JPS63184206A - Manufacture of conducting 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] [Industrial application field] The present invention relates to a continuous method for producing conductive films.

In particular, the present invention relates to a method for continuously producing conductive films using heterocyclic compounds.

[Prior art and its problems]

It is well known that heterocyclic compounds can be polymerized by oxidizing agents for a long time to obtain insoluble and infusible polymers. For example, pyrrole can be polymerized by inorganic acids, iron chloride, benzoquinone, hydrogen peroxide, etc. The formation of polymers such as pyrrole black and pyrrole red is the result of atopane cis inheterocyclic chemistry (^dvan).
ces in Heter.

Cyclic Chemistry) Volume 15, page 67 (1973).

Similarly, furans, thiophenes, other heterocyclic compounds, or their substituted derivatives are also polymers.

On the other hand, it is also known that film-like polymers such as pyrrole, furan, and thiophene can be obtained by electrolytic polymerization in the presence of an appropriate organic electrolyte.
tion) 635 pages (1979), Japan
Journal of Applied Physics (Jap
a Journal of Applied Phys.
sics) Volume 21 (1982), Poly+wer Preprint Japan (Poly+wer Preprint
TS Japan) Volume 33 (1984) and many other reports.

Since these reports all involve electrolytic polymerization, it is difficult to produce a large-area membranous product (film);
Since the adhesion between the electrode substrate and the product was poor and only a TiI film could be obtained, there were problems such as a lack of mechanical strength and uniformity.

In order to solve these problems, improvements are being made gradually in terms of both devices and methods.

Recently, by contacting a polymer compound substrate containing a polymerization catalyst with a heterocyclic compound, the substrate surface and
Forming a conductive polymer inside was disclosed in Japanese Patent Application Laid-open No. 61-15.
It is shown in Japanese Patent No. 7522.

In the above-mentioned publication, there is no established method or apparatus for producing a conductive film, and there is no established method or apparatus for producing a conductive film. We have successfully developed a manufacturing method and equipment for producing conductive films of any width using a continuous winding method.

It's dark.

(Problem to be solved) A polymer film is placed on a polymer compound substrate containing a polymerization catalyst disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 61-157522, and the polymer film and a heterocyclic compound are continuously bonded. It is thought that a conductive polymer film can be obtained by contacting with the polymer, but both the equipment and method were insufficient.

In particular, a series of continuous equipment that includes film formation of polymer resins containing polymerization catalysts, reaction with heterocyclic compounds, and post-treatment processes such as drying requires larger machines and lacks multi-step processes. First, the resulting conductive film lacks stability, resulting in an expensive conductive film.

In general, methods for forming polymer films include (a) a calendar method, (b) an inflation method, (c) a T-shaped die method, and (ii) a solution casting method.

However, in all of the above methods, a polymer resin is heated and melted, softened, formed into a film, and then subjected to a cooling process to finally obtain a film.

At this time, in order to melt and soften the polymer resin by heating, it is necessary to raise the temperature to a fairly high temperature of 100° C. or higher, although this varies depending on the type of polymer resin.

Therefore, even if a polymeric resin containing a polymerization catalyst is formed into a film at such high temperatures by the methods described in (a) to (c), the polymerization catalyst may be altered or denatured, and furthermore, decomposition may occur. Activity will be lost.

On the other hand, in this method, the polymerization catalyst and polymer resin are both dissolved in a solvent at room temperature, the solvent is then dried and removed, and a film is formed, so that the activity of the polymerization catalyst is not lost and it is uniformly dispersed in the polymer resin. .

Therefore, the present invention uses the second 78 liquid casting method of the film forming method and completes the reaction with the heterocyclic compounds at the same time as film formation, thereby quickly stabilizing a continuous conductive film. The object of the present invention is to provide a method for producing a conductive film obtained by the method.

[Means for solving problems]

A polymer resin solution containing a certain amount of polymerization catalyst is cast onto an endless belt or drum to obtain a polymer film containing the polymerization catalyst. This polymeric film is obtained by removing the carrier on an endless or drum. This is a method for producing a conductive film in which the solvent is removed and the reaction with the heterocyclic compound is simultaneously carried out in the open air where the solvent is removed.

First, the resin containing the polymerization catalyst cast from the hopper contains a considerable amount of solvent, and requires a drying step in an oven to form a perfect film.

In this process, in order to simultaneously react with the heterocyclic compounds, hot air containing the heterocyclic compounds is blown onto the resin containing the polymerization catalyst that has entered the open air, and at the same time, exhaust air is continuously released. By performing this step, a polymer layer made of a heterocyclic compound is formed on the surface and inside of the polymer film, thereby obtaining a conductive film.

If it is desired to impart further conductivity to this conductive film, it may be subjected to an auxiliary reaction step with a heterocyclic compound in the next step, and optionally may be post-dried. It is obtained as a continuous conductive film on a winding roll.

Examples of the polymer film used in the present invention include polyvinyl alcohol, polyvinyl fluoride, cellulose acetate, soft polyvinyl chloride, hard polyvinyl chloride, polystyrene, and hydrochloric acid rubber.

Examples of polymerization catalysts include ferric chloride, cupric chloride, and sulfuric acid.
There are metal salts such as copper, metal oxides such as lead dioxide, peroxo salts such as potassium persulfate, ammonium persulfate, and quinones such as benzoquinone, diazonium salts such as Hensendiazonium chloride salt, and ,
Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and chlorosulfonic acid may also be used.

Heterocyclic compounds include pyrrole, thiophene, furan,
N-alkylpyrrole, N-71J-)Lipyrrole,
Monoalkylpyrrole substituted at the 3-position, monohalogenated pyrrole, dialkylpyrrole substituted at the 3- and 4-position, and dihalogenated pyrrole, monoalkylthiophene substituted at the 3-position, monohalogenated thiophene, 3-position substituted monoalkylpyrrole, monohalogenated pyrrole, , and dialkylthiophene substituted at the 4-position,
and dihalogenated thiophene, monoalkylfuran substituted at the 3-position, monohalogenated furan, dialkylfuran substituted at the 3- and 4-position, and dihalogenated furan, aniline, aniline derivatives, N-alkylaniline, N- - One or more compounds selected from dialkylaniline, halogenated aniline, dihalogenated aniline, halogenated N-alkylaniline, halogenated N-dialkylaniline, and dihalogenated N-acetylaniline. Any type of material that can supply hot air while open can be used.

For hot air, basically endless held or
In order to remove the solvent in the polymer resin cast onto the drum, an appropriate air volume at a temperature above room temperature is sufficient.

In addition, by passing through the open circuit, it is possible to form a polymer film and provide conductivity at the same time in a dry manner.
Although the drying step of the post-treatment is not necessary, a drying step may be provided as a post-process as necessary, such as when another auxiliary step, a reaction step with a heterocyclic compound, is provided.

[Effect]

As described above, by performing the process of forming a polymer film containing a polymerization catalyst and the reaction process of a cough polymer film with heterocyclic compounds in the same process, the process can be shortened and the machine can be made smaller. This method enables the production of existing polymer films by supplying heterocyclic compounds to the polymer film along with hot air in the drying process using a film forming machine using a solution casting method.
And by drying, a conductive polymer film imparted with conductivity can be stably and continuously obtained.

(Example-1) Ferric chloride, hexahydrate (reagent, special grade, unpurified) was used as the polymerization catalyst, and polyvinyl alcohol (GL-05 type, manufactured by Nippon Gosei Chemical Industry, unpurified) was used as the polymer resin. was used, the catalyst concentration (*) was set to 20 (wtχ), water was used as a solvent, and a polymer aqueous solution containing a polymerization catalyst (c
) was adjusted. The viscosity at this time is 150c at 23°C.
It was p.

