JPH03234734A - Tabular polymer particle and its production - Google Patents
Tabular polymer particle and its productionInfo
- Publication number
- JPH03234734A JPH03234734A JP2029880A JP2988090A JPH03234734A JP H03234734 A JPH03234734 A JP H03234734A JP 2029880 A JP2029880 A JP 2029880A JP 2988090 A JP2988090 A JP 2988090A JP H03234734 A JPH03234734 A JP H03234734A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- plate
- dispersion
- fine particles
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 68
- 239000002245 particle Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000007710 freezing Methods 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 14
- 239000002612 dispersion medium Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 36
- 239000004815 dispersion polymer Substances 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 abstract description 13
- 229920002223 polystyrene Polymers 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002537 cosmetic Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004587 chromatography analysis Methods 0.000 abstract description 3
- 239000003456 ion exchange resin Substances 0.000 abstract description 3
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241001272720 Medialuna californiensis Species 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、板状ポリマー微粒子及びその製造法、詳しく
は、化粧料、塗料、イオン交換樹脂の母材、クロマトグ
ラフィー用の充填剤などに使用し得る均一な板状ポリマ
ー微粒子、及びその製造法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to plate-shaped polymer fine particles and a method for producing the same, in particular, to cosmetics, paints, base materials for ion exchange resins, fillers for chromatography, etc. The present invention relates to usable uniform plate-like polymer fine particles and a method for producing the same.
板状ポリマー微粒子の製造法としては、従来よりポリマ
ーフィルム及び球状ポリマー粉体を機械的に粉砕、偏平
化する方法がある。例えば、ポリマーフィルム成形後、
液体窒素下で冷却粉砕する方法（特開昭５７−７８４６
６号公報）、球状ポリマー粉末を、（ガラス）ビーズ存
在下で該ポリマーに対し不活性な溶媒中で混合撹拌する
ことにより偏平化する方法（特開昭６２−１６４７３１
号公報）がある。またこれらの他に、ポリマー溶液の微
小液滴を平板上で固化させる方法（特開昭６３−１１７
０４０号公報）もある。As a method for producing plate-like polymer fine particles, there is a conventional method of mechanically crushing and flattening a polymer film and spherical polymer powder. For example, after forming a polymer film,
Method of cooling and pulverizing under liquid nitrogen (Japanese Patent Application Laid-Open No. 57-7846
6), a method of flattening a spherical polymer powder by mixing and stirring it in a solvent inert to the polymer in the presence of (glass) beads (JP-A No. 62-164731)
Publication No.). In addition to these methods, there is also a method of solidifying minute droplets of a polymer solution on a flat plate (Japanese Patent Laid-Open No. 63-117
No. 040) is also available.
〔発明が解決しようとする課題］
上記のような従来の製造法では、均一かつ確実に板状ポ
リマー粒子が得られなかったり、操作が複雑で困難であ
ったり、ポリマ一種の選択の幅が狭いなどの問題がある
。その上、従来の製造法では、より微細な板状ポリマー
粒子（平均厚みが１μｍ以下のもの）を得ることは容易
ではなかった。[Problems to be solved by the invention] With the conventional production methods described above, plate-shaped polymer particles cannot be obtained uniformly and reliably, operations are complicated and difficult, and the selection range of polymer types is narrow. There are problems such as. Furthermore, with conventional production methods, it is not easy to obtain finer plate-like polymer particles (those with an average thickness of 1 μm or less).
従って、本発明の目的は、均一な板状ポリマー微粒子を
提供すること、及びその製造法、即ち、操作が簡便かつ
容易で、しかも均一かつ確実に板状ポリマー微粒子を得
ることができ、また製造条件の選択によって板状ポリマ
ー微粒子の厚み及びサイズ（長片）を容易に制御でき、
より微細（例えば、平均厚みが約０．１μｍで長片が厚
みの約１０倍程度）な板状ポリマー微粒子の製造も容易
に可能で、その上、熱や溶剤に対し安定な架橋型ポリマ
ーについても板状への成形加工が可能で、更にポリマ一
種の選択の幅の非常に広い、板状ポリマー微粒子の製造
法を提供することにある。Therefore, an object of the present invention is to provide uniform plate-like polymer fine particles and a method for producing the same, that is, the operation is simple and easy, and the plate-like polymer fine particles can be obtained uniformly and reliably. The thickness and size (long pieces) of plate-like polymer particles can be easily controlled by selecting conditions.
