JPH0539376A - Continuous production of composite conductive polymer film - Google Patents

Abstract

PURPOSE:To provide the subject film improved in strength by bringing a semipermeable membrane tube filled with a solution of a monomer of a conductive polymer into contact with a catalyst solution to form conductive polymer films on both sides of the tube, followed by cutting, water-washing and drying. CONSTITUTION:A solution 7 of a monomer of a conductive polymer with a concentration of 0.1-10mol/l is poured from a pipe 6 into a semipermeable membrane tube 3 with a thickness of 500mum or less molded through a tube- forming mold 5. The tube 3 is passed through a catalyst vessel 1 storing a catalyst solution 2 at -50 to 150 deg.C to form conductive polymer films 8 on both sides of the tube 3, cut lengthwise with a cutter 9, washed in a water- washing vessel 10 filled with water, and then dried in a drying chamber 12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for continuously producing a conductive polymer composite membrane by a simple operation.

[0002]

2. Description of the Related Art Recently, a conductive polymer having a π-conjugated electronic structure has been attracting attention as a new conductive material and is being applied to various fields. Among them, much research is being conducted on the use of conductive polymers formed into a film as a functional material, and along with this, a great deal of research has been conducted on the method for forming conductive polymers. ing.

The following methods are known as conventional film forming methods for conductive polymers.

(1) A conductive polymer is deposited on a flat electrode by an electrolytic polymerization method to form a conductive polymer film at the same time as a polymerization reaction.

(2) Using a soluble and fusible conductive polymer, L
It is manufactured by the B method, the spin coating method, and the coating and drying method.

(3) It is manufactured by using plasma CVD.

(4) It is manufactured by coating a ready-made film by a spray atomization method.

However, the methods (1), (2) and (3) cannot continuously produce a conductive film having a large area, and the method (4) is uniform. I can't get the film. Furthermore, all of these methods are difficult to work with and cannot be easily manufactured.

Recently, as an improvement of these methods, a method of producing a conductive polymer composite membrane by a diaphragm method has been developed. That is, a method for easily producing a conductive polymer composite film by encapsulating an aqueous solution of aniline hydrochloride with a cellophane film and immersing it in an aqueous solution of FeCl ₃ to form polyaniline films on the front and back of the cellophane film. Was developed (Pol
y, Prep. Jpn, Vol. 40, No. 3 (19
91), 1046).

The aniline film obtained by this method is excellent in strength because the cellophane film is inserted between the aniline films, and the polyaniline is firmly adhered to the cellophane film, so that the polyaniline can be peeled off even if it is rubbed. Since the aniline film does not need to be left in the FeCl ₃ aqueous solution for several hours as described above, a polyaniline composite film having excellent strength can be obtained without requiring complicated operations.

However, according to this method, the size of the composite membrane produced by encapsulating the aqueous solution of aniline hydrochloride in the cellophane tube is limited to the size of the tube and cannot be continuously produced. There was a problem.

[0012]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies aimed at remedying such drawbacks, the present invention has developed a method for producing a conductive polymer composite membrane continuously and by a simple operation.

[0013]

According to the present invention, a semipermeable membrane tube enclosing a conductive polymer monomer solution is run in a catalyst solution at a predetermined speed, and a conductive polymer membrane is formed on both sides of the tube. After being formed, the tube is cut open in the longitudinal direction, followed by washing with water and drying.

That is, in the method of the present invention, a conductive polymer composite film is produced by using a diaphragm method, and a semipermeable membrane is continuously supplied to continuously form a conductive polymer composite film having a uniform thickness. Moreover, it is intended to be manufactured by a simple method.

[0015]

In the present invention, as the conductive polymer monomer, aniline or its derivative, pyrrole or its derivative, thiophene or its derivative aromatic compound, etc. are used, and this conductive polymer monomer is used as a solution. Water, acetonitrile, chloroform or the like is used as a solvent for the above.

When the concentration of the above solution is high, it is difficult to maintain the uniformity of the film, and when it is low, the growth of the film is hindered.
It is preferably 1 to 10 mol / L.

The semipermeable membrane tube for enclosing the solution may be any one having a semipermeable membrane function, for example, polyvinyl alcohol, cellophane, etc. may be used. If it is too thick, the growth of the film is hindered, so that the thickness is usually preferably 500 μm or less.

On the other hand, a Lewis acid is usually used as the catalyst, but FeCl ₃ is preferable from the viewpoint of stability. As the solvent for forming the catalyst solution, it is preferable to use the same solvent as the solvent for the conductive polymer monomer in view of the relationship with the osmotic pressure.

The concentration of this solution is preferably the same as that of the conductive polymer monomer before use.

The temperature of the catalyst solution varies depending on the types of the conductive polymer monomer and the catalyst, but the liquid temperature is preferably in the range of -50 to 150 ° C.

The speed of the semipermeable membrane tube which is run in the catalyst solution varies depending on the production rate of the composite membrane, but the tube is usually immersed in the catalyst solution for 30 minutes to 3 minutes.
Need to soak for hours. The reason is that if the time of immersion in the catalyst solution is short, the film does not grow sufficiently, and
This is because the growth of the film does not appear remarkably even after soaking for more than a time.

[0022]

【Example】

[Example (1)] First, as shown in FIG.
Mol / L FeCl ₃ aqueous solution 2 was injected and the liquid temperature of the aqueous solution was maintained at 40 ° C. On the other hand, a polyvinyl alcohol membrane 4 having a thickness of 15 μm is used as the semipermeable membrane tube 3, and the membrane 4 is molded into a tube shape through a tube molding die 5 at 180 ° C. After injecting 2 mol / L aniline hydrochloride aqueous solution 7 through a pipe 6 to fill it as shown, the tube 3 is allowed to run in the above FeCl ₃ aqueous solution 2 at a speed of 5 m / min. A 10 mol / L aniline hydrochloride aqueous solution is supplied through the pipe 6 at a dropping rate of 40 mol / min.

Then, the aniline hydrochloride aqueous solution 7 is enclosed in the semipermeable membrane tube 3 and kept in the FeCl ₃ aqueous solution 2 for about 2 hours to form the polyaniline-polyvinyl alcohol composite film 8 and then The tube is cut open in the lengthwise direction with a cutter 9 to form a film, then introduced into a washing tank 11 filled with water 10 for washing, and then dried in a drying chamber 12 at about 100 ° C. Thirteen
The film was wound on to obtain a conductive polymer composite film of the present invention.

[Example (2)] Using a device similar to that shown in FIG. 1, 2 mol / L of a FeCl ₃ chloroform solution was injected into the catalyst tank, and the liquid temperature was maintained at 50 ° C. to obtain a semipermeable membrane. A polyvinyl alcohol film having a film thickness of 15 μm was used as a tube, and this was molded into a tube shape through a tube-molding mold at 180 ° C., and then 2 mol / L of (3 -Octylthiophene) -chloroform solution was filled and filled with 10 mol / L of (3-octyl) from the tube while running in the FeCl ₃ chloroform solution at a speed of 5 m / min. Thiophene) -chloroform solution 3
Supply at an appropriate rate of 0 mol / min.

Then, the (3-octylthiophene) -chloroform solution was sealed in the semipermeable membrane tube and kept in the FeCl ₃ chloroform solution to form a poly (3-octylthiophene) -polyvinyl alcohol composite film. This tube was cut open in the length direction with a cutter to form a film, introduced into a water washing tank and washed for 5 seconds, and further dried in a drying chamber at about 100 ° C.,
The conductive polymer composite film of the present invention was obtained.

[Comparative Example (1)] A polyethylene film having a thickness of 15 μm was introduced into a spray chamber, and polypyrrole was sprayed on the film to obtain a conductive composite film.

[Comparative Example (2)] A 15 μm thick polyethylene film was coated with a chloroform solution of (3-octylthiophene) having a concentration of 1 mol / L by a roll and dried to obtain a conductive composite film. ..

With respect to the conductive polymer composite film of the present invention thus obtained and the conductive composite film of the comparative example, the uniformity of the film thickness and the volume resistivity were measured. The results are shown in Table 1.

[0029]

[Table 1]

[0030]

Industrial Applicability According to the method of the present invention, a conductive polymer composite film having a uniform film thickness can be continuously produced by a simple operation, and is industrially extremely useful.

[Brief description of drawings]

FIG. 1 is an explanatory view showing steps of the method of the present invention.

FIG. 2 is an explanatory view showing a step of injecting a conductive polymer monomer into a semipermeable membrane tube in the method of the present invention.

[Explanation of symbols]

1 ... Catalyst tank, 2 ... FeCl ₃ aqueous solution, 3 ... Semipermeable membrane tube, 4 ... Polyvinyl alcohol membrane, 5 ... Mold, 6 ... Pipe, 7 ... Aniline hydrochloride aqueous solution, 8 ... Polyaniline-polyvinyl alcohol composite membrane, 9 … Cutter, 10… water,
11 ... Washing tank, 11 ... Drying room.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 7, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Then, the (3-octylthiophene) -chloroform solution was sealed in the semipermeable membrane tube and kept in the FeCl ₃ chloroform solution for about 2 hours to obtain a poly (3-octylthiophene) -polyvinyl alcohol complex. This tube having a film formed is cut open in the lengthwise direction with a cutter to form a film, introduced into a washing tank and washed for 5 seconds, and then dried in a drying chamber at about 100 ° C. A polymer composite film was obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

With respect to the conductive polymer composite film of the present invention thus obtained and the conductive composite film of the comparative example, the film thickness uniformity and I
The volume resistivity after _two- doping was measured. The results are shown in Table 1.

Claims (1)

[Claims] 1. A semipermeable membrane tube for enclosing a conductive polymer monomer solution is formed in such a manner that a conductive polymer membrane is formed on both surfaces of the tube while running in a catalyst solution, and then the tube is lengthwise. A continuous process for producing a conductive polymer composite film, which comprises cutting into pieces, followed by washing with water and drying.