JPH01134805A - conductive material - Google Patents
conductive materialInfo
- Publication number
- JPH01134805A JPH01134805A JP29323887A JP29323887A JPH01134805A JP H01134805 A JPH01134805 A JP H01134805A JP 29323887 A JP29323887 A JP 29323887A JP 29323887 A JP29323887 A JP 29323887A JP H01134805 A JPH01134805 A JP H01134805A
- Authority
- JP
- Japan
- Prior art keywords
- conductive
- conductive material
- conductive polymer
- base material
- porous
- 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.)
- Granted
Links
- 239000004020 conductor Substances 0.000 title claims description 23
- 229920001940 conductive polymer Polymers 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- -1 lumps Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、導電性ポリマーからなる導電材料に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a conductive material made of a conductive polymer.
〈従来の技術〉
近年、導電性ポリマーを主体とする導電材料が注目され
ている。<Prior Art> In recent years, conductive materials mainly composed of conductive polymers have attracted attention.
この導電性ポリマーは、各種アニオンやカチオン等のド
ーパントをドーピングすることが可能であり、ドーピン
グによりその導電性が飛躍的に向上する。この種の導電
性ポリマーは粉状。This conductive polymer can be doped with dopants such as various anions and cations, and doping dramatically improves its conductivity. This type of conductive polymer is in powder form.
粒状、塊状、フィルム状等の様々な形状で１ｑられ、帯
電防止材料、電磁波遮蔽材料、光電変換素子、光メモリ
（ホログラフィックメモリ）等や各種センサーなどの機
能素子９表示素子（エレクトロクロミズム）、スイッチ
、各種ハイブリッド材料（透明導電性フィルム等）、各
種端末機器、並びに蓄電池等の広い分野への応用が検討
されている。It can be used in various shapes such as granules, lumps, and films, and is used as functional elements such as antistatic materials, electromagnetic shielding materials, photoelectric conversion elements, optical memories (holographic memories), various sensors, display elements (electrochromism), and switches. Applications are being considered in a wide range of fields, including various hybrid materials (transparent conductive films, etc.), various terminal devices, and storage batteries.
しかしながら、この種の導電性ポリマーは一般に成型性
及び加工性に乏しく、特にフィルム状の導電性ポリマー
を１ｑるには、特別の方法を用いなければならない。現
在、このような導電性ポリマーとしては、例えば、重合
触媒を塗１５したガラス壁にアセチレンを吹込んで形成
した後にこのガラス壁より剥離して１１られるポリアセ
チレンフィルムや、電気化学的酸化反応（電解酸化重合
）によって電解電極上に形成した後、この電極より剥離
して得られるポリチェニレンフィルムやポリピロールフ
ィルム等が知られている。However, this type of conductive polymer generally has poor moldability and processability, and in particular, a special method must be used to prepare a film-like conductive polymer. At present, such conductive polymers include, for example, polyacetylene films that are formed by blowing acetylene onto a glass wall coated with a polymerization catalyst and then peeled off from the glass wall, and polyacetylene films that are formed using electrochemical oxidation reactions (electrolytic oxidation). Polythenylene films, polypyrrole films, etc., which are obtained by forming on an electrolytic electrode by polymerization and then peeling from the electrode are known.
ところが、上記従来の導電性ポリマーフィルムでは、ポ
リアセチレンフィルムの場合は空気中で不安定で酸化劣
化が進行し易く且つ機械的強度が弱いという欠点があり
、また上記電解酸化重合により得られるポリチェニレン
フィルム等ではフィルムの大きさが電解電極の大きさに
規制されまた製造工程が煩雑でコスト高であるといった
欠点がある。However, the above-mentioned conventional conductive polymer films have the drawbacks that polyacetylene films are unstable in the air, prone to oxidative deterioration, and have low mechanical strength; Films and the like have disadvantages in that the size of the film is regulated by the size of the electrolytic electrode, and the manufacturing process is complicated and costly.
