JPH04188502A - Manufacture of conductive polymer material - Google Patents

Abstract

PURPOSE:To enable easy manufacture of a conductive polymer material with uniform film thickness and without generation of separation and crack by supporting a conductive sheet-shaped base material with connected conductive supporters to perform polymerization. CONSTITUTION:A conductive sheet-shaped base material 1, on an insulating support 3, is conveyed to an electrolytic polymerization bath 5, and polymerization of conductive polymer is performed in a polymerization position 6 of the lower part of an opposite electrode 2. That is, the conductive sheet-shaped base material 1 is supported to be conveyed between two connected conductive supporters 4. Therefore, even a short conductive sheet-shaped base material 1 can be conveyed, a desired shape can be obtained without necessity to truncate the manufactured conductive polymer material, and a highly reliable conductive polymer material without separation and crack of the conductive polymer material can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing conductive polymer materials by electrolytic polymerization. [Prior art] Polymer materials represented by polypyrrole, polythiophene, polyphenylene, polyaniline, etc. [Polypyrrole:
A., F., Dinz, J., Chem., Soc.
, Chem, Commun.

1975, 635, Polythiophene: JP-A-56-47
42L polyphenylene: Electro-chem,
, Acta, 27.61 (1982), Polyaniline: F, Diazz Electroanal,
Chem, 111, 1524 (1980) It is known that by doping impurities, an insulator or semiconductor can be made to have electrical conductivity similar to that of a metal, and that this doping is reversible and that color Because it involves changes, it is being actively researched for applications in display elements, secondary batteries, electromagnetic shielding materials, various sensors, etc.

These materials can be produced by an electrolytic polymerization method in which the corresponding monomers (virol, thiophene, benzene, aniline, etc.) are electrochemically oxidized and polymerized in an electrolytic solution. Compared to other conductive polymer manufacturing methods, such as chemical polymerization using oxidizing agents and oxidation catalysts, this method has the advantage that materials of any size and thickness can be obtained by changing the electrode area and current application time.
The use of a conductive substrate such as a metal for the electrode has the advantage that it can be combined with the conductive substrate in one step.

Regarding the production of conductive polymers in large quantities, several methods using continuous electrolytic polymerization equipment have been proposed.
No. 2 and JP-A-60-137923 contain
Electrolytic polymerization on a lumi electrode and continuous electrolytic polymerization on a conductive substrate have been disclosed.

[Problem to be solved by the invention]

However, in the above-mentioned method, the conductive polymer material can only be produced in a long length, and it must be cut and used later, or there is a risk of peeling or cracking of the conductive polymer from the substrate at the cut surface. Ta. In addition, since it is a continuous sheet, once the conveyance is stopped, the part immersed in the electrolytic polymerization tank becomes unusable.
In addition to the above-mentioned problems, when several tanks, such as a cleaning tank and a reduction tank, are connected in series, the conductive polymer material used for calibration is left in the air, making it easy for the membrane to dry out and oxidize. If the sheet-like base material is damaged (cut), the conductive polymer will be wasted, and it will take time to re-operate the device. In addition, in order to increase the thickness of the conductive polymer film, the conductive sheet-like base material must be kept in an electric field until a specified amount of polymerization is reached, which requires a large electrolytic polymerization tank. do.

The present invention aims to solve the above-mentioned problems, and its purpose is to easily manufacture a conductive polymer material with a uniform film thickness and without peeling and cracking. Our goal is to provide ways to do what we do.

[Means to solve the problem]

The present invention relates to a method for producing a conductive polymer material by an electrolytic polymerization method, which is characterized in that electrolytic polymerization is carried out by supporting a conductive note-like base material on a continuous conductive carrier. Regarding the manufacturing method.

Next, the present invention will be explained in detail.

An example of the apparatus used in the present invention is shown in FIGS. 1(a) and 1(b).

FIG. 1(a) is a schematic diagram thereof, and FIG. 1(b) shows the state of the conductive sheet-like base material in the portion facing the counter electrode.

