JP2003081884A - Method for performing chemical reaction occurring in solution, in solid - Google Patents

Method for performing chemical reaction occurring in solution, in solid

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Publication number
JP2003081884A
JP2003081884A JP2001275999A JP2001275999A JP2003081884A JP 2003081884 A JP2003081884 A JP 2003081884A JP 2001275999 A JP2001275999 A JP 2001275999A JP 2001275999 A JP2001275999 A JP 2001275999A JP 2003081884 A JP2003081884 A JP 2003081884A
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JP
Japan
Prior art keywords
solvent
solid
solution
medium
chemical reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2001275999A
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Japanese (ja)
Inventor
Masao Kaneko
正夫 金子
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Individual
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Individual
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Filing date
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Priority to JP2001275999A priority Critical patent/JP2003081884A/en
Publication of JP2003081884A publication Critical patent/JP2003081884A/en
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Classifications

    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

PROBLEM TO BE SOLVED: To provide a method for performing a chemical reaction occurring in a solution, in a solid. SOLUTION: This method for performing the chemical reaction occurring in the solution, in the solid is provided by using a natural or synthetic polymer material capable of becoming a solid containing a large amount of the solvent by cooling after making it a solution under heating as a medium, and performing the chemical reaction in the solid medium. This solvent-containing solid forms a molecular flask. As the natural or synthetic polymer material, a polysaccharide or protein is e.g. used, and as the solvent, an aqueous solvent is used. The solvent-containing solid can be used as a medium for a chemical reaction and chemical synthesis, medium for a microanalysis, medium for a combinatorial chemistry, etc.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、溶液中で起こる溶
液化学反応を、固体中で行わせる方法に関する。本発明
の方法は、化学反応や合成反応、太陽電池、燃料電池、
１次電池若しくは２次電池、水の電気分解、電気化学測
定や反応、ミクロ分析、コンビナトリアルケミストリ
ー、センサ、ラボラトリー・オン・チップスなどに好適
に用いることができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for carrying out a solution chemical reaction that occurs in a solution in a solid state. The method of the present invention includes chemical reaction, synthetic reaction, solar cell, fuel cell,
It can be suitably used for primary or secondary batteries, water electrolysis, electrochemical measurement and reaction, microanalysis, combinatorial chemistry, sensor, laboratory-on-chips and the like.

【０００２】[0002]

【従来の技術】従来、合成反応、触媒反応、重合反応、
センシング反応等の化学反応は、溶液中で起こるので、
これらの実施においては、液体を媒体に用いるのが一般
的であった。例えば電池等の電気化学反応や正・負電荷
の輸送を行わせる電気化学素子においては、水や有機溶
媒を使用する液体電解質を用いるのが基本である。2. Description of the Related Art Conventionally, synthetic reactions, catalytic reactions, polymerization reactions,
Since chemical reactions such as sensing reactions occur in solution,
In these practices, it was common to use liquids as the medium. For example, a liquid electrolyte using water or an organic solvent is basically used in an electrochemical element such as a battery for carrying out an electrochemical reaction or transporting positive and negative charges.

【０００３】しかして、電池やセンサなどにおいて液体
電解質を使用した場合は、電解液の漏洩や、小型化、薄
膜化の困難性等の問題があるため、当該液体電解質に代
わって、信頼性、取扱い容易性、効率向上等の観点か
ら、膜状の固体電解質の利用が検討されてきた。例え
ば、高分子固体電解質のように、編み目状の高分子マト
リックス中に液体電解質を包含せしめることによりイオ
ンを分散させたもの、あるいはイオン交換膜のように、
高分子固体膜中に液体を含ませたものなどが挙げられ
る。しかしながら、これら高分子電解質等においては、
本質的には、固体である高分子材料が主成分であるた
め、その固体中におけるイオンや分子の拡散は遅く、液
体中と同様な化学反応を行わせることは困難であった。However, when a liquid electrolyte is used in a battery, a sensor, or the like, there are problems such as leakage of the electrolyte solution, miniaturization, and difficulty in forming a thin film. Therefore, in place of the liquid electrolyte, reliability, The use of a membrane-shaped solid electrolyte has been studied from the viewpoints of ease of handling and improvement of efficiency. For example, as in a solid polymer electrolyte, in which a liquid electrolyte is contained in a knitted polymer matrix to disperse ions, or as in an ion exchange membrane,
An example is one in which a liquid is contained in a polymer solid film. However, in these polymer electrolytes and the like,
Essentially, since a solid polymer material is the main component, diffusion of ions and molecules in the solid is slow, and it is difficult to cause the same chemical reaction as in liquid.

【０００４】なお、一方では、多量の液体を含有したい
わゆる高分子ゲルは、従来より知られていたが、これら
は材料的には柔らかで崩れやすく、また強度も弱いため
任意の形状に成形して安定に用いることはできず、実用
上、問題があった。また当然のことながら、このゲル中
に含有された液体中におけるイオンや分子の反応挙動に
ついては、従来ほとんど検討はされておらず、なんらの
知見も存在しないといってよい。On the other hand, so-called polymer gels containing a large amount of liquid have been heretofore known, but since they are soft in terms of material and easily broken, and have weak strength, they are molded into an arbitrary shape. Therefore, it could not be used stably, and there was a problem in practical use. Further, as a matter of course, the reaction behavior of ions and molecules in the liquid contained in this gel has hardly been studied so far, and it can be said that there is no knowledge.

【０００５】[0005]

【発明が解決しようとする課題】かくして本発明の目的
は、液体を主成分として含有するものでありながら、そ
の外観は、安定でかつ任意の形態に成形することができ
る固体状の固体媒体材料を提供することであり、当該固
体媒体材料中で、通常の純液体中と全く同様な化学反応
を実施する方法を提供することである。Thus, although the object of the present invention is to contain a liquid as a main component, its appearance is stable and a solid solid medium material that can be molded into an arbitrary shape. And to provide a method for carrying out a chemical reaction in the solid medium material, which is exactly the same as in a normal pure liquid.

【０００６】[0006]

【課題を解決するための手段】本発明は以上の目的を達
成するためになされたもので、本発明に従えば、以下の
（１）〜（７）の発明が提供される。すなわち、The present invention has been made to achieve the above object, and the following inventions (1) to (7) are provided according to the present invention. That is,

【０００７】（１）の発明は、加熱下で溶液にした後、
冷却するとその溶媒を大量に含んだ含溶媒固体となるよ
うな天然又は合成の高分子材料の含溶媒固体を媒体とし
て用い、当該固体媒体中で化学反応を行わせることを特
徴とする、溶液化学反応の固体中における実施方法、で
ある。In the invention of (1), after being made into a solution under heating,
Solution chemistry, characterized in that a solvent-containing solid of a natural or synthetic polymer material that becomes a solvent-containing solid containing a large amount of the solvent when cooled is used as a medium and a chemical reaction is performed in the solid medium. The method for carrying out the reaction in solid form.