そこで、本発明者らは既に、特願昭６０−２２５７６１
号で、酸化剤の存在下、この酸化剤を保持し得る空間を
有する基材上で、共役二重結合を有する化合物を気相重
合させて得られる、上記の欠点のない新規な導電材料を
提案した。Therefore, the present inventors have already filed the patent application No. 60-225761.
No. 1 describes a new conductive material free from the above-mentioned drawbacks, which is obtained by vapor-phase polymerization of a compound having a conjugated double bond on a substrate having a space capable of holding the oxidizing agent in the presence of the oxidizing agent. Proposed.
〈発明が解決しようとする問題点〉
この特願昭６０−２２５７６１ 号の導電材料によれば
、製造工程が簡略化しまた低コスト化等が図り得る導電
性ポリマーが得られる。しか゛しながら、この導電材料
では導電性ポリマーが基材中の空間に保持されているこ
とから、導電性ポリマー同士が不連続となり、このため
導電率が低いという問題がある。<Problems to be Solved by the Invention> According to the conductive material of Japanese Patent Application No. 60-225761, a conductive polymer can be obtained which can simplify the manufacturing process and reduce costs. However, in this conductive material, since the conductive polymer is held in the space within the base material, the conductive polymers become discontinuous with each other, resulting in a problem of low conductivity.
く問題点を解決するための手段〉
この発明は、上記特願昭６０−２２５７６１ 号の導電
材料を改良した導電材料に関するもので、酸化剤を保持
しまた溶媒に可溶な材質の多孔性基Ｈ中で導電性ポリマ
ーを重合させてこの多孔性基材中の空間に前記ポリマー
を形成し、更に前記溶媒で前記多孔性基材を溶解除去し
て得られる導電性ポリマー多孔体からなることを要旨と
する。Means for Solving Problems> The present invention relates to a conductive material that is an improved conductive material of the above-mentioned Japanese Patent Application No. 60-225761. A conductive polymer porous body obtained by polymerizing a conductive polymer in H to form the polymer in the space in the porous base material, and then dissolving and removing the porous base material with the solvent. This is the summary.
上記のような多孔性基材並びに溶媒としては、例えば第
１表のような組み合せのものが挙げられる。Examples of the above-mentioned porous substrates and solvents include combinations as shown in Table 1.
第１表
〈作 用〉
上記のように酸化剤を保持させた多孔性基材中で導電性
ポリマーを重合させた場合、多孔性基材中の空間に沿っ
て導電性ポリマーのフィブリル（小繊維）が形成される
ため、長くまた径の揃ったフィブリルを多数有し更には
連続的に繋がった導電性ポリマー多孔体が、多孔性基材
中に作製される。従って、多孔性基材を溶解除去して１
ｑられたこの導電性ポリマー多孔体は、導電性が上記従
来のものに比べて格段に向上する。加えて、この導電性
ポリマーはその表面積が大きくこのためドープ可能償が
増大するので、これもこの多孔体の導電性を向上させる
一因となる。Table 1 <Function> When a conductive polymer is polymerized in a porous base material holding an oxidizing agent as described above, fibrils (small fibers) of the conductive polymer are formed along the spaces in the porous base material. ) is formed, so that a conductive polymer porous body having a large number of long fibrils with uniform diameters and furthermore continuously connected is produced in the porous base material. Therefore, by dissolving and removing the porous base material,
This conductive polymer porous body subjected to the oxidation process has significantly improved conductivity compared to the above-mentioned conventional porous body. In addition, the conductive polymer has a large surface area, which increases its dopability, which also contributes to improving the conductivity of the porous body.
また、この導電性ポリマー多孔体では、これら多数のフ
ィブリルが相互に絡み合った状態となっているため、従
来の粉末状のものに比べては勿論フィルム状導電性ポリ
マーに比べても十分大きな機械的強度を有しており、従
って保存時あるいは使用時等において亀裂（クラック）
が入ったりあるいは剥離するということが殆んどなく、
これらに起因する導電性の低下が殆んどない。In addition, in this conductive polymer porous material, many of these fibrils are entangled with each other, so it has a sufficiently large mechanical strength compared to conventional powder-like conductive polymers, as well as compared to film-like conductive polymers. It has strength and therefore does not cause cracks during storage or use.
There is almost no chance of it getting in or peeling off.
There is almost no decrease in conductivity due to these factors.
〈実施例〉
ニトリルゴム（以下ｒＮＢＲＪという）をメチルエチル
ケトンに溶解させた溶液に過塩素酸第二鉄を溶解させ、
この混合溶液を幅１０ｃｍ、長ざ１Ｑｃｍ、高さｉＱｃ
ｍの容器に入れ、次いでこの混合溶液を乾燥しメチルエ
チルケトンを蒸発させて、過塩素酸第二鉄（酸化剤）を
その孔中に保持した多孔性基材を作製した。<Example> Ferric perchlorate was dissolved in a solution of nitrile rubber (hereinafter referred to as rNBRJ) dissolved in methyl ethyl ketone,
Spread this mixed solution into a sheet with a width of 10 cm, a length of 1 Q cm, and a height of iQc.
The mixed solution was then dried to evaporate the methyl ethyl ketone to produce a porous base material holding ferric perchlorate (oxidizing agent) in its pores.
次いで、上記の多孔性基材をピロールの気体雰囲気下に
おき、ピロールの蒸気を接触させることで、過塩素酸第
二鉄が保持された基材孔中でピロールを化学的に重合さ
せ、ポリピロールを生成させた。Next, the above porous substrate is placed in a pyrrole gas atmosphere and brought into contact with pyrrole vapor to chemically polymerize pyrrole in the pores of the substrate holding ferric perchlorate, resulting in polypyrrole. was generated.
その後、この多孔性基材を、メチルエチルケトンに浸漬
し、基材中のＮＢＲ１未反応のピロール並びに過塩素酸
第二鉄を洗浄除去して、この発明に係わるポリピロール
多孔体からなる導電材料（導電材料Ａ）を作製した。Thereafter, this porous base material is immersed in methyl ethyl ketone to wash and remove the unreacted pyrrole and ferric perchlorate in the base material. A) was produced.
また、モノマーとして、ピロールに代えアニリンを用い
た他は同様にして、ポリアニリン多孔体からなる導電材
料（導電子Ａ料Ｂ）を作製した。In addition, a conductive material (conductive material A material B) made of a porous polyaniline material was produced in the same manner except that aniline was used instead of pyrrole as the monomer.
一方、厚さ１ｍｍ、縦’ｌＱｃｍ、横２０ｃｍのナイロ
ン製不織布を過塩素酸第二鉄水溶液に浸漬し、次いで乾
燥して、過塩素酸第二鉄（酸化剤）をこの不織布に保持
した。そして、こうして得た不織布をピロールの蒸気に
接触ざゼることで、不織布上でピロールを化学的に重合
させ、ポリピロール層を不織布中に形成した。On the other hand, a nylon nonwoven fabric with a thickness of 1 mm, a length of 1Q cm, and a width of 20 cm was immersed in an aqueous ferric perchlorate solution and then dried to retain ferric perchlorate (oxidizing agent) in the nonwoven fabric. The thus obtained nonwoven fabric was brought into contact with pyrrole vapor to chemically polymerize pyrrole on the nonwoven fabric, thereby forming a polypyrrole layer in the nonwoven fabric.
このように処理した不織布をメタノールに浸漬して、未
反応ピロール及び過塩素酸第二鉄を抽出除去して、従来
技術に係わる導電材料（導電材料Ｃ）を作製した。The nonwoven fabric treated in this manner was immersed in methanol to extract and remove unreacted pyrrole and ferric perchlorate to produce a conductive material (conductive material C) according to the prior art.
また、七ツマ−として、ピロールに代えアニリンを用い
た他は導電材料Ｃと同様にして、ポリアニリン層を不織
布中に形成してなる導電材料（導電材料Ｄ）を作製した
。Further, a conductive material (conductive material D) in which a polyaniline layer was formed in a nonwoven fabric was produced in the same manner as conductive material C except that aniline was used instead of pyrrole as a seven-layer material.
以上の４つの導電材料Ａ−Ｄの導電率をそれぞれ測定し
たところ、第１表に示づ結果をｊｑた。When the conductivities of the above four conductive materials A to D were measured, the results are shown in Table 1.
第１表
導電率（Ｓ Ｃｍ” ）
導電材料Ａ １０
導電材料Ｂ ３５
導電材料Ｃ３，ＯＸ １０−１
導電材料Ｄ ４．６Ｘ １０−１本発明に係わ
る導電材料Ａ、Ｂの導電率がこのように高いのは、これ
らは径が揃って長く且つ連続したフィブリルが絡み合っ
た楢造であること、製造時におけるドープ量が大きいこ
と、更にはこれらのポリマーが導電性ポリマーが連続に
繋がっており且つ１００％導電性ポリマーで形成される
こと等により、導電性が向上したためと思われる。Table 1 Conductivity (S Cm") Conductive material A 10 Conductive material B 35 Conductive material C3, OX 10-1 Conductive material D 4.6X 10-1 The conductivity of conductive materials A and B according to the present invention is as follows. The reason why these polymers are so high is that they have a structure of long, continuous fibrils with uniform diameters intertwined together, that the amount of doping during production is large, and that these polymers are made of continuously connected conductive polymers. This is thought to be due to improved conductivity due to the fact that it is made of 100% conductive polymer.
〈発明の効果〉
以上のように、この発明によれば、導電性が非常に高く
、更に製造容易で低コス１〜の導電材料を提供すること
ができ、その工業上の利用価値は大きい。<Effects of the Invention> As described above, according to the present invention, it is possible to provide a conductive material that has very high conductivity, is easy to manufacture, and has a low cost of 1 or more, and has great industrial utility value.
Claims (1)
中で導電性ポリマーを重合させてこの多孔性基材中の空
間に前記ポリマーを形成し、更に前記溶媒で前記多孔性
基材を溶解除去して得られる導電性ポリマー多孔体から
なることを特徴とする導電材料。1. A conductive polymer is polymerized in a porous base material that retains an oxidizing agent and is soluble in a solvent to form the polymer in a space in the porous base material, and the porous base material is further polymerized with the solvent. A conductive material comprising a porous conductive polymer obtained by dissolving and removing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29323887A JPH0664928B2 (en) | 1987-11-20 | 1987-11-20 | Conductive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29323887A JPH0664928B2 (en) | 1987-11-20 | 1987-11-20 | Conductive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01134805A true JPH01134805A (en) | 1989-05-26 |
| JPH0664928B2 JPH0664928B2 (en) | 1994-08-22 |
Family
ID=17792221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29323887A Expired - Fee Related JPH0664928B2 (en) | 1987-11-20 | 1987-11-20 | Conductive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0664928B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0853566A (en) * | 1994-08-10 | 1996-02-27 | Nec Corp | Conductive polymer molded product and method for producing the same |
| US5591482A (en) * | 1993-02-17 | 1997-01-07 | Inoac Corporation | Conductive polyurethane foam and its manufacture |
| US6214260B1 (en) | 1997-11-10 | 2001-04-10 | World Properties, Inc. | Conductive elastomeric foams by in-situ vapor phase polymerization of pyrroles |
-
1987
- 1987-11-20 JP JP29323887A patent/JPH0664928B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591482A (en) * | 1993-02-17 | 1997-01-07 | Inoac Corporation | Conductive polyurethane foam and its manufacture |
| JPH0853566A (en) * | 1994-08-10 | 1996-02-27 | Nec Corp | Conductive polymer molded product and method for producing the same |
| US6214260B1 (en) | 1997-11-10 | 2001-04-10 | World Properties, Inc. | Conductive elastomeric foams by in-situ vapor phase polymerization of pyrroles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0664928B2 (en) | 1994-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |