JPS6172031A - Production of polypyrrole composite film - Google Patents

Abstract

PURPOSE:To produce a uniform composite film in high productivity, by immersing a rotary roll or belt having an electrically-conductive surface in a pyrrole- containing electrolyte tank, and subjecting pyrrole to electrolytic polymerization while feeding a film to the tank. using it as a rotary electrode. CONSTITUTION:In polymerizing pyrrole and making a polypyrrole composite film on the surface and/or the interior of an electrical insulating plastic film by an electrochemical reaction, a rotary roll or rotary endless belt having an electrically-conductive surface is immersed in a pyrrole-containing electrolyte tank, used as a rotary electrode, pyrrole is subjected to electrolytic polymerization while feeding a film to the tank, to form a composite film, and the film is continuously taken out to the outside of the electrolyte tank.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a continuous conductive plastic film useful as a material for antistatic materials, electromagnetic wave rolling materials, photoelectric films, optical switch elements, electrodes, color-changing films, various sensors, etc. manufacturing method (related).

[Description of prior art]

Conventional methods for making plastic films conductive include:
Composite materials made by mixing metals and carbon into an insulating plastic film have been put into practical use. This method had the disadvantage that it was extremely difficult to mold it into a thin film due to the relationship with the Ronin material, and even if it was molded, there were problems with its strength.

For this reason, polymer materials such as polypyrrole, polyaniline, polythenylene, and polyacetylene are attracting attention as conductive plastic films whose polymers themselves are conductive, and studies are being conducted to make them into films. However, these plastic films also have drawbacks such as poor moldability, easy deterioration in the air, and lack of strength, so they have not yet been put into practical use industrially.

For example, polyacetylene has high electrical conductivity comparable to that of metals, but has the disadvantage of being easily oxidized in the air. Furthermore, polypyrrole, polythenylene, and polyaniline contain heteroatoms such as nitrogen and sulfur in their polymers, and can be easily formed into films through electrochemical reactions, and are stable even in air. However, since these do not dissolve in solvents and cannot be melted, their moldability is extremely poor, they tend to break when made into thin films, and it is difficult to control electrical conductivity.

On the other hand, Niwa et al. of Dentsu Corporation Ibaraki Rento have proposed a manufacturing method for polypyrrole composite film based on a different idea (Rentou News, %282.1984.5.
16). In other words, a general-purpose plastic is coated on an electrically conductive material such as stainless steel, Hastelloy alloy, titanium, nickel, platinum, or conductive carbon material by a method such as spin cord or casting, and this material is used as an electrode (anode) using virol. When a voltage is applied between the electrode and the counter electrode in a solvent containing an electrolyte to cause an electrochemical reaction, polypyrrole, a type of conductive polymer material, is electrolyzed on the surface and/or inside of the general-purpose plastic film. By polymerizing and growing on the fibers and separating them from the electrode, a polypyrrole composite film with high electrical conductivity can be obtained.

[Problems to be solved by the invention]

However, if a fixed electrode (anode) is coated with a general-purpose plastic, a polypyrrole composite film is formed as a coating film, and then separated from the electrode, productivity is low and the resulting polypyrrole composite film becomes expensive. . In order to solve these problems, the present inventors carefully studied continuous production processes, and as a result, a film was placed on a rotating anode plate, and the film was doped with virol in an electrolytic solution, which was simultaneously electrolytically polymerized. The inventors have discovered that this enables continuous production of conductive polypyrrole composite films with high productivity, and have completed the present invention.

[Disclosure of the invention]

That is, the present invention is a method for producing a conductive plastic composite film by polymerizing and compounding pyrrole on the surface and/or inside of an insulating plastic film through an electrochemical reaction, the method comprising: A rotating roll or rotating endless belt having a pyrrole is immersed in a pyrrole-containing electrolyte bath to serve as a rotating electrode, and while supplying the film to the immersed roll or endless belt, pyrrole is electrolytically polymerized to form a composite film. The present invention also provides a method for continuously producing a polypyrrole composite film, characterized in that the formed composite film is continuously taken out of the electrolytic cell.

Insulating plastic films that can be made conductive in the present invention include common general-purpose plastic films, such as polyvinyl chloride; polyvinylidene chloride; polystyrene; polyamides such as nylon-6, knife 7-6/6, and nylon-12; Polyethers such as polyethylene oxide, polypropylene oxide, and polytetramethylene ether; Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polydiallyl phthalate; Polyvinyl carbazole; Polyvinyl pyridine; Polyvinyl pyrrolidone; Polyvinyl alcohol; Polyvinyl acetate; Polyacrylic ester; Methyl methacrylate; polyacrylonitrile; polyurethane; polyethylene; polypropylene; polybutadiene; polycarbonate; phenol resin; urea resin; melamine resin; silicone resin; polyfluorinated ethylene resin; polyfluorinated propylene resin, etc., but of course it is not limited to these isn't it. Of course, two or more of these may be used as a blend or a copolymer thereof may be used. Furthermore, it can also be applied to rubber-like stretchable films.

