JP3380131B2 - Method for producing polymer particles - Google Patents
Method for producing polymer particlesInfo
- Publication number
- JP3380131B2 JP3380131B2 JP35124196A JP35124196A JP3380131B2 JP 3380131 B2 JP3380131 B2 JP 3380131B2 JP 35124196 A JP35124196 A JP 35124196A JP 35124196 A JP35124196 A JP 35124196A JP 3380131 B2 JP3380131 B2 JP 3380131B2
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- Japan
- Prior art keywords
- suspension
- weight
- particles
- average particle
- polymer particles
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、重合体粒子の製造
方法に関する。更に詳しくは、本発明は、所望の範囲に
重量平均粒子径の揃った重合体粒子の製造方法に関す
る。本発明の製造方法により得られた重合体粒子は、ス
ペーサー、光拡散剤、滑り性付与剤、トナー、塗料のつ
や消し剤、機能性担体等として使用できる。TECHNICAL FIELD The present invention relates to a method for producing polymer particles. More specifically, the present invention relates to a method for producing polymer particles whose weight average particle diameter is uniform in a desired range. The polymer particles obtained by the production method of the present invention can be used as a spacer, a light diffusing agent, a slipperiness imparting agent, a toner, a delustering agent for paints, a functional carrier and the like.
【０００２】[0002]
【従来の技術】微細な重合体粒子は色々な方面で必要と
されている。とくに、粒子の大きさが１〜１００μｍの
範囲内にある粒度分布の均一な重合体粒子は、スペーサ
ー、滑り性付与剤、トナー、塗料のつや消し剤、機能性
担体等として適しているので、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 uniform particle size distribution having a particle size within the range of 1 to 100 μm are suitable as spacers, slipperiness imparting agents, toners, delustering agents for paints, functional carriers, etc. Widely demanded in various fields. 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、通
常乳化重合法によって単量体を重合させればよいと考え
るであろう。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、１μｍ以上の大きさの粒度分布の均一な粒子を容易
に作ることは困難である。また、これまでの懸濁重合法
によっても粒子の大きさを揃えることは困難である。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
大きさをおおよそ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。高速回転式撹拌機としてはホモミキサーが一般に使
用されるが、ホモミキサーで懸濁液としたのでは、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。For example, in order to make fine polymer particles, it will be considered that the monomers are usually polymerized by an emulsion polymerization method. However, if the emulsion polymerization method is used, the size of the particles is usually 1 μm or less, and it is difficult to easily prepare particles having a uniform particle size distribution of 1 μm or more. Further, it is difficult to make the particle sizes uniform even by the conventional suspension polymerization methods. That is, when a monomer is added to an aqueous medium and the suspension is stirred by an ordinary high-speed rotary stirrer to form a suspension, the size of the monomer particles is approximately in the range of 5 to 100 μm. However, the size of the particles is widely distributed within the range, and the particle size distribution is not concentrated in the narrow range. A homomixer is generally used as a high-speed rotary stirrer. However, if a homomixer is used to form a suspension, the liquid cannot be sheared with uniform stirring, and therefore the size of the particles is not uniform. Be uniform. For this reason, the obtained suspension polymerization methods have not been able to achieve a uniform particle size.
【０００４】他方、乳化液、懸濁液等を作る装置とし
て、高い圧力の下にある液体を流して、液流を互いに衝
突あるいは所定の平面部に衝突させてさせてその衝撃に
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
ることを原理とするナノマイザー、ハーモナイザー又は
マイクロフルイダイザー等の装置がある。On the other hand, as a device for producing emulsions, suspensions, etc., liquids under high pressure are caused to flow, and the liquid flows are caused to collide with each other or collide with a predetermined flat surface portion, and the impact causes There is a device such as a nanomizer, a harmonizer, or a microfluidizer whose principle is to pulverize suspended particles contained therein to make them fine, and thereby to make a suspension of fine particles having a uniform size.
【０００５】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
重量平均粒子径が３０〜４０μｍの単量体油滴の１次懸
濁液を作り、この１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２次懸濁液を作り、その後２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。In Japanese Patent Laid-Open No. 4-156555, the suspension particles are made into fine particles by the collision of the above liquid flows to form a suspension, and this suspension is suspension-polymerized to obtain a toner for electrostatic development. The method of making is disclosed. 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 stirred to obtain a weight average particle diameter. A primary suspension of monomer oil droplets of 30 to 40 μm is prepared, the primary suspension is divided into a plurality of streams under pressure, and the liquid streams thus obtained are caused to collide with each other. Is further miniaturized to form a secondary suspension, and then the secondary suspension is suspension-polymerized to obtain fine polymer particles.
【０００６】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２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
要となり、その改良法として特開平７−２９２０２５号
公報の技術が生まれた。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 made using such a large amount of surfactant, the sizes of suspended particles are still uneven, and therefore the particles have a narrow particle size distribution and fine particles of uniform size. It was found that coalesced particles could not be obtained. Therefore, in order to produce a fine polymer having a uniform size, it is necessary to develop another production method, and the technique disclosed in JP-A-7-292025 was born as an improved method.
【０００７】この技術は、大量の界面活性剤を使用せず
に、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重量平均粒
子径が３〜１０μｍの油滴として１次懸濁液を作り、次
いでこれを加圧下液体同士を衝突させると微細化とは逆
に粒子の合着が起り、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が得ら
れるものであり、その合着の程度すなわち得られる粒径
は１次懸濁液に加える圧力の加減により容易に調節でき
るという方法である。In this technique, the amount of the surfactant used is 0.5 times or less of the critical micelle concentration without using a large amount of the surfactant, and the weight average particle diameter of the monomer is adjusted by a high-speed rotary stirring device. When a primary suspension is formed as oil droplets of 3 to 10 μm, and then liquids are made to collide with each other under pressure, coalescence of particles occurs contrary to micronization, which causes the particles to become large on the contrary. Particles having a particle size in the range of 4 to 100 μm and localized within a desired narrow region are obtained, and the degree of coalescence, that is, the obtained particle size is the primary suspension. It is a method that can be easily adjusted by adjusting the pressure applied to.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら上記公報
で示される方法では、粒度分布の均一化の手段として１
次懸濁液の重量平均粒子径を３〜１０μｍと一旦目的と
する重量平均粒子径よりも小さくする必要があるため、
ホモミキサーのような高速型分散機を長時間（例えば１
００００ｒｐｍで１０分以上）運転しなければならずエ
ネルギー的にも時間的にも不利であった。However, in the method disclosed in the above-mentioned publication, as a means for making the particle size distribution uniform,
Since it is necessary to make the weight average particle diameter of the next suspension 3 to 10 μm once smaller than the intended weight average particle diameter,
Use a high-speed disperser such as a homomixer for a long time (for example, 1
It had to be operated at 0000 rpm for 10 minutes or more), which was disadvantageous in terms of energy and time.
