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JP2006035132A - Method for producing solid particles using microchannel structure and display capsule obtained thereby - Google Patents

Method for producing solid particles using microchannel structure and display capsule obtained thereby Download PDF

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JP2006035132A
JP2006035132A JP2004220362A JP2004220362A JP2006035132A JP 2006035132 A JP2006035132 A JP 2006035132A JP 2004220362 A JP2004220362 A JP 2004220362A JP 2004220362 A JP2004220362 A JP 2004220362A JP 2006035132 A JP2006035132 A JP 2006035132A
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solid particles
producing solid
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JP4385886B2 (en
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Hideaki Kiritani
英昭 桐谷
Hidekazu Yoshizawa
秀和 吉澤
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Tosoh Corp
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Abstract

【課題】微小流路構造体の連続相と分散相交差部において得られる液滴の分散度を保持したままゲル化あるいはカプセル化等することにより固体状粒子を製造する方法、またカプセル内の微小粒子の移動を損なわないカプセルの製造方法を提供する。
【解決の手段】分散相を導入するための導入口及び導入流路と、連続相を導入するための導入口及び導入流路と、分散相及び連続相を介して生成された粒子を排出させるための排出流路及び排出口とを備えた微小流路構造体を用いて固体状粒子を製造する方法であって、あらかじめ流体の一部をオリゴマー及び/又はポリマーにした流体を送液し、液滴を生成させるとともに当該液滴表面に皮膜を生成させ、その後未反応成分により皮膜を硬化する固体状粒子の製造方法及びそれにより得られる表示用カプセルを用いる。
【選択図】なし
Disclosed is a method for producing solid particles by gelling or encapsulating while maintaining the degree of dispersion of droplets obtained at the intersection of a continuous phase and a dispersed phase of a microchannel structure. Provided is a capsule production method that does not impair the movement of particles.
An inlet and an introduction channel for introducing a dispersed phase, an inlet and an introduction channel for introducing a continuous phase, and particles generated through the dispersed phase and the continuous phase are discharged. A method for producing solid particles using a microchannel structure having a discharge channel and a discharge port for supplying a fluid in which a part of the fluid is previously made into an oligomer and / or polymer, A method for producing solid particles in which droplets are generated and a film is formed on the surface of the droplets, and then the film is cured by an unreacted component, and a display capsule obtained thereby are used.
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Description

本発明は、粒子径の揃ったゲルやマイクロカプセル等の固体状粒子の製造方法に関する。特に、磁気泳動または電気泳動マイクロカプセルを用いた表示用として用いることができるマイクロカプセルに関する。   The present invention relates to a method for producing solid particles such as gels and microcapsules having a uniform particle diameter. In particular, the present invention relates to a microcapsule that can be used for display using magnetophoresis or electrophoresis microcapsules.

近年、数cm角のガラス基板上に長さが数cm程度で、幅と深さがサブmmから数百mmの微小流路を有する微小流路構造体を用い、流体を微小流路へ導入することにより液滴の生成を行う研究が注目されており、界面張力の異なる2種類の液体を、前記2種類の流体の交差部が存在する流路に導入することにより均一な微小液滴からなるエマルションを調整することができる(例えば、特許文献1あるいは非特許文献1参照)。なおここでいうエマルションとは、二つの互いに溶け合わない液体の一方が他の液体の中に微細な粒子として分散している系をいう。   In recent years, a fluid is introduced into a microchannel using a microchannel structure having a microchannel having a length of about several centimeters on a glass substrate of several cm square and a width and depth of sub mm to several hundred mm. Research has been attracting attention for the generation of droplets by introducing two types of liquids having different interfacial tensions into a microscopic droplet by introducing them into a channel where the intersection of the two types of fluids exists. Can be prepared (see, for example, Patent Document 1 or Non-Patent Document 1). The emulsion here refers to a system in which one of two insoluble liquids is dispersed as fine particles in the other liquid.

例えば、特許文献1あるいは非特許文献1に示されている手法は、図1及び図1中のA−A’断面を示す図2に示すように、基板(1)に連続相導入口(2)、連続相を導入する流路(以下、連続相導入流路(3)という)、分散相導入口(4)、分散相を導入する流路(以下、分散相導入流路(5)という)、連続相中に液滴化した分散相を排出する流路(以下、排出流路(7)という)及び排出口(8)を有したT字型の流路を有し、基板の流路面側にカバー体を接合した微小流路構造体であり、マイクロチャンネル中を流れる連続相に対し、分散相を前記連続相の流れに交差する向きで分散相供給口より排出し、前記連続相のせん断力によって、前記分散相の供給チャンネルの幅より径の小さい微小液滴を得ている。しかしながら、この方法で、得られた液滴は、微小な液滴を含む上、均一な液滴をそのままの分散度を保ったままゲル化、または、マイクロカプセル化することは困難であった。   For example, the technique disclosed in Patent Document 1 or Non-Patent Document 1 has a continuous phase inlet (2) in the substrate (1) as shown in FIG. 2 and FIG. 2 showing the AA ′ cross section in FIG. ), A flow path for introducing a continuous phase (hereinafter referred to as a continuous phase introduction flow path (3)), a dispersed phase introduction port (4), and a flow path for introducing a dispersed phase (hereinafter referred to as a dispersed phase introduction flow path (5)). ), A T-shaped channel having a channel (hereinafter referred to as a discharge channel (7)) for discharging the dispersed phase formed into droplets in the continuous phase and a discharge port (8), and the flow of the substrate It is a micro flow channel structure in which a cover body is joined to the road surface side, and with respect to the continuous phase flowing in the microchannel, the dispersed phase is discharged from the dispersed phase supply port in a direction crossing the flow of the continuous phase, and the continuous phase Due to the shearing force, fine droplets having a diameter smaller than the width of the supply channel of the dispersed phase are obtained. However, in this method, the obtained droplets contain minute droplets, and it has been difficult to gel or microencapsulate uniform droplets while maintaining the same degree of dispersion.

国際公開WO02/068104号パンフレットInternational Publication WO02 / 068104 Pamphlet 西迫貴志ら、「マイクロチャネルにおける液中微小液滴生成」、第4回化学とマイクロシステム研究会講演予稿集、59頁、2001年発行Takashi Nishisako et al., “Liquid microdroplet generation in microchannels”, Proceedings of the 4th Chemistry and Microsystem Study Group, 59 pages, 2001

微小流路構造体を介して得られたエマルションのゲル化やカプセル化においては、従来から用いられているような攪拌機構を有する構造体の中で攪拌しながら加温してゲル化する方法では、ゲル化時に攪拌による再分裂や合一により分散度が悪くなるという課題があった。また、液滴を生成した排出流路内で重合する方法では、流路が閉塞したり、ゲル化、カプセル化が不十分であるなどの課題があった。さらには、カプセル化した微粒子の壁に内部の微小粒子が固着して内部での自由な移動が妨げられるという課題があり、最適な方法が望まれていた。   In the gelation and encapsulation of the emulsion obtained through the microchannel structure, the gelation is performed by heating while stirring in the structure having a stirring mechanism as conventionally used. However, there was a problem that the dispersibility deteriorated due to re-division and coalescence by stirring during gelation. In addition, the method of polymerizing in the discharge flow path in which the droplets are generated has problems such as the flow path being clogged and insufficient gelation and encapsulation. Furthermore, there is a problem that the internal microparticles adhere to the wall of the encapsulated fine particles and the free movement inside is hindered, and an optimal method has been desired.

本発明は、上記課題に鑑みてなされたもので、微小流路構造体の連続相と分散相交差部において得られる液滴の分散度を保持したままゲル化あるいはカプセル化等することにより固体状粒子を製造する方法、またカプセル内の微小粒子の移動を損なわない固体状粒子の製造方法、及びそれにより得られる表示用カプセルを提供することにある。   The present invention has been made in view of the above-mentioned problems. The solid state is obtained by gelling or encapsulating while maintaining the degree of dispersion of the droplets obtained at the continuous phase and dispersed phase intersection of the microchannel structure. An object of the present invention is to provide a method for producing particles, a method for producing solid particles that do not impair movement of microparticles in the capsule, and a display capsule obtained thereby.

本発明は、分散相を導入するための導入口及び導入流路と、連続相を導入するための導入口及び導入流路と、分散相及び連続相を介して生成された粒子を排出させるための排出流路及び排出口とを備えた微小流路構造体を用いて固体状粒子を製造する方法であって、あらかじめ流体の一部をオリゴマー及び/又はポリマーにした流体を送液し、液滴を生成させるとともに当該液滴表面に皮膜を生成させ、その後未反応成分により皮膜を硬化する固体状粒子の製造方法であり、固体状粒子としてカプセルを製造するに好適である。また、あらかじめ送液する分散相中に微粒子を含んでいてもよい。   The present invention is to introduce an inlet and an introduction channel for introducing a dispersed phase, an introduction port and an introduction channel for introducing a continuous phase, and particles generated through the dispersed phase and the continuous phase. A method for producing solid particles using a micro-channel structure having a discharge channel and a discharge port, wherein a fluid in which a part of the fluid is converted into an oligomer and / or polymer in advance is sent to the liquid This is a method for producing solid particles in which droplets are formed, a film is formed on the surface of the droplets, and then the film is cured by an unreacted component, and is suitable for producing capsules as solid particles. Further, fine particles may be contained in the dispersed phase to be fed in advance.

さらに本発明は、連続相または分散相中のあらかじめ一部をオリゴマーまたはポリマーにする流体中に、界面活性剤を含む固体状粒子の製造方法であり、また、あらかじめ液滴の表面を被覆する皮膜の原料のオリゴマーまたはポリマーを、連続相に含んでいる固体状粒子の製造方法であり、また、あらかじめ液滴の表面を被覆する皮膜の原料のオリゴマーまたはポリマーを、分散相に実質的に含んでいない固体状粒子の製造方法である。   Furthermore, the present invention relates to a method for producing solid particles containing a surfactant in a fluid in which a part of the continuous phase or dispersed phase is previously oligomerized or polymerized, and a film that covers the surface of the droplets in advance. The solid phase particle or oligomer polymer is contained in the continuous phase, and the coating phase oligomer or polymer that covers the surface of the droplets in advance is substantially included in the dispersed phase. It is a manufacturing method of the solid particle which is not.

本発明は、あらかじめカプセル皮膜の原料の一部をオリゴマーまたはポリマーにした連続相中に、カプセル皮膜の原料のモノマーやオリゴマーやポリマーを含まない分散相を導入し、液滴を調製するとともにカプセル皮膜を生成し、その後、細管中で送液しながら連続相中の未反応のモノマーや架橋剤によって皮膜を硬化することを特徴とする固体状粒子の製造方法であり、また、あらかじめ送液する分散相中に微粒子を含んでいてもよい。   The present invention introduces a dispersed phase that does not contain monomers, oligomers or polymers of the raw material of the capsule film into a continuous phase in which a part of the raw material of the capsule film is made into an oligomer or polymer in advance, and prepares a droplet and capsule film And then the film is cured with unreacted monomers and a crosslinking agent in the continuous phase while being fed in a thin tube, and the dispersion is carried out in advance. Fine particles may be contained in the phase.

また本発明は、微粒子を含んだカプセルが、磁気泳動または電気泳動マイクロカプセルを用いた表示用である固体状粒子の製造方法であり、カプセル内の液体が着色しているものであってもよい。   The present invention is also a method for producing solid particles in which the capsule containing fine particles is for display using a magnetophoresis or electrophoresis microcapsule, and the liquid in the capsule may be colored. .

また本発明は、固体状粒子の製造方法により得られるカプセルであって、その分散度が3%以下である表示用カプセルである。   The present invention also provides a capsule for display obtained by a method for producing solid particles, the dispersion of which is 3% or less.

以下、本発明をさらに詳細に説明する。   Hereinafter, the present invention will be described in more detail.

本発明において用いられる微小流路とは、一般的に幅500mm以下、深さ300mm以下のサイズの流路を示し、微小流路はマイクロチャンネルと言うこともある。また以下では、前述のように定義した微小流路と微小流路より大きい幅と深さの流路を総じて、流路ということもある。また、排出流路は連続相導入流路と実質的に連続しており、連続相導入流路の延長として排出流路が存在する。   The micro channel used in the present invention generally indicates a channel having a width of 500 mm or less and a depth of 300 mm or less, and the micro channel may be called a micro channel. In the following, the microchannel defined as described above and the channel having a width and depth larger than the microchannel may be collectively referred to as a channel. The discharge channel is substantially continuous with the continuous phase introduction channel, and the discharge channel exists as an extension of the continuous phase introduction channel.

本発明では、分散相導入流路はマイクロチャンネルであることに限定されるが、連続相導入流路は特にマイクロチャンネルに限定されておらず、マイクロチャンネルであっても良いし、マイクロチャンネルでなくても良い。従って、連続相導入流路と実質的に連続している排出流路もマイクロチャンネルに限定されておらず、排出流路はマイクロチャンネルであっても良いし、マイクロチャンネルでなくても良い。むしろ、後述するように本発明の目的であるゲルまたはカプセルの粒径分散度を向上させるためには、連続相導入流路及び排出流路はマイクロチャンネルでないこと好ましく、特に排出流路をマイクロチャンネルにしないことがさらに好ましい。   In the present invention, the dispersed phase introduction flow path is limited to being a microchannel, but the continuous phase introduction flow path is not particularly limited to a microchannel, and may be a microchannel or not a microchannel. May be. Therefore, the discharge flow path substantially continuous with the continuous phase introduction flow path is not limited to the microchannel, and the discharge flow path may be a microchannel or not a microchannel. Rather, in order to improve the particle size dispersion of the gel or capsule, which is the object of the present invention, as described later, it is preferable that the continuous phase introduction flow path and the discharge flow path are not microchannels. More preferably not.

本発明におけるエマルションとは、連続相中に分散相から生成される微小液滴を含む懸濁液である。   The emulsion in the present invention is a suspension containing fine droplets generated from a dispersed phase in a continuous phase.

