JP3007792B2 - Method for producing fine polymer particles of uniform size - Google Patents
Method for producing fine polymer particles of uniform sizeInfo
- Publication number
- JP3007792B2 JP3007792B2 JP6110454A JP11045494A JP3007792B2 JP 3007792 B2 JP3007792 B2 JP 3007792B2 JP 6110454 A JP6110454 A JP 6110454A JP 11045494 A JP11045494 A JP 11045494A JP 3007792 B2 JP3007792 B2 JP 3007792B2
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- Prior art keywords
- suspension
- particles
- monomer
- particle size
- polymer particles
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】この発明は、大きさの揃った微細
な重合体粒子の製造方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 method for producing fine polymer particles having a uniform size.
【０００２】[0002]
【従来の技術】微細な重合体粒子は色々な方面で要求さ
れている。とくに、粒子の大きさが１〜１００μｍの範
囲内にある重合体粒子は、スペーサー、滑り性付与剤、
トナー、塗料のつや出し剤、機能性担体等として使用す
るに適しているので、この方面で広く要望されている。
ところが、この要望を満たすに適した粒子を提供するに
は困難があった。2. Description of the Related Art Fine polymer particles are required in various fields. In particular, polymer particles having a particle size in the range of 1 to 100 μm are a spacer, a slipperiness imparting agent,
Since it is suitable for use as a toner, a polishing agent for paint, a functional carrier, and the like, it is widely demanded in this field.
However, it has been difficult to provide particles suitable for satisfying this demand.
【０００３】例えば、微細な重合体粒子を作るには、乳
化重合法によって単量体を重合させればよいと誰しも考
える。ところが、乳化重合法によったのでは、粒子の大
きさが通常１μｍ以下の微細なものとなってしまい、１
μｍ以上の大きさの粒子を作ることが困難である。ま
た、これまでの懸濁重合法によっては粒子の大きさを揃
えることが困難である。すなわち、単量体を水性媒体中
に加え、これを普通の高速回転式撹拌機で撹拌して懸濁
液とすれば、単量体粒子の大きさを凡そ５〜１００μｍ
の範囲内のものにすることはできるが、粒子の大きさが
その範囲内に広く分布して、粒度分布が狭い範囲内に集
中したものとならない。[0003] For example, everyone thinks that in order to produce fine polymer particles, monomers may be polymerized by an emulsion polymerization method. However, when the emulsion polymerization method is used, the particle size is usually as fine as 1 μm or less, and
It is difficult to produce particles having a size of μm or more. Further, it is difficult to make the particle size uniform by the conventional suspension polymerization method. That is, if a monomer is added to an aqueous medium and this is stirred with a normal high-speed rotary stirrer to form a suspension, the size of the monomer particles is approximately 5 to 100 μm.
However, the particle size is widely distributed in the range, and the particle size distribution is not concentrated in a narrow range.
【０００４】高速回転式撹拌機としてはホモミキサーが
一般に使用された。ところが、ホモミキサーで懸濁液と
したのでは、懸濁がバッチ式で行われるために、槽内を
全く均一に撹拌して液体に剪断を与えることができず、
従って粒子の大きさが不均一になる。そのために、これ
までの懸濁重合法では得られる粒子の大きさがよく揃う
に至らなかった。[0004] A homomixer was generally used as a high-speed rotary stirrer. However, if the suspension is made with a homomixer, the suspension is performed in a batch system, so that the inside of the tank cannot be completely uniformly stirred and the liquid cannot be sheared.
Therefore, the size of the particles becomes uneven. For this reason, the size of the particles obtained by the conventional suspension polymerization method has not been sufficiently uniform.
【０００５】他方、乳化液、懸濁液等を作る装置とし
て、ナノマイザー、ハーモナイザー又はマイクロフルイ
ダイザー等の商品名で販売されている装置がある。この
装置は、懸濁している粒子を粉砕して微細化させること
を目的とするものである。この装置は、表面から裏面へ
２個の孔を貫通させた円板の表面上に、高い圧力の下に
ある液体を流して、２個の孔から液体を流出させ、２個
の液流を互いに衝突させてその衝撃によりその中に含ま
れている懸濁粒子を粉砕して微細化し、これによって大
きさの揃った微細粒子の懸濁液を作ることを原理として
いる。[0005] On the other hand, as devices for producing emulsions, suspensions and the like, there are devices sold under trade names such as nanomizer, harmonizer and microfluidizer. The purpose of this device is to pulverize suspended particles to make them finer. This device allows a liquid under high pressure to flow over a surface of a disk having two holes penetrating from the front to the back, causing the liquid to flow out of the two holes, and causing the two liquid streams to flow. The principle is to collide with each other and pulverize and break up the suspended particles contained therein by the impact, thereby producing a suspension of fine particles of uniform size.
【０００６】特開平４−１５６５５５号公報は、上記の
液流同士の衝突によって懸濁粒子を微細化して懸濁液を
作り、この懸濁液を懸濁重合させて静電現像用のトナー
を作る方法を開示している。この公報によれば、エチレ
ン系単量体と、この単量体に可溶な重合開始剤と、界面
活性剤と、分散安定剤とを水性媒体中に加え、撹拌して
平均粒子径が３０〜４０μｍの単量体油滴の一次懸濁液
を作り、この一次懸濁液をマイクロフルイダイザーに通
して、一次懸濁液を加圧下に複数の流れに分けて流し、
こうして得た液流同士を衝突させて単量体粒子をさらに
微細化して二次懸濁液を作り、その後二次懸濁液を懸濁
重合させて微細な重合体粒子を得ている。[0006] Japanese Patent Application Laid-Open No. 4-156555 discloses that a suspension is formed by making the suspended particles fine by collision of the liquid streams, and the suspension is subjected to suspension polymerization to prepare a toner for electrostatic development. It discloses how to make it. According to this publication, an ethylene-based monomer, a polymerization initiator soluble in this monomer, a surfactant, and a dispersion stabilizer are added to an aqueous medium, and the mixture is stirred to have an average particle diameter of 30. Make a primary suspension of ４０40 μm monomer oil droplets, pass this primary suspension through a microfluidizer, and divide the primary suspension into multiple streams under pressure,
The liquid streams thus obtained are made to collide with each other to further refine the monomer particles to form a secondary suspension, and then the secondary suspension is subjected to suspension polymerization to obtain fine polymer particles.
【０００７】[0007]
【発明が解決しようとする課題】上記公報が開示する技
術は、界面活性剤を臨界ミセル濃度の０．５〜２．０倍
という程の大量に使用することを必要としている。とこ
ろが、このような大量の界面活性剤を用いて二次懸濁液
を作ったのでは、懸濁粒子の大きさがなお不揃いとな
り、従って狭い粒度分布を持ち，大きさの揃った微細な
重合体粒子が得られないことが判明した。そこで、大き
さの揃った微細な重合体を作るには、さらに別な製造方
法を開発することが必要となった。この発明は、このよ
うな必要に応じて生まれたものである。The technique disclosed in the above publication requires the use of a surfactant in a large amount of 0.5 to 2.0 times the critical micelle concentration. However, when a secondary suspension is prepared using such a large amount of surfactant, the size of the suspended particles is still uneven, and therefore, the fine particles have a narrow particle size distribution and uniform size. It was found that no coalesced particles could be obtained. Therefore, in order to produce a fine polymer having a uniform size, it was necessary to develop still another production method. The present invention has been made in response to such a need.
【０００８】[0008]
【課題を解決するための手段】この発明者は、上記公報
が教えるような大量の界面活性剤を使用しないで、界面
活性剤の使用量を臨界ミセル濃度の０．５倍以下とし、
高速回転撹拌装置によって単量体を平均粒子径が３〜１
０μｍの油滴として一次懸濁液を作り、次いでこれをナ
ノマイザーに通すと、ナノマイザー内で微細化とは逆に
粒子の合着が起こり、これによって粒子が逆に大きくな
り、その結果粒径が４〜１００μｍの大きさの範囲内で
あって、且つ所望の狭い領域内に局限された粒子の得ら
れることを見出した。しかも、その合着の程度すなわち
得られる粒径は一次懸濁液に加える圧力の加減により容
易に調節できることを見出した。この発明は、このよう
な知見に基づいて完成されたものである。The inventor of the present invention did not use a large amount of surfactant as taught by the above-mentioned publication but reduced the amount of surfactant to 0.5 times or less of the critical micelle concentration,
The average particle size of the monomer is 3 to 1
When a primary suspension is prepared as oil droplets of 0 μm and then passed through a nanomizer, coalescence of the particles occurs in the nanomizer, contrary to the miniaturization, whereby the particles become larger and consequently the particle size increases. It has been found that particles confined within a size range of 4-100 μm and within a desired narrow area are obtained. In addition, they have found that the degree of coalescence, that is, the particle size obtained, can be easily adjusted by adjusting the pressure applied to the primary suspension. The present invention has been completed based on such knowledge.
【０００９】この発明は、エチレン系単量体と、この単
量体に可溶な重合開始剤と、界面活性剤と、分散安定剤
とを水性媒体中に加えて撹拌して単量体粒子の一次懸濁
液を作り、この一次懸濁液に圧力を加えて複数の流れに
分けて流し、液流同士を衝突させて単量体粒子の二次懸
濁液を作り、この二次懸濁液を懸濁重合させて重合体粒
子を製造する方法において、界面活性剤の使用量を少な
くして臨界ミセル濃度の０．５倍以下とし、一次懸濁液
中の単量体を平均粒子径が３〜１０μｍの油滴とし、一
次懸濁液に加える圧力を加減して単量体粒子の合着程度
を加減し、これによって粒子の大きさを所望の狭い領域
内に分布させることを特徴とする、大きさの揃った微細
な重合体粒子の製造方法を提供するものである。According to the present invention, an ethylene-based monomer, a polymerization initiator soluble in the monomer, a surfactant, and a dispersion stabilizer are added to an aqueous medium and stirred to form monomer particles. A primary suspension is applied, pressure is applied to the primary suspension, the mixture is flowed into a plurality of streams, and the liquid streams collide with each other to form a secondary suspension of monomer particles. In the method of producing polymer particles by suspension polymerization of a suspension, the amount of the surfactant is reduced to 0.5 times or less of the critical micelle concentration, and the monomer in the primary suspension is reduced to an average particle size. Oil droplets having a diameter of 3 to 10 μm are adjusted by adjusting the pressure applied to the primary suspension to adjust the degree of coalescence of the monomer particles, thereby distributing the particle size within a desired narrow area. An object of the present invention is to provide a method for producing fine polymer particles having a uniform size.
【００１０】この発明は、エチレン系単量体と、この単
量体に可溶な重合開始剤と、界面活性剤と、分散安定剤
とを水性媒体中に加え、撹拌して単量体粒子の一次懸濁
液を作る点では、特開平４−１５６５５５号公報の開示
と同じである。しかし、上記公報の開示は、界面活性剤
を臨界ミセル濃度の０．５〜２．０倍量もの大量に使用
することを必要とするのに対し、この発明は、０．５倍
以下の少量使用すべきだとしている点で異なっている。According to the present invention, an ethylene-based monomer, a polymerization initiator soluble in the monomer, a surfactant, and a dispersion stabilizer are added to an aqueous medium, and the mixture is stirred to obtain monomer particles. The production of the primary suspension is the same as that disclosed in Japanese Patent Application Laid-Open No. 4-156555. However, while the disclosure of the above publication requires the use of a surfactant in a large amount of 0.5 to 2.0 times the critical micelle concentration, the present invention discloses a small amount of 0.5 times or less. They differ in that they should be used.
【００１１】界面活性剤はアニオン系のものを用いるの
が好ましい。好ましいアニオン系の界面活性剤は、例え
ばラウリル硫酸ナトリウム、ドデシルベンゼンスルホン
酸ナトリウム、ポリオキシエチレンラウリルエーテル硫
酸ナトリウム、ジオクチルスルホコハク酸ナトリウムで
ある。It is preferable to use an anionic surfactant. Preferred anionic surfactants are, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl ether sulfate, and sodium dioctyl sulfosuccinate.
【００１２】界面活性剤は、少量が水に溶解されている
だけで、低濃度の水溶液を形成している間は、分子状に
分散している。ところが、界面活性剤がある濃度を超え
るに至ると、界面活性剤の分子が集合して、水溶液中で
ミセルと呼ばれるコロイド大の会合体を形成するに至
る。このようなミセルの形成が起こる濃度を臨界ミセル
濃度と云う。界面活性剤は、臨界ミセル濃度において水
溶液の浸透圧、電気伝導度、表面張力などの物理化学的
性質を急激に変化させる。臨界ミセル濃度は各界面活性
剤について固有な値である。例えば、ラウリル硫酸ナト
リウムは０．２３％が臨界ミセル濃度である。The surfactant is only dissolved in a small amount in water and is molecularly dispersed while forming a low-concentration aqueous solution. However, when the concentration of the surfactant exceeds a certain concentration, molecules of the surfactant aggregate to form a colloid-sized aggregate called a micelle in an aqueous solution. The concentration at which such micelle formation occurs is called the critical micelle concentration. Surfactants rapidly change physicochemical properties such as osmotic pressure, electrical conductivity and surface tension of an aqueous solution at a critical micelle concentration. The critical micelle concentration is a unique value for each surfactant. For example, sodium lauryl sulfate has a critical micelle concentration of 0.23%.
【００１３】この発明において、一次懸濁液を作るに
は、剪断力によって粒子を分散させる機構のものが使用
される。装置としては、ホモミキサー等の高速回転式撹
拌機を使用する。一次懸濁液では、エチレン系単量体を
平均粒子径が３〜１０μｍの油滴とすることが必要とさ
れる。In the present invention, in order to produce a primary suspension, a suspension having a mechanism for dispersing particles by shearing force is used. As a device, a high-speed rotary stirrer such as a homomixer is used. In the primary suspension, the ethylene-based monomer needs to be formed into oil droplets having an average particle diameter of 3 to 10 μm.
【００１４】この発明では、エチレン系単量体を平均粒
子径が３〜１０μｍの油滴とした一次懸濁液を、例えば
ナノマイザーと呼ばれるような装置に通す。この装置
は、前述のように、一次懸濁液を加圧下に複数個の流れ
に分けて流し、その複数個の流れを互いに衝突させて、
懸濁粒子を衝撃により粉砕する装置である。In the present invention, the primary suspension in which the ethylene monomer is made into oil droplets having an average particle diameter of 3 to 10 μm is passed through a device called, for example, a nanomizer. As described above, this device divides the primary suspension into a plurality of streams under pressure, and collides the plurality of streams with each other.
This is a device that crushes suspended particles by impact.
【００１５】ナノマイザーと呼ばれる装置は、その要部
が図１に分解して示したような部分によって構成されて
いる。円板１は表面から裏面に貫通する２個の貫通孔１
１と１２とを備え、円板２に向かう裏面上に孔１１と１
２とを結ぶ溝１３が付設されている。円板２も円板１と
同様に２個の貫通孔２１と２２とを備え、円板１に向か
う裏面上に孔２１と２２とを結ぶ溝２３が付設されてい
る。円板１は押さえ３によって円板２に向かって押さ
れ、円板２は押さえ４によって円板１に向かって押さ
れ、その結果円板１と円板２とは裏面同士が互いに密接
している。しかし、孔１１と孔１２とは、何れも孔２１
と孔２２とに重なるところに位置しないで、溝１３と溝
２３とが互いに垂直に延びるような関係に配置されてい
る。An apparatus called a nanomizer has a main part constituted by a part as shown in FIG. The disc 1 has two through holes 1 penetrating from the front surface to the back surface.
1 and 12 with holes 11 and 1 on the back side facing disc 2
2 are provided. The disc 2 also has two through holes 21 and 22 like the disc 1, and a groove 23 connecting the holes 21 and 22 is provided on the back surface facing the disc 1. The disc 1 is pressed toward the disc 2 by the presser 3, and the disc 2 is pressed toward the disc 1 by the presser 4, and as a result, the discs 1 and 2 come into close contact with each other. I have. However, both holes 11 and 12 are holes 21
The groove 13 and the groove 23 are arranged so as not to overlap with the hole 22 and the groove 13 and the groove 23 extend perpendicularly to each other.
【００１６】押さえ３から加圧下に一次懸濁液が供給さ
れる。このとき、一次懸濁液には１０〜３０００ｋｇ／
ｃｍ2 の範囲内の圧力が加えられる。すると、懸濁液
は、孔１１と１２とを通って２個の液流として流れ、溝
１３に沿って流れて互いに衝突する。衝突した懸濁液は
円板２がわに移り、溝２３に沿って２つに分かれて流
れ、次いで孔２１と２２とを通って円板２を去り、押さ
え４へ入って合流し、流れて行く。溝１３と溝２３とを
通るときに、一次懸濁液は、衝突の衝撃によりその中の
単量体粒子が粉砕されて、微細化される。The primary suspension is supplied from the presser 3 under pressure. At this time, 10 to 3000 kg /
A pressure in the range of cm 2 is applied. Then, the suspension flows as two liquid flows through the holes 11 and 12, flows along the groove 13, and collides with each other. The impinging suspension is displaced by the disc 2 and flows in two along the groove 23, then leaves the disc 2 through the holes 21 and 22, enters the presser 4 and merges, Go. When passing through the groove 13 and the groove 23, the primary suspension is pulverized by the impact of the collision, whereby the monomer particles therein are pulverized and pulverized.
【００１７】ナノマイザーは一般に懸濁液中の粒子を粉
砕するものとされて来た。懸濁液中に界面活性剤が大量
に含まれているときは、確かに粒子が粉砕されて微細な
ものとなる。ところが、この発明のように、界面活性剤
の使用量が少なくて、界面活性剤が臨界ミセル濃度の
０．５倍以下とされているときは、ナノマイザーを通す
ことにより粒子が合着されて逆に大きくなり、大きい範
囲内で粒子の大きさがよく揃ったものとなる。従って、
一次懸濁液中の単量体油滴を平均粒子径が３〜１０μｍ
の大きさにしておくと、ナノマイザー中で粒子の合着が
起こり、粒子は大きくなって４〜１００μｍの範囲内で
大きさのよく揃ったものとなる。その大きさの程度、す
なわち平均粒子径は、主としてナノマイザーを通すとき
一次懸濁液に加える圧力によって定まるので、圧力の調
節により容易に調節できる。[0017] Nanomizers have generally been described as milling particles in suspension. When a large amount of surfactant is contained in the suspension, the particles are certainly crushed into fine particles. However, as in the present invention, when the amount of the surfactant used is small and the surfactant is not more than 0.5 times the critical micelle concentration, the particles are coalesced by passing through a nanomizer and the reverse And the size of the particles is well uniform within a large range. Therefore,
The average particle diameter of the monomer oil droplets in the primary suspension is 3 to 10 μm.
When the particle size is set to a value, coalescence of particles occurs in the nanomizer, and the particles become large and have a uniform size within the range of 4 to 100 μm. The degree of the size, that is, the average particle diameter is mainly determined by the pressure applied to the primary suspension when passing through the nanomizer, and thus can be easily adjusted by adjusting the pressure.
【００１８】こうして、４〜１００μｍの範囲内でとく
に希望する平均粒子径を持った二次懸濁液が得られたあ
とで、この発明では二次懸濁液を懸濁重合させる。この
とき、二次懸濁液は既に重合開始剤を含んでいるので、
例えばこの懸濁液を加熱するだけで重合を開始させるこ
とができる。加熱は重合開始剤、単量体の種類に応じて
適当な温度にするが、通常は２５〜１００℃の範囲内で
あり、好ましくは５０〜９０℃の範囲内である。重合さ
せると、単量体は二次懸濁液中の粒子大そのままで重合
体となり、ここに粒子の大きさのよく揃った重合体が得
られる。After a secondary suspension having a desired average particle size in the range of 4 to 100 μm is thus obtained, the secondary suspension is subjected to suspension polymerization in the present invention. At this time, since the secondary suspension already contains a polymerization initiator,
For example, polymerization can be initiated only by heating the suspension. The heating is performed at an appropriate temperature depending on the type of the polymerization initiator and the type of the monomer, but is usually in the range of 25 to 100 ° C, preferably in the range of 50 to 90 ° C. When polymerized, the monomer becomes a polymer as it is in the form of particles in the secondary suspension, and a polymer having a uniform particle size can be obtained.
【００１９】重合後は、濾過、遠心分離等によって重合
体粒子を水性媒体から分離し、水洗又は溶剤で洗浄後、
乾燥して粉体として使用する。After the polymerization, the polymer particles are separated from the aqueous medium by filtration, centrifugation or the like, washed with water or washed with a solvent,
Dry and use as powder.
【００２０】この発明で用いることのできるエチレン系
単量体は、例えば、スチレン、ｐ−メチルスチレン、ｐ
−クロロスチレン等のスチレン系単量体；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
ル等のアクリル酸エステル系単量体；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等のメタ
クリル酸エステル系単量体；ポリエチレングリコールモ
ノ（メタ）アクリレート、メチルビニルエーテル等のア
ルキルビニルエーテル；酢酸ビニル、酪酸ビニル等のビ
ニルエステル系単量体；Ｎ−メチルアクリルアミド、Ｎ
−エチルアクリルアミド等のＮ−アルキル置換アクリル
アミド；アクリロニトリル、メタアクリロニトリル等の
ニトリル系単量体；ジビニルベンゼン、エチレングリコ
ール（メタ）アクリレート、トリメチロールプロパント
リアクリレート等の多官能性単量体等である。これらの
単量体は必要に応じて、単独または２種類以上を混合し
て用いることができる。The ethylene monomers usable in the present invention include, for example, styrene, p-methylstyrene, p-methylstyrene and p-methylstyrene.
Styrene monomers such as chlorostyrene; acrylate monomers such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; methacrylate esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate Alkyl vinyl ethers such as polyethylene glycol mono (meth) acrylate and methyl vinyl ether; vinyl ester monomers such as vinyl acetate and vinyl butyrate; N-methylacrylamide, N
N-alkyl-substituted acrylamides such as ethyl acrylamide; nitrile monomers such as acrylonitrile and methacrylonitrile; and polyfunctional monomers such as divinylbenzene, ethylene glycol (meth) acrylate and trimethylolpropane triacrylate. These monomers can be used alone or as a mixture of two or more, if necessary.
【００２１】本発明において重合開始剤としては、一般
に用いられる油溶性重合触媒であれば特に限定されるこ
となく使用でき、例えば過酸化ベンゾイル、過酸化ラウ
ロイル、ｔ−ブチルペルオキシオクトエート等の過酸化
物系触媒、アゾビスイソブチロニトリル、アゾビスイソ
バレロニトリル等のアゾ系触媒が使用できる。The polymerization initiator used in the present invention can be used without any particular limitation as long as it is a generally used oil-soluble polymerization catalyst. For example, peroxides such as benzoyl peroxide, lauroyl peroxide and t-butylperoxyoctoate can be used. Catalysts such as azobisisobutyronitrile and azobisisovaleronitrile can be used.
【００２２】分散安定剤としてはポリビニルアルコー
ル、メチルセルロース、ポリビニルピロリドン、ゼラチ
ン等の保護コロイド、硫酸バリウム、硫酸カルシウム、
炭酸マグネシウム、りん酸カルシウム、ピロリン酸マグ
ネシウム等の難水溶性無機塩等が挙げられるが、好まし
くは難水溶性無機塩が用いられる。Examples of the dispersion stabilizer include protective colloids such as polyvinyl alcohol, methylcellulose, polyvinylpyrrolidone and gelatin, barium sulfate, calcium sulfate, and the like.
Examples thereof include poorly water-soluble inorganic salts such as magnesium carbonate, calcium phosphate, and magnesium pyrophosphate, and preferably, poorly water-soluble inorganic salts are used.
【００２３】[0023]
【発明の効果】この発明方法によれば、エチレン系単量
体と、この単量体に可溶な重合開始剤と、界面活性剤
と、分散安定剤とを水性媒体中に加えて撹拌して単量体
粒子の一次懸濁液を作るという従来の方法において、界
面活性剤の使用量を少なくして臨界ミセル濃度の０．５
倍以下とし、単量体を平均粒子径が３〜１０μｍの油滴
とするのであるから、一次懸濁液の製造は従来方法と大
きく変わることなく容易に実施することができる。こう
して得た一次懸濁液をナノマイザーのような装置に通
し、流体同士を衝突させると、界面活性剤の使用量が少
ないために粒子の合着が起こり、ここに４〜１００μｍ
の粒子大の範囲内で大きさの揃った二次懸濁液が得られ
る。こうして得た二次懸濁液を重合させると、ここに４
〜１００μｍの粒子大の範囲内で粒度分布の狭い重合体
粒子が得られる。従って、この発明方法によれば、簡単
な操作で４〜１００μｍの粒子大の範囲内で粒度分布の
狭い重合体粒子が得られる。この粒子は大きさが揃って
いるために、スペーサー、滑り付与剤、トナー、塗料の
つや出し剤などとして使用するに好適なものとなる。こ
の発明はこのような利益を与えるものである。According to the method of the present invention, an ethylene monomer, a polymerization initiator soluble in the monomer, a surfactant, and a dispersion stabilizer are added to an aqueous medium and stirred. In the conventional method of preparing a primary suspension of monomer particles by using a surfactant, the amount of surfactant is reduced and the critical micelle concentration is reduced to 0.5.
Since it is twice or less and the monomer is oil droplets having an average particle diameter of 3 to 10 μm, the production of the primary suspension can be easily carried out without largely changing the conventional method. When the primary suspension thus obtained is passed through a device such as a nanomizer and the fluids collide with each other, coalescence of the particles occurs due to the small amount of the surfactant used.
A secondary suspension having a uniform size is obtained within the range of the particle size. When the secondary suspension thus obtained was polymerized, it was found that
Polymer particles having a narrow particle size distribution can be obtained in the range of the particle size of １００100 μm. Therefore, according to the method of the present invention, polymer particles having a narrow particle size distribution within a particle size range of 4 to 100 μm can be obtained by a simple operation. Since the particles are uniform in size, they are suitable for use as a spacer, a slip imparting agent, a toner, a polishing agent for paint, and the like. The present invention provides such benefits.
【００２４】[0024]
【実施例】次に、実施例と比較例とを挙げて、この発明
のすぐれている所以を具体的に明らかにする。Next, the advantages of the present invention will be specifically described with reference to examples and comparative examples.
【００２５】[0025]
【実施例１】アゾビスイソバレロニトリル１．５ｇを溶
解したメタクリル酸メチル４７５ｇ、エチレングリコー
ルジメタクリレート２５ｇ、ラウリル硫酸ナトリウム
（臨界ミセル濃度：０．２３％）１．６ｇ、難水溶性リ
ン酸三カルシウム９６ｇ、水３２００ｇを含む水系混合
液をＴ・ＫホモミキサーＭＡＲＫII２．５型（特殊機化
工業製）を用いて１６０００ｒｐｍにて１５分間処理
し、平均粒子径５μｍの一次懸濁液を調製する。Example 1 475 g of methyl methacrylate in which 1.5 g of azobisisovaleronitrile was dissolved, 25 g of ethylene glycol dimethacrylate, 1.6 g of sodium lauryl sulfate (critical micelle concentration: 0.23%), and poorly water-soluble triphosphate An aqueous mixed solution containing 96 g of calcium and 3200 g of water is treated with a TK homomixer MARK II 2.5 (manufactured by Tokushu Kika Kogyo) at 16,000 rpm for 15 minutes to prepare a primary suspension having an average particle diameter of 5 μm. .
【００２６】次いで、ナノマイザー社製ナノマイザーＬ
Ａ−３１型を用いて、上記の一次懸濁液を１３００ｋｇ
／ｃｍ2 の圧力下に１回通して二次懸濁液を作った。Next, Nanomizer L manufactured by Nanomizer Co., Ltd.
Using the A-31 type, 1300 kg of the above primary suspension
A single suspension was made under a pressure of / cm 2 to form a secondary suspension.
【００２７】この二次懸濁液を内容積が５リットルの重
合反応槽に仕込み、いかり型の撹拌翼で３００ｒｐｍの
緩やかな撹拌下で５０℃で８時間懸濁重合させて重合体
粒子を得た。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and subjected to suspension polymerization at 50 ° C. for 8 hours under a gentle stirring at 300 rpm with an irrigating stirring blade to obtain polymer particles. Was.
【００２８】得られた重合体粒子について、コールター
社製のコールターカウンターにより粒子の重量分布を調
べたところ、図２に示したような重量分布を示した。こ
の粒子分布は平均粒径が９．７μｍで、標準偏差が２．
０μｍ、変動係数が２０．３％であって、粒度分布が狭
い領域内に局限されていて、粒子の大きさがよく揃った
ものであった。When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., Ltd., the weight distribution as shown in FIG. 2 was shown. This particle distribution has an average particle size of 9.7 μm and a standard deviation of 2.
The particle size distribution was 0 μm, the coefficient of variation was 20.3%, the particle size distribution was confined within a narrow area, and the particles had a uniform size.