Hereinafter, the method of the present invention will be explained with reference to the drawings.

Conceptual diagrams of apparatus suitable for carrying out the method of the invention are shown in FIGS. 1, 2, 3 and 4. 1 and 2 show a rotating roll electrode type electrolytic cell, and FIGS. 3 and 4 show a rotating endless belt electrode type electrolytic cell.

Also, Figures 1 and 3 show roll electrodes or endless belt electrodes partially immersed in electrolyte, and Figures 2 and 4 show roll electrodes or endless belt electrodes that are entirely immersed in electrolyte. be.

In the electrolytic cell device, 10 is a plastic film sending roll, 20 is a polypyrrole composite film winding roll, 30 is a rotating roll electrode (anode), 40 is a counter electrode (cathode), 50 is a plastic film, 60 is a polypyrrole composite film, 70 Reference numeral 80 indicates an electrolytic solution (electrolyte+solvent virol) and a rotating roll driving the endless rotating belt.

The rotating roll 30 or the endless belt 80 has at least a conductive surface on the surface that is in contact with the fill, and is made of stainless steel, Hastelloy alloy, titanium, nickel, platinum, conductive carbon material, etc. It is something that

These are immersed in an electrolytic solution containing pyrrole to form a rotating roll electrode 30 (anode) or an endless belt electrode 80 (anode). Note that, as described above, these electrodes may be partially immersed in the electrolytic solution or may be entirely immersed.

The electrolyte in the electrolytic solution 70 is tetra-n-butylammonium tetrafluoroborate ((CH3(CH2)3)4
N@BF4), tetra-n-butylammonium perchlorate ((CH3(CH2)3:) + N-(4o4),
Tetra-n-butylammonium P-toluenesulfonate ([CH3(CH2)3)4 N-os "<=>-
cH3) etc.

However, since there are differences in the properties of these anions, BF: and ClO4, they affect the structure and physical properties of the polypyrrole composite film obtained, so an appropriate anion is selected in consideration of these factors.

The solvent used during electrolytic polymerization is generally acetonitrile, but propylene carbonate, γ-butyllactone, dimethoxyethane, etc. can also be used.

A raw plastic film 50 to be made into a composite film is continuously supplied to the rotating roll electrode 30 or the endless belt electrode 80 configured as described above from an external supply roll 10, and a DC voltage is applied between it and the counter electrode (cathode) 40. In this way, the pyrrole in the electrolytic solution is electrolytically polymerized on the surface and/or inside of the plastic film. That is, by doping the film with pyrrole present in an electrolytic solution and electrolytically polymerizing the film, the doped pyrrole is combined with the film to obtain a conductive polypyrrole composite film.

The formed composite film is continuously taken out of the electrolytic cell by a winding roll 20 or the like.

The properties of the resulting polypyrrole composite film naturally vary depending on the type of original plastic film, the type of electrolyte, the composition of the electrolytic solution, the polymerization conditions, etc. The thickness and electrical conductivity of the film can be controlled arbitrarily by changing the electrolysis time, but generally the thickness is from several microns to several hundred microns, and the electrical conductivity is too,? ,7+
You can reach up close. Further, the weight percentage of polypyrrole contained in the polypyrrole composite film may be arbitrary, but is preferably about 0.1 wt% to several tens of wt%, more preferably 1 wt% to 30 wt%. If the content of polypyrrole becomes too high, the film not only becomes expensive but also has poor processability.

In addition, when performing electrolytic polymerization, the film may be stretched to bring about anisotropy in the conductivity of the film, or the surface of the film may be reversed with respect to the electrode surface using a roll, etc., and electrolytic polymerization may be performed from both sides of the film. Of course, it is also possible to do so. In addition, in the electrolytic cell shown in Fig. 2 or 4, the entire roll electrode or belt electrode is immersed in the electrolyte, so polypyrrole grows from both sides of the plastic film surface and becomes composite. In the case of , as is clear from the figure, only one side of the film is composited.

The structures of these electrolytic cells are merely general conceptual diagrams, and it goes without saying that this does not limit the scope of application of the present invention. That is, if there is a substantially rotating electrode, a plastic film is continuously supplied to the electrode, and after electrolytic polymerization, the produced polypyrrole composite film can be continuously taken out from the electrode. It's good.

Preferred embodiments of the present invention will be described below in more detail with reference to Examples, but these are merely illustrative, and the technical scope of the present invention as defined in Article 70 of the Patent Act shall be interpreted in a limited manner by these Examples. It must not be interpreted as such.

[Preferred mode for carrying out the invention] Example 1 Using the apparatus shown in Fig. 1, polypyrrole was electrolyzed in an electrolytic cell consisting of five metal titanium rotating roll electrodes (width 30 m, outer diameter 14 cm). Polymerization was carried out.

However, the effective area of the rotating roll electrode involved in the electrochemical reaction was 1385 cJ. Acetonitrile was used as a solvent, and during electropolymerization, the concentration of pyrrole was maintained at 0.5 mol/l, and the concentration of tetra-n-butylammonium perchlorate was maintained at 1 mol/l. A titanium wire mesh was used as the counter electrode (cathode).

A polyvinyl chloride film (manufactured by Mitsui Toatsu Chemical Co., Ltd.) with a width of 30 crrL and a thickness of 30 microns was continuously supplied from the delivery roll 10 to the rotating roll electrode at a speed of 2.7 m/min under the condition of a constant current of 30 A. , electrolytically polymerized. The film composited with polypyrrole was wound up with a winding roll 20. The obtained polypyrrole composite film has a resistance of 20Ω
--D exhibited high electrical conductivity, and the polypyrrole content was estimated to be about 2 wt% based on elemental analysis.

Example 2 Electrolytic polymerization was carried out using the apparatus of Example 1 under the same conditions as in Example 1. From the feed roll 10, the width is 30 mm and the thickness is 30 mm.
Micron's Barex resin film (Trademark of Sohio, USA, sold by Mitsui Toatsu Chemical Co., Ltd., acrylonitrile, methyl acrylate, butadiene copolymer, graft polymer)
was continuously supplied to a rotating roll electrode at a rate of 2.7 rrL/min, and electrolytically polymerized under the condition of a constant current of 3OA. The film composited with polypyrrole was wound up with a winding roll 20. The obtained polypyrrole composite film is 8F
It exhibited high electrical conductivity of 'ctn', and the polypyrrole content was estimated to be 2.3 Wt% based on elemental analysis.

Example 3 Electrolytic polymerization was carried out using the apparatus of Example 1 under the same conditions as in Example 1. From the feed roll 10, the width is 30 mm and the thickness is 20 mm.
Micron polystyrene resin film (Mitsui Toatsu Chemicals)
Co., Ltd.; TOPORESOX/HI polystyrene) 4m/
The mixture was continuously supplied to a rotating roll electrode at a rate of 1 minute, and electrolytically polymerized under a constant current of 30 A. The film composited with polypyrrole was wound up with a winding roll 20. The obtained polypyrrole composite film exhibited a high electrical conductivity of 30 Ω° 1, and the polypyrrole content was estimated to be 2.9 wt % based on elemental analysis.

Example 4 Using the apparatus shown in FIG.
7rL, effective electrode area involved in electrochemical reaction 30('
Polypyrrole was electrolytically polymerized in an electrolytic cell consisting of )ncm). Acetonitrile was used as a solvent, and during electropolymerization, the concentration of pyrrole was maintained at 0.5-EJ/l and the concentration of tetra-n-butylammonium perchlorate was maintained at 1 mol A.

A titanium wire mesh was used as the counter electrode (cathode). A nylon-6 resin film (manufactured by Toshiku Co., Ltd.) with a width of 30 cTL and a thickness of 10 microns (manufactured by Toshiku Co., Ltd.) is continuously supplied from the delivery roll 10 to a rotating endless belt electrode at a speed of 9 m/min.
Electrolytic polymerization was carried out under constant current conditions.

The film composited with polypyrrole was wound up with a winding roll 20. The obtained polypyrrole composite film exhibited a high electrical conductivity of 15Ω-1, and the polypyrrole content was estimated to be about 4 wt% based on elemental analysis.

Example 5 Using the apparatus of Example 4, various general-purpose plastic films were electrolytically polymerized under the same conditions as in Example 4. The results are shown in Table 1.

[Effects of the invention and industrial applicability As stated above,
The present invention uses a rotating roll or an endless belt as an electrode (anode), continuously supplies an inexpensive general-purpose plastic film to the electrode (anode) from the outside, and applies a voltage between it and a counter electrode (cathode). The pyrrole in the electrolytic solution is electrolytically polymerized on the surface and/or inside of the plastic, and the obtained conductive polypyrrole composite film is continuously taken out from the electrolytic cell and wound up,
It is possible to industrially and continuously produce a uniform N-conducting polypyrrole composite film with extremely high productivity.

The conductive polypyrrole composite film obtained by the method of the present invention can be suitably used in various fields such as antistatic materials, electromagnetic shielding materials, and photoelectric films.

[Brief explanation of drawings]

1 to 4 are conceptual diagrams showing apparatus suitable for carrying out the present invention. Patent applicant Mitsui Toatsu Chemical Co., Ltd. Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] (1) A method for producing a conductive plastic composite film by polymerizing and compositing pyrrole on the surface and/or inside of an insulating plastic film by electrochemical reaction, the method comprising: a rotating film having at least a conductive surface; A roll or a rotating endless belt is immersed in a pyrrole-containing electrolytic solution bath to serve as a rotating electrode, and the pyrrole is electrolytically polymerized while supplying the film to the immersed roll or endless belt to form a composite film. A method for continuously producing a polypyrrole composite film, characterized by continuously taking out the composite film outside an electrolytic cell.