JPH044332B2 - - Google Patents
Info
- Publication number
- JPH044332B2 JPH044332B2 JP17533183A JP17533183A JPH044332B2 JP H044332 B2 JPH044332 B2 JP H044332B2 JP 17533183 A JP17533183 A JP 17533183A JP 17533183 A JP17533183 A JP 17533183A JP H044332 B2 JPH044332 B2 JP H044332B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- polythienylene
- methyl derivative
- heat treatment
- amorphous
- 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
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子デバイスの分野に利用される高
分子フイルム及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a polymer film used in the field of electronic devices and a method for manufacturing the same.
従来例の構成とその問題点
従来、高分子を無定形状態にする方法として、
一般的に知られているのは、高分子を溶融状態か
ら室温に急冷する方法である。Structure of conventional examples and their problems Conventionally, as a method to make polymers into an amorphous state,
A commonly known method is to rapidly cool a polymer from a molten state to room temperature.
ここで無定形状態とは、高分子フイルムを形成
する高分子鎖が規則性を持たずに配列しているこ
とと定義する。また、この無定形状態はＸ線回折
による測定で、回折像が得られてもごくわずかで
あることによつて確認される。 Here, the amorphous state is defined as a state in which the polymer chains forming the polymer film are arranged without regularity. Further, this amorphous state is confirmed by X-ray diffraction measurement, in which very few diffraction images are obtained.
ポリチエニレンおよびそのメチル誘導体は急冷
法により無定形状態にして、アモルフアス化（無
定形状態化）ポリチエニレンおよびそのメチル誘
導体を製造しようとしてもできない。 Even if it is attempted to make polythienylene and its methyl derivative into an amorphous state by a rapid cooling method to produce amorphous (amorphous) polythienylene and its methyl derivative, it is not possible.
というのは、ポリチエニレンおよびそのメチル
誘導体フイルムは、はつきりとした融点を持た
ず、溶融状態のポリチエニレン誘導体が得られな
いからである。 This is because polythienylene and its methyl derivative film do not have a sharp melting point, and a polythienylene derivative in a molten state cannot be obtained.
発明の目的
本発明は、アモルフアス化したポリチエニレン
もしくはそのメチル誘導体とその簡単な製造法を
提供することを目的とする。OBJECTS OF THE INVENTION An object of the present invention is to provide amorphized polythienylene or its methyl derivative and a simple method for producing the same.
発明の構成
本発明のアモルフアス化ポリチエニレンもしく
はそのメチル誘導体は、高分子鎖が無定形状態に
なつている。そのため、本発明のフイルムは通常
の、一部結晶状態を持つポリチエニレンもしくは
そのメチル誘導体フイルムに比べて、柔軟性に富
み、強靭である。Structure of the Invention In the amorphized polythienylene or methyl derivative thereof of the present invention, the polymer chain is in an amorphous state. Therefore, the film of the present invention is more flexible and tougher than the usual film of polythienylene or its methyl derivative, which has a partially crystalline state.
このアモルフアス化ポリチエニレンもしくはそ
のメチル誘導体は、通常の合成手段により得られ
たポリチエニレンもしくはそのメチル誘導体を熱
処理することにより得られる。熱処理することに
よつて、高分子鎖が動きやすくなり、ばらばらに
なつて規則性を失うことによつて得られる。 This amorphized polythienylene or its methyl derivative can be obtained by heat-treating polythienylene or its methyl derivative obtained by conventional synthetic means. By heat treatment, the polymer chains become more mobile, break up, and lose their regularity.
この方法は急冷法と違つて、ポリチエニレンも
しくはそのメチル誘導体を溶融する必要がないの
で、簡単にアモルフアス化できる。 Unlike the rapid cooling method, this method does not require melting polythienylene or its methyl derivative, so it can be easily amorphized.
ここで、熱処理は不活性雰囲気で行なうのがよ
い。 Here, the heat treatment is preferably performed in an inert atmosphere.
この不活性雰囲気とは、ポリチエニレンもしく
はそのメチル誘導体フイルムを数百度に加熱して
も、酸化あるいは熱分解しない雰囲気のことであ
る。 This inert atmosphere is an atmosphere in which polythienylene or its methyl derivative film is not oxidized or thermally decomposed even if it is heated to several hundred degrees.