本発明において用いられる分散相と連続相は、液滴を生成させるための液状物であり、お互いに相溶しない液体である。このうち、連続相は、分散相をせん断して液滴を生成させるために用いられる。例えば、ポリビニルアルコールなどの分散剤を適当な溶媒に溶解した媒体や、ドデシル硫酸ナトリウムや、poly(ethylene−alt−maleic anhydride)(poly(EMA))等の界面活性剤を含んだ媒体、また、ゲルやカプセルを形成する原料やPHを調整した媒体などを指す。   The dispersed phase and the continuous phase used in the present invention are liquid materials for generating droplets and are liquids that are not compatible with each other. Among these, the continuous phase is used for shearing the dispersed phase to generate droplets. For example, a medium in which a dispersant such as polyvinyl alcohol is dissolved in a suitable solvent, a medium containing a surfactant such as sodium dodecyl sulfate or poly (ethylene-alt-maleic anhydride) (poly (EMA)), It refers to a raw material for forming a gel or capsule, a medium with adjusted pH, and the like.

また、分散相は、連続相中に分散して液滴となる、最終的にゲルやカプセルの一部や全体を形成する流体であって、ドデカンなどの媒体やチタニア粉末などの1種以上の微粒子を含む媒体、またオイルブルーNなどの染色された媒体、界面活性剤を含んだ媒体、また、ゲルやカプセルを形成する原料やPHを調整した媒体などを指す。   The dispersed phase is a fluid that is dispersed in a continuous phase to form droplets, and finally forms part or the whole of a gel or capsule, and is a medium such as dodecane or one or more types of titania powder. It refers to a medium containing fine particles, a dyed medium such as Oil Blue N, a medium containing a surfactant, a raw material for forming a gel or a capsule, or a medium in which pH is adjusted.

ここで、あらかじめ一部をオリゴマーまたはポリマーにする液体と、これと相溶しない液体は、微小流路を送液することによって均一な大きさに液滴を調整するために、微小流路を閉塞しない程度に流動性を持つことが必要である。あらかじめ一部をオリゴマーまたはポリマーにする液体は、微小流路内で、分散相流路と連続相流路とが合流する部位以前の流路内で、加熱、光照射などによって、オリゴマーまたはポリマーを含む液体にしても良い。例えば、分散相として水相を用いた場合には連続相としては水に実質的に溶解しないドデカンといった有機相が用いられることとなる。また、連続相として水相を用いた場合にはその逆となる。   Here, a liquid partially made of an oligomer or a polymer and a liquid that is not compatible with this partially block the microchannel in order to adjust the droplets to a uniform size by feeding the microchannel. It is necessary to have fluidity to the extent that it does not. The liquid in which a part of the oligomer or polymer is previously formed is heated in the microchannel and before the portion where the dispersed phase channel and the continuous phase channel meet by heating, light irradiation, etc. It may be a liquid containing. For example, when an aqueous phase is used as the dispersed phase, an organic phase such as dodecane that does not substantially dissolve in water is used as the continuous phase. Moreover, the reverse is true when an aqueous phase is used as the continuous phase.

微小流路中で、分散相は、分散相流路と連続相流路とが合流する部位である合流部以降に連続相中に分散されるとともに、あらかじめオリゴマーやポリマーになったゲルやカプセル被膜の原料によって被膜を形成した液滴となる。   In the microchannel, the dispersed phase is dispersed in the continuous phase after the junction where the dispersed phase channel and the continuous phase channel are merged, and the gel or capsule coating that has become an oligomer or polymer in advance. It becomes the droplet which formed the film with this raw material.

微小流路内で生成する液滴は、微小流路交差部や排出流路の形状と、送液する連続相や分散相の粘度や界面張力、また、微小流路に送液する流体の速度によってその大きさを制御することができるが、これは、流路内を液柱となって移動してきた分散相の先端部が、連続相と合流した場所において、微小流路壁面と分散相流による均一な剪断力が掛かり、大きさのそろった液滴となる。   The droplets generated in the microchannel are the shape of the intersection of the microchannels and the discharge channel, the viscosity and interfacial tension of the continuous phase and dispersed phase to be sent, and the speed of the fluid to be sent to the microchannel The size can be controlled by means of the microchannel wall surface and the dispersed phase flow at the place where the tip of the dispersed phase that has moved as a liquid column in the flow channel joins the continuous phase. A uniform shearing force is applied to form droplets of uniform size.

液滴形成後の微小流路排出部は、生成した液滴が被膜を形成して合一や分裂が抑制されるが、液滴生成部以上に広いことが壁面からの影響を小さくするためには望ましい。   The micro-channel discharge part after droplet formation forms a film and the coalescence and splitting are suppressed, but it is wider than the droplet generation part in order to reduce the influence from the wall surface Is desirable.

また液滴生成時には、液体中に未反応モノマーやオリゴマーやポリマーが存在するが、液滴形成後に生成した液滴を含むエマルジョンを加熱、光照射することなどにより、これらを原料にして固体状とすることで、最終的に強固なゲルまたはカプセルとすることができる。   At the time of droplet formation, unreacted monomers, oligomers and polymers are present in the liquid. By heating and irradiating the emulsion containing droplets generated after droplet formation, these are used as raw materials. By doing so, it is finally possible to obtain a strong gel or capsule.

ここで、液体の一部をオリゴマーやポリマーにする液体中側に界面活性剤を含むことによって、オリゴマーやポリマー中に界面活性剤が取り込まれて、連続相と分散相界面に被膜形成が促進される。このとき、界面活性剤は、分子量の大きいポリマーであると、効率的にオリゴマーやポリマーを液滴の界面被膜形成を促進しやすい。さらには、界面活性剤が、被膜を形成する原料と重合して取り込まれる場合には、さらに被膜形成が促進される。   Here, the surfactant is incorporated into the oligomer or polymer by forming a part of the liquid into an oligomer or polymer, and the film formation is promoted at the interface between the continuous phase and the dispersed phase. The At this time, if the surfactant is a polymer having a large molecular weight, it is easy to efficiently promote formation of an interface film of the oligomer or polymer droplets. Furthermore, when the surfactant is polymerized and taken in with the raw material for forming the film, the film formation is further promoted.

こうして、微小流路内で、分散相が連続相中に均一な大きさの液滴となると同時に被膜を形成し、その後、完全なゲル化やカプセル被膜化する場合にも、液滴生成時に形成した被膜が液滴の合一・分裂を抑制し、液滴生成時の粒子径の分布を小さいままゲル、またはカプセルに硬化することが可能となる。   In this way, even when the dispersed phase becomes droplets of a uniform size in the continuous phase in the microchannel and at the same time a film is formed, and then completely gelled or encapsulated, it is also formed at the time of droplet generation The coated film suppresses the coalescence and breakage of the droplets, and can be cured into a gel or a capsule with a small particle size distribution at the time of droplet generation.

また、あらかじめオリゴマーやポリマーになったゲルやカプセル被膜の原料を連続相中に含むことによって、液滴内部に封入したい物質をカプセル被膜原料と混合することなく封入したい組成のままで液滴化し、カプセル化することが可能となる。   In addition, by including in the continuous phase the material of the gel or capsule film that has become an oligomer or polymer in advance, the substance to be encapsulated inside the droplet is formed into droplets with the composition desired to be encapsulated without mixing with the capsule film material, It becomes possible to encapsulate.

さらに、微小流路内では、重力による影響が界面張力や粘性力の影響に比較して小さくなるため、分散相の液体と比重の異なる微粒子などを内部に封入したい場合に液滴からの脱離が小さく、効率的に液滴内に取り込むことができる。また、液滴を硬化する際には、液滴内に取り込んだ粒子は、分散相に被膜原料を含まないようにすることで、連続相中のみに含まれる未反応モノマーやオリゴマーやポリマーは加熱や光照射によって、液滴表面外側に被膜を形成するので、液滴内部粒子が被膜中に取り込まれて固着することを抑制することができる。   In addition, since the influence of gravity is smaller in the microchannel than the influence of interfacial tension and viscous force, it is possible to detach from the droplet when enclosing fine particles with a specific gravity different from that of the liquid in the dispersed phase. Is small and can be efficiently taken into the droplet. In addition, when curing the droplets, the particles taken into the droplets are heated so that the unreacted monomers, oligomers, and polymers contained only in the continuous phase are not heated in the dispersed phase. Since the coating is formed on the outer surface of the droplet by irradiation with light or light, it is possible to prevent the particles inside the droplet from being taken in and fixed in the coating.

こうして作製した微粒子を内包するカプセルは、内部の粒子が外部の電気や磁気に感応して移動することを目的とする表示用あるいは記録用カプセルとすることができる。たとえば、磁性微粒子や、チタニアやカーボン粉末などの正負に帯電した微粒子などを含んだカプセルは、皮膜に微粒子固着せず、外部からの刺激に感応して自由に移動することができるので、表示時と非表示時のシグナル比を大きくすることができる。また、カプセルの分散度が小さいため、平面上に高密度な配置をすることが可能となり、精細な表示を行うことが可能となる。また、それぞれのカプセル内に異なる色を内包し、表示、非表示させることによって、カラー表示も可能となる。   The capsule enclosing the fine particles thus produced can be a display or recording capsule intended to move the internal particles in response to external electricity or magnetism. For example, capsules containing magnetic fine particles or positively or negatively charged fine particles such as titania or carbon powder do not adhere to the film and can move freely in response to external stimuli. The signal ratio when not displayed can be increased. In addition, since the dispersion degree of the capsule is small, it is possible to arrange the capsules at a high density on a plane, and to perform a fine display. In addition, color display is also possible by including different colors in each capsule and displaying or not displaying them.

本発明のゲルまたはカプセル製造方法において、ゲルまたはカプセルの用途の例として、高速液体クロマトグラフィー用カラムの充填剤、圧力測定フィルム、ノーカーボン(感圧複写)紙、トナー、熱膨張剤、熱媒体、調光ガラス、ギャップ剤(スペーサ)、サーモクロミック(感温液晶、感温染料)、磁気泳動カプセル、農薬、人工飼料、人工種子、芳香剤、マッサージクリーム、口紅、ビタミン類カプセル、活性炭、含酵素カプセル、DDS(ドラッグデリバリーシステム)などのマイクロカプセルやゲルが挙げられる。   In the method for producing a gel or capsule of the present invention, examples of the use of the gel or capsule include a high-performance liquid chromatography column filler, pressure measurement film, carbonless (pressure-sensitive copying) paper, toner, thermal expansion agent, and heat medium. , Light control glass, gap agent (spacer), thermochromic (thermosensitive liquid crystal, thermosensitive dye), magnetophoresis capsule, pesticide, artificial feed, artificial seed, fragrance, massage cream, lipstick, vitamin capsule, activated carbon Examples include enzyme capsules, microcapsules such as DDS (drug delivery system), and gels.

本発明で用いる微小流路構造体は、以上に述べた構造、性能を有しているが、分散相と連続相を導入するための導入部及び導入流路と、導入流路が交わる交差部と、液体を排出させるための排出流路及び排出口を備えた微小流路構造体が、少なくとも一方の面に流路が形成された基板と、流路が形成された基板面を覆うように、流路の所定の位置に、流路と微小流路構造体外部とを連通するための小穴が配置されたカバー体とが積層一体化されていてもよい。これにより、微小流路構造体外部から流路へ流体を導入し、再び微小流路構造体外部へ流体を排出することができ、流体が微小量であったとしても、流体を安定して流路内を通過させることが可能となる。流体の送液は、シリンジポンプやマイクロポンプ、加圧送液などの機械的または、物理的手段によって可能となる。   The microchannel structure used in the present invention has the above-described structure and performance, but the introduction part for introducing the dispersed phase and the continuous phase, the introduction channel, and the intersection where the introduction channel intersects. And a micro-channel structure having a discharge channel and a discharge port for discharging the liquid so as to cover the substrate having the channel formed on at least one surface and the substrate surface having the channel formed thereon. In addition, a cover body in which a small hole for communicating the flow channel and the outside of the micro flow channel structure may be laminated and integrated at a predetermined position of the flow channel. As a result, the fluid can be introduced from the outside of the microchannel structure into the channel and discharged again to the outside of the microchannel structure, and the fluid can be stably flowed even if the amount of fluid is small. It is possible to pass through the road. The fluid can be fed by mechanical or physical means such as a syringe pump, a micro pump, or pressurized fluid feeding.

流路が形成された基板及びカバー体の材質としては、流路の形成加工が可能であって、耐薬品性に優れ、適度な剛性を備えたものが望ましい。例えば、ガラス、石英、セラミック、シリコン、あるいは金属や樹脂等であっても良い。基板やカバー体の大きさや形状については特に限定はないが、厚みは数mm以下程度とすることが望ましい。カバー体に配置された小穴は、流路と微小流路構造体外部とを連通し、流体の導入口または排出口として用いる場合には、その径が例えば数百mm程度から数mm程度であることが望ましい。カバー体の小穴の加工には、化学的に、機械的に、あるいはレーザー照射やイオンエッチングなどの各種の手段によって可能とされる。   As the material of the substrate and the cover body on which the flow path is formed, it is desirable that the flow path can be formed, has excellent chemical resistance, and has an appropriate rigidity. For example, glass, quartz, ceramic, silicon, or metal or resin may be used. The size and shape of the substrate and cover body are not particularly limited, but the thickness is preferably about several mm or less. The small hole arranged in the cover body communicates the flow channel and the outside of the micro flow channel structure and has a diameter of, for example, about several hundred mm to several mm when used as a fluid inlet or outlet. It is desirable. The small holes in the cover body can be processed chemically, mechanically, or by various means such as laser irradiation or ion etching.

また本発明の微小流路構造体は、流路が形成された基板とカバー体とを熱処理接合あるいは熱硬化樹脂などの接着剤を用いた接着等の手段により積層一体化することができる。   In the microchannel structure of the present invention, the substrate on which the channel is formed and the cover body can be laminated and integrated by means such as heat bonding or bonding using an adhesive such as a thermosetting resin.

また、固化する部位の構造体は、微小流路構造体と同様の手段によっても作製、加工出来るが、既存のチューブや、容器を用いても良い。   Moreover, the structure of the solidified part can be produced and processed by the same means as the microchannel structure, but an existing tube or container may be used.

本発明のゲルまたはカプセル製造装置は、分散相を導入するための導入口及び分散相導入流路と、連続相を導入するための導入口及び連続相導入流路と、分散相及び連続相により生成された液滴を排出させるための排出流路及び排出口とを備えた流路からなることを特徴とする微小流路構造体中に、あらかじめ一部をオリゴマーまたはポリマーにした流体を送液して、液滴を生成すると同時に表面皮膜を生成し、その後未反応のモノマーや架橋剤によって皮膜を硬化することによって、液滴の合一を抑制することができるため、均一なゲルまたはカプセルを得ることが可能となる。   The gel or capsule production apparatus of the present invention comprises an introduction port for introducing a dispersed phase and a dispersed phase introduction channel, an introduction port for introducing a continuous phase and a continuous phase introduction channel, and a dispersed phase and a continuous phase. A microchannel structure having a discharge channel and a discharge port for discharging the generated liquid droplets is supplied to a fluid partially made into an oligomer or polymer in advance. Then, by forming a surface film at the same time as generating droplets, and then curing the film with unreacted monomer or crosslinking agent, coalescence of the droplets can be suppressed. Can be obtained.

以下では、本発明の実施例を示し、更に詳しく発明の実施の形態について説明する。なお、本発明は以下の実施例に限定されるものではなく、本発明の要旨を逸脱しない範囲で、任意に変更可能であることは言うまでもない。   Examples of the present invention will be described below, and the embodiments of the present invention will be described in more detail. It is needless to say that the present invention is not limited to the following examples and can be arbitrarily changed without departing from the gist of the present invention.

本発明の第1の実施例における微小流路を図3及び図3中のL−L’断面図である図4、M−M’断面図である図5に示す。70mm×20mm×1t(厚さ)のパイレックス(登録商標)ガラス上に、幅170μm、深さ69μmの連続相導入流路(3)、幅137μm、深さ69μmの微小流路に相当する分散相導入流路(5)及び幅170μm、深さ69μm、長さが40mmの排出流路(7)であり連続相導入流路(3)と分散相導入流路(5)とが44°の角度にて交わる交差部を持ったY字形状の流路を1本形成した基板(1)を作製した。   The microchannel according to the first embodiment of the present invention is shown in FIGS. 3 and 4 which are L-L 'sectional views and FIG. 5 which is an M-M' sectional view in FIGS. On a Pyrex (registered trademark) glass of 70 mm × 20 mm × 1 t (thickness), a dispersed phase corresponding to a continuous phase introduction channel (3) having a width of 170 μm and a depth of 69 μm, and a microchannel having a width of 137 μm and a depth of 69 μm The introduction channel (5) is a discharge channel (7) having a width of 170 μm, a depth of 69 μm and a length of 40 mm, and the continuous phase introduction channel (3) and the dispersed phase introduction channel (5) are at an angle of 44 °. A substrate (1) on which one Y-shaped channel having an intersecting portion intersecting with each other was formed.

この流路を有する微小流路構造体は、図6に示すように、厚さ1mmで70mm×20mmのガラス基板の一方の面に、微小流路を一般的なフォトリソグラフィーとウェットエッチングによりガラス基板に形成し、この基板(1)の流路を有する面に、流路の導入口(11)と排出口(8)にあたる位置に予め直径1.2mmの小穴を、機械的加工手段を用いて設けた厚さ1mmで70mm×20mmのガラス製のカバー体(16)を熱接合し製作した。   As shown in FIG. 6, the microchannel structure having the channel is formed on one surface of a glass substrate having a thickness of 1 mm and a size of 70 mm × 20 mm by a general photolithography and wet etching. A small hole having a diameter of 1.2 mm is formed in advance on the surface of the substrate (1) having the flow path at positions corresponding to the introduction port (11) and the discharge port (8) of the flow path using mechanical processing means. A provided glass cover body (16) having a thickness of 1 mm and a size of 70 mm × 20 mm was thermally bonded.

次に本実施例の微小粒子製造方法について説明する。図7に示すように微小流路構造体(10)に液体が送液可能なようにホルダー(11)などで保持すると共に、テフロン(登録商標)チューブ(14)及びフィレットジョイント(18)をホルダーに固定する。テフロン(登録商標)チューブのもう一方はマイクロシリンジ(20)に接続する。これで微小流路構造体に液体の送液が可能となる。加えて排出側テフロン(登録商標)チューブの先に内径500μm、10mのテフロン(登録商標)チューブ(15)を加温容器内に平置して接続した。   Next, the fine particle manufacturing method of the present embodiment will be described. As shown in FIG. 7, a holder (11) or the like is used so that liquid can be fed to the microchannel structure (10), and the Teflon (registered trademark) tube (14) and fillet joint (18) are attached to the holder. To fix. The other end of the Teflon tube is connected to the microsyringe (20). Thus, liquid can be fed to the microchannel structure. In addition, a Teflon (registered trademark) tube (15) having an inner diameter of 500 μm and a diameter of 10 m was connected to the tip of the discharge side Teflon (registered trademark) in a heating container.

次に微小液滴を生成するための分散相にドデカンとOil Blue Nを、また連続相にpoly(E−MA)3.3wt%と尿素3.3wt%、レソルシノール0.33%を純水93.07wt%の水溶液75gを1N NaOHによりpH3.50に調整した。この水溶液3gに対して0.25gのホルムアルデヒド水溶液を75℃で20分間水相が白濁するまで加熱攪拌し、これを分散相として用いた。このとき、水相の透明度は約4%であり、1mlシリンジにつめて、向こう側が透けて見えない程度であった。また、粘度は約4mPa・s程度であった。このことから、流体である水相は75℃で20分間の加熱により、少なくともその一部がオリゴマー化あるいはポリマー化したことが分かる。   Next, dodecane and Oil Blue N are used as a dispersed phase for generating microdroplets, and 3.3 wt% poly (E-MA), 3.3 wt% urea, and 0.33% resorcinol are used as pure water in a continuous phase. 75 g of a 0.07 wt% aqueous solution was adjusted to pH 3.50 with 1N NaOH. To 3 g of this aqueous solution, 0.25 g of formaldehyde aqueous solution was heated and stirred at 75 ° C. for 20 minutes until the aqueous phase became cloudy, and this was used as a dispersed phase. At this time, the transparency of the aqueous phase was about 4%, which was such that the other side was not visible through the 1 ml syringe. The viscosity was about 4 mPa · s. From this, it is understood that at least a part of the aqueous phase as a fluid was oligomerized or polymerized by heating at 75 ° C. for 20 minutes.

次いで、連続相である水相と、分散相である有機相をそれぞれのマイクロシリンジに注入し、マイクロシリンジポンプ(19)で送液を行った。送液速度は分散相及び連続相はそれぞれ5μl/min、50μl/minである。送液速度が共に安定した状態で、微小流路構造体の分散相及び連続相が交わる交差部にて微小液滴の生成が観察された。生成された微小液滴を観察すると図8に示すように平均粒径106μm、粒径分散度を示すCV値(%)1.6%の均一な微小液滴であった。   Next, an aqueous phase as a continuous phase and an organic phase as a dispersed phase were injected into each microsyringe, and liquid feeding was performed with a microsyringe pump (19). The liquid feeding speed is 5 μl / min and 50 μl / min for the dispersed phase and the continuous phase, respectively. Formation of microdroplets was observed at the intersection where the disperse phase and continuous phase of the microchannel structure intersect, with both the liquid feed rates stable. When the generated microdroplets were observed, they were uniform microdroplets having an average particle size of 106 μm and a CV value (%) of 1.6% indicating the particle size dispersion as shown in FIG.

この微小液滴を含むエマルション溶液を、50℃に加温した容器内に静置した内径500μm、10mのテフロン(登録商標)チューブ中に送液し排出口(16)マイクロカプセルを得た。   The emulsion solution containing the fine droplets was fed into a Teflon (registered trademark) tube having an inner diameter of 500 μm and a diameter of 10 m, which was allowed to stand in a container heated to 50 ° C., to obtain a discharge port (16) microcapsule.

得られたマイクロカプセルを観察すると、凝集はなく、図9に示すように、内部にドデカン溶液を含む、平均粒子径107μm、分散度1.35%の均一な尿素/ホルマリン樹脂被膜のマイクロカプセルであった。   When the obtained microcapsules were observed, there was no aggregation, and as shown in FIG. 9, the microcapsules with a uniform urea / formalin resin coating with a mean particle size of 107 μm and a dispersity of 1.35% were contained. there were.

本実施例1で示すように、送液する被膜やカプセルの原料を、あらかじめ加熱し、オリゴマーやポリマーにすることによって、分散度を実質上悪化することなく、内部に液体内包したマイクロカプセル微小粒子の作製ができるようになった。   As shown in Example 1, the microcapsule fine particles encapsulated in the liquid without substantially deteriorating the dispersibility by heating the coating film or capsule raw material to be an oligomer or polymer in advance. Can now be made.

比較例における微小流路及び加熱容器は、実施例1と同様のものを用いた。実施例1と同様な方法で、送液したが、皮膜原料を含む連続相である水相は加熱処理しなかった。送液速度は分散相及び連続相も実施例1と同様に、それぞれ5μl/min、50μl/minである。送液速度が共に安定した状態で、微小流路構造体の分散相及び連続相が交わる交差部にて微小液滴の生成が観察された。   The same microchannel and heating container as those in Example 1 were used in the comparative example. Although the liquid was sent in the same manner as in Example 1, the aqueous phase, which is a continuous phase containing the film raw material, was not heat-treated. The liquid feeding speed is 5 μl / min and 50 μl / min for the dispersed phase and the continuous phase, respectively, as in Example 1. Formation of microdroplets was observed at the intersection where the disperse phase and continuous phase of the microchannel structure intersect, with both the liquid feed rates stable.

生成された微小液滴を観察すると図13に示すように平均粒径108μm、粒径分散度を示すCV値(%)は3.1%の均一な微小液滴であった。この微小液滴を含むエマルション溶液を、50℃に加温した容器内に静置した内径500μm、10mのテフロン(登録商標)チューブ中に送液し排出口(16)マイクロカプセルを得た。   When the generated microdroplets were observed, as shown in FIG. 13, the CV value (%) indicating an average particle size of 108 μm and a particle size dispersion degree was 3.1% and uniform. The emulsion solution containing the fine droplets was fed into a Teflon (registered trademark) tube having an inner diameter of 500 μm and a diameter of 10 m, which was allowed to stand in a container heated to 50 ° C., to obtain a discharge port (16) microcapsule.

得られたマイクロカプセルを観察すると、図10に示すように、凝集したカプセルと凝集のないカプセルが生成した。凝集のないカプセルの平均粒子は111μm、分散度8.5%の尿素/ホルマリン樹脂被膜のマイクロカプセルであった。   When the obtained microcapsules were observed, aggregated capsules and non-aggregated capsules were formed as shown in FIG. The average particle size of the capsules without agglomeration was 111 μm and a microcapsule of urea / formalin resin film having a dispersity of 8.5%.

比較例1で示すように、送液する被膜やカプセルの原料をオリゴマーやポリマーにすることなく送液すると、微小流路で生成した液滴は、硬化時に、分散度が実質上悪化すると同時に収率を低下させることになった。   As shown in Comparative Example 1, when the coating film or capsule material to be fed is fed without using an oligomer or polymer, the droplets generated in the microchannels are collected at the same time as the degree of dispersion substantially deteriorates during curing. The rate was reduced.

本発明の第2の実施例における微小流路は、実施例1と同様のものを用いた。実施例2と同様な方法で、送液したが、微小液滴を生成するための分散相に、青色染料Oil Blue N 1.3wt%を溶解させたIsoparG溶液90.5wt%に、チタニア(デュポン社製)3.2wt%及び、油溶性分散安定剤solsperse3000 5.0wt%を溶解し、超音波振動により良く分散させたものを用いた。   The microchannel in the second example of the present invention was the same as that in Example 1. In the same manner as in Example 2, the solution was sent, but in a dispersed phase for producing microdroplets, a blue dye Oil Blue N 1.3 wt% was dissolved in 90.5 wt% of Isopar G solution, titania (DuPont). A product obtained by dissolving 3.2 wt% of an oil-soluble dispersion stabilizer and 5.0 wt% of an oil-soluble dispersion stabilizer, and dispersing well by ultrasonic vibration was used.

連続相には、実施例1と同様にして調整したものを用いた。分散相と連続相をそれぞれマイクロシリンジに注入し、マイクロシリンジポンプ(19)で送液を行った。送液速度は分散相及び連続相はそれぞれ5.0μl/min、100μl/minである。   As the continuous phase, one prepared in the same manner as in Example 1 was used. The dispersed phase and the continuous phase were each injected into a microsyringe, and the solution was fed with a microsyringe pump (19). The liquid feeding speed is 5.0 μl / min and 100 μl / min for the dispersed phase and the continuous phase, respectively.

送液速度が共に安定した状態で、微小流路構造体の分散相流路及び連続相流路が交わる交差部にて微小液滴の生成が観察された。生成された微小液滴を観察すると図12に示すように平均粒径70μm、粒径分散度を示すCV値(%)は3.4%の均一な微小液滴であった。この微小液滴を含むエマルション溶液を50℃に加熱した。この加熱により、水相の透明度は約4%であり、1mlシリンジにつめて、向こう側が透けて見えない程度であった。また、粘度は約4mPa・s程度であった。このことから、流体である微小液滴は50℃の加熱により、少なくともその一部がオリゴマー化あるいはポリマー化したことが分かる。   Formation of microdroplets was observed at the intersection where the dispersed phase channel and the continuous phase channel intersect in the microchannel structure with both the liquid feeding speeds stabilized. When the generated microdroplets were observed, as shown in FIG. 12, the CV value (%) indicating an average particle size of 70 μm and a particle size dispersion degree was 3.4% and uniform. The emulsion solution containing these microdroplets was heated to 50 ° C. By this heating, the transparency of the aqueous phase was about 4%, which was such that the other side was not visible through the 1 ml syringe. The viscosity was about 4 mPa · s. From this, it can be seen that at least a part of the microdroplet, which is a fluid, was oligomerized or polymerized by heating at 50 ° C.

この微小液滴を含むエマルション溶液を、50℃に加温した容器内に静置した内径500μm、10mのテフロン(登録商標)チューブ中に送液し排出口(16)マイクロカプセルを得た。   The emulsion solution containing the fine droplets was fed into a Teflon (registered trademark) tube having an inner diameter of 500 μm and a diameter of 10 m, which was allowed to stand in a container heated to 50 ° C., to obtain a discharge port (16) microcapsule.

得られたマイクロカプセルを観察すると、凝集はなく、図13に示すように、内部にドデカン溶液を含む、平均粒子径70μm、分散度2.5%のチタニアを内包した均一な尿素/ホルマリン樹脂被膜のマイクロカプセルであった。   When the obtained microcapsules were observed, there was no aggregation, and as shown in FIG. 13, a uniform urea / formalin resin coating containing titania having an average particle size of 70 μm and a dispersion degree of 2.5% containing a dodecane solution inside. It was a microcapsule.

また、作製したマイクロカプセルを水に分散した状態でITO薄膜を成膜したガラスに滴下し、乾燥させ、もう一枚のITO成膜ガラスとの間に挟み込んだセルを作製した。作製したセルに400V(1.0Hz)の電圧をかけ、カプセル内の微粒子による色の変化を確認した。図14に示すように、白表示時には均一な白色表示が確認できた。   In addition, the prepared microcapsules were added dropwise to a glass on which an ITO thin film was formed in a state of being dispersed in water and dried to prepare a cell sandwiched between another ITO film-formed glass. A voltage of 400 V (1.0 Hz) was applied to the produced cell, and the color change due to the fine particles in the capsule was confirmed. As shown in FIG. 14, a uniform white display was confirmed during white display.

また、図15に示すように、青色表示時には、微小流路を用いずに作製したカプセルとカプセルの輪郭部を比較すると、図17に示すような、微小流路を用いずに作製した粒子には輪郭部に白い陰が確認できるのとに対して、本実施例2で作製したカプセルには見られないように、本実施例2によるカプセル内部の微粒子がカプセル膜にとらわれずに移動しやすい微粒子内包カプセルを作製することができた。   In addition, as shown in FIG. 15, when a blue color is displayed, comparing the capsule produced without using the microchannel and the outline of the capsule, the particles produced without using the microchannel as shown in FIG. In contrast to the fact that a white shade can be confirmed in the outline portion, the fine particles inside the capsule according to Example 2 are easy to move without being bound by the capsule film, as seen in the capsule produced in Example 2. A fine particle-encapsulating capsule could be produced.

本発明の第2の比較例におけるカプセル作製は、分散相に実施例2と同様の青色染料Oil Blue N 1.3wt%を溶解させたIsoparG溶液90.5wt%に、チタニア(デュポン社製)3.2wt%及び、油溶性分散安定剤solsperse3000 5.0wt%を溶解し、超音波振動により良く分散させたものを用いた。また連続相にpoly(E−MA)3.3wt%と尿素3.3wt%、レソルシノール0.33%を純水93.07wt%の水溶液75gを1N NaOHによりpH3.50に調整し、この水溶液3gに対して0.25gのホルムアルデヒド水溶液を加えて連続相とした。   Capsule preparation in the second comparative example of the present invention was carried out by using titania (manufactured by DuPont) 3 in 90.5 wt% of Isopar G solution in which 1.3 wt% of blue dye Oil Blue N similar to that of Example 2 was dissolved in the dispersed phase. .2 wt% and oil-soluble dispersion stabilizer solsperse 5.0 wt% were dissolved and dispersed well by ultrasonic vibration. In addition, 75 g of an aqueous solution of 3.3 wt% poly (E-MA), 3.3 wt% urea, 0.33% wt resorcinol, and 93.07 wt% pure water was adjusted to pH 3.50 with 1N NaOH to 3 g of this aqueous solution. 0.25 g of formaldehyde aqueous solution was added to form a continuous phase.

これを攪拌翼を用いて懸濁しながら50℃3時間加熱して、マイクロカプセルを得た。作製したマイクロカプセルを実施例2と同様に、水に分散した状態でITO薄膜を成膜したガラスに滴下し、乾燥させ、もう一枚のITO成膜ガラスとの間に挟み込んだセルを作製した。   This was heated at 50 ° C. for 3 hours while being suspended using a stirring blade to obtain microcapsules. Similarly to Example 2, the produced microcapsules were dropped on the glass on which the ITO thin film was formed in a state of being dispersed in water, and dried to produce a cell sandwiched between the other ITO-formed glass. .

作製したセルに400V(1.0Hz)の電圧をかけ、カプセル内の微粒子による色の変化を確認した。図16に示すように、白色表示時には不均一な粒子径と不均一な白色表示であった。また、図17に示すように、青色表示時には粒子の輪郭部に白い陰が確認でき、カプセル内部の微粒子がカプセル膜にとらわれて移動しにくい微粒子内包カプセルであることがわかる。   A voltage of 400 V (1.0 Hz) was applied to the produced cell, and the color change due to the fine particles in the capsule was confirmed. As shown in FIG. 16, at the time of white display, a non-uniform particle size and a non-uniform white display were obtained. In addition, as shown in FIG. 17, when the blue color is displayed, a white shade can be confirmed in the particle outline, and it can be seen that the capsule is a fine particle-containing capsule in which the fine particles inside the capsule are hardly caught by the capsule film.

従来の微小粒子を生成する微小流路を示す概略図である。It is the schematic which shows the microchannel which produces the conventional microparticles. 図1の従来の微小粒子を生成する微小流路中のA−A’断面図である。It is A-A 'sectional drawing in the microchannel which produces | generates the conventional microparticle of FIG. 第1の実施例における微小流路を示す概念図である。It is a conceptual diagram which shows the microchannel in a 1st Example. 図3における流路のL−L’断面図である。It is L-L 'sectional drawing of the flow path in FIG. 図3における流路のM−M’断面図である。FIG. 4 is a cross-sectional view taken along the line M-M ′ in FIG. 3. 第1の実施例における微小流路構造体を示す概念図である。It is a conceptual diagram which shows the microchannel structure in a 1st Example. 第1の実施例における微小液滴及びゲル、カプセルの製造方法について説明した図である。It is a figure explaining the manufacturing method of the micro droplet, gel, and capsule in a 1st Example. 第1の実施例において捕集した微小液滴の写真である。It is a photograph of the micro droplet collected in the 1st example. 第1の実施例において生成されたマイクロカプセルである。It is the microcapsule produced | generated in the 1st Example. 第1の比較例において捕集した微小液滴の写真である。It is a photograph of the micro droplet collected in the 1st comparative example. 第1の比較例において生成されたマイクロカプセルである。It is the microcapsule produced | generated in the 1st comparative example. 第2の実施例において捕集した微小液滴の写真である。It is a photograph of the micro droplet collected in the 2nd example. 第2の実施例において生成されたマイクロカプセルである。It is the microcapsule produced | generated in the 2nd Example. 第2の実施例において白色表示させたマイクロカプセルの写真である。It is the photograph of the microcapsule displayed in white in the 2nd Example. 第2の実施例において青色表示させたマイクロカプセルの写真である。It is the photograph of the microcapsule displayed in blue in 2nd Example. 微小流路を用いずに作製したマイクロカプセルを白色表示させた写真である。It is the photograph which displayed the microcapsule produced without using a microchannel in white. 微小流路を用いずに作製したマイクロカプセルを青色表示させた写真である。It is the photograph which displayed the microcapsule produced without using a microchannel in blue.

符号の説明Explanation of symbols

1:基板
2:連続相導入口
3:連続相導入流路
4:分散相導入口
5:分散相導入流路
6:交差部
7:排出流路
8:排出口
9:導入口
10:カバー体
11:ホルダー
12:微小流路構造体
13:加熱容器
14:テフロン(登録商標)チューブ
15:硬化用テフロン(登録商標)チューブ
16:硬化用テフロン(登録商標)チューブ排出口
17:フィレットジョイント
18:マイクロシリンジポンプ
19、20:マイクロシリンジ
1: Substrate 2: Continuous phase introduction port 3: Continuous phase introduction channel 4: Dispersed phase introduction port 5: Dispersed phase introduction channel 6: Intersection 7: Discharge channel 8: Discharge port 9: Inlet port 10: Cover body 11: Holder 12: Microchannel structure 13: Heating container 14: Teflon (registered trademark) tube 15: Teflon (registered trademark) tube for curing 16: Teflon (registered trademark) tube for curing 17: Fillet joint 18: Micro syringe pump 19, 20: Micro syringe

Claims (12)

分散相を導入するための導入口及び導入流路と、連続相を導入するための導入口及び導入流路と、分散相及び連続相を介して生成された粒子を排出させるための排出流路及び排出口とを備えた微小流路構造体を用いて固体状粒子を製造する方法であって、あらかじめ流体の一部をオリゴマー及び/又はポリマーにした流体を送液し、液滴を生成させるとともに当該液滴表面に皮膜を生成させ、その後未反応成分により皮膜を硬化することを特徴とする固体状粒子の製造方法。 Introduction port and introduction flow path for introducing a dispersed phase, introduction port and introduction flow path for introducing a continuous phase, and discharge flow path for discharging particles generated through the dispersed phase and the continuous phase In addition, a method for producing solid particles using a micro-channel structure having a discharge port and a liquid in which a part of the fluid is previously made into an oligomer and / or polymer is sent to generate droplets. And producing a solid particle by forming a film on the surface of the droplet and then curing the film with an unreacted component. 連続相または分散相中のあらかじめ一部をオリゴマーまたはポリマーにする流体中に、界面活性剤を含むことを特徴とする請求項1に記載の固体状粒子の製造方法。 The method for producing solid particles according to claim 1, wherein a surfactant is contained in a fluid in which a part of the continuous phase or dispersed phase is previously oligomerized or polymerized. あらかじめ液滴の表面を被覆する皮膜の原料のオリゴマーまたはポリマーを、連続相に含んでいることを特徴とする請求項1に記載の固体状粒子の製造方法。 2. The method for producing solid particles according to claim 1, wherein the continuous phase contains an oligomer or polymer as a raw material for the coating that covers the surface of the droplets in advance. あらかじめ液滴の表面を被覆する皮膜の原料のオリゴマーまたはポリマーを、分散相に実質的に含んでいないことを特徴とする請求項1に記載の固体状粒子の製造方法。 2. The method for producing solid particles according to claim 1, wherein the dispersed phase does not substantially contain an oligomer or polymer as a raw material for the coating that covers the surface of the droplets in advance. 固体状粒子としてカプセルを製造することを特徴とする請求項1〜4のいずれかに記載の固体状粒子の製造方法。 Capsules are produced as solid particles, and the method for producing solid particles according to any one of claims 1 to 4. あらかじめ送液する分散相中に微粒子を含んでいることを特徴とする請求項5に記載の固体状粒子の製造方法。 The method for producing solid particles according to claim 5, wherein fine particles are contained in the dispersed phase to be fed in advance. 微粒子を含んだカプセルが、磁気泳動または電気泳動マイクロカプセルを用いた表示用であることを特徴とする請求項6に記載の固体状粒子の製造方法。 7. The method for producing solid particles according to claim 6, wherein the capsule containing the fine particles is for display using magnetophoresis or electrophoresis microcapsules. カプセル内の液体が着色していることを特徴とする請求項5〜7のいずれかに記載の固体状粒子の製造方法。 8. The method for producing solid particles according to claim 5, wherein the liquid in the capsule is colored. あらかじめカプセル皮膜の原料の一部をオリゴマーまたはポリマーにした連続相中に、カプセル皮膜の原料のモノマーやオリゴマーやポリマーを含まない分散相を導入し、液滴を調製するとともにカプセル皮膜を生成し、その後、細管中で送液しながら連続相中の未反応のモノマーや架橋剤によって皮膜を硬化することを特徴とする固体状粒子の製造方法。 Introducing a dispersed phase that does not contain monomer, oligomer, or polymer of the capsule film raw material into a continuous phase in which a part of the raw material of the capsule film is previously made into an oligomer or polymer, prepares a droplet and produces a capsule film, Thereafter, the film is cured with unreacted monomers or a crosslinking agent in the continuous phase while being fed in a thin tube, and the method for producing solid particles is characterized. あらかじめ送液する分散相中に微粒子を含んでいることを特徴とする請求項9に記載の固体状粒子の製造方法。 The method for producing solid particles according to claim 9, wherein fine particles are contained in the dispersed phase to be fed in advance. 微粒子を含んだカプセルが、磁気泳動または電気泳動マイクロカプセルを用いた表示用であることを特徴とする請求項9又は請求項10に記載の固体状粒子の製造方法。 The method for producing solid particles according to claim 9 or 10, wherein the capsule containing fine particles is for display using a magnetophoresis or electrophoresis microcapsule. 請求項1〜11のいずれかに記載の固体状粒子の製造方法により得られるカプセルであって、その分散度が3%以下であることを特徴とする表示用カプセル。
A capsule for display obtained by the method for producing solid particles according to any one of claims 1 to 11, wherein the dispersity is 3% or less.
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JP2003290647A (en) * 2002-03-29 2003-10-14 Toyo Ink Mfg Co Ltd Method for producing microcapsules enclosing electrophoretic particle dispersion and reversible display medium using the capsules
JP2004122107A (en) * 2002-04-25 2004-04-22 Tosoh Corp Microchannel structure, method for producing microparticles using the same, and solvent extraction method using microchannel structure
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JP2009276567A (en) * 2008-05-14 2009-11-26 Nippon Shokubai Co Ltd Manufacturing method of microcapsule for electrophoretic display
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