JP2006078636A - Conductive elastic member and image forming apparatus using the same - Google Patents

Conductive elastic member and image forming apparatus using the same Download PDF

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JP2006078636A
JP2006078636A JP2004260746A JP2004260746A JP2006078636A JP 2006078636 A JP2006078636 A JP 2006078636A JP 2004260746 A JP2004260746 A JP 2004260746A JP 2004260746 A JP2004260746 A JP 2004260746A JP 2006078636 A JP2006078636 A JP 2006078636A
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elastic member
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JP4480524B2 (en
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Junji Sakata
純二 坂田
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Bridgestone Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive elastic member having low hardness and low compression set, hardly causing aggregation and fusion of toner and surface scraping, and being superior in durability. <P>SOLUTION: The conductive elastic member is made of urethane foam, obtained by mechanically stirring and foaming raw materials for urethane foam including a urethane prepolymer synthesized from a polyol and a polyisocyanate, a chain extender, a catalyst, a foam regulating agent and a conductive agent, wherein the polyol used for synthesizing the urethane prepolymer contains a lactone modified polyether polyol having average of 2-4 functional groups and a molecular weight of 3,000-10,000 and the polyisocyanate is tolylene diisocyanate (TDI). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、導電性弾性部材及びそれを用いた画像形成装置に関し、特に電子写真プロセス等に使用され、硬度及び圧縮永久歪が低く、トナーが凝集・融着し難く、表面が削れ難く、耐久性に優れた導電性弾性部材に関するものである。   The present invention relates to a conductive elastic member and an image forming apparatus using the same, and is particularly used in an electrophotographic process or the like, and has low hardness and compression set, toner is difficult to agglomerate and fuse, the surface is difficult to scrape, and durability The present invention relates to a conductive elastic member having excellent properties.

近年、電子写真システムのカラー化、高速化、高画質化、省エネルギー化に伴い、低融点のトナーを使用したカラー・レーザー・プリンターが増えつつある。ここで、低融点のトナーを使用する場合、該低融点のトナーが、各部品間で圧縮又は摩擦を繰り返し受けることによりダメージを受けて、トナーが凝集・融着する等して、画像不良が発生し易いため、低硬度のローラが要求される。   In recent years, color laser printers using toner with a low melting point are increasing as color, speed, image quality, and energy saving of electrophotographic systems increase. Here, when a low-melting toner is used, the low-melting toner is damaged by repeated compression or friction between components, and the toner is aggregated and fused. Since it tends to occur, a low hardness roller is required.

しかしながら、従来、通常用いられるウレタンエラストマー製のローラは、ローラのアスカーC硬度が65〜80度と高いため、低融点トナーの凝集・融着を引き起こしやすい。そのため、低融点トナーを使用した電子写真システムにおいては、ローラのアスカーC硬度が40〜60度程度のものが求められている。   However, conventionally used rollers made of urethane elastomer have a high Asker C hardness of 65 to 80 degrees, and thus tend to cause aggregation and fusion of low melting point toner. Therefore, an electrophotographic system using a low-melting toner is required to have a roller Asker C hardness of about 40 to 60 degrees.

一方、電子写真システムに低硬度のローラを用いた場合、ローラ表面に感光ドラム、ブレード、供給ローラ等による圧接痕が発生し易いため、低硬度ローラには圧縮永久歪の低い材料を用いる必要がある。しかしながら、低硬度の材料は、圧縮永久歪が大きくなる傾向があるため、硬度及び圧縮永久歪の両方を十分に低くバランスすることが、非常に難しかった(特許文献1〜3参照)。   On the other hand, when a low-hardness roller is used in an electrophotographic system, pressure contact marks due to a photosensitive drum, a blade, a supply roller, etc. are likely to be generated on the roller surface. is there. However, since materials with low hardness tend to have large compression set, it has been very difficult to balance both hardness and compression set sufficiently low (see Patent Documents 1 to 3).

特開2003−252947号公報JP 2003-252947 A 特開平9−34216号公報JP-A-9-34216 特開平9−114190号公報JP-A-9-114190

そこで、本発明の目的は、上記従来技術の問題を解決し、硬度及び圧縮永久歪が低く、トナーが凝集・融着し難く、表面が削れ難く、耐久性に優れた導電性弾性部材を提供することにある。また、本発明の他の目的は、かかる導電性弾性部材を用いた画像形成装置を提供することにある。   Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a conductive elastic member that has low hardness and compression set, toner is difficult to agglomerate and fuse, is difficult to scrape, and has excellent durability. There is to do. Another object of the present invention is to provide an image forming apparatus using such a conductive elastic member.

本発明者は、上記目的を達成するために鋭意検討した結果、ポリオール及びポリイソシアネートから合成したウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られる発泡ウレタン製の導電性弾性部材において、ウレタンプレポリマーの合成に特定のポリオール及び特定のポリイソシアネートを用いることで、導電性弾性部材の硬度及び圧縮永久歪を十分に低くでき、該導電性弾性部材を現像ローラとして画像形成装置に用いることで、画像形成装置の画像品質及び耐久性を改善できることを見出し、本発明を完成させるに至った。   As a result of intensive studies to achieve the above object, the present inventor mechanically foamed a foamed urethane raw material containing a urethane prepolymer synthesized from a polyol and a polyisocyanate, a chain extender, a catalyst, a foam stabilizer and a conductive agent. In the conductive elastic member made of urethane foam obtained by using the specific polyol and specific polyisocyanate for the synthesis of the urethane prepolymer, the hardness and compression set of the conductive elastic member can be sufficiently reduced. The present inventors have found that the image quality and durability of the image forming apparatus can be improved by using the elastic elastic member as a developing roller in the image forming apparatus, and the present invention has been completed.

即ち、本発明の導電性弾性部材は、ポリオール及びポリイソシアネートから合成したウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られる発泡ウレタン製の導電性弾性部材において、
前記ウレタンプレポリマーの合成に用いるポリオールは、平均官能基数が2〜4で且つ分子量が3000〜10000のラクトン変性ポリエーテルポリオールを含み、前記ポリイソシアネートがトリレンジイソシアネート(TDI)であって、
外径φ16mm、芯金径φ8mmのローラでのアスカーC硬度が40〜60度であり、
外径φ16mm、芯金径φ8mmのローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後の表面変形量が7μm以下であることを特徴とする。ここで、アスカーC硬度及び表面変形量は、外径φ16mm、芯金径φ8mmのローラ形状での値であるが、本発明の導電性弾性部材の形状は、これに限られるものではない。
That is, the conductive elastic member of the present invention is made of urethane foam obtained by mechanically foaming a urethane foam raw material containing a urethane prepolymer synthesized from polyol and polyisocyanate, a chain extender, a catalyst, a foam stabilizer and a conductive agent. In the conductive elastic member of
The polyol used for the synthesis of the urethane prepolymer includes a lactone-modified polyether polyol having an average functional group number of 2 to 4 and a molecular weight of 3000 to 10,000, and the polyisocyanate is tolylene diisocyanate (TDI),
The Asker C hardness is 40-60 degrees with a roller with an outer diameter of φ16mm and a cored bar diameter of φ8mm.
Place a roller with an outer diameter of φ16mm and a cored bar diameter of φ8mm on a flat plate, apply a load of 1000g to each end of the roller, leave it under an environment of temperature 40 ℃ and humidity 95% RH for 3 days, The amount of surface deformation is 7 μm or less. Here, the Asker C hardness and the surface deformation amount are values in a roller shape having an outer diameter of φ16 mm and a cored bar diameter of φ8 mm, but the shape of the conductive elastic member of the present invention is not limited to this.

