JP6464563B2 - Method for producing coated fine particles - Google Patents
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Description
本発明は、被覆された微粒子の製造方法に関し、特に高分子ポリマーで被覆された微粒子の製造方法に関する。 The present invention relates to a method for producing coated fine particles, and more particularly to a method for producing fine particles coated with a polymer.
従来、微粒子を高分子ポリマーで被覆する際には、有機溶媒若しくは水系にて実施している。特に水系にて実施する際には条件により過剰な重合が起こり、このことが原因で高分子ポリマーの粗大物や微粒子凝集体が生成するという問題があった。 Conventionally, when coating fine particles with a polymer, it has been carried out in an organic solvent or an aqueous system. In particular, when the reaction is carried out in an aqueous system, excessive polymerization occurs depending on conditions, which causes a problem that coarse polymers or fine particle aggregates are formed.
本発明は、微粒子を高分子ポリマーで被覆する際に、水系にて実施しても過剰な重合を起こしにくく、高分子ポリマーの粗大物や微粒子凝集体の生成を抑制することができる方法を提供するものである。 The present invention provides a method that, when coated with a polymer, can prevent excessive polymerization even when carried out in an aqueous system, and can suppress the formation of coarse polymers and aggregates of the polymer. To do.
本発明者は、鋭意検討の結果、以下の方法をとることで、上記問題点を解決しうることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has found that the above problems can be solved by taking the following method, and has completed the present invention.
即ち、本発明は以下のとおりである。
（１）微粒子を高分子ポリマーで被覆する際に、１回の被覆に用いられる高分子ポリマーの量が、微粒子の単位表面積あたり０．０１〜０．５ｇ／ｍ２であることを特徴とする、被覆された微粒子の製造方法。
（２）微粒子が磁性体を有する、（１）に記載の方法。
（３）上述の（１）又は（２）に記載の方法を複数回繰り返して行う、（１）又は（２）に記載の方法。
That is, the present invention is as follows.
(1) When the fine particles are coated with the high molecular polymer, the amount of the high molecular polymer used for one coating is 0.01 to 0.5 g / m 2 per unit surface area of the fine particles. A method for producing coated fine particles.
(2) The method according to (1), wherein the fine particles have a magnetic material.
(3) The method according to (1) or (2), wherein the method according to (1) or (2) is repeated a plurality of times.
以下に本発明を更に詳細に説明する。 The present invention is described in further detail below.
本発明で用いられる微粒子とは、ガラス、金属、セラミックス等の無機物であってもよく、また高分子ポリマー等の有機物であってもよい。ここでいう高分子ポリマーは、後述する被覆に用いる高分子ポリマーと同じであってもよく、また異なっていてもよい。また本発明に用いられる微粒子は磁性体を含むものであってもよい。微粒子の粒子径は０．１から５０μｍが好ましく、さらには１から１０μｍが好ましい。また微粒子は細孔を有しても有さなくてもよい。 The fine particles used in the present invention may be inorganic substances such as glass, metal, and ceramics, and may be organic substances such as a polymer. The high molecular polymer here may be the same as or different from the high molecular polymer used for the coating described later. The fine particles used in the present invention may contain a magnetic material. The particle diameter of the fine particles is preferably from 0.1 to 50 μm, more preferably from 1 to 10 μm. The fine particles may or may not have pores.
本発明では、微粒子を高分子ポリマーで被覆するが、これは既に高分子ポリマーとして存在しているものを用いて微粒子を被覆してもよいが、微粒子表面でモノマーを重合させて高分子ポリマーを生成させつつ被覆してもよい。ここで微粒子表面とは、微粒子の外表面ばかりでなく、細孔を有する微粒子の場合は細孔内表面をも含めるものとする。また被覆とは、微粒子の少なくとも一部を覆うことを意味し、微粒子全体を覆うものであってもよい。 In the present invention, the fine particles are coated with a high molecular polymer, and this may be coated with a polymer already existing as a high molecular polymer. You may coat | cover while producing | generating. Here, the surface of the fine particles includes not only the outer surface of the fine particles but also the surface inside the fine pores in the case of fine particles having pores. Further, the coating means covering at least part of the fine particles, and may cover the entire fine particles.