【００２９】[0029]
【実施例２】実施例１に示したと同じ一次懸濁液を、ナ
ノマイザーＬＡ−３１型を用いて、処理圧力３００ｋｇ
／ｃｍ2 とした以外は実施例１と同様に操作を行った。
得られた重合体粒子の粒径をコールターカウンターを用
いて測定した結果を図３に示す。上記重合体粒子は平均
粒径が１９．１μｍ、標準偏差が４．０μｍ、変動係数
が２１．２％であって、粒度分布が狭い領域内に局限さ
れていた。Example 2 The same primary suspension as shown in Example 1 was treated at a processing pressure of 300 kg using a Nanomizer LA-31.
The operation was performed in the same manner as in Example 1 except that / cm 2 was used.
FIG. 3 shows the results of measuring the particle size of the obtained polymer particles using a Coulter counter. The polymer particles had an average particle size of 19.1 μm, a standard deviation of 4.0 μm, a coefficient of variation of 21.2%, and were confined to a narrow particle size distribution region.
【００３０】[0030]
【実施例３】実施例１に示したと同じ一次懸濁液を、ハ
ーモナイザーＬＥＨ−Ｉ型（ナノマイザー社製）を用い
て処理圧力１０ｋｇ／ｃｍ2 とした以外は実施例１と同
様に操作を行った。得られた重合体粒子の粒径をコール
ターカウンターを用いて測定した結果を図４に示す。上
記重合体粒子は平均粒径が３９．０μｍ、標準偏差が
９．１μｍ、変動係数が２３．２％であって、狭い粒径
分布を示し、粒子の大きさがよく揃ったものであった。Example 3 The same operation as in Example 1 was carried out except that the same primary suspension as in Example 1 was treated at a processing pressure of 10 kg / cm 2 using a Harmonizer LEH-I (manufactured by Nanomizer). Was. FIG. 4 shows the result of measuring the particle size of the obtained polymer particles using a Coulter counter. The polymer particles had an average particle size of 39.0 μm, a standard deviation of 9.1 μm, a coefficient of variation of 23.2%, showed a narrow particle size distribution, and had a uniform particle size. .
【００３１】[0031]
【比較例１】実施例１に示したと同じ一次懸濁液を同様
の条件で懸濁重合を行った。得られた重合体粒子の粒径
をコールターカウンターを用いて測定した結果を図５に
示す。上記重合体粒子は平均粒径が４．９μｍ、標準偏
差が２．５μｍ、変動係数が５０．２％であって、幅広
い粒度分布を示し、従って粒子の大きさが不揃いであっ
た。Comparative Example 1 The same primary suspension as shown in Example 1 was subjected to suspension polymerization under the same conditions. FIG. 5 shows the results of measuring the particle size of the obtained polymer particles using a Coulter counter. The polymer particles had an average particle size of 4.9 μm, a standard deviation of 2.5 μm, and a coefficient of variation of 50.2%, showed a wide particle size distribution, and thus had irregular particle sizes.
【００３２】[0032]
【実施例４】過酸化ベンゾイル１．５ｇを溶解したスチ
レン４４０ｇ、ジビニルベンゼン６０ｇ（純分８１
％）、ラウリル硫酸ナトリウム０．８ｇ、ピロリン酸マ
グネシウム４８ｇ、水３２００ｇを含む水系混合液をＴ
・ＫホモミキサーＭＡＲＫII２・５型を用いて１６００
０ｒｐｍにて１５分間処理し、平均粒子径６μｍの一次
懸濁液を調製する。Example 4 440 g of styrene in which 1.5 g of benzoyl peroxide was dissolved and 60 g of divinylbenzene (pure content: 81
%), Sodium lauryl sulfate 0.8 g, magnesium pyrophosphate 48 g, and water 3200 g containing T
・ 1600 using K homomixer MARKII2.5 type
The mixture is treated at 0 rpm for 15 minutes to prepare a primary suspension having an average particle size of 6 μm.
【００３３】次いでナノマイザーＬＡ−３１型を用いて
上記の一次懸濁液を１３００ｋｇ／ｃｍ2 の圧力下に１
回通して二次懸濁液を作った。Next, the above-mentioned primary suspension was subjected to pressure reduction of 1300 kg / cm 2 using Nanomizer LA-31.
A secondary suspension was made by passing through.
【００３４】この二次懸濁液を内容積５リットルの重合
反応槽に仕込み、いかり型の撹拌翼で３００ｒｐｍの緩
やかな撹拌下で８０℃にて８時間反応させた。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and reacted at 80 ° C. for 8 hours under a gentle stirring at 300 rpm with an irrigated stirring blade.
【００３５】得られた重合体粒子の粒度をコールターカ
ウンターを用いて測定した結果を図６に示す。上記重合
体粒子は平均粒子径が７．９μｍ、標準偏差１．７μ
ｍ、変動係数２１．９％であって、粒子の大きさがよく
揃ったものであった。FIG. 6 shows the results of measuring the particle size of the obtained polymer particles using a Coulter counter. The polymer particles have an average particle size of 7.9 μm and a standard deviation of 1.7 μm.
m, the coefficient of variation was 21.9%, and the particles were well-sized.
