JPS60146406A - Conductive polymer film and method of producing same - 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 Field of Application] The present invention relates to an improved conductive polymer film and a method for producing the same.

[Prior art]

Polyacetylene (OH)x has the characteristics of a semiconductor due to the conjugated di-JEk combination, and by doping with arsenic 57nide and iodine, a semiconductor-metal transition occurs, resulting in a high
) Becomes air conductive.

However, polyacetylene is very unstable to oxygen and has a metallic luster when polymerized, but after being exposed to the atmosphere for several days, the surface loses its luster and becomes dark in color. After using the device for another 1 to 2 months, the electrical conductivity becomes 10-110-'
Dlr-" is the value of the insulator below. As described above, polyacetylene film is expected to be a conductive film, but (1) it does not exhibit metallic electrical conductivity unless it is doped with an appropriate dopant; (2) There are drawbacks such as poor stability in the atmosphere, oxidation by oxygen and no longer showing electrical conductivity, and (3) weak film strength.

[Purpose of the invention]

An object of the present invention is to provide a conductive polymer film with a new structure and a method for producing the same, which does not have the drawbacks of the conventional film and has improved stability and conductivity.

[Structure of the invention]

To summarize the present invention, the first invention of the present invention relates to a polyacetylene film formed on an electrode substrate, and an electrochemical film formed on the substrate by electrolytic oxidation. It is characterized by being made of an aromatic polymer material formed from.

Further, a second invention of the present invention is an invention relating to a method for manufacturing the conductive polymer film of the first invention, comprising:
A process of producing a polyacetylene film on an electrode substrate,
And the aromatic polymer 4-+ by electrolytic oxidation
All features include each step 1fUk of the process of forming.

Furthermore, a third invention of the present invention relates to another conductive molecular film, which includes a polyacetylene film formed on an electrode substrate, and a polymer having a shape of 111E L formed on the polyacetylene film. It is characterized by consisting of a film and an aromatic polymer material electrochemically formed on the substrate by electrolytic oxidation.

Furthermore, a fourth invention of the present invention relates to a method for producing the material-resistant film of the third invention, which comprises a step of producing a polyacetylene film on an electrode substrate, and a step of producing a polyacetylene film on an electrode substrate, It is characterized by including the steps of layering a molecular film v4°h, and forming a 1% aromatic molecular material entirely thereon by electrolytic oxidation.

Aromatic intersystem molecular materials such as polypyrrole are usually prepared in a solution prepared by dissolving a monomer, or an electrolyte, in an organic solvent such as IJ (gold, acetonate, etc.). , along with a counter electrode, and by applying current between both electrodes. At this time, if the electrode substrate is coated with an insulating material, no conductive film will be formed. However, the present inventors found that I
When using a substrate coated with A-molecule film,
We have discovered that a uniform polymer/conductive polymer composite can be formed as a whole by swelling the polymer film with an electrolyte and diffusing monomer molecules into the film. Utilizing this reaction, the present inventors were able to protect the electrode with an aromatic polymer material such as a polyacetylene film formed on an electrode substrate or a polypyrrole formed by electrolysis. Similarly, on an electrode substrate with a polyacetylene film coated with an insulating polymer, electrolytic oxidation of an aromatic compound such as pyrrole is performed, and polyacetylene fibrils are retained by a polymer/aromatic polymer material composite. Ta.

Furthermore, in the case of aromatic compounds, anion doping occurs simultaneously during '-deoxidation, so this effect made it possible to simultaneously dope the polyacetylene film.

However, in this case, it is necessary to adjust the composition of the electrolytic bath solution appropriately for the polymer. That is, the electrolytic solution may be one that satisfies the following conditions.

(11) Must not dissolve the polymer (2) Must be capable of dissolving the aromatic compound that is the 7-mer and a suitable electrolyte salt (3) 'A film pre-formed by the 7-mer and the salt in the electrolytic bath solution Examples of aromatic uncompounds used in the present invention include 5-methylpyrrole, N-methylpyrrole, thiophene, azulene, methylazulene, and pyrene.