【０００８】（２）の発明は、加熱下で溶液にした後、
冷却するとその溶媒を大量に含んだ含溶媒固体となるよ
うな前記天然又は合成の高分子材料として多糖類又はタ
ンパク質を用いる（１）に記載の方法、である。In the invention of (2), after being made into a solution under heating,
The method according to (1), wherein a polysaccharide or protein is used as the natural or synthetic polymer material that becomes a solvent-containing solid containing a large amount of the solvent when cooled.

【０００９】（３）の発明は、前記溶媒が水系溶媒であ
る（１）又は（２）に記載の方法、である。The invention of (3) is the method according to (1) or (2), wherein the solvent is an aqueous solvent.

【００１０】（４）の発明は、前記含溶媒固体を膜状に
形成して用いる（１）〜（３）のいずれかに記載の方
法、である。The invention of (4) is the method according to any one of (1) to (3), wherein the solvent-containing solid is used in the form of a film.

【００１１】（５）の発明は、（４）に記載の含溶媒固
体の膜が、水の電気分解用の膜（隔膜）であるか、又は
前記膜を備えることを特徴とする太陽電池、燃料電池、
１次若しくは２次電池、又はセンサ、である。In the invention (5), the solvent-containing solid film according to (4) is a film (diaphragm) for electrolysis of water, or a solar cell comprising the film. Fuel cell,
It is a primary or secondary battery or a sensor.

【００１２】（６）の発明は、前記含溶媒固体中に電極
が挿入され、当該電極を備えた固体媒体中で化学反応を
行わせる（１）〜（４）いずれかに記載の方法、であ
る。The invention of (6) is the method according to any one of (1) to (4), wherein an electrode is inserted into the solvent-containing solid to cause a chemical reaction in a solid medium equipped with the electrode. is there.

【００１３】（７）の発明は、（１）〜（４）のいずれ
かに記載の含溶媒固体からなることを特徴とする化学反
応若しくは化学合成用媒体、ミクロ分析用媒体、コンビ
ナトリアルケミストリー用媒体、又はラボラトリー・オ
ン・チップス用媒体、である。The invention of (7) is characterized by comprising the solvent-containing solid described in any of (1) to (4), a medium for chemical reaction or chemical synthesis, a medium for microanalysis, a medium for combinatorial chemistry. , Or a medium for laboratory on chips.

【００１４】[0014]

【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

【００１５】本発明においては、基本的に、溶液化学反
応を行わせるための媒体として、加熱下で溶媒に溶解し
て溶液にした後、冷却するとその溶媒を大量に含んだ含
溶媒固体となるような天然又は合成の高分子材料の含溶
媒固体を用いることを特徴とする。In the present invention, basically, as a medium for carrying out a solution chemical reaction, the solvent-containing solid containing a large amount of the solvent is obtained by dissolving the solvent in a solvent under heating to form a solution. It is characterized by using a solvent-containing solid of such a natural or synthetic polymer material.

【００１６】すなわち本発明の特徴は、このように、加
熱下で溶媒中に溶解し、当該溶液を冷却した後に、ある
種の３次元ネットワークを作って固体化し、固体であり
ながらそのネットワークの内部に大量の当該溶媒を安定
に保持するような高分子材料を用いることにある。本発
明者の知見によれば、かかる含溶媒固体を用いた場合、
当該固体中に存在する溶媒に溶存したイオンや分子の拡
散や反応は、液体中と同様に挙動するのである。That is, the feature of the present invention is that, as described above, after dissolving in a solvent under heating and cooling the solution, a certain kind of three-dimensional network is formed and solidified. In particular, it is to use a polymer material that stably holds a large amount of the solvent. According to the knowledge of the present inventor, when such a solvent-containing solid is used,
Diffusion and reaction of ions and molecules dissolved in the solvent present in the solid behave like in liquid.

【００１７】本発明者らは、かる高分子材料からなる含
溶媒固体を、「分子フラスコ」と命名している。これ
は、当該含溶媒固体媒体においては、当該高分子の分子
が恐らく３次元分子ネットワークと思われる化学構造を
形成しているため、フラスコなどの容器を使用すること
無しに、それ自身で特定の固体形状を安定的に維持しう
るとともに、当該ネットワーク中に大量の溶媒が保持さ
れているので、当該固体に含有されている溶媒中では、
純液体中と実質的に同様な化学反応を実施することがで
きることに由来する。すなわち、当該含溶媒固体が、そ
の内部に液体を安定に保持しうるあたかもフラスコのよ
うな機能を有する、「分子から構成される分子サイズの
容器」という意味である。The present inventors have named a solvent-containing solid composed of such a polymer material as a "molecular flask". This is because, in the solvent-containing solid medium, the molecules of the polymer form a chemical structure that is considered to be a three-dimensional molecular network, so that the specific structure can be specified by itself without using a container such as a flask. A solid form can be stably maintained, and since a large amount of solvent is retained in the network, in the solvent contained in the solid,
This is because it is possible to carry out a chemical reaction substantially similar to that in a pure liquid. That is, it means that the solvent-containing solid has a function like a flask capable of stably holding a liquid inside, and is a “molecular-sized container composed of molecules”.

【００１８】本発明におけるこのような分子フラスコ
は、従来知られている柔らかで一定の形状を保ちがたい
高分子ゲルとは異なり、加熱溶解状態において、または
冷却する過程で、粘度が適宜増加した状態において、通
常の高分子材料の溶融加工のごとく、押出成形、射出成
形、流延成形、注型（キャスト）成形等により、ブロッ
ク状、膜状、シート状、板状、線状、棒状、繊維状等、
任意の形状のものとして成形できる。かつ、冷却固化後
は、その成形された形状を安定に保ち、例えば自立可能
な（self-standing）膜等として使用できる。なお、一
旦室温下に戻して冷却して固体化した後は、再び温度を
上げてもその形状、性質は大幅には変わらない。Unlike the conventionally known polymer gel which is hard to maintain a soft and constant shape, the molecular flask of the present invention has a viscosity increased appropriately in a heating and melting state or in a cooling process. In the state, like a usual polymer material melt processing, extrusion molding, injection molding, casting molding, cast molding, etc., block shape, film shape, sheet shape, plate shape, linear shape, rod shape, Fibrous, etc.
It can be molded into any shape. After cooling and solidification, the molded shape can be kept stable and can be used, for example, as a self-standing film. Note that, once the temperature is returned to room temperature, it is cooled and solidified, the shape and properties thereof do not change significantly even if the temperature is raised again.

