JP6083031B2 - Submerged electrospray method and submerged electrospray apparatus - Google Patents
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、化学反応場の設計・制御に係り、特にエレクトロスプレーによる材料加工法およびマイクロ反応場制御法に関する。 The present invention relates to design and control of a chemical reaction field, and more particularly to a material processing method by electrospray and a micro reaction field control method.
高分子化合物を溶剤中に溶解して、エレクトロスプレーノズルに一定流速で供給し、エレクトロスプレーノズルと対向電極間に強電場を形成することにより、高分子溶液をノズルから対向電極に向かって噴霧し高分子化合物の形状を繊維状または粒子状に制御することができる（エレクトロスピニング法）（例えば、特許文献１参照。）。 The polymer compound is dissolved in a solvent, supplied to the electrospray nozzle at a constant flow rate, and a strong electric field is formed between the electrospray nozzle and the counter electrode, whereby the polymer solution is sprayed from the nozzle toward the counter electrode. The shape of the polymer compound can be controlled to be fibrous or particulate (electrospinning method) (see, for example, Patent Document 1).
しかし、濃度増加による粘度の増加、及び高電場における放電によって制限を受けるため、精密な加工に適用するには十分ではないという問題があった。また液滴が周囲に飛散するため、回収効率が低いという問題があった。さらに、エレクトロスプレーにおいて液滴を形成する液体としては、揮発性有機化合物（ＶＯＣ）に該当するものも多く、従来のエレクトロスプレーでは、かかるＶＯＣが一部環境中に放出されてしまう、作業者が吸引してしまう問題があった。また、液滴を形成する液体として水等の誘電率の高いもの、電解質を含むものを用いた場合、液滴が大きくなりすぎ、噴霧をすることができないという問題もあった。ここで、液滴の誘電率を下げるためエタノール等を混合すると、溶質の種類によっては液滴に含有させる溶質濃度を下げなければならない等の問題もあった。さらに従来のエレクトロスプレーは、空気中への放電の危険性もあった。 However, since it is limited by an increase in viscosity due to an increase in concentration and discharge in a high electric field, there is a problem that it is not sufficient for application to precise processing. Further, since the droplets are scattered around, there is a problem that the recovery efficiency is low. Furthermore, many of the liquids that form droplets in electrospray correspond to volatile organic compounds (VOCs), and in conventional electrosprays, some of the VOCs are released into the environment. There was a problem of sucking. Further, when a liquid having a high dielectric constant such as water or a liquid containing an electrolyte is used as a liquid for forming the liquid droplets, there is a problem that the liquid droplets become too large to be sprayed. Here, when ethanol or the like is mixed in order to lower the dielectric constant of the droplet, there is a problem that the concentration of the solute contained in the droplet must be lowered depending on the kind of solute. Furthermore, the conventional electrospray has a risk of discharge into the air.
一方、異なる液体を高効率で混合する方法としてマイクロミキサーが知られている。マイクロミキサーとは、金属やガラスの基板上にμｍオーダーの液体流路を形成させて、複数の流路を合流させることによって液体を混合する手法である。混合のための移動距離が数十〜数百μｍ以内で短いために混合体積を小さく、また混合速度（効率）を大きくすることができる。このマイクロミキサーの特徴を利用した液相の化学反応制御が試みられている（非特許文献１）。 On the other hand, a micromixer is known as a method for mixing different liquids with high efficiency. The micromixer is a method of mixing liquids by forming a liquid flow path on the order of μm on a metal or glass substrate and joining a plurality of flow paths. Since the moving distance for mixing is short within several tens to several hundreds of μm, the mixing volume can be reduced and the mixing speed (efficiency) can be increased. Attempts have been made to control the chemical reaction in the liquid phase utilizing the characteristics of this micromixer (Non-patent Document 1).
例えば、塩化金酸（ＨＡｕＣｌ4）溶液と還元剤を含む溶液（水素化ホウ素ナトリウム、クエン酸、アスコルビン酸溶液等）を混合することによって金イオンを還元し金原子を生成する反応について、両溶液をマイクロミキサーで混合することによって微小混合体積内で高効率の混合による還元反応を起こし、共存させた分散剤によって金原子の自己会合を抑えて金ナノ粒子を合成する方法が提案されている。 For example, both solutions for the reaction of reducing gold ions to produce gold atoms by mixing a chloroauric acid (HAuCl 4 ) solution and a solution containing a reducing agent (sodium borohydride, citric acid, ascorbic acid solution, etc.) A method of synthesizing gold nanoparticles by causing a reduction reaction by highly efficient mixing in a micromixing volume by mixing them with a micromixer and suppressing self-association of gold atoms with a coexisting dispersant has been proposed.
ここで、金ナノ粒子のサイズをより小さく制御するためには、混合する反応溶液の体積をできるだけ小さくする必要がある。この例のような溶液中の連続的あるいは連鎖的な化学反応の制御方法として、反応溶液の体積を制御することは極めて有効な方法である。反応溶液の濃度を小さくすることによって金ナノ粒子サイズを小さくすることも可能であるが、排出物や使用エネルギー等による環境負荷の観点からも、反応溶液の体積による制御が望ましい。 Here, in order to control the size of the gold nanoparticles to be smaller, it is necessary to make the volume of the reaction solution to be mixed as small as possible. As a method for controlling a continuous or chain chemical reaction in a solution as in this example, controlling the volume of the reaction solution is a very effective method. Although it is possible to reduce the size of the gold nanoparticles by reducing the concentration of the reaction solution, control from the volume of the reaction solution is desirable also from the viewpoint of environmental load due to discharged matter and energy used.
かかる状況の下、２つまたはそれ以上の対向するエレクトロスプレーノズルに正・負電位を供給して、対向するエレクトロスプレーノズル間に強電場を作り、液体試料を一定の流速で供給することにより、正及び負に帯電した微小液滴を各ノズルから噴霧させ、それら荷電液滴間の静電的相互作用によって、液滴間で衝突・融合させ、混合体積の最小化と混合速度の最大化が実現されている（例えば、特許文献２参照。）。 Under such circumstances, by supplying positive or negative potential to two or more opposing electrospray nozzles, creating a strong electric field between the opposing electrospray nozzles, and supplying a liquid sample at a constant flow rate, Small and positively charged droplets are sprayed from each nozzle, and electrostatic interaction between these charged droplets causes collision and fusion between the droplets, minimizing mixing volume and maximizing mixing speed. (For example, refer patent document 2).
しかし、かかる方法においても、気中で静電的に融合した液滴が周囲に飛散するため、回収効率が低いという問題、ＶＯＣが一部環境中に放出されてしまう問題、作業者が吸引してしまうという問題、誘電率の高い液体試料を用いた場合噴霧できない問題、空気放電の問題等があった。 However, even in such a method, since the electrostatically fused droplets in the air are scattered to the surroundings, there is a problem that the recovery efficiency is low, a problem that a part of the VOC is discharged into the environment, and an operator sucks. There is a problem that the liquid sample having a high dielectric constant cannot be sprayed, a problem of air discharge, and the like.
本発明が解決すべき課題は、得られた生成物を高効率で回収することができ、ＶＯＣの作業者の吸引及び環境への放出が抑制されたエレクトロスプレー法を提供することにある。本発明が解決すべき課題はまた、エレクトロスピニング法による高分子材料の精密な形状制御法を提供することである。 The problem to be solved by the present invention is to provide an electrospray method in which the obtained product can be recovered with high efficiency and the suction and release of the VOC to the environment are suppressed. The problem to be solved by the present invention is also to provide a precise shape control method of a polymer material by an electrospinning method.
本発明者らは鋭意研究した結果、エレクトロスプレー法において、液体試料を気体中ではなく液体中に静電噴霧することにより、上記課題を解決できることを見出した。本発明はかかる新規の知見に基づくものである。 As a result of intensive studies, the present inventors have found that in the electrospray method, the above problem can be solved by electrostatically spraying a liquid sample in a liquid rather than in a gas. The present invention is based on such novel findings.
従って、本発明は、下記の項にかかる発明を提供する：
項１．所定の化合物を含有する第１液体試料を電場中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）及びＥＳＮ１との間に電場を形成するための対向電極（ＣＥ）を媒体液体中に設置し、該ＥＳＮ１とＣＥとの間に電位差を与えて第１液体試料を媒体液体中で帯電した液滴状に断片化し、該ＥＳＮ１から該ＣＥに向かって静電噴霧する液中エレクトロスプレー法。
Accordingly, the present invention provides the invention according to the following items:
Item 1. A first liquid spray nozzle (ESN1) for electrostatically spraying a first liquid sample containing a predetermined compound in the electric field and a counter electrode (CE) for forming an electric field between the first liquid sample and ESN1 in the medium liquid A submerged electrospray method in which a first liquid sample is fragmented into droplets charged in a medium liquid by applying a potential difference between the ESN1 and the CE and electrostatically sprayed from the ESN1 toward the CE .
