JP3334111B2 - Manufacturing method of conductive polymer film - Google Patents
Manufacturing method of conductive polymer filmInfo
- Publication number
- JP3334111B2 JP3334111B2 JP22191892A JP22191892A JP3334111B2 JP 3334111 B2 JP3334111 B2 JP 3334111B2 JP 22191892 A JP22191892 A JP 22191892A JP 22191892 A JP22191892 A JP 22191892A JP 3334111 B2 JP3334111 B2 JP 3334111B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- substituted
- conductive polymer
- tcne
- polymer film
- 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
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電性高分子フィルムの
製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive polymer film.
【０００２】[0002]
【従来の技術】導電性高分子は共役系有機高分子とし
て、そのπ電子の電気的、化学的更には光学的な特性を
利用し、多くの機能を有する材料として注目されてい
る。しかし不溶不融のため高分子特有の成型性に欠け、
その応用範囲は限られていた。最近では共役系主鎖に置
換基を導入し、可溶化することが開示され、同時に溶解
した高分子を溶液状態のまま酸化ドープする試みもされ
ている。2. Description of the Related Art A conductive polymer has attracted attention as a conjugated organic polymer as a material having many functions by utilizing the electrical, chemical and optical properties of its π electrons. However, lacking the moldability unique to polymers due to insolubility and infusibility,
Its application range was limited. Recently, it has been disclosed that a substituent is introduced into a conjugated main chain to solubilize the conjugated main chain, and at the same time, an attempt has been made to oxidize and dope a dissolved polymer in a solution state.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、酸化状態に
おいても可溶性を失わず、その溶液から強靱でしかも導
電性を有する有用なフィルムを得ることである。SUMMARY OF THE INVENTION An object of the present invention is to obtain a useful film having toughness and conductivity from a solution which does not lose its solubility even in an oxidized state.
【０００４】[0004]
【課題を解決するための手段】本発明は、ポリピロール
誘導体の溶液と有機電子受容体との均一溶液から成膜す
ることを特徴とする導電性高分子フィルムの製法であ
る。本発明におけるポリピロール誘導体は溶媒に可溶な
ものであって一般式〔Ι〕SUMMARY OF THE INVENTION The present invention is a method for producing a conductive polymer film, wherein a film is formed from a homogeneous solution of a polypyrrole derivative solution and an organic electron acceptor. The polypyrrole derivative in the present invention is soluble in a solvent and has a general formula [Ι]
【０００５】[0005]
【化１】 Embedded image
【０００６】（式中、Ｒ1 は置換又は未置換のアルキ
ル、置換又は未置換のアルコキシ、ハロゲン、置換又は
未置換のフェニルを、Ｒ2 は置換又は未置換アルキル、
置換又は未置換のフェニルを表わす。）で表わされるも
のでｎが２〜１０００のもの、好ましくは１０〜５００
である。(Wherein, R 1 is substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, halogen, substituted or unsubstituted phenyl, R 2 is substituted or unsubstituted alkyl,
Represents a substituted or unsubstituted phenyl. ) Wherein n is 2 to 1000, preferably 10 to 500
It is.
【０００７】溶媒としては、１，２−ジクロロエタン、
クロロホルム、エーテル、ＴＨＦ、ＤＭＦ、酢酸エチ
ル、アセトン等が用いられる。有機電子受容体として
は、ＤＤＱ、ＴＣＮＱ、ＴＣＮＥ、クロラニル、テトラ
フルオロテトラシアノキノジメタン（ＴＦ−ＴＣＮ
Ｑ）、ＤＡＭＮ誘導体（テトラシアノピラジン、テトラ
シアノテトラアザナフタレン等）等であり、溶液中電荷
移動錯体を形成し、溶解性を失わず、均一安定な溶液と
なることが分った。更にこの溶液を一般のフィルム作成
方法（キャスト、ロールコーター、浸漬等）により導電
性高分子フィルムを得ることができる。As the solvent, 1,2-dichloroethane,
Chloroform, ether, THF, DMF, ethyl acetate, acetone and the like are used. As organic electron acceptors, DDQ, TCNQ, TCNE, chloranil, tetrafluorotetracyanoquinodimethane (TF-TCN)
Q), DAMN derivatives (tetracyanopyrazine, tetracyanotetraazanaphthalene, etc.) and the like, forming a charge-transfer complex in the solution, without losing the solubility, and becoming a uniform and stable solution. Further, a conductive polymer film can be obtained from this solution by a general film forming method (cast, roll coater, dipping, etc.).
【０００８】[0008]
【実施例】次に実施例を挙げ、本発明を更に具体的に示
す。 実施例１ ３−ヘキシルピロール−４−カルボン酸メチル（化２）
のポリマーのＴＨＦ１wt ％の溶液に、モノマー単位８
ヶ当りＴＣＮＥ１モルの割合でＴＣＮＥを加えた。The present invention will be described more specifically with reference to the following examples. Example 1 Methyl 3-hexylpyrrole-4-carboxylate
In a solution of 1% by weight of THF in a polymer of
TCNE was added at a rate of 1 mole of TCNE per unit.
【０００９】[0009]
【化２】 Embedded image
【００１０】この溶液は均一安定であった。溶液は黄赤
色から暗紫色に変化した。この溶液をガラス板上に塗布
し、ＴＨＦを蒸発乾燥後、二探針の導電性測定方法によ
り測定し、結果を第１表に示した。This solution was homogeneous and stable. The solution changed from yellow-red to dark purple. This solution was applied on a glass plate, THF was evaporated and dried, and then measured by a two-probe conductivity measurement method. The results are shown in Table 1.
【００１１】実施例２ ３−メチルピロール−４−カルボン酸ヘキシル（化３）
のポリマーを実施例１と同様にして、ＴＣＮＥの添加量
を変えて行った。Example 2 Hexyl 3-methylpyrrole-4-carboxylate
Was carried out in the same manner as in Example 1 except that the amount of TCNE added was changed.
【００１２】[0012]
【化３】 Embedded image
【００１３】結果を対比例と共に第１表に示した。The results are shown in Table 1 together with comparative examples.
【００１４】実施例３〜８ 実施例１、２と同様に高分子フィルムを製造し、結果を
第１表に示した。Examples 3 to 8 Polymer films were produced in the same manner as in Examples 1 and 2, and the results are shown in Table 1.
【００１５】実施例９ ３−メチルピロール−４−カルボン酸ブチル（化４）
０．６０３ｇ（３．３ｍｍｏｌ）と３−メチルピロール
−４−カルボン酸エチル（化５）１．０２ｇ（６．７ｍ
ｍｏｌ）を無水塩化鉄４．８８ｇ（３０ｍｍｏｌ）／塩
化エチレン・メタノール（４：１ ｖｏｌ）１００ｍｌ
の溶液に加えた。EXAMPLE 9 Butyl 3-methylpyrrole-4-carboxylate
0.603 g (3.3 mmol) and 1.02 g of ethyl 3-methylpyrrole-4-carboxylate (Formula 5) (6.7 m
mol) with 4.88 g (30 mmol) of anhydrous iron chloride / 100 ml of ethylene chloride / methanol (4: 1 vol)
Was added to the solution.
【化４】 Embedded image
【化５】 この溶液をガラス板に流し込み、溶媒を減圧下除去し
た。得られた重合体（黒色フィルム）をメタノール、８
０％ＮＨ2 ＮＨ2 、水の順序で洗浄し、乾燥した。重合
収率は８５％であり、このものはＴＨＦに溶解した。Ｔ
ＨＦ高分子溶液の４ wt ％にモノマー単位当たりＴＣＮ
Ｅのモル比４／１となるＴＣＮＥを添加した。Embedded image This solution was poured into a glass plate, and the solvent was removed under reduced pressure. The obtained polymer (black film) was treated with methanol and 8
It was washed with 0% NH 2 NH 2 and water in that order and dried. The polymerization yield was 85%, which was dissolved in THF. T
TCN per monomer unit to 4 wt% of HF polymer solution
TCNE was added to give a molar ratio of E of 4/1.
【００１６】この溶液は均一安定であった。溶液は黄赤
色から暗紫色に変化した。この溶液をガラス板上に塗布
し、ＴＨＦを蒸発乾燥後、二探針の導電性測定方法によ
り測定し、結果を第１表に示した。This solution was homogeneous and stable. The solution changed from yellow-red to dark purple. This solution was applied on a glass plate, THF was evaporated and dried, and then measured by a two-probe conductivity measurement method. The results are shown in Table 1.
【００１７】実施例１０ ３−メチルピロール−４−カルボン酸プロピル（化６）
１．１３ｇ（６．７ｍｍｏｌ）と３−メチルピロール−
４−カルボン酸エチル（化７）０．５０５ｇ（３．３ｍ
ｍｏｌ）に変え同様に重合体を得た。Example 10 Propyl 3-methylpyrrole-4-carboxylate
1.13 g (6.7 mmol) and 3-methylpyrrole-
0.505 g (3.3 m) of ethyl 4-carboxylate (Formula 7)
mol) and a polymer was obtained in the same manner.
【化６】 Embedded image
【化７】 重合率は８８％であり、ＴＨＦに溶解した。ＴＨＦ高分
子溶液の４ wt ％にモノマー単位当たりＴＣＮＥのモル
比７／１となるＴＣＮＥを添加した。Embedded image The polymerization rate was 88%, and it was dissolved in THF. TCNE was added to 4 wt% of the THF polymer solution so that the molar ratio of TCNE per monomer unit was 7/1.
