JP5021903B2 - Microcapsule and semi-continuous production apparatus for fine particles, and particle adhesion prevention method using floating stirrer in stirring reaction tank of semi-continuous production apparatus - Google Patents
Microcapsule and semi-continuous production apparatus for fine particles, and particle adhesion prevention method using floating stirrer in stirring reaction tank of semi-continuous production apparatus Download PDFInfo
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本発明は、エマルション送入管および洗浄水送入管を備え、これらのバルブ開閉を系統的に行うことによるマイクロカプセルまたは微粒子の半連続製造装置において、反応槽内部および撹拌翼に対する粒子付着防止に関するものである。 The present invention relates to the prevention of particle adhesion to the inside of a reaction vessel and a stirring blade in a microcapsule or fine particle semi-continuous manufacturing apparatus provided with an emulsion feeding pipe and a washing water feeding pipe and systematically opening and closing these valves. Is.
特許文献１に記載のものでは、重合反応装置の連続操作は塊状重合、乳化重合やスラリー重合において実施されているが、懸濁重合ではポリマー粒子の付着が大きな障害となっており、実用化に問題がある。 In the method described in Patent Document 1, continuous operation of the polymerization reaction apparatus is carried out in bulk polymerization, emulsion polymerization or slurry polymerization. However, in suspension polymerization, the adhesion of polymer particles is a major obstacle, making it practical. There's a problem.
また、特許文献２にはポリマー等の付着に関して、回分式重合操作においてもその原料投入法の工夫でできるだけ反応器壁等への付着を防ぐ方法が提案されている。また、塊状重合反応装置においても、気相部での冷却凝縮液（モノマー）による反応器壁面等への洗浄を取り入れる方法が提案されている。しかし、気相部のモノマーを冷却凝集させる際に、モノマーがポリマー化し、ポリマーの付着が起こる可能性がある。 Further, Patent Document 2 proposes a method for preventing adhesion of a polymer or the like to a reactor wall or the like as much as possible by devising a raw material charging method even in a batch polymerization operation. Also in the bulk polymerization reaction apparatus, a method has been proposed in which washing of the reactor wall surface or the like with a cooling condensate (monomer) in the gas phase portion is performed. However, when the monomer in the gas phase is cooled and aggregated, the monomer may be polymerized and the polymer may be attached.
懸濁重合法における高分子微粒子の連続製造法（特許文献３）は、撹拌翼（機）を用いないという面で特徴があるが、粒子付着により生産効率が悪く実用性に乏しい。 The continuous production method of polymer fine particles in the suspension polymerization method (Patent Document 3) is characterized in that a stirring blade (machine) is not used, but the production efficiency is low due to particle adhesion, and the practicality is poor.
撹拌反応槽での懸濁重合においてはポリマー粒子の付着は避け難く回分操作を実施し、重合終了後器内を洗浄するのが通例である。したがって、１バッチごとに原料の調製、仕込量の調整、運搬・仕込み作業、温度設定、撹拌条件の設定、調製物の反応槽からの取出し、製品の運搬作業等といった多くの操作を行わなければならないという問題があった。 In suspension polymerization in a stirred reaction tank, it is difficult to avoid adhesion of polymer particles, and batch operation is generally performed, and the inside of the vessel is washed after completion of polymerization. Therefore, many operations such as raw material preparation, batch adjustment, transportation / preparation work, temperature setting, stirring condition setting, removal of the preparation from the reaction tank, product transportation work, etc. must be performed for each batch. There was a problem of not becoming.
本発明の課題は、撹拌反応槽を用いて、反応を繰り返し行う回分操作と反応液を連続的に送入する連続操作を組み合わせた微粒子またはマイクロカプセルを半連続的に製造する操作法において、生成したポリマー微粒子が反応槽内壁に付着することなく、多量に製造できる操作法を提供することを目的とする。 An object of the present invention is to produce a semi-continuous microparticle or microcapsule produced by combining a batch operation in which a reaction is repeated using a stirred reaction tank and a continuous operation in which a reaction solution is continuously fed. An object of the present invention is to provide an operation method in which a large amount of polymer fine particles can be produced without adhering to the inner wall of the reaction vessel.
