JP2001002716A - Singly particle diameter-dispersed particle, method for producing the same and use by using the same - Google Patents
Singly particle diameter-dispersed particle, method for producing the same and use by using the sameInfo
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- JP2001002716A JP2001002716A JP2000127634A JP2000127634A JP2001002716A JP 2001002716 A JP2001002716 A JP 2001002716A JP 2000127634 A JP2000127634 A JP 2000127634A JP 2000127634 A JP2000127634 A JP 2000127634A JP 2001002716 A JP2001002716 A JP 2001002716A
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- Japan
- Prior art keywords
- particles
- carbon atoms
- monodisperse
- seed
- polymerization
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本願発明は、粒径が１μｍ〜
１０００μｍ程度の範囲にあり、粒径が単分散である粒
子及びその粒子を製造する方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to the present invention, wherein the particle size is 1 μm or more.
The present invention relates to a particle having a diameter of about 1000 μm and a monodispersed particle size, and a method for producing the particle.
【０００２】[0002]
【従来の技術】粒径が数μｍから数百μｍであり、粒径
が単分散である粒子を作成する方法として、乳化重合に
おけるシード重合法、二段膨潤シード重合法、膜乳化法
等が広く知られている。乳化重合によるシード重合法で
は、例えば米国特許第４２４７４３４号公報に記載され
ているように、粒径単分散のシード粒子を用いること、
及び乳化重合時の乳化剤濃度を規定することにより、２
から４０μｍの粒子の膨潤と重合を繰り返しながら合成
することが可能である。しかしこの場合には、一度に膨
潤可能な体積は数倍程度であり、大粒径の粒子を得よう
とすると前記のような操作を数十回繰り返す必要がある
ことや、凝集を押さえるため、宇宙空間のような無重力
条件下で重合を行う必要性があることから、実用性に課
題があった。更には粒子の架橋度を大きくすると異形粒
子の発生、新粒子の発生が起こるため、事実上は架橋度
が１％以下の非常に弱い粒子しか作製できないという課
題もあった。2. Description of the Related Art Seed polymerization in emulsion polymerization, two-stage swelling seed polymerization, membrane emulsification, etc. are known as methods for producing particles having a particle size of several μm to several hundred μm and having a monodispersed particle size. Widely known. In the seed polymerization method by emulsion polymerization, for example, as described in US Pat. No. 4,247,434, use of monodispersed seed particles,
And by defining the concentration of the emulsifier during the emulsion polymerization,
It can be synthesized while repeating swelling and polymerization of particles having a particle size of from 40 μm to 40 μm. However, in this case, the volume that can be swollen at a time is about several times, and it is necessary to repeat the above operation several tens of times to obtain particles having a large particle size, and to suppress aggregation, There is a problem in practicality due to the necessity of performing polymerization under zero-gravity conditions such as in space. Further, when the degree of cross-linking of the particles is increased, irregular shaped particles and new particles are generated. Therefore, there is also a problem that only very weak particles having a degree of cross-linking of 1% or less can be produced.
【０００３】米国特許第４３３６１７３号公報には二段
膨潤シード重合法が記載されている。この方法は、油溶
性物質に対して微量の高疎水性有機化合物を混合した後
に乳化することにより、油溶性物質の乳化液の安定性が
飛躍的に高まる現象を利用したものであり、高疎水性物
質の粒径単分散油滴を作製し、これに対してモノマーを
吸収させて単分散粒子を作製する方法である。[0003] US Pat. No. 4,336,173 describes a two-stage swelling seed polymerization process. This method utilizes the phenomenon that the stability of an emulsion of an oil-soluble substance is dramatically increased by mixing and emulsifying a small amount of a highly hydrophobic organic compound with an oil-soluble substance. This is a method in which monodisperse oil droplets of an active substance having a particle size are prepared, and a monomer is absorbed into the droplets to prepare monodisperse particles.
【０００４】しかしこの方法では、単分散の高疎水モノ
マー性物質の油滴を作製するために、まず単分散ポリス
チレンの水分散液を作製し、この水相に対してアセトン
を添加することで水相の有機溶媒濃度を上げ、高疎水性
物質を吸収しやすくした後、高疎水性物質の乳化液をこ
れに添加し、その後水相のアセトン濃度を低下させると
いうように煩雑な操作が必要があった。However, in this method, in order to prepare monodisperse oil droplets of a highly hydrophobic monomeric substance, first, an aqueous dispersion of monodisperse polystyrene is prepared, and acetone is added to the aqueous phase to prepare water. After increasing the organic solvent concentration of the phase and making it easier to absorb the highly hydrophobic substance, a complicated operation such as adding an emulsion of the highly hydrophobic substance to this and then lowering the acetone concentration of the aqueous phase is required. there were.
【０００５】この方法では、架橋度が任意の粒子を作製
することができ、また単に単分散のポリスチレン粒子を
モノマーにより直接膨潤させるよりは大きい膨潤倍率を
達成できるとされている。しかし、膨潤倍率でみると、
出発のポリスチレン粒子に対する膨潤倍率では１５０倍
程度が達成されるが、高疎水性物資を吸収した油滴に対
しての膨潤倍率では５０倍程度の膨潤倍率にしかならな
い。このことから、膨潤倍率については実際上高膨潤倍
率を達成できるものではない。また高疎水性物質を単分
散ポリスチレンに吸収させる工程が必要で、本来吸収さ
れにくい高疎水性物質を吸収させるために、高疎水性物
質の乳化液と単分散ポリスチレン分散液の混合物にアセ
トン等を添加する必要があり、混合系が不安定となりや
すい。このため工程の維持には細心の注意を払う必要が
あり、シード粒子合成から膨潤までの段階において多段
階の工程が必要となっていた。According to this method, particles having an arbitrary degree of cross-linking can be prepared, and a higher swelling ratio can be achieved than by simply swelling monodisperse polystyrene particles directly with a monomer. However, looking at the swelling ratio,
The swelling ratio for the starting polystyrene particles is about 150 times, but the swelling ratio for oil droplets having absorbed highly hydrophobic substances is only about 50 times. For this reason, a high swelling ratio cannot be achieved in practice. In addition, a step of absorbing the highly hydrophobic substance into the monodisperse polystyrene is necessary, and acetone or the like is added to the mixture of the emulsion of the highly hydrophobic substance and the monodisperse polystyrene dispersion in order to absorb the highly hydrophobic substance which is originally hardly absorbed. It needs to be added, and the mixed system tends to be unstable. For this reason, meticulous care must be taken to maintain the process, and a multi-stage process is required from the stage of seed particle synthesis to swelling.
【０００６】更に、高疎水性物質を併用することから、
これが生成する粒子に対し細孔を形成する際に悪影響を
及ぼす可能性もある。なお、ポリスチレンシード粒子を
用いたシード重合法を行った場合、モノマーとしてポリ
スチレンと相溶性の低いアクリル系モノマーを用いた場
合だけではなく、同種のスチレンを用いた場合にも、得
られた粒子にはシード粒子が相分離した細孔が生じるこ
とが広く知られている。Further, since a highly hydrophobic substance is used in combination,
This can have an adverse effect on the resulting particles in forming the pores. In addition, when the seed polymerization method using polystyrene seed particles is performed, not only when an acrylic monomer having low compatibility with polystyrene is used as a monomer, but also when using the same type of styrene, It is widely known that pores formed by phase separation of seed particles occur.
【０００７】単分散ポリマー粒子をシードとして、これ
に直接モノマーを吸収膨潤させる一段膨潤シード重合法
では、例えば特開昭６２−１２７０１号公報に記載され
たように、モノマーの乳化液の油滴粒子径を規定し、膨
潤時間を規定することで、高膨潤倍率を達成することが
可能である。In the one-stage swelling seed polymerization method in which monodisperse polymer particles are used as a seed and the monomer is directly absorbed and swelled, oil droplet particles of an emulsion of the monomer are used as described in, for example, JP-A-62-2701. By defining the diameter and the swelling time, a high swelling ratio can be achieved.
【０００８】しかしながら、この方法ではシード粒子の
粒子径に対してモノマーの乳化液の油滴粒子径を規定す
る必要があるが、かかる規定は実際の製造上非常に困難
である。また膨潤時間に最適時間帯が存在することにな
り、製造上好ましくない。However, in this method, it is necessary to define the oil droplet particle size of the emulsion of the monomer with respect to the particle size of the seed particles, but such a definition is extremely difficult in actual production. In addition, there is an optimum time zone for the swelling time, which is not preferable in production.
【０００９】米国特許第５４９６８９７号公報には、重
合性モノマーに親水性有機化合物を添加し、これを水中
で乳化した後、ポリマーシード粒子に吸収させる方法が
記載されている。この方法によれば、１０％前後の親水
性有機化合物を併用することで５０〜６０倍の膨潤倍率
を達成することができるが、親水性有機化合物を併用す
ることから、これが生成する粒子に対し細孔を形成する
際に悪影響を及ぼす可能性がある。US Pat. No. 5,468,897 describes a method in which a hydrophilic organic compound is added to a polymerizable monomer, which is emulsified in water and then absorbed by polymer seed particles. According to this method, it is possible to achieve a swelling ratio of 50 to 60 times by using a hydrophilic organic compound of about 10% in combination. It can have a bad effect when forming pores.