It is possible to easily produce finer plate-shaped polymer particles (for example, the average thickness is about 0.1 μm and the length of the long pieces is about 10 times the thickness), and moreover, it is possible to produce cross-linked polymers that are stable against heat and solvents. It is an object of the present invention to provide a method for producing plate-shaped polymer fine particles which can be molded into a plate shape and which allows for a very wide selection of polymer types.
本発明は、上記目的を、下記（］）の板状ポリマー微粒
子を提供すること、及びその製造法として下記（２）の
板状ポリマー微粒子の製造法を提供することにより遠戚
したものである。The present invention is a distant relative of the above-mentioned object by providing the following plate-like polymer fine particles (]) and the following method (2) for producing the plate-like polymer fine particles. .
（１）微粒子ポリマー分散液を、分散媒の凍結温度以下
に冷却した後、該ポリマーのガラス転移温度未満まで昇
温させて得られた、平均厚みが０．０１〜１００ｔ！ｍ
、長片が厚みの１０倍以上である板状ポリマー微粒子。(1) The average thickness obtained by cooling the fine particle polymer dispersion to below the freezing temperature of the dispersion medium and then raising the temperature to below the glass transition temperature of the polymer is 0.01 to 100 tons! m
, plate-shaped polymer fine particles whose long pieces are 10 times or more thicker.
（２）平均粒径が５００ｎｍ以下の微粒子ポリマー分散
液を、分散媒の凍結温度以下に冷却した後、該ポリマー
のガラス転移温度未満まで昇温させ、平均厚みが０．０
１〜１００μｍ、長片が厚みの１０倍以上である板状ポ
リマー微粒子を得ることを特徴とする板状ポリマー微粒
子の製造法。(2) A fine particle polymer dispersion having an average particle diameter of 500 nm or less is cooled to below the freezing temperature of the dispersion medium, and then heated to below the glass transition temperature of the polymer, so that the average thickness is 0.0 nm.
1. A method for producing plate-like polymer fine particles, which comprises obtaining plate-like polymer fine particles having a length of 1 to 100 μm and a long piece that is 10 times or more thicker.
以下、本発明の板状ポリマー微粒子を、本発明の製造法
に基づいて詳述する。Hereinafter, the plate-shaped polymer fine particles of the present invention will be explained in detail based on the manufacturing method of the present invention.
本発明で原料として用いられるポリマーとしては、その
種類が特に制限されるものではなく、汎用ポリマー、例
えば、スチレン系、アクリル酸系、メタクリル酸系及び
これらの共重合体、ジビニルベンゼンなどにより架橋さ
れたものなどを用いることができ、一般に知られている
乳化重合法によって容易に微粒子ポリマー分散液が得ら
れるものが好ましい。The type of polymer used as a raw material in the present invention is not particularly limited, and general-purpose polymers such as styrene, acrylic acid, methacrylic acid, copolymers thereof, divinylbenzene, etc. It is preferable that a fine particle polymer dispersion can be easily obtained by a generally known emulsion polymerization method.
上記ポリマーとしては、平均粒径が５００ ｎｍ以下、
好ましくは３０〜２５０ｎｍの微粒子ポリマーを用いる
。平均粒径が５００ｎｍ超のポリマーを用いると、微粒
子間の融着か弱く、板状成形が困難となる。The above polymer has an average particle size of 500 nm or less,
Preferably, fine particle polymers of 30 to 250 nm are used. If a polymer with an average particle diameter of more than 500 nm is used, the fusion between the fine particles will be weak, making it difficult to form into a plate.
ポリマーの粒径は、サブミクロン粒子分析器（サブミク
ロン パーティクル アナライザーＣ０ＵＬＴＥＲＮ４
、コールタ−エレクトロニック カンパニー社製）によ
り測定することができる。The particle size of the polymer was determined using a submicron particle analyzer (submicron particle analyzer C0ULTERN4).
