JPH06161156A - Manufacture of toner for electrostatic latent image development - Google Patents

Abstract

PURPOSE:To obtain toner of small grain diameter while preventing undesirable emulsion polymerization and adjusting electrification optionally by using the mixture of a positive charge control agent and a negative charge control agent as a charge control agent. CONSTITUTION:A coloring agent such as carbon black is mixed and agitated together with a monomer such as styrene under the presence of a peroxide using a ball mill or the like so as to disperse the coloring agent uniformly and fine in the monomer. Charge control agent grain is then dispersed uniformly and fine in the mixture of the coloring agent and monomer. In this case, the mixture of a negative charge control agent and a positive charge control agent is used as the charge control agent. The negative charge control agent is a metal complex pigment containing azo group, and the positive charge control agent is nigrosine group dye. The weight ratio of the positive charge control agent/negative charge control agent is 10/1-1/10. As a dispersion stabilizer, tertiary calcium phosphate is used desirably.

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、電子写真において形成
される静電潜像を現像するためのトナーの製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a toner for developing an electrostatic latent image formed in electrophotography.

【０００２】[0002]

【従来の技術】従来、静電潜像を現像するためのトナー
は、一般に、粉砕法によつて製造されている。この粉砕
法によれば、溶融させた熱可塑性樹脂にカーボンブラツ
ク等の着色剤粒子、トナーに所要の摩擦帯電性を付与す
るためのある種の染料である帯電制御剤粒子、耐オフセ
ツト性を付与するためのワツクス粒子等、トナー特性付
与剤と称される種々の添加剤を混練、分散させ、冷却し
た後、得られた塊状の物質をジエツトミル等を用いて所
要の粒径にまで粉砕し、分級することによつて製造され
ている。2. Description of the Related Art Conventionally, a toner for developing an electrostatic latent image is generally manufactured by a crushing method. According to this pulverization method, the colorant particles such as carbon black are added to the molten thermoplastic resin, the charge control agent particles which are a kind of dye for imparting the required triboelectric charging property to the toner, and the offset resistance are imparted. Wax particles and the like for kneading, dispersing various additives called a toner property imparting agent, cooling, and then crushing the obtained lumpy substance to a required particle size using a jet mill, etc., It is manufactured by classifying.

【０００３】しかし、この粉砕法によれば、上記粒子状
のトナー特性付与剤を熱可塑性樹脂中に均一に混合分散
させることが容易でなく、また、粉砕及び分級工程にお
いて、所要粒径をはずれる微細粉や粗大粉が生成し、こ
れを除去するので、製品としてのトナーの収率が低い。
従つて、また、粉砕法によれば、トナー中にトナー特性
付与剤が微細且つ均一に分散された平均粒子径が約６μ
ｍ以下の高解像度トナーを得ることが困難である。However, according to this pulverization method, it is not easy to uniformly mix and disperse the particulate toner property imparting agent in the thermoplastic resin, and the required particle size is deviated in the pulverization and classification steps. Since fine powder and coarse powder are generated and removed, the yield of the toner as a product is low.
Therefore, according to the pulverization method, the toner property imparting agent is finely and uniformly dispersed in the toner and has an average particle diameter of about 6 μm.
It is difficult to obtain a high resolution toner of m or less.

【０００４】このように、従来の所謂粉砕法によるトナ
ーは、種々の欠点を有するために、近年、着色剤粒子等
のトナー特性付与剤を含む重合性単量体を所要の粒径を
有するように水性分散媒中に微粒子状に分散させた後、
これを懸濁重合して、直接にトナーを製造する方法が種
々提案されている。この懸濁重合法によれば、トナー特
性付与剤粒子が樹脂中に均一に分散された球状の粒子と
してトナーを得ることができる。As described above, the conventional so-called pulverization toner has various drawbacks. Therefore, in recent years, a polymerizable monomer containing a toner property-imparting agent such as colorant particles has a required particle size. After being dispersed in an aqueous dispersion medium into fine particles,
Various methods have been proposed for directly producing a toner by subjecting this to suspension polymerization. According to this suspension polymerization method, the toner can be obtained as spherical particles in which the toner property imparting agent particles are uniformly dispersed in the resin.

【０００５】しかし、かかる懸濁重合法によつても、前
述したように、平均粒子径が約６μｍ以下であるトナー
を得ることができるように、トナーの小粒子径化を行な
うとき、トナー粒子の比表面積が大きくなるので、トナ
ー粒子の単位重量当たりの帯電量Ｑ／Ｍが過度に高くな
り、特に、重合性単量体の懸濁重合において、第三リン
酸カルシウムを分散安定剤として用いて得たトナー粒子
は、帯電量が一層大きく、かくして、適正な帯電量を有
して、高解像度の複写画像を与える小粒子径化トナーを
製造することができない。However, even by such a suspension polymerization method, as described above, when the toner particle size is reduced so that a toner having an average particle size of about 6 μm or less can be obtained. Since the specific surface area of the toner becomes large, the charge amount Q / M per unit weight of the toner particles becomes excessively high. Particularly, in the suspension polymerization of the polymerizable monomer, tricalcium phosphate can be used as a dispersion stabilizer. Further, the toner particles have a larger charge amount, and thus it is impossible to manufacture a toner having a small particle size, which has an appropriate charge amount and gives a high-resolution copy image.

【０００６】このような問題を解決する一つの方策とし
て、懸濁重合に際して、単量体に配合される帯電制御剤
を減量することが考えられる。しかし、帯電制御剤とし
て、前述したような含金属錯塩顔料を用いるとき、特開
昭６０−８８４９号公報に記載されているように、この
ような含金属錯塩顔料は、懸濁重合に際して、水相中に
おける好ましくない乳化重合が起こるのを防止する効果
をも有するので、得られるトナーの帯電量を制御するた
めに、上記含金属錯塩顔料の配合量を減らせば、懸濁重
合に際して、好ましくない乳化重合が起こりやすくな
る。As one measure to solve such a problem, it can be considered to reduce the amount of the charge control agent blended in the monomer during suspension polymerization. However, when a metal-containing complex salt pigment as described above is used as the charge control agent, such a metal-containing complex salt pigment is used in suspension polymerization as described in JP-A-60-8849. Since it also has the effect of preventing undesired emulsion polymerization in the phase, it is not preferable in suspension polymerization if the compounding amount of the above metal-containing complex salt pigment is reduced in order to control the charge amount of the toner obtained. Emulsion polymerization is likely to occur.

【０００７】このように、懸濁重合において、乳化重合
が起こるときは、生成する懸濁重合による重合体粒子の
表面に乳化重合による微小な重合体粒子が付着し、この
乳化重合による重合体粒子は、懸濁重合の終了後に、得
られたトナー粒子を洗浄しても、その表面から除去する
ことが困難であるので、既に知られているように、例え
ば、高速の気流中で重合体粒子に衝撃処理を行なつて、
乳化重合による重合体粒子を懸濁重合による重合体粒子
の表面に固定化することが必要となる。乳化重合による
重合体粒子を懸濁重合による重合体粒子の表面に固定化
しないときは、静電プロセスにおいて、キヤリア汚染を
起こし、その結果、かぶり等の種々の画像欠陥が複写画
像に生じる。As described above, when emulsion polymerization occurs in suspension polymerization, fine polymer particles formed by emulsion polymerization adhere to the surface of polymer particles formed by suspension polymerization, and the polymer particles formed by emulsion polymerization are attached. Since it is difficult to remove the toner particles from the surface thereof even after washing the obtained toner particles after the completion of suspension polymerization, as already known, for example, polymer particles in a high-speed air stream are used. Shock treatment to
It is necessary to immobilize polymer particles obtained by emulsion polymerization on the surface of polymer particles obtained by suspension polymerization. When the polymer particles obtained by emulsion polymerization are not fixed on the surface of the polymer particles obtained by suspension polymerization, carrier contamination occurs in the electrostatic process, resulting in various image defects such as fogging in the copied image.

【０００８】[0008]

【発明が解決しようとする課題】本発明は、懸濁重合に
よるトナーの製造における上記した問題を解決するため
になされたものであつて、好ましくない乳化重合を防止
しつつ、且つ、帯電量を任意に適正な値に調節しつつ、
懸濁重合によつて平均粒子径約６μｍ以下の小粒子径化
トナーを製造する方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in the production of toner by suspension polymerization, and prevents undesired emulsion polymerization while reducing the charge amount. While adjusting to an appropriate value arbitrarily,
It is an object of the present invention to provide a method for producing a toner having a small particle size having an average particle size of about 6 μm or less by suspension polymerization.

【０００９】[0009]

【課題を解決するための手段】本発明による静電潜像現
像用トナーの製造方法は、帯電制御剤粒子を分散させた
単量体を水性分散媒中に分散させ、分散安定剤の存在下
に懸濁重合して、トナーを製造する方法において、帯電
制御剤が正帯電制御剤と負帯電制御剤との混合物である
ことを特徴とする。The method for producing a toner for developing an electrostatic latent image according to the present invention comprises the steps of dispersing a monomer in which charge control agent particles are dispersed in an aqueous dispersion medium, and adding a dispersion stabilizer in the presence of the dispersion stabilizer. In the method for producing a toner by suspension polymerization, the charge control agent is a mixture of a positive charge control agent and a negative charge control agent.

【００１０】本発明による方法において、単量体は、特
に限定されるものではなく、一般に、従来の重合法によ
るトナーの製造において用いられている任意のラジカル
重合性単量体を用いることができる。このような単量体
として、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、ｐ−クロロスチ
レン、酢酸ビニル、プロピオン酸ビニル、アクリル酸メ
チル、アクリル酸エチル、アクリル酸プロピル、アクリ
ル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ
−オクチル、アクリル酸ドデシル、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、アクリル酸フエニル、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、メタクリル酸フエニル、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、アクリロニトリル、メタクリロニトリ
ル、アクリルアミド、アクリル酸グリシジル、メタクリ
ル酸グリシジル、アクリル酸、メタクリル酸、２−ビニ
ルピリジン、４−ビニルピリジン等を挙げることができ
る。In the method according to the present invention, the monomer is not particularly limited, and in general, any radical polymerizable monomer used in the production of toner by the conventional polymerization method can be used. . Examples of such a monomer include styrene, o-methylstyrene, m-
Methylstyrene, p-methylstyrene, p-chlorostyrene, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n acrylate
-Octyl, dodecyl 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, 2-ethylhexyl methacrylate,
Stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, 2-vinylpyridine, 4-vinylpyridine. Etc. can be mentioned.

【００１１】しかし、本発明においては、これら単量体
のなかでも、特に、スチレンや、スチレンとアクリル酸
エステル、メタクリル酸エステルとの混合物が好ましく
用いられる。更に、本発明においては、トナーの定着性
や耐オフセツト性を高めるために、単量体は、多官能性
単量体を少量含有していてもよい。かかる多官能性単量
体として、例えば、ジビニルベンゼン、エチレングリコ
ールジメタクリレート等を挙げることができる。このよ
うな多官能性単量体は、余りに多く用いるときは、得ら
れる重合体粒子が加熱溶融し難くなり、トナーとしての
定着性に劣ることとなるので、通常、単量体の約１重量
％以下の範囲で用いられる。However, in the present invention, among these monomers, styrene and a mixture of styrene and an acrylic acid ester or a methacrylic acid ester are particularly preferably used. Further, in the present invention, the monomer may contain a small amount of a polyfunctional monomer in order to improve the fixing property and the offset resistance of the toner. Examples of such polyfunctional monomers include divinylbenzene and ethylene glycol dimethacrylate. When such a polyfunctional monomer is used in an excessively large amount, the resulting polymer particles are less likely to be heated and melted, resulting in poor fixability as a toner. Used in the range of% or less.

【００１２】本発明の方法によれば、先ず、ボールミル
等を用いて、カーボンブラツクのような着色剤をパーオ
キサイド化合物の存在下に単量体と共に混合攪拌するこ
とによつて、着色剤を単量体中に均一微細に分散させ
る。ここに、パーオキサイド化合物としてはアシルパー
オキサイドが好ましく、例えば、ラウロイルパーオキサ
イドのように、脂肪酸から誘導されるパーオキサイド化
合物が好ましく用いられる。According to the method of the present invention, first, a colorant such as carbon black is mixed and stirred with a monomer in the presence of a peroxide compound by using a ball mill or the like to remove the colorant. Disperse uniformly and finely in the monomer. Here, as the peroxide compound, acyl peroxide is preferable, and for example, a peroxide compound derived from a fatty acid such as lauroyl peroxide is preferably used.

【００１３】着色剤としてカーボンブラツクを用いる場
合、上記したように、単量体とカーボンブラツクとを上
記したようなパーオキサイド化合物の存在下に、数時間
攪拌することによつて、カーボンブラツクを１μｍ以
下、好ましくは0.５μｍ以下の粒径にて単量体中に均一
微細に分散させることができる。この分散処理は、カー
ボンブラツクの単量体中への分散速度を速めるために、
５０〜８０℃の温度にて行なつてもよい。When carbon black is used as the colorant, as described above, the monomer and the carbon black are agitated in the presence of the peroxide compound as described above for several hours to give a carbon black of 1 μm. Hereafter, it can be dispersed uniformly and finely in the monomer with a particle size of preferably 0.5 μm or less. This dispersion treatment, in order to increase the dispersion speed of the carbon black in the monomer,
You may perform at the temperature of 50-80 degreeC.

【００１４】このように、パーオキサイド化合物がカー
ボンブラツクの単量体への分散に有効に働く理由とし
て、カーボンブラツクの官能基にパーオキサイド化合物
から誘導されるラジカルが反応して、カーボンブラツク
の単量体中への均一な分散を可能とするものとみられ
る。本発明においては、着色剤は、通常、単量体１００
重量部に対して、２〜１０重量部の範囲で用いられる。
一方、前記パーオキサイド化合物は、着色剤１００重量
部について、通常、１０〜５０重量部、好ましくは１０
〜４０重量部の範囲で用いられる。着色剤１００重量部
について、パーオキサイド化合物が１０重量部よりも少
ないときは、単量体中に着色剤を微細且つ一様に分散さ
せることができず、他方、５０重量部を越えるときは、
パーオキサイド化合物の分解切片が得られる重合体粒子
中に過多に残存する結果、トナーを加熱定着時に異臭を
発生し、実用上、好ましくない。As described above, the reason why the peroxide compound works effectively in dispersing the carbon black in the monomer is that the radicals derived from the peroxide compound react with the functional groups of the carbon black to cause the carbon black to stand alone. It seems that it enables uniform dispersion in the polymer. In the present invention, the colorant is usually a monomer 100.
It is used in the range of 2 to 10 parts by weight with respect to parts by weight.
On the other hand, the peroxide compound is usually 10 to 50 parts by weight, preferably 10 parts by weight with respect to 100 parts by weight of the colorant.
It is used in the range of up to 40 parts by weight. When the amount of the peroxide compound is less than 10 parts by weight with respect to 100 parts by weight of the colorant, the colorant cannot be finely and uniformly dispersed in the monomer, while when it exceeds 50 parts by weight,
Too much residual in the polymer particles from which decomposed sections of the peroxide compound are obtained, resulting in an offensive odor during heat fixing of the toner, which is not preferable in practice.

【００１５】着色剤の具体例は、例えば、特開昭６２−
２４６０７３号公報に記載されている。単量体に溶解し
ない着色剤を用いるときは、カーボンブラツクを用いる
場合と同様にして、パーオキサイド化合物やその他の適
宜の分散剤を用いることによつて、微細且つ均一に分散
させることができる。しかし、本発明において、着色剤
は、単量体に溶解するものでも用いることができる。Specific examples of the colorant are, for example, JP-A-62-162.
It is described in Japanese Patent No. 246073. When a colorant that does not dissolve in the monomer is used, it can be finely and uniformly dispersed by using a peroxide compound or another appropriate dispersant, as in the case of using carbon black. However, in the present invention, the colorant may be one that is soluble in the monomer.

【００１６】次いで、本発明の方法によれば、以上のよ
うにして着色剤と単量体との混合物に帯電制御剤粒子を
均一微細に分散させる。即ち、着色剤を分散させた単量
体に帯電制御剤粒子と共に上記単量体に可溶性の分散剤
を単量体に加えて、分散剤を単量体中に溶解させ、これ
を、例えば、ボールミル内にて、通常、５０〜２００時
間攪拌する。かかる方法によつて、帯電制御剤粒子を約
0.５μｍ以下、好ましくは、約0.３μｍ程度の粒径に
て、単量体中に一様に分散させることができる。この分
散処理も、帯電制御剤粒子の単量体中への分散速度を速
めるために、５０〜８０℃の温度にて行なつてもよい。
このような方法によるときは、帯電制御剤粒子は、通
常、ラジカル重合性単量体１００重量部に対して、約0.
０１〜１０重量部、好ましくは約0.０５〜５重量部、最
も好ましくは約0.１〜１重量部の範囲で用いられる。Next, according to the method of the present invention, the particles of the charge control agent are uniformly and finely dispersed in the mixture of the colorant and the monomer as described above. That is, a dispersant soluble in the monomer is added to the monomer together with the charge control agent particles in the monomer in which the colorant is dispersed, and the dispersant is dissolved in the monomer. In a ball mill, stirring is usually performed for 50 to 200 hours. By this method, the charge control agent particles are
It can be uniformly dispersed in the monomer with a particle size of 0.5 μm or less, preferably about 0.3 μm. This dispersion treatment may also be performed at a temperature of 50 to 80 ° C. in order to accelerate the dispersion speed of the charge control agent particles in the monomer.
When such a method is used, the charge control agent particles are usually about 0.
It is used in the range of 01 to 10 parts by weight, preferably about 0.05 to 5 parts by weight, and most preferably about 0.1 to 1 part by weight.

【００１７】本発明においては、帯電制御剤粒子を分散
させた単量体を水性分散媒中に分散させ、分散安定剤の
存在下に懸濁重合して、トナーを製造するに際して、帯
電制御剤として、正帯電制御剤と負帯電制御剤との混合
物を用いることによつて、好ましくない単量体の乳化重
合を防止しつつ、平均粒子径約６μｍ程度の小粒子径化
トナーを製造することができる。In the present invention, the monomer in which the particles of the charge control agent are dispersed is dispersed in an aqueous dispersion medium, and suspension polymerization is carried out in the presence of a dispersion stabilizer to prepare a toner. As the above, by using a mixture of a positive charge control agent and a negative charge control agent, it is possible to produce a small particle size toner having an average particle size of about 6 μm while preventing emulsion polymerization of undesired monomers. You can

【００１８】本発明においては、正帯電制御剤と負帯電
制御剤とは、合計量にて、単量体１００重量部に対し
て、0.１〜１０重量部、好ましくは、0.１〜５重量部の
範囲で用いられる。特に、本発明においては、負帯電制
御剤としては、含金属錯塩顔料が好ましく、なかでも、
次式（Ｉ）In the present invention, the total amount of the positive charge control agent and the negative charge control agent is 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the monomer. Used in the range of 5 parts by weight. Particularly, in the present invention, as the negative charge control agent, a metal-containing complex salt pigment is preferable, and among them,
Formula (I)

【００１９】[0019]

【化１】 [Chemical 1]

【００２０】（式中、Ｘ⁺ はカチオン種を示す。）で表
わされるアゾ系含クロム錯塩顔料、又は次式（II）An azo-based chromium-containing complex salt pigment represented by the formula (wherein X ⁺ represents a cation species), or the following formula (II)

【００２１】[0021]

【化２】 [Chemical 2]

【００２２】（式中、Ｙ⁺ はカチオン種を示す。）で表
わされるアゾ系含鉄錯塩顔料が好ましく用いられる。こ
のような顔料は、市販品を用いることができる。上記式
（Ｉ）で表わされるアゾ系含クロム錯塩顔料は、例え
ば、保土谷化学工業（株）製スピロンブラツクＴＲＨと
して入手することができ、また、上記式（II）で表わさ
れるアゾ系含鉄錯塩顔料は、例えば、保土谷化学工業
（株）製スピロンブラツクＴ−７７として入手すること
ができる。An azo iron-containing complex salt pigment represented by the formula (Y ⁺ represents a cationic species) is preferably used. As such a pigment, a commercially available product can be used. The azo-based chromium-containing complex salt pigment represented by the above formula (I) can be obtained, for example, as Spiron Black TRH manufactured by Hodogaya Chemical Co., Ltd., and the azo-based iron-containing complex represented by the above formula (II). The complex salt pigment can be obtained, for example, as Spiron Black T-77 manufactured by Hodogaya Chemical Co., Ltd.

【００２３】また、本発明においては、正帯電制御剤と
しては、一般に、ニグロシン系染料が好ましく用いられ
る。ニグロシン系染料は、代表的には、次式（III)で表
わされる構造を有している。In the present invention, a nigrosine dye is generally preferably used as the positive charge control agent. The nigrosine dye typically has a structure represented by the following formula (III).

【００２４】[0024]

【化３】 [Chemical 3]

【００２５】（式中、Ｚ^- はアニオン種を示す。）(In the formula, Z ⁻ represents an anion species.)

【００２６】本発明においては、このような正帯電制御
剤と負帯電制御剤とは、目的とするトナーの正負いずれ
かの帯電性によつて、いずれかの帯電制御剤が多く用い
られる。例えば、負帯電性のトナーを得るときは、正帯
電制御剤よりも負帯電制御剤の比率を大きくし、しか
も、その負帯電性の度合いは、正帯電制御剤に対する負
帯電制御剤の比率によつて調節することができる。正帯
電性のトナーを得るときは、負帯電制御剤よりも正帯電
制御剤の比率を大きくすればよい。本発明においては、
上述したように、正帯電制御剤と負帯電制御剤との混合
物を用いるが、正帯電制御剤／負帯電制御剤の重量比
は、目的とするトナーの正負いずれかの帯電性によつ
て、１０／１〜１／１０の範囲であることが好ましい。In the present invention, as the positive charge control agent and the negative charge control agent, any one of the charge control agents is often used depending on the chargeability of the toner to be positive or negative. For example, when obtaining a toner having negative chargeability, the ratio of the negative charge control agent is set to be larger than that of the positive charge control agent, and the degree of the negative chargeability is determined by the ratio of the negative charge control agent to the positive charge control agent. It can be adjusted. To obtain a positively chargeable toner, the ratio of the positive charge control agent to the negative charge control agent may be increased. In the present invention,
As described above, a mixture of a positive charge control agent and a negative charge control agent is used, but the weight ratio of the positive charge control agent / negative charge control agent depends on whether the target toner has positive or negative chargeability. It is preferably in the range of 10/1 to 1/10.

【００２７】本発明の方法によれば、以上のようにし
て、単量体中にカーボンブラツクのような着色剤と帯電
制御剤粒子を共に粒径１μｍ以下の微粒子状に微細に且
つ均一に分散させた後、この分散液に、更に必要に応じ
て、付加的な所要の単量体を加え、或いは得られるトナ
ーに耐オフセツト性を付与するためのワツクス等を加え
ると共に、重合開始剤として、アゾビス系重合開始剤を
添加して、ここに、重合のための単量体組成物を得る。
上記アゾビス系重合開始剤としては、例えば、アゾビス
ジメチルバレロニトリル、アゾビスイソブチロニトリル
等が用いられるが、特に、油溶性であるアゾビスジメチ
ルバレロニトリルが好ましく用いられる。According to the method of the present invention, as described above, both the colorant such as carbon black and the particles of the charge control agent are finely and uniformly dispersed in the form of fine particles having a particle size of 1 μm or less in the monomer. After that, to this dispersion, further, if necessary, an additional required monomer is added, or a wax or the like for imparting offset resistance to the obtained toner is added, and as a polymerization initiator, An azobis-based polymerization initiator is added to obtain a monomer composition for polymerization.
As the azobis-based polymerization initiator, for example, azobisdimethylvaleronitrile, azobisisobutyronitrile and the like are used, and particularly oil-soluble azobisdimethylvaleronitrile is preferably used.

【００２８】上記アゾビス系重合開始剤の量は、本発明
の方法においては、単量体１００重量部に対して、１〜
１０重量部、好ましくは、２〜５重量部の範囲である。
アゾビス系重合開始剤の添加量が、単量体１００重量部
に対して１重量部よりも少ないときは、単量体の重合速
度が遅く、重合率１００％にて重合させることが困難で
ある。他方、アゾビス系重合開始剤の添加量が、単量体
１００重量部に対して１０重量部よりも多いときは、得
られる重合体の分子量が低く、トナーとしては、耐オフ
セツト性に劣ることとなるので好ましくない。In the method of the present invention, the amount of the azobis-based polymerization initiator is 1 to 100 parts by weight of the monomer.
It is in the range of 10 parts by weight, preferably 2 to 5 parts by weight.
When the addition amount of the azobis-based polymerization initiator is less than 1 part by weight with respect to 100 parts by weight of the monomer, the polymerization rate of the monomer is slow and it is difficult to polymerize at a polymerization rate of 100%. . On the other hand, when the amount of the azobis-based polymerization initiator added is more than 10 parts by weight with respect to 100 parts by weight of the monomer, the molecular weight of the obtained polymer is low, and the toner has poor offset resistance. Therefore, it is not preferable.

【００２９】本発明の方法によれば、次いで、このよう
にアゾビスニトリル系重合開始剤を含有する単量体組成
物を水性分散媒中に分散させ、単量体組成物の分散液を
調製し、加熱して、単量体を懸濁重合させる。本発明に
おいては、水性分散媒は、分散安定剤として、第三リン
酸カルシウムが好ましく用いられる。このような分散安
定剤は、通常、水性分散媒中で単量体１００重量部に対
して、0.１〜２０重量部、好ましくは0.５〜１５重量部
の範囲にて用いられる。According to the method of the present invention, the monomer composition containing the azobisnitrile-based polymerization initiator is thus dispersed in the aqueous dispersion medium to prepare a dispersion liquid of the monomer composition. And heat to cause the suspension polymerization of the monomers. In the present invention, the aqueous dispersion medium is preferably tricalcium phosphate as a dispersion stabilizer. Such a dispersion stabilizer is usually used in an aqueous dispersion medium in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the monomer.

【００３０】このようにして、単量体を水性分散媒中に
分散させた後、通常、単量体の分散液を４０〜９５℃、
好ましくは、５０〜９０℃程度の温度で攪拌して、単量
体を懸濁重合させることによつて、平均粒子径が６μｍ
以下である重合体粒子を得ることができる。かかる重合
体粒子を塩酸のような酸の水溶液にて洗浄し、次いで、
水洗を数回繰り返した後、減圧下に乾燥すれば、トナー
を得ることができる。In this way, after the monomer is dispersed in the aqueous dispersion medium, the dispersion liquid of the monomer is usually kept at 40 to 95 ° C.
Preferably, the average particle diameter is 6 μm by stirring at a temperature of about 50 to 90 ° C. to carry out suspension polymerization of the monomer.
The following polymer particles can be obtained. Washing such polymer particles with an aqueous solution of an acid such as hydrochloric acid, then
The toner can be obtained by repeating washing with water several times and then drying under reduced pressure.

【００３１】[0031]

【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。尚、参考例１においては、スチレンにカーボンブラ
ツク、正帯電制御剤又は負帯電制御剤をそれぞれ分散さ
せた混合物を調製した。The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In Reference Example 1, a mixture was prepared by dispersing carbon black, a positive charge control agent or a negative charge control agent in styrene.

【００３２】参考例１ （カーボンブラツク分散単量体液）スチレン１１８重量
部にラウロイルパーオキサイド２重量部とカーボンブラ
ツク（（三菱化成工業（株）製ダイアブラツク＃５２、
揮発分0.８％、pH8.０、粒径２７μｍ）２０重量部を加
え、ボールミルにて３０分間混合して、カーボンブラツ
クをスチレン中に分散させた。次いで、得られた混合物
をオートクレーブ内で７０℃で１時間攪拌した。この分
散処理の後は、単量体中において、カーボンブラツクは
0.１μｍ程度の粒径を有して、その沈降は認められなか
つた。Reference Example 1 (Carbon Black Dispersed Monomer Liquid) 118 parts by weight of styrene, 2 parts by weight of lauroyl peroxide and carbon black (manufactured by Mitsubishi Kasei Co., Ltd., Dia Black # 52,
20 parts by weight of volatile matter 0.8%, pH 8.0, particle size 27 μm) were added and mixed in a ball mill for 30 minutes to disperse the carbon black in styrene. Then, the obtained mixture was stirred at 70 ° C. for 1 hour in an autoclave. After this dispersion treatment, the carbon black in the monomer
It had a particle size of about 0.1 μm and no sedimentation was observed.

【００３３】（負帯電制御剤分散単量体液）スチレン１
５６重量部にエチレン−酢酸ビニル共重合体（日本合成
化学工業（株）製ソアブレンＣＨ）４重量部を溶解さ
せ、次いで、負帯電制御剤としての顔料「スピロンブラ
ツクＴＲＨ」（保土谷化学工業（株）製）１０重量部を
加え、ボールミルにて１００時間混合して、上記負帯電
制御剤をスチレン中に分散させた。この分散処理の後
は、負帯電制御剤は粒子径が約0.３μｍであつて、単量
体中で負帯電制御剤の沈降は認められなかつた。(Negative charge control agent dispersed monomer liquid) Styrene 1
4 parts by weight of ethylene-vinyl acetate copolymer (Soabren CH manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 56 parts by weight, and then the pigment "spiron black TRH" (Hodogaya Chemical Industry Co., Ltd.) as a negative charge control agent was dissolved. (Manufactured by K.K.) was added and mixed in a ball mill for 100 hours to disperse the negative charge control agent in styrene. After this dispersion treatment, the negative charge control agent had a particle size of about 0.3 μm, and no precipitation of the negative charge control agent was observed in the monomer.

【００３４】（正帯電制御剤分散単量体液）スチレン１
５６重量部にエチレン−酢酸ビニル共重合体（日本合成
化学工業（株）製ソアブレンＣＨ）４重量部を溶解さ
せ、次いで、正帯電制御剤としてのニグロシン系染料で
ある「ボントロンＮ−０７」（オリエント化学工業
（株）製）１０重量部を加え、ボールミルにて１００時
間混合して、上記正帯電制御剤をスチレン中に分散させ
た。この分散処理の後は、正帯電制御剤は粒子径が約0.
３μｍであつて、単量体中で正帯電制御剤の沈降は認め
られなかつた。(Positive charge control agent dispersed monomer liquid) Styrene 1
4 parts by weight of ethylene-vinyl acetate copolymer (Soabren CH manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 56 parts by weight, and then "Bontron N-07" which was a nigrosine dye as a positive charge control agent ( 10 parts by weight of Orient Chemical Industry Co., Ltd. was added and mixed in a ball mill for 100 hours to disperse the positive charge control agent in styrene. After this dispersion treatment, the particle size of the positive charge control agent is about 0.
At 3 μm, no sedimentation of the positive charge control agent was observed in the monomer.

【００３５】実施例１ 上記カーボンブラツク分散単量体液３５重量部（カーボ
ンブラツクとして５重量部）と負帯電制御剤分散単量体
液3.４重量部（スピロンブラツクＴＲＨとして0.２重量
部）と正帯電制御剤分散単量体液1.７重量部（ボントロ
ンＮ−０７として0.１重量部）とを混合し、得られた混
合物に更にスチレン５７重量部、２−エチルヘキシルア
クリレート１３重量部、ジビニルベンゼン0.２重量部及
びオフセツト防止剤としてのポリプロピレンワツクス３
重量部を加え、更に、これに重合開始剤アゾビスジメチ
ルバレロニトリル３重量部を加えて、重合用単量体組成
物を調製した。Example 1 35 parts by weight of the above-mentioned carbon black dispersion monomer liquid (5 parts by weight as carbon black) and 3.4 parts by weight of the negative charge control agent dispersion monomer liquid (0.2 parts by weight as spiron black TRH). And 1.7 parts by weight of the positive charge control agent-dispersed monomer liquid (0.1 parts by weight as Bontron N-07) were mixed, and 57 parts by weight of styrene and 13 parts by weight of 2-ethylhexyl acrylate were added to the resulting mixture. 0.2 parts by weight divinylbenzene and polypropylene wax 3 as anti-offset agent
3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator was added thereto to prepare a monomer composition for polymerization.

【００３６】次いで、第三リン酸カルシウム６重量部を
含む水溶液４００重量部にドデシルベンゼンスルホン酸
ナトリウム0.０２重量部を加え、ホモミキサー（特殊機
化工業（株）製ＴＫ−Ｍ型）を用いて回転数８０００rp
m の攪拌下に、この水溶液中に上記重合用単量体組成物
を加え、更に、１０分間高剪断下に攪拌して、上記単量
体組成物を分散させた。Then, 0.02 part by weight of sodium dodecylbenzenesulfonate was added to 400 parts by weight of an aqueous solution containing 6 parts by weight of tricalcium phosphate, and a homomixer (TK-M type manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. Rotation speed 8000rp
The above-mentioned monomer composition for polymerization was added to this aqueous solution under stirring of m 3, and further stirred under high shear for 10 minutes to disperse the above-mentioned monomer composition.

【００３７】このようにして得られた単量体組成物の分
散液を６０℃で１０時間、低速攪拌し、単量体を重合さ
せて、重合体粒子を得た。得られた重合体粒子の体積平
均粒子径は5.８μｍであつた。得られた重合体粒子を塩
酸水溶液で洗浄し、次いで、水洗を数回、繰り返した
後、減圧下に乾燥して、トナーを得た。このトナー粒子
をＳＥＭ観察したところ、表面は平滑であつて、乳化重
合による重合体粒子の生成はみられなかつた。The thus obtained dispersion liquid of the monomer composition was stirred at 60 ° C. for 10 hours at a low speed to polymerize the monomer to obtain polymer particles. The volume average particle diameter of the obtained polymer particles was 5.8 μm. The obtained polymer particles were washed with a hydrochloric acid aqueous solution, and then washed with water several times, and then dried under reduced pressure to obtain a toner. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed.

【００３８】このトナー１００重量部に疎水性シリカＲ
９７２（日本アエロジル（株）製疎水性シリカＲ９７
２）0.３重量部を均一に配合し、キヤリア「Ｚ−２００
Ｂ」（パウダーテツク（株）製）を含むトナー濃度５重
量％の現像剤を調製した。この現像剤をブローオフ粉体
帯電量測定装置（東芝ケミカル（株）製）にて摩擦帯電
量を測定したところ、このトナーの摩擦帯電量は−３１
μＣ／ｇであつた。To 100 parts by weight of this toner, hydrophobic silica R
972 (hydrophobic silica R97 manufactured by Nippon Aerosil Co., Ltd.)
2) 0.3 part by weight is uniformly blended, and the carrier "Z-200" is used.
B ”(manufactured by Powder Tech Co., Ltd.) having a toner concentration of 5% by weight was prepared. When the triboelectric charge amount of this developer was measured with a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.), the triboelectric charge amount of this toner was -31.
It was μC / g.

【００３９】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、電子写真
複写を行なつたところ、常温常湿下及び高温高湿下共
に、画像のかぶりや所謂黒べた部に濃度むらがなく、文
字部や線部の散り等が殆どない解像度の高い高品質の複
写画像を得ることができた。更に、このトナーを用い
て、常温常湿下において、連続して１万枚の複写を行な
つた後、現像剤をメタノールにて洗浄し、トナーを除去
した後のキヤリアをトルエン中に浸漬し、トルエンに溶
解する所謂スペントトナー量は非常に少ないものであつ
た。When this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) to perform electrophotographic copying, the image was obtained under both normal temperature and normal humidity and high temperature and high humidity. It was possible to obtain a high-quality copy image having high resolution with no fog or so-called black solid portion having uneven density and almost no scattering of character portions or line portions. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００４０】実施例２ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液１７重量部（スピロンブラツ
クＴＲＨとして1.０重量部）と正帯電制御剤分散単量体
液4.２５重量部（ボントロンＮ−０７として0.２５重量
部）とを混合し、得られた混合物に更にスチレン３6.６
重量部、２−エチルヘキシルアクリレート１３重量部、
ジビニルベンゼン0.２重量部及びオフセツト防止剤とし
てのポリプロピレンワツクス３重量部を加え、更に、こ
れに重合開始剤アゾビスジメチルバレロニトリル３重量
部を加えて、重合用単量体組成物を調製した。Example 2 In the same manner as in Example 1, 35 parts by weight of the above carbon black dispersion monomer liquid (5 parts by weight as carbon black) and 17 parts by weight of the negative charge control agent dispersion monomer liquid (as spiron black TRH) 1.0 parts by weight) and 4.25 parts by weight of the positive charge control agent-dispersed monomer liquid (0.25 parts by weight as Bontron N-07) were mixed, and the resulting mixture was further mixed with styrene 36.6.
Parts by weight, 13 parts by weight of 2-ethylhexyl acrylate,
0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent were added, and further 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator were added to prepare a monomer composition for polymerization. did.

【００４１】この後、実施例１と同様に処理して、体積
平均粒子径は5.６μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は−４４μＣ／ｇであつ
た。Thereafter, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.6 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was -44 μC / g.

【００４２】また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下及び高温高湿下共に、画像のかぶ
りや所謂黒べた部に濃度むらがなく、文字部や線部の散
り等が殆どない解像度の高い高品質の複写画像を得るこ
とができた。また、このトナーを用いて、常温常湿下に
おいて、連続して１万枚の複写を行なつた後、現像剤を
メタノールにて洗浄し、トナーを除去した後のキヤリア
をトルエン中に浸漬し、トルエンに溶解する所謂スペン
トトナー量は非常に少ないものであつた。Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly, under high temperature and high humidity both under normal temperature and high humidity, there is no image fogging or so-called black solid part density unevenness, and there is almost no scattering of character parts or line parts. I was able to. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００４３】実施例３ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液3.４重量部（スピロンブラツ
クＴＲＨとして0.２重量部）と正帯電制御剤分散単量体
液１3.６重量部（ボントロンＮ−０７として0.８重量
部）とを混合し、得られた混合物に更にスチレン４1.９
重量部、２−エチルヘキシルアクリレート１３重量部、
ジビニルベンゼン0.２重量部及びオフセツト防止剤とし
てのポリプロピレンワツクス３重量部を加え、更に、こ
れに重合開始剤アゾビスジメチルバレロニトリル３重量
部を加えて、重合用単量体組成物を調製した。Example 3 In the same manner as in Example 1, 35 parts by weight of the above carbon black-dispersed monomer liquid (5 parts by weight as a carbon black) and 3.4 parts by weight of the negative charge control agent-dispersed monomer liquid (spiron black) were used. TRH (0.2 parts by weight) and a positive charge control agent-dispersed monomer liquid (13.6 parts by weight) (Bontron N-07: 0.8 parts by weight) were mixed, and the resulting mixture was further mixed with styrene 41.9.
Parts by weight, 13 parts by weight of 2-ethylhexyl acrylate,
0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent were added, and further 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator were added to prepare a monomer composition for polymerization. did.

【００４４】この後、実施例１と同様に処理して、体積
平均粒子径は5.８μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は＋４５μＣ／ｇであつ
た。Thereafter, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.8 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was +45 μC / g.

【００４５】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、反転現像
による電子写真複写を行なつたところ、常温常湿下及び
高温高湿下共に、画像のかぶりや所謂黒べた部に濃度む
らがなく、文字部や線部の散り等が殆どない解像度の高
い高品質の複写画像を得ることができた。更に、このト
ナーを用いて、常温常湿下において、連続して１万枚の
複写を行なつた後、現像剤をメタノールにて洗浄し、ト
ナーを除去した後のキヤリアをトルエン中に浸漬し、ト
ルエンに溶解する所謂スペントトナー量は非常に少ない
ものであつた。Further, this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) to perform electrophotographic copying by reversal development. In both cases, it was possible to obtain a high-quality copy image having a high resolution with no image fog or so-called black solid portion having uneven density and almost no scattering of character portions or line portions. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００４６】比較例１ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液５9.５重量部（スピロンブラ
ツクＴＲＨとして3.５重量部）とを混合し、得られた混
合物に更にスチレン2.９重量部、２−エチルヘキシルア
クリレート１３重量部、ジビニルベンゼン0.２重量部及
びオフセツト防止剤としてのポリプロピレンワツクス３
重量部を加え、更に、これに重合開始剤アゾビスジメチ
ルバレロニトリル３重量部を加えて、重合用単量体組成
物を調製した。Comparative Example 1 In the same manner as in Example 1, 35 parts by weight of the above-mentioned carbon black dispersion monomer liquid (5 parts by weight as carbon black) and 59.5 parts by weight of the negative charge control agent dispersion monomer liquid (spiron black) were used. TRH (3.5 parts by weight), and the resulting mixture was further mixed with 2.9 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and polypropylene wax as an anti-offset agent. Three
3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator was added thereto to prepare a monomer composition for polymerization.

【００４７】この後、実施例１と同様に処理して、体積
平均粒子径は6.２μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は−７２μＣ／ｇであつ
た。Thereafter, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 6.2 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was -72 μC / g.

【００４８】また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下においては、複写画像のかぶりや
所謂黒べた部に濃度むらがなく、文字部や線部の散り等
が殆どない解像度の高い高品質の複写画像を得ることが
できた。しかし、高温高湿下では、複写画像にかぶりが
みられた。また、このトナーを用いて、常温常湿下で連
続して１万枚の複写を行なつた後、現像剤をメタノール
にて洗浄し、トナーを除去した後のキヤリアをトルエン
中に浸漬し、トルエンに溶解する所謂スペントトナー量
は非常に少ないものであつた。Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly, under normal temperature and normal humidity, it is possible to obtain a high-quality copy image with high resolution, which has no fog on the copy image, uneven density in the so-called black solid part, and almost no scattering of characters and lines. It was However, under high temperature and high humidity, fog was seen in the copied image. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene, The amount of so-called spent toner dissolved in toluene was very small.

【００４９】比較例２ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液0.１７重量部（スピロンブラ
ツクＴＲＨとして0.０１重量部）とを混合し、得られた
混合物に更にスチレン５７重量部、２−エチルヘキシル
アクリレート１３重量部、ジビニルベンゼン0.２重量部
及びオフセツト防止剤としてのポリプロピレンワツクス
３重量部を加え、更に、これに重合開始剤アゾビスジメ
チルバレロニトリル３重量部を加えて、重合用単量体組
成物を調製した。Comparative Example 2 In the same manner as in Example 1, 35 parts by weight of the above carbon black dispersion monomer liquid (5 parts by weight as carbon black) and 0.17 parts by weight of the negative charge control agent dispersion monomer liquid (spiron black) were used. TRH as 0.01 parts by weight), and the resulting mixture is further mixed with 57 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent. Then, 3 parts by weight of a polymerization initiator azobisdimethylvaleronitrile was added thereto to prepare a monomer composition for polymerization.

【００５０】この後、実施例１と同様に処理して、体積
平均粒子径は5.５μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面には、乳化重合によ
る微小な重合体粒子が多数、付着しているのがみられ
た。このトナーを用いて、実施例１と同様にして、現像
剤を調製した。この現像剤の摩擦帯電量は−３５μＣ／
ｇであつた。Thereafter, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.5 μm. As a result of SEM observation of the toner particles, it was found that a large number of fine polymer particles adhered on the surface by emulsion polymerization. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer is -35 μC /
It was g.

【００５１】また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下において、複写画像にかぶりがみ
られ、高温高湿下では、複写画像に著しいかぶりがみら
れた。また、このトナーを用いて、常温常湿下で連続し
て１万枚の複写を行なつた後、現像剤をメタノールにて
洗浄し、トナーを除去した後のキヤリアをトルエン中に
浸漬したところ、多量のスペントトナーがみられた。Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly to the above, the fog was observed on the copied image under normal temperature and normal humidity, and the fog was observed on the copied image under high temperature and high humidity. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene. , A large amount of spent toner was observed.

【００５２】比較例３ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
正帯電制御剤分散単量体液0.１７重量部（ボントロンＮ
−０７として0.０１重量部）とを混合し、得られた混合
物に更にスチレン５７重量部、２−エチルヘキシルアク
リレート１３重量部、ジビニルベンゼン0.２重量部及び
オフセツト防止剤としてのポリプロピレンワツクス３重
量部を加え、更に、これに重合開始剤アゾビスジメチル
バレロニトリル３重量部を加えて、重合用単量体組成物
を調製した。Comparative Example 3 In the same manner as in Example 1, 35 parts by weight of the carbon black dispersion monomer liquid (5 parts by weight as a carbon black) and 0.17 parts by weight of the positive charge control agent dispersion monomer liquid (Bontron N) were used.
0.01 parts by weight as -07) and 57 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and polypropylene wax 3 as an anti-offset agent. 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator was added thereto to prepare a monomer composition for polymerization.

【００５３】この後、実施例１と同様に処理して、体積
平均粒子径は5.６μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面には、乳化重合によ
る微小な重合体粒子が多数、付着しているのがみられ
た。このトナーを用いて、実施例１と同様にして、現像
剤を調製した。この現像剤の摩擦帯電量は＋３９μＣ／
ｇであつた。Then, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.6 μm. As a result of SEM observation of the toner particles, it was found that a large number of fine polymer particles adhered on the surface by emulsion polymerization. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer is +39 μC /
It was g.

【００５４】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、反転現像
による電子写真複写を行なつたところ、常温常湿下にお
いて、複写画像にかぶりがみられた。また、このトナー
を用いて、常温常湿下で連続して１万枚の複写を行なつ
た後、現像剤をメタノールにて洗浄し、トナーを除去し
た後のキヤリアをトルエン中に浸漬したところ、多量の
スペントトナーがみられた。以上の結果を表１及び表２
にまとめて示す。When this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) to perform electrophotographic copying by reversal development, a copied image was obtained under normal temperature and normal humidity. There was a fogging. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene. , A large amount of spent toner was observed. The above results are shown in Table 1 and Table 2.
Are shown together.

【００５５】[0055]

【表１】 [Table 1]

【００５６】[0056]

【表２】 [Table 2]

【００５７】参考例２ （カーボンブラツク分散単量体液）参考例１と同様にし
て調製した。 （負帯電制御剤分散単量体液）スチレン１５６重量部に
エチレン−酢酸ビニル共重合体（日本合成化学工業
（株）製ソアブレンＣＨ）４重量部を溶解させ、次い
で、負帯電制御剤としての顔料「スピロンブラツクＴ−
７７」（保土谷化学工業（株）製）１０重量部を加え、
ボールミルにて１００時間混合して、上記帯電制御剤を
スチレン中に分散させた。この分散処理の後は、帯電制
御剤は粒子径が約0.３μｍであつて、単量体中で帯電制
御剤の沈降は認められなかつた。 （正帯電制御剤分散単量体液）参考例１と同様にして調
製した。Reference Example 2 (Carbon Black Dispersed Monomer Solution) The same preparation as in Reference Example 1 was carried out. (Negative charge control agent-dispersed monomer liquid) 4 parts by weight of ethylene-vinyl acetate copolymer (Soavelen CH manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 156 parts by weight of styrene, and then a pigment as a negative charge control agent was dissolved. "Spiron Black T-
77 "(Hodogaya Chemical Co., Ltd.) 10 parts by weight,
The above charge control agent was dispersed in styrene by mixing in a ball mill for 100 hours. After this dispersion treatment, the charge control agent had a particle size of about 0.3 μm and no precipitation of the charge control agent was observed in the monomer. (Positive charge control agent-dispersed monomer liquid) It was prepared in the same manner as in Reference Example 1.

【００５８】実施例４ 上記カーボンブラツク分散単量体液３５重量部（カーボ
ンブラツクとして５重量部）と負帯電制御剤分散単量体
液3.４重量部（スピロンブラツクＴ−７７として0.２重
量部）と正帯電制御剤分散単量体液1.７重量部（ボント
ロンＮ−０７として0.１重量部）とを混合し、得られた
混合物に更にスチレン５７重量部、２−エチルヘキシル
アクリレート１３重量部、ジビニルベンゼン0.２重量部
及びオフセツト防止剤としてのポリプロピレンワツクス
３重量部を加え、更に、これに重合開始剤アゾビスジメ
チルバレロニトリル３重量部を加えて、重合用単量体組
成物を調製した。Example 4 35 parts by weight of the above carbon black-dispersed monomer liquid (5 parts by weight as a carbon black) and 3.4 parts by weight of a negative charge control agent-dispersed monomer liquid (0.2 parts by weight as Spiron-Black T-77). Part) and 1.7 parts by weight of a positive charge control agent-dispersed monomer liquid (0.1 parts by weight as Bontron N-07) are mixed, and 57 parts by weight of styrene and 13 parts by weight of 2-ethylhexyl acrylate are added to the resulting mixture. Parts, 0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent, and further 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator to obtain a monomer composition for polymerization. Was prepared.

【００５９】次いで、第三リン酸カルシウム６重量部を
含む水溶液４００重量部にドデシルベンゼンスルホン酸
ナトリウム0.０２重量部を加え、ホモミキサー（特殊機
化工業（株）製ＴＫ−Ｍ型）を用いて回転数８０００rp
m の攪拌下に、この水溶液中に上記重合用単量体組成物
を加え、更に、１０分間高剪断下に攪拌して、上記単量
体組成物を分散させた。Next, 0.02 part by weight of sodium dodecylbenzenesulfonate was added to 400 parts by weight of an aqueous solution containing 6 parts by weight of tricalcium phosphate, and a homomixer (TK-M type manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. Rotation speed 8000rp
The above-mentioned monomer composition for polymerization was added to this aqueous solution under stirring of m 3, and further stirred under high shear for 10 minutes to disperse the above-mentioned monomer composition.

【００６０】このようにして得られた単量体組成物の分
散液を６０℃で１０時間、低速攪拌し、単量体を重合さ
せて、重合体粒子を得た。得られた重合体粒子の体積平
均粒子径は5.８μｍであつた。得られた重合体粒子を塩
酸水溶液で洗浄し、次いで、水洗を数回、繰り返した
後、減圧下に乾燥して、トナーを得た。このトナー粒子
をＳＥＭ観察したところ、表面は平滑であつて、乳化重
合による重合体粒子の生成はみられなかつた。The dispersion liquid of the monomer composition thus obtained was stirred at 60 ° C. for 10 hours at a low speed to polymerize the monomer to obtain polymer particles. The volume average particle diameter of the obtained polymer particles was 5.8 μm. The obtained polymer particles were washed with a hydrochloric acid aqueous solution, and then washed with water several times, and then dried under reduced pressure to obtain a toner. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed.

【００６１】このトナー１００重量部に疎水性シリカＲ
９７２（日本アエロジル（株）製疎水性シリカＲ９７
２）0.３重量部を均一に配合し、キヤリア「Ｚ−２００
Ｂ」（パウダーテツク（株）製）を含むトナー濃度５重
量％の現像剤を調製した。この現像剤をブローオフ粉体
帯電量測定装置（東芝ケミカル（株）製）にて摩擦帯電
量を測定したところ、このトナーの摩擦帯電量は−３３
μＣ／ｇであつた。To 100 parts by weight of this toner, hydrophobic silica R
972 (hydrophobic silica R97 manufactured by Nippon Aerosil Co., Ltd.)
2) 0.3 part by weight is uniformly blended, and the carrier "Z-200" is used.
B ”(manufactured by Powder Tech Co., Ltd.) having a toner concentration of 5% by weight was prepared. When the triboelectric charge amount of this developer was measured by a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.), the triboelectric charge amount of this toner was -33.
It was μC / g.

【００６２】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、電子写真
複写を行なつたところ、常温常湿下及び高温高湿下共
に、画像のかぶりや所謂黒べた部に濃度むらがなく、文
字部や線部の散り等が殆どない解像度の高い高品質の複
写画像を得ることができた。更に、このトナーを用い
て、常温常湿下において、連続して１万枚の複写を行な
つた後、現像剤をメタノールにて洗浄し、トナーを除去
した後のキヤリアをトルエン中に浸漬し、トルエンに溶
解する所謂スペントトナー量は非常に少ないものであつ
た。Further, when this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) and electrophotographic copying was performed, images were obtained under both normal temperature and normal humidity and high temperature and high humidity. It was possible to obtain a high-quality copy image having high resolution with no fog or so-called black solid portion having uneven density and almost no scattering of character portions or line portions. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００６３】実施例５ 実施例４と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液１７重量部（スピロンブラツ
クＴ−７７として1.０重量部）と正帯電制御剤分散単量
体液4.２５重量部（ボントロンＮ−０７として0.２５重
量部）とを混合し、得られた混合物に更にスチレン３6.
６重量部、２−エチルヘキシルアクリレート１３重量
部、ジビニルベンゼン0.２重量部及びオフセツト防止剤
としてのポリプロピレンワツクス３重量部を加え、更
に、これに重合開始剤アゾビスジメチルバレロニトリル
３重量部を加えて、重合用単量体組成物を調製した。Example 5 In the same manner as in Example 4, 35 parts by weight of the carbon black dispersion monomer liquid (5 parts by weight as a carbon black) and 17 parts by weight of the negative charge control agent dispersion monomer liquid (Spyron Black T- No. 77 as 1.0 part by weight) and 4.25 parts by weight of a positive charge control agent-dispersed monomer liquid (0.25 part by weight as Bontron N-07) were mixed, and the resulting mixture was further mixed with styrene 36.
6 parts by weight, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent were added, and further 3 parts by weight of a polymerization initiator azobisdimethylvaleronitrile was added thereto. In addition, a monomer composition for polymerization was prepared.

【００６４】この後、実施例１と同様に処理して、体積
平均粒子径は5.６μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は−４７μＣ／ｇであつ
た。Thereafter, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.6 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was -47 μC / g.

【００６５】また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下及び高温高湿下共に、画像のかぶ
りや所謂黒べた部に濃度むらがなく、文字部や線部の散
り等が殆どない解像度の高い高品質の複写画像を得るこ
とができた。また、このトナーを用いて、常温常湿下に
おいて、連続して１万枚の複写を行なつた後、現像剤を
メタノールにて洗浄し、トナーを除去した後のキヤリア
をトルエン中に浸漬し、トルエンに溶解する所謂スペン
トトナー量は非常に少ないものであつた。Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly, under high temperature and high humidity both under normal temperature and high humidity, there is no image fogging or so-called black solid part density unevenness, and there is almost no scattering of character parts or line parts. I was able to. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００６６】実施例６ 実施例１と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液3.４重量部（スピロンブラツ
クＴ−７７として0.２重量部）と正帯電制御剤分散単量
体液１3.６重量部（ボントロンＮ−０７として0.８重量
部）とを混合し、得られた混合物に更にスチレン４1.９
重量部、２−エチルヘキシルアクリレート１３重量部、
ジビニルベンゼン0.２重量部及びオフセツト防止剤とし
てのポリプロピレンワツクス３重量部を加え、更に、こ
れに重合開始剤アゾビスジメチルバレロニトリル３重量
部を加えて、重合用単量体組成物を調製した。Example 6 In the same manner as in Example 1, 35 parts by weight of the above-mentioned carbon black-dispersed monomer liquid (5 parts by weight as a carbon black) and 3.4 parts by weight of a negative charge control agent-dispersed monomer liquid (spiron black) were used. 0.2 parts by weight as T-77) and 13.6 parts by weight of the positive charge control agent-dispersed monomer liquid (0.8 parts by weight as Bontron N-07) were mixed, and the resulting mixture was further mixed with styrene 41. 9
Parts by weight, 13 parts by weight of 2-ethylhexyl acrylate,
0.2 parts by weight of divinylbenzene and 3 parts by weight of polypropylene wax as an anti-offset agent were added, and further 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator were added to prepare a monomer composition for polymerization. did.

【００６７】この後、実施例１と同様に処理して、体積
平均粒子径は5.８μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は＋４２μＣ／ｇであつ
た。Then, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.8 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was +42 μC / g.

【００６８】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、反転現像
による電子写真複写を行なつたところ、常温常湿下及び
高温高湿下共に、画像のかぶりや所謂黒べた部に濃度む
らがなく、文字部や線部の散り等が殆どない解像度の高
い高品質の複写画像を得ることができた。更に、このト
ナーを用いて、常温常湿下において、連続して１万枚の
複写を行なつた後、現像剤をメタノールにて洗浄し、ト
ナーを除去した後のキヤリアをトルエン中に浸漬し、ト
ルエンに溶解する所謂スペントトナー量は非常に少ない
ものであつた。Further, this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) to perform electrophotographic copying by reversal development. Under normal temperature and normal humidity and high temperature and high humidity, In both cases, it was possible to obtain a high-quality copy image having a high resolution with no image fog or so-called black solid portion having uneven density and almost no scattering of character portions or line portions. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was dipped in toluene. The amount of so-called spent toner dissolved in toluene was very small.

【００６９】比較例４ 実施例４と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液５9.５重量部（スピロンブラ
ツクＴ−７７として3.５重量部）とを混合し、得られた
混合物に更にスチレン2.９重量部、２−エチルヘキシル
アクリレート１３重量部、ジビニルベンゼン0.２重量部
及びオフセツト防止剤としてのポリプロピレンワツクス
３重量部を加え、更に、これに重合開始剤アゾビスジメ
チルバレロニトリル３重量部を加えて、重合用単量体組
成物を調製した。Comparative Example 4 In the same manner as in Example 4, 35 parts by weight of the above carbon black-dispersed monomer liquid (5 parts by weight as carbon black) and 59.5 parts by weight of the negative charge control agent-dispersed monomer liquid (spiron black) were used. T-77 (3.5 parts by weight), and the resulting mixture was further mixed with 2.9 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and polypropylene as an offset inhibitor. 3 parts by weight of wax and 3 parts by weight of a polymerization initiator azobisdimethylvaleronitrile were further added to prepare a monomer composition for polymerization.

【００７０】この後、実施例１と同様に処理して、体積
平均粒子径は6.１μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面は平滑であつて、乳
化重合による重合体粒子の生成はみられなかつた。この
トナーを用いて、実施例１と同様にして、現像剤を調製
した。この現像剤の摩擦帯電量は−７６μＣ／ｇであつ
た。Then, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 6.1 μm. When the toner particles were observed by SEM, the surface was smooth and no formation of polymer particles by emulsion polymerization was observed. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer was -76 μC / g.

【００７１】また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下においては、複写画像のかぶりや
所謂黒べた部に濃度むらがなく、文字部や線部の散り等
が殆どない解像度の高い高品質の複写画像を得ることが
できた。しかし、高温高湿下では、複写画像にかぶりが
みられた。また、このトナーを用いて、常温常湿下で連
続して１万枚の複写を行なつた後、現像剤をメタノール
にて洗浄し、トナーを除去した後のキヤリアをトルエン
中に浸漬し、トルエンに溶解する所謂スペントトナー量
は非常に少ないものであつた。Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly, under normal temperature and normal humidity, it is possible to obtain a high-quality copy image with high resolution, which has no fog on the copy image, uneven density in the so-called black solid part, and almost no scattering of characters and lines. It was However, under high temperature and high humidity, fog was seen in the copied image. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene, The amount of so-called spent toner dissolved in toluene was very small.

【００７２】比較例５ 実施例４と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
負帯電制御剤分散単量体液0.１７重量部（スピロンブラ
ツクＴ−７７として0.０１重量部）とを混合し、得られ
た混合物に更にスチレン５７重量部、２−エチルヘキシ
ルアクリレート１３重量部、ジビニルベンゼン0.２重量
部及びオフセツト防止剤としてのポリプロピレンワツク
ス３重量部を加え、更に、これに重合開始剤アゾビスジ
メチルバレロニトリル３重量部を加えて、重合用単量体
組成物を調製した。Comparative Example 5 In the same manner as in Example 4, 35 parts by weight of the carbon black dispersion monomer liquid (5 parts by weight as a carbon black) and 0.17 parts by weight of the negative charge control agent dispersion monomer liquid (spiron black) were used. T-77 as 0.01 part by weight), and the resulting mixture was further mixed with 57 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and polypropylene wax as an anti-offset agent. 3 parts by weight was added, and further 3 parts by weight of the polymerization initiator azobisdimethylvaleronitrile was added thereto to prepare a monomer composition for polymerization.

【００７３】この後、実施例１と同様に処理して、体積
平均粒子径は5.７μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面には、乳化重合によ
る微小な重合体粒子が多数、付着しているのがみられ
た。このトナーを用いて、実施例１と同様にして、現像
剤を調製した。この現像剤の摩擦帯電量は−３８μＣ／
ｇであつた。また、この現像剤を用いて、実施例１と同
様の電子写真複写を行なつたが、その結果は、実施例１
と同様に、常温常湿下において、複写画像にかぶりがみ
られ、高温高湿下では、複写画像に著しいかぶりがみら
れた。また、このトナーを用いて、常温常湿下で連続し
て１万枚の複写を行なつた後、現像剤をメタノールにて
洗浄し、トナーを除去した後のキヤリアをトルエン中に
浸漬したところ、多量のスペントトナーがみられた。Then, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.7 μm. As a result of SEM observation of the toner particles, it was found that a large number of fine polymer particles adhered on the surface by emulsion polymerization. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer is -38 μC /
It was g. Further, using this developer, electrophotographic copying was carried out in the same manner as in Example 1, and the results are shown in Example 1.
Similarly to the above, the fog was observed on the copied image under normal temperature and normal humidity, and the fog was observed on the copied image under high temperature and high humidity. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene. , A large amount of spent toner was observed.

【００７４】比較例６ 実施例４と同様にして、前記カーボンブラツク分散単量
体液３５重量部（カーボンブラツクとして５重量部）と
正帯電制御剤分散単量体液0.１７重量部（ボントロンＮ
−０７として0.０１重量部）とを混合し、得られた混合
物に更にスチレン５７重量部、２−エチルヘキシルアク
リレート１３重量部、ジビニルベンゼン0.２重量部及び
オフセツト防止剤としてのポリプロピレンワツクス３重
量部を加え、更に、これに重合開始剤アゾビスジメチル
バレロニトリル３重量部を加えて、重合用単量体組成物
を調製した。Comparative Example 6 In the same manner as in Example 4, 35 parts by weight of the carbon black dispersion monomer liquid (5 parts by weight as a carbon black) and 0.17 parts by weight of the positive charge control agent dispersion monomer liquid (Bontron N) were used.
0.01 parts by weight as -07) and 57 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene and polypropylene wax 3 as an anti-offset agent. 3 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator was added thereto to prepare a monomer composition for polymerization.

【００７５】この後、実施例１と同様に処理して、体積
平均粒子径は5.６μｍのトナー粒子を得た。このトナー
粒子をＳＥＭ観察したところ、表面には、乳化重合によ
る微小な重合体粒子が多数、付着しているのがみられ
た。このトナーを用いて、実施例１と同様にして、現像
剤を調製した。この現像剤の摩擦帯電量は＋３９μＣ／
ｇであつた。Then, the same treatment as in Example 1 was carried out to obtain toner particles having a volume average particle diameter of 5.6 μm. As a result of SEM observation of the toner particles, it was found that a large number of fine polymer particles adhered on the surface by emulsion polymerization. Using this toner, a developer was prepared in the same manner as in Example 1. The triboelectric charge of this developer is +39 μC /
It was g.

【００７６】また、この現像剤を電子写真複写機（三洋
電機（株）製ＳＦＴ−１１０２）に適用して、反転現像
による電子写真複写を行なつたところ、常温常湿下にお
いて、複写画像にかぶりがみられた。また、このトナー
を用いて、常温常湿下で連続して１万枚の複写を行なつ
た後、現像剤をメタノールにて洗浄し、トナーを除去し
た後のキヤリアをトルエン中に浸漬したところ、多量の
スペントトナーがみられた。以上の結果を表３及び表４
にまとめて示す。When this developer was applied to an electrophotographic copying machine (SFT-1102 manufactured by Sanyo Electric Co., Ltd.) to perform electrophotographic copying by reversal development, a copied image was obtained under normal temperature and normal humidity. There was a fogging. Further, using this toner, after continuously copying 10,000 sheets at room temperature and normal humidity, the developer was washed with methanol, and the carrier after removing the toner was immersed in toluene. , A large amount of spent toner was observed. The above results are shown in Table 3 and Table 4.
Are shown together.

【００７７】[0077]

【表３】 [Table 3]

【００７８】[0078]

【表４】 [Table 4]

【００７９】[0079]

【発明の効果】以上のように、本発明によれば、帯電制
御剤粒子を分散させた単量体を水性分散媒中に分散さ
せ、分散安定剤の存在下に懸濁重合して、トナーを製造
する方法において、帯電制御剤として、正帯電制御剤と
負帯電制御剤との混合物を用いることによつて、好まし
くない乳化重合を防止しつつ、且つ、帯電性を任意に調
節しつつ、帯電量を適正とした平均粒子径６μｍ以下の
小粒子径化トナーを得ることができる。従つて、かかる
トナーによれば、かぶり等の画像欠陥のない高解像度の
複写画像を得ることができる。As described above, according to the present invention, the toner in which the charge control agent particles are dispersed is dispersed in the aqueous dispersion medium, and the suspension polymerization is carried out in the presence of the dispersion stabilizer to obtain the toner. In the method for producing, by using a mixture of a positive charge control agent and a negative charge control agent as the charge control agent, while preventing undesired emulsion polymerization, and while optionally adjusting the chargeability, It is possible to obtain a toner having a small particle size and an average particle size of 6 μm or less with an appropriate charge amount. Therefore, with such toner, it is possible to obtain a high-resolution copied image without image defects such as fog.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】帯電制御剤粒子を分散させた単量体を水性
分散媒中に分散させ、分散安定剤の存在下に懸濁重合し
て、トナーを製造する方法において、帯電制御剤が負帯
電制御剤と正帯電制御剤との混合物であることを特徴と
する静電潜像現像用トナーの製造方法。1. A method for producing a toner by dispersing a monomer in which particles of a charge control agent are dispersed in an aqueous dispersion medium and carrying out suspension polymerization in the presence of a dispersion stabilizer to obtain a toner. A method for producing a toner for developing an electrostatic latent image, which is a mixture of a charge control agent and a positive charge control agent. 【請求項２】負帯電制御剤がアゾ系含金属錯塩顔料であ
ることを特徴とする請求項１記載の静電潜像現像用トナ
ーの製造方法。2. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the negative charge control agent is an azo metal-containing complex salt pigment. 【請求項３】正帯電制御剤がニグロシン系染料であるこ
とを特徴とする請求項１記載の静電潜像現像用トナーの
製造方法。3. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the positive charge control agent is a nigrosine dye. 【請求項４】帯電制御剤粒子を分散させた単量体を水性
分散媒中に分散させ、分散安定剤の存在下に懸濁重合し
て、トナーを製造する方法において、帯電制御剤が負帯
電制御剤であるアゾ系含金属錯塩顔料と正帯電制御剤で
あるニグロシン系染料との混合物であり、正帯電制御剤
／負帯電制御剤の重量比が１０／１〜１／１０であるこ
とを特徴とする請求項１、２又は３記載の静電潜像現像
用トナーの製造方法。4. A method of producing a toner by dispersing a monomer in which particles of a charge control agent are dispersed in an aqueous dispersion medium and performing suspension polymerization in the presence of a dispersion stabilizer, wherein the charge control agent is negative. It is a mixture of an azo metal complex complex pigment which is a charge control agent and a nigrosine dye which is a positive charge control agent, and the weight ratio of positive charge control agent / negative charge control agent is 10/1 to 1/10. The method for producing a toner for developing an electrostatic latent image according to claim 1, 2, or 3. 【請求項５】トナーが平均粒子径６μｍ以下を有するこ
とを特徴とする請求項１記載の静電潜像現像用トナーの
製造方法。5. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the toner has an average particle size of 6 μm or less. 【請求項６】分散安定剤が第三リン酸カルシウムである
ことを特徴とする請求項１記載の静電潜像現像用トナー
の製造方法。6. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the dispersion stabilizer is tricalcium phosphate.