JPS6348330A - Production of electroconductive polymer - Google Patents
Production of electroconductive polymerInfo
- Publication number
- JPS6348330A JPS6348330A JP19325986A JP19325986A JPS6348330A JP S6348330 A JPS6348330 A JP S6348330A JP 19325986 A JP19325986 A JP 19325986A JP 19325986 A JP19325986 A JP 19325986A JP S6348330 A JPS6348330 A JP S6348330A
- Authority
- JP
- Japan
- Prior art keywords
- film
- electroconductive polymer
- furan
- pyrrole
- thiophene
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 title abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 7,7,8,8- tetracyanoquinodimethane anion Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 6
- 229930192474 thiophene Natural products 0.000 claims abstract description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000012769 display material Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 21
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は電子部品関連の電極材料、保護膜材料、表示材
料に利用できる導電性高分子の製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing conductive polymers that can be used as electrode materials, protective film materials, and display materials related to electronic components.
従来の技術
導電性高分子の製法としては次のようなものが知られて
いる。BACKGROUND OF THE INVENTION The following methods are known as methods for producing conductive polymers.
■ 高分子体中に金属粉末を分散させる。■ Disperse metal powder in a polymer.
■ ポリアクリロニトリル（ＰＡＮ）や芳香族有機化合
物を焼成させる。■ Sintering polyacrylonitrile (PAN) and aromatic organic compounds.
■ ＣＶＤ法を用いてつくる。■Made using the CVD method.
■ 電解重合法
発明が解決しようとする問題点
ところが、以上の高分子の製法では、用途的（二はある
限定条件が入る。即ち■の場合は金属粉末の分散状態が
問題となるし、高分子膜化する場合、熱成形、あるいは
溶液キャスト法などを利用するが薄膜化がむずかしい。■ Problems to be solved by the electrolytic polymerization method invention However, in the above-mentioned polymer production method, certain limiting conditions apply (second). Namely, in the case of When forming a molecular film, thermoforming or solution casting methods are used, but it is difficult to form a thin film.
■の場合は焼成を行って、導電性繊維あるいは導電性フ
ィルム化する。この場８、焼ユ温度、雰囲気。間ヨヵ、
あ１）、まえ、井′らを利用する（二は他の高分子との
複合化などが必要となる。■の場合は、無機膜の製法と
類似したもので、製造装置上からの制約が大きく、容易
には均一な良好な大面積の膜は得られない。■の方法は
電気化学的な反応を利用した製法であるから、重合反応
を行うためには導電性基板上でなければならない制約が
あり、平滑で均一な膜は得られにくい。In the case of (2), firing is performed to form conductive fibers or conductive films. This place 8, grilling temperature, atmosphere. Interlude,
A1), first, using I' et al. (Second) requires compositing with other polymers, etc. In the case of ■, it is similar to the manufacturing method of inorganic membranes, and there are restrictions from the manufacturing equipment. is large, and it is not easy to obtain a good, uniform, large-area film.Since method (2) uses an electrochemical reaction, it must be on a conductive substrate in order to carry out the polymerization reaction. There are certain limitations that make it difficult to obtain a smooth and uniform film.
また最近、ピロールを用いて、電解重合法で導電性高分
子を製造することが盛んに行われている。Furthermore, recently, the production of conductive polymers using pyrrole by electrolytic polymerization has been actively carried out.
ピロールを溶解した電解液中に電極を浸漬して電解をか
けると陽極側にポリピロール膜が生成できる。アニオン
がドーピングされた状態で低い電気抵抗、脱ドーピング
された状態で高い電気抵抗を有する。しかしながらこの
方法も上述の通りの制約や問題を有しており、しかも厚
膜な形成するのが困難であるという問題点もある。When an electrode is immersed in an electrolytic solution in which pyrrole is dissolved and electrolysis is applied, a polypyrrole film can be formed on the anode side. It has low electrical resistance when doped with anions and high electrical resistance when undoped. However, this method also has the limitations and problems described above, and furthermore, it is difficult to form a thick film.
本発明はかかる問題点を解決するためになされたもので
、重合法が容易、導電性付与が容易、製膜化が容易及び
耐熱性が高い導電性高分子が得られる製造方法を提供す
ることを目的とするものである。The present invention has been made in order to solve these problems, and provides a manufacturing method that allows for easy polymerization, easy imparting of conductivity, easy film formation, and obtaining a conductive polymer with high heat resistance. The purpose is to
問題点を解決するための手段
本発明は上記目的を達成するもので、ビロール、チオフ
ーン、フランから選ばれる複素五員環化合物と、７．７
．８．８−テトラシアノキノジメタンアニオンの混合物
とから加熱処理により生成される導電性高分子の製造方
法である。Means for Solving the Problems The present invention achieves the above objects, and includes a five-membered heterocyclic compound selected from virol, thiophone, and furan;
．． 8. A method for producing a conductive polymer produced by heat treatment from a mixture of 8-tetracyanoquinodimethane anions.
作 用
本発明によれはビロール、テオフーン、あるいはフラン
とＴＣＮＱ塩の重合体を加熱処理のみで容易に重合体を
生成させることができ、かつ導電性の付与も容易である
。この重合体は製膜化も容易で耐熱性のある膜をつくる
ことができる。Effects According to the present invention, a polymer of virol, theophone, or furan and TCNQ salt can be easily produced by simply heating the polymer, and it is also easy to impart conductivity to the polymer. This polymer is easy to form into a film and can be used to form a heat-resistant film.
七ツマ−であるビロール、チオフェン、フランなどの複
素五員環化合物とＴＣＮＱ塩を混合したものから、加熱
処理により導電性の高分子体をつくることを提供するこ
とが本発明の特徴である。A feature of the present invention is to provide a method for producing a conductive polymer by heat treatment from a mixture of a five-membered heterocyclic compound such as pyrrole, thiophene, or furan, which is a heptadum, and a TCNQ salt.
ビロールなどは液状であるから、ＴＣＮＱ塩との混合も
容易で、ＴＣＮＱ塩によってはビロール（二溶解するも
の溶液状態、溶解しないものはペースト状にすることに
より、重合反応を行うことができる。重合反応は、はや
いものはビロールとＴＣＮＱ塩を混合したのみでおこる
。重合反応は加熱することにより、反応速度は、はやま
り、かつ重合度も高まる。Since virol and the like are liquid, they can be easily mixed with TCNQ salts, and depending on the TCNQ salt, virol (dissolved ones can be made into a solution state, and those which are not soluble can be made into a paste form to carry out the polymerization reaction.Polymerization The reaction can be carried out quickly by simply mixing virol and TCNQ salt. By heating the polymerization reaction, the reaction rate is accelerated and the degree of polymerization is also increased.
ＴＣＮＱ塩の導電度は数Ωａｍから〜１０１６Ω・Ｃｍ
のものがあり、ポリピロールの重合体のみでも１０°Ω
・ｃｍ以下になることが知られている。ビロールとＴＣ
ＮＱ塩の混合重合体においてもＴＣＮＱ塩の選択とビロ
ールの酸化状態をかえることにより、導電度も広い範囲
にわたって容易にかえることができる。製膜化はビロー
ルが液状のため、ＴＣＮＱ塩と混合しても、溶液状ある
いはペースト状が得られるため、様々の基板、あるいは
フィルム面上に塗布できる。均一な薄膜を得たい場合は
、ピローノベＴＣＮＱ塩がともに溶解するような溶媒で
希釈などを行うと得やすい。また、ビロール重合体は架
橋反応を生じるために、耐熱性が高く、硬い膜が得られ
る。２５０〜３００°Ｃ程度までは十分に安定な膜が得
られる。ＴＣＮＱ塩としては、Ａ（ＴＣＮＱ）２−Ｘ組
成であり、 ＡはＬ＋”、 Ｎａ−１−、Ｆｅ２＋、
Ｃｕ２＋、 Ｎ１２＋、Ｃｕ２＋、 Ａｇ” （ｘは
Ｏから１）などの金属イオンであったり、４級化１＋
した、−Ｎ−イオンを有するよう有機化合物からなる。The conductivity of TCNQ salt is from several Ωam to ~1016Ω・Cm
Polypyrrole polymer alone has a resistance of 10°Ω.
・It is known that it becomes less than cm. Virol and TC
Even in a mixed polymer of NQ salts, the conductivity can be easily varied over a wide range by changing the selection of TCNQ salts and the oxidation state of virol. When forming a film, since virol is in a liquid state, a solution or paste form can be obtained even when mixed with TCNQ salt, so it can be applied to various substrates or film surfaces. If you want to obtain a uniform thin film, you can easily obtain it by diluting it with a solvent that dissolves the Pillow Nove TCNQ salt. Further, since the virol polymer undergoes a crosslinking reaction, it has high heat resistance and a hard film can be obtained. A sufficiently stable film can be obtained up to about 250 to 300°C. The TCNQ salt has a composition of A(TCNQ)2-X, where A is L+'', Na-1-, Fe2+,
It may be a metal ion such as Cu2+, N12+, Cu2+, Ag'' (x is from O to 1), or it may be made of an organic compound having a quaternized 1+ -N- ion.
実施例 以下に本発明の実施例について述べる。Example Examples of the present invention will be described below.
〈実施例１〉
ＴＣＮＱ塩としてインキツリウム（ＴＣＮＱ）２を用い
、ビロールと重量比で２＝１で混合して、ペースト状に
したのち、スライドガラス面上に塗布した。これを８０
°Ｃ１ＩＨはど大気中で加熱したところ、このペースト
は固体膜化した。さらに１５０°Ｃで２０分間はど処理
したところ、重合反応はさらにすすみ、硬い固体膜が得
られた。これをさらに３００°Ｃ雰囲気に放出したとこ
ろ、この膜は溶融することなく安定な膜状態であった。<Example 1> Inquiturium (TCNQ) 2 was used as the TCNQ salt and mixed with virol at a weight ratio of 2=1 to form a paste, which was then applied onto the surface of a slide glass. This is 80
When heated in the atmosphere at °C1IH, this paste became a solid film. When further treated at 150°C for 20 minutes, the polymerization reaction proceeded further and a hard solid film was obtained. When this was further released into a 300°C atmosphere, the film remained stable without melting.
この膜の電気抵抗は１０ ΩＣｍ程度であった。The electrical resistance of this film was about 10 ΩCm.
〈実施例２〉
実施例１の膜を酸性ガス雰囲気において処理したところ
、導電度は２けたほど高くなった。<Example 2> When the film of Example 1 was treated in an acidic gas atmosphere, the conductivity increased by two orders of magnitude.
〈実施例３〉
キノリウム（ＴＣＮＱ）２とビロールをアセトニトリル
（二溶解して、ガラス基板上にスピナー法により塗布し
て、加熱処理したところ厚さは、５０００Ａより均一で
平滑な膜が得られた。<Example 3> Quinolium (TCNQ) 2 and virol were dissolved in acetonitrile (2), coated on a glass substrate by a spinner method, and heat treated. A film with a thickness more uniform and smooth than 5000A was obtained. .
実施例１．２．３と同様な実験をその他のカチオンとな
る金属ＬＬ＋、Ｃｕ２＋などやアミン、ピリジンなどを
用いても同様な傾向の特性が得られた。Even when the same experiment as in Example 1.2.3 was carried out using other cationic metals such as LL+, Cu2+, amine, pyridine, etc., similar characteristics were obtained.
〈実施例４〉
チオフェンおよびフラン１００ ｃｃ ＋二対し、Ｎ−
ｎ−プロピルイソキノリウム（ＴＣＮＱ）２を２Ｏ２混
合し、５０°Ｃで２時間加熱したところ、 黒〜緑色の
固体が得られた。比抵抗はそれぞれ１０−４１０−５Ω
ｃｍであった。<Example 4> Thiophene and furan 100 cc + 2 pairs, N-
When n-propylisoquinolium (TCNQ) 2 was mixed with 2O 2 and heated at 50°C for 2 hours, a black to green solid was obtained. Specific resistance is 10-410-5Ω respectively
It was cm.
発明の効果
以上要するに本発明はビロール、チオフェンおよびフラ
ンから選ばれる複素五員環化合物とＴＣＮＱ塩の混合物
を加熱処理すること（二より、導電性特性を必要とする
電子部品関連の電極や保護膜として、容易に様々な基板
上に耐熱性の高い膜として製膜化できる利点を有する。Effects of the Invention In short, the present invention heat-treats a mixture of a five-membered heterocyclic compound selected from virol, thiophene, and furan and TCNQ salt (Secondly, it can be used for electrodes and protective films related to electronic components that require conductive properties). It has the advantage that it can be easily formed as a highly heat-resistant film on various substrates.
Claims (1)
化合物と７，７，８，８−テトラシアノキノジメタンア
ニオンの混合物とから加熱処理により生成される導電性
高分子の製造方法。A method for producing a conductive polymer produced by heat treatment from a mixture of a five-membered heterocyclic compound selected from pyrrole, thiophene, and furan and a 7,7,8,8-tetracyanoquinodimethane anion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19325986A JPS6348330A (en) | 1986-08-19 | 1986-08-19 | Production of electroconductive polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19325986A JPS6348330A (en) | 1986-08-19 | 1986-08-19 | Production of electroconductive polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6348330A true JPS6348330A (en) | 1988-03-01 |
Family
ID=16304970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19325986A Pending JPS6348330A (en) | 1986-08-19 | 1986-08-19 | Production of electroconductive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6348330A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2553764A (en) * | 2016-09-07 | 2018-03-21 | Sumitomo Chemical Co | Stable ink formulations suitable for the manufacture of thermoelectric legs |
| WO2018207699A1 (en) * | 2017-05-08 | 2018-11-15 | 学校法人 慶應義塾 | Polymer having graphite- or graphene-like lamellar structure |
-
1986
- 1986-08-19 JP JP19325986A patent/JPS6348330A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2553764A (en) * | 2016-09-07 | 2018-03-21 | Sumitomo Chemical Co | Stable ink formulations suitable for the manufacture of thermoelectric legs |
| WO2018207699A1 (en) * | 2017-05-08 | 2018-11-15 | 学校法人 慶應義塾 | Polymer having graphite- or graphene-like lamellar structure |
| JPWO2018207699A1 (en) * | 2017-05-08 | 2020-03-26 | 学校法人慶應義塾 | Polymer having graphite or graphene-like layered structure |
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