(manufactured by Coulter Electronic Company).
また、ポリマー分散液の分散媒としては、ポリマーを熔
解させず分散できるものであれば、いずれのものでも用
いることができ、例えば、水及び水と相溶性のある溶剤
などが用いられ、分散の簡便さから、水、低級アルコー
ル及びそれらの混合物が好ましい。Furthermore, as the dispersion medium for the polymer dispersion, any medium can be used as long as it can disperse the polymer without melting it. For example, water and water-compatible solvents can be used to improve dispersion. For convenience, water, lower alcohols and mixtures thereof are preferred.
上記分散媒には分散剤を添加することが好ましく、かか
る分散剤としては、水溶性ポリマー、アニオン界面活性
剤、カチオン界面活性剤、両性界面活性剤、非イオン界
面活性剤及びこれらの混合物が用いられ、特に、アニオ
ン界面活性剤、カチオン界面活性剤などが好ましい。It is preferable to add a dispersant to the dispersion medium, and such dispersants include water-soluble polymers, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof. Among them, anionic surfactants, cationic surfactants, etc. are particularly preferred.
而して、本発明の板状ポリマー微粒子の製造法を実施す
るには、まず、上記微粒子ポリマーを上記分散媒に分散
させた分散液を、分散媒の凍結温度以下に冷却し分散媒
を凍結させる。Therefore, in order to carry out the method for producing plate-shaped polymer fine particles of the present invention, first, a dispersion liquid in which the fine particle polymer is dispersed in the dispersion medium is cooled to a temperature below the freezing temperature of the dispersion medium to freeze the dispersion medium. let
この際、凍結時の製造条件、即ち、冷却凍結温度、ポリ
マー分散液の微粒子ポリマー濃度、微粒子ポリマーの粒
径、分散剤の種類、凍結容器の形状などを適宜変化させ
ることにより、生成する板状ポリマー微粒子のサイズ及
び厚みの制御が容易に可能である。At this time, by appropriately changing the manufacturing conditions during freezing, that is, the cooling freezing temperature, the concentration of the fine particles in the polymer dispersion, the particle size of the fine particles, the type of dispersant, the shape of the freezing container, etc., the plate-shaped The size and thickness of polymer particles can be easily controlled.
例えば、ポリマー分散液の冷却を急激に行うことにより
、より微細な板状ポリマー微粒子が得られる。即ち、冷
却凍結温度を低くしたり、凍結容器の形状をポリマー分
散液と冷却媒との接触面積が大きくなる形状とするなど
の条件を選択することにより、より微細な板状ポリマー
微粒子が得られる。For example, by rapidly cooling the polymer dispersion, finer plate-like polymer particles can be obtained. In other words, finer plate-like polymer particles can be obtained by selecting conditions such as lowering the cooling freezing temperature or selecting a shape of the freezing container that increases the contact area between the polymer dispersion and the cooling medium. .
また、ポリマー分散液のポリマー濃度を低くすることに
よっても、より微細な板状ポリマー微粒子が得られる。Further, finer plate-like polymer fine particles can also be obtained by lowering the polymer concentration of the polymer dispersion.
凍結は、完全に行えばその条件は問わないが、ポリマー
分散液を内部まで完全に凍結させるため、凍結状態を１
５分間以上保持することが好ましい。Freezing conditions do not matter as long as it is completely frozen, but in order to completely freeze the polymer dispersion to the inside, the freezing condition should be set to 1.
It is preferable to hold for 5 minutes or more.
また、ポリマー分散液の調製は、例えば、上記微粒子ポ
リマー、上記分散媒及び上記分散剤を屋舎撹拌すれば良
く、また、ポリマーとして乳化重合法によって容易に微
粒子ポリマー分散液が得られるものを用いる場合は、乳
化重合によって得られる乳化重合液をそのままポリマー
分散液として使用できる。In addition, the polymer dispersion can be prepared by, for example, stirring the fine particle polymer, the dispersion medium, and the dispersant, and a polymer that can be easily obtained by emulsion polymerization is used as the polymer. In this case, the emulsion polymerization solution obtained by emulsion polymerization can be used as it is as a polymer dispersion.
