JPS63254125A - Manufacturing method of conductive composite material - 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] <Industrial application field> The present invention relates to a method for manufacturing a conductive composite material.

The conductive composite material obtained by the present invention has good conductivity without impairing the inherent properties of conventional materials, and can be made conductive by a simple method, so it can be used in a wide range of application fields of conductive materials. It is possible.

<Conventional technology> In recent years, research has been conducted on conductive polymers in which the polymer itself is conductive, and polyacetylene, polyparaphenylene, polyphenylene sulfide, polythiophene, polypyrrole, etc. have attracted attention, and research into a wide range of conductive fields has been carried out. being done. However, when considering the application of conductive polymers,
Material stability and moldability are major issues. First, regarding stability, when polyacetylene film is exposed to air, it reacts with oxygen and becomes brittle. Other polymers are relatively stable in the undoped state, but polymers doped with impurities are unstable in air. The only exception is polypyrrole, which is stable even in films doped with impurities. It is known that pyrrole forms an insoluble and infusible polymer when treated with an oxidizing agent. For example, it has been reported in the Journal of Polymer Science that pyrrole can be polymerized in aqueous solution under the action of potassium persulfate, and the polymer precipitates out in the form of a fine black powder.

1089-1095. (19B 2). There is also a method of dissolving pyrrole in a suitable electrolyte and obtaining a pyrrole polymer on the electrode by electrolytic oxidation polymerization (
For example, Chemical Communication, p. 635,
(1979)).

However, these stably obtained pyrrole polymers are insoluble and infusible powders or lumps, and cannot be molded into desired shapes by conventional methods. Furthermore, although a specific film-like product can be obtained by electrolytic polymerization, it is not possible to obtain the desired shape, and moreover, it requires expensive equipment (IIF).
There were problems such as requiring f.

<Problems to be Solved by the Invention> In view of the above circumstances, the present invention provides a simple method for manufacturing composite materials with good conductivity by improving the moldability of conductive polymers, which has been considered a drawback in the past. The purpose is to provide

<Means for Solving the Problems> The present invention provides that in a specific solvent, even in the presence of FeCl36H□0, which is a polymerization catalyst for pyrrole, polymerization of pyrrole hardly proceeds, and a polymer of pyrrole does not precipitate. The present invention was completed by discovering that pyrrole can only be polymerized by obtaining a uniform liquid mixture and removing the organic solvent from this liquid mixture, and is characterized by having the following requirements.

That is, by applying an organic solvent in which pyrrole and/or a pyrrole derivative, a polymerization catalyst, and a thermoplastic resin are dissolved to a base material and drying it, a conductive composite polymer is formed on the surface and/or inside of the base material. This is a method for producing a conductive composite material.

Examples of the compounds used in the present invention include pyrrole, N-alkylpyrrole, N-arylpyrrole, and pyrrole substituted with monoalkyl or G-oxyhalogen at the carbon atom. Usually, pyrrole is most preferably used.

As the organic solvent, cyclic ether is effectively used.

Examples of the cyclic ether include tetrahydrofuran and dioxane. It is also possible to use a mixture of these organic solvents. Further, it may be mixed with a solvent other than the cyclic ether as long as it does not impede the effects of this patent.

The pyrrole polymerization catalyst used in the present invention is mainly Fe
Cl3, FeCl3”6H20, CuCIz 2+12
A chloride such as 0 is effective.

In the present invention, a specific I! The solvent, polymerization catalyst, and pyrrole are mixed, but there are no particular restrictions on the mixing method; simply adding pyrrole to a solution of the polymerization catalyst and thermoplastic resin in an organic solvent and stirring and mixing as necessary is sufficient. It is. Furthermore, there are no particular limitations on the treatment temperature and time, and it is usually sufficient to carry out the mixing treatment at room temperature for 1 minute to 10 hours.

The amount of polymerization catalyst used is 0 per mole of pyrrole.
．． It is appropriate to use 2 to 5 moles.

If the amount of polymerization catalyst is less than 0.2 mole, the polymerization of pyrrole will not proceed sufficiently. In addition, in order to polymerize the entire amount of pyrrole,
5 moles is sufficient.

Examples of the thermoplastic resin to be dissolved in the organic solvent include vinyl chloride resin, methacrylic resin, styrene resin, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, polyamide resin, and the like. The amount of thermoplastic resin to be used can be set arbitrarily as long as it is soluble in the organic solvent.

The amount of organic solvent may be within a range that dissolves the polymerization catalyst and thermoplastic resin. The mixture of the specific organic solvent, polymerization catalyst, thermoplastic resin, and pyrrole thus obtained is coated or immersed to adhere to the substrate, and then dried to remove the organic solvent. A conductive composite polymer is formed on the surface and/or inside of the conductive polymer.

As the base material used in the present invention, various synthetic polymers, natural polymers, inorganic materials, etc. are used. Any material that can be painted or dipped can be used. For example, thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, vinyl chloride resin, polyethylene resin, polypropylene resin, styrene resin, methacrylic resin, polyamide resin, etc. natural polymers such as thermoplastic resins, cellulose, starch, and natural rubber;
Polymer compounds such as inorganic polymers such as glass, silica, and alumina, and inorganic materials such as metals and ceramics, as well as cotton, linen, silk, wool, rayon, cupra, acetate, vinylon, nylon, hnylidene, and vinyl chloride fibers. Also effective are fibers and cloths such as acrylic fibers and polyester fibers, and papers such as high-quality paper, art paper, coated paper, kraft paper, glassine paper, Japanese paper, cardboard paper, and filter paper.

There are no particular restrictions on the method of applying the mixture of pyrrole, other polymerization catalysts, thermoplastic resins, etc. dissolved in an organic solvent, but methods include methods such as immersing the substrate in the mixture, casting the mixture onto the substrate, All the attachment methods commonly used can be used, such as surface coating with a coater and spray coating.

There are also no particular restrictions on the drying method for removing the organic solvent; natural drying is usually sufficient, but if the organic solvent is difficult to evaporate, drying under reduced pressure or raising the drying temperature may be effective. It is true.

Inorganic fillers such as carbon, finely powdered silica, calcium carbonate, etc. may also be added to the polymer solution.

<Examples> Hereinafter, examples will be specifically described. In addition, the electrical conductivity in Examples was measured by the four-probe method.

Example-1 A solution in which 4 g of FeC1z 61120 was dissolved in 10 d of tetrahydrofuran was mixed with a solution in which polyvinyl chloride powder (Sumirit SX-132 manufactured by Sumitomo Chemical (+1) Ig was dissolved in 1 Q ml of tetrahydrofuran. Virol was added to this mixed solution. 1 g was added and stirred for 30 minutes. At this time, the mixed solution was a dark yellow transparent homogeneous solution. A polyvinyl chloride film was soaked in this mixed solution and wetted uniformly. The color of the film at this time was yellow. 3
The film was left to stand for ~5 minutes, and as the tetrahydrofuran was volatilized and dried, virol was polymerized on the film surface, producing a composite film. The adhesion between the base material and the conductive polymer was good, the polymer formation was uniform, and the color tone was black. Also, the conductivity of the film is 2゜I x 1O-2
It was S/cm.

Example 2 The same procedure as in Example 1 was carried out, except that the base material was a polypropylene film instead of a polyvinyl chloride film.

The color tone of the obtained conductive film was black, and the state of polymer formation was uniform. Moreover, the adhesion between the base material and the conductive polymer was good.

The conductivity of the film was 6.3 x 10-'S/cm.

Example 3 A conductive composite material was prepared in the same manner as in Example 1, except that the type of base material was changed.

Table 1 shows the color tone, polymer formation status, and conductivity of the obtained conductive composite material.

19=-8= Table-1 Example-4 The same procedure as in Example-1 was carried out, except that 1 g of methacrylic resin powder was used instead of 1 g of polyvinyl chloride powder. The color tone of the obtained conductive film was black, and the state of polymer formation was uniform. Moreover, the adhesion between the base material and the conductive polymer was good. The conductivity of the film is 3. I x 10""
It was S/c river.

Example-5 Operate in the same manner as Example-1, except that FeC]361
10% of tetrahydrofuran is an organic solvent that dissolves 1□0.
10 ml of dioxane was used instead of me. The color tone of the obtained conductive film was black, and the state of polymer formation was uniform. Moreover, the adhesion between the base material and the conductive polymer was good (-10=). The conductivity of the film is 1.2X
It was 10-”57cm.

Comparative Example-1 The same procedure as in Example-2 was carried out, except that polyvinyl chloride powder was not used. The polymer of the obtained conductive film was non-uniform, and the adhesion between the base material and the conductive polymer was poor.

<Effects of the invention> As described above, by implementing the method of the present invention,
It becomes possible to produce a conductive composite material that can be molded by a simple method, and in particular, it is possible to impart conductivity to a molded article having a complicated shape, which is extremely valuable industrially.

-11-0 fish)

Claims (1)

[Claims] 1) By applying an organic solvent in which pyrrole and/or a pyrrole derivative, a polymerization catalyst, and a thermoplastic resin are dissolved to a substrate and drying it, it can be applied to the surface and/or inside of the substrate. A method for producing a conductive composite material, the method comprising producing a conductive composite polymer. 2) The method for producing a conductive composite material according to claim 1, wherein the organic solvent is a cyclic ether. 3) The method for producing a conductive composite material according to claim 2, wherein the cyclic ether is tetrahydrofuran or dioxane.