本発明は、特に「マイクロカプセルまたは微粒子の半連続製造装置」（特開２００３−１９０７６６）によって提供されるマイクロカプセル半連続製造装置において、振動反応器の代わりに撹拌反応槽を採用し、しかも撹拌反応槽内で複数個の自由に移動できる浮遊型撹拌子を動かすことで、マイクロカプセルおよび微粒子の反応槽内壁や撹拌翼への付着を防ぎ、安定的に装置を操作する方法および装置に関するものである。 The present invention is a microcapsule semi-continuous manufacturing apparatus provided by a “microcapsule or fine particle semi-continuous manufacturing apparatus” (Japanese Patent Application Laid-Open No. 2003-190766). It relates to a method and apparatus for stably operating the apparatus by preventing the microcapsules and fine particles from adhering to the inner wall of the reaction tank and the stirring blade by moving a plurality of freely floating floating stirring elements in the reaction tank. is there.
すなわち、第１の発明は、連続エマルション送入装置、エマルション送入本管、槽内で自由に移動できる浮遊型撹拌子を持つ１つまたは２つ以上からなる撹拌反応槽、複数の二方もしくは三方バルブ、洗浄液送入管からなる半連続製造装置において、前記撹拌反応槽内部に球状、直方体状あるいは不定形の金属、プラスチックおよび木片からなる浮遊型撹拌子を２種類以上の組合せで使用し、前記撹拌反応槽内で自由に移動可能な前記浮遊型撹拌子を動かすことにより、製造されるマイクロカプセルまたは微粒子の反応槽内壁および撹拌翼に対する粒子付着を防止するようにしたことを特徴とする。 That is, the first invention includes a continuous emulsion feeding apparatus, an emulsion feeding main, a stirring reaction tank composed of one or two or more floating floating stirrers that can move freely in the tank, a plurality of two-way or In a semi-continuous manufacturing apparatus consisting of a three-way valve and a cleaning liquid feed pipe, a floating stirrer made of spherical, rectangular parallelepiped or amorphous metal, plastic and wood pieces is used in a combination of two or more in the stirring reaction tank. By moving the floating stirrer that is freely movable in the stirring reaction vessel, the microcapsules or fine particles to be produced are prevented from adhering to the inner wall of the reaction vessel and the stirring blade.
また、本発明の撹拌反応槽における粒子付着防止方法において、密度0.3〜1.5 g/cm3を持つ前記浮遊型撹拌子を用いることを特徴とする。 In the particle adhesion preventing method in the stirring reaction tank of the present invention, the floating stirring bar having a density of 0.3 to 1.5 g / cm 3 is used.
また、本発明の撹拌反応槽における粒子付着防止方法において、直径0.3〜5cmもしくは撹拌翼径の1/50〜1/3の大きさの浮遊型撹拌子を用いることを特徴とする。 In the method for preventing particle adhesion in the stirring reaction tank of the present invention, a floating stirrer having a diameter of 0.3 to 5 cm or 1/50 to 1/3 of the stirring blade diameter is used.
また、本発明の撹拌反応槽における粒子付着防止方法において、前記半連続製造装置におけるぜ撹拌反応槽の撹拌速度を10〜800rpmで操作することを特徴とする。 Moreover, in the particle adhesion prevention method in the stirring reaction tank of the present invention, the stirring speed of the peripheral stirring reaction tank in the semi-continuous manufacturing apparatus is operated at 10 to 800 rpm.
また、本発明による半連続製造装置は、連続エマルション送入装置、エマルション送入本管、槽内で自由に移動できる球状、直方体状あるいは不定形の金属、プラスチックおよび木片からなる２種類以上の組合せの浮遊型撹拌子を持つ１つまたは２つ以上からなる撹拌反応槽、複数の二方もしくは三方バルブおよび洗浄液送入管からなることを特徴とする。 Moreover, the semi-continuous manufacturing apparatus according to the present invention includes a continuous emulsion feeding apparatus, an emulsion feeding main pipe, a combination of two or more kinds of spherical, rectangular parallelepiped or amorphous metal, plastic and wood pieces that can freely move in a tank. It is characterized by comprising one or two or more stirring reaction tanks having a floating stirrer, a plurality of two-way or three-way valves, and a cleaning liquid feed pipe.