また、ポリマー分散液のポリマー濃度は、ポリマー環や
目的とする板状ポリマー微粒子のサイズ及び厚みなどに
よっても異なるが、通常１〜２０重量％が好ましい。Further, the polymer concentration of the polymer dispersion varies depending on the size and thickness of the polymer ring and the intended plate-shaped polymer fine particles, but is usually preferably 1 to 20% by weight.
次に、上述の如くして凍結したポリマー分散液を、該ポ
リマーのガラス転移温度未満、好ましくは該ガラス転移
温度より５°Ｃ程低い温度まで昇温させ融解させる。昇
温方法としては、例えば、凍結したポリマー分散液を常
温もしくは加熱した水に溶解し、必要に応してさらに加
熱する方法、上記分散液を凍結乾燥し加熱する方法、上
記分散液を室温に放置する方法、及び上記分散液を容器
のまま加熱する方法などが挙げられ、凍結したポリマー
分散液を室温に放置する方法など、上記分散液を徐々に
加温する方法が好ましい。Next, the polymer dispersion frozen as described above is heated to a temperature below the glass transition temperature of the polymer, preferably about 5° C. below the glass transition temperature, and is melted. Examples of methods for raising the temperature include: dissolving a frozen polymer dispersion in room temperature or heated water and heating it further if necessary; freeze-drying the dispersion and heating it; and heating the dispersion to room temperature. Examples include a method of allowing the dispersion to stand, and a method of heating the dispersion in a container, and a method of gradually warming the dispersion, such as a method of leaving a frozen polymer dispersion at room temperature, is preferred.
昇温時、ガラス転移温度を越えるとポリマー表面が粘弾
性を有し、ポリマー同士の融着により形状が保持されな
い。従って、原料として用いるポリマーは、ガラス転移
温度が好ましくは室温以上、より好ましくは５０°Ｃ以
上のものであり、製造時の界層条件を考慮すればガラス
転移温度が５０〜９０’Ｃのものが特に好ましい。When the temperature rises and the temperature exceeds the glass transition temperature, the polymer surface becomes viscoelastic and the shape is not maintained due to fusion between the polymers. Therefore, the polymer used as a raw material should preferably have a glass transition temperature of room temperature or higher, more preferably 50°C or higher, and if the interfacial conditions during production are considered, the glass transition temperature should be 50 to 90'C. is particularly preferred.
このようにして、本発明の板状ポリマー微粒子が形成さ
れる。In this way, the plate-shaped polymer fine particles of the present invention are formed.
形成された板状ポリマー微粒子は、吸引濾過法、遠心分
離法など公知の方法により分散媒から単離することがで
きる。The formed plate-like polymer fine particles can be isolated from the dispersion medium by a known method such as a suction filtration method or a centrifugation method.
このようにして得られる本発明の板状ポリマー微粒子は
、平均厚みが０．０１〜１００μｍ、長片が厚みの１０
倍以上のもので、微細な板状で形状も均一なため、化粧
品用粉体、着色料等に有用である。The plate-shaped polymer fine particles of the present invention thus obtained have an average thickness of 0.01 to 100 μm, and the long pieces have a thickness of 10 μm.
It is more than twice as large and has a uniform shape in the form of fine plates, making it useful for cosmetic powders, colorants, etc.
以下に実施例を示し、本発明を更に詳しく説明する。 The present invention will be explained in more detail with reference to Examples below.
実施例１
窒素ガス導入管、還流冷却器、温度計及び撹拌装置（撹
拌片は弦の長さ６ｃｍの半月形のもの）を備えた１００
０ｄの五つロセバラブルフラスコ中に３％のドデシル硫
酸ナトリウム水溶液４００ｄを加え、そこに重合開始剤
である過硫酸アンモニウムを１．０ｇ加え、系内に窒素
ガスを吹き込みながらかつオイルバスを６５℃に保ち、
１１００ｒｐ。Example 1 100 equipped with a nitrogen gas inlet pipe, a reflux condenser, a thermometer, and a stirring device (the stirring piece is half-moon shaped with a string length of 6 cm)
Add 400 d of a 3% sodium dodecyl sulfate aqueous solution into a five-point rose-detachable flask, add 1.0 g of ammonium persulfate as a polymerization initiator, and heat the system in an oil bath at 65° C. while blowing nitrogen gas into the system. keep it to
1100rp.
