle size) of the island component was measured by obtaining the longest particle diameter that is the maximum in the observation range from the observation image of the laser microscope as shown in FIG. 6 (reference numeral 33 in FIG. 6). Represents the sea and 34 represents an island.)
<Example 2>
Polycarbonate-glycidyl methacrylate-styrene-based on 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, manufactured by Ciba Specialty Chemicals) and 60% by weight of ABS resin (GR-0500, manufactured by Denki Kagaku Kogyo Co., Ltd.) A resin composition obtained by adding 4.5 parts by weight of acrylonitrile copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading it at 220 ° C. is injected onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering by molding. Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. And on the surface of the resistance adjustment layer 27, a film thickness of about 3000 mm by a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35 wt% with respect to the total solid content). A protective layer 28 having a thickness of 10 μm was formed, and a charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下（そのほとんどが５〜１０μｍ）であった。 When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less (most of which was 5 to 10 μm).
ところで、図７は、このときの抵抗調整層２７の拡大写真であるが（株式会社キーエンス製の超深度カラー３Ｄ形状測定顕微鏡 ＶＫ−９５００にて撮影）、このままでは海島構造の識別が必ずしも容易ではないので、その抵抗調整層２７を切り出した後に樹脂封入及び研磨を行いメチルエチルケトンにて表面を洗浄し、ＡＢＳ成分及び相溶化剤を洗い流して撮影を行った（図９）。そして、その撮影画像にコントラストを強調する画像処理を施すことによって、ＡＢＳ成分がなくなり凹となった部分を暗部として表出させることができるが（図１０において符号３５で表す部分）、この暗部は島成分に対応するので、この部分の径を測定することにより島の径を求めることができる。なお、メチルエチルケトンによる洗浄処理を行わずに上記画像処理を施した例は図８に示す。
〈実施例３〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）７０重量％及びＡＢＳ樹脂（ＧＲ−０５００、電気化学工業株式会社製）３０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面に、アクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
By the way, FIG. 7 is an enlarged photograph of the resistance adjustment layer 27 at this time (taken with an ultra-deep color 3D shape measurement microscope VK-9500 manufactured by Keyence Corporation), but it is not always easy to identify the sea-island structure as it is. Since the resistance adjusting layer 27 was cut out, the resin was sealed and polished, the surface was washed with methyl ethyl ketone, the ABS component and the compatibilizing agent were washed away, and photographing was performed (FIG. 9). Then, by performing image processing that emphasizes the contrast on the captured image, a portion where the ABS component disappears and becomes concave can be expressed as a dark portion (portion represented by reference numeral 35 in FIG. 10). Since it corresponds to the island component, the diameter of the island can be obtained by measuring the diameter of this portion. An example in which the image processing is performed without performing the cleaning processing with methyl ethyl ketone is shown in FIG.
<Example 3>
Polycarbonate-glycidyl methacrylate-styrene with respect to 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, manufactured by Ciba Specialty Chemicals) and 70% by weight of ABS resin (GR-0500, manufactured by Denki Kagaku Kogyo Co., Ltd.) A resin composition obtained by adding 4.5 parts by weight of acrylonitrile copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading it at 220 ° C. is injected onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering by molding. Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. And on the surface of the resistance adjustment layer 27, a film thickness of about 3000 mm by a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35 wt% with respect to the total solid content). A protective layer 28 having a thickness of 10 μm was formed, and a charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下であった。
〈実施例４〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）５０重量％及びＨＩ−ＰＳ樹脂（Ｈ４５０、東洋スチレン株式会社製）５０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面に、アクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less.
<Example 4>
Polycarbonate-glycidyl methacrylate-styrene-acrylonitrile with respect to 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, manufactured by Ciba Specialty Chemicals) and 50% by weight of HI-PS resin (H450, manufactured by Toyo Styrene Co., Ltd.) A resin composition obtained by adding 4.5 parts by weight of a copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading this at 220 ° C. is injection-molded onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering with Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. And on the surface of the resistance adjustment layer 27, a film thickness of about 3000 mm by a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35 wt% with respect to the total solid content). A protective layer 28 having a thickness of 10 μm was formed, and a charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下であった。
〈実施例５〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）６０重量％及びＨＩ−ＰＳ樹脂（Ｈ４５０、東洋スチレン株式会社製）４０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面に、アクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less.
<Example 5>
Polycarbonate-glycidyl methacrylate-styrene-acrylonitrile with respect to 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, Ciba Specialty Chemicals) 60% by weight and HI-PS resin (H450, Toyo Styrene Co., Ltd.) 40% by weight. A resin composition obtained by adding 4.5 parts by weight of a copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading this at 220 ° C. is injection-molded onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering with Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. And on the surface of the resistance adjustment layer 27, a film thickness of about 3000 mm by a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35 wt% with respect to the total solid content). A protective layer 28 having a thickness of 10 μm was formed, and a charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下であった。
〈実施例６〉
ポリエーテルエステルアミド（ＩＲＧＡＳＴＡＴ Ｐ１８、チバスペシャリティケミカルズ社製）７０重量％及びＨＩ−ＰＳ樹脂（Ｈ４５０、東洋スチレン株式会社製）３０重量％の混合物１００重量部に対し、ポリカーボネート−グリシジルメタクリレート−スチレン−アクリロニトリル共重合体（モディパーＣ Ｌ４４０−Ｇ、日本油脂株式会社製）を４．５重量部を加え、これを２２０℃で溶融混練した樹脂組成物を、ステンレスからなる直径９ｍｍの芯軸２６に射出成形により被覆させて抵抗調整層２７を形成した。次いで、この抵抗調整層２７の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサ２９に挿入して接着し、切削によりスペーサ２９の外径を１２．１ｍｍ、抵抗調整層２７の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層２７の表面にアクリルシリコン樹脂（３０００ＶＨ−Ｐ、川上塗料株式会社製）、硬化剤及び導電性カーボンブラック（全固形分に対して３５重量％）からなる混合物により膜厚約１０μｍの保護層２８を形成し、φ１２の帯電ローラ１２を得た。
When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less.
<Example 6>
Polycarbonate-glycidyl methacrylate-styrene-acrylonitrile with respect to 100 parts by weight of a mixture of polyether ester amide (IRGASTAT P18, Ciba Specialty Chemicals) 70% by weight and HI-PS resin (H450, Toyo Styrene Co., Ltd.) 30% by weight. A resin composition obtained by adding 4.5 parts by weight of a copolymer (Modiper C L440-G, manufactured by Nippon Oil & Fats Co., Ltd.) and melt-kneading this at 220 ° C. is injection-molded onto a core shaft 26 made of stainless steel and having a diameter of 9 mm. The resistance adjusting layer 27 was formed by covering with Next, both ends in the axial direction of the resistance adjusting layer 27 are inserted and bonded to a ring-shaped spacer 29 made of polyethylene resin (Sunfine UH-900, manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the spacer 29 is cut by cutting. Were simultaneously finished so that the outer diameter of the film was 12.1 mm and the outer diameter of the resistance adjusting layer 27 was 12.0 mm. The surface of the resistance adjustment layer 27 is made of a mixture of acrylic silicon resin (3000 VH-P, manufactured by Kawakami Paint Co., Ltd.), a curing agent and conductive carbon black (35% by weight with respect to the total solid content), and a film thickness of about 10 μm. , A charging roller 12 having a diameter of 12 was obtained.
この帯電ローラ１２の抵抗調整層２７をレーザー顕微鏡で観察すると、抵抗調整層２７はポリエーテルエステルアミドの海にＡＢＳ樹脂の島が粒状に分散する海島構造となっており、島成分の粒子の径は２０μｍ以下であった。
〈比較例１〉
ポリエーテル成分を含有する高分子型導電剤（アクアコークＴＷ 住友精化株式会社製）３０重量％及びポリプロピレン樹脂（ＭＡ０３ 日本ポリケム株式会社製）７０重量％の混合物を、溶融混練を行わずにステンレスからなる直径９ｍｍの芯軸に射出成形により被覆させて抵抗調整層を形成した。次いで、この抵抗調整層の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサに挿入して接着し、切削によりスペーサの外径を１２．１ｍｍ、抵抗調整層の外径を１２．０ｍｍとなるように同時に仕上げてφ１２の帯電ローラを得た。
When the resistance adjusting layer 27 of the charging roller 12 is observed with a laser microscope, the resistance adjusting layer 27 has a sea-island structure in which islands of ABS resin are dispersed in the polyether ester amide sea. Was 20 μm or less.
<Comparative example 1>
A mixture of a polymer type conductive agent containing a polyether component (Aqua Coke TW, manufactured by Sumitomo Seika Co., Ltd.) 30% by weight and a polypropylene resin (MA03, manufactured by Nippon Polychem Co., Ltd.) 70% by weight is prepared without melting and kneading. A resistance adjusting layer was formed by coating a core shaft of 9 mm in diameter by injection molding. Next, both end portions in the axial direction of the resistance adjusting layer are inserted and bonded to a ring-shaped spacer made of polyethylene resin (Sunfine UH-900 manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the outer diameter of the spacer is cut by cutting. Were simultaneously finished so that the outer diameter of the resistance adjusting layer was 12.0 mm, and a charging roller of φ12 was obtained.
この帯電ローラの抵抗調整層をレーザー顕微鏡で観察すると、抵抗調整層はポリプロピレンの海にポリエーテル含有高分子型導電剤の島が粒状に分散する海島構造となっており、島成分の粒子の径は２００μｍ以下であった。
〈比較例２〉
四級アンモニウム塩基を含有するイオン導電性の高分子化合物（レオレックスＡＳ−１７２０ 第一工業製薬株式会社製）３０重量％及びポリプロピレン樹脂（ＭＡ０２ 日本ポリケム株式会社製）７０重量％の混合物を、溶融混練を行わずにステンレスからなる直径９ｍｍの芯軸に射出成形により被覆させて円筒状の抵抗調整層を形成した。次いで、この抵抗調整層の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサに挿入して接着し、切削によりスペーサの外径を１２．１ｍｍ、抵抗調整層の外径を１２．０ｍｍとなるように同時に仕上げてφ１２の帯電ローラを得た。
When the resistance adjustment layer of the charging roller is observed with a laser microscope, the resistance adjustment layer has a sea-island structure in which islands of a polyether-containing polymer-type conductive agent are dispersed in a polypropylene sea in the form of particles. Was 200 μm or less.
<Comparative example 2>
A mixture of 30% by weight of an ion conductive polymer compound containing quaternary ammonium base (Roleex AS-1720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 70% by weight of polypropylene resin (made by MA02 Nippon Polychem Co., Ltd.) was melted. Without kneading, a core resistance shaft made of stainless steel having a diameter of 9 mm was coated by injection molding to form a cylindrical resistance adjusting layer. Next, both end portions in the axial direction of the resistance adjusting layer are inserted and bonded to a ring-shaped spacer made of polyethylene resin (Sunfine UH-900 manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the outer diameter of the spacer is cut by cutting. Were simultaneously finished so that the outer diameter of the resistance adjusting layer was 12.0 mm, and a charging roller of φ12 was obtained.
この帯電ローラの抵抗調整層をレーザー顕微鏡で観察すると、抵抗調整層はポリプロピレンの海にイオン導電性の高分子化合物の島が筋状に分散する海島構造となっており、島成分の粒子の径は２００μｍ以下であった。
〈比較例３〉
ポリプロピレン樹脂（ＭＡ０３ 日本ポリケム株式会社製）１００重量部に対し、導電性カーボンブラック（ケッチェンプラックＥＣ、ケッチェンプラックインターナショナル社製）１５重量部を配合した組成物を、ステンレスからなる直径９ｍｍの芯軸に射出成形により被覆させて抵抗調整層を形成した。次いで、この抵抗調整層の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサに挿入して接着し、切削によりスペーサの外径を１２．１ｍｍ、抵抗調整層の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層の表面にポリアミド樹脂（ダイアミドＴ−１７１、ダイセルヒュルス社製）及びカーボンブラック（全固形分に対して１０重量％）からなる混合物により膜厚約１０μｍの保護層を形成し、φ１２の帯電ローラを得た。
〈比較例４〉
ポリプロピレン樹脂（ＭＡ０３ 日本ポリケム株式会社製）１００重量部に対し、過塩素酸リチウム２重量部を配合した組成物を、ステンレスからなる直径９ｍｍの芯軸に射出成形により被覆させて抵抗調整層を形成した。次いで、この抵抗調整層の軸方向両端部を、分子量約３００万のポリエチレン樹脂（サンファインＵＨ−９００ 旭硝子株式会社製）からなるリング状のスペーサに挿入して接着し、切削によりスペーサの外径を１２．１ｍｍ、抵抗調整層の外径を１２．０ｍｍとなるように同時に仕上げた。そして、抵抗調整層の表面にポリビニルプチラール樹脂（デンカブチラール３０００−Ｋ、電気化学工業株式会社製）、イソシアネート系硬化剤及び酸化スズ（全固形分に対して６０重量％）からなる混合物により膜厚約１０μｍの保護層を形成し、φ１２の帯電ローラを得た。
When the resistance adjustment layer of the charging roller is observed with a laser microscope, the resistance adjustment layer has a sea-island structure in which islands of ion-conductive polymer compounds are dispersed in a polypropylene sea in the sea of polypropylene. Was 200 μm or less.
<Comparative Example 3>
A 9 mm diameter core made of stainless steel is prepared by blending a composition in which 15 parts by weight of conductive carbon black (Ketjen Plaque EC, Ketjen Plaque International) is blended with 100 parts by weight of polypropylene resin (MA03 Nippon Polychem Co., Ltd.). The shaft was covered by injection molding to form a resistance adjusting layer. Next, both end portions in the axial direction of the resistance adjusting layer are inserted and bonded to a ring-shaped spacer made of polyethylene resin (Sunfine UH-900 manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the outer diameter of the spacer is cut by cutting. Were simultaneously finished so that the outer diameter of the resistance adjusting layer was 12.0 mm. Then, a protective layer having a film thickness of about 10 μm is formed on the surface of the resistance adjustment layer with a mixture of polyamide resin (Daiamide T-171, manufactured by Daicel Huls Co., Ltd.) and carbon black (10% by weight with respect to the total solid content). A charging roller of φ12 was obtained.
<Comparative example 4>
A composition in which 2 parts by weight of lithium perchlorate is blended with 100 parts by weight of polypropylene resin (MA03 manufactured by Nippon Polychem Co., Ltd.) is coated on a 9 mm diameter core shaft made of stainless steel by injection molding to form a resistance adjusting layer. did. Next, both end portions in the axial direction of the resistance adjusting layer are inserted and bonded to a ring-shaped spacer made of polyethylene resin (Sunfine UH-900 manufactured by Asahi Glass Co., Ltd.) having a molecular weight of about 3 million, and the outer diameter of the spacer is cut by cutting. Were simultaneously finished so that the outer diameter of the resistance adjusting layer was 12.0 mm. And on the surface of the resistance adjusting layer, a film made of a mixture of polyvinyl petital resin (Denka Butyral 3000-K, manufactured by Denki Kagaku Kogyo Co., Ltd.), an isocyanate curing agent and tin oxide (60% by weight with respect to the total solid content). A protective layer having a thickness of about 10 μm was formed to obtain a charging roller of φ12.
上記各実施例及び各比較例をまとめて表１に示す。 The above Examples and Comparative Examples are summarized in Table 1.
〈試験１〉
試験１では、複写機１を使用して３００，０００枚の複写を行い、ローラ割れが発生するまでの耐久枚数を調べた。この際、帯電ローラに印加する電圧はＤＣ＝−８００Ｖ、ＡＣ＝２４００Ｖｐｐ（周波数＝２ｋＨｚ）、評価環境を２３℃、６０％ＲＨとした。この試験結果を表２に示す。
<Test 1>
In Test 1, 300,000 copies were made using the copying machine 1, and the durable number of sheets until a roller crack occurred was examined. At this time, the voltage applied to the charging roller was DC = −800 V, AC = 2400 Vpp (frequency = 2 kHz), and the evaluation environment was 23 ° C. and 60% RH. The test results are shown in Table 2.
〈試験２〉
試験２では、複写機１を使用して感光体ドラム１１の帯電電位測定及び画像評価を行った。この際、帯電ローラと感光体ドラムとの間の空隙を５０μｍとなるように設定し、帯電ローラに印加する電圧はＤＣ＝−８００Ｖ、ＡＣ＝２４００Ｖｐｐ（周波数＝２ｋＨｚ）、評価環境を２３℃、６０％ＲＨとした。さらに、複写機１による連続複写を行い、１００，０００枚通紙後の帯電ローラ表面へのトナー固着評価及び画像評価を行った。この試験結果を表３に示す。
<Test 2>
In Test 2, the charged potential of the photosensitive drum 11 was measured and the image was evaluated using the copying machine 1. At this time, the gap between the charging roller and the photosensitive drum is set to 50 μm, the voltage applied to the charging roller is DC = −800 V, AC = 2400 Vpp (frequency = 2 kHz), and the evaluation environment is 23 ° C. 60% RH. Further, continuous copying by the copying machine 1 was performed, and toner adhesion evaluation and image evaluation on the surface of the charging roller after passing 100,000 sheets were performed. The test results are shown in Table 3.