Further, the polyacetylene may be obtained by a conventional method such as stopping acetylene in the presence of a Ziegler type catalyst.

In addition, the present inventors have already developed a "three-dimensional cross-linked polymer film" (patent application) as the lower layer madder molecular film on the substrate in a conductive molecular film using aromatic and UI molecular materials. 58-186991), "Thermoplastic resin film" (% application No. 58-2152015),
or “sieve molecular film formed by plasma polymerization” (
We have developed a device using Japanese Patent Application No. 58-215205).

However, the "polyacetylene film" in the present invention is not included in any of the above-mentioned five unique molecular films, and the conductive film of the present invention is a new 4'd conductive polymer film.

The conductive polymer film of the present invention has improved stability in the atmosphere compared to the original polyacetylene film, and even when used as a polyacetylene film,
It is also advantageous in that the entire structure is electrically conductive since it does not require an insulating protective film as in the conventional case.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

In addition, FIG. 1 shows an example of the conductive polymer film of the present invention. This is a cut-side model diagram for l'lA-, and No. 44 1 in Fig. 1 is polypyrrole, 2
means polyacetylene and 61 quartz glass substrate.

Example 1 Polyacetylene was polymerized on a Nesa glass substrate with a thickness of 0.6-07 μm (polymerization was carried out at room temperature, catalyst 100 mm% L/l, AA/Ti; 4).

The electrode with this polyacetylene film was used as a positive electrode, and the negative electrode was used as a platinum electrode, immersed in an electrolytic bath solution, and an electrolytic polymerization of virol was carried out in an N2 atmosphere at a constant pressure of 1.5V. The electrolyte is acetonitrile, pyrrole 1M, in salt [tetraethylammonium, tetrafluoroborey] (0z
A solution of 0.3M Hs)4NBF4) was used. Polyacetylene 7 on the substrate after about 50 minutes of electropolymerization
(/I'mu['11%) The substrate with the bonding film was coated with a black-blue polypyrrole thin film. After rinsing the substrate with acetonitrile, the film was peeled off from the Nesa substrate, transferred to another quartz substrate, and dried under reduced pressure. I did it.

After drying, a certain area of gold was vapor-deposited on the film using a metal mask to form a '+6 pole, a lead wire was taken out from there, and electrical conductivity IW was measured by the four-terminal method. all
As a result of the determination of polyacetylene-polypyrrole film,
The drowsiness conductivity was 100.0"0, which was 18 degrees.

The electrical conductivity of this sample after being left in the air for a week was 4.
00-"071-", the stability is significantly improved compared to a normal polyacetylene film, which has a significantly lower cage density.

In order to investigate the stability of the polyacetylene-polypyrrole film combined with VC4M in detail, an electrical conductivity model kUi as shown in FIG. 1 was established, and only the change in b4+ air conductivity of polyacetylene was calculated. Although the model is completely two-layered, it does not necessarily have to be actually two-layered.
! It is calculated assuming that it is a construction. Assuming that all sides of the electrical conductivity 11 are added in the direction of 1, the electrical conductivity of only polypyrrole in the composite membrane is Gp, and the electrical conductivity of only polyacetylene is Ga. - Also, as shown in the figure, the length t5 and the width W, the film thickness of the polypyrrole jacket is tp,
The film thickness of polyacetylene j is assumed to be '4 ta.

In this way, Gt, Gp, and Ga can be folded together as shown in the following equation.

Gt = Gt...(+1 W (ta+tp) σ1)" Gp□...(2) tp Here, Gt, Gp, and Ga are the composite membrane, respectively,
This is the conductance of polypyrrole I and polyacetylene AJ. The following equation holds between these conductances.

Gt=Ga+Gp @ # + ・(4) Here σt
from 100Ω-”cm-” to 40Ω-1cm in a week
From equation (1), we can calculate the change in σa when
) Calculate 6 using the formula. For calculation, ta=α75μm,
Using the value of tp = 1 μm1σp = 55-1t1n-1, it was assumed that these 1 shifts do not change due to oxidation. σa is 160Ω-”cn-’ to 200 in weeks
-''(ff+-') In polyacetylene doped with iodine, it decreases by about two orders of magnitude in -weeks at 25°C in the air.Here, if polypyrrole does not exist (Fa decreases from 160 Ω-1 crn-' 1Ω-”cn
r-"li degree. Therefore, the isoelectric molecular film of the present invention provides stability 20 times more.

Examples 2 to 6 In the same manner as in Example 1, pyrrole was electrolytically polymerized on a conductive substrate (NESA, Si, Atl vapor deposited glass) coated with polyacetylene.

At this time, the electrolytic salt anions ep-) luene suchlorate (Cl0a-) (Example 3), pentafluoride hydrogen chloride (A8
Fs-) (Example 4), PF, "" (Example 5),
It was changed to H3O47 (Example 6).

In both cases, the polyacetylene fibrils were protected by polypyrrole and exhibited commercial 4J properties due to anion doping. Film electrical qI degree (f - shown in Table 1).

Table 1 Examples 7 to 12 Using the same substrate as in Example 1 (polyacetylene coated Nesa Glass), chloromethylated polystyrene (CMS) (Example 7), Novolak resin (Example 8), polyvinyl carbazole (PVOZ) (Example 9), polymethacrylate (PMMA)
(Example 10), polyglycidyl methacrylate) (
After applying PGMA) (Example 11) and polyvinyl chloride (Example 12), electrolytic oxidation of virol was performed to protect the fibrils of the polyacetylene film with a polymer/polypyrrole composite. As a result, the electrical conductivity decreased slightly, but the stability in the atmosphere - Here, practical electrical conductivity values and stability examples of polyacetylene when polychloride/vinyl chloride is used as the polymer. Calculated using the same model and same month method as in 1. σt decreased from −75Ω−1cnI−” to 650−”Or+−” after being left in the atmosphere for − weeks.
The film thickness tp of polysalt ivinyl was 1.0 μm in Example 1.
The polymer/polypyrrole composite membrane produced with the reliability of 2 had a conduction value σp of 3Ω-”cnl-’.

Similarly, if these clays change due to oxidation, then by solving 14)2 from equation (1), σa is 1710.
1480-" after being left in the atmosphere for -1"
cm-''. A stability improvement of 74 times compared to Example 1 and 148 times compared to unprotected polyacetylene was observed.

As is clear from the results of Examples 7 to 12, there are many other polymer materials to be coated on the kyriacetylene film other than the examples, so the present invention is not limited to these examples. [Effects of the invention] Carved above 1. As explained above, according to the present specification, the electrical conductivity of the polyacetylene film is as follows:
The stability in the atmosphere in the atmosphere was improved greatly due to the anion of -, and because of the protective binder formed by poly 1 and acetylene glycol 1 mVC, stability in the atmosphere was improved.

Furthermore, in this system, compared to the conventional protective film using plasma film, since the protective polymer itself is electrically conductive, there are no dead spots on the surface, and the entire film is highly conductive. It's advantageous.

[Brief explanation of the drawing]

FIG. 1 is a still image model diagram for calculating the electrical conductivity of 11 examples of the frost-inducing film of the present invention. 1: Polypyrrole, 2: Polyacetylene, 6: Quartz glass substrate Patent applicant (Hiroto Moto, Akira Inoue, agent of Kameshin Tunko Corporation)

Claims (1)

[Claims] 1. A conductive polymer comprising a polyacetylene film formed on an electrode substrate and an aromatic polymer material electrochemically formed on the substrate by electrolytic oxidation. film. 2.'iM, a conductive polymer film comprising the steps of producing an acetylene film on a polar substrate and an extreme pressure plate, and forming an aromatic polymer material entirely thereon by electrolytic oxidation. of! ! ! How to send. (v) a polyacetylene film formed on the electrode substrate;
1. A conductive polymer film comprising a polymer film formed on the polyacetylene film and an aromatic polymer material vapor-chemically formed on the substrate by electrolytic oxidation. 4. The steps of producing a V acetylene film on the electrode substrate, laminating a polymer film on the film, and forming an aromatic polymer material thereon by electrolytic oxidation. A method for producing a conductive polymer film, comprising: