JP2768099B2 - Conductive polymer compound solution - Google Patents
Conductive polymer compound solutionInfo
- Publication number
- JP2768099B2 JP2768099B2 JP3354493A JP35449391A JP2768099B2 JP 2768099 B2 JP2768099 B2 JP 2768099B2 JP 3354493 A JP3354493 A JP 3354493A JP 35449391 A JP35449391 A JP 35449391A JP 2768099 B2 JP2768099 B2 JP 2768099B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- polymer compound
- solution
- poly
- polyaniline
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電性高分子化合物塗膜
の製造に有利に利用される導電性高分子化合物溶液に関
し、さらに詳しくは、高濃度でも長時間にわたり沈殿等
を生じない安定化された導電性高分子溶液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polymer compound solution which is advantageously used for producing a conductive polymer compound coating film. The present invention relates to the obtained conductive polymer solution.
【０００２】[0002]
【従来の技術】これまで炭素数４以上のアルキル基を置
換基とするポリ（３−アルキルチオフェン）、ポリ（Ｎ
−アルキルピロール）、ポリ（３−アルキルピロール）
をクロロホルム等の有機溶媒に溶解させた溶液や、ポリ
アニリンをＮ−メチル−２−ピロリドンに溶解させたポ
リアニリン等の導電性高分子化合物溶液が開発されてい
る。2. Description of the Related Art Hitherto, poly (3-alkylthiophene) and poly (N
-Alkylpyrrole), poly (3-alkylpyrrole)
And a conductive polymer compound solution such as polyaniline obtained by dissolving polyaniline in N-methyl-2-pyrrolidone.
【０００３】[0003]
【発明が解決しようとする課題】導電性高分子化合物溶
液のうち可溶性ポリアニリンのＮ−メチル−２−ピロリ
ドン溶液では導電性高分子の重量が０．５重量％以上で
は室温で長時間放置するとゲル化し、またポリ（３−ア
ルキルチオフェン）のクロロホルム溶液では導電性高分
子の濃度が２重量％を越えると溶液が部分的に凝集す
る。従って可溶性導電性高分子化合物の溶液は、導電性
高分子の塗膜を得る方法として有効ではあるが、高濃度
溶液ではゲル化や凝集が起きるため安定に保存できない
という問題点があった。また可溶性導電性高分子化合物
を溶解後、直ちにキャストした場合にも溶媒の蒸発に伴
って濃度が上昇し、部分的に凝集が生じて均一なフィル
ムが得られないという問題点があった。本発明の目的
は、前記の問題点を解消することにより、安定な導電性
高分子化合物溶液を提供することにある。Among the conductive polymer compound solutions, in the case of a solution of soluble polyaniline in N-methyl-2-pyrrolidone, when the weight of the conductive polymer is 0.5% by weight or more, the gel is left standing at room temperature for a long time. In a chloroform solution of poly (3-alkylthiophene), if the concentration of the conductive polymer exceeds 2% by weight, the solution partially aggregates. Therefore, a solution of a soluble conductive polymer compound is effective as a method for obtaining a coating film of a conductive polymer, but has a problem in that a high-concentration solution cannot be stored stably because gelation or aggregation occurs. In addition, even when the soluble conductive polymer compound is cast immediately after dissolution, there is a problem in that the concentration increases with evaporation of the solvent, and partial aggregation occurs, so that a uniform film cannot be obtained. An object of the present invention is to provide a stable conductive polymer compound solution by solving the above problems.
【０００４】[0004]
【課題を解決するための手段】本発明は、ポリアニリ
ン、アルコキシル基置換ポリアニリンまたは炭素数４以
上のアルキル置換ポリチオフェンから選ばれる導電性高
分子化合物の濃度が０．５重量％以上であり、該導電性
高分子化合物を構成する単量体の総モル量に対して２モ
ル％以上の尿素を含むことを特徴とする導電性高分子化
合物溶液である。According to the present invention, the conductive polymer compound selected from the group consisting of polyaniline, an alkoxyl-substituted polyaniline and an alkyl-substituted polythiophene having 4 or more carbon atoms has a concentration of 0.5% by weight or more. A conductive polymer compound solution comprising 2 mol% or more of urea based on the total molar amount of monomers constituting the conductive polymer compound.
【０００５】本発明において、導電性高分子とはドーピ
ングによって導電性となり得る構造を有する電子共役系
の高分子であり、脱ドープ状態のものも含まれる。この
ような導電性高分子化合物としては、その全部あるいは
一部が溶媒に可溶な導電性高分子化合物であり、例えば
ポリアニリン，ポリ（ｏ−メトキシアニリン），ポリ
（ｍ−メトキシアニリン），ポリ（ｏ−エトキシアニリ
ン），ポリ（ｍ−エトキシアニリン）等のポリアニリン
およびポリアニリン誘導体、ポリ（３−ブチルチオフェ
ン），ポリ（３−ヘキシルチオフェン），ポリ（３−オ
クチルチオフェン），ポリ（３−ドデシルチオフェン）
等のポリ（３−アルキルチオフェン）等が挙げられる。
本発明で用いるジアミン化合物は、分子内にアミノ基を
含むものであれば特に限定されないが、なかでもカルボ
ニル基を同時に含む尿素等のカルバモイル化合物が有機
溶媒への溶解性の面で好ましい。[0005] In the present invention, the conductive polymer is an electron conjugated polymer having a structure that can be made conductive by doping, and includes an undoped polymer. Such a conductive polymer compound is a conductive polymer compound that is wholly or partially soluble in a solvent, such as polyaniline, poly (o-methoxyaniline), poly (m-methoxyaniline), and poly (m-methoxyaniline). (O-ethoxyaniline), polyaniline and polyaniline derivatives such as poly (m-ethoxyaniline), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-octylthiophene), poly (3-dodecyl) Thiophene)
And poly (3-alkylthiophene).
The diamine compound used in the present invention is not particularly limited as long as it contains an amino group in the molecule, and among them, a carbamoyl compound such as urea containing a carbonyl group at the same time is preferable in terms of solubility in an organic solvent.
【０００６】本発明では上記のジアミン化合物を導電性
高分子化合物の溶液に添加するが、ジアミン化合物を完
全に溶解した状態および懸濁した状態で用いられる。本
発明において導電性高分子化合物溶液の調合は、導電性
高分子化合物とジアミン化合物とを同時に溶解する、あ
るいは予め導電性高分子化合物を溶解させた後にジアミ
ン化合物を添加するといういずれの方法も可能である。
本発明において導電性高分子化合物溶液に混合するジア
ミン化合物の割合は、２モル％以下では溶液の安定性が
徐々に失われてしまいゲル化が進行する。本発明におい
て導電性高分子化合物溶液の溶媒は、導電性高分子化合
物を溶解させるものであれば特に限定されない。これら
の例として、クロロホルム、テトラヒドロフラン、ヘキ
サン、ニトロベンゼン、アセトニトリル、Ｎ−メチル−
２−ピロリドン、ジメチルホルムアミド、ジメチルスル
ホキシド等が挙げられる。これらのうち特に好ましいの
は、ポリアニリンおよびポリアニリン誘導体に関しては
Ｎ−メチル−２−ピロリドン、ポリ（３−アルキルチオ
フェン）誘導体に関してはクロロホルムが挙げられる。In the present invention, the above-mentioned diamine compound is added to the solution of the conductive polymer compound, and the diamine compound is used in a completely dissolved or suspended state. In the present invention, the preparation of the conductive polymer compound solution can be performed by simultaneously dissolving the conductive polymer compound and the diamine compound, or adding the diamine compound after dissolving the conductive polymer compound in advance. It is.
In the present invention, when the proportion of the diamine compound mixed with the conductive polymer compound solution is 2 mol% or less, the stability of the solution is gradually lost and gelation proceeds. In the present invention, the solvent of the conductive polymer compound solution is not particularly limited as long as the solvent dissolves the conductive polymer compound. Examples of these include chloroform, tetrahydrofuran, hexane, nitrobenzene, acetonitrile, N-methyl-
2-pyrrolidone, dimethylformamide, dimethylsulfoxide and the like. Of these, particularly preferred are N-methyl-2-pyrrolidone for polyaniline and polyaniline derivatives, and chloroform for poly (3-alkylthiophene) derivatives.
【０００７】[0007]
【実施例】次に本発明の実施例について説明する。 実施例１ アニリンを、ペルオキシ二硫酸アンモニウムを酸化剤と
して−５℃で重合し、アンモニア水で脱ドープしたのち
乾燥し、ポリアニリン粉末を得た。この粉末１５重量
％、尿素をアニリン単量体に対して２０モル％含有した
Ｎ−メチル−２−ピロリドン溶液を調合し、室温で３時
間放置したが、ゲル化は全く見られなかった。またこの
溶液をキャストしたのち１規定硫酸で１時間ドーピング
し、その導電率を測定したところ、３．５［Ｓ／ｃｍ］
という良好な導電率であった。Next, an embodiment of the present invention will be described. Example 1 Aniline was polymerized at −5 ° C. using ammonium peroxydisulfate as an oxidizing agent, dedoped with aqueous ammonia, and dried to obtain a polyaniline powder. An N-methyl-2-pyrrolidone solution containing 15% by weight of this powder and 20 mol% of urea relative to the aniline monomer was prepared and left at room temperature for 3 hours, but no gelation was observed. After casting this solution, it was doped with 1N sulfuric acid for 1 hour, and its conductivity was measured to be 3.5 [S / cm].
Good electrical conductivity.
【０００８】実施例２ ｏ−メトキシアニリンを、ペルオキシ二硫酸アンモニウ
ムを酸化剤として重合し、アンモニア水で脱ドープした
のち乾燥し、ポリ（ｏ−メトキシアニリン）粉末を得
た。この粉末１０重量％、尿素をｏ−メトキシアニリン
単量体に対して１５モル％含有したアセトニトリル溶液
を調合し、室温で３時間放置したが、ゲル化は全く見ら
れなかった。またこの溶液をキャストしたのち１規定塩
酸で１時間ドーピングし、その導電率を測定したとこ
ろ、０．２５［Ｓ／ｃｍ］という良好な導電率であっ
た。Example 2 o-Methoxyaniline was polymerized using ammonium peroxydisulfate as an oxidizing agent, dedoped with aqueous ammonia, and dried to obtain a poly (o-methoxyaniline) powder. An acetonitrile solution containing 10% by weight of this powder and 15 mol% of urea relative to the o-methoxyaniline monomer was prepared and left at room temperature for 3 hours, but no gelation was observed. Further, after casting this solution, it was doped with 1 N hydrochloric acid for 1 hour, and its electric conductivity was measured. As a result, a good electric conductivity of 0.25 [S / cm] was obtained.
【０００９】実施例３ ３−オクチルチオフェンを、塩化第二鉄を酸化剤として
重合し、メタノールで洗浄したのち乾燥し、ポリ（３−
オクチルチオフェン）を得た。これを５重量％、尿素を
３−オクチルチオフェン単量体に対して５モル％含有し
たクロロホルム溶液を調合し、室温で３時間放置した
が、ゲル化は特に見られなかった。また部分的な凝集も
見られなかった。この溶液をキャストしたのち塩化第二
鉄のニトリルメタン溶液で３０分間ドーピングし、導電
率を測定したところ、２７［Ｓ／ｃｍ］という良好な導
電率であった。Example 3 3-octylthiophene was polymerized using ferric chloride as an oxidizing agent, washed with methanol, dried, and treated with poly (3-
Octylthiophene). A chloroform solution containing 5% by weight of this and 5 mol% of urea relative to the 3-octylthiophene monomer was prepared and left at room temperature for 3 hours, but no particular gelation was observed. No partial aggregation was observed. After casting this solution, the solution was doped with a nitrile methane solution of ferric chloride for 30 minutes, and the conductivity was measured. As a result, a good conductivity of 27 [S / cm] was obtained.