【０００９】[0009]
【課題を解決するための手段】そこで、本発明の発明者
は、１次懸濁液をノズルより噴出させるという単純な機
構であれば、上記公報で示されているように１次懸濁液
の重量平均粒子径を３〜１０μｍと一旦目的とする重量
平均粒子径よりも小さくすることなしに粒度分布の均一
化が図れるということを見いだした。The inventor of the present invention, as long as a simple mechanism of ejecting the primary suspension from a nozzle is used, as described in the above publication, the primary suspension is disclosed. It was found that the particle size distribution can be made uniform without making the weight average particle size of 3 to 10 μm smaller than the target weight average particle size.
【００１０】かくして本発明によれば、懸濁重合可能な
疎水性単量体、この単量体に可溶な重合開始剤、界面活
性剤及び分散安定剤を水性媒体中に加えて重量平均粒子
径が５〜１００μｍの単量体粒子の１次懸濁液を作り、
この１次懸濁液を加圧下、その流路方向を強制的に変化
させずにノズルから噴出させ単量体粒子の２次懸濁液を
作り、この２次懸濁液を懸濁重合させて重量平均粒子径
が４〜１００μｍでかつ変動係数が１０〜２５％である
領域内に粒子が分布した重合体粒子を得ることを特徴と
する重合体粒子の製造方法が提供される。Thus, according to the present invention, a suspension-polymerizable hydrophobic monomer, a polymerization initiator soluble in this monomer, a surfactant and a dispersion stabilizer are added to an aqueous medium to obtain weight-average particles. Make a primary suspension of monomer particles with a diameter of 5-100 μm,
This primary suspension is ejected from a nozzle under pressure without forcibly changing the flow path direction to form a secondary suspension of monomer particles, and this secondary suspension is subjected to suspension polymerization. And a weight average particle diameter of 4 to 100 μm and a coefficient of variation of 10 to 25% to obtain polymer particles in which the particles are distributed.
【００１１】[0011]
【発明の実施の形態】本発明で用いることのできる懸濁
重合可能な疎水性単量体は、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（メタ）アクリレート等の多官能
性単量体等が挙げられる。これらの単量体は必要に応じ
て、単独又は２種類以上を混合して用いることができ
る。またこの単量体中に分散あるいは溶解可能な染料及
び顔料等の添加物を添加することも可能である。BEST MODE FOR CARRYING OUT THE INVENTION Suspension-polymerizable hydrophobic monomers that can be used in the present invention include, for example, styrene-based monomers such as styrene, p-methylstyrene, p-chlorostyrene; ethyl acrylate. Acrylic acid ester-based monomers such as butyl acrylate and 2-ethylhexyl acrylate;
Methacrylate ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; polyethylene glycol mono (meth) acrylate, alkyl vinyl ethers such as methyl vinyl ether; vinyl acetate,
Vinyl ester-based monomers such as vinyl butyrate; N-alkyl-substituted acrylamides such as N-methyl acrylamide and N-ethyl acrylamide; Nitrile-based monomers such as acrylonitrile and methacrylonitrile; divinylbenzene, ethylene glycol (meth) acrylate, Examples include polyfunctional monomers such as trimethylolpropane tri (meth) acrylate. These monomers may be used alone or in combination of two or more, if necessary. It is also possible to add additives such as dyes and pigments that can be dispersed or dissolved in this monomer.
【００１２】本発明における重合開始剤は、上記単量体
に可溶な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 in the present invention can be used without particular limitation as long as it is a generally used oil-soluble polymerization catalyst which is soluble in the above-mentioned monomer, and examples thereof include benzoyl peroxide, lauroyl peroxide and t-butyl. Peroxide octoate and other peroxide catalysts and azobisisobutyronitrile and azobisisovaleronitrile and other azo catalysts can be used.
【００１３】上記単量体にこれら重合開始剤を溶解し、
分散安定剤と界面活性剤又は必要に応じて添加される分
散安定補助剤等を含む水相に添加した後、１次懸濁液が
作成される。この時の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及び、酸化ケイ素、
酸化チタン等の金属酸化物等が挙げられる。この内、難
水溶性無機塩や金属酸化物等の無機化合物が好ましい。These polymerization initiators are dissolved in the above monomers,
After adding to the aqueous phase containing the dispersion stabilizer and the surfactant or the dispersion stabilization auxiliary agent and the like added as necessary, a primary suspension is prepared. As the dispersion stabilizer at this time, polyvinyl alcohol, methyl cellulose, polyvinyl pyrrolidone,
Protective colloid such as gelatin, sparingly water-soluble inorganic salt such as barium sulfate, calcium sulfate, magnesium carbonate, calcium phosphate, magnesium pyrophosphate, and silicon oxide,
Examples thereof include metal oxides such as titanium oxide. Of these, inorganic compounds such as poorly water-soluble inorganic salts and metal oxides are preferable.
【００１４】この時の界面活性剤としては、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
面活性剤としては、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が挙げられる。これら界面活性剤
は、その種類にもよるが、臨界ミセル濃度の０．５倍以
下で使用することが好ましく、０．０２〜０．３倍の範
囲で使用することが特に好ましい。臨界ミセル濃度と
は、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濃度で、界
面活性剤に固有な値である。たと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から、水に
対して０．１１５％以下で使用するのが好ましい。この
時、水溶性界面活性剤の代わりに、単量体中に油溶性界
面活性剤を加えてもよい。At this time, it is preferable to use an anionic surfactant as the surfactant. Examples of preferable anionic surfactants include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl ether sulfate, and sodium dioctylsulfosuccinate. Depending on the type, these surfactants are preferably used at 0.5 times or less the critical micelle concentration, and particularly preferably in the range of 0.02 to 0.3 times. The critical micelle concentration is a concentration unique to a surfactant, which is a concentration at which molecules of the surfactant are aggregated to form a colloid-sized aggregate called a micelle in an aqueous solution. For example, since sodium lauryl sulfate has a critical micelle concentration of 0.23%, it is preferably used at 0.115% or less with respect to water. At this time, an oil-soluble surfactant may be added to the monomer instead of the water-soluble surfactant.
【００１５】本発明において、１次懸濁液を作るには、
剪断力によって単量体を分散させる機構の装置が使用さ
れる。装置としては、通常の攪拌装置あるいはホモミキ
サー等の高速回転式撹拌機を使用し、この装置を所定の
攪拌速度で所定時間攪拌する。１次懸濁液では、単量体
を重量平均粒子径が５〜１００μｍの油滴とすることが
必要とされる。なお、本発明での１次懸濁液の製造時間
は、分散機械の処理能力や処理量にもよるが、例えば２
０μｍとするには、一般的にはホモミキサーで４０００
ｒｐｍで、２分程度でよく、上記特開平７−２９２０２
５号公報記載の方法で５μｍとする場合に比べ、低速ｒ
ｐｍでかつ製造時間も約２割となる。In the present invention, to prepare a primary suspension,
An apparatus having a mechanism of dispersing a monomer by shearing force is used. As an apparatus, a normal stirring apparatus or a high-speed rotary stirrer such as a homomixer is used, and this apparatus is stirred at a predetermined stirring speed for a predetermined time. In the primary suspension, the monomer is required to be oil droplets having a weight average particle size of 5 to 100 μm. The production time of the primary suspension in the present invention depends on the processing capacity and the processing amount of the dispersing machine, but is, for example, 2 times.
To obtain 0 μm, it is generally 4000 with a homomixer.
It takes about 2 minutes at rpm, and the above-mentioned JP-A-7-29202
Compared with the case of setting the thickness to 5 μm by the method described in Japanese Patent Publication No.
It is pm and the manufacturing time is about 20%.
【００１６】本発明では、懸濁重合可能な疎水性単量体
を重量平均粒子径が５〜１００μｍの油滴とした１次懸
濁液を、例えばノズルから懸濁液を噴射するタイプのプ
ロセッサーを接続したナノマイザーと呼ばれるような装
置を使用して加圧噴射する。この装置は、懸濁液を加圧
下で液同士あるいは液を所定の平面に衝突させることな
しにノズルより単に噴射させる装置であり、この装置を
使用し、噴射させた２次懸濁液の流速が０．５〜１００
ｍ／分となるような配管を接続して２次懸濁液を得る。
この時、２次懸濁液の流速が０．５ｍ／分より遅くなる
ような配管を接続すれば、懸濁液が噴出直後放射状に噴
出し、乱流を発生するため粗大粒子が生成し、粒度分布
が不均一となる。また、１００ｍ／分より速ければ管壁
で２次懸濁液が、ずり剪断力を受け微小粒子が生成しや
すくなり粒度分布が不均一となる。According to the present invention, a processor of the type in which a suspension-polymerizable hydrophobic monomer is sprayed from a nozzle, for example, a primary suspension made of oil droplets having a weight average particle diameter of 5 to 100 μm. It sprays under pressure using a device called nanomizer which is connected to. This device is a device for simply ejecting a suspension from a nozzle under pressure without causing liquids to collide with each other or a liquid on a predetermined plane, and using this device, the flow velocity of a secondary suspension liquid ejected. Is 0.5-100
A secondary suspension is obtained by connecting a pipe having a flow rate of m / min.
At this time, if a pipe is connected so that the flow velocity of the secondary suspension is slower than 0.5 m / min, the suspension is jetted radially immediately after jetting, and turbulent flow is generated to generate coarse particles, The particle size distribution becomes non-uniform. On the other hand, if the speed is higher than 100 m / min, the secondary suspension on the wall of the tube is likely to be subjected to shearing shear force to generate fine particles and the particle size distribution becomes non-uniform.
【００１７】この時に使用されるプロセッサーのノズル
径については、流量と圧力により任意のものが選択され
る。こうして、５〜１００μｍの範囲内でとくに希望す
る重量平均粒子径を持った２次懸濁液が得られたあと
で、２次懸濁液を懸濁重合させる。このとき、２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４０〜１００℃、０．５〜１０時間の範囲
内であり、好ましくは５０〜９０℃、１〜５時間の範囲
内である。重合させると、単量体は２次懸濁液中の重量
平均粒子径そのままで重合体となるので、大きさのよく
揃った重合体粒子が得られる。The nozzle diameter of the processor used at this time is arbitrarily selected depending on the flow rate and pressure. Thus, after the secondary suspension having a particularly desired weight average particle diameter within the range of 5 to 100 μm is obtained, the secondary suspension is subjected to suspension polymerization. At this time, since the secondary suspension already contains the polymerization initiator, the polymerization can be initiated by simply heating the suspension. The heating is carried out at an appropriate temperature depending on the type of the polymerization initiator and the monomer, but it is usually within the range of 40 to 100 ° C and 0.5 to 10 hours, preferably 50 to 90 ° C and 1 to 5 It is within the range of time. When polymerized, the monomer becomes a polymer with the weight average particle diameter of the secondary suspension as it is, so that polymer particles having a uniform size can be obtained.