以上説明したように本発明により、連続エマルション送入装置、エマルション送入本管、槽内で自由に移動できる浮遊型撹拌子を持つ１つまたは２つ以上からなる撹拌反応槽、複数の二方もしくは三方バルブ、洗浄液送入管からなる半連続製造装置を用いることで、生成したマイクロカプセルおよび微粒子が反応槽内壁および撹拌翼に粒子付着が防止することができた。 As described above, according to the present invention, a continuous emulsion feeding apparatus, an emulsion feeding main pipe, a stirring reaction tank composed of one or more with a floating stirrer that can freely move in a tank, a plurality of two-way Alternatively, by using a semi-continuous manufacturing apparatus comprising a three-way valve and a cleaning liquid feeding pipe, the produced microcapsules and fine particles could be prevented from adhering to the reaction vessel inner wall and the stirring blade.
浮遊型撹拌子を使用すれば、マイクロカプセルおよび微粒子の付着を防ぐことができるために、この方法を採用した撹拌反応槽で構成された半連続的マイクロカプセル製造装置は格段に優れた長期運転性を示すことができる。したがって、回分操作を連続的に実施する本発明の半連続操作において浮遊型撹拌子を用いない従来法であれば、２回程度の回分操作終了後に、反応槽内壁の付着マイクロカプセルおよび微粒子の除去作業を行う必要性があったが、少なくとも２０回程度の回分操作を連続的に行えるようになる。 Because the use of a floating stirrer can prevent the adhesion of microcapsules and fine particles, the semi-continuous microcapsule production equipment composed of a stirred reaction tank using this method has a much superior long-term operability. Can be shown. Therefore, in the semi-continuous operation of the present invention in which the batch operation is continuously performed, if the conventional method does not use a floating stirrer, the microcapsules and fine particles removed from the inner wall of the reaction vessel are removed after the batch operation is completed twice. Although there was a necessity to perform work, at least about 20 batch operations can be continuously performed.
以下、本発明に従いマイクロカプセルおよび微粒子の半連続製造装置の撹拌反応槽に浮遊型撹拌子を利用する粒子付着防止方法に関する各工程に関する本発明の実施の形態について説明する。 Embodiments of the present invention relating to each step relating to a particle adhesion preventing method using a floating stirrer in a stirring reaction tank of a semi-continuous production apparatus for microcapsules and fine particles according to the present invention will be described below.
本発明の半連続プロセス工程は、撹拌反応槽（もしくは反応器）R1〜Rnと、三方バルブ（M1〜Mn,E1〜En,W1〜Wn、O1〜On,V1〜Vn）と、連続エマルション送入装置Eと、洗浄液送入装置Wと、エマルション送入管ETと、洗浄液送入管WTとから構成される装置において行われる（図１）。 The semi-continuous process steps of the present invention consist of a stirred reaction vessel (or reactor) R1-Rn, a three-way valve (M1-Mn, E1-En, W1-Wn, O1-On, V1-Vn), and a continuous emulsion feed. This is performed in an apparatus including an inlet device E, a cleaning liquid inlet device W, an emulsion inlet pipe ET, and a cleaning liquid inlet pipe WT (FIG. 1).
図２に示した撹拌反応槽の容積500mlのｎ基を、図１に示すように並列に連結する。撹拌反応槽ｎは、1<n<10であればよい。撹拌反応槽内部に球状、直方体状あるいは不定形の金属、プラスチックおよび木片からなる浮遊型撹拌子を入れる。引き続き、反応液を導入する。反応液は、スチレンモノマー、ジビニルベンゼン、トリメチロールプロパントリメタクリレート、アクリル酸等の反応性モノマー(20〜80wt%)、縮合ヘキサリシノレインサン酸ヘキサングリセリン、ソルビタンモノオレート等の油溶性界面活性剤(0.5〜3wt%)、アゾビスバレロニトリル等の油溶性重合開始剤（0.1〜2wt%）、酢酸エチル、ヘキサン、デカン、ドレカン、ノナン、トルエン、ベンゼン、キシレン等の希釈有機溶媒（0.5〜40wt%）からなる有機相（O）と蒸留水(50〜99wt%)、ポリビニルアルコール、ポリビニルピロリドン等の分散安定剤（0.1〜30wt%）の水溶液水溶液（W）からなる。Oの分散相体積分率0.05〜0.5のO／Wエマルションを送入する。エマルションを反応槽へ送入後、流路内に残留したエマルションの固化を防止するため、流通内に残留しているエマルションを洗浄水で置換する。 The n groups having a volume of 500 ml in the stirred reaction tank shown in FIG. 2 are connected in parallel as shown in FIG. The stirring reaction tank n may be 1 <n <10. A floating stirrer made of spherical, rectangular parallelepiped or amorphous metal, plastic and wood pieces is placed in the stirring reaction vessel. Subsequently, the reaction solution is introduced. The reaction solution is a reactive monomer (20 to 80 wt%) such as styrene monomer, divinylbenzene, trimethylolpropane trimethacrylate, acrylic acid, an oil-soluble surfactant (0.5 mg condensed hexaricinoleic acid hexane glycerin, sorbitan monooleate, etc. ~ 3wt%), oil-soluble polymerization initiators such as azobisvaleronitrile (0.1-2wt%), diluted organic solvents such as ethyl acetate, hexane, decane, dodecane, nonane, toluene, benzene, xylene (0.5-40wt%) And an aqueous solution (W) of a dispersion stabilizer (0.1-30 wt%) such as distilled water (50-99 wt%), polyvinyl alcohol, polyvinyl pyrrolidone and the like. An O / W emulsion having an O dispersed phase volume fraction of 0.05 to 0.5 is fed. After feeding the emulsion into the reaction vessel, the emulsion remaining in the flow is replaced with washing water in order to prevent the emulsion remaining in the flow path from solidifying.
エマルションを撹拌反応槽に満たしながら、10〜800ｒｐｍで撹拌を開始し、マイクロカプセルおよび微粒子の付着を防止するために浮遊型撹拌子を浮遊させ、反応槽内における反応を進行させる。 While filling the emulsion into the stirring reaction tank, stirring is started at 10 to 800 rpm, the floating stirrer is suspended to prevent the microcapsules and fine particles from adhering, and the reaction in the reaction tank proceeds.
使用する浮遊型撹拌子の密度は0.3〜1.5g/cm3である。また、浮遊型撹拌子の大きさは0.3〜5cmもしくは撹拌翼径の1/50〜1/3である。浮遊型撹拌子の材質は、木や竹等の木質素材、ポリスチレン、ポリアクリロニトリル、ポリメチルメタクリレート、ポリカーボネート、テフロン（登録商標）、ポリエチレン、ポリプロピレン、ポリ塩化ビニール、ポリエチレンテレフタレート等のプラスチック、ステンレス、銅、真鍮、アルミニウム、チタン等である。１種類または２種類以上を組み合わせてもよい。 The density of the floating stirrer used is 0.3 to 1.5 g / cm 3 . The size of the floating type stirring bar is 0.3 to 5 cm or 1/50 to 1/3 of the stirring blade diameter. The material of the floating stirrer is woody material such as wood or bamboo, polystyrene, polyacrylonitrile, polymethyl methacrylate, polycarbonate, Teflon (registered trademark), polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, plastic, stainless steel, copper Brass, aluminum, titanium and the like. One type or two or more types may be combined.
必要な数(n)の反応器（R1〜Rn）を並列に連結される。この系列に乳化器Eに連結されたエマルション送入本管ETおよび洗浄水源に連結された洗浄水送入本管WTを並列に配管する。エマルション送入本管ETにはバルブE1〜Enを取り付け、経路RTで各反応器へ連結される。経路RTにはそれぞれバルブM1〜Mnが取り付けられる。また、洗浄液送入管WTにはバルブW1〜Wnを取り付け、それぞれ経路を経てバルブM1〜Mnへ連結される。洗浄液送入管WTは製品排出経路がバルブO1〜Onで連結される。 The required number (n) of reactors (R1 to Rn) are connected in parallel. In this series, the emulsion feed main ET connected to the emulsifier E and the wash water feed main WT connected to the wash water source are connected in parallel. Valves E1 to En are attached to the emulsion delivery main pipe ET, and are connected to each reactor through a route RT. Valves M1 to Mn are attached to the path RT, respectively. Further, valves W1 to Wn are attached to the cleaning liquid inlet pipe WT, and are connected to the valves M1 to Mn through paths. The product discharge path of the cleaning liquid inlet pipe WT is connected by valves O1 to On.
撹拌反応槽５基を例に操作説明をする。
（１）：連続エマルション送入装置EよりチューブTEを通って反応液（エマルション）をバルブE1→M1→反応器R1へ送入する。反応器R1に反応液が充満した後、
（２）：バルブE1を切り替え、反応液（エマルション）をバルブE2→M2→反応器R2へ送入する。
（３）：操作（２）と同時に、チューブTEを通して洗浄水ＷをバルブO1→W1→M1→反応器R1に送入して、反応器R1までの経路中の反応液を洗浄水置換した後、バルブM1を閉じる。
（４）：反応器R2に反応液が充満した後、反応液をバルブE3→M3→反応器R3へ送入する。
（５）：操作（４）と同時に、操作（３）と同様にして、バルブO2→W2→M2→反応器R2に洗浄水を送入して、反応器R2までの経路中の反応液を洗浄水で置換した後、バルブM2を閉じる。
（６）：操作（２）および（４）と同様に、反応器R3が反応液で満たされた後、反応液をバルブE4→M4→反応器R4へ送入する。
（７）：操作（６）と同時に、バルブO3→W3→M3→反応器R3に洗浄水を送入して、反応器R3までの経路中の反応液を洗浄水で置換した後、バルブM3を閉じる。
（８）：操作（２）および（４）と同様に、反応器R4が反応液で満たされた後、反応液をバルブE5→M5→反応器R5へ送入する。
（９）：操作（６）と同時に、バルブO4→W4→M4→反応器R4に洗浄水を送入して、反応器R4までの経路中の反応液を洗浄水で置換した後、バルブM4を閉じる。
（１０）：操作（６）と同時に、バルブO5→W5→M5→反応器R5に洗浄水を送入して、反応器R5までのチューブ中の反応液を洗浄水で置換した後、バルブM5を閉じる。
The operation will be described with an example of five stirred reaction vessels.
(1): The reaction liquid (emulsion) is sent from the continuous emulsion feeding device E through the tube TE to the valve E1 → M1 → reactor R1. After the reactor R1 is filled with the reaction solution,
(2): Switch the valve E1 and send the reaction liquid (emulsion) to the valve E2 → M2 → reactor R2.
(3): At the same time as the operation (2), after supplying the washing water W through the tube TE to the valve O1 → W1 → M1 → reactor R1, and replacing the reaction solution in the path to the reactor R1 with washing water Close valve M1.
(4): After the reactor R2 is filled with the reaction solution, the reaction solution is sent to the valve E3 → M3 → reactor R3.
(5): Simultaneously with operation (4), in the same manner as in operation (3), wash water is fed into valve O2 → W2 → M2 → reactor R2, and the reaction solution in the path to reactor R2 is removed. After replacing with washing water, close valve M2.
(6): Similarly to the operations (2) and (4), after the reactor R3 is filled with the reaction solution, the reaction solution is sent to the valve E4 → M4 → reactor R4.
(7): Simultaneously with the operation (6), flush water is fed into the valve O3 → W3 → M3 → reactor R3, and the reaction liquid in the path to the reactor R3 is replaced with wash water, and then the valve M3 Close.
(8): Similarly to the operations (2) and (4), after the reactor R4 is filled with the reaction solution, the reaction solution is sent to the valve E5 → M5 → reactor R5.
(9): Simultaneously with the operation (6), wash water is fed into the valve O4 → W4 → M4 → reactor R4, and the reaction solution in the path to the reactor R4 is replaced with wash water, and then the valve M4 Close.
(10): Simultaneously with the operation (6), wash water is supplied to the valve O5 → W5 → M5 → reactor R5, and the reaction solution in the tube up to the reactor R5 is replaced with wash water, and then the valve M5 Close.
この時点で撹拌反応槽にはすべて反応液が満たされ、撹拌を続けながら重合（または液中乾燥）によって粒子が調製される。反応器R1に反応液が満たされた後、マイクロカプセルおよび微粒子が形成される所定時間経過した後、反応器R1では完全なマイクロカプセルおよび微粒子が形成される。形成されたマイクロカプセルおよび微粒子を含む溶液を、バルブM1→W1→O1で系外へ排出する。 At this point, all of the stirred reaction tank is filled with the reaction solution, and particles are prepared by polymerization (or drying in the solution) while continuing stirring. After the reaction liquid is filled in the reactor R1, a predetermined time after the formation of microcapsules and fine particles has elapsed, and in the reactor R1, complete microcapsules and fine particles are formed. The solution containing the formed microcapsules and microparticles is discharged out of the system through the valve M1 → W1 → O1.
以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれに何ら限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
本発明装置を図３に示す。本図においてR1からR6で示した撹拌反応槽は内径75m、外径105mm、槽高150mm（内容積約500ml）の二重管構造円筒形ガラスである。円筒外側には温水を流し、内管の温度を調節した。反応槽上部には内径75mm、中管内径24mm、側管内径15mmのガラス製四つ口セパラブルカバーを設置した。撹拌翼には長さ180mm、直径8mmのステンレス製の棒にステンレス製のプロペラ型の撹拌翼を使用した。浮遊型撹拌子として直径10.6mm（密度0.42g/cm3）のプラスチックボール５個および10mm×10mm×7mm（密度1.23g/cm3）の木片５個を使用した。これらはあらかじめ撹拌反応槽に投入しておいた。 The device of the present invention is shown in FIG. In this figure, the stirring reaction tanks indicated by R1 to R6 are double-pipe structure cylindrical glass having an inner diameter of 75 m, an outer diameter of 105 mm, and a tank height of 150 mm (inner volume of about 500 ml). Hot water was allowed to flow outside the cylinder to adjust the temperature of the inner tube. A glass four-neck separable cover having an inner diameter of 75 mm, a middle tube inner diameter of 24 mm, and a side tube inner diameter of 15 mm was installed in the upper part of the reaction tank. As the stirring blade, a stainless steel propeller-type stirring blade was used on a stainless steel rod having a length of 180 mm and a diameter of 8 mm. Five floating plastic balls with a diameter of 10.6 mm (density 0.42 g / cm 3 ) and five pieces of wood 10 mm × 10 mm × 7 mm (density 1.23 g / cm 3 ) were used. These were previously put into a stirred reaction tank.
マイクロカプセル調製に関して、有機相には反応性モノマーとしてスチレンモノマーやジビニルベンゼン（カプセル壁材）、界面活性剤として縮合リシノレインサン酸ヘキサングリセリン、重合開始剤として2,2-アゾビス（4-メトキシ-2,4-ジメチルバレロニトリル）を希釈剤（酢酸エチル、トルエン、イソオクタン）に溶解した有機溶液を用いた。外水相には蒸留水に分散安定剤であるポリビニルアルコールを溶解した水溶液を用いた。試薬精製に関して、スチレンモノマーとジビニルベンゼンは、in situ重合に先立ち分液漏斗を用いて10wt%の水酸化ナトリウム水溶液と３回接触洗浄することにより重合禁止剤を除去した。さらに、処理した有機相と同体積の蒸留水を用いて同様の操作を３回繰り返した後、水相がpH７になったのを確認してからシリカゲルを加え脱水した。その後、スチレンモノマー及びジビニルベンゼンは冷蔵保存した。 Regarding the preparation of microcapsules, the organic phase contains styrene monomer and divinylbenzene (capsule wall material) as reactive monomers, condensed ricinoleic acid hexane glycerin as a surfactant, and 2,2-azobis (4-methoxy-2 as a polymerization initiator) , 4-dimethylvaleronitrile) was used in an organic solution in a diluent (ethyl acetate, toluene, isooctane). As the outer aqueous phase, an aqueous solution in which polyvinyl alcohol as a dispersion stabilizer was dissolved in distilled water was used. Regarding the reagent purification, the polymerization inhibitor was removed from the styrene monomer and divinylbenzene by contact washing with a 10 wt% aqueous sodium hydroxide solution three times using a separatory funnel prior to in situ polymerization. Further, the same operation was repeated three times using distilled water having the same volume as the treated organic phase, and after confirming that the aqueous phase had reached pH 7, silica gel was added for dehydration. Thereafter, the styrene monomer and divinylbenzene were stored refrigerated.
調製した有機相及び外水相溶液を、それぞれ送液ポンプを用いて所定の流量で振動乳化器へ導入し（O／W）エマルションを調製した。エマルションが定常状態に達した後、（O／W）エマルションを[E]⇒[ML1]⇒[E1]⇒[M1]⇒[R1]の順に流して、反応器へ導入した。 The prepared organic phase and outer aqueous phase solution were each introduced into a vibration emulsifier (O / W) at a predetermined flow rate using a liquid feed pump to prepare an emulsion. After the emulsion reached a steady state, the (O / W) emulsion was flowed in the order of [E] ⇒ [ML1] ⇒ [E1] ⇒ [M1] ⇒ [R1] and introduced into the reactor.
[R1]導入終了後、[M1]ラインを洗浄水で数分間洗浄し、また[E1]ラインも約５分間洗浄すると同時に（O／W）エマルションを[E]⇒[ML1]⇒[ML2]⇒[E2]⇒[M2]⇒[R2]の順に送り反応器へ導入した。 [R1] After the introduction, the [M1] line is washed with washing water for several minutes, and the [E1] line is also washed for about 5 minutes (O / W). At the same time, the emulsion is [E] ⇒ [ML1] ⇒ [ML2] => [E2] => [M2] => [R2].
