JPH04134252A - Storing method for electroconductive highpolymer film - Google Patents
Storing method for electroconductive highpolymer filmInfo
- Publication number
- JPH04134252A JPH04134252A JP2255321A JP25532190A JPH04134252A JP H04134252 A JPH04134252 A JP H04134252A JP 2255321 A JP2255321 A JP 2255321A JP 25532190 A JP25532190 A JP 25532190A JP H04134252 A JPH04134252 A JP H04134252A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyaniline
- oxygen
- polyaniline film
- preserving
- 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
Links
- 238000000034 method Methods 0.000 title claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 7
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 11
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 abstract description 29
- 108090000790 Enzymes Proteins 0.000 abstract description 6
- 102000004190 Enzymes Human genes 0.000 abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- -1 polyethylene Polymers 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000006392 deoxygenation reaction Methods 0.000 abstract 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 5
- 108010093096 Immobilized Enzymes Proteins 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
発明の背景
技術分野
この発明はポリアニリン膜およびその誘導体膜を含む導
電性高分子膜の保存方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving conductive polymer films including polyaniline films and derivative films thereof.
従来技術とその問題点
導電性高分子膜の一種であるポリアニリン膜を例にとっ
て説明する。ポリアニリン膜は溶液中のｐＨ濃度に応じ
て吸収スペクトルが変化するので、これを用いて光検出
型のｐＨセンサを構成することができる。また、ポリア
ニリン膜に酵素を固定化した固定化酵素膜は溶液中の基
質を分解して酸またはアルカリを生じさせ、この酸また
はアルカリによる ｐＨ濃度の変化に対して吸収スペク
トルか変化するので、これを用いて光検出型の酵素セン
サを構成することができる。さらにポリアニリン膜は酸
性ガスまたはカルアリ性ガスに接触すると吸収スペクト
ルが変化するので、これを用いて光検出型のガス・セン
サを構成することができる。さらにポリアニリン膜は溶
液中のｐＨ濃度に応じて電極電位が変化するのでこれを
用いて電位検出型のｐＨセンサを構成することができ、
同じように電位検出型のガス・センサを構成することも
できる。ポリアニリン膜に酵素を固定化した固定化酵素
膜を用いて電位検出型の酵素センサを構成することもで
きる。Prior art and its problems will be explained by taking a polyaniline film, which is a type of conductive polymer film, as an example. Since the absorption spectrum of the polyaniline film changes depending on the pH concentration in the solution, it can be used to construct a photodetection type pH sensor. In addition, an immobilized enzyme membrane in which an enzyme is immobilized on a polyaniline membrane decomposes a substrate in a solution to produce acid or alkali, and the absorption spectrum changes in response to changes in pH concentration due to this acid or alkali. A photodetection type enzyme sensor can be constructed using this. Furthermore, since the absorption spectrum of the polyaniline film changes when it comes into contact with acidic gas or calariic gas, it can be used to construct a photodetection type gas sensor. Furthermore, since the electrode potential of the polyaniline membrane changes depending on the pH concentration in the solution, it can be used to construct a potential detection type pH sensor.
A potential detection type gas sensor can also be constructed in the same way. A potential detection type enzyme sensor can also be constructed using an immobilized enzyme membrane in which an enzyme is immobilized on a polyaniline membrane.
しかしながら、ポリアニリン膜は空気中に長時間放置し
ておくと、徐々にその吸収スペクトルが変化し、特性が
劣化するので長期保存ができないという問題点かあった
。However, if a polyaniline film is left in the air for a long time, its absorption spectrum will gradually change and its properties will deteriorate, so there is a problem that it cannot be stored for a long time.
発明の概要
この発明は導電性高分子膜の特性を劣化させることなく
長期的に保存できる方法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method that allows conductive polymer membranes to be stored for a long period of time without deteriorating their properties.
この発明による保存方法は導電性高分子膜を酸素を除い
た雰囲気中で保存するものである。The preservation method according to the present invention is to preserve a conductive polymer film in an atmosphere excluding oxygen.
この発明による保存方法は、導電性高分子膜を脱酸素剤
（たとえば活性酸化鉄）を入れた密封容器内で保存する
ものである。吸湿剤（たとえばシリカゲル）を密封容器
内に入れると一層好ましい。容器とは気密性の高い袋を
含む。The preservation method according to the present invention is to preserve a conductive polymer film in a sealed container containing an oxygen scavenger (for example, activated iron oxide). More preferably, the hygroscopic agent (eg silica gel) is placed in a sealed container. Containers include airtight bags.
後に詳述するように導電性高分子膜の特性劣化は酸素の
存在に起因するので、酸素を排除した状態で保存するこ
とにより吸収スペクトルの変化等の特性劣化を殆ど生じ
させることなく長期にわたって保存できるようになる。As will be explained in detail later, the deterioration of the properties of conductive polymer films is due to the presence of oxygen, so by storing them in a state in which oxygen is excluded, they can be stored for long periods of time without causing any deterioration of properties such as changes in the absorption spectrum. become able to.
実施例
ポリアニリン膜は、波長８００ｎｍにおける吸光度光検
出型のｐＨセンサとして使用できる（特願平１−９９９
８２号参照）。しかし、ポリアニリン膜は長時間空気中
に放置しておくと、徐々にその吸収スペクトルが変化し
、保存時間の長さや保存状態により測定値かばらつく、
長期保存ができないなどの問題点かあった。現象的にい
うと、塩酸酸性アニリン水溶液から電解重合法によって
得られたポリアニリン膜は緑色であるが、空気中に放置
すると徐々に青味を帯びてくる。The polyaniline film of the example can be used as an absorbance photodetection type pH sensor at a wavelength of 800 nm (Patent application No. 1-999).
(See No. 82). However, if a polyaniline film is left in the air for a long time, its absorption spectrum will gradually change, and the measured values will vary depending on the length of storage time and storage conditions.
There were some problems, such as the inability to store it for a long time. In terms of phenomena, a polyaniline film obtained by electrolytic polymerization from an aqueous solution of aniline acidified with hydrochloric acid is green in color, but gradually becomes bluish when left in the air.
このポリアニリン膜の空気中での劣化の原因は、ポリア
ニリン膜の表面が空気中に存在する酸素により酸化され
るためと考えられ、これを確かめるために以下の実験を
行なった。The reason for this deterioration of the polyaniline film in the air is thought to be that the surface of the polyaniline film is oxidized by oxygen present in the air, and the following experiment was conducted to confirm this.
まず１透明電極（ＮＥＳＡ／ ＩＴＯ／無アルカリガラ
ス基板）上に電解重合法によりポリアニリン膜を作成し
た。このポリアニリン膜を、（１）酸素＋吸湿剤、（２
）酸素、（３）空気＋吸湿剤、（４）空気。First, a polyaniline film was formed on a transparent electrode (NESA/ITO/alkali-free glass substrate) by electrolytic polymerization. This polyaniline film is divided into (1) oxygen + moisture absorbent, (2)
) oxygen, (3) air + moisture absorbent, (4) air.
（５）空気＋脱酸素剤、および（６）空気＋脱酸素剤中
吸湿剤をそれぞれ入れた気密性の高い袋にそれぞれ別個
に密封し、７日間放置した。吸湿剤としてはシリカゲル
を、脱酸素剤としては活性酸化鉄を用いた。作製直後（
保存前）と保存後の波長８００ｒ＋Ｉ１１におけるポリ
アニリン膜の吸光度を分光光度計を用いて測定し、その
変化率を評価した。この結果が第１図に示されている。(5) air + oxygen absorber and (6) air + moisture absorber in oxygen absorber were respectively sealed in airtight bags and left for 7 days. Silica gel was used as a moisture absorbent, and activated iron oxide was used as an oxygen scavenger. Immediately after fabrication (
The absorbance of the polyaniline film at a wavelength of 800r+I11 (before storage) and after storage was measured using a spectrophotometer, and the rate of change was evaluated. The results are shown in FIG.
第１図において、縦軸は波長ａｏＯｎａｉにおける吸光
度の変化率（％）を示し、それは。In FIG. 1, the vertical axis indicates the rate of change (%) in absorbance at wavelength aoOnai, which is .
で表わされる。It is expressed as
第２図は一例として、ポリアニリン膜の吸光度の分光特
性を示すものである。実線は保存前のスペクトルを、破
線は７日間空気中に保存した後のスペクトルをそれぞれ
示している。FIG. 2 shows, as an example, the spectral characteristics of the absorbance of a polyaniline film. The solid line shows the spectrum before storage, and the broken line shows the spectrum after storage in air for 7 days.
ポリアニリン膜を酸素の存在する雰囲気中で保存した場
合、吸光度の変化率は大きいことが分った。とくに吸湿
剤を併用すると変化率はさらに大きくなる。これに対し
、ポリアニリン膜を脱酸素剤を入れた雰囲気中で保存し
た場合、波長８００ｎｍにおける吸光度の変化率は小さ
いことか分った。It was found that when a polyaniline film was stored in an atmosphere containing oxygen, the rate of change in absorbance was large. In particular, when a moisture absorbent is used in combination, the rate of change becomes even greater. On the other hand, it was found that when the polyaniline film was stored in an atmosphere containing an oxygen scavenger, the rate of change in absorbance at a wavelength of 800 nm was small.
これにより、ポリアニリン膜の吸収スペクトルが空気中
で徐々に変化する主因は酸素であることか明らかになっ
た。また脱酸素剤と吸湿剤を併用することにより、さら
に吸収スペクトルの変化を抑制できることが分った。This revealed that oxygen is the main cause of the gradual change in the absorption spectrum of polyaniline films in air. It was also found that changes in the absorption spectrum can be further suppressed by using an oxygen scavenger and a moisture absorbent together.
これらの事実は、ポリアニリン膜を脱酸素剤。These facts make polyaniline membrane an oxygen scavenger.
または脱酸素剤と吸湿剤を用いた雰囲気中に保存するこ
とによって、保存時間の長さの差による測定値のばらつ
きを小さくすることができ、とくに光検出型のｐＨセン
サとして使用できることを示している。ポリアニリン膜
に酵素を・固定化した固定化酵素膜についても同じであ
り、また電位検出型のｐＨセンサとして用いる場合も同
様に考えることができる。Alternatively, by storing it in an atmosphere containing oxygen scavengers and moisture absorbers, it is possible to reduce the variation in measured values due to differences in storage time, and it has been shown that it can be used particularly as a photodetection type pH sensor. There is. The same applies to an immobilized enzyme membrane in which an enzyme is immobilized on a polyaniline membrane, and can be considered similarly when used as a potential detection type pH sensor.
具体的な保存方法正してはポリアニリン膜または固定化
酵素ポリアニリン膜を、酸素透過率の大きいフィルム（
ポリエチレン）または通気性のよい紙に包んだ脱酸素剤
（活性酸化鉄）とともに密封性のよい容器に入れて保存
するとよい。Specific preservation method The correct method is to store the polyaniline membrane or immobilized enzyme polyaniline membrane in a film with high oxygen permeability (
It is best to store it in a well-sealed container with an oxygen absorber (active iron oxide) wrapped in polyethylene) or breathable paper.
第１図は各種雰囲気中に保存したポリアニリン膜の波長
８００ｎｍにおける吸光度の変化率を示すグラフである
。
第２図はポリアニリン膜の吸光度の保存前後の分光特性
を示すグラフである。
以 上FIG. 1 is a graph showing the rate of change in absorbance at a wavelength of 800 nm for polyaniline films stored in various atmospheres. FIG. 2 is a graph showing the spectral characteristics of the absorbance of a polyaniline film before and after storage. that's all
Claims (1)
る，導電性高分子膜の保存方法。（２）導電性高分子膜
を，脱酸素剤を入れた密封容器内で保存する，導電性高
分子膜の保存方法。 （３）上記密封容器内に吸湿剤を入れることを特徴とす
る請求項（２）に記載の導電性高分子膜の保存方法。[Scope of Claims] (1) A method for preserving a conductive polymer film, in which the conductive polymer film is stored in an atmosphere excluding oxygen. (2) A method for preserving a conductive polymer film, in which the conductive polymer film is stored in a sealed container containing an oxygen scavenger. (3) The method for preserving a conductive polymer film according to claim (2), characterized in that a moisture absorbent is placed in the sealed container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255321A JPH04134252A (en) | 1990-09-27 | 1990-09-27 | Storing method for electroconductive highpolymer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255321A JPH04134252A (en) | 1990-09-27 | 1990-09-27 | Storing method for electroconductive highpolymer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04134252A true JPH04134252A (en) | 1992-05-08 |
Family
ID=17277159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255321A Pending JPH04134252A (en) | 1990-09-27 | 1990-09-27 | Storing method for electroconductive highpolymer film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04134252A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019054191A1 (en) * | 2017-09-14 | 2019-03-21 | 富士フイルム株式会社 | Solid electrolyte composition, method for producing same, storage method and kit, solid electrolyte-containing sheet, storage method and kit therefor, and all-solid secondary battery |
-
1990
- 1990-09-27 JP JP2255321A patent/JPH04134252A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019054191A1 (en) * | 2017-09-14 | 2019-03-21 | 富士フイルム株式会社 | Solid electrolyte composition, method for producing same, storage method and kit, solid electrolyte-containing sheet, storage method and kit therefor, and all-solid secondary battery |
| US11621436B2 (en) | 2017-09-14 | 2023-04-04 | Fujifilm Corporation | Solid electrolyte composition, manufacturing method thereof, storage method thereof, kit thereof, solid electrolyte-containing sheet, storage method thereof, kit thereof, and all-solid state secondary battery |
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