【００３６】[0036]
【比較例２】実施例４に示したと同じ一次懸濁液を同様
の条件で懸濁重合を行った。得られた重合体粒子の粒径
をコールターカウンターを用いて測定した結果を図７に
示す。上記重合体粒子は平均粒子径が６．１μｍ、標準
偏差２．４μｍ、変動係数３８．８％であって、幅広い
粒径分布を有していた。Comparative Example 2 The same primary suspension as shown in Example 4 was subjected to suspension polymerization under the same conditions. FIG. 7 shows the result of measuring the particle size of the obtained polymer particles using a Coulter counter. The polymer particles had an average particle size of 6.1 μm, a standard deviation of 2.4 μm, and a variation coefficient of 38.8%, and had a wide particle size distribution.
【図１】この発明で二次懸濁液を作るに用いられる装置
の要部分解斜視図である。FIG. 1 is an exploded perspective view of a main part of an apparatus used for producing a secondary suspension according to the present invention.
【図２】実施例１で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 2 is a graph showing the particle size distribution of polymer particles obtained in Example 1.
【図３】実施例２で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 3 is a graph showing the particle size distribution of the polymer particles obtained in Example 2.
【図４】実施例３で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 4 is a graph showing the particle size distribution of the polymer particles obtained in Example 3.
【図５】比較例１で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 5 is a graph showing the particle size distribution of the polymer particles obtained in Comparative Example 1.
【図６】実施例４で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 6 is a graph showing the particle size distribution of the polymer particles obtained in Example 4.
【図７】比較例２で得られた重合体粒子の粒度分布を示
したグラフである。FIG. 7 is a graph showing the particle size distribution of the polymer particles obtained in Comparative Example 2.
【符号の説明】 １ 円板 ２ 円板 ３ 押さえ ４ 押さえ １１ 孔 １２ 孔 １３ 溝 ２１ 孔 ２２ 孔 ２３ 溝[Description of Signs] 1 disk 2 disk 3 retainer 4 retainer 11 hole 12 hole 13 groove 21 hole 22 hole 23 groove
Claims (1)
な重合開始剤と、界面活性剤と、分散安定剤とを水性媒
体中に加えて撹拌して単量体粒子の一次懸濁液を作り、
この一次懸濁液に圧力を加えて複数の流れに分けて流
し、液流同士を衝突させて単量体粒子の二次懸濁液を作
り、この二次懸濁液を懸濁重合させて重合体粒子を製造
する方法において、界面活性剤の使用量を少なくして臨
界ミセル濃度の０．５倍以下とし、一次懸濁液中の単量
体を平均粒子径が３〜１０μｍの油滴とし、一次懸濁液
に加える圧力を加減して単量体粒子の合着程度を加減
し、これによって粒子の大きさを所望の狭い領域内に分
布させることを特徴とする、大きさの揃った微細な重合
体粒子の製造方法。1. An ethylene-based monomer, a polymerization initiator soluble in this monomer, a surfactant, and a dispersion stabilizer are added to an aqueous medium and stirred to form primary particles of monomer particles. Make a suspension,
A pressure is applied to this primary suspension to divide it into a plurality of streams, and the liquid streams collide with each other to form a secondary suspension of monomer particles, and this secondary suspension is subjected to suspension polymerization. In the method for producing polymer particles, the amount of the surfactant is reduced to 0.5 times or less of the critical micelle concentration, and the monomers in the primary suspension are oil droplets having an average particle diameter of 3 to 10 μm. And adjusting the pressure applied to the primary suspension to adjust the degree of coalescence of the monomer particles, thereby distributing the particle size within a desired narrow region. Of producing fine polymer particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6110454A JP3007792B2 (en) | 1994-04-25 | 1994-04-25 | Method for producing fine polymer particles of uniform size |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6110454A JP3007792B2 (en) | 1994-04-25 | 1994-04-25 | Method for producing fine polymer particles of uniform size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07292003A JPH07292003A (en) | 1995-11-07 |
| JP3007792B2 true JP3007792B2 (en) | 2000-02-07 |
Family
ID=14536127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6110454A Expired - Fee Related JP3007792B2 (en) | 1994-04-25 | 1994-04-25 | Method for producing fine polymer particles of uniform size |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3007792B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001261313A (en) * | 2000-03-16 | 2001-09-26 | Sekisui Plastics Co Ltd | Method of producing amorphous calcium phosphate slurry and method of producing polymeric particle |
| JP3784336B2 (en) * | 2002-03-04 | 2006-06-07 | 積水化成品工業株式会社 | Method for producing polymer particles |
| JP5297846B2 (en) * | 2009-03-16 | 2013-09-25 | 積水化成品工業株式会社 | Suspension production method and polymer particle production method |
| JP6313974B2 (en) * | 2013-03-29 | 2018-04-18 | 積水化成品工業株式会社 | Crosslinked acrylic resin particles and method for producing the same, resin composition and packaging article |
-
1994
- 1994-04-25 JP JP6110454A patent/JP3007792B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07292003A (en) | 1995-11-07 |
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