JP5920948B2 - Detection method and detection sensor - Google Patents
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Description
本発明は、フッ化物の検出方法及び検出センサーに関し、特に、オクタフルオロシクロペンテン、ヘキサフルオロブタジエンなどの分子内に炭素の不飽和結合を有するフッ化炭化水素化合物類の検出方法及び検出センサーに関する。 The present invention relates to a fluoride detection method and a detection sensor, and more particularly to a detection method and a detection sensor for fluorinated hydrocarbon compounds having a carbon unsaturated bond in a molecule such as octafluorocyclopentene and hexafluorobutadiene.
含フッ素化合物は、地球温暖化物質として京都議定書における協議以来、その削減が求められており、地球環境の保全、多くの生物種や人類の存続のため、その微量検出や除去、分解、使用量の削減、回収技術が求められている。
特に、ドライエッチングガスとして用いられてきた四フッ化炭素、オクタフルオロシクロブタンなどの飽和フルオロカーボン類は地球温暖化への悪影響から使用が制限されており、これらの代替物として、オクタフルオロシクロペンテン（Ｃ5Ｆ8）、ヘキサフルオロブタジエン（Ｃ4Ｆ6）、ヘキサフルオロシクロブテン（Ｃ4Ｆ6）などの分子内に炭素の不飽和結合を有するフッ化炭化水素化合物が開発されてきている。これらの炭素の不飽和結合を有するフッ化炭化水素化合物（以下、「フッ素化不飽和炭化水素」という）は、選択比が高く微細加工のための高性能なマテリアルとして知られ、各半導体プロセスにおいて一部使用されている。これらは、地球温暖化係数は改善されているものの、元来その蒸気圧の高さや毒性の課題から管理基準濃度２ｐｐｍの規制が布かれている。さらには、現存する環境負荷の観点から、またプロセス現場において環境中のガスコンタミ源ともなり、高感度に検出する技術等が求められている。
Fluorine-containing compounds have been required to be reduced since the discussion in the Kyoto Protocol as a global warming substance. For the preservation of the global environment and the survival of many species and humans, trace amounts are detected, removed, decomposed, and used. Reduction and recovery technology is required.
In particular, saturated fluorocarbons such as carbon tetrafluoride and octafluorocyclobutane, which have been used as dry etching gases, are restricted in use due to adverse effects on global warming. As an alternative to these, fluorocarbons such as octafluorocyclopentene (C 5 F 8 ), hexafluorobutadiene (C 4 F 6 ), hexafluorocyclobutene (C 4 F 6 ) and other fluorinated hydrocarbon compounds having an unsaturated carbon bond have been developed. These fluorinated hydrocarbon compounds having unsaturated bonds of carbon (hereinafter referred to as “fluorinated unsaturated hydrocarbons”) are known as high-performance materials for microfabrication with high selectivity, and in each semiconductor process. Some are used. Although the global warming potential has been improved, the regulation of the control standard concentration of 2 ppm is originally distributed due to the problem of high vapor pressure and toxicity. Furthermore, from the viewpoint of the existing environmental load, and a gas contamination source in the environment at the process site, there is a demand for a technique for highly sensitive detection.
フッ素化不飽和炭化水素の検出手法としては、現在までに、過マンガン酸塩を用いた手法と熱分解を用いた手法が開発されている。
前者の手法は、Ｃ5Ｆ8やＣ4Ｆ6と過マンガン酸塩との反応により、過マンガン酸塩の消色を利用した方法である（特許文献１）。しかしながら、以下のデメリットがある。
(１)反応が鈍く、測定できる濃度が５０ｐｐｍ以上の濃い条件でしか感知が難しい、(２)検出するまでの時間が５０ｐｐｍで平均約１９分以上と長くかかる、（３）無機物を使用しているため加工性に難点があり、検出のための形態が制限される、（４）強い酸化剤である過マンガン酸塩を使用するため、ボロン誘導体などの水素化物や錯化物などの試剤により消色が起こり誤報の原因となる。
To date, a method using permanganate and a method using thermal decomposition have been developed as detection methods for fluorinated unsaturated hydrocarbons.
The former method is a method using decolorization of permanganate by reaction between C 5 F 8 or C 4 F 6 and permanganate (Patent Document 1). However, there are the following disadvantages.
(1) The reaction is slow, and it is difficult to detect only under conditions where the concentration that can be measured is 50 ppm or higher. (2) The time until detection takes 50 ppm and takes an average of about 19 minutes or longer. (3) Using inorganic substances Therefore, there are difficulties in processability, and the form for detection is limited. (4) Since permanganate, which is a strong oxidant, is used, it is eliminated by hydrides such as boron derivatives and complex reagents. Colors can cause false alarms.
後者の手法は、Ｃ5Ｆ8やＣ4Ｆ6の熱分解を用いた方法であって、気体中に存在するＣ5Ｆ8やＣ4Ｆ6を熱分解炉において熱分解し、その際発生する酸性ガスを敏速に光学的に検出する方法である（特許文献２）。しかしながら、以下のデメリットがある。
(１)熱分解を行うため大きなエネルギーを消費する、(２)高温における熱分解を行うため、洗浄剤、絶縁体等で多用されるフッ素系液体などのガスからも同様の酸性ガスが発生し誤報の原因となる、(３)高温における熱分解を行うため、非常に危険な酸性ガスHFを発生させてしまう、(４)最終的にはその非常に危険な酸性ガスを検出しているので、他の類似の酸性ガスそのものが混入した場合、これも誤報の原因となる。
The latter approach is a method using the thermal decomposition of C 5 F 8 or C 4 F 6, a C 5 F 8 or C 4 F 6 present in the gas is thermally decomposed in the thermal decomposition furnace, in which This is a method for quickly and optically detecting the generated acidic gas (Patent Document 2). However, there are the following disadvantages.
(1) A large amount of energy is consumed for thermal decomposition. (2) Since thermal decomposition is performed at high temperatures, the same acidic gas is generated from gases such as fluorine-based liquids frequently used in cleaning agents and insulators. (3) Because it decomposes at high temperatures, it generates very dangerous acid gas HF. (4) Eventually, the extremely dangerous acid gas is detected. When other similar acid gas itself is mixed, this also causes false alarms.