【００１８】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ことが好ましい。上記本発
明の製造方法により得られた重合体粒子は、重量平均粒
子径が４〜１００μｍでかつ変動係数が１０〜２５％で
ある領域内に粒子径を有しており、所望の範囲内に重量
平均粒子径の揃った重合体粒子を得ることができる。更
に、標準偏差も０．４〜２５μｍとすることができる。
なお、本発明において重量平均粒子径は、コールター法
により測定した平均粒子径を意味する。After the polymerization, the polymer particles are separated from the aqueous medium by filtration, centrifugation, etc., and after washing with water or a solvent,
It is preferably dried and used as a powder. The polymer particles obtained by the production method of the present invention have a weight average particle diameter of 4 to 100 μm and a coefficient of variation of 10 to 25% within a region having a particle diameter within a desired range. Polymer particles having a uniform weight average particle diameter can be obtained. Further, the standard deviation can be 0.4 to 25 μm.
In addition, in this invention, a weight average particle diameter means the average particle diameter measured by the Coulter method.
【００１９】本発明は、懸濁重合可能な疎水性単量体、
この単量体に可溶な重合開始剤、界面活性剤及び分散安
定剤を水性媒体中に加え、撹拌して単量体粒子の１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、分散液同
士を衝突させたり、器壁に衝突させるのに対し、本発明
は図１で示されるように単にノズルから噴出させるだけ
で目的が達成されるという点で異なっている。図１中、
１はノズル、２は１次懸濁液注入口、３は２次懸濁液噴
出口を示している。The present invention is a suspension-polymerizable hydrophobic monomer,
From the viewpoint of adding a polymerization initiator soluble in the monomer, a surfactant and a dispersion stabilizer to an aqueous medium and stirring the mixture to prepare a primary suspension of the monomer particles, JP-A-4-156555. This is the same as disclosed in the publication. However, in the disclosure of the above publication, the dispersions are collided with each other or collided with the vessel wall, whereas the present invention achieves the object by simply ejecting from the nozzle as shown in FIG. Is different. In Figure 1,
Reference numeral 1 is a nozzle, 2 is a primary suspension injection port, and 3 is a secondary suspension ejection port.
【００２０】本発明の製造方法により得られた重合体粒
子は、スペーサー、光拡散剤、滑り性付与剤、トナー、
塗料のつや消し剤、機能性担体等の原料として又はその
まま使用することができる。The polymer particles obtained by the production method of the present invention include a spacer, a light diffusing agent, a slipperiness imparting agent, a toner,
It can be used as a raw material for a matting agent for paints, a functional carrier, or the like, or as it is.
【００２１】[0021]
【実施例】次に、実施例と比較例とを挙げて、本発明の
すぐれている点を具体的に明らかにする。但し、本発明
は以下の実施例には限定されない。EXAMPLES Next, the advantages of the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
【００２２】［実施例１］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル０．５重量部をメタクリル酸メチル９５
重量部、エチレングリコールジメタクリレート５重量部
に溶解し、ラウリル硫酸ナトリウム０．０６重量部（臨
界ミセル濃度の０．１３倍）、複分解ピロリン酸マグネ
シウム５重量部を含む水２００重量部に加え、ＴＫホモ
ミキサー（特殊機化製）にて、重量平均粒子径２０μｍ
となるよう１次懸濁液を調製した。この時の所要時間
は、４０００ｒｐｍで２分であった。Example 1 0.5 parts by weight of azobis-N, N-dimethylvaleronitrile was added to 95% of methyl methacrylate.
Dissolved in 5 parts by weight of ethylene glycol dimethacrylate, added to 200 parts by weight of water containing 0.06 parts by weight of sodium lauryl sulfate (0.13 times the critical micelle concentration) and 5 parts by weight of metathesis magnesium pyrophosphate, and TK Homomixer (made by Tokushu Kiki), weight average particle diameter 20μm
The primary suspension was prepared so that The time required at this time was 2 minutes at 4000 rpm.
【００２３】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を３
００ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると５４ｍ／分であった。Next, a nozzle type processor (LNP-20 / nanomizer LA-33 (manufactured by Nanomizer) was added.
300) and an SUS pipe with an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is mixed with 3
A secondary suspension was made by passing once under a pressure of 00 kg / cm 2 . The flow velocity of the secondary suspension at the outlet of the pipe at this time was 54 m / min when calculated from the flow rate.
【００２４】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で５
０℃で８時間懸濁重合させて重合体粒子を得た。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、この粒
子は重量平均粒子径が９．３μｍで、標準偏差が２．２
７μｍ、変動係数が２４．４％であり、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred at 300 rpm under mild agitation.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 8 hours. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 9.3 μm and the standard deviation was 2.2.
The particle size distribution was 7 μm, the coefficient of variation was 24.4%, the particle size distribution was limited to a narrow region, and the particle sizes were well aligned.
【００２５】［実施例２］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル０．５重量部をメタクリル酸メチル９５
重量部、エチレングリコールジメタクリレート５重量部
に溶解し、ラウリル硫酸ナトリウム０．０５重量部（臨
界ミセル濃度の０．１１倍）、複分解ピロリン酸マグネ
シウム３重量部、を含む水２００重量部に加え、プロペ
ラ翼を備えた攪拌機にて、重量平均粒子径８０μｍとな
るよう１次懸濁液を調製した。この時の所要時間は４０
０ｒｐｍで４分であった。Example 2 0.5 parts by weight of azobis-N, N-dimethylvaleronitrile was added to 95 parts of methyl methacrylate.
Parts, dissolved in 5 parts by weight of ethylene glycol dimethacrylate, added to 200 parts by weight of water containing 0.05 parts by weight of sodium lauryl sulfate (0.11 times the critical micelle concentration), 3 parts by weight of metathesis magnesium pyrophosphate, A primary suspension was prepared with a stirrer equipped with a propeller blade so that the weight average particle diameter was 80 μm. The time required at this time is 40
It was 4 minutes at 0 rpm.
【００２６】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を１
５０ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると４２ｍ／分であった。Next, a nozzle type processor (LNP-20 / nanomizer LA-33 (manufactured by Nanomizer) was added.
300) and an SUS pipe having an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is
A second suspension was made by passing once under a pressure of 50 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was 42 m / min when calculated from the flow rate.
【００２７】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で５
０℃で８時間懸濁重合させて重合体粒子を得た。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、この粒
子は重量平均粒子径が１８．０μｍで、標準偏差が４．
１８μｍ、変動係数が２３．２％、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred at 300 rpm under mild agitation.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 8 hours. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 18.0 μm and the standard deviation was 4.
The particle size distribution was 18 μm, the coefficient of variation was 23.2%, the particle size distribution was localized within a narrow region, and the particle sizes were well aligned.
【００２８】［実施例３］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル１．０重量部をスチレン９４重量部、ジ
ビニルベンゼン（純度８２％）６重量部に溶解し、ジオ
クチルスルホコハク酸ナトリウム０．０６重量部（臨界
ミセル濃度の０．３倍）、複分解ピロリン酸マグネシウ
ム３重量部、を含む水２００重量部に加え、プロペラ翼
を備えた攪拌機にて、重量平均粒子径８０μｍとなるよ
う１次懸濁液を調製した。この時の所要時間は、６００
ｒｐｍで５分であった。Example 3 1.0 part by weight of azobis-N, N-dimethylvaleronitrile was dissolved in 94 parts by weight of styrene and 6 parts by weight of divinylbenzene (purity: 82%) to obtain 0.06 part by weight of sodium dioctylsulfosuccinate. Parts (0.3 times the critical micelle concentration), 200 parts by weight of water containing 3 parts by weight of metathesis magnesium pyrophosphate, and primary suspension with a stirrer equipped with a propeller blade to a weight average particle size of 80 μm. A liquid was prepared. The time required at this time is 600
It was 5 minutes at rpm.
【００２９】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を１
５０ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると４０ｍ／分であった。Next, the Nanomizer LA-33 (manufactured by Nanomizer Co., Ltd.) is connected to a nozzle type processor (LNP-20 /
300) and an SUS pipe having an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is
A second suspension was made by passing once under a pressure of 50 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was 40 m / min when calculated from the flow rate.
【００３０】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で６
０℃で１０時間懸濁重合させて重合体粒子を得た。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、この
粒子は重量平均粒子径が１９．２μｍで、標準偏差が
４．４７μｍ、変動係数が２３．３％、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。This secondary suspension was charged into a polymerization reaction vessel having an internal volume of 5 liters, and the mixture was stirred under gentle stirring at 300 rpm for 6 minutes.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 10 hours. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 19.2 μm, the standard deviation was 4.47 μm, and the coefficient of variation was 23.3. %, And the particle size distribution was localized within a narrow region, and the particle sizes were well aligned.
【００３１】［実施例４］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル１．０重量部をスチレン９４重量部、ジ
ビニルベンゼン（純度８２％）６重量部に溶解し、ラウ
リル硫酸ナトリウム０．０１重量部（臨界ミセル濃度の
０．０２倍）、複分解ピロリン酸マグネシウム５重量
部、を含む水２００重量部に加え、プロペラ翼を備えた
攪拌機にて、重量平均粒子径１００μｍとなるよう１次
懸濁液を調製した。この時の所要時間は６００ｒｐｍで
４分であった。Example 4 1.0 part by weight of azobis-N, N-dimethylvaleronitrile was dissolved in 94 parts by weight of styrene and 6 parts by weight of divinylbenzene (purity: 82%), and 0.01 part by weight of sodium lauryl sulfate was added. (0.02 times the critical micelle concentration), 200 parts by weight of water containing 5 parts by weight of metathesis magnesium pyrophosphate, and a primary suspension having a weight average particle diameter of 100 μm with a stirrer equipped with a propeller blade. Was prepared. The time required at this time was 4 minutes at 600 rpm.
【００３２】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を１
５０ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると４２ｍ／分であった。Next, a nozzle type processor (LNP-20 / nanomizer LA-33 (manufactured by Nanomizer Co., Ltd.) is added.
300) and an SUS pipe having an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is
A second suspension was made by passing once under a pressure of 50 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was 42 m / min when calculated from the flow rate.
【００３３】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、１００ｒｐｍの緩やかな撹拌下で６
０℃で１０時間懸濁重合させて重合体粒子を得た。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、この
粒子は重量平均粒子径が７０．３μｍで、標準偏差が１
４．８μｍ、変動係数が２１．０％、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred under gentle stirring at 100 rpm for 6 minutes.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 10 hours. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter was 70.3 μm and the standard deviation was 1
The particle size distribution was 4.8 μm, the coefficient of variation was 21.0%, the particle size distribution was limited to a narrow region, and the particle sizes were well aligned.
【００３４】［実施例５］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル１．０重量部、カプロラクトンＥ．０変
性リン酸ジメタクリレート０．０５重量部をスチレン９
４重量部、ジビニルベンゼン（純度８２％）６重量部に
溶解し、複分解ピロリン酸マグネシウム３重量部、を含
む水２００重量部に加え、プロペラ翼を備えた攪拌機に
て、重量平均粒子径８０μｍとなるよう１次懸濁液を調
製した。この時の所要時間は４００ｒｐｍで２分であっ
た。Example 5 Azobis-N, N-dimethylvaleronitrile 1.0 part by weight, caprolactone E. 0-modified phosphate dimethacrylate 0.05 parts by weight with styrene 9
4 parts by weight, 6 parts by weight of divinylbenzene (purity 82%), and 200 parts by weight of water containing 3 parts by weight of metathesis magnesium pyrophosphate were added, and a weight average particle diameter of 80 μm was obtained with a stirrer equipped with a propeller blade. A primary suspension was prepared so that The time required at this time was 2 minutes at 400 rpm.
【００３５】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を３
００ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると５２ｍ／分であった。Next, a nozzle type processor (LNP-20 / nanomizer LA-33 (manufactured by Nanomizer) was added.
300) and an SUS pipe with an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is mixed with 3
A secondary suspension was made by passing once under a pressure of 00 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was 52 m / min when calculated from the flow rate.
【００３６】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で６
０℃で１０時間懸濁重合させて重合体粒子を得た。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、この
粒子は重量平均粒子径が１３．２μｍで、標準偏差が
２．１１μｍ、変動係数が１６．０％、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred under gentle stirring at 300 rpm for 6 minutes.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 10 hours. When the weight distribution of the obtained polymer particles was examined by a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 13.2 μm, the standard deviation was 2.11 μm, and the coefficient of variation was 16.0. %, And the particle size distribution was localized within a narrow region, and the particle sizes were well aligned.
【００３７】［実施例６］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル１．０重量部をスチレン３０重量部、ジ
ビニルベンゼン（純度８２％）２０重量部、酢酸エチル
５０重量部に溶解し、ジオクチルスルホコハク酸ナトリ
ウム０．０６重量部（臨界ミセル濃度の０．３倍）、複
分解ピロリン酸マグネシウム５重量部、を含む水２００
重量部に加え、ＴＫホモミキサーにて、重量平均粒子径
２０μｍとなるよう１次懸濁液を調製した。この時の所
要時間は４０００ｒｐｍで２分であった。Example 6 1.0 part by weight of azobis-N, N-dimethylvaleronitrile was dissolved in 30 parts by weight of styrene, 20 parts by weight of divinylbenzene (purity 82%) and 50 parts by weight of ethyl acetate, and dioctylsulfosuccinic acid was added. Water 200 containing 0.06 parts by weight of sodium acidate (0.3 times the critical micelle concentration) and 5 parts by weight of metathesis magnesium pyrophosphate
In addition to the parts by weight, a TK homomixer was used to prepare a primary suspension having a weight average particle diameter of 20 μm. The time required at this time was 2 minutes at 4000 rpm.
【００３８】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１６０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を３
００ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると５５ｍ／分であった。Next, the Nanomizer LA-33 (manufactured by Nanomizer Co., Ltd.) is provided with a nozzle type processor (LNP-20 /
300) and an SUS pipe with an inner diameter of 5 mm and a length of 160 mm are connected to the processor outlet, and the above-mentioned primary suspension is mixed with 3
A secondary suspension was made by passing once under a pressure of 00 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was calculated from the flow rate to be 55 m / min.
【００３９】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で６
０℃で１５時間懸濁重合させて重合体粒子を得た。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、この
粒子は重量平均粒子径が９．２μｍで、標準偏差が１．
７８μｍ、変動係数が１９．３％、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。また、電子顕微鏡によりこの粒子を
観察したところ得られた粒子は多孔質であった。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred under gentle stirring at 300 rpm for 6 minutes.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 15 hours. When the weight distribution of the obtained polymer particles was examined by a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 9.2 μm and the standard deviation was 1.
The particle size was 78 μm, the coefficient of variation was 19.3%, the particle size distribution was localized within a narrow region, and the particle sizes were well aligned. The particles obtained by observing the particles with an electron microscope were porous.
【００４０】［実施例７］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル０．５重量部をメタクリル酸メチル９５
重量部、エチレングリコールジメタクリレート５重量部
に溶解し、ラウリル硫酸ナトリウム０．０４重量部（臨
界ミセル濃度の０．２１倍）、塩化ナトリウム３重量
部、第３リン酸カルシウム１０重量部、水１９０重量部
の混合液中に加え、ＴＫホモミキサー（特殊機化製）に
て、重量平均粒子径２０μｍとなるよう１次懸濁液を調
製した。この時の所要時間は４０００ｒｐｍで２分であ
った。Example 7 Azobis-N, N-dimethylvaleronitrile (0.5 parts by weight) was added to methyl methacrylate (95 parts by weight).
Parts by weight, dissolved in ethylene glycol dimethacrylate 5 parts by weight, sodium lauryl sulfate 0.04 parts by weight (0.21 times the critical micelle concentration), sodium chloride 3 parts by weight, tertiary calcium phosphate 10 parts by weight, water 190 parts by weight A primary suspension was prepared with a TK homomixer (made by Tokushu Kiki Co., Ltd.) so that the weight average particle diameter was 20 μm. The time required at this time was 2 minutes at 4000 rpm.
【００４１】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１５０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を１
５０ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると６０ｍ／分であった。Next, the Nanomizer LA-33 (manufactured by Nanomizer Co., Ltd.) is connected to a nozzle type processor (LNP-20 /
300) and an SUS pipe having an inner diameter of 5 mm and a length of 150 mm are connected to the processor outlet, and the above-mentioned primary suspension is
A second suspension was made by passing once under a pressure of 50 kg / cm 2 . The flow rate of the secondary suspension at the pipe outlet at this time was calculated from the flow rate to be 60 m / min.
【００４２】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で５
０℃で８時間懸濁重合させて重合体粒子を得た。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、
この粒子は重量平均粒子径が１３．４μｍで、標準偏差
が２．２９μｍ、変動係数が１７．１％、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred under gentle stirring at 300 rpm for 5 hours.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 8 hours. When the weight distribution of particles was examined with a Coulter counter,
The particles had a weight average particle diameter of 13.4 μm, a standard deviation of 2.29 μm, and a coefficient of variation of 17.1%, and the particle size distribution was confined to a narrow region, and the particle size was good. It was a complete set.
【００４３】［実施例８］アゾビス−Ｎ，Ｎ−ジメチル
バレロニトリル０．５重量部をメタクリル酸メチル９５
重量部、エチレングリコールジメタクリレート５重量部
に溶解し、コロイダルシリカ（粒子径２０ｎｍ）３重量
部，塩化ナトリウム６０重量部、水２４０重量部の混合
液中に加え、ＴＫホモミキサーにて、重量平均粒子径２
０μｍとなるよう１次懸濁液を調製した。この時の所要
時間は５０００ｒｐｍで３分であった。Example 8 0.5 parts by weight of azobis-N, N-dimethylvaleronitrile was added to 95 parts of methyl methacrylate.