【００１８】この溶液は均一安定であった。溶液は黄赤
色から暗紫色に変化した。この溶液をガラス板上に塗布
し、ＴＨＦを蒸発乾燥後、二探針の導電性測定方法によ
り測定した。その結果を第１表に示した。This solution was homogeneous and stable. The solution changed from yellow-red to dark purple. This solution was applied on a glass plate, THF was evaporated and dried, and then measured by a two-probe conductivity measurement method. The results are shown in Table 1.
【００１９】[0019]
【表１０１】 [Table 101]
【００２０】[0020]
【表１０２】 [Table 102]
【００２１】[0021]
【表１０３】 [Table 103]
【００２２】[0022]
【発明の効果】本発明の高分子溶液は、静電防止材料、
電磁波シールド材（ケーブルシールド材）、アルミ電解
コンデンサー等の電解質としての用途、絶縁体から半導
体領域にいたる液晶のベースフィルム、透明電極など従
来煩雑であった電解酸化重合もしくはドーピング処理な
どを必要とせず、塗布等の手段で導電性を有する強靱な
膜材料を提供できる。The polymer solution of the present invention comprises an antistatic material,
Electromagnetic wave shielding material (cable shielding material), use as electrolyte such as aluminum electrolytic capacitor, liquid crystal base film from insulator to semiconductor area, transparent electrode, etc. A tough film material having conductivity can be provided by means such as coating and application.
【図１】化３のポリマー（ＴＨＦ中）とＴＣＮＥ（ＴＨ
Ｆ中）の夫々の可視・紫外吸収スペクトル。FIG. 1 shows a polymer of formula 3 (in THF) and TCNE (TH
F) visible / ultraviolet absorption spectrum of each.
【図２】実施例２において、ＴＣＮＥの添加量１２／１
（モノマー単位／ＴＣＮＥ）のときの可視・紫外吸収ス
ペクトル。FIG. 2 shows the amount of TCNE added in Example 2 at 12/1.
The visible / ultraviolet absorption spectrum when (monomer unit / TCNE).
【図３】実施例２において、ＴＣＮＥの添加量８／１
（モノマー単位／ＴＣＮＥ）のときの可視・紫外吸収ス
ペクトル。FIG. 3 shows that in Example 2, the amount of TCNE added was 8/1.
The visible / ultraviolet absorption spectrum when (monomer unit / TCNE).
フロントページの続き (56)参考文献 特開 昭63−136419（ＪＰ，Ａ) 特開 平５−132547（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 61/12 C08J 5/18 Continuation of the front page (56) References JP-A-63-136419 (JP, A) JP-A-5-132547 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 61 / 12 C08J 5/18
Claims (1)
置換のアルコキシ、ハロゲン、置換又は未置換のフェニ
ルを、Ｒ 2 は置換又は未置換アルキル、置換又は未置換
のフェニルを、ｎは２〜１０００を表わす。）で表され
るポリピロール誘導体の溶液と有機電子受容体との均一
溶液から成膜することを特徴とする導電性高分子フィル
ムの製法。1. A compound of the general formula [I] (Wherein R 1 is a substituted or unsubstituted alkyl, a substituted or unsubstituted
Substituted alkoxy, halogen, substituted or unsubstituted phenyl
And R 2 is a substituted or unsubstituted alkyl, substituted or unsubstituted
And n represents 2 to 1000. )
Preparation of the conductive polymer film, which comprises depositing from a homogeneous solution of a solution and the organic electron acceptor polypyrrole derivatives that.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22191892A JP3334111B2 (en) | 1991-11-19 | 1992-07-29 | Manufacturing method of conductive polymer film |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32985491 | 1991-11-19 | ||
| JP5972692 | 1992-02-14 | ||
| JP3-329854 | 1992-02-14 | ||
| JP4-59726 | 1992-02-14 | ||
| JP22191892A JP3334111B2 (en) | 1991-11-19 | 1992-07-29 | Manufacturing method of conductive polymer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05287088A JPH05287088A (en) | 1993-11-02 |
| JP3334111B2 true JP3334111B2 (en) | 2002-10-15 |
Family
ID=27296982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22191892A Expired - Fee Related JP3334111B2 (en) | 1991-11-19 | 1992-07-29 | Manufacturing method of conductive polymer film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3334111B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0201593D0 (en) * | 2002-01-24 | 2002-03-13 | Univ Durham | Ferromagnetic polymer |
| EP3270433A4 (en) * | 2015-03-13 | 2019-02-20 | Nissan Chemical Corporation | Composition for forming charge-transporting thin film for organic electroluminescent elements, charge-transporting thin film for organic electroluminescent elements, and organic electroluminescent element |
-
1992
- 1992-07-29 JP JP22191892A patent/JP3334111B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05287088A (en) | 1993-11-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |