JPH0593005A - Suspension polymerization process - Google Patents
Suspension polymerization processInfo
- Publication number
- JPH0593005A JPH0593005A JP28036891A JP28036891A JPH0593005A JP H0593005 A JPH0593005 A JP H0593005A JP 28036891 A JP28036891 A JP 28036891A JP 28036891 A JP28036891 A JP 28036891A JP H0593005 A JPH0593005 A JP H0593005A
- Authority
- JP
- Japan
- Prior art keywords
- suspension
- particles
- polymerization
- continuous phase
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、間隙保持剤、滑り性付
与剤、機能性担体、表面活性を有する単分散粒子、標準
粒子、トナー、塗料の流動性や、つや特性を制御する機
能性充填剤などの粒子工業で使用するに適した重合生成
物粒子、特に制御された粒子径および粒子径分布を有す
る粒子を得る方法に関し、特に懸濁重合法における分散
工程で生ずる１ミクロン以下の乳化粒子の生成を防止し
た懸濁重合法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluidity control agent for controlling the fluidity and gloss characteristics of a space-preserving agent, a slipperiness-imparting agent, a functional carrier, surface-active monodisperse particles, standard particles, toners and paints. TECHNICAL FIELD The present invention relates to a method for obtaining particles of a polymerization product suitable for use in a particle industry such as a filler, particularly particles having a controlled particle size and particle size distribution, and particularly, an emulsion of 1 micron or less generated in a dispersion step in a suspension polymerization method. The present invention relates to a suspension polymerization method in which the generation of particles is prevented.
【０００２】[0002]
【従来の技術】近年粒子自身の機能を利用する粒子工業
の重要性が高まりつつあるが、その応用分野として知ら
れている間隙保持剤、滑り性付与剤、機能性担体、表面
活性を有する単分散粒子、標準粒子、トナー、塗料の流
動性や、つや特性を制御する機能性充填剤などの用途の
粒子を重合法で得るには、現在のところ主として乳化重
合方法に頼っているのが現状である。さらに特殊な用途
にあっては、ソープフリー重合、分散重合、シード重
合、膨潤重合なども応用されている。然しながら、これ
らの重合法には幾つかの欠点がある。例えば、乳化剤等
の無視できない不純物の除去が大変困難であること、得
られる粒子の粒子径に制限があること、極めてコストが
高いこと、製造法が煩雑で大量の生産に不向きなこと等
の欠点がある。また、狭い粒子径分布を有する粒子を得
るには、主として乳化重合法が用いられているが、乳化
重合法では得られる粒子の粒子径は大きくてもたかだか
１μｍ程度であり、それ以上の大きさの粒子を得ること
は極めて困難である。2. Description of the Related Art In recent years, the importance of the particle industry utilizing the function of the particles themselves has been increasing. However, it is known as a field of application for such materials as a gap-retaining agent, a slipperiness-imparting agent, a functional carrier, and a surface-active monomer. At present, in order to obtain particles for use as dispersed particles, standard particles, toners, functional fillers that control the fluidity and gloss properties of paints, etc., by a polymerization method, currently mainly relying on an emulsion polymerization method. Is. For special applications, soap-free polymerization, dispersion polymerization, seed polymerization, swelling polymerization, etc. are also applied. However, these polymerization methods have some drawbacks. For example, it is very difficult to remove non-negligible impurities such as emulsifiers, the particle size of the obtained particles is limited, the cost is extremely high, and the manufacturing method is complicated and unsuitable for mass production. There is. Emulsion polymerization is mainly used to obtain particles having a narrow particle size distribution, but the particle size obtained by emulsion polymerization is at most about 1 μm and larger than that. Is difficult to obtain.
【０００３】これに対して懸濁重合法は、得られる製品
が粒子状であるが、粒子径が不均一で、かつ粒子径分布
の広いものしか得られておらず、これが重合物の機械的
強度、耐薬品性、色相、透明性及び成型性等の性能と重
要な関係があるために改良が望まれている。すなわち懸
濁重合では攪拌分散された液滴が様々な径を有し、さら
に、分散時に液滴は***と合一を繰り返すために得られ
る粒子の粒子径分布は極めて広いものとなり、特に粒子
径分布の狭い単分散粒子状の粒子を得ることは困難であ
ると言われている。従って容易に均質な粒子を得ること
のできる懸濁重合技術の確立が、前記粒子工業の分野に
おける重要な課題として要望されている。On the other hand, in the suspension polymerization method, the product obtained is in the form of particles, but only those having a non-uniform particle size and a wide particle size distribution are obtained, which is the mechanical property of the polymer. Improvements are desired because they have important relationships with properties such as strength, chemical resistance, hue, transparency, and moldability. That is, in suspension polymerization, the droplets dispersed by stirring have various diameters, and the droplets repeat dispersion and coalescence during dispersion, so the particle size distribution of the particles obtained is extremely wide. It is said that it is difficult to obtain monodisperse particles having a narrow distribution. Therefore, establishment of a suspension polymerization technique capable of easily obtaining homogeneous particles is demanded as an important subject in the field of the particle industry.
【０００４】本発明者らは先に上記問題を容易に解決で
きる新たな製造法を見いだした（特願平２−４３９８０
号参照）。即ち、分散相（単量体組成物相）と連続相と
を各々独立した槽に保持し、それらの槽より、分散相及
び連続相を、それぞれ独立した経路を通して、同時に連
続して供給できる装置により、所望の大きさの液滴を持
つ懸濁液を得ることのできる造粒機へ１回ないし２回以
上供給、通過させ、しかる後重合槽中に導いて重合を完
結させて重合体を得る懸濁重合法である。この方法は分
散のための剪断力発生場に被分散液が直接供給される構
造であって、被分散液が剪断力場を離脱するとき必ずそ
の剪断力場を通過せしめるようにした懸濁重合法であ
り、かかる方法により粒子径分布の狭い所望の粒子径を
有する粒子を安定して得ることができる。しかしなが
ら、上記の如き懸濁重合法においても懸濁液を作成する
際に生じる粒子径が１ミクロン以下の乳化粒子が生成さ
れることは避けられず、また、求める重合粒子の収率を
低下させたり、更に、高度に狭い粒子径分布が要求され
る時に上記のような１ミクロン以下の乳化粒子が混在し
てしまうという問題を有するものであった。The present inventors have previously found a new manufacturing method that can easily solve the above problems (Japanese Patent Application No. 2-43980).
No.). That is, an apparatus capable of holding the dispersed phase (monomer composition phase) and the continuous phase in independent tanks, and simultaneously supplying the dispersed phase and the continuous phase simultaneously through independent paths from the tanks. According to the above method, the suspension is supplied once or twice or more to a granulator capable of obtaining a suspension having droplets of a desired size, and then passed through the granulator, and then introduced into a polymerization tank to complete the polymerization to obtain a polymer. It is a suspension polymerization method to obtain. This method has a structure in which the liquid to be dispersed is directly supplied to the shear force generation field for dispersion, and when the liquid to be dispersed leaves the shear force field, the suspension load must be made to pass through the shear force field. This is a legal method, and particles having a desired particle size with a narrow particle size distribution can be stably obtained by such a method. However, even in the suspension polymerization method as described above, it is unavoidable that emulsion particles having a particle size of 1 micron or less are generated when a suspension is prepared, and the yield of the desired polymer particles is lowered. In addition, when a highly narrow particle size distribution is required, the above emulsified particles of 1 micron or less are mixed.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、懸濁重合法
において狭い粒子径分布を有する所望の粒子径、特に粒
子径の小さい均一な重合体粒子を容易に得ることがで
き、かつ、１ミクロン以下の乳化粒子の生成を防止した
懸濁重合法を提供するものである。DISCLOSURE OF THE INVENTION The present invention makes it possible to easily obtain uniform polymer particles having a desired particle size having a narrow particle size distribution, particularly a small particle size, in a suspension polymerization method. It is intended to provide a suspension polymerization method in which the generation of submicron emulsified particles is prevented.
【０００６】[0006]
【課題を解決するための手段】本発明は、少なくとも重
合性単量体からなる分散相と連続相とを各々独立した槽
に保持し、それぞれ独立した経路を通して、両者を制御
された比率で１回ないし２回以上造粒機に供給して所望
の大きさの重合性液滴を有する懸濁液を得て、しかる後
該懸濁液を重合槽中に導いて重合を完結させて重合体を
得る懸濁重合法において、連続相中に下記一般式で表わ
されるモノアゾ染料の金属錯体化合物を含有することを
特徴とする懸濁重合法である。According to the present invention, at least a dispersed phase composed of a polymerizable monomer and a continuous phase are held in independent tanks, respectively, and each of them is controlled at a controlled ratio through independent paths. It is supplied to the granulator once or twice or more to obtain a suspension having polymerizable droplets of a desired size, and then the suspension is introduced into a polymerization tank to complete the polymerization to obtain a polymer. In the suspension polymerization method for obtaining, a suspension polymerization method is characterized in that a metal complex compound of a monoazo dye represented by the following general formula is contained in a continuous phase.
【化２】 式中、Ａ，Ａ′は非置換または置換基を有するフェニレ
ン基であり、Ｂ，Ｂ′は非置換または置換基を有するナ
フチル基である。ここで、フェニレン基およびナフチル
基の置換基としては特に限定されるものではないが、例
えばハロゲン，カルボキシ基，スルフォン酸基，ニトロ
基，アミノ基，アミド基等が挙げられる。また、Ｍは金
属を表わし、例えばＣｒ，Ｃｏ，Ｆｅ，Ｖ等が挙げら
れ、Ｒ1，Ｒ2 ，Ｒ3 ，Ｒ4 はＯ，ＮＨ，Ｏ−Ｏを表わ
すものである。[Chemical 2] In the formula, A and A ′ are unsubstituted or substituted phenylene groups, and B and B ′ are unsubstituted or substituted naphthyl groups. Here, the substituent of the phenylene group and the naphthyl group is not particularly limited, but examples thereof include a halogen, a carboxy group, a sulfonic acid group, a nitro group, an amino group and an amide group. Further, M represents a metal, for example, Cr, Co, Fe, V or the like, and R 1 , R 2 , R 3 , and R 4 represent O, NH, and O—O.
【０００７】まず本発明の懸濁重合法を実施するための
装置の一例について図面を参照しつつ説明する。図１に
示すように、連続相をいれた連続相槽１と分散相をいれ
た凝縮機６を備えた分散相槽２とをそれぞれ定量ポンプ
４，４を介して造粒機５に一定比率で同時に導入するよ
うにしてあり、ここで剪断力を与えて懸濁液としてこの
液滴のサイズをある範囲として排出し、凝縮機６を備え
た重合槽３に導き、この重合槽３の周囲に設けられてい
る加熱用ジャケット７により必要な加熱をして、重合反
応を完結させ、粒子径が小さく、粒度分布の揃ったもの
が得られる。ここに用いられる造粒機５の一例は図２に
示すとうりで、下部は流入二重管、上部は攪拌、排出部
を構成し、下部は中心に内管流入口１９を有する二重管
内管１６、その周囲に外管流入口１８を有する二重管外
管１７を備え、開口径調整用フランジ２０を介して上部
と結合している。上部の中央にはタービン回転軸１１、
攪拌シール１２分散液吐出口１３と、下部との間に軸受
け１４、タービン１５を有している。本発明では上記の
重合法において、特に連続相に前記の如き構造を有する
モノアゾ染料の金属錯体化合物を分散して用いることに
より、従来より粒子径分布が狭く、所望の粒子径を有す
る、特に粒子径の小さい重合体粒子を得ることができ、
かつ、１ミクロン以下の微細粒子をほとんど含まない均
一な重合体粒子を収率よく得ることができるものであ
る。なお、本発明における連続相中におけるモノアゾ染
料の金属錯体化合物の添加量は、０．０１〜１０重量％
が適当である。ここで、０．０１％未満では本発明にお
ける上記の如き効果が得られにくく、１０％を越えると
重合を阻害するおそれがあり好ましくない。First, an example of an apparatus for carrying out the suspension polymerization method of the present invention will be described with reference to the drawings. As shown in FIG. 1, a continuous phase tank 1 containing a continuous phase and a dispersion phase tank 2 having a condenser 6 containing a dispersed phase are provided to a granulator 5 at constant ratios via metering pumps 4 and 4, respectively. At the same time, a shearing force is applied to discharge the droplets as a suspension in a certain range of size, and the droplets are guided to a polymerization tank 3 equipped with a condenser 6, and the periphery of the polymerization tank 3 is surrounded. Necessary heating is carried out by the heating jacket 7 provided in, to complete the polymerization reaction and obtain a product having a small particle size and a uniform particle size distribution. An example of the granulator 5 used here is the one shown in FIG. 2, in which the lower part constitutes the inflow double pipe, the upper part constitutes the stirring and discharging part, and the lower part has the inner pipe inlet 19 in the center thereof. A pipe 16 and a double pipe outer pipe 17 having an outer pipe inflow port 18 around the pipe 16 are provided, and are connected to the upper portion via an opening diameter adjusting flange 20. At the center of the upper part, the turbine rotating shaft 11,
A bearing 14 and a turbine 15 are provided between the stirring seal 12 and the dispersion liquid discharge port 13 and the lower part. In the present invention, in the above-mentioned polymerization method, in particular, by using a metal complex compound of a monoazo dye having a structure as described above dispersed in a continuous phase, the particle size distribution is narrower than in the past, and a desired particle size is obtained. It is possible to obtain polymer particles having a small diameter,
In addition, it is possible to obtain uniform polymer particles containing almost no fine particles of 1 micron or less in good yield. The addition amount of the metal complex compound of the monoazo dye in the continuous phase in the present invention is 0.01 to 10% by weight.
Is appropriate. Here, if it is less than 0.01%, it is difficult to obtain the above effects in the present invention, and if it exceeds 10%, polymerization may be hindered, which is not preferable.
【０００８】本発明における分散相は、少なくとも重合
性単量体を含有するもので、必要に応じて重合開始剤、
着色顔料、その他重合体粒子の用途に応じて各種添加剤
を用いることができる。本発明に用いられる重合性単量
体としては、例えば下記の化合物があげられる。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−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，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
ン等のスチレン及びその誘導体；エチレン，プロピレ
ン，ブチレン，イソブチレン等のエチレン不飽和モノオ
レフィン類；塩化ビニル，塩化ビニリデン，臭化ビニ
ル，フッ化ビニル等のハロゲン化ビニル類；酢酸ビニ
ル，プロピオン酸ビニル，ベンゾエ酸ビニル等の有機酸
ビニルエステル類；メタクリル酸，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
アミノエチル等のメタクリル酸及びその誘導体；アクリ
ル酸，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
等のアクリル酸及びその誘導体；ビニルメチルエーテ
ル，ビニルエチルエーテル，ビニルイソブチルエーテル
等のビニルエーテル類；ビニルメチルケトン，ビニルヘ
キシルケトン，ビニルイソプロペニルケトン等のビニル
ケトン類；Ｎ−ビニルピロール，Ｎ−ビニルカルバゾー
ル，Ｎ−ビニルインドール，Ｎ−ビニルピロリドン等の
Ｎ−ビニル化合物；ビニルナフフタリン類；アクリロニ
トリル，メタクリロニトリル，アクリルアミド等。The dispersed phase in the present invention contains at least a polymerizable monomer, and if necessary, a polymerization initiator,
Various additives can be used depending on the use of the color pigment and other polymer particles. Examples of the polymerizable monomer used in the present invention include the following compounds. Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl styrene,
Styrene and its derivatives such as pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene and pn-decylstyrene; ethylene, Ethylenically unsaturated monoolefins such as propylene, butylene, isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl acetate, vinyl propionate, vinyl benzoate, etc. Kinds; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylic acid and its derivatives such as stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate. , N-octyl acrylate, dodecyl acrylate,
Acrylic acid and its derivatives such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone , Vinyl ketones such as vinyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalines; acrylonitrile, methacrylonitrile, acrylamide and the like.
【０００９】本発明に用いることのできる重合開始剤は
重合性単量体に可溶であることが好ましい。このような
重合開始剤としては、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），２，２′−アゾビス−４−メトキシ−
２，４−ジメチルバレロニトリル、その他のアゾ系また
はジアゾ系重合開始剤；ベンゾイルパーオキサイド，メ
チルエチルケトンパーオキサイド，イソプロピルパーオ
キシカーボネート、その他の過酸化物系重合開始剤等が
挙げられる。また、着色顔料としては、カーボンブラッ
ク、各種カラー用顔料等を適宜用いることができる。こ
のような着色顔料を添加して重合することにより、例え
ば電子写真用トナーの製造にも容易に応用することがで
きる。The polymerization initiator that can be used in the present invention is preferably soluble in the polymerizable monomer. Examples of such a polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis-4-methoxy-
2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators; benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, other peroxide polymerization initiators and the like. Further, as the color pigment, carbon black, various color pigments, and the like can be appropriately used. By adding such a color pigment and polymerizing, it can be easily applied to the production of, for example, an electrophotographic toner.
【００１０】次に、本発明における連続相は、水性媒質
よりなる連続層成分によって形成され、前述のモノアゾ
染料の金属錯体化合物のほか、懸濁安定剤やその助剤等
の添加剤が適宜含有されている。懸濁安定剤としては、
一般に懸濁重合で用いられる懸濁安定剤を用いることが
でき、その分子中に親水性基と疎水性基を有する水溶性
ポリマーが多く用いられている。懸濁安定剤は親水性基
として水酸基、カルボキシル基及びその塩、スルホン基
及びその塩等の極性基を有し、疎水性基として、脂肪族
及び芳香族等の無極性基で構成されており、造粒工程に
より形成された単量体組成物粒子の合一を防ぎ、安定化
する能力を有する化合物である。このような懸濁安定剤
は、例えば、ポリビニルアルコール，カゼイン，ゼラチ
ン，メチルセルロース，メチルハイドロキシプロピルセ
ルロース，エチルセルロース等のセルロース誘導体、澱
粉及びその誘導体、ポリ（メタ）アクリル酸及びそれら
の塩等が用いられている。またそのほかにもリン酸カル
シウム，微粉末シリカ等の無機粉体もしばしば用いられ
ている。これらの懸濁安定剤は、重合中は、液滴表面を
被覆し液滴の合一、集塊を防止する働きをしている。さ
らに懸濁安定剤の助剤として界面活性剤、例えばドデシ
ルスルフォン酸ナトリウム，ドデシルベンゼンスルフォ
ン酸ナトリなどを加えることも可能である。そのほか連
続相（水相）に塩化ナトリウム、硫酸ナトリウム等の中
性塩を乳化防止の目的で加えてもよい。また造粒工程に
より形成された単量体組成物粒子の合一を防ぐ目的で、
グリセリン，エチレングリコール等の増粘剤を加えても
よい。Next, the continuous phase in the present invention is formed by a continuous layer component consisting of an aqueous medium, and in addition to the metal complex compound of the monoazo dye described above, additives such as suspension stabilizers and auxiliary agents thereof are appropriately contained. Has been done. As a suspension stabilizer,
A suspension stabilizer generally used in suspension polymerization can be used, and a water-soluble polymer having a hydrophilic group and a hydrophobic group in its molecule is often used. The suspension stabilizer has a polar group such as a hydroxyl group, a carboxyl group and a salt thereof, a sulfone group and a salt thereof as a hydrophilic group, and is composed of an apolar group such as an aliphatic or aromatic group as a hydrophobic group. The compound having the ability to prevent and stabilize coalescence of the monomer composition particles formed by the granulation step. Such suspension stabilizers include, for example, cellulose derivatives such as polyvinyl alcohol, casein, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, starch and its derivatives, poly (meth) acrylic acid and salts thereof. ing. In addition, inorganic powders such as calcium phosphate and fine powder silica are often used. During the polymerization, these suspension stabilizers serve to coat the surface of the droplets and prevent coalescence and agglomeration of the droplets. Further, a surfactant such as sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate can be added as an auxiliary agent of the suspension stabilizer. In addition, neutral salts such as sodium chloride and sodium sulfate may be added to the continuous phase (aqueous phase) for the purpose of preventing emulsification. For the purpose of preventing coalescence of the monomer composition particles formed by the granulation step,
Thickeners such as glycerin and ethylene glycol may be added.
【００１１】[0011]
【実施例】以下、実施例に基づいて本発明を具体的に説
明する。 実施例１ 連続相として第三リン酸カルシウムの１０％水分散液を
水に対して５０％，硫酸ナトリウムを水に対して３％，
ドデシルベンゼンスルフォン酸ナトリウムを０．０１％
の水溶液を調製し、さらにこの分散液に下記構造式
（１）（ｎ＝１，２の混合物）に示すモノアゾ染料の金
属錯体化合物０．１％を分散させた液を図１に示す連続
相槽にいれた。EXAMPLES The present invention will be specifically described below based on examples. Example 1 As a continuous phase, a 10% aqueous dispersion of tricalcium phosphate was 50% in water, sodium sulfate was 3% in water,
0.01% sodium dodecylbenzene sulfonate
Of the metal complex compound of the monoazo dye represented by the following structural formula (1) (mixture of n = 1 and 2) is dispersed in this dispersion to prepare a continuous phase shown in FIG. I put it in the tank.
【化３】 また、分散相としてスチレン４０００ｇ，アクリル酸ブ
チル１０００ｇの混合液に２，２′−アゾビスイソプチ
ロニトリル１５ｇを溶解させた液を調製し、この混合液
にカーボンブラック（三菱化成社製 ＭＡ−１００）４
００ｇを分散させた。この溶液を図１に示す分散相槽に
いれた。次に、分散相を１００ｍｌ／分，連続相を４０
ｍｌ／分で１０分間造粒機に供給した。造粒機は、図２
に示す造粒機を用いて１００００ｒｐｍで運転した。造
粒機を通過した懸濁液を、タービン型攪拌翼で３００ｒ
ｐｍで攪拌しながら図１に示す重合槽中に導き、８時間
反応させた。その後反応液を濾別し、重合体粒子を得、
さらにこの粒子を３％硝酸と水とにより充分洗浄した
後、４０℃で１２時間減圧乾燥して本発明の懸濁重合法
による重合体粒子を得た。[Chemical 3] Further, as a disperse phase, a mixture of 4000 g of styrene and 1000 g of butyl acrylate was dissolved in 15 g of 2,2'-azobisisobutyronitrile to prepare a carbon black (MA-100 manufactured by Mitsubishi Kasei). ) 4
00 g was dispersed. This solution was placed in the dispersion phase tank shown in FIG. Next, disperse phase 100 ml / min, continuous phase 40
Feed to the granulator for 10 minutes at ml / min. Granulator, Figure 2
It operated at 10,000 rpm using the granulator shown in. The suspension that has passed through the granulator is 300 r with a turbine type stirring blade.
While stirring at pm, it was introduced into the polymerization tank shown in FIG. 1 and reacted for 8 hours. After that, the reaction solution is filtered to obtain polymer particles,
Further, the particles were thoroughly washed with 3% nitric acid and water, and then dried under reduced pressure at 40 ° C. for 12 hours to obtain polymer particles by the suspension polymerization method of the present invention.
【００１２】比較例１ 実施例１において、モノアゾ染料の金属錯体化合物を用
いない以外は、実施例１と全く同様にして比較用の重合
体粒子を得た。 実施例２ 実施例１において、連続相に用いたモノアゾ染料の金属
錯体化合物として下記構造式（２）の化合物を用い、分
散相に用いたカーボンブラックに代えて赤色染料（ＯＩ
Ｌ ＰＩＮＫ３１２，オリエント化学社製）を用いた以
外は、実施例１と全く同様にして本発明の懸濁重合法に
よる重合体粒子を得た。Comparative Example 1 Comparative polymer particles were obtained in the same manner as in Example 1 except that the metal complex compound of the monoazo dye was not used. Example 2 In Example 1, the compound of the following structural formula (2) was used as the metal complex compound of the monoazo dye used in the continuous phase, and the red dye (OI was used instead of the carbon black used in the dispersed phase).
Polymer particles obtained by the suspension polymerization method of the present invention were obtained in exactly the same manner as in Example 1, except that L PINK312, manufactured by Orient Chemical Co., Ltd.) was used.
【化４】 [Chemical 4]
【００１３】比較例２ 実施例２において、モノアゾ染料の金属錯体化合物を用
いない以外は、実施例２と全く同様にして比較用の重合
体粒子を得た。上記の実施例１〜２および比較例１〜２
で得た重合体粒子の粒子径分布をマイクロトラック粒度
分析計（日機装社製）にて測定した結果は図３および図
４のとおりであり、本発明の懸濁重合法により得られる
重合体粒子は１ミクロン以下の微小粒子の生成がなく粒
子径分布の狭いことが確認された。Comparative Example 2 Comparative polymer particles were obtained in the same manner as in Example 2 except that the metal complex compound of the monoazo dye was not used. Examples 1-2 and Comparative Examples 1-2 above
The particle size distribution of the polymer particles obtained in 1. was measured with a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.) as shown in FIGS. 3 and 4, and the polymer particles obtained by the suspension polymerization method of the present invention. It was confirmed that there was no generation of fine particles of 1 micron or less and the particle size distribution was narrow.
【００１４】[0014]
【発明の効果】本発明の懸濁重合法は、懸濁液で生成さ
れる１ミクロン以下の乳化粒子の生成を防止することが
できるため、微小粒子を含まない非常に狭い粒子径分布
を有する重合体粒子を得ることができるという優れた効
果を有するものである。しかも、ミクロンオーダーの小
さい粒子を１ミクロン以下の微小粒子を含むことなく得
ることができるため、電子写真用トナーをはじめとして
多方面にわたって高機能性粒子として用いることが期待
される。INDUSTRIAL APPLICABILITY The suspension polymerization method of the present invention can prevent the formation of emulsion particles of 1 micron or less formed in suspension, and therefore has a very narrow particle size distribution containing no fine particles. It has an excellent effect that polymer particles can be obtained. Moreover, since particles of micron order can be obtained without including fine particles of 1 micron or less, it is expected to be used as highly functional particles in various fields including electrophotographic toners.
【００１５】[0015]
【図１】図１は本発明の懸濁重合法に用いられる重合装
置の一例である。FIG. 1 is an example of a polymerization apparatus used in the suspension polymerization method of the present invention.
【図２】図２は本発明の懸濁重合法に用いられる造粒機
の一例である。FIG. 2 is an example of a granulator used in the suspension polymerization method of the present invention.
【図３】図３は本発明の実施例１および比較例１で得た
重合体粒子の粒子径分布を示すグラフである。FIG. 3 is a graph showing a particle size distribution of polymer particles obtained in Example 1 of the present invention and Comparative Example 1.
【図４】図４は本発明の実施例２および比較例２で得た
重合体粒子の粒子径分布を示すグラフである。FIG. 4 is a graph showing the particle size distribution of polymer particles obtained in Example 2 of the present invention and Comparative Example 2.
１ 連続相槽 ２ 分散相槽 ３ 重合槽 ４ 定量ポンプ ５ 造粒機 ６ 凝縮機 ７ 加熱用ジャケット １１ タービン回転軸 １２ 攪拌シール １３ 分散液吐出口 １４ 軸受け １５ タービン １６ 二重管内管 １７ 二重管外管 １８ 外管流入口 １９ 内管流入口 ２０ 開口径調整用フランジ 1 Continuous phase tank 2 Dispersion phase tank 3 Polymerization tank 4 Metering pump 5 Granulator 6 Condenser 7 Heating jacket 11 Turbine rotating shaft 12 Stirring seal 13 Dispersion liquid discharge port 14 Bearing 15 Turbine 16 Double pipe inner pipe 17 Double pipe Outer pipe 18 Outer pipe inlet 19 Inner pipe inlet 20 Flange for adjusting opening diameter
Claims (1)
と連続相とを各々独立した槽に保持し、それぞれ独立し
た経路を通して、両者を制御された比率で１回ないし２
回以上造粒機に供給して所望の大きさの重合性液滴を有
する懸濁液を得て、しかる後該懸濁液を重合槽中に導い
て重合を完結させて重合体を得る懸濁重合法において、
連続相中に下記一般式で表わされるモノアゾ染料の金属
錯体化合物を含有することを特徴とする懸濁重合法。 【化１】 （式中、Ａ，Ａ′は非置換または置換基を有するフェニ
レン基であり、Ｂ，Ｂ′は非置換または置換基を有する
ナフチル基である。また、Ｍは金属を表わし、Ｒ1 ，Ｒ
2 ，Ｒ3 ，Ｒ4 はＯ，ＮＨ，Ｏ−Ｏを表わす。）1. A dispersed phase and a continuous phase each comprising at least a polymerizable monomer are held in independent tanks, respectively, and they are passed through independent paths once to 2 times at a controlled ratio.
It is supplied to the granulator more than once to obtain a suspension having polymerizable droplets of a desired size, and then the suspension is introduced into a polymerization tank to complete the polymerization to obtain a polymer. In the turbid polymerization method,
A suspension polymerization method characterized in that a metal complex compound of a monoazo dye represented by the following general formula is contained in a continuous phase. [Chemical 1] (In the formula, A and A'are unsubstituted or substituted phenylene groups, B and B'are unsubstituted and substituted naphthyl groups. M represents a metal, and R 1 and R
2 , R 3 and R 4 represent O, NH and OO. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28036891A JP2597254B2 (en) | 1991-10-02 | 1991-10-02 | Suspension polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28036891A JP2597254B2 (en) | 1991-10-02 | 1991-10-02 | Suspension polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0593005A true JPH0593005A (en) | 1993-04-16 |
| JP2597254B2 JP2597254B2 (en) | 1997-04-02 |
Family
ID=17624045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28036891A Expired - Fee Related JP2597254B2 (en) | 1991-10-02 | 1991-10-02 | Suspension polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2597254B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0684261A2 (en) | 1994-05-27 | 1995-11-29 | Nippon Shokubai Co., Ltd. | Emulsion polymerisation inhibitor and suspension polymerisation method using the agent |
-
1991
- 1991-10-02 JP JP28036891A patent/JP2597254B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0684261A2 (en) | 1994-05-27 | 1995-11-29 | Nippon Shokubai Co., Ltd. | Emulsion polymerisation inhibitor and suspension polymerisation method using the agent |
| US5605992A (en) * | 1994-05-27 | 1997-02-25 | Nippon Shokubai Co., Ltd. | Emulsion polymerization inhibitor and suspension polymerization method using the agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2597254B2 (en) | 1997-04-02 |
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