JPH0656987A - Produciton of conductive polymer - Google Patents
Produciton of conductive polymerInfo
- Publication number
- JPH0656987A JPH0656987A JP23413592A JP23413592A JPH0656987A JP H0656987 A JPH0656987 A JP H0656987A JP 23413592 A JP23413592 A JP 23413592A JP 23413592 A JP23413592 A JP 23413592A JP H0656987 A JPH0656987 A JP H0656987A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polymer
- conductive polymer
- aminobenzenesulfonic acid
- aminobenzenesulfonic
- 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
Abstract
Description
【０００１】[0001]
【産業の利用分野】この出願発明は導電性高分子の製造
方法に関する。さらに詳述すると、アミノベンゼンスル
ホン酸系化合物またはアミノベンゼンスルホン酸系化合
物とアニリン系化合物を含む単量体を化学酸化重合する
ことによる水に可溶な導電性高分子の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a conductive polymer. More specifically, it relates to a method for producing a water-soluble conductive polymer by chemically oxidatively polymerizing an aminobenzenesulfonic acid compound or a monomer containing an aminobenzenesulfonic acid compound and an aniline compound.
【０００２】[0002]
【従来の技術】近年、それ自身が導電能力をもつポリア
ニリン、ポリピロール、ポリチオフェン等の導電性高分
子が、電池電極材料、コンデンサー電極材料、ＩＣやフ
ロッピィディスクの帯電防止材料として注目されてい
る。2. Description of the Related Art In recent years, conductive polymers such as polyaniline, polypyrrole and polythiophene, which have conductive ability themselves, have been attracting attention as antistatic materials for battery electrode materials, capacitor electrode materials, ICs and floppy disks.
【０００３】[0003]
【発明が解決しようとする課題】これらの導伝性高分子
は、一般的には、それらの単量体を化学的又は電気化学
的に重合することにより製造される。一般的に、導電性
高分子は、その剛直な構造が故に、不溶不融であって成
形したり塗料化することがむずかしく、それらを実際の
用途に適用する場合に、大きな問題となっている。These conductive polymers are generally produced by polymerizing their monomers chemically or electrochemically. In general, conductive polymers are insoluble and infusible due to their rigid structure, making it difficult to mold or make them into paints, which is a major problem when they are applied to actual applications. .
【０００４】そこで、溶剤に可溶性の導電性高分子を得
ることが試み始められている。例えば、チオフェンのβ
−アルキル誘導体、アニリンのＮ−アルキル誘導体など
を重合して、有機溶媒に可溶性とした例がある。しか
し、いずれも比較的長鎖のアルキル基をもつため、可溶
性とはなるが、導電性能は低いレベルに留まっている。Therefore, attempts have been made to obtain a conductive polymer that is soluble in a solvent. For example, β for thiophene
There is an example in which an -alkyl derivative or an N-alkyl derivative of aniline is polymerized to make it soluble in an organic solvent. However, since each has a relatively long-chain alkyl group, it becomes soluble but its conductive performance remains at a low level.
【０００５】最近、アニリンを酸化重合してポリアニリ
ンとなし、これを発煙硫酸でスルホン化処理をして、水
溶性にした例もある。この場合は、重合及びスルホン化
処理と反応が２段となるうえ、ポリアニリンはスルホン
化処理液に溶解しないために固−液反応となるので、反
応を制御して必要な構造のものを得ることはかなり難し
い。Recently, there is also an example in which aniline is oxidatively polymerized to form polyaniline, which is subjected to a sulfonation treatment with fuming sulfuric acid to make it water-soluble. In this case, the polymerization and sulfonation treatment and the reaction take two steps, and since polyaniline does not dissolve in the sulfonation treatment liquid, a solid-liquid reaction occurs, so that the reaction is controlled to obtain the one having the required structure. Is quite difficult.
【０００６】また、種々のアニリン誘導体を選び、電解
酸化による重合体の生成および得られた重合体被覆電極
の性質についての検討も行われている（木谷ら、日本化
学会誌、１９８５、（６）、ｐ．１１２４−１１３
０）。その中で、アミノベンゼンスルホン酸について
は、ｏ−アミノベンゼンスルホン酸の場合、電極上に皮
膜が得られるが電位走査を繰り返してもピーク電流値が
増大しないと述べられているにすぎない。また、ｏ−ア
ミノベンゼンスルホン酸およびｍ−アミノベンゼンスル
ホン酸については、電極上にはポリマ−が析出せずレド
ックス応答のある可溶性の生成物が得られるとしている
にすぎない。このようにいずれの場合も、生成物が重合
体であること、ましてや導電性の重合体であることは確
認されていない。In addition, various aniline derivatives have been selected and the formation of polymers by electrolytic oxidation and the properties of the obtained polymer-coated electrodes have also been investigated (Kitani et al., Journal of the Chemical Society of Japan, 1985, (6). , P. 1124-113
0). Among them, regarding aminobenzenesulfonic acid, in the case of o-aminobenzenesulfonic acid, it is merely stated that a film is obtained on the electrode, but the peak current value does not increase even if potential scanning is repeated. Further, regarding o-aminobenzenesulfonic acid and m-aminobenzenesulfonic acid, it is merely stated that a polymer is not deposited on the electrode and a soluble product having a redox response is obtained. Thus, in any case, it was not confirmed that the product was a polymer, let alone a conductive polymer.
【０００７】ところで、電解酸化法は、ポリマ−の生成
量を通電電荷量によってコントロ−ルできるという特徴
を有している。そのために、例えば電極上に厚さのコン
トロ−ルされた導電性ポリマ−の薄膜を作成しようとす
る場合等には有効であるといえるが、一方、導電性ポリ
マ−を大量に生成させ実用に供しようという場合には、
極めて不向きな方法である。上記のような状況のもと
に、この出願の発明者らは鋭意検討した結果、酸化剤を
用いて化学的に重合させることにより、水に可溶な導電
性高分子を簡単に、大量にかつ安価に得る方法を見い出
すことができた。By the way, the electrolytic oxidation method is characterized in that the amount of polymer produced can be controlled by the amount of electric charge applied. Therefore, it can be said that it is effective, for example, when trying to form a thin film of a conductive polymer having a controlled thickness on an electrode, but on the other hand, a large amount of the conductive polymer is generated and put into practical use. If you want to serve,
This is an extremely unsuitable method. Under the circumstances as described above, the inventors of the present application have earnestly studied, and as a result, by chemically polymerizing with an oxidizing agent, a water-soluble conductive polymer can be easily and in large amounts. And I was able to find a way to get it cheaply.
【０００８】[0008]
【課題を解決するための手段】この出願発明によれば、
合成反応の原料としてアミノベンゼンスルホン酸系化合
物またはアミノベンゼンスルホン酸系化合物とアニリン
系化合物を含む単量体を用い、これを化学酸化重合する
ことによって水に可溶性の導電性高分子を合成するもの
である。通常、酸化重合は、水溶液中で行われるが、こ
の出願発明では、原料、重合反応生成物いずれも水溶液
に溶解するために、反応は最初から最後まで液相で行わ
れることになり、反応の制御が容易で均質な生成物が得
ることができる。以下に、この出願発明についてさらに
詳述する。According to the invention of this application,
Synthesis of a water-soluble conductive polymer by chemically oxidatively polymerizing an aminobenzenesulfonic acid-based compound or a monomer containing an aminobenzenesulfonic acid-based compound and an aniline-based compound as a raw material for a synthesis reaction Is. Usually, the oxidative polymerization is carried out in an aqueous solution, but in the present invention, since the raw material and the polymerization reaction product are both dissolved in the aqueous solution, the reaction is carried out in the liquid phase from the beginning to the end. A homogeneous product that is easy to control can be obtained. The invention of this application will be described in more detail below.
【０００９】この出願発明で用いられるアミノベンゼン
スルホン酸系化合物は、アミノベンゼンスルホン酸及び
それらの誘導体であって、具体的には、ｏ−アミノベン
ゼンスルホン酸、ｍ−アミノベンゼンスルホン酸、ｐ−
アミノベンゼンスルホン酸、アミノベンゼン−２，５−
ジスルホン酸、アミノベンゼン−２，４−ジスルホン酸
等であり、また、アミノベンゼンスルホン酸系化合物と
アニリン系化合物との混合物は、具体的には、ｏ−アミ
ノベンゼンスルホン酸、ｍ−アミノベンゼンスルホン
酸、ｐ−アミノベンゼンスルホン酸、アミノベンゼン−
２，５−ジスルホン酸、アミノベンゼン−２，４−ジス
ルホン酸等のアミノベンゼンスルホン酸系化合物とアニ
リン、ヒドロキシアニリン、カルボキシアニリン、クロ
ロアニリン、Ｎ−メチルアニリン等のアニリン系化合物
との混合物である。The aminobenzenesulfonic acid compounds used in the present invention are aminobenzenesulfonic acid and derivatives thereof, and specifically, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid.
Aminobenzenesulfonic acid, aminobenzene-2,5-
Examples of the mixture of disulfonic acid, aminobenzene-2,4-disulfonic acid and the like, and a mixture of an aminobenzenesulfonic acid type compound and an aniline type compound include o-aminobenzenesulfonic acid and m-aminobenzenesulfone. Acid, p-aminobenzenesulfonic acid, aminobenzene-
It is a mixture of an aminobenzenesulfonic acid compound such as 2,5-disulfonic acid and aminobenzene-2,4-disulfonic acid with an aniline compound such as aniline, hydroxyaniline, carboxyaniline, chloroaniline and N-methylaniline. .
【００１０】この出願発明における酸化重合方法とし
て、重合反応液は、酸性溶液、中性溶液、あるいはアル
カリ性溶液のいずれでもよい。酸性水溶液としては、フ
ッ化水素酸、塩酸、硝酸、過塩素酸、ホウフッ化水素
酸、硫酸、酢酸、リン酸、トリフルオロ酢酸、ベンゼン
スルホン酸、トルエンスルホン酸等があげられる。これ
らの中、塩酸、硫酸、ホウフッ化水素酸が好ましい。ア
ルカリ性水溶液としては、例えば、水酸化ナトリウム、
水酸化カリウム、水酸化リチウムなど、１価の金属水酸
化物の水溶液、水酸化カルシウム、水酸化マグネシウム
など、２価の金属水酸化物の水溶液、あるいは、アンモ
ニアを溶解させた水溶液があげられる。これらの中、水
酸化ナトリウム、アンモニアの水溶液が好ましい。ま
た、アミノベンゼンスルフン酸系の単量体は、酸性水溶
液よりもアルカリ性水溶液への溶解性が高い。従って、
アルカリ性水溶液系の方が単量体の高濃度溶液を得易
く、酸化重合して生成される高分子の量も多く、工業的
見地から考えると有用である。重合液における単量体の
濃度は、一般的には、０．０１〜５モル／ｌで、好まし
くは０．１〜３モル／ｌが用いられる。酸性水溶液の酸
濃度としては、０．０１〜１０モル／ｌ、好ましくは
０．１〜６モル／ｌが用いられる。アルカリ性水溶液の
アルカリ濃度としては、０．０１〜１０モル／ｌ、好ま
しくは０．１〜３モル／ｌが用いられる。In the oxidative polymerization method of the present invention, the polymerization reaction liquid may be an acidic solution, a neutral solution or an alkaline solution. Examples of the acidic aqueous solution include hydrofluoric acid, hydrochloric acid, nitric acid, perchloric acid, hydrofluoric acid, sulfuric acid, acetic acid, phosphoric acid, trifluoroacetic acid, benzenesulfonic acid, toluenesulfonic acid and the like. Of these, hydrochloric acid, sulfuric acid, and fluoroboric acid are preferable. Examples of the alkaline aqueous solution include sodium hydroxide,
Examples thereof include aqueous solutions of monovalent metal hydroxides such as potassium hydroxide and lithium hydroxide, aqueous solutions of divalent metal hydroxides such as calcium hydroxide and magnesium hydroxide, or aqueous solutions in which ammonia is dissolved. Of these, aqueous solutions of sodium hydroxide and ammonia are preferable. Further, the aminobenzenesulphonic acid-based monomer has higher solubility in an alkaline aqueous solution than in an acidic aqueous solution. Therefore,
The alkaline aqueous solution system is easier to obtain a high-concentration solution of the monomer, and the amount of the polymer produced by the oxidative polymerization is larger, which is useful from the industrial viewpoint. The concentration of the monomer in the polymerization liquid is generally 0.01 to 5 mol / l, preferably 0.1 to 3 mol / l. The acid concentration of the acidic aqueous solution is 0.01 to 10 mol / l, preferably 0.1 to 6 mol / l. The alkali concentration of the alkaline aqueous solution is 0.01 to 10 mol / l, preferably 0.1 to 3 mol / l.
【００１１】この出願発明で用いられる化学酸化重合法
で用いられる酸化剤としては、公知の酸化剤が用いられ
るが、例えば、酸化第二鉄、過硫酸アンモニウム、重ク
ロム酸カリウム、過マンガン酸カリウム、二酸化マンガ
ン、過酸化水素などがある。特に、過マンガン酸カリウ
ム、過硫酸アンモニウムが好ましい。また、用いる酸化
剤の量は、各々の酸化剤の反応機構に応じて適宜使用さ
れる。重合に際しての温度は適宜選択されるが、一般的
には、室温付近ないし室温より低い温度、例えば４０〜
−１０゜Ｃが副反応が少なく好ましい。As the oxidizing agent used in the chemical oxidative polymerization method used in the present invention, known oxidizing agents can be used. For example, ferric oxide, ammonium persulfate, potassium dichromate, potassium permanganate, Examples include manganese dioxide and hydrogen peroxide. Particularly, potassium permanganate and ammonium persulfate are preferable. Further, the amount of the oxidizing agent used is appropriately used according to the reaction mechanism of each oxidizing agent. The temperature at the time of polymerization is appropriately selected, but generally, the temperature is around room temperature or lower than room temperature, for example, 40 to
-10 ° C is preferable because it has less side reaction.
【００１２】重合が完了した後は、重合体は水溶液のま
ま用いることができ、また、酸またはアルカリを用いて
適当なＰＨに調製して用いることもできる。アルカリ性
水溶液で処理して生成された重合体を水溶液のまま使用
する場合には、乾燥して得られた重合体の固形物は、ス
ルホン酸基がナトリウムやカリウム等の金属塩、あるい
はアンモニウム塩などの塩となっていると考えられるの
で、高い導電性は期待できない。高い導電性を得るため
には、塩酸、硫酸、ホウフッ化水素酸等の酸で脱塩処理
することが好ましい。重合体の分離精製が必要な用途に
用いる場合は、例えば、重合液に重合体の非溶剤を加え
ることにより重合体を分離精製することもできる。非溶
剤としてはメタノ−ル、エタノ−ル、アセトン等の水に
良く混じる溶液が好ましい。After the polymerization is completed, the polymer can be used as an aqueous solution, or can be prepared by using an acid or an alkali to have an appropriate pH. When a polymer produced by treating with an alkaline aqueous solution is used as an aqueous solution, a solid product of the polymer obtained by drying is a metal salt having a sulfonic acid group such as sodium or potassium, or an ammonium salt. Since it is thought that it is a salt of the above, high conductivity cannot be expected. In order to obtain high conductivity, it is preferable to carry out desalting treatment with an acid such as hydrochloric acid, sulfuric acid, or hydrofluoric acid. When the polymer is used for applications requiring separation / purification, the polymer can be separated / purified by adding a non-solvent for the polymer to the polymerization solution. As the non-solvent, a solution such as methanol, ethanol or acetone which is well mixed with water is preferable.
【００１３】[0013]
【発明の効果】上記のようにして、アミノベンゼンスル
ホン酸系化合物またはアミノベンゼンスルホン酸系化合
物とアニリン系化合物を含む単量体を酸化重合すること
により、簡単な方法で水溶性の導電性高分子を容易に得
ることができる。得られた導電性高分子は水溶性である
から、容易に染料や塗料にすることができる。この出願
発明の導電性高分子で、繊維、樹脂、ゴム、金属、セラ
ミックスなどの表面処理を行うことにより、それらの材
料を帯電防止、金属の防食、電磁波シ−ルドなどができ
る。As described above, by oxidizing and polymerizing the aminobenzene sulfonic acid type compound or the monomer containing the aminobenzene sulfonic acid type compound and the aniline type compound, the water-soluble highly conductive compound can be obtained by a simple method. The molecule can be easily obtained. Since the obtained conductive polymer is water-soluble, it can be easily used as a dye or a paint. By surface-treating fibers, resins, rubbers, metals, ceramics and the like with the conductive polymer of the present invention, these materials can be antistatic, anticorrosive to metals, electromagnetic wave shield, etc.
【００１４】以下に、実施例により、この出願発明を具
体的に説明するが、この出願発明は、下記の実施例に限
定されるものではない。The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００１５】[0015]
【実施例１】単量体として、下記の、ｏ−、ｍ−、ｐ−
アミノベンゼンスルホン酸を用いて化学酸化重合を行っ
た。化学酸化重合は、アミノベンゼンスルホン酸を０．
１２５モル／ｌ、硫酸を０．５モル／ｌ、過マンガン酸
カリウムを０．２５モル／ｌそれぞれ使用し、攪半を２
時間続けて反応を行った。重合は、いずれも溶液状態で
進行し、重合体の析出は見られなかった。重合後の溶液
を減圧濃縮した後に、多量のメタノ−ル中に、溶液を滴
下して重合体を析出させ、濾別後減圧乾燥させて、重合
体を得た。構造を赤外吸収スペクトルで示すと、図１の
とおりである。重合収量、各重合体の導電率をつぎに示
す。いずれも導電性の重合体であることが確認された。
これらの重合体は、いずれも水、アルカリ水溶液および
酸性水溶液によく溶解した。 単量体 重合収量（ｇ） 導電率（ｓ／ｃｍ） ｏ−アミノベンゼンスルホン酸 ０．３６ ０．３ ｍ−アミノベンゼンスルホン酸 ０．３９ ０．５ ｐ−アミノベンゼンスルホン酸 ０．２８ ０．０２Example 1 As a monomer, the following o-, m-, p-
Chemical oxidative polymerization was carried out using aminobenzene sulfonic acid. Chemical oxidative polymerization was carried out by adding aminobenzene sulfonic acid to 0.2
125 mol / l, sulfuric acid 0.5 mol / l, and potassium permanganate 0.25 mol / l, respectively.
The reaction was continued for a period of time. The polymerization proceeded in a solution state, and no polymer precipitation was observed. After the solution after polymerization was concentrated under reduced pressure, the solution was dropped into a large amount of methanol to precipitate a polymer, which was separated by filtration and dried under reduced pressure to obtain a polymer. The structure is shown by infrared absorption spectrum as shown in FIG. The polymerization yield and the conductivity of each polymer are shown below. It was confirmed that each was a conductive polymer.
All of these polymers were well dissolved in water, alkaline aqueous solution and acidic aqueous solution. Monomer Polymerization yield (g) Conductivity (s / cm) o-Aminobenzenesulfonic acid 0.36 0.3 m-Aminobenzenesulfonic acid 0.39 0.5 p-Aminobenzenesulfonic acid 0.28 0. 02
【００１６】同様にして、アミノベンゼンスルホン酸の
代わりに、アミノベンゼン−２，５−ジスルホン酸、ア
ミノベンゼン−２，４−ジスルホン酸を用いることによ
り対応する重合体を得ることができる。Similarly, the corresponding polymer can be obtained by using aminobenzene-2,5-disulfonic acid or aminobenzene-2,4-disulfonic acid instead of aminobenzenesulfonic acid.
【００１７】[0017]
【実施例２】単量体として、ｍ−アミノベンゼンスルホ
ン酸及びアニリンを用いて化学酸化重合を行った。化学
酸化重合は、アミノベンゼンスルホン酸を０．１２５モ
ル／ｌ、アニリンを０．０５モル／ｌ、硫酸を０．５モ
ル／ｌ、過マンガン酸カリウムを０．２５モル／ｌそれ
ぞれ使用し攪はんを２時間続けて反応を行った。得られ
た重合体は、０．４３ｇであった。さらに、その導電率
を測定したところ、０．５ｓ／ｃｍであった。Example 2 Chemical oxidative polymerization was carried out using m-aminobenzenesulfonic acid and aniline as monomers. For chemical oxidative polymerization, 0.125 mol / l of aminobenzenesulfonic acid, 0.05 mol / l of aniline, 0.5 mol / l of sulfuric acid and 0.25 mol / l of potassium permanganate were used. The reaction was continued for 2 hours with stirring. The amount of the polymer obtained was 0.43 g. Furthermore, the conductivity was measured and found to be 0.5 s / cm.
【００１８】同様にして、アミノベンゼンスルホン酸と
アニリンの代わりに、アミノベンゼン−２，５−ジスル
ホン酸あるいはアミノベンゼン−２，４−ジスルホン酸
とヒドロキシアニリンあるいはカルボキシアニリンとの
混合物を用いることにより対応する重合体を得ることが
できる。Similarly, in place of aminobenzenesulfonic acid and aniline, a mixture of aminobenzene-2,5-disulfonic acid or aminobenzene-2,4-disulfonic acid and hydroxyaniline or carboxyaniline is used. The polymer which does can be obtained.
【００１９】[0019]
【比較例１】単量体として、ｍ−アミノベンゼンスルホ
ン酸を用いて電解酸化重合を行った。化学酸化重合は、
ｍ−アミノベンゼンスルホン酸を０．１２５モル／ｌ
（総仕込量は０．５ｇ）、２．５ｍＡ／８ｃｍ2の定電
流を流し、２時間の電解時間によって反応を行った。得
られた重合体は、０．１４ｇ（２．８％）であった。Comparative Example 1 Electrolytic oxidative polymerization was carried out using m-aminobenzenesulfonic acid as a monomer. Chemical oxidative polymerization
0.125 mol / l of m-aminobenzenesulfonic acid
(The total amount charged was 0.5 g), a constant current of 2.5 mA / 8 cm 2 was passed, and the reaction was performed for 2 hours of electrolysis. The amount of the polymer obtained was 0.14 g (2.8%).
【００２０】[0020]
【比較例２】電解時間が１０時間である点を除き、比較
例１と同様に反応させることにより、重合体０．７ｇ
（１４％）を得た。[Comparative Example 2] 0.7 g of a polymer was obtained by the same reaction as in Comparative Example 1 except that the electrolysis time was 10 hours.
(14%) was obtained.
【図１】 実施例１によって得られた重合体の赤外吸収
スペクトルを示す。1 shows an infrared absorption spectrum of the polymer obtained in Example 1. FIG.
Claims (1)
アミノベンゼンスルホン酸系化合物とアニリン系化合物
を含む単量体を化学酸化重合することを特徴とする水に
可溶性の導電性高分子の製造方法1. A method for producing a water-soluble conductive polymer, which comprises chemically oxidatively polymerizing an aminobenzenesulfonic acid compound or a monomer containing an aminobenzenesulfonic acid compound and an aniline compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23413592A JPH0656987A (en) | 1992-08-11 | 1992-08-11 | Produciton of conductive polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23413592A JPH0656987A (en) | 1992-08-11 | 1992-08-11 | Produciton of conductive polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0656987A true JPH0656987A (en) | 1994-03-01 |
Family
ID=16966189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23413592A Pending JPH0656987A (en) | 1992-08-11 | 1992-08-11 | Produciton of conductive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0656987A (en) |
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|---|---|---|---|---|
| US5589108A (en) * | 1993-12-29 | 1996-12-31 | Nitto Chemical Industry Co., Ltd. | Soluble alkoxy-group substituted aminobenzenesulfonic acid aniline conducting polymers |
| US5776659A (en) * | 1994-10-12 | 1998-07-07 | Fujitsu Limited | Ionizing radiation exposure method utilizing water soluble aniline antistatic polymer layer |
| EP0837112A3 (en) * | 1996-10-15 | 1998-11-11 | Nitto Chemical Industry Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| US5980784A (en) * | 1996-10-02 | 1999-11-09 | Mitsubishi Rayon Co., Ltd. | Method for producing soluble conductive polymer having acidic group |
| US5993694A (en) * | 1996-06-10 | 1999-11-30 | Nippon Shokubai Co., Ltd. | Water-soluble electrically-conductive polyaniline and method for production thereof and antistatic agent using water-soluble electrically-conductive polymer |
| US6024895A (en) * | 1995-08-11 | 2000-02-15 | Mitsubishi Rayon Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
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| WO2018147318A1 (en) | 2017-02-10 | 2018-08-16 | 三菱ケミカル株式会社 | Conductive composition, method for producing conductive composition, and method for producing conductor |
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-
1992
- 1992-08-11 JP JP23413592A patent/JPH0656987A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589108A (en) * | 1993-12-29 | 1996-12-31 | Nitto Chemical Industry Co., Ltd. | Soluble alkoxy-group substituted aminobenzenesulfonic acid aniline conducting polymers |
| US5700399A (en) * | 1993-12-29 | 1997-12-23 | Nitto Chemical Industry Co., Ltd. | Soluble alkoxy-group substituted aminobenzenesulfonic acid aniline conducting polymers |
| US5932144A (en) * | 1993-12-29 | 1999-08-03 | Mitsubishi Rayon Co., Ltd. | Soluble aniline conducting polymers |
| US5776659A (en) * | 1994-10-12 | 1998-07-07 | Fujitsu Limited | Ionizing radiation exposure method utilizing water soluble aniline antistatic polymer layer |
| US6024895A (en) * | 1995-08-11 | 2000-02-15 | Mitsubishi Rayon Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| US5993694A (en) * | 1996-06-10 | 1999-11-30 | Nippon Shokubai Co., Ltd. | Water-soluble electrically-conductive polyaniline and method for production thereof and antistatic agent using water-soluble electrically-conductive polymer |
| US5980784A (en) * | 1996-10-02 | 1999-11-09 | Mitsubishi Rayon Co., Ltd. | Method for producing soluble conductive polymer having acidic group |
| EP0837112A3 (en) * | 1996-10-15 | 1998-11-11 | Nitto Chemical Industry Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| AU734424B2 (en) * | 1996-10-15 | 2001-06-14 | Mitsubishi Rayon Company Limited | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| US7645400B2 (en) | 2002-11-01 | 2010-01-12 | Mitsubishi Rayon Co., Ltd. | Composition containing carbon nanotubes having a coating |
| WO2012165447A1 (en) * | 2011-05-30 | 2012-12-06 | Ｎｅｃトーキン株式会社 | Conductive polymer, conductive polymer aqueous solution, conductive polymer film, solid electrolytic capacitor and method for producing same |
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| US10096395B2 (en) | 2012-07-24 | 2018-10-09 | Mitsubishi Chemical Corporation | Conductor, conductive composition and laminate |
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