JPH0354976B2 - - Google Patents
Info
- Publication number
- JPH0354976B2 JPH0354976B2 JP10938186A JP10938186A JPH0354976B2 JP H0354976 B2 JPH0354976 B2 JP H0354976B2 JP 10938186 A JP10938186 A JP 10938186A JP 10938186 A JP10938186 A JP 10938186A JP H0354976 B2 JPH0354976 B2 JP H0354976B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- membered heterocyclic
- heterocyclic compound
- film
- polymer
- 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
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistors
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits by conductive adhesives
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は異方導電性膜の製造方法に関する。さ
らに詳しくは高分子膜面に対して垂直方向に異方
導電性を有する複素５員環式化合物重合体複合膜
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing an anisotropically conductive film. More specifically, the present invention relates to a method for producing a five-membered heterocyclic compound polymer composite membrane having anisotropic conductivity in the direction perpendicular to the surface of the polymer membrane.
複素５員環式化合物重合体は空気中でも比較的
安定な導電性高分子であることが知られており、
有機導電性材料として、たとえばセンサー材料、
オプトエレクトロニクス材料、エレクトロニクス
デバイスなどの種々の機能素子などに利用でき
る。さらにこれらの導電性高分子の機能性を高め
るため、電気伝導度の異方性を有する導電膜の開
発が行なわれている。このような異方導電性膜の
製造方法としては、たとえばポリピロールの延伸
などが行なわれているが充分な異方性は得られて
いない。一方電気化学的重合方法により、例えば
ポリピロールを高分子表面上に水平に配向させる
方法〔ジヤパニーズ・ジヤーナル・オフ・アプラ
イド・フイジクス（Jap.J.Appl.Phys.）24巻L79
項（1985年）〕や、また面に対して垂直方向の異
方導電性を有する膜の製造方法〔ポリマー・プレ
プリント・オフ・ジヤパン（Polymer
Preprimts、Japan）34巻８号（1985年）2345項〕
が報告されている。
Five-membered heterocyclic compound polymers are known to be conductive polymers that are relatively stable even in the air.
As an organic conductive material, for example, a sensor material,
It can be used in various functional elements such as optoelectronic materials and electronic devices. Furthermore, in order to enhance the functionality of these conductive polymers, conductive films having anisotropy in electrical conductivity are being developed. As a method for manufacturing such an anisotropic conductive film, for example, stretching of polypyrrole has been carried out, but sufficient anisotropy has not been obtained. On the other hand, an electrochemical polymerization method, for example, a method in which polypyrrole is horizontally aligned on a polymer surface [Japanese Journal of Applied Physics (Jap.J.Appl.Phys.) Vol. 24 L79
(1985)] and a method for producing films with anisotropic conductivity in the direction perpendicular to the surface [Polymer Preprint Off Japan (Polymer Preprint Off Japan)].
Preprimts, Japan) Vol. 34, No. 8 (1985) Section 2345]
has been reported.
しかしながら、これら電気化学的重合方法によ
つて製造するためには特殊な電極や電解質あるい
は電解装置を必要とし、また、電極表面に絶縁性
の高分子をコーテングするため、充分な機械的強
度を持つた膜が得られにくく、また大面積化が困
難であり、コストが大きくなるほどの問題があつ
た。
However, manufacturing using these electrochemical polymerization methods requires special electrodes, electrolytes, or electrolytic equipment, and because the electrode surface is coated with an insulating polymer, it has sufficient mechanical strength. It is difficult to obtain a thin film, it is difficult to enlarge the area, and the cost increases.
本発明の目的は上記問題を解決して安価に容易
に異方導電性を有する複素５員環式化合物重合体
複合膜を得る方法を提供することにある。 An object of the present invention is to provide a method for solving the above problems and easily obtaining a five-membered heterocyclic compound polymer composite film having anisotropic conductivity at low cost.
本発明者らは上記問題点を解決する方法につい
て鋭意検討し、本発明を完成した。
The inventors of the present invention have conducted extensive studies on methods for solving the above problems, and have completed the present invention.
