JPH08292599A - Toner for electrostatic charge development and its production - Google Patents

Toner for electrostatic charge development and its production

Info

Publication number
JPH08292599A
JPH08292599A JP12315295A JP12315295A JPH08292599A JP H08292599 A JPH08292599 A JP H08292599A JP 12315295 A JP12315295 A JP 12315295A JP 12315295 A JP12315295 A JP 12315295A JP H08292599 A JPH08292599 A JP H08292599A
Authority
JP
Japan
Prior art keywords
toner
fine particles
colored resin
particles
resin particles
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.)
Pending
Application number
JP12315295A
Other languages
Japanese (ja)
Inventor
Kenkichi Muto
憲吉 武藤
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.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Priority to JP12315295A priority Critical patent/JPH08292599A/en
Publication of JPH08292599A publication Critical patent/JPH08292599A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE: To obtain a toner having satisfactory releasability, flowability and transferability and capable of stably forming an image having high image quality without causing a change with the lapse of time or image defects. CONSTITUTION: Fine particles of a releasing agent and inorg. fine particles are fixed on the surfaces of colored resin particles consisting essentially of a colorant and a resin and coating films of a silane coupling agent are formed on the outsides of the resin particles, and then the result is treated with the coupling agent to obtain the object toner. At least the fine particles of the releasing agent are preferably fixed by being embedded in the surfaces of the resin particles.

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、静電印刷
法、静電記録法などに用いられる静電荷現像用トナー及
びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge developing toner used in electrophotography, electrostatic printing, electrostatic recording and the like, and a method for producing the same.

【０００２】[0002]

【従来の技術】一般に、電子写真法或いは静電印刷法等
は、静電潜像担持体上に種々の方法によって形成された
静電潜像を現像剤によって現像して顕像とし、その顕像
を、必要に応じて紙等の被複写材に転写し、加熱、圧力
等によって定着して複写物を得る方法である。2. Description of the Related Art Generally, in an electrophotographic method or an electrostatic printing method, an electrostatic latent image formed by various methods on an electrostatic latent image carrier is developed with a developer to obtain a visible image. This is a method in which an image is transferred onto a material to be copied such as paper, if necessary, and fixed by heating, pressure or the like to obtain a copy.

【０００３】静電潜像を現像する現像剤としては乾式現
像剤が多く利用されており、乾式現像剤においては、結
着樹脂中に染顔料等の着色剤、更に必要により離型剤、
帯電制御剤などを分散したトナーが用いられる。A dry developer is often used as a developer for developing an electrostatic latent image. In the dry developer, a coloring agent such as a dye or pigment is contained in a binder resin, and if necessary, a release agent,
A toner in which a charge control agent or the like is dispersed is used.

【０００４】このトナーを用いて静電潜像を現像する方
法としては、（１）トナーとブレード、ローラーなどの
帯電部材とを接触、摩擦させてトナーに帯電させ、帯電
したトナーの薄層をローラー等の表面に形成させ、その
トナーの薄層を静電潜像に近接又は接触させることによ
り静電潜像を現像する一成分現像法、（２）トナーと磁
性粉キャリアとを混合、摩擦させてトナーに帯電させ、
磁気ブラシ方式により帯電したトナーを静電潜像と接触
させ静電潜像を現像する二成分現像法、などがある。ま
た、トナー像を定着する方式としては、加熱ローラーに
よる加熱圧着方式が一般的であり、この方法は、熱効率
がよく高速定着が可能であるが、加熱ローラー表面と溶
融状態のトナー像とが加圧下で接触するため、トナー像
の一部が加熱ローラー表面に付着し、付着したトナーが
被複写材に再転写されて複写画像を汚染する所謂オフセ
ット現象を発生せしめることがある。この現象を防止す
る目的で加熱ローラー表面をトナーに対する離型性に優
れたシリコンゴムやフッ素樹脂で形成し、さらにその表
面にシリコーンオイル等の離型性液体を供給する方法が
行われている。この方法はトナーのオフセット現象を防
止する点では極めて有効であるが、オフセット防止用液
体が、加熱されて蒸発し、不快臭を与えることや、また
オフセット防止液体を供給するための装置が必要となる
等の問題がある。As a method of developing an electrostatic latent image using this toner, (1) the toner and a charging member such as a blade or a roller are contacted and rubbed to charge the toner, and a thin layer of the charged toner is formed. A one-component developing method of developing an electrostatic latent image by forming it on the surface of a roller or the like and bringing a thin layer of the toner close to or in contact with the electrostatic latent image, (2) mixing toner and magnetic powder carrier, and rubbing To charge the toner,
There is a two-component developing method in which toner charged by a magnetic brush method is brought into contact with an electrostatic latent image to develop the electrostatic latent image. In addition, as a method for fixing the toner image, a thermocompression bonding method using a heating roller is generally used. Although this method has high thermal efficiency and enables high-speed fixing, the heating roller surface and the molten toner image are added together. Since they come into contact with each other under pressure, a part of the toner image may adhere to the surface of the heating roller, and the adhered toner may be retransferred to the material to be copied to cause a so-called offset phenomenon that contaminates the copied image. For the purpose of preventing this phenomenon, a method is used in which the surface of the heating roller is formed of silicone rubber or fluororesin having excellent releasability for toner, and a releasable liquid such as silicone oil is supplied to the surface. This method is extremely effective in preventing the offset phenomenon of the toner, but the offset prevention liquid is heated and vaporized to give an unpleasant odor, and a device for supplying the offset prevention liquid is required. There is a problem such as becoming.

【０００５】このような問題を解決する為に、トナーに
離型性のある樹脂等の離型剤を含有させる方法（特公昭
５２−３３０４号公報）があるが、この内添方法では離
型剤をトナー中に比較的多量に含有させなければ十分な
効果が得られず、さらに、結着樹脂と離型剤の相溶性の
悪さから、均一に混合、分散し難い等の欠点がある。In order to solve such a problem, there is a method of adding a release agent such as resin having releasability to the toner (Japanese Patent Publication No. 52-3304). A sufficient effect cannot be obtained unless the agent is contained in a relatively large amount in the toner, and further, it is difficult to uniformly mix and disperse due to poor compatibility of the binder resin and the release agent.

【０００６】また、特開昭６３−１１９５５号公報、特
開昭６３−３０８６１号公報、特開昭６３−６１２６５
号公報、特開昭６３−２４４０５３号公報等には、トナ
ー外面に低融点ワックス、ポリオレフィン等の離型剤を
用いた離型剤層を設けたトナー及びその製造方法が開示
されている。しかし、このトナーは表面が低分子量の離
型剤で覆われているため、トナーの流動性が悪化して現
像部でのトナーの供給が円滑に行えなかったり、静電潜
像を現像して形成された静電潜像担持体上のトナー画像
の被複写材への転写が円滑に行えないという欠点があ
る。Further, JP-A-63-11955, JP-A-63-30861, and JP-A-63-61265.
JP-A No. 63-244053 and the like disclose a toner in which a release agent layer using a release agent such as low melting point wax and polyolefin is provided on the outer surface of the toner, and a method for producing the toner. However, since the surface of this toner is covered with a release agent having a low molecular weight, the fluidity of the toner is deteriorated and the toner cannot be smoothly supplied in the developing section, or the electrostatic latent image is not developed. There is a drawback in that the toner image formed on the electrostatic latent image carrier cannot be smoothly transferred to the copy material.

【０００７】特開昭６３−３００２４５号公報には、水
系の離型剤ワックスエマルジョンにトナーを混合し離型
剤微粒子を固着させたトナーが開示されているが、この
トナーも上記と同様に流動性、転写性に難点があり、ま
た離型剤微粒子の脱離が起り易く離型性が失われるばか
りでなく、脱離した離型剤微粒子が静電潜像担持体であ
る電子写真感光体、或いは現像剤中のキャリアなどに付
着し、それらの性能を劣化させるという欠点がある。ま
た、これら離型剤を表面に固着させたトナーに充分な流
動性や転写性を与えるために、無機微粉体などの流動化
剤を多量に添加することが必要となるが、この場合に
は、流動化剤が電子写真感光体等に付着することによる
スジ状の画像抜け等が発生するという難点がある。Japanese Patent Laid-Open No. 63-300245 discloses a toner in which a toner is mixed with a water-based release agent wax emulsion and fine particles of the release agent are fixed, and this toner also flows in the same manner as above. Of electrophotographic photosensitive member in which the releasing agent fine particles are not only the electrostatic latent image carrier but also the releasing agent fine particles are easily detached and the releasing property is lost. Alternatively, it has a drawback that it adheres to a carrier or the like in the developer and deteriorates their performance. Further, in order to give sufficient fluidity and transferability to the toner having these release agents adhered to the surface, it is necessary to add a large amount of fluidizing agent such as inorganic fine powder. In this case, However, there is a problem in that streak-shaped image loss occurs due to the fluidizing agent adhering to the electrophotographic photosensitive member or the like.

【０００８】特開平１−１８５６６号公報、特開平１−
２５７８５３号公報、特開平３−１２５１５６号公報等
には離型剤を含有する樹脂微粒子を作りこれをトナー表
面に固着させたトナーが開示されているが、離型剤が樹
脂で被覆されているのでトナーの流動性、転写性は改良
されるものの、離型剤を含有する樹脂微粒子を製造する
工程が繁雑であり、また離型剤が樹脂で被覆されている
ため充分な離型性が得られないという欠点がある。ま
た、特開平２−２６４２６６号公報には樹脂微粒子と離
型剤微粒子の混合物を機械的衝撃力によりトナー表面に
固着する方法が開示されているが、この方法では機械的
衝撃力により離型剤微粒子がトナー表面に圧延されて固
着しておりトナーの流動性や転写性が充分に改良されな
いという不具合がある。Japanese Unexamined Patent Publication Nos. 1-18566 and 1-
No. 2,578,531 and Japanese Patent Laid-Open No. 3-125156 disclose a toner in which fine resin particles containing a release agent are prepared and fixed on the toner surface. The release agent is coated with a resin. Therefore, although the fluidity and transferability of the toner are improved, the process of producing resin fine particles containing a releasing agent is complicated, and sufficient releasing ability is obtained because the releasing agent is coated with resin. There is a drawback that you cannot do it. Further, Japanese Patent Application Laid-Open No. 2-264266 discloses a method of fixing a mixture of resin fine particles and release agent fine particles on the toner surface by mechanical impact force. In this method, the release agent is mechanically impacted. Since the fine particles are rolled and adhered to the toner surface, there is a problem that the fluidity and transferability of the toner are not sufficiently improved.

【０００９】特開平４−１８２６６１号公報、特開平４
−１８２６６６号公報には樹脂微粒子と離型剤微粒子を
トナー表面に付着させ、樹脂微粒子を溶解する溶剤で処
理して離型剤を含む被覆層をトナー表面に形成する方法
が開示されているが、離型剤が樹脂により被覆されてお
り、トナーの流動性や転写性は改良されるものの、充分
な離型性は得られず、またこの方法は処理の工程が繁雑
であるという欠点がある。Japanese Unexamined Patent Publication Nos. 4-182661 and 4
Japanese Patent Laid-Open No. 182666 discloses a method in which resin fine particles and release agent fine particles are adhered to the toner surface and treated with a solvent that dissolves the resin fine particles to form a coating layer containing the release agent on the toner surface. Since the release agent is coated with the resin, the fluidity and transferability of the toner are improved, but sufficient release property is not obtained, and this method has a drawback that the processing steps are complicated. .

【００１０】更に、トナーをシランカップリング剤によ
り処理する方法としては、特開昭５０−６２６３７号公
報にシランカップリング剤（特にクロロシラン）蒸気で
処理する方法が開示されているが、トナーはシランカッ
プリング剤との反応性に乏しくトナーに離型性を持たせ
るに必要な皮膜を得るには煩雑な操作を繰り返さねばな
らないという難点がある。また特開昭５９−１５２４６
５号公報、特開昭５９−１５２４５２号公報には懸濁重
合時に無機微粒子の付着したトナーをカップリング剤で
処理する方法が開示されているが、この方法ではトナー
の耐湿性は改良されるがトナーに離型性を持たせること
は困難である。Further, as a method of treating a toner with a silane coupling agent, Japanese Patent Application Laid-Open No. 506262/1975 discloses a method of treating with a silane coupling agent (particularly chlorosilane) vapor. There is a drawback that complicated operations must be repeated in order to obtain a film necessary for imparting releasability to the toner due to its poor reactivity with the coupling agent. Also, JP-A-59-15246
No. 5, JP-A-59-152452 discloses a method of treating a toner having inorganic fine particles adhered thereto with a coupling agent during suspension polymerization, but this method improves the moisture resistance of the toner. It is difficult to give the toner releasability.

【００１１】更に上記の定着に関する要求に加えて、最
近では高画質の画像が得られ且つ耐久性に優れたトナー
が要求されるようになってきており、そのために、トナ
ーの粒径が小さいこと、トナーの粒度分布が狭いこと、
トナーの表面形状が滑らかであること、及びトナー中に
帯電制御剤が均一に分散されていること等が要求されて
いる。トナーの粒径が大きいと解像力、シャープ度、ハ
ーフトーン再現性などが良好な高画質の画像が得られ難
く、また粒度分布が広いと特定粒径の選択現像が生じ、
現像時に用いられるトナーの粒径が経時変化するため高
画質の画像を安定して得ることができなくなる。更に、
表面形状が滑らかでない場合には、トナーを帯電させる
際の帯電部材やキャリアとの摩擦、或いは現像部におけ
る撹拌時などのストレスにより、トナー表面の部分粉砕
が生じて超微粉体が発生し、一成分現像法においてはそ
の超微粉体がトナー薄層形成用部材に融着し、帯電した
トナーの薄層をローラー等の表面に均一に形成すること
ができず、トナーによって現像された画像に白スジが発
生するようになり、また二成分現像法においては超微粉
体がキャリアに融着し、トナーに帯電させる性能を低下
させる等、現像剤としての耐久性を劣化させる原因とな
る。Further, in addition to the above-mentioned requirement for fixing, a toner capable of obtaining a high quality image and having excellent durability has recently been demanded. Therefore, the toner particle size is small. , The toner particle size distribution is narrow,
It is required that the surface shape of the toner is smooth and that the charge control agent is uniformly dispersed in the toner. If the toner particle size is large, it is difficult to obtain a high-quality image with good resolution, sharpness, halftone reproducibility, and if the particle size distribution is wide, selective development of a specific particle size occurs.
Since the particle size of the toner used during development changes with time, it becomes impossible to stably obtain a high-quality image. Furthermore,
If the surface shape is not smooth, friction with the charging member or the carrier when charging the toner, or stress such as stirring at the developing portion causes partial pulverization of the toner surface to generate ultrafine powder, In the one-component developing method, the ultrafine powder is fused to the toner thin layer forming member, and the thin layer of charged toner cannot be formed uniformly on the surface of the roller, etc. In addition, white streaks are generated on the surface, and in the two-component development method, ultrafine powder is fused to the carrier, which lowers the performance of charging the toner and causes deterioration in durability as a developer. .

【００１２】従来の乾式現像用トナーの一般的な製造方
法、例えば、樹脂、染顔料、離型剤、帯電制御剤などを
溶融混練し、機械式あるいは空気衝突式の粉砕機によっ
て粉砕した後分級を行なってトナーを製造する方法にお
いては、特に小粒径で粒度分布の狭いトナーを得ようと
した場合、生産能力や収率が著しく低下し、コスト高に
なり、更に粒径を小さくするほど、帯電制御剤などの分
散不均一による影響が大きく現れるため良好な帯電特性
を有するトナーを得ることが困難になり、また、このよ
うな粉砕で得られた粒子はかなり突起物の多い表面形状
を有しており、トナーを帯電させる際の帯電部材やキャ
リアとの摩擦、或いは現像部における撹拌時などのスト
レスを受けてトナー表面の部分粉砕が生じて超微粉体が
発生し、これがトナー薄層形成用部材或いはキャリアに
融着する現象が起き易いという問題がある。A conventional general method for producing a toner for dry development, for example, a resin, a dye / pigment, a release agent, a charge control agent and the like are melt-kneaded and then pulverized by a mechanical or air collision pulverizer and then classified. In the method of producing a toner by performing the above, particularly when an attempt is made to obtain a toner having a small particle size and a narrow particle size distribution, the production capacity and the yield are significantly reduced, the cost is increased, and the smaller the particle size is, the more However, it becomes difficult to obtain a toner having good charging characteristics because the influence of non-uniformity of the charge control agent and the like becomes large, and the particles obtained by such pulverization have a surface shape with many protrusions. In addition, when the toner is charged, friction with the charging member or the carrier, or stress such as stirring at the developing section causes partial pulverization of the toner surface to generate ultrafine powder. It is liable to occur a phenomenon of fusing the over thin layer forming member or carrier.

【００１３】[0013]

【発明が解決しようとする課題】上記のように、加熱ロ
ーラーによる加熱圧着方式においてトナー像の一部が加
熱ローラー表面に付着し、加熱ローラー表面に付着しト
ナーが被複写材に転写されることにより複写画像を汚染
する所謂オフセット現象を防止するために、トナーに離
型性を持たせる方法が種々提案されているが、従来の方
法では、加熱ローラー表面に対するトナーの離型性を向
上させると、トナーの流動性が悪化して現像部でのトナ
ーの供給が円滑に行えなかったり、トナーの転写性が悪
化して静電潜像担持体上のトナー画像を被複写材へ円滑
に転写できないという問題があり、またトナーに離型性
を持たせながらトナーの流動性及びトナーの転写性を改
良しようとするトナーの離型性が劣化し、トナーの離型
性、流動性及び転写性を同時に満足するトナーを得るこ
とは困難であるという問題がある。As described above, in the thermocompression bonding method using the heating roller, a part of the toner image adheres to the surface of the heating roller and adheres to the surface of the heating roller, and the toner is transferred to the material to be copied. In order to prevent a so-called offset phenomenon that contaminates a copied image by the method described above, various methods have been proposed in which the toner has releasability. However, in the conventional method, when the releasability of the toner to the surface of the heating roller is improved, , The fluidity of the toner deteriorates and the toner cannot be smoothly supplied in the developing section, or the transferability of the toner deteriorates and the toner image on the electrostatic latent image carrier cannot be smoothly transferred to the copy material. In addition, the toner releasability, which is an attempt to improve the toner fluidity and the toner transferability while giving the toner releasability, deteriorates. There is a problem that it is difficult to obtain a toner satisfying sex at the same time.

【００１４】また、従来の乾式現像用トナーの一般的な
製造方法では、小粒径で粒度分布が狭く且つ表面形状の
滑らかなトナーを得ることが困難であり、解像力、シャ
ープ度、ハーフトーン再現性などが良好な高画質の画像
を、経時による変化や画像欠陥を発生させることなく安
定して得ることができないという問題がある。更に、小
粒径で粒度分布が狭いトナーを製造する従来の方法は、
生産能力や収率が低くコスト高になり、また離型性を有
するトナーを製造する従来の方法は、処理の工程が繁雑
である等の問題がある。Further, it is difficult to obtain a toner having a small particle size, a narrow particle size distribution, and a smooth surface shape by the conventional general method for producing a dry developing toner, and resolution, sharpness, and halftone reproduction are possible. There is a problem that a high-quality image having good properties and the like cannot be stably obtained without causing a change with time or an image defect. Further, the conventional method for producing a toner having a small particle size and a narrow particle size distribution is
The conventional method for producing a toner having a low production capacity and a low yield and a high releasability has problems such as complicated processing steps.

【００１５】そこで本発明の課題はこのような問題点を
解決することである。従って、本発明の目的は、離型
性、流動性及び転写性が共に良好な静電荷現像用トナー
を提供することにある。また、本発明の目的は、離型
性、流動性及び転写性が良好であり、且つ小粒径で粒径
分布が狭く表面形状が滑らかで、解像力、シャープ度、
ハーフトーン再現性などが良好な高画質の画像を、経時
による変化や画像欠陥を発生させることなく安定して得
ることができる静電荷現像用トナーを提供することにあ
る。さらに、本発明の目的は、上記静電荷現像用トナー
を簡易に得ることのできる静電荷現像用トナーの製造方
法を提供することにある。Therefore, an object of the present invention is to solve such a problem. Therefore, an object of the present invention is to provide a toner for electrostatic charge development, which has good releasability, fluidity and transferability. Further, the object of the present invention is that the releasability, fluidity and transferability are good, and that the particle size is small, the particle size distribution is narrow, the surface shape is smooth, and the resolution, sharpness,
It is an object of the present invention to provide a toner for electrostatic charge development capable of stably obtaining a high-quality image having good halftone reproducibility and the like without causing a change with time or an image defect. Further, it is an object of the present invention to provide a method for producing an electrostatic charge developing toner, by which the above electrostatic charge developing toner can be easily obtained.

【００１６】[0016]

【課題を解決するための手段】本発明の上記目的は、前
記特許請求の範囲に記載の静電荷現像用トナー及びその
製造方法によって達成される。すなわち、請求項１の発
明は、着色剤と樹脂を主成分とし表面に離型剤微粒子と
無機微粒子とが固着されてなる着色樹脂粒子の外面にシ
ランカップリング剤の皮膜を有することを特徴とする静
電荷現像用トナーである。請求項２の発明は、請求項１
の発明において、着色樹脂粒子表面に離型剤微粒子が埋
設され固着されていることを特徴とする静電荷現像用ト
ナーである。請求項３の発明は、請求項１の発明におい
て、着色樹脂粒子表面に離型剤微粒子と無機微粒子とが
埋設され固着されていることを特徴とする静電荷現像用
トナーである。請求項４の発明は、請求項１、２または
３の発明において、着色樹脂粒子が分散重合により得ら
れた樹脂粒子を染料によって着色してなる着色樹脂粒子
であることを特徴とする静電荷現像用トナーである。請
求項５の発明は、請求項１、２、３または４の発明にお
いて、離型剤微粒子及び無機微粒子の固着量が、着色樹
脂粒子１００重量部に対し、１乃至５重量部及び０．１
乃至１．５重量部であることを特徴とする静電荷現像用
トナーである。請求項６の発明は、請求項１、２、３、
４または５の発明において、シランカップリング剤の付
着量が、表面に離型剤微粒子と無機微粒子とが固着され
てなる着色樹脂粒子１００重量部に対し０．２乃至２．
０重量部であることを特徴とする静電荷現像用トナーで
ある。請求項７の発明は、着色剤と樹脂を主成分とする
着色樹脂粒子表面に離型剤微粒子と無機微粒子とを固着
させた後シランカップリング剤で処理することを特徴と
する静電荷現像用トナーの製造方法である。請求項８の
発明は、請求項７の発明において、着色樹脂粒子表面に
離型剤微粒子を固着させた後に無機微粒子を固着させる
ことを特徴とする静電荷現像用トナーの製造方法であ
る。請求項９の発明は、請求項７の発明において、着色
樹脂粒子表面に離型剤微粒子を付着させた後、該着色樹
脂粒子を膨潤しうる分散媒中で加熱し離型剤微粒子を着
色樹脂粒子表面に埋設させて固着させ、その後着色樹脂
粒子表面に無機微粒子を固着させることを特徴とする静
電荷現像用トナーの製造方法である。請求項１０の発明
は、請求項７の発明において、着色樹脂粒子表面に離型
剤微粒子と無機微粒子を付着させた後、該着色樹脂粒子
を膨潤しうる分散媒中で加熱し離型剤微粒子と無機微粒
子とを着色樹脂粒子表面に埋設させて固着させることを
特徴とする静電荷現像用トナーの製造方法にある。請求
項１１の発明は、請求項７、８、９または１０の発明に
おいて、着色樹脂粒子が分散重合により得られた樹脂粒
子を染料によって着色してなる着色樹脂粒子であること
を特徴とする静電荷現像用トナーの製造方法である。The above object of the present invention can be achieved by the electrostatic charge developing toner and the method for producing the same described in the appended claims. That is, the invention of claim 1 is characterized in that a coating film of a silane coupling agent is provided on the outer surface of the colored resin particles which are composed mainly of a coloring agent and a resin, and the release agent particles and the inorganic particles are fixed to the surface. Is a toner for electrostatic charge development. The invention of claim 2 relates to claim 1
In the invention, the toner for electrostatic charge development is characterized in that the release agent fine particles are embedded and fixed on the surface of the colored resin particles. A third aspect of the present invention is the toner for electrostatic charge development according to the first aspect, wherein the release agent fine particles and the inorganic fine particles are embedded and fixed on the surfaces of the colored resin particles. The invention of claim 4 is the electrostatic charge development according to the invention of claim 1, 2 or 3, wherein the colored resin particles are colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye. For toner. According to a fifth aspect of the present invention, in the invention of the first, second, third or fourth aspect, the amount of the release agent fine particles and the inorganic fine particles adhered is 1 to 5 parts by weight and 0.1 parts by weight per 100 parts by weight of the colored resin particles.
To 1.5 parts by weight of the electrostatic charge developing toner. The invention of claim 6 relates to claim 1, 2, 3,
In the invention of 4 or 5, the amount of the silane coupling agent attached is 0.2 to 2. with respect to 100 parts by weight of the colored resin particles in which the release agent fine particles and the inorganic fine particles are fixed to the surface.
It is an electrostatic charge developing toner characterized by being 0 parts by weight. The invention according to claim 7 is characterized in that the release agent fine particles and the inorganic fine particles are fixed to the surface of the colored resin particles containing the colorant and the resin as the main components, and then treated with a silane coupling agent. It is a method of manufacturing a toner. The invention of claim 8 is the method of producing a toner for electrostatic charge development according to the invention of claim 7, characterized in that the release agent particles are fixed to the surface of the colored resin particles, and then the inorganic particles are fixed. According to the invention of claim 9, in the invention of claim 7, after the release agent fine particles are adhered to the surface of the colored resin particles, the release agent fine particles are heated in a dispersion medium capable of swelling the release agent fine particles. A method for producing a toner for electrostatic charge development, characterized in that the toner is embedded and fixed on the surface of particles, and then the inorganic fine particles are fixed on the surface of the colored resin particles. According to the invention of claim 10, in the invention of claim 7, after the release agent fine particles and the inorganic fine particles are adhered to the surface of the colored resin particles, the release agent particles are heated in a dispersion medium capable of swelling. And an inorganic fine particle are embedded and fixed on the surface of the colored resin particle, and a method for producing a toner for electrostatic charge development is characterized. The invention of claim 11 is characterized in that, in the invention of claim 7, 8, 9 or 10, the colored resin particles are colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye. This is a method for producing a charge developing toner.

【００１７】本発明の静電荷現像用トナーは、着色樹脂
粒子を製造する工程、離型剤微粒子を着色樹脂粒子表面
に固着する工程、無機微粒子を着色樹脂粒子表面に固着
する工程、及び着色樹脂粒子表面に離型剤微粒子と無機
微粒子を固着させた後シランカップリング剤により処理
する工程によって製造される。以下にそれぞれの工程に
ついて説明する。The toner for electrostatic charge development of the present invention comprises a step of producing colored resin particles, a step of fixing release agent fine particles to the surface of the colored resin particles, a step of fixing inorganic fine particles to the surface of the colored resin particles, and a colored resin. It is manufactured by a step of fixing release agent fine particles and inorganic fine particles to the surface of the particles and then treating with a silane coupling agent. Each step will be described below.

【００１８】（１）着色樹脂粒子の製造 本発明における着色樹脂粒子は、着色剤と結着樹脂とを
混練して粉砕し、或いは、単量体を懸濁重合、乳化重
合、分散重合により得られる樹脂粒子を着色剤により着
色して製造されるが、特に小粒径で粒径分布が狭く且つ
表面形状の滑らかな樹脂粒子が容易に得られる点から、
樹脂粒子は分散重合により製造することが好ましい。分
散重合は、単量体は溶解するが単量体の重合によって生
成する重合体は溶解しない溶媒中で、該溶媒に溶解する
分散安定剤の存在下で重合する方法である。(1) Production of Colored Resin Particles The colored resin particles in the present invention are obtained by kneading and pulverizing a colorant and a binder resin, or by subjecting a monomer to suspension polymerization, emulsion polymerization or dispersion polymerization. It is produced by coloring the resin particles to be colored with a coloring agent, but in particular, it is easy to obtain resin particles having a small particle size, a narrow particle size distribution, and a smooth surface shape.
The resin particles are preferably produced by dispersion polymerization. Dispersion polymerization is a method of polymerizing in a solvent in which a monomer dissolves but a polymer produced by polymerization of the monomer does not dissolve in the presence of a dispersion stabilizer which dissolves in the solvent.

【００１９】単量体としては、ビニル系単量体が好まし
く、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチ
ルスチレン、ｐ−メチルスチレン、α−メチルスチレ
ン、ｐ−エチルスチレン、２，４−ジメチルスチレン、
ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレ
ン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチ
レン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレ
ン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレ
ン、ｐ−フェニルスチレン、ｐ−クロルスチレン、３，
４−ジクロルスチレンなどのスチレン類、アクリル酸メ
チル、アクリル酸エチル、アクリル酸ｎ−ブチル、アク
リル酸イソブチル、アクリル酸プロピル、アクリル酸ｎ
−オクチル、アクリル酸ドデシル、アクリル酸ラウリ
ル、アクリル酸２−エチルヘキシル、アクリル酸ステア
リル、アクリル酸２−クロルエチル、アクリル酸フェニ
ル、α−クロルアクリル酸メチル、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸プロピル、メタ
クリル酸ｎ−ブチル、メタクリル酸イソブチル、メタク
リル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリ
ル酸ラウリル、メタクリル酸２−エチルヘキシル、メタ
クリル酸ステアリル、メタクリル酸フェニル、メタクリ
ル酸ジメチルアミノエチル、メタクリル酸ジエチルアミ
ノエチルなどのα−メチル脂肪酸モノカルボン酸エステ
ル類、アクリロニトリル、メタクリロニトリル、アクリ
ルアミドなどのアクリル酸もしくはメタクリル酸誘導
体、塩化ビニル、塩化ビニリデン、臭化ビニル、弗化ビ
ニルなどのハロゲンビニル類などが挙げられ、これらを
単独または２種以上混合して用いることができる。The monomer is preferably a vinyl monomer, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4- Dimethyl styrene,
pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p -Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
Styrenes such as 4-dichlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n acrylate
-Octyl, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. α-Methyl fatty acid monocarboxylic acid esters, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide, vinyl chloride, vinyl chloride Examples thereof include halogen vinyls such as lidene, vinyl bromide and vinyl fluoride, and these can be used alone or in admixture of two or more.

【００２０】また、本発明における樹脂粒子の製造にお
いては、耐オフセット性を高めるために、重合性の二重
結合を二個以上有するいわゆる架橋剤を存在させて重合
し、架橋重合させてもよい。好ましく用いられる架橋剤
としては、ジビニルベンゼン、ジビニルナフタレン及び
それらの誘導体である芳香族ジビニル化合物、その他エ
チレングリコールジメタクリレート、ジエチレングリコ
ールメタクリレート、トリエチレングリコールメタクリ
レート、トリメチロールプロパントリアクリレート、ア
リルメタクリレート、テトラエチレングリコールジメタ
クリレート、１，３−ブタンジオールジメタクリレート
などのジエチレン性カルボン酸エステル、Ｎ，Ｎ−ジビ
ニルアニリン、ジビニルエーテル、ジビニルスルフイ
ド、ジビニルスルホンなど全てのジビニル化合物及び三
個以上のビニル基を持つ化合物などが挙げられ、これら
を単独または２種以上混合して用いることができる。特
に重合時に上記架橋剤を添加して部分的に架橋させたＴ
ＨＦ不溶分を含有する樹脂粒子は、溶媒による膨潤によ
って生じる粘着性の増加が著しくなく、後述する離型剤
微粒子を着色樹脂粒子表面に埋設する工程において着色
樹脂粒子の凝集を少なくすることが出来るので好まし
い。また、樹脂粒子における平均分子量を調節すること
を目的として連鎖移動定数の大きな化合物を共存させて
重合を行なってもよい。このような化合物としては、例
えば、メルカプト基を持つ低分子化合物や四塩化炭素、
四臭化炭素等が挙げられる。Further, in the production of the resin particles in the present invention, in order to enhance the offset resistance, a so-called cross-linking agent having two or more polymerizable double bonds may be allowed to be present to carry out the cross-linking polymerization. . The cross-linking agent preferably used is an aromatic divinyl compound which is divinylbenzene, divinylnaphthalene or a derivative thereof, other ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, tetraethylene glycol. All divinyl compounds such as dimethacrylate, diethylenic carboxylic acid ester such as 1,3-butanediol dimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone and 3 or more vinyl groups Examples thereof include compounds, which may be used alone or in combination of two or more. In particular, the above-mentioned crosslinking agent was added at the time of polymerization to partially crosslink
The resin particles containing the HF insoluble matter do not significantly increase the adhesiveness caused by swelling with a solvent, and can reduce the aggregation of the colored resin particles in the step of embedding the releasing agent particles on the surface of the colored resin particles described later. Therefore, it is preferable. Further, the polymerization may be carried out in the presence of a compound having a large chain transfer constant for the purpose of adjusting the average molecular weight of the resin particles. As such a compound, for example, a low molecular weight compound having a mercapto group or carbon tetrachloride,
Examples thereof include carbon tetrabromide.

【００２１】前記単量体の重合反応の際に用いる重合開
始剤としては、例えば、２，２′−アゾビスイソブチロ
ニトリル、２，２′−アゾビス（２，４−ジメチルバレ
ロニトリル）などのアゾ系重合開始剤、ラウリルパーオ
キシド、ベンソイルパーオキシド、ｔｅｒｔ−ブチルパ
ーオクトエートなどの過酸化物系重合開始剤、過硫酸カ
リウムの様な過硫化物系重合開始剤あるいはこれにチオ
硫酸ナトリウム、アミンなどを併用した系が挙げられ
る。重合開始剤の使用量はビニル単量体１００重量部に
対して０．１〜１０重量部が好ましい。Examples of the polymerization initiator used in the polymerization reaction of the above-mentioned monomers include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile). Polymerization initiators such as azo polymerization initiators, lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate and other peroxide polymerization initiators, persulfate polymerization initiators such as potassium persulfate or thiosulfate Examples include a system in which sodium, amine and the like are used in combination. The amount of the polymerization initiator used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer.

【００２２】溶媒としては親水性有機液体が好ましく、
例えば、メチルアルコール、エチルアルコール、変性エ
チルアルコール、イソプロピルアルコール、ｎ−ブチル
アルコール、イソブチルアルコール、ｔｅｒｔ−ブチル
アルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ア
ミルアルコール、３−ペンタノール、オクチルアルコー
ル、ベンジルアルコール、シクロヘキサノール、フルフ
リルアルコール、テトラヒドロフルフリルアルコール、
エチレングリコール、グリセリン、ジエチレングリコー
ル等のアルコール類、メチルセロソルブ、セロソルブ、
インプロピルセロソルブ、ブチルセロソルブ、エチレン
グリコールモノメチルエーテル、エチレングリコールモ
ノエチルエーテル、ジエチレングリコールモノメチルエ
ーテル、ジエチレングリコールモノエチルエーテル等の
エーテルアルコール類などが挙げられる。これら親水性
有機液体には、必要により水または溶解可能な親油性有
機液体を混合して使用することもできる。単量体と親水
性有機液体の使用割合は、単量体／親水性有機液体の値
が、およそ１以下、好ましくは１／２以下が適当であ
る。The solvent is preferably a hydrophilic organic liquid,
For example, methyl alcohol, ethyl alcohol, denatured ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol, octyl alcohol, benzyl alcohol, cyclo. Hexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol,
Alcohols such as ethylene glycol, glycerin, and diethylene glycol, methyl cellosolve, cellosolve,
Examples thereof include ether alcohols such as inpropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. If desired, water or a soluble lipophilic organic liquid may be mixed with these hydrophilic organic liquids before use. The ratio of the monomer to the hydrophilic organic liquid used is such that the value of the monomer / hydrophilic organic liquid is about 1 or less, preferably 1/2 or less.

【００２３】分散安定剤としては、親水性基を有する単
量体の単独重合体又は共重合体、或いは親水性基を有す
る単量体とその単量体と重合可能な他の単量体との共重
合体で親水性有機液体に可溶な高分子分散安定剤が好ま
しく用いられる。親水性基を有する単量体としては、例
えばアクリル酸、メタクリル酸、フマル酸、マレイン
酸、無水マレイン酸、アクリル酸２−ヒドロキシエチ
ル、メタクリル酸２−ヒドロキシエチル、グリセリンモ
ノアクリル酸エステル、グリセリンモノメタクリル酸エ
ステル、ビニルアルコール、ビニルメチルエーテル、ビ
ニルエチルエーテル、酢酸ビニル、プロピオン酸ビニ
ル、アクリルアミド、メタクリルアミド、ビニルピリジ
ン、ビニルピロリドン、ビニルイミダゾール、エチレン
イミン等が挙げられる。分散安定剤の使用量は、目的と
する樹脂粒子形成用の単量体の種類によって異なるが、
親水性有機液体に対し、０．１〜１０重量％、特に１〜
５重量％が好ましい。As the dispersion stabilizer, a homopolymer or copolymer of a monomer having a hydrophilic group, or a monomer having a hydrophilic group and another monomer polymerizable with the monomer Polymer dispersion stabilizers which are soluble in hydrophilic organic liquids and are copolymers of are preferably used. Examples of the monomer having a hydrophilic group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycerin monoacrylic ester, glycerin mono Methacrylic acid ester, vinyl alcohol, vinyl methyl ether, vinyl ethyl ether, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine and the like can be mentioned. The amount of the dispersion stabilizer used varies depending on the type of the monomer for forming the desired resin particles,
0.1 to 10% by weight, particularly 1 to 10% by weight relative to the hydrophilic organic liquid
5% by weight is preferred.

【００２４】樹脂粒子の製造は、親水性有機液体等の溶
媒に、高分子分散安定剤を完全に溶解した後、一種また
は二種以上のビニル単量体を添加し、反応容器内を窒
素、アルゴン等の不活性ガスで置換した後、重合開始剤
を添加し槽内の流れが均一になるような速度で撹拌しな
がら、用いた開始剤の分解速度に対応した温度に加熱し
重合が行なわれるようにすればよい。重合を高重合率域
で行なうには５〜４０時間の重合時間が必要であるが、
所望の粒子径、粒子径分布の状態で重合を停止させた
り、また、重合開始剤を順次添加したり、高圧下で反応
を行なうことなどにより重合速度を速めることができ
る。重合終了後は、そのまま着色剤による着色工程に用
いてもよいし、沈降分離、遠心分離、デカンテーション
などの操作により不必要な微粒子、残存モノマー、高分
子分散安定剤などを除いた後に、重合体スラリーとして
回収し、着色を行なってもよい。分散安定剤を除去しな
い方が着色系の安定性が高く、不要な凝集が抑制される
ので好ましい。The resin particles are produced by completely dissolving the polymer dispersion stabilizer in a solvent such as a hydrophilic organic liquid, adding one or more vinyl monomers, and then adding nitrogen in the reaction vessel. After substituting with an inert gas such as argon, the polymerization initiator is added and polymerization is carried out by heating at a temperature corresponding to the decomposition rate of the initiator used while stirring at a rate such that the flow in the tank becomes uniform. It should be done. It takes 5 to 40 hours to carry out the polymerization in a high polymerization rate range.
The polymerization rate can be increased by stopping the polymerization in the state of desired particle size and particle size distribution, sequentially adding a polymerization initiator, and conducting the reaction under high pressure. After completion of the polymerization, it may be used as it is in the coloring step with a coloring agent, or after unnecessary particles, residual monomers, polymer dispersion stabilizer, etc. are removed by operations such as sedimentation, centrifugation, decantation, etc. It may be collected as a combined slurry and colored. It is preferable not to remove the dispersion stabilizer because the stability of the coloring system is high and unnecessary aggregation is suppressed.

【００２５】本発明における樹脂粒子着色工程は次のよ
うにして行われる。すなわち、樹脂粒子の表面に顔料等
の着色剤を固着して着色することができるが、染料によ
り着色することが着色剤の脱落がなく着色安定性に優れ
ている点から好ましい。着色樹脂粒子を染料によって着
色するには、樹脂粒子を溶解しない有機溶媒中に樹脂粒
子を分散し、この樹脂粒子の分散前又は分散後に前記溶
媒中に染料を溶解させ、染料を樹脂粒子中に浸透させる
ことによって着色すればよい。染料としては、染料のＳ
Ｐ値が樹脂粒子の樹脂のＳＰ値に近い染料が好ましく、
また染料の有機溶媒に対する溶解度〔Ｄ1〕及び樹脂粒
子の樹脂に対する染料の溶解度〔Ｄ2〕の関係が、
〔Ｄ1〕／〔Ｄ2〕≦０．５となる染料を選択使用するこ
とが好ましい。これにより、樹脂粒子の深部まで染料が
浸透（拡散）した着色樹脂粒子を効率よく得ることがで
きる。また、樹脂粒子及び染料を含有する有機溶媒の液
温を樹脂粒子のガラス転移温度以下に保ち、撹拌するこ
とが好ましい。これにより、樹脂粒子中への染料の浸透
速度を早めることができ、約３０分〜６時間程度で充分
に着色された樹脂粒子を得ることが可能となる。また、
分散重合等で重合終了時に得られるスラリー、つまり有
機溶媒中に重合樹脂粒子が分散している状態の分散液
に、染料を直接添加して前記の条件にて加熱撹拌しても
よい。The resin particle coloring step in the present invention is performed as follows. That is, a coloring agent such as a pigment can be fixed and colored on the surface of the resin particles, but coloring with a dye is preferable because the coloring agent does not fall off and the coloring stability is excellent. To color the colored resin particles with a dye, the resin particles are dispersed in an organic solvent that does not dissolve the resin particles, and the dye is dissolved in the solvent before or after the dispersion of the resin particles, and the dye is added to the resin particles. It may be colored by being permeated. As the dye, dye S
A dye having a P value close to the SP value of the resin of the resin particles is preferable,
The relationship between the solubility of the dye in the organic solvent [D 1 ] and the solubility of the dye in the resin of the resin particles [D 2 ] is
It is preferable to select and use a dye satisfying [D 1 ] / [D 2 ] ≦ 0.5. This makes it possible to efficiently obtain colored resin particles in which the dye has penetrated (diffused) to the deep part of the resin particles. Further, it is preferable to keep the liquid temperature of the organic solvent containing the resin particles and the dye below the glass transition temperature of the resin particles and stir. As a result, the permeation rate of the dye into the resin particles can be increased, and it is possible to obtain sufficiently colored resin particles in about 30 minutes to 6 hours. Also,
The dye may be directly added to the slurry obtained at the end of the polymerization by dispersion polymerization or the like, that is, the dispersion liquid in which the polymerized resin particles are dispersed in the organic solvent, and the mixture may be heated and stirred under the above conditions.

【００２６】染料としてはバット染料、分散染料、油溶
性染料の使用が好ましく、特に油溶性染料が好ましい。
所望の色調に応じて数種の染料を併用することもでき
る。また、染料と樹脂粒子との比率（重量）は、着色度
に応じて任意に選択されるが、通常は樹脂粒子１００重
量部に対して、染料１〜５０重量部の割合で用いるのが
好ましい。さらに具体的には、例えば、有機溶媒として
ＳＰ値の高いメタノール、エタノール等のアルコール類
を使用し、樹脂粒子としてＳＰ値９程度のスチレン−ア
クリル系樹脂を使用した場合、好ましい染料としては、 Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＹＥＬＬＯＷ（６、９、１
７、３１、３５、１００、１０２、１０３、１０５） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＯＲＡＮＧＥ（２、７、１
３、１４、６６） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＲＥＤ（５、１６、１７、１
８、１９、２２、２３、１４３、１４５、１４６、１４
９、１５０、１５１、１５７、１５８） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＶＩＯＬＥＴ（３１、３２、
３３、３７） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＢＬＵＥ（２２、６３、７
８、８３〜８６、９１、９４、９５、１０４） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＧＲＥＥＮ（２４、２５） Ｃ．Ｉ．ＳＯＬＶＥＮＴ ＢＲＯＷＮ（３、９）等が挙
げられる。As the dyes, vat dyes, disperse dyes and oil-soluble dyes are preferably used, and oil-soluble dyes are particularly preferable.
Several kinds of dyes can be used in combination depending on the desired color tone. Further, the ratio (weight) of the dye and the resin particles is arbitrarily selected according to the degree of coloring, but it is usually preferable to use 1 to 50 parts by weight of the dye with respect to 100 parts by weight of the resin particles. . More specifically, for example, when alcohols such as methanol and ethanol having a high SP value are used as the organic solvent and a styrene-acrylic resin having an SP value of about 9 is used as the resin particles, a preferable dye is C ． I. SOLVENT YELLOW (6, 9, 1
7, 31, 35, 100, 102, 103, 105) C.I. I. SOLVENT ORANGE (2, 7, 1
3, 14, 66) C.I. I. SOLVENT RED (5, 16, 17, 1
8, 19, 22, 23, 143, 145, 146, 14
9, 150, 151, 157, 158) C.I. I. SOLVENT VIOLET (31, 32,
33, 37) C.I. I. SOLVENT BLUE (22, 63, 7
8, 83-86, 91, 94, 95, 104) C.I. I. SOLVENT GREEN (24, 25) C.I. I. SOLVENT BROWN (3, 9) and the like.

【００２７】また、市販染料としては、例えば、保土谷
化学工業社製の愛染ＳＯＴ染料Ｙｅｌｌｏｗ−１、３、
４、Ｏｒａｎｇｅ−１、２、３、Ｓｃａｒｌｅｔ−１、
Ｒｅｄ−１、２、３、Ｂｒｏｗｎ−２、Ｂｌｕｅ−１、
２、Ｖｉｏｌｅｔ−１、Ｇｒｅｅｎ−１、２、３、Ｂｌ
ａｃｋ−１、４、６、８、ＢＡＳＦ社製のｓｕｄａｎ染
料、Ｙｅｌｌｏｗ−１４０、１５０、Ｏｒａｎｇｅ−２
２０、Ｒｅｄ−２９０、３８０、４６０、Ｂｌｕｅ−６
７０や三菱化成社製のダイアレジン、Ｙｅｌｌｏｗ−３
Ｇ、Ｆ、Ｈ２Ｇ、ＨＧ、ＨＣ、ＨＩ、Ｏｒａｎｇｅ−Ｈ
Ｓ、Ｇ、Ｒｅｄ−ＧＧ、ＳＨ、Ｓ、Ａ、Ｋ、Ｈ５８、Ｖ
ｉｏｌｅｔ−Ｄ、Ｂｌｕｅ−Ｊ、Ｇ、Ｎ、Ｋ、Ｐ、Ｈ３
Ｇ、４Ｇ、Ｇｒｅｅｎ−Ｃ、Ｂｒｏｗｎ−Ａやオリエン
ト化学社製のオイルカラー、Ｙｅｌｌｏｗ−３Ｇ、ＧＧ
−Ｓ、＃１０５、Ｏｒａｎｇｅ−ＰＳ、ＰＲ、＃２０
１、Ｓｃａｒｌｅｔ−＃３０８、Ｒｅｄ−５Ｂ、Ｂｒｏ
ｗｎ−ＧＲ、＃４１６、Ｇｒｅｅｎ−ＢＧ、＃５０２、
Ｂｌｕｅ−ＢＯＳ、ＨＮ、Ｂｌａｃｋ−ＨＢＢ、＃８０
３、ＥＥ、ＥＸ、住友化学工業社製のスミプラスト、ブ
ルーＧＰ、ＯＲレッドＦＢ、３Ｂ、イエローＦＬ７Ｇ、
ＧＣ、日本化薬社製のカロヤン、ポリエステルブラック
ＥＸ−ＳＨ３００、カヤセットＲｅｄ−Ｂ、ブルーＡ−
２Ｒ等を使用することができる。もちろん、染料は、樹
脂粒子と有機溶媒との組合せによって適宜選択できるた
め、上記例に限られるものではない。Examples of commercially available dyes include Aizen SOT dyes Yellow-1, 3, manufactured by Hodogaya Chemical Co., Ltd.
4, Orange-1, 2, 3, Scarlet-1,
Red-1, 2, 3, Brown-2, Blue-1,
2, Violet-1, Green-1, 2, 3, Bl
ack-1, 4, 6, 8 and BASF's sudan dye, Yellow-140, 150, Orange-2.
20, Red-290, 380, 460, Blue-6
70 or Mitsubishi Kasei dial resin, Yellow-3
G, F, H2G, HG, HC, HI, Orange-H
S, G, Red-GG, SH, S, A, K, H58, V
iolet-D, Blue-J, G, N, K, P, H3
G, 4G, Green-C, Brown-A and oil colors manufactured by Orient Chemical Co., Yellow-3G, GG
-S, # 105, Orange-PS, PR, # 20
1, Scarlet- # 308, Red-5B, Bro
wn-GR, # 416, Green-BG, # 502,
Blue-BOS, HN, Black-HBB, # 80
3, EE, EX, Sumiplast manufactured by Sumitomo Chemical Co., Ltd., Blue GP, OR Red FB, 3B, Yellow FL7G,
GC, Nippon Kayaku's Caroyan, Polyester Black EX-SH300, Kayaset Red-B, Blue A-
2R or the like can be used. Of course, the dye is not limited to the above examples because it can be appropriately selected depending on the combination of the resin particles and the organic solvent.

【００２８】（２）着色樹脂粒子表面への離型剤微粒子
の固着 着色樹脂粒子表面に離型剤微粒子を固着させるには、着
色樹脂粒子表面に離型剤微粒子を付着させ、次いで、着
色樹脂粒子表面に付着した離型剤微粒子を着色樹脂粒子
表面に埋設させることにより固着させることが好まし
い。着色樹脂粒子表面に離型剤微粒子を均一に付着させ
るためには、離型剤微粒子の粒径が、着色樹脂粒子の粒
径の１／１０程度以下であることが好ましく、また、着
色樹脂粒子表面に効率よく埋設を行なうために、特に１
／２０以下であることが好ましい。更に、効率よく埋設
させて静電荷現像用トナーとしての転写性を向上させる
ためには、着色樹脂粒子の粒径に関係なく、０．２μｍ
以下、特に０．１μｍ以下であることが好ましい。ま
た、離型剤微粒子は着色樹脂粒子１００重量部に対し、
１〜５重量部固着させるのが好ましい。１重量部未満で
あると静電荷現像用トナーとしての有効な離型性を発揮
することができず、また５重量部より多いと流動性、転
写性が不充分なものとなる。(2) Fixing Release Agent Fine Particles on the Surface of Colored Resin Particles In order to fix the release agent fine particles on the surface of the colored resin particles, the release agent fine particles are attached to the surface of the colored resin particles, and then the colored resin is added. It is preferable that the release agent particles adhered to the surface of the particles are embedded in the surface of the colored resin particles to be fixed. In order to evenly attach the release agent particles to the surface of the colored resin particles, the particle size of the release agent particles is preferably about 1/10 or less of the particle size of the colored resin particles. To efficiently bury the surface, especially 1
It is preferably / 20 or less. Further, in order to improve the transferability as a toner for electrostatic charge development by embedding it efficiently, 0.2 μm is used regardless of the particle size of the colored resin particles.
It is particularly preferable that the thickness is 0.1 μm or less. Further, the release agent fine particles are based on 100 parts by weight of the colored resin particles,
It is preferable to fix 1 to 5 parts by weight. If it is less than 1 part by weight, the effective releasability as a toner for electrostatic charge development cannot be exhibited, and if it is more than 5 parts by weight, the fluidity and transferability become insufficient.

【００２９】以下に、着色樹脂粒子表面への離型剤微粒
子の付着、離型剤微粒子の着色樹脂粒子表面への固着に
ついて、それぞれ更に詳細に説明する。The adhesion of the release agent particles to the surface of the colored resin particles and the adhesion of the release agent particles to the surface of the colored resin particles will be described in more detail below.

【００３０】（イ）着色樹脂粒子表面への離型剤微粒子
の付着 離型剤微粒子を着色樹脂粒子表面に均一に固着させるた
めには、まず離型剤微粒子を着色樹脂粒子表面に均一に
付着させることが必要である。このためには、付着の工
程において、離型剤微粒子及び着色樹脂粒子は凝集する
ことなく均一な分散状態にあることが必要であり、離型
剤微粒子分散液に着色樹脂粒子を添加してもよいが、離
型剤微粒子分散液と着色樹脂粒子分散液を混合する方が
より凝集なく均一な分散状態が得られるので好ましい。
着色樹脂粒子表面に離型剤微粒子を付着させるには、単
に離型剤微粒子分散液に着色樹脂粒子を添加して混合
し、或いは離型剤微粒子分散液と着色樹脂粒子分散液を
混合してもよいが、強固に付着させるために次のいずれ
かの方法によることが好ましい。すなわち、（ａ）着色
樹脂粒子及び離型剤微粒子を含有する分散液に酸又はア
ルカリを添加し、ｐＨを調整する方法、（ｂ）着色樹脂
粒子及び離型剤微粒子を含有する分散液にアニオン界面
活性剤又はカチオン界面活性剤を添加する方法、（ｃ）
着色樹脂粒子及び離型剤微粒子を含有する分散液に電解
質を添加する方法等によることが好ましい。これらの方
法により、条件を適正に設定することによって分散液中
での着色樹脂粒子と離型剤微粒子の電位を逆極性、又は
同極性でも電位の差を大きくすること等により、離型剤
微粒子を着色樹脂粒子表面に強固に付着させることがで
きる。これらの電位の調整は両者の分散液の混合前に行
っても良く、また混合後に行っても良い。(A) Adhesion of release agent fine particles to the surface of the colored resin particles In order to uniformly fix the release agent fine particles to the surface of the colored resin particles, first, the release agent fine particles are uniformly attached to the surface of the colored resin particles. It is necessary to let For this purpose, it is necessary that the release agent fine particles and the colored resin particles are in a uniform dispersed state without agglomerating in the attaching step, and even if the colored resin particles are added to the release agent fine particle dispersion liquid. However, it is preferable to mix the release agent fine particle dispersion liquid and the colored resin particle dispersion liquid because a more dispersed state can be obtained without aggregation.
To attach the release agent fine particles to the surface of the colored resin particles, simply add the colored resin particles to the release agent fine particle dispersion and mix them, or mix the release agent fine particle dispersion and the colored resin particle dispersion. However, it is preferable to use any one of the following methods in order to firmly adhere. That is, (a) a method of adding an acid or an alkali to a dispersion liquid containing the colored resin particles and the release agent fine particles to adjust the pH, and (b) an anion in the dispersion liquid containing the colored resin particles and the release agent fine particles. A method of adding a surfactant or a cationic surfactant, (c)
It is preferable to use a method of adding an electrolyte to a dispersion liquid containing colored resin particles and release agent particles. By these methods, by appropriately setting the conditions, the potentials of the colored resin particles and the release agent fine particles in the dispersion liquid have opposite polarities, or even if the polarities are the same, the potential difference is increased. Can be firmly adhered to the surface of the colored resin particles. The adjustment of these potentials may be performed before mixing both dispersion liquids, or may be performed after mixing them.

【００３１】離型剤微粒子分散液を得る方法としては、
例えば以下に示す方法があり、また市販品としても入手
可能である。 離型剤を溶解する溶剤ａと、溶剤ａとは相溶するが離
型剤微粒子を溶解しない液体ｂを用い、離型剤をａに溶
解した後、それを高速撹拌している液体ｂに加えて離型
剤微粒子を析出させ離型剤微粒子の分散液を得る方法、 離型剤を熱溶融させた液体に高速撹拌しながら熱水を
加え、得られた分散液を冷却させることにより離型剤微
粒子の分散液を得る方法、 離型剤を溶解しない液体ｃと離型剤とを混合し、ボー
ルミル等の分散装置を用いて分散し離型剤微粒子の分散
液を得る方法、など一般公知の方法が使用できる。また
これらの分散液には分散安定剤として一般公知の界面活
性剤、高分子分散剤、無機イオン等を単独または複数種
含有せしめることができる。As a method for obtaining a release agent fine particle dispersion,
For example, there are the following methods, and they are also available as commercial products. A solvent a that dissolves the release agent and a liquid b that is compatible with the solvent a but does not dissolve the release agent particles are used. After the release agent is dissolved in a, the liquid b is stirred at high speed. In addition, a method of precipitating release agent particles to obtain a dispersion of release agent particles, hot water is added to a liquid obtained by heat-melting the release agent while stirring at high speed, and the obtained dispersion is cooled to release. Generally, a method for obtaining a dispersion liquid of fine release agent particles, a method for obtaining a dispersion liquid of release agent fine particles by mixing a liquid c which does not dissolve the release agent and a release agent, and dispersing the mixture using a dispersing device such as a ball mill. Known methods can be used. Further, these dispersions may contain generally known surfactants, polymer dispersants, inorganic ions and the like as dispersion stabilizers, alone or in combination.

【００３２】ここで言う離型剤は、加熱ローラーによる
加熱圧着方式の定着を行う際に溶融して加熱ローラーに
静電荷現像用トナーが付着するのを防止する効果を有す
る物質であれば何でもよく、これらの物質の具体例とし
ては、例えば、ポリプロピレン、ポリエチレン、酸化ポ
リプロピレン、酸化ポリエチレン等の数平均分子量が１
０００〜２００００の低分子量ポリオレフィン、キャン
デリラ、カルナウバ、ライス、木ロウ、ホホバ等の植物
系天然ワックス、モンタン、セレシン、オゾケライト等
の鉱物系天然ワックス、パラフィン、マイクロクリスタ
リン、ペトリラクタム等の石油系ワックス、及びその変
性ワックス、パルミチン酸、ステアリン酸、ベヘン酸等
の固体高級脂肪酸、ステアリン酸カルシウム、ステアリ
ン酸アルミニウム、パルミチン酸カルシウム、パルミチ
ン酸亜鉛等の高級脂肪酸アルカリ金属塩、亜鉛塩、アル
ミニウム塩、ステアリン酸オクタデシル、グリセリンモ
ノステアレート等の高級脂肪酸エステル、ラウリン酸ア
ミド、ステアリン酸アミド、Ｎ，Ｎ′−エチレンビスオ
レイン酸アミド、Ｎ，Ｎ′−エチレンビスステアリン酸
アミド等のアミド類、ジヘプタデシルケトン、ジウンデ
シルケトン等のケトン類などが挙げられる。The release agent referred to herein may be any substance as long as it is a substance which has an effect of preventing the electrostatic charge developing toner from adhering to the heating roller by being melted when fixing by the heating and pressure bonding method by the heating roller. As specific examples of these substances, for example, polypropylene, polyethylene, polypropylene oxide, polyethylene oxide and the like have a number average molecular weight of 1
000 to 20,000 low molecular weight polyolefin, candelilla, carnauba, rice, wax, jojoba and other plant natural waxes, mineral natural waxes such as montan, ceresin and ozokerite, petroleum waxes such as paraffin, microcrystalline and petrylactam, And its modified wax, solid higher fatty acids such as palmitic acid, stearic acid and behenic acid, calcium stearate, higher fatty acids such as aluminum stearate, calcium palmitate and zinc palmitate, alkali metal salts, zinc salts, aluminum salts, octadecyl stearate , Higher fatty acid esters such as glycerin monostearate, lauric acid amides, stearic acid amides, amides such as N, N'-ethylenebisoleic acid amides, N, N'-ethylenebisstearic acid amides , Di heptadecyl ketone, and the like ketones such as diundecyl ketone.

【００３３】上記のようにして得られた離型剤微粒子が
付着した着色樹脂粒子においては、離型剤微粒子が表面
に突出した状態であり、この状態では静電荷現像用トナ
ーとしての相互の接触が離型剤微粒子間で起る確率が高
く、静電荷現像用トナーの流動性や転写性を低下させ、
また現像剤の撹拌などで容易に離型剤微粒子の脱離が起
り、感光体やキャリアを汚染する不具合がある。この
為、離型剤微粒子を付着した後に、離型剤微粒子を着色
樹脂粒子表面に固着することが好ましい。In the colored resin particles to which the release agent fine particles obtained as described above are attached, the release agent fine particles are in a state of protruding on the surface, and in this state, mutual contact as the electrostatic charge developing toner is made. Is likely to occur between the release agent particles, reducing the fluidity and transferability of the electrostatic charge developing toner,
Further, there is a problem that the release agent fine particles are easily detached by stirring the developer or the like, thereby contaminating the photoreceptor and the carrier. Therefore, it is preferable to fix the release agent particles to the surface of the colored resin particles after attaching the release agent particles.

【００３４】（ロ）離型剤微粒子の着色樹脂粒子表面へ
の固着 離型剤微粒子の着色樹脂粒子表面への固着は、離型剤微
粒子を着色樹脂粒子表面に埋設させることにより行うこ
とが好ましい。ここで言う埋設とは離型剤微粒子の体積
の大部分が着色樹脂粒子表面より進入した状態で表面よ
り突出した部分が少ない状態で存在していることを指し
ている。この状態は静電荷現像用トナーの断面を透過型
電子顕微鏡により容易に観察することが出来る。離型剤
微粒子の着色樹脂粒子表面への埋設は、離型剤微粒子の
付着した着色樹脂粒子を膨潤させることによって行うこ
とができる。着色樹脂粒子を膨潤させるには、離型剤微
粒子の付着した着色樹脂粒子を含有する分散液に、着色
樹脂粒子を膨潤させる液体を添加すればよく、その液体
の濃度を高めること、その液体が添加された上記着色樹
脂粒子分散液を加熱することなどにより膨潤を促進する
ことができる。膨潤を促進するための方法としては、加
熱する方法が操作も簡単で効果的に埋設固着を行なうこ
とができ好ましい。加熱温度は３０℃〜６０℃が好まし
い。３０℃未満では埋設が不充分であり、６０℃より高
いと着色樹脂粒子の融着・合一が起り易く好ましくな
い。加熱時間は着色樹脂粒子の樹脂、離型剤微粒子の離
型剤材料、着色樹脂粒子を膨潤させる液体、処理温度に
よっても異るが２時間〜１０時間が好ましい。着色樹脂
粒子を膨潤させる液体としては、着色樹脂粒子を構成す
る樹脂によっても異るが、メタノール、エタノール、ｎ
−プロピルアルコール、イソプロピルアルコール等のア
ルコール類およびこれらアルコール類を５０重量％以上
含有する水との混合液、アセトン、メチルエチルケトン
の水溶液等が好ましく用いられる。(B) Fixing of Release Agent Fine Particles to Colored Resin Particle Surfaces The release agent fine particles are preferably fixed to the colored resin particle surfaces by embedding the release agent fine particles in the colored resin particle surfaces. . The term “embedded” as used herein means that most of the volume of the release agent fine particles is present in a state where the release agent fine particles enter from the surface of the colored resin particles and a small portion protrudes from the surface. In this state, the cross section of the electrostatic charge developing toner can be easily observed with a transmission electron microscope. The embedding of the release agent particles on the surface of the colored resin particles can be performed by swelling the colored resin particles to which the release agent particles are attached. In order to swell the colored resin particles, it is sufficient to add a liquid for swelling the colored resin particles to the dispersion liquid containing the colored resin particles to which the release agent fine particles are adhered. To increase the concentration of the liquid, the liquid is Swelling can be promoted by, for example, heating the added colored resin particle dispersion liquid. As a method for promoting swelling, a heating method is preferable because the operation is simple and the embedded fixing can be effectively performed. The heating temperature is preferably 30 ° C to 60 ° C. If the temperature is lower than 30 ° C, the embedding is insufficient, and if the temperature is higher than 60 ° C, the fusion and coalescence of the colored resin particles easily occur, which is not preferable. The heating time varies depending on the resin of the colored resin particles, the release agent material of the release agent particles, the liquid for swelling the colored resin particles, and the treatment temperature, but is preferably 2 hours to 10 hours. As the liquid for swelling the colored resin particles, methanol, ethanol, n
-Alcohols such as propyl alcohol and isopropyl alcohol, mixed solutions with water containing 50% by weight or more of these alcohols, and aqueous solutions of acetone and methyl ethyl ketone are preferably used.

【００３５】（３）無機微粒子の着色樹脂粒子表面への
固着 無機微粒子を着色樹脂粒子表面に固着させる方法として
は、（ａ）離型剤微粒子の固着と同時に無機微粒子を固
着させる方法、（ｂ）離型剤微粒子を固着させてから無
機微粒子を固着させる方法とがある。(3) Fixing of Inorganic Fine Particles to Colored Resin Particle Surfaces As a method of fixing the inorganic fine particles to the colored resin particle surface, (a) a method of fixing the release agent fine particles and the inorganic fine particles at the same time (b) ) There is a method of fixing the release agent fine particles and then fixing the inorganic fine particles.

【００３６】（ａ）の方法では、無機微粒子は離型剤微
粒子と同様の界面化学的性質を有することが望ましい。
このことにより離型剤微粒子を付着させたのと同様の操
作により無機微粒子も同様に着色樹脂粒子表面へ付着さ
せることができる。すなわち、着色樹脂粒子分散液に離
型剤微粒子分散液と無機微粒子を添加し均一に混合分散
する。無機微粒子の添加は、無機微粒子を付着時に用い
る分散媒と同様の分散媒中にボールミル等の分散手段に
より分散し分散液として添加することが好ましい。着色
樹脂粒子、離型剤微粒子及び無機微粒子の三成分分散液
に離型剤微粒子を付着させたのと同様な操作を行うこと
により着色樹脂粒子表面に離型剤微粒子と無機微粒子と
を同時に付着させることができる。また離型剤微粒子を
埋設させたのと同様の操作により無機微粒子も埋設さ
せ、離型剤微粒子と無機微粒子とを着色樹脂粒子表面に
固着させることができる。In the method (a), it is desirable that the inorganic fine particles have the same surface chemical properties as the release agent fine particles.
In this way, the inorganic fine particles can be similarly attached to the surface of the colored resin particles by the same operation as that for the release agent fine particles. That is, the release agent fine particle dispersion and the inorganic fine particles are added to the colored resin particle dispersion and uniformly mixed and dispersed. The inorganic fine particles are preferably added as a dispersion by dispersing the inorganic fine particles in a dispersion medium similar to the dispersion medium used at the time of attachment by a dispersing means such as a ball mill. The release agent fine particles and the inorganic fine particles are simultaneously attached to the surface of the colored resin particles by performing the same operation as the release agent fine particles are attached to the three-component dispersion liquid of the colored resin particles, the release agent fine particles and the inorganic fine particles. Can be made. In addition, the inorganic fine particles can be embedded by the same operation as that in which the release agent fine particles are embedded, and the release agent fine particles and the inorganic fine particles can be fixed to the surface of the colored resin particles.

【００３７】（ｂ）の方法では、前記の方法により離型
剤微粒子を付着させ、離型剤微粒子の付着した着色樹脂
粒子を一旦濾別、洗浄したのち、新規な分散媒に分散し
てからその分散液の無機微粒子を添加し、離型剤微粒子
を付着させたのと同様な操作を行うことにより離型剤微
粒子の付着した着色樹脂粒子に無機微粒子を付着させる
ことができる。無機微粒子を付着させた後、前記の方法
で離型剤微粒子と無機微粒子とを着色樹脂粒子表面に埋
設させ、固着させることができる。また、前記の方法で
離型剤微粒子を付着し埋設したのち濾別、洗浄を行い乾
燥し粉体とし、これと無機微粒子とをＶブレンダー、ミ
キサー等で混合し静電的に付着させてもよい。この場合
の無機微粒子の着色樹脂粒子表面への埋設は、ボールミ
ル、自動乳鉢、メカノフュージョン（ホソカワミクロン
社製）、Ｉ式ミル（日本ニューマチック工業社製）、ハ
イブリダイゼーションシステム（奈良機械社製）等によ
り機械的衝撃力を与え乾式処理で行うことが好ましい。In the method (b), the release agent fine particles are adhered by the above method, the colored resin particles to which the release agent fine particles are adhered are once filtered and washed, and then dispersed in a new dispersion medium. The inorganic fine particles can be attached to the colored resin particles to which the release agent fine particles are attached by performing the same operation as adding the inorganic fine particles of the dispersion and attaching the release agent fine particles. After the inorganic fine particles are attached, the release agent fine particles and the inorganic fine particles can be embedded and fixed on the surface of the colored resin particles by the above method. Further, after the release agent particles are adhered and embedded by the above method, filtered, washed, and dried to obtain a powder, and this is mixed with the inorganic particles by a V blender, a mixer or the like to be electrostatically adhered. Good. In this case, the inorganic fine particles are embedded on the surface of the colored resin particles by ball mill, automatic mortar, mechanofusion (manufactured by Hosokawa Micron Corporation), type I mill (manufactured by Nippon Pneumatic Industrial Co., Ltd.), hybridization system (manufactured by Nara Machine Co., Ltd.), etc. It is preferable to carry out dry treatment by applying mechanical impact force.

【００３８】無機微粒子としては、用いられる分散媒の
液体に不溶であり、粒径が１μｍ以下のものが好まし
い。また、これら無機微粒子は、この後の処理に用いる
カップリング剤と良好な反応性を有するものであること
が好ましい。これらの無機微粒子の具体例としては、酸
化ケイ素、酸化亜鉛、酸化アルミニウム、酸化チタン等
の酸化物、硫酸バリウム、硫酸カルシウム等の硫酸塩、
炭酸カルシウム、炭酸マグネシウム等の炭酸塩、リン酸
カルシウム等のリン酸塩、ベントナイト、酸性白土等が
挙げられる。無機微粒子の固着量は着色樹脂粒子１００
重量部に対し０．１重量部〜１．５重量部、好ましくは
０．２重量部〜１．０重量部である。固着量が０．１重
量部未満では静電荷現像用トナーとしての流動性、転写
性を改良する効果が少なく、１．５重量部より多いと定
着性が低下する。着色樹脂粒子表面に無機微粒子を固着
させることにより、離型剤微粒子による静電荷現像用ト
ナー相互間及び静電荷現像用トナーと現像部部材や静電
潜像担持体との間の付着力はかなり低減され、静電荷現
像用トナーとしての流動性、転写性が改善され、且つ離
型性も維持されるが、次のカップリング剤による処理に
より更にこれらの特性が改善される。The inorganic fine particles are preferably those which are insoluble in the liquid of the dispersion medium used and have a particle size of 1 μm or less. Further, it is preferable that these inorganic fine particles have good reactivity with the coupling agent used in the subsequent treatment. Specific examples of these inorganic particles include silicon oxide, zinc oxide, aluminum oxide, oxides such as titanium oxide, barium sulfate, sulfates such as calcium sulfate,
Examples thereof include carbonates such as calcium carbonate and magnesium carbonate, phosphates such as calcium phosphate, bentonite, and acid clay. The fixed amount of the inorganic fine particles is 100
The amount is 0.1 part by weight to 1.5 parts by weight, preferably 0.2 part by weight to 1.0 part by weight. If the fixing amount is less than 0.1 parts by weight, the effect of improving the fluidity and transferability of the toner for electrostatic charge development is small, and if it is more than 1.5 parts by weight, the fixing property is lowered. By fixing the inorganic fine particles on the surface of the colored resin particles, the adhesion force between the electrostatic charge developing toners by the release agent particles and between the electrostatic charge developing toner and the developing member or the electrostatic latent image carrier is considerably increased. Although it is reduced, the fluidity and transferability as a toner for electrostatic charge development are improved, and the releasability is maintained, but these properties are further improved by the subsequent treatment with a coupling agent.

【００３９】（４）着色樹脂粒子表面に離型剤微粒子と
無機微粒子を固着させた後のシランカップリング剤によ
る処理 シランカップリング剤による処理は、表面に離型剤微粒
子と無機微粒子とが固着された着色樹脂粒子にシランカ
ップリング剤を付着させ、加熱によりシランカップリン
グ剤を重合させることによって行われる。シランカップ
リング剤の付着は、表面に離型剤微粒子と無機微粒子と
が固着された着色樹脂粒子をＶブレンダー、ヘンシェル
ミキサー等で撹拌混合しながらシランカップリング剤溶
液を噴霧する方法、表面に離型剤微粒子と無機微粒子と
が固着された着色樹脂粒子の分散液にシランカップリン
グ剤溶液を添加し撹拌してから上記着色樹脂粒子を濾別
し乾燥する方法等により行うことができる。シランカッ
プリング剤を付着させた後、加熱によりシランカップリ
ング剤の重合が行われるが、着色樹脂粒子の融着を避け
るため樹脂のガラス転移温度（Ｔｇ）以下で行うことが
好ましい。例えば、５０℃〜７０℃で３時間〜５時間加
熱すれば充分にシランカップリング剤による処理の効果
を発揮することができる。シランカップリング剤は着色
樹脂粒子を溶解しない水または水とメタノールの混合液
などに溶解し用いるのが好ましい。(4) Treatment with a Silane Coupling Agent After Fixing Release Agent Fine Particles and Inorganic Fine Particles on the Surface of Colored Resin Particles In the treatment with a silane coupling agent, the release agent fine particles and the inorganic fine particles are fixed on the surface. A silane coupling agent is attached to the colored resin particles thus prepared, and the silane coupling agent is polymerized by heating. The adhesion of the silane coupling agent is carried out by spraying the silane coupling agent solution while stirring and mixing colored resin particles having release agent fine particles and inorganic fine particles adhered on the surface with a V blender, a Henschel mixer, or the like. The method can be carried out by adding a silane coupling agent solution to a dispersion liquid of colored resin particles to which the mold fine particles and the inorganic fine particles are fixed, stirring the mixture, and then filtering and drying the colored resin particles. After the silane coupling agent is attached, the silane coupling agent is polymerized by heating, but it is preferably performed at the glass transition temperature (Tg) or lower of the resin in order to avoid fusion of the colored resin particles. For example, heating at 50 ° C. to 70 ° C. for 3 hours to 5 hours can sufficiently exert the effect of the treatment with the silane coupling agent. The silane coupling agent is preferably used by dissolving it in water or a mixed solution of water and methanol that does not dissolve the colored resin particles.

【００４０】シランカップリング剤としては、モノアル
コキシ、ジアルコキシ、トリアルコキシ、テトラアルコ
キシシランのいずれも用いられるが、オルガノトリアル
コキシシランが好ましく用いられる。また、シランカッ
プリング剤が極性制御能をもつ官能基を持つ場合には上
記着色樹脂粒子に摩擦帯電能を付与することもできる。
シランカップリング剤の具体例としては、トリメチルメ
トキシシラン、ジメチルジメトキシシラン、トリメチル
トリメトキシシラン、テトラメトキシシラン、トリメチ
ルエトキシシラン、ジメチルジエトキシシラン、メチル
トリメトキシシラン、メチルトリプロポキシシラン、メ
チルトリブトキシシラン、フェニルトリメトキシシラ
ン、フェニルトリエトキシシラン、ビニルトリメトキシ
シラン、ビニルトリエトキシシラン、Ｎ−（２−アミノ
エチル）３−アミノプロピルメチルジメトキシシラン、
Ｎ−（２−アミノエチル）３−アミノプロピルトリメト
キシシラン、３−アミノプロピルトリメトキシシラン、
３−クロロプロピルトリメトキシシラン、ナノフルオロ
ブチルエチルメトキシシラン、パーフルオロオクチルエ
チルトリエトキシシラン、トリフルオロメチルエチルト
リメトキシシラン、パーフルオロオクチルエチルトリメ
トキシシラン、パーフルオロブチルエチルトリメトキシ
シラン等が例示できる。シランカップリング剤の付着量
としては、表面に離型剤微粒子と無機微粒子とが固着量
された着色樹脂粒子１００重量部に対し０．２重量部〜
２．０重量部が好ましい。このように離型剤微粒子と無
機微粒子を固着した後、シランカップリング剤で処理す
ることにより、表面に離型剤微粒子と無機微粒子とが固
着された着色樹脂粒子の外面にシランカップリング剤の
皮膜が形成され、静電荷現像用トナーとしての離型性を
充分に維持しながら流動性及び転写性がより改良され、
さらに耐久性、耐候性等の特性も改良される。As the silane coupling agent, any of monoalkoxy, dialkoxy, trialkoxy and tetraalkoxysilane can be used, and organotrialkoxysilane is preferably used. When the silane coupling agent has a functional group having a polarity controllability, the colored resin particles can be imparted with a triboelectric chargeability.
Specific examples of the silane coupling agent include trimethylmethoxysilane, dimethyldimethoxysilane, trimethyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, and methyltributoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,
Examples include 3-chloropropyltrimethoxysilane, nanofluorobutylethylmethoxysilane, perfluorooctylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, perfluorooctylethyltrimethoxysilane, and perfluorobutylethyltrimethoxysilane. . The amount of the silane coupling agent attached is 0.2 parts by weight to 100 parts by weight of the colored resin particles having the release agent particles and the inorganic particles adhered to the surface.
2.0 parts by weight is preferred. After fixing the release agent fine particles and the inorganic fine particles in this manner, by treating with the silane coupling agent, the release agent fine particles and the inorganic fine particles are fixed on the outer surface of the colored resin particles. A film is formed, and the fluidity and transferability are further improved while sufficiently maintaining the releasability as a toner for electrostatic charge development,
Further, characteristics such as durability and weather resistance are also improved.

【００４１】以上のようにして、本発明の静電荷現像用
トナーを得ることができる。さらに、静電荷現像用トナ
ーには、流動化剤を加え混合しても良い。流動化剤の添
加により静電荷現像用トナーの流動性、転写性は更に向
上する。これら流動化剤としては疎水性シリカ、シリ
カ、酸化チタン、酸化亜鉛等の無機微粉末、ステアリン
酸カルシウム、ステアリン酸亜鉛等の脂肪酸金属塩が用
いられる。混合方法としてはＶブレンダー、ヘンシェル
ミキサー等の一般的な混合装置を使用すれば良い。ま
た、静電荷現像用トナーを２成分現像剤として用いる場
合には、キャリアと混合して用いればよい。キャリアと
しては公知のものが使用可能で例えば、鉄、マグネタイ
ト、ヘマタイト、フェライト等の磁性を有する粉体、ガ
ラスビーズ等が挙げられる。これらキャリアの粒径は３
０μｍ〜５００μｍである。特に、シリコーン樹脂で被
覆されたキャリアが好ましく用いられる。キャリアに対
し静電荷現像用トナーを０．５重量％〜５重量％添加
し、上に挙げた一般的な混合装置で混合し２成分現像剤
を作ることができる。The electrostatic charge developing toner of the present invention can be obtained as described above. Further, a fluidizing agent may be added to and mixed with the electrostatic charge developing toner. Addition of a fluidizing agent further improves the fluidity and transferability of the electrostatic charge developing toner. As the fluidizing agent, hydrophobic silica, inorganic fine powder such as silica, titanium oxide and zinc oxide, and fatty acid metal salt such as calcium stearate and zinc stearate are used. As a mixing method, a general mixing device such as a V blender or a Henschel mixer may be used. When the electrostatic charge developing toner is used as a two-component developer, it may be mixed with a carrier and used. As the carrier, known carriers can be used, and examples thereof include magnetic powders such as iron, magnetite, hematite and ferrite, and glass beads. The particle size of these carriers is 3
It is 0 μm to 500 μm. In particular, a carrier coated with a silicone resin is preferably used. A two-component developer can be prepared by adding 0.5% to 5% by weight of the electrostatic charge developing toner to the carrier and mixing them with the above-mentioned general mixing device.

【００４２】[0042]

【作用】本発明の静電荷現像用トナーによれば、表面に
離型剤微粒子と無機微粒子とが固着された着色樹脂粒子
の外面にシランカップリング剤の皮膜を有することによ
り、静電荷現像用トナー相互間で離型剤微粒子が直接接
触することが防止されて静電荷現像用トナー同士の固着
が発生せず、また静電荷現像用トナーが現像部の部材に
接触したときに離型剤微粒子がそれら部材に直接接触す
ることが防止されるため、静電荷現像用トナーの流動性
が向上し、また静電潜像担持体上の静電潜像を現像した
ときに離型剤微粒子が静電潜像担持体に直接接触するこ
とが防止されるため、静電潜像担持体上のトナー画像を
被複写材に転写する際の転写性が向上し、さらにシラン
カップリング剤皮膜の低表面エネルギーと硬質性によ
り、流動性、転写性の向上が更に大きなものとなってい
るものと考えられる。また、トナー画像を加熱ローラー
によって加熱定着する際には、静電荷現像用トナーの表
面近傍に均一に分布している離型剤微粒子がトナー表面
に均一に溶出し効率よくオフセット防止ができるものと
考えられる。According to the toner for electrostatic charge development of the present invention, since the coating film of the silane coupling agent is provided on the outer surface of the colored resin particles having the release agent fine particles and the inorganic fine particles adhered to the surface, the toner for electrostatic charge development is provided. The release agent fine particles are prevented from directly contacting each other to prevent the electrostatic charge developing toner particles from sticking to each other, and the release agent fine particles are contacted when the electrostatic charge developing toner comes into contact with the member of the developing section. Are prevented from directly contacting those members, the fluidity of the toner for electrostatic charge development is improved, and when the electrostatic latent image on the electrostatic latent image carrier is developed, the release agent fine particles are statically removed. Direct contact with the latent electrostatic image bearing member is prevented, which improves transferability when the toner image on the latent electrostatic image bearing member is transferred to the material to be copied, and the low surface of the silane coupling agent film. Flowability and transferability due to energy and hardness Improved it can be considered to have become even greater things. In addition, when the toner image is heated and fixed by the heating roller, the release agent fine particles uniformly distributed in the vicinity of the surface of the electrostatic charge developing toner are uniformly eluted on the toner surface, and the offset can be efficiently prevented. Conceivable.

【００４３】着色樹脂粒子表面に離型剤微粒子と無機微
粒子が埋設され固着されている場合には、離型剤微粒子
の接触が更によりよく防止され、また静電荷現像用トナ
ー表面がより滑らかとなるため、静電荷現像用トナーの
流動性、転写性がより向上するとともに、オフセット防
止も充分に発揮できるものと考えられる。また、着色樹
脂粒子として、分散重合により得られた樹脂粒子を染料
によって着色してなる着色樹脂粒子を用いることによ
り、小粒径で粒径分布が狭くかつ表面形状が更に滑らか
な静電荷現像用トナーを得ることができ、その静電荷現
像用トナーを用いることによって、解像力、シャープ
度、ハーフトーン再現性などが良好な高画質の画像を、
経時による変化や画像欠陥を発生させることなく安定し
て得ることができる。When the release agent fine particles and the inorganic fine particles are embedded and fixed on the surface of the colored resin particles, the contact of the release agent fine particles is further prevented, and the electrostatic charge developing toner surface is made smoother. Therefore, it is considered that the fluidity and transferability of the electrostatic charge developing toner are further improved, and offset prevention can be sufficiently exerted. Further, by using colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye as the colored resin particles, for electrostatic charge development having a small particle size, a narrow particle size distribution, and a smoother surface shape. Toner can be obtained, and by using the toner for electrostatic charge development, a high-quality image with good resolution, sharpness, halftone reproducibility, etc. can be obtained.
A stable image can be obtained without causing a change with time or an image defect.

【００４４】さらに、本発明の静電荷現像用トナーの製
造方法によれば、離型性、流動性及び転写性の良好な静
電荷現像用トナーを簡易に得ることのできる。これは、
表面に離型剤微粒子と共に無機微粒子を固着させた着色
樹脂粒子シランカップリング剤で処理することにより、
無機微粒子がシランカップリング剤の反応の中心となり
静電荷現像用トナーのほぼ全面がシランカップリング剤
の重合物皮膜により容易に被覆されるからであると考え
られる。また、本発明の静電荷現像用トナーによれば、
離型剤微粒子の付着によるキャリア、電子写真感光体の
汚染も防止できて現像剤、電子写真感光体の耐久性が向
上する。Further, according to the method for producing an electrostatic charge developing toner of the present invention, an electrostatic charge developing toner having good releasability, fluidity and transferability can be easily obtained. this is,
By treating with colored resin particles silane coupling agent in which inorganic fine particles are fixed together with release agent fine particles on the surface,
It is considered that the inorganic fine particles become the center of the reaction of the silane coupling agent and almost the entire surface of the electrostatic charge developing toner is easily covered with the polymer film of the silane coupling agent. Further, according to the electrostatic charge developing toner of the present invention,
Contamination of the carrier and the electrophotographic photosensitive member due to the adhesion of the release agent particles can be prevented, and the durability of the developer and the electrophotographic photosensitive member is improved.

【００４５】[0045]

【実施例】次に、実施例により本発明を更に詳細に説明
する。以下に示す「部」「％」はいずれも重量基準であ
る。Next, the present invention will be described in more detail by way of examples. All “parts” and “%” shown below are based on weight.

【００４６】（樹脂粒子分散液の製造例）メチルビニル
エーテル無水マレイン酸共重合体（重量平均分子量４０
０００）７部をメタノール１００部に加熱溶解し分散安
定剤溶液を得た。撹拌装置、冷却管、窒素導入管、温度
計を備えた４つ口フラスコに 分散安定剤溶液 ２５０部 スチレン ６０部 アクリル酸メチル ４０部 ドデシルメルカプタン １部 １，３−ブタンジオールジメタクリレート １．５部 を仕込みＮ2ガスで空気を完全にパージし液温を６０℃
とした後、２，２′−アゾビスイソブチロニトリル２．
０部を添加し重合を開始し、１００ｒｐｍの撹拌回転で
２４時間重合を行い樹脂粒子分散液を得た。得られた樹
脂粒子はコールターマルチサイザーによる２０μｍパー
チヤーチューブでの粒径分布測定では、粒子個数５万カ
ウントで体積平均粒径が６．７３μｍ、個数平均粒径が
６．６００μｍ、その比が１．０２であった。また重量
法により重合率を測定したところ９５．２％であった。(Production Example of Resin Particle Dispersion) Methyl vinyl ether maleic anhydride copolymer (weight average molecular weight 40
000) 7 parts by heating in 100 parts of methanol to obtain a dispersion stabilizer solution. Dispersion stabilizer solution 250 parts Styrene 60 parts Methyl acrylate 40 parts Dodecyl mercaptan 1 part 1,3-Butanediol dimethacrylate 1.5 parts In a four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer. And purge the air completely with N 2 gas to maintain the liquid temperature at 60 ° C.
, 2,2'-azobisisobutyronitrile 2.
Polymerization was started by adding 0 part, and the polymerization was carried out for 24 hours at 100 rpm with stirring and rotation to obtain a resin particle dispersion. The particle size distribution of the resin particles thus obtained was measured by a Coulter Multisizer in a 20 μm perforated tube, and the volume average particle size was 6.73 μm and the number average particle size was 6.600 μm at a particle count of 50,000. It was 0.02. Further, the polymerization rate was measured by the gravimetric method and found to be 95.2%.

【００４７】（着色樹脂粒子の製造例）オイルブラック
８６０（オリエント化学社製）６部を上記樹脂粒子分散
液に加え、５０℃で２時間撹拌し、その後分散液を室温
まで冷却し遠心沈降し上澄みを除き、メタノール５０部
と水５０部の混合溶媒に再分散する操作を３回行い洗浄
した後、吸引濾過し、これを３５℃で減圧乾燥し着色樹
脂粒子を得た。(Production Example of Colored Resin Particles) 6 parts of Oil Black 860 (manufactured by Orient Chemical Co., Ltd.) were added to the above resin particle dispersion and stirred at 50 ° C. for 2 hours, after which the dispersion was cooled to room temperature and spun down. The supernatant was removed, and re-dispersion in a mixed solvent of 50 parts of methanol and 50 parts of water was repeated three times for washing, followed by suction filtration and drying under reduced pressure at 35 ° C. to obtain colored resin particles.

【００４８】（離型剤微粒子分散液の製造例）オイルバ
ス中に設置した、撹拌装置、冷却管、滴下ロートを備え
た密閉可能な容器にカルナウバワックス（１号）２６部
を入れ徐々に加温し１００℃で溶融した後撹拌しながら
非イオン性界面活性剤ポリオキシエチレンノニフェニル
エーテル（平均オキシエチレン付加モル数＝１５）４部
を加え完全に溶解した。その後撹拌しながら９８℃の水
７０部を徐々に添加し１時間撹拌した後、撹拌しながら
２５℃まで急冷した。撹拌を停止し６時間放置した後沈
降物を取り除き離型剤微粒子分散液を得た。さらにイオ
ン交換水で固型分濃度３０％に調整した。得られた離型
剤微粒子分散液を動的光散乱計ＤＬＳ７００（大塚電子
（株）社製）で測定したところ離型剤微粒子の体積平均
粒径は０．１５１μｍ、個数平均粒径は０．１１μｍで
あった。(Production Example of Release Agent Fine Particle Dispersion) 26 parts of carnauba wax (No. 1) was gradually placed in a sealable container equipped with an agitator, a cooling pipe and a dropping funnel, which was installed in an oil bath. After heating and melting at 100 ° C., 4 parts of a nonionic surfactant polyoxyethylene noniphenyl ether (average number of moles of oxyethylene added = 15) was added with stirring and completely dissolved. Then, 70 parts of 98 ° C. water was gradually added with stirring and stirred for 1 hour, and then rapidly cooled to 25 ° C. with stirring. After stirring was stopped and the mixture was left standing for 6 hours, the precipitate was removed to obtain a release agent fine particle dispersion. Further, the solid content concentration was adjusted to 30% with ion-exchanged water. The obtained release agent fine particle dispersion was measured with a dynamic light scattering meter DLS700 (manufactured by Otsuka Electronics Co., Ltd.), and the release agent fine particles had a volume average particle diameter of 0.151 μm and a number average particle diameter of 0.15 μm. It was 11 μm.

【００４９】（無機微粒子分散液の製造例１）酸化ケイ
素（アエロジル２００、日本アエロジル社製）１０部を
水４５部とメタノール４５部の混合液に加え、４ｍｍ径
のアルミナボールを入れたボールミルにより５時間ボー
ルミル分散して無機微粒子分散液を得た。(Preparation Example 1 of Inorganic Fine Particle Dispersion) 10 parts of silicon oxide (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) was added to a mixed solution of 45 parts of water and 45 parts of methanol, and a ball mill containing 4 mm diameter alumina balls was added. Ball mill dispersion was carried out for 5 hours to obtain an inorganic fine particle dispersion.

【００５０】（無機微粒子分散液の製造例２）酸化ケイ
素の代わりに酸化チタン（Ｐ２５、日本アエロジル社
製）を用いた以外は製造例１と同じ方法により無機微粒
子分散液を得た。(Production Example 2 of Inorganic Fine Particle Dispersion Liquid) An inorganic fine particle dispersion liquid was obtained in the same manner as in Production Example 1 except that titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was used instead of silicon oxide.

【００５１】実施例１ 製造例で得られた着色樹脂粒子３０部を水：メタノール
＝３０部：７０部の混合液２７０部に添加し撹拌した後
超音波分散を行い着色樹脂粒子分散液を得た。この着色
樹脂粒子分散液を撹拌装置、冷却管、温度計を備えた４
つ口フラスコにとり、室温で製造例の離型剤微粒子分散
液３部を加え、撹拌下ステアリルアミンアセテートの
０．４％メタノール溶液１０部を滴下し、離型剤微粒子
を着色樹脂粒子表面に付着させた。この後、恒温水槽で
５０℃、１時間加熱して離型剤微粒子を着色樹脂粒子表
面に固着させた。冷却後水８０部を加え目開き２２μｍ
のステンレス製ふるいを通過させた。この通過分散液を
吸引濾過後、水：メタノール＝５０部：５０部の混合液
１００部に再分散し室温で３０分撹拌した後吸引濾過し
た。この離型剤微粒子を固着した着色樹脂粒子を水：メ
タノール＝３０部：７０部の混合液２７０部に再分散し
た。この分散液を前と同じ４つ口フラスコにとり、製造
例１の酸化ケイ素分散液１．５部を添加し撹拌下ステア
リルアミンアセテートの０．４％メタノール溶液１０部
を滴下し、無機微粒子を着色樹脂粒子表面に付着させ
た。この後、恒温水槽で５０℃で１時間加熱して無機微
粒子を着色樹脂粒子表面に固着させた。この分散液に３
％メチルトリメトキシシラン水溶液１０部を添加し５０
℃で４時間加熱した。これを吸引濾過後、水：メタノー
ル＝５０部：５０部の混合液１００部に再分散し室温で
３０分撹拌後吸引濾過し、さらに５０℃で５時間減圧乾
燥して実施例１の静電荷現像用トナーを得た。この静電
荷現像用トナーを走査型電子顕微鏡（ＳＥＭ）により観
察したところ、離型剤微粒子及び無機微粒子は、それぞ
れの径の約１０〜２０％が着色樹脂粒子表面と融合した
状態で固着されていた。Example 1 30 parts of the colored resin particles obtained in the production example was added to 270 parts of a mixed solution of water: methanol = 30 parts: 70 parts, stirred and ultrasonically dispersed to obtain a colored resin particle dispersion liquid. It was This colored resin particle dispersion liquid was equipped with a stirrer, a cooling pipe, and a thermometer.
Transfer to a one-necked flask, add 3 parts of the release agent fine particle dispersion liquid of the production example at room temperature, and add 10 parts of 0.4% methanol solution of stearylamine acetate with stirring to attach the release agent fine particles to the surface of the colored resin particles. Let Then, the release agent particles were fixed on the surface of the colored resin particles by heating in a constant temperature water bath at 50 ° C. for 1 hour. After cooling, add 80 parts of water and open the mesh 22μm.
Through a stainless steel sieve. This passing dispersion was suction filtered, redispersed in 100 parts of a mixed solution of water: methanol = 50 parts: 50 parts, stirred at room temperature for 30 minutes, and then suction filtered. The colored resin particles to which the release agent particles were fixed were redispersed in 270 parts of a mixed solution of water: methanol = 30 parts: 70 parts. This dispersion was placed in the same 4-neck flask as before, 1.5 parts of the silicon oxide dispersion of Production Example 1 was added, and 10 parts of a 0.4% methanol solution of stearylamine acetate was added dropwise with stirring to color the inorganic fine particles. It was attached to the surface of the resin particles. Then, the particles were heated in a constant temperature water bath at 50 ° C. for 1 hour to fix the inorganic fine particles to the surface of the colored resin particles. 3 in this dispersion
% 10% aqueous solution of methyltrimethoxysilane was added to 50
Heated at ° C for 4 hours. This was suction filtered, redispersed in 100 parts of a mixed solution of water: methanol = 50 parts: 50 parts, stirred at room temperature for 30 minutes, suction filtered, and further dried under reduced pressure at 50 ° C. for 5 hours to obtain the electrostatic charge of Example 1. A developing toner was obtained. When the electrostatic charge developing toner is observed by a scanning electron microscope (SEM), about 10 to 20% of the respective diameters of the release agent fine particles and the inorganic fine particles are fixed in a state of being fused with the surface of the colored resin particles. It was

【００５２】実施例２ 製造例で得られた着色樹脂粒子３０部を水：メタノール
＝３０部：７０部の混合液２７０部に添加し撹拌した後
超音波分散を行い着色樹脂粒子分散液を得た。この着色
樹脂粒子分散液を実施例１と同様の４つ口フラスコにと
り、室温で製造例の離型剤微粒子分散液３部と製造例２
の酸化チタン分散液１．５部を加え撹拌下ステアリルア
ミンアセテートの０．４％メタノール溶液１０部を滴下
し、離型剤微粒子と酸化チタン微粒子を着色樹脂粒子表
面に付着させた。この後、恒温水槽で５０℃で１時間加
熱し離型剤微粒子と酸化チタン微粒子を着色樹脂粒子表
面に固着させた。その後３％トリメトキシシラン水溶液
１０部を添加し５０℃で５時間加熱撹拌した後吸引濾過
し、水：メタノール＝５０部：５０部の混合液１００部
に再分散した。この分散液を室温で３０分撹拌した後吸
引濾過し、これを５０℃で５時間減圧乾燥して実施例２
の静電荷現像用トナーを得た。Example 2 30 parts of the colored resin particles obtained in the production example was added to 270 parts of a mixed solution of water: methanol = 30 parts: 70 parts and stirred, and then ultrasonically dispersed to obtain a colored resin particle dispersion liquid. It was This colored resin particle dispersion liquid was placed in a four-necked flask similar to that of Example 1, and 3 parts of the release agent fine particle dispersion liquid of Production Example and Production Example 2 were allowed to stand at room temperature.
1.5 parts of the titanium oxide dispersion of was added and 10 parts of a 0.4% methanol solution of stearylamine acetate was added dropwise with stirring to adhere the release agent particles and the titanium oxide particles to the surface of the colored resin particles. Then, the release agent fine particles and the titanium oxide fine particles were fixed to the surface of the colored resin particles by heating in a constant temperature water bath at 50 ° C. for 1 hour. Thereafter, 10 parts of a 3% trimethoxysilane aqueous solution was added, and the mixture was heated and stirred at 50 ° C. for 5 hours, suction filtered, and redispersed in 100 parts of a mixed solution of water: methanol = 50 parts: 50 parts. The dispersion was stirred at room temperature for 30 minutes, suction filtered, and dried under reduced pressure at 50 ° C. for 5 hours to give Example 2.
To obtain a toner for electrostatic charge development.

【００５３】実施例３ 製造例で得られた着色樹脂粒子３０部を水：メタノール
＝３０部：７０部の混合液２７０部に添加し撹拌した後
超音波分散を行い着色樹脂粒子分散液を得た。この着色
樹脂粒子分散液を実施例１と同様の４つ口フラスコにと
り、室温で製造例の離型剤微粒子分散液３部を加え撹拌
下ステアリルアミンアセテートの０．４％メタノール溶
液１０部を滴下し、離型剤微粒子を着色樹脂粒子表面に
付着させた。この後、恒温水槽で５０℃、５時間加熱し
た。冷却した後水８０部を加え目開き２２μｍのステン
レス製ふるいを通過させた。この通過分散液を吸引濾過
後、水：メタノール＝５０部：５０部の混合液１００部
に再分散し室温で３０分撹拌した後吸引濾過し減圧乾燥
を行い、離型剤微粒子を表面に埋設した着色樹脂粒子を
得た。この着色樹脂粒子３０部に酸化ケイ素微粒子（ア
エロジル２００、日本アエロジル社製）０．１５部をミ
キサーで混合した後、４ｍｍ径のアルミナボールを入れ
たボールミルで５時間ボールミルし酸化ケイ素微粒子を
着色樹脂粒子表面に埋設固着させた。この着色樹脂粒子
を水：メタノール＝５０部：５０部の混合液３０部に分
散し、これに３％メチルトリメトキシシラン水溶液１０
部を加え５０℃で５時間加熱した後吸引濾過した。これ
を５０℃で５時間減圧乾燥し実施例３の静電荷現像用ト
ナーを得た。この静電荷現像用トナーを走査型電子顕微
鏡（ＳＥＭ）により観察したところ、離型剤微粒子及び
無機微粒子は、それぞれの径の約８０〜９０％が着色樹
脂粒子表面に埋め込まれて融合した状態で固着されてい
た。Example 3 30 parts of the colored resin particles obtained in the production example was added to 270 parts of a mixed solution of water: methanol = 30 parts: 70 parts and stirred, and then ultrasonically dispersed to obtain a colored resin particle dispersion liquid. It was This colored resin particle dispersion is placed in a four-necked flask similar to that of Example 1, 3 parts of the release agent fine particle dispersion of the production example is added at room temperature, and 10 parts of a 0.4% methanol solution of stearylamine acetate is added dropwise with stirring. Then, the release agent particles were attached to the surface of the colored resin particles. After that, it was heated in a constant temperature water bath at 50 ° C. for 5 hours. After cooling, 80 parts of water was added and the mixture was passed through a stainless sieve having a mesh of 22 μm. This passing dispersion is suction filtered, redispersed in 100 parts of a mixed solution of water: methanol = 50 parts: 50 parts, stirred at room temperature for 30 minutes, suction filtered and dried under reduced pressure to embed release agent fine particles on the surface. The colored resin particles thus obtained were obtained. 30 parts of the colored resin particles were mixed with 0.15 part of silicon oxide fine particles (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) with a mixer and then ball-milled for 5 hours with a ball mill containing alumina balls having a diameter of 4 mm. It was embedded and fixed on the surface of the particles. The colored resin particles were dispersed in 30 parts of a mixed solution of water: methanol = 50 parts: 50 parts, and a 3% methyltrimethoxysilane aqueous solution 10
Then, the mixture was heated at 50 ° C. for 5 hours and then suction filtered. This was dried under reduced pressure at 50 ° C. for 5 hours to obtain a toner for electrostatic charge development of Example 3. Observation of this electrostatic charge developing toner with a scanning electron microscope (SEM) revealed that about 80 to 90% of the respective diameters of the release agent fine particles and the inorganic fine particles were embedded and fused in the surface of the colored resin particles. It was fixed.

【００５４】実施例４ 実施例３の酸化ケイ素を酸化チタン微粒子（Ｐ２５、日
本アエロジル社製）に代えた以外は実施例３と同じ方法
により実施例４の静電荷現像用トナーを得た。Example 4 A toner for electrostatic charge development of Example 4 was obtained in the same manner as in Example 3, except that the silicon oxide of Example 3 was replaced with titanium oxide fine particles (P25, manufactured by Nippon Aerosil Co., Ltd.).

【００５５】実施例５ 実施例３のメチルトリメトキシシランをトリフルオロメ
チルエチルトリメトキシシランに代えた以外は実施例３
と同じ方法により実施例５の静電荷現像用トナーを得
た。Example 5 Example 3 was repeated except that the methyltrimethoxysilane of Example 3 was replaced with trifluoromethylethyltrimethoxysilane.
A toner for developing an electrostatic charge of Example 5 was obtained by the same method as described above.

【００５６】実施例６ 実施例３のメチルトリメトキシシランをフェニルトリメ
トキシシランに代えた以外は実施例３と同じ方法により
実施例６の静電荷現像用トナーを得た。Example 6 An electrostatic charge developing toner of Example 6 was obtained in the same manner as in Example 3, except that methyltrimethoxysilane in Example 3 was replaced with phenyltrimethoxysilane.

【００５７】実施例７ 製造例の着色樹脂粒子３０部を水：メタノール＝３０
部：７０部の混合液２７０部に添加した後超音波分散し
着色樹脂粒子分散液を得た。これに実施例３と同じ方法
により離型剤微粒子を固着させ、さらに酸化ケイ素を乾
式で固着したのち、実施例３と同じ方法でメチルトリメ
トキシシランによる処理を行い実施例７の静電荷現像用
トナーを得た。Example 7 30 parts of the colored resin particles of the production example were mixed with water: methanol = 30.
Parts: Added to 270 parts of 70 parts of the mixed solution and then ultrasonically dispersed to obtain a colored resin particle dispersion. The release agent fine particles are fixed to this by the same method as in Example 3, and further silicon oxide is fixed by dry method, and then treated with methyltrimethoxysilane in the same method as in Example 3 to perform electrostatic charge development of Example 7. Toner was obtained.

【００５８】比較例１ 酸化ケイ素の固着及びメチルトリメトキシシランによる
処理を行わない他は実施例７と同じ方法で着色樹脂粒子
に離型剤微粒子を固着させ比較例１の静電荷現像用トナ
ーを得た。Comparative Example 1 The electrostatic charge developing toner of Comparative Example 1 was prepared by fixing release agent fine particles to colored resin particles in the same manner as in Example 7 except that fixing of silicon oxide and treatment with methyltrimethoxysilane were not performed. Obtained.

【００５９】比較例２ 酸化ケイ素の固着を行わない他は実施例７と同じ方法で
着色樹脂粒子に離型剤微粒子を固着しメチルトリメトキ
シシランによる処理を行い比較例２の静電荷現像用トナ
ーを得た。Comparative Example 2 Toner for electrostatic charge development of Comparative Example 2 was carried out by fixing fine particles of a release agent to colored resin particles and treating with methyltrimethoxysilane in the same manner as in Example 7 except that silicon oxide was not fixed. Got

【００６０】比較例３ 実施例３と同じ方法で着色樹脂粒子に離型剤微粒子を固
着したのち疎水性酸化ケイ素微粒子を固着し、メチルト
リメトキシシランによる処理を行わないで比較例３の静
電荷現像用トナーを得た。Comparative Example 3 In the same manner as in Example 3, the release agent particles were fixed to the colored resin particles, and then the hydrophobic silicon oxide particles were fixed to the colored resin particles, and the electrostatic charge of Comparative Example 3 was applied without treatment with methyltrimethoxysilane. A developing toner was obtained.

【００６１】実施例及び比較例の静電荷現像用トナー２
０部に疎水性シリカ０．２部をミキサーで混合し、これ
をシリコーン樹脂被覆した７５μｍのフェライトキャリ
ア７８０部とボールミルを用いて混合して現像剤を作製
した。これらの現像剤を用いＰＰＣ複写機（イマジオ４
２０、リコー社製）により、静電潜像の現像、トナー画
像の転写紙への転写、転写紙上のトナー画像の加熱ロー
ラーによる定着、分離爪による転写紙の加熱ローラーか
らの分離を行い、下記の方法によって転写性（転写
率）、離型性、画像のシャープ性、定着性の評価を行っ
た。その結果を表１に示す。なお、加熱ローラーによる
定着では加熱ローラーへのシリコーンオイル塗布は行な
わなかった。Toner 2 for electrostatic charge development of Examples and Comparative Examples
0.2 part of hydrophobic silica was mixed with 0 part with a mixer, and this was mixed with 780 parts of 75 μm ferrite carrier coated with silicone resin using a ball mill to prepare a developer. PPC copiers (Imagio 4) using these developers
20, manufactured by Ricoh Co., Ltd.), the electrostatic latent image is developed, the toner image is transferred to the transfer paper, the toner image on the transfer paper is fixed by the heating roller, and the transfer paper is separated from the heating roller by the separating claw. The transferability (transfer rate), the releasability, the sharpness of the image, and the fixing property were evaluated by the method described above. Table 1 shows the results. In the fixing with the heating roller, silicone oil was not applied to the heating roller.

【００６２】（転写率）全面黒の原稿を現像し転写途中
で機械を停止し、感光体上の転写部および未転写部のト
ナーを重量既知、面積一定の粘着紙に移しとり、各々重
量を測定し転写率を下記の様に求めた。 〔（未転写部の重量−転写部の重量）／未転写部の重
量〕×１００ （離型性）全面黒（黒ベタ）画像を複写し分離爪の爪跡
の発生状態（爪跡の長さ）を５段階で評価した。加熱ロ
ーラーからの離型性が不良であると、加熱ローラーから
転写紙を引き剥がすための分離用爪のひっかき跡（爪
跡）が全面に黒（黒ベタ）画像を有する転写紙に数本の
線状となって残ることから、爪跡の長さを測定し、その
平均長さにより下記の５段階で評価を行った。 ５：爪跡発生なし ４：爪跡１ｍｍ未満 ３：爪跡１ｍｍ以上１０ｍｍ未満 ２：爪跡１０ｍｍ以上２０ｍｍ未満 １：爪跡２０ｍｍ以上 （画像濃度）直径１０ｍｍの円形画像の反射濃度をマク
ベス濃度計で測定した。 （画像のシャープ性）ドット画像を光学顕微鏡で観察し
画像の状態を５段階評価した。 ５：トナーがドット部分のみに存在し輪郭が明瞭。 ４：トナーの大部分がドット部分に存在するが輪郭はや
や不明瞭。 ３：トナーがドット部分に多く存在するが輪郭が不明
瞭。 ２：トナーの散りが大であるがドットの存在は判別でき
る。 １：トナーの散りが大でドットの存在が判別できない。 判定は限度見本による。 （定着性）イマジオ４２０の定着装置（条件一定）で定
着後、黒ベタ画像を描画試験機にかけ画像の脱離状態を
５段階で評価した。 ５：描画部分の大部分が剥離していない。 ４：描画部分が点状に剥離している。 ３：描画部分が破線状に剥離している。 ２：描画部分が全部剥離し、剥離の巾が狭い。 １：描画部分が全部剥離し、剥離の巾が広い。 判定は限度見本による。(Transfer Rate) A black original document is developed, the machine is stopped in the middle of the transfer, and the toners of the transferred portion and the untransferred portion on the photoconductor are transferred to an adhesive paper of known weight and constant area, and the weight of each is transferred. The transfer rate was measured and determined as follows. [(Weight of untransferred portion-Weight of transferred portion) / Weight of untransferred portion] x 100 (Releasability) Fully black (black solid) Copying an image, the state of occurrence of nail marks on separated nails (length of nail marks) Was evaluated on a 5-point scale. If the releasability from the heating roller is poor, the scratch marks (nail marks) on the separating nail for peeling the transfer paper from the heating roller have a black (black solid) image on the entire surface. Since it remains in a shape, the length of the nail mark was measured, and the average length was used to evaluate the following 5 grades. 5: No nail mark generation 4: Nail mark less than 1 mm 3: Nail mark 1 mm or more and less than 10 mm 2: Nail mark 10 mm or more and less than 20 mm 1: Nail mark 20 mm or more (Image density) The reflection density of a circular image having a diameter of 10 mm was measured with a Macbeth densitometer. (Sharpness of image) The dot image was observed with an optical microscope, and the state of the image was evaluated in five levels. 5: Toner is present only in the dot portion and the contour is clear. 4: Most of the toner exists in the dot portion, but the outline is slightly unclear. 3: A lot of toner is present in the dot portion, but the outline is unclear. 2: The toner is largely scattered, but the existence of dots can be identified. 1: The amount of toner is large and the presence of dots cannot be determined. The judgment is based on the limit sample. (Fixability) After fixing with the fixing device of IMAGEO 420 (constant conditions), a black solid image was put on a drawing tester and the detached state of the image was evaluated on a five-point scale. 5: Most of the drawn portion is not peeled off. 4: The drawn portion is peeled off like dots. 3: The drawn portion is peeled off in a broken line shape. 2: The drawn portion is completely peeled off, and the peeling width is narrow. 1: All the drawn parts are peeled off, and the peeling width is wide. The judgment is based on the limit sample.

【００６３】[0063]

【表１】 [Table 1]

【００６４】表１から明らかなように、（１）本発明の
静電荷現像用トナーは、疎水性無機微粒子を固着しシラ
ンカップリング剤による処理を行わなかった比較例３の
静電荷現像用トナーに比べ、特に転写性が優れているも
のである。（２）本発明の静電荷現像用トナーは、無機
微粒子の固着及びシランカップリング剤の処理を行わな
かった比較例１の静電荷現像用トナーに比較し、定着性
が若干低下するが、離型性、転写性、画像濃度及び画像
のシャープ性に優れているものである。（３）本発明の
静電荷現像用トナーは、離型剤微粒子を固着し、無機微
粒子の固着を行わずにシランカップリング剤の処理を行
った比較例２の静電荷現像用トナーに比較し、定着性が
若干低下するが、離型性、転写性、画像濃度及び画像の
シャープ性に優れているものである。すなわち、本発明
の静電荷現像用トナーは、離型性に優れ、且つ転写性に
も優れているものである。また、画像濃度が高く、画像
のシャープ性に優れ高画質のトナー画像が得られるもの
である。更に、本発明の静電荷現像用トナーの製造方法
においては、離型剤微粒子を固着した後無機微粒子を固
着したほうが転写性が良好であり、無機微粒子を機械的
衝撃力で固着したほうが転写性が良好である。また、着
色樹脂粒子を膨潤しうる分散媒中で加熱して、着色樹脂
粒子表面に付着している離型剤微粒子を着色樹脂粒子表
面に埋設し固着したほうが転写性が優れている。As is clear from Table 1, (1) the electrostatic charge developing toner of the present invention is the electrostatic charge developing toner of Comparative Example 3 in which the hydrophobic inorganic fine particles are fixed and the treatment with the silane coupling agent is not performed. In particular, it has excellent transferability. (2) The electrostatic charge developing toner of the present invention is slightly lower in fixability than the electrostatic charge developing toner of Comparative Example 1 in which the inorganic fine particles are not fixed and the silane coupling agent is not treated. It is excellent in moldability, transferability, image density and image sharpness. (3) The electrostatic charge developing toner of the present invention is compared with the electrostatic charge developing toner of Comparative Example 2 in which the release agent particles are fixed and the silane coupling agent is treated without fixing the inorganic particles. Although the fixing property is slightly lowered, it is excellent in releasability, transferability, image density and image sharpness. That is, the toner for electrostatic charge development of the present invention is excellent in releasability and transferability. In addition, the image density is high, the sharpness of the image is excellent, and a high-quality toner image can be obtained. Furthermore, in the method for producing a toner for electrostatic charge development of the present invention, the transferability is better when the release agent particles are fixed and then the inorganic particles are fixed, and the transferability is obtained when the inorganic particles are fixed by mechanical impact force. Is good. The transferability is better when the colored resin particles are heated in a swellable dispersion medium so that the release agent particles adhered to the surface of the colored resin particles are embedded and fixed on the surface of the colored resin particles.

【００６５】[0065]

【発明の効果】本発明の静電荷現像用トナーによれば、
良好な離型性、流動性及び転写性が得られる。また、分
散重合により得られた樹脂粒子を染料によって着色して
なる着色樹脂粒子を用いた本発明の静電荷現像用トナー
によれば、離型性、流動性及び転写性が良好であること
に加え、静電荷現像用トナーが小粒径で粒径分布が狭く
表面形状が滑らかであることにより、高画質の画像を、
経時による変化や画像欠陥を発生させることなく安定し
て得ることができる。さらに、本発明の静電荷現像用ト
ナーの製造方法によれば、上記性能を有する静電荷現像
用トナーを簡易に得ることができる。According to the electrostatic charge developing toner of the present invention,
Good releasability, fluidity and transferability are obtained. Further, according to the toner for electrostatic charge development of the present invention using colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye, good releasability, fluidity and transferability are obtained. In addition, since the toner for electrostatic charge development has a small particle size, a narrow particle size distribution, and a smooth surface shape, a high quality image can be obtained.
A stable image can be obtained without causing a change with time or an image defect. Further, according to the method for producing an electrostatic charge developing toner of the present invention, it is possible to easily obtain the electrostatic charge developing toner having the above performance.

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】 着色剤と樹脂を主成分とし表面に離型剤
微粒子と無機微粒子とが固着されてなる着色樹脂粒子の
外面にシランカップリング剤の皮膜を有することを特徴
とする静電荷現像用トナー。1. An electrostatic charge development characterized in that a coating film of a silane coupling agent is provided on the outer surface of colored resin particles which are composed mainly of a coloring agent and a resin and on which fine particles of a releasing agent and inorganic particles are fixed. For toner. 【請求項２】 着色樹脂粒子表面に離型剤微粒子が埋設
され固着されていることを特徴とする請求項１記載の静
電荷現像用トナー。2. The electrostatic charge developing toner according to claim 1, wherein release agent fine particles are embedded and fixed on the surface of the colored resin particles. 【請求項３】 着色樹脂粒子表面に離型剤微粒子と無機
微粒子が埋設され固着されていることを特徴とする請求
項１記載の静電荷現像用トナー。3. The toner for electrostatic charge development according to claim 1, wherein release agent fine particles and inorganic fine particles are embedded and fixed on the surface of the colored resin particles. 【請求項４】 着色樹脂粒子が分散重合により得られた
樹脂粒子を染料によって着色してなる着色樹脂粒子であ
ることを特徴とする請求項１、２または３記載の静電荷
現像用トナー。4. The toner for electrostatic charge development according to claim 1, wherein the colored resin particles are colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye. 【請求項５】 離型剤微粒子及び無機微粒子の固着量
が、着色樹脂粒子１００重量部に対し、それぞれ１乃至
５重量部及び０．１乃至１．５重量部であることを特徴
とする請求項１、２、３または４記載の静電荷現像用ト
ナー。5. The releasing agent fine particles and the inorganic fine particles are fixed in an amount of 1 to 5 parts by weight and 0.1 to 1.5 parts by weight, respectively, relative to 100 parts by weight of the colored resin particles. Item 4. The electrostatic charge developing toner according to item 1, 2, 3 or 4. 【請求項６】 シランカップリング剤の付着量が、表面
に離型剤微粒子と無機微粒子が固着されてなる着色樹脂
粒子１００重量部に対し０．２乃至２．０重量部である
ことを特徴とする請求項１、２、３、４または５記載の
静電荷現像用トナー。6. The amount of the silane coupling agent adhered is 0.2 to 2.0 parts by weight with respect to 100 parts by weight of the colored resin particles having release agent fine particles and inorganic fine particles adhered to the surface thereof. The electrostatic charge developing toner according to claim 1, 2, 3, 4, or 5. 【請求項７】 着色剤と樹脂を主成分とする着色樹脂粒
子表面に離型剤微粒子と無機微粒子とを固着させた後シ
ランカップリング剤で処理することを特徴とする静電荷
現像用トナーの製造方法。7. A toner for electrostatic charge development, characterized in that release agent fine particles and inorganic fine particles are adhered to the surface of a colored resin particle containing a colorant and a resin as main components and then treated with a silane coupling agent. Production method. 【請求項８】 着色樹脂粒子表面に離型剤微粒子を固着
させた後に無機微粒子を固着させることを特徴とする請
求項７記載の静電荷現像用トナーの製造方法。8. The method for producing a toner for electrostatic charge development according to claim 7, wherein the release agent fine particles are fixed to the surface of the colored resin particles, and then the inorganic fine particles are fixed. 【請求項９】 着色樹脂粒子表面に離型剤微粒子を付着
させた後、該着色樹脂粒子を膨潤しうる分散媒中で加熱
し離型剤微粒子を着色樹脂粒子表面に埋設させて固着さ
せ、その後着色樹脂粒子表面に無機微粒子を固着させる
ことを特徴とする請求項７記載の静電荷現像用トナーの
製造方法。9. After the release agent fine particles are attached to the surface of the colored resin particles, the release agent fine particles are embedded in the surface of the colored resin particles and fixed by heating in a dispersion medium capable of swelling the colored resin particles, The method for producing a toner for electrostatic charge development according to claim 7, wherein inorganic fine particles are fixed to the surface of the colored resin particles. 【請求項１０】 着色樹脂粒子表面に離型剤微粒子と無
機微粒子を付着させた後、該着色樹脂粒子を膨潤しうる
分散媒中で加熱し離型剤微粒子と無機微粒子とを着色樹
脂粒子表面に埋設させて固着させることを特徴とする請
求項７記載の静電荷現像用トナーの製造方法。10. The release agent fine particles and the inorganic fine particles are adhered to the surface of the colored resin particles, and then the release agent fine particles and the inorganic fine particles are heated in a dispersion medium capable of swelling the colored resin particles to form the surface of the colored resin particles. 8. The method for producing a toner for electrostatic charge development according to claim 7, wherein the toner is embedded in and fixed to the toner. 【請求項１１】 着色樹脂粒子が分散重合により得られ
た樹脂粒子を染料によって着色してなる着色樹脂粒子で
あることを特徴とする請求項７、８、９または１０記載
の静電荷現像用トナーの製造方法。11. The electrostatic charge developing toner according to claim 7, wherein the colored resin particles are colored resin particles obtained by coloring resin particles obtained by dispersion polymerization with a dye. Manufacturing method.
JP12315295A 1995-04-24 1995-04-24 Toner for electrostatic charge development and its production Pending JPH08292599A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12315295A JPH08292599A (en) 1995-04-24 1995-04-24 Toner for electrostatic charge development and its production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12315295A JPH08292599A (en) 1995-04-24 1995-04-24 Toner for electrostatic charge development and its production

Publications (1)

Publication Number Publication Date
JPH08292599A true JPH08292599A (en) 1996-11-05

Family

ID=14853477

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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US10345726B2 (en) 2017-05-15 2019-07-09 Canon Kabushiki Kaisha Method of manufacturing toner
US10353308B2 (en) 2017-05-15 2019-07-16 Canon Kabushiki Kaisha Toner
CN108873631B (en) * 2017-05-15 2022-08-12 佳能株式会社 Toner and image forming apparatus
CN108873634B (en) * 2017-05-15 2022-08-02 佳能株式会社 Toner and image forming apparatus
US10895815B2 (en) 2017-05-15 2021-01-19 Canon Kabushiki Kaisha Toner
JP2018205385A (en) * 2017-05-31 2018-12-27 キヤノン株式会社 toner
DE102019101893B4 (en) 2018-01-26 2022-05-12 Canon Kabushiki Kaisha toner
US10539893B2 (en) 2018-01-26 2020-01-21 Canon Kabushiki Kaisha Toner
DE102019101893A1 (en) 2018-01-26 2019-08-01 Canon Kabushiki Kaisha toner

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