このように、これまでのフッ素化不飽和炭化水素の検出方法には、種々の問題があるため、これまでの手法とは原理の全く異なる、新たな方法を用いた、高性能で、より経済的な検出方法が必要とされている。
本発明は、上記の従来の技術における実状に鑑みてなされたものであって、高温熱分解や強い酸化剤を使用せずに室温付近で検出でき、簡便にＣ5Ｆ8やＣ4Ｆ6等のフッ素化不飽和炭化水素の検出方法を提供することを目的とするものである。
As described above, because there are various problems with the conventional detection methods for fluorinated unsaturated hydrocarbons, a high-performance, more economical method using a new method that is completely different in principle from the conventional methods. Is needed.
The present invention has been made in view of the actual situation in the above-described conventional technology, and can be detected near room temperature without using high-temperature thermal decomposition or a strong oxidizing agent, and can be easily performed with C 5 F 8 or C 4 F 6. It aims at providing the detection method of fluorinated unsaturated hydrocarbons, such as.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、Ｃ5Ｆ8やＣ4Ｆ6等のフッ素化不飽和炭化水素の反応を利用することにより、上記の目的を達成しうるという知見を得た。すなわち、Ｃ5Ｆ8やＣ4Ｆ6等の不飽和炭化水素のフッ化物との選択的な反応について鋭意検討を重ねた結果、特定の窒素化合物群を用いた、反応を見出し、対象とするフッ素化不飽和炭化水素を検出することが可能となることが判明した。 As a result of intensive studies to solve the above problems, the present inventors have achieved the above object by utilizing the reaction of fluorinated unsaturated hydrocarbons such as C 5 F 8 and C 4 F 6. The knowledge that it is possible was obtained. That is, as a result of intensive studies on selective reaction with unsaturated hydrocarbon fluorides such as C 5 F 8 and C 4 F 6 , the reaction using a specific group of nitrogen compounds is found and targeted. It has been found that it is possible to detect fluorinated unsaturated hydrocarbons.
本発明はこれらの知見に基づいて完成に至ったものであり、本発明によれば、以下の発明が提供される。
［１］フッ素化不飽和炭化水素と、下記の一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物との反応を用いて、前記のフッ化物を検出することを特徴とするフッ化物の検出方法。
［２］前記反応による光学的変化を検出することを特徴とする［１］に記載の検出方法。
［３］前記反応による発光状態変化を検出することを特徴とする［１］に記載の検出方法。
［４］前記一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物以外の有機物が共存する態様を用いて検出することを特徴とする［１］〜［３］のいずれかに記載の検出方法。
［５］前記のフッ素化不飽和炭化水素が、Ｃ5Ｆ8又はＣ4Ｆ6或いはこれらの混合物であることを特徴とする［１］〜［４］のいずれかに記載の検出方法。
［６］前記Ｃ5Ｆ8が、オクタフルオロシクロペンテンである［５］に記載の検出方法。
［７］前記Ｃ4Ｆ6が、ヘキサフルオロブタジエン又はヘキサフルオロシクロブテン或いはこれらの混合物である［５］に記載の検出方法。
［８］前記反応における、吸光度、反射率、赤外振動、発光、蛍光、燐光、屈折率、液晶状態、及びＸ線による光電子運動エネルギーの変化の群から選ばれる１つ又は２つ以上の光学的変化を検出することを特徴とする［１］〜［７］のいずれかに記載の検出方法。
［９］前記反応における、発光状態の変化を用いることにより、濃度が０．１％以下のフッ素化不飽和炭化水素を検出することを特徴とする［１］〜［７］のいずれかに記載の検出方法。
［１０］フッ素化不飽和炭化水素を検出するために用いられる検出剤であって、下記の一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物を有効成分とすることを特徴とするフッ素化不飽和炭化水素の検出剤。
［１１］フッ素化不飽和炭化水素を検出するためのセンサーであって、検出部に、下記の一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物を用いたことを特徴とするフッ素化不飽和炭化水素の検出センサー。
［１２］前記一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物を含む液体が多孔質材に含浸されていることを特徴とする［１１］に記載のフッ素化不飽和炭化水素の検出センサー。
［１３］前記多孔質材が、セルロース、ポリマー又は多孔質アルミナである［１２］に記載のフッ素化不飽和炭化水素の検出センサー。
［１４］前記一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物を含有するポリマーを用いることを特徴とする［１１］〜［１３］のいずれかに記載のフッ素化不飽和炭化水素の検出センサー。
The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] Detection of fluoride characterized by detecting the above-mentioned fluoride using a reaction between a fluorinated unsaturated hydrocarbon and a compound having an imidazoline skeleton represented by the following general formula (I) Method.
[2] The detection method according to [1], wherein an optical change due to the reaction is detected.
[3] The detection method according to [1], wherein a change in luminescence state due to the reaction is detected.
[4] The detection method according to any one of [1] to [3], wherein detection is performed using an embodiment in which an organic substance other than the compound having an imidazoline skeleton represented by the general formula (I) is present. .
[5] The detection method according to any one of [1] to [4], wherein the fluorinated unsaturated hydrocarbon is C 5 F 8 or C 4 F 6 or a mixture thereof.
[6] The detection method according to [5], wherein the C 5 F 8 is octafluorocyclopentene.
[7] The detection method according to [5], wherein the C 4 F 6 is hexafluorobutadiene, hexafluorocyclobutene, or a mixture thereof.
[8] One or more opticals selected from the group consisting of absorbance, reflectance, infrared vibration, light emission, fluorescence, phosphorescence, refractive index, liquid crystal state, and change in photoelectron kinetic energy due to X-rays in the reaction. The detection method according to any one of [1] to [7], wherein the change is detected.
[9] The fluorinated unsaturated hydrocarbon having a concentration of 0.1% or less is detected by using a change in the luminescence state in the reaction, according to any one of [1] to [7] Detection method.
[10] A detection agent used for detecting a fluorinated unsaturated hydrocarbon, comprising a compound having an imidazoline skeleton represented by the following general formula (I) as an active ingredient Unsaturated hydrocarbon detector.
[11] A sensor for detecting fluorinated unsaturated hydrocarbons, characterized in that a compound having an imidazoline skeleton represented by the following general formula (I) is used for the detection part. Saturated hydrocarbon detection sensor.
[12] The fluorinated unsaturated hydrocarbon detection sensor according to [11], wherein a porous material is impregnated with a liquid containing a compound having an imidazoline skeleton represented by the general formula (I). .
[13] The fluorinated unsaturated hydrocarbon detection sensor according to [12], wherein the porous material is cellulose, polymer, or porous alumina.
