JP2002194007A - Method for producing resin particulate - Google Patents
Method for producing resin particulateInfo
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- JP2002194007A JP2002194007A JP2000397539A JP2000397539A JP2002194007A JP 2002194007 A JP2002194007 A JP 2002194007A JP 2000397539 A JP2000397539 A JP 2000397539A JP 2000397539 A JP2000397539 A JP 2000397539A JP 2002194007 A JP2002194007 A JP 2002194007A
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- Prior art keywords
- stirring
- blade
- suspension
- stirring blade
- polymerization
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂微粒子の製造
方法およびその方法により製造される樹脂微粒子に関
し、さらに詳しくは（メタ）アクリル酸エステル系単量
体またはスチレン系単量体の懸濁重合において、粗大粒
子や凝集粒子の発生を低減する樹脂微粒子の製造方法お
よびその方法により製造される樹脂微粒子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing resin fine particles and resin fine particles produced by the method, and more particularly to suspension polymerization of a (meth) acrylate monomer or a styrene monomer. The present invention relates to a method for producing fine resin particles which reduces the generation of coarse particles and aggregated particles, and fine resin particles produced by the method.
【０００２】[0002]
【従来の技術】近年、球状樹脂微粒子、殊に平均粒子径
１〜５０μｍの球状樹脂微粒子が、滑り性付与剤、トナ
ー、塗料用艶消し剤、光拡散用の添加剤などの分野で広
く使用されている。これらの球状樹脂微粒子を製造する
方法としては、種々の重合方法が用いられており、一般
的には乳化重合、分散重合、シード重合、懸濁重合等が
採用されている。しかしながら、これらの方法のうち、
乳化重合による場合には、乳化剤などの無視できない不
純物を目的物から除去しなければならず、この不純物の
除去が困難であるという問題がある。また、分散重合お
よびシード重合では、操作が煩雑でしかも長時間を要す
るため、コスト的に不利であり、大量生産に不向きであ
るという問題がある。2. Description of the Related Art In recent years, spherical resin fine particles, particularly spherical resin fine particles having an average particle diameter of 1 to 50 .mu.m, have been widely used in fields such as a slipperiness imparting agent, a toner, a matting agent for paint, and an additive for light diffusion. Have been. Various polymerization methods are used as a method for producing these spherical resin fine particles, and generally, emulsion polymerization, dispersion polymerization, seed polymerization, suspension polymerization, and the like are employed. However, of these methods,
In the case of emulsion polymerization, non-negligible impurities such as an emulsifier must be removed from a target substance, and there is a problem that it is difficult to remove these impurities. In addition, dispersion polymerization and seed polymerization require complicated operations and require a long time, which is disadvantageous in terms of cost and is not suitable for mass production.
【０００３】一方、懸濁重合によれば、粒子径が１〜５
０μｍ程度の球状樹脂微粒子を大量に、かつ比較的安価
に製造することが可能であるが、一般に、攪拌による剪
断により、液滴が様々な径を有し、さらに***と合一を
繰り返すため、得られる粒子の粒度分布が広くなり、粒
子径と粒度分布の制御が難しいという問題がある。特
に、平均粒子径から大きく離れた粒子（以下、粗大粒子
という）や凝集粒子の存在は、球状樹脂微粒子が使用さ
れる前記のような分野において問題となるため、そのよ
うな粒子を分級等の方法で取り除くことが行われている
が、この操作は煩雑で長時間を要するため、費用がかさ
むという問題がある。[0003] On the other hand, according to the suspension polymerization, the particle diameter is 1 to 5
Although it is possible to produce a large amount of spherical resin fine particles of about 0 μm and relatively inexpensively, in general, the droplets have various diameters due to shearing by stirring, and furthermore, because the droplets repeatedly split and coalesce, There is a problem that the particle size distribution of the obtained particles is widened and it is difficult to control the particle size and the particle size distribution. In particular, since the presence of particles (hereinafter, referred to as coarse particles) or agglomerated particles far apart from the average particle diameter becomes a problem in the above-described fields where spherical resin fine particles are used, such particles are classified and classified. Although the removal is performed by a method, this operation is complicated and takes a long time, so that there is a problem that the cost is increased.
【０００４】このような問題点を解決するために、剪断
力を付与する特定の分散機でモノマーを分散液に分散処
理する方法や、その他の分散方法により、予め所望の大
きさの液滴を含む分散液を得（均質化処理）、次いでこ
の分散液を重合槽に導入して通常の攪拌下に重合を行う
ことにより、得られる樹脂粒子の粒子径や粒度分布を制
御する方法が提案されている（特開平３−１３１６０３
号）。また、攪拌が強すぎると液滴が衝突して合一する
ことにより、粗大粒子が増加するという問題や、穏やか
な攪拌では重合反応熱の除去が不十分となるような問題
に対応して、上記と同様に均質化処理を施した後、特定
の攪拌装置を用いることで相対的に強い攪拌下におき、
界面活性剤を使用した塩化ビニルを微細懸濁重合または
乳化重合することにより、スケールおよび凝集物の生成
が少ない、ペースト用塩化ビニル樹脂粉状体を製造する
方法が提案されている（特開平６−２８７２０３号）。[0004] In order to solve such a problem, droplets of a desired size are previously prepared by a method of dispersing a monomer into a dispersion liquid using a specific disperser that applies a shearing force, or other dispersion methods. A method for controlling the particle size and particle size distribution of the obtained resin particles by obtaining a dispersion containing (homogenization treatment), then introducing this dispersion into a polymerization tank and performing polymerization under ordinary stirring has been proposed. (Japanese Patent Application Laid-Open No. 3-131603)
issue). In addition, if the stirring is too strong, the droplets collide and coalesce, thereby increasing the number of coarse particles and responding to the problem that gentle stirring causes insufficient removal of the heat of polymerization reaction. After performing the homogenization treatment in the same manner as above, put under relatively strong stirring by using a specific stirring device,
There has been proposed a method for producing a powdery vinyl chloride resin powder for pastes, which produces a small amount of scale and agglomerates by subjecting vinyl chloride to fine suspension polymerization or emulsion polymerization using a surfactant (Japanese Patent Application Laid-Open No. Hei 6 (1994) -163). -287203).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、このよ
うな方法では、球状樹脂粒子が用いられる前記のような
分野で一般的に用いられる（メタ）アクリル酸エステル
系単量体またはスチレン系単量体の懸濁重合において、
粗大粒子や凝集粒子をほとんど有さずに実用上支障のな
い樹脂粒子を得ることはできず、場合によっては分散不
良となり、重合を途中で断念しなければならないことも
ある。本発明は、このような問題を解決することを課題
とするものであり、具体的には、（メタ）アクリル酸エ
ステル系単量体またはスチレン系単量体の懸濁重合にお
いて、粗大粒子や凝集粒子の少ない樹脂微粒子の製造方
法を提供することを課題とする。However, in such a method, a (meth) acrylate-based monomer or a styrene-based monomer generally used in the above-mentioned field where spherical resin particles are used is used. In the suspension polymerization of
It is not possible to obtain resin particles having practically no problem, having almost no coarse particles or aggregated particles, and in some cases, poor dispersion, and it may be necessary to give up the polymerization in the middle. An object of the present invention is to solve such a problem. Specifically, in suspension polymerization of a (meth) acrylate monomer or a styrene monomer, coarse particles or An object of the present invention is to provide a method for producing resin fine particles having few aggregated particles.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記の課題
を解決するために、攪拌翼の形状・構成、攪拌速度およ
び懸濁液の物性と、粗大粒子や凝集粒子が生成される関
連について研究を進めた結果、特定範囲の粘性を有する
懸濁液を、特定範囲の攪拌速度において、効率よく均一
に混合し得る特定の形状・構成を有する攪拌翼で攪拌す
ることにより、上記の課題を解決できることを見出し、
本発明を完成するに至った。In order to solve the above-mentioned problems, the present inventor has proposed a structure and a configuration of a stirring blade, a stirring speed and a physical property of a suspension, and a description of a relation between coarse particles and aggregated particles. As a result of research on the above, the above-mentioned problem was solved by stirring a suspension having a specific range of viscosity with a specific range of stirring speed using a stirring blade having a specific shape and configuration capable of mixing efficiently and uniformly. Can be solved,
The present invention has been completed.
【０００７】かくして本発明によれば、無機系懸濁安定
剤を含む水性媒体中に（メタ）アクリル酸エステル系単
量体またはスチレン系単量体を分散してなり、０．１〜
２．０Ｐａ・ｓの粘度を有する懸濁液を、重合開始剤の
存在下で、略円筒状の攪拌槽と、該攪拌槽の中心部に垂
設された回転軸に垂直に保持された複数の攪拌翼を前記
回転軸の高さ方向に上下２段以上に装着されてなり、最
下段の攪拌翼の外端部が回転方向に対して後退している
パドル型攪拌翼とを有する攪拌装置により、攪拌しなが
ら加熱して重合することを特徴とする樹脂微粒子の製造
方法が提供される。また、本発明によれば、上記方法に
より製造される樹脂微粒子が提供される。Thus, according to the present invention, a (meth) acrylate monomer or a styrene monomer is dispersed in an aqueous medium containing an inorganic suspension stabilizer.
In the presence of a polymerization initiator, a suspension having a viscosity of 2.0 Pa · s is mixed with a substantially cylindrical stirring tank and a plurality of suspensions held perpendicularly to a rotating shaft suspended from the center of the stirring tank. And a paddle type stirring blade in which the stirring blades are mounted in two or more stages in the height direction of the rotating shaft, and the outer end of the lowermost stirring blade is retracted in the rotation direction. Thus, there is provided a method for producing fine resin particles, which comprises heating and polymerizing while stirring. Further, according to the present invention, resin fine particles produced by the above method are provided.
【０００８】[0008]
【発明の実施の形態】本発明の方法では、無機系懸濁安
定剤を含む水性媒体中に（メタ）アクリル酸エステル系
単量体またはスチレン系単量体を分散してなり、０．１
〜２．０Ｐａ・ｓの粘度を有する懸濁液を、重合開始剤
の存在下で、縦型略円筒状の攪拌槽と、該攪拌槽の中心
部に垂設された回転軸に垂直に保持された複数の攪拌翼
を前記回転軸の高さ方向に上下２段以上に装着されてな
り、最下段の攪拌翼の外端部が回転方向に対して後退す
るパドル型攪拌翼とを有する攪拌装置により攪拌しなが
ら加熱して重合することを特徴とする。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, a (meth) acrylate monomer or a styrene monomer is dispersed in an aqueous medium containing an inorganic suspension stabilizer.
A suspension having a viscosity of ~ 2.0 Pa · s is held in the presence of a polymerization initiator in a direction substantially perpendicular to a vertical, substantially cylindrical stirring tank and a rotating shaft suspended from the center of the stirring tank. And a paddle-type stirring blade in which the outer ends of the lowermost stirring blade are retreated in the rotation direction. It is characterized in that polymerization is carried out by heating while stirring with an apparatus.
【０００９】本発明の方法により使用される（メタ）ア
クリル酸エステル系単量体としては、例えば、アクリル
酸メチル、アクリル酸エチル、アクリル酸ブチル、アク
リル酸２エチルヘキシル、メタクリル酸メチル、メタク
リル酸エチル、メタクリル酸ブチル、メタクリル酸ベン
ジル、メタクリル酸シクロヘキシル、メタクリル酸イソ
ボルニル、メタクリル酸ヒドロフルフリル、メタクリル
酸グリシジル等が挙げられる。これらはそれぞれ単独
で、または２種類以上を組合わせて用いることができ
る。また、本発明の方法に使用されるスチレン系単量体
としては、例えば、スチレン、α−メチルスチレン、ｐ
−メチルスチレン、ｔ−ブチルスチレン等のスチレン誘
導体が挙げられ、これらはそれぞれ単独で、または２種
類以上を組合わせて用いることができる。The (meth) acrylate monomers used in the method of the present invention include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate Butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, hydrofurfuryl methacrylate, glycidyl methacrylate and the like. These can be used alone or in combination of two or more. The styrene monomer used in the method of the present invention includes, for example, styrene, α-methylstyrene,
And styrene derivatives such as -methylstyrene and t-butylstyrene. These can be used alone or in combination of two or more.
【００１０】上記の（メタ）アクリル酸エステル系単量
体およびスチレン系単量体には、本発明の効果を損わな
い範囲で、得られる樹脂微粒子の改質等の目的に応じて
共重合可能な他の単量体を併せて用いることができる。
そのような他の単量体としては、例えば、アクリル酸等
の付加重合性不飽和カルボン酸系単量体、メチルビニル
エーテル等のアルキルビニル系単量体、酢酸ビニル等の
ビニルエステル系単量体、アクリロニトリル等のニトリ
ル系単量体等が挙げられる。また架橋の目的でジビニル
ベンゼン、エチレングリコールジメタクリレート等の多
官能ビニル単量体を併せて用いることもできる。The above-mentioned (meth) acrylic acid ester monomer and styrene monomer are copolymerized according to the purpose such as modification of the obtained resin fine particles as long as the effects of the present invention are not impaired. Other possible monomers can be used in combination.
Examples of such other monomers include, for example, addition-polymerizable unsaturated carboxylic acid monomers such as acrylic acid, alkyl vinyl monomers such as methyl vinyl ether, and vinyl ester monomers such as vinyl acetate. And nitrile monomers such as acrylonitrile. For the purpose of crosslinking, a polyfunctional vinyl monomer such as divinylbenzene or ethylene glycol dimethacrylate may be used in combination.
【００１１】本発明の方法で使用される重合開始剤とし
ては、通常、懸濁重合で用いられる油溶性の有機過酸化
物あるいはアゾ化合物等を用いることができ、例えば過
酸化ベンゾイル、過酸化ラウロイル、オルソメトキシ過
酸化ベンゾイル、メチルエチルケトンパーオキサイド、
ジイソプロピルパーオキシカーボネート、キュメンハイ
ドロパーオキサイド、シクロヘキサノンパーオキサイ
ド、ｔ−ブチルハイドロパーオキサイド等の過酸化物系
重合開始剤、２，２’−アゾビスイソブチロニトリル、
２，２’−アゾビス（２−メチルブチロニトリル）、
２，２’−（２，３−ジメチルブチロニトリル）、２，
２’−（２，３，３−トリメチルブチロニトリル）、
２，２’−アゾビス（２−イソプロピルブチロニトリ
ル）、２，２’−アゾビス（シクロへキサン−１−カル
ボニトリル）、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）、２−（カルバモ
イルアゾ）イソブチロニトリル、４，４’−アゾビス
（４−シアノバレリン酸）、ジメチル−２，２’−アゾ
ビスイソブチレート等が挙げられる。これらの中でも、
過酸化ベンゾイル、過酸化ラウロイル、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）が特に好ましい。As the polymerization initiator used in the method of the present invention, an oil-soluble organic peroxide or an azo compound which is usually used in suspension polymerization can be used. Examples thereof include benzoyl peroxide and lauroyl peroxide. , Orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile,
2,2′-azobis (2-methylbutyronitrile),
2,2 ′-(2,3-dimethylbutyronitrile), 2,
2 ′-(2,3,3-trimethylbutyronitrile),
2,2′-azobis (2-isopropylbutyronitrile), 2,2′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azo Bisisobutyrate and the like can be mentioned. Among these,
Benzoyl peroxide, lauroyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4
-Dimethylvaleronitrile) is particularly preferred.
【００１２】重合開始剤の使用割合は、重合開始剤の種
類および用いられる単量体の重合性や重合温度等の条件
により適宜選択されるが、一般的には単量体１００重量
部に対して０．０１〜２．０重量部程度である。本発明
の方法における懸濁重合では、懸濁させた粒子の安定化
を図るために、単量体１００重量部に対して、水１００
〜１０００重量部程度が用いられ、さらに無機系懸濁安
定剤が添加される。The proportion of the polymerization initiator to be used is appropriately selected depending on the type of the polymerization initiator and the conditions such as the polymerizability of the monomer used and the polymerization temperature. About 0.01 to 2.0 parts by weight. In the suspension polymerization in the method of the present invention, 100 parts by weight of monomer is added to 100 parts by weight of water in order to stabilize the suspended particles.
About 1000 parts by weight are used, and an inorganic suspension stabilizer is further added.
【００１３】無機系懸濁安定剤としては、特に限定され
ないが、例えばリン酸カルシウム、ピロリン酸マグネシ
ウム等のリン酸塩、炭酸カルシウム、水酸化カルシウ
ム、硫酸カルシウム、コロイダルシリカ等の難水溶性無
機化合物が挙げられる。これらの安定剤はそれぞれ単独
で、または２種類以上を組合わせて用いることもでき
る。中でも第三リン酸カルシウムや複分解生成法による
ピロリン酸マグネシウム、コロイダルシリカは、本発明
の樹脂微粒子が安定して得られるという点で好ましい。
また、無機系懸濁安定剤の使用割合は、所望する粒子
径、重合条件等により、適宜調節されるが、一般的には
単量体１００重量部に対して０．５〜１５重量部程度で
ある。なお、本発明の方法では、無機系懸濁安定剤とと
もに界面活性剤を用いることもできる。The inorganic suspension stabilizer is not particularly restricted but includes, for example, phosphates such as calcium phosphate and magnesium pyrophosphate, and poorly water-soluble inorganic compounds such as calcium carbonate, calcium hydroxide, calcium sulfate and colloidal silica. Can be These stabilizers can be used alone or in combination of two or more. Among them, tricalcium phosphate, magnesium pyrophosphate, and colloidal silica produced by a double decomposition method are preferable in that the resin fine particles of the present invention can be stably obtained.
The use ratio of the inorganic suspension stabilizer is appropriately adjusted depending on the desired particle size, polymerization conditions, and the like, but is generally about 0.5 to 15 parts by weight based on 100 parts by weight of the monomer. It is. In the method of the present invention, a surfactant may be used together with the inorganic suspension stabilizer.
【００１４】界面活性剤としては、特に限定されない
が、例えばオレイン酸ナトリウム等の高級脂肪酸塩、ラ
ウリル硫酸ナトリウム等のアルキル硫酸エステル塩、ド
デシルベンゼンスルホン酸ナトリウム等のアルキルベン
ゼンスルホン酸塩、ジアルキルスルホコハク酸塩、アル
キルリン酸エステル塩等のアニオン性界面活性剤、ラウ
リルアミンアセテート等のアルキルアミン塩、ラウリル
トリメチルアンモニウムクロライド等の第４級アンモニ
ウム塩等のカチオン性界面活性剤、ラウリルジメチルア
ミンオキサイド等の両性界面活性剤、ポリオキシエチレ
ンアルキルエーテル、ポリオキシアルキルフェニルエー
テル、ポリオキシエチレン脂肪酸エステル、ソルビタン
脂肪酸エステル、ポリオキシソルビタン脂肪酸エステ
ル、ポリオキシエチレンアルキルアミン、グリセリン脂
肪酸エステル、オキシエチレン−オキシプロピレンブロ
ックポリマー等のノニオン性界面活性剤等が挙げられ
る。これらの界面活性剤は、それぞれ単独で、または２
種類以上を組合わせて用いることができる。Examples of the surfactant include, but are not particularly limited to, higher fatty acid salts such as sodium oleate, alkyl sulfates such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and dialkyl sulfosuccinates. , Anionic surfactants such as alkyl phosphate esters, alkylamine salts such as laurylamine acetate, quaternary ammonium salts such as lauryltrimethylammonium chloride, and amphoteric surfactants such as lauryldimethylamine oxide. Activator, polyoxyethylene alkyl ether, polyoxyalkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene Alkylamines, glycerol fatty acid ester, polyoxyethylene - nonionic surfactants such as polyoxypropylene block polymers. These surfactants can be used alone or in combination.
More than one type can be used in combination.
【００１５】特に、無機系懸濁安定剤として難水溶性リ
ン酸塩を用いる場合には、アニオン性界面活性剤である
アルキル硫酸ナトリウム、アルキルベンゼンスルホン酸
ナトリウム、α−オレフィンスルホン酸ナトリウムなど
が好適に使用される。界面活性剤の使用割合は、目的と
する樹脂微粒子の粒子径等により適宜調節されるが、一
般的には水に対して０．００１〜０．１重量％程度であ
る。本発明の方法で使用される、水性媒体中に単量体の
微細な液滴を分散させた懸濁液は、例えば、無機系懸濁
安定剤および界面活性剤を含む水性媒体中に、重合開始
剤を溶解した単量体を加え、ホモミキサー等の高速剪断
型分散機または超音波分散機等で処理することにより得
られる。In particular, when a poorly water-soluble phosphate is used as the inorganic suspension stabilizer, anionic surfactants such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, and sodium α-olefin sulfonate are preferably used. used. The proportion of the surfactant used is appropriately adjusted depending on the particle size of the target resin fine particles, but is generally about 0.001 to 0.1% by weight based on water. A suspension in which fine droplets of a monomer are dispersed in an aqueous medium used in the method of the present invention is, for example, polymerized in an aqueous medium containing an inorganic suspension stabilizer and a surfactant. It is obtained by adding a monomer in which an initiator is dissolved, and treating it with a high-speed shearing disperser such as a homomixer or an ultrasonic disperser.
【００１６】また、粒子径の揃った樹脂微粒子を得るに
は、液滴相互の衝突や器壁への衝突を利用した高圧型分
散機等で処理するのが好ましい。本発明の方法における
懸濁液の粘度は、０．１〜２．０Ｐａ・ｓであり、０．
２〜１．５Ｐａ・ｓがより好ましい。懸濁液の粘度が
０．１Ｐａ・ｓ未満であると、重合過程において合一が
起こり易く、粗大粒子や凝集粒子が増加するので好まし
くない。また、懸濁液の粘度が２．０Ｐａ・ｓを超える
と、攪拌による均一な混合が困難となって、凝集粒子等
が増加するので好ましくない。Further, in order to obtain resin fine particles having a uniform particle diameter, it is preferable to carry out treatment with a high-pressure disperser or the like utilizing collision between droplets or collision with a vessel wall. The viscosity of the suspension in the method of the present invention is 0.1 to 2.0 Pa · s.
2 to 1.5 Pa · s is more preferable. If the viscosity of the suspension is less than 0.1 Pa · s, coalescence easily occurs in the polymerization process, and coarse particles and aggregated particles increase, which is not preferable. On the other hand, if the viscosity of the suspension exceeds 2.0 Pa · s, uniform mixing by stirring becomes difficult, and aggregated particles and the like increase, which is not preferable.
【００１７】懸濁液の粘度を上記の範囲に調節する方法
としては、例えば、単量体に対する無機系懸濁安定剤の
使用割合や、単量体に対する水の使用割合を変えること
によって行うことができる。具体的には、無機系懸濁安
定剤の使用割合を増やすか、水の使用割合を減らすと懸
濁液の粘度を増加させることができる。無機系懸濁安定
剤の使用割合は、単量体１００重量部に対して１〜１０
０重量部程度であり、水の使用割合は、単量体１００重
量部に対して１００〜１０００重量部程度である。As a method of adjusting the viscosity of the suspension to the above-mentioned range, for example, by changing the use ratio of the inorganic suspension stabilizer to the monomer or the use ratio of water to the monomer. Can be. Specifically, the viscosity of the suspension can be increased by increasing the use ratio of the inorganic suspension stabilizer or decreasing the use ratio of water. The use ratio of the inorganic suspension stabilizer is 1 to 10 with respect to 100 parts by weight of the monomer.
The amount of water is about 0 parts by weight, and the use ratio of water is about 100 to 1000 parts by weight based on 100 parts by weight of the monomer.
【００１８】本発明の方法における懸濁重合は、略円筒
状の攪拌槽と、特定の形状を有するパドル型攪拌翼とを
有する攪拌装置により、攪拌しながら加熱下に行われ
る。略円筒状の攪拌槽は、縦型、横型のいずれでもよい
が、後述する特定形状のパドル型攪拌翼を容易に備える
ことができるという点において、縦型のものが好まし
い。パドル型攪拌翼は、略円筒状の攪拌槽の中心部に垂
設された回転軸に垂直に保持された複数の攪拌翼を回転
軸の高さ方向に上下２段以上に装着してなる。攪拌翼が
一段のみであると、低速攪拌下においては、懸濁液が攪
拌翼の回転と共回りしてしまい、均一に混合されず、凝
集粒子等が増加するので好ましくない。The suspension polymerization in the method of the present invention is carried out with stirring by a stirrer having a substantially cylindrical stirring tank and a paddle type stirring blade having a specific shape. The substantially cylindrical stirring tank may be either a vertical type or a horizontal type, but is preferably a vertical type in that a paddle type stirring blade having a specific shape described later can be easily provided. The paddle type stirring blade is configured by mounting a plurality of stirring blades vertically held on a rotating shaft vertically provided at a center portion of a substantially cylindrical stirring tank in two or more stages in the height direction of the rotating shaft. If the number of stirring blades is only one, it is not preferable because the suspension rotates together with the rotation of the stirring blades under low-speed stirring, so that the suspension is not uniformly mixed and aggregated particles increase.
【００１９】パドル型攪拌翼は、最下段の攪拌翼の翼径
が、他の段の翼径よりも大きいのが好ましい。最下段の
攪拌翼の翼径が他の段の翼径よりも小さいと、攪拌槽壁
面近傍の懸濁液の流れが下部へ向かい、攪拌槽上部の懸
濁液の混合が不十分となって凝集粒子等が増加しやすい
ので好ましくない。In the paddle type stirring blade, it is preferable that the blade diameter of the lowermost stirring blade is larger than the blade diameter of the other stages. If the blade diameter of the lowermost stirring blade is smaller than that of the other stages, the flow of the suspension near the wall of the stirring tank goes to the lower part, and the mixing of the suspension in the upper part of the stirring tank becomes insufficient. It is not preferable because aggregated particles and the like easily increase.
【００２０】最下段の攪拌翼の翼径は、特に限定されな
いが、より均一な混合を得るためには、攪拌槽内径の
０．６〜０．９５倍程度であるのが好ましい。この翼径
が攪拌槽内径の０．６倍未満であると、翼先端と攪拌槽
内壁との距離が大きく、その間に存在する懸濁液が均一
に混合されないため、凝集粒子等が増加するので好まし
くない。また、最下段の攪拌翼の翼径が攪拌槽内径の
０．９５倍を超えると、翼先端と攪拌槽内壁との距離が
小さすぎて、その間に存在する懸濁液が大きな力を受け
て、合一が生じ易くなるため、粗大粒子や凝集粒子が増
加するので好ましくない。The diameter of the lowermost stirring blade is not particularly limited, but is preferably about 0.6 to 0.95 times the inner diameter of the stirring tank in order to obtain more uniform mixing. If the blade diameter is less than 0.6 times the inner diameter of the stirring tank, the distance between the tip of the blade and the inner wall of the stirring tank is large, and the suspension existing between the blades is not uniformly mixed. Not preferred. Further, when the blade diameter of the lowermost stirring blade exceeds 0.95 times the inner diameter of the stirring tank, the distance between the tip of the blade and the inner wall of the stirring tank is too small, and the suspension existing therebetween receives a large force. This is not preferable because coalescence easily occurs, and coarse particles and aggregated particles increase.
【００２１】最下段の攪拌翼は、その攪拌翼と攪拌槽底
部内面との間に、攪拌槽内径の約０．０５倍以上の間隔
を有するのが好ましい。最下段の攪拌翼の形状は、特に
限定されず、例えば長方形、正方形等の四角形、半円形
または扇型のいずれであってもよく、また、攪拌槽内径
の輪郭に沿って象られた形状であってもよい。攪拌翼の
回転軸の高さ方向の翼幅（図１に示されるｈ１およびｈ
２）は、攪拌槽内径の０．２〜２．０倍程度である。上
下で隣接する各攪拌翼の間隔は、最下段の攪拌翼の翼幅
の０．０２〜０．１５倍程度である。The lowermost stirring blade preferably has a space between the stirring blade and the inner surface of the bottom of the stirring tank which is at least about 0.05 times the inner diameter of the stirring tank. The shape of the lowermost stirring blade is not particularly limited, and may be, for example, a rectangle such as a rectangle, a square, a semicircle, or a fan, or a shape drawn along the contour of the inner diameter of the stirring tank. There may be. Blade width in the height direction of the rotation axis of the stirring blade (h1 and h1 shown in FIG. 1)
2) is about 0.2 to 2.0 times the inner diameter of the stirring tank. The spacing between the upper and lower adjacent stirring blades is about 0.02 to 0.15 times the blade width of the lowermost stirring blade.
【００２２】攪拌翼の回転軸の高さ方向の翼幅が攪拌槽
内径の０．３倍以上であり、各攪拌翼の上下の間隔が最
下段の攪拌翼の翼幅の０．１５倍以下であると、懸濁液
がより均一に混合されるので好ましい。また、上下に隣
接する各攪拌翼は、３０〜８０度の交差角度（下段の攪
拌翼に対する上段の攪拌翼の回転方向への進み角度：図
２に示されるθ１）を有するのが好ましい。最下段の攪
拌翼は、外端部において回転方向に対して後退してい
る。このような形状を有することにより、懸濁液を均一
に混合することができる。The blade width in the height direction of the rotation axis of the stirring blade is at least 0.3 times the inner diameter of the stirring tank, and the vertical interval between each stirring blade is 0.15 times or less the blade width of the lowest stirring blade. Is preferable because the suspension is more uniformly mixed. It is preferable that each of the stirring blades vertically adjacent to each other has an intersection angle of 30 to 80 degrees (advancing angle of the upper stirring blade with respect to the lower stirring blade in the rotation direction: θ1 shown in FIG. 2). The lowermost stirring blade retreats in the rotation direction at the outer end. By having such a shape, the suspension can be uniformly mixed.
【００２３】最下段の攪拌翼の後退している部分の長さ
は、最下段の攪拌翼の翼先端から回転軸までの長さの１
〜４０％が好ましく、２〜３０％がより好ましい。後退
している部分の長さが１％未満では、翼先端の後面にお
いて液体の吸い込みが起こり、攪拌流が乱れるため、液
滴同士の衝突頻度が大きくなって合一が生じやすくな
り、凝集粒子等が増加するので好ましくない。最下段の
攪拌翼の後退している部分は、平面であってもよいし、
曲面であってもよい。後退している部分が平面である場
合、最下段の攪拌翼と後退している部分との角度（以
下、後退角度という：図２に示されるθ２）は、１００
〜１７０度が好ましく、１２０〜１６０度がさらに好ま
しい。後退角度が１００度未満では、攪拌槽内壁付近の
懸濁液が均一に混合されず、凝集粒子等が増加しやすい
ので好ましくない。また、後退角度が１７０度を超える
と、翼先端の後面において液体の吸い込みが起こり、攪
拌流が乱れるため、衝突頻度が大きくなって合一が生じ
やすくなり、凝集粒子等が増加しやすいので好ましくな
い。The length of the retreating portion of the lowermost stirring blade is one of the length from the blade tip of the lowermost stirring blade to the rotation axis.
-40% is preferable, and 2-30% is more preferable. If the length of the receding portion is less than 1%, liquid is sucked on the rear surface of the blade tip and the agitated flow is disturbed. Etc. increase, which is not preferable. The retreating part of the lowermost stirring blade may be flat,
It may be a curved surface. When the receding portion is a flat surface, the angle between the lowermost stirring blade and the receding portion (hereinafter, referred to as the receding angle: θ2 shown in FIG. 2) is 100.
It is preferably from 170 to 170 degrees, more preferably from 120 to 160 degrees. If the receding angle is less than 100 degrees, the suspension near the inner wall of the stirring tank is not uniformly mixed, and aggregate particles and the like are likely to increase. On the other hand, if the receding angle exceeds 170 degrees, the suction of the liquid occurs on the rear surface of the blade tip, and the stirring flow is disturbed, so that the collision frequency increases, coalescence easily occurs, and the agglomerated particles and the like are easily increased. Absent.
【００２４】また、後退している部分が曲面である場
合、その曲率半径は翼径に対して０．２〜５．０程度で
あり、０．４〜３．０が好ましい。懸濁重合の際の攪拌
速度は、最下段の攪拌翼の先端周速度が、０．１〜２．
０ｍ／ｓであるのが好ましく、０．２〜１．６ｍ／ｓで
あるのがさらに好ましい。この周速度が０．１ｍ／ｓ未
満では、懸濁液の混合が不十分となって凝集粒子等が増
加しやすくなるので好ましくない。また、周速度が２．
０ｍ／ｓを超えると、粒子の衝突頻度が大きくなって合
一が生じ易くなり、粗大粒子や凝集粒子が増加しやすく
なるので好ましくない。懸濁重合の反応温度は、通常、
３０〜１００℃が好ましく、４０〜８０℃がさらに好ま
しい。反応時間は、通常、０．１〜１０時間程度であ
る。When the receding portion is a curved surface, its radius of curvature is about 0.2 to 5.0 with respect to the blade diameter, and preferably 0.4 to 3.0. The stirring speed at the time of suspension polymerization is such that the peripheral speed of the tip of the lowermost stirring blade is 0.1 to 2.
It is preferably 0 m / s, and more preferably 0.2 to 1.6 m / s. If the peripheral speed is less than 0.1 m / s, the mixing of the suspension becomes insufficient and aggregated particles and the like tend to increase, which is not preferable. In addition, the peripheral speed is 2.
If it exceeds 0 m / s, the collision frequency of the particles increases, and coalescence easily occurs, and coarse particles and aggregated particles tend to increase. The reaction temperature of the suspension polymerization is usually
30-100 degreeC is preferable, and 40-80 degreeC is more preferable. The reaction time is usually about 0.1 to 10 hours.
【００２５】[0025]
【実施例】以下、本発明を実施例および比較例を挙げて
さらに具体的に説明するが、本発明はこれらによって限
定されるものでない。 （評価方法） ＜懸濁液の粘度測定＞Ｂ型粘度計（株式会社トキメック
製、商品名：Ｂ８Ｈ型）を用いて、次の手順で測定す
る。懸濁液１５０ｇを２００ｃｃのビーカーに入れ、ロ
ーター（Ｎｏ．４）を懸濁液中の所定の位置にセットし
て、５０ｒｐｍで回転させた後、Ｂ型粘度計の針が安定
したときの目盛りを読み取り、目盛りの値を算出表に照
らし合わせることにより、懸濁液の粘度を測定する。 ＜樹脂微粒子の粒子径の測定＞コールターカウンター
（コールター社製）およびアパーチャー（孔径５０μ
ｍ）を用いて測定する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. (Evaluation Method) <Measurement of Viscosity of Suspension> The viscosity is measured using a B-type viscometer (trade name: B8H, manufactured by Tokimec Co., Ltd.) according to the following procedure. 150 g of the suspension was placed in a 200 cc beaker, the rotor (No. 4) was set at a predetermined position in the suspension, and the rotor was rotated at 50 rpm. Is read, and the viscosity of the suspension is measured by comparing the value of the scale with a calculation table. <Measurement of particle size of resin fine particles> Coulter counter (manufactured by Coulter) and aperture (pore size 50 μm)
m).
【００２６】実施例１ 卓上型ホモミキサー（特殊機化社製）およびプロペラ翼
付き攪拌装置を備えた２リットル容器に水１２００ｇを
入れ、攪拌下にラウリル硫酸ナトリウム１ｇを投入して
溶解し、次いで第三リン酸カルシウム２０ｇを投入して
分散させることにより水性媒体を作成した。これとは別
に、１リットル容器にメタクリル酸メチル３９２ｇを入
れ、エチレングリコールジメタクリレート８ｇおよびア
ゾビスイソブチロニトリル２ｇを加えて混合・溶解し
た。この単量体組成物を上記の２リットル容器中で攪拌
されている水性媒体中に投入して混合し、さらにホモミ
キサーを用いて高速剪断下で微分散処理を行い、液滴の
径が約７μｍである懸濁液を得た。この懸濁液の粘度は
０．６Ｐａ・ｓであった。Example 1 1200 g of water was placed in a 2 liter vessel equipped with a tabletop homomixer (manufactured by Tokushu Kika Co., Ltd.) and a stirrer equipped with a propeller blade, and 1 g of sodium lauryl sulfate was added and dissolved with stirring, and then dissolved. An aqueous medium was prepared by adding and dispersing 20 g of tricalcium phosphate. Separately, 392 g of methyl methacrylate was placed in a 1-liter container, and 8 g of ethylene glycol dimethacrylate and 2 g of azobisisobutyronitrile were added and mixed and dissolved. This monomer composition was put into the aqueous medium stirred in the 2 liter container and mixed, and then subjected to a fine dispersion treatment under high-speed shearing using a homomixer. A suspension that was 7 μm was obtained. The viscosity of this suspension was 0.6 Pa · s.
【００２７】懸濁液を、翼径が８５ｍｍ、翼幅が９０ｍ
ｍ、後退している部分の長さが１５ｍｍ、後退角度が１
３５度である下段の攪拌翼と、翼径が７５ｍｍ、翼幅が
９０ｍｍである上段の攪拌翼とを備え、上段と下段の攪
拌翼の間隔が８ｍｍ、上段と下段の攪拌翼の交差角が４
５度であるパドル型攪拌機を有するジャケット付きの２
リットルステンレス製オートクレーブ（直径１０５ｍ
ｍ、最深部の深さ２６０ｍｍ）に入れて、攪拌数１３５
ｒｐｍ（最下段の攪拌翼の先端周速度０．６０ｍ／ｓ）
で攪拌しながら、７０℃まで昇温し、５時間保持して重
合を行った。得られた分散液を濾過し、洗浄し、脱水
し、乾燥して樹脂微粒子を得た。得られた樹脂微粒子
は、重量平均粒子径が７．０μｍであり、２０μｍを超
えるような粗大粒子や凝集粒子は見られなかった。The suspension was prepared with a blade diameter of 85 mm and a blade width of 90 m.
m, the length of the receding part is 15 mm, and the receding angle is 1
Equipped with a lower stirring blade of 35 degrees and an upper stirring blade having a blade diameter of 75 mm and a blade width of 90 mm, the interval between the upper and lower stirring blades is 8 mm, and the intersection angle of the upper and lower stirring blades is 4
Jacketed 2 with 5 degree paddle stirrer
Liter stainless steel autoclave (105m in diameter)
m, the depth of the deepest part is 260 mm) and the stirring number is 135
rpm (Circumferential velocity of the tip of the lowermost stirring blade is 0.60 m / s)
While stirring at, the temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to carry out polymerization. The obtained dispersion was filtered, washed, dehydrated and dried to obtain fine resin particles. The obtained resin fine particles had a weight average particle diameter of 7.0 μm, and no coarse particles or aggregated particles exceeding 20 μm were found.
【００２８】実施例２ 第三リン酸カルシウムの使用量を３６ｇに代え、微分散
処理をマイクロフルイダイザー（みずほ工業社製）を圧
力６００ｋｇ／ｃｍ2で用いて液滴相互の衝突や器壁へ
の衝突力を利用した高圧型分散機にて行うことに代えた
以外は、実施例１と同様にして樹脂微粒子を製造した。
このときの懸濁液の粘度は、１．２Ｐａ・ｓであった。
得られた樹脂微粒子は、重量平均粒子径が３．９μｍで
あり、２０μｍを超えるような粗大粒子や凝集粒子は見
られなかった。Example 2 The amount of tribasic calcium phosphate used was changed to 36 g, and the microdispersion was performed using a microfluidizer (manufactured by Mizuho Industry Co., Ltd.) at a pressure of 600 kg / cm 2 , so that the droplets collided with each other and collided with the vessel wall. Resin fine particles were produced in the same manner as in Example 1 except that the process was performed using a high-pressure type dispersing machine utilizing force.
At this time, the viscosity of the suspension was 1.2 Pa · s.
The obtained resin fine particles had a weight average particle size of 3.9 μm, and no coarse particles or aggregated particles exceeding 20 μm were found.
【００２９】実施例３ ２リットルのオートクレーブの重合時の攪拌数を３００
ｒｐｍ（下段の攪拌翼の先端周速度１．３３５ｍ／ｓ）
に代えた以外は、実施例１と同様にして樹脂微粒子を製
造した。得られた樹脂微粒子は、重量平均粒子径が７．
１μｍであり、２０μｍを超えるような粗大粒子や凝集
粒子は見られなかった。Example 3 The number of agitation during polymerization in a 2 liter autoclave was 300
rpm (peripheral speed of the tip of the lower stirring blade 1.335 m / s)
The resin fine particles were produced in the same manner as in Example 1 except that the above procedure was replaced with The obtained resin fine particles have a weight average particle diameter of 7.
It was 1 μm, and no coarse particles or aggregated particles exceeding 20 μm were found.
【００３０】実施例４ 翼径が９０ｍｍ、翼幅が６０ｍｍ、後退している部分の
長さが１５ｍｍ、後退角度が１３５度である下段の攪拌
翼と、翼径が８０ｍｍ、翼幅が６０ｍｍである中段の攪
拌翼と、翼径が７０ｍｍ、翼幅が６０ｍｍである上段攪
拌翼とを備え、下段と中段、および中段と上段の攪拌翼
の間隔がそれぞれ６ｍｍであり、下段と中段、および中
段と上段の攪拌翼の交差角がそれぞれ４５度であるパド
ル型攪拌翼を有する攪拌装置を使用する以外は、実施例
１と同様にして樹脂微粒子を製造した。得られた樹脂微
粒子は、重量平均粒子径が７．６μｍであり、２０μｍ
を超えるような粗大粒子や凝集粒子は見られなかった。Example 4 A lower stirring blade having a blade diameter of 90 mm, a blade width of 60 mm, a length of a receding portion of 15 mm, and a receding angle of 135 degrees, a blade diameter of 80 mm, a blade width of 60 mm A certain middle-stage stirring blade and an upper-stage stirring blade having a blade diameter of 70 mm and a blade width of 60 mm are provided. The lower-stage and middle-stage, and the intervals of the middle-stage and upper-stage stirring blades are each 6 mm, and the lower-stage, middle-stage, and middle-stage. Resin fine particles were produced in the same manner as in Example 1, except that a stirrer having a paddle-type stirring blade having a crossing angle of 45 ° between the and the upper stirring blades was used. The obtained resin fine particles had a weight average particle size of 7.6 μm and a particle size of 20 μm.
No coarse particles or aggregated particles exceeding 0.1% were found.
【００３１】比較例１ パドル型攪拌翼を１段のいかり型翼（水平翼径６５ｍ
ｍ、翼幅２０ｍｍ）に代えた以外は、実施例１と同様に
して樹脂微粒子を製造した。得られた樹脂微粒子の結果
を表１に示す。 比較例２ パドル型攪拌翼を１段（翼径８５ｍｍ、翼幅２００ｍ
ｍ）に代えた以外は、実施例１と同様にして樹脂微粒子
を製造した。得られた樹脂微粒子の結果を表１に示す。COMPARATIVE EXAMPLE 1 A paddle-type stirring blade was replaced with a single-stage sword blade (horizontal blade diameter: 65 m).
m, blade width 20 mm), except that resin fine particles were produced in the same manner as in Example 1. Table 1 shows the results of the obtained resin fine particles. Comparative Example 2 One stage of paddle type stirring blade (blade diameter 85 mm, blade width 200 m)
Except for changing to m), resin fine particles were produced in the same manner as in Example 1. Table 1 shows the results of the obtained resin fine particles.
【００３２】比較例３ 難水溶性の第三リン酸カルシウムの代わりにＰＶＡ（日
本合成化学社製、商品名：ゴーセノールＧＨ−２３）２
４ｇを用いる以外は、実施例１と同様にして樹脂微粒子
を製造した。得られた樹脂微粒子の結果を表１に示す。 比較例４ 難水溶性の第三リン酸カルシウムを用いず、ラウリル硫
酸ナトリウムの量を９．６ｇに変更した以外は、実施例
１と同様にして樹脂微粒子を製造した。得られた樹脂微
粒子の結果を表１に示す。 比較例５ 下段の攪拌翼を後退している部分を有さないものに代え
た以外は、実施例１と同様にして樹脂微粒子を製造し
た。得られた樹脂微粒子の結果を表１に示す。Comparative Example 3 PVA (trade name: Gohsenol GH-23, manufactured by Nippon Synthetic Chemical Co., Ltd.) 2 in place of poorly water-soluble tribasic calcium phosphate
Except for using 4 g, resin fine particles were produced in the same manner as in Example 1. Table 1 shows the results of the obtained resin fine particles. Comparative Example 4 Resin fine particles were produced in the same manner as in Example 1 except that the sparingly water-soluble tribasic calcium phosphate was not used and the amount of sodium lauryl sulfate was changed to 9.6 g. Table 1 shows the results of the obtained resin fine particles. Comparative Example 5 Resin fine particles were produced in the same manner as in Example 1, except that the lower stirring blade was replaced with one having no recessed portion. Table 1 shows the results of the obtained resin fine particles.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明の方法によれば、所望の粒子径、
粒度分布に調製された単量体液滴を懸濁重合して樹脂微
粒子を製造するにあたり、その重合条件に一部限定を加
えるという簡易な手段で、合一による樹脂粒子の粗大化
や凝集化を著しく低減することができる。したがって、
本発明の方法によって得られる樹脂微粒子には、粗大粒
子や凝集粒子がほとんど含まれないので、重合後のそれ
らの除去が不要である。これにより、煩雑な後処理工程
にかかる手間や時間を減じ、コストを低く抑えることが
できる。According to the method of the present invention, the desired particle size,
In producing resin fine particles by suspension polymerization of monomer droplets prepared in a particle size distribution, coarsening and agglomeration of resin particles due to coalescence can be achieved by simple means of partially limiting the polymerization conditions. It can be significantly reduced. Therefore,
Since the resin fine particles obtained by the method of the present invention hardly contain coarse particles or aggregated particles, it is not necessary to remove them after polymerization. As a result, the labor and time required for complicated post-processing steps can be reduced, and the cost can be kept low.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の方法に用いられる攪拌装置を正面から
見た断面図である。FIG. 1 is a sectional view of a stirring device used in the method of the present invention as viewed from the front.
【図２】本発明の方法に用いられる攪拌装置を上から見
た図である。FIG. 2 is a top view of a stirring device used in the method of the present invention.
Ｄ 攪拌槽内径 ｄ１ 下段の攪拌翼の翼径 ｄ２ 上段の攪拌翼の翼径 ｈ１ 下段の攪拌翼の翼幅 ｈ２ 上段の攪拌翼の翼幅 θ１ 上段と下段の攪拌翼の交差角度 θ２ 下段の攪拌翼と後退している部分との角度 D Stirring tank inner diameter d1 Blade diameter of lower stirring blade d2 Blade diameter of upper stirring blade h1 Blade width of lower stirring blade h2 Blade width of upper stirring blade θ1 Intersection angle of upper and lower stirring blades θ2 Lower stirring Angle between wing and receding part
Claims (3)
（メタ）アクリル酸エステル系単量体またはスチレン系
単量体を分散してなり、０．１〜２．０Ｐａ・ｓの粘度
を有する懸濁液を、 重合開始剤の存在下で、略円筒状の攪拌槽と、 該攪拌槽の中心部に垂設された回転軸に垂直に保持され
た複数の攪拌翼を前記回転軸の高さ方向に上下２段以上
に装着されてなり、最下段の攪拌翼の外端部が回転方向
に対して後退しているパドル型攪拌翼とを有する攪拌装
置により攪拌しながら加熱して重合することを特徴とす
る樹脂微粒子の製造方法。1. A (meth) acrylate monomer or a styrene monomer dispersed in an aqueous medium containing an inorganic suspension stabilizer, and has a viscosity of 0.1 to 2.0 Pa · s. In the presence of a polymerization initiator, a suspension having a substantially cylindrical stirring tank, and a plurality of stirring blades held vertically to a rotation axis vertically provided at the center of the stirring tank, Heated while being stirred by a stirrer having a paddle type stirring blade which is mounted in two or more stages in the height direction of the upper and lower stages, and the outer end of the lowermost stirring blade is retreated in the rotation direction. A method for producing resin fine particles, comprising polymerizing.
２．０ｍ／ｓである請求項１に記載の樹脂微粒子の製造
方法。2. The peripheral speed of the tip of the lowermost stirring blade is 0.1 to
The method for producing resin fine particles according to claim 1, wherein the flow rate is 2.0 m / s.
造される樹脂微粒子。3. Fine resin particles produced by the method according to claim 1.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009084401A (en) * | 2007-09-28 | 2009-04-23 | Sekisui Plastics Co Ltd | Method for manufacturing monodispersed resin particles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02147602A (en) * | 1988-11-30 | 1990-06-06 | Mita Ind Co Ltd | Polymerization |
| JPH05178915A (en) * | 1992-01-07 | 1993-07-20 | Asahi Chem Ind Co Ltd | Suspension polymerization method |
| JPH0616708A (en) * | 1992-04-28 | 1994-01-25 | Sumitomo Dow Ltd | Production of polymer latex |
| JPH06287203A (en) * | 1993-03-31 | 1994-10-11 | Nippon Zeon Co Ltd | Production of vinyl chloride resin |
| JPH07278210A (en) * | 1994-04-05 | 1995-10-24 | Mitsui Toatsu Chem Inc | Production of emulsion |
| JPH09132607A (en) * | 1995-11-07 | 1997-05-20 | Sekisui Plastics Co Ltd | Production of styrene resin particle for expansion, expandable styrene resin particle and its production |
-
2000
- 2000-12-27 JP JP2000397539A patent/JP3739280B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02147602A (en) * | 1988-11-30 | 1990-06-06 | Mita Ind Co Ltd | Polymerization |
| JPH05178915A (en) * | 1992-01-07 | 1993-07-20 | Asahi Chem Ind Co Ltd | Suspension polymerization method |
| JPH0616708A (en) * | 1992-04-28 | 1994-01-25 | Sumitomo Dow Ltd | Production of polymer latex |
| JPH06287203A (en) * | 1993-03-31 | 1994-10-11 | Nippon Zeon Co Ltd | Production of vinyl chloride resin |
| JPH07278210A (en) * | 1994-04-05 | 1995-10-24 | Mitsui Toatsu Chem Inc | Production of emulsion |
| JPH09132607A (en) * | 1995-11-07 | 1997-05-20 | Sekisui Plastics Co Ltd | Production of styrene resin particle for expansion, expandable styrene resin particle and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009084401A (en) * | 2007-09-28 | 2009-04-23 | Sekisui Plastics Co Ltd | Method for manufacturing monodispersed resin particles |
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