【００１９】本発明において、分子フラスコを構成しう
る高分子材料（以下、「分子フラスコ材料」と称するこ
とがある。）としては、固体内部に溶媒を安定的に保持
できる構造、例えばマクロな構造全体にわたって３次元
ネットワークを作りうる、天然または合成の高分子材料
やその誘導体が用いられる。In the present invention, the polymer material capable of forming a molecular flask (hereinafter, sometimes referred to as "molecular flask material") has a structure capable of stably holding a solvent inside a solid, for example, a macro structure. A natural or synthetic polymer material or its derivative that can form a three-dimensional network throughout is used.

【００２０】かかる高分子材料としては、特に限定する
ものではないが、疎水的な主鎖と親水的な側鎖を持つ天
然又は合成の高分子材料又はその誘導体が好ましく、ま
た、３次元ネットワーを形成し、なおかつ安定な形状を
保持するためには、水素結合や他の共有結合が可能な官
能基、例えばカルボキシル基、水酸基、アミノ基、アミ
ド基、スルホン基などを有するものが好ましい。The polymer material is not particularly limited, but a natural or synthetic polymer material having a hydrophobic main chain and a hydrophilic side chain or a derivative thereof is preferable, and a three-dimensional network is also preferable. In order to form the compound and maintain a stable shape, those having a functional group capable of hydrogen bond or other covalent bond, for example, a carboxyl group, a hydroxyl group, an amino group, an amide group, a sulfone group and the like are preferable.

【００２１】かかる好ましい天然高分子又はその誘導体
としては、カラゲニン（carrageenan）、アガロース（a
garose）、寒天、キチン、キトサン、セルロース、デン
プン、アミロース、アミロペクチン、コンドロイチン、
コンドロイチン硫酸、マンナン、グルコマンナンなどの
多糖類やその誘導体；ゼラチン、コラーゲン、カゼイ
ン、アルブミン、フィブロイン、ケラチン、グロブリン
などのタンパク質やその誘導体；などが挙げられる。The preferred natural polymer or its derivative is carrageenan or agarose (a).
garose), agar, chitin, chitosan, cellulose, starch, amylose, amylopectin, chondroitin,
Examples thereof include polysaccharides such as chondroitin sulfate, mannan and glucomannan and derivatives thereof; proteins such as gelatin, collagen, casein, albumin, fibroin, keratin and globulin and derivatives thereof; and the like.

【００２２】また合成高分子としては、ポリアクリルア
ミド、ポリアクリル酸、ポリメタクリルアミド、ポリメ
タクリル酸、ポリビニルアルコール、ポリビニルピリジ
ン、ポリビニルスルホン酸、或いはアミノ化、スルホン
化、ヒドロキシル化したポリスチレン、或いはこれらを
部分的に架橋した高分子材料などが挙げられる。As the synthetic polymer, polyacrylamide, polyacrylic acid, polymethacrylamide, polymethacrylic acid, polyvinyl alcohol, polyvinyl pyridine, polyvinyl sulfonic acid, or aminated, sulfonated, hydroxylated polystyrene, or these. Partially cross-linked polymeric materials and the like can be mentioned.

【００２３】本発明において、これら高分子材料から含
溶媒固体を形成するには、当該高分子材料を所定の溶媒
に添加し、これを加熱・溶解して当該高分子材料の溶液
とする。In the present invention, in order to form a solvent-containing solid from these polymeric materials, the polymeric material is added to a predetermined solvent and heated and dissolved to form a solution of the polymeric material.

【００２４】溶媒としては、溶質である分子やイオン等
（金属元素、非金属元素、有機化合物分子、無機化合物
分子、錯化合物、陽イオン、陰イオン、錯イオン等）を
溶解して溶液とし、当該溶液中で、当該溶質の結合、置
換、分解、脱離、重合、酸化、還元等の化学反応や、分
子やイオンの輸送（拡散）等の化学過程を起こしうるも
のであれば、特に限定するものではない。As the solvent, solute molecules and ions (metal element, non-metal element, organic compound molecule, inorganic compound molecule, complex compound, cation, anion, complex ion, etc.) are dissolved to prepare a solution, It is particularly limited as long as it can cause a chemical reaction such as binding, substitution, decomposition, desorption, desorption, polymerization, oxidation and reduction of the solute and a chemical process such as transport (diffusion) of molecules and ions in the solution. Not something to do.

【００２５】例えば、水、メタノール、エタノール、イ
ソプロパノール、グリセリン、エチレングリコール、プ
ロピレングリコール、フェノール、クレゾール、キシレ
ノール、ベンジルアルコール等のアルコール；酢酸メチ
ル、酢酸エチル、プロピオン酸メチル、プロピオン酸エ
チル等のエステル；アセトン、メチルエチルケトン、ジ
エチルケトン、アセトフェノン等のケトン；ジエチルエ
ーテル、エチルブチルエーテル等のエーテル；ヘキサ
ン、ヘプタン、四塩化炭素、メチレンクロライド等の脂
肪族炭化水素；ベンゼン、トルエン、キシレン、ジクロ
ロベンゼン等の芳香族炭化水素等が好ましいものとして
挙げられる。これらは単独で又は２種以上を混合して使
用することができる。特に好ましくは、水、又は水を主
体としこれと混和又は混合しうる少量の、例えば５０質
量％以下、好ましくは３０質量％以下の、さらに好まし
くは１５質量％以下程度のメタノールやエタノール等の
有機溶媒との混合溶媒である。本発明においては、この
ような水又は水を主体とする溶媒を水系溶媒と称するこ
とにする。For example, water, alcohols such as methanol, ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, phenol, cresol, xylenol and benzyl alcohol; esters such as methyl acetate, ethyl acetate, methyl propionate and ethyl propionate; Acetone, methyl ethyl ketone, diethyl ketone, acetophenone, and other ketones; diethyl ether, ethyl butyl ether, and other ethers; hexane, heptane, carbon tetrachloride, methylene chloride, and other aliphatic hydrocarbons; benzene, toluene, xylene, dichlorobenzene, and other aromatic hydrocarbons Hydrocarbons are preferred. These may be used alone or in combination of two or more. Particularly preferably, water, or a small amount of water such as methanol or ethanol, which is mainly composed of water and can be mixed or mixed with it, for example, 50 mass% or less, preferably 30 mass% or less, more preferably 15 mass% or less. It is a mixed solvent with a solvent. In the present invention, such water or a solvent composed mainly of water will be referred to as an aqueous solvent.

【００２６】分子フラスコを構成しうる高分子材料に対
し、使用する水系溶媒等の溶媒は、得られる含溶媒固体
中に少なくとも２０質量％以上、好ましくは５０質量％
以上、さらに好ましくは８０質量％以上、一層好ましく
は９０質量％以上、より一層好ましくは９５質量％以
上、さらにより一層好ましくは９８質量％以上、最も好
ましくは９９質量％以上、９９．９９質量％以下であ
る。本発明において、溶媒を「大量に含んだ」含溶媒固
体とは、この程度の溶媒含有量を意味する。A solvent such as an aqueous solvent to be used is at least 20% by mass or more, preferably 50% by mass, in the obtained solvent-containing solid, based on the polymer material which can constitute the molecular flask.
Or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, most preferably 99% by mass or more, 99.99% by mass. It is the following. In the present invention, the solvent-containing solid “containing a large amount of solvent” means such a solvent content.

【００２７】上記高分子材料をこのような溶媒に添加し
て加熱し、当該高分子材料を溶媒に溶解して溶液とす
る。The polymeric material is added to such a solvent and heated to dissolve the polymeric material in the solvent to form a solution.

【００２８】加熱温度は、高分子材料の種類、添加量、
溶媒の種類等によって変わりうるが、通常４０〜２００
℃、好ましくは５０〜１５０℃、さらに好ましくは６０
〜１００℃程度である。また、加熱する手段は特に限定
するものではなく、オイルバスやウオーターバスによる
加熱、電気ヒーターによる加熱、近赤外線や遠赤外線を
用いる赤外線加熱、高周波加熱（マイクロ波加熱）（所
謂電子レンジ）等が採用できる。これらは、高分子材料
の種類や量に応じて適宜選択するが、例えば一般に高分
子材料の使用量が少なく、例えば１質量％以下程度の場
合は、電気ヒーター等による加熱だけで、充分に溶解が
可能であるが、例えば２質量％以上の場合は、電子レン
ジ等の高周波加熱の使用がより良好な結果を与える。な
お、溶媒としては上記したように、水単独使用の他、種
々の有機媒体と水との混合媒体である水系溶媒が好まし
く用いられる。The heating temperature depends on the type of polymer material, the amount added,
Although it may vary depending on the type of solvent, it is usually 40 to 200.
C, preferably 50 to 150 C, more preferably 60.
It is about 100 ° C. The heating means is not particularly limited, and heating by an oil bath or a water bath, heating by an electric heater, infrared heating using near infrared rays or far infrared rays, high frequency heating (microwave heating) (so-called microwave oven), etc. Can be adopted. These are appropriately selected according to the kind and amount of the polymer material, but, for example, when the amount of the polymer material used is generally small, for example, about 1% by mass or less, it is sufficiently dissolved by heating with an electric heater or the like. However, when the content is 2% by mass or more, the use of high-frequency heating such as a microwave oven gives better results. As described above, as the solvent, in addition to using water alone, an aqueous solvent which is a mixed medium of various organic media and water is preferably used.

【００２９】以上のごとくして、加熱溶解の後に、当該
溶液を冷却すると、その溶媒を大量に含んだ含溶媒固体
が得られる。すなわち、当該高分子材料は、ある種の３
次元ネットワークを作って固体化し、かつ、固体であり
ながら、そのネットワークの内部に大量の当該溶媒を安
定的に保持するのである。従って、この固体の中に含有
される溶媒中に溶存したイオンや分子の輸送過程（すな
わち、拡散係数により表示される。）は、純液体中と実
質的に同程度の挙動を示すので、純溶媒中の溶質と、同
様な化学反応を、当該固体中で行わせることができるの
である。As described above, when the solution is cooled after dissolution by heating, a solvent-containing solid containing a large amount of the solvent is obtained. That is, the polymer material is
A dimensional network is formed and solidified, and a large amount of the solvent is stably retained inside the network while being solid. Therefore, the transport process of ions and molecules dissolved in the solvent contained in this solid (that is, represented by the diffusion coefficient) behaves in a manner substantially similar to that in pure liquid. A similar chemical reaction with a solute in a solvent can occur in the solid.

【００３０】冷却温度は、特に限定するものではない
が、通常、−３０〜３５℃、好ましくは−１０〜３０
℃、さらに好ましくは０〜３０℃程度である。また冷却
方法は、自然放冷によってもよいし、または氷や冷却媒
体を用いる強制冷却のいずれでも構わない。The cooling temperature is not particularly limited, but is usually -30 to 35 ° C, preferably -10 to 30.
C., more preferably 0 to 30.degree. The cooling method may be natural cooling or forced cooling using ice or a cooling medium.

【００３１】本発明における含溶媒固体は、剛性も高
く、それ自身かなりの強度を有するものである。すでに
述べたように、本発明においては、分子フラスコを構成
しうる高分子材料を溶媒に添加・加熱溶解した後に、適
度な粘性を保持している状態で、通常の高分子材料の溶
融成形と同様な、射出成形、押出成形、流延（キャス
ト）成形、注型成形することができるが、また、適当な
基体（例えば電極等であってもよい。）上に、当該溶液
を刷毛塗りやスプレー又はスピンコート等により塗布し
たり、又はディッピング等により、当該基体上に薄膜を
形成することができる。The solvent-containing solid in the present invention has a high rigidity and has a considerable strength by itself. As described above, in the present invention, after adding a polymer material capable of constituting a molecular flask to a solvent and heating and dissolving it, while maintaining an appropriate viscosity, the melt molding of a usual polymer material is performed. Similarly, injection molding, extrusion molding, casting (cast) molding, and cast molding can be performed, but the solution may be brushed or applied onto a suitable substrate (eg, an electrode or the like). A thin film can be formed on the substrate by applying by spraying or spin coating, or by dipping.

【００３２】以上のごとく、加熱・溶解した液を、成形
してから冷却、固体化すれば、任意の形状に成形するこ
とができる。例えばブロック状、板状、薄膜状、線材
状、繊維状、或いは他の任意の形状を作ることができ
る。As described above, if the heated and melted liquid is molded, then cooled and solidified, it can be molded into an arbitrary shape. For example, a block shape, a plate shape, a thin film shape, a wire shape, a fiber shape, or any other shape can be formed.

【００３３】これらの任意の形状の固体中で純液体中と
同じ化学反応を行わせることができるので、実用上、次
の用途などが挙げられる。すなわち、本発明における含
溶媒固体を媒体として用いることにより、Since the same chemical reaction as in a pure liquid can be carried out in a solid having any of these shapes, it can be practically used for the following purposes. That is, by using the solvent-containing solid in the present invention as a medium,

【００３４】１）不安定な液体を扱うことなく、またフ
ラスコ、ビーカー、反応容器等の特別な容器を用いるこ
となく、固体の中で純液体中と同じ化学反応や合成反
応、或いは電気化学反応を行うことができる。従って工
業的に、安定な操作を安全に任意の場所で行わせること
ができる。1) The same chemical reaction, synthetic reaction, or electrochemical reaction in a solid as in a pure liquid without handling an unstable liquid and without using a special container such as a flask, a beaker, or a reaction container. It can be performed. Therefore, industrially, stable operation can be safely performed at any place.

【００３５】これらはミクロ分析用媒体、コンビナトリ
アルケミストリー用媒体、ラボラトリー・オン・チップ
ス用媒体などにも用いることができる。これらはまた、
授業や講習会などにおける化学関係の教材として、化学
教育上のデモンストレーションを行うための材料として
も用いられる。These can also be used as a medium for microanalysis, a medium for combinatorial chemistry, a medium for laboratory-on-chips and the like. These are also
It is also used as a chemistry-related teaching material in classes and workshops, as a material for demonstrating chemistry education.

【００３６】２）本発明における含溶媒固体を膜状に形
成した場合は、強度の高い固体膜中で純液体中と同じ速
度でイオンや分子の拡散及び／又は化学反応が起こるの
で、この膜を備えた色素増感型の太陽電池、種々の電気
化学センサ、発光プローブセンサ、燃料電池用電解質
膜、水の電気分解用隔膜、１次電池や２次電池の電解質
膜やレドックス剤用膜等に好適に適用できる。2) When the solvent-containing solid according to the present invention is formed into a film, the diffusion of ions and / or molecules and / or chemical reaction occurs at the same rate as in a pure liquid in a solid film having high strength. Dye-sensitized solar cells, various electrochemical sensors, luminescent probe sensors, electrolyte membranes for fuel cells, membranes for electrolysis of water, electrolyte membranes for primary and secondary batteries, membranes for redox agents, etc. Can be suitably applied to.

【００３７】本発明における含溶媒固体は、液体の蒸散
速度が遅く、通常の空気下で用いることができるが、液
体の蒸発をさらに抑制したい場合には、本固体の表面を
プラスチック膜などで被覆してやることにより、液体の
蒸発を抑えて安定に用いることができる。The solvent-containing solid in the present invention has a low evaporation rate of liquid and can be used under normal air. However, in order to further suppress evaporation of the liquid, the surface of the solid is coated with a plastic film or the like. By doing so, evaporation of the liquid can be suppressed and the liquid can be used stably.

【００３８】[0038]

【作用】本発明における含溶媒固体が、このように液体
を主成分としながら全体としては安定な固体状態を保つ
理由については、次のようであろうと推定される。すな
わち、本発明における分子フラスコ材料は、加熱下で溶
媒に溶解した後、恐らく冷却の過程で分子からなる強固
な３次元ネットワークを形成する。これが見かけ上は安
定な固体を形成しながら、その内部においては、当該ネ
ットワーク中に大量の液体（溶媒）を保持し、当該保持
された溶媒は純液体と同様な性質を保っている理由と考
えられる。The reason why the solvent-containing solid in the present invention maintains a stable solid state as a whole while containing a liquid as the main component is presumed to be as follows. That is, the molecular flask material in the present invention, after being dissolved in a solvent under heating, probably forms a strong three-dimensional network of molecules in the course of cooling. This is considered to be the reason why a large amount of liquid (solvent) is retained inside the network while forming an apparently stable solid, and the retained solvent retains the same properties as a pure liquid. To be

【００３９】例えば、アガロースやカラゲニン或いは他
の多糖類では、多糖の主鎖がヘリックスまたはダブルヘ
リックス構造をとり、これが分子フラスコのための適切
な大きさの堅い網目を構成するのに寄与していると推定
される。また、側鎖にあるイオン性官能基が、溶媒とし
て水系溶媒を用いた場合に、これを保持するのに寄与す
ると考えられる。さらにこのような３次元ネットワーク
は、水素結合により安定に保持されているとも推定され
る。なお、分子間架橋が起こるように、高分子側鎖にカ
ルボキシル基、アミノ基、アミド基、水酸基、ピリジル
基、ビニル基などを導入し、溶解時に２官能性架橋剤を
共存させて分子間架橋により、３次元ネットワーク構造
を作らせることも有効な手段であると考えられる。For example, in agarose, carrageenan or other polysaccharides, the backbone of the polysaccharide has a helix or double helix structure, which contributes to the construction of a rigid mesh of suitable size for the molecular flask. It is estimated to be. Further, it is considered that the ionic functional group in the side chain contributes to holding the ionic functional group when the aqueous solvent is used as the solvent. Furthermore, it is presumed that such a three-dimensional network is stably held by hydrogen bonds. In order to cause intermolecular crosslinking, a carboxyl group, an amino group, an amide group, a hydroxyl group, a pyridyl group, a vinyl group or the like is introduced into the side chain of the polymer, and a bifunctional crosslinking agent is allowed to coexist during the dissolution to cause the intermolecular crosslinking. Therefore, creating a three-dimensional network structure is also considered to be an effective means.

【００４０】[0040]

【実施例】以下、本発明を実施例により詳細に説明する
が、本発明の技術的範囲は、なんらこれらに限定される
ものでない。The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited to these.

【００４１】〔実施例１〕純水を溶媒とし、この中に１
質量％のアガロース粉末を添加し、さらにレドックス反
応分子として、Ｒｕ錯体であるトリス(２，２’-ジピリ
ジン)ルテニウム(ＩＩ)２塩化物（以下、Ｒｕ(ｂｐｙ)3
2+と略記する。）を濃度が０．５ｍＭ（Ｍ＝ｍｏｌｄｍ
-3）となるように溶解し、また電解質として硝酸カリウ
ム（ＫＮＯ 3）を０．１Ｍになるように溶解した。[Example 1] Pure water was used as a solvent, and 1
Add% by weight agarose powder and add redox solution.
As the responsive molecule, the Ru complex tris (2,2'-dipyrrole) is used.
Gin) ruthenium (II) dichloride (hereinafter Ru (bpy)3
2+Is abbreviated. ) At a concentration of 0.5 mM (M = moldm
-3), And potassium nitrate as the electrolyte.
Mu (KNO 3) Was dissolved to have a concentration of 0.1M.

【００４２】この混合液を８０℃に加熱してアガロース
を完全に溶解した。当該溶液状態のものに電導性ガラス
(ＩＴＯ)作用極、銀−塩化銀参照極及び白金対極を挿入
し、このまま室温下まで冷却して全体を固化させ、含溶
媒固体を得た。This mixed solution was heated to 80 ° C. to completely dissolve the agarose. Conductive glass in the solution state
A (ITO) working electrode, a silver-silver chloride reference electrode, and a platinum counter electrode were inserted, and the whole was solidified by cooling to room temperature to obtain a solvent-containing solid.

【００４３】当該含溶媒固体について固体状態のまま作
用極の電位を掃引してサイクリックボルタモグラムを測
定したところ、図１に示したように、溶媒である水中で
測定したものと全く同様なボルタモグラムが得られた。When the cyclic voltammogram was measured by sweeping the potential of the working electrode in the solid state of the solvent-containing solid, a voltammogram exactly the same as that measured in water as the solvent was obtained as shown in FIG. Was obtained.

