JP2005274146A - Metal ion detection film, its manufacturing method, and metal ion quantification method using it - Google Patents
Metal ion detection film, its manufacturing method, and metal ion quantification method using it Download PDFInfo
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本発明は、金属イオンの比色分析あるいは蛍光分析等の発光分析に用いられる試薬を微粒子でメンブランフィルターに担持させた、簡易分析に適した金属イオン検出フィルム、その製造方法及びそれを用いた金属イオン定量方法に関するものである。 The present invention relates to a metal ion detection film suitable for simple analysis, in which a reagent used for luminescence analysis such as colorimetric analysis or fluorescence analysis of metal ions is supported on a membrane filter, a method for producing the same, and a metal using the same The present invention relates to an ion determination method.
比色分析法や蛍光分析法等の発光分析法は、光の吸収や発光の変化や濃淡から化学物質を特定し、その濃度を簡易に計測する手法として、環境分析、金属分析、生理活性物質の定量などに広範に応用されている。分析対象物質と反応して吸光や発光の変化を起こす多数の分析試薬が開発されているが、そのうちの多くはアゾ色素に代表される疎水性の芳香族化合物や多環状芳香族化合物を含み、有機溶媒には溶けるが水に不溶性又は難溶性であるものである。そのため、このような非水溶性又は難水溶性試薬についてはスルホン化や４級アンモニウム塩への誘導体化、界面活性剤の添加等により水溶性化が試みられている。 Luminescence analysis methods such as colorimetric analysis and fluorescence analysis are methods for identifying chemical substances from light absorption, changes in light emission, and light intensity, and for easily measuring their concentrations as environmental analysis, metal analysis, and physiologically active substances. It has been widely applied to the determination of Numerous analytical reagents have been developed that react with analytes to cause changes in light absorption and luminescence, but many of them contain hydrophobic aromatic compounds and polycyclic aromatic compounds typified by azo dyes, It is soluble in organic solvents but insoluble or sparingly soluble in water. For this reason, attempts have been made to make such water-insoluble or poorly water-soluble reagents water-soluble by sulfonation, derivatization to quaternary ammonium salts, addition of surfactants, and the like.
しかし、このように水溶性試薬は、その種類が制限され、また、界面活性剤の添加は分析に際して妨害を起こすおそれがあるし、また、溶液系の光透過、発光を計測原理とするため、汚濁や着色した検液試料の分析には不向きである。
また、非水溶性又は難水溶性試薬を有機溶媒に溶かして、水溶液と振り混ぜることにより目的物質を溶媒抽出した後、有機溶媒相を比色又は蛍光分析する方法も知られているが、この方法は有害で可燃性の有機溶媒を多量に用いる必要があるし、また、抽出分離操作が煩雑である。
However, the type of the water-soluble reagent is limited as described above, and the addition of the surfactant may cause interference in the analysis, and the measurement principle is light transmission and luminescence of the solution system. It is not suitable for analysis of contaminated or colored test samples.
Also known is a method in which a water-insoluble or poorly water-soluble reagent is dissolved in an organic solvent and the target substance is subjected to solvent extraction by shaking with an aqueous solution, followed by colorimetric or fluorescence analysis of the organic solvent phase. The method requires the use of a large amount of harmful and flammable organic solvents, and the extraction and separation operation is complicated.
一方、スペーサー基を介してポリマーに結合したイオン認識基質を多孔質のウェブに組み込んだ比色分析用材が知られている（特許文献１参照）。 On the other hand, a colorimetric material is known in which an ion recognition substrate bonded to a polymer via a spacer group is incorporated into a porous web (see Patent Document 1).
ところで、有害化学物質による汚染と健康被害は、産業界のみならず一般社会に重大な関心事として深く浸透し、環境保全のため、鉱工業排水や河川水、飲料水などに含まれる有害な重金属イオンなどの金属イオンのモニターは産業上の重要課題とされ、このような金属イオンを、特殊な装置を用いることなく分析現場で速やかに検出できる、簡便で汎用性のある計測技術の開発が急務となってきている。
本発明の課題は、このような事情の下、前記の、ポリマーに結合させたイオン認識基質を用いた従来の比色分析用材とはタイプが異なるものであって、金属イオンを簡便に分析現場等で検出することができる金属イオン検出用材、その製造方法、及びそれを用いた金属イオン定量方法を提供することにある。
By the way, pollution and health hazards caused by hazardous chemicals have deeply penetrated into the general public as well as the industrial world. To protect the environment, harmful heavy metal ions contained in industrial wastewater, river water, drinking water, etc. The monitoring of metal ions such as these is considered an important industrial issue, and there is an urgent need to develop a simple and versatile measurement technology that can quickly detect such metal ions at the analysis site without using special equipment. It has become to.
Under such circumstances, the problem of the present invention is that the type is different from the conventional colorimetric analysis material using an ion recognition substrate bonded to a polymer, and metal ions can be easily analyzed in the field. An object of the present invention is to provide a metal ion detection material that can be detected by a method, a manufacturing method thereof, and a metal ion determination method using the same.
本発明者らは、前記した好ましい特性を有する金属イオン検出用材を開発するために種々研究を重ねた結果、非水溶性又は難水溶性で、親水性溶媒に可溶性の金属イオン検出試薬を、親水性溶媒に溶解し、これを水と混合攪拌して生成させた金属イオン検出試薬の微粒子、例えばナノレベルないしサブミクロンレベルの微粒子の分散液を、メンブレンフィルターでろ過したり、また該フィルターに含浸させたりすることにより、該微粒子を該フィルターに被覆させて薄膜化しうることを見出し、この知見に基づいて本発明をなすに至った。 The inventors of the present invention have made various studies in order to develop a metal ion detection material having the above-described preferable characteristics. As a result, a water-insoluble or sparingly water-soluble metal ion detection reagent soluble in a hydrophilic solvent has been developed. Metal ion detection reagent fine particles, for example, nano-level to sub-micron level dispersions, dissolved in water-soluble solvents and mixed and stirred, are filtered with a membrane filter or impregnated into the filter In other words, it was found that the fine particles can be coated on the filter to form a thin film, and the present invention has been made based on this finding.
すなわち、本発明は、以下のとおりのものである。
（１）非水溶性又は難水溶性で、親水性溶媒に可溶性である金属イオン検出試薬の微粒子をメンブレンフィルターに膜状に被覆させてなる金属イオン検出フィルム。
（２）金属イオン検出試薬が、金属イオンと錯体を形成して発色し、金属イオンの濃度に応じて色調及び／又はその強度を変化させるものである前記（１）記載の金属イオン検出フィルム。
（３）金属イオン検出試薬が、金属イオンと錯体を形成して発光し、金属イオンの濃度に応じて発光の色調及び／又はその強度を変化させるものである前記（１）記載の金属イオン検出フィルム。
（４）メンブレンフィルターが、網目状繊維からなる不織布、フィブリル化ポリマーシート、ファイバーシート、溶液キャスト多孔質ポリマーシート、延伸多孔性フィルム、放射線照射多孔性フィルム、多孔質セラミックスシート及び多孔質ガラスシートの中から選ばれた少なくとも１種であって、孔径１０〜１０００ｎｍの範囲の細孔を有するものである前記（１）、（２）又は（３）記載の金属イオン検出フィルム。
（５）微粒子が５〜５００ｎｍの粒径を有する前記（１）ないし（４）のいずれかに記載の金属イオン検出フィルム。
（６）非水溶性又は難水溶性で、親水性溶媒に可溶性である金属イオン検出試薬を、親水性溶媒に溶解し、これを水と混合攪拌して金属イオン検出試薬の微粒子を生成、分散させたのち、得られた分散液を、メンブレンフィルターでろ過するか或いは該フィルターに含浸し、該微粒子を該フィルターに膜状に被覆させることを特徴とする金属イオン検出フィルムの製造方法。
（７）金属イオン検出試薬が、金属イオンと錯体を形成して発色し、金属イオンの濃度に応じて色調及び／又はその強度を変化させるものである前記（６）記載の方法。
（８）金属イオン検出試薬が、金属イオンと錯体を形成して発光し、金属イオンの濃度に応じて発光の色調及び／又はその強度を変化させるものである前記（６）記載の方法。
（９）メンブレンフィルターが、網目状繊維からなる不織布、フィブリル化ポリマーシート、ファイバーシート、溶液キャスト多孔質ポリマーシート、延伸多孔性フィルム、放射線照射多孔性フィルム、多孔質セラミックスシート及び多孔質ガラスシートの中から選ばれた少なくとも１種であって、孔径１０〜１０００ｎｍの範囲の細孔を有するものである前記（６）、（７）又は（８）記載の方法。
（１０）微粒子が５〜５００ｎｍの粒径を有する前記（６）ないし（９）のいずれかに記載の方法。
（１１）金属イオン検出フィルムに金属イオン含有試料検液を含浸或いは通液して金属イオンを捕捉し、発色又は発光させ、色調及び／又はその強度に基づき、金属イオン濃度を求めることを特徴とする金属イオン定量方法。
本発明において、シートにはフィルムも包含される。
That is, the present invention is as follows.