項２．高分子化合物の形状を制御するための項１に記載の液中エレクトロスプレー法であって、前記第１液体試料が高分子化合物溶液である、方法。 Item 2. Item 2. The submerged electrospray method for controlling the shape of a polymer compound according to Item 1, wherein the first liquid sample is a polymer compound solution.
項３．所定の化合物を含有する第１液体試料を電場中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）及び所定の化合物を含有する第２液体試料を電場中に静電噴霧するための第２エレクトロスプレーノズル（ＥＳＮ２）を媒体液体中に設置し、該ＥＳＮ１と該ＥＳＮ２との間に電位差を与え、正及び負に帯電した液滴をＥＳＮ１及びＥＳＮ２から静電噴霧し、正に帯電した液滴と負に帯電した液滴とを静電引力によって衝突・融合させる、液中エレクトロスプレー法。 Item 3. A first electrospray nozzle (ESN1) for electrostatically spraying a first liquid sample containing a predetermined compound into the electric field and a second electrospray for electrostatically spraying a second liquid sample containing the predetermined compound into the electric field Two electrospray nozzles (ESN2) were installed in the medium liquid, a potential difference was applied between ESN1 and ESN2, and positively and negatively charged droplets were electrostatically sprayed from ESN1 and ESN2 to be positively charged. A submerged electrospray method in which droplets and negatively charged droplets collide and fuse by electrostatic attraction.
項４．第１液体試料が金属イオンを含み、第２液体試料が還元剤を含む、項３に記載の方法。 Item 4. Item 4. The method according to Item 3, wherein the first liquid sample contains metal ions and the second liquid sample contains a reducing agent.
項５．媒体液体を格納する容器と
所定の化合物を含有する第１液体試料を供給する第１液体試料供給源及び該第１液体試料供給源に接続されかつ該第１液体試料供給源から供給される第１液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）を備えた第１噴霧手段と
ＥＳＮ１との間に電場を形成するための対向電極（ＣＥ）とを
備える液中エレクトロスプレー装置。
Item 5. A container for storing a medium liquid, a first liquid sample supply source for supplying a first liquid sample containing a predetermined compound, and a first liquid sample supply source connected to and supplied from the first liquid sample supply source A counter for forming an electric field between the first spraying means having a first electrospray nozzle (ESN1) for electrostatically spraying one liquid sample into the medium liquid stored in the storage container, and ESN1 A submerged electrospray apparatus comprising an electrode (CE).
項６．媒体液体を格納する容器と
所定の化合物を含有する第１液体試料を供給する第１液体試料供給源及び該第１液体試料供給源に接続されかつ該第１液体試料供給源から供給される第１液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）を備えた第１噴霧手段と
所定の化合物を含有する第２液体試料を供給する第２液体試料供給源及び該第２液体試料供給源に接続されかつ該第２液体試料供給源から供給される第２液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第２エレクトロスプレーノズル（ＥＳＮ２）を備えた第２噴霧手段とを
備える液中エレクトロスプレー装置。
Item 6. A container for storing a medium liquid, a first liquid sample supply source for supplying a first liquid sample containing a predetermined compound, and a first liquid sample supply source connected to and supplied from the first liquid sample supply source A first spraying means having a first electrospray nozzle (ESN1) for electrostatically spraying one liquid sample into a medium liquid stored in the storage container and a second liquid sample containing a predetermined compound are supplied. The second liquid sample supply source and the second liquid sample connected to the second liquid sample supply source and supplied from the second liquid sample supply source into the medium liquid stored in the storage container A submerged electrospray apparatus comprising: a second spraying means including a second electrospray nozzle (ESN2) for performing the operation.
本発明によれば、媒体液体中でエレクトロスプレーを行うことにより、エレクトロスピニングにおける高分子材料の加工等において、媒体液体との物理・化学的相互作用による反応制御が可能となり、精密な制御に利用可能である。また、本発明は、液中で、正・負に荷電した液滴どうしを静電力によって衝突させ、液滴内で異なる液体を混合することを可能にするため、マイクロリアクターとしての利用が可能である。本発明は、液滴を反応場とするため、既存の流路内で2液を混合するマイクロリアクターで問題となる生成物による閉塞の問題が起こらない。さらに、気中のエレクトロスプレーで正・負荷電液滴を衝突・混合させるマイクロリアクター技術に比べ、回収効率を飛躍的に向上させることができる。さらに、ＶＯＣの環境中への放出も著しく抑えることができる。また、気中でのエレクトロスプレーと異なり、水等の誘電率の高い媒体を含む液体、電解質を含む液体等においても静電噴霧ができる。そして、エレクトロスプレーを液中で行うことにより放電が抑制されるという効果も得られる。 According to the present invention, by performing electrospraying in a medium liquid, it becomes possible to control the reaction by physical / chemical interaction with the medium liquid in processing of a polymer material in electrospinning, etc. Is possible. In addition, the present invention allows liquid droplets charged positively and negatively to collide with each other by an electrostatic force in a liquid and mix different liquids in the liquid droplets, so that it can be used as a microreactor. is there. In the present invention, since a droplet is used as a reaction field, the problem of clogging with a product which is a problem in a microreactor that mixes two liquids in an existing channel does not occur. Furthermore, the collection efficiency can be dramatically improved compared to the microreactor technology that collides and mixes positive and negative charged droplets with electrospray in the air. Furthermore, the release of VOC into the environment can be significantly suppressed. Further, unlike electrospray in the air, electrostatic spraying can also be performed on a liquid containing a medium having a high dielectric constant such as water, a liquid containing an electrolyte, or the like. And the effect that discharge is suppressed by performing electrospray in a liquid is also acquired.
以下、本発明を実施するための最良の形態として、液中エレクトロスプレー法と、該手法によるマイクロ反応場制御法の典型的な実施形態を図面を用いて説明するが、本発明は、図面に記載の具体的な実施形態に限定はされない。 Hereinafter, as the best mode for carrying out the present invention, typical embodiments of an electrospray method in liquid and a micro reaction field control method using the method will be described with reference to the drawings. It is not limited to the specific embodiments described.
本発明は、所定の化合物を含有する第１液体試料を電場中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）及びＥＳＮ１との間に電場を形成するための対向電極（ＣＥ）を媒体液体中に設置し、該ＥＳＮ１とＣＥとの間に電位差を与えて第１液体試料を媒体液体中で帯電した液滴状に断片化し、該ＥＳＮ１から該ＣＥに向かって静電噴霧する液中エレクトロスプレー法を提供する。 The present invention includes a first electrospray nozzle (ESN1) for electrostatically spraying a first liquid sample containing a predetermined compound into an electric field, and a counter electrode (CE) for forming an electric field between the first electrospray nozzle (ESN1) and ESN1. A liquid which is placed in a medium liquid, a potential difference is applied between the ESN1 and CE to fragment the first liquid sample into droplets charged in the medium liquid, and electrostatically sprayed from the ESN1 toward the CE Provide medium electrospray method.
本発明において、液中エレクトロスプレー法とは、液体媒体中で液体試料を静電噴霧する方法を意味する。 In the present invention, the in-liquid electrospray method means a method of electrostatic spraying a liquid sample in a liquid medium.
本発明において液体試料を噴霧する媒体となる媒体液体は電場を形成することができるものであれば特に限定されないが、誘電率が低いもの（本明細書において、低誘電率液体と示すこともある）が好ましい。 In the present invention, the medium liquid that is a medium for spraying the liquid sample is not particularly limited as long as it can form an electric field, but has a low dielectric constant (in this specification, sometimes referred to as a low dielectric constant liquid). ) Is preferred.
本発明において、低誘電率液体とは、比誘電率が２５以下、好ましくは２０以下、より好ましくは１５以下、さらに好ましくは１０以下、さらに好ましくは５以下である液体を示す。かかる媒体液体としてはｎ−ヘキサン、ペンタン、デカン等の炭化水素；エタノール（比誘電率２４．５５）、１−ブタノール（比誘電率１７．５１）、１−ペンタノール（比誘電率１３．９）、１−オクタノール（比誘電率１０．３）等のアルコール；塩化ベンジル（比誘電率７．０）、クロロホルム（比誘電率６．１５）、１−クロロオクタン（比誘電率５．０５）、四塩化炭素（比誘電率２．２３８）、パーフルオロヘキサン等のハロゲン化炭化水素等が挙げられ、炭化水素等が好ましい。ハロゲン化炭化水素に含まれるハロゲンとしては、塩素、フッ素、臭素、ヨウ素等が挙げられる。これらの媒体液体は１種単独で又は２種類以上を混合して用いることができる。本発明においては、電位差を生じさせても実質的に通電しない低誘電率液体を用いることによって、ＥＳＮ１とＣＥとの間に電場が形成され、第１液体試料を帯電した液滴状で静電噴霧することができるため好ましい。 In the present invention, the low dielectric constant liquid refers to a liquid having a relative dielectric constant of 25 or less, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and further preferably 5 or less. Examples of the medium liquid include hydrocarbons such as n-hexane, pentane, and decane; ethanol (relative permittivity 24.55), 1-butanol (relative permittivity 17.51), 1-pentanol (relative permittivity 13.9). ), Alcohols such as 1-octanol (relative permittivity 10.3); benzyl chloride (relative permittivity 7.0), chloroform (relative permittivity 6.15), 1-chlorooctane (relative permittivity 5.05) , Halogenated hydrocarbons such as carbon tetrachloride (relative dielectric constant 2.238), perfluorohexane, and the like, and hydrocarbons and the like are preferable. Examples of the halogen contained in the halogenated hydrocarbon include chlorine, fluorine, bromine and iodine. These medium liquids can be used alone or in combination of two or more. In the present invention, an electric field is formed between ESN1 and CE by using a low dielectric constant liquid that does not substantially energize even if a potential difference is generated, and the first liquid sample is charged in the form of charged droplets. Since it can spray, it is preferable.
本発明において第１液体試料は、形状の制御または反応に供するための所定の化合物を含有する液体を意味し、当該所定の化合物を溶媒に溶解、分散したもの等が挙げられる。 In the present invention, the first liquid sample means a liquid containing a predetermined compound for use in shape control or reaction, and includes those obtained by dissolving and dispersing the predetermined compound in a solvent.
第１液体試料に用いる化合物としては、高分子化合物等が挙げられる。高分子化合物としては、エレクトロスピニング法に用いられるものを広く使用することができ、例えば、セルロース又はその誘導体（アセチルセルロース等）、ポリビニルアルコール、ポリアクリルニトリル、ポリアクリル酸、ポリフッ化ビニリデン、ポリエチレンオキシド、ポリエステル等が挙げられ、セルロース又はその誘導体等が好ましい。これらの高分子化合物は１種単独で又は２種類以上を混合して用いることができる。 Examples of the compound used for the first liquid sample include a polymer compound. As the polymer compound, those used in the electrospinning method can be widely used. For example, cellulose or a derivative thereof (acetylcellulose, etc.), polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyvinylidene fluoride, polyethylene oxide Polyester and the like, and cellulose or a derivative thereof is preferable. These polymer compounds can be used alone or in combination of two or more.
第１液体試料に用いる溶媒としては、例えば、上記化合物を溶解又は分散できるものであれば限定されず、例えば、水、エタノール、ＤＭＦ、アセトン等が挙げられ、ＤＭＦ、アセトン等が好ましい。これらの溶媒は１種単独で又は２種類以上を混合して用いることができる。かかる溶媒としては、媒体液体に対し相溶性の高いものであっても相溶性の低いものであってもよい。かかる溶媒には適宜電解質を溶解してもよい。 The solvent used for the first liquid sample is not limited as long as it can dissolve or disperse the above compound, and examples thereof include water, ethanol, DMF, and acetone, and DMF, acetone, and the like are preferable. These solvents can be used alone or in combination of two or more. Such a solvent may be either highly compatible with the medium liquid or low compatible. An electrolyte may be appropriately dissolved in such a solvent.
第１液体試料の高分子化合物の濃度は特に限定されないが、上記化合物及び溶媒の種類によって、例えば、２〜３０ｗｔ％、好ましくは５〜２０ｗｔ％等の範囲内で適宜設定することができる。 Although the density | concentration of the high molecular compound of a 1st liquid sample is not specifically limited, For example, 2-30 wt%, Preferably it can set within the range of 5-20 wt% etc. according to the kind of said compound and solvent.
ＥＳＮ１としては、ＣＥとの間で電場を形成させるために、ステンレスチューブ、表面を金等の金属でメッキしたキャピラリーチューブ等が挙げられる。かかるキャピラリーチューブはさらに、その先端が露出するような状態でステンレス等の金属のチューブでその一部が覆われていてもよい。 Examples of ESN1 include a stainless steel tube and a capillary tube whose surface is plated with a metal such as gold in order to form an electric field with CE. The capillary tube may be further partially covered with a metal tube such as stainless steel in a state where the tip is exposed.
ＣＥとしては、ＥＳＮ１との間で電場が形成されるようなものであれば、その形状、素材等は特に限定されず、形状としては、例えば、リング状、板状、メッシュ状、棒状等が挙げられる。またＣＥの素材としては、例えば、ステンレス、白金、アルミニウム、銅等の金属が挙げられる。 As long as an electric field is formed between the CE and the ESN, the shape, material, and the like are not particularly limited. Examples of the shape include a ring shape, a plate shape, a mesh shape, and a rod shape. Can be mentioned. Examples of the CE material include metals such as stainless steel, platinum, aluminum, and copper.
ＥＳＮ１とＣＥとの間の距離は特に限定されず、例えば、１ｃｍ以上、好ましくは２ｃｍ以上の範囲内で適宜設定することができる。ＥＳＮ１とＣＥとの間の距離の上限は特に限定されず、エレクトロスプレー装置の寸法に合わせて適宜設定し得る。 The distance between ESN1 and CE is not particularly limited, and can be appropriately set within a range of, for example, 1 cm or more, preferably 2 cm or more. The upper limit of the distance between ESN1 and CE is not particularly limited, and can be appropriately set according to the dimensions of the electrospray apparatus.
ＥＳＮ１とＣＥとの間に与える電位差の下限は特に限定されず、例えば、０．１ｋＶ以上、好ましくは２ｋＶ以上の範囲内で適宜設定することができる。ＥＳＮ１とＣＥとの間に与える電位差の上限は特に限定されず、例えば、２０ｋＶ以下、好ましくは１５ｋＶ以下の範囲内で適宜設定することができる。ＥＳＮ１とＣＥとの間に与える電位差を与える方法は特に限定されず、例えば、１つの電源をＥＳＮ１及びＣＥに接続し、ＥＳＮ１とＣＥとの間に電圧を印加しても、ＥＳＮ１とＣＥとの間に基準となる電位を設定した上で、２つの電源を使用して基準となる電位に対するＥＳＮ１の電位及び基準となる電位に対するＣＥを制御する方法を用いてもよい。本発明の方法においては、ＥＳＮ１とＣＥとの間に電位差が生じればよく、例えば、ＥＳＮ１を＋の電位としＣＥを−の電位としても、ＥＳＮ１を−の電位としＣＥを＋の電位としても、ＥＳＮ１の電位が０でＣＥが−の電位であっても、ＥＳＮ１の電位が０でＣＥが＋の電位であっても、ＥＳＮ１が−の電位でＣＥの電位が０であっても、ＥＳＮ１が＋の電位でＣＥの電位が０であってもよい。 The lower limit of the potential difference applied between ESN1 and CE is not particularly limited, and can be set as appropriate within a range of 0.1 kV or more, preferably 2 kV or more, for example. The upper limit of the potential difference given between ESN1 and CE is not particularly limited, and can be appropriately set within a range of, for example, 20 kV or less, preferably 15 kV or less. There is no particular limitation on the method of providing the potential difference applied between ESN1 and CE. For example, even if one power supply is connected to ESN1 and CE and a voltage is applied between ESN1 and CE, there is no difference between ESN1 and CE. A method of controlling the potential of ESN1 with respect to the reference potential and the CE with respect to the reference potential using two power supplies after setting a reference potential in between may be used. In the method of the present invention, it is sufficient that a potential difference is generated between ESN1 and CE. For example, ESN1 may be a positive potential, CE may be a negative potential, ESN1 may be a negative potential, and CE may be a positive potential. Even if the potential of ESN1 is 0 and CE is-, the potential of ESN1 is 0, the potential of ESN1 is 0 and CE is +, or the potential of ESN1 is-and CE is 0. May be a positive potential and the CE potential may be zero.
本発明によれば、高分子化合物溶液の濃度、溶剤の種類、媒体液体の種類等を調整することによって、ＥＳＮ１から静電噴霧される高分子化合物溶液と媒体液体との物理・化学的相互作用を制御し、ＥＳＮ１-ＣＥ間の電圧制御を併用して高分子化合物の形状を制御することができる。特に、媒体液体と第１液体試料に含まれる溶媒との相溶性を調整することにより、形状の制御をすることができる。本発明において、形状の制御としては、形状を繊維状にすること、繊維状化合物の太さを調整すること等が挙げられる。 According to the present invention, the physical / chemical interaction between the polymer compound solution electrostatically sprayed from the ESN 1 and the medium liquid is adjusted by adjusting the concentration of the polymer compound solution, the type of solvent, the type of medium liquid, and the like. And the shape of the polymer compound can be controlled by using voltage control between ESN1 and CE together. In particular, the shape can be controlled by adjusting the compatibility between the medium liquid and the solvent contained in the first liquid sample. In the present invention, examples of the shape control include making the shape fibrous, adjusting the thickness of the fibrous compound, and the like.
図１（ａ）に本発明に係わる液中エレクトロスプレー法の一実施形態を示す。媒体液体中に対向して設置した第１液体試料を媒体液体中に導入するための第１エレクトロスプレーノズル（ＥＳＮ１）と対向電極（ＣＥ）間に強電場を形成することによって、一定流速で供給される第１液体試料がマイクロメータサイズの荷電液滴に断片化され、荷電液滴はＥＳＮ１とＣＥ間の電場に沿って移動する。図１（ａ）の電場では、第１液体試料が正電荷を持った液滴に断片化され、ＣＥに向かって移動するが、ＥＳＮ１とＣＥ間の電場の方向が図１（ａ）と反対の極性となるときは、負電荷を持った液滴が生成し、ＥＳＮ１からＣＥに向かって移動する。該液中エレクトロスプレー法は、媒体液体を使用することで、気中のエレクトロスプレーよりも好適に静電噴霧を液中で行うことを可能にした。これによりＥＳＮ１−ＣＥ間の放電を抑制し、静電噴霧された液体の飛散を防止し、静電噴霧された荷電液滴と媒体液体との物理・化学的相互作用を制御して、高分子材料加工などへの適用を可能にした。 FIG. 1A shows an embodiment of an in-liquid electrospray method according to the present invention. Supply at a constant flow rate by forming a strong electric field between the first electrospray nozzle (ESN1) and the counter electrode (CE) for introducing the first liquid sample placed facing the medium liquid into the medium liquid. The first liquid sample is fragmented into micrometer-sized charged droplets, and the charged droplets move along the electric field between ESN1 and CE. In the electric field of FIG. 1 (a), the first liquid sample is fragmented into positively charged droplets and moves toward CE, but the direction of the electric field between ESN1 and CE is opposite to that of FIG. 1 (a). In the case of a negative polarity, a droplet having a negative charge is generated and moves from ESN 1 toward CE. In the submerged electrospray method, by using a medium liquid, electrostatic spraying can be performed in the liquid more favorably than the electrospray in the air. This suppresses the discharge between ESN1 and CE, prevents scattering of the electrostatically sprayed liquid, controls the physical / chemical interaction between the electrostatically sprayed charged droplet and the medium liquid, and Applicable to material processing.
高分子加工法に適用するには、前述の高分子化合物を溶剤に溶かした第１液体試料を媒体液体中でエレクトロスプレーを行う。従来のＥＳＮ１とＣＥ間の電圧、及び第１液体試料の濃度による高分子材料の形状制御に加えて、媒体液体と第１液体試料との化学的な相互作用による形状制御をプラスすることにより、繊維状・粒子状・複合化・中空構造等の形状制御を精密に実現できる。また、条件設定により、従来の気中でのエレクトロスピニング法よりも細い繊維を製造することができる。従って、本発明の方法によれば、太い繊維から細い繊維まで高精度に製造することができる。 For application to the polymer processing method, the first liquid sample in which the above-described polymer compound is dissolved in a solvent is electrosprayed in a medium liquid. In addition to the conventional shape control of the polymer material by the voltage between the ESN1 and the CE and the concentration of the first liquid sample, by adding the shape control by the chemical interaction between the medium liquid and the first liquid sample, Precise control of the shape of fibers, particles, composites, hollow structures, etc. can be realized. Further, by setting the conditions, it is possible to produce a finer fiber than the conventional electrospinning method in the air. Therefore, according to the method of the present invention, it is possible to manufacture from a thick fiber to a thin fiber with high accuracy.
例えば、第１液体試料に２種以上の高分子化合物を含有させ、当該少なくとも１種類の高分子化合物が媒体液体中に可溶であるようなものにすることで、媒体液体中にエレクトロスプレーして制御する高分子化合物の形状を中空（ポーラス）構造とすることができる。 For example, when the first liquid sample contains two or more polymer compounds and the at least one polymer compound is soluble in the medium liquid, the first liquid sample is electrosprayed in the medium liquid. The shape of the polymer compound to be controlled can be a hollow structure.
また、媒体液体中に金属ナノ粒子等の機能性材料を分散させ、ＥＳＮ１から高分子化合物溶液をエレクトロスプレーすることにより、形状制御された高分子材料と機能性材料とを複合化させることもできる。 In addition, by dispersing a functional material such as metal nanoparticles in a medium liquid and electrospraying a polymer compound solution from ESN1, it is possible to combine the shape-controlled polymer material and the functional material. .
別の実施形態において、本発明は、所定の化合物を含有する第１液体試料を電場中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）及び所定の化合物を含有する第２液体試料を電場中に静電噴霧するための第２エレクトロスプレーノズル（ＥＳＮ２）を媒体液体中に設置し、該ＥＳＮ１と該ＥＳＮ２との間に電位差を与え、正及び負に帯電した液滴をＥＳＮ１及びＥＳＮ２から静電噴霧し、正に帯電した液滴と負に帯電した液滴とを静電引力によって衝突・融合させる、液中エレクトロスプレー法を提供する。 In another embodiment, the present invention provides a first electrospray nozzle (ESN1) for electrostatically spraying a first liquid sample containing a predetermined compound into an electric field and a second liquid sample containing the predetermined compound. A second electrospray nozzle (ESN2) for electrostatic spraying in an electric field is installed in the medium liquid, a potential difference is applied between the ESN1 and the ESN2, and the positively and negatively charged droplets are transferred to the ESN1 and ESN2 In-liquid electrospray method in which positively charged droplets and negatively charged droplets collide and fuse by electrostatic attraction force.
本実施形態においても、媒体液体としては、特に限定されず、例えば、前述したものを適宜使用することができる。 Also in the present embodiment, the medium liquid is not particularly limited, and for example, those described above can be used as appropriate.
本実施形態において第１液体試料及び第２液体試料は、反応に供するための所定の化合物を含有する液体を意味し、当該所定の化合物を溶媒に溶解、分散したもの等が挙げられる。 In this embodiment, the 1st liquid sample and the 2nd liquid sample mean the liquid containing the predetermined compound for using for reaction, and what dissolved and disperse | distributed the said predetermined compound in the solvent etc. are mentioned.
本実施形態においては、正又は負に帯電した第１液体試料の液滴と第２液体試料の液滴とを媒体液体中で衝突融合させることにより非常に微小な反応場で第１液体試料と第２液体試料との含有物を反応させる。従って、本発明の方法は、２種類の溶液を混合させることにより行う多種多様な化学反応に応用することができる。例えば、本発明の方法は、金属ナノ粒子、有機ナノ結晶、半導体ナノ粒子等の粒子、高分子系ナノ粒子等の合成に用いることができる。 In the present embodiment, the droplet of the first liquid sample and the droplet of the second liquid sample, which are positively or negatively charged, are collided and fused in the medium liquid with the first liquid sample in a very small reaction field. The contents with the second liquid sample are reacted. Therefore, the method of the present invention can be applied to a wide variety of chemical reactions performed by mixing two kinds of solutions. For example, the method of the present invention can be used for the synthesis of particles such as metal nanoparticles, organic nanocrystals, and semiconductor nanoparticles, and polymer nanoparticles.
金ナノ粒子等の金属ナノ粒子合成法等の化学反応制御法に適用するには、金属イオン溶液と還元剤溶液を正及び負のＥＳＮノズルから静電噴霧し、媒体液体中で金属イオン溶液と還元剤溶液の各液滴を静電力によって衝突混合させ、金属イオンの還元反応を液滴内で起こし、金属ナノ粒子を合成する。液滴内で合成された金属ナノ粒子を安定剤溶液中に回収すれば、高い回収率で金属ナノ粒子のコロイド溶液を得ることができる。かかる方法によれば、正−負液滴の衝突・混合によってナノ粒子の合成反応を起こさせ、反応後の液滴を回収することにより、生成したナノ粒子が容器内に沈着・凝集せず長時間安定して連続合成できる。 To apply to a chemical reaction control method such as a method of synthesizing metal nanoparticles such as gold nanoparticles, a metal ion solution and a reducing agent solution are electrostatically sprayed from positive and negative ESN nozzles, and the metal ion solution Each droplet of the reducing agent solution is collided and mixed by an electrostatic force to cause a metal ion reduction reaction within the droplet to synthesize metal nanoparticles. If the metal nanoparticles synthesized in the droplets are recovered in the stabilizer solution, a colloidal solution of metal nanoparticles can be obtained with a high recovery rate. According to such a method, a nanoparticle synthesis reaction is caused by collision and mixing of positive and negative droplets, and the droplets after the reaction are collected, so that the generated nanoparticles are not deposited or aggregated in the container for a long time. Continuous synthesis is possible with stable time.
かかる実施形態において、金属イオン溶液としては、特に限定されないが、例えば、金イオン、銀イオン等の貴金属イオン；鉄イオン、銅イオン、錫イオン、亜鉛イオン、アルミニウムイオン等のベースメタルイオン；パラジウムイオン、ルテニウムイオン、ロジウムイオン、チタンイオン等のレアメタルイオン等の溶液が挙げられる。これらの金属イオンは１種単独で又は２種類以上を混合して用いることができる。還元剤としては、特に限定されないが、例えば、アスコルビン酸、ヒドラジン、水素化ホウソナトリウム、クエン酸等が挙げられる。これらの還元剤は１種単独で又は２種類以上を混合して用いることができる。 In this embodiment, the metal ion solution is not particularly limited. For example, noble metal ions such as gold ions and silver ions; base metal ions such as iron ions, copper ions, tin ions, zinc ions and aluminum ions; palladium ions And solutions of rare metal ions such as ruthenium ions, rhodium ions, and titanium ions. These metal ions can be used alone or in combination of two or more. Although it does not specifically limit as a reducing agent, For example, ascorbic acid, hydrazine, sodium borohydride, a citric acid etc. are mentioned. These reducing agents can be used individually by 1 type or in mixture of 2 or more types.
第１液体試料及び第２液体試料に用いる溶媒としては、特に限定されず、例えば、水、アルコール（エタノール等）等が挙げられる。これらの溶媒は１種単独で又は２種類以上を混合して用いることができる。かかる溶媒としては、媒体液体に対し相溶性の高いものであっても相溶性の低いものであってもよい。第１液体試料の溶媒と第２液体試料の溶媒とがそれぞれ同じ種類の溶媒を含むことが、液滴を融合しやすくさせるために好ましい。当該実施形態においては、溶媒の少なくとも１部としてアルコールを配合することにより表面張力が小さくなり、静電噴霧の際の液滴サイズが小さくなる。その結果、第１液体試料由来の液滴と第２液体試料由来の液滴との融合により得られる反応場が小さくなり、得られる反応生成物（金属粒子等）のサイズを小さくすることができる。このように溶媒の選択により表面張力を調整することによって、得られる反応生成物（金属粒子等）のサイズを制御することができる。 It does not specifically limit as a solvent used for a 1st liquid sample and a 2nd liquid sample, For example, water, alcohol (ethanol etc.), etc. are mentioned. These solvents can be used alone or in combination of two or more. Such a solvent may be either highly compatible with the medium liquid or low compatible. It is preferable that the solvent of the first liquid sample and the solvent of the second liquid sample each contain the same type of solvent so that the droplets can be easily fused. In the present embodiment, by adding alcohol as at least a part of the solvent, the surface tension is reduced, and the droplet size during electrostatic spraying is reduced. As a result, the reaction field obtained by the fusion of the droplet derived from the first liquid sample and the droplet derived from the second liquid sample is reduced, and the size of the reaction product (metal particles, etc.) obtained can be reduced. . Thus, by adjusting the surface tension by selecting the solvent, the size of the reaction product (metal particles or the like) obtained can be controlled.
第１液体試料及び第２液体試料に含まれる反応原料となる化合物の濃度は特に限定されないが、上記反応原料及び溶媒の種類によって、例えば、０．１〜５０ｗｔ％、好ましくは１〜４０ｗｔ％、より好ましくは２〜３０ｗｔ％、さらに好ましくは５〜２０ｗｔ％等の範囲内で適宜設定することができる。好ましい実施形態において、第１液体試料及び第２液体試料に含まれる化合物の濃度としては、溶質が溶ける範囲であればよく、例えば、１ｍｏｌ／Ｌ以下、０．１ｍｏｌ／Ｌ以下の範囲で適宜設定できる。 The concentration of the compound serving as the reaction raw material contained in the first liquid sample and the second liquid sample is not particularly limited, but is, for example, 0.1 to 50 wt%, preferably 1 to 40 wt%, depending on the type of the reaction raw material and the solvent. More preferably, it can be suitably set within the range of 2 to 30 wt%, more preferably 5 to 20 wt%. In a preferred embodiment, the concentration of the compound contained in the first liquid sample and the second liquid sample may be in the range in which the solute dissolves, and is appropriately set in the range of, for example, 1 mol / L or less and 0.1 mol / L or less. it can.
ＥＳＮ１とＥＳＮ２との間の距離は特に限定されず、例えば、１ｃｍ以上、好ましくは２ｃｍ以上の範囲内で適宜設定することができる。ＥＳＮ１とＥＳＮ２との間の距離の上限は特に限定されず、エレクトロスプレー装置の寸法に合わせて適宜設定し得る。 The distance between ESN1 and ESN2 is not particularly limited, and can be appropriately set within a range of, for example, 1 cm or more, preferably 2 cm or more. The upper limit of the distance between ESN1 and ESN2 is not particularly limited, and can be appropriately set according to the dimensions of the electrospray device.
本実施形態におけるＥＳＮ１及びＥＳＮ２としては、ノズル間で電場を形成させることができるようなものであれば特に限定されず、上記実施形態の説明で例示したＥＳＮ１と同様のものを適宜使用することができる。 The ESN1 and ESN2 in the present embodiment are not particularly limited as long as an electric field can be formed between the nozzles, and the same ESN1 exemplified in the description of the above embodiment may be used as appropriate. it can.
ＥＳＮ１とＥＳＮ２との間に与える電位差の下限は特に限定されず、例えば、０．１ｋＶ以上、好ましくは２ｋＶ以上の範囲内で適宜設定することができる。ＥＳＮ１とＥＳＮ２との間に与える電位差の上限は特に限定されず、例えば、２０ｋＶ以下、好ましくは１５ｋＶ以下の範囲内で適宜設定することができる。ＥＳＮ１とＥＳＮ２との間に与える電位差を与える方法は特に限定されず、例えば、１つの電源をＥＳＮ１及びＥＳＮ２に接続し、ＥＳＮ１とＥＳＮ２との間に電圧を印加しても、ＥＳＮ１とＥＳＮ２との間に基準となる電位を設定した上で、２つの電源を使用して基準となる電位に対するＥＳＮ１の電位及び基準となる電位に対するＥＳＮ２を制御する方法を用いてもよい。本発明の方法においては、ＥＳＮ１とＥＳＮ２との間に電位差が生じればよく、例えば、ＥＳＮ１を＋の電位としＥＳＮ２を−の電位としても、ＥＳＮ１を−の電位としＥＳＮ２を＋の電位としても、ＥＳＮ１の電位が０でＥＳＮ２が−の電位であっても、ＥＳＮ１の電位が０でＥＳＮ２が＋の電位であっても、ＥＳＮ１が−の電位でＥＳＮ２の電位が０であっても、ＥＳＮ１が＋の電位でＥＳＮ２の電位が０であってもよい。 The lower limit of the potential difference applied between ESN1 and ESN2 is not particularly limited, and can be appropriately set within a range of, for example, 0.1 kV or higher, preferably 2 kV or higher. The upper limit of the potential difference applied between ESN1 and ESN2 is not particularly limited, and can be appropriately set within a range of, for example, 20 kV or less, preferably 15 kV or less. There is no particular limitation on a method for providing a potential difference between ESN1 and ESN2. For example, even when one power source is connected to ESN1 and ESN2 and a voltage is applied between ESN1 and ESN2, the difference between ESN1 and ESN2 A method of controlling the potential of ESN1 with respect to the reference potential and ESN2 with respect to the reference potential using two power supplies after setting a reference potential in between may be used. In the method of the present invention, it is sufficient that a potential difference is generated between ESN1 and ESN2. For example, ESN1 may be a positive potential, ESN2 may be a negative potential, ESN1 may be a negative potential, and ESN2 may be a positive potential. Even if ESN1 is 0 and ESN2 is-, ESN1 is 0 and ESN2 is +, ESN1 is-, and ESN2 is 0, May be a positive potential and the potential of ESN2 may be zero.
ＥＳＮ１としては、電荷を付与するために表面を金等の金属でメッキしたキャピラリーチューブ等が挙げられる。かかるキャピラリーチューブはさらに、その先端が露出するような状態でステンレス等の金属のチューブでその一部が覆われていてもよい。 Examples of the ESN 1 include a capillary tube whose surface is plated with a metal such as gold in order to impart an electric charge. The capillary tube may be further partially covered with a metal tube such as stainless steel in a state where the tip is exposed.
本発明によれば、かかる方法により微小液滴間の衝突・混合によってマイクロ反応場を形成することができる。より具体的には、本発明によれば、第１液体試料と第２液体試料との二種の溶液の混合によって起こる液相の連続的あるいは連鎖的化学反応であって、該二液の微小液滴間の衝突・混合によって反応を開始させ、微小液滴の体積が小さいことにより、微小液滴間の混合速度が非常に早くかつごく微小な反応場を提供することができ、また混合後の液滴からの生成物の回収速度が大きいという特徴を有している。 According to the present invention, a micro reaction field can be formed by collision and mixing between microdroplets by such a method. More specifically, according to the present invention, a liquid phase continuous or chain chemical reaction caused by mixing two kinds of solutions of a first liquid sample and a second liquid sample, The reaction is initiated by collision / mixing between droplets, and the volume of the microdroplets is small, so the mixing speed between the microdroplets is very fast and a very small reaction field can be provided. The recovery rate of the product from the liquid droplets is high.
図１（ｂ）は液中エレクトロスプレー法によるマイクロ反応場制御法の一実施形態を示す。対向する二つのＥＳＮに正及び負の電位を印加し、対向する該ＥＳＮ間に強電場を形成させることにより、各ＥＳＮから正及び負に帯電した液滴がスプレーされ、それらの静電的相互作用によって、液滴間の衝突・融合を実現できる。異なる第１液体試料及び第２液体試料をこの手法で静電噴霧し混合することにより、極微小液滴内で化学反応を起こすことができる。従来の気中における正・負エレクトロスプレーの衝突・融合では、衝突後の飛散のために、反応効率低下と作業環境悪化が問題となったが、本発明では、衝突後の液滴の飛散が無いため、これらの問題が生じない。 FIG.1 (b) shows one Embodiment of the micro reaction field control method by the electrospray method in a liquid. By applying positive and negative potentials to two opposing ESNs to form a strong electric field between the opposing ESNs, positively and negatively charged droplets are sprayed from each ESN, and their electrostatic mutual By action, collision and fusion between droplets can be realized. By spraying and mixing different first liquid sample and second liquid sample by this method, a chemical reaction can be caused in the micro droplet. In conventional collisions and fusion of positive and negative electrosprays in the air, scattering after the collision has caused problems such as a decrease in reaction efficiency and deterioration of the working environment. In the present invention, however, droplets after the collision are scattered. None of these problems arise because
本発明は、前述したエレクトロスプレー法に用いるための装置も提供する。 The present invention also provides an apparatus for use in the electrospray method described above.
具体的には、本発明は、媒体液体を格納する容器と
所定の化合物を含有する第１液体試料を供給する第１液体試料供給源及び該第１液体試料供給源に接続されかつ該第１液体試料供給源から供給される第１液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）を備えた第１噴霧手段と
ＥＳＮ１との間に電場を形成するための対向電極（ＣＥ）とを
備える液中エレクトロスプレー装置、ならびに
媒体液体を格納する容器と
所定の化合物を含有する第１液体試料を供給する第１液体試料供給源及び該第１液体試料供給源に接続されかつ該第１液体試料供給源から供給される第１液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）を備えた第１噴霧手段と
所定の化合物を含有する第２液体試料を供給する第２液体試料供給源及び該第２液体試料供給源に接続されかつ該第２液体試料供給源から供給される第２液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第２エレクトロスプレーノズル（ＥＳＮ２）を備えた第２噴霧手段とを
備える液中エレクトロスプレー装置
を提供する。本発明の典型的な実施形態における装置を図１（ａ）（ｂ）に示す。
Specifically, the present invention includes a container for storing a medium liquid, a first liquid sample supply source for supplying a first liquid sample containing a predetermined compound, and the first liquid sample supply source connected to the first liquid sample supply source. A first spraying means including a first electrospray nozzle (ESN1) for electrostatically spraying a first liquid sample supplied from a liquid sample supply source into a medium liquid stored in the storage container, and ESN1 A submerged electrospray apparatus having a counter electrode (CE) for forming an electric field therebetween, a container for storing a medium liquid, a first liquid sample supply source for supplying a first liquid sample containing a predetermined compound, and A first electrospray nozzle connected to the first liquid sample supply source and electrostatically sprays a first liquid sample supplied from the first liquid sample supply source into a medium liquid stored in the storage container ( A first spraying means having ESN1), a second liquid sample supply source for supplying a second liquid sample containing a predetermined compound, and a second liquid sample supply source connected to and supplied from the second liquid sample supply source A submerged electrospray apparatus comprising: a second spraying means having a second electrospray nozzle (ESN2) for electrostatically spraying a second liquid sample to be sprayed into a medium liquid stored in the storage container To do. An apparatus according to an exemplary embodiment of the present invention is shown in FIGS.
本発明の装置は、上記構成に加え、ＥＳＮ１とＣＥとの間、又はＥＳＮ１とＥＳＮ２との間に電圧を印加するための電圧印加手段をさらに備えていてもよい。好ましい実施形態において、電圧印加手段は格納容器の外に配置される。また、本発明の装置は、エレクトロスプレーにより得られた生成物を回収するための回収手段をさらに含んでいてもよい。かかる回収手段は、媒体液体を格納する容器に接続された当該容器とは別の容器であっても、媒体液体を格納する容器と一体化したかたちであってもよい。例えば、図２に示すように、ｎ−ヘキサン等の媒体液体の層下に、当該媒体液体と相溶性の低い液体の層を回収層として配置しておく方法等も本発明に含まれる。また媒体液体の種類、第１液体試料の溶媒及び／又は第２液体試料の溶媒の種類等によっては、上記回収層を媒体液体の上層に配置することも可能である。 In addition to the above configuration, the apparatus of the present invention may further include a voltage applying unit for applying a voltage between ESN1 and CE or between ESN1 and ESN2. In a preferred embodiment, the voltage applying means is arranged outside the containment vessel. Moreover, the apparatus of the present invention may further include a recovery means for recovering a product obtained by electrospray. Such a recovery means may be a container different from the container connected to the container for storing the medium liquid, or may be integrated with the container for storing the medium liquid. For example, as shown in FIG. 2, the present invention includes a method in which a liquid layer having low compatibility with the medium liquid is disposed as a recovery layer under a medium liquid layer such as n-hexane. In addition, depending on the type of the medium liquid, the solvent of the first liquid sample and / or the type of the solvent of the second liquid sample, the recovery layer can be disposed in the upper layer of the medium liquid.
また、本発明の装置には媒体液体が格納された状態のものだけでなく、媒体液体が格納されていない状態のものも含まれる。 Further, the apparatus of the present invention includes not only a state in which the medium liquid is stored but also a state in which the medium liquid is not stored.
以下、液中エレクトロスプレー法、及び液中エレクトロスプレー法によるマイクロ反応場制御法について実施例を用いて詳述するが、本発明はかかる特定の実施形態に限定されない。 Hereinafter, the electrospray method in liquid and the micro reaction field control method by the electrospray method in liquid will be described in detail using examples, but the present invention is not limited to such specific embodiments.
実施例１
図１（ａ）で示した液中エレクトロスプレー法の概念図における低誘電率液体としてｎ−ヘキサンを用い、第１液体試料として水を用い、対向電極として直径２０ｍｍのリング状のステンレス電極を用い、ＥＳＮ１−ＣＥ間の距離を３０ｍｍとして、ＥＳＮ１−ＣＥ間に３ｋＶ以上の高電圧を印加し、ＥＳＮ１より０．０２ｍＬ／ｍｉｎで水をｎ−ヘキサン中の高電場に導入することにより、電荷を帯びた微小水滴がＥＳＮ１−ＣＥ間の電場に沿って移動することを見出した。微小水滴の電荷は、ＥＳＮ１の電位がより正の場合は正電荷、より負の場合は負電荷となる。
Example 1
In the conceptual diagram of the submerged electrospray method shown in FIG. 1A, n-hexane is used as the low dielectric constant liquid, water is used as the first liquid sample, and a ring-shaped stainless steel electrode having a diameter of 20 mm is used as the counter electrode. By applying a high voltage of 3 kV or more between ESN1 and CE and introducing water into the high electric field in n-hexane at a rate of 0.02 mL / min from ESN1, the distance between ESN1 and CE is 30 mm. It has been found that minute water droplets move along the electric field between ESN1 and CE. The charge of the minute water droplet is a positive charge when the potential of ESN1 is more positive and a negative charge when the potential of ESN1 is more negative.
実施例２
図１（ｂ）で示したマイクロ反応場制御法の概念図における低誘電率液体としてｎ−ヘキサンを用い、第１液体試料及び第２液体試料として共に水を用い、対向するＥＳＮ間の距離を３０ｍｍとして、対向するＥＳＮ間に５ｋＶ以上の高電圧を印加し、各ＥＳＮより０．０２ｍＬ／ｍｉｎで水をｎ−ヘキサン中の高電場に導入することにより、電荷を帯びた微小水滴が電場に沿って移動し、電場の中央付近で正−負微小液滴間の衝突・融合が静電力によって起こることを確認した。その映像のスナップショットを図２に示す。
Example 2
In the conceptual diagram of the micro reaction field control method shown in FIG. 1B, n-hexane is used as the low dielectric constant liquid, water is used as both the first liquid sample and the second liquid sample, and the distance between the opposing ESNs is determined. 30 mm, a high voltage of 5 kV or more is applied between the ESNs facing each other, and water is introduced into the high electric field in n-hexane at 0.02 mL / min from each ESN, so that charged water droplets are applied to the electric field. It was confirmed that collision and fusion between positive and negative microdroplets occurred by electrostatic force near the center of the electric field. A snapshot of the video is shown in FIG.
実施例３
図３に示す装置を用いてマイクロ反応場制御法により金ナノ粒子合成を行った。具体的には、正電位（＋５ｋＶ）のＥＳＮ１から塩化金酸（ＨＡｕＣｌ3，０．１ｍｏｌ／Ｌ）水溶液、負電位（−３ｋＶ）のＥＳＮ２から還元剤として機能するアスコルビン酸（０．１ｍｏｌ／Ｌ）水溶液を０．０２ｍＬ／ｍｉｎでｎ−ヘキサン中に送液した。対向するＥＳＮ間の距離を２５ｍｍとした。各ＥＳＮから両水溶液の荷電微小液滴が生成し、対向するＥＳＮ間の中央付近で両液滴が静電的に衝突・混合し、Ａｕ3+がアスコルビン酸によって還元された。図３の写真下部の容器は２層の液体が封入されており、下層の液体部分は、ポリビニルピロリドン（ＰＶＰ，２ｗｔ％）水溶液でマグネティックスターラにより撹拌している。塩化金酸水溶液とアスコルビン酸水溶液の荷電液滴が静電的に衝突・混合後、ＰＶＰ水溶液相に回収され、金ナノ粒子コロイドとして安定化した状態の写真である。送液開始から約３分で図３のような金ナノコロイドの生成が確認できた。なお、金ナノコロイドの生成は、１０ナノメートル程度の金ナノ粒子に特有な表面プラズモン共鳴による吸光によって赤色を呈したことから確認できた。
Example 3
Gold nanoparticles were synthesized by the micro reaction field control method using the apparatus shown in FIG. Specifically, ascorbic acid (0.1 mol / L) functioning as a reducing agent from ESN1 of positive potential (+5 kV) to chloroauric acid (HAuCl 3 , 0.1 mol / L), ESN2 of negative potential (−3 kV). ) The aqueous solution was fed into n-hexane at 0.02 mL / min. The distance between the opposing ESNs was 25 mm. Charged microdroplets of both aqueous solutions were generated from each ESN, both droplets electrostatically collided and mixed near the center between the opposing ESNs, and Au 3+ was reduced by ascorbic acid. The container in the lower part of FIG. 3 is filled with two layers of liquid, and the lower part of the liquid is agitated with a polyvinyl pyrrolidone (PVP, 2 wt%) aqueous solution by a magnetic stirrer. It is a photograph of a state in which charged droplets of a chloroauric acid aqueous solution and an ascorbic acid aqueous solution are electrostatically collided and mixed and then collected in a PVP aqueous solution phase and stabilized as a gold nanoparticle colloid. The formation of gold nanocolloid as shown in FIG. 3 was confirmed in about 3 minutes from the start of liquid feeding. In addition, the production | generation of gold nano colloid has been confirmed from having exhibited red by the light absorption by the surface plasmon resonance peculiar to about 10 nanometer gold nanoparticles.
実施例４
下記条件を採用する以外は、実施例３と同様にして、金ナノ粒子合成法を行った。
正極：
電位：＋４ｋＶ，
第１液体試料溶質：塩化金酸（０．０５ｍｏｌ／Ｌ）
第１液体試料溶媒：エタノール／水（５０／５０ｖｏｌ）
送液速度：０．０２ｍＬ／ｍｉｎ
負極：
電位：−４ｋＶ，
第２液体試料溶質：アスコルビン酸（０．０５ｍｏｌ／Ｌ）
第２液体試料溶媒：エタノール／水（５０／５０ｖｏｌ）
送液速度：０．０２ｍＬ／ｍｉｎ。
Example 4
A gold nanoparticle synthesis method was performed in the same manner as in Example 3 except that the following conditions were adopted.
Positive electrode:
Potential: +4 kV,
First liquid sample solute: chloroauric acid (0.05 mol / L)
First liquid sample solvent: ethanol / water (50/50 vol)
Liquid feeding speed: 0.02 mL / min
Negative electrode:
Potential: -4 kV,
Second liquid sample solute: ascorbic acid (0.05 mol / L)
Second liquid sample solvent: ethanol / water (50/50 vol)
Liquid feeding speed: 0.02 mL / min.
反応を４５分行った。金ナノ粒子の粒径は動的光散乱法により測定した。反応時間１２分時点及び４５分時点での金ナノ粒子の粒径分布を図４に示す。図４上に示すように、得られた金ナノ粒子の粒径は、そのほとんどが４ｎｍ以下に集中しており、非常に高い精度で粒径を制御できることが分かる。また、図３に示すように、還元反応の生じる低誘電率液体層（ｎ−ヘキサン層）の直下に回収層である水層があるため、還元反応で得られた金ナノ粒子はそのほとんどが回収層に移動し、高い回収率で金ナノ粒子を得ることができる。さらに、図４上と図４下との比較から明らかなように、反応時間１２分時点と４５分時点とで粒径分布がほとんど変化しておらず、高い精度で粒径を制御した状態で、長時間連続合成ができていることが分かる。 The reaction was performed for 45 minutes. The particle size of the gold nanoparticles was measured by a dynamic light scattering method. The particle size distribution of the gold nanoparticles at the reaction time of 12 minutes and 45 minutes is shown in FIG. As shown in FIG. 4, most of the particle diameters of the obtained gold nanoparticles are concentrated to 4 nm or less, and it can be seen that the particle diameter can be controlled with very high accuracy. Also, as shown in FIG. 3, since there is an aqueous layer that is a recovery layer directly under the low dielectric constant liquid layer (n-hexane layer) where the reduction reaction occurs, most of the gold nanoparticles obtained by the reduction reaction are The gold nanoparticles can be obtained with a high recovery rate by moving to the recovery layer. Further, as apparent from the comparison between FIG. 4 and the bottom of FIG. 4, the particle size distribution hardly changed between the reaction time of 12 minutes and 45 minutes, and the particle size was controlled with high accuracy. It can be seen that continuous synthesis can be performed for a long time.
実施例５
図１（ａ）に概略を示すような装置で、アセチルセルロース（ＣＡ、平均重合度１５０、置換度２．４）の１０ｗｔ％溶液（溶媒：ＤＭＦ：アセトンの体積比８０：２０の混合液）を約３００ｍＬのヘキサン中で静電噴霧した。ノズルは内径０．５ｍｍ、外形１／１６インチのステンレス製チューブを用い、コレクターにはアルミ箔を支持具に装着して用いた。ノズル先端とコレクター間の距離は約２５ｍｍ、０．０２ｍＬ／ｍｉｎで送液し、ノズル側に＋１０ｋＶの電圧を印加した。コレクター上に堆積したＣＡファイバーは、アルミ箔から剥離し、ろ紙上室温で乾燥させた。得られたＣＡファイバーのＳＥＭ写真を図５上に示す。当該図５上に示す液中エレクトロスプレーにより得られたＣＡファイバーは非常に細く、気中エレクトロスプレーでは得られなかった程の細さであった。
Example 5
1 wt% solution of acetylcellulose (CA, average polymerization degree 150, substitution degree 2.4) (mixture of solvent: DMF: acetone volume ratio 80:20) in an apparatus as schematically shown in FIG. Was electrostatically sprayed in about 300 mL of hexane. The nozzle used was a stainless steel tube having an inner diameter of 0.5 mm and an outer shape of 1/16 inch, and the collector was used with aluminum foil attached to a support. The distance between the nozzle tip and the collector was about 25 mm, and the liquid was fed at 0.02 mL / min, and a voltage of +10 kV was applied to the nozzle side. The CA fiber deposited on the collector was peeled from the aluminum foil and dried on a filter paper at room temperature. An SEM photograph of the obtained CA fiber is shown in FIG. The CA fiber obtained by submerged electrospray shown in FIG. 5 was very thin, so thin that it could not be obtained by air electrospray.
比較例１
次に、ノズル先端とコレクター間の距離を約１００ｍｍとして気中で静電噴霧する以外、上記と同様にして、気中静電噴霧を行ったが、ファイバーは得られなかった。さらにＣＡ溶液に用いる溶媒をアセトンとする以外上記と同様の条件で気中静電噴霧を行った。得られたＣＡファイバーのＳＥＭ写真を図５下に示す。
Comparative Example 1
Next, air electrostatic spraying was performed in the same manner as described above except that the distance between the nozzle tip and the collector was about 100 mm and air electrostatic spraying was performed, but no fiber was obtained. Further, air electrostatic spraying was performed under the same conditions as described above except that the solvent used in the CA solution was acetone. The SEM photograph of the obtained CA fiber is shown in the lower part of FIG.
実施例６
次に、下記条件とする以外、実施例５と同様の液中エレクトロスプレーを行うことによりＣＡファイバーを調製した。得られたＣＡファイバーのＳＥＭ写真を図６に示す：
図６左欄上段：
第１液体試料：ＣＡ１０ｗｔ％溶液（溶媒、ＤＭＦ：アセトン＝８０：２０）
媒体液体：ｎ−ヘキサン
電圧：５．２ｋＶ
ノズル先端とコレクター間の距離：約２５ｍｍ
図６右欄上段：
第１液体試料：ＣＡ５ｗｔ％＋ＰＶＰ（ポリビニルピロリドン Ｋ９０、粘度平均分子量６３００００）５ｗｔ％溶液（溶媒：ＤＭＦ：アセトン＝８０：２０）、
媒体液体：ｎ−ヘキサン
電圧：１０ｋＶ
ノズル先端とコレクター間の距離：約２５ｍｍ
図６左欄中段：
第１液体試料：ＣＡ８ｗｔ％＋ＰＶＰ２ｗｔ％溶液（溶媒、ＤＭＦ：アセトン＝８０：２０）
媒体液体：ｎ−ヘキサン
電圧：１０ｋＶ
ノズル先端とコレクター間の距離：約２５ｍｍ
図６右欄中段：
第１液体試料：ＣＡ１５ｗｔ％溶液（溶媒、ＤＭＦ：アセトン＝８０：２０）
媒体液体：ｎ−ヘキサン
電圧：４．８ｋＶ
ノズル先端とコレクター間の距離：約２５ｍｍ
図６左欄下段：
第１液体試料：ＣＡ８ｗｔ％溶液（溶媒：ＤＭＦ：アセトン＝８０：２０）
媒体液体：ｎ−ヘキサン
電圧：５．２ｋＶ
ノズル先端とコレクター間の距離：約２５ｍｍ
ＣＡ溶液濃度、電位差等を調整することにより、種々の太さのＣＡファイバーを得ることができた。
Example 6
Next, CA fiber was prepared by performing the electrospray in a liquid similar to Example 5 except having set it as the following conditions. An SEM photograph of the obtained CA fiber is shown in FIG.
The upper left column of FIG. 6:
First liquid sample: CA 10 wt% solution (solvent, DMF: acetone = 80: 20)
Medium liquid: n-hexane Voltage: 5.2 kV
Distance between nozzle tip and collector: approx. 25mm
Upper right column of FIG. 6:
First liquid sample: CA 5 wt% + PVP (polyvinylpyrrolidone K90, viscosity average molecular weight 630000) 5 wt% solution (solvent: DMF: acetone = 80: 20),
Medium liquid: n-hexane Voltage: 10 kV
Distance between nozzle tip and collector: approx. 25mm
Middle left column of FIG. 6:
First liquid sample: CA 8 wt% + PVP 2 wt% solution (solvent, DMF: acetone = 80: 20)
Medium liquid: n-hexane Voltage: 10 kV
Distance between nozzle tip and collector: approx. 25mm
Middle of the right column of FIG. 6:
First liquid sample: CA 15 wt% solution (solvent, DMF: acetone = 80: 20)
Medium liquid: n-hexane Voltage: 4.8 kV
Distance between nozzle tip and collector: approx. 25mm
Lower left column of FIG. 6:
First liquid sample: CA 8 wt% solution (solvent: DMF: acetone = 80: 20)
Medium liquid: n-hexane Voltage: 5.2 kV
Distance between nozzle tip and collector: approx. 25mm
By adjusting the CA solution concentration, potential difference, etc., CA fibers of various thicknesses could be obtained.
実施例７
次に、下記条件とする以外、実施例５と同様の液中エレクトロスプレーを行うことによりＣＡファイバーを調製した。得られたＣＡファイバーの光学顕微鏡写真を図７に示す。図７の各写真において、格子１ますの間隔は１ｍｍである：
図７上：
第１液体試料：ＣＡ１０ｗｔ％溶液（溶媒、アセトン）
媒体液体：ｎ−ヘキサン
電圧：１０ｋＶ
送液速度：０．０５ｍＬ／ｍｉｎ
ノズル先端とコレクター間の距離：約２５ｍｍ
図７下：
第１液体試料：ＣＡ５ｗｔ％溶液（溶媒、アセトン）
媒体液体：ｎ−ヘキサン
電圧：９ｋＶ
送液速度：０．０５ｍＬ／ｍｉｎ
ノズル先端とコレクター間の距離：約２５ｍｍ。
Example 7
Next, CA fiber was prepared by performing the electrospray in a liquid similar to Example 5 except having set it as the following conditions. An optical micrograph of the obtained CA fiber is shown in FIG. In each picture of FIG. 7, the spacing of the grid 1 is 1 mm:
Fig. 7 top:
First liquid sample: CA 10 wt% solution (solvent, acetone)
Medium liquid: n-hexane Voltage: 10 kV
Liquid feeding speed: 0.05 mL / min
Distance between nozzle tip and collector: approx. 25mm
Figure 7 bottom:
First liquid sample: CA 5 wt% solution (solvent, acetone)
Medium liquid: n-hexane Voltage: 9 kV
Liquid feeding speed: 0.05 mL / min
Distance between nozzle tip and collector: about 25 mm.
実施例８
図８に示す構成の装置を用いて、スプレー実験を行った。具体的には、金メッキキャピラリーチューブをノズルとして用い、これをシリコン栓に通した。シリコン栓を貫通する箇所については１／１６インチのステンレスチューブで覆っている。ＣＥとしては、ステンレス製のメッシュを用い、当該メッシュからステンレス線を延ばして容器外にある電源に接続した。ステンレス線のうち、媒体液体に接する部分についてはテフロン（登録商標）コーティングを施した。媒体液体として１−オクタノールを用い、第１液体試料として０．１ｍｏｌ／Ｌ ＫＣｌ（塩化カリウム）水溶液を用いて、ＣＥの電極を基準にノズルに種々の電位を与えてスプレー実験を行った。その結果、＋０．５ｋＶからスプレーを確認、＋４ｋＶまで安定にスプレーが発生した。
Example 8
A spray experiment was performed using the apparatus having the configuration shown in FIG. Specifically, a gold-plated capillary tube was used as a nozzle, and this was passed through a silicon stopper. The portion penetrating the silicon stopper is covered with a 1/16 inch stainless steel tube. As the CE, a stainless steel mesh was used, and a stainless steel wire was extended from the mesh and connected to a power source outside the container. Of the stainless steel wire, the portion in contact with the medium liquid was coated with Teflon (registered trademark). Using 1-octanol as the medium liquid and 0.1 mol / L KCl (potassium chloride) aqueous solution as the first liquid sample, various potentials were applied to the nozzle based on the CE electrode, and spray experiments were conducted. As a result, the spray was confirmed from +0.5 kV, and the spray was stably generated up to +4 kV.
次に、媒体液体として１−オクタノールに代えて１−ブタノールを行う以外、上記の試験を行った。その結果、ノズル電位＋０．４ｋＶからスプレーが起こった。そして、電圧は＋１ｋＶまでかけられた。上記のように、液中エレクトロスプレー法であれば、誘電率の高い電解質水溶液であっても静電噴霧をすることができる。 Next, the above test was performed except that 1-butanol was used instead of 1-octanol as the medium liquid. As a result, spraying occurred from the nozzle potential +0.4 kV. The voltage was then applied to +1 kV. As described above, in the case of the electrospray method, electrostatic spraying can be performed even with an electrolyte aqueous solution having a high dielectric constant.
比較例として、媒体液体を用いずに同実験を気中で行った結果、＋４．５ｋＶ未満だと大きな液滴が単にノズルから下に滴下されるだけでスプレー状とはならなかった。＋４．５ｋＶ以上で液滴が結合した液滴流が発生した。しかし、液滴のサイズは液中エレクトロスプレーに比べて極めて大きかった。 As a comparative example, the same experiment was carried out in the air without using a medium liquid. As a result, when it was less than +4.5 kV, a large droplet was simply dropped from the nozzle and did not form a spray. A droplet flow in which droplets were combined at +4.5 kV or more was generated. However, the size of the droplets was very large compared to the electrospray in liquid.
ＥＳＮ１ 第１エレクトロスプレーノズル
ＥＳＮ２ 第２エレクトロスプレーノズル
ＣＥ 対向電極
Ｌ−ＰＵＭＰ 液体試料供給手段
ＨＶ 高電圧印加手段
ESN1 1st electrospray nozzle ESN2 2nd electrospray nozzle CE Counter electrode L-PUMP Liquid sample supply means HV High voltage application means
Claims (5)
該媒体液体層の上層又は下層に配置した回収層により、静電噴霧により得られた生成物を回収する工程A step of recovering a product obtained by electrostatic spraying with a recovery layer disposed in an upper layer or a lower layer of the medium liquid layer
を含む、請求項１に記載の方法。The method of claim 1 comprising:
所定の化合物を含有する第１液体試料を供給する第１液体試料供給源及び該第１液体試料供給源に接続されかつ該第１液体試料供給源から供給される第１液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第１エレクトロスプレーノズル（ＥＳＮ１）を備えた第１噴霧手段と
所定の化合物を含有する第２液体試料を供給する第２液体試料供給源及び該第２液体試料供給源に接続されかつ該第２液体試料供給源から供給される第２液体試料を該格納容器内に格納された媒体液体中に静電噴霧するための第２エレクトロスプレーノズル（ＥＳＮ２）を備えた第２噴霧手段とを
備える液中エレクトロスプレー装置。 A container for storing a medium liquid, a first liquid sample supply source for supplying a first liquid sample containing a predetermined compound, and a first liquid sample supply source connected to and supplied from the first liquid sample supply source A first spraying means having a first electrospray nozzle (ESN1) for electrostatically spraying one liquid sample into a medium liquid stored in the storage container and a second liquid sample containing a predetermined compound are supplied. The second liquid sample supply source and the second liquid sample connected to the second liquid sample supply source and supplied from the second liquid sample supply source into the medium liquid stored in the storage container A submerged electrospray apparatus comprising: a second spraying means including a second electrospray nozzle (ESN2) for performing the operation.
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