[14] The detection of a fluorinated unsaturated hydrocarbon according to any one of [11] to [13], wherein a polymer containing a compound having an imidazoline skeleton represented by the general formula (I) is used. sensor.
本発明によれば、高温を使用せず、室温付近で簡便に迅速に、Ｃ5Ｆ8やＣ4Ｆ6等の不飽和炭化水素のフッ化物及び／又は少なくとも水素を有する含フッ素化合物を検出でき、さらにフッ素系液体からの妨害ガスの干渉もうけず、それらを検出することができる。また、本発明の方法は、Ｃ5Ｆ8やＣ4Ｆ6等の不飽和炭化水素のフッ化物や少なくとも水素を有する含フッ素化合物を効率よく検出する、センサー、警報装置、測定機器等に適用でき、さらには選択的な除去分解技術に応用することができる。 According to the present invention, a fluoride of an unsaturated hydrocarbon such as C 5 F 8 or C 4 F 6 and / or a fluorine-containing compound having at least hydrogen can be detected easily and quickly near room temperature without using a high temperature. Furthermore, they can be detected without interference of interfering gases from the fluorinated liquid. The method of the present invention is also applicable to sensors, alarm devices, measuring instruments, etc. that efficiently detect fluorides of unsaturated hydrocarbons such as C 5 F 8 and C 4 F 6 and fluorine-containing compounds having at least hydrogen. Furthermore, it can be applied to selective removal and decomposition techniques.
本発明は、Ｃ5Ｆ8やＣ4Ｆ6等のフッ素化不飽和炭化水素を、下記一般化学式（Ｉ）で表される化合物に接触させることで、反応を起こさせ、前記フッ化物の除去を行うことを特徴とするものである。 In the present invention, a fluorinated unsaturated hydrocarbon such as C 5 F 8 or C 4 F 6 is brought into contact with a compound represented by the following general chemical formula (I) to cause a reaction, thereby removing the fluoride. It is characterized by performing.
上記の一般式（Ｉ）で表される化合物において、Ｒ5とＲ6の間では少なくとも環状構造にならない。Ｒ1〜Ｒ4すべてが水素の場合と、Ｒ2およびＲ4のみが水素の場合と、Ｒ2とＲ4とが存在せず根元の部分が二重結合になっている場合があり、Ｒ6は少なくとも水素ではない。水素ではないＲ1〜Ｒ6は、一般的な炭化水素基を含む置換基であり、前記置換基がポリマーである場合および前記置換基がＲ1とＲ3の間で環状部分を形成する場合も含む。 In the compound represented by the general formula (I), at least a cyclic structure is not formed between R 5 and R 6 . When R 1 to R 4 are all hydrogen, only R 2 and R 4 are hydrogen, R 2 and R 4 are not present, and the root part may be a double bond. 6 is at least not hydrogen. R 1 to R 6 that are not hydrogen are substituents including a general hydrocarbon group, and the substituent is a polymer and the substituent forms a cyclic portion between R 1 and R 3. Including.
すなわち、上記の一般式（Ｉ）において、Ｒ1〜Ｒ6のそれぞれは、イミダゾリン骨格に化学結合をする置換基であり、イミダゾリン骨格には、基本的に水素、又は、アミノ基もしくはメチレン基（ＣＨ2）もしくはベンゼンなどの炭素や他のヘテロ原子が結合する。Ｒ1〜Ｒ6は、一般的な炭化水素基を含む置換基であり、この置換基は、ポリマー（オリゴマーも含む）である場合もあり、また、隣どうしのＲ間で環状の構造をとり、それらの置換基がさらなる環状部分を形成する場合を含む。ただし、Ｒ5とＲ6の間では少なくとも環状構造にならない。
ここで、一般的な炭化水素基を含む置換基とは、上記の一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物において、フッ素化不飽和炭化水素との反応、及びそのフッ素化物の検出を妨げない有機化学における一般的な官能基であり、例えば一例として、アルキル、アルケン、アルキン、フェニル、ナフチル、アントラセニル、ヒドロキシ、アルコキシ、アルデヒド、ケトン、エーテル、クラウンエーエル、ポリエチレングリコール、カルボン酸エステル、アセタール、エポキシ、アミノ、アミド、イミノ、チオール、スルフィド、ジスルフィド、スルフィン酸エステル、スルホン酸エステル、ピリジン、ピロール、ピロリジン、ピペリジン、モルフォリン、ピペラジン、アルリジン、チオフェン、フランなどの置換基、またはこれらの置換基を含むものが挙げられる。
That is, in the above general formula (I), each of R 1 to R 6 is a substituent that chemically bonds to the imidazoline skeleton, and the imidazoline skeleton basically includes hydrogen, an amino group, or a methylene group ( Carbons such as CH 2 ) or benzene and other heteroatoms are bonded. R 1 to R 6 are substituents containing a general hydrocarbon group, and this substituent may be a polymer (including an oligomer) and has a cyclic structure between adjacent Rs. Including those where the substituents form additional cyclic moieties. However, at least a cyclic structure is not formed between R 5 and R 6 .
Here, the substituent containing a general hydrocarbon group is a reaction with a fluorinated unsaturated hydrocarbon in the compound having an imidazoline skeleton represented by the above general formula (I), and detection of the fluorinated product thereof. For example, alkyl, alkene, alkyne, phenyl, naphthyl, anthracenyl, hydroxy, alkoxy, aldehyde, ketone, ether, crown eel, polyethylene glycol, carboxylic acid ester, Substituents such as acetal, epoxy, amino, amide, imino, thiol, sulfide, disulfide, sulfinate, sulfonate, pyridine, pyrrole, pyrrolidine, piperidine, morpholine, piperazine, arridine, thiophene, furan, etc. They include those containing substituents.
一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物の例を実施例で記述しているが、これらに限定されるものではない。これらの化合物は、有機合成などで用いられる塩基性試薬として既に公知のもの、或いは、それらから誘導される化合物である。
例えば、2-Methyl-1-methylimidazoline、2-Methyl-1-propylimidazoline、2-Naphthyl-1-propylimidazoline、2-(4-Dimethylaminophenylethylyl)-1-methylbenzimidazoleなどがある。
Examples of the compound having an imidazoline skeleton represented by the general formula (I) are described in the Examples, but are not limited thereto. These compounds are those already known as basic reagents used in organic synthesis or the like, or compounds derived therefrom.
Examples include 2-Methyl-1-methylimidazoline, 2-Methyl-1-propylimidazoline, 2-Naphthyl-1-propylimidazoline, 2- (4-Dimethylaminophenylethylyl) -1-methylbenzimidazole.
本発明における検出対象であるフッ素化不飽和炭化水素は、少なくとも炭素とフッ素から成り、分子内に炭素−炭素二重及び／又は炭素−炭素三重結合化合物を少なくとも有する不飽和炭化水素のフッ化物であり、イミダゾリン骨格を有する化合物との反応による光学的変化を引き起こす。これらの中には、塩素、臭素、ヨウ素、酸素、硫黄、窒素など他の原子が置換されている化合物も含み、京都議定書において、評価した一連のガス状化合物であるフッ化炭化水素が一部属する。
例えば一例として、Ｃ2Ｆ4、Ｃ3Ｆ6、Ｃ4Ｆ6、ｃ−Ｃ4Ｆ8、ｃ−Ｃ5Ｆ8、ＣＦ3ＯＣＦ＝ＣＦ2、Ｃ2Ｆ5ＯＣＦ＝ＣＦ2（ｃ−はcyclic：環状を表し、c-Ｃ5Ｆ8は、前述のＣ5Ｆ8と同じである、Ｃ4Ｆ6には前述の２種類がある）等があり、それらすべてイミダゾリン骨格を有する化合物との反応による光学的変化を引き起こす。またこれらの一部は、半導体プロセスでエッチングガスとして使われることが多い。
The fluorinated unsaturated hydrocarbon to be detected in the present invention is an unsaturated hydrocarbon fluoride comprising at least carbon and fluorine and having at least a carbon-carbon double and / or carbon-carbon triple bond compound in the molecule. Yes, it causes an optical change by reaction with a compound having an imidazoline skeleton. These include compounds in which other atoms such as chlorine, bromine, iodine, oxygen, sulfur, and nitrogen are substituted, and some of the fluorinated hydrocarbons that are a series of gaseous compounds evaluated in the Kyoto Protocol. Belongs.
For example, as an example, C 2 F 4, C 3 F 6, C 4 F 6, c-C 4 F 8, c-C 5 F 8, CF 3 OCF = CF 2, C 2 F 5 OCF = CF 2 (c -Represents cyclic: c-C 5 F 8 is the same as the above-mentioned C 5 F 8, and C 4 F 6 has the above-mentioned two types), all of which have an imidazoline skeleton Causes optical changes due to reaction with compounds. Some of these are often used as etching gases in semiconductor processes.
一般式（Ｉ）で表されるイミダゾリン骨格を有する化合物は、それ以外の有機物と共存させて、混合物として使用できる。
混合する有機物としては、一般的な有機溶媒（例えば、エタノールやエチレングリコールやグリセリンなどのアルコール類、ジメチルホルムアミド（DMF）やＮ−メチル-2-ピロリドン（NMP）やヘキサメチルリン酸トリアミド（HMPA）などのアミド類、テトラヒドロフラン（THF）やジオキサンなどのエーテル類）、ジイソプロピルアミン(LDA用)やトリイソブチルアミンやジシクロヘキシルメチルアミンやペンタメチルピペリドンなどの有機液体、ウレア類などの有機固体、セルロースやポリエチレンやポリブタジエンやポリエチレンアクリレートやポリイミドポリ安息香酸などの有機ポリマー、などが挙げられる。
一般式（Ｉ）で表されるイミダゾリン誘導体の含有量は、０．１〜９９．９質量％の範囲である。好ましくは、１０〜８０質量％の範囲である。
The compound having an imidazoline skeleton represented by the general formula (I) can be used as a mixture by coexisting with other organic substances.
Organic substances to be mixed include general organic solvents (for example, alcohols such as ethanol, ethylene glycol, and glycerin, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and hexamethylphosphoric triamide (HMPA)). Amides such as tetrahydrofuran (THF) and ethers such as dioxane), organic liquids such as diisopropylamine (for LDA), triisobutylamine, dicyclohexylmethylamine and pentamethylpiperidone, organic solids such as ureas, cellulose and Examples thereof include organic polymers such as polyethylene, polybutadiene, polyethylene acrylate, and polyimide polybenzoic acid.
Content of the imidazoline derivative represented with general formula (I) is the range of 0.1-99.9 mass%. Preferably, it is the range of 10-80 mass%.
検出のための反応は、イミダゾリン骨格を有する化合物と、検出対象とする前述のフッ化物が接触すればよく、該化合物の使用形態は、有機溶剤に溶解して液体として用いる、該液体を基材に塗布する、該液体を多孔質材に含浸させる、或いは、該化合物を含有するポリマーを基板に塗布する等、どんな態様であってもよい。
これらの種々の形態を用いた検出の形態としては、例えば、
（１）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだ液体へ接触させる態様、
（２）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだポリマー膜に接触させる態様、
（３）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだセルロースに接触させる態様、
（４）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだテープ上もしくはシート上に接触させる態様、
（５）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだビーズもしくは粒子を内包した筒の内部に接触させる態様、
（６）検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだビーズもしくは粒子を固定したテープに接触させる態様
などがあり、あらゆる態様を含む。例えば、検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだ液体へバブリングする態様や検出対象とするフッ素化不飽和炭化水素を、イミダゾリン骨格を有する化合物を含んだセルロースに通過させる態様のように、検知対象とするフッ化物があらゆる基材の物質に接触する。尚、イミダゾリン骨格を有する化合物を含有する、もしくは有するポリマーとは、有機ポリマー（オリゴマーも含む）中に物理的にイミダゾリン誘導体が混合されている場合、もしくは、イミダゾリン誘導体が化学的な結合形態をとっている場合を意味する。
検出対象とする流体を接触させる態様の際に、検出対象とする流体を流す速度、すなわち流量が設定されるが、これに限定されることはない。反応を促進させる観点からは、流量は８００ｍＬ/分以上が好ましい。装置の観点からは、２００〜２０００ｍＬ/分が好ましい。省エネの観点からは、２０〜５００ｍＬ/分が好ましい。
For the reaction for detection, the compound having an imidazoline skeleton and the above-mentioned fluoride to be detected may be in contact with each other. The compound is used as a liquid after being dissolved in an organic solvent. It may be applied in any manner, such as being applied to the substrate, impregnating the liquid with a porous material, or applying a polymer containing the compound to a substrate.
As a form of detection using these various forms, for example,
(1) A mode in which a fluorinated unsaturated hydrocarbon to be detected is brought into contact with a liquid containing a compound having an imidazoline skeleton,
(2) A mode in which a fluorinated unsaturated hydrocarbon to be detected is brought into contact with a polymer film containing a compound having an imidazoline skeleton,
(3) A mode in which a fluorinated unsaturated hydrocarbon to be detected is brought into contact with cellulose containing a compound having an imidazoline skeleton,
(4) A mode in which a fluorinated unsaturated hydrocarbon to be detected is brought into contact with a tape or a sheet containing a compound having an imidazoline skeleton,
(5) A mode in which a fluorinated unsaturated hydrocarbon to be detected is brought into contact with the inside of a tube containing beads or particles containing a compound having an imidazoline skeleton,
(6) There are embodiments in which the fluorinated unsaturated hydrocarbon to be detected is brought into contact with a tape on which beads or particles containing a compound having an imidazoline skeleton are fixed, and all embodiments are included. For example, a mode in which a fluorinated unsaturated hydrocarbon to be detected is bubbled into a liquid containing a compound having an imidazoline skeleton, or a fluorinated unsaturated hydrocarbon to be detected is converted into a cellulose containing a compound having an imidazoline skeleton. Like the mode of passing through, the fluoride to be detected comes into contact with the substance of any substrate. A polymer containing or having a compound having an imidazoline skeleton means that an imidazoline derivative is physically mixed in an organic polymer (including oligomers), or the imidazoline derivative has a chemically bonded form. Means that
In the aspect in which the fluid to be detected is brought into contact, the speed at which the fluid to be detected is flowed, that is, the flow rate is set, but the present invention is not limited to this. From the viewpoint of promoting the reaction, the flow rate is preferably 800 mL / min or more. From the viewpoint of the apparatus, 200 to 2000 mL / min is preferable. From the viewpoint of energy saving, 20 to 500 mL / min is preferable.
本発明は、イミダゾリン骨格を有する化合物を利用したスムーズに進行する反応により対象とするガスを除去することができる。設定される反応温度は、摂氏１００度以下であり、０〜５０度が好ましい。室温付近（摂氏２０度±１０度）が最も好ましい。 The present invention can remove a target gas by a smoothly proceeding reaction using a compound having an imidazoline skeleton. The set reaction temperature is 100 degrees Celsius or less, and preferably 0 to 50 degrees. Near room temperature (20 degrees Celsius ± 10 degrees Celsius) is most preferable.
本発明において、光学的な変化は、分子の反応に伴うすべての光学的変化を使うことができる。中でも、発光変化を用いることが好ましい。
吸光度の変化は、紫外可視光領域における波長の光の透過率の変化に起因するもので、本発明における紫外可視光領域とは、真空紫外線を含む紫外光領域から紫、青、緑、黄、橙、赤色を含む可視光領域の光の領域を意味し、波長では２００〜８００ｎｍの範囲が好ましい。光源の観点から特に３００〜７００ｎｍの範囲が最も好ましい。可視光においては、それを目視し、比色によっても検出ができる。
In the present invention, the optical change can be any optical change accompanying a molecular reaction. Among these, it is preferable to use a light emission change.
The change in absorbance is due to a change in the transmittance of light having a wavelength in the ultraviolet-visible light region, and the ultraviolet-visible light region in the present invention refers to the ultraviolet light region including vacuum ultraviolet light from purple, blue, green, yellow, It means the visible light region including orange and red, and the wavelength is preferably in the range of 200 to 800 nm. The range of 300 to 700 nm is most preferable from the viewpoint of the light source. In visible light, it can be detected visually by colorimetry.
また、反射率の変化は、紫外可視光領域における波長の光の透過率の変化や散乱の変化による表面の反射率変化に起因するもので、吸光度の変化と強い関連がある。吸光度の変化と同様に、紫外可視光領域とは、真空紫外線を含む紫外光領域から紫、青、緑、黄、橙、赤色を含む可視光領域の光の領域を意味し、波長では２００〜８００ｎｍの範囲が好ましい。光源の観点から特に３００〜７００ｎｍの範囲が最も好ましい。 The change in reflectance is caused by a change in the reflectance of the surface due to a change in transmittance of light having a wavelength in the ultraviolet-visible light region or a change in scattering, and is strongly related to a change in absorbance. Similar to the change in absorbance, the ultraviolet-visible light region means the light region from the ultraviolet light region including vacuum ultraviolet light to the visible light region including purple, blue, green, yellow, orange, and red, and the wavelength ranges from 200 to 200. A range of 800 nm is preferred. The range of 300 to 700 nm is most preferable from the viewpoint of the light source.
赤外振動の変化は、赤外線領域における分子内の各結合における伸縮や振動の変化に起因するもので、本発明における赤外振動とは、近赤外から赤外、さらには遠赤外の領域における振動である。カイザーでは、１０〜４０００ｃｍ-1の範囲が好ましい。測定の観点から特に１０００〜１５００ｃｍ-1の範囲が最も好ましい。 The change in infrared vibration is caused by a change in expansion and contraction in each bond in the molecule in the infrared region, and the infrared vibration in the present invention is a region from the near infrared region to the infrared region, and further to the far infrared region. It is vibration in. For Kaiser, a range of 10 to 4000 cm −1 is preferred. From the viewpoint of measurement, the range of 1000-1500 cm −1 is most preferable.
発光や燐光の変化は、分子の反応に伴って変化する分子の励起状態から基底状態へのエネルギー移動の際放出される光の変化であり、本発明において、励起状態は励起光により生成される。従って使用する光の領域は、吸光度や反射率の変化において用いられた領域と同じである。発光や燐光の変化は、その強度が増大する場合と減少する場合がある。屈折率の変化は、分子の反応に伴って変化する部分の誘電率の変化に起因する。測定は空気中で行われることが多く、使用する光は紫外可視光領域のものが好ましく、値は０．１〜３．２の範囲における変化が好ましい。液晶状態の変化は分子の反応に伴って変化する分子の配向状態の変化に起因するもので、特に等方的液体状態とネマティック液晶もしくはスメクティック液晶との間の変化を用いる。偏光した紫外可視光領域の光を用いる。 A change in light emission or phosphorescence is a change in light emitted during energy transfer from the excited state of the molecule to the ground state, which changes with the reaction of the molecule. In the present invention, the excited state is generated by the excited light. . Therefore, the region of light used is the same as the region used for changes in absorbance and reflectance. Changes in emission or phosphorescence may increase or decrease in intensity. The change in refractive index is caused by the change in the dielectric constant of the portion that changes with the reaction of the molecule. The measurement is often performed in air, and the light used is preferably in the ultraviolet and visible light region, and the value is preferably changed in the range of 0.1 to 3.2. The change in the liquid crystal state is caused by a change in the orientation state of the molecule that changes with the reaction of the molecule, and in particular, a change between the isotropic liquid state and the nematic liquid crystal or the smectic liquid crystal is used. Polarized light in the UV-visible region is used.
Ｘ線による光電子運動エネルギーの変化は、分子の反応に伴って変化する分子内の原子状態の変化に起因するもので、観測される光電子運動エネルギーの変化を測定する。光源として、ＭｇＫαやＡｌＫαのＸ線を用いるのが好ましい。反応の観点から測定する光電子運動エネルギーの変化は２００〜８００ｅＶの範囲を測定することが好ましい。以上の１つもしくは２つ以上の組み合わせの光学的変化を用いることで、感度よく、検出対象とするフッ素化不飽和炭化水素を検出できる。 The change in photoelectron kinetic energy due to X-rays is caused by the change in the atomic state in the molecule that changes with the reaction of the molecule, and the change in the observed photoelectron kinetic energy is measured. As the light source, X-rays of MgKα and AlKα are preferably used. The change in photoelectron kinetic energy measured from the viewpoint of reaction is preferably measured in the range of 200 to 800 eV. By using the optical change of the above one or a combination of two or more, the fluorinated unsaturated hydrocarbon to be detected can be detected with high sensitivity.
本発明を用いることで、感度よく、フッ素化不飽和炭化水素を検出することができる。例えば、５０〜１０００ｐｐｍの検出対象のガスの検出ができる。実用化の観点から、５ｐｐｍの濃度の検出が望ましくそれが可能である。管理基準濃度の観点からは、２ｐｐｍの濃度の検出が望ましくそれが可能である。事業化および信頼性の向上のためには、１分以内で０．１ｐｐｍ以下の濃度の検出が望ましい。 By using the present invention, fluorinated unsaturated hydrocarbons can be detected with high sensitivity. For example, the detection target gas of 50 to 1000 ppm can be detected. From the viewpoint of practical use, detection of a concentration of 5 ppm is desirable and possible. From the viewpoint of the control reference concentration, detection of a concentration of 2 ppm is desirable and possible. For commercialization and improvement of reliability, it is desirable to detect a concentration of 0.1 ppm or less within 1 minute.
本発明は、イミダゾリン誘導体を利用した室温付近でスムーズに進行する反応により、光学的変化を測定するが、有機分子特有の反応群を利用するため、特徴的な選択性が発揮される。すなわち、空気中の二酸化炭素などの影響を受けない。 The present invention measures an optical change by a reaction that proceeds smoothly around room temperature using an imidazoline derivative, but exhibits a characteristic selectivity because it uses a reaction group unique to organic molecules. That is, it is not affected by carbon dioxide in the air.
本発明は、イミダゾリン誘導体を利用した室温付近でスムーズに進行する特殊な反応により、光学的変化を測定するが、そのシグナルの処理は、装置、パソコン、ソフトを組み合わせることで測定でき、それらの機種や種類、形態に限定されることはなく、現存するもしくは作製されたものを工夫して用いることで十分に測定できる。光学的変化は、各スペクトルの特定の波長のピーク強度の変化やある波長域の積分値の変化やスペクトル形状の変化で捉えることができる。その際、基準となる各スペクトルの特定の波長のピーク強度やある波長域の積分値やスペクトル形状を設定することでより正確な変化を捉えることができる。これらの組み合わせにより、最終的に、検出対象とするフッ素化不飽和炭化水素を、選択的に感度よく検出できる。 The present invention measures optical changes by a special reaction that progresses smoothly around room temperature using an imidazoline derivative, but the signal processing can be measured by combining devices, personal computers, and software. It is not limited to the type or form, and it can be measured sufficiently by devising and using existing or produced. An optical change can be grasped by a change in peak intensity at a specific wavelength in each spectrum, a change in an integrated value in a certain wavelength region, or a change in spectrum shape. At that time, a more accurate change can be captured by setting a peak intensity of a specific wavelength of each spectrum serving as a reference, an integral value of a certain wavelength region, or a spectrum shape. By these combinations, finally, the fluorinated unsaturated hydrocarbon to be detected can be selectively detected with high sensitivity.
以下、実施例により本発明を説明するが、本発明はこれらの実施例により何ら限定されるものではない。本発明の技術思想の範囲内での変更及び他の態様又は実施例は、全て本発明に含まれる。尚、紫外可視光吸収スペクトルおよび発光スペクトルの測定は市販の装置を用いて行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples. All modifications and other embodiments or examples within the scope of the technical idea of the present invention are included in the present invention. The ultraviolet-visible light absorption spectrum and emission spectrum were measured using a commercially available apparatus.
（実施例１）
1-Propyl-2-methylimidazoleをアセトニトリルに溶解させ約０．２５ｍｍｏｌ／Ｌの溶液を作製した。その溶液を発光スペクトル用のセルに導入し、窒素ベースのガス状の濃度約２０ｐｐｍのＣ5Ｆ8を流量約５０ｍＬ/分で３０秒バブリングし、励起光３５０ｎｍによる発光スペクトルを観測した。４５０ｎｍ前後±５０ｎｍにおいて約４３０ｎｍにピークを有する特徴的なスペクトルが得られた。このスペクトルはバブリング直後から５分後までその強度を増強させることがわかった。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
Example 1
The 1-Propyl-2-methylimidazol e to produce a solution of about 0.25 mmol / L dissolved in acetonitrile. The solution was introduced into a cell for emission spectrum, C 5 F 8 having a nitrogen-based gaseous concentration of about 20 ppm was bubbled for 30 seconds at a flow rate of about 50 mL / min, and an emission spectrum by excitation light at 350 nm was observed. A characteristic spectrum having a peak at about 430 nm at about ± 50 nm around 450 nm was obtained. This spectrum was found to increase its intensity from just after bubbling to 5 minutes later.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例２）
1-Proryl-2-methylimidazolineをアセトニトリルに溶解させ約２．５ｍｍｏｌ／Ｌの溶液を作製した。その溶液を発光スペクトル用のセルに導入し、窒素ベースのガス状の濃度約２ｐｐｍのＣ5Ｆ8を流量約２００ｍＬ/分で１０秒バブリングし、励起光３６５ｎｍによる発光スペクトルを観測した。本実施例では発光スペクトルにおける４５０ｎｍの強度をモニタリングし、その結果、その強度が２分以内に増大することがわかった。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
(Example 2)
1-Proryl-2-methylimidazoline was dissolved in acetonitrile to prepare a solution of about 2.5 mmol / L. The solution was introduced into a cell for emission spectrum, and nitrogen-based gaseous C 5 F 8 having a concentration of about 2 ppm was bubbled at a flow rate of about 200 mL / min for 10 seconds, and an emission spectrum with excitation light of 365 nm was observed. In this example, the intensity of 450 nm in the emission spectrum was monitored, and as a result, it was found that the intensity increased within 2 minutes.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例３）
1-Propyl-2-methylimidazolineをアセトニトリルに溶解させ、吸収スペクトル用のセルに導入し、窒素ベースのガス状の濃度約１０％（１０5ｐｐｍ）のＣ5Ｆ8を１〜５ｍLバブリングしたところ、３００ｎｍ前後±１００ｎｍにおいてスペクトル変化が観測され、特に約２５５ｎｍのピーク強度が時間とともに（約８分まで）増大することがわかった。
以上、光学的変化の手法の一つを使うことにより、ガス状の不飽和炭化水素のフッ化物の一種であるＣ5Ｆ8を検出できた。
(Example 3)
1-Propyl-2-methylimidazoline was dissolved in acetonitrile, introduced into an absorption spectrum cell, and nitrogen-based gaseous concentration of about 10% (10 5 ppm) of C 5 F 8 was bubbled for 1 to 5 mL. Spectral changes were observed at around ± 100 nm around 300 nm, and in particular, it was found that the peak intensity at about 255 nm increased with time (up to about 8 minutes).
As described above, C 5 F 8 , which is a kind of gaseous unsaturated hydrocarbon fluoride, can be detected by using one of the optical change methods.
（実施例４）
1,2-dimethylbenzimidazole約１４６ｍｇを有機溶媒の１種であるN-メチル-2-ピロリドン（NMP）１ｍＬに混合した。そこへ濃度約１ＭのＣ5Ｆ8のacetone溶液１ｍＬを加えると黄褐色の変化が、紫外可視吸収４２０ｎｍ前後±１００ｎｍにおいて確認できた。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
Example 4
About 146 mg of 1,2-dimethylbenzimidazole was mixed with 1 mL of N-methyl-2-pyrrolidone (NMP) which is one kind of organic solvent. When 1 mL of a C 5 F 8 acetone solution having a concentration of about 1 M was added thereto, a yellowish brown change was confirmed at UV-visible absorption around 420 nm ± 100 nm.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例５）
1-Propyl-2-methylimidazolineをアセトニトリルに溶解させ、吸収スペクトル用のセルに導入し、窒素ベースのガス状の濃度約１００％（１０6ｐｐｍ）のＣ5Ｆ8を１ｍＬバブリングしたところ、３００ｎｍ前後±１００ｎｍにおいてスペクトル変化が観測され、特に約２５５ｎｍと約３６５ｎｍのピーク強度が時間とともに増大することがわかった。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
(Example 5)
1-Propyl-2-methylimidazoline was dissolved in acetonitrile, introduced into an absorption spectrum cell, and 1 mL of nitrogen-based gaseous concentration of about 100% (10 6 ppm) of C 5 F 8 was bubbled around 300 nm. Spectral changes were observed at ± 100 nm, and it was found that the peak intensities at about 255 nm and about 365 nm increased with time.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例６）
2-Naphtyl-1-propylimidazoline５ｍｇを、エタノール５ｍＬと０．５ｍＬのＰＥＧ２００（低分子量ポリエチレングリコール）に溶解させ、その混合溶液を、ポリスチレンビーズ（２００−４００ｍｅｓｈ）５００ｍｇに浸み込ませた。得られた粉体を自然乾燥後、約２時間ロータリーポンプで減圧下におき十分に乾燥させた。次に、乾燥した粉体をキャピラリーガラス管に約１ｃｍほど詰め、窒素ベースのガス状の濃度約１％（１０4ｐｐｍ）のＣ5Ｆ8を約１０ｍＬ通したところ、励起光３６５ｎｍにおいて、明らかな蛍光が顕微鏡により観測された。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
(Example 6)
2-Naphtyl-1-propylimidazoline (5 mg) was dissolved in ethanol (5 mL) and 0.5 mL of PEG200 (low molecular weight polyethylene glycol), and the mixed solution was immersed in 500 mg of polystyrene beads (200-400 mesh). The obtained powder was air-dried and then dried under a reduced pressure with a rotary pump for about 2 hours. Next, the dried powder was packed in a capillary glass tube by about 1 cm, and about 10 mL of nitrogen-based gaseous concentration of about 1% (10 4 ppm) C 5 F 8 was passed through. Fluorescence was observed with a microscope.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例７）
2-Naphtyl-1-propylimidazoline８ｍｇを、エタノール５ｍＬと０．５ｍＬのＰＥＧ２００（低分子量ポリエチレングリコール）に溶解させ、その混合溶液を、ポリスチレンビーズ（２００−４００ｍｅｓｈ）５００ｍｇに浸み込ませた。得られた粉体を自然乾燥後、約３０分間ロータリーポンプで減圧下におき乾燥させた。次に、乾燥した粉体を両面テープで貼ったガラス板に押し付けて固定し、発光用セル内に設置した。そこへ約３６５ｎｍの紫外線を照射しながら、窒素ベースのガス状の濃度約２ｐｐｍのＣ5Ｆ8を流量約５００ｍＬ/分で１分ずつ通しながら、励起光４５０ｎｍによる４９０〜５６０ｎｍの範囲において発光スペクトルを記録したところ、明らかな発光の増強が観測された。特に、５１０ｎｍ前後の変化が観測された。尚、発光スペクトル測定中には約３６５ｎｍの紫外線は照射しない。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
(Example 7)
8 mg of 2-Naphtyl-1-propylimidazoline was dissolved in 5 mL of ethanol and 0.5 mL of PEG200 (low molecular weight polyethylene glycol), and the mixed solution was immersed in 500 mg of polystyrene beads (200-400 mesh). The obtained powder was naturally dried and then dried under reduced pressure with a rotary pump for about 30 minutes. Next, the dried powder was pressed and fixed to a glass plate pasted with a double-sided tape, and placed in a light emitting cell. Emission spectrum in the range of 490 to 560 nm with excitation light of 450 nm, while passing nitrogen-based gaseous concentration of about 2 ppm C 5 F 8 at a flow rate of about 500 mL / min for 1 minute while irradiating it with ultraviolet rays of about 365 nm. As a result, a clear enhancement of light emission was observed. In particular, a change around 510 nm was observed. During the emission spectrum measurement, ultraviolet rays of about 365 nm are not irradiated.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例８）
2-(4-Dimethylaminophenylvinyl)-1-methylbenzimidazole約１０ｍｇをBis(pentamethylene)urea５０ｍｇにとかし、Poly(butadiene)８０ｍｇに混ぜたものをガラス上に展開し、乾燥しフィルム状にした。室温ではBis(pentamethylene)urea固体状であるが、６０℃では、ゲルのような液体状になり反応性が増す。そこで６０℃ホットプレート上でセル内に固定した該フィルムに、ドライ窒素ベースのガス状の濃度約５０ｐｐｍのＣ5Ｆ8を流量約２Ｌ/分で流し、発光の状態を観測した。発光の測定には、励起波長４６０ｎｍの光を用い、その際、該基板表面から発せられる４９０〜５６０ｎｍの光を観測した。その結果、約５２０ｎｍ前後に特異的な発光が観測され、その発光強度が系統的に変化することがわかった。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8の混合ガスを、イミダゾリン誘導体を含んだテープ上もしくはシート上に吹き付ける態様で検出できた。
(Example 8)
2- (4-Dimethylaminophenylvinyl) dissolved -1-methylbenzimidazol e about 10mg to Bis (pentamethylene) urea50mg, those mixed with Poly (butadiene) 80mg were applied to glass, and in a dry film form. Bis (pentamethylene) urea is solid at room temperature, but at 60 ° C., it becomes a gel-like liquid and the reactivity increases. Therefore, dry nitrogen-based gaseous C 5 F 8 was flowed at a flow rate of about 2 L / min on the film fixed in the cell on a 60 ° C. hot plate, and the state of luminescence was observed. For measurement of light emission, light having an excitation wavelength of 460 nm was used, and light at 490 to 560 nm emitted from the substrate surface was observed at that time. As a result, specific light emission was observed around about 520 nm, and the light emission intensity was systematically changed.
As described above, by using one of the optical change methods, it is possible to detect a mixed gas of C 5 F 8 which is a kind of fluorinated unsaturated hydrocarbon on a tape or sheet containing an imidazoline derivative. It was.
（実施例９）
2-(4-Dimethylaminophenylvinyl)-1-decylbenzimidazole約５ｍｇおよび溶媒の１種であるＮ−メチル−２−ピロリドン（NMP）０．５ｍＬを含んだクロロホルム混合液を約４５℃に加熱し、そこへドライ窒素ベースのガス状の飽和Ｃ5Ｆ8をバブリングし、吸収スペクトルの状態を観測した。その結果、約４８０ｎｍ前後に特異的な吸収が観測されることがわかった。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8の混合ガスを、その態様によることなく検出できた。
Example 9
A chloroform mixture containing about 5 mg of 2- (4-Dimethylaminophenylvinyl) -1-decylbenzimidazole and 0.5 mL of N-methyl-2-pyrrolidone (NMP), one of the solvents, is heated to about 45 ° C. and dried there. Nitrogen-based gaseous saturated C 5 F 8 was bubbled and the state of the absorption spectrum was observed. As a result, it was found that specific absorption was observed around about 480 nm.
As described above, by using one of the optical change techniques, a mixed gas of C 5 F 8 which is a kind of fluorinated unsaturated hydrocarbon can be detected without depending on the mode.
（実施例１０）
2-Naphtyl-1-propyimidazoline５ｍｇを、エタノール５ｍＬと０．５ｍＬのＰＥＧ２００（低分子量ポリエチレングリコール）に溶解させ、その混合溶液を、ポリスチレンビーズ（２００−４００ｍｅｓｈ）５００ｍｇに浸み込ませた。得られた粉体を自然乾燥後、約２時間ロータリーポンプで減圧下におき十分に乾燥させた。次に、乾燥した粉体をキャピラリーガラス細管に約１ｃｍ詰め、窒素ベースのガス状の濃度約１％（１０4ｐｐｍ）のＣ4Ｆ6を約１０ｍL通したところ、励起光３６５ｎｍにおいて、明らかな蛍光が顕微鏡により観測された。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素の一種であるＣ5Ｆ8を検出できた。
(Example 10)
2-Naphtyl-1-propyimidazoline (5 mg) was dissolved in ethanol (5 mL) and 0.5 mL of PEG200 (low molecular weight polyethylene glycol), and the mixed solution was immersed in 500 mg of polystyrene beads (200-400 mesh). The obtained powder was air-dried and then dried under a reduced pressure with a rotary pump for about 2 hours. Next, the dried powder was packed in a capillary glass capillary tube by about 1 cm, and about 10 mL of nitrogen-based gaseous concentration of about 1% (10 4 ppm) of C 4 F 6 was passed through. Fluorescence was observed with a microscope.
As described above, C 5 F 8 , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.
（実施例１１）
2-Naphtyl-1-propylimidazoline約１００ｍｇと３−ヒドロキシフラボン約３００ｍｇを溶媒の１種であるＮ−メチル−２−ピロリドン（NMP）５ｍＬへ混合した。そこへドライ窒素ベースのガス状の濃度約５００ｐｐｍのＣ5Ｆ8を約５ｍＬバブリングしたところ、可視吸収変化が５００〜６００ｎｍにおいて確認できた。
以上、光学的変化の手法の一つを使うことにより、フッ素化不飽和炭化水素であるＣ5Ｆ8を検出できた。
(Example 11)
About 100 mg of 2-Naphtyl-1-propylimidazoline and about 300 mg of 3-hydroxyflavone were mixed with 5 mL of N-methyl-2-pyrrolidone (NMP) which is one kind of solvent. When about 5 mL of C 5 F 8 having a gaseous concentration of about 500 ppm based on dry nitrogen was bubbled therein, a change in visible absorption could be confirmed at 500 to 600 nm.
As described above, C 5 F 8 which is a fluorinated unsaturated hydrocarbon can be detected by using one of the optical change methods.
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