JPH0651554A - Developer for developing electrostatic charge image and image forming method - Google Patents

Developer for developing electrostatic charge image and image forming method

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Publication number
JPH0651554A
JPH0651554A JP5134665A JP13466593A JPH0651554A JP H0651554 A JPH0651554 A JP H0651554A JP 5134665 A JP5134665 A JP 5134665A JP 13466593 A JP13466593 A JP 13466593A JP H0651554 A JPH0651554 A JP H0651554A
Authority
JP
Japan
Prior art keywords
fine powder
treated
image
silicone oil
developer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP5134665A
Other languages
Japanese (ja)
Other versions
JP2974545B2 (en
Inventor
Masakichi Kato
政吉 加藤
Koichi Tomiyama
晃一 冨山
Hiroshi Yusa
寛 遊佐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
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  • Electrostatic Charge, Transfer And Separation In Electrography (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

PURPOSE:To provide a developer for developing an electrostatic charge image having low dependency on environment and giving a high quality image and an image forming method using the developer. CONSTITUTION:When a transfer roll 2 is brought into contact with a latent image carrying body (photosensitive body) 1 under >=3g/cm linear pressure and a toner image is electrostatically transferred to a transfer material to form an image, a developer for developing an electrostatic charge image contg. fine silica powder so treated as to stick 3-8wt.% carbon with silicone oil is used. A high density satisfactory image excellent in durability is stably obtd. without leaving a drop-out during transfer even when a transparent film is used.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、電子写真法、静電記録
法、静電印刷法の如き画像形成方法における静電荷像を
可視化するための静電荷像現像用現像剤及び画像形成方
法に関する。さらに詳しくは、直接法または間接電子写
真現像法において均一に強く帯電し、環境依存性の少な
い高品質な画像を与える静電荷像現像用現像剤及び該現
像剤を用いる画像形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing developer and an image forming method for visualizing an electrostatic charge image in an image forming method such as an electrophotographic method, an electrostatic recording method and an electrostatic printing method. . More specifically, the present invention relates to a developer for developing an electrostatic charge image, which gives a high-quality image which is highly strongly charged uniformly in a direct method or an indirect electrophotographic developing method, and an image forming method using the developer.

【０００２】[0002]

【従来の技術】従来、電子写真法としては米国特許第
２，２９７，６９１号明細書、特公昭４２−２３９１０
号公報（米国特許第３，６６６，３６３号明細書）、特
公昭４３−２４７４８号公報（米国特許第４，０７１，
３６１号明細書）等、多数の方法が知られている。一般
には光導電生物質を利用し、種々の手段により感光体上
に電気的潜像を形成し、次いで該潜像を現像粉（以下ト
ナーと称す）を用いて現像し、必要に応じて紙の如き転
写材にトナー画像を転写した後、加熱、圧力、加熱加圧
あるいは溶剤蒸気により定着して複写物を得るものであ
る。2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
No. 3 (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,071).
No. 361), and many other methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with a developing powder (hereinafter referred to as toner), and if necessary, paper. After the toner image is transferred onto the transfer material as described above, it is fixed by heating, pressure, heating and pressurizing or solvent vapor to obtain a copy.

【０００３】トナー画像を転写する工程を有する場合に
は、通常、感光体上の残余のトナーを除去するための工
程が設けられている。When there is a step of transferring a toner image, a step for removing the residual toner on the photosensitive member is usually provided.

【０００４】電気的潜像をトナーを用いて可視化する現
像方法は、例えば米国特許第２，８７４，０６３号明細
書に記載されている磁気ブラシ法、米国特許第２，６１
８，５５２号明細書に記載されているカスケード現像
法、及び米国特許第２，２２１，７７６号明細書に記載
されている粉末雲法がある。磁性トナーを使用する方法
として米国特許第３，９０９，２５８号明細書に記載さ
れている導電性トナーを使用するマグネドライ法、トナ
ー粒子の誘電分極を使用する方法、また、特開昭５４−
４２１２１号公報、特開昭５５−１８６５６号公報の如
き潜像に対してトナー粒子を飛翔させて現像する方法が
ある。A developing method for visualizing an electric latent image by using a toner is, for example, a magnetic brush method described in US Pat. No. 2,874,063 and US Pat. No. 2,61.
There is a cascade development method described in US Pat. No. 8,552, and a powder cloud method described in US Pat. No. 2,221,776. As a method using a magnetic toner, a magnetic dry method using a conductive toner described in US Pat. No. 3,909,258, a method using dielectric polarization of toner particles, and JP-A-54-
No. 42121 and Japanese Patent Application Laid-Open No. 55-18656, there is a method of developing toner particles by causing toner particles to fly.

【０００５】従来、潜像担持体（感光体）表面に形成し
た転写の可能なトナー像を、紙またはプラスチックのシ
ート状の転写材に静電的に転写する工程を含む画像形成
装置において、回転円筒状または無端ベルト状の如く無
端状に走行する像担持体を使用し、バイアスを印加した
転写装置をこれに圧接してこれら両者間に転写材を通過
させて、潜像担持体側のトナー像を転写材に転写するよ
うに構成したもの（例えば、特開昭５９−４６６６４号
公報の如き装置）が提案されている。Conventionally, in an image forming apparatus including a step of electrostatically transferring a transferable toner image formed on the surface of a latent image carrier (photoreceptor) to a sheet-like transfer material such as paper or plastic. A toner image on the latent image carrier side is formed by using an image carrier that runs in an endless shape such as a cylindrical shape or an endless belt, presses a transfer device to which a bias is applied to the transfer device, and allows the transfer material to pass between them. A device (for example, a device as disclosed in Japanese Patent Laid-Open No. 59-46664) configured to transfer an image on a transfer material has been proposed.

【０００６】このような装置は、従来からひろく実用さ
れているコロナ放電を利用した転写手段に比して、転写
ローラの潜像担持体への圧接力を調製することによって
転写材の潜像担持体への吸着領域を拡大することがで
き、転写材を転写部位において積極的に押圧支持するの
で、転写材搬送手段による同期不良や転写材に存在する
ループ、カールなどによる転写ずれを生ずるおそれが少
なく、近来におけるこの種の画像形成装置の小型化に伴
う転写材搬送路の短縮化、潜像担持体の小径化などの要
請にも対応しやすい。反面、当接により転写を行なう装
置に於いては、当接部位より転写電流が供給される為、
ある程度の圧力を転写装置に加圧する必要がある。当接
圧が加えられた場合、潜像担持体上のトナー像にも圧力
が加わり、トナーの凝集が起りやすい。In such an apparatus, the latent image bearing of the transfer material is carried out by adjusting the pressure contact force of the transfer roller to the latent image bearing member, as compared with the conventionally widely used transfer means utilizing corona discharge. Since the adsorption area to the body can be enlarged and the transfer material is positively pressed and supported at the transfer portion, there is a possibility that transfer failure may occur due to poor synchronization due to the transfer material transporting means or loops and curls existing in the transfer material. It is easy to meet demands such as shortening of the transfer material conveying path and downsizing of the latent image carrier due to recent downsizing of this type of image forming apparatus. On the other hand, in a device that performs transfer by contact, since the transfer current is supplied from the contact part,
It is necessary to apply a certain amount of pressure to the transfer device. When the contact pressure is applied, the pressure is also applied to the toner image on the latent image carrier, and the toner is apt to aggregate.

【０００７】さらに潜像担持体表面が樹脂で構成されて
いる場合には、トナー凝集物と潜像担持体との間でも密
着が発生し、転写材への移行が阻害され、極端な場合、
密着が強固な部分が全く転写せず、画像が欠損する現象
が起る。Further, when the surface of the latent image bearing member is made of resin, the toner agglomerates and the latent image bearing member also come into close contact with each other, and the transfer to the transfer material is hindered.
A phenomenon in which an image is lost because a portion having strong adhesion is not transferred at all.

【０００８】この現象は０．１〜２ｍｍのライン部に於
いて特に顕著になる。これは、ライン部ではエッジ現象
により、トナーが多くのり、加圧による凝集が起りやす
く、転写による欠損が起りやすいことによる。この時の
転写画像は輪郭部のみ画像が形成された複写物となり、
「転写中抜け」とよばれる。図１（ａ）は中抜けのない
正常な画像であり、図１（ｂ）は中抜けの発生した画像
である。This phenomenon becomes particularly remarkable in the line portion of 0.1 to 2 mm. This is because the line portion has a large amount of toner due to the edge phenomenon, aggregation due to pressure is likely to occur, and defects due to transfer are likely to occur. The transfer image at this time is a copy with an image formed only on the outline,
It is called "truncated omission". FIG. 1 (a) is a normal image with no voids, and FIG. 1 (b) is an image with voids.

【０００９】「転写中抜け」は、１００ｇ／ｃｍ2 以上
の厚紙、平滑度の高いトランスペアレンシーフィルム等
で特に発生しやすい。厚紙及びフィルムの如き転写材
は、厚い為に、転写電界の効果が少ないこと及び加圧が
強くなり中抜けしやすくなる事が考えられる。The "transfer dropout" is particularly apt to occur on thick paper of 100 g / cm 2 or more, a transparency film having high smoothness, and the like. Since a transfer material such as a thick paper and a film is thick, it is considered that the effect of the transfer electric field is small and that the pressure is strong so that the hollow portion easily occurs.

【００１０】以上より、当接部材による転写装置の場
合、小型化、低電力等多数の利点がある反面、転写材に
対する条件が狭くなる傾向にある。As described above, in the case of the transfer device using the contact member, there are many advantages such as downsizing and low power consumption, but the conditions for the transfer material tend to be narrowed.

【００１１】従来、電子写真装置における帯電手段とし
てコロナ放電器が知られている。しかし、コロナ放電器
は高電圧を印加しなければならない、オゾンの発生量が
多い等の問題点を有している。Conventionally, a corona discharger is known as a charging means in an electrophotographic apparatus. However, the corona discharger has problems that a high voltage must be applied and that the amount of ozone generated is large.

【００１２】そこで、最近ではコロナ放電器を利用しな
いで接触帯電手段を利用することが検討されている。具
体的には帯電部材である導電性ローラに電圧を印加して
ローラを被帯電体である感光体に接触させて感光体表綿
を所定の電位に帯電させるものである。この様な接触帯
電手段を用いればコロナ放電器と比較して低電圧化がは
かれ、オゾン発生量を減少させることも可能である。Therefore, recently, it has been considered to use the contact charging means without using the corona discharger. Specifically, a voltage is applied to a conductive roller, which is a charging member, to bring the roller into contact with a photosensitive member, which is a member to be charged, to charge the surface of the photosensitive member to a predetermined potential. If such a contact charging means is used, the voltage can be lowered as compared with the corona discharger, and the ozone generation amount can be reduced.

【００１３】例えば、特公昭５０−１３６６１号公報に
おいては、芯金にナイロンまたはポリウレタンゴムから
なる誘電体を被覆したローラを使うことによって感光紙
を荷電する時に低電圧印加を可能にしている。For example, in Japanese Patent Publication No. 50-13661, a roller having a core metal coated with a dielectric material of nylon or polyurethane rubber is used to enable application of a low voltage when charging the photosensitive paper.

【００１４】しかしながら、上記接触帯電手段を用いた
場合、被帯電体と十分な接触を保つことができないと、
帯電不良を生じるという問題を有する。当接部において
は、感光体表面に残留現像剤が存在すると、帯電部材は
所定の当接圧をもって接しているため、帯電部材及び感
光体表面に残留現像剤が固着し、画像に影響がでてしま
う問題も有している。However, when the contact charging means is used, it is impossible to maintain sufficient contact with the body to be charged.
There is a problem that charging failure occurs. At the contact portion, when the residual developer is present on the surface of the photoconductor, the charging member contacts with a predetermined contact pressure, so that the residual developer adheres to the charging member and the surface of the photoconductor, and the image is not affected. It also has the problem of being lost.

【００１５】上述のような接触帯電装置では、帯電部材
に直流電圧もしくは直流電圧に交流電圧を重畳したもの
を印加して用いている。この際、帯電部材と感光体ドラ
ムの接触部分周辺では、特に粒子径が小さく、重量の軽
い残留現像剤の異常な帯電や飛翔運動の反復が繰り返さ
れ、このため、帯電部材や感光体ドラム表面への残留現
像剤の静電吸着や埋め込みが行われやすい状況にあり、
従来のコロナ放電器による非接触帯電手段を用いる場合
と非常に異なる。In the contact charging device as described above, a DC voltage or a DC voltage superposed with an AC voltage is applied to the charging member. At this time, in the vicinity of the contact portion between the charging member and the photosensitive drum, the abnormal charging and the flying motion of the residual developer having a particularly small particle diameter and a small weight are repeated. It is easy to electrostatically attract or embed the residual developer in the
This is very different from the case of using a non-contact charging means using a conventional corona discharger.

【００１６】これらの現像法に適用するトナーとして
は、従来、天然あるいは合成樹脂中に染料、顔料を分散
させた微粉末が使用されている。例えば、ポリスチレン
の如き結着樹脂中に着色剤を分散させたものを１〜３０
μｍ程度に微粉砕した粒子がトナー粒子として用いられ
る。磁性トナーとしてはマグネタイトの如き磁性体粒子
を含有せしめたものが用いられている。二成分系現像剤
を用いる方式の場合には、トナーは、通常ガラスビー
ズ、鉄粉、フェライト粒子の如きキャリアー粒子と混合
して用いられる。As the toner applied to these developing methods, fine powder in which a dye or a pigment is dispersed in a natural or synthetic resin has been conventionally used. For example, 1 to 30 is obtained by dispersing a colorant in a binder resin such as polystyrene.
Particles finely pulverized to about μm are used as toner particles. A magnetic toner containing magnetic particles such as magnetite is used. In the case of a system using a two-component developer, the toner is usually used as a mixture with carrier particles such as glass beads, iron powder and ferrite particles.

【００１７】一方、近年、小型で安価なパーソナルユー
スの複写機やレーザープリンターが出現し、これらの小
型機においては、メンテナンスフリーの立場から、感光
体、現像器、クリーニング装置等を一体化したカートリ
ッジ方式が用いられている。現像剤としても現像器の構
造を簡単にできることから一成分系磁性現像剤を使用す
ることが有利である。On the other hand, in recent years, small and inexpensive personal use copying machines and laser printers have appeared, and in these small machines, a cartridge in which a photoconductor, a developing device, a cleaning device, etc. are integrated from the standpoint of maintenance-free. The scheme is used. As the developer, it is advantageous to use a one-component magnetic developer because the structure of the developing device can be simplified.

【００１８】この様な乾式現像剤を使用する方法におい
て、良好な画質の可視画像を形成するためには、現像剤
が高い流動性を有し、かつ均一な帯電性を有することが
必要である。そのために従来よりケイ酸微粉体をトナー
粉末に添加混合することが行われている。ケイ酸微粉体
はそのままでは親水性であるためにこれが添加された現
像剤は空気中の湿気により凝集を生じて流動性が低下し
たり、はなはだしい場合にはケイ酸微粉体の吸湿により
現像剤の帯電性能を低下させてしまう。そこで疎水化処
理したシリカ微粉体を用いることが特開昭４６−５７８
２号公報、特開昭４８−４７３４５号公報、特開昭４８
−４７３４６号公報等で提案されている。具体的にはケ
イ酸微粉体とシランカップリング剤を反応させ、ケイ酸
微粉体表面のシラノール基を有機基で疎水化する方法で
ある。シランカップリング剤としては例えばジメチルジ
クロルシラン、トリメチルアルコオキシシラン等が使用
されている。In the method using such a dry developer, in order to form a visible image of good image quality, it is necessary that the developer has high fluidity and uniform chargeability. . Therefore, it has been customary to add fine silica powder to toner powder for mixing. Since the fine silica powder is hydrophilic as it is, the developer to which it is added causes agglomeration due to moisture in the air to lower the fluidity, or in the worst case, the moisture of the fine silica powder absorbs the developer. This will reduce the charging performance. Therefore, it is preferable to use a silica fine powder that has been subjected to a hydrophobic treatment.
No. 2, JP-A-48-47345, JP-A-48.
It is proposed in Japanese Patent Laid-Open No. 47346/1997. Specifically, it is a method in which a silicic acid fine powder and a silane coupling agent are reacted to make the silanol group on the surface of the silicic acid fine powder hydrophobic with an organic group. As the silane coupling agent, for example, dimethyldichlorosilane, trimethylalcooxysilane, etc. are used.

【００１９】さらに、疎水化を十分に行わせるために、
シランカップリング剤で処理された後に、さらにＡ／２
５±Ａ／３０重量部（Ａ：ケイ酸微粉体の比表面積）の
シリコーンオイルで処理され、疎水化度が９０％以上の
ケイ酸微粉体を使用することが特開昭６３−１３９３６
７号公報、特開昭６３−１３９３６９号公報等で提案さ
れている。Further, in order to sufficiently perform the hydrophobization,
After being treated with a silane coupling agent, further A / 2
It is possible to use fine silicic acid powder treated with 5 ± A / 30 parts by weight (A: specific surface area of fine silicic acid powder) of silicone oil and having a hydrophobicity of 90% or more.
No. 7, JP-A-63-139369, and the like.

【００２０】しかしながら、上記ケイ酸微粉体のような
無機微粉体をトナーに外添した現像剤においては、現像
剤自体の研磨効果が強く、画像形成時に、感光体表面を
強く摺擦するため、感光体表面を削ったり傷つけたり、
または傷に起因する残留現像剤の融着やフィルミングを
生じるという問題を有していた。この問題は、前記当接
部材による転写装置や前記帯電部材の如き感光体表面に
所定の当接圧をもって接触している当接部材を用いてい
る場合に顕著に現れやすい。However, in a developer in which an inorganic fine powder such as the above-mentioned fine silica powder is externally added to the toner, the polishing effect of the developer itself is strong and the surface of the photoreceptor is strongly rubbed during image formation. Scratch or scratch the surface of the photoconductor
Also, there is a problem that fusion of the residual developer and filming occur due to scratches. This problem is apt to appear remarkably when a contact member that is in contact with the surface of the photoconductor with a predetermined contact pressure, such as a transfer device using the contact member or the charging member, is used.

【００２１】近年、複写物の高画質化を目的としてトナ
ーの微小粒径化が行われ、従来よりトナーを均一に帯電
させることが難しくなっている。トナー粒子が小さくな
るに従って単位重量当りのトナーの表面積が増大し、ト
ナー粒子同志が外圧によって密着する可能性が高くなっ
ており、さらに高い流動性を保つために、従来より多量
の無機微粉体をトナーに添加混合することが必要であ
り、上記問題は、より顕著に現れやすい。In recent years, toner particles have been made finer for the purpose of improving the image quality of a copy, and it has become more difficult to uniformly charge the toner than in the past. As the toner particles become smaller, the surface area of the toner per unit weight increases, and there is a high possibility that the toner particles will adhere to each other due to external pressure.In order to maintain higher fluidity, a larger amount of inorganic fine powder than in the past has been used. It is necessary to add and mix with the toner, and the above problems are more likely to appear.

【００２２】これを防止するにはシリカ微粉体の如き、
流動性向上剤を増量すれば効果がある。しかしながら、
特にプロセススピードが速い機械において感光体表面に
傷が生じ易くなること及びトナーの定着性が低下する等
の弊害をひきおこす原因となるため増量には限界があ
る。To prevent this, such as silica fine powder,
It is effective to increase the amount of the fluidity improver. However,
Particularly in a machine having a high process speed, the amount of the amount is limited because it may cause scratches on the surface of the photoconductor and cause deterioration of toner fixing property.

【００２３】近年、廃棄物に対する問題が顕在化してお
り、トナー画像を転写する工程において、感光体上の残
余のトナーを除去及び回収を行っている。回収トナーの
量を減少させる必要性が高まっており、特に微小粒径化
したトナーの回収量を減らすには、よりトナーの均一帯
電性を増すことが求められている。In recent years, the problem of waste has become apparent, and residual toner on the photoconductor is removed and collected in the step of transferring the toner image. There is an increasing need to reduce the amount of collected toner, and in particular, in order to reduce the amount of collected toner having a fine particle size, it is required to increase the uniform charging property of the toner.

【００２４】[0024]

【発明が解決しようとする課題】本発明の目的は、上述
の問題点を解決した静電荷像現像用現像剤及び画像形成
方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a developer for developing an electrostatic charge image and an image forming method which solve the above problems.

【００２５】本発明の目的は高温高湿や低温低湿などの
環境変化に対しても安定であり、常に良好な特性を発揮
することのできる静電荷現像用現像剤を提供することに
ある。An object of the present invention is to provide a developer for electrostatic charge development which is stable against environmental changes such as high temperature and high humidity and low temperature and low humidity and can always exhibit good characteristics.

【００２６】本発明の他の目的は、現像、定着及びクリ
ーニング等のプロセスを含む電子写真法において、長期
にわたり多数の画像を形成した場合にも安定した画像が
得られる、耐久性に優れた現像剤を提供することにあ
る。Another object of the present invention is to provide an electrophotographic method including processes such as development, fixing and cleaning, which provides stable images even when a large number of images are formed over a long period of time and which has excellent durability. To provide the agent.

【００２７】本発明の他の目的は、従来の荷電性トナー
にまつわる種々の問題点を解決し、均一に強く帯電し、
静電荷像を可視化してカブリやエッジ周辺へのトナーの
飛び散りのない高品質な画像を与える現像剤を提供する
ことにある。Another object of the present invention is to solve various problems associated with the conventional chargeable toner, to uniformly and strongly charge the toner,
It is an object of the present invention to provide a developer that visualizes an electrostatic charge image and provides a high-quality image without fog or toner scattering around edges.

【００２８】特に、微小粒径化したトナーを均一に強く
帯電し、高画質で現像性に優れた現像剤を提供すること
にある。In particular, it is to provide a developer having a high image quality and excellent developability by uniformly and strongly charging a toner having a fine particle size.

【００２９】本発明の他の目的は、当接転写方法のよう
な加圧転写による画像形成方法において、転写材の条件
によらず、潜像に忠実である高品位な画像が得られる転
写工程を有する画像形成方法を提供することにある。Another object of the present invention is, in an image forming method by pressure transfer such as a contact transfer method, a transfer step in which a high-quality image faithful to a latent image can be obtained irrespective of conditions of a transfer material. It is to provide an image forming method having.

【００３０】本発明の他の目的は、「転写中抜け」の現
象がないか、または、該現象が抑制されている画像形成
方法を提供することにある。Another object of the present invention is to provide an image forming method in which there is no "transfer dropout" phenomenon or the phenomenon is suppressed.

【００３１】本発明の他の目的は、厚い転写材を用いて
も転写中抜けのない高品質な画像を与えるトナーを使用
する画像形成方法を提供することにある。Another object of the present invention is to provide an image forming method using a toner which gives a high-quality image with no voids in the transfer even if a thick transfer material is used.

【００３２】本発明の他の目的は、帯電部材と被帯電体
表面への現像剤による傷や削れ、さらには現像剤の固着
等の汚染を防止することで、帯電部材と被帯電体との接
触を十分に保つことができ、帯電不良や帯電ムラを起こ
さない帯電工程を有する画像形成方法を提供することに
ある。Another object of the present invention is to prevent the charging member and the surface of the member to be charged from being scratched or scraped by the developer, and further to prevent the developer from being contaminated such as sticking of the developer. An object of the present invention is to provide an image forming method having a charging step that can sufficiently maintain contact and does not cause charging failure or uneven charging.

【００３３】[0033]

【課題を解決するための手段及び作用】具体的には、本
発明は、トナー及びシリコーンオイルまたはシリコーン
ワニスで処理された処理微粉体を含有している静電荷像
現像用現像剤において、シリコーンオイルまたはシリコ
ーンワニスで処理された処理微粉体は、シリコーンオイ
ルまたはシリコーンワニスで処理される前の微粉体の比
表面積の０．４〜０．８倍のＢＥＴ比表面積を有するこ
とを特徴とする静電荷像現像用現像剤に関する。Specifically, the present invention relates to a developer for electrostatic charge image development containing toner and treated fine powder treated with silicone oil or silicone varnish. Alternatively, the treated fine powder treated with silicone varnish has a BET specific surface area which is 0.4 to 0.8 times the specific surface area of the fine powder before treated with silicone oil or silicone varnish. The present invention relates to a developer for image development.

【００３４】さらに、本発明は、静電荷像担持体を帯電
し、帯電された静電荷像担持体に静電荷像を形成し静電
荷像を現像剤で現像してトナー像を形成しトナー像を、
転写材を介して該静電荷像担持体と線圧３ｇ／ｃｍ以上
で当接されている転写手段で転写材へ転写する画像形成
方法において、該現像剤は、トナー及びシリコーンオイ
ルまたはシリコーンワニスで処理された処理微粉体を含
有しており、シリコーンオイルまたはシリコーンワニス
で処理された該処理微粉体は、シリコーンオイルまたは
シリコーンワニスで処理される前の微粉体の比表面積の
０．４〜０．８倍のＢＥＴ比表面積を有することを特徴
とする画像形成方法に関する。Further, in the present invention, a toner image is formed by charging the electrostatic charge image carrier, forming an electrostatic charge image on the charged electrostatic charge image carrier, and developing the electrostatic charge image with a developer to form a toner image. To
In an image forming method of transferring to a transfer material by a transfer means that is in contact with the electrostatic image carrier at a linear pressure of 3 g / cm 2 or more through the transfer material, the developer is toner and silicone oil or silicone varnish. The treated fine powder containing the treated fine powder treated and treated with silicone oil or silicone varnish has a specific surface area of 0.4 to 0. The present invention relates to an image forming method having a BET specific surface area of 8 times.

【００３５】本発明者らは、種々の微粉体について検討
を行った結果、シリコーンオイルまたはシリコーンワニ
ス処理による処理前後の比表面積比の範囲を限定した微
粉体を使用することにより、高性能な現像剤が得られる
ことを見出した。The inventors of the present invention have studied various fine powders, and as a result, by using fine powders having a limited specific surface area ratio before and after treatment with silicone oil or silicone varnish, high-performance development is achieved. It was found that an agent was obtained.

【００３６】本発明では、処理前の微粉体の物性、特に
表面性を、従来知られているものとは異なる状態に制御
することにより、シリコーンオイルまたはシリコーンワ
ニスの処理状態をより均一にすることができ、その微粉
体を使用した現像剤の性能が一段と向上することを見い
出したものである。In the present invention, the physical properties of the fine powder before treatment, especially the surface properties, are controlled to a state different from those known in the prior art to make the treated state of silicone oil or silicone varnish more uniform. It was found that the performance of the developer using the fine powder is further improved.

【００３７】本発明において、線圧は次式で算定する。In the present invention, the linear pressure is calculated by the following equation.

【００３８】（線圧）［ｇ／ｃｍ］＝（転写部材に加え
られる総圧）［ｇ］÷（当接されている長さ）［ｃｍ］(Linear pressure) [g / cm] = (Total pressure applied to transfer member) [g] ÷ (Abutting length) [cm]

【００３９】当接圧が３ｇ未満であると転写部材の搬送
ブレ、転写電流不足による転写不良がおこり好ましくな
い。特に好ましくは線圧が２０ｇ以上である。If the contact pressure is less than 3 g, transfer failure of the transfer member and transfer failure due to insufficient transfer current occur, which is not preferable. Particularly preferably, the linear pressure is 20 g or more.

【００４０】本発明に用いられる転写装置としては、図
２に見られるような転写ローラー、或いは図３に見られ
るような転写ベルトが挙げられる。図２は典型的なこの
種の画像形成装置の要部の概略構成図であって、図示の
装置は、紙面に垂直方向にのび、矢印Ａ方向に回転する
円筒状の静電荷像担持体（以下、「感光体」と記す）
１、これに当接する導電性転写ローラー２が配設してあ
る。The transfer device used in the present invention includes a transfer roller as shown in FIG. 2 or a transfer belt as shown in FIG. FIG. 2 is a schematic configuration diagram of a main part of a typical image forming apparatus of this type. The apparatus shown in the drawing is a cylindrical electrostatic charge image carrier (a carrier extending in the direction perpendicular to the plane of the drawing and rotating in the direction of arrow A). Hereinafter referred to as "photoreceptor")
1. A conductive transfer roller 2 is provided which is in contact with this.

【００４１】感光体１の周辺には、その表面を一様に帯
電させるための一次帯電器、該帯電面に画像変調された
レーザー光、原稿からの反射光などの光像を投写し、当
該部分の電位を減衰させて静電潜像を形成する露光部、
現像器、転写後も感光体表面に残る残留トナーを除去す
るクリーナその他画像形成に必要な部材が配設してある
が、それらは省略してある。A primary charger for uniformly charging the surface of the photoconductor 1 and an optical image such as image-modulated laser light or reflected light from an original are projected on the charged surface, and An exposure unit that attenuates the potential of a part to form an electrostatic latent image,
A developing device, a cleaner for removing residual toner remaining on the surface of the photoconductor after transfer, and other members necessary for image formation are provided, but they are omitted.

【００４２】転写ローラ２は芯金２ａと導電性弾性層２
ｂとを有し、導電性弾性層２ｂはカーボンの如き導電材
を分散させたポリウレタンまたはＥＰＤＭ（エチレン・
プロピレンゴム）等で形成されている体積抵抗約１０6
〜１０10Ω・ｃｍの弾性体でつくられている。芯金２ａ
には定電圧電源３によりバイアスが印加されている。The transfer roller 2 includes a core metal 2a and a conductive elastic layer 2
b, and the conductive elastic layer 2b is made of polyurethane or EPDM (ethylene.
Volume resistance of about 10 6 made of propylene rubber, etc.
It is made of elastic material of -10 10 Ω · cm. Core metal 2a
A bias is applied from the constant voltage power supply 3 to the.

【００４３】芯金２ａには定電圧電源８によりバイアス
が印加されている。バイアス条件としては、電流値０．
１〜５０μＡ、電圧（絶対値）１００〜５０００Ｖ（好
ましくは５００〜４０００Ｖ）が好ましい。A bias is applied to the core metal 2a by a constant voltage power source 8. As the bias condition, a current value of 0.
1 to 50 μA and voltage (absolute value) of 100 to 5000 V (preferably 500 to 4000 V) are preferable.

【００４４】図３は本発明に転写ベルトに適用したもの
である。転写ベルト６は導電ローラー７により支持駆動
される。転写ローラーへの加圧は通常、芯金２ａの端部
軸受を加圧する事により行われる。FIG. 3 shows a transfer belt according to the present invention. The transfer belt 6 is supported and driven by a conductive roller 7. The pressure applied to the transfer roller is usually performed by applying pressure to the end bearing of the cored bar 2a.

【００４５】次に、本発明の画像形成方法に適用可能な
接触帯電工程について具体的に説明する。Next, the contact charging step applicable to the image forming method of the present invention will be specifically described.

【００４６】図４は、本発明の一実施例を示した接触帯
電装置の概略構成図である。１は被帯電体である感光体
ドラムであり、アルミニウム製のドラム基体１ａの外周
面に感光体層である有機光導電体（ＯＰＣ）１ｂを形成
してなるもので矢印方向に所定の速度で回転する。本実
施例において、感光ドラム１は外径３０ｍｍφである。
４２は上記感光体ドラム１に所定圧力をもって接触させ
た帯電部材である帯電ローラであり、金属芯金４２ａに
導電性ゴム層４２ｂを設け、さらにその周面に離型性被
膜である表面層４２ｃを設けてある。本実施例での表面
層は、離型性被膜であり、離型性被膜を設けることは本
発明の画像形成方法とのマッチング上好ましい。但し、
離型性被膜は、抵抗が大きすぎると感光体ドラム１が帯
電されず、抵抗が小さすぎると感光体ドラム１に大きな
電圧がかかり過ぎ、ドラムの損傷、ピンホールの発生が
起きやすい。離型性被膜の体積抵抗率は１０9 〜１０14
Ω・ｃｍが良く、この時の離型性被膜の厚さは３．０μ
ｍ以内が好ましい。皮膜の厚さの下限は被膜ハガレ、メ
クレがなければ良い。例えば、下限は、５μｍくらいで
ある。FIG. 4 is a schematic configuration diagram of a contact charging device showing an embodiment of the present invention. Reference numeral 1 denotes a photoconductor drum which is a member to be charged, and is formed by forming an organic photoconductor (OPC) 1b which is a photoconductor layer on an outer peripheral surface of a drum base body 1a made of aluminum, at a predetermined speed in an arrow direction. Rotate. In this embodiment, the photosensitive drum 1 has an outer diameter of 30 mmφ.
Reference numeral 42 is a charging roller which is a charging member brought into contact with the photosensitive drum 1 with a predetermined pressure. The metal cored bar 42a is provided with a conductive rubber layer 42b, and the peripheral surface thereof is a surface layer 42c which is a release film. Is provided. The surface layer in this embodiment is a releasable coating, and it is preferable to provide the releasable coating in terms of matching with the image forming method of the present invention. However,
If the resistance of the releasable coating is too large, the photosensitive drum 1 is not charged, and if the resistance is too small, a large voltage is applied to the photosensitive drum 1, and the drum is likely to be damaged or pinholes are likely to occur. The volume resistivity of the release film is 10 9 to 10 14
Ω · cm is good, and the thickness of the release film at this time is 3.0μ
It is preferably within m. The lower limit of the thickness of the coating is good as long as there is no peeling or peeling of the coating. For example, the lower limit is about 5 μm.

【００４７】本実施例では帯電ローラ４２の外径は１２
ｍｍφであり、導電性ゴム層４２ｂはＥＰＤＭ、表面層
４１ｃには厚み１０μｍのナイロン系樹脂を用いた。帯
電ローラ４１の硬度は５４．５°（ＡＳＫＥＲ−Ｃ）と
した。Ｅはこの帯電ローラ４１に電圧を印加する電源
で、所定の電圧を帯電ローラ４２の芯金４２ａに供給す
る。図４においてＥは直流電圧を示しているが、直流電
圧に交流電圧を重畳したものが好ましい。In this embodiment, the outer diameter of the charging roller 42 is 12
The conductive rubber layer 42b was made of EPDM, and the surface layer 41c was made of nylon resin having a thickness of 10 μm. The hardness of the charging roller 41 was 54.5 ° (ASKER-C). E is a power source for applying a voltage to the charging roller 41, and supplies a predetermined voltage to the core metal 42a of the charging roller 42. In FIG. 4, E indicates a DC voltage, but it is preferable that the AC voltage is superimposed on the DC voltage.

【００４８】この場合好ましいプロセス条件を下記に示
す。In this case, preferable process conditions are shown below.

【００４９】当接圧 ：５〜５００ｇ／ｃｍ 交流電圧 ：０．５〜５Ｖpp 交流周波数：５０〜３０００Ｈｚ 直流電圧 ：−２００〜−９００ＶContact pressure: 5 to 500 g / cm AC voltage: 0.5 to 5 V pp AC frequency: 50 to 3000 Hz DC voltage: -200 to -900 V

【００５０】図５は本発明の他の実施例を示す接触帯電
部材の概略構成図である。FIG. 5 is a schematic diagram of a contact charging member showing another embodiment of the present invention.

【００５１】図４の装置との共通部材には同一の符号を
付して再度の説明は省略する。The same members as those of the apparatus shown in FIG. 4 are designated by the same reference numerals and their repeated description will be omitted.

【００５２】本実施例の接触帯電部材５３は感光ドラム
１に所定圧力をもって順方向に当接されたブレード状の
ものであり、このブレード５３は電圧に供給される金属
支持部材５３ａに導電性ゴム５３ｂが支持され、感光体
ドラム１との当接部分には、離型性被膜となる表面層５
３ｃが設けられている。表面層５３ｃとしては厚み１０
μｍのナイロンを用いた。この実施例によれば、ブレー
ドと感光体ドラムとの接着といった不具合もなく前記実
施例と同様の作用効果がある。The contact charging member 53 of this embodiment is a blade-shaped member which is brought into contact with the photosensitive drum 1 in the forward direction with a predetermined pressure, and the blade 53 is made of a conductive rubber on a metal supporting member 53a supplied with a voltage. The surface layer 5 serving as a releasable coating is provided on the contacting portion with the photoconductor drum 1 on which 53b is supported.
3c is provided. The thickness of the surface layer 53c is 10
μm nylon was used. According to this embodiment, there is no problem such as adhesion between the blade and the photosensitive drum, and the same operational effect as that of the above embodiment can be obtained.

【００５３】前記した実施例では帯電部材としてローラ
状、ブレード状のものを使用したが、これに限るもので
なく、他の形状でも良い。Although the roller-shaped or blade-shaped charging member is used in the above-mentioned embodiment, the charging member is not limited to this and may have another shape.

【００５４】本実施例では帯電部材が導電性ゴム層と離
型性被膜から構成されているが、導電性ゴム層と離型性
被膜表層間に感光体へのリーク防止のために高抵抗層
（例えば環境変動の小さいヒドリンゴム層）を配置して
も良い。In this embodiment, the charging member is composed of a conductive rubber layer and a release coating, but a high resistance layer is provided between the conductive rubber layer and the surface of the release coating to prevent leakage to the photoreceptor. (For example, a hydrin rubber layer having a small environmental change) may be arranged.

【００５５】離型性被膜としてナイロン系樹脂の代りに
ＰＶＤＦ（ポリフッ化ビニリデン）、ＰＶＤＣ（ポリ塩
化ビニリデン）を用いても良い。感光体としては、アモ
ルファスシリコン、セレン、ＺｎＯ等でも使用可能であ
る。特に、感光体にアモルファスシリコンを用いた場
合、他のものを使用した場合に比べて、導電性ゴム層の
軟化剤が感光体に少しでも付着すると、画像流れはひど
くなるので導電性ゴム層の外側に絶縁性被膜したことに
よる効果は大となる。PVDF (polyvinylidene fluoride) or PVDC (polyvinylidene chloride) may be used as the release coating instead of the nylon resin. Amorphous silicon, selenium, ZnO or the like can also be used as the photoconductor. In particular, when amorphous silicon is used for the photoconductor, compared to the case where other materials are used, even if a small amount of the softening agent for the conductive rubber layer adheres to the photoconductor, the image deletion becomes worse. The effect of the insulating coating on the outside is great.

【００５６】本発明に係るクリーニング工程について説
明する。一般にトナー像転写後の感光体ドラムはブレー
ドやローラの如きクリーニング部材により転写後に残留
しているトナー分やその他の汚染物の拭掃除去を受けて
洗浄面化され、繰り返して像形成に供される。The cleaning process according to the present invention will be described. Generally, the photoconductor drum after the toner image transfer is cleaned and cleaned by a cleaning member such as a blade or a roller to wipe off the residual toner after transfer and other contaminants, and is repeatedly used for image formation. It

【００５７】係るクリーニング工程を、電子写真法に関
わる帯電工程や現像工程、あるいは転写工程の中で同時
に行うことも可能である。It is possible to perform the cleaning step at the same time as the charging step, the developing step, or the transfer step related to electrophotography.

【００５８】本発明は、感光体の表面が有機化合物であ
る画像形成装置に対し特に有効である。有機化合物が表
面層を形成している場合、トナー中に含まれる結着樹脂
と接着しやすく、それを、本発明は良好に回避し得るか
らである。The present invention is particularly effective for an image forming apparatus in which the surface of the photoconductor is an organic compound. This is because when the organic compound forms the surface layer, it easily adheres to the binder resin contained in the toner, and the present invention can satisfactorily avoid it.

【００５９】本発明に用いる感光体の表面物質として
は、シリコーン樹脂、塩化ビニリデン樹脂、エチレンー
塩化ビニル樹脂、スチレンーメチルメタクリレート樹
脂、スチレンーアクリロニトリル樹脂、スチレン樹脂、
ポリエチレンテレフタレート、ポリカーボネート等が挙
げられる。これらに限定されることはなく、他のモノマ
ーあるいは、例示樹脂間での共重合、ブレンド等も使用
することができる。As the surface substance of the photoreceptor used in the present invention, silicone resin, vinylidene chloride resin, ethylene-vinyl chloride resin, styrene-methyl methacrylate resin, styrene-acrylonitrile resin, styrene resin,
Examples thereof include polyethylene terephthalate and polycarbonate. The present invention is not limited to these, and other monomers or copolymers or blends between the exemplified resins can be used.

【００６０】本発明は、感光体の直径が５０ｍｍ以下の
小径ドラムを有する画像形成装置に対し特に有効であ
る。小径の感光ドラムの場合、同一の線圧にしても曲率
が大きいため、当接部において圧力の集中が起りやす
く、感光ドラム表面に傷が発生しやすいが、本発明は、
それを良好に抑制し得る。The present invention is particularly effective for an image forming apparatus having a small-diameter drum whose photosensitive member has a diameter of 50 mm or less. In the case of a small-diameter photosensitive drum, since the curvature is large even if the linear pressure is the same, concentration of pressure is likely to occur at the abutting portion and scratches are likely to occur on the surface of the photosensitive drum.
It can be suppressed well.

【００６１】ベルト感光体でも同一の現象があると考え
られ、転写部での曲率半径２５ｍｍ以下の画像形成装置
に対しても有効である。It is considered that the same phenomenon occurs with the belt photosensitive member, and it is effective for an image forming apparatus having a radius of curvature of 25 mm or less at the transfer portion.

【００６２】次に、本発明の現像剤について説明する。Next, the developer of the present invention will be described.

【００６３】本発明の現像剤に係るシリコーンオイルま
たはシリコーンワニス処理においては、シリコーンオイ
ルまたはシリコーンワニスが微粉体の表面に均一塗布さ
れることにより、表面を完全に覆いかくすことができ、
耐湿性は飛躍的に向上する。In the silicone oil or silicone varnish treatment of the developer of the present invention, the surface of the fine powder can be completely covered by uniformly applying the silicone oil or silicone varnish,
Moisture resistance is dramatically improved.

【００６４】本発明に係る微粉体は、負帯電性の強いシ
リコーンオイルまたはシリコーンワニスでの処理が行わ
れるため、強く負に帯電し、現像剤に添加した場合、現
像剤に強く均一な負荷電性を与えることができる。この
特性は帯電の不安定になりやすい磁性一成分トナーには
有効である。特に、高画質化に目的とする微小粒径化し
たトナーには有効である。Since the fine powder according to the present invention is treated with silicone oil or silicone varnish having a strong negative charge property, it is strongly negatively charged, and when added to the developer, it has a strong and uniform negative charge on the developer. Can give sex. This characteristic is effective for the magnetic one-component toner in which charging becomes unstable easily. In particular, it is effective for a toner having a fine particle diameter for the purpose of achieving high image quality.

【００６５】本発明に用いられる微粉体の材質は無機化
合物が好ましい。例えば、ケイ酸、アルミナ、酸化チタ
ンの如き、第３族または第４族の金属酸化物の微粉体が
好ましい。好ましい微粉体としては、ケイ素ハロゲン化
合物の蒸気相酸化により生成されたいわゆる乾式法また
はヒュームドシリカと称される乾式シリカ、及び水ガラ
ス等から製造されているいわゆる湿式シリカの両方が使
用可能である。表面及びケイ酸微粉体の内部にあるシラ
ノール基が少なく、またＮａ2 Ｏ，ＳＯ3 2- 等の製造残
渣の少ない乾式シリカの方が好ましい。乾式シリカにお
いては製造工程において例えば、塩化アルミニウムまた
は塩化チタンなど他の金属ハロゲン化合物をケイ素ハロ
ゲン化合物と共に用いることによってシリカと他の金属
酸化物の複合微粉体を得る事も可能であり、それらも乾
式シリカとして使用可能である。その粒径は平均の一次
粒径として、０．００１〜２μｍの範囲である事が好ま
しく、特に好ましくは０．００２〜０．２μｍの範囲の
シリカ微粉体の如き微粉体を使用するのが良い。The material of the fine powder used in the present invention is preferably an inorganic compound. For example, fine powders of Group 3 or Group 4 metal oxides such as silicic acid, alumina, and titanium oxide are preferable. As preferable fine powders, both so-called dry method produced by vapor phase oxidation of silicon halogen compound or dry silica called fumed silica and so-called wet silica produced from water glass can be used. . Dry silica having less silanol groups on the surface and inside the silicic acid fine powder and less production residues such as Na 2 O and SO 3 2- is preferable. In the case of dry silica, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the manufacturing process. It can be used as silica. Its particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably fine powder such as silica fine powder in the range of 0.002 to 0.2 μm is used. .

【００６６】また、シリコーンオイルまたはシリコーン
ワニスの処理を、本発明の主旨に沿うように均一に行な
うためには、上記微粉体は疎水化度７０％以上、より好
ましくは８０％以上に調整されていることが好ましい。In order to uniformly treat the silicone oil or the silicone varnish according to the gist of the present invention, the fine powder is adjusted to have a hydrophobicity of 70% or more, more preferably 80% or more. Is preferred.

【００６７】本発明における微粉体の疎水化度は、以下
の方法で測定される。密栓式の容器に純水１００ｍｌ及
び試料１ｇを入れ、振とう機にて１０分間振とうする。
振とう後静置し、粉末層と水槽が分離した後水層を採取
し、５００ｎｍの波長で微粉体を入れていないブランク
の純水を基準として透過率を測定し、その透過率の値を
もって微粉体の疎水化度とする。The degree of hydrophobicity of the fine powder in the present invention is measured by the following method. 100 ml of pure water and 1 g of a sample are placed in a sealed stopper type container and shaken for 10 minutes on a shaker.
After shaking and standing, the water layer was separated after the powder layer and the water tank were separated, and the transmittance was measured at a wavelength of 500 nm with reference to pure pure water containing no fine powder. The degree of hydrophobicity of the fine powder.

【００６８】本発明に使用されるシリコーンオイルまた
はシリコーンワニスの固形分は、一般に次の式で示され
るものであり、The solid content of the silicone oil or silicone varnish used in the present invention is generally represented by the following formula:

【００６９】[0069]

【外１】 〔式中、ＲはＣ1 〜Ｃ3 のアルキル基を示し、Ｒ′は、
アルキル、ハロゲン変性アルキル、未置換フェニル、置
換基を有するフェニルの如きシリコーンオイル変性期を
示し、Ｒ″はＣ1 〜Ｃ3 のアルキル基またはアルコオキ
シル基を示す。〕[Outer 1] [In the formula, R represents a C 1 to C 3 alkyl group, and R ′ is
Shows a silicone oil modification period such as alkyl, halogen modified alkyl, unsubstituted phenyl, and phenyl having a substituent, and R ″ represents a C 1 to C 3 alkyl group or an alkoxyl group.]

【００７０】例えば、ジメチルシリコーンオイル、アル
キル変性シリコーンオイル、ａ−メチルスチレン変性シ
リコーンオイル、クロルフェニルシリコーンオイル、フ
ッ素変性シリコーンオイル等が挙げられる。Examples thereof include dimethyl silicone oil, alkyl-modified silicone oil, a-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.

【００７１】上記シリコーンオイルは好ましくは２５℃
における粘度が５０〜１０００センチストークスのもの
が用いられる。粘度が低く分子量が低すぎるとシリコー
ンオイルは加熱処理等により、揮発分が発生することが
あり、また、粘度が高く分子量が高すぎると処理操作が
しにくくなる。The silicone oil is preferably 25 ° C.
The viscosity at 50 to 1000 centistokes is used. If the viscosity is low and the molecular weight is too low, the silicone oil may generate volatile components due to heat treatment and the like, and if the viscosity is high and the molecular weight is too high, the processing operation becomes difficult.

【００７２】シリコーンオイルまたはシリコーンワニス
処理の方法は公知の技術が用いられる。As a method for treating the silicone oil or the silicone varnish, known techniques are used.

【００７３】例えば微粉体とシリコーンオイルとをヘン
シェルミキサー等の混合機を用いて直接混合しても良い
し、ベースの微粉体へシリコーンオイルを噴霧する方法
によっても良い。より好ましくは、適当な溶剤にシリコ
ーンオイルを溶解あるいは分散せしめた後、ベースの微
粉体とを混合した後、溶剤を除去して作成する方法が良
い。For example, the fine powder and the silicone oil may be directly mixed by using a mixer such as a Henschel mixer, or the silicone oil may be sprayed on the base fine powder. More preferably, it is prepared by dissolving or dispersing silicone oil in a suitable solvent, mixing with the fine powder of the base, and then removing the solvent.

【００７４】本発明におけるシリコーンオイルまたはシ
リコーンワニスの処理は、処理後の比表面積が、該処理
前の比表面積の０．４倍〜０．８倍になるように処理す
ることが好ましく、該処理による炭素の付着量が微粉体
の３〜８重量％であることがさらに好ましい。ここで、
炭素の付着量とは元素分析装置（ＣＨＮ計）により求め
た値であり、微粉体の比表面積とはＢＥＴ法におけるＮ
2 吸着から求めた値である。シリコーンオイルまたはシ
リコーンワニス処理により、微粉体の疎水化度は８０％
以上、より好ましくは９０％以上が良い。The treatment of the silicone oil or silicone varnish in the present invention is preferably such that the specific surface area after the treatment is 0.4 to 0.8 times the specific surface area before the treatment. It is more preferable that the amount of carbon adhering to the powder is 3 to 8% by weight of the fine powder. here,
The carbon deposition amount is a value obtained by an elemental analyzer (CHN meter), and the specific surface area of the fine powder is N in the BET method.
2 The value obtained from adsorption. Hydrophobicity of fine powder is 80% by treatment with silicone oil or silicone varnish
The above is more preferable, and 90% or more is more preferable.

【００７５】本発明の最大の目的である転写性を考えた
場合、感光体表面に現像されたトナー粒子の潜像担持体
表面との離型性を向上させ、さらにトナー粒子同志の外
圧による密着を防止するには表面エネルギーの小さいシ
リコーンオイルまたはシリコーンワニスで均一に処理さ
れた微粉体が非常に有効である。Considering the transferability, which is the most important object of the present invention, the releasability of the toner particles developed on the surface of the photosensitive member from the surface of the latent image bearing member is improved, and the toner particles adhere to each other by external pressure. To prevent this, fine powder uniformly treated with silicone oil or silicone varnish having a small surface energy is very effective.

【００７６】上記の処理具合を限定した理由は、シリコ
ーンオイルまたはシリコーンワニス処理による微粉体の
比表面積の減少が少ない場合は、シリコーンオイルまた
はシリコーンワニスによる処理が少ない場合、もしくは
不均一な場合である。このような場合、トナー粒子と感
光体表面及び、トナー粒子同志の離型効果は低下し、こ
れに伴い転写性も低下する。この他、耐湿性も不十分と
なり高湿下ではケイ酸微粉体が吸湿してしまい高品位の
画像が得られなくなったり、帯電が不均一となり良好な
結果が得られにくくなる。特に微小粒径のトナーを有す
る現像剤に適用した場合、トナー画像を転写する工程に
おいて、感光体上の残余のトナーの量を減少させること
ができないなどの問題点が生じる。一方、シリコーンオ
イルまたはシリコーンワニス処理による微粉体の比表面
積の減少が多すぎる場合は、ケイ酸微粉体の凝集体及び
合一が生じ、現像剤に適用した場合、流動性が十分に向
上せず、現像性、転写性、耐久性等に悪影響を及ぼし、
満足な結果が得られにくくなる。The reason why the above treatment conditions are limited is that the reduction of the specific surface area of the fine powder due to the treatment with silicone oil or silicone varnish is small, the treatment with silicone oil or silicone varnish is little, or the treatment is non-uniform. . In such a case, the releasing effect of the toner particles, the surface of the photoconductor, and the toner particles are reduced, and the transferability is also reduced accordingly. In addition, the moisture resistance becomes insufficient, and the fine silica powder absorbs moisture under high humidity, so that a high-quality image cannot be obtained, and charging becomes uneven, and it becomes difficult to obtain a good result. Particularly when applied to a developer having a toner having a fine particle diameter, there arises a problem that the amount of residual toner on the photoconductor cannot be reduced in the step of transferring the toner image. On the other hand, when the specific surface area of the fine powder is excessively reduced by the treatment with silicone oil or silicone varnish, aggregates and coalescence of the fine powder of silicic acid occur, and when applied to the developer, the fluidity is not sufficiently improved. Adversely affects the developability, transferability, durability, etc.
It becomes difficult to obtain a satisfactory result.

【００７７】本発明の現像剤を用いた場合、転写性が非
常に優れ特に従来克服することが困難であったトランス
ペアレンシーフィルムの転写中抜けをほとんどなくすこ
とが可能となる。さらに、転写の不利な微小粒径のトナ
ーを用いた場合も該微粉体の量をそれほど増加させなく
ても十分な効果があり、過剰に添加しても微粉体表面が
ほぼ完全に処理されており非常に優れた滑性を有するた
め感光体ドラム表面への傷は少なくなる。When the developer of the present invention is used, the transferability is excellent, and in particular, it is possible to almost eliminate voids in the transfer film, which were difficult to overcome in the past. Further, even when a toner having a fine particle size which is disadvantageous in transfer is used, there is a sufficient effect even if the amount of the fine powder is not increased so much, and even if it is added excessively, the surface of the fine powder is almost completely treated. Since it has extremely excellent lubricity, scratches on the surface of the photosensitive drum are reduced.

【００７８】現像性、耐久性、環境安定性等にも優れて
おり非常に良好な画像を安定に提供することが可能であ
る。It is also excellent in developability, durability, environmental stability and the like, and it is possible to stably provide a very good image.

【００７９】本発明の接触帯電工程を有する画像形成方
法において、感光体表面へのトナー融着の防止に効果を
示すのは、以下の理由が考えられる。The reason why the image forming method having the contact charging step of the present invention is effective in preventing the toner fusion on the surface of the photosensitive member is considered as follows.

【００８０】感光体表面へのトナー融着の原因となるの
は、接触帯電装置を有する画像形成装置において、クリ
ーニングブレードからすり抜けた現像剤が付着した接触
帯電部材によって感光体表面がこすられた際の傷に、感
光体表面に残留した粒子径が小さく重量の軽い現像剤
が、接触帯電部材によって感光体表面に押しつけられ、
固着、埋め込みが生じるためである。The cause of toner fusion on the surface of the photoconductor is that when the surface of the photoconductor is rubbed by the contact charging member to which the developer slipped from the cleaning blade adheres in the image forming apparatus having the contact charging device. On the scratch of, the developer with a small particle size remaining on the surface of the photoconductor and a light weight is pressed against the surface of the photoconductor by the contact charging member.
This is because sticking and embedding occur.

【００８１】本発明の現像剤は、特定の条件に、潤滑性
を有するシリコーンオイルまたはシリコーンワニスで均
一に十分に処理された微粉体を有しており、磁性現像剤
の表面に存在する微粉体の潤滑性が働くため、接触帯電
部材と感光体との間で潤滑剤として働くので感光体表面
を傷つけることがなく融着を防止する。The developer of the present invention has a fine powder uniformly and sufficiently treated with a silicone oil or a silicone varnish having lubricity under specific conditions, and the fine powder present on the surface of the magnetic developer is present. Since the lubricating property of 1 works as a lubricant between the contact charging member and the photoconductor, the surface of the photoconductor is not damaged and fusion is prevented.

【００８２】現像剤が強く均一に帯電されるため、前述
の融着の原因となる。感光体表面に残留する現像剤の減
少がはかれる。Since the developer is strongly and uniformly charged, it causes the above-mentioned fusion. The amount of developer remaining on the surface of the photoconductor is reduced.

【００８３】一般に、シリコーンオイルまたはシリコー
ンワニスの処理に際し、仕込まれるシリコーンオイルま
たはシリコーンワニスの固形分の量は、微粉体１００重
量部に対し、好ましくは３〜５０重量部より好ましくは
５〜３０重量部であるのが良い。Generally, when the silicone oil or the silicone varnish is treated, the solid content of the silicone oil or the silicone varnish is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the fine powder. Good part.

【００８４】本発明に用いられる微粉体は、まずシラン
カップリング剤で処理し、疎水性を高めておいてからし
かる後にシリコーンオイルまたはシリコーンワニスで処
理することがより好ましい。It is more preferable that the fine powder used in the present invention is first treated with a silane coupling agent to enhance its hydrophobicity and then treated with silicone oil or silicone varnish.

【００８５】一般にシリコーンオイルまたはシリコーン
ワニス処理のみでは、微粉体表面を覆うためのシリコー
ンオイル量が多くなると、処理中に微粉体の凝集体がで
きやすく、現像剤に適用した場合、現像剤の流動性が悪
くなる等の問題点を生じるため、シリコーンオイルまた
はシリコーンワニスの処理工程を十分注意する必要があ
る。そこで良好な耐湿性を保持しつつ、微粉体の凝集を
除くために、微粉体をシランカップリング剤で処理した
後、シリコーンオイルまたはシリコーンワニスで処理す
る方がシリコーンオイルまたはシリコーンワニスの処理
効果を十分発揮できる。Generally, only with the treatment of silicone oil or silicone varnish, when the amount of silicone oil for covering the surface of the fine powder is large, fine powder aggregates are likely to be formed during the treatment, and when applied to the developer, the flow of the developer flows. Therefore, it is necessary to pay close attention to the process of treating the silicone oil or the silicone varnish, since problems such as deterioration of the properties will occur. Therefore, in order to remove the agglomeration of the fine powder while maintaining good moisture resistance, it is better to treat the fine powder with a silane coupling agent and then to treat with silicone oil or silicone varnish, which is more effective for treating silicone oil or silicone varnish. It can be fully demonstrated.

【００８６】本発明に用いられるシランカップリング剤
は一般式 Ｒm ＳｉＹn 〔式中、Ｒはアルコオキシ基または塩素原子を示し、ｍ
は１〜３の整数を示し、Ｙはアルキル基、ビニル基、グ
リシド基、メタクリル基を含む炭化水素を示し、ｎは３
〜１の整数を示す〕で表わされる。例えば代表的にはジ
メチルジクロルシラン、トリメチルクロルシラン、アリ
ルジメチルクロルシラン、ヘキサメチルジシラザン、ア
リルフェニルジクロルシラン、ベンジルジメチルクロル
シラン、ビニルトリエトキシシラン、γ−メタクリルオ
キシプロピルトリエトキシシラン、ビニルトリアセトキ
シシラン、ジビニルクロルシラン、ジメリルビニルクロ
ルシラン等を挙げることができる。The silane coupling agent used in the present invention has a general formula R m SiY n [wherein R represents an alkoxy group or a chlorine atom, m
Represents an integer of 1 to 3, Y represents a hydrocarbon containing an alkyl group, a vinyl group, a glycid group or a methacryl group, and n is 3
Represents an integer of 1]. For example, typically, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyl. Examples thereof include triacetoxysilane, divinylchlorosilane, and dimerylvinylchlorosilane.

【００８７】さらに好ましくは、予め、ジメチルジクロ
ルシラン、ジメチルジメトキシシラン、モノメチルトリ
クロルシラン、モノメチルトリメトキシシラン等のモノ
又はジメチル基を有するカップリング剤で処理した後
に、Ｒ−Ｓｉ−Ｙ3 又はＲ2 −Ｓｉ−Ｙ2 さらにヘキサ
メチルジシラザン、トリメチルクロルシラン、トリメチ
ルメトキシシラン等のトリメチル基を有するカップリン
グ剤で処理すると、シリコーンオイル又はシリコーンワ
ニス処理前の微粉体自体の疎水化度を高く維持でき、か
つ微粉体表面のシリコーンオイルまたはシリコーンワニ
スとの親和性も向上するため、より均一な処理が可能と
なる。More preferably, it is previously treated with a coupling agent having a mono- or dimethyl group such as dimethyldichlorosilane, dimethyldimethoxysilane, monomethyltrichlorosilane, monomethyltrimethoxysilane, and then R-Si-Y 3 or R 2 -Si-Y 2 When treated with a coupling agent having a trimethyl group such as hexamethyldisilazane, trimethylchlorosilane and trimethylmethoxysilane, the degree of hydrophobicity of the fine powder itself before the silicone oil or silicone varnish treatment is kept high. In addition, the affinity with the silicone oil or the silicone varnish on the surface of the fine powder is improved, so that a more uniform treatment is possible.

【００８８】シランカップリング剤を用いる場合、一般
に微粉体１００重量部に対し２〜３０重量部、より好ま
しくは５〜２５重量部を仕込むのが良い。When a silane coupling agent is used, it is generally preferable to add 2 to 30 parts by weight, more preferably 5 to 25 parts by weight, to 100 parts by weight of fine powder.

【００８９】上記微粉体のシランカップリング剤処理
は、微粉体を攪拌等によりクラウド状としたものに気化
したシランカップリング剤を反応させる乾式処理また
は、微粉体を溶媒中に分散させシランカップリング剤を
滴下反応させる湿式法等一般に知らされた方法で処理す
ることができる。The fine powder is treated with a silane coupling agent by a dry treatment in which the vaporized silane coupling agent is reacted with a fine powder made into a cloud by stirring or the like, or a silane coupling is performed by dispersing the fine powder in a solvent. The treatment can be performed by a generally known method such as a wet method in which the agent is dropped and reacted.

【００９０】これらの処理微粉体の現像剤に対する適用
量は磁性トナー１００重量部に対して０．０１〜２０重
量部、より好ましくは０．１〜３重量部が良い。The amount of the treated fine powder applied to the developer is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the magnetic toner.

【００９１】本発明のトナーに用いられる結着樹脂とし
てはポリスチレン、ポリビニルトルエンなどのスチレン
及びその置換体の単重合体；スチレン−ビニルトルエン
共重合体、スチレン−ビニルナフタリン共重合体、スチ
レン−アクリル酸メチル共重合体、スチレン−アクリル
酸エチル共重合体、スチレン−アクリル酸ブチル共重合
体、スチレン−アクリル酸オクチル共重合体、スチレン
−アクリル酸ジメチルアミノエチル共重合体、スチレン
−メタアクリル酸メチル共重合体、スチレン−メタアク
リル酸エチル共重合体、スチレン−メタアクリル酸ブチ
ル共重合体、スチレン−メタアクリル酸ジメチルアミノ
エチル共重合体、スチレン−ビニルメチルエーテル共重
合体、スチレン−ビニルエチルエーテル共重合体、スチ
レン−ビニルメチルケトン共重合体、スチレン−ブタジ
エン共重合体、スチレン−イソブレン共重合体、スチレ
ン−マレイン酸共重合体、スチレン−マレイン酸エステ
ル共重合体の如きスチレン系共重合体；ポリメチルメタ
クリレート、ポリブチルメタクリレート、ポリ酢酸ビニ
ル、ポリエチレン、ポリプロピレン、ポリビニルブチラ
ール、ポリアクリル酸樹脂、ロジン、変性ロジン、テン
ペン樹脂、フェノール樹脂、脂肪族または脂環族炭化水
素樹脂、芳香族系石油樹脂、パラフィンワックス、カル
ナバワックスなどが挙げられる。これらは、単独あるい
は混合して使用できる。The binder resin used in the toner of the present invention is a homopolymer of styrene such as polystyrene and polyvinyltoluene, or a substitution product thereof; styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acryl. Methyl acid copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate Copolymer, Styrene-Ethyl Methacrylate Copolymer, Styrene-Butyl Methacrylate Copolymer, Styrene-Dimethylaminoethyl Methacrylate Copolymer, Styrene-Vinyl Methyl Ether Copolymer, Styrene-Vinyl Ethyl Ether Copolymer, styrene-vinyl methyl Styrene-based copolymers such as ketone copolymers, styrene-butadiene copolymers, styrene-isobrene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, tempene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax, etc. Is mentioned. These can be used alone or in combination.

【００９２】本発明のトナーに添加しうる着色材料とし
ては、従来公知のカーボンブラック、銅フタロシアニン
の如き顔料または染料が使用できる。As the coloring material that can be added to the toner of the present invention, conventionally known pigments or dyes such as carbon black and copper phthalocyanine can be used.

【００９３】磁性トナーの場合には、鉄、コバルト、ニ
ッケルなどの強磁性金属の粉末、もしくはマグネタイ
ト、γ−Ｆｅ2 Ｏ3 、フェライトなどの合金や化合物、
その他の強磁性合金などの磁性体の磁性粉が結着樹脂と
ともに使用される。In the case of magnetic toner, powders of ferromagnetic metals such as iron, cobalt and nickel, or alloys and compounds such as magnetite, γ-Fe 2 O 3 and ferrite,
Magnetic powders of magnetic materials such as other ferromagnetic alloys are used together with the binder resin.

【００９４】トナーには必要に応じて添加剤を混合して
も良い。そのような添加剤としては例えばテフロン粉
末、ステアリン酸亜鉛粉末の如き滑剤、あるいは定着助
剤（例えば低分子量ポリエチレンなど）、あるいは導電
性付与剤として酸化スズ粉末の如き金属酸化物粉末等が
ある。If necessary, additives may be mixed with the toner. Examples of such additives include lubricants such as Teflon powder and zinc stearate powder, fixing aids (such as low molecular weight polyethylene), and metal oxide powders such as tin oxide powder as a conductivity-imparting agent.

【００９５】トナーは、一般に重量平均粒径３〜１５μ
ｍを有するトナー粉を使用する。The toner generally has a weight average particle diameter of 3 to 15 μm.
Toner powder with m is used.

【００９６】さらに図７を参照しながら、本発明の画像
形成方法を説明する。The image forming method of the present invention will be described with reference to FIG.

【００９７】一次帯電器７０２で感光体表面を負極性に
帯電し、レーザ光による露光７０５によりイメージスキ
ヤニングによりデジタル潜像を形成し、磁性ブレード７
１１および磁石７１４を内包している現像スリーブ７０
４を具備する現像器７０９の一成分系磁性現像剤７１０
で該潜像を反転現像する。現像部において感光ドラム１
の導電性基体は接地され、現像スリーブ７０４にはバイ
アス印加手段７１２により交互バイアス、パルスバイア
ス及び／又は直流バイアスが印加されている。転写紙Ｐ
が搬送されて、転写部にくるとローラ転写手段２により
転写紙Ｐの背面（感光ドラム側と反対面）から電圧印加
手段８で帯電をすることにより、感光ドラム表面上の現
像画像（トナー像）が接触転写手段２によって転写紙Ｐ
上へ転写される。感光ドラム７０１から分離された転写
紙Ｐは、加熱加圧ローラ定着器７０７により転写紙Ｐ上
のトナー画像を定着するために定着処理される。The surface of the photoconductor is negatively charged by the primary charger 702, and a digital latent image is formed by image scanning by exposure 705 with a laser beam.
11 and magnet 714 are included in the developing sleeve 70.
One component magnetic developer 710 of developing unit 709 including 4
The latent image is reversely developed. Photosensitive drum 1 in the developing section
The conductive substrate is grounded, and the developing sleeve 704 is applied with an alternate bias, a pulse bias and / or a DC bias by the bias applying means 712. Transfer paper P
Is conveyed and reaches the transfer portion, the roller transfer means 2 charges the transfer paper P from the back surface (the surface opposite to the photosensitive drum side) by the voltage applying means 8 to thereby develop a developed image (toner image) on the photosensitive drum surface. ) Is the transfer paper P by the contact transfer means 2.
Transferred to the top. The transfer paper P separated from the photosensitive drum 701 is subjected to a fixing process by a heating and pressure roller fixing device 707 to fix the toner image on the transfer paper P.

【００９８】転写工程後の感光ドラムに残留する一成分
系現像剤は、クリーニングブレードを有するクリーニン
グ器７０８で除去される。クリーニング後の感光ドラム
７０１は、イレース露光７０６により徐電され、再度、
一次帯電器７０２による帯電工程から始まる工程が繰り
返される。The one-component developer remaining on the photosensitive drum after the transfer process is removed by a cleaning device 708 having a cleaning blade. The photosensitive drum 701 after cleaning is gradually discharged by the erase exposure 706, and again,
The process starting from the charging process by the primary charger 702 is repeated.

【００９９】静電荷像保持体（感光ドラム）は感光層及
び導電性基体を有し、矢印方向に動く。トナー担持体で
ある非磁性円筒の現像スリーブ７０４は、現像部におい
て静電像保持体表面と同方向に進むように回転する。非
磁性円筒スリーブ７０４の内部には、磁界発生手段であ
る多極永久磁石（マグネットロール）が回転しないよう
に配されている。現像器７０９内の一成分系絶縁性磁性
現像剤７１０は非磁性円筒面上に塗布され、かつ現像ス
リーブ７０４の表面と磁性トナー粒子との摩擦によっ
て、磁性トナー粒子は、例えばマイナスのトリボ電荷が
与えられる。さらに鉄製の磁性ドクターブレード７１１
を円筒表面に近接して（間隔５０μｍ〜５００μｍ）、
多極永久磁石の一つの磁極位置に対向して配置すること
により、現像剤層の厚さを薄く（３０μｍ〜３００μ
ｍ）且つ均一に規制して、現像部における静電荷像保持
体１とトナー担持体７０４の間隙よりも薄い現像剤層を
非接触となるように形成する。このトナー担持体７０４
の回転速度を調整することにより、スリーブ表面速度が
静電像保持面の速度と実質的に当速、もしくはそれに近
い速度となるようにする。磁性ドクターブレード７１１
として鉄のかわりに永久磁石を用いて対向磁極を形成し
てもよい。現像部においてトナー担持体７０４に交流バ
イアスまたはパルスバイアスをバイアス手段７１２によ
り印加しても良い。この交流バイアスはｆが２００〜
４，０００Ｈｚ、Ｖｐｐが５００〜３，０００Ｖであれ
ば良い。The electrostatic image carrier (photosensitive drum) has a photosensitive layer and a conductive substrate, and moves in the direction of the arrow. The non-magnetic cylindrical developing sleeve 704, which is a toner carrier, rotates so as to move in the same direction as the surface of the electrostatic image carrier in the developing section. Inside the non-magnetic cylindrical sleeve 704, a multi-pole permanent magnet (magnet roll) that is a magnetic field generating means is arranged so as not to rotate. The one-component insulating magnetic developer 710 in the developing unit 709 is applied on the non-magnetic cylindrical surface, and due to the friction between the surface of the developing sleeve 704 and the magnetic toner particles, the magnetic toner particles have a negative triboelectric charge, for example. Given. Furthermore, iron magnetic doctor blade 711
Close to the cylindrical surface (spacing 50 μm to 500 μm),
The developer layer is made thin (30 μm to 300 μm) by arranging it so as to face one magnetic pole position of the multi-pole permanent magnet.
m) and regulate it uniformly so that a developer layer thinner than the gap between the electrostatic charge image carrier 1 and the toner carrier 704 in the developing section is formed so as not to contact. This toner carrier 704
The surface speed of the sleeve is adjusted to be substantially the same as or close to the speed of the electrostatic image holding surface by adjusting the rotational speed of. Magnetic doctor blade 711
As an alternative, permanent magnets may be used instead of iron to form the opposing magnetic poles. An AC bias or a pulse bias may be applied to the toner carrier 704 by the bias means 712 in the developing section. This AC bias f is 200-
It may be 4,000 Hz and Vpp of 500 to 3,000 V.

【０１００】現像部分における磁性トナー粒子の移転に
際し、静電像保持面の静電的力及び交流バイアスまたは
パルスバイアスの作用によってトナー粒子は静電像側に
移転する。When the magnetic toner particles are transferred in the developing portion, the toner particles are transferred to the electrostatic image side by the action of the electrostatic force of the electrostatic image holding surface and the AC bias or the pulse bias.

【０１０１】磁性ドクターブレード７１１のかわりに、
シリコーンゴムの如き弾性材料で形成された弾性ブレー
ドを用いて押圧によって現像剤層の層厚を規制し、現像
剤担持体上に現像剤を塗布しても良い。Instead of the magnetic doctor blade 711,
The layer thickness of the developer layer may be regulated by pressing with an elastic blade made of an elastic material such as silicone rubber, and the developer may be applied onto the developer carrier.

【０１０２】図８には、バイアス印加手段７４３から電
圧を印加されている接触帯電手段７４２及びコロナ転写
手段７０３を有する画像形成装置が示されている。FIG. 8 shows an image forming apparatus having a contact charging means 742 and a corona transfer means 703 to which a voltage is applied from the bias applying means 743.

【０１０３】図９には、接触帯電手段７４２及び接触転
写手段２を有する画像形成装置が示されている。FIG. 9 shows an image forming apparatus having a contact charging means 742 and a contact transfer means 2.

【０１０４】[0104]

【実施例】以下実施例に基づいて具体的に本発明を説明
する。しかしながら、これによって本発明の実施の形態
がなんら限定されるものではない。EXAMPLES The present invention will be specifically described below based on Examples. However, this does not limit the embodiments of the present invention in any way.

【０１０５】実施例及び比較例に記載されている部数は
重量部を示す。The number of parts described in Examples and Comparative Examples means parts by weight.

【０１０６】実施例１ ・スチレン−アクリル酸ブチル−ジビニルベンゼン共重
合体 １００部（共重合比８０／１９．５／０．５、重
量平均分子量３２０，０００） ・磁性体（平均粒径約０．２μｍ）１００部 ・低分子量ポリプロピレン ３部 ・モノアゾ染料のクロム錯体 ４部 Example 1 Styrene-butyl acrylate-divinylbenzene copolymer 100 parts (copolymerization ratio 80 / 19.5 / 0.5, weight average molecular weight 320,000) Magnetic substance (average particle size of about 0) .2 μm) 100 parts-Low molecular weight polypropylene 3 parts-Monoazo dye chromium complex 4 parts

【０１０７】上記混合物を、１４０℃に加熱された２軸
混練押出機で溶融混練し、冷却した混練物をハンマーミ
ルで粗粉砕し、粗粉砕物をジェットミルで微粉砕し得ら
れた微粉砕物を多分割分級機で超微粉及び粗粉を分級除
去して重量平均粒径６．３μｍの磁性トナーを得た。The above mixture was melt-kneaded by a twin-screw kneading extruder heated to 140 ° C., the cooled kneaded product was coarsely pulverized by a hammer mill, and the coarsely pulverized product was finely pulverized by a jet mill. The fine powder and coarse powder were classified and removed by a multi-division classifier to obtain a magnetic toner having a weight average particle diameter of 6.3 μm.

【０１０８】次にケイ酸微粉体（アエロジル＃３００，
日本アエロジル社製；親水性シリカ）１００部をジメチ
ルジクロルシラン２０部で処理した後、さらにヘキサメ
チルジシラザン１０部で処理を行ない、疎水化度９６．
１％、炭素付着量２．５ｗｔ％、ＢＥＴ比表面積１７２
ｍ2 ／ｇの微粉体を得た。この微粉体を攪拌しながらジ
メチルシリコーンオイル（ＫＦ−９６，１００ＣＳ，信
越化学工業社製）１５部をスプレー噴霧で塗布した後、
１９０℃で５時間加熱処理し、疎水化度９８．２％、炭
素付着量８．４ｗｔ％、ＢＥＴ比表面積１１５ｍ2 ／ｇ
の処理ケイ酸微粉体を得た。シリコーンオイル処理によ
る比表面積の変化は０．６７倍であり、炭素付着量は
５．９ｗｔ％であった。Next, fine silica powder (Aerosil # 300,
100 parts of hydrophilic silica) manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of dimethyldichlorosilane, and further treated with 10 parts of hexamethyldisilazane to obtain a hydrophobicity of 96.
1%, carbon deposition amount 2.5 wt%, BET specific surface area 172
A fine powder of m 2 / g was obtained. While stirring this fine powder, 15 parts of dimethyl silicone oil (KF-96, 100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by spraying spray,
Heat-treated at 190 ° C. for 5 hours, hydrophobicity 98.2%, carbon deposition amount 8.4 wt%, BET specific surface area 115 m 2 / g
A treated silicic acid fine powder was obtained. The change in specific surface area due to the silicone oil treatment was 0.67 times, and the carbon deposition amount was 5.9 wt%.

【０１０９】前述の磁性トナー１００部と、上記処理ケ
イ酸微粉体１部をヘンシェルミキサーで混合し、一成分
系磁性現像剤を得た。100 parts of the above-mentioned magnetic toner and 1 part of the above treated silicic acid fine powder were mixed with a Henschel mixer to obtain a one-component magnetic developer.

【０１１０】上記一成分系磁性現像剤をキヤノン製レー
ザービームプリンターＬＢＰ−８１１（ＯＰＣ感光ドラ
ムを使用）を８枚／分から１６枚／分に改造し、さらに
図２に示す転写装置を組みこんだ改造機を用いて画出し
評価を行った。A laser beam printer LBP-811 manufactured by Canon Inc. (using an OPC photosensitive drum) was used as the above one-component magnetic developer, which was modified from 8 sheets / minute to 16 sheets / minute, and a transfer device shown in FIG. 2 was incorporated. Images were evaluated using a modified machine.

【０１１１】転写ローラーの条件としては、転写ローラ
ーの表面ゴム硬度２７°、転写電流１μＡ、転写電圧＋
２０００Ｖ、当接圧５０［ｇ／ｃｍ］とした。転写ロー
ラの導電性弾性層は、導電性カーボンを分散したＥＰＤ
Ｍで形成されており、体積抵抗１０8 Ω・ｃｍを有して
いた。As conditions for the transfer roller, the surface rubber hardness of the transfer roller was 27 °, the transfer current was 1 μA, and the transfer voltage was +
The contact pressure was 2000 V and the contact pressure was 50 [g / cm]. The conductive elastic layer of the transfer roller is an EPD in which conductive carbon is dispersed.
It was formed of M and had a volume resistance of 10 8 Ω · cm.

【０１１２】一次帯電が−７００Ｖであり、感光ドラム
と現像ドラム（磁石内包）上の現像剤層を非接触に間隙
を設定し、交流バイアス（ｆ＝１，８００Ｈｚ，Ｖｐｐ
＝１，６００Ｖ）および直流バイアス（ＶDC＝−５００
Ｖ）とを現像ドラムに印加しながら８，０００枚の画出
しを行った。画出しされ、加熱加圧ローラ定着されたト
ナー定着画像を評価したところ、画像濃度は１．４以
上、１２０ｇ／ｍ2 の厚紙や厚さ約１１０μｍのトラン
スペアレンシーフィルムでの転写中抜けもなく、極めて
良好であり、ＯＰＣ感光ドラム表面の傷は極めて少なか
った。The primary charge is -700 V, a gap is set in a non-contact manner between the photosensitive drum and the developer layer on the developing drum (including magnet), and an AC bias (f = 1,800 Hz, Vpp) is set.
= 1,600 V) and DC bias (V DC = -500)
V) was applied to the developing drum, and 8,000 images were printed. Evaluation of the toner-fixed image that has been imaged and fixed by a heating / pressurizing roller shows that the image density is 1.4 or more, and there is no dropout in transfer on 120 g / m 2 thick paper or a transparency film with a thickness of about 110 μm. The surface of the OPC photosensitive drum was very few scratches.

【０１１３】通常の複写機用普通紙（７５ｇ／ｍ2 ）
４，０００枚通紙時の画像濃度の維持状態により下記の
如く評価した。結果を表１に示す。Plain paper for ordinary copying machines (75 g / m 2 ).
Evaluation was made as follows based on the state of maintaining the image density when 4,000 sheets were passed. The results are shown in Table 1.

【０１１４】○（良） ：１．３５以上 △（可） ：１．０〜１．３４ ×（不可）：１．０以下Good (good): 1.35 or more Fair (good): 1.0 to 1.34 x (bad): 1.0 or less

【０１１５】実施例２ ケイ酸微粉体（アエロジル＃３００日本アエロジル社
製）１００部にジメチルジクロルシラン３０部で処理を
行った後（疎水化度８２．３％、比表面積２３０ｍ2 ／
ｇ、炭素含有量：２．２ｗｔ％）、ジメチルシリコーン
オイル（ＫＦ−９６１００ｃｓ信越化学工業社製）１５
部を溶剤で希釈したものに混合した後、溶剤を減圧下で
揮発させた後、１８０℃で加熱処理を行い、疎水化度９
１．４％、比表面積１２０ｍ2 ／ｇ、炭素含有量６．５
ｗｔ％（即ち、シリコーンオイル処理による炭素の付着
量：４．３ｗｔ％）の処理ケイ酸微粉体を得た。 Example 2 100 parts of silica fine powder (Aerosil # 300, manufactured by Nippon Aerosil Co., Ltd.) was treated with 30 parts of dimethyldichlorosilane (hydrophobicity 82.3%, specific surface area 230 m 2 /
g, carbon content: 2.2 wt%), dimethyl silicone oil (KF-96100cs manufactured by Shin-Etsu Chemical Co., Ltd.) 15
After mixing with a part diluted with a solvent, the solvent is volatilized under reduced pressure and then heat-treated at 180 ° C. to obtain a hydrophobicity of 9
1.4%, specific surface area 120 m 2 / g, carbon content 6.5
A treated silicic acid fine powder having a wt% (that is, the amount of carbon deposited by the silicone oil treatment: 4.3 wt%) was obtained.

【０１１６】実施例１と同様に生成した磁性トナー１０
０部と、処理ケイ酸微粉体を混合して３種の一成分系磁
性現像剤を調製した。Magnetic toner 10 produced in the same manner as in Example 1.
Three parts of one-component magnetic developer were prepared by mixing 0 parts of the treated silicic acid fine powder.

【０１１７】これを実施例１と同様にして４０００枚の
画出しを行なった。画出しされ、加熱加圧ローラ定着さ
れたトナー定着画像を評価した。結果を表１に示す。In the same manner as in Example 1, 4000 sheets were printed. The toner-fixed image that was imaged and fixed by the heating and pressure roller was evaluated. The results are shown in Table 1.

【０１１８】実施例３ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にジメチルジクロルシラン２５部で処
理を行った後（疎水化度８３．６％、比表面積１７２ｍ
2 ／ｇ、炭素含有量：１．５ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）５部を溶剤で希釈したものに混合した後、溶剤を減
圧下で揮発させた後、１８０℃で加熱処理を行って得
た、疎水化度８４．８％、比表面積１２９ｍ2 ／ｇ、炭
素含有量４．６ｗｔ％（シリコーンオイル処理による炭
素付着量：３．１ｗｔ％）の処理ケイ酸微粉体１．２部
を用いた現像剤を使用する以外は実施例１と同様にして
画出し試験を行った。耐久後のＯＰＣドラム表面の傷が
若干多かった他は表１に示すとおり良好な結果が得られ
た。 Example 3 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 25 parts of dimethyldichlorosilane (hydrophobicity 83.6%, specific surface area 172 m
2 / g, carbon content: 1.5 wt%), 5 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. After that, it was obtained by heat treatment at 180 ° C., having a hydrophobicity of 84.8%, a specific surface area of 129 m 2 / g, and a carbon content of 4.6 wt% (amount of carbon deposited by silicone oil treatment: 3.1 wt%). An image development test was conducted in the same manner as in Example 1 except that a developer containing 1.2 parts of the treated silicic acid fine powder was used. Good results were obtained as shown in Table 1 except that the number of scratches on the surface of the OPC drum after the durability test was slightly large.

【０１１９】実施例４ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００、親水性、比表面積２００ｍ2 ／ｇ）に、ジメチ
ルシリコーンオイル（ＫＦ−９６ １００ｃｓ，信越化
学工業社製）３０部を溶剤で希釈したものに混合した
後、溶剤を減圧下で揮発させた後、２００℃で加熱処理
を行って得た、疎水化度８７．２％、比表面積８６ｍ2
／ｇ、炭素含有量７．９ｗｔ％（シリコーンオイル処理
による炭素付着量：７．９ｗｔ％）の処理ケイ酸微粉体
０．８部を用いた現像剤を使用する以外は実施例１と同
様にして画出し試験を行った。結果を表１に示す。 Example 4 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200, hydrophilic, specific surface area 200 m 2 / g) was mixed with 30 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a solvent, and then the solvent was evaporated under reduced pressure. After that, a heat treatment was performed at 200 ° C. to obtain a hydrophobicity of 87.2% and a specific surface area of 86 m 2.
/ G, carbon content 7.9 wt% (carbon deposition amount by silicone oil treatment: 7.9 wt%) The same as in Example 1 except that a developer using 0.8 parts of treated silicic acid fine powder is used. Then, an image production test was conducted. The results are shown in Table 1.

【０１２０】実施例５ 実施例２の現像剤を使用し、転写ローラーの潜像担持体
への当接圧を５ｇ／ｃｍにした以外は実施例１と同様の
試験を行なった。結果を表１に示す。 Example 5 The same test as in Example 1 was conducted except that the developer of Example 2 was used and the contact pressure of the transfer roller to the latent image carrier was set to 5 g / cm. The results are shown in Table 1.

【０１２１】比較例１ 処理ケイ酸微粉体としてケイ酸微粉体（アエロジル＃３
００）１００部にジメチルジクロルシラン３０部で処理
した疎水性シリカ（シリコーンオイル処理による炭素付
着量：０ｗｔ％）を用い、転写ローラーの潜像担持体へ
の当接圧を線圧で２ｇ／ｃｍにした以外は実施例１と同
様に試験を行なったところ、画像濃度の耐久性が悪く、
文字画像の中抜けが目立つ画像しか得ることができなか
った。中抜けの他にも、転写のブレが生じた部分があ
り、これは転写圧の不足が原因である。その他、耐久後
のドラム表面には無数の細かい傷ができておりこれはシ
リカの処理表面の滑性の違いに原因があった。 Comparative Example 1 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil # 3) was used.
00) 100 parts of hydrophobic silica treated with 30 parts of dimethyldichlorosilane (carbon deposition amount by silicone oil treatment: 0 wt%) was used, and the contact pressure of the transfer roller to the latent image carrier was 2 g / linear pressure. A test was performed in the same manner as in Example 1 except that the image density was changed to cm.
I was able to obtain only images where the voids in the character images were noticeable. In addition to the hollow area, there is a portion where transfer blurring occurs, which is caused by insufficient transfer pressure. In addition, countless minute scratches were formed on the surface of the drum after running, which was caused by the difference in the slipperiness of the treated surface of silica.

【０１２２】[0122]

【表１】 [Table 1]

【０１２３】実施例６ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にジメチルジクロルシラン２０部で処
理を行った後（疎水化度８２．６％、比表面積１８０ｍ
2 ／ｇ、炭素含有量：１．１ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）１５部を溶剤で希釈したものに混合した後、溶剤を
減圧下で揮発させた後、１８０℃で加熱処理を行って得
た、疎水化度９０．８％、比表面積１００ｍ2 ／ｇ、炭
素含有量５．２ｗｔ％（シリコーンオイル処理による炭
素付着量：４．１ｗｔ％）の処理ケイ酸微粉体を用いた
現像剤を使用する以外は実施例１と同様の試験を行っ
た。結果を表２に示す。 Example 6 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 20 parts of dimethyldichlorosilane (hydrophobicity 82.6%, specific surface area 180 m
2 / g, carbon content: 1.1 wt%), 15 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. Then, a heat treatment was performed at 180 ° C. to obtain a hydrophobicity of 90.8%, a specific surface area of 100 m 2 / g, and a carbon content of 5.2 wt% (carbon deposition amount by silicone oil treatment: 4.1 wt%). The same test as in Example 1 was carried out except that a developer using the treated silicic acid fine powder was used. The results are shown in Table 2.

【０１２４】実施例７ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にジメチルジクロルシラン３０部で処
理を行った後（疎水化度８２．３％、比表面積２３０ｍ
2 ／ｇ、炭素含有量２．２ｗｔ％）、ジメチルシリコー
ンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）２０部を溶剤で希釈したものに混合した後、溶剤を
減圧下で揮発させた後、１５０℃で加熱処理を行って得
た、疎水化度９５．４％、比表面積１２０ｍ2 ／ｇ（シ
リコーンオイル処理前の比表面積の０．５２倍）、炭素
含有量８．５ｗｔ％の処理ケイ酸微粉体を用いた現像剤
を使用する以外は実施例１と同様の試験を行った。結果
を表２に示す。 Example 7 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300) 100 parts after treatment with 30 parts of dimethyldichlorosilane (hydrophobicity 82.3%, specific surface area 230 m
2 / g, carbon content of 2.2 wt%), 20 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and the solvent was evaporated under reduced pressure. , A hydrophobization degree of 95.4%, a specific surface area of 120 m 2 / g (0.52 times the specific surface area before silicone oil treatment), and a carbon content of 8.5 wt% The same test as in Example 1 was conducted except that a developer containing fine silicic acid powder was used. The results are shown in Table 2.

【０１２５】実施例８ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にジメチルジクロルシラン３５部で処
理を行った後（疎水化度８５．８％、比表面積：２１０
ｍ2 ／ｇ、炭素含有量２．６ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）５部を溶剤で希釈したものに混合した後、溶剤を減
圧下で揮発させた後、１５０℃で加熱処理を行って得
た、疎水化度８３．６％、比表面積１２５ｍ2 ／ｇ（シ
リコーンオイル処理前の比表面積の０．５９倍）、炭素
含有量７．１ｗｔ％の処理ケイ酸微粉体１．２部を用い
た現像剤を使用する以外は実施例１と同様の試験を行っ
た。 Example 8 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300 parts) was treated with 35 parts of dimethyldichlorosilane (hydrophobicity 85.8%, specific surface area: 210)
m 2 / g, carbon content 2.6 wt%), 5 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. After that, it was obtained by heat treatment at 150 ° C., having a hydrophobicity of 83.6%, a specific surface area of 125 m 2 / g (0.59 times the specific surface area before silicone oil treatment), and a carbon content of 7.1 wt%. The same test as in Example 1 was conducted except that a developer containing 1.2 parts of the treated silicic acid fine powder was used.

【０１２６】この結果は、耐久後のＯＰＣドラム表面の
傷が若干多かった他は表２に示すとおり良好であった。The results were good as shown in Table 2 except that the number of scratches on the surface of the OPC drum after running was slightly large.

【０１２７】実施例９ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００、親水性、比表面積：２００ｍ2 ／ｇ）に、ジメ
チルシリコーンオイル（ＫＦ−９６ １００ｃｓ，信越
化学工業社製）３５部を溶剤で希釈したものに混合した
後、溶剤を減圧下で揮発させた後、１５０℃で加熱処理
を行って得た、疎水化度８９．２％、比表面積８０ｍ2
／ｇ（シリコーンオイル処理前の比表面積の０．４０
倍）、炭素含有量８．０ｗｔ％の処理ケイ酸微粉体を用
いた現像剤を使用する以外は実施例１と同様の試験を行
った。結果を表２に示す。 Example 9 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200, hydrophilic, specific surface area: 200 m 2 / g), mixed with 35 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a solvent, and then volatilized the solvent under reduced pressure. And then subjected to heat treatment at 150 ° C. to obtain a hydrophobicity of 89.2% and a specific surface area of 80 m 2.
/ G (0.40 of specific surface area before silicone oil treatment)
2 times), and the same test as in Example 1 was performed except that a developer using treated silicic acid fine powder having a carbon content of 8.0 wt% was used. The results are shown in Table 2.

【０１２８】実施例１０ 転写ローラーの潜像担持体への当接圧を５ｇ／ｃｍにし
た以外は実施例６と同様の試験を行なった。 Example 10 The same test as in Example 6 was conducted except that the contact pressure of the transfer roller to the latent image carrier was set to 5 g / cm.

【０１２９】比較例２ 処理ケイ酸微粉体として、（アエロジル＃２００）１０
０部にジメチルジクロルシラン２０部で処理を行なった
ものを用い転写ローラーの潜像担持体への当接圧を線圧
２ｇ／ｃｍにした以外は実施例６と同様に試験を行なっ
たところ、画像濃度の耐久性が悪く、文字画像の中抜け
が目立つ画像しか得られなかった。 Comparative Example 2 (Aerosil # 200) 10 was used as the treated silicic acid fine powder.
A test was conducted in the same manner as in Example 6 except that the contact pressure of the transfer roller to the latent image bearing member was changed to 0 g and the linear pressure was 2 g / cm. However, the durability of the image density was poor, and only an image in which the hollow portion of the character image was conspicuous was obtained.

【０１３０】中抜けの他にも転写のブレが生じた部分が
あり、これは、転写圧が低いことが原因である。その
他、耐久後のＯＰＣドラム表面には無数の細かい傷がで
きており、これはシリカの処理表面の滑性の違いに原因
がある。In addition to the hollow portion, there is a portion where transfer blurring occurs, and this is because the transfer pressure is low. In addition, countless fine scratches are formed on the surface of the OPC drum after the endurance, which is caused by the difference in lubricity of the treated surface of silica.

【０１３１】[0131]

【表２】 [Table 2]

【０１３２】実施例１１ 実施例１の現像剤を、キヤノン製レーザービームプリン
ターＬＢＰ−８ＩＩを８枚／分から１６枚／分に改造し
たＬＢＰプリンターに入れ画出し試験を行った。常温常
湿（２３℃、６０％ＲＨ）の条件下１万５千枚画出しに
おいて画像濃度は、１．４〜１．５と安定で、画質も良
好であり、クリーニングにより回収されたトナーも少量
であった。 Example 11 The developer of Example 1 was put in an LBP printer in which Canon laser beam printer LBP-8II was modified from 8 sheets / minute to 16 sheets / minute, and an image forming test was conducted. Toner collected at the time of normal temperature and normal humidity (23 ° C., 60% RH) with a stable image density of 1.4 to 1.5 when printing 15,000 sheets and good image quality, and toner collected by cleaning. Was also a small amount.

【０１３３】高温高湿（３２．５℃，９０％ＲＨ）条件
下に放置し、同様に１万枚の画出し試験を行ったとこ
ろ、画像濃度は１．４以上であり、トランスペアレンシ
ーフィルムへの印字も転写中抜けもなく良好であった。The image density of 1.4 or more was obtained when the image forming test of 10,000 sheets was carried out similarly under the condition of high temperature and high humidity (32.5 ° C., 90% RH). The printing was good and there was no omission in the transfer.

【０１３４】実施例１２ ケイ酸微粉体（アエロジル＃２００，日本アエロジル社
製；親水性シリカ）１００部をジメチルジクロルシラン
１０部で処理した後、ヘキサメチルジシラザン１５部で
さらに処理し、疎水化度９８．２％、炭素付着量２．１
ｗｔ％、ＢＥＴ比表面積１５５ｍ2 ／ｇの微粉体を得
た。この微粉体を攪拌しながらジメチルシリコーンオイ
ル（ＫＦ−９６ １００ｃｓ）１２部をスプレー噴霧で
塗布した後１８０℃で７時間加熱処理し、疎水化度９
６．７％、炭素付着量８．４ｗｔ％、ＢＥＴ比表面積１
１３ｍ2 ／ｇの処理ケイ酸微粉体を得た。シリコーンオ
イル処理による比表面積の変化は０．７３倍であり、炭
素付着量６．３ｗｔ％であった。 Example 12 100 parts of silicic acid fine powder (Aerosil # 200, manufactured by Nippon Aerosil Co., Ltd .; hydrophilic silica) was treated with 10 parts of dimethyldichlorosilane, and then further treated with 15 parts of hexamethyldisilazane to obtain hydrophobicity. Chemical conversion 98.2%, carbon deposition 2.1
A fine powder having a wt% and a BET specific surface area of 155 m 2 / g was obtained. While stirring this fine powder, 12 parts of dimethyl silicone oil (KF-96 100 cs) was applied by spray spraying and then heat-treated at 180 ° C. for 7 hours to give a hydrophobicity of 9
6.7%, carbon adhesion amount 8.4wt%, BET specific surface area 1
13 m 2 / g of treated silicic acid fine powder was obtained. The change in specific surface area due to the silicone oil treatment was 0.73 times, and the carbon deposition amount was 6.3 wt%.

【０１３５】次に実施例１の磁性トナー１００部と、上
記処理ケイ酸微粉体１．２部とをヘンシェルミキサーで
混合し、磁性一成分系現像剤とし、実施例１１と同様の
画出し評価を行なった。実施例１と同様の良好な結果が
得られた。Next, 100 parts of the magnetic toner of Example 1 and 1.2 parts of the treated silicic acid fine powder are mixed by a Henschel mixer to prepare a magnetic one-component developer, and the same image as in Example 11 is obtained. An evaluation was performed. Good results similar to those of Example 1 were obtained.

【０１３６】実施例１３ ケイ酸微粉体（アエロジル＃３００）１００部をメチル
トリクロルシラン２０部で処理した後、ヘキサメチルジ
シラザン５部でさらに処理し、疎水化度８８．６％、炭
素付着量１．８ｗｔ％、ＢＥＴ比表面積２２６ｍ2 ／ｇ
の微粉体を得た。さらにジメチルシリコーンオイルＫＦ
−９６ １００ｃｓ １８部を溶剤で希釈したものに上
記微粉体を混合した後、溶剤を減圧下で揮発させた後、
１９０℃で１０時間加熱処理して疎水化度９３．４％、
炭素付着量８．９ｗｔ％、ＢＥＴ比表面積１２７ｍ2 ／
ｇの処理ケイ酸微粉体を得た。シリコーンオイル処理に
よる比表面積の変化は０．５６倍であり、炭素付着量は
７．１ｗｔ％であった。 Example 13 100 parts of silicic acid fine powder (Aerosil # 300) was treated with 20 parts of methyltrichlorosilane and then further treated with 5 parts of hexamethyldisilazane to obtain a hydrophobicity of 88.6% and a carbon deposition amount. 1.8 wt%, BET specific surface area 226 m 2 / g
A fine powder of Further dimethyl silicone oil KF
-96 100 cs 18 parts diluted with a solvent was mixed with the above fine powder, and the solvent was evaporated under reduced pressure.
Heat treated at 190 ° C. for 10 hours to give a hydrophobicity of 93.4%,
Carbon deposition amount 8.9 wt%, BET specific surface area 127 m 2 /
g of treated silicic acid fine powder was obtained. The change in specific surface area due to the silicone oil treatment was 0.56 times, and the carbon deposition amount was 7.1 wt%.

【０１３７】次に上記処理ケイ酸微粉体を用いた以外
は、実施例１と同様にして磁性一成分現像剤を得、実施
例１１と同様に画出し評価を行なったところ、同様の良
好な結果が得られた。Next, a magnetic one-component developer was obtained in the same manner as in Example 1 except that the above treated silicic acid fine powder was used, and the same image as in Example 11 was evaluated. The results were obtained.

【０１３８】実施例１４ ケイ酸微粉体（アエロジル＃３００ 日本アエロジル社
製）１００部にジメチルジクロルシラン３０部で処理を
行った後（疎水化度８２．３％、比表面積２３０ｍ2 ／
ｇ、炭素含有量：２．２ｗｔ％）、ジメチルシリコーン
オイル（ＫＦ−９６ １００ｃｓ 信越化学工業社製）
１５部を溶剤で希釈したものに混合した後、溶剤を減圧
下で揮発させた後、１８０℃で加熱処理を行い、疎水化
度９１．４％、比表面積１２０ｍ2 ／ｇ、炭素含有量
６．５ｗｔ％（即ち、シリコーンオイル処理による炭素
の付着量：４．３ｗｔ％）の処理ケイ酸微粉体を得た。 Example 14 100 parts of silica fine powder (Aerosil # 300 manufactured by Nippon Aerosil Co., Ltd.) was treated with 30 parts of dimethyldichlorosilane (hydrophobicity 82.3%, specific surface area 230 m 2 /
g, carbon content: 2.2 wt%), dimethyl silicone oil (KF-96 100cs manufactured by Shin-Etsu Chemical Co., Ltd.)
After mixing 15 parts with a solution diluted with a solvent, the solvent was evaporated under reduced pressure and then heat-treated at 180 ° C. to obtain a hydrophobicity of 91.4%, a specific surface area of 120 m 2 / g and a carbon content of 6 The treated silicic acid fine powder was obtained in an amount of 0.5 wt% (that is, the amount of carbon deposited by the silicone oil treatment: 4.3 wt%).

【０１３９】実施例１の磁性トナー１００部とジメチル
ジクロルシラン処理後ジメチルシリコーンオイルで処理
したケイ酸微粉体０．８部をヘンシェルミキサーで混合
し磁性一成分系現像剤を得た。100 parts of the magnetic toner of Example 1 and 0.8 part of silica fine powder treated with dimethyldichlorosilane and then treated with dimethyl silicone oil were mixed with a Henschel mixer to obtain a magnetic one-component developer.

【０１４０】該現像剤を用いて実施例１１と同様にして
常温常湿、高温高湿で、各々８千枚ずつ画像出しを行な
った。実施例１１と同様の良好な結果が得られた。Using the developer, in the same manner as in Example 11, 8,000 sheets of images were printed at room temperature and normal humidity and at high temperature and high humidity. Good results similar to those in Example 11 were obtained.

【０１４１】比較例３ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部をジメチルジクロルシラン３０部で処
理を行ったものを用いた以外は実施例１４と同様の試験
を行った。 Comparative Example 3 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
The same test as in Example 14 was performed except that 100 parts of 300) treated with 30 parts of dimethyldichlorosilane was used.

【０１４２】常温常湿では画像濃度１．３の良好な画像
が得られたが、高温高湿放置１日で１．０まで画像濃度
が下がってしまった。A good image having an image density of 1.3 was obtained at room temperature and normal humidity, but the image density decreased to 1.0 in a day of standing at high temperature and high humidity.

【０１４３】実施例１５ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にジメチルジクロルシラン２０部で処
理を行った後（疎水化度８２．６％，比表面積１８０ｍ
2 ／ｇ，炭素含有量：１．１ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）１５部を溶剤で希釈したものに混合した後、溶剤を
減圧下で揮発させた後、１８０℃で加熱処理を行って得
た、疎水化度９０．８％、比表面積１００ｍ2 ／ｇ、炭
素含有量５．２ｗｔ％（シリコーンオイル処理による炭
素付着量：４．１ｗｔ％）の処理ケイ酸微粉体を用いた
以外は実施例１４と同様の試験を行った。 Example 15 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 20 parts of dimethyldichlorosilane (hydrophobicity 82.6%, specific surface area 180 m
2 / g, carbon content: 1.1 wt%), 15 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent diluted, and then the solvent was evaporated under reduced pressure. Then, a heat treatment was performed at 180 ° C. to obtain a hydrophobicity of 90.8%, a specific surface area of 100 m 2 / g, and a carbon content of 5.2 wt% (carbon deposition amount by silicone oil treatment: 4.1 wt%). The same test as in Example 14 was conducted except that the treated silicic acid fine powder was used.

【０１４４】高温高湿下に放置した場合も画像濃度が
１．４以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.4 or more was obtained, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１４５】実施例１６ 処理ケイ酸微粉体として、ジメチルシリコーンオイル
（ＫＦ−９６ １００ｃｓ 信越化学工業社製）の処理
量を２０部にした以外は実施例５と同様にして得た、疎
水化度９５．１％、比表面積９１ｍ2 ／ｇ、炭素含有量
７．３ｗｔ％（シリコーンオイル処理による炭素付着
量：６．２ｗｔ％）の処理ケイ酸微粉体を用い、実施例
１４と同様の試験を行った。 Example 16 The degree of hydrophobization obtained in the same manner as in Example 5 except that the treated amount of dimethyl silicone oil (KF-96 100cs manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 20 parts as the treated silicic acid fine powder. The same test as in Example 14 was performed using a treated silicic acid fine powder having 95.1%, a specific surface area of 91 m 2 / g, and a carbon content of 7.3 wt% (carbon adhesion amount by silicone oil treatment: 6.2 wt%). went.

【０１４６】実施例１５と同様に各環境下で良好な画像
が得られた。Similar to Example 15, good images were obtained under each environment.

【０１４７】実施例１７ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にジメチルジクロルシラン２５部で処
理を行った後（疎水化度８３．６％，比表面積１７２ｍ
2 ／ｇ，炭素含有量：１．５ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）５部を溶剤で希釈したものに混合した後、溶剤を減
圧下で揮発させた後、１８０℃で加熱処理を行って得
た、疎水化度８４．８％，比表面積１２９ｍ2 ／ｇ，炭
素含有量４．６ｗｔ％（シリコーンオイル処理による炭
素付着量：３．１ｗｔ％）の処理ケイ酸微粉体を用いた
以外は実施例１４と同様の試験を行った。 Example 17 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 25 parts of dimethyldichlorosilane (hydrophobicity 83.6%, specific surface area 172 m
2 / g, carbon content: 1.5 wt%), 5 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and the solvent was evaporated under reduced pressure. After that, a heat treatment was performed at 180 ° C. to obtain a hydrophobicity of 84.8%, a specific surface area of 129 m 2 / g, and a carbon content of 4.6 wt% (carbon deposit amount by silicone oil treatment: 3.1 wt%). The same test as in Example 14 was conducted except that the treated silicic acid fine powder was used.

【０１４８】高温高湿下に放置した場合も画像濃度が
１．３以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。また、各環境下で
の画出し試験でも良好な画像が得られ、回収された感光
体上の残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.3 or more was obtained, and the printing on the transparency film was also good. In addition, a good image was obtained in the image output test under each environment, and the amount of the residual toner on the collected photoconductor was small.

【０１４９】実施例１８ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にトリメチルクロルシラン３０部で処
理を行った後（疎水化度９２．２％，比表面積２１３ｍ
2 ／ｇ，炭素含有量：３．５ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）１０部を溶剤で希釈したものに混合した後、溶剤を
減圧下で揮発させた後、１５０℃で加熱処理を行って得
た、疎水化度９６．３％，比表面積１４７ｍ2 ／ｇ，炭
素含有量７．１ｗｔ％（シリコーンオイル処理による炭
素付着量：３．６ｗｔ％）の処理ケイ酸微粉体を用いた
以外は実施例１４と同様の試験を行った。 Example 18 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300 parts) was treated with 30 parts of trimethylchlorosilane (hydrophobicity 92.2%, specific surface area 213 m).
2 / g, carbon content: 3.5 wt%), 10 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. After that, the product was subjected to heat treatment at 150 ° C., and had a hydrophobicity of 96.3%, a specific surface area of 147 m 2 / g, and a carbon content of 7.1 wt% (carbon deposit amount by silicone oil treatment: 3.6 wt%). The same test as in Example 14 was conducted except that the treated silicic acid fine powder was used.

【０１５０】高温高湿下に放置した場合も画像濃度が
１．４以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.4 or more was obtained, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１５１】実施例１９ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００、親水性、比表面積２００ｍ2 ／ｇ）に、ジメチ
ルシリコーンオイル（ＫＦ−９６ １００ｃｓ，信越化
学工業社製）３０部を溶剤で希釈したものに混合した
後、溶剤を減圧下で揮発させた後、２００℃で加熱処理
を行って得た、疎水化度８７．２％、比表面積８６ｍ2
／ｇ、炭素含有量７．９ｗｔ％（シリコーンオイル処理
による炭素付着量：７．９ｗｔ％）の処理ケイ酸微粉体
を用いた以外は実施例１４と同様の試験を行った。 Example 19 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200, hydrophilic, specific surface area 200 m 2 / g) was mixed with 30 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a solvent, and then the solvent was evaporated under reduced pressure. After that, a heat treatment was performed at 200 ° C. to obtain a hydrophobicity of 87.2% and a specific surface area of 86 m 2.
/ G, carbon content was 7.9 wt% (carbon deposition amount by silicone oil treatment: 7.9 wt%), and the same test as in Example 14 was performed except that the treated silicic acid fine powder was used.

【０１５２】低温低湿下で画像濃度が１．２と若干低か
ったものの、高温高湿下に放置した場合も画像濃度が
１．３以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。Although the image density was slightly low at 1.2 under low temperature and low humidity, a good image with an image density of 1.3 or more was obtained even when left under high temperature and high humidity, and printing on a transparency film was also possible. It was good.

【０１５３】実施例２０ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にジメチルクロルシラン３０部で処理
を行った後（疎水化度７７．３％となるように調製し
た、比表面積２３０ｍ2 ／ｇ、炭素含有量：２．２ｗｔ
％）、α−メチルスチレン変性シリコーンオイル（ＫＦ
−４１０，信越化学工業社製）１５部を溶剤で希釈した
ものに混合した後、溶剤を減圧下で揮発させた後、１５
０℃で加熱処理を行って得た、疎水化度８６．８％、比
表面積１４３ｍ2 ／ｇ、炭素含有量６．１ｗｔ％（シリ
コーンオイル処理による炭素付着量：３．９ｗｔ％）の
処理ケイ酸微粉体を用いた以外は実施例１４と同様の試
験を行った。高温高湿下に放置した場合も画像濃度が
１．３以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。 Example 20 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300 parts of 100 parts was treated with 30 parts of dimethylchlorosilane (prepared to have a hydrophobicity of 77.3%, specific surface area of 230 m 2 / g, carbon content: 2.2 wt)
%), Α-methylstyrene modified silicone oil (KF
-410, manufactured by Shin-Etsu Chemical Co., Ltd.) 15 parts by dilution with a solvent, and then the solvent was evaporated under reduced pressure.
A treated silica having a hydrophobicity of 86.8%, a specific surface area of 143 m 2 / g, and a carbon content of 6.1 wt% (carbon deposition amount by silicone oil treatment: 3.9 wt%) obtained by performing heat treatment at 0 ° C. The same test as in Example 14 was carried out except that the acid fine powder was used. A good image with an image density of 1.3 or more was obtained even when left under high temperature and high humidity, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１５４】実施例２１ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にトリメチルクロルシラン２０部で処
理を行った後（疎水化度８４．１％、比表面積１６０ｍ
2 ／ｇ、炭素含有量：２．５ｗｔ％）、ジメチルシリコ
ーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業社
製）１５部を溶剤で希釈し噴霧による処理を行い乾燥し
た後、１５０℃で加熱処理を行って得た、疎水化度９
２．６％、比表面積９５ｍ2 ／ｇ、炭素含有量７．５ｗ
ｔ％（シリコーンオイル処理による炭素付着量：５．０
ｗｔ％）の処理ケイ酸微粉体を用いた以外は実施例１１
と同様の試験を行った。高温高湿下に放置した場合も画
像濃度が１．３以上の良好な画像が得られ、トランスペ
アレンシーフィルムへの印字も良好であった。各環境下
での画出し試験でも良好な画像が得られ、回収された感
光体上の残余のトナーも少量であった。 Example 21 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) 100 parts after treatment with 20 parts of trimethylchlorosilane (hydrophobicity 84.1%, specific surface area 160 m
2 / g, carbon content: 2.5 wt%), 15 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with a solvent, treated by spraying, dried and then heat-treated at 150 ° C. Hydrophobicity of 9
2.6%, specific surface area 95 m 2 / g, carbon content 7.5 w
t% (Amount of carbon deposited by silicone oil treatment: 5.0
wt%) treated silicic acid fine powder was used in Example 11
The same test was performed. A good image with an image density of 1.3 or more was obtained even when left under high temperature and high humidity, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１５５】比較例４ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部をジメチルジクロルシラン２０部で処
理を行ったものを用いた以外は実施例１９と同様の試験
を行った。 Comparative Example 4 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
The same test as in Example 19 was carried out except that 100 parts of 200) was treated with 20 parts of dimethyldichlorosilane.

【０１５６】常温常湿では画像濃度１．３の良好な画像
が得られたが、高温高湿放置１日で１．０まで画像濃度
が下がってしまった。A good image having an image density of 1.3 was obtained at room temperature and normal humidity, but the image density decreased to 1.0 after 1 day of standing at high temperature and high humidity.

【０１５７】実施例２２ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にジメチルジクロルシラン３０部で処
理を行った後（疎水化度８２．３％、比表面積：２３０
ｍ2 ／ｇ、炭素含有量：２．２ｗｔ％）、ジメチルシリ
コーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業
社製）２０部を溶剤で希釈したものに混合した後、溶剤
を減圧下で揮発させた後、１５０℃で加熱処理を行って
得た、疎水化度９５．４％、比表面積１２０ｍ2 ／ｇ
（シリコーンオイル処理前の比表面積の０．５２倍）、
炭素含有量８．５ｗｔ％の処理ケイ酸微粉体を用いた以
外は実施例１４と同様の試験を行った。 Example 22 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300) 100 parts after treatment with 30 parts of dimethyldichlorosilane (hydrophobicity 82.3%, specific surface area: 230
m 2 / g, carbon content: 2.2 wt%), 20 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. And then subjected to heat treatment at 150 ° C. to obtain a hydrophobicity of 95.4% and a specific surface area of 120 m 2 / g.
(0.52 times the specific surface area before silicone oil treatment),
The same test as in Example 14 was performed except that the treated silicic acid fine powder having a carbon content of 8.5 wt% was used.

【０１５８】高温高湿下に放置した場合も画像濃度が
１．４以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.4 or more was obtained, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１５９】実施例２３ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
３００）１００部にジメチルジクロルシラン３５部で処
理を行った後（疎水化度８５．８％、比表面積：２１０
ｍ2 ／ｇ、炭素含有量：２．６ｗｔ％）、ジメチルシリ
コーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業
社製）５部を溶剤で希釈したものに混合した後、溶剤を
減圧下で揮発させた後、１５０℃で加熱処理を行って得
た、疎水化度８３．６％、比表面積１２５ｍ2 ／ｇ（シ
リコーンオイル処理前の比表面積の０．５９倍）、炭素
含有量７．１ｗｔ％の処理ケイ酸微粉体を用いた以外は
実施例１４と同様の試験を行った。 Example 23 As a treated silicic acid fine powder, silicic acid fine powder (Aerosil #
300 parts) was treated with 35 parts of dimethyldichlorosilane (hydrophobicity 85.8%, specific surface area: 210)
m 2 / g, carbon content: 2.6 wt%), dimethyl silicone oil (KF-96 100cs, after mixing Etsu Chemical Co., Ltd.) 5 parts to those diluted with a solvent, the solvent evaporated under reduced pressure And then subjected to heat treatment at 150 ° C. to obtain a hydrophobicity of 83.6%, a specific surface area of 125 m 2 / g (0.59 times the specific surface area before silicone oil treatment), and a carbon content of 7.1 wt%. The same test as in Example 14 was carried out except that the treated silicic acid fine powder of Example 1 was used.

【０１６０】高温高湿下に放置した場合も画像濃度が
１．３以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。また、各環境下で
の画出し試験でも良好な画像が得られ、回収された感光
体上の残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.3 or more was obtained, and the printing on the transparency film was also good. In addition, a good image was obtained in the image output test under each environment, and the amount of the residual toner on the collected photoconductor was small.

【０１６１】実施例２４ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にトリメチルクロルシラン２０部で処
理を行った後（疎水化度８４．１％、比表面積：１６０
ｍ2 ／ｇ、炭素含有量：２．５ｗｔ％）、ジメチルシリ
コーンオイル（ＫＦ−９６ １００ｃｓ，信越化学工業
社製）１０部を溶剤で希釈したものに混合した後、溶剤
を減圧下で揮発させた後、１８０℃で加熱処理を行って
得た、疎水化度８８．６％、比表面積９０ｍ2 ／ｇ（シ
リコーンオイル処理前の比表面積の０．５６倍）、炭素
含有量７．０ｗｔ％の処理ケイ酸微粉体を用いた以外は
実施例１４と同様の試験を行った。 Example 24 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 20 parts of trimethylchlorosilane (hydrophobicity 84.1%, specific surface area: 160
m 2 / g, carbon content: 2.5 wt%), 10 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent, and then the solvent was evaporated under reduced pressure. After that, heat treatment was performed at 180 ° C. to obtain a hydrophobicity of 88.6%, a specific surface area of 90 m 2 / g (0.56 times the specific surface area before silicone oil treatment), and a carbon content of 7.0 wt%. The same test as in Example 14 was carried out except that the treated silicic acid fine powder of Example 1 was used.

【０１６２】高温高湿下に放置した場合も画像濃度が
１．４以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.4 or more was obtained, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１６３】実施例２５ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００、親水性、比表面積：２００ｍ2 ／ｇ）に、ジメ
チルシリコーンオイル（ＫＦ−９６ １００ｃｓ，信越
化学工業社製）３５部を溶剤で希釈したものに混合した
後、溶剤を減圧下で揮発させた後、１５０℃で加熱処理
を行って得た、疎水化度８９．２％、比表面積８０ｍ2
／ｇ（シリコーンオイル処理前の比表面積の０．４０
倍）、炭素含有量８．０ｗｔ％の処理ケイ酸微粉体を用
いた以外は実施例１４と同様の試験を行った。 Example 25 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200, hydrophilic, specific surface area: 200 m 2 / g), mixed with 35 parts of dimethyl silicone oil (KF-96 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a solvent, and then volatilized the solvent under reduced pressure. And then subjected to heat treatment at 150 ° C. to obtain a hydrophobicity of 89.2% and a specific surface area of 80 m 2.
/ G (0.40 of specific surface area before silicone oil treatment)
The same test as in Example 14 was performed, except that treated silicic acid fine powder having a carbon content of 8.0 wt% was used.

【０１６４】低温低湿下で画像濃度が１．２と若干低か
ったものの、高温高湿下に放置した場合も画像濃度が
１．３以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。Although the image density was slightly low at 1.2 under low temperature and low humidity, a good image with an image density of 1.3 or more was obtained even when left under high temperature and high humidity, and printing on a transparency film was also possible. It was good.

【０１６５】実施例２６ 処理ケイ酸微粉体として、ケイ酸微粉体（アエロジル＃
２００）１００部にトリメチルクロルシラン２０部で処
理を行った後（疎水化度８４．１％、比表面積：１６０
ｍ2 ／ｇ、炭素含有量：７．４ｗｔ％）、α−メチルス
チレン変性シリコーンオイル（ＫＦ−４１０，信越化学
工業社製）１５部を溶剤で希釈したものに混合した後、
溶剤を減圧下で揮発させた後、１５０℃で加熱処理を行
って得た、比表面積８０ｍ2 ／ｇ（シリコーンオイル処
理前の比表面積の０．５０倍）の処理ケイ酸微粉体を用
いた以外は実施例１４と同様の試験を行った。 Example 26 As the treated silicic acid fine powder, silicic acid fine powder (Aerosil #
200) After treating 100 parts with 20 parts of trimethylchlorosilane (hydrophobicity 84.1%, specific surface area: 160
m 2 / g, carbon content: 7.4 wt%), alpha-methylstyrene-modified silicone oil (KF-410, were mixed by Shin-Etsu Chemical Co., Ltd.) 15 parts to those diluted with a solvent,
A treated silicic acid fine powder having a specific surface area of 80 m 2 / g (0.50 times the specific surface area before silicone oil treatment) obtained by volatilizing the solvent under reduced pressure and then heat-treating at 150 ° C. was used. The same test as in Example 14 was carried out except for the above.

【０１６６】高温高湿下に放置した場合も画像濃度が
１．４以上の良好な画像が得られ、トランスペアレンシ
ーフィルムへの印字も良好であった。各環境下での画出
し試験でも良好な画像が得られ、回収された感光体上の
残余のトナーも少量であった。Even when it was left under high temperature and high humidity, a good image having an image density of 1.4 or more was obtained, and the printing on the transparency film was also good. A good image was obtained in the image output test under each environment, and the amount of residual toner on the collected photoconductor was small.

【０１６７】実施例２７ 実施例１２の磁性現像剤を図４に示す接触帯電装置を有
する画像形成装置（キヤノン製レーザービームプリンタ
ーＬＢＰ−８ＩＩ改造機）を用い、直流電圧と交流電圧
（５００Ｈｚ、２０００ＶPP）を印加し１６枚（Ａ４）
／分のプリント速度で連続して反転現像方式でトナー画
像を形成する実写テストを常温常湿（２５℃、６０％Ｒ
Ｈ）、高温高湿（３２．５℃、８５％ＲＨ）及び低温低
湿（１５℃、１０％ＲＨ）で各々８０００枚行ないプリ
ントアウト画像を評価した。同時に帯電部材（ローラー
型）及び感光ドラム表面の様子を観察した。 Example 27 The magnetic developer of Example 12 was used in an image forming apparatus having a contact charging device shown in FIG. 4 (Canon laser beam printer LBP-8II remodeling machine), and DC voltage and AC voltage (500 Hz, 2000 V). 16 sheets (A4) by applying PP )
A real-time test of continuously forming a toner image with a reversal development method at a print speed of 1 minute / min was performed at room temperature and normal humidity (25 ° C, 60%
H), high temperature and high humidity (32.5 ° C., 85% RH) and low temperature and low humidity (15 ° C., 10% RH) were performed on 8,000 sheets each, and printout images were evaluated. At the same time, the states of the charging member (roller type) and the surface of the photosensitive drum were observed.

【０１６８】帯電ローラ２は、直径１２ｍｍを有し、芯
金は直径５ｍｍを有し、導電性ゴム層２ｂは約３．５ｍ
ｍの厚さを有し、メトキシメチル化ナイロンで形成され
た離型性被膜は厚さ２０μｍを有し、総圧１．２Ｋｇ
（線圧５５ｇ／ｃｍ）でＯＰＣ感光ドラムに圧接した。The charging roller 2 has a diameter of 12 mm, the core metal has a diameter of 5 mm, and the conductive rubber layer 2b has a diameter of about 3.5 m.
m has a thickness of 20 .mu.m and the total pressure is 1.2 kg.
It was pressed against the OPC photosensitive drum at a linear pressure of 55 g / cm.

【０１６９】結果としては、いずれの環境とも画像濃度
は１．３５以上と良好であり、又、続けて画出しを行な
った１２，０００枚後も感光体や帯電部材へのトナー融
着はまったく見られなかった。As a result, the image density was as good as 1.35 or more in any of the environments, and the toner was not fused to the photosensitive member or the charging member even after 12,000 sheets were continuously printed. I couldn't see it at all.

【０１７０】実施例２８ 実施例１の磁性トナー１００部に対し１．０部の実施例
１４で用いたジメチルジクロルシラン処理後ジメチルシ
リコーンオイルで処理したケイ酸微粉体をヘンシェルミ
キサーで外添し磁性現像剤を得た。 Example 28 To 100 parts of the magnetic toner of Example 1, 1.0 part of the silicic acid fine powder treated with dimethyl silicone oil after the treatment with dimethyldichlorosilane used in Example 14 was externally added with a Henschel mixer. A magnetic developer was obtained.

【０１７１】この磁性現像剤を実施例２７の画像形成装
置に投入し、実施例２７と同様に各環境で６０００枚の
プリントアウトを行ない、画像評価をした。続いて１０
０００枚まで画出しを行ない帯電部材及び感光ドラム表
面の様子を観察した。This magnetic developer was put into the image forming apparatus of Example 27, and 6000 sheets were printed out in each environment in the same manner as in Example 27, and image evaluation was performed. Then 10
Images were output up to 000 sheets and the states of the charging member and the surface of the photosensitive drum were observed.

【０１７２】結果を表３に示す。The results are shown in Table 3.

【０１７３】以下に評価基準を示す。The evaluation criteria are shown below.

【０１７４】感光ドラム、帯電部材への融着レベル： ○ …全く融着しない ○△…Ａ４ベタ黒中に１〜３点の融着 △ …Ａ４ベタ黒中に４〜１０点の融着 × …Ａ４ベタ黒中に１１点以上の融着 Level of fusion to the photosensitive drum and charging member: ○ : No fusion at all ○ Δ: Fusion of 1 to 3 points in A4 solid black Δ: Fusion of 4 to 10 points in A4 solid black × … A4 solid black fusion of 11 points or more

【０１７５】実施例２９ 処理ケイ酸微粉体として、実施例１５で用いたケイ酸微
粉体（アエロジル＃２００）１００部にジメチルジクロ
ルシラン２０部で処理を行った後（炭素含有量：１．１
ｗｔ％）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）１５部を溶剤で希釈した
ものに混合した後、溶剤を減圧下で揮発させた後、１８
０℃で加熱処理を行って得た、炭素含有量５．２ｗｔ％
（シリコーンオイル処理による炭素付着量：４．１ｗｔ
％）の処理ケイ酸微粉体を用いた以外は実施例２８と同
様に磁性現像剤を得た。 Example 29 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Example 15 was treated with 20 parts of dimethyldichlorosilane (carbon content: 1. 1
wt%), dimethyl silicone oil (KF-96,1
15 parts (00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with what was diluted with a solvent, and the solvent was evaporated under reduced pressure.
Carbon content of 5.2 wt% obtained by heat treatment at 0 ° C.
(Amount of carbon deposited by silicone oil treatment: 4.1 wt
%) Treated magnetic fine powder was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder was used.

【０１７６】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１７７】実施例３０ 処理ケイ酸微粉体として、実施例１６で用いた処理ケイ
酸微粉体を用いた以外は、実施例２８と同様に磁性現像
剤を得た。 Example 30 A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder used in Example 16 was used as the treated silicic acid fine powder.

【０１７８】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１７９】実施例３１ 処理ケイ酸微粉体として、実施例１７で用いたケイ酸微
粉体（アエロジル＃２００）１００部にジメチルジクロ
ルシラン２５部で処理を行った後（炭素含有量：１．５
ｗｔ％）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）５部を溶剤で希釈したも
のに混合した後、溶剤を減圧下で揮発させた後、１８０
℃で加熱処理を行って得た、炭素含有量４．６ｗｔ％
（シリコーンオイル処理による炭素付着量：３．１ｗｔ
％）の処理ケイ酸微粉体を用いた以外は実施例２８と同
様に磁性現像剤を得た。 Example 31 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Example 17 was treated with 25 parts of dimethyldichlorosilane (carbon content: 1. 5
wt%), dimethyl silicone oil (KF-96,1
(00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts were diluted with a solvent, and then the solvent was evaporated under reduced pressure, and then 180
Carbon content 4.6% by weight obtained by heat treatment at ℃
(Amount of carbon deposited by silicone oil treatment: 3.1 wt
%) Treated magnetic fine powder was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder was used.

【０１８０】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１８１】実施例３２ 処理ケイ酸微粉体として、実施例１８で用いたケイ酸微
粉体（アエロジル＃３００）１００部にトリメチルクロ
ルシラン３０部で処理を行った後（炭素含有量：３．５
ｗｔ％）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）１０部を溶剤で希釈した
ものに混合した後、溶剤を減圧下で揮発させた後、１５
０℃で加熱処理を行って得た、炭素含有量７．１ｗｔ％
（シリコーンオイル処理による炭素付着量：３．６ｗｔ
％）の処理ケイ酸微粉体を用いた以外は実施例２８と同
様磁性現像剤を得た。 Example 32 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 300) used in Example 18 was treated with 30 parts of trimethylchlorosilane (carbon content: 3.5).
wt%), dimethyl silicone oil (KF-96,1
(00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts were diluted with a solvent, and then the solvent was evaporated under reduced pressure.
Carbon content 7.1 wt% obtained by heat treatment at 0 ° C
(Amount of carbon deposited by silicone oil treatment: 3.6 wt
%) Treated magnetic fine powder was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder was used.

【０１８２】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１８３】実施例３３ 処理ケイ酸微粉体として、実施例１９で用いたケイ酸微
粉体アエロジル＃２００に、ジメチルシリコーンオイル
（ＫＦ−９６，１００ｃｓ，信越化学工業社製）３０部
を溶剤で希釈したものに混合した後、溶剤を減圧下で揮
発させた後、２００℃で加熱処理を行って得た、炭素含
有量７．９ｗｔ％（シリコーンオイル処理による炭素付
着量：７．９ｗｔ％）の処理ケイ酸微粉体を用いた以外
は実施例２８と同様に磁性現像剤を得た。 Example 33 As the treated silicic acid fine powder, 30 parts of dimethyl silicone oil (KF-96, 100 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with a solvent to the silicic acid fine powder Aerosil # 200 used in Example 19. Of the carbon content of 7.9 wt% (carbon deposition amount by silicone oil treatment: 7.9 wt%) obtained by heating the mixture at 200 ° C. after volatilizing the solvent under reduced pressure. A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder was used.

【０１８４】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１８５】実施例３４ 処理ケイ酸微粉体として、実施例２０で用いたケイ酸微
粉体（アエロジル＃３００）１００部にジメチルジクロ
ルシラン３０部で処理を行った後（炭素含有量：２．２
ｗｔ％）、α−メチルスチレン変性シリコーンオイル
（ＫＦ−４１０，信越化学工業社製）１５部を溶剤で希
釈したものに混合した後、溶剤を減圧下で揮発させた
後、１５０℃で加熱処理を行って得た、炭素含有量６．
１ｗｔ％（シリコーンオイル処理による炭素付着量：
３．９ｗｔ％）の処理ケイ酸微粉体を用いた以外は実施
例２８と同様に磁性現像剤を得た。 Example 34 As a treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 300) used in Example 20 was treated with 30 parts of dimethyldichlorosilane (carbon content: 2. Two
wt%), and 15 parts of α-methylstyrene-modified silicone oil (KF-410, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent diluted, and the solvent was evaporated under reduced pressure, and then heat treatment was performed at 150 ° C. The carbon content obtained by performing.
1 wt% (Amount of carbon deposited by silicone oil treatment:
A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder (3.9 wt%) was used.

【０１８６】これを図５に示す接触帯電装置を有する画
像形成装置（キヤノン製レーザービームプリンターＬＢ
Ｐ−８ＩＩ改造機）を用い、実施例２８と同様に評価し
た。表３に評価結果を示す。An image forming apparatus (a laser beam printer LB manufactured by Canon Inc.) having a contact charging device shown in FIG.
P-8II modified machine) and evaluated in the same manner as in Example 28. Table 3 shows the evaluation results.

【０１８７】実施例３５ 処理ケイ酸微粉体として、実施例２１で用いたケイ酸微
粉体（アエロジル＃２００）１００部にトリメチルクロ
ルシラン２０部で処理を行った後（炭素含有量：２．５
ｗｔ％）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）１５部を溶剤で希釈し噴
霧による処理を行い乾燥した後、１５０℃で加熱処理を
行って得た、炭素含有量７．５ｗｔ％（シリコーンオイ
ル処理による炭素付着量：５．０ｗｔ％）の処理ケイ酸
微粉体を用いた以外は実施例２８と同様の試験を行なっ
た。 Example 35 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Example 21 was treated with 20 parts of trimethylchlorosilane (carbon content: 2.5).
wt%), dimethyl silicone oil (KF-96,1
7.5 parts by weight (carbon deposition amount by silicone oil treatment) obtained by diluting 15 parts of a solvent (00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) with a solvent, spraying and drying, and then heat-treating at 150 ° C. The same test as in Example 28 was performed, except that the treated silicic acid fine powder of (5.0 wt%) was used.

【０１８８】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１８９】比較例５ 微粉体として、未処理のケイ酸微粉体（アエロジル＃３
００）を用いた以外は実施例２８と同様に磁性現像剤を
得た。 Comparative Example 5 As the fine powder, untreated fine silica powder (Aerosil # 3) was used.
A magnetic developer was obtained in the same manner as in Example 28 except that (00) was used.

【０１９０】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１９１】比較例６ 処理ケイ酸微粉体として、比較例１で用いたケイ酸微粉
体（アエロジル＃３００）１００部にジメチルジクロル
シラン３０部で処理を行ったものを用いた以外は実施例
２８と同様に磁性現像剤を得た。 Comparative Example 6 Example except that 100 parts of the silicic acid fine powder (Aerosil # 300) used in Comparative Example 1 was treated with 30 parts of dimethyldichlorosilane as the treated silicic acid fine powder. A magnetic developer was obtained in the same manner as in No. 28.

【０１９２】これを実施例２８と同様に評価した。表３
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 3
The evaluation results are shown in.

【０１９３】[0193]

【表３】 [Table 3]

【０１９４】実施例３６ 実施例２２で用いた処理ケイ酸微粉体を用い、実施例２
８と同様に磁性現像剤を得た。 Example 36 Using the treated silicic acid fine powder used in Example 22, Example 2
A magnetic developer was obtained in the same manner as in No. 8.

【０１９５】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０１９６】実施例３７ 処理ケイ酸微粉体として、実施例２３で用いたケイ酸微
粉体（アエロジル＃３００）１００部にジメチルジクロ
ルシラン３５部で処理を行った後（比表面積：２１０ｍ
2 ／ｇ）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）５部を溶剤で希釈したも
のに混合した後、溶剤を減圧下で揮発させた後、１５０
℃で加熱処理を行って得た、比表面積１２５ｍ2 ／ｇ
（シリコーンオイル処理前の比表面積の０．５９倍）の
処理ケイ酸微粉体を用いた以外は実施例２８と同様に磁
性現像剤を得た。 Example 37 As a treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 300) used in Example 23 was treated with 35 parts of dimethyldichlorosilane (specific surface area: 210 m).
2 / g), dimethyl silicone oil (KF-96, 1
(00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts were diluted with a solvent, and then the solvent was evaporated under reduced pressure to obtain 150
Specific surface area of 125 m 2 / g obtained by heat treatment at ℃
A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder (0.59 times the specific surface area before silicone oil treatment) was used.

【０１９７】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０１９８】実施例３８ 処理ケイ酸微粉体として、実施例１４で用いたケイ酸微
粉体（アエロジル＃２００）１００部にトリメチルクロ
ルシラン２０部で処理を行った後（比表面積：１６０ｍ
2 ／ｇ）、ジメチルシリコーンオイル（ＫＦ−９６，１
００ｃｓ，信越化学工業社製）１０部を溶剤で希釈した
ものに混合した後、溶剤を減圧下で揮発させた後、１８
０℃で加熱処理を行って得た、比表面積９０ｍ2 ／ｇ
（シリコーンオイル処理前の比表面積の０．５６倍）の
処理ケイ酸微粉体を用いた以外は実施例２８と同様に磁
性現像剤を得た。 Example 38 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Example 14 was treated with 20 parts of trimethylchlorosilane (specific surface area: 160 m).
2 / g), dimethyl silicone oil (KF-96, 1
(00 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 10 parts diluted with a solvent, and the solvent was evaporated under reduced pressure.
Specific surface area of 90 m 2 / g obtained by heat treatment at 0 ° C.
A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder (0.56 times the specific surface area before silicone oil treatment) was used.

【０１９９】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０２００】実施例３９ 処理ケイ酸微粉体として、実施例１５で用いたケイ酸微
粉体（アエロジル＃２００，比表面積：２００ｍ2 ／
ｇ）に、ジメチルシリコーンオイル（ＫＦ−９６，１０
０ｃｓ，信越化学工業社製）３５部を溶剤で希釈したも
のに混合した後、溶剤を減圧下で揮発させた後、１５０
℃で加熱処理を行って得た、比表面積８０ｍ2 ／ｇ（シ
リコーンオイル処理前の比表面積の０．４０倍）の処理
ケイ酸微粉体を用いた以外は実施例２８と同様に磁性現
像剤を得た。 Example 39 As the treated silicic acid fine powder, the silicic acid fine powder used in Example 15 (Aerosil # 200, specific surface area: 200 m 2 /
g), dimethyl silicone oil (KF-96,10
0 cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and mixed with 35 parts diluted with a solvent, and then the solvent was evaporated under reduced pressure, and then 150
A magnetic developer was used in the same manner as in Example 28 except that treated silicic acid fine powder having a specific surface area of 80 m 2 / g (0.40 times the specific surface area before silicone oil treatment), which was obtained by heat treatment at 0 ° C., was used. Got

【０２０１】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０２０２】実施例４０ 処理ケイ酸微粉体として、実施例２６で用いたケイ酸微
粉体（アエロジル＃２００）１００部にトリメチルクロ
ルシラン２０部で処理を行った後（比表面積：１６０ｍ
2 ／ｇ）、α−メチルスチレン変性シリコーンオイル
（ＫＦ−４１０，信越化学工業社製）１５部を溶剤で希
釈したものに混合した後、溶剤を減圧下で揮発させた
後、１５０℃で加熱処理を行って得た、比表面積８０ｍ
2 ／ｇ（シリコーンオイル処理前の比表面積の０．５０
倍）の処理ケイ酸微粉体を用いた以外は実施例２８と同
様に磁性現像剤を得た。 Example 40 As the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Example 26 was treated with 20 parts of trimethylchlorosilane (specific surface area: 160 m).
2 / g) and 15 parts of α-methylstyrene-modified silicone oil (KF-410, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a solvent diluted, and the solvent was evaporated under reduced pressure and then heated at 150 ° C. 80m specific surface area obtained by treatment
2 / g (0.50 of specific surface area before silicone oil treatment)
A magnetic developer was obtained in the same manner as in Example 28 except that the treated silicic acid fine powder was used.

【０２０３】これを図５に示す接触帯電装置を有する画
像形成装置（キヤノン製レーザービームプリンターＬＢ
Ｐ−８ＩＩ改造機）を用い、実施例２８と同様に評価し
た。表４に評価結果を示す。An image forming apparatus (a laser beam printer LB manufactured by Canon Inc.) having a contact charging device shown in FIG.
P-8II modified machine) and evaluated in the same manner as in Example 28. Table 4 shows the evaluation results.

【０２０４】比較例７ 微粉体として、未処理のケイ酸微粉体（アエロジル＃２
００）を用いた以外は実施例２８と同様に磁性現像剤を
得た。 Comparative Example 7 As a fine powder, untreated silicic acid fine powder (Aerosil # 2) was used.
A magnetic developer was obtained in the same manner as in Example 28 except that (00) was used.

【０２０５】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０２０６】比較例８ 処理ケイ酸微粉体として、比較例２で用いたケイ酸微粉
体（アエロジル＃２００）１００部にジメチルジクロル
シラン２０部で処理を行ったものを用いた以外は実施例
２８と同様に磁性現像剤を得た。 Comparative Example 8 Example except that as the treated silicic acid fine powder, 100 parts of the silicic acid fine powder (Aerosil # 200) used in Comparative Example 2 was treated with 20 parts of dimethyldichlorosilane. A magnetic developer was obtained in the same manner as in No. 28.

【０２０７】これを実施例２８と同様に評価した。表４
に評価結果を示す。This was evaluated in the same manner as in Example 28. Table 4
The evaluation results are shown in.

【０２０８】[0208]

【表４】 [Table 4]

【０２０９】実施例４１ 実施例１の現像剤を使用し、図９に示す画像形成装置に
適用して画出しをおこなった所、良好な結果が得られ
た。 Example 41 When the developer of Example 1 was used and the image was formed by applying it to the image forming apparatus shown in FIG. 9, good results were obtained.

【０２１０】[0210]

【発明の効果】本発明によれば、高温高湿、低温低湿等
の環境下においても高濃度であり、高品質な画像を与え
る静電荷像現像用現像剤を提供できる。According to the present invention, it is possible to provide a developer for developing an electrostatic charge image, which has a high density even in an environment of high temperature and high humidity, low temperature and low humidity, and gives a high quality image.

【０２１１】特に、微小粒径化したトナーを均一に強く
帯電し、高画質で現像性に優れた現像剤を提供できる。In particular, it is possible to uniformly and strongly charge a toner having a fine particle diameter, and to provide a developer having high image quality and excellent developability.

【０２１２】本発明によれば高濃度で耐久安定性に優
れ、トランスペアレンシーフィルムを用いた際にも転写
中抜けを生じない良好な画像が安定に得られる。また、
感光体ドラム表面を傷つけることが少なく、感光体ドラ
ムの耐久性も向上する。According to the present invention, it is possible to stably obtain a good image having a high density and excellent durability and stability, even when a transparency film is used, without causing voids in the transfer. Also,
The surface of the photosensitive drum is less damaged, and the durability of the photosensitive drum is improved.

【０２１３】さらに、本発明によれば、現像剤として特
定の微粉体を含有する磁性現像剤を用いることにより、
現像剤に潤滑性を持たせ、帯電部材が被帯電体に接触さ
せて外部より電圧を印加し帯電を行う帯電工程と上記被
帯電体より現像剤を除去するクリーニング工程を有する
画像形成方法において、感光体表面へのトナー融着を防
ぎ、トナー汚染の生じない高画質の画像を得ることがで
きる。Furthermore, according to the present invention, by using a magnetic developer containing a specific fine powder as the developer,
In an image forming method, which includes a charging step in which a developer has lubricity, a charging member is brought into contact with a member to be charged and a voltage is applied from the outside to charge the member, and a cleaning step in which the developer is removed from the member to be charged, It is possible to prevent fusion of the toner on the surface of the photoconductor and obtain a high quality image without toner contamination.

【図面の簡単な説明】[Brief description of drawings]

【図１】転写中抜け状態を説明するためにトナー像を模
式的に示した図である。FIG. 1 is a diagram schematically showing a toner image for explaining a missing state during transfer.

【図２】本発明の画像形成方法に用いられる転写装置の
一例を示す概略構成図である。FIG. 2 is a schematic configuration diagram showing an example of a transfer device used in the image forming method of the present invention.

【図３】本発明の画像形成方法に用いられる転写装置の
他の例を示す概略構成図である。FIG. 3 is a schematic configuration diagram showing another example of a transfer device used in the image forming method of the present invention.

【図４】本発明の画像形成方法に用いられる接触帯電装
置の一例を示す概略構成図である。FIG. 4 is a schematic configuration diagram showing an example of a contact charging device used in the image forming method of the present invention.

【図５】本発明の画像形成方法に用いられる接触帯電装
置の他の例を示す概略構成図である。FIG. 5 is a schematic configuration diagram showing another example of the contact charging device used in the image forming method of the present invention.

【図６】本発明の画像形成方法に用いられる他の接触帯
電装置の他の例を示す概略構成図である。FIG. 6 is a schematic configuration diagram showing another example of another contact charging device used in the image forming method of the present invention.

【図７】本発明の画像形成方法を実施するための画像形
成装置の概略図を示す。FIG. 7 is a schematic view of an image forming apparatus for carrying out the image forming method of the present invention.

【図８】本発明の画像形成方法を実施するための他の画
像形成装置の概略図を示す。FIG. 8 is a schematic view of another image forming apparatus for carrying out the image forming method of the present invention.

【図９】本発明の画像形成方法を実施するための他の画
像形成装置の概略図を示す。FIG. 9 is a schematic view of another image forming apparatus for carrying out the image forming method of the present invention.

【符号の説明】[Explanation of symbols]

１ 潜像担持体（感光体） １ａ 感光体ドラム基体 １ｂ 有機光導電体（ＯＰＣ） ２ 転写ローラー ２ａ 芯金 ２ｂ 導電性弾性層 ３ 定電圧電源 ４、５ 転写材搬送ガイド ６ 転写ベルト ７ 導電性ローラー ４２、５３ 帯電部材 ４２ａ、５３ａ 芯金（金属支持部材） ４２ｂ、５３ｂ 導電性ゴム層 ４２ｃ、５３ｃ 表面層 Ｅ 電源 1 Latent Image Carrier (Photoreceptor) 1a Photoreceptor Drum Base 1b Organic Photoconductor (OPC) 2 Transfer Roller 2a Core Metal 2b Conductive Elastic Layer 3 Constant Voltage Power Supply 4, 5 Transfer Material Conveying Guide 6 Transfer Belt 7 Conductivity Rollers 42, 53 Charging members 42a, 53a Cores (metal support members) 42b, 53b Conductive rubber layers 42c, 53c Surface layer E Power source

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】 トナー及びシリコーンオイルまたはシリ
コーンワニスで処理された処理微粉体を含有している静
電荷像現像用現像剤において、シリコーンオイルまたは
シリコーンワニスで処理された処理微粉体は、シリコー
ンオイルまたはシリコーンワニスで処理される前の微粉
体の比表面積の０．４〜０．８倍のＢＥＴ比表面積を有
することを特徴とする静電荷像現像用現像剤。1. A developer for developing an electrostatic charge image containing a toner and treated fine powder treated with silicone oil or silicone varnish, wherein the treated fine powder treated with silicone oil or silicone varnish is silicone oil or A developer for developing an electrostatic charge image, which has a BET specific surface area of 0.4 to 0.8 times the specific surface area of fine powder before being treated with a silicone varnish. 【請求項２】 処理微粉体は、シリコーンオイルまたは
シリコーンワニスの付着量が炭素の付着量で３〜８重量
％である請求項１の静電荷像現像用現像剤。2. The electrostatic charge image developing developer according to claim 1, wherein the treated fine powder has a silicone oil or silicone varnish adhered in an amount of 3 to 8% by weight in terms of carbon adhering amount. 【請求項３】 処理微粉体は、シリコーンオイルで処理
されたケイ酸微粉体である請求項１または２の静電荷像
現像用現像剤。3. The developer for developing an electrostatic charge image according to claim 1, wherein the treated fine powder is a silicic acid fine powder treated with silicone oil. 【請求項４】 処理微粉体は、ケイ酸微粉体をジメチル
ジクロロシランで処理し、次いでヘキサメチルジシラザ
ンで処理し、次いでジメチルシリコーンオイルで処理す
ることにより調製された疎水性ケイ酸微粉体である請求
項３の静電荷像現像用現像剤。4. The treated fine powder is a hydrophobic fine silicic acid powder prepared by treating fine silicic acid powder with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. The developer for developing an electrostatic charge image according to claim 3. 【請求項５】 静電荷像担持体を帯電し、 帯電された静電荷像担持体に静電荷像を形成し静電荷像
を現像剤で現像してトナー像を形成しトナー像を、転写
材を介して該静電荷像担持体と線圧３ｇ／ｃｍ以上で当
接されている転写手段で転写材へ転写する画像形成方法
において、 該現像剤は、トナー及びシリコーンオイルまたはシリコ
ーンワニスで処理された処理微粉体を含有しており、シ
リコーンオイルまたはシリコーンワニスで処理された該
処理微粉体は、シリコーンオイルまたはシリコーンワニ
スで処理される前の微粉体の比表面積の０．４〜０．８
倍のＢＥＴ比表面積を有することを特徴とする画像形成
方法。5. An electrostatic charge image bearing member is charged, an electrostatic charge image is formed on the charged electrostatic charge image bearing member, and the electrostatic charge image is developed with a developer to form a toner image. In the image forming method of transferring to a transfer material by a transfer means that is in contact with the electrostatic image carrier at a linear pressure of 3 g / cm 2 or more via a toner, the developer is treated with toner and silicone oil or silicone varnish. The treated fine powder treated with silicone oil or silicone varnish has a specific surface area of 0.4 to 0.8 of the fine powder before treated with silicone oil or silicone varnish.
An image forming method having a double BET specific surface area. 【請求項６】 処理微粉体は、シリコーンオイルまたは
シリコーンワニスの付着量が炭素の付着量で３〜８重量
％である請求項５の画像形成方法。6. The image forming method according to claim 5, wherein the treated fine powder has a deposition amount of silicone oil or silicone varnish of 3 to 8% by weight based on the deposition amount of carbon. 【請求項７】 処理微粉体は、シリコーンオイルで処理
されたケイ酸微粉体である請求項５または６の画像形成
方法。7. The image forming method according to claim 5, wherein the treated fine powder is a silicic acid fine powder treated with silicone oil. 【請求項８】 処理微粉体は、ケイ酸微粉体をジメチル
ジクロロシランで処理し、次いでヘキサメチルジシラザ
ンで処理し、次いでジメチルシリコーンオイルで処理す
ることにより調製された疎水性ケイ酸微粉体である請求
項７の画像形成方法。8. The treated fine powder is a hydrophobic silicic acid fine powder prepared by treating fine silicic acid powder with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. The image forming method according to claim 7.
JP5134665A 1992-06-04 1993-06-04 Electrostatic latent image developing developer and image forming method Expired - Fee Related JP2974545B2 (en)

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JP16824592 1992-06-04
JP4-168245 1992-06-04
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09288400A (en) * 1996-04-23 1997-11-04 Canon Inc Contact electrifying member and contact electrifying device
JP2001194825A (en) * 1999-10-27 2001-07-19 Shin Etsu Chem Co Ltd Electrostatic charge image developing toner external additive
JP2002258522A (en) * 2001-03-01 2002-09-11 Ricoh Co Ltd Image formed method, toner used for the same and photoreceptor
JP2003149855A (en) * 2001-11-14 2003-05-21 Denki Kagaku Kogyo Kk Hydrophobic silica fine powder, method for manufacturing the same and its use
US8168360B2 (en) 2007-07-20 2012-05-01 Sharp Kabushiki Kaisha External additive, toner, and image forming apparatus
JP2017141378A (en) * 2016-02-10 2017-08-17 富士ゼロックス株式会社 Resin particle composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09288400A (en) * 1996-04-23 1997-11-04 Canon Inc Contact electrifying member and contact electrifying device
JP2001194825A (en) * 1999-10-27 2001-07-19 Shin Etsu Chem Co Ltd Electrostatic charge image developing toner external additive
JP2002258522A (en) * 2001-03-01 2002-09-11 Ricoh Co Ltd Image formed method, toner used for the same and photoreceptor
JP2003149855A (en) * 2001-11-14 2003-05-21 Denki Kagaku Kogyo Kk Hydrophobic silica fine powder, method for manufacturing the same and its use
US8168360B2 (en) 2007-07-20 2012-05-01 Sharp Kabushiki Kaisha External additive, toner, and image forming apparatus
JP2017141378A (en) * 2016-02-10 2017-08-17 富士ゼロックス株式会社 Resin particle composition

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