【００４４】〔実施例２〕実施例１において、作用極電
位を０から１．３Ｖ(ｖｓ．Ａｇ／ＡｇＣｌ)にステップ
させ、そのときの電流値からＲｕ錯体の拡散係数（Ｄ）
を測定した。Ｄは、Ｒｕ錯体濃度によって異なるが、濃
度２〜１０ｍＭの範囲では、６〜８×１０ -6ｃｍ2ｓ-1
であり、純水中の拡散係数よりかえって大きかった。[Example 2] In Example 1, the working electrode
Step from 0 to 1.3V (vs. Ag / AgCl)
And the diffusion coefficient (D) of the Ru complex from the current value at that time.
Was measured. D depends on the Ru complex concentration, but
In the range of 2 to 10 mM, 6 to 8 × 10 -6cm2s-1
And was larger than the diffusion coefficient in pure water.

【００４５】〔比較例１〕カチオン交換体として電気分
解や燃料電池に膜としてよく用いられるパーフルオロ陽
イオン交換膜であるナフィオン（デュポン社商標）の膜
をそのアルコール溶液からＩＴＯ電極上にキャスト法で
被覆形成した。Comparative Example 1 A membrane of Nafion (trademark of DuPont), which is a perfluoro cation exchange membrane often used as a membrane in electrolysis or a fuel cell as a cation exchanger, is cast from its alcohol solution onto an ITO electrode. To form a coating.

【００４６】この膜中に、Ｒｕ(ｂｐｙ)3 2+を水溶液か
ら吸着し、これをＫＮＯ3水溶液につけて実施例２と同
様な方法により拡散係数を測定した。In this film, Ru (bpy) 3 2+ was adsorbed from an aqueous solution, and this was immersed in a KNO 3 aqueous solution, and the diffusion coefficient was measured by the same method as in Example 2.

【００４７】この結果、ナフィオン膜中のＤは、１０
-10ｃｍ2ｓ-1であって、本発明における固体媒体中にお
ける拡散係数値よりも、４〜５桁も低い値であることが
わかった。すなわち、本発明の含溶媒固体材料は、既存
のカチオン交換体等の膜材料と異なり、大量に含有され
ている溶媒中に溶解させたイオンや分子が、純溶液中と
同じ速度で拡散できる極めて優れた材料であることが示
される。As a result, D in the Nafion film was 10
It was found to be −10 cm 2 s −1 , which is 4 to 5 orders of magnitude lower than the diffusion coefficient value in the solid medium of the present invention. That is, the solvent-containing solid material of the present invention differs from existing membrane materials such as cation exchangers in that ions and molecules dissolved in a large amount of solvent can diffuse at the same rate as in a pure solution. It is shown to be an excellent material.

【００４８】〔実施例３〕水溶媒として２質量％のカラ
ゲニンを加温下で溶解し、これにＲｕ(ｂｐｙ)3 2 +を１
０μＭ、またメチルビオロゲン(以下、ＭＶ2+と表記す
る。)を０から１０ｍＭの範囲となるようにそれぞれ溶
解し、この溶液を冷却して異なる濃度のＭＶ 2+を含有す
る５種類の含溶媒固体を得た。Example 3 As a water solvent, 2% by mass of color was used.
Genin is dissolved under heating, and Ru (bpy) is added to it.3 2 +1
0 μM, methyl viologen (hereinafter MV2+Is written as
It ) In the range of 0 to 10 mM.
Then, the solution is cooled and MV of different concentrations 2+Contains
Five kinds of solvent-containing solids were obtained.

【００４９】Ｒｕ錯体の光励起状態からＭＶ2+への電子
移動反応速度を求めるために、各含溶媒固体試料につい
てＲｕ錯体の光励起状態からの発光（極大が６０３ｎｍ
のリン光）強度（Ｉ）を測定し、ＭＶ2+が存在しないと
きの発光強度（Ｉ0）と（Ｉ）の発光強度の相対値（Ｉ0
／Ｉ）を、ＭＶ2+濃度に対してプロットすると直線とな
った。In order to determine the electron transfer reaction rate from the photoexcited state of the Ru complex to MV 2+ , the emission from the photoexcited state of the Ru complex (maximum 603 nm) was obtained for each solvent-containing solid sample.
The phosphorescence intensity (I) of (I) is measured, and the relative value (I 0 ) of the emission intensity (I 0 ) in the absence of MV 2+ and the emission intensity of (I).
/ I) was plotted against the MV 2+ concentration to give a straight line.

【００５０】また、発光寿命（τ）を単光子計測法によ
り測定し、ＭＶ2+が存在しないときの発光寿命（τo）
との相対値（τo/τ）を、同じグラフにプロットする
と、Ｉ0／Ｉと同じ直線上に乗ることがわかった。The emission lifetime (τ) was measured by the single photon measurement method, and the emission lifetime (τo) when MV 2+ was not present was measured.
When the relative values (τo / τ) with and were plotted on the same graph, it was found that they were on the same straight line as I 0 / I.

【００５１】以上のことから、本含溶媒固体中において
は、純水中と同様にＲｕ錯体とＭＶ 2+とが互いに拡散、
衝突して反応する動的機構が起こっていることが明らか
である。この傾きと、ＭＶ2+が存在しないときの発光寿
命（τo）から、２次反応速度定数として４×１０9ｄｍ
3ｍｏｌ-1ｓ-1が得られた。この反応速度定数の値は、
純水中の反応速度定数より１桁大きかった．すなわち、
本発明における固体媒体中においては、純水中と同じ
か、またはかえって大きな反応速度で、反応を行わせる
ことができることがわかる。From the above, in the solvent-containing solid of the present invention,
Is the Ru complex and MV as in pure water. 2+And spread each other,
It is clear that a dynamic mechanism of collision and reaction is occurring
Is. This inclination and MV2+Luminous life when there is no
From life (τo), 4 × 10 as second-order reaction rate constant9dm
3mol-1s-1was gotten. The value of this reaction rate constant is
It was an order of magnitude larger than the reaction rate constant in pure water. That is,
In the solid medium of the present invention, the same as in pure water
Or, rather, let the reaction proceed at a high reaction rate
You can see that you can.

【００５２】〔実施例４〕アガロースの代わりにポリア
クリルアミドを用い、またＲｕ(ｂｐｙ)3 2+の代わりに
フェロシアン化カリウムを用いたほかは、実施例１と同
様な実験を行い、含溶媒固体を得た。この含溶媒固体中
でサイクリックボルタモグラムを測定したところ、純水
中と同様なボルタモグラムが得られた。Example 4 The same experiment as in Example 1 was conducted except that polyacrylamide was used in place of agarose, and potassium ferrocyanide was used in place of Ru (bpy) 3 2+. Obtained. When the cyclic voltammogram was measured in this solvent-containing solid, a voltammogram similar to that in pure water was obtained.