【００１０】膜乳化法は、例えばＪｏｕｒｎａｌ ｏｆ
Ａｐｐｌｉｅｄ ＰｏｌｙｍｅｒＳｃｉｅｎｃｅ Ｖ
ｏｌ．５１ １−１１（１９９４年）に記載されている
ように、均質な細孔を有するＳＰＧ膜（シラスポーラス
グラス膜）を介し、乳化剤を含む水性媒体中に均一粒径
の油滴を作製する方法である。この方法により重合性モ
ノマーを直接均質粒径油滴とし、重合することにより、
比較的単分散な粒子を合成するこが可能で、また単分散
の高疎水性有機化合物油滴を作製し、これに重合性モノ
マーを吸収させ重合するシード重合を行うことも可能で
ある。The membrane emulsification method is, for example, a Journal of
Applied PolymerScience V
ol. As described in 511-11 (1994), a method of producing oil droplets having a uniform particle size in an aqueous medium containing an emulsifier through an SPG film (silas porous glass film) having uniform pores. It is. In this method, the polymerizable monomer is directly converted into oil droplets having a uniform particle size and polymerized.
It is possible to synthesize relatively monodisperse particles, and it is also possible to prepare monodisperse highly hydrophobic organic compound oil droplets and to perform seed polymerization in which polymerizable monomers are absorbed and polymerized.
【００１１】この方法では、疎水性の高いスチレンモノ
マーのようなモノマーを用いた場合、膜の細孔径の５倍
程度の粒径を有する単分散粒子は合成可能であるが、比
較的親水性が高いモノマーを用いた場合、膜の親水性が
高いために膜表面で該モノマーが広がってしまい、単分
散油滴を作製することが困難となる課題がある。また更
には、高疎水性有機化合物の単分散油滴を作製し、シー
ド重合により粒子を作製する場合に於いても、作製可能
な高疎水性有機化合物の単分散油滴の粒径は数μｍと比
較的大きいために、１０μｍ以下の粒子を作製する場合
は膨潤倍率が低くなり、モノマーに対する高疎水性有機
化合物の割合が大きくなって細孔形成に悪影響を与えて
しまう。According to this method, when a monomer such as a styrene monomer having high hydrophobicity is used, monodispersed particles having a particle diameter of about 5 times the pore diameter of the membrane can be synthesized, but relatively hydrophilic. When a high monomer is used, the monomer is spread on the film surface due to high hydrophilicity of the film, and there is a problem that it is difficult to prepare monodisperse oil droplets. Furthermore, when a monodisperse oil droplet of a highly hydrophobic organic compound is produced and particles are produced by seed polymerization, the particle diameter of a monodisperse oil droplet of a highly hydrophobic organic compound that can be produced is several μm. When particles having a size of 10 μm or less are produced, the swelling ratio decreases, and the ratio of the highly hydrophobic organic compound to the monomer increases, which adversely affects pore formation.
【００１２】[0012]
【発明が解決しようとする課題】そこで本願発明は、以
上のごとき課題を解決し、粒径が１μｍ〜１０００μｍ
程度の範囲にある粒径が単分散である粒子、該粒子をよ
り簡便に製造する方法、該粒子を充填してなる液体クロ
マトグラフィー用カラム、そして該カラムを用いる液体
クロマトグラフィー分析法を提供することを目的とする
ものである。Accordingly, the present invention has solved the above-mentioned problems and has a particle diameter of 1 μm to 1000 μm.
A monodisperse particle having a particle size in the range of about 1, a method for producing the particle more easily, a column for liquid chromatography filled with the particle, and a liquid chromatography analysis method using the column. The purpose is to do so.
【００１３】[0013]
【課題を解決するための手段】前記目的を達成するため
になされた本願請求項１の発明は、炭素数６以上の直鎖
アルキル基、炭素数６以上の脂肪族環状アルキル基、フ
ェニル基、ベンジル基又は炭素数３以上のハロゲン化ア
ルキル基を少なくとも一種類以上含むポリ（メタ）アク
リル酸エステルからなる粒径単分散なポリマーシード粒
子に、重合性モノマーを含む水性乳化液を添加して膨潤
させた後、重合して得られる粒径単分散粒子である。Means for Solving the Problems To achieve the above object, the invention of claim 1 of the present invention is directed to a linear alkyl group having 6 or more carbon atoms, an aliphatic cyclic alkyl group having 6 or more carbon atoms, a phenyl group, Addition of an aqueous emulsion containing a polymerizable monomer to monodispersed polymer seed particles of poly (meth) acrylate containing at least one benzyl group or at least one halogenated alkyl group having 3 or more carbon atoms, followed by swelling It is a monodisperse particle obtained by polymerization after polymerization.
【００１４】また前記目的を達成するためになされた本
願請求項７の発明は、炭素数６以上の直鎖アルキル基、
炭素数６以上の脂肪族環状アルキル基、フェニル基、ベ
ンジル基又は炭素数３以上のハロゲン化アルキル基を少
なくとも一種類以上含むポリ（メタ）アクリル酸エステ
ルからなる粒径単分散なポリマーシード粒子に、重合性
モノマーを含む水性乳化液を添加して膨潤させた後、重
合させる粒径単分散粒子の製造法である。In order to achieve the above object, the invention of claim 7 of the present invention provides a linear alkyl group having 6 or more carbon atoms,
Monodispersed polymer seed particles of poly (meth) acrylate containing at least one kind of aliphatic cyclic alkyl group having 6 or more carbon atoms, phenyl group, benzyl group or halogenated alkyl group having 3 or more carbon atoms. This is a method for producing monodisperse particles having a particle size to be polymerized after adding and swelling an aqueous emulsion containing a polymerizable monomer.
【００１５】また前記目的を達成するためになされた本
願請求項１３の発明は、前記粒径単分散粒子を充填して
なる液体クロマトグラフィー用カラムである。そして前
記目的を達成するためになされた本願請求項１４の発明
は、前記カラムを用いる液体クロマトグラフィー分析法
である。以下、本願発明を詳細に説明する。[0015] Further, the invention of claim 13 of the present invention made to achieve the above object is a liquid chromatography column packed with the monodisperse particles. The invention of claim 14 made to achieve the above object is a liquid chromatography analysis method using the column. Hereinafter, the present invention will be described in detail.
【００１６】本願発明における粒径単分散粒子の製造方
法を工程順に下記に記す。The method for producing monodisperse particles of the present invention will be described below in the order of steps.
【００１７】第一段階としては、粒径単分散のシード粒
子を作製する工程である。シード粒子作製法としては、
乳化重合法及び分散重合法を用いることができる。The first step is a step for producing monodispersed seed particles. As a method for preparing seed particles,
Emulsion polymerization and dispersion polymerization can be used.
【００１８】第二段階としては、シード粒子を膨潤、重
合する工程である。この工程ではシード粒子分散液とモ
ノマー乳化液を任意の割合で混合することで膨潤が進行
する。本願発明のシード粒子を用いることにより、従来
知られている二段膨潤法等とは異なり、高疎水性物質を
シード粒子分散液と混合し、アセトン等の膨潤助剤を添
加して、高疎水性物質の油滴を作製する必要もなく、高
膨潤倍率を達成できる。また、従来油滴の合一、分断等
による粒子径分布の拡大を防ぐ方法として、油滴を安定
化させるために、ポリビニルアルコール等の水溶性高分
子を添加する方法が知られているが、これらの添加はシ
ード粒子のモノマーによる膨潤を妨げることが知られて
いる。このため、従来膨潤倍率を高く設定する場合、水
溶性高分子の添加は、膨潤工程が終了した後に行うこと
が一般的であった。しかし本願発明におけるシード粒子
を用いることにより、水溶性高分子の添加が可能とな
り、膨潤工程における粒子径分布の拡大を防ぐことが可
能となった。重合工程は従来から知られている方法と異
なることはなく、容易に進行させることができる。The second step is a step of swelling and polymerizing the seed particles. In this step, the swelling proceeds by mixing the seed particle dispersion and the monomer emulsion at an arbitrary ratio. By using the seed particles of the present invention, unlike the conventionally known two-stage swelling method and the like, a highly hydrophobic substance is mixed with a seed particle dispersion, and a swelling aid such as acetone is added to the mixture to form a highly hydrophobic substance. A high swelling ratio can be achieved without the necessity of preparing oily drops of a conductive substance. In addition, as a method of preventing coalescence of oil droplets, expansion of the particle size distribution due to fragmentation and the like, a method of adding a water-soluble polymer such as polyvinyl alcohol to stabilize the oil droplets is known. These additions are known to prevent monomer swelling of the seed particles. For this reason, conventionally, when the swelling ratio is set to be high, the addition of the water-soluble polymer is generally performed after the swelling step is completed. However, by using the seed particles in the present invention, it became possible to add a water-soluble polymer, and it was possible to prevent the particle size distribution from expanding in the swelling step. The polymerization step does not differ from conventionally known methods and can be easily advanced.
【００１９】第三段階は、必要に応じて行われる重合体
粒子の洗浄である。例えばシード粒子ポリマーを重合体
から取り出す場合には、ケトン系溶媒、酢酸エステル系
溶媒、芳香族系溶媒等の広範囲の溶媒で洗浄を行えば、
容易にシード粒子ポリマーを重合体粒子から取り去るこ
とができる。The third step is an optional washing of the polymer particles. For example, when removing the seed particle polymer from the polymer, if washed with a wide range of solvents such as ketone solvents, acetate solvents, and aromatic solvents,
The seed particle polymer can be easily removed from the polymer particles.