なお、本発明は上述した形態に限られるものではなく、例えば高分子型イオン導電材料はポリエーテルエステルアミドを含有する化合物に、熱可塑性樹脂組成物はスチレン系熱可塑性樹脂に、グラフトコポリマーは主鎖にポリカーボネート樹脂を有して側鎖にアクリロニトリル−スチレン−グリシジルメタクリレート共重合体に必ずしも限定されるものではない。 The present invention is not limited to the above-described form. For example, the polymer-type ion conductive material is a compound containing polyether ester amide, the thermoplastic resin composition is a styrenic thermoplastic resin, and the graft copolymer is mainly used. It is not necessarily limited to a copolymer having a polycarbonate resin in the chain and an acrylonitrile-styrene-glycidyl methacrylate copolymer in the side chain.
また、海島構造の海／島の識別方法は上述したように洗浄及び画像処理によらず、他の方法によってもかまわない。 In addition, as described above, the sea / island identification method of the sea-island structure may be based on other methods instead of cleaning and image processing.
１ 複写機（画像形成装置）
１２ 帯電ローラ（帯電部材）
１８ プロセスカートリッジ
１９ 筐体（本体部）
２６ 芯軸（導電性支持体）
２７ 抵抗調整層
２８ 保護層
1 Copying machine (image forming device)
12 Charging roller (charging member)
18 Process cartridge 19 Housing (main part)
26 Core shaft (conductive support)
27 Resistance adjustment layer 28 Protective layer
Claims (12)
前記抵抗調整層が、高分子型イオン導電材料と、熱可塑性樹脂組成物と、前記高分子型イオン導電材料及び前記熱可塑性樹脂組成物の双方に親和性を有するグラフトコポリマーとを含む樹脂組成物からなり、前記高分子型イオン導電材料を海、前記熱可塑性樹脂組成物を島とする海島構造を有することを特徴とする帯電部材。 A charging member having a resistance adjustment layer formed on a conductive support and a protective layer covering the surface of the resistance adjustment layer,
A resin composition in which the resistance adjusting layer includes a polymer ion conductive material, a thermoplastic resin composition, and a graft copolymer having affinity for both the polymer ion conductive material and the thermoplastic resin composition. A charging member comprising: a sea-island structure in which the polymeric ion conductive material is the sea and the thermoplastic resin composition is an island.
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| JP2003328963A JP4170186B2 (en) | 2003-09-19 | 2003-09-19 | Charging member, process cartridge, and image forming apparatus |
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| JP2007052168A (en) * | 2005-08-17 | 2007-03-01 | Ricoh Co Ltd | Conductive member, process cartridge, and image forming apparatus |
| JP4938294B2 (en) * | 2005-11-10 | 2012-05-23 | 株式会社リコー | Conductive member, charging member using the conductive member, process cartridge using the charging member, and image forming apparatus using the process cartridge |
| JP4880310B2 (en) * | 2006-01-19 | 2012-02-22 | 株式会社リコー | Conductive member, process cartridge having the same, and image forming apparatus having the process cartridge |
| JP5162864B2 (en) * | 2006-09-13 | 2013-03-13 | 株式会社リコー | Conductive member, process cartridge, and image forming apparatus |
| JP5118366B2 (en) * | 2007-03-08 | 2013-01-16 | 株式会社リコー | Conductive member, process cartridge using the conductive member, and image forming apparatus using the process cartridge |
| JP5541961B2 (en) | 2010-04-30 | 2014-07-09 | 富士フイルム株式会社 | Antistatic laminate, optical film, polarizing plate, and image display device |
| JP6637758B2 (en) * | 2015-12-24 | 2020-01-29 | 住友理工株式会社 | Conductive members for electrophotographic equipment |
| JP7337649B2 (en) | 2019-10-18 | 2023-09-04 | キヤノン株式会社 | Process cartridge and electrophotographic device |
| US11487214B2 (en) * | 2020-11-09 | 2022-11-01 | Canon Kabushiki Kaisha | Charging roller, process cartridge, and electrophotographic image forming apparatus |
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