Parts by weight, dissolved in 5 parts by weight of ethylene glycol dimethacrylate, added to a mixed solution of 3 parts by weight of colloidal silica (particle diameter 20 nm), 60 parts by weight of sodium chloride and 240 parts by weight of water, and weight averaged with a TK homomixer. Particle size 2
A primary suspension was prepared so as to have a size of 0 μm. The time required at this time was 3 minutes at 5000 rpm.
【００４４】次いで、ナノマイザーＬＡ−３３（ナノマ
イザー社製）にノズル型プロセッサー（ＬＮＰ−２０／
３００）と内径５ｍｍ、長さ１５０ｍｍのＳＵＳ製配管
をプロセッサー出口に接続して、上記の１次懸濁液を１
５０ｋｇ／ｃｍ2 の圧力下に１回通して２次懸濁液を作
った。この時の配管出口での２次懸濁液の流速を流量か
ら求めると６２ｍ／分であった。Next, the Nanomizer LA-33 (manufactured by Nanomizer Co., Ltd.) is connected to a nozzle type processor (LNP-20 /
300) and an SUS pipe having an inner diameter of 5 mm and a length of 150 mm are connected to the processor outlet, and the above-mentioned primary suspension is
A second suspension was made by passing once under a pressure of 50 kg / cm 2 . The flow velocity of the secondary suspension at the pipe outlet at this time was 62 m / min when calculated from the flow rate.
【００４５】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの緩やかな撹拌下で５
０℃で８時間懸濁重合させて重合体粒子を得た。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、この粒
子は重量平均粒子径が８．９μｍで、標準偏差が１．８
３μｍ、変動係数が２０．６％、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。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred at 300 rpm under mild agitation.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 8 hours. The weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter. The weight average particle diameter of the particles was 8.9 μm, and the standard deviation was 1.8.
The particle size distribution was 3 μm, the coefficient of variation was 20.6%, the particle size distribution was limited to a narrow region, and the particle sizes were well aligned.
【００４６】［比較例１］実施例１に示したと同じ１次
懸濁液を更にＴＫホモミキサーで重量平均粒子径が９μ
ｍとなるように調整し（攪拌時間５分）、ナノマイザー
で処理せずにそのまま懸濁重合を行った。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、この粒子は重
量平均粒子径が８．３μｍで、標準偏差が２．９２μ
ｍ、変動係数が３５．２％であり、通常の懸濁重合で得
られる、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 in Example 1 was further mixed with a TK homomixer to give a weight average particle diameter of 9μ.
It was adjusted to m (stirring time: 5 minutes), and suspension polymerization was carried out as it was without treatment with a nanomizer. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 8.3 μm and the standard deviation was 2.92 μ.
m, the coefficient of variation was 35.2%, and showed a wide particle size distribution obtained by ordinary suspension polymerization, and therefore the particle sizes were uneven.
【００４７】［比較例２］実施例１に示したと同じ１次
懸濁液をＴＫホモミキサーにて重量平均粒子径が５μｍ
となるように調整した（攪拌時間１０分）。この一次懸
濁液を液−液衝突型のプロセッサー（ＬＤ−５００）を
取り付けたナノマイザーＬＡ−３３で１０００Ｋｇ／ｃ
ｍ2 の圧力下で１回処理して２次懸濁液を作った。[Comparative Example 2] The same primary suspension as used in Example 1 was mixed with a TK homomixer to give a weight average particle diameter of 5 μm.
Was adjusted (stirring time: 10 minutes). This primary suspension is 1000 kg / c in Nanomizer LA-33 equipped with a liquid-liquid collision type processor (LD-500).
It was treated once under a pressure of m 2 to make a secondary suspension.
【００４８】この２次懸濁液を内容積が５リットルの重
合反応槽に仕込み、３００ｒｐｍの穏やかな攪拌下で５
０℃で８時間懸濁重合させて重合体粒子を得た。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、この粒
子は重量平均粒子径が８．３μｍで、標準偏差が２．０
５μｍで、変動係数が２４．７％であり、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。しかしながら、１次懸濁液調整時の所要
時間は１００００ｒｐｍで１０分であった。This secondary suspension was charged into a polymerization reaction tank having an internal volume of 5 liters, and the mixture was stirred at 300 rpm under gentle stirring for 5 hours.
Polymer particles were obtained by suspension polymerization at 0 ° C. for 8 hours. The weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., Ltd., and the weight average particle diameter of the particles was 8.3 μm and the standard deviation was 2.0.
The particle size distribution was 5 μm, the coefficient of variation was 24.7%, the particle size distribution was localized within a narrow region, and the particle sizes were well aligned. However, the time required for preparing the primary suspension was 10 minutes at 10,000 rpm.
【００４９】［比較例３］実施例１でプロセッサーに接
続する配管径を１．７ｍｍに変更する以外は同条件で行
った。この時の配管内流速は２１０ｍ／分であった。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、こ
の粒子は重量平均粒子径が８．９μｍで、標準偏差が
２．３８μｍ、変動係数が２６．７％であって、通常の
懸濁重合で得られる粒度分布よりも均一な分布ではあっ
たものの、実施例１に比べ、従って粒子の大きさが不揃
いであった。[Comparative Example 3] The same procedure as in Example 1 was repeated except that the diameter of the pipe connected to the processor was changed to 1.7 mm. The flow velocity in the pipe at this time was 210 m / min. When the weight distribution of the obtained polymer particles was examined with a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 8.9 μm, the standard deviation was 2.38 μm, and the coefficient of variation was 26.7. %, And the particle size distribution was more uniform than the particle size distribution obtained by ordinary suspension polymerization, but the particle size was uneven compared with Example 1.