不活性雰囲気の例としては、窒素ガス中、ヘリ
ウムガス中、ネオンガス中、アルゴンガス中ある
いは、空気圧が10mmHg以下の減圧状態などがあ
げられる。 Examples of the inert atmosphere include nitrogen gas, helium gas, neon gas, argon gas, or a reduced pressure state where the air pressure is 10 mmHg or less.
空気圧が数十mmHgになると、酸素の影響を受
けやすくなる。そのため、減圧の場合は、１mm
Hg以下が望ましい。 When the air pressure reaches tens of mmHg, it becomes more susceptible to the effects of oxygen. Therefore, in the case of reduced pressure, 1 mm
Hg or less is desirable.
熱処理温度は、熱処理時間と深い関係があり、
例えば、400℃なら20分、600℃なら１分、800℃
なら30秒程度である。熱処理温度が低いほど、熱
処理時間を長くする必要がある。熱処理温度とし
ては、100〜1000℃が有効で、望ましくは400〜
800℃である。 Heat treatment temperature has a deep relationship with heat treatment time.
For example, 400℃ for 20 minutes, 600℃ for 1 minute, 800℃
If so, it will take about 30 seconds. The lower the heat treatment temperature, the longer the heat treatment time needs to be. Effective heat treatment temperature is 100-1000℃, preferably 400-1000℃.
The temperature is 800℃.
実施例の説明
実施例 １
チオフエン5.05ｇ、支持電解質としてのテトラ
−ｎ−ブチル アンモニウム パークロレート
2.05ｇを300mmのニトロベンゼンに溶解する。
陰極として白金板を用い、陽極としてスズをドー
プした酸化インジウム薄膜を備えたガラス電極を
用い、電解酸化重合を行ない、緑黒色のフイルム
状の重合体を陽極上に得た。電流密度は2mA／
cm2、反応温度は５℃、反応時間は10分とした。そ
の後、引き続いて、２つの電極を反転し、電解還
元を行なつた。電流密度は4mA／cm2、反応時間
は３分とした。反応後、フイルムを電極面から剥
離し、メタノールで洗浄後、一昼夜真空燥し、ポ
リチエニレンフイルムを得た。DESCRIPTION OF EXAMPLES Example 1 5.05 g of thiophene, tetra-n-butyl ammonium perchlorate as supporting electrolyte.
Dissolve 2.05 g in 300 mm of nitrobenzene.
Electrolytic oxidative polymerization was carried out using a platinum plate as the cathode and a glass electrode equipped with a tin-doped indium oxide thin film as the anode, and a green-black film-like polymer was obtained on the anode. Current density is 2mA/
cm 2 , reaction temperature was 5° C., and reaction time was 10 minutes. Thereafter, the two electrodes were subsequently reversed to perform electrolytic reduction. The current density was 4 mA/cm 2 and the reaction time was 3 minutes. After the reaction, the film was peeled off from the electrode surface, washed with methanol, and vacuum dried overnight to obtain a polythienylene film.
このフイルムを、石英ガラス製の密封管に入れ
て脱気した後、窒素ガスを封入し、電気炉で600
℃の温度で１分間加熱した。熱処理後、封管の温
度が室温に下がつてから、ポリチエニレンフイル
ムを取り出した。緑赤色のフイルムを得た。 This film was placed in a sealed quartz glass tube and degassed, then filled with nitrogen gas and heated in an electric furnace for 600 hours.
℃ for 1 minute. After the heat treatment, the polythienylene film was taken out after the temperature of the sealed tube had fallen to room temperature. A green-red film was obtained.
実施例 ２
実施例１において、ポリチエニレンフイルム
を、１mmHgに減圧した密封管中で、同じ条件で
熱処理し、緑赤色のポリチエニレンフイルムを得
た。Example 2 In Example 1, a polythienylene film was heat-treated under the same conditions in a sealed tube with a reduced pressure of 1 mmHg to obtain a green-red polythienylene film.
実施例 ３
実施例１において、チオフエン5.05ｇを３−メ
チルチオフエン5.89ｇにかえて同様の実験を行な
い、黄赤色のフイルムを得た。Example 3 A similar experiment was carried out in Example 1 except that 5.05 g of thiophene was replaced with 5.89 g of 3-methylthiophene to obtain a yellow-red film.
実施例 ４
実施例１において、チオフエン5.05ｇを３−メ
チルチオフエン5.89ｇにかえ、また、熱処理を１
mmHgに減圧した密封管で、同じ条件で熱処理し、
黄赤色のフイルムを得た。Example 4 In Example 1, 5.05 g of thiophene was changed to 5.89 g of 3-methylthiophene, and the heat treatment was changed to 1
Heat treated under the same conditions in a sealed tube with reduced pressure to mmHg,
A yellow-red film was obtained.
実施例１〜４で得られたフイルムは、熱処理前
のフイルムに比べて、いずれのフイルムも柔軟性
に富み、引つ張り強度は数倍強靭であつた。ま
た、理学電機FR−Ｂ、Ｘ線発生器とArndt−
Wanacottオツシレーシヨンカメラを用いて0.1×
0.1mmのCuKα放射線をフイルム面に垂直に入射さ
せてこれらのフイルムのラウエ写真を撮つた。い
ずれの写真も、回折像は、はつきりとしたパター
ンが見えず、無定形状態を示していた。その１例
として、ポリ（３−メチルチエニレン）（実施例
４）のラウエ写真を図に示す。 The films obtained in Examples 1 to 4 were all highly flexible and several times stronger in tensile strength than the films before heat treatment. In addition, Rigaku Denki FR-B, X-ray generator and Arndt-
0.1× using Wanacott oscillation camera
Laue photographs of these films were taken with 0.1 mm of CuKα radiation incident perpendicularly to the film surface. In both photographs, no clear pattern was visible in the diffraction images, indicating an amorphous state. As an example, a Laue photograph of poly(3-methylthienylene) (Example 4) is shown in the figure.
発明の効果
以上の説明から明らかなように、本発明のアモ
ルフアス化ポリチエニレンもしくはメチル誘導体
フイルムは、柔軟性に富みかつ強靭である。ま
た、本発明の製造法を用いることにより、簡単に
アモルフアス化ポリチエニレンもしくはそのメチ
ル誘導体フイルムが得られる。Effects of the Invention As is clear from the above explanation, the amorphized polythienylene or methyl derivative film of the present invention is highly flexible and strong. Further, by using the production method of the present invention, an amorphous polythienylene or a methyl derivative film thereof can be easily obtained.
図は、ポリ（３−メチルチエニレン）のＸ線回
折像である。
The figure is an X-ray diffraction image of poly(3-methylthienylene).
Claims (1)
持電解質の存在下で通電し電解酸化重合して、陽
極上にポリチエニレンもしくはそのメチル誘導体
フイルムを形成する工程，電極の極性を反転し、
前記ポリチエニレンフイルムもしくはそのメチル
誘導体フイルムを電解還元する工程，不活性雰囲
気下で少なくとも30秒間100〜1000℃で熱処理し
て前記フイルムをアモルフアス化する工程を有す
ることを特徴とする、ポリチエニレンもしくはそ
のメチル誘導体フイルムの製造法。1 Step of electrolytically oxidizing and polymerizing thiophene or its methyl derivative by applying current in the presence of a supporting electrolyte to form a polythienylene or its methyl derivative film on the anode, reversing the polarity of the electrode,
Polythienylene or its methyl derivative film, comprising the steps of electrolytically reducing the polythienylene film or its methyl derivative film, and heat-treating the film at 100 to 1000°C for at least 30 seconds in an inert atmosphere to make the film amorphous. Method for producing methyl derivative film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175331A JPS6067534A (en) | 1983-09-22 | 1983-09-22 | Polythienylene or film thereof and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175331A JPS6067534A (en) | 1983-09-22 | 1983-09-22 | Polythienylene or film thereof and its manufacture |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1283257A Division JPH0791383B2 (en) | 1989-10-30 | 1989-10-30 | Polychenylene or its methyl derivative film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067534A JPS6067534A (en) | 1985-04-17 |
| JPH044332B2 true JPH044332B2 (en) | 1992-01-28 |
Family
ID=15994200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58175331A Granted JPS6067534A (en) | 1983-09-22 | 1983-09-22 | Polythienylene or film thereof and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067534A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310621A (en) * | 1986-03-12 | 1988-01-18 | Katsumi Yoshino | Production of highly electroconductive substance |
-
1983
- 1983-09-22 JP JP58175331A patent/JPS6067534A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067534A (en) | 1985-04-17 |
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