【００１０】比較例１ 実施例１と同様にポリアニリン粉末１５重量％のＮ−メ
チル−２−ピロリドン溶液を調合し、室温で放置したと
ころ約３０分でほぼ完全にゲル化してしまいキャスト膜
を得ることができなかった。Comparative Example 1 A 15% by weight solution of polyaniline powder in N-methyl-2-pyrrolidone was prepared in the same manner as in Example 1, and when left at room temperature, it gelled almost completely in about 30 minutes to obtain a cast film. I couldn't do that.
【００１１】[0011]
【発明の効果】以上説明したように、本発明によれば高
濃度な導電性高分子化合物溶液をゲル化させず安定化さ
せることが可能になり、電子デバイス、電磁シールド、
帯電防止剤等へ広く応用でき、その効果は大である。As described above, according to the present invention, it is possible to stabilize a high-concentration conductive polymer compound solution without gelling it, and to provide an electronic device, an electromagnetic shield,
It can be widely applied to antistatic agents and the like, and its effect is great.
フロントページの続き (72)発明者 佐藤 正春 東京都港区芝５丁目７番１号 日本電気 株式会社内 (56)参考文献 特開 昭60−133027（ＪＰ，Ａ) 特開 昭62−64828（ＪＰ，Ａ) 特開 平３−259922（ＪＰ，Ａ) 特表 平６−510555（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 79/00 C08K 5/21 C08L 65/00 ＣＡ（ＳＴＮ)Continuation of the front page (72) Inventor Masaharu Sato 5-7-1 Shiba, Minato-ku, Tokyo Within NEC Corporation (56) References JP-A-60-1333027 (JP, A) JP-A-62-264828 ( JP, A) JP-A-3-259922 (JP, A) JP-A-6-510555 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 79/00 C08K 5/21 C08L 65/00 CA (STN)
Claims (1)
アニリンまたは炭素数４以上のアルキル置換ポリチオフ
ェンから選ばれる導電性高分子化合物の濃度が０．５重
量％以上であり、該導電性高分子化合物を構成する単量
体の総モル量に対して２モル％以上の尿素を含むことを
特徴とする導電性高分子化合物溶液。1. A polyaniline or an alkoxyl-substituted poly.
Aniline or alkyl-substituted polythiophene having 4 or more carbon atoms
The concentration of the conductive polymer compound selected from the group is 0.5% by weight or more, and contains 2% by mole or more of urea based on the total molar amount of the monomers constituting the conductive polymer compound. A conductive polymer compound solution, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3354493A JP2768099B2 (en) | 1991-12-20 | 1991-12-20 | Conductive polymer compound solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3354493A JP2768099B2 (en) | 1991-12-20 | 1991-12-20 | Conductive polymer compound solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05171010A JPH05171010A (en) | 1993-07-09 |
| JP2768099B2 true JP2768099B2 (en) | 1998-06-25 |
Family
ID=18437940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3354493A Expired - Fee Related JP2768099B2 (en) | 1991-12-20 | 1991-12-20 | Conductive polymer compound solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2768099B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200619301A (en) * | 2004-09-22 | 2006-06-16 | Showa Denko Kk | The water-soluable composition of antistatic agent, the antistatic agent, the method of forming antistatic film, coated products and pattern by using the same the agent |
| KR102031628B1 (en) | 2012-07-24 | 2019-10-15 | 미쯔비시 케미컬 주식회사 | Conductor, conductive composition, and laminate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60133027A (en) * | 1983-12-21 | 1985-07-16 | Nitto Electric Ind Co Ltd | Production of electrically conductive organic polymer |
| JPS6264828A (en) * | 1985-09-17 | 1987-03-23 | Showa Denko Kk | Production of electroconductive polymer composition |
| SE465012B (en) * | 1989-12-08 | 1991-07-15 | Freja Invest Kommanditbolag | CLEANING AID FOR ACHIEVEMENT OF POINTING OF BODY PARTS |
| JP2942785B2 (en) * | 1990-03-09 | 1999-08-30 | 日東電工株式会社 | Organic polymer solution |
-
1991
- 1991-12-20 JP JP3354493A patent/JP2768099B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05171010A (en) | 1993-07-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |