JPS5950452A - Electrostatic image developing toner and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a toner capable of dispersing carbon black well, and obtaining a high-quality image, by polymerizing a monomer obtd. dispersing carbon black surface-treated with an aluminum chelating compd. into said monomer. CONSTITUTION:Said aluminum chelating compd. is represented by the formula shown on the right in which R1 is 1-10C alkyl; R2 is 1-20C alkyl or alkenyl, such as lauryl acetate aluminum dipropylate. Carbon black is immersed into this soln., the carbon black is filtered from the slurry, heated and dried to obtain the surface-treated carbon black. The intended toner is obtained by dispersing said carbon black together with additives, such as polymn. initiator, into a monomer to form an oil phase dispersion, dispersing said dispersion into an aq. phase contg. a dispersion stabilizer dissolved or dispersed, polymerizing said monomer with stirring at raised temp., filtering, washing, and drying the obtained polymer.

Description

【発明の詳細な説明】 本発す」は市子刀真法、箔ｊ嵐記録法およびＨＰ　ＭＣ
印刷法ｌこおいて静１ｆｆ、りｊ像を現像するための乾
式トナーおよびそＵ〕製造力法に臥ｊする。[Detailed description of the invention] "This issue" is based on Toshin Ichiko, Hakuj Arashi Recording Method and HP MC.
In the printing method, the dry toner for developing the image and the manufacturing power method are used.

着色剤と樹脂を主成分とする乾式トナーを用いる現像方
法としては、 ｉ）乾式トナーをトナーより大きい粒径のキャリヤーと
ンｊｌ＋Ｘ合し１■擦・Ｎ”ｉ　＋（ｉ、によりトナー
に静電潜像の電荷とは逆極性の電荷全力え、トナーとキ
ャリヤーの混合物である現像剤を静電潜像と接触させ静
電、潜像を現像する二成分Ｎ像剤 １１）磁性体を含有したトナー８静電潜像と接触又は近
接させて現像する一成分現像剤 がある。A developing method using a dry toner whose main components are a colorant and a resin is as follows: i) The dry toner is mixed with a carrier having a particle size larger than the toner, and the toner is statically coated with 1. A two-component N developer that develops an electrostatic latent image by bringing a developer, which is a mixture of toner and carrier, into contact with the electrostatic latent image. 11) Contains a magnetic material. There is a one-component developer that is developed by being in contact with or in close proximity to the toner 8 electrostatic latent image.

従来、これらのトナーを得るために、熱可塑性樹脂を溶
融し、これに染料、顔料等の着色剤心裏″により磁性体
、摩擦帝亀制伺剤、オフセット防止剤、潤滑剤等を加え
充分に混合した後、冷却固化し、これを微粉砕した後所
要の粒径ををうる為の分級を行う方法が実施されていた
。Conventionally, in order to obtain these toners, a thermoplastic resin is melted, and a magnetic material, a friction control agent, an anti-offset agent, a lubricant, etc. are added to it with a coloring agent such as a dye or a pigment, and the mixture is thoroughly melted. After mixing, the mixture is cooled and solidified, pulverized, and then classified to obtain the desired particle size.

しかしながら上述した方法には才筆々の欠点が存在する
。第一には樹脂製造の為の重合装５，７、混線の為の装
置、粉砕機、分紡機等の多くの工程に伴う装置が必要で
あり工程数も多くエネルギー消費も大きい事が、コスト
が高くなるｊ銀囚となっている。第二にはγＩ？、練工
程で均一な混合体が得かＩＥいことで、特に均一に分散
させる為の条件が微妙であることがあげられる。第三に
は粉砕工程においてはｆ＋を明てかぶりのない画像を得
るための鏑切な微粉体粒子径ＷＩＪ、囲υ）ものだけが
得ら１７るわけではなく、微粉と第１１粉が副産し分級
して除去しなければならないなどの工程の枚雑さ、希望
粒径範囲を１ける収率の悲さなとコストアップにつなが
る欠点が存在する。第四に１ｕられた生成粉体は粉砕に
より不定形の形状を有し、微粉体の（Ａ（、動性の悪さ
、卿（擦帝市、を行なう際にイ）ν拌による再粉砕で生
ずる１皮粉が原因となる画１′４！　０）かぶりがあけ
られる。However, the methods described above have considerable drawbacks. Firstly, equipment accompanying many processes is required, such as polymerization units 5 and 7 for resin production, cross-wire equipment, crushers, spinning machines, etc., resulting in a large number of processes and high energy consumption, which leads to high costs. It has become a silver prisoner as the price increases. Secondly, γI? However, it is difficult to obtain a uniform mixture during the kneading process, and the conditions for uniform dispersion are particularly delicate. Thirdly, in the grinding process, not only the fine powder particle diameter WIJ, boxed υ) is obtained in order to obtain an image with clear f+ and no fog, but also fine powder and No. 11 powder are produced as by-products. There are drawbacks such as complicated processes such as the need to classify and remove particles, poor yields that are less than the desired particle size range, and increased costs. Fourthly, the powder produced after 1U has an irregular shape due to the grinding, and the fine powder is not re-pulverized by stirring. Image 1'4 caused by the resulting 1 skin powder! 0) The fog is opened.

こイ１．ｉこメリして特公昭３６−１０２３１号、特公
昭４７−５．１　ｓ　３ｕ号、特公昭５１−１４８９５
号等の公報には、詩濁小合法によるトナーυ）製造方法
が記・；アされ−Ｃいる。この懸７Ｎ−ｊｆｔ合法は、
粉砕を必↓！とぜず製造」−程も簡略化され、ｔｉｉｌ
述の欠点を改良したもυ〕と黒える。しかしながら、懸
濁重合に伴う問題がある。Koi 1. I Komeri Special Publication No. 36-10231, Special Publication No. 5.1 s 3u of 1977, Special Publication No. 14895 of 1973
Publications such as No. 1, etc. describe a method for manufacturing toner υ) using the Shikoku Ko method. This hanging 7N-jft legal is,
Must be crushed! "Tozezu manufacturing" - process is also simplified, till
Even though the above-mentioned shortcomings have been improved, υ] is still a problem. However, there are problems associated with suspension polymerization.

即ら、乾式トナーは熱用塑性樹脂を主体とするが、これ
に各種の機能を何カし改善する為の材料が添加混合され
ており、染料、顔料等０）着色剤、摩擦帯電性を改良す
る帯電制御剤、現像ローラーへの付着性を与える（面性
材料、或いは定着ローラーへのトナーの付着を防止する
オフセット防止剤、トナー流動性向上剤等がある。In other words, dry toner is mainly made of thermoplastic resin, but to this it is mixed with materials to improve various functions, including dyes, pigments, coloring agents, and triboelectric properties. Examples include a charge control agent to improve the toner's adhesion to the developing roller (surface-forming material), an anti-offset agent to prevent toner from adhering to the fixing roller, and a toner fluidity improver.

これら材料が重合性単用体中に均一【こ溶解し、重合反
応を阻害しない（１）であれば特に問題（才ないが、添
加される多くの物質が重電性単量体に不溶か難溶であり
、重合性単量体に対する親和性に欠けるために、これら
材料を重合体ｉＱ子中に均一な状態で存在せしめる事が
困御である。If these materials are uniformly dissolved in the polymerizable monomer and do not inhibit the polymerization reaction (1), there is a particular problem (although it may be difficult to explain why many of the substances added are insoluble in the heavy electrical monomer). Since these materials are poorly soluble and lack affinity for polymerizable monomers, it is difficult to make these materials exist in a uniform state in the polymer iQ molecules.

そして添加した材料の重合性単元一体に対づ−る親和性
が著るしく劣る場合には重合中に水相に移行し重合した
トナー粒子中に添加したオ（料が存在しない場合も生ず
る。If the added material has significantly poor affinity for the polymerizable unit, it may migrate to the aqueous phase during polymerization and the added material may not be present in the polymerized toner particles.

この様に添付した材料がトナー中に不均一に存在するｆ
こめに、充分な帯電が為されない等トナーとしての機能
が充分発揮する事ができない。The material attached in this way exists unevenly in the toner.
In addition, the toner cannot fully perform its function as it is not sufficiently charged.

優れた画像品質を得ることはできない。It is not possible to obtain excellent image quality.

特に、着色剤もしくは帯′亀制御剤として使用されるカ
ーボンブラックは４１油性であるが一次粒子が１　ｏ　
ｍｐ　〜３ｏ　ｍｐ　（！：　（？細テアル上、製造時
生ずる一次絣集体、さらに凝集の進んだ二次凝集体を形
成し、単にボールミル等の分散手段によっては重電性単
量体中に分散する串は困難であり、この様に分散不良の
カーボッブラックを含有するトナー粒子ではトナーの黒
色度が低下し黒色の両像ヲうる事ができないばかりでな
く、トナー粒子のｔｔＬ気抵抗抵抗振号′…、詩の、Ｓ
ラッキを増太し陰れた画像品質をつる事はできない。In particular, carbon black, which is used as a colorant or as a band control agent, is 41 oil-based, but the primary particles are 1 o
mp ~3o mp (!: (? Due to the fine tear, primary Kasuri aggregates generated during production, and secondary aggregates with advanced aggregation are formed, and simply dispersed in heavy electric monomers by dispersion means such as a ball mill. In this way, toner particles containing poorly dispersed carbo black not only reduce the blackness of the toner and make it impossible to obtain both black images, but also reduce the ttL air resistance vibration of the toner particles. No.'..., poem, S
It is not possible to improve image quality by increasing the amount of money.

１特開昭５６−１１６０４４号、特開昭５６−１２３５
５３号、特開昭５７−３７３５４号等の公報には、懸濁
重合で製造するトナーにおいてカーボンの分散を改良す
る方法が記載されている。しかし、いづ′れも製造工程
を増加させるもので、製造工程を増加する事は懸濁重合
の利点を減するものであり、添加剤による分散安定性の
改良も、多くの添加剤はトナーの′眠気抵抗、摩擦帯電
性等のｔ属気１時性の湿度依存性を高めるという問題が
ある。1 JP-A-56-116044, JP-A-56-1235
Publications such as No. 53 and JP-A No. 57-37354 describe methods for improving carbon dispersion in toners produced by suspension polymerization. However, all of them increase the manufacturing process, and increasing the manufacturing process reduces the advantages of suspension polymerization. 'There is a problem of increasing the humidity dependence of t-temporal properties such as drowsiness resistance and triboelectric charging properties.

従って、カーボンブラックは一回の工程で仙の添加剤と
同時に重合性単用体中に分散する１１■が望ましい。才
たこの為に用いるカーボッブラックの分散剤は、トナー
の電気抵抗、ｇｌ、振号１１１、特性、熱特性に悪い影
響を力えトナーの１ｔ−Ｉυ１１性、耐久性、保存性等
を低下させるものてあってはならない。Therefore, it is desirable that the carbon black be dispersed in the polymerizable monomer at the same time as the additives in a single process. The dispersant of Carboblack used for this purpose has a negative effect on the electrical resistance, GL, number 111, properties, thermal properties of the toner, and reduces the 1t-Iυ11 property, durability, storage stability, etc. of the toner. Nothing should be allowed to happen.

本発明の第１　Ｃ／）目的は十分なカーボンブランクの
分散状態を有し優れた画像品質の得られるトナーを提供
する事にあり、第２０）　Ｌｌ的は）１υ濁取合法の欠
点を改良したトナーの製造方法を提供する半にある。The first objective of the present invention is to provide a toner that has a sufficient carbon blank dispersion state and provides excellent image quality, and the second objective is to improve the drawbacks of the 1υ turbidity removal method. The present invention is in the process of providing a method for manufacturing toner.

本発明者等は上記目標を達成°リーる１こめに蝕λ・（
検ｄ寸の結果、有機アルミニウム化合物そ塩有さぜた車
舎外単ｔ４゛体中にカーボンブランクを分散するか、あ
るいは治機アルミニウド 而処理を行なったカーポンブランクラ３＋（電性Ｊ１ｔ
Ｆ，を体中に分散したとき著しくカーフ１、／フラ゛ツ
クの分散状態が改良された４１ｆ見出し本発明に至った
。The present inventors achieved the above goal by reducing the eclipse λ・(
As a result of the d size inspection, carbon blank 3+ (electric J1t) was prepared by dispersing the carbon blank in the outside of the car body with organic aluminum compound salt, or by dispersing the carbon blank in the aluminum body.
The present invention has been achieved based on the finding that the dispersion state of calf 1/flake was significantly improved when F, was dispersed throughout the body.

本発明で月ｊいらＩｌ、るアルミニラｔ・キレート化合
物の代表例としては １１ （式中、Ｒ１はＯ，％Ｃ２ｏＯ）　ｆｌ鎖また（ま分岐
したアルキ／Ｌ／基、几、は０１−０２゜好ましくは（
、’　Ｂ　〜Ｃ２ｏＯ）　ｉｉ釦または分１！ＩＡ　Ｌ
だアルキル鬼才たけアルケニル基を岩わず。） の一般式で表わされるものが挙げられる。Typical examples of the alumina chelate compounds used in the present invention include 11 (wherein, R1 is O, %C2oO), or a branched alkyl/L/ group, 01-02゜Preferably (
,'B~C2oO) ii button or minute 1! IA L
Even though he is an alkyl genius, he doesn't care about alkenyl groups. ) is represented by the general formula.

このアルミニウムキレート化合物を含有するトナー及び
そＱ）製造方σζについてｔｌ・卸１に説明する。The toner containing this aluminum chelate compound and its manufacturing method σζ will be explained below.

アルミニウム１−レート化合物ζこよるカーボンブラッ
クの０．゛ミ面処理はアルミニウムキレ−１・化合物ｆ
　（Ｍ　ｊ＋’（Ｌ／た浴液にカーホンブラックを浸漬
しスラリー状とした仮、戸別Ｊたは減圧乾燥により浴剤
イ１除去する４１により行なわれる。溶剤Ｑ〕除去後さ
らに加熱を行い処理を行う事が奸才しい。この様な処理
方法は特ｌこ他の添加剤がアルミニウムキレート化合物
と反応性を有するときは好ましい方法である。次に表面
処理されたカーボンブランクと重合開始剤等の添加剤と
を亀舎外単肴体中に分散し油相溶液を調製する。0.0% of carbon black due to aluminum 1-rate compound ζ. Dim surface treatment is aluminum clean-1/compound f
(M j+'(L/3) immerse carphone black in a bath solution to form a slurry, remove the bath agent A1 by door-to-door J or vacuum drying. After removing the solvent Q, heat the mixture further. This treatment method is particularly preferred when other additives have reactivity with the aluminum chelate compound.Next, the surface-treated carbon blank and the polymerization initiator are An oil phase solution is prepared by dispersing the following additives in a Kameshagai simple dish.

また重合性単量体中にカーボンブラックと共にポリマー
、オリゴマー等が添加される場合は溶融したポリマー、
オリゴマーにカーボンブランク、アルミニウム化合物を
加え、ニーダ−笠で分散した後重合性単量体中にぢＳ加
し油相溶液をｐｉＩｒｓ製しても良い。In addition, when polymers, oligomers, etc. are added together with carbon black to the polymerizable monomer, the molten polymer,
A carbon blank and an aluminum compound may be added to the oligomer, dispersed in a kneader cap, and then diS may be added to the polymerizable monomer to prepare an oil phase solution using piIrs.

次いで、水難溶性無機粉体、水溶性高分子等の分散安定
剤及び水相での重合糸止剤等を均一に溶解あるいは分散
した水相に、前記油相の分散液を加わえて、ホモミキサ
ー、ホモジナイザー等の分散手段により５〜３０μの油
滴に分散する。油相と水相とのｉｔ比は１：２〜１：１
０の範囲で、取合中粒子の合一が起らない範囲で設定さ
れる。油相を水相中に均一ζこ分散した分散液を搏拌装
屑、コンデンサー、温皿肘、窒素導入管を伺した七パラ
プルフラスコに移し、重合開始剤の分解するτｌ、Ａ　
Ｉ蕉（５０〜９０℃）に昇温し窒素へ１．流下ｒ４τ合
を行なわせる。Next, the dispersion of the oil phase is added to the aqueous phase in which poorly water-soluble inorganic powder, a dispersion stabilizer such as a water-soluble polymer, and a polymerization stopper in the aqueous phase are uniformly dissolved or dispersed, and a homomixer is added. , disperse into oil droplets of 5 to 30 μm using a dispersing means such as a homogenizer. The IT ratio between the oil phase and the water phase is 1:2 to 1:1.
It is set within a range of 0, in which coalescence of particles during the combination does not occur. The dispersion in which the oil phase was uniformly dispersed in the aqueous phase was transferred to a seven-paraple flask equipped with a stirring device, a condenser, a hot plate head, and a nitrogen inlet pipe, and the polymerization initiator was decomposed.
1. Raise the temperature to 50-90°C and add nitrogen. The downstream r4τ combination is performed.

重合完了後、ｐ別し水相を除き、併イ長粉体がトナー表
面にイづ着している場合は、希酸で処理して除き、水６
を後噴霧乾燥、八ツ乾燥等の手段で水分を除きトナーが
製造さＩ−する。After the polymerization is completed, the aqueous phase is separated, and if the long powder is stuck to the toner surface, it is removed by treatment with dilute acid, and then the aqueous phase is removed.
After that, moisture is removed by spray drying, drying, etc. to produce a toner.

本発明に使用ｆＴＪ能な重合性単量体及び各種添加剤の
具体例を挙げると次の通りである。Specific examples of the fTJ-capable polymerizable monomer and various additives used in the present invention are as follows.

重合性単量体：重合可能なずべての単−級体が含まれる
が特にスチレン、メチルメタクリレート、アクリル酸メ
チル、地代ビニル、エチレン、ビニルメチルエーテル、
ビニルメチルケトン、Ｎ−ビニルカルノ々ゾール等のビ
ニル化合物が好ましい。またジピニルペンゼノ、エチＬ
／　ンクＩＪコールジアクリレート、トリメチロールプ
ロパントリアクリレート等のジビニル化合物もビニル化
合物に対しＱ、　ｆｌ　０５重ｗ＃チ〜２ｏ重験チの範
囲で用いる事ができる。Polymerizable monomer: includes all polymerizable monomers, especially styrene, methyl methacrylate, methyl acrylate, vinyl, ethylene, vinyl methyl ether,
Vinyl compounds such as vinyl methyl ketone and N-vinylcarnozole are preferred. Also dipinyl penzeno, ethi L
Divinyl compounds such as cold diacrylate and trimethylolpropane triacrylate can also be used in the range of Q, fl 05 weight w#ch to 2o heavy weight x for the vinyl compound.

重合開始剤：　２　、２’−アゾビスインブチロニトリ
ル、２．２′−アゾビス−２，４−ジメチルノζレロニ
トリル等のアゾ化合物、ペンゾイルノに＝オキサイド、
ラウロイルパーオキサイド等の禍酸化物が用いられる。Polymerization initiator: azo compound such as 2,2'-azobisinbutyronitrile, 2,2'-azobis-2,4-dimethylnoζleronitrile, penzoylnooxide,
A harmful oxide such as lauroyl peroxide is used.

才だ重合体の分子辰を所要の範囲に抑えるためにドデシ
ルメルカプタン等の連釦移動剤を用いる事ができる。A link transfer agent such as dodecyl mercaptan can be used to keep the molecular weight of the polymer within the required range.

着　色　剤：カーボンブラック、シアニン、キクナトリ
ア等の顔料、アニリノブラック、ニクロシン等の染料が
用いられる。これら染料は摩擦帯酸性ｌこ優れる場合は
帯電制御剤として用いる事ができる。Coloring agent: Pigments such as carbon black, cyanine, and chrysanthemum, and dyes such as anilino black and nicrosin are used. These dyes can be used as charge control agents if they have excellent tribostatic acidity.

磁　性　体：酸化鉄、フェライト、鉄等の１μ以下の微
粒の強磁性体が用いられ、特に黒色の場合は届色材料を
添加せずに用いる事ができる。Magnetic material: A ferromagnetic material with fine particles of 1μ or less such as iron oxide, ferrite, iron, etc. is used, and especially in the case of black, it can be used without adding a coloring material.

ポリマー、オリコマ−、ゾレポリマー：ポリエチレン、
ポリプロピレン、エチレン酢ピコポリマー、塩素化ポリ
エチレンワックス、ポリアミド、ポリエステル、ポリウ
レタン、ポリビニルブチラール、シタジエン系ゴム、フ
ェノール樹脂、エポキシイ何脂、「ｊジン変性樹脂、シ
リコーンオイル、シリコ−７ワツクスをオフセット防止
、流Ｒｉｌ＋　性改良、定着性の改良、流動４ｑ：、ｏ
）向上等の目的に用いる串ができる。Polymer, oricomer, sol polymer: polyethylene,
Prevents offset and flow of polypropylene, ethylene acetate picopolymer, chlorinated polyethylene wax, polyamide, polyester, polyurethane, polyvinyl butyral, sitadiene rubber, phenolic resin, epoxy resin, resin-modified resin, silicone oil, and silicone-7 wax. Ril+ Improved properties, improved fixability, flow 4q:, o
) A skewer is made for purposes such as improvement.

仙ｌこ、７儂合１１１゛中活体および′６．．’ｉ加物
からなる油相を水相に均一に分散する目的で、シリカ、
アルミナ、クルク、炭酸ノフルシウム等水が１を溶性の
微粉体又はポリビニルアルコール、ヒドロギンセルロー
ス、ゼラチン等の水溶性ポリマーを単独又は併用して用
いる小ができる。またドデシルベンゼンスルポン酸ナト
リウム等の界面活性剤を無機微粉体または水溶性高分子
と共に用いても良い。また水相に塩化准ジニ鉄、チオシ
アン酸アンモン、過酸化水素等の重合禁止剤を添加する
事は乳化１ａ合による極微粒子（１）発生を防止づ−る
点でイ］効である。Senlko, 7th class 111゛ medium active body and '6. ．． 'i In order to uniformly disperse the oil phase consisting of additives in the water phase, silica,
Water-soluble fine powders such as alumina, curcum, nofrucium carbonate, etc. or water-soluble polymers such as polyvinyl alcohol, hydrogine cellulose, gelatin, etc. can be used alone or in combination. Further, a surfactant such as sodium dodecylbenzenesulfonate may be used together with an inorganic fine powder or a water-soluble polymer. Furthermore, adding a polymerization inhibitor such as diiron chloride, ammonium thiocyanate, hydrogen peroxide, etc. to the aqueous phase is effective in preventing the generation of ultrafine particles (1) due to emulsion 1a.

次−ζ本Ｍｌ〜明の実施例を示す。Next - ζ Examples of the book Ml~Bright are shown.

実施例 ラウリルアセト７セテートアルミニウ１１ジプロピレー
ト０．５　ｔ’ｔ１〜をトルエン５０部にｍＷ（させ、
これ？ζカーポ／ブランク５部を浸漬した。この後６０
℃の湯浴上で慣拌しながら溶媒を蒸発させた。その後１
２０℃で２時間熱処理して一３％　ｉｒｌ改ＩＡカーボ
ンブラック粉体を得た。Example: 0.5 t't1~ of lauryl acetate 7 acetate aluminum 11 dipropylate was added to 50 parts of toluene at mW.
this? 5 parts of zeta capo/blank were soaked. 60 after this
The solvent was evaporated with constant stirring on a water bath at .degree. then 1
Heat treatment was performed at 20° C. for 2 hours to obtain a 3% irl modified IA carbon black powder.

一方、スチレン２８部、ｎ−プチルメタクリレート１２
部ζこ低分子量ポリプロピレン４部、負帯電染料０８部
と上記表面改質したカーボンブランク２部を加えボール
ミルで９時間分散した。こＱ）分散液に２，２′−アソ
ビスイソプチロニトリル０６３２部を溶解した後、ポリ
ビニルアルコール（利合度５　ｆｌ　（＋　、ケン化度
８８％）の１％水溶液１６０部に増化第二鉄１，６部を
浴１１＋’＃した水溶液に加え、ホモミキサー（３ｏｏ
ｏｒｐｍ）で１分間攪拌した。攪拌後の油滴を光学）仙
倣鋭で観だすると安定化しており、完全な黒色を呈して
いた。こυ）Ｍ濁液をセノξラブルフラスコ中窒素気流
下で８０℃６時間反応させ重合体粒子の懸濁液をえた。On the other hand, 28 parts of styrene, 12 parts of n-butyl methacrylate
To part ζ, 4 parts of low molecular weight polypropylene, 08 parts of negatively charged dye and 2 parts of the surface-modified carbon blank were added and dispersed in a ball mill for 9 hours. Q) After dissolving 0632 parts of 2,2'-asobisisobutyronitrile in the dispersion liquid, the mixture was increased to 160 parts of a 1% aqueous solution of polyvinyl alcohol (gain ratio 5 fl (+, degree of saponification 88%)). Add 1.6 parts of iron to an aqueous solution of 11+'# in a homomixer (3oo
orpm) for 1 minute. When the oil droplets after stirring were observed with an optical microscope, they were stabilized and had a completely black color. The M suspension was reacted at 80° C. for 6 hours under a nitrogen stream in a seno-X rubber flask to obtain a suspension of polymer particles.

これを遠心分離、水洗をくり返した後減圧乾燥して球状
の黒色トナー粉体をえた。このトナーはブローオフ装置
て測定すると−１４，２／”／、　ｖ〕帯ｇｐａ−ｒ；
、−示した。キャリヤーの℃′（粉々混合し、リコビー
ＦＴ６２００で現像するさ胛１色θ）　！ｆＹ門な画像
かえられた。This was centrifuged, washed with water repeatedly, and then dried under reduced pressure to obtain spherical black toner powder. When measured with a blow-off device, this toner has a band of -14,2/''/v] band gpa-r;
,-shown. ℃' of carrier (1 color θ after mixing powder and developing with Ricoby FT6200)! The fY gate image has been changed.

比岬例 表面処ｊ（１１をしないカーボンブラック２．０２を用
いた他は実施例１と全く同一の条件で重合を行った。Himisaki Example Polymerization was carried out under exactly the same conditions as in Example 1, except that carbon black 2.02 without surface treatment J (11) was used.

ボールミルから取り出した重合性混合物はカーボンブラ
ックの凝集か見られ、分散状態は不良であった。生成し
た重合体は球状の１０〜２０μσ）粒子であったが、粒
子中でカーボンブラックは偏在しており、透明な部分お
よび透明な粒子がかなり多く存在し、えられた粉体も黒
色ではなくむしろ灰色を呈していた。丈だ粒子内に取り
込丈れないカーボンブラックも存在し粒子表面に固着し
たり、単独に存在しているのが確認された。又、併重１
量は−３，６μｃ　／　ｆであった。The polymerizable mixture taken out from the ball mill showed agglomeration of carbon black, and the dispersion state was poor. The produced polymer was spherical (10 to 20 μσ) particles, but carbon black was unevenly distributed in the particles, and there were quite a lot of transparent parts and transparent particles, and the obtained powder was not black. Rather, it looked gray. It was confirmed that there was carbon black that could not be incorporated into the particles, and it was found to stick to the particle surface or exist alone. Also, concurrent weight 1
The amount was -3,6 μc/f.

このように帯電沿が低いきいうことの原因はカーボンブ
ラックの分散不良のためと考えられる。The reason for such a low charging distance is considered to be poor dispersion of carbon black.

実施例２ スチレン２８部、ｎ〜ブチルメタクリレート１２部の混
合液にカーボンブラック２部、オレイルアセテートアル
ミニウムジプロピレート０４部、低分子量ポリプロピレ
ン４部、負惜’屯染料０．８部を加えボールミルで９時
間分散した。Example 2 2 parts of carbon black, 0.4 parts of oleyl acetate aluminum dipropylate, 4 parts of low molecular weight polypropylene, and 0.8 parts of negative dye were added to a mixed solution of 28 parts of styrene and 12 parts of n-butyl methacrylate using a ball mill. Dispersed for 9 hours.

この分散液を実施例１と同様の方法てポリビニルアルコ
ール水溶液中に懸濁さぜた。懸濁した油滴は完全Ｉこ黒
色で安定性も良好であった。This dispersion was suspended in an aqueous polyvinyl alcohol solution in the same manner as in Example 1. The suspended oil droplets were completely black and had good stability.

この懸７蜀液に実施例１と同様に重合開始剤を加え重合
を行った所黒色球状α）ｌ　Ｏ〜１５　Ｎ（１）粒子を
えた。ブローオフ装置で帯’（’Ａ：鍛を測定すると一
１２８μｃ　／　ｆを示し、その電気抵抗値も加圧成ｌ
（すしベレットにして変成器ブリッジにて６１１］定す
ると３．２８Ｘ１０’°Ωｃｗｔ　（Ｉ　ＫＩ−１ｚ　
）とトナーとして増圧ｔλ饋であった。また鉄粉キャリ
ヤー々、Ｉ？　　　　　’ットミルで混合攪拌した後も
トナーは球状を示し破砕されなかった。A polymerization initiator was added to this suspended liquid in the same manner as in Example 1, and polymerization was carried out to obtain black spherical α)lO~15N(1) particles. When the band'('A: forging) was measured with a blow-off device, it showed -128 μc/f, and its electrical resistance value was also determined by pressure forming.
(611 with transformer bridge as a sushi pellet) is determined as 3.28X10'°Ωcwt (I KI-1z
) and the toner was pressurized tλ. Also iron powder carriers, I? The toner remained spherical and was not crushed even after being mixed and stirred in a mill.

実施例３ カーボンブラック３０部、２−エチルへキシルアセトア
セートアルミニウムジプロピレート３部を溶融した低分
子°階ポリゾロピレン６０部に加えロールミルで分散し
た。このカーボンブラック、醪すプロピレン混合物６部
をスチレン２８部、ｎ−ブチルメタクリレート１２部の
混合液に加え、加熱後冷却し、カーホンブラック、ポリ
プロピレノを均一に飾濁させた。これにＤ帯？ｄ、染料
０．８部を加え、ボールミルで４時間分散後丈廁ド・す
１と同様に１１合開始剤を加え水）１１１中に懸濁した
。Example 3 30 parts of carbon black and 3 parts of 2-ethylhexyl acetoacetate aluminum dipropylate were added to 60 parts of molten low molecular weight polyzoropylene and dispersed in a roll mill. This carbon black and 6 parts of the propylene mixture were added to a mixture of 28 parts of styrene and 12 parts of n-butyl methacrylate, heated and then cooled to uniformly cloud the carbon black and polypropylene. Is this a D band? d. 0.8 part of the dye was added and dispersed in a ball mill for 4 hours, and then an initiator was added to the mixture in the same manner as in 1) and suspended in water) 111.

シ！・冑掩した油ｆｉｉ％　（ｉ完全に４！、＋、色を
呈し安定であった。これを火１ｊｉｉｉ例１と同様の方
法で升合を行った所１　ｎ−１５／Ｉの球状の黒色粒子
をえた。こθ）粒子の＠紀敞は−１３，４μｃ　／　ｆ
で・Ｎｔ、気抵抗Ｌ１３、９　ｆ１×１０１０Ω口でｔ
ｉ）−Ｊだ。Shi!・The filtered oil fii% (i completely exhibited a color of 4!, +, and was stable. When this was combined in the same manner as in Example 1, a spherical shape of 1 n-15/I was obtained. A black particle was obtained. This θ) particle @ Kisho is -13,4μc/f
・Nt, air resistance L13, 9 f1×1010Ω t at the mouth
i)-J.

特許出願人　株式会社　リ　コ　− 手続補正書 昭和５７年１１月２１１ 特許庁長官　若　杉　和　夫　殿 ２、発明の名称 事件との関係　特許出願人 東京都大田区中馬込１丁目３番６号 （６７４）株式会社　リ　コ　− 代表者　犬　植　　武　士 ４、代　理　人 ム　補正の内容 １）明細書の第９頁第１２行の「アクリル酸メヂル」を
「メチルアクリレート」に補正する。Patent Applicant Ricoh Co., Ltd. - Procedural Amendment November 1982 211 Commissioner of the Japan Patent Office Kazuo Wakasugi 2 Relationship with the Name of Invention Case Patent Applicant 1-3-6 Nakamagome, Ota-ku, Tokyo ( 674) Ricoh Co., Ltd. - Representative: Takeshi 4, Representative: Human Contents of amendment 1) "Medyl acrylate" on page 9, line 12 of the specification is amended to "methyl acrylate."

２）第１２頁末行の「このトナーは」の１１１に「次に
分級して体積平均粒径１２．３μのトナー粒子とした。2) At 111 of "This toner" on the last line of page 12, it says, "Then, it was classified into toner particles with a volume average particle diameter of 12.3 μm.

このトナーは２００メツシユの篩を完全に通過し、凝集
体はみとめられず、また５１：ｌｊ包紙等へのｆ”ｌ’
　＊：＋はほとんど起らず、流動性が非常に侵れていた
。」を加入する。This toner completely passed through a 200 mesh sieve, no aggregates were observed, and f"l' to 51:lj wrapping paper etc.
*: + almost never occurred, and the fluidity was extremely impaired. ” to join.

以　　上 ３that's all 3

Claims (1)

【特許請求の範囲】 １　アルミニウムキレート化合物ｆ”Ａ有する静電荷像
現像用トナー。 ２、　　ｇＣ合ｆ１中（゛、ｉ体中にカーボンブラック
を分散した後、懸濁７ｆｊ合を行う静’ｔｂ、り［１♀
：　Ｊｌｆ、像用トナーの製造方法１こおいて、アルミ
ニウムキレート化合物の存在下でカーボンブラックをｍ
合件単解体中に分散することを特徴吉するにイ霜。 省１［１象Ｊｌｌ１１１♀ｊ用トナーＵ］製造方法。[Scope of Claims] 1. A toner for developing an electrostatic image having an aluminum chelate compound f''A. 2. A static image forming method in which carbon black is dispersed in gC mixture f1 (i), and then suspension 7fj mixture is carried out. ,ri [1♀
: Jlf, Method for producing an image toner 1, in which carbon black is mixed in the presence of an aluminum chelate compound.
It is characterized by the fact that it disperses during demolition. Ministry 1 [Toner U for 1 elephant Jll111♀j] Manufacturing method.