即ち、本発明は
膜面に対して略垂直方向に直孔性の細孔を有す
る多孔質高分子膜に酸化剤を含有させた後複素５
員環式化合物のガスを接触させて、該多孔質高分
子膜内部に複素５員環式化合物重合体を生成せし
めることを特徴とする異方導電性膜の製造方法で
ある。 That is, the present invention provides a porous polymer membrane having straight pores in a direction substantially perpendicular to the membrane surface, after which an oxidizing agent is contained therein.
This is a method for producing an anisotropically conductive membrane, characterized in that a five-membered heterocyclic compound polymer is produced inside the porous polymer membrane by bringing a gas of a membered cyclic compound into contact with the membrane.
本発明の方法において使用する多孔質膜は、高
分子膜面に対して略垂直方向に直孔性の細孔を有
するもので、その孔径は通常0.1μｍ〜100μｍであ
り、材質としては有機化合物高分子や無機化合物
高分子が用いられ、例えば、ポリエチレン、ポリ
プロピレン、ポリ塩化ビニル、ポリスチレン、ホ
リカーボネート、ポリエステル、ポリアミド、ポ
リイミドなどの薄膜などが具体例として挙げられ
る。 The porous membrane used in the method of the present invention has straight pores in a direction substantially perpendicular to the surface of the polymer membrane, and the pore diameter is usually 0.1 μm to 100 μm, and the material is an organic compound. Polymers and inorganic polymers are used, and specific examples include thin films of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyester, polyamide, polyimide, and the like.
上記膜面に略垂直方向に直孔性の細孔を有する
多孔質膜の製造方法については特に制限はなく、
例えばイオンビーム加工、レーザビーム加工など
の微細加工技術を利用した方法が挙げられる。 There is no particular restriction on the method for manufacturing the porous membrane having straight pores in a direction substantially perpendicular to the membrane surface.
Examples include methods using microfabrication techniques such as ion beam processing and laser beam processing.
本発明の方法において用いられる酸化剤として
は無機酸、有機酸、金属の化合物が挙げられる。
具体的には例えば塩酸、硫酸、硝酸などの無機酸
類、トルエンスルホン酸、トリフルオロ酢酸など
の有機酸類、チタン、クロム、モリブデン、マン
ガン、鉄、ルテニウム、白金、銅などの金属のハ
ロゲン化物、あるいはそれらの金属の無機酸塩類
が挙げられ、殊にこれらの金属の化合物でもルイ
ス酸として知られている例えば塩化第二鉄、塩化
ルテニウム、塩化白金、塩化モリブデンなどの化
合物が好適な酸化剤として挙げられる。これらの
酸化剤は単独でも、また２種以上の混合としても
用いることができる。 Oxidizing agents used in the method of the present invention include inorganic acids, organic acids, and metal compounds.
Specifically, for example, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, organic acids such as toluenesulfonic acid and trifluoroacetic acid, metal halides such as titanium, chromium, molybdenum, manganese, iron, ruthenium, platinum, and copper; Suitable oxidizing agents include inorganic acid salts of these metals, and in particular compounds of these metals known as Lewis acids, such as ferric chloride, ruthenium chloride, platinum chloride, and molybdenum chloride. It will be done. These oxidizing agents can be used alone or in combination of two or more.
本発明の方法で使用される複素５員環式化合物
とは４個の炭素原子と１個のヘテロ原子を有する
不飽和５員環を基本骨格とする化合物であつて、
たとえばピロール、チオフエン、フラン、セレノ
フエン、テルロフエンおよびそれらの誘導体であ
る。これらの化合物は単独でも、また２種以上を
用いることができる。 The 5-membered heterocyclic compound used in the method of the present invention is a compound whose basic skeleton is an unsaturated 5-membered ring having 4 carbon atoms and 1 heteroatom,
Examples are pyrrole, thiophene, furan, selenophene, tellurofene and their derivatives. These compounds can be used alone or in combination of two or more.
本発明の方法においては、前述の酸化剤を液状
にすることが必要であり、通常は適当な溶剤、た
とえば水、アルコール類、エステル類、エーテル
類、ハロゲン化炭化水素、ニトロ化炭化水素、芳
香族炭化水素、ニトリル類などに溶解して用い
る。本発明の方法ではこの溶液を多孔性高分子膜
上に塗布あるいは流延したり、多孔性高分子膜を
この溶液中に浸漬したりすることにより多孔質高
分子の細孔中にこれらの溶液を含浸させたのち、
上述の複素５員環式化合物のガスを、必要に応じ
窒素やアルゴンなどの不活性ガスで希釈して接触
させる。 In the process of the invention, it is necessary to liquefy the aforementioned oxidizing agent, which is usually carried out in a suitable solvent such as water, alcohols, esters, ethers, halogenated hydrocarbons, nitrated hydrocarbons, aromatic Used by dissolving in group hydrocarbons, nitriles, etc. In the method of the present invention, these solutions are poured into the pores of the porous polymer by coating or casting the solutions on the porous polymer membrane or by immersing the porous polymer membrane in the solutions. After impregnating with
The gas of the above-mentioned five-membered heterocyclic compound is diluted with an inert gas such as nitrogen or argon as necessary and brought into contact.
接触処理の温度、時間には特に制限はなく、所
望の反応量となるように定めれば良い。通常は常
温で充分反応し、時間は0.1〜100時間である。 The temperature and time of the contact treatment are not particularly limited and may be determined so as to achieve a desired reaction amount. Usually, the reaction is sufficient at room temperature, and the reaction time is 0.1 to 100 hours.
以下実施例により本発明をさらに詳細に説明す
る。
The present invention will be explained in more detail with reference to Examples below.
実施例 １
酸化剤として塩化第二鉄を用い、多孔質膜とし
て、直孔性の細孔を有するニユークリポアメンブ
レンフイルター（ニユークリポアコーポレーシヨ
ン社製 厚さ10μｍ、平均孔径8μｍ）を用いた。Example 1 Ferric chloride was used as the oxidizing agent, and a Nuclepore membrane filter with straight pores (manufactured by Nuclepore Corporation, thickness 10 μm, average pore diameter 8 μm) was used as the porous membrane. .
重合方法は、塩化第二鉄・６水塩５ｇを水30ml
に溶解した溶液に多孔質膜を浸して細孔内に酸化
剤溶液を浸透させた後、この多孔質膜を水10mlと
ピロール１mlを入れたデシケータ中に入れた。30
分後に多孔質膜を取り出しメタノールで洗浄した
後乾燥させた。 The polymerization method is to add 5 g of ferric chloride hexahydrate to 30 ml of water.
After the porous membrane was immersed in a solution dissolved in the oxidizing agent solution to infiltrate the pores of the oxidizing agent solution, the porous membrane was placed in a desiccator containing 10 ml of water and 1 ml of pyrrole. 30
After a few minutes, the porous membrane was taken out, washed with methanol, and then dried.
この膜の平面方向の電導性は約10-6S／cmであ
り、膜厚方向の電導性は0.2S／cmであつた。すな
わち、膜に対して垂直方向に異方導電性が形成さ
れていた。 The electrical conductivity of this film in the planar direction was approximately 10 -6 S/cm, and the electrical conductivity in the thickness direction was 0.2 S/cm. That is, anisotropic conductivity was formed in the direction perpendicular to the film.
実施例 ２
多孔質膜としてポリエチレンフイルム（厚さ
0.1mm）に300μｍ間隔で50μｍの細孔を開けたもの
を用い、触媒として、無水塩化第二鉄をクロロホ
ルムに飽和させた溶液を用い、複素５員環式化合
物としてチオフエンを用いて窒素ガス雰囲気中で
実施例１と同様な方法で重合を行なつた。Example 2 Polyethylene film (thickness:
0.1 mm) with 50 μm pores opened at 300 μm intervals, a solution of anhydrous ferric chloride saturated in chloroform was used as the catalyst, thiophene was used as the 5-membered heterocyclic compound, and a nitrogen gas atmosphere was used. Polymerization was carried out in the same manner as in Example 1.
得られたチオフエンを重合した膜をヨウ素でド
ーピングしたのちの、この膜の平面方向の電導性
は約10-12S／cmであり、膜厚方向の電導性は５×
10-2S／cmであつた。 After doping the obtained thiophene-polymerized film with iodine, the conductivity in the plane direction of this film is approximately 10 -12 S/cm, and the conductivity in the thickness direction is 5×
It was 10 -2 S/cm.