Pyrrole (Croda, made in Japan, unrefined) was used as the heterocyclic compound and was blown into the open space along with hot air.

The absolute amount of pyrrole at this time was unknown.

As shown in FIG. 1, film formation is carried out using a drying drum 4 that rotates at the center, a hopper 1 on the outer periphery of the drying drum 4, a hot air supply port 8.8 containing heterocyclic compounds, a wandering outlet 9.9, and a substrate. The experiment was carried out using an apparatus having an oven 6 surrounded by an outer wall 11 having a 1° opening for supplying and discharging the material film, and a drying section 7 for post-treatment of the oven 6.

Film deposition line speed is 5.10, 20m/+in
.

The thickness of the film was about 25μ.

The surface resistance and light transmittance of the obtained film were measured. The results are shown in Table-1.

This catalyst concentration (wtX) - (catalyst weight) / (catalyst weight +
(weight of polymer resin)
, ferric chloride hexahydrate (reagent, special grade) as a polymerization catalyst,
Virol (manufactured by Croda Japan, unrefined) was used as the heterocyclic compound, and the catalyst concentration was adjusted to 10 (wtX).
The line speed was set to 5.10, 20m/+win.

The table shows the surface resistance and light transmittance measured in the same manner as in the example.
Shown in 1.

Table 1 (Comparative example) Using the same equipment as in (Example-1), the catalyst concentration was 20 (w
tX) and contained polyvinyl alcohol resin (
A pre-formed and dried film consisting of the same material as in the actual example is supplied from the base film supply and discharge port 10 shown in FIG. 1 (at this time, no resin solution is flowing from the hopper 1). Under the same conditions, hot air containing virol was wound up with a winding roll.

At this time, the film line speed was changed and the surface resistance and light transmittance were measured in the same manner as in Example 1. The results are shown in Table 2.

Further, the same procedure was carried out by lowering the line speed to a fraction of that in Example 1, and the surface resistance and light transmittance were measured. The results are shown in Table 2.

Table 2 As can be seen from Comparative Examples 1 to 3, even if a preformed and dried polymer film containing a catalyst was brought into contact with virol, the reaction was insufficient when it was flowed at the same line speed as in Example 1. , there is a significant difference in conductivity compared to that obtained by the method of the present invention.

Furthermore, it can be seen that in order to obtain the same level of conductivity as in (Example-1), the film must be flowed at an extremely low speed. (Comparative Examples 4 to 6) (Example-3) As can be seen from the results of (Example-1) and (Example-2), the line speed of 20 m/min has a large surface resistance. As shown in Figure 2, a conductive film was obtained through a reaction process with pyrrole following the film formation process. The results are shown in Table-3.

Table 3 [Effects] As described above, the present invention enables film formation using an existing film forming machine.
By blowing hot air containing pyrrole during drying to form a film, a conductive film can be stably and continuously obtained.

In this way, it is possible to easily continuously obtain a conductive film with high added value of conductivity, so it can be manufactured at a low cost, and it provides a method for continuous production of a conductive film that is extremely commercially valuable. It is.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are explanatory diagrams of an example of the method for manufacturing a conductive film of the present invention.

Claims (1)

[Scope of Claims] 1) When a polymer resin containing a polymerization catalyst is formed into a film by a solution casting method, the resin is brought into contact with a heterocyclic compound while swollen with a solvent to form a film. A method for continuously producing a conductive film, characterized in that: 2) The conductive film according to claim 1, wherein the heterocyclic compound is one or more compounds selected from pyrrole, thiophene, furan, aniline, and alkyl substituted products and derivatives thereof. manufacturing method. 3) The polymer film according to claim 1 or 2, wherein the polymer film is one selected from soft polyvinyl chloride, hard polyvinyl chloride, polyvinyl alcohol, hydrochloric acid rubber, polyvinyl fluoride, and cellulose acetate. Method for manufacturing conductive film.