本発明の導電性弾性部材の好適例においては、前記ウレタンプレポリマーの合成に用いるポリオールが、前記ラクトン変性ポリエーテルポリオール単独、又は前記ラクトン変性ポリエーテルポリオールとその他のポリオールとのブレンドからなる。   In a preferred example of the conductive elastic member of the present invention, the polyol used for the synthesis of the urethane prepolymer is the lactone-modified polyether polyol alone or a blend of the lactone-modified polyether polyol and other polyols.

本発明の導電性弾性部材は、現像ローラとして好適である。   The conductive elastic member of the present invention is suitable as a developing roller.

また、本発明の画像形成装置は、上記導電性弾性部材を用いたことを特徴とする。   An image forming apparatus according to the present invention uses the conductive elastic member.

本発明によれば、ポリオール及びポリイソシアネートから合成したウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られる発泡ウレタン製の導電性弾性部材において、ウレタンプレポリマーの合成に特定のポリオール及び特定のポリイソシアネートを用いることで、硬度及び圧縮永久歪が十分に低い導電性弾性部材を提供することができる。また、かかる導電性弾性部材を用いた、画像品質及び耐久性に優れた画像形成装置を提供することができる。   According to the present invention, a conductive elastic member made of urethane foam obtained by mechanically stirring and foaming a urethane foam raw material containing a urethane prepolymer synthesized from a polyol and a polyisocyanate, a chain extender, a catalyst, a foam stabilizer and a conductive agent. In Example 1, a conductive elastic member having sufficiently low hardness and compression set can be provided by using a specific polyol and a specific polyisocyanate for the synthesis of the urethane prepolymer. In addition, an image forming apparatus using such a conductive elastic member and having excellent image quality and durability can be provided.

以下に、本発明を詳細に説明する。本発明の導電性弾性部材は、ポリオール及びポリイソシアネートから合成したウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られる発泡ウレタン製の導電性弾性部材であって、前記ウレタンプレポリマーの合成に用いるポリオールが、平均官能基数が2〜4で且つ分子量が3000〜10000のラクトン変性ポリエーテルポリオールを含み、前記ポリイソシアネートがトリレンジイソシアネート(TDI)であることを特徴とする。なお、上記発泡ウレタン原料には、必要に応じて、その他の公知の添加剤を用いることができる。   The present invention is described in detail below. The conductive elastic member of the present invention is a urethane urethane conductive material obtained by mechanically stirring and foaming a foamed urethane raw material containing a urethane prepolymer synthesized from polyol and polyisocyanate, a chain extender, a catalyst, a foam stabilizer and a conductive agent. The polyol used for the synthesis of the urethane prepolymer includes a lactone-modified polyether polyol having an average number of functional groups of 2 to 4 and a molecular weight of 3000 to 10,000, and the polyisocyanate is tolylene diisocyanate (TDI). ). In addition, another well-known additive can be used for the said foaming urethane raw material as needed.

上記ウレタンプレポリマーの合成に用いるポリオールは、平均官能基数が2〜4で且つ分子量が3000〜10000のラクトン変性ポリエーテルポリオールを少なくとも含み、その他のポリオールを含んでもよい。ここで、他のポリオールとしては、プロピレンオキサイドやエチレンオキサイドを付加させてなるポリエーテルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール、プロピレンオキサイド変性ポリブタジエンポリオール等が挙げられる。これらポリオールは、1種単独で用いてもよいし、2種以上をブレンドして用いてもよい。上記ウレタンプレポリマーの合成にラクトン変性ポリエーテルポリオールと他のポリオールをブレンドして用いる場合、ポリオール中のラクトン変性ポリエーテルポリオールの割合は、70質量%以上の範囲が好ましい。該ラクトン変性ポリエーテルポリオールは、例えば、グリセリン等のポリオールにプロピレンオキサイド等のアルキレンオキサイドを付加して生成させたポリエーテルポリオールの末端を、ε-カプロラクトン等のラクトンで変性して製造することができ、市販品を利用することもできる。なお、上記ウレタンプレポリマーの合成に用いるポリオールは、水酸基価が10〜120mgKOH/gの範囲にあるのが好ましい。   The polyol used for the synthesis of the urethane prepolymer contains at least a lactone-modified polyether polyol having an average functional group number of 2 to 4 and a molecular weight of 3000 to 10,000, and may contain other polyols. Here, examples of other polyols include polyether polyols, polybutadiene polyols, polyisoprene polyols, propylene oxide-modified polybutadiene polyols obtained by adding propylene oxide or ethylene oxide. These polyols may be used alone or in a blend of two or more. When blending and using a lactone-modified polyether polyol and another polyol for the synthesis of the urethane prepolymer, the ratio of the lactone-modified polyether polyol in the polyol is preferably in the range of 70% by mass or more. The lactone-modified polyether polyol can be produced, for example, by modifying the end of a polyether polyol produced by adding an alkylene oxide such as propylene oxide to a polyol such as glycerin with a lactone such as ε-caprolactone. Commercial products can also be used. In addition, it is preferable that the polyol used for the synthesis | combination of the said urethane prepolymer exists in the range of 10-120 mgKOH / g of hydroxyl values.

上記ウレタンプレポリマーの合成に用いるポリイソシアネートは、トリレンジイソシアネート(TDI)である。該TDIには、異性体が複数存在するが、それらの中でも、2,4-トリレンジイソシアネート及び2,6-トリレンジイソシアネートが好ましい。また、本発明に用いるTDIとしては、2,4-トリレンジイソシアネート/2,6-トリレンジイソシアネートが質量比で65/35〜100/0の範囲にあるものが更に好ましい。   The polyisocyanate used for the synthesis of the urethane prepolymer is tolylene diisocyanate (TDI). The TDI has a plurality of isomers, among which 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are preferable. The TDI used in the present invention is more preferably 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate in a mass ratio of 65/35 to 100/0.

上記ポリオール及びポリイソシアネートから合成されるウレタンプレポリマーは、NCO(イソシアネート基)含有率が1〜10%の範囲にあるのが好ましい。   The urethane prepolymer synthesized from the polyol and polyisocyanate preferably has an NCO (isocyanate group) content of 1 to 10%.

また、上記発泡ウレタン原料として用いられる鎖延長剤は、上記ウレタンプレポリマー同士を連結する化合物であり、特に限定されるものではなく、従来、発泡ポリウレタン用の鎖延長剤として用いられるものを用いることができる。該鎖延長剤として、具体的には、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、ポリエーテルポリオール、ポリテトラメチレングリコール、プロピレンオキサイド(PO)変性ポリブタジエンポリオール、ポリブタジエンポリオール及びポリイソプレンポリオール等が挙げられる。これら鎖延長剤は、1種単独で用いてもよいし、2種以上をブレンドして用いてもよい。なお、上記鎖延長剤は、水酸基価が10〜1300mgKOH/gの範囲にあるのが好ましい。また、該鎖延長剤の使用量は、上記ウレタンプレポリマーのイソシアネート基(NCO)と鎖延長剤の水酸基(OH)とのモル比(NCO/OH)が90/100〜120/100の範囲になるよう、適宜選択されることが好ましい。   Moreover, the chain extender used as the urethane foam raw material is a compound that links the urethane prepolymers together, and is not particularly limited, and those conventionally used as a chain extender for polyurethane foam are used. Can do. Specific examples of the chain extender include propylene glycol, butanediol, pentanediol, hexanediol, octanediol, polyether polyol, polytetramethylene glycol, propylene oxide (PO) -modified polybutadiene polyol, polybutadiene polyol, and polyisoprene polyol. Etc. These chain extenders may be used alone or in a combination of two or more. The chain extender preferably has a hydroxyl value in the range of 10 to 1300 mgKOH / g. The chain extender is used in a molar ratio (NCO / OH) between the isocyanate group (NCO) of the urethane prepolymer and the hydroxyl group (OH) of the chain extender in the range of 90/100 to 120/100. It is preferable to select as appropriate.

上記発泡ウレタン原料に用いる触媒は、ウレタン化反応用の触媒であり、例えば、ジブチルスズジラウレート,ジブチルスズジアセテート,ジブチルスズチオカルボキシレート,ジブチルスズジマレエート,ジオクチルスズチオカルボキシレート,オクテン酸スズ等の有機スズ化合物;オクテン酸鉛等の有機鉛化合物;トリエチルアミン,ジメチルシクロヘキシルアミン等のモノアミン類;テトラメチルエチレンジアミン,テトラメチルプロパンジアミン,テトラメチルヘキサンジアミン等のジアミン類;ペンタメチルジエチレントリアミン,ペンタメチルジプロピレントリアミン,テトラメチルグアニジン等のトリアミン類;トリエチレンジアミン,ジメチルピペラジン,メチルエチルピペラジン,メチルモルホリン,ジメチルアミノエチルモルホリン,ジメチルイミダゾール等の環状アミン類;ジメチルアミノエタノール,ジメチルアミノエトキシエタノール,トリメチルアミノエチルエタノールアミン,メチルヒドロキシエチルピペラジン,ヒドロキシエチルモルホリン等のアルコールアミン類;ビス(ジメチルアミノエチル)エーテル,エチレングリコールビス(ジメチル)アミノプロピルエーテル等のエーテルアミン類等が挙げられる。これら触媒の中でも、有機スズ化合物が好ましい。これら触媒は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。上記触媒の使用量は、上記ウレタンプレポリマー100質量部に対して0.001〜2.0質量部の範囲が好ましい。   The catalyst used for the urethane foam raw material is a catalyst for urethanization reaction, for example, organic tin such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, etc. Compounds; Organic lead compounds such as lead octenoate; Monoamines such as triethylamine and dimethylcyclohexylamine; Diamines such as tetramethylethylenediamine, tetramethylpropanediamine, and tetramethylhexanediamine; Pentamethyldiethylenetriamine, Pentamethyldipropylenetriamine, Tetra Triamines such as methylguanidine; triethylenediamine, dimethylpiperazine, methylethylpiperazine, methylmorpholine, dimethylaminoethyl Cyclic amines such as morpholine and dimethylimidazole; Alcohol amines such as dimethylaminoethanol, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, methylhydroxyethylpiperazine, and hydroxyethylmorpholine; bis (dimethylaminoethyl) ether, ethylene glycol bis And ether amines such as (dimethyl) aminopropyl ether. Of these catalysts, organotin compounds are preferred. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the catalyst used is preferably in the range of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

上記発泡ウレタン原料に用いる整泡剤としては、ポリエーテル変性シリコーンオイル等のシリコーン系整泡剤の他、イオン性界面活性剤、ノニオン性界面活剤等を用いることができる。該整泡剤の使用量は、上記ウレタンプレポリマー100質量部に対して0.5〜5.0質量部の範囲が好ましい。   As the foam stabilizer used for the urethane foam raw material, an ionic surfactant, a nonionic surfactant, or the like can be used in addition to a silicone-based foam stabilizer such as polyether-modified silicone oil. The amount of the foam stabilizer used is preferably in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

上記発泡ウレタン原料に用いる導電剤としては、導電性カーボン、イオン導電剤、金属酸化物粉末、金属粉末等が挙げられる。これら導電剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。導電剤の使用量は、上記ウレタンプレポリマー100質量部に対して0.1〜10質量部の範囲が好ましい。   Examples of the conductive agent used for the urethane foam raw material include conductive carbon, ionic conductive agent, metal oxide powder, and metal powder. These electrically conductive agents may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the conductive agent used is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

本発明の導電性弾性部材は、外径φ16mm、芯金径φ8mmのローラ形状でのアスカーC硬度が40〜60度である。ローラ形状でのアスカーC硬度が上記の範囲を満たすことで、現像ローラ等の弾性部材として十分な硬度を確保しつつ、低融点トナーの凝集・融着を防止することができる。   The conductive elastic member of the present invention has an Asker C hardness of 40 to 60 degrees in a roller shape having an outer diameter of φ16 mm and a core metal diameter of φ8 mm. When the Asker C hardness in the roller shape satisfies the above range, aggregation and fusion of the low melting point toner can be prevented while securing sufficient hardness as an elastic member such as a developing roller.

本発明の導電性弾性部材は、外径φ16mm、芯金径φ8mmのローラとして平板に載せ、ローラの両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除いて30分後のローラ表面の変形量が7μm以下である。本発明の導電性弾性部材は、長期間他の部材に圧接されても、圧接状態から解放することで元の形状に戻りやすく、即ち、圧縮永久歪が小さいため、現像ローラ等の精密部品として好適である。   The conductive elastic member of the present invention is mounted on a flat plate as a roller having an outer diameter of φ16 mm and a cored bar diameter of φ8 mm, a load of 1000 g is applied to both ends of the roller, and left for 3 days in an environment of a temperature of 40 ° C. and a humidity of 95% RH. After that, the deformation amount of the roller surface after 30 minutes after removing the load is 7 μm or less. Even if the conductive elastic member of the present invention is pressed against another member for a long period of time, it is easy to return to its original shape by releasing from the pressed contact state. That is, since the compression set is small, as a precision component such as a developing roller. Is preferred.

本発明の導電性弾性部材を構成する発泡ウレタンは、上記ウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られるプレポリマー・メカニカル・フロス法発泡成形ウレタンである。該発泡ウレタンは、発泡剤を用いることなく、ウレタン原料を機械的に撹拌して気泡を混入させる方法で発泡させてなる。本発明の導電性弾性部材は、機械撹拌発泡で得られ、ウレタンプレポリマーの原料として、ポリエーテルポリオール系のラクトン変性ポリエーテルポリオールを使用しているため、発泡倍率が高い。また、発泡ウレタンの形成を、所望の形状の金型内で行うことで、所望の形状の導電性弾性部材を製造することができる。   The urethane foam constituting the conductive elastic member of the present invention is a prepolymer / mechanical floss obtained by mechanically agitating and foaming a urethane foam raw material containing the urethane prepolymer, chain extender, catalyst, foam stabilizer and conductive agent. It is a process foamed urethane. The foamed urethane is foamed by a method in which a urethane raw material is mechanically stirred and bubbles are mixed without using a foaming agent. The conductive elastic member of the present invention is obtained by mechanical stirring and foaming, and since a polyether polyol-based lactone-modified polyether polyol is used as a raw material for the urethane prepolymer, the expansion ratio is high. Moreover, a conductive elastic member having a desired shape can be manufactured by forming the urethane foam in a mold having a desired shape.

本発明の導電性弾性部材は、画像形成装置の現像ローラとして好適である。この場合、該現像ローラは、上記発泡ウレタン以外に、金属製シャフト等の他の材料を備えてもよい。該現像ローラは、例えば、中心部に金属製のシャフトを配置した所望の形状の金型内に上記ウレタン原料を混合撹拌して注入し、硬化させて製造することができ、更に、該現像ローラの外表面には、熱硬化性塗液を塗布する等して塗膜を形成してもよい。   The conductive elastic member of the present invention is suitable as a developing roller for an image forming apparatus. In this case, the developing roller may include other materials such as a metal shaft in addition to the urethane foam. The developing roller can be manufactured, for example, by mixing and injecting the urethane raw material into a mold having a desired shape in which a metal shaft is disposed at the center, stirring and curing, and further developing the developing roller. A coating film may be formed on the outer surface by applying a thermosetting coating liquid.

本発明の画像形成装置は、上記の導電性弾性部材を用いることを特徴とし、上記の導電性弾性部材を現像ローラとして備えるのが好ましい。本発明の画像形成装置は、上記導電性弾性部材を用いる以外、特に制限はなく、公知の方法で製造することができる。   The image forming apparatus of the present invention uses the above-described conductive elastic member, and preferably includes the conductive elastic member as a developing roller. The image forming apparatus of the present invention is not particularly limited except that the conductive elastic member is used, and can be manufactured by a known method.

以下に、図を参照して本発明の画像形成装置を詳細に説明する。図1は、本発明の画像形成装置の一例の部分断面図である。図示例の画像形成装置は、トナー1を供給するためのトナー供給ローラ2と、静電潜像を保持した感光ドラム3と、トナー供給ローラ2と感光ドラム3との間に配置された現像ローラ4と、現像ローラ4の上部に設けられた現像ブレード5と、感光ドラム3の下方に位置する転写部6と、感光ドラム3に隣接して設けられたクリーニング部7とを備える。なお、本発明の画像形成装置は、更に画像形成装置に通常用いられる公知の部品(図示せず)を備えることができる。   The image forming apparatus of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a partial cross-sectional view of an example of the image forming apparatus of the present invention. The image forming apparatus of the illustrated example includes a toner supply roller 2 for supplying toner 1, a photosensitive drum 3 holding an electrostatic latent image, and a developing roller disposed between the toner supply roller 2 and the photosensitive drum 3. 4, a developing blade 5 provided above the developing roller 4, a transfer unit 6 located below the photosensitive drum 3, and a cleaning unit 7 provided adjacent to the photosensitive drum 3. The image forming apparatus of the present invention can further include known components (not shown) that are normally used in the image forming apparatus.

図示例の画像形成装置においては、トナー供給ローラ2と、現像ローラ4と、感光ドラム3とが、図中の矢印方向に回転することで、トナー供給ローラ2上のトナー1が現像ローラ4を経て感光ドラム3に送られる。トナー1は、現像ローラ4上で現像ブレード5により均一な薄層に整えられ、更に現像ローラ4と感光ドラム3とが接触しながら回転することにより、現像ローラ4から感光ドラム3の静電潜像に付着し、該潜像が可視化する。潜像に付着したトナー1は、転写部6で紙等の記録媒体に転写され、また、転写後に感光ドラム3上に残留するトナー1は、クリーニング部7のクリーニングブレード8によって除去される。本発明の画像形成装置においては、例えば、現像ローラ4に上述の硬度及び圧縮永久歪が低い導電性弾性部材を用いることで、トナー1の融点が通常より低くても、トナー1の凝集・融着が抑制することができ、長期に渡って良好な画像を形成することができる。   In the illustrated image forming apparatus, the toner supply roller 2, the developing roller 4, and the photosensitive drum 3 rotate in the direction of the arrow in FIG. Then, it is sent to the photosensitive drum 3. The toner 1 is adjusted to a uniform thin layer by the developing blade 5 on the developing roller 4 and further rotated while the developing roller 4 and the photosensitive drum 3 are in contact with each other. It adheres to the image and the latent image becomes visible. The toner 1 attached to the latent image is transferred to a recording medium such as paper by the transfer unit 6, and the toner 1 remaining on the photosensitive drum 3 after the transfer is removed by the cleaning blade 8 of the cleaning unit 7. In the image forming apparatus of the present invention, for example, by using the conductive elastic member having the low hardness and compression set described above for the developing roller 4, even if the melting point of the toner 1 is lower than usual, the aggregation / melting of the toner 1 is performed. Wear can be suppressed, and a good image can be formed over a long period of time.

以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(実施例1)
グリセリンにプロピレンオキサイドを付加した3官能で分子量3,000のポリエーテルポリオールにラクトンを付加して得られる3官能で分子量4,000のラクトン変性ポリエーテルポリオール(水酸基価42.8mgKOH/g)100質量部と、2,4-トリレンジイソシアネート及び2,6-トリレンジイソシアネートの質量比(2,4-異性体/2,6-異性体)が80/20のトリレンジイソシアネート(TDI-80)23.5質量部とを密閉容器内で60℃で48時間撹拌しながら反応させ、ウレタンプレポリマーを合成した。なお、得られたウレタンプレポリマーのNCO含有率は、6.6%であった。このウレタンプレポリマー100質量部と、導電性カーボンブラック[電気化学工業社製, デンカブラック]2.0質量部とを減圧下で混合撹拌して、導電性カーボンが分散したウレタンプレポリマーを作製し、これをA成分とした。
Example 1
100 parts by mass of a trifunctional, molecular weight 4,000 lactone-modified polyether polyol (hydroxyl value 42.8 mg KOH / g) obtained by adding lactone to a trifunctional, molecular weight 3,000 polyether polyol obtained by adding propylene oxide to glycerin; Sealed with 23.5 parts by mass of tolylene diisocyanate (TDI-80) having a mass ratio of 2,6-tolylene diisocyanate and 2,6-tolylene diisocyanate (2,4-isomer / 2,6-6-isomer) of 80/20 A urethane prepolymer was synthesized by reacting in a container at 60 ° C. with stirring for 48 hours. The obtained urethane prepolymer had an NCO content of 6.6%. 100 parts by mass of this urethane prepolymer and 2.0 parts by mass of conductive carbon black [Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.] were mixed and stirred under reduced pressure to prepare a urethane prepolymer in which conductive carbon was dispersed. Was designated as component A.

一方、平均官能基数2.0、分子量400のプロピレンオキサイド付加ポリオール21.0質量部と、平均官能基数3.0、分子量430のプロピレンオキサイド付加ポリオール6.0質量部と、ポリエーテル変性シリコーンオイル(整泡剤)4.0質量部と、ジブチルスズジラウレート(DBTDL)0.3質量部とを混合撹拌して、混合物を調製し、これをB成分とした。   On the other hand, 21.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 2.0 and a molecular weight of 400, 6.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 3.0 and a molecular weight of 430, and 4.0 parts by mass of a polyether-modified silicone oil (foam stabilizer) And 0.3 parts by mass of dibutyltin dilaurate (DBTDL) were mixed and stirred to prepare a mixture, which was designated as component B.

上記A成分とB成分とをメカニカル・フロス発泡機にて、A成分とB成分との流量比(A/B)が102.0/31.3になるようにして撹拌、混合、発泡させ、内面にフッ素樹脂コートを施した内径16.0mmで中央に外径寸法φ8mmの芯金がセットされた筒型に注入した。次に、該筒型の両端を密閉し、110℃の熱風循環オーブンで30分間加熱キュアーした後、筒型から成形品を取り出し、更に、該成形品の表面に熱硬化性塗液を塗布し、60℃で1時間加熱乾燥して、外径寸法がφ16.0mmの導電性ローラを得た。   The above A component and B component are stirred, mixed and foamed with a mechanical floss foaming machine so that the flow rate ratio (A / B) between the A component and B component is 102.0 / 31.3, and the inner surface is fluororesin The inner diameter of the coated inner diameter was 16.0 mm, and the core was poured into a core having an outer diameter of φ8 mm set in the center. Next, both ends of the cylindrical mold are sealed, and after being heated and cured in a hot air circulating oven at 110 ° C. for 30 minutes, the molded product is taken out from the cylindrical mold, and a thermosetting coating liquid is applied to the surface of the molded product. Then, it was heated and dried at 60 ° C. for 1 hour to obtain a conductive roller having an outer diameter of φ16.0 mm.

得られた導電性ローラは、室温での抵抗値が104.8Ωで、アスカーC硬度が51度で、フォーム密度が0.52g/cm3であった。この導電性ローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後のローラ表面の変形量(凹み量)を測定したところ、変形量は4.7μmであった。 The obtained conductive roller had a resistance value of 10 4.8 Ω at room temperature, an Asker C hardness of 51 degrees, and a foam density of 0.52 g / cm 3 . Place this conductive roller on a flat plate, apply a load of 1000g to each end of the roller, leave it for 3 days in an environment of temperature 40 ° C and humidity 95% RH, remove the load, and deform the roller surface after 30 minutes ( The amount of deformation was measured to be 4.7 μm.

この導電性ローラを現像ローラとして乾式電子写真装置に組み込み、温度40℃、湿度95%RHの環境下で2週間放置した後、グレー(濃度8%)の画像を印刷したところ、良好な画像が得られた。次に、この乾式電子写真装置を、温度20℃、湿度50%RHの環境下で48時間放置後、グレー(濃度8%)の画像を印刷したところ、良好な画像が得られた。更に連続して10000枚印刷した後、グレーの画像を印刷したところ、トナーの凝集・融着に起因する白スジ等の画像不良はなく、良好な画像が得られた。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、現像ローラ表面には感光ドラム、現像ブレード、トナー供給ローラ等による圧接痕や削れ等が無いことが分かった。更に、現像ローラの近くのトナーを顕微鏡で観察したところ、トナーは初期状態を維持しており、凝集・融着は観察されなかった。   This conductive roller is incorporated into a dry electrophotographic apparatus as a developing roller and left for 2 weeks in an environment of temperature 40 ° C and humidity 95% RH. After printing a gray (8% density) image, a good image is obtained. Obtained. Next, this dry electrophotographic apparatus was allowed to stand for 48 hours in an environment of a temperature of 20 ° C. and a humidity of 50% RH, and a gray image (density 8%) was printed. As a result, a good image was obtained. Further, after continuous printing of 10,000 sheets, a gray image was printed. As a result, there was no image defect such as white streaks due to toner aggregation and fusion, and a good image was obtained. Further, when the used toner cartridge was disassembled and the surface of the developing roller was observed, it was found that the surface of the developing roller was free from scratches or scratches due to a photosensitive drum, a developing blade, a toner supply roller, or the like. Further, when the toner near the developing roller was observed with a microscope, the toner maintained the initial state, and no aggregation or fusion was observed.

(実施例2)
グリセリンにプロピレンオキサイドを付加した3官能で分子量3,000のポリエーテルポリオールにラクトンを付加して得られる3官能で分子量4,000のラクトン変性ポリエーテルポリオール(水酸基価42.8mgKOH/g)70質量部と、グリセリンにプロピレンオキサイドを付加した3官能で分子量5,100のポリエーテルポリオール(水酸基価33.3mgKOH/g)30質量部と、2,4-トリレンジイソシアネート及び2,6-トリレンジイソシアネートの質量比(2,4-異性体/2,6-異性体)が80/20のトリレンジイソシアネート(TDI-80)23.0質量部とを密閉容器内で60℃で48時間撹拌しながら反応させ、ウレタンプレポリマーを合成した。なお、得られたウレタンプレポリマーのNCO含有率は、6.6%であった。このウレタンプレポリマー100質量部と、導電性カーボンブラック[電気化学工業社製, デンカブラック]2.0質量部とを減圧下で混合撹拌して、導電性カーボンが分散したウレタンプレポリマーを作製し、これをA成分とした。
(Example 2)
70 parts by mass of a trifunctional, molecular weight 4,000 lactone-modified polyether polyol (hydroxyl value 42.8 mgKOH / g) obtained by adding lactone to a trifunctional, molecular weight 3,000 polyether polyol obtained by adding propylene oxide to glycerin; 30 parts by mass of a tri-functional 5,100 molecular weight polyether polyol (hydroxyl value 33.3 mgKOH / g) to which propylene oxide has been added and the mass ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (2,4- A urethane prepolymer was synthesized by reacting 23.0 parts by mass of tolylene diisocyanate (TDI-80) having an isomer / 2,6-isomer of 80/20 with stirring at 60 ° C. for 48 hours. In addition, the NCO content rate of the obtained urethane prepolymer was 6.6%. 100 parts by mass of this urethane prepolymer and 2.0 parts by mass of conductive carbon black [Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.] were mixed and stirred under reduced pressure to prepare a urethane prepolymer in which conductive carbon was dispersed. Was designated as component A.

一方、平均官能基数2.0、分子量400のプロピレンオキサイド付加ポリオール21.0質量部と、平均官能基数3.0、分子量430のプロピレンオキサイド付加ポリオール6.0質量部と、ポリエーテル変性シリコーンオイル(整泡剤)4.0質量部と、ジブチルスズジラウレート(DBTDL)0.3質量部とを混合撹拌して、混合物を調製し、これをB成分とした。   On the other hand, 21.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 2.0 and a molecular weight of 400, 6.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 3.0 and a molecular weight of 430, and 4.0 parts by mass of a polyether-modified silicone oil (foam stabilizer) And 0.3 parts by mass of dibutyltin dilaurate (DBTDL) were mixed and stirred to prepare a mixture, which was designated as component B.