実施例 ３
複素５員環式化合物として、セレノフエンを用
いた以外は実施例２と同様にして行なつた。Example 3 The same procedure as in Example 2 was carried out except that selenophene was used as the 5-membered heterocyclic compound.
セレノフエンを重合した膜をヨウ素でドーピン
グした後の、この膜の平面方向の電導性は約
10-12S／cmであり、膜厚方向の電導性は８×
10-5S／cmであつた。 After doping a selenophene polymerized film with iodine, the in-plane conductivity of the film is approximately
10 -12 S/cm, and the conductivity in the film thickness direction is 8×
It was 10 -5 S/cm.
本発明の方法を実施することにより高分子膜面
に対して垂直方向に異方導電性を有する複素５員
環式化合物重合体複合膜が安価に容易に得られ、
工業的に極めて価値がある。
By carrying out the method of the present invention, a five-membered heterocyclic compound polymer composite membrane having anisotropic conductivity in the direction perpendicular to the surface of the polymer membrane can be easily obtained at low cost.
It is extremely valuable industrially.
Claims (1)
する多孔質高分子膜に酸化剤を含有させた後複素
５員環式化合物のガスを接触させて、該多孔質高
分子膜内部に複素５員環式化合物重合体を生成せ
しめることを特徴とする異方導電性膜の製造方
法。1. An oxidizing agent is added to a porous polymer membrane having straight pores in a direction substantially perpendicular to the membrane surface, and then a gas of a five-membered heterocyclic compound is brought into contact with the porous polymer membrane. 1. A method for producing an anisotropically conductive film, which comprises producing a five-membered heterocyclic compound polymer inside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10938186A JPS62267334A (en) | 1986-05-15 | 1986-05-15 | Production of film having anisotropic electrical conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10938186A JPS62267334A (en) | 1986-05-15 | 1986-05-15 | Production of film having anisotropic electrical conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62267334A JPS62267334A (en) | 1987-11-20 |
| JPH0354976B2 true JPH0354976B2 (en) | 1991-08-21 |
Family
ID=14508798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10938186A Granted JPS62267334A (en) | 1986-05-15 | 1986-05-15 | Production of film having anisotropic electrical conductivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62267334A (en) |
-
1986
- 1986-05-15 JP JP10938186A patent/JPS62267334A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62267334A (en) | 1987-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4617228A (en) | Process for producing electrically conductive composites and composites produced therein | |
| Wang et al. | Preparation, properties and applications of polypyrroles | |
| US4582575A (en) | Electrically conductive composites and method of preparation | |
| US4696835A (en) | Process for applying an electrically conducting polymer to a substrate | |
| JPS6059087A (en) | Electrochemical polymerization for pyrrole and anode therefor | |
| JPS61218643A (en) | Composite forming material from porous material and conductive polymer | |
| JPH0564970B2 (en) | ||
| EP0437857A2 (en) | A method for producing a solid capacitor and a solid capacitor obtainable by said method | |
| US4720393A (en) | Method of manufacturing a layer with electrical conductivity | |
| JP2575672B2 (en) | Non-conductive material plating method | |
| JPH0354976B2 (en) | ||
| Yang et al. | Polypyrrole—polypropylene composite films: preparation and properties | |
| JPH0349287B2 (en) | ||
| JPS62136712A (en) | Method for making resin mold surface conductive | |
| JPH01293101A (en) | Composite separation membrane | |
| JPH042958A (en) | Electrode for gas sensor using electrode reaction | |
| JP2731537B2 (en) | Method for producing highly conductive organic polymer film | |
| JPH0727731B2 (en) | Method for manufacturing conductive composite film | |
| JPH0348933B2 (en) | ||
| JPS62209132A (en) | Pyrrole/iodine complex plasma polymerized film and its production | |
| JPH061647B2 (en) | Method for producing conductive composite laminate | |
| JPH05479B2 (en) | ||
| JPH0274019A (en) | Manufacture of solid electrolytic condenser | |
| RU1781239C (en) | Process for producing metal-polymer composite from a metal and an electrically conducting polymer | |
| JPS62136709A (en) | Manufacture of conductive pattern |