で撹拌しながら１００ｇのスチレンモノマーを１時間で
滴下した。そして、３時間重合を行い、その後、系内の
温度を７５°Ｃに昇温し撹拌を止め、１時間程熟戒する
と、残存モノマー臭がほとんどなくなった。そして、室
温まで徐冷しポリスチレンエマルジョン（粒径が７２．
２ｎｍ）を得た０次いで、この２０％ポリスチレンエマ
ルジョン５−を直径２Ｃ１１のサンプル瓶に入れ、液体
窒素中で１５分間冷却凍結させた。そして、これを室温
にて放置して融解させた。その結果、平均厚みが５μｍ
、長片が厚みの約１０倍である板状ポリスチレンが得ら
れた。While stirring, 100 g of styrene monomer was added dropwise over 1 hour. Then, polymerization was carried out for 3 hours, after which the temperature in the system was raised to 75° C., stirring was stopped, and after careful observation for about 1 hour, the residual monomer odor almost disappeared. Then, it was slowly cooled to room temperature and a polystyrene emulsion (particle size of 72.
2nm) was obtained.Then, this 20% polystyrene emulsion 5- was placed in a sample bottle with a diameter of 2C11, and cooled and frozen in liquid nitrogen for 15 minutes. This was then allowed to stand at room temperature to melt. As a result, the average thickness was 5 μm.
A plate-like polystyrene whose long pieces were about 10 times the thickness was obtained.
実施例２
実施例１で得られた２０％ポリスチレンエマルジョンを
５％に希釈し、これを実施例１と同様に凍結、融解を行
った。その結果、平均厚みが１μｍ、長片が厚みの約２
０倍である板状ポリスチレンが得られた。この板状ポリ
スチレンの電子顕微鏡写真（ｘ２００）を第１図に示す
。Example 2 The 20% polystyrene emulsion obtained in Example 1 was diluted to 5%, and this was frozen and thawed in the same manner as in Example 1. As a result, the average thickness was 1 μm, and the long piece was about 2 μm thick.
A plate-shaped polystyrene with a thickness of 0 times was obtained. An electron micrograph (x200) of this plate-shaped polystyrene is shown in FIG.
実施例３
窒素ガス導入管、還流冷却器、温度計及び撹拌装置（撹
拌片は弦の長さ６Ｃ１の半月形のもの）を備えた１００
０−の五つロセパラブルフラスコ中に３％のラウリルト
リメチルアンモニウムクロライド水溶液４００ｍを加え
、そこに重合開始剤である２、２アゾビス（２−アミジ
ノプロパン）二塩酸塩０．７ｇ加え、系内に窒素ガスを
吹き込みながらかつオイルバスを６５°Ｃに保ち、１０
０ ｒｐｍ。Example 3 100 equipped with a nitrogen gas inlet pipe, a reflux condenser, a thermometer, and a stirring device (the stirring piece is half-moon shaped with a string length of 6C1)
400ml of a 3% lauryltrimethylammonium chloride aqueous solution was added to a five-piece removable flask, and 0.7g of 2,2azobis(2-amidinopropane) dihydrochloride, a polymerization initiator, was added to the system. While blowing nitrogen gas into the tank and keeping the oil bath at 65°C,
0 rpm.
で撹拌しながら１００ｇのメタクリル酸エチルとメタク
リル酸ｎ−ブチルとの１：１混合物を１時間で滴下した
。そして、３時間重合を行い、その後、系内の温度を７
５°Ｃに昇温し撹拌を止め、１時間程熟成すると、残存
モノマー臭がほとんどなくなった。そして、室温まで徐
冷しポリメタクリル酸エチル／ｎ−ブチル共重合体エマ
ルジョン（粒径が８０．８ ｎ ｍ ）を得た。次いで
、この２０％ポリメタクリル酸エチル／ｎ−ブチル共重
合体エマルジョン５ｙｄを直径２Ｃ１１のサンプル瓶に
入れ、液体窒素中で１５分間冷却凍結させた。そして、
これを室温にて放置して融解させ、５０°Ｃの水浴中に
浸し、１時間熱処理・焼結した（板状ポリマーのｍｙ＜
強度が増大）。次にそれを濾過することにより平均厚み
が３μｍ、長片が厚みの約３０倍である板状ポリメタク
リル酸エチル／ｎ〜ブチル共重合体が粉体として得られ
た。この板状ポリメタクリル酸エチル／ｎ−ブチル共重
合体の電子顕微鏡写真（Ｘ３０００）を第２図に示す。While stirring, 100 g of a 1:1 mixture of ethyl methacrylate and n-butyl methacrylate was added dropwise over 1 hour. Then, polymerization was carried out for 3 hours, and then the temperature in the system was lowered to 7
After raising the temperature to 5°C, stopping stirring, and aging for about 1 hour, the residual monomer odor almost disappeared. Then, it was slowly cooled to room temperature to obtain a polyethyl methacrylate/n-butyl copolymer emulsion (particle size: 80.8 nm). Next, this 20% polyethyl methacrylate/n-butyl copolymer emulsion 5yd was placed in a sample bottle with a diameter of 2C11, and cooled and frozen in liquid nitrogen for 15 minutes. and,
This was left to melt at room temperature, immersed in a 50°C water bath, and heat-treated and sintered for 1 hour (my<
strength). Next, by filtering it, a plate-like polyethyl methacrylate/n-butyl copolymer having an average thickness of 3 μm and a length of about 30 times the thickness was obtained as a powder. FIG. 2 shows an electron micrograph (X3000) of this plate-like polyethyl methacrylate/n-butyl copolymer.
実施例４
実施例３で得られた２０％ポリメタクリル酸エチル／ｎ
−ブチル共重合体エマルジョン（粒径が８０．８ｎｍ）
５ｍを直径２ｃｉ＋のサンプル瓶に入れ、２３°Ｃで冷
却、凍結、融解を行った。その結果、平均厚みが２０μ
ｍ、長片が厚みの約１５倍である板状ポリメタクリル酸
エチル／ｎ−ブチル共重合体が得られた。Example 4 20% polyethyl methacrylate/n obtained in Example 3
-Butyl copolymer emulsion (particle size is 80.8 nm)
A sample of 5 m was placed in a sample bottle with a diameter of 2 ci+, and the sample was cooled, frozen, and thawed at 23°C. As a result, the average thickness was 20μ
m, a plate-like polyethyl methacrylate/n-butyl copolymer having long pieces approximately 15 times the thickness was obtained.
実施例５
実施例３で得られた２０％ポリメタクリル酸エチル／ｎ
−ブチル共重合体エマルジョン（粒径が８０．８ｎｍ）
５ｗ１を直径４ｃＩ１１のサンプル瓶に入れ、液体窒素
中で１５分間冷却し、凍結、融解させた。Example 5 20% polyethyl methacrylate/n obtained in Example 3
-Butyl copolymer emulsion (particle size is 80.8 nm)
5w1 was placed in a sample bottle with a diameter of 4cI11 and cooled in liquid nitrogen for 15 minutes to freeze and thaw.
その結果、平均厚みが２μｍ、長片が厚みの約３０倍で
ある板状ポリメタクリル酸エチル／ｎ−フチル共重合体
が得られた。As a result, a plate-shaped polyethyl methacrylate/n-phthyl copolymer with an average thickness of 2 μm and long pieces approximately 30 times the thickness was obtained.
実施例６
窒素ガス導入管、還流冷却器、温度計及び撹拌装置（撹
拌片は弦の長さ６ｃｍの半月形のもの）を備えた１００
０ｄの五つロセパラブルフラスコ中に４％のドデシル硫
酸ナトリウム水溶液４００１ｄを加え、そこに重合開始
剤である過硫酸カリウムを１．５ｇ加え、系内に窒素ガ
スを吹き込みながらかつオイルバスを６５℃に保ち、３
００ｒｐｍ、で撹拌しながら１００ｇのスチレンモノマ
ーを１時間で滴下した。そして、３時間重合を行い、そ
の後、系内の温度を７５°Ｃに昇温し撹拌を止め、１時
間程熟戒すると、残存モノマー臭がほとんどなくなった
。そして、室温まで徐冷しポリスチレンエマルジョン（
粒径が２９．０ｎｍ）を得た。次いで、この２０％ポリ
スチレンエマルジョン５−を直径２ｃ＋＋＋のサンプル
瓶に入れ、液体窒素中で１５分間冷却凍結させた。そし
て、これを室温にて放置して融解させた。その結果、平
均厚みが０．５μｍ、長片が厚みの約５０倍である板状
ポリスチレンが得られた。この板状ポリスチレンの電子
顕微鏡写真（Ｘ３０００）を第３図に示す。Example 6 100 equipped with a nitrogen gas introduction pipe, a reflux condenser, a thermometer, and a stirring device (the stirring piece was half-moon shaped with a string length of 6 cm).
A 4% aqueous solution of sodium dodecyl sulfate (4001d) was added to a five-piece 0d removable flask, 1.5g of potassium persulfate as a polymerization initiator was added thereto, and the system was heated in an oil bath while blowing nitrogen gas into the system. Keep at 3℃
While stirring at 00 rpm, 100 g of styrene monomer was added dropwise over 1 hour. Then, polymerization was carried out for 3 hours, after which the temperature in the system was raised to 75° C., stirring was stopped, and after careful observation for about 1 hour, the residual monomer odor almost disappeared. Then, the polystyrene emulsion (
A particle size of 29.0 nm) was obtained. Next, this 20% polystyrene emulsion 5- was placed in a sample bottle with a diameter of 2c+++, and cooled and frozen in liquid nitrogen for 15 minutes. This was then allowed to stand at room temperature to melt. As a result, a polystyrene plate having an average thickness of 0.5 μm and a long piece approximately 50 times the thickness was obtained. An electron micrograph (X3000) of this plate-shaped polystyrene is shown in FIG.
本発明の板状ポリマー微粒子は、平均厚みが０゜０１〜
１００μｍ、長片が厚みの１０倍以上のもので、微細な
板状で形状も均一なため、化粧料、塗料、イオン交換樹
脂の母材、クロマトグラフィー用の充填剤などに使用で
きる。The plate-shaped polymer fine particles of the present invention have an average thickness of 0°01 to
The length is 100 μm, the length is more than 10 times the thickness, and the shape is uniform in the form of fine plates, so it can be used for cosmetics, paints, base materials for ion exchange resins, fillers for chromatography, etc.
また、本発明の板状ポリマー微粒子の製造法は、操作が
簡便かつ容易で、しかも均一かつ確実に本発明の板状ポ
リマー微粒子を得ることができ、また製造条件の選択に
よって板状ポリマー微粒子の厚み及びサイズ（長片）を
容易に制御でき、より微細（例えば、平均厚みが約０．
１μｍで長片が厚みの約１０倍程度）な板状ポリマー微
粒子の製造も容易に可能で、その上、熱や溶剤に対し安
定な架橋型ポリマーについても板状への成形加工が可能
で、更にポリマ一種の選択の幅が非常に広いなどの効果
を有する。In addition, the method for producing plate-like polymer fine particles of the present invention is simple and easy to operate, and allows the plate-like polymer fine particles of the present invention to be obtained uniformly and reliably. Thickness and size (long pieces) can be easily controlled and finer (e.g. average thickness of about 0.5 mm) can be easily controlled.
It is possible to easily produce plate-shaped polymer fine particles with a length of 1 μm (long pieces are about 10 times the thickness), and furthermore, cross-linked polymers that are stable against heat and solvents can also be formed into plate shapes. Furthermore, it has the advantage that there is a very wide range of choices for the type of polymer.
第１図は実施例２で得られた板状ポリスチレンの粒子構
造を示す電子顕微鏡写真、第２図は実施例３で得られた
板状ポリメタクリル酸エチル／ｎ−ブチル共重合体の粒
子構造を示す電子顕微鏡写真、及び第３図は実施例６で
得られた板状ポリスチレンの粒子構造を示す電子顕微鏡
写真である。Figure 1 is an electron micrograph showing the particle structure of the plate-shaped polystyrene obtained in Example 2, and Figure 2 is the particle structure of the plate-shaped polyethyl methacrylate/n-butyl copolymer obtained in Example 3. FIG. 3 is an electron micrograph showing the particle structure of the plate-shaped polystyrene obtained in Example 6.
Claims (2)
に冷却した後、該ポリマーのガラス転移温度未満まで昇
温させて得られた、平均厚みが０．０１〜１００μｍ、
長片が厚みの１０倍以上である板状ポリマー微粒子。(1) An average thickness of 0.01 to 100 μm obtained by cooling a fine particle polymer dispersion to a temperature below the freezing temperature of the dispersion medium and then raising the temperature to below the glass transition temperature of the polymer;
Plate-shaped polymer fine particles whose long pieces are 10 times or more thicker.
液を、分散媒の凍結温度以下に冷却した後、該ポリマー
のガラス転移温度未満まで昇温させ、平均厚みが０．０
１〜１００μｍ、長片が厚みの１０倍以上である板状ポ
リマー微粒子を得ることを特徴とする板状ポリマー微粒
子の製造法。(2) A fine particle polymer dispersion having an average particle diameter of 500 nm or less is cooled to below the freezing temperature of the dispersion medium, and then heated to below the glass transition temperature of the polymer, so that the average thickness is 0.0 nm.
1. A method for producing plate-like polymer fine particles, which comprises obtaining plate-like polymer fine particles having a length of 1 to 100 μm and a long piece that is 10 times or more thicker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2029880A JP2849146B2 (en) | 1990-02-09 | 1990-02-09 | Plate-shaped polymer fine particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2029880A JP2849146B2 (en) | 1990-02-09 | 1990-02-09 | Plate-shaped polymer fine particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03234734A true JPH03234734A (en) | 1991-10-18 |
| JP2849146B2 JP2849146B2 (en) | 1999-01-20 |
Family
ID=12288294
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2029880A Expired - Fee Related JP2849146B2 (en) | 1990-02-09 | 1990-02-09 | Plate-shaped polymer fine particles and method for producing the same |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794448B2 (en) | 2000-03-21 | 2004-09-21 | Sekisui Plastics Co., Ltd. | Resin particles and process for producing the same |
| JP2006188558A (en) * | 2004-12-28 | 2006-07-20 | Kao Corp | Method for producing organic sheet-shaped particle |
| JP2010285609A (en) * | 2009-05-11 | 2010-12-24 | Kose Corp | Shape-anisotropic tabular particle, method for producing the same, and cosmetic obtained by formulating shape-anisotropic tabular particle |
| CN104084179A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院化学研究所 | Polymer monolithic column, and preparation method and application thereof |
-
1990
- 1990-02-09 JP JP2029880A patent/JP2849146B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794448B2 (en) | 2000-03-21 | 2004-09-21 | Sekisui Plastics Co., Ltd. | Resin particles and process for producing the same |
| JP2006188558A (en) * | 2004-12-28 | 2006-07-20 | Kao Corp | Method for producing organic sheet-shaped particle |
| JP4509770B2 (en) * | 2004-12-28 | 2010-07-21 | 花王株式会社 | Method for producing organic plate-like particles |
| JP2010285609A (en) * | 2009-05-11 | 2010-12-24 | Kose Corp | Shape-anisotropic tabular particle, method for producing the same, and cosmetic obtained by formulating shape-anisotropic tabular particle |
| JP2010285610A (en) * | 2009-05-11 | 2010-12-24 | Kose Corp | Tabular particle having hydrophilic and hydrophobic anisotropy, method for producing the same, and emulsifier comprising the same |
| CN104084179A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院化学研究所 | Polymer monolithic column, and preparation method and application thereof |
| CN104084179B (en) * | 2014-07-07 | 2015-12-02 | 中国科学院化学研究所 | A kind of polyalcohol integral pole and preparation method thereof and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2849146B2 (en) | 1999-01-20 |
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