ここで被覆に用いられる高分子ポリマーとしては、その組成、重合度には特に限定はなく、例えばポリジビニルベンゼン、ポリスチレン、ポリグリシジルメタクリレート等があげられる。 Here, the composition and degree of polymerization of the high molecular polymer used for coating are not particularly limited, and examples thereof include polydivinylbenzene, polystyrene, polyglycidyl methacrylate, and the like.
本発明では、微粒子を高分子ポリマーで被覆する際に、１回の被覆に用いられる高分子ポリマーの量が、微粒子の単位表面積あたり０．０１〜０．５ｇ／ｍ２であることを特徴とする。この１回の被覆に用いられる高分子ポリマーの量は、好ましくは０．０２〜０．３ｇ／ｍ２、さらに好ましくは０．０５〜０．２ｇ／ｍ２である。 In the present invention, when the fine particles are coated with the high molecular polymer, the amount of the high molecular polymer used for one coating is 0.01 to 0.5 g / m 2 per unit surface area of the fine particles. To do. The amount of high molecular polymer used in the coating of the one is preferably 0.02~0.3g / m 2, more preferably at 0.05 to 0.2 g / m 2.
この被覆処理は１回だけ行ってもよいが、複数回繰り返して行ってもよい。好ましくは３回以上、さらに好ましくは４回以上行うことにより、微粒子表面をより均一に被覆することができる。なお被覆回数の上限は特に限定されるものではないが、効果との兼ね合いで好ましくは２０回以下、更に好ましくは１０回以下である。 This coating treatment may be performed only once, but may be repeated a plurality of times. The surface of the fine particles can be coated more uniformly by performing the treatment three times or more, more preferably four times or more. The upper limit of the number of times of coating is not particularly limited, but is preferably 20 times or less, more preferably 10 times or less in view of the effect.
本発明の方法について、モノマーを重合させて高分子ポリマーを生成させつつ被覆する場合を例にして、以下により具体的に説明する。 The method of the present invention will be described in more detail below, taking as an example the case of coating while polymerizing monomers to form a polymer.
まず、分散安定剤、乳化剤を含む水溶液に微粒子を分散させる。この際に回転数は５０ｒｐｍ以上３００ｒｐｍ以下であることが好ましい。ここで分散安定剤としては特に限定されるものではないが、例えばポリオキシエチレンステアリルエーテル、ポリビニルピロリドン、ポリビニルアルコールなどが例示される。また乳化剤としては特に限定されるものではないが、例えばウンデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、オクタデシルスルホン酸ナトリウムなどが例示される。加温はしても良いが４０℃以下が好ましい。 First, fine particles are dispersed in an aqueous solution containing a dispersion stabilizer and an emulsifier. At this time, the rotational speed is preferably 50 rpm or more and 300 rpm or less. Here, the dispersion stabilizer is not particularly limited, and examples thereof include polyoxyethylene stearyl ether, polyvinyl pyrrolidone, and polyvinyl alcohol. The emulsifier is not particularly limited, and examples thereof include sodium undecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and sodium octadecyl sulfonate. Although it may be heated, it is preferably 40 ° C. or lower.
次に、高分子ポリマーのモノマーを微粒子分散液に添加する。この際、予め少量の分散安定剤、乳化剤をモノマー水溶液に加えておくことが好ましく、ホモジナイザーなどで乳化操作をしておくことがさらに好ましい。また。このときの回転数は５０ｒｐｍ以上３００ｒｐｍ以下が好ましい。また加温しても良いが４０℃以下が好ましい。モノマーを全量添加した後に、４０℃以上に加熱することが好ましい。本発明では、モノマー水溶液を添加する際、１回の被覆に用いられる高分子ポリマーの量が、微粒子の単位表面積あたり０．０１ｇ／ｍ２〜０．５ｇ／ｍ２となるように換算して添加する。そしてこの被覆操作を合計で３回以上繰り返して行うことが好ましい。被覆が終了した微粒子は通常の方法で分離・回収することができる。 Next, a polymer monomer is added to the fine particle dispersion. At this time, it is preferable to add a small amount of a dispersion stabilizer and an emulsifier in advance to the aqueous monomer solution, and it is more preferable to carry out an emulsification operation with a homogenizer or the like. Also. The number of rotations at this time is preferably 50 rpm or more and 300 rpm or less. Moreover, although it may heat, 40 degrees C or less is preferable. It is preferable to heat to 40 ° C. or higher after all the monomer has been added. In the present invention, when the monomer addition an aqueous solution, the amount of high molecular polymer used in one coating, in terms such that the unit surface area per 0.01g / m 2 ~0.5g / m 2 of fine particles Added. And it is preferable to repeat this covering operation 3 times or more in total. The fine particles that have been coated can be separated and collected by ordinary methods.
本発明により、微粒子に高分子ポリマーを被覆する際に過剰な重合を抑制し、高分子ポリマーの粗大物や微粒子凝集体の生成を抑制することが可能である。 According to the present invention, it is possible to suppress excessive polymerization when the fine particles are coated with the high molecular polymer, and to suppress the formation of coarse polymers or fine particle aggregates.
以下、実施例により本発明を詳細に説明する。しかし本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited only to these examples.
（比較例１）
室温にて、ウンデシルベンゼンスルホン酸ナトリウム０．５％、ポリオキシエチレンステアリルエーテル０．５％の水溶液５０ｍＬに微粒子１ｇ（粒子径２．５μｍ、磁性体としてマグネタイト（Ｆｅ３Ｏ４）を表面に有するポリジビニルベンゼン微粒子）を回転数１００ｒｐｍにて分散させた。ウンデシルベンゼンスルホン酸ナトリウム０．５％、ポリオキシエチレンステアリルエーテル０．５％の水溶液５ｍＬにグリシジルメタクリレート１．３５ｇ、エチレングリコールジメタクリレート０．１５ｇ、Ｖ−６５ ０．０３ｇを添加し、ホモジナイザーにて３０秒間乳化した。これを微粒子分散液に回転数１００ｒｐｍを維持したまま２分かけて添加した。全量添加した後に６０℃に加熱し、この状態を維持したまま１５時間反応させた。これは微粒子単位表面積あたり０．７５ｇ／ｍ２の高分子ポリマー（エチレングリコールジメタクリレートで架橋されたポリグリシジルメタクリレート）を用いたことに相当する。反応終了後、網目４０μｍの金網にてろ過したところ０．５３ｇの反応物が金網上に残った。網目４０μｍの金網を通過した懸濁液を網目２０μｍにてろ過したところ、０．３２ｇの反応物が金網上に残った。二つの金網を通過した反応物は０．２３ｇであった。
(Comparative Example 1)
At room temperature, 1 g of fine particles (particle size 2.5 μm, magnetite (Fe 3 O 4 ) as a magnetic material) on 50 mL of an aqueous solution of 0.5% sodium undecylbenzenesulfonate and 0.5% polyoxyethylene stearyl ether The polydivinylbenzene fine particles) were dispersed at a rotation speed of 100 rpm. To 5 mL of an aqueous solution of 0.5% sodium undecylbenzenesulfonate and 0.5% polyoxyethylene stearyl ether, 1.35 g of glycidyl methacrylate, 0.15 g of ethylene glycol dimethacrylate, and 0.03 g of V-65 were added to the homogenizer. For 30 seconds. This was added to the fine particle dispersion over 2 minutes while maintaining the rotational speed of 100 rpm. After adding the whole amount, the mixture was heated to 60 ° C. and reacted for 15 hours while maintaining this state. This corresponds to using 0.75 g / m 2 of a high molecular polymer (polyglycidyl methacrylate crosslinked with ethylene glycol dimethacrylate) per unit surface area of fine particles. After completion of the reaction, the mixture was filtered through a wire mesh having a mesh size of 40 μm, and 0.53 g of the reaction product remained on the wire mesh. When the suspension that passed through the wire mesh having a mesh size of 40 μm was filtered with a mesh size of 20 μm, 0.32 g of the reaction product remained on the wire mesh. The reaction product that passed through the two wire meshes was 0.23 g.
（実施例１）
室温にて、ウンデシルベンゼンスルホン酸ナトリウム０．５％、ポリオキシエチレンステアリルエーテル０．５％の水溶液５０ｍＬに微粒子１ｇ（粒子径２．５μｍ、磁性体としてマグネタイト（Ｆｅ３Ｏ４）を表面に有するポリジビニルベンゼン微粒子）を回転数１００ｒｐｍにて分散させた。ウンデシルベンゼンスルホン酸ナトリウム０．５％、ポリオキシエチレンステアリルエーテル０．５％の水溶液１．２５ｍＬにグリシジルメタクリレート０．３４ｇ、エチレングリコールジメタクリレート０．０４ｇ、Ｖ−６５ ０．００８ｇを添加し、ホモジナイザーにて３０秒間乳化した。これを微粒子分散液に回転数１００ｒｐｍを維持したまま２分かけて添加した。全量添加した後に６０℃に加熱し、この状態を維持したまま１５時間反応させた。これは微粒子単位表面積あたり０．１９ｇ／ｍ２の高分子ポリマー（エチレングリコールジメタクリレートで架橋されたポリグリシジルメタクリレート）を用いたことに相当する。反応終了後にウンデシルベンゼンスルホン酸ナトリウム０．５％、ポリオキシエチレンステアリルエーテル０．５％の水溶液にて洗浄を実施した後に、上述の高分子ポリマーによる被覆反応をさらに３回繰り返して行ない、合計で４回の被覆を行なった。４回目の反応終了後、網目４０μｍの金網にてろ過したところ、ほぼすべての反応物が金網を通過した。網目４０μｍの金網を通過した懸濁液を網目２０μｍにてろ過したところ、０．１５ｇの反応物が金網上に残った。二つの金網を通過した反応物は１．１２ｇであった。比較例１と比較して実施例１では４．９倍の微粒子を得た。比較例１と比べて、実施例１の方法によれば、高分子ポリマーの原料モノマーの過剰な重合を抑制し、高分子ポリマーの粗大物や微粒子凝集体の生成を抑制できることが明らかである。
Example 1
At room temperature, 1 g of fine particles (particle size 2.5 μm, magnetite (Fe 3 O 4 ) as a magnetic material) on 50 mL of an aqueous solution of 0.5% sodium undecylbenzenesulfonate and 0.5% polyoxyethylene stearyl ether The polydivinylbenzene fine particles) were dispersed at a rotation speed of 100 rpm. Add glycidyl methacrylate 0.34g, ethylene glycol dimethacrylate 0.04g, V-65 0.008g to 1.25mL aqueous solution of sodium undecylbenzenesulfonate 0.5%, polyoxyethylene stearyl ether 0.5%, The mixture was emulsified with a homogenizer for 30 seconds. This was added to the fine particle dispersion over 2 minutes while maintaining the rotational speed of 100 rpm. After adding the whole amount, the mixture was heated to 60 ° C. and reacted for 15 hours while maintaining this state. This corresponds to the use of 0.19 g / m 2 of high molecular polymer (polyglycidyl methacrylate crosslinked with ethylene glycol dimethacrylate) per unit surface area of fine particles. After completion of the reaction, after washing with an aqueous solution of sodium undecylbenzenesulfonate 0.5% and polyoxyethylene stearyl ether 0.5%, the coating reaction with the above polymer was repeated three more times. The coating was performed 4 times. After completion of the fourth reaction, the reaction mixture was filtered through a wire mesh having a mesh size of 40 μm. As a result, almost all the reaction product passed through the wire mesh. When the suspension that passed through the wire mesh having a mesh size of 40 μm was filtered through a mesh of 20 μm, 0.15 g of the reaction product remained on the wire mesh. The reaction product which passed through the two wire meshes was 1.12 g. Compared with the comparative example 1, the fine particle of 4.9 times was obtained in the example 1. As compared with Comparative Example 1, it is apparent that the method of Example 1 can suppress the excessive polymerization of the raw material monomer of the high molecular polymer and suppress the formation of coarse polymer particles and fine particle aggregates.
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