[R2]導入終了後、[M2]ラインを洗浄水で約５分間洗浄し、また[E2]ラインも約５分間洗浄すると同時に（O／W）エマルションを[E]⇒[ML1]⇒[ML2]⇒[ML3]⇒[E3]⇒[M3]⇒[R3]の順に送り反応器へ導入した。 [R2] After the introduction, the [M2] line is washed with washing water for about 5 minutes, and the [E2] line is also washed for about 5 minutes (O / W). At the same time, the emulsion is [E] ⇒ [ML1] ⇒ [ML2 ] ⇒ [ML3] ⇒ [E3] ⇒ [M3] ⇒ [R3].
この操作を[R6]まで順次繰り返し行い、これを１サイクルとした。[R6]への（O／W）エマルション導入時点で[R1]は６時間の重合が終了しているため、スチレン微粒子は[R1]⇒[M1]⇒[E1]⇒[W1]を流通させ回収した。回収後、反応器内に蒸留水を導入し洗浄した。再び、[R1]へエマルションを導入すると同時に、[R2]からの微粒子の回収を行った。連続運転はこの操作を繰り返し行った。
図４に１０サイクル６０時間後の撹拌反応槽の写真を示す。
This operation was sequentially repeated until [R6], and this was defined as one cycle. Since [R1] has been polymerized for 6 hours when (O / W) emulsion is introduced into [R6], styrene fine particles are distributed as [R1] ⇒ [M1] ⇒ [E1] ⇒ [W1]. It was collected. After recovery, distilled water was introduced into the reactor and washed. Again, the emulsion was introduced into [R1], and at the same time, the fine particles from [R2] were collected. This operation was repeated for continuous operation.
FIG. 4 shows a photograph of the stirred reaction tank after 10 hours of 60 cycles.
in situ 重合によるスチレン骨格マイクロカプセル調製を表１〜３の条件で実施した。 Preparation of styrene skeleton microcapsules by in situ polymerization was performed under the conditions shown in Tables 1 to 3.
[比較例]
浮遊型撹拌子を使用しない以外は実施例と全く同じ条件で本発明装置を用い、運転を実施した。図５は、１サイクル６時間後の撹拌反応槽の写真を示す。
[Comparative example]
The operation was carried out using the apparatus of the present invention under exactly the same conditions as in the examples except that the floating type stirring bar was not used. FIG. 5 shows a photograph of the stirred reaction tank after 6 hours of one cycle.
R1〜Rn 撹拌反応槽（反応器）
M1〜Mn,E1〜En,W1〜Wn、O1〜On,V1〜Vn 三方バルブ
E 連続エマルション送入装置
W 洗浄液送入装置
ET エマルション送入管
WT 洗浄液送入管
R1 ~ Rn Stirred reaction tank (reactor)
M1-Mn, E1-En, W1-Wn, O1-On, V1-Vn 3-way valve
E Continuous emulsion feeding device
W Cleaning liquid feeding device
ET emulsion feed pipe
WT cleaning liquid feed pipe
Claims (5)
前記撹拌反応槽内部に球状、直方体状あるいは不定形の金属、プラスチックおよび木片からなる浮遊型撹拌子を２種類以上の組合せで使用し、
前記撹拌反応槽内で自由に移動可能な前記浮遊型撹拌子を動かすことにより、製造されるマイクロカプセルまたは微粒子の反応槽内壁および撹拌翼に対する粒子付着を防止するようにしたことを特徴とする撹拌反応槽における粒子付着防止方法。 From continuous emulsion feeding device, emulsion feeding main, one or more stirring reaction tanks with floating stirrer that can move freely in the tank, multiple two-way or three-way valves, cleaning liquid feeding pipe In the semi-continuous manufacturing equipment
A floating type stirring bar made of spherical, rectangular parallelepiped or amorphous metal, plastic and wood pieces is used in a combination of two or more in the stirring reaction tank,
Agitation characterized by preventing the microcapsules or fine particles to be produced from adhering to the inner wall of the reaction vessel and the stirring blade by moving the floating type stirring element that is freely movable in the stirring reaction vessel. A method for preventing particle adhesion in a reaction vessel.
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