JPS63211508A - Conducting resin 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 The present invention relates to a conductive plastic film with improved heat resistance and solvent resistance.

In recent years, research has been conducted into conductive plastic films in which conductive polymers such as polyparaphenylene and polypyrrole are dispersed in plastic using various methods. The reason is that conductive polymers have poor moldability.
It is dispersed in plastic or elastomer and molded into any shape, such as a film.

However, a problem with these films is, for example, that although the conductive cylinder molecules themselves have high heat resistance and chemical resistance, the resulting plastic film itself does not have sufficiently high heat resistance and chemical resistance.

The present inventors have completed the present invention as a result of intensive research to solve these conventional problems.

That is, the conductive plastic film of the present invention is produced by dispersing a conductive polymer having interlocking double bonds in a thermoplastic resin or elastomer, forming it into a film, and then crosslinking it by a desired crosslinking method. It is characterized by the fact that it can be obtained at least.

It has thus been revealed that, according to the present invention, a conductive plastic film having excellent heat resistance and chemical resistance can be obtained. For example, even if the film of the present invention is heated to 80 to 100°C by passing an electric current through it, it does not deform (also, it can be used as an electrode or as an electrode in an acidic atmosphere or an organic solvent). It can also be used as a covering material with almost no deformation.

The thermoplastic resin used in the present invention is a resin that is solid at room temperature and can flow by heating. Low-density or high-density polyethylene as polyolefin,
Polymers of α-olefins such as polypropylene and polybutene-1, or copolymers of these with other α-olefins and vinyl acetate, polyvinyl chloride, polystyrene, polymethyl acrylate, polymethyl methacrylate, polycarbonate, PET, PBT , polyamide resins such as polysulfone, polyphenylene sulfide, polyethylene sulfide, nylon 6 and nylon 66, and fluororesins such as PVF and PVFZ.

Further, the elastomer used in the present invention is solid at room temperature, and includes natural rubber, butadiene-styrene copolymer, butyl rubber, butadiene-acrylonitrile copolymer, chloroprene rubber, urethane rubber, silicone rubber, fluororubber, etc. . A preferred elastomer is NBR
, SBR, etc.

The reason for this is that the conductive polymer has excellent dispersibility.

The conductive polymer used in the present invention is a polymer having conjoint double bonds, such as polyacetylene, polyparaphenylene, polyphenylene sulfide, polypyrrole, polyphenylene, polyselenophene, polyfuran,
These include polybenzocarbazole, polyaniline, poly(diphenylamine), and the like.

In the present invention, the conductive polymer can be dispersed into the thermoplastic resin or elastomer by various methods.

It is also possible to mix the conductive polymer powder synthesized in advance with the thermoplastic resin or elastomer while heating it using a roller inneater or the like.

Alternatively, a thermoplastic resin or elastomer can be impregnated with a conductive polymer monomer and then polymerized.

Furthermore, a thin layer of resin or elastomer is coated on the platinum electrode, and platinum is used as the counter electrode, and the electrode is heated at a constant potential in an aqueous solution or an organic electrolyte containing a monomer.
Alternatively, a well-dispersed film can be obtained by performing so-called electrolytic oxidation polymerization while sweeping the potential or using a constant current.

Among these, it is preferable to use a dispersion film preparation method using electrolytic synthesis, since it is possible to obtain a uniform film with high conductivity.

Crosslinking in the present invention is carried out on a film in which a conductive polymer is dispersed, and methods include a chemical crosslinking method using sulfur or f-organic peroxide, and a radiation crosslinking method using an electron beam.

In the former method, a chemical crosslinking agent is added at the same time or prior to dispersing the conductive polymer in a thermoplastic resin or elastomer, and chemical crosslinking is performed by heating under pressure or normal pressure. A crosslinking accelerator may be added together with a chemical crosslinking agent. In vulcanization systems, various vulcanizing agents and vulcanization aids are used, and in organic peroxide systems, triallyl cyanurate, triallyl isocyanurate,
Examples include trimethylol, propane triacrylate, and triallyl phosphate.

Next, when using ionizing radiation, I Mrad to 100 Mrad
An absorbed dose of irradiation is usually given. The above-mentioned polyfunctional monomer as a crosslinking accelerator is dispersed in advance, and then irradiation is performed. Crosslinking by irradiation with ionizing radiation is preferred.

The present invention will be further explained below with reference to Examples.

[Dispersion of polypyrrole in NBR film] Platinum electrode (
30 mm x 50 mm) 2 was coated with an NBR emulsion solution and dried to form a film 1 with a thickness of about 10 μm (FIG. 1).

Using platinum of the same size as the counter electrode 4, pyrrole was electrolytically polymerized in an electrolytic apparatus as shown in FIG.

Electrolytic polymerization was carried out using a platinum electrode positive electrode coated with an NBR emulsion solution, and constant potential synthesis was performed for about 5 minutes by applying 0.7 μ based on SCE standards, and then taking it out, dipping it in acetonitrile, drying it, and then drying it. The electrical conductivity was measured using the four-terminal method.

[Crosslinking step using electron beam] Triallyl cyanurate was liquefied at about 50° C. and impregnated into the polypyrrole-dispersed film for about 1 hour. This sheet was thoroughly wiped and exposed to a 50KV electron beam irradiation device at 20°C in a nitrogen stream for 20 minutes.
Mrad irradiation was performed.

Comparative Example 1 A conductive plastic film was obtained in substantially the same manner as in Example 1, except that crosslinking by electron beam irradiation was not performed.

[Characteristics of the obtained product] The conductive plastic film obtained in this example showed increased strength and increased heat resistance, and had the following properties compared to Comparative Example 1, which was not crosslinked. Ta.

Example 1 Comparative Example 1 Strength 2.5 kg/cm” 0.
3 kg/cm21 resistance 3 S/c
m 5 S/cm or more, the device according to this example can be used as a planar heating element.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view schematically showing an NBR coating film formed on a platinum electrode plate during a process in an embodiment of the present invention, and FIG. FIG. 1 is an explanatory diagram schematically showing an electrolytic polymerization apparatus. 1...NBR film 2...Platinum electrode 3...
・Reference electrode (SCE) 4... Counter electrode (platinum) 5.
... Electrolyte (pyrrole 0.2 mol/l LiBF40.4 mol/1 acetonitrile) 6... Electrolytic container patent applicant Furukawa Electric Co., Ltd. Figure 1 Figure 2

Claims (1)

[Claims] 1. A conductive polymer having a conjoint double bond is dispersed in a thermoplastic resin or an elastomer, formed into a film, and then crosslinked by a desired crosslinking method. A conductive plastic film featuring: 2. The conductive polymer is polyacetylene, polyparaphenylene, polyphenylene sulfide, polypyrrole, polyphenylene, polyfuran, polybenzocarbazole,
The conductive plastic film according to claim 1, characterized in that it is one or more conductive polymers selected from the group of polyaniline and poly(diphenylamine).