JPS62100525A - Production of electroconductive polymeric membrane - Google Patents

Abstract

PURPOSE:In the formation of an electroconductive polymeric membrane by electrolytic polymerization, the monomers and electrolytes are allowed to include in the polymeric membrane before electrolysis whereby conductivity is advantageously given with increased efficiency of polymer formation, as the membrane is inhibited from dissolving in the solution. CONSTITUTION:When an electroconductive polymeric membrane is formed by effecting electrolysis in an electrolytic solution containing monomers to be converted into a conductive polymer by electrolytic polymerization such as pyrrole, or thiophene in the state where an insulative polymeric membrane is brought into close contact with the anode surface an the conductive membrane is formed on the insulative membrane, the above-cited monomers and electrolytes such as LiBF3 are allowed to include in the polymeric membrane beforehand. The process according to the present invention is applicable to the case where conductivity is given to an epoxy adhesive polymeric membrane or a nitrile rubber adhesive polymeric membrane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a conductive polymer membrane using an electrolytic polymerization method.

[Prior art and its problems]

For example, as shown in FIG. 1, if a polymer membrane 2 made of polyvinyl chloride or the like is closely attached to the surface of an anode 1 and electrolysis is performed with this membrane facing a negative PiA 4 in an electrolytic solution 3 containing pyrrole, It is known that conductive polypyrrole is generated within the polymer membrane 2 by electrolytic polymerization and can impart conductivity to the polymer membrane 2 (Collection of Abstracts of the 1st Polymer Possibility Lecture 1985 of the Society of Polymer Science 52 Conductivity can be imparted to various polymer membranes by using the method described in (pages 57 to 57), but experiments have shown that depending on the type of polymer membrane, the polymer membrane may dissolve in the electrolyte during electrolysis. It turned out that it would come out. Therefore, in the case of a polymer film that easily dissolves into the electrolytic solution, as electrolysis continues, almost no polymer film is left on the anode surface, leaving only a thin film of polymerized conductive polymer. This phenomenon occurs, for example, in adhesive polymer films such as epoxy or polyamide.
This is seen when trying to impart electrical properties.

[Means for solving problems and their effects]

In order to solve the problems of the prior art as described above, the present invention has been developed by applying an insulating polymer membrane to the anode surface in an electrolytic solution containing a monomer that becomes a conductive polymer through electrolytic polymerization. In a method for producing a conductive polymer membrane by electrolyzing and producing a conductive polymer in a J-biped polymer membrane, electrolysis is performed in a state in which the monomer and electrolyte are pre-impregnated in the polymer membrane. It is characterized by the fact that

The reason why the polymer film on the anode surface dissolves into the electrolyte during electrolytic polymerization is thought to be due to the energy generated when ions (ionized electrolyte) and monomers in the electrolyte collide with the polymer film.1. As the electrolysis time becomes longer, the amount of elution increases accordingly. Therefore, in order to reduce the amount of elution from a polymer membrane, it is necessary to increase the production efficiency of conductive polymer in the polymer membrane.
It is best to complete the electrolysis in as short a time as possible.

Therefore, the present invention improves the production efficiency of a conductive polymer by performing electrolysis in a state in which a monomer and an electrolyte are preliminarily contained in a polymer membrane.

Examples of polymer films that can be imparted with electrical conductivity according to the present invention include epoxy-based adhesive polymer films, polyamide-based melt-adhesive polymer films, and nitrile rubber-based adhesive polymer films.

In addition, as a monomer which becomes a conductive polymer by electrolytic polymerization, vinylcol, dried phen, N-methylvirol, etc. can be used.

In addition, as electrolytes, L i B F h, L IC1
, a, etc. can be used.

Further, as the chemical compound 1j, acetonitrile, tetrahydrofuran, methyl ethyl ketone, etc. can be used.

〔Example〕

The present invention will be explained in detail below.

(1) First, a polymer film containing an electrolyte and a monomer was formed on the anode surface in the following manner.

XA361-3 (liquid nitrile rubber adhesive polymer): 100m/LiBF, (electrolyte): 1g virol (monomer that becomes a conductive polymer through electrolytic polymerization): lcc were mixed and stirred thoroughly, and then It was coated on the surface of the anode (indium tin oxide-coated glass plate) to a thickness of about 201 Jm using a dip method. Next, this is placed in a constant temperature bath at 100°C for 5 to 10 minutes to evaporate the solvent, and a B-stage polymer film (containing monomer and electrolyte) is placed on the anode surface.
was formed.

(2) Next, add 1 cc of virol to this anode with a polymer membrane,
1 g of LiBFa and) 100 ml of medium! The electrode was immersed in an electrolytic solution consisting of the following, and electrolysis was performed with the electrode facing the cathode.

The current density was 4 mA/cm''.

After about 2 minutes, the electrolysis was interrupted and the polymer film on the anode was observed. Elution was observed, so another polymer film was formed using the same method as in (1) above, and then the same method as in (2) above was performed. Electrolysis was performed using the method. By repeating the above steps, a thickness of 20 μm was obtained.
We were able to produce a conductive polymer film in which polypyrrole grew throughout the film thickness.

Since the conductive polymer film produced in this manner has adhesive properties, it is useful, for example, when electrically connecting printed circuit boards.

In the above embodiments, the formation of the polymer film and the electrolysis were repeated, but if the thickness of the required conductive layer is thin, the repetition may not be necessary.

Further, in the above embodiment, a case has been described in which almost the entire surface of the polymer film is made conductive, but if the anode surface is divided into a conductive region and an insulating region, it is possible to make it conductive according to the division.

The present invention is not limited to the above embodiments, but is generally applicable to cases in which conductivity is to be imparted to a polymer membrane that tends to dissolve into an electrolytic solution during electrolysis.

〔Effect of the invention〕

As explained above, according to the present invention, electrolytic polymerization is performed in a state in which the monomer and electrolyte are pre-impregnated in the polymer membrane, so that the production efficiency of the conductive polymer in the polymer membrane is increased and This method has the advantage that a conductive polymer film can be produced with little elution of the molecular film.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing a method of imparting conductivity to a polymer membrane by electrolytic polymerization. 1 - Positive electrode, 2 - Polymer membrane, 3 - Electrolyte, 4 - Cathode.

Claims (1)

[Claims] By performing electrolysis with an insulating polymer membrane in close contact with the anode surface in an electrolytic solution containing a monomer that becomes a conductive polymer through electrolytic polymerization, a conductive polymer is generated in the polymer membrane. A method for producing a conductive polymer membrane, characterized in that electrolysis is performed in a state in which the monomer and electrolyte are previously contained in the polymer membrane.