JPH05262804A - Production of fine polymer particle of good dispersibility - Google Patents
Production of fine polymer particle of good dispersibilityInfo
- Publication number
- JPH05262804A JPH05262804A JP9488492A JP9488492A JPH05262804A JP H05262804 A JPH05262804 A JP H05262804A JP 9488492 A JP9488492 A JP 9488492A JP 9488492 A JP9488492 A JP 9488492A JP H05262804 A JPH05262804 A JP H05262804A
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- Prior art keywords
- polymer
- vinyl monomer
- dispersion
- fine particles
- polymerization
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粒径分布が狭く、且つ
分散性に優れた重合体微粒子の製造法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing fine polymer particles having a narrow particle size distribution and excellent dispersibility.
【０００２】[0002]
【従来の技術】分散重合法は、モノマ−は溶解するが、
ポリマ−は溶解しない媒体中にモノマ−を溶解させ、開
始剤を添加してラジカル重合を行いポリマ−の微粒子を
生成する方法である。この方法に於いて、生成する重合
体粒子の粒径をコントロ−ルする因子として、モノマ−
濃度、開始剤濃度、媒体とポリマ−との親和性等が関係
するが、分散性の優れた且つ粒径の均一な微粒子を得る
ために、分散安定剤を加える方法が知られている。この
分散安定剤は媒体に均一に溶解することが必要である。
分散安定剤の作用機構は明確でないが、モノマ−の重合
の進行にともなって析出するポリマ−微粒子の表面に吸
着し、媒体中でこの一次粒子の会合を防ぐ役目を持って
いるものと考えられる。したがって分散安定剤の化学構
造は重要であるが、ポリマ−微粒子との相関は明確には
わかっていない。2. Description of the Related Art In a dispersion polymerization method, a monomer is dissolved but
Polymer is a method in which a monomer is dissolved in a medium in which it is not dissolved, and an initiator is added to carry out radical polymerization to produce fine particles of the polymer. In this method, as a factor controlling the particle size of the polymer particles produced, the monomer
Although the concentration, the initiator concentration, the affinity between the medium and the polymer, etc. are related, a method of adding a dispersion stabilizer is known in order to obtain fine particles having excellent dispersibility and a uniform particle size. This dispersion stabilizer needs to be uniformly dissolved in the medium.
Although the mechanism of action of the dispersion stabilizer is not clear, it is considered that it is adsorbed on the surface of polymer fine particles that precipitate as the polymerization of the monomer progresses and prevents the association of these primary particles in the medium. .. Therefore, the chemical structure of the dispersion stabilizer is important, but the correlation with the polymer particles is not clear.
【０００３】ところで、従来、非水系でのポリメチルメ
タクリレ−トの分散重合に関して、分散安定剤としてス
チレンとジメチルシロキサンのブロックポリマ−或いは
スチレンとメチルメタクリレ−トのブロックポリマ−等
を用いることが知られている〔Ｍａｋｒｏｍｏｌ．ｃｈ
ｅｍ. Ｍａｋｒｏｍｏｌ．ｓｙｍｐ．１０／１１、４８
３−５０１（１９８７）〕。この文献にも記載されてい
るように、非水系での分散重合においては、この重合を
安定に行い、均一な粒径の微粒子を得るには如何に有効
な分散安定剤を選ぶかが重要である。そして、従来の多
くの分散安定剤においては、分散重合の際、あるモノマ
−濃度範囲（１０〜３５ｗｔ％）では重合系の安定性を
維持することができず、ポリマ−微粒子の凝集が起こる
ことが知られている。By the way, conventionally, in the dispersion polymerization of polymethyl methacrylate in a non-aqueous system, a block polymer of styrene and dimethyl siloxane or a block polymer of styrene and methyl methacrylate is used as a dispersion stabilizer. Is known [Makromol. ch
em. Makromol. symp. October 11, 48
3-501 (1987)]. As described in this document, in dispersion polymerization in a non-aqueous system, it is important to select an effective dispersion stabilizer in order to stably perform this polymerization and obtain fine particles having a uniform particle size. is there. In many conventional dispersion stabilizers, during dispersion polymerization, the stability of the polymerization system cannot be maintained within a certain monomer concentration range (10 to 35 wt%), and aggregation of polymer fine particles occurs. It has been known.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、広いモノマ
−濃度範囲で安定に重合が行え、しかも分散性に優れ且
つ粒径均一性に優れた重合体微粒子を得ることができる
分散重合方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a dispersion polymerization method capable of stably polymerizing in a wide monomer concentration range and obtaining polymer fine particles having excellent dispersibility and particle size uniformity. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】すなわち本発明は、ビニ
ルモノマ−を非水系分散重合させて重合体微粒子を製造
する方法において、分散安定剤として、ビニルモノマ−
を主鎖成分とし、枝成分としてポリジメチルシロキサン
を有する重合体を用いることを特徴とする分散性の優れ
た重合体微粒子の製造方法である。That is, the present invention provides a method for producing fine polymer particles by non-aqueous dispersion polymerization of a vinyl monomer, wherein the vinyl monomer is used as a dispersion stabilizer.
Is used as a main chain component and a polymer having polydimethylsiloxane as a branch component is used, which is a method for producing fine polymer particles having excellent dispersibility.
【０００６】以下に本発明を詳しく説明する。本発明
は、ビニルモノマ−を非水系分散重合させて重合体微粒
子を製造する方法において、特定の分散安定剤を使用す
るものである。この本発明で用いる分散安定剤の特徴
は、ビニルモノマ−を主鎖成分とし、枝成分としてポリ
ジメチルシロキサンを有する重合体である。すなわち、
本発明の分散安定剤に用いる重合体は、ビニルモノマ−
の重合体が幹（主鎖）を構成し、この幹にポリジメチル
シロキサンが枝状に結合しているグラフト状の構造の重
合体である。この共重合体は、ビニル基を有するポリジ
メチルシロキサン（ＰＤＭＳマクロマ−と略記する。）
とビニルモノマ−とを共重合させることにより得られ
る。The present invention will be described in detail below. The present invention uses a specific dispersion stabilizer in a method for producing polymer fine particles by non-aqueous dispersion polymerization of a vinyl monomer. The feature of the dispersion stabilizer used in the present invention is a polymer having a vinyl monomer as a main chain component and polydimethylsiloxane as a branch component. That is,
The polymer used in the dispersion stabilizer of the present invention is a vinyl monomer.
Is a polymer having a graft-like structure in which a polydimethylsiloxane is branchedly bonded to the trunk (main chain). This copolymer is a polydimethylsiloxane having a vinyl group (abbreviated as PDMS macromer).
It is obtained by copolymerizing a vinyl monomer with a vinyl monomer.
【０００７】ＰＤＭＳマクロマ−は、例えば、The PDMS macromer is, for example,
【０００８】[0008]
【化１】 [Chemical 1]
【０００９】で表されるようなポリジメチルシロキサン
（式中、ｎは整数である）、A polydimethylsiloxane represented by the formula (wherein n is an integer),
【００１０】[0010]
【化２】 [Chemical 2]
【００１１】で表されるようなメタクリロキシプロピル
含有Ｔ構造ポリジメチルシロキサン（式中、ｌ、ｍ、ｎ
は整数である）などである。Methacryloxypropyl-containing T-structure polydimethylsiloxane represented by the formula (wherein, 1, m, n
Is an integer) and so on.
【００１２】ＰＤＭＳマクロマ−と共重合可能なビニル
モノマ−としてはスチレン、α−メチルスチレン、ｐ−
クロルスチレン等のスチレン系モノマ−；メチルメタク
リレ−ト、エチルメタクリレ−ト等のメタクリレ−ト系
モノマ−；メチルアクリレ−ト、エチルアクリレ−ト、
ブチルアクリレ−ト等のアクリレ−ト系モノマ−；アク
リル酸、メタクリル酸、アクリロニトリル、アクリルア
ミド、酢酸ビニル、無水マレイン酸、塩化ビニル、ビニ
リデンクロライド、ビニルピリヂン等公知のビニルモノ
マ−を用いることが可能である。ＰＤＭＳマクロマ−と
ビニルモノマ−との共重合はラジカル重合で行うことが
できる。The vinyl monomer copolymerizable with the PDMS macromer is styrene, α-methylstyrene, p-
Styrene-based monomers such as chlorostyrene; methacrylate-based monomers such as methyl methacrylate and ethyl methacrylate; methyl acrylate and ethyl acrylate,
Acrylate monomers such as butyl acrylate; known vinyl monomers such as acrylic acid, methacrylic acid, acrylonitrile, acrylamide, vinyl acetate, maleic anhydride, vinyl chloride, vinylidene chloride and vinyl pyridin can be used. The copolymerization of PDMS macromer and vinyl monomer can be carried out by radical polymerization.
【００１３】しかして、ＰＤＭＳマクロマ−と共重合さ
せるビニルモノマ−としては、目的とする重合体微粒子
を構成するビニルモノマ−と同じビニルモノマ−を用い
るのが好ましい。この理由は明らかでないが、非水系分
散重合の際に、分散安定剤である上記共重合体が、分散
重合により生成する重合体微粒子の表面に吸着し易くな
るためと思われる。またＰＤＭＳマクロマ−とビニルモ
ノマ−との共重合割合は、ポリジメチルシロキサン側鎖
の分子量と共に重要な因子である。一般にポリジメチル
シロキサンの分子量が大きいと、共重合体中のＰＤＭＳ
マクロマ−のモル分率は小さくて良く、逆にポリジメチ
ルシロキサンの分子量が小さいとモル分率を大きくする
必要がある。However, as the vinyl monomer to be copolymerized with the PDMS macromer, it is preferable to use the same vinyl monomer as the vinyl monomer constituting the desired polymer fine particles. The reason for this is not clear, but it is considered that during the non-aqueous dispersion polymerization, the above-mentioned copolymer, which is a dispersion stabilizer, is easily adsorbed on the surface of polymer fine particles produced by the dispersion polymerization. The copolymerization ratio of the PDMS macromer and the vinyl monomer is an important factor together with the molecular weight of the polydimethylsiloxane side chain. Generally, when the molecular weight of polydimethylsiloxane is large, PDMS in the copolymer
The mole fraction of the macromer may be small, and conversely, when the molecular weight of polydimethylsiloxane is small, the mole fraction needs to be increased.
【００１４】本発明者らの検討結果では、ポリジメチル
シロキサンの分子量は５００から１０，０００、好まし
くは５００から５０００の間である。また共重合体中の
ＰＤＭＳマクロマ−のモル分率は０．１〜３０モル％、
好ましくは０．５〜１５モル％の範囲である。ポリジメ
チルシロキサンの分子量及びＰＤＭＳマクロマ−のモル
分率が上記範囲外の領域では、分散性に優れた、しかも
粒径の均一な重合体粒子を安定に製造することは困難で
ある。According to the results of studies by the present inventors, the molecular weight of polydimethylsiloxane is 500 to 10,000, preferably 500 to 5,000. The mole fraction of PDMS macromer in the copolymer is 0.1 to 30 mol%,
It is preferably in the range of 0.5 to 15 mol%. When the molecular weight of polydimethylsiloxane and the mole fraction of PDMS macromer are out of the above ranges, it is difficult to stably produce polymer particles having excellent dispersibility and having a uniform particle size.
【００１５】本発明方法は、ビニルモノマ−を非水系で
分散重合させ、重合体微粒子を製造する公知の分散重合
法に適用できる。この分散重合させるビニルモノマ−と
しては、先に述べたビニルモノマ−の他に、更にジビニ
ルベンゼン、エチレングリコ−ルジメタクリレ−ト等の
ジビニルモノマ−、弗素化（メタ）アクリレ−ト系モノ
マ−等も用いることができる。この場合ジビニルモノマ
−は架橋剤として作用するため、他の１官能性ビニルモ
ノマ−との共重合体成分として使用する場合が多い。The method of the present invention can be applied to a known dispersion polymerization method for producing polymer fine particles by dispersing and polymerizing a vinyl monomer in a non-aqueous system. As the vinyl monomer to be dispersed and polymerized, in addition to the vinyl monomer described above, divinyl benzene, ethylene glycol dimethacrylate, and other divinyl monomers, and fluorinated (meth) acrylate monomers can also be used. it can. In this case, since the divinyl monomer acts as a crosslinking agent, it is often used as a copolymer component with other monofunctional vinyl monomer.
【００１６】本発明における分散安定剤を用いて分散重
合を行うと、公知のビニルモノマ−より非水系におい
て、ラジカル重合により、分散性の優れた、数十ｎｍか
ら数十μｍの平均粒径を有する均一な微粒子を得ること
ができる。本発明方法で得られた重合体微粒子は、上記
優れた性質を有するので、塗料用充填剤、化粧品、トナ
−等の記録材料、流動性改良剤、表面処理剤等産業上広
く利用される。When dispersion polymerization is carried out using the dispersion stabilizer of the present invention, the average particle diameter of several tens of nm to several tens of μm, which is excellent in dispersibility by radical polymerization in a non-aqueous system than a known vinyl monomer, is obtained. Uniform fine particles can be obtained. Since the polymer fine particles obtained by the method of the present invention have the above-mentioned excellent properties, they are widely used industrially such as fillers for paints, cosmetics, recording materials such as toners, fluidity improvers and surface treatment agents.
【００１７】本発明の好ましい実施態様は次のとおりで
ある。 １．重合体の主鎖成分を構成するビニルモノマ−の主成
分が、重合体微粒子の重合体成分と同じビニルモノマ−
である請求項１記載の重合体微粒子の製造方法。 ２．
ビニルモノマ−が（メタ）アクリレ−トである請求項１
記載の重合体微粒子の製造方法。The preferred embodiment of the present invention is as follows. 1. The main component of the vinyl monomer constituting the main chain component of the polymer is the same vinyl monomer as the polymer component of the polymer fine particles.
The method for producing polymer fine particles according to claim 1, wherein 2.
The vinyl monomer is a (meth) acrylate.
A method for producing the polymer fine particles described.
【００１８】[0018]
【実施例】以下実施例を用いて本発明をさらに詳しく説
明する。 分散安定剤の製造例 片末端メタクロイルオキシプロピルのポリジメチルシロ
キサン（分子量１０００）４０重量部とメチルメタクリ
レ−ト（ＭＭＡ）４０重量部をトルエン１００重量部中
に溶解し、過酸化ベンゾイル１．２重量を開始剤として
加え、９０℃で５時間撹拌機付き３リットル容量のフラ
スコ内で重合した。この重合溶液を大量のメタノ−ル中
に加え、ポリマ−を沈澱回収して、共重合体を得た。得
られた共重合体は、メチルメタクリレ−トを主とする重
合体が幹部（主鎖）を形成し、ポリジメチルシロキサン
を枝部とするグラフト状の共重合体であった。The present invention will be described in more detail with reference to the following examples. Production Example of Dispersion Stabilizer 40 parts by weight of polydimethylsiloxane (molecular weight 1000) having one terminal methacryloyloxypropyl and 40 parts by weight of methyl methacrylate (MMA) were dissolved in 100 parts by weight of toluene to prepare benzoyl peroxide 1. 2 weight was added as an initiator, and polymerization was carried out at 90 ° C. for 5 hours in a 3 liter flask equipped with a stirrer. This polymerization solution was added to a large amount of methanol, and the polymer was precipitated and recovered to obtain a copolymer. The obtained copolymer was a graft copolymer in which a polymer mainly composed of methyl methacrylate forms a trunk portion (main chain) and polydimethylsiloxane serves as a branch portion.
【００１９】実施例１〜３ 製造例で合成した共重合体を分散安定剤としてポリメチ
ルメタクリレ−トの微粒子を非水系で分散重合を行っ
た。重合条件は以下の通りである。 １）分散安定剤／メチルメタクリレ−ト（ＭＭＡ）＝１
／２０（重量比） ２）開始剤（ＡＩＢＮ）／ＭＭＡ＝１／５０
（重量比） ３）媒体：シクロヘキサン ４）重合温度：７０℃Examples 1 to 3 Dispersion polymerization of fine particles of polymethylmethacrylate in a non-aqueous system was carried out by using the copolymer synthesized in Production Example as a dispersion stabilizer. The polymerization conditions are as follows. 1) Dispersion stabilizer / methyl methacrylate (MMA) = 1
/ 20 (weight ratio) 2) Initiator (AIBN) / MMA = 1/50
(Weight ratio) 3) Medium: cyclohexane 4) Polymerization temperature: 70 ° C
【００２０】撹拌棒を装着した３つ口１リットル容量の
セパラブルフラスコ中に媒体を所定量仕込み分散安定剤
を溶解した。次いでアゾイソブチロニトリル（ＡＩＢ
Ｎ）を溶解したメチルメタクリレ−トを撹拌しながらフ
ラスコ内に加え、７０℃で撹拌重合を行った。重合の進
行と共にポリマ−微粒子が析出し、系は白濁した。重合
率が９０％以上達した後、重合系を冷却し、ポリマ−微
粒子を濾過し、過剰のシクロヘキサンで洗浄した。１部
粒径の小さい微粒子は、遠心分離機によりポリマ−微粒
子を回収した。A predetermined amount of the medium was charged into a separable flask having a three-necked capacity of 1 liter equipped with a stirring rod to dissolve the dispersion stabilizer. Then azoisobutyronitrile (AIB
M) in which N) was dissolved was added to the flask with stirring, and the polymerization was carried out at 70 ° C. with stirring. As the polymerization proceeded, fine polymer particles were precipitated and the system became cloudy. After the polymerization rate reached 90% or more, the polymerization system was cooled, the polymer particles were filtered, and washed with excess cyclohexane. The fine particles having a small particle diameter of 1 part were collected as polymer fine particles by a centrifuge.
【００２１】本実施例では、重合系のメチルメタクリレ
−トモノマ−濃度を媒体に対して２０ｗｔ％，４０ｗｔ
％，５０ｗｔ％と変更しておこなったが、いずれも分散
安定性に優れていた。なお分散安定性の評価は、光学顕
微鏡、走査型電子顕微鏡による微粒子の観察により、ま
た平均粒子系は遠心分離法（島津製作所製 ＳＡ−ＣＰ
３形）により求めた。その結果を表１に示す。またモノ
マ−濃度５０ｗｔ％の時に得られた粒子の顕微鏡写真を
図１、図２に示す。これらの結果より、分散安定性の優
れた粒径の均一な微粒子が得られたことがわかる。In this embodiment, the polymerization system methyl methacrylate monomer concentration was 20 wt% and 40 wt% with respect to the medium.
% And 50 wt%, but both were excellent in dispersion stability. The dispersion stability was evaluated by observing fine particles with an optical microscope or a scanning electron microscope, and the average particle system was measured by a centrifugal separation method (Shimadzu SA-CP).
3 form). The results are shown in Table 1. 1 and 2 are micrographs of particles obtained when the monomer concentration was 50 wt%. From these results, it can be seen that fine particles having a uniform particle size and excellent dispersion stability were obtained.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例４〜８ 製造例で重合した分散安定剤を用いて、モノマ−の種類
を変更して実施例３と同じ方法で各種の重合体微粒子を
合成した。その結果を表２にまとめて示す。Examples 4 to 8 Various polymer fine particles were synthesized in the same manner as in Example 3 except that the type of the monomer was changed by using the dispersion stabilizer polymerized in the Production Example. The results are summarized in Table 2.
【００２４】[0024]
【表２】 [Table 2]
【００２５】表２において、括弧内の数値は、モノマ−
の媒体に対する重量％である。 ＥＤＭＡ：エチレングリコ−ルジメタクリレ−ト ＢＡ ：ブチルアクリレ−ト ３ＦＭ ：In Table 2, the numerical values in parentheses are monomers.
Is the weight% with respect to the medium. EDMA: ethylene glycol dimethacrylate BA: butyl acrylate 3FM:
【００２６】[0026]
【化３】 [Chemical 3]
【００２７】 Ｓｔ ：スチレン ＤＶＢ ：ジビニルベンゼンSt: Styrene DVB: Divinylbenzene
【００２８】比較例１ 分散安定剤としてエチレンと酢酸ビニルの共重合体（酢
酸ビニル含量２８モル％）を用いて実施例３と同様にし
て、メチルメタクリレ−ト重合体微粒子を合成した。得
られた微粒子の粒子径は０．３〜４μｍと分布が広くし
かも図３、図４に見るごとく粒子同志が凝集して分散安
定性の悪いものであった。Comparative Example 1 Methyl methacrylate polymer fine particles were synthesized in the same manner as in Example 3 using a copolymer of ethylene and vinyl acetate (vinyl acetate content 28 mol%) as a dispersion stabilizer. The obtained fine particles had a wide particle size distribution of 0.3 to 4 μm, and as shown in FIGS. 3 and 4, the particles were agglomerated and the dispersion stability was poor.
【００２９】[0029]
【発明の効果】本発明によれば、ビニルモノマ−を非水
系分散重合させて重合体微粒子を製造する方法におい
て、前記特定の分散安定剤を用いたので、数十ｎｍから
数十μｍに至る迄の平均粒径を有する重合体微粒子を安
定に製造することができる。また、その粒径の分布も狭
く、特に重合原料のビニルモノマ−として（メタ）アク
リレ−トを用いた場合には、均質な粒径を有する微粒子
が得られる。したがって、本発明方法を採用することに
より、流動性改良剤、表面改質剤、粉末成型用バインダ
−、トナ−用添加剤等として各種工業用途に有用な微粒
子を提供できる。According to the present invention, in the method for producing fine polymer particles by non-aqueous dispersion polymerization of a vinyl monomer, the specific dispersion stabilizer is used. It is possible to stably produce polymer fine particles having an average particle diameter of. Further, the particle size distribution is narrow, and particularly when (meth) acrylate is used as a vinyl monomer as a polymerization raw material, fine particles having a uniform particle size can be obtained. Therefore, by adopting the method of the present invention, it is possible to provide fine particles useful for various industrial purposes as a fluidity improver, a surface modifier, a binder for powder molding, an additive for a toner and the like.
【図１】実施例３によって得られたメチルメタクリレ−
ト重合体微粒子の光学顕微鏡写真（４００倍）である。1 is a methyl methacrylate obtained according to Example 3. FIG.
It is an optical microscope photograph (400 times) of the polymer fine particles.
【図２】実施例３によって得られたメチルメタクリレ−
ト重合体微粒子の走査型電子顕微鏡写真である。2 is a methyl methacrylate obtained according to Example 3. FIG.
3 is a scanning electron microscopic photograph of polymer particles.
【図３】比較例１によって得られたメチルメタクリレ−
ト重合体微粒子の光学顕微鏡写真（４００倍）である。3 is a methyl methacrylate obtained in Comparative Example 1. FIG.
It is an optical microscope photograph (400 times) of the polymer fine particles.
【図４】比較例１によって得られたメチルメタクリレ−
ト重合体微粒子の走査型電子顕微鏡写真である。4 is a methyl methacrylate obtained in Comparative Example 1. FIG.
3 is a scanning electron microscopic photograph of polymer particles.
Claims (1)
合体微粒子を製造する方法において、分散安定剤とし
て、ビニルモノマ−を主鎖成分とし、枝成分としてポリ
ジメチルシロキサンを有する重合体を用いることを特徴
とする分散性の優れた重合体微粒子の製造方法。1. A method for producing fine polymer particles by non-aqueous dispersion polymerization of a vinyl monomer, wherein a polymer having vinyl monomer as a main chain component and polydimethylsiloxane as a branch component is used as a dispersion stabilizer. A method for producing polymer fine particles having excellent dispersibility.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09488492A JP3245822B2 (en) | 1992-03-23 | 1992-03-23 | Method for producing polymer fine particles having excellent dispersibility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09488492A JP3245822B2 (en) | 1992-03-23 | 1992-03-23 | Method for producing polymer fine particles having excellent dispersibility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05262804A true JPH05262804A (en) | 1993-10-12 |
| JP3245822B2 JP3245822B2 (en) | 2002-01-15 |
Family
ID=14122476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09488492A Expired - Lifetime JP3245822B2 (en) | 1992-03-23 | 1992-03-23 | Method for producing polymer fine particles having excellent dispersibility |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3245822B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069918A1 (en) * | 1999-05-13 | 2000-11-23 | Research Laboratories Of Australia Pty Ltd. | Polymerisation stabilisers |
| US6346592B1 (en) | 1997-01-20 | 2002-02-12 | Norsk Hydro Asa | Self-activated polymer particles with a narrow size distribution and procedure for production thereof |
| JP2008274249A (en) * | 2007-03-30 | 2008-11-13 | Sekisui Plastics Co Ltd | Resin particle, its production method and silicone oil dispersion thereof |
| KR100905664B1 (en) * | 2007-09-05 | 2009-06-30 | 인하대학교 산학협력단 | Dispersion Polymerization of Vinyl Monomers in the Absence of Stabilizer |
-
1992
- 1992-03-23 JP JP09488492A patent/JP3245822B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6346592B1 (en) | 1997-01-20 | 2002-02-12 | Norsk Hydro Asa | Self-activated polymer particles with a narrow size distribution and procedure for production thereof |
| WO2000069918A1 (en) * | 1999-05-13 | 2000-11-23 | Research Laboratories Of Australia Pty Ltd. | Polymerisation stabilisers |
| JP2002544336A (en) * | 1999-05-13 | 2002-12-24 | リサーチ ラボラトリーズ オブ オーストラリアプロプライエタリイ リミテッド | Polymerization stabilizer |
| US6579654B1 (en) | 1999-05-13 | 2003-06-17 | Research Laboratories Of Australia Pty Ltd | Polymerization stabilizers |
| JP2008274249A (en) * | 2007-03-30 | 2008-11-13 | Sekisui Plastics Co Ltd | Resin particle, its production method and silicone oil dispersion thereof |
| KR100905664B1 (en) * | 2007-09-05 | 2009-06-30 | 인하대학교 산학협력단 | Dispersion Polymerization of Vinyl Monomers in the Absence of Stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3245822B2 (en) | 2002-01-15 |
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