【００５３】〔実施例５〕１００ｍｌのビーカー中でア
ガロース１ｇを溶媒である純水１００ｇ中に入れ、加熱
してアガロースを完全に溶解した後、室温下で冷却して
固体化し含溶媒固体を得た。Example 5 In a 100 ml beaker, 1 g of agarose was placed in 100 g of pure water as a solvent and heated to completely dissolve the agarose, followed by cooling at room temperature to solidify to obtain a solvent-containing solid. It was

【００５４】当該含溶媒固体にメチルオレンジ水溶液の
数滴を注入したところ、メチルオレンジは拡散し、固体
全体はメチルオレンジの黄色を呈した。ビーカーを取り
去って固体のブロックを取り出し、これに濃塩酸１ｍｌ
を注入したところ、濃塩酸は固体中に拡散し、固体全体
が酸性となってメチルオレンジは赤色に変化することが
認められた。When a few drops of an aqueous methyl orange solution were injected into the solvent-containing solid, the methyl orange diffused and the whole solid had a yellow color of methyl orange. Remove the beaker, remove the solid block, and add 1 ml of concentrated hydrochloric acid to it.
It was confirmed that concentrated hydrochloric acid diffused into the solid, and the whole solid became acidic and methyl orange turned red.

【００５５】〔実施例６〕カラゲニン４質量％を水中に
添加し、電子レンジで注意深く加熱して溶液状態とし
た。当該溶液を室温下で冷却して粘度の高い状態となっ
たときに延伸して、直径２ｍｍ、長さ５０ｃｍの線材を
作製し、さらに冷却して固体化した。[Example 6] 4% by mass of carrageenin was added to water and carefully heated in a microwave oven to prepare a solution state. When the solution was cooled at room temperature to reach a high viscosity state, it was stretched to prepare a wire rod having a diameter of 2 mm and a length of 50 cm, which was further cooled and solidified.

【００５６】この線材の一端よりメチルオレンジ水溶液
をシリンジにて注入したところ、メチルオレンジは拡散
して線材全体が黄色となった。次に濃塩酸を端から注入
したところ、線材に含まれた液全体が酸性となり、線材
全体のメチルオレンジは、赤に変色することが観察され
た。When a methyl orange aqueous solution was injected from one end of this wire rod with a syringe, the methyl orange was diffused and the whole wire rod became yellow. Next, when concentrated hydrochloric acid was injected from the end, it was observed that the entire liquid contained in the wire rod became acidic and the methyl orange of the entire wire rod turned red.

【００５７】〔実施例７〕フッ素ドープしたＳｎＯ2透
明電極上に、二酸化チタン(Ｐ−２５、日本アエロジル
社製)微粒子粉末のコロイド水溶液をスピンコーティン
グし、４５０℃で３０分間焼成して薄膜化した。続いて
二酸化チタンコロイド水溶液をスピンコーティングして
１００℃で３０分間焼成した。以上のスピンコーティン
グ、１００℃焼成の工程を繰り返し行って、９μｍ厚さ
の二酸化チタン多孔質薄膜とした後、最後にもう一度ス
ピンコーティング、４５０℃、３０分間焼成を行った。Example 7 A colloidal aqueous solution of fine particles of titanium dioxide (P-25, manufactured by Nippon Aerosil Co., Ltd.) was spin-coated on a fluorine-doped SnO 2 transparent electrode and baked at 450 ° C. for 30 minutes to form a thin film. did. Subsequently, an aqueous titanium dioxide colloid solution was spin-coated and baked at 100 ° C. for 30 minutes. The above steps of spin coating and baking at 100 ° C. were repeated to form a titanium dioxide porous thin film having a thickness of 9 μm, and finally, spin coating was performed again and baking was performed at 450 ° C. for 30 minutes.

【００５８】このようにして得た二酸化チタン多孔質薄
膜を、ビス（４，４’−ジカルボキシビス−２，２’−
ジピリジン）Ｒｕ（ＩＩ）チオシアナート色素のエタノ
ール溶液に浸漬して色素を多孔質膜中に吸着させた。The titanium dioxide porous thin film thus obtained was treated with bis (4,4'-dicarboxybis-2,2'-
The dye was immersed in an ethanol solution of dipyridine) Ru (II) thiocyanate dye to adsorb the dye in the porous film.

【００５９】別にカラゲニン１質量％を含む水を加熱し
て溶液とし、この溶液にヨウ化カリウムとヨウ素がそれ
ぞれ濃度０．５Ｍと０．０５Ｍになるように溶解し、こ
の溶液に上記の色素を吸着した二酸化チタン膜を浸漬し
た。カラゲニン溶液を二酸化チタン膜に吸着して、溶液
から取り出した後に、対極として白金を被覆したガラス
板を二酸化チタン膜の上に乗せ、圧着して電池とした。
この固体膜を用いた色素増感太陽電池は、約１％の変換
効率で太陽光を電力に変換することが確認された。Separately, water containing 1% by mass of carrageenin was heated to form a solution, and potassium iodide and iodine were dissolved in the solution to a concentration of 0.5 M and 0.05 M, respectively, and the above dye was added to the solution. The adsorbed titanium dioxide film was immersed. After the carrageenin solution was adsorbed on the titanium dioxide film and taken out of the solution, a glass plate coated with platinum as a counter electrode was placed on the titanium dioxide film and pressure-bonded to obtain a battery.
It was confirmed that the dye-sensitized solar cell using this solid film converts sunlight into electric power with a conversion efficiency of about 1%.

【００６０】〔実施例８〕１０質量％のポリアクリルア
ミドを水に入れて加熱下で溶解し、これにＲｕ(ｂｐｙ)
3 2+が１０μＭ濃度になるように添加した。Example 8 10% by mass of polyacrylamide was put in water and dissolved under heating, and Ru (bpy) was added thereto.
3 2+ was added to a 10μM concentration.

【００６１】室温下で冷却して粘度が高い状態になった
ものをガラス板上にキャストしてさらに冷却し、厚さ約
１０μｍの薄膜を得た。The material cooled to room temperature and having a high viscosity was cast on a glass plate and further cooled to obtain a thin film having a thickness of about 10 μm.

【００６２】この固体膜中のＲｕ錯体からの発光は、共
存する酸素分子によって純水中と同様に消光した。相対
発光強度の酸素濃度依存性の検量線を予め作製すること
により、未知の酸素濃度を発光で測定できる発光プロー
ブセンサとして用いることができた。The light emission from the Ru complex in this solid film was quenched by coexisting oxygen molecules as in pure water. By preparing in advance a calibration curve of oxygen concentration dependence of relative luminescence intensity, it was possible to use as a luminescence probe sensor capable of measuring unknown oxygen concentration by luminescence.

【００６３】[0063]

【発明の効果】本発明によれば、液状の溶媒を主成分と
して含有するものでありながら、その外観は、安定でか
つ任意の形状に成形することができる含溶媒固体からな
る媒体が提供され、当該固体媒体中において、通常の純
液体中と全く同様な化学反応や化学過程を実施すること
ができるのでその産業上の利用可能性は、きわめて大き
いと言わざるを得ない。EFFECTS OF THE INVENTION According to the present invention, there is provided a medium composed of a solvent-containing solid which contains a liquid solvent as a main component but has a stable appearance and can be molded into an arbitrary shape. Since it is possible to carry out the same chemical reaction and chemical process in the solid medium as in the normal pure liquid, it must be said that its industrial applicability is extremely large.

【図面の簡単な説明】[Brief description of drawings]

【図１】Ｒｕ(ｂｐｙ)3 2+水溶液含有アガロース固体媒
体のサイクリックボルタモグラム図である。FIG. 1 is a cyclic voltammogram diagram of an agarose solid medium containing a Ru (bpy) 3 2+ aqueous solution.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０１Ｎ 27/27 Ｈ０１Ｍ 2/16 Ｐ ５Ｈ０２６ Ｈ０１Ｌ 31/04 14/00 Ｐ ５Ｈ０３２ Ｈ０１Ｍ 2/16 Ｇ０１Ｎ 27/46 Ａ 14/00 Ｈ０１Ｌ 31/04 Ｚ Ｆターム(参考） 2G054 BB12 BB13 CA08 CE02 CE08 EA01 JA06 4H006 AA02 AC90 5F051 AA14 5G301 CD01 CE01 5H021 EE01 EE02 EE17 5H026 AA06 BB01 5H032 AA00 AA06 CC06 EE04 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) G01N 27/27 H01M 2/16 P 5H026 H01L 31/04 14/00 P 5H032 H01M 2/16 G01N 27/46 A 14/00 H01L 31/04 Z F term (reference) 2G054 BB12 BB13 CA08 CE02 CE08 EA01 JA06 4H006 AA02 AC90 5F051 AA14 5G301 CD01 CE01 5H021 EE01 EE02 EE17 5H026 AA06 BB01 5H032 AA00EEA06 CC06

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 加熱下で溶液にした後、冷却するとその
溶媒を大量に含んだ含溶媒固体となるような天然又は合
成の高分子材料の含溶媒固体を媒体として用い、当該固
体媒体中で化学反応を行わせることを特徴とする溶液化
学反応の固体中における実施方法。1. A solvent-containing solid of a natural or synthetic polymer material, which is a solvent-containing solid containing a large amount of the solvent when the solution is heated and then cooled, is used in the solid medium. A method for carrying out a solution chemical reaction in a solid, which comprises causing a chemical reaction. 【請求項２】 加熱下で溶液にした後、冷却するとその
溶媒を大量に含んだ含溶媒固体となるような前記天然又
は合成の高分子材料として多糖類又はタンパク質を用い
る請求項１に記載の方法。2. The polysaccharide or protein is used as the natural or synthetic polymer material, which becomes a solvent-containing solid containing a large amount of the solvent when the solution is heated and then cooled. Method. 【請求項３】 前記溶媒が水系溶媒である請求項１又は
２に記載の方法。3. The method according to claim 1, wherein the solvent is an aqueous solvent. 【請求項４】 前記含溶媒固体を膜状に形成して用いる
請求項１〜３のいずれかに記載の方法。4. The method according to claim 1, wherein the solvent-containing solid is used in the form of a film. 【請求項５】 請求項４に記載の含溶媒固体の膜が、電
気分解用の膜であるか、又は前記膜を備えることを特徴
とする太陽電池、燃料電池、１次若しくは２次電池又は
センサ。5. The solvent-containing solid film according to claim 4, which is a film for electrolysis, or comprises the film, a solar cell, a fuel cell, a primary or secondary battery, or Sensor. 【請求項６】 前記含溶媒固体中に電極が挿入され、当
該電極を備えた固体媒体中で化学反応を行わせる請求項
１〜４のいずれかに記載の方法。6. The method according to claim 1, wherein an electrode is inserted into the solvent-containing solid, and a chemical reaction is carried out in a solid medium equipped with the electrode. 【請求項７】 請求項１〜４のいずれかに記載の含溶媒
固体からなることを特徴とする化学反応若しくは化学合
成用媒体、ミクロ分析用媒体、コンビナトリアルケミス
トリー用媒体、又はラボラトリー・オン・チップス用媒
体。7. A medium for chemical reaction or chemical synthesis, a medium for microanalysis, a medium for combinatorial chemistry, or a laboratory-on-chips, comprising the solvent-containing solid according to any one of claims 1 to 4. Medium for use.
JP2001275999A 2001-09-12 2001-09-12 Method for performing chemical reaction occurring in solution, in solid Pending JP2003081884A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005071688A (en) * 2003-08-21 2005-03-17 Koa Corp Solid dye-sensitized solar cell and manufacturing method thereof
WO2008007468A1 (en) * 2006-07-10 2008-01-17 Toto Ltd. Electrolyte-containing sheet for use in specific detection of analyte using photocurrent, and, employing the sheet, method of detection, sensor unit and measuring apparatus
JP2008192770A (en) * 2007-02-02 2008-08-21 Toto Ltd Sensor chip to be used for specifically detecting test substance using photocurrent, and measuring apparatus using the same
JP2009231224A (en) * 2008-03-25 2009-10-08 Hitachi Zosen Corp Photoelectric conversion element, and manufacturing method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1040957A (en) * 1996-07-25 1998-02-13 Fujitsu Ltd Solid electrolytic battery
JP2001210359A (en) * 2000-01-27 2001-08-03 Toyota Motor Corp Lithium ion second battery
JP2001243985A (en) * 2000-02-29 2001-09-07 Hitachi Maxell Ltd Polymer electrolyte battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1040957A (en) * 1996-07-25 1998-02-13 Fujitsu Ltd Solid electrolytic battery
JP2001210359A (en) * 2000-01-27 2001-08-03 Toyota Motor Corp Lithium ion second battery
JP2001243985A (en) * 2000-02-29 2001-09-07 Hitachi Maxell Ltd Polymer electrolyte battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005071688A (en) * 2003-08-21 2005-03-17 Koa Corp Solid dye-sensitized solar cell and manufacturing method thereof
JP4514420B2 (en) * 2003-08-21 2010-07-28 コーア株式会社 Method for producing solid dye-sensitized solar cell
WO2008007468A1 (en) * 2006-07-10 2008-01-17 Toto Ltd. Electrolyte-containing sheet for use in specific detection of analyte using photocurrent, and, employing the sheet, method of detection, sensor unit and measuring apparatus
JP2008192770A (en) * 2007-02-02 2008-08-21 Toto Ltd Sensor chip to be used for specifically detecting test substance using photocurrent, and measuring apparatus using the same
JP2009231224A (en) * 2008-03-25 2009-10-08 Hitachi Zosen Corp Photoelectric conversion element, and manufacturing method thereof

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