The conductive sheet-like base material 1 is placed in an electrolytic polymerization tank 5 with an insulating carrier 3
The conductive polymer is transported through the interior, and the conductive polymer is polymerized at the polymerization site 6 at the lower part of the counter electrode 2. In this example, FIG.
), the conductive sheet-like base material 1 is carried between two continuous conductive carriers 4 and conveyed. This makes it possible to transport even short conductive sheet-like substrates, so the manufactured conductive polymer material can be obtained in the desired shape without the need to cut it. , it is possible to obtain a highly reliable conductive polymer material with no cracks or the like. Since the conductive sheet-like base material 1 can be conveyed even if it is not continuous but independent, there is no need to move it continuously, and electrochemical reactions such as polymerization can be easily controlled. Furthermore, even if there is an abnormality in the electrolytic device or in the conveyance of the conductive sheet-like substrate, the proportion of composites that are wasted is small, and the time required to re-operate the device can be shortened. Furthermore, since the conductive sheet-like base material 1 is conveyed in steps, in cases where the electrolytic cells are continuous,
Even if other tanks (cleaning tank, reduction tank, etc.) are connected, the time the conductive polymer is exposed to the air is extremely short.
It can prevent drying of the conductive polymer, precipitation of electrolyte in the membrane, and oxidation of the membrane.

The connection point between the conductive sheet-like base material 1 and the conductive carrier 4 is the first
In Figure (b), there are four locations, but the locations are not limited, and may be set as appropriate depending on the size of the sheet-like base material to be polymerized. Further, it is preferable that the surface of the conductive carrier 4 is insulated by coating with a resin or the like, except for the connecting portion between the conductive sheet-like base material 1 and the conductive carrier 4. This is because, if the conductive carrier 4 is not coated, polymerization will proceed to the conductive carrier 4 as well. Also,
In the case where the conductive sheet base material 1 and the conductive carrier 4 are coated, the part of the carrier where the electric field is applied (A in Figure 1) other than the connection part between the conductive sheet-like base material 1 and the conductive carrier 4 must not be coated. Of course. In the case of continuous polymerization, it is necessary to take this point into account and install a conductive sheet-like base material and insulate the carrier.

In addition, according to the present invention, when a conductive polymer material with a thick film thickness such as a battery electrode or an electromagnetic shielding material is produced under a constant current, constant voltage, or potential, a conductive sheet-like base material can be used. Since the film thickness of the conductive polymer can be increased by transporting 1 in steps, there is no need to enlarge the electrolytic polymerization tank as in the conventional case.

In this example, an example in which the conductive polymer is polymerized on one side of the conductive sheet-like base material 1 has been described, but it goes without saying that it is possible to polymerize the conductive polymer on both sides of the conductive sheet-like base material 1.

FIG. 2 shows another example of the device used in the present invention.

In FIG. 2, several counter electrodes 2 are installed in the vertical direction. Therefore, since there are several polymerization sites 6 in the conductive sheet-like base material 1, the film thickness of the conductive polymer in the conductive sheet-like base material l can be increased, and several sets of conductive sheet-like When the polymerization of the base material 1 is allowed to proceed simultaneously, the electrolytic cell can be small.

The conductive carrier 4 used in the present invention is not particularly limited as long as it is a good conductor and has strength. It is possible to use various metal wires and sheets.

Further, the insulating carrier 3 of the present invention may be a single cylindrical roll, or preferably, as shown in FIG. It is preferable that

In the present invention, since the movable parts do not directly touch the conductive sheet-like base material 1, two
If the conductive polymer is supported by two insulating rolls 7, it is possible to lead the conductive polymer to the outside of the electrolytic polymerization tank 5 without damaging the film, even if only an extremely weak film is formed during polymerization, such as polyaniline. On the other hand, if the insulating carrier 3 is a single cylindrical roll, there is a possibility that the conductive polymer will come into direct contact with the roll, causing the conductive polymer film to touch or crack.

The conductive sheet-like base material 1 used in the present invention is a metal sheet made of nickel, aluminum, stainless steel, copper, etc., or a plastic sheet such as carbon fiber cloth, carbon dispersed plastic sheet, or polyester. A plastic sheet whose surface is coated with a material by vapor deposition or sputtering to make it conductive may be used, but the material is not limited thereto. In addition to these working electrodes, the surface of the conductive sheet-like base material 1 may be rough if importance is placed on the adhesion between the sheet-like base material and the conductive polymer to be polymerized. Preferably, surface roughening treatment such as blasting,
Furthermore, if a through hole is provided, the conductive sheet-like base material 1
It is possible to obtain a composite with good adhesion between the conductive polymer and the conductive polymer. In the case where the conductive polymer is used over the conductive sheet-like base material 1, it is preferable that the surface of the conductive sheet-like base material 1 is smooth.

The polymer material polymerized on the conductive sheet-like substrate 1 by the method of the present invention is, for example, a hetero five-membered ring compound polymer containing monomers such as pyrrole and thiophene, and monomers containing benzene, azulene, etc. Examples include aromatic hydrocarbon compound polymers, and amine compound polymers containing aniline, diphenylbenzidine, etc. as monomers, but there are no particular limitations as long as they can be synthesized by electrolytic polymerization. For example, materials such as phthalocyanine are also possible.

Next, the electrolytic polymerization method will be described.

The electrolytic polymerization method is generally described, for example, by J Electr.

-chem, 5oc1. Vol, 130. No.7.
1506-1509 (1983), Electoche
m, Acta,, Vol. 27. No, 1.61~6
5 (1982), J. Cheo+, Soc, Che.
A solution prepared by dissolving a monomer and an electrolyte in a solvent is placed in a designated electrolytic bath, the electrodes are immersed, and electropolymerization is carried out by anodic oxidation or cathodic reduction, as described in This can be done by causing a reaction.

As the electrolyte, for example, as an anion, BF4-,
AsF, -, SbF, -, PF6-, ClO4-
, H3O4-, SO4'-, and aromatic sulfonic acid anions, and cations include H+, quaternary ammonium cations, lithium, sodium, or potassium, but are not particularly limited to these. . In addition, as a solvent, for example, water, acetonitrile, benzonitrile, propylene carbonate, γ
Examples include, but are not limited to, butyrolactone, dichloromethane, dioxane, dimethylformamide, and nitro solvents such as nitromethane, nitroethane, nitropropane, and nitrobenzene. For electrolytic polymerization, any of constant voltage electrolysis, constant current electrolysis, and constant potential electrolysis is possible, and constant current electrolysis and constant potential electrolysis are suitable, and constant current electrolysis is particularly preferred from the viewpoint of mass production.

Example Next, the present invention will be explained by giving examples.

Using SUS wire as the conductive carrier, blasting was performed as the conductive sheet-like base material, thickness 20 μm, width 15 an
, SU with a through hole (0.9mmΦ) with a length of 10cm
Using three SUS plates as the S sheet and the counter electrode, the second
As shown in the figure, a counter electrode was installed in the vertical direction, and a conductive sheet-like base material was supported on a conductive carrier. Further, a 3.0M HBF4 aqueous solution containing aniline IM was used as a polymerization solution.

After moving the conductive sheet-like base material between the opposing electrodes, the conveyance was stopped, constant current electrolysis was performed at a current density of 3 mA/cffl, and polymerization was performed at a charge amount of 13 C/d'. After the polymerization was completed, transportation was started again and the polyaniline composite electrode was taken out of the electrolytic polymerization tank. The obtained polyaniline conductive polymer material had an average thickness of 820 μm and was free of cracks. Further, since the western end of the conductive sheet-like base material was almost entirely covered with the polymer, the conductive polymer did not peel off from the conductive sheet-like base material due to handling.

〔Effect of the invention〕

As is clear from the above description, according to the present invention, it is possible to easily produce a conductive polymer material with no peeling or cracking of the conductive polymer and with a uniform film thickness.

[Brief explanation of drawings]

FIG. 1(a) is a schematic explanatory diagram of one embodiment of the device used in the present invention, and FIG. 1(b) shows the portion of the conductive sheet-like base material facing the counter electrode in FIG. 1(a). FIG. 2 is a schematic illustration of another embodiment of the device used in the present invention, and FIG. 3 is a perspective view of an embodiment of the insulating carrier. l... Conductive sheet-like base material, 2... Counter electrode, 3...
... Insulating carrier, 4... Conductive carrier, 5... Electrolytic polymerization tank, 6... Polymerization site, 7... Insulating roll. Applicant Rico Co., Ltd. - Figure 2

Claims (1)

[Claims] A method for producing a conductive polymer material by an electrolytic polymerization method, characterized in that electrolytic polymerization is carried out by supporting a conductive sheet-like base material on a continuous conductive carrier.