上記A成分とB成分とをメカニカル・フロス発泡機にて、A成分とB成分との流量比(A/B)が102.0/31.3になるようにして撹拌、混合、発泡させ、内面にフッ素樹脂コートを施した内径16.0mmで中央に外径寸法φ8mmの芯金がセットされた筒型に注入した。次に、該筒型の両端を密閉し、110℃の熱風循環オーブンで30分間加熱キュアーした後、筒型から成形品を取り出し、更に、該成形品の表面に熱硬化性塗液を塗布し、60℃で1時間加熱乾燥して、外径寸法がφ16.0mmの導電性ローラを得た。   The above A component and B component are stirred, mixed and foamed with a mechanical floss foaming machine so that the flow rate ratio (A / B) between the A component and B component is 102.0 / 31.3, and the inner surface is fluororesin The inner diameter of the coated inner diameter was 16.0 mm, and the core was poured into a core having an outer diameter of φ8 mm set in the center. Next, both ends of the cylindrical mold are sealed, and after being heated and cured in a hot air circulating oven at 110 ° C. for 30 minutes, the molded product is taken out from the cylindrical mold, and a thermosetting coating liquid is applied to the surface of the molded product. Then, it was heated and dried at 60 ° C. for 1 hour to obtain a conductive roller having an outer diameter of φ16.0 mm.

得られた導電性ローラは、室温での抵抗値が104.4Ωで、アスカーC硬度が52度で、フォーム密度が0.51g/cm3であった。この導電性ローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後のローラ表面の変形量(凹み量)を測定したところ、変形量は6.4μmであった。 The resulting conductive roller had a resistance value of 10 4.4 Ω at room temperature, an Asker C hardness of 52 degrees, and a foam density of 0.51 g / cm 3 . Place this conductive roller on a flat plate, apply a load of 1000g to each end of the roller, leave it for 3 days in an environment of temperature 40 ° C and humidity 95% RH, remove the load, and deform the roller surface after 30 minutes ( The amount of deformation was measured to be 6.4 μm.

この導電性ローラを現像ローラとして乾式電子写真装置に組み込み、温度40℃、湿度95%RHの環境下で2週間放置した後、グレー(濃度8%)の画像を印刷したところ、良好な画像が得られた。次に、この乾式電子写真装置を、温度20℃、湿度50%RHの環境下で48時間放置後、グレー(濃度8%)の画像を印刷したところ、良好な画像が得られた。更に連続して10000枚印刷した後、グレーの画像を印刷したところ、トナーの凝集・融着に起因する白スジ等の画像不良はなく、良好な画像が得られた。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、現像ローラ表面には感光ドラム、現像ブレード、トナー供給ローラ等による圧接痕や削れ等が無いことが分かった。更に、現像ローラの近くのトナーを顕微鏡で観察したところ、トナーは初期状態を維持しており、凝集・融着は観察されなかった。   This conductive roller is incorporated into a dry electrophotographic apparatus as a developing roller and left for 2 weeks in an environment of temperature 40 ° C and humidity 95% RH. After printing a gray (8% density) image, a good image is obtained. Obtained. Next, this dry electrophotographic apparatus was allowed to stand for 48 hours in an environment of a temperature of 20 ° C. and a humidity of 50% RH, and a gray image (density 8%) was printed. As a result, a good image was obtained. Further, after continuous printing of 10,000 sheets, a gray image was printed. As a result, there was no image defect such as white streaks due to toner aggregation and fusion, and a good image was obtained. Further, when the used toner cartridge was disassembled and the surface of the developing roller was observed, it was found that the surface of the developing roller was free from scratches or scratches due to a photosensitive drum, a developing blade, a toner supply roller, or the like. Further, when the toner near the developing roller was observed with a microscope, the toner maintained the initial state and no aggregation or fusion was observed.

(比較例1)
グリセリンにプロピレンオキサイド(PO)とエチレンオキサイド(EO)とを付加した3官能で分子量5,000、水酸基価34mgKOH/gのポリエーテルポリオール100質量部と、2,4-トリレンジイソシアネート及び2,6-トリレンジイソシアネートの質量比(2,4-異性体/2,6-異性体)が80/20のトリレンジイソシアネート(TDI-80)21.9質量部とを密閉容器内で60℃で48時間撹拌しながら反応させ、ウレタンプレポリマーを合成した。なお、得られたウレタンプレポリマーのNCO含有率は、6.6%であった。このウレタンプレポリマー100質量部と、導電性カーボンブラック[電気化学工業社製, デンカブラック]2.0質量部とを減圧下で混合撹拌して、導電性カーボンが分散したウレタンプレポリマーを作製し、これをA成分とした。
(Comparative Example 1)
100 parts by mass of a polyether polyol having a molecular weight of 5,000 and a hydroxyl value of 34 mgKOH / g, which is obtained by adding propylene oxide (PO) and ethylene oxide (EO) to glycerin, 2,4-tolylene diisocyanate and 2,6-triol While stirring 21.9 parts of tolylene diisocyanate (TDI-80) having a weight ratio of 2,4-isomer of 2,4-isomer / 2,6-isomer of 48/20 at 60 ° C. for 48 hours. By reacting, a urethane prepolymer was synthesized. In addition, the NCO content rate of the obtained urethane prepolymer was 6.6%. 100 parts by mass of this urethane prepolymer and 2.0 parts by mass of conductive carbon black [Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.] were mixed and stirred under reduced pressure to prepare a urethane prepolymer in which conductive carbon was dispersed. Was A component.

一方、平均官能基数2.0、分子量400のプロピレンオキサイド付加ポリオール20.0質量部と、平均官能基数3.0、分子量430のプロピレンオキサイド付加ポリオール6.0質量部と、ポリエーテル変性シリコーンオイル(整泡剤)4.0質量部と、ジブチルスズジラウレート(DBTDL)0.3質量部とを混合撹拌して、混合物を調製し、これをB成分とした。   On the other hand, 20.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 2.0 and a molecular weight of 400, 6.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 3.0 and a molecular weight of 430, and 4.0 parts by mass of a polyether-modified silicone oil (foam stabilizer) And 0.3 parts by mass of dibutyltin dilaurate (DBTDL) were mixed and stirred to prepare a mixture, which was designated as component B.

上記A成分とB成分とをメカニカル・フロス発泡機にて、A成分とB成分との流量比(A/B)が102.0/31.3になるようにして撹拌、混合、発泡させ、内面にフッ素樹脂コートを施した内径16.0mmで中央に外径寸法φ8mmの芯金がセットされた筒型に注入した。次に、該筒型の両端を密閉し、110℃の熱風循環オーブンで30分間加熱キュアーした後、筒型から成形品を取り出し、更に、該成形品の表面に熱硬化性塗液を塗布し、60℃で1時間加熱乾燥して、外径寸法がφ16.0mmの導電性ローラを得た。   The above A component and B component are stirred, mixed and foamed with a mechanical floss foaming machine so that the flow rate ratio (A / B) between the A component and B component is 102.0 / 31.3, and the inner surface is fluororesin The inner diameter of the coated inner diameter was 16.0 mm, and the core was poured into a core having an outer diameter of φ8 mm set in the center. Next, both ends of the cylindrical mold are sealed, and after being heated and cured in a hot air circulating oven at 110 ° C. for 30 minutes, the molded product is taken out from the cylindrical mold, and a thermosetting coating liquid is applied to the surface of the molded product. Then, it was heated and dried at 60 ° C. for 1 hour to obtain a conductive roller having an outer diameter of φ16.0 mm.

得られた導電性ローラは、室温での抵抗値が104.2Ωで、アスカーC硬度が52度で、フォーム密度が0.53g/cm3であった。この導電性ローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後のローラ表面の変形量(凹み量)を測定したところ、変形量は8.3μmであった。 The obtained conductive roller had a resistance value of 10 4.2 Ω at room temperature, an Asker C hardness of 52 degrees, and a foam density of 0.53 g / cm 3 . Place this conductive roller on a flat plate, apply a load of 1000g to each end of the roller, leave it for 3 days in an environment of temperature 40 ° C and humidity 95% RH, remove the load, and deform the roller surface after 30 minutes ( The amount of deformation was measured to be 8.3 μm.

この導電性ローラを現像ローラとして乾式電子写真装置に組み込み、温度40℃、湿度95%RHの環境下で2週間放置した後、グレー(濃度8%)の画像を印刷したところ、現像ローラの長さ方向と同一方向のスジ状の画像不良が確認された。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、現像ローラ表面に現像ブレード及び感光ドラムとの圧接痕が観測された。次に、この乾式電子写真装置を、温度20℃、湿度50%RHの環境下で48時間放置後、グレー(濃度8%)の画像を印刷したところ、同様に画像にスジ状の不良が確認された。更に連続して10000枚印刷した後、グレーの画像を印刷したところ、現像ローラの長さ方向と同一方向のスジ状の画像不良、現像ローラの長さ方向と直角方向のスジ状の画像不良が確認された。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、既に観察された現像ブレード及び感光ドラムとの圧接痕の他に、現像ローラの長さ方向と直角方向の白スジが発生した位置に対応する現像ローラの表面に削れがあることが分かった。更に、削れた部分の近くのトナーを顕微鏡で観察したところ、トナーが凝集・融着していた。   This conductive roller was incorporated into a dry electrophotographic apparatus as a developing roller, left in an environment of temperature 40 ° C and humidity 95% RH for 2 weeks, and after printing a gray image (density 8%), the length of the developing roller A streak-like image defect in the same direction as the vertical direction was confirmed. Further, the used toner cartridge was disassembled and the surface of the developing roller was observed. As a result, pressure contact marks between the developing blade and the photosensitive drum were observed on the surface of the developing roller. Next, this dry electrophotographic device was left for 48 hours in an environment of temperature 20 ° C and humidity 50% RH, and after printing a gray (density 8%) image, streaky defects were confirmed in the image as well. It was done. Furthermore, after printing 10,000 sheets continuously, when a gray image was printed, a streak-like image defect in the same direction as the length direction of the developing roller and a streak-like image defect perpendicular to the length direction of the developing roller occurred. confirmed. In addition, when the used toner cartridge was disassembled and the surface of the developing roller was observed, white streaks in the direction perpendicular to the length direction of the developing roller were generated in addition to the previously observed pressure contact marks between the developing blade and the photosensitive drum. It was found that the surface of the developing roller corresponding to the position was scraped. Further, when the toner near the shaved portion was observed with a microscope, the toner was agglomerated and fused.

(比較例2)
グリセリンにプロピレンオキサイドを付加した3官能で分子量5,100、水酸基価33mgKOH/gのポリエーテルポリオール100質量部と、2,4-トリレンジイソシアネート及び2,6-トリレンジイソシアネートの質量比(2,4-異性体/2,6-異性体)が80/20のトリレンジイソシアネート(TDI-80)21.7質量部とを密閉容器内で60℃で48時間撹拌しながら反応させ、ウレタンプレポリマーを合成した。なお、得られたウレタンプレポリマーのNCO含有率は、6.6%であった。このウレタンプレポリマー100質量部と、導電性カーボンブラック[電気化学工業社製, デンカブラック]2.0質量部とを減圧下で混合撹拌して、導電性カーボンが分散したウレタンプレポリマーを作製し、これをA成分とした。
(Comparative Example 2)
Mass ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (100 parts by mass of polyether polyol having a trifunctional molecular weight of 5,100 and a hydroxyl value of 33 mgKOH / g) obtained by adding propylene oxide to glycerin A urethane prepolymer was synthesized by reacting 21.7 parts by mass of tolylene diisocyanate (TDI-80) having an isomer / 2,6-isomer of 80/20 with stirring at 60 ° C. for 48 hours. The obtained urethane prepolymer had an NCO content of 6.6%. 100 parts by mass of this urethane prepolymer and 2.0 parts by mass of conductive carbon black [Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.] were mixed and stirred under reduced pressure to prepare a urethane prepolymer in which conductive carbon was dispersed. Was designated as component A.

一方、平均官能基数2.0、分子量400のプロピレンオキサイド付加ポリオール20.0質量部と、平均官能基数3.0、分子量430のプロピレンオキサイド付加ポリオール6.0質量部と、ポリエーテル変性シリコーンオイル(整泡剤)4.0質量部と、ジブチルスズジラウレート(DBTDL)0.3質量部とを混合撹拌して、混合物を調製し、これをB成分とした。   On the other hand, 20.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 2.0 and a molecular weight of 400, 6.0 parts by mass of a propylene oxide addition polyol having an average functional group number of 3.0 and a molecular weight of 430, and 4.0 parts by mass of a polyether-modified silicone oil (foam stabilizer) And 0.3 parts by mass of dibutyltin dilaurate (DBTDL) were mixed and stirred to prepare a mixture, which was designated as component B.

上記A成分とB成分とをメカニカル・フロス発泡機にて、A成分とB成分との流量比(A/B)が102.0/31.3になるようにして撹拌、混合、発泡させ、内面にフッ素樹脂コートを施した内径16.0mmで中央に外径寸法φ8mmの芯金がセットされた筒型に注入した。次に、該筒型の両端を密閉し、110℃の熱風循環オーブンで30分間加熱キュアーした後、筒型から成形品を取り出し、更に、該成形品の表面に熱硬化性塗液を塗布し、60℃で1時間加熱乾燥して、外径寸法がφ16.0mmの導電性ローラを得た。   The above A component and B component are stirred, mixed and foamed with a mechanical floss foaming machine so that the flow rate ratio (A / B) between the A component and B component is 102.0 / 31.3, and the inner surface is fluororesin The inner diameter of the coated inner diameter was 16.0 mm, and the core was poured into a core having an outer diameter of φ8 mm set in the center. Next, both ends of the cylindrical mold are sealed, and after being heated and cured in a hot air circulating oven at 110 ° C. for 30 minutes, the molded product is taken out from the cylindrical mold, and a thermosetting coating liquid is applied to the surface of the molded product. Then, it was heated and dried at 60 ° C. for 1 hour to obtain a conductive roller having an outer diameter of φ16.0 mm.

得られた導電性ローラは、室温での抵抗値が104.5Ωで、アスカーC硬度が51度で、フォーム密度が0.54g/cm3であった。この導電性ローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後のローラ表面の変形量(凹み量)を測定したところ、変形量は8.4μmであった。 The resulting conductive roller had a resistance value of 10 4.5 Ω at room temperature, an Asker C hardness of 51 degrees, and a foam density of 0.54 g / cm 3 . Place this conductive roller on a flat plate, apply a load of 1000g to each end of the roller, leave it for 3 days in an environment of temperature 40 ° C and humidity 95% RH, remove the load, and deform the roller surface after 30 minutes ( When the amount of dents was measured, the amount of deformation was 8.4 μm.

この導電性ローラを現像ローラとして乾式電子写真装置に組み込み、温度40℃、湿度95%RHの環境下で2週間放置した後、グレー(濃度8%)の画像を印刷したところ、現像ローラの長さ方向と同一方向のスジ状の画像不良が確認された。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、現像ローラ表面に現像ブレード及び感光ドラムとの圧接痕が観測された。次に、この乾式電子写真装置を、温度20℃、湿度50%RHの環境下で48時間放置後、グレー(濃度8%)の画像を印刷したところ、同様に画像にスジ状の不良が確認された。更に連続して10000枚印刷した後、グレーの画像を印刷したところ、現像ローラの長さ方向と同一方向のスジ状の画像不良、現像ローラの長さ方向と直角方向のスジ状の画像不良が確認された。また、使用したトナーカートリッジを分解し、現像ローラの表面を観察したところ、既に観察された現像ブレード及び感光ドラムとの圧接痕の他に、現像ローラの長さ方向と直角方向の白スジが発生した位置に対応する現像ローラの表面に削れがあることが分かった。更に、削れた部分の近くのトナーを顕微鏡で観察したところ、トナーが凝集・融着していた。   This conductive roller was incorporated into a dry electrophotographic apparatus as a developing roller, left in an environment of temperature 40 ° C and humidity 95% RH for 2 weeks, and after printing a gray image (density 8%), the length of the developing roller A streak-like image defect in the same direction as the vertical direction was confirmed. Further, the used toner cartridge was disassembled and the surface of the developing roller was observed. As a result, pressure contact marks between the developing blade and the photosensitive drum were observed on the surface of the developing roller. Next, this dry electrophotographic device was left for 48 hours in an environment with a temperature of 20 ° C and a humidity of 50% RH, and after printing a gray (density 8%) image, a streak-like defect was confirmed on the image as well. It was done. Furthermore, after printing 10,000 sheets continuously, when a gray image was printed, a streak-like image defect in the same direction as the length direction of the developing roller and a streak-like image defect perpendicular to the length direction of the developing roller occurred. confirmed. In addition, when the used toner cartridge was disassembled and the surface of the developing roller was observed, white streaks in the direction perpendicular to the length direction of the developing roller were generated in addition to the previously observed pressure contact marks between the developing blade and the photosensitive drum. It was found that the surface of the developing roller corresponding to the position was scraped. Further, when the toner near the shaved portion was observed with a microscope, the toner was agglomerated and fused.

Figure 2006078636
Figure 2006078636

表1から明らかなように、ウレタンプレポリマーの合成に特定のポリオール及びポリイソシアネートを用いて得られた発泡ウレタン製の導電性ローラは、硬度及び圧縮永久歪が低く、該ローラを現像ローラとして用いた画像形成装置は、高温・高湿下でも良好な画像を形成することができると共に、耐久性にも優れている。   As is clear from Table 1, the urethane foam conductive roller obtained by using a specific polyol and polyisocyanate for the synthesis of the urethane prepolymer has low hardness and compression set, and the roller is used as a developing roller. The conventional image forming apparatus can form a good image even under high temperature and high humidity, and has excellent durability.

本発明の画像形成装置の一例の部分断面図である。1 is a partial cross-sectional view of an example of an image forming apparatus of the present invention.

符号の説明Explanation of symbols

1 トナー
2 トナー供給ローラ
3 感光ドラム
4 現像ローラ
5 現像ブレード
6 転写部
7 クリーニング部
8 クリーニングブレード
DESCRIPTION OF SYMBOLS 1 Toner 2 Toner supply roller 3 Photosensitive drum 4 Developing roller 5 Developing blade 6 Transfer part 7 Cleaning part 8 Cleaning blade

Claims (4)

ポリオール及びポリイソシアネートから合成したウレタンプレポリマー、鎖延長剤、触媒、整泡剤並びに導電剤を含む発泡ウレタン原料を機械撹拌発泡して得られる発泡ウレタン製の導電性弾性部材において、
前記ウレタンプレポリマーの合成に用いるポリオールが、平均官能基数が2〜4で且つ分子量が3000〜10000のラクトン変性ポリエーテルポリオールを含み、前記ポリイソシアネートがトリレンジイソシアネート(TDI)であって、
外径φ16mm、芯金径φ8mmのローラでのアスカーC硬度が40〜60度であり、
外径φ16mm、芯金径φ8mmのローラを平板にのせ、ローラ両端に各1000gの荷重をかけ、温度40℃、湿度95%RHの環境下で3日間放置した後、荷重を取り除き30分後の表面変形量が7μm以下であることを特徴とする導電性弾性部材。
In the conductive elastic member made of urethane foam obtained by mechanically agitating and foaming urethane raw material containing urethane prepolymer synthesized from polyol and polyisocyanate, chain extender, catalyst, foam stabilizer and conductive agent,
The polyol used for the synthesis of the urethane prepolymer includes a lactone-modified polyether polyol having an average functional group number of 2 to 4 and a molecular weight of 3000 to 10,000, and the polyisocyanate is tolylene diisocyanate (TDI),
The Asker C hardness is 40-60 degrees with a roller with an outer diameter of φ16mm and a cored bar diameter of φ8mm.
Place a roller with an outer diameter of φ16mm and a cored bar diameter of φ8mm on a flat plate, apply a load of 1000g to each end of the roller, leave it under an environment of temperature 40 ℃ and humidity 95% RH for 3 days, then remove the load and after 30 minutes A conductive elastic member having a surface deformation amount of 7 μm or less.
前記ウレタンプレポリマーの合成に用いるポリオールが、前記ラクトン変性ポリエーテルポリオール単独、又は前記ラクトン変性ポリエーテルポリオールとその他のポリオールとのブレンドからなることを特徴とする請求項1に記載の導電性弾性部材。   2. The conductive elastic member according to claim 1, wherein the polyol used for the synthesis of the urethane prepolymer comprises the lactone-modified polyether polyol alone or a blend of the lactone-modified polyether polyol and other polyols. . 前記導電性弾性部材が現像ローラであることを特徴とする請求項1又は2に記載の導電性弾性部材。   The conductive elastic member according to claim 1, wherein the conductive elastic member is a developing roller. 請求項1〜3のいずれかに記載の導電性弾性部材を用いた画像形成装置。   An image forming apparatus using the conductive elastic member according to claim 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009109861A (en) * 2007-10-31 2009-05-21 Canon Inc Image developing roller and manufacturing method therefor, process cartridge, and electrophotographic device
US8550968B2 (en) * 2005-11-11 2013-10-08 Bridgestone Corporation Developing roller and imaging apparatus comprising the same
US10216113B2 (en) 2015-08-26 2019-02-26 Hp Printing Korea Co., Ltd. Roller for image forming apparatus

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8550968B2 (en) * 2005-11-11 2013-10-08 Bridgestone Corporation Developing roller and imaging apparatus comprising the same
JP2009109861A (en) * 2007-10-31 2009-05-21 Canon Inc Image developing roller and manufacturing method therefor, process cartridge, and electrophotographic device
US10216113B2 (en) 2015-08-26 2019-02-26 Hp Printing Korea Co., Ltd. Roller for image forming apparatus

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