【００５０】［比較例４］実施例４で界面活性剤量を
０．１重量部に変更する以外は同条件で行った。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、この粒
子は重量平均粒子径が６．９μｍで、標準偏差が１．９
３μｍ、変動係数が２８．０％であって、通常の懸濁重
合で得られるものと同等な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 4] The same procedure as in Example 4 was repeated except that the amount of the surfactant was changed to 0.1 part by weight. When the weight distribution of the obtained polymer particles was examined by a Coulter counter manufactured by Coulter Co., the weight average particle diameter of the particles was 6.9 μm and the standard deviation was 1.9.
The particle size was 3 μm and the coefficient of variation was 28.0%, showing a broad particle size distribution equivalent to that obtained by ordinary suspension polymerization, and therefore the particle sizes were uneven.
【００５１】[0051]
【発明の効果】本発明の製造方法によれば、懸濁重合可
能な疎水性単量体、この単量体に可溶な重合開始剤、界
面活性剤及び分散安定剤を水性媒体中に加えて撹拌して
単量体粒子の１次懸濁液をノズルを備えたナノマイザー
のような装置により加圧噴射させ、２次懸濁液の流速が
０．５〜１００ｍ／分となるような配管を通過さすと、
４〜１００μｍの重量平均粒子径の範囲内で大きさの揃
った２次懸濁液が得られる。こうして得た２次懸濁液を
重合させると、ここに４〜１００μｍの重量平均粒子径
の範囲内で粒度分布の狭い重合体粒子が得られる。According to the production method of the present invention, a suspension-polymerizable hydrophobic monomer, a polymerization initiator soluble in this monomer, a surfactant and a dispersion stabilizer are added to an aqueous medium. A pipe in which the primary suspension of monomer particles is pressurized and jetted by a device such as a nanomizer equipped with a nozzle by stirring to cause the flow rate of the secondary suspension to be 0.5 to 100 m / min. When you pass
A secondary suspension having a uniform size within the range of the weight average particle diameter of 4 to 100 μm is obtained. When the secondary suspension thus obtained is polymerized, polymer particles having a narrow particle size distribution within a weight average particle diameter range of 4 to 100 μm are obtained.
【００５２】従って、本発明の方法によれば、１次懸濁
液の重量平均粒子径を、目的とする重量平均粒子径より
も小さくすることなく、効率よく４〜１００μｍの重量
平均粒子径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、滑り性付与剤、トナー、光拡散剤、塗料のつや消し
剤、機能性担体等として使用するに好適なものとなる。Therefore, according to the method of the present invention, the weight average particle size of the primary suspension can be efficiently adjusted to 4-100 μm without making the weight average particle size smaller than the target weight average particle size. Within the range, polymer particles having a narrow particle size distribution can be obtained. Since these particles have uniform sizes, they are suitable for use as spacers, slipperiness imparting agents, toners, light diffusing agents, delustering agents for paints, functional carriers and the like.
【図１】本発明の製造方法に使用される装置の要部の概
略断面図である。FIG. 1 is a schematic sectional view of a main part of an apparatus used in a manufacturing method of the present invention.
１ ノズル ２ １次懸濁液注入口 ３ ２次懸濁液噴出口 1 nozzle 2 Primary suspension inlet 3 Secondary suspension jet
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/00 - 2/60 G03G 9/08 Front page continuation (58) Fields surveyed (Int.Cl. 7 , DB name) C08F 2/00-2/60 G03G 9/08
Claims (3)
体に可溶な重合開始剤、界面活性剤及び分散安定剤を水
性媒体中に加えて重量平均粒子径が５〜１００μｍの単
量体粒子の１次懸濁液を作り、この１次懸濁液を加圧
下、その流路方向を強制的に変化させずにノズルから噴
出させ単量体粒子の２次懸濁液を作り、この２次懸濁液
を懸濁重合させて重量平均粒子径が４〜１００μｍでか
つ変動係数が１０〜２５％である領域内に粒子が分布し
た重合体粒子を得ることを特徴とする重合体粒子の製造
方法。1. A suspension-polymerizable hydrophobic monomer, a polymerization initiator soluble in this monomer, a surfactant and a dispersion stabilizer are added to an aqueous medium to give a weight average particle diameter of 5 to 100 μm. The primary suspension of the monomer particles is prepared, and the secondary suspension of the monomer particles is jetted from the nozzle under pressure without changing the flow direction of the primary suspension. And the secondary suspension is subjected to suspension polymerization to obtain polymer particles in which the particles are distributed in a region having a weight average particle diameter of 4 to 100 μm and a coefficient of variation of 10 to 25%. Of producing polymer particles.
ｍ／分の平均流速を有する請求項１の製造方法。2. The secondary suspension is 0.5 to 100 after jetting.
The method of claim 1 having an average flow rate of m / min.
度の０．５倍以下の量で使用される請求項１の製造方
法。3. The method according to claim 1, wherein the surfactant is used in an amount not more than 0.5 times the critical micelle concentration in pure water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35124196A JP3380131B2 (en) | 1996-09-24 | 1996-12-27 | Method for producing polymer particles |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-251899 | 1996-09-24 | ||
| JP25189996 | 1996-09-24 | ||
| JP35124196A JP3380131B2 (en) | 1996-09-24 | 1996-12-27 | Method for producing polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10152506A JPH10152506A (en) | 1998-06-09 |
| JP3380131B2 true JP3380131B2 (en) | 2003-02-24 |
Family
ID=26540419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35124196A Expired - Fee Related JP3380131B2 (en) | 1996-09-24 | 1996-12-27 | Method for producing polymer particles |
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| Country | Link |
|---|---|
| JP (1) | JP3380131B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3784336B2 (en) * | 2002-03-04 | 2006-06-07 | 積水化成品工業株式会社 | Method for producing polymer particles |
| JP3977272B2 (en) * | 2003-03-25 | 2007-09-19 | 積水化成品工業株式会社 | Method for producing resin 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 |
| KR101409467B1 (en) * | 2009-09-24 | 2014-06-19 | 코오롱인더스트리 주식회사 | Polymeric beads having a good thermal stability in the high temperature conditions |
-
1996
- 1996-12-27 JP JP35124196A patent/JP3380131B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
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