(1) A metal ion detection film obtained by coating a membrane filter with fine particles of a metal ion detection reagent that is water-insoluble or sparingly water-soluble and soluble in a hydrophilic solvent.
(2) The metal ion detection film according to (1), wherein the metal ion detection reagent forms a complex with the metal ion and develops color, and changes the color tone and / or the intensity thereof according to the concentration of the metal ion.
(3) The metal ion detection reagent according to (1), wherein the metal ion detection reagent forms a complex with the metal ion and emits light, and changes a color tone and / or intensity of the light emission according to the concentration of the metal ion. the film.
(4) The membrane filter is a nonwoven fabric composed of network fibers, a fibrillated polymer sheet, a fiber sheet, a solution cast porous polymer sheet, a stretched porous film, a radiation irradiated porous film, a porous ceramic sheet, and a porous glass sheet. The metal ion detection film according to (1), (2) or (3), which is at least one selected from the above and has pores having a pore diameter in the range of 10 to 1000 nm.
(5) The metal ion detection film according to any one of (1) to (4), wherein the fine particles have a particle diameter of 5 to 500 nm.
(6) A metal ion detection reagent that is water-insoluble or sparingly water-soluble and soluble in a hydrophilic solvent is dissolved in a hydrophilic solvent, and this is mixed with water and stirred to produce and disperse the metal ion detection reagent fine particles. A method for producing a metal ion detection film, wherein the obtained dispersion is filtered with a membrane filter or impregnated in the filter, and the fine particles are coated on the filter in a film form.
(7) The method according to (6) above, wherein the metal ion detection reagent is colored by forming a complex with the metal ion and changes the color tone and / or its intensity according to the concentration of the metal ion.
(8) The method according to (6) above, wherein the metal ion detection reagent forms a complex with the metal ion and emits light, and changes the color and / or intensity of the light emission according to the concentration of the metal ion.
(9) The membrane filter is a nonwoven fabric composed of network fibers, a fibrillated polymer sheet, a fiber sheet, a solution cast porous polymer sheet, a stretched porous film, a radiation irradiated porous film, a porous ceramic sheet, and a porous glass sheet. The method according to the above (6), (7) or (8), which is at least one selected from the above and has pores having a pore diameter in the range of 10 to 1000 nm.
(10) The method according to any one of (6) to (9), wherein the fine particles have a particle size of 5 to 500 nm.
(11) A metal ion detection film is impregnated or passed with a metal ion-containing sample test solution to capture metal ions, to cause color development or light emission, and to obtain a metal ion concentration based on the color tone and / or its intensity. Metal ion determination method.
In the present invention, the sheet includes a film.
本発明に用いられる金属イオン検出試薬は、水に不溶性又は難溶性であって、かつ親水性溶媒、例えばアセトン、メチルアルコール、エチルアルコール、アセトニトリル、テトラヒドロフラン、ジメチルスルホキシド（ＤＭＳＯ）等に溶解するものであればよく、特に制限されないが、好ましくは分子量が３０００以下、中でも１０００以下の低分子量のもの、特に金属イオンと錯体を形成して発色し、金属イオンの濃度に応じて色調及び／又はその強度を変化させる発色性化合物や、金属イオンと錯体を形成して発光し、金属イオンの濃度に応じて発光の色調及び／又はその強度を変化させる発光性化合物、例えば蛍光性化合物等が挙げられる。
これらの発色性化合物や発光性化合物は、分子量が３０００以下、中でも１０００以下の低分子量のものが好ましく、このようなものとしては、例えばピリジルアゾレゾルシノール、ピリジルアゾナフトール、チアゾリルアゾナフトール、ジチゾン、ジフェニルチオカルバジド、１‐ニトロソ‐２‐ナフトール、ｏ‐，ｍ‐，ｐ‐フェナントロリンやバソフェナントロリン等のフェナントロリン類、８‐キノリノール等のオキシキノリン類、ジメチルグリオキシム、２，６，７‐トリオキシ‐９‐フェニル‐６‐フルオロン（慣用名フェニルフルオロン）等のフルオロン、テトラフェニルポルフィリン等のポルフィリンなどが挙げられる。
金属イオン検出試薬によりイオンとして検出される金属については、例えば、環境基準の設けられている、Ｚｎ、Ｃｄ、Ｈｇ、Ｃｕ、Ｐｂ、Ａｓ、Ｓｅ、Ｓｂ等や、有用金属、中でもＰｔ、Ｐｄ、Ｒｕ等の白金族元素、Ａｕ、Ａｇ、希土類元素、Ｉｎ、Ｔｌ、Ｇｅ、Ｈｆ、Ｔｈ、Ｂｉ、Ｔａ、Ｔｅ、Ｍｏ、Ｗ、Ｕ、Ｒｅ等のレアメタルなどが挙げられる。
The metal ion detection reagent used in the present invention is insoluble or hardly soluble in water and dissolves in a hydrophilic solvent such as acetone, methyl alcohol, ethyl alcohol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide (DMSO) and the like. There is no particular limitation, but the molecular weight is preferably 3000 or less, particularly 1000 or less, particularly a color formed by forming a complex with a metal ion, and depending on the concentration of the metal ion and / or its intensity. And a luminescent compound that emits light by forming a complex with a metal ion and changes the color tone and / or intensity of the light emission according to the concentration of the metal ion, such as a fluorescent compound.
These chromophoric compounds and luminescent compounds preferably have a molecular weight of 3000 or less, especially 1000 or less, and examples thereof include pyridylazoresorcinol, pyridylazonaphthol, thiazolylazonaphthol, and dithizone. , Diphenylthiocarbazide, 1-nitroso-2-naphthol, phenanthrolines such as o-, m-, p-phenanthroline and bathophenanthroline, oxyquinolines such as 8-quinolinol, dimethylglyoxime, 2,6,7- Examples include fluorones such as trioxy-9-phenyl-6-fluorone (common name phenylfluorone) and porphyrins such as tetraphenylporphyrin.
As for the metals detected as ions by the metal ion detection reagent, for example, Zn, Cd, Hg, Cu, Pb, As, Se, Sb, etc., which are provided with environmental standards, useful metals, among them Pt, Pd, Examples include platinum group elements such as Ru, Au, Ag, rare earth elements, rare metals such as In, Tl, Ge, Hf, Th, Bi, Ta, Te, Mo, W, U, and Re.
また、本発明に用いられるメンブレンフィルターは、孔径が１μｍ以下、好ましくはサブミクロンレベル、より好ましくは１０〜２００ｎｍの範囲の細孔を有するものがよく、また、膜厚は通常５μｍ〜５ｍｍ、好ましくは７０μｍ〜１ｍｍの範囲で選ばれる。
メンブレンフィルターとしては、例えば繊維状素材の不織布、フィブリル化ポリマーシート、ファイバーシート、溶液キャスト多孔質ポリマーシート、延伸多孔性フィルム、放射線照射多孔性フィルム、金属酸化物などの微粒子を融着あるいは焼結した多孔質シート等の多孔質セラミックスシート、多孔質ガラスシートなどが挙げられる。
メンブレンフィルターの材質としては、例えばセルロースアセテートなどのセルロースエステル、ニトロセルロースとセルロースアセテートの混合物等からなるセルロース混合エステル、これらのエステルの１種又は２種以上を、ポリエチレンテレフタレート等のポリエステルにコートしたもの、ポリエチレンテレフタレート等のポリエステル、ホリエチレンやポリプロピレンやポリスチレン等のポリオレフィン系樹脂、ポリカーボネート、テトラフルオロエチレン等のフッ素樹脂、ニトロセルロース、ポリエーテルスルホンなどが挙げられる。
The membrane filter used in the present invention has a pore size of 1 μm or less, preferably a submicron level, more preferably a pore having a range of 10 to 200 nm, and the film thickness is usually 5 μm to 5 mm, preferably Is selected in the range of 70 μm to 1 mm.
As membrane filters, for example, nonwoven fabrics of fibrous materials, fibrillated polymer sheets, fiber sheets, solution cast porous polymer sheets, stretched porous films, radiation irradiated porous films, metal oxides and other fine particles are fused or sintered. Examples thereof include porous ceramic sheets such as the prepared porous sheets, and porous glass sheets.
Examples of the material for the membrane filter include cellulose esters such as cellulose acetate, cellulose mixed esters composed of a mixture of nitrocellulose and cellulose acetate, and one or more of these esters coated on polyester such as polyethylene terephthalate. And polyesters such as polyethylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and polystyrene, fluororesins such as polycarbonate and tetrafluoroethylene, nitrocellulose, and polyethersulfone.
本発明検出フィルムは、非水溶性又は難水溶性で、親水性溶媒に可溶性である金属イオン検出試薬を、親水性溶媒に溶解し、これを水と混合攪拌し、金属イオン検出試薬の微粒子を生成、分散させたのち、得られた分散液を、メンブレンフィルターでろ過するか或いは該フィルターに含浸し、該微粒子を該フィルターに被覆させることにより作製される。 The detection film of the present invention is a water-insoluble or sparingly water-soluble metal ion detection reagent that is soluble in a hydrophilic solvent, dissolved in a hydrophilic solvent, mixed and stirred with water, and the metal ion detection reagent fine particles are removed. After the production and dispersion, the resulting dispersion is filtered through a membrane filter or impregnated in the filter, and the fine particles are coated on the filter.
この際、先ず、金属イオン検出試薬の微粒子を生成させて分散液が調製される。
従来、水分散微粒子形成法としては、例えばイオウを無水アルコールに溶解した後、水中に注入したり、また、カロチンをアセトンに溶解した後、水に注ぐ方法（１９６７年、培風館発行、Ｂ．ヤーゲンス他（玉虫訳）「コロイド化学」、２０頁及び２５６頁参照）や、良溶媒に溶解した有機材料を貧溶媒に混入して有機微粒子を形成させる方法（特開平６−７９１６８号公報、特開２００３−８４３２２号公報参照）などが知られているが、金属イオン検出試薬については試みられていない。
At this time, first, a dispersion liquid is prepared by generating fine particles of a metal ion detection reagent.
Conventional methods for forming water-dispersed fine particles include, for example, a method in which sulfur is dissolved in anhydrous alcohol and then poured into water, or carotene is dissolved in acetone and then poured into water (1967, issued by Bafukan, B. Yagens Others (see translation of Tamamushi, “Colloid Chemistry”, pages 20 and 256) and other methods of forming organic fine particles by mixing an organic material dissolved in a good solvent into a poor solvent (JP-A-6-79168, JP However, no attempt has been made to detect a metal ion detection reagent.
上記分散液を調製する際には、金属イオン検出試薬を親水性溶媒、例えばアセトンなど水と混和しうる溶媒、好ましくは水と任意の比率で混ざる溶媒などに溶かし、この溶液をキャピラリーから、攪拌されている水、好ましくは５００〜２０００ｒｐｍ程度に激しく攪拌されている水の中に一気に射出、注入するのがよい。この操作により、金属イオン検出試薬を例えば数十ｎｍオーダーから数百ｎｍオーダーの粒径を有する微粒子として水に均一に分散させることができる。また、必要に応じ、より大きな粒子を目の粗いろ紙（例えばミクロンレベルのろ紙）でろ過して除いた後、ろ液を、おおよそ上記微粒子の粒径程度ないし粒径より若干大き目、例えばおおよそサブミクロンレベルの細孔径のメンブレンフィルターを通してろ過、好ましくは吸引ろ過する。この操作により、金属イオン検出試薬粒子を均一な分布で被覆させたフィルターが得られ、また、ろ液はほとんど透明となる。金属イオン検出試薬微粒子は、フィルターに捕捉されているため、容易にははがれず水溶液中に流出しない。 In preparing the dispersion, the metal ion detection reagent is dissolved in a hydrophilic solvent, for example, a solvent miscible with water such as acetone, preferably a solvent mixed with water at an arbitrary ratio, and the solution is stirred from the capillary. It is preferable to inject and inject into the water which is being stirred vigorously at about 500 to 2000 rpm. By this operation, the metal ion detection reagent can be uniformly dispersed in water, for example, as fine particles having a particle size of the order of several tens of nm to several hundreds of nm. Also, if necessary, after removing larger particles by filtering with coarse filter paper (for example, micron-level filter paper), the filtrate is roughly about the particle size of the fine particles or slightly larger than the particle size, for example, approximately sub-particles. Filtration through a membrane filter having a micron level pore size, preferably suction filtration. By this operation, a filter in which the metal ion detection reagent particles are coated with a uniform distribution is obtained, and the filtrate is almost transparent. Since the metal ion detection reagent fine particles are captured by the filter, they are not easily peeled off and do not flow out into the aqueous solution.
本発明検出フィルムにより検液における金属イオンを定量するには、検液を必要に応じｐＨ調整し、これを該フィルムに含浸又は通液した後に取り出し、標準色調表や標準蛍光表と目視で対比したり、或いは分光光度計等の分析機器で計測したりすればよい。
分光光度計には、例えば薄層クロマトグラフィー用スキャナー、光ファイバ分光器、積分球付きの分光器などが用いられる。
In order to quantify metal ions in the test solution using the detection film of the present invention, the pH of the test solution is adjusted as necessary, taken out after impregnating or passing through the film, and visually compared with a standard color table or standard fluorescence table. Or measurement with an analytical instrument such as a spectrophotometer.
As the spectrophotometer, for example, a scanner for thin layer chromatography, an optical fiber spectrometer, a spectrometer with an integrating sphere, and the like are used.
本発明によれば、従来非水溶性又は難水溶性なため使用方法が制限されていた多くの金属イオン検出試薬を安定に保持させたフィルム型の簡易な金属イオン検出材とすることができ、着色・汚濁した排水等の検液からの検出、定量操作にも十分対応することができる。また、標準色系列や標準蛍光系列と比較することで目視判定が可能となるので、現場で直ちに分析に供することができる。
本発明の定量方法によれば、検出フィルムを金属イオン含有被検液と接触させることで、例えば色調や蛍光の変化を起こさせ、標準比色表や標準蛍光表と比較するかあるいは分光光度計等の分析機器で計測するなどして、簡便に金属イオンを検出、定量することができる。
According to the present invention, it can be a film-type simple metal ion detection material that stably holds many metal ion detection reagents that have been conventionally water-insoluble or sparingly water-soluble and have been limited in use. It can fully handle detection and quantitative operations from colored and contaminated wastewater samples. Moreover, since visual determination is possible by comparing with a standard color series or a standard fluorescence series, it can be immediately subjected to analysis in the field.
According to the quantification method of the present invention, the detection film is brought into contact with a test solution containing metal ions, for example, to cause a change in color tone or fluorescence, and compared with a standard colorimetric table or standard fluorescence table, or a spectrophotometer. The metal ions can be easily detected and quantified by measuring with an analytical instrument such as the above.
次に実施例により本発明を実施するための最良の形態を説明するが、本発明はこれらの例によって何ら限定されるものではない。
なお、各実施例の各操作や処理は室温で行った。
Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.
In addition, each operation and process of each Example were performed at room temperature.
テトラフェニルポルフィリン（ＴＰＰ）６．１４ｍｇをテトラヒドロフラン１０ｍｌに溶解して濃度１ｍＭのＴＰＰテトラヒドロフラン液を調製した。ビーカーに純水２０ｍｌを加え、スターラーで激しく攪拌し、これに、上記ＴＰＰテトラヒドロフラン液２００μｌをキャピラリーから一気に射出注入して黄褐色の透明な高分散液を調製した。
この高分散液を直ちにポリカーボネート製の円板状メンブレンフィルター（直径４７ｍｍ、孔径０．１μｍ、厚さ６μｍ）で５０ｍｍＨｇの減圧下に吸引ろ過し、該フィルターのろ過面にＴＰＰ微粒子からなる黄褐色薄膜を被覆させ、この被覆フィルターを水洗後、風乾した。このようにして得られた金属イオン検出フィルムを、電子顕微鏡にて観察した。該フィルムにおけるＴＰＰ粒子のＳＥＭ写真を図１に示す。
6.14 mg of tetraphenylporphyrin (TPP) was dissolved in 10 ml of tetrahydrofuran to prepare a TPP tetrahydrofuran solution having a concentration of 1 mM. 20 ml of pure water was added to a beaker and stirred vigorously with a stirrer, and 200 μl of the above TPP tetrahydrofuran solution was injected at once from a capillary to prepare a yellowish-brown transparent high dispersion.
The highly dispersed liquid is immediately suction filtered through a polycarbonate disk membrane filter (diameter 47 mm, pore diameter 0.1 μm, thickness 6 μm) under a reduced pressure of 50 mmHg, and a yellowish brown thin film made of TPP fine particles is formed on the filter surface. The coated filter was washed with water and then air-dried. The metal ion detection film thus obtained was observed with an electron microscope. An SEM photograph of TPP particles in the film is shown in FIG.
ピリジルアゾナフトール（ＰＡＮ）６．２５ｍｇをアセトン２５ｍｌに溶解して濃度１ｍＭのＰＡＮアセトン溶液を調製した。ビーカーに純水２０ｍｌを加え、マグネティックスターラーで激しく攪拌し、これに、上記ＰＡＮアセトン溶液２００μｌをキャピラリー又はマイクロシリンジから一気に射出注入して黄色の透明な高分散液を調製した。
この高分散液を直ちにセルロース混合エステル製の円板状メンブレンフィルター（直径４７ｍｍ、孔径０．１μｍ、厚さ１１０μｍ）で５０ｍｍＨｇの減圧下に吸引ろ過し、該フィルターのろ過面にＰＡＮ微粒子からなる黄色薄膜を被覆させ、この被覆フィルターを水洗後、風乾した。このようにして得られた金属イオン検出フィルムの写真を図２に示す。
6.25 mg of pyridylazonaphthol (PAN) was dissolved in 25 ml of acetone to prepare a PAN acetone solution having a concentration of 1 mM. 20 ml of pure water was added to a beaker and stirred vigorously with a magnetic stirrer, and 200 μl of the PAN acetone solution was injected and injected at once from a capillary or a microsyringe to prepare a yellow transparent high dispersion.
This highly dispersed liquid was immediately suction filtered under a reduced pressure of 50 mmHg with a disk-shaped membrane filter (diameter 47 mm, pore diameter 0.1 μm, thickness 110 μm) made of cellulose mixed ester, and the yellow surface consisting of PAN fine particles on the filter surface of the filter. A thin film was coated, and the coated filter was washed with water and then air-dried. A photograph of the metal ion detection film thus obtained is shown in FIG.
実施例２で得た検出フィルムを、ｐＨ８．４に調整した、亜鉛（ＩＩ）イオンを６．５、３２．７、６５．４、１３０．８、３９２．４及び１３０８ｐｐｂの濃度で含む各水溶液試料、及び比較のための水にそれぞれ浸し、３０分後に引き上げた。この処理後の各フィルムの写真及びスペクトルをそれぞれ図３及び図４に示す。図４中、ａ〜ｇは、それぞれ亜鉛（ＩＩ）イオン濃度が０、６．５、３２．７、６５．４、１３０．８、３９２．４、１３０８ｐｐｂである場合を示す。 Each detection film obtained in Example 2 was adjusted to pH 8.4, and each aqueous solution containing zinc (II) ions at concentrations of 6.5, 32.7, 65.4, 130.8, 392.4 and 1308 ppb Each sample was immersed in water for comparison and pulled up after 30 minutes. The photograph and spectrum of each film after this processing are shown in FIGS. 3 and 4, respectively. In FIG. 4, a to g indicate cases where the zinc (II) ion concentrations are 0, 6.5, 32.7, 65.4, 130.8, 392.4, and 1308 ppb, respectively.
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