【００２０】本願発明で用いる（メタ）アクリル酸エス
テルポリマーシード粒子は、炭素数６以上の直鎖アルキ
ル基、炭素数６以上の脂肪族環状アルキル基、フェニル
基、ベンジル基又は炭素数３以上のハロゲン化アルキル
基をエステル部に有するポリマー粒子であり、一種を用
いても良いし、二種以上を混合して用いても良い。これ
らの例としては、（メタ）アクリル酸ｎ−ヘキシルエス
テル、（メタ）アクリル酸２−エチルヘキシルエステ
ル、（メタ）アクリル酸ステアリルエステル、（メタ）
アクリル酸ｎ−オクチルエステル、（メタ）アクリル酸
ｔ−ブチルシクロヘキシルエステル、（メタ）アクリル
酸シクロヘキシルエステル、（メタ）アクリル酸２，３
−ジブロモプロピルエステル、（メタ）アクリル酸１
Ｈ，１Ｈ，２Ｈ，２Ｈ−ヘプタフルオロ−ｎ−デシルエ
ステル、（メタ）アクリル酸１，１，１，３，３，３―
ヘキサフルオロイソプロピルエステル、（メタ）アクリ
ル酸フェニルエステル、（メタ）アクリル酸４−メチル
フェニルエステル、（メタ）アクリル酸２−メチルフェ
ニルエステル、（メタ）アクリル酸３−メチルフェニル
エステル、（メタ）アクリル酸ベンジルエステル等を例
示することができる。なかでも直鎖状アルキル基、脂肪
族環状アルキル基又はベンジル基を有するポリマー粒子
を用いると、後の重合性モノマーを重合した場合に、幅
広い種類の重合性モノマーにおいて、シード粒子の相分
離による影響が現れずに良好な表面形状を有する粒径単
分散粒子を得ることが可能であり、特に好ましい。一
方、膨潤倍率を重視する場合には直鎖アルキルエステル
を用いることが好ましく、シード粒子の製造安定性や保
存安定性を重視する場合には脂肪族環状エステル又はベ
ンジルエステルを用いることが好ましい。The (meth) acrylic acid ester polymer seed particles used in the present invention may be a linear alkyl group having 6 or more carbon atoms, an aliphatic cyclic alkyl group having 6 or more carbon atoms, a phenyl group, a benzyl group, or a C3 or more. It is a polymer particle having a halogenated alkyl group in the ester portion, and may be used alone or as a mixture of two or more. Examples of these are n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate
N-octyl acrylate, t-butyl cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,3 (meth) acrylic acid
-Dibromopropyl ester, (meth) acrylic acid 1
H, 1H, 2H, 2H-heptafluoro-n-decyl ester, (meth) acrylic acid 1,1,1,3,3,3-
Hexafluoroisopropyl ester, (meth) acrylic acid phenyl ester, (meth) acrylic acid 4-methylphenyl ester, (meth) acrylic acid 2-methylphenyl ester, (meth) acrylic acid 3-methylphenyl ester, (meth) acrylic Acid benzyl ester and the like can be exemplified. In particular, when polymer particles having a linear alkyl group, an aliphatic cyclic alkyl group, or a benzyl group are used, when polymerizable monomers are subsequently polymerized, the effect of phase separation of seed particles on a wide variety of polymerizable monomers. It is particularly preferable since monodisperse particles having a good surface shape can be obtained without the appearance of a particle. On the other hand, when importance is placed on the swelling ratio, a linear alkyl ester is preferably used, and when importance is placed on the production stability and storage stability of the seed particles, an aliphatic cyclic ester or a benzyl ester is preferably used.
【００２１】用いるシード粒子の分子量に特別の制限は
ないが、後の重合性モノマーを含む有機化合物混合体を
吸収させる工程において膨潤倍率を大きく設定できるこ
とから、重量平均分子量において５０，０００以下のも
のが好ましい。The molecular weight of the seed particles to be used is not particularly limited. However, since the swelling ratio can be set large in the subsequent step of absorbing the organic compound mixture containing a polymerizable monomer, those having a weight average molecular weight of 50,000 or less are used. Is preferred.
【００２２】上記シード粒子は、従来の有機溶媒系での
分散重合又は水溶媒系での乳化重合法を用いて合成する
ことができる。シード粒子を分散重合で作製する場合に
は、シード粒子分散液を水性分散液に置換する必要が頻
繁に生じることがあるため、乳化重合により作製するこ
とが好ましい。The seed particles can be synthesized by a conventional dispersion polymerization in an organic solvent system or an emulsion polymerization method in an aqueous solvent system. When the seed particles are prepared by dispersion polymerization, it is necessary to frequently replace the seed particle dispersion with an aqueous dispersion. Therefore, it is preferable to prepare the seed particles by emulsion polymerization.
【００２３】乳化重合法を行う場合には、ソープフリー
乳化重合を用い、連鎖移動剤を併用することが、分子
量、平均粒径、粒径分散度の再現性良好なシード粒子を
作製するうえで好ましい。連鎖移動剤としては一般的な
連鎖移動剤を使用することができるが、その一例として
１，１，３，３−テトラメチルブタン−１−チオール、
シクロヘキシルメルカプタン、ｔ−テトラデカンチオー
ル、オクタデシルメルカプタン、１−ペンタンチオー
ル、１−ヘキサデカンチオール、２−メチル−２−プロ
パンチオ−ル、２−プロペンチオール、１−ペンタンチ
オール、１−ドデカンチオール、１−オクタンチオー
ル、１−ヘキサンチオール、１−ブタンチオール等の直
鎖又は脂肪族環状アルキルチオール類、ナフタレンチオ
ール、ペンタフルオルチオフェノール、２−メトキシベ
ンゼンチオ−ル、４−メトキシベンゼンチオール、２−
クロロチオフェノール、ｏ−ブロモチオフェノール、２
−イソプロピルチオフェノール、１，３−ベンゼンチオ
ール、チオフェノール、ｍ−チオクレゾール、チオキシ
レノール等の芳香族チオール類、チオグリコール酸メチ
ル、チオグリコール酸エチル、チオグリコール酸２−エ
チルヘキシル等のチオグリコール酸エステル類、３−メ
ルカプトプロピオン酸エステル類、チオサリチル酸エス
テル類を例示することができるが、なかでも炭素数８以
下のエステル部を有するチオグリコール酸エステルを用
いることが好ましい。連鎖移動剤として分子内に陰イオ
ン交換基を有する連鎖移動剤を用いると乳化重合中に凝
集を引き起こす可能性があり、注意を要する。また分子
内に２個以上のチオール基を有する連鎖移動剤の使用
は、分子量を小さくするため使用しないことが好まし
い。In the case of carrying out the emulsion polymerization method, soap-free emulsion polymerization may be used in combination with a chain transfer agent in order to produce seed particles having good reproducibility of the molecular weight, the average particle diameter and the degree of dispersion of the particle diameter. preferable. As the chain transfer agent, a general chain transfer agent can be used. For example, 1,1,3,3-tetramethylbutane-1-thiol,
Cyclohexylmercaptan, t-tetradecanethiol, octadecylmercaptan, 1-pentanethiol, 1-hexadecanethiol, 2-methyl-2-propanethiol, 2-propenethiol, 1-pentanethiol, 1-dodecanethiol, 1-octanethiol , 1-hexanethiol, linear or aliphatic cyclic alkylthiols such as 1-butanethiol, naphthalene thiol, pentafluorothiophenol, 2-methoxybenzenethiol, 4-methoxybenzenethiol,
Chlorothiophenol, o-bromothiophenol, 2
-Aromatic thiols such as -isopropylthiophenol, 1,3-benzenethiol, thiophenol, m-thiocresol and thioxylenol; thioglycolic acid such as methyl thioglycolate, ethyl thioglycolate and 2-ethylhexyl thioglycolate Esters, 3-mercaptopropionic esters, and thiosalicylic esters can be exemplified, and among them, thioglycolic acid esters having an ester portion having 8 or less carbon atoms are preferable. If a chain transfer agent having an anion exchange group in the molecule is used as the chain transfer agent, there is a possibility of causing aggregation during the emulsion polymerization, and thus care must be taken. It is preferable not to use a chain transfer agent having two or more thiol groups in the molecule in order to reduce the molecular weight.
【００２４】乳化重合法等を行って合成したシード粒子
は特に精製等する必要なしに、そのまま、後の工程に使
用することができる。なお、本願発明により得られた粒
径単分散粒子をシード粒子として用い、さらに大粒径の
粒径単分散粒子を得ることも可能である。また、従来知
られている２段階膨潤重合法のシード粒子として用い、
高疎水性物質を吸収させることも可能である。この場
合、従来高疎水性物質を吸収させるために、高疎水性物
質乳化液とシード粒子分散液の混合物に添加していたア
セトン等の膨潤助剤を添加せずとも、膨潤が進行し、粒
子のそろった高疎水性物質の単分散油滴を作製すること
が可能である。The seed particles synthesized by the emulsion polymerization method and the like can be used as they are in subsequent steps without any need for purification. In addition, it is also possible to obtain a monodisperse particle having a larger particle diameter by using the monodisperse particle having the particle diameter obtained by the present invention as a seed particle. Further, it is used as seed particles for a conventionally known two-stage swelling polymerization method,
It is also possible to absorb highly hydrophobic substances. In this case, the swelling proceeds without adding a swelling aid such as acetone which was conventionally added to the mixture of the highly hydrophobic substance emulsion and the seed particle dispersion in order to absorb the highly hydrophobic substance. It is possible to produce monodispersed oil droplets of a highly hydrophobic substance with uniformity.
【００２５】重合性モノマーを含む水性乳化液は、重合
性モノマー、重合開始剤、乳化剤及び水から構成される
が、必要に応じて粒子に細孔を形成するための細孔形成
剤を添加しても良い。乳化方法はホモジナイザーなどを
用いる等の一般的な方法を用いることができる。The aqueous emulsion containing a polymerizable monomer is composed of a polymerizable monomer, a polymerization initiator, an emulsifier, and water. If necessary, a pore-forming agent for forming pores in the particles may be added. May be. As the emulsifying method, a general method such as using a homogenizer can be used.
【００２６】重合性モノマーとしては、水に対する溶解
度が０．００１重量％以上であれば特に制限はなく、ま
た非架橋性モノマーと架橋性モノマーは任意の割合で用
いることができる。重合性モノマーとしてはスチレン、
４−メチルスチレン、ジビニルベンゼン、クロロメチル
スチレン等のスチレン誘体、（メタ）アクリル酸メチ
ル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘ
キシル、（メタ）アクリル酸２−ヒドロキシエチル、
（メタ）アクリル酸グリシジル等の（メタ）アクリル酸
エステル類、（メタ）アクリル酸アミド類、アクリロニ
トリル、マレイン酸エステル類、マレイン酸アミド類、
マレイン酸イミド類、塩化ビニル、酢酸ビニル、トリア
リルイソシアヌレート、ブタジエン等を例示することが
できるが、水溶性の高いカチオン性モノマーを用いると
シード粒子が凝集することがあるため、非イオン性又は
アニオン性であるモノマーを使用することが特に好まし
い。The polymerizable monomer is not particularly limited as long as its solubility in water is 0.001% by weight or more, and the non-crosslinkable monomer and the crosslinkable monomer can be used in any ratio. Styrene as a polymerizable monomer,
Styrene derivatives such as 4-methylstyrene, divinylbenzene, chloromethylstyrene, methyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
(Meth) acrylic esters such as glycidyl (meth) acrylate, (meth) acrylic amides, acrylonitrile, maleic esters, maleic amides,
Maleic imides, vinyl chloride, vinyl acetate, triallyl isocyanurate, butadiene, etc. can be exemplified, but if a highly water-soluble cationic monomer is used, the seed particles may aggregate, so that nonionic or It is particularly preferred to use monomers that are anionic.
【００２７】細孔を形成するために必要に応じて添加す
る細孔形成剤としては、一般的な懸濁重合法に於いて粒
子の細孔形成剤として用いられる有機物を使用すること
ができる。例えば、トルエン、キシレン、ベンジルアル
コール、フタル酸エステル類、安息香酸エステル等の芳
香族化合物、酢酸エステル類、酢酸アミド類、ブタノー
ル、ペンタノール、ヘキサノール等の高級アルコール
類、エチレンジクロライド、１、３−ジクロロプロパ
ン、クロロベンゼン類、クロロフォルム等のハロゲン化
化合物を例示することができる。これらの細孔形成剤の
使用量に特に制限はないが、生成した粒子の強度上の問
題からモノマー１重量に対して０〜２重量部程度用いる
ことが一般的である。As the pore-forming agent to be added as needed for forming the pores, an organic substance used as a pore-forming agent for particles in a general suspension polymerization method can be used. For example, aromatic compounds such as toluene, xylene, benzyl alcohol, phthalates, and benzoates; acetates, acetate amides; higher alcohols such as butanol, pentanol, and hexanol; ethylene dichloride; Examples thereof include halogenated compounds such as dichloropropane, chlorobenzenes, and chloroform. The amount of the pore forming agent is not particularly limited, but is generally used in an amount of about 0 to 2 parts by weight based on 1 part of the monomer due to the problem of the strength of the produced particles.
【００２８】重合開始剤としては、油溶性重合開始剤を
使用することが好ましい。例えばアゾイソブチロバレロ
ニトリル、２，２’−アゾビス（２，４−ジメチルバレ
ロニトリル）等のアゾ系重合開始剤や過酸化ベンゾイ
ル、ｔ−ブチルペルオキシ−２−エチルヘキサノエート
等の有機過酸化物等を例示することができる。As the polymerization initiator, it is preferable to use an oil-soluble polymerization initiator. For example, azo-based polymerization initiators such as azoisobutyrovaleronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) and organic peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. Oxides and the like can be exemplified.
【００２９】重合性モノマー、必要に応じて添加する細
孔形成剤そして重合開始剤の混合比は特に制限されず、
目的に応じて任意の割合で用いることができる。The mixing ratio of the polymerizable monomer, the pore forming agent to be added as required, and the polymerization initiator is not particularly limited.
It can be used at any ratio depending on the purpose.
【００３０】乳化剤としてはノニオン系又はアニオン系
の乳化剤が好ましい。例えばポリエチレングリコールラ
ウリルエーテル、ポリエチレングリコールドデシルエー
テル等のポリエチレングリコール誘導体、アルキルスル
ホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキ
ル燐酸塩類、アルキルカルボン酸塩類等を例示すること
ができる。これらの乳化剤の使用量は、作製する乳化液
の安定性を十分に保てれば良く、特に制限はない。そし
て前記水性乳化液を構成する各成分、すなわち重合性モ
ノマーを含む有機物混合体を水中に乳化する場合の割合
は、同体積以上の水を用いることが好ましい。As the emulsifier, a nonionic or anionic emulsifier is preferable. Examples thereof include polyethylene glycol derivatives such as polyethylene glycol lauryl ether and polyethylene glycol dodecyl ether, alkyl sulfonates, alkyl benzene sulfonates, alkyl phosphates, alkyl carboxylate salts and the like. The amount of these emulsifiers used is not particularly limited as long as the stability of the emulsion to be prepared is sufficiently maintained. In addition, it is preferable to use the same volume or more of water when emulsifying the components of the aqueous emulsion, that is, the organic mixture containing the polymerizable monomer, in water.
【００３１】前記したように、本願発明により得られた
粒径単分散粒子をシード粒子として用い、更に大粒径の
粒子を作製する場合には、水性乳化液に連鎖移動剤を添
加することが好ましい。添加方法としては、水性乳化液
作製時に重合性モノマーなどと混合して用いる方法や、
シード粒子のモノマー膨潤に先立って連鎖移動剤のみの
乳化液を作製しシード粒子に吸収させる方法を例示でき
る。これらに使用される連鎖移動剤は一般的な油溶性連
鎖移動剤で良い。その使用量に特別の制限はなく、目標
とする分子量作製に見合った必要量を添加すればよい。As described above, when the monodispersed particles having the particle size obtained according to the present invention are used as seed particles and a particle having a larger particle size is produced, a chain transfer agent may be added to the aqueous emulsion. preferable. As an addition method, a method of mixing with a polymerizable monomer or the like when preparing an aqueous emulsion, or
Prior to the monomer swelling of the seed particles, a method in which an emulsion containing only the chain transfer agent is prepared and absorbed by the seed particles can be exemplified. The chain transfer agent used for these may be a common oil-soluble chain transfer agent. There is no particular limitation on the amount used, and it is sufficient to add a necessary amount corresponding to the target molecular weight production.
【００３２】ポリマーシード粒子と重合性モノマー及び
細孔形成剤の割合は、ポリマーシード粒子の体積に対し
て、１０〜５００００倍が好適である。The ratio of the polymer seed particles to the polymerizable monomer and the pore-forming agent is preferably 10 to 50,000 times the volume of the polymer seed particles.
【００３３】また上記ポリマーシード粒子に重合性モノ
マーを含む水性乳化液を添加し、ポリマーシード粒子を
膨潤させる工程では、油滴安定化のために必要に応じて
高分子分散安定剤を用いることができる。高分子分散安
定剤を添加する時期は、ポリマーシード粒子分散液に高
分子分散安定剤を添加し、その後重合性モノマーを含む
水性乳化液を添加してもよいし、ポリマーシード粒子分
散液に重合性モノマーを含む水性乳化液を添加した後に
高分子分散安定剤を添加してもよい。高分子分散安定剤
としては、ノニオン系及びアニオン系の高分子分散安定
剤であれば特に制限はない。例えばポリビニルアルコー
ル、ポリビニルピロリドン、ヒドロキシプロピルセルロ
ース、カルボキシメチルセルロース、デキストラン、
（メタ）アクリル酸塩共重合物等を例示することができ
る。添加する量としては、重合中に粒子の分散を保つ必
要量あれば十分であり、一般的には水中の濃度で０．５
重量％から４重量％あれば十分である。In the step of adding an aqueous emulsion containing a polymerizable monomer to the polymer seed particles and swelling the polymer seed particles, a polymer dispersion stabilizer may be used as necessary for stabilizing oil droplets. it can. When adding the polymer dispersion stabilizer, a polymer dispersion stabilizer may be added to the polymer seed particle dispersion, and then an aqueous emulsion containing a polymerizable monomer may be added, or the polymer seed particle dispersion may be polymerized. The polymer dispersion stabilizer may be added after the aqueous emulsion containing the hydrophilic monomer is added. The polymer dispersion stabilizer is not particularly limited as long as it is a nonionic or anionic polymer dispersion stabilizer. For example, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose, carboxymethylcellulose, dextran,
A (meth) acrylate copolymer and the like can be exemplified. The amount to be added is sufficient as long as it is necessary to keep the particles dispersed during the polymerization.
From 4% by weight to 4% by weight is sufficient.
【００３４】本願発明では、水相での乳化重合が進行す
ることを阻止する目的で、水溶性重合禁止剤を添加する
ことができる。例えば、亜硝酸ナトリュウム、塩化銅、
ヒドロキシエチルアミン、芳香族二級アミン構造を有す
る化合物等を例示することができる。In the present invention, a water-soluble polymerization inhibitor can be added for the purpose of preventing the progress of emulsion polymerization in the aqueous phase. For example, sodium nitrite, copper chloride,
Examples thereof include hydroxyethylamine and compounds having an aromatic secondary amine structure.
【００３５】上記のように、ポリマーシード粒子に水性
乳化液の各構成成分、すなわち重合性モノマーを含む有
機混合物を吸収させた後、重合を行う。重合は定法に従
い、必要に応じて窒素置換等を行いつつ、重合開始剤に
適した重合温度で行えば良い。As described above, the polymerization is carried out after each component of the aqueous emulsion, that is, the organic mixture containing the polymerizable monomer is absorbed by the polymer seed particles. The polymerization may be carried out at a polymerization temperature suitable for a polymerization initiator according to a conventional method, while performing nitrogen substitution and the like as necessary.
【００３６】重合が終了した粒子は、例えば高分子分散
安定剤を使用した場合には、これを取り除く意味で温水
を用いて洗浄することが好ましい。また粒子の用途によ
って、シード粒子ポリマーを取り除く必要がある場合
は、アセトンなどの溶媒により洗浄してこれを取り除く
ことが好ましい。The particles after polymerization are preferably washed with warm water in order to remove them when, for example, a polymer dispersion stabilizer is used. If it is necessary to remove the seed particle polymer depending on the use of the particles, it is preferable to remove the polymer by washing with a solvent such as acetone.
【００３７】[0037]
【発明の実施の形態】以下に本願発明を更に詳細に説明
するために実施例を記載するが、本願発明はこれらの実
施例に限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００３８】実施例１ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
シクロヘキシルメタクリレート（試薬特級）３０ｇ、エ
チルヘキシルチオグリコール酸エステル０．６ｍｌを入
れよく攪拌した。イオン交換水２００ｍｌを該三つ口フ
ラスコに入れ、冷却管及び温度計を取り付けた。三つ口
フラスコを窒素置換して、オイルバス温度を７０度に設
定し加温した。１時間後、２０ｍｌイオン交換水に過硫
酸カリュウム０．６ｇを溶解した液を三つ口フラスコに
投入した。バス温度を７０度に保ったまま、２０時間重
合を継続した。重合終了後、２００μｍメッシュのふる
いを用いて凝集物を取り除いた。得られたシクロヘキシ
ル粒子の平均粒径はレーザー散乱粒度分布計（堀場社
製）を用いて測定した。得られた結果は、体積平均粒径
０．６５μｍ、ＣＶ４．５％の均一粒径粒子であった。
また分子量をゲルパーミテェーションクロマトグラフィ
ー法により測定した結果、平均分子量１７，０００であ
った。また固形分濃度は１１．６％であった。Example 1 A 300 ml three-necked flask was attached to an oil bath.
30 g of cyclohexyl methacrylate (special grade reagent) and 0.6 ml of ethylhexyl thioglycolate were added and stirred well. 200 ml of ion-exchanged water was put into the three-necked flask, and a condenser and a thermometer were attached. The three-necked flask was purged with nitrogen, and the temperature of the oil bath was set at 70 ° C., and the flask was heated. One hour later, a solution prepared by dissolving 0.6 g of potassium persulfate in 20 ml of ion-exchanged water was charged into a three-necked flask. The polymerization was continued for 20 hours while maintaining the bath temperature at 70 ° C. After completion of the polymerization, aggregates were removed using a 200 μm mesh sieve. The average particle size of the obtained cyclohexyl particles was measured using a laser scattering particle size distribution meter (manufactured by Horiba). The obtained result was particles having a volume average particle diameter of 0.65 μm and a uniform particle diameter of 4.5% CV.
The molecular weight was measured by gel permeation chromatography to find that the average molecular weight was 17,000. The solid concentration was 11.6%.
【００３９】５００ｍｌの三つ口フラスコをオイルバス
に取り付け、上記の方法で得られたシード粒子分散液を
１．７１ｇ（固形分量０．２ｇ）をはかり取り、これに
８％ポリビニルアルコール水溶液（クラレ２２４）を３
０ｇ加えて室温下攪拌した。これとは別に、５００ｍｌ
フラスコにスチレン（試薬特級）１５ｇ、ジビニルベン
ゼン（試薬５５％ジビニルベンゼン）１０ｇ、トルエン
（試薬特級）２５ｇ及び２，２’−アゾビス（２，４−
ジメチルバレロニトリル）（以下Ｖ−６５（和光純薬
製））０．３ｇをはかり取り混合した。これにドデシル
ベンゼンスルホン酸ナトリュウム（試薬）０．５ｇをは
かり取り、イオン交換水２００ｍｌを加えた。次いで超
音波ホモジナイザー（ＢＲＡＮＳＯＮ社製）を用いて乳
化した。この乳化液を上記シード粒子分散液に加え、ゆ
っくりと室温下攪拌した。６時間後、光学顕微鏡観察に
より、モノマー乳化液は完全にシード粒子に吸収され、
均一油滴が生成していた。この溶液に第二塩化銅（試
薬）０．３ｇを添加し、バス温度を７０度に設定し、窒
素気流下重合を行った。３時間後の重合転化率を逆相液
体クロマトグラフィー法で測定したところ、スチレン９
５％、ジビニルベンゼン９８％であった。得られた粒子
を温水及びアセトンを用いて洗浄後、電子顕微鏡観察を
行ったところ、数平均粒径４．０μｍ、ＣＶ９．８％の
均一粒径粒子であり、シード粒子相分離に伴う粒子の細
孔発生等は観察されなかった。この粒子の電子顕微鏡写
真を図１に示す。A 500 ml three-necked flask was attached to an oil bath, 1.71 g (solid content: 0.2 g) of the seed particle dispersion obtained by the above method was weighed, and an 8% aqueous solution of polyvinyl alcohol (Kuraray) was weighed. 224) to 3
0 g was added and the mixture was stirred at room temperature. Separately, 500ml
15 g of styrene (special grade reagent), 10 g of divinylbenzene (55% divinylbenzene reagent), 25 g of toluene (special grade reagent) and 2,2′-azobis (2,4-
0.3 g of dimethylvaleronitrile (hereinafter referred to as V-65 (manufactured by Wako Pure Chemical Industries)) was weighed and mixed. 0.5 g of sodium dodecylbenzenesulfonate (reagent) was weighed, and 200 ml of ion-exchanged water was added thereto. Next, the mixture was emulsified using an ultrasonic homogenizer (manufactured by BRANSON). This emulsion was added to the seed particle dispersion and stirred slowly at room temperature. Six hours later, the monomer emulsion was completely absorbed into the seed particles by observation with an optical microscope.
Uniform oil droplets had formed. 0.3 g of cupric chloride (reagent) was added to this solution, the bath temperature was set to 70 ° C., and polymerization was performed under a nitrogen stream. The polymerization conversion after 3 hours was measured by reversed-phase liquid chromatography.
5% and 98% of divinylbenzene. After the obtained particles were washed with warm water and acetone and observed with an electron microscope, they were found to be particles having a number average particle diameter of 4.0 μm and a uniform particle diameter of CV 9.8%. No generation of pores was observed. An electron micrograph of the particles is shown in FIG.
【００４０】実施例２ 重合性モノマーをグリシジルメタクリレート３７．５ｇ
及びエチレングリコールジメタクリレート１２．５ｇに
変更し、細孔形成剤は使用せず、かつ第二塩化銅は添加
せずに重合を行った以外は実施例１と同様に合成をおこ
なった。得られた粒子は数平均粒径４．２μｍ、ＣＶ１
１．２％の均一粒径あり、シード粒子相分離による細孔
発生などは観察されなかった。この粒子の電子顕微鏡写
真を図２に示す。EXAMPLE 2 37.5 g of glycidyl methacrylate was used as the polymerizable monomer.
And 12.5 g of ethylene glycol dimethacrylate, and the synthesis was carried out in the same manner as in Example 1, except that the polymerization was carried out without using a pore forming agent and without adding cupric chloride. The obtained particles had a number average particle size of 4.2 μm and CV1.
It had a uniform particle size of 1.2%, and no generation of pores due to seed particle phase separation was observed. An electron micrograph of the particles is shown in FIG.
【００４１】実施例３ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
ｎ−ヘキシルメタクリレート（試薬特級）３０ｇ、エチ
ルヘキシルチオグリコール酸エステル０．６ｍｌを入れ
よく攪拌した。イオン交換水２００ｍｌを該三つ口フラ
スコに入れ、冷却管及び温度計を取り付けた。三つ口フ
ラスコを窒素置換して、オイルバス温度を７０度に設定
し加温した。１時間後、２０ｍｌイオン交換水に過硫酸
カリュウム０．６ｇを溶解した液を三つ口フラスコに投
入した。バス温度を７０度に保ったまま、２０時間重合
を継続した。重合終了後、２００μｍメッシュのふるい
を用いて凝集物を取り除いた。得られたｎ−ヘキシルメ
タクリレート粒子の平均粒径はレーザー散乱粒度分布計
（堀場社製）を用いて測定した。得られた結果は、体積
平均粒径１．０μｍ、ＣＶ４．６％の均一粒径粒子であ
った。また分子量をゲルパーミテェーションクロマトグ
ラフィー法により測定した結果、平均分子量３９，００
０であった。また固形分濃度は５．９％であった。Example 3 A 300 ml three-necked flask was attached to an oil bath.
30 g of n-hexyl methacrylate (special grade reagent) and 0.6 ml of ethylhexyl thioglycolate were added and stirred well. 200 ml of ion-exchanged water was put into the three-necked flask, and a condenser and a thermometer were attached. The three-necked flask was purged with nitrogen, and the temperature of the oil bath was set at 70 ° C., and the flask was heated. One hour later, a solution prepared by dissolving 0.6 g of potassium persulfate in 20 ml of ion-exchanged water was charged into a three-necked flask. The polymerization was continued for 20 hours while maintaining the bath temperature at 70 ° C. After completion of the polymerization, aggregates were removed using a 200 μm mesh sieve. The average particle size of the obtained n-hexyl methacrylate particles was measured using a laser scattering particle size distribution analyzer (manufactured by Horiba). The obtained result was particles having a volume average particle diameter of 1.0 μm and a uniform particle diameter of 4.6% CV. The molecular weight was measured by gel permeation chromatography to find that the average molecular weight was 39,00.
It was 0. The solid concentration was 5.9%.
【００４２】上記の方法で得られたシード粒子分散液
１．６９ｇ（固形分０．１ｇ）とした以外は実施例１と
同様に合成を行った。得られた粒子は数平均粒径８．１
μｍ、ＣＶ５．６％の均一粒径あり、シード粒子相分離
による細孔発生などは観察されなかった。この粒子の電
子顕微鏡写真を図３に示す。The synthesis was carried out in the same manner as in Example 1 except that the seed particle dispersion obtained in the above manner was 1.69 g (solid content: 0.1 g). The obtained particles had a number average particle size of 8.1.
It had a uniform particle size of μm and CV of 5.6%, and no generation of pores due to seed particle phase separation was observed. An electron micrograph of the particles is shown in FIG.
【００４３】実施例４ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
２−エチルヘキシルメタクリレート（試薬特級）３０
ｇ、エチルヘキシルチオグリコール酸エステル０．６ｍ
ｌを入れよく攪拌した。イオン交換水２００ｍｌを該三
つ口フラスコに入れ、冷却管及び温度計を取り付けた。
三つ口フラスコを窒素置換して、オイルバス温度を７０
度に設定し加温した。１時間後、２０ｍｌイオン交換水
に過硫酸カリュウム０．６ｇを溶解した液を三つ口フラ
スコに投入した。バス温度を７０度に保ったまま、２０
時間重合を継続した。重合終了後、２００μｍメッシュ
のふるいを用いて凝集物を取り除いた。得られた２−エ
チルヘキシルメタクリレート粒子の平均粒径はレーザー
散乱粒度分布計（堀場社製）を用いて測定した。得られ
た結果は、体積平均粒径０．９５μｍ、ＣＶ５．６％の
均一粒径粒子であった。また分子量をゲルパーミテェー
ションクロマトグラフィー法により測定した結果、平均
分子量２７，０００であった。また固形分濃度は４．４
％であった。Example 4 A 300 ml three-necked flask was attached to an oil bath.
2-ethylhexyl methacrylate (special grade reagent) 30
g, ethylhexyl thioglycolate 0.6m
and stirred well. 200 ml of ion-exchanged water was put into the three-necked flask, and a condenser and a thermometer were attached.
Replace the three-necked flask with nitrogen and raise the oil bath temperature to 70
The temperature was set and heated. One hour later, a solution prepared by dissolving 0.6 g of potassium persulfate in 20 ml of ion-exchanged water was charged into a three-necked flask. Keep the bath temperature at 70 degrees
The polymerization was continued for hours. After completion of the polymerization, aggregates were removed using a 200 μm mesh sieve. The average particle size of the obtained 2-ethylhexyl methacrylate particles was measured using a laser scattering particle size distribution meter (manufactured by Horiba). The results obtained were particles having a uniform average particle size of 0.95 μm in volume average particle size and 5.6% in CV. The molecular weight was measured by gel permeation chromatography to find that the average molecular weight was 27,000. The solid concentration is 4.4.
%Met.
【００４４】上記の方法で得られたシード粒子分散液
２．２７ｇ（固形分０．１ｇ）とした以外は実施例１と
同様に合成を行った。得られた粒子は数平均粒径７．３
μｍ、ＣＶ６．７％の均一粒径あり、シード粒子相分離
による細孔発生などは観察されなかった。Synthesis was carried out in the same manner as in Example 1 except that 2.27 g (solid content: 0.1 g) of the seed particle dispersion obtained by the above method was used. The obtained particles had a number average particle size of 7.3.
It had a uniform particle size of μm and a CV of 6.7%, and no generation of pores due to seed particle phase separation was observed.
【００４５】実施例５ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
ベンジルメタクリレート（試薬特級）３０ｇ、エチルヘ
キシルチオグリコール酸エステル１．２ｍｌを入れよく
攪拌した。イオン交換水２００ｍｌを該三つ口フラスコ
に入れ、冷却管及び温度計を取り付けた。三つ口フラス
コを窒素置換して、オイルバス温度を７０度に設定し加
温した。１時間後、２０ｍｌイオン交換水に過硫酸カリ
ュウム０．６ｇを溶解した液を三つ口フラスコに投入し
た。バス温度を７０度に保ったまま、２０時間重合を継
続した。重合終了後、２００μｍメッシュのふるいを用
いて凝集物を取り除いた。得られたベンジルメタクリレ
ート粒子の平均粒径はレーザー散乱粒度分布計（堀場社
製）を用いて測定した。得られた結果は、体積平均粒径
０．８μｍ、ＣＶ５．０％の均一粒径粒子であった。ま
た分子量をゲルパーミテェーションクロマトグラフィー
法により測定した結果、平均分子量１３，０００であっ
た。また固形分濃度は１１．８％であった。Example 5 A 300 ml three-necked flask was attached to an oil bath,
30 g of benzyl methacrylate (special grade reagent) and 1.2 ml of ethylhexyl thioglycolate were added and stirred well. 200 ml of ion-exchanged water was put into the three-necked flask, and a condenser and a thermometer were attached. The three-necked flask was purged with nitrogen, and the temperature of the oil bath was set at 70 ° C., and the flask was heated. One hour later, a solution prepared by dissolving 0.6 g of potassium persulfate in 20 ml of ion-exchanged water was charged into a three-necked flask. The polymerization was continued for 20 hours while maintaining the bath temperature at 70 ° C. After completion of the polymerization, aggregates were removed using a 200 μm mesh sieve. The average particle size of the obtained benzyl methacrylate particles was measured using a laser scattering particle size distribution meter (manufactured by Horiba). The obtained results were uniform particle diameter particles having a volume average particle diameter of 0.8 μm and a CV of 5.0%. The molecular weight was measured by gel permeation chromatography, and as a result, the average molecular weight was 13,000. The solid concentration was 11.8%.
【００４６】上記の方法で得られたシード粒子分散液
３．３９ｇ（固形分０．４ｇ）とし、重合モノマーをス
チレン３０ｇ及びジビニルベンゼン２０ｇとし、細孔形
成剤を使用せず、それ以外は実施例１と同様に合成を行
った。得られた粒子は数平均粒径４．０μｍ、ＣＶ７．
６％の均一粒径粒子であり、シード粒子相分離に伴う粒
子の細孔発生等は観察されなかった。The seed particle dispersion obtained by the above method was 3.39 g (solid content: 0.4 g), the polymerization monomer was 30 g of styrene and 20 g of divinylbenzene, and no other pore-forming agent was used. Synthesis was carried out as in Example 1. The obtained particles had a number average particle size of 4.0 μm and a CV of 7.0.
The particles had a uniform particle diameter of 6%, and generation of pores in the particles due to seed particle phase separation was not observed.
【００４７】実施例６ １０００ｍｌの三つ口フラスコをオイルバスに取り付
け、実施例５で得られたシード粒子分散液を０．１３ｇ
（固形分量０．０１５ｇ）をはかり取り、これに４％ポ
リビニルアルコール水溶液（クラレ２２４）を１５０ｇ
加えて室温下攪拌した。これとは別に、５００ｍｌフラ
スコに重合性モノマーとして、グリシジルメタクリレー
ト（試薬特級）３３．０ｇ、エチレングリコールジメタ
クリレート（試薬）２７．０ｇ及び細孔形成剤としてシ
クロヘキサノール（試薬特級）９０．０ｇ及び２，２
‘−アゾビス（２，４−ジメチルバレロニトリル）（以
下Ｖ−６５（和光純薬製））０．６ｇをはかり取り混合
した。これにドデシルベンゼンスルホン酸ナトリュウム
（試薬）０．７ｇをはかり取り、イオン交換水１５０ｍ
ｌを加えた。次いで超音波ホモジナイザー（ＢＲＡＮＳ
ＯＮ社製）を用いて乳化した。この乳化液を上記シード
粒子分散液に加え、ゆっくりと室温下三日間攪拌した。
光学顕微鏡観察により、モノマー乳化液は完全にシード
粒子に吸収され、均一油滴が生成していた。バス温度を
７０度に設定し、窒素気流下重合を行った。得られた粒
子を温水及びアセトンを用いて洗浄後、電子顕微鏡観察
を行ったところ、数平均粒径１７μｍ、ＣＶ４．９％の
均一粒径粒子であり、シード粒子相分離に伴う粒子の細
孔発生等は観察されなかった。この粒子の電子顕微鏡写
真を図６に示す。Example 6 A 1000 ml three-necked flask was attached to an oil bath, and 0.13 g of the seed particle dispersion obtained in Example 5 was used.
(Solid content 0.015 g) was weighed, and 150 g of a 4% aqueous solution of polyvinyl alcohol (Kuraray 224) was added thereto.
In addition, the mixture was stirred at room temperature. Separately, 33.0 g of glycidyl methacrylate (reagent grade), 27.0 g of ethylene glycol dimethacrylate (reagent) as polymerizable monomers, 90.0 g of cyclohexanol (reagent grade) as a pore-forming agent and 2 , 2
0.6 g of '-azobis (2,4-dimethylvaleronitrile) (hereinafter V-65 (manufactured by Wako Pure Chemical Industries)) was weighed and mixed. 0.7 g of sodium dodecylbenzenesulfonate (reagent) is weighed, and 150 m of ion-exchanged water is added thereto.
1 was added. Next, an ultrasonic homogenizer (BRANS)
(Manufactured by ON Corporation). This emulsion was added to the seed particle dispersion and stirred slowly at room temperature for 3 days.
According to the observation with an optical microscope, the monomer emulsion was completely absorbed by the seed particles, and uniform oil droplets were formed. The bath temperature was set to 70 ° C., and polymerization was performed under a nitrogen stream. The obtained particles were washed with warm water and acetone and observed with an electron microscope. The particles were found to have a number average particle diameter of 17 μm and a uniform particle diameter of CV 4.9%. No occurrence was observed. An electron micrograph of the particles is shown in FIG.
【００４８】実施例７ 実施例４で作製されたシード粒子分散液２．７２ｇ（固
形分０．３２ｇ）とし、重合性モノマーをグリシジルメ
タクリレート４０ｇ、エチレングリコールジメタクリレ
ート１８ｇ及び細孔形成剤として１，２−エチレンジク
ロライド１１０ｇとし、また膨潤時間を一週間と変更し
た以外は、実施例６と同様に合成を行った。得られた粒
子は数平均粒径６．３μｍ、ＣＶ９．７％の均一粒径粒
子であった。Example 7 2.72 g (solid content: 0.32 g) of the seed particle dispersion prepared in Example 4 was used. The polymerizable monomer was 40 g of glycidyl methacrylate, 18 g of ethylene glycol dimethacrylate, and 1 as a pore-forming agent. Synthesis was performed in the same manner as in Example 6, except that the amount of 2-ethylene dichloride was changed to 110 g and the swelling time was changed to one week. The particles obtained were particles having a number average particle diameter of 6.3 μm and a uniform particle diameter of 9.7% CV.
【００４９】実施例８ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
実施例５で得られたシード粒子分散液を０．５１ｇ（固
形分量０．０６ｇ）をはかり取り、これに４％ポリビニ
ルアルコール水溶液（クラレ２２４）を１０ｇ加えて室
温下攪拌した。これとは別に、１００ｍｌフラスコにチ
オグリコール酸エチルヘキシル２．３ｍｌ及びドデシル
ベンゼンスルホン酸ナトリュウム（試薬）０．１ｇをは
かり取り、イオン交換水１０ｍｌを加えた。次いで超音
波ホモジナイザー（ＢＲＡＮＳＯＮ社製）を用いて乳化
した。この乳化液を上記シード粒子分散液に加え、ゆっ
くりと室温下一週間攪拌した。光学顕微鏡観察により、
連鎖移動剤乳化液は完全にシード粒子に吸収されてい
た。新たに、３００ｍｌフラスコにベンジルメタクリレ
ート５０ｇ及びＶ−６５ ０．６ｇ及びドデシルベンゼ
ンスルホン酸ナトリュウム０．３ｇをはかり取りイオン
交換水５０ｍｌを加えた。次いで超音波ホモジナイザー
（ＢＲＡＮＳＯＮ社製）を用いて乳化した。この乳化液
を上記シード粒子分散液に加え、ゆっくりと室温下１６
時間攪拌した。光学顕微鏡観察により、モノマー乳化液
は完全にシード粒子に吸収されていた。Example 8 A 300 ml three-necked flask was attached to an oil bath.
0.51 g (solid content: 0.06 g) of the seed particle dispersion obtained in Example 5 was weighed, and 10 g of a 4% aqueous solution of polyvinyl alcohol (Kuraray 224) was added thereto, followed by stirring at room temperature. Separately, 2.3 ml of ethylhexyl thioglycolate and 0.1 g of sodium dodecylbenzenesulfonate (reagent) were weighed into a 100 ml flask, and 10 ml of ion-exchanged water was added. Next, the mixture was emulsified using an ultrasonic homogenizer (manufactured by BRANSON). This emulsion was added to the seed particle dispersion, and the mixture was slowly stirred at room temperature for one week. By optical microscope observation,
The chain transfer agent emulsion was completely absorbed by the seed particles. 50 g of benzyl methacrylate, 0.6 g of V-65 and 0.3 g of sodium dodecylbenzenesulfonate were newly weighed into a 300 ml flask, and 50 ml of ion-exchanged water was added. Next, the mixture was emulsified using an ultrasonic homogenizer (manufactured by BRANSON). This emulsion is added to the seed particle dispersion and slowly added at room temperature to room temperature.
Stirred for hours. According to the observation with an optical microscope, the monomer emulsion was completely absorbed by the seed particles.
【００５０】バス温度を７０度に設定し、窒素気流下重
合を行った。得られた粒子分散液をシードシード粒子分
散液として固形分量０．２８ｇとした以外は、実施例６
と同様に合成を行った。得られた粒子を光学顕微鏡観察
したところ、数平均粒径４０μｍ、ＣＶ７．９％の均一
粒径粒子であった。この粒子の光学顕微鏡写真を図７に
示す。The bath temperature was set at 70 ° C., and polymerization was carried out under a nitrogen stream. Example 6 except that the obtained particle dispersion was used as a seed / seed particle dispersion and the solid content was 0.28 g.
The synthesis was performed in the same manner as described above. Observation of the obtained particles with an optical microscope revealed that the particles had a number average particle size of 40 μm and a uniform particle size of CV 7.9%. An optical micrograph of the particles is shown in FIG.
【００５１】比較例１ ３００ｍｌの三つ口フラスコをオイルバスに取り付け、
スチレン（試薬特級）３０ｇ、エチルヘキシルチオグリ
コール酸エステル０．６ｍｌを入れよく攪拌した。イオ
ン交換水２００ｍｌを該三つ口フラスコに入れ、冷却管
及び温度計を取り付けた。三つ口フラスコを窒素置換し
て、オイルバス温度を７０度に設定し加温した。 １時
間後、２０ｍｌイオン交換水に過硫酸カリュウム０．６
ｇを溶解した液を三つ口フラスコに投入した。バス温度
を７０度に保ったまま、２０時間重合を継続した。重合
終了後、２００μｍメッシュのふるいを用いて凝集物を
取り除いた。得られたポリスチレン粒子の平均粒径は体
積平均粒径１．１μｍ、ＣＶ４．９％の均一粒径粒子で
あった。また分子量は平均分子量４８，０００であっ
た。また固形分濃度は１５．０％であった。。Comparative Example 1 A 300 ml three-necked flask was attached to an oil bath.
30 g of styrene (special grade reagent) and 0.6 ml of ethylhexyl thioglycolate were added and stirred well. 200 ml of ion-exchanged water was put into the three-necked flask, and a condenser and a thermometer were attached. The three-necked flask was purged with nitrogen, and the temperature of the oil bath was set at 70 ° C., and the flask was heated. One hour later, 0.6 ml of calcium persulfate was added to 20 ml of ion-exchanged water.
g in a three-necked flask. The polymerization was continued for 20 hours while maintaining the bath temperature at 70 ° C. After completion of the polymerization, aggregates were removed using a 200 μm mesh sieve. The average particle diameter of the obtained polystyrene particles was 1.1 μm in volume average particle diameter and uniform particle diameter of CV 4.9%. Also, the molecular weight was 48,000. The solid content concentration was 15.0%. .
【００５２】５００ｍｌの三つ口フラスコをオイルバス
に取り付け、上記の方法で得られたシード粒子分散液を
１１．１ｇ（固形分量１．６７ｇ）を用いた以外は、実
施例１と同様に合成を行った。得られた粒子を温水及び
アセトンを用いて洗浄後、電子顕微鏡観察を行ったとこ
ろ、数平均粒径３．２μｍ、ＣＶ７．８％の均一粒径粒
子であったが、シード粒子由来の細孔を生じた粒子であ
った。この粒子の電子顕微鏡写真を図４に示す。Synthesis was performed in the same manner as in Example 1 except that a 500 ml three-necked flask was attached to an oil bath, and 11.1 g (solid content: 1.67 g) of the seed particle dispersion liquid obtained by the above method was used. Was done. The obtained particles were washed with warm water and acetone, and then observed under an electron microscope. As a result, the particles had a number average particle size of 3.2 μm and a uniform particle size of CV 7.8%. Were generated. An electron micrograph of the particles is shown in FIG.
【００５３】比較例２ 比較例１で作製したシード粒子分散液３．３ｇ（固形分
濃度０．５ｇ）を用いて実施例１と同様に合成を行っ
た。得られた粒子を温水及びアセトンを用いて洗浄後、
電子顕微鏡観察を行ったところ、目的粒子以外の大粒径
粒子や、微粒子分が多数存在したものであった。Comparative Example 2 Synthesis was carried out in the same manner as in Example 1 using 3.3 g of the seed particle dispersion liquid (solid concentration 0.5 g) prepared in Comparative Example 1. After washing the obtained particles using warm water and acetone,
Electron microscopic observation revealed that large particles other than the target particles and a large number of fine particles were present.
【００５４】比較例３ 比較例１で作製されたシード粒子分散液６．６ｇ（固形
分濃度１．０ｇ）とした以外は実施例２と同様に合成を
行った。得られた粒子を温水及びアセトンを用いて洗浄
後、電子顕微鏡観察を行ったところ、数平均粒径３．２
μｍであったが、油滴合一による大粒径粒子が大量に存
在し且つ、シード粒子由来の細孔を生じた非円形粒子で
あった。この粒子の電子顕微鏡写真を図５に示す。Comparative Example 3 Synthesis was carried out in the same manner as in Example 2 except that 6.6 g (solid concentration: 1.0 g) of the seed particle dispersion prepared in Comparative Example 1 was used. The obtained particles were washed with warm water and acetone, and then observed with an electron microscope. As a result, the number average particle size was 3.2.
It was a non-circular particle having a large particle size due to oil droplet coalescence and having pores derived from seed particles. An electron micrograph of the particles is shown in FIG.
【００５５】[0055]
【発明の効果】これまで説明してきたように、本願発明
によれば、粒径が１μｍ〜１０００μｍ程度の範囲にあ
る粒径が単分散である粒子を従来技術に比較して非常に
簡便に製造することができる。また、粒子径の揃った単
分散粒子を液体クロマトグラフィー用充填剤として液体
クロマトグラフィー用カラムに充填し、液体クロマトグ
ラフィー分析に用いることにより、測定圧力の減少、測
定試料のピーク形状の改善、そして分離性能の向上等、
種々の効果を達成することができる。As described above, according to the present invention, monodisperse particles having a particle size in the range of about 1 μm to 1000 μm can be produced much more easily than in the prior art. can do. In addition, by packing monodispersed particles having a uniform particle size into a liquid chromatography column as a filler for liquid chromatography and using the same for liquid chromatography analysis, the measurement pressure decreases, the peak shape of the measurement sample improves, and Improvement of separation performance, etc.
Various effects can be achieved.
【図１】図１は、実施例１で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。FIG. 1 is an electron micrograph showing the particle structure of the particles produced in Example 1.
【図２】図２は、実施例２で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。FIG. 2 is an electron micrograph showing the particle structure of the particles produced in Example 2.
【図３】図３は、実施例３で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。FIG. 3 is an electron micrograph showing the particle structure of the particles produced in Example 3.
【図４】図４は、比較例１で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。FIG. 4 is an electron micrograph showing the particle structure of the particles produced in Comparative Example 1.
【図５】図２は、比較例３で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。FIG. 2 is an electron micrograph showing the particle structure of the particles produced in Comparative Example 3.
【図６】図６は、実施例６で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。図中のスケール１メ
モリは２．５μｍに相当する。FIG. 6 is an electron micrograph showing the particle structure of the particles produced in Example 6. The scale 1 memory in the figure corresponds to 2.5 μm.
【図７】図７は、実施例８で作製した粒子の粒子構造を
示すための電子顕微鏡写真である。図中のスケール１メ
モリは５μｍに相当する。FIG. 7 is an electron micrograph showing the particle structure of the particles produced in Example 8. The scale 1 memory in the figure corresponds to 5 μm.
Claims (14)
以上の脂肪族環状アルキル基、フェニル基、ベンジル基
又は炭素数３以上のハロゲン化アルキル基を少なくとも
一種類以上含むポリ（メタ）アクリル酸エステルからな
る粒径単分散なポリマーシード粒子に、重合性モノマー
を含む水性乳化液を添加して膨潤させた後、重合して得
られる粒径単分散粒子。1. A linear alkyl group having 6 or more carbon atoms, 6 carbon atoms.
Monodispersed polymer seed particles of poly (meth) acrylate containing at least one kind of the above-mentioned aliphatic cyclic alkyl group, phenyl group, benzyl group or halogenated alkyl group having 3 or more carbon atoms are polymerizable. Monodisperse particles obtained by adding an aqueous emulsion containing a monomer, swelling, and then polymerizing.
下のポリマーシード粒子を用いて得られる請求項１記載
の粒径単分散粒子。2. The monodisperse particles according to claim 1, which are obtained by using polymer seed particles having a molecular weight of not more than 50,000 in weight average molecular weight.
リマーシード粒子を用いれて得られる請求項１又は２記
載の粒径単分散粒子。3. The monodisperse particles according to claim 1, which are obtained by using polymer seed particles produced by soap-free emulsion polymerization.
を用いて製造されたポリマーシード粒子を用いて得られ
る請求項３記載の粒径単分散粒子。4. The monodisperse particle according to claim 3, which is obtained by using polymer seed particles produced by using a chain transfer agent in soap-free emulsion polymerization.
リコール酸エステルである連鎖移動剤を用いて得られる
請求項４記載の粒径単分散粒子。5. The monodispersed particles according to claim 4, which are obtained by using a chain transfer agent which is a thioglycolic acid ester having an ester moiety having 8 or less carbon atoms.
の重合性モノマーを用いて得られる請求項１記載の粒径
単分散粒子。6. The monodisperse particles according to claim 1, which are obtained by using a polymerizable monomer having a solubility in water of 0.001% by weight or more.
以上の脂肪族環状アルキル基、フェニル基、ベンジル基
又は炭素数３以上のハロゲン化アルキル基を少なくとも
一種類以上含むポリ（メタ）アクリル酸エステルからな
る粒径単分散なポリマーシード粒子に、重合性モノマー
を含む水性乳化液を添加して膨潤させた後、重合させる
粒径単分散粒子の製造法。7. A linear alkyl group having 6 or more carbon atoms, 6 carbon atoms.
Monodispersed polymer seed particles of poly (meth) acrylate containing at least one kind of the above-mentioned aliphatic cyclic alkyl group, phenyl group, benzyl group or halogenated alkyl group having 3 or more carbon atoms are polymerizable. A method of producing monodisperse particles having a particle size to be polymerized after adding and swelling an aqueous emulsion containing a monomer.
下のポリマーシード粒子を用いる請求項７記載の粒径単
分散粒子の製造法。8. The method for producing monodisperse particles according to claim 7, wherein polymer seed particles having a molecular weight of 50,000 or less in weight average molecular weight are used.
リマーシード粒子を用いる請求項７又は８記載の粒径単
分散粒子の製造法。9. The method for producing monodispersed particles according to claim 7, wherein polymer seed particles produced by soap-free emulsion polymerization are used.
剤を用いて製造されたポリマーシード粒子を用いる請求
項９記載の粒径単分散粒子の製造法。10. The method for producing monodisperse particles according to claim 9, wherein polymer seed particles produced by using a chain transfer agent in soap-free emulsion polymerization are used.
グリコール酸エステルである連鎖移動剤を用いる請求項
１０記載の粒径単分散粒子の製造法。11. The process for producing monodispersed particles according to claim 10, wherein a chain transfer agent which is a thioglycolic acid ester having an ester moiety having 8 or less carbon atoms is used.
上の重合性モノマーを用いる請求項７記載の粒径単分散
粒子の製造法。12. The method according to claim 7, wherein a polymerizable monomer having a solubility in water of 0.001% by weight or more is used.
充填してなる液体クロマトグラフィー用カラム。13. A column for liquid chromatography, which is packed with the monodisperse particles according to claim 1.
充填してなる液体クロマトグラフィー用カラムを用いる
液体クロマトグラフィー分析法。14. A liquid chromatography analysis method using a liquid chromatography column packed with the monodisperse particles having a particle size according to claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62227903A (en) * | 1986-03-29 | 1987-10-06 | Nitto Electric Ind Co Ltd | Production of solvent-resistant porous fine particle of uniform particle diameter |
| JPS6379065A (en) * | 1986-09-22 | 1988-04-09 | Nitto Electric Ind Co Ltd | Filler for liquid chromatography |
| JPH1149810A (en) * | 1997-06-06 | 1999-02-23 | Nippon Shokubai Co Ltd | High-molecular weight polymer, its production and drag reducer |
-
2000
- 2000-04-24 JP JP2000127634A patent/JP4779186B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62227903A (en) * | 1986-03-29 | 1987-10-06 | Nitto Electric Ind Co Ltd | Production of solvent-resistant porous fine particle of uniform particle diameter |
| JPS6379065A (en) * | 1986-09-22 | 1988-04-09 | Nitto Electric Ind Co Ltd | Filler for liquid chromatography |
| JPH1149810A (en) * | 1997-06-06 | 1999-02-23 | Nippon Shokubai Co Ltd | High-molecular weight polymer, its production and drag reducer |
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