JPS61245413A - Manufacture of conductive high polymer composite film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a conductive polymer film, and more specifically, a method for manufacturing a conductive polymer film, in which a polymer film is integrally laminated on a pre-formed conductive polymer thin film. This invention relates to a method for obtaining a conductive polymer composite membrane.

2. Description of the Related Art Conventionally, as a method for producing a conductive composite using a polymer, a method has been used in which a certain amount or more of a conductive filler is added to a polymer matrix. However, this method has the drawback that the physical properties of the composite are significantly reduced by the addition of filler, and that the conductivity can only be controlled within the range of the filler used. Furthermore, when used in electronics-related applications, it is difficult to form complex patterns on the film surface.
Additionally, there was a risk that the filler would fall off.

In addition, Nippon Telegraph and Telephone Corporation and IBM have announced technology for making polymer membranes conductive through electrolytic polymerization, such as Polymer Brebrants, Japan, Vol. 33, No. 9, 2515-
18 (1984) etc., polyvinyl chloride (
PVO) solution was applied and dried to form a thin PVO film on the electrode surface.

A PVO thin film is made conductive by electrolytic polymerization in an electrolyte solution consisting of pyrrole, tetraethylammonium verchlorate and acetonitrile,
Although this method solves the above-mentioned drawbacks, this method has drawbacks such as limitations in the usable polymers due to restrictions on electrolytic polymerization conditions and difficulty in obtaining thick films.

Problems to be Solved by the Invention As a result of intensive research in order to solve the above-mentioned drawbacks, the inventor of the present invention formed a conductive polymer thin film in advance, and then integrated another polymer film on the conductive thin film. We have discovered that if the conductive polymer thin film is laminated to form a composite film, the conductive polymer thin film will be transferred to another polymer film, and a conductive polymer composite film with excellent workability and without the above-mentioned drawbacks will be formed. Based on this knowledge, we have completed the present invention.

Means for Solving the Problems The object of the present invention is to form a thin film of conductive polymer on the electrode surface in advance by electrolytic polymerization, and then integrally laminate another polymer film on the thin film to form a composite film. This is achieved by peeling off the membrane from the electrode and using a conductive polymer thin film as a surface layer.

The conductive polymer thin film described here is an aromatic compound that has the ability to form a conductive polymer.

Refers to a compound formed on an electrode surface by electrolytic polymerization in an electrolyte solution containing one or more of a heterocyclic compound or a derivative thereof as a monomer component.

Examples of the aromatic compounds include benzene, toluene, xylene, aniline, etc., and examples of the heterocyclic compounds include torrole, N-methylpyrrole, N-phenylpyrrole, 2,3.2',3'pyrrolovirol, indole, purine, azulene, indolizine, imidazole,
Thiophene, furan.

Oxazole, benzofuran, benzothiophene.

Chenothiophene, dibenzofuran, chepin.

1, 3.4 thiadiazole, and the like.

In general, polymer materials have high electrical insulation properties, with a rate of 10S/c
It has an electrical conductivity of about m or less. Other polymers of the present invention refer to polymer materials having such electrical conductivity, and examples of polymers belonging to this include olefinic polymers such as polyethylene and polypropylene; polybutadiene, polyisoprene, styrene-butadiene rubber, acrylonitrile-based polymers, etc. Diene polymers such as butadiene rubber, styrene, butadiene, styrene, styrene, isoprene, styrene, acrylonitrile, butadiene, and styrene resin; polyvinyl chloride, ethylene/vinyl acetate copolymer-vinyl chloride graft polymer, polystyrene, etc. .

Vinylidene polymer; polyurethane, polyamide.

Nitrogen-containing polymers such as polyurea and polyimide; polymers such as acrylic polymers such as polyacrylate and polyacrylonitrile; and polymer blends thereof.

If desired, conductive filler, conductive m#, antistatic agent, etc. can be added to other polymers in the present invention. Conductive fillers include carbon black, metal powders such as Ag and Ou, metal oxide powders such as InO2゜SnO3, or carriers such as glass beads carrying the above metal powders and metal oxide powders. The term "conductive fibers" refers to carbon fibers, metal fibers, or conductive whiskers.

Further, examples of the antistatic agent include anionic and cationic surfactants.

Possible electrode materials include metals, metal oxides, carbon, etc., but when using metals or metal oxides for the anode or metal oxides for the cathode, the polymerization potential and 1! It is necessary to take care of the ionization potential of the electrode material. Particularly in systems where metals and metal oxides are eluted as ions at the anode, polymers are not produced.

To describe the procedure of the method of the present invention, an electrolyte solution consisting of a monomer capable of forming the above-mentioned conductive polymer, an electrolyte, and a solvent is prepared. voltage using a platinum electrode as the cathode.

Electrolytic polymerization reaction is carried out by setting electrolytic conditions such as electrolyte temperature and electrolysis time, and a conductive polymer' is deposited on the anode! Form the IJM.

After the electrolysis is completed, the anode on which the polymer has been deposited is washed and dried, and then another polymer film is integrally laminated on this polymer thin film.

This integral layering method involves applying a solution obtained by dissolving other polymers in a solvent onto the thin film and evaporating the solvent to form a polymer film, or using other polymers prepared in advance. There is a method of integrally laminating a molecular thin film on a conductive thin film by adhesion, heat fusion, etc., and the method may be selected as appropriate depending on the purpose. A composite film having a conductive polymer film as a surface layer can be obtained by peeling from the film.

Effects of the Invention Thus, according to the present invention, compared to the prior art, conductivity can be imparted over almost the entire range from transparent conductivity of 10,087 cm to insulators without deteriorating the physical properties of other polymers. By devising the shape of the electrode, a complex shape can be easily obtained, and there is no fear of the conductive film falling off.

Furthermore, since the formation of the conductive polymer and the formation of other polymer films are separate processes, other polymers may not be used.

There is no need to change electrolytic polymerization conditions depending on the type of molecule, and conductive polymer composite films with a wide range of film thicknesses can be obtained.

EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 An electrolyte solution consisting of 0.6 mol of virol, 1 mol of tetraethylammonium barchlorate α, and 11 mol of acetonitrile was used with Nesa glass electrodes as the anode and counter electrode.
After carrying out an electrolytic polymerization reaction at 2.5 V for 2 minutes at ℃, it was washed and dried. To this, polyvinyl chloride (Zeon 103 made by Nippon Zeon Co., Ltd. 1! 310 g, tetrahydrofuran 9
After applying and drying a polyvinyl chloride solution consisting of 0 g to a thickness of LOfi, the polymer film was peeled off from the electrode surface.

Film thickness is 100 μm'C', surface group conductivity tfi 10-"
A conductive composite membrane with S 7 cm was obtained.

Example 2 After carrying out the same electrolytic polymerization reaction as in Example 1, the electrode was washed and dried, and a polyurethane solution (Lesamin ME 361
2 LP (manufactured by Dainichiseika Co., Ltd.) was applied to a thickness of α25 m and dried, and then the polymer film was peeled off from the electrode surface.

A conductive polyurethane composite film suitable for practical use with a film thickness of 80 μm and a surface group conductivity of IQ-2 s/cm was obtained.

Comparative Example 1 - The polyvinyl chloride solution used in Example 1 was coated onto Nesa glass to a thickness of 01 and dried, and using an electrode with a film thickness of 10 μm, an electrolytic polymerization reaction was carried out at 20° C. with 2 VC' for 2 minutes.
Although a conductive composite film having a surface group conductivity of O-2S/Cm was obtained, the film thickness of this level was thin and had a problem in mechanical strength.

Comparative Example 2 The same polyvinyl chloride solution as used in Example 1 was applied to Nesa glass with α5 thickness and dried to form a vinyl chloride thin film with a thickness of 50 μm.

This was used as a sample electrode, untreated Nesa glass was used as a counter electrode, and the same electrolyte solution as in Example 1 was used at 20°C.
Electrolysis was carried out for a long time of 2 hours at t'Z5V, but no formation of polypyrrole complex was observed.

Example 3 Thiophene 01 mole, lithium tetrafluoroborate 0
An electrolytic polymerization reaction was carried out at 20 V for 2 minutes using an electrolyte solution consisting of 1 mol of acetonitrile 11 using Nesa glass as an anode and a platinum electrode as a counter electrode, and after drying, 10 g of polyvinyl chloride (Zeon 103 EP, manufactured by Nippon Zeon Co., Ltd.) , a polyvinyl chloride solution consisting of 90 g of tetrahydrofuran
．． After coating and drying, the polymer film was peeled off from the electrode surface.

Film thickness is 100 umt', surface group conductivity is 10-287c
A conductive polyvinyl chloride composite membrane of m was obtained.

Claims (1)

[Claims] 1. Form a conductive polymer thin film on the electrode surface in advance by electrolytic polymerization, integrally laminate another polymer film on top of the thin film, and peel the composite film from the electrode to form the conductive polymer thin film. A method for producing a conductive polymer composite film, comprising producing a composite film as a surface layer.