JPS63308032A - Method for manufacturing conductive film - Google Patents

Abstract

PURPOSE:To obtain the titled film of any size in a simple and continuous mass production system, by electrochemical polymerization of pyrrole in an electrolyte solution while moving both the anode and cathode members in said solution parallel and continuously. CONSTITUTION:The objective film can be obtained by electro chemical polymerization of pyrrole or between pyrrole and a comonomer (pref. furan) in an electrolyte (pref. THF) solution while moving both the anode and cathode members in said solution parallel and continuously to make the objective polypyrrole film separate out on the surface of the anode member. Specifically, a drum whose surface is constructed with a raw material of the anode member and a second drum whose surface is constructed with a raw material of the cathode member are immersed in the electrolyte solution to carry out electrolysis while revolving said drums. In general, said electrolyte solution is preferably incorporated with an electrically conductive salt such as tetraethylammonium p- toluenesulfonate supporting salt.

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a method for producing a conductive film, and particularly to a method for producing a conductive film made of a polymer containing beer as a monomer component. The conductive composite film produced by the present invention can be used for conductive materials such as switches, switches, shielding plates, etc.; electrode materials for power storage systems, batteries, etc.; shielding materials; semicircular elements; solar cells, etc. Light density conversion element; @medium; Used in a wide range of technical fields as an antistatic treatment agent for plastics. [Conventional technology] Conventionally, as conductive polymer compounds, polyacetylene,
Many are known, such as polyparaphenyline, polyparaphenylene vinylene, polyparaphenylene sulfide, polypyrrole, polythenylene, polythiophene, and polypyridazine. When these polymers are doped (oxidation and reduction of polymer compounds), they usually have a concentration of 1 to 1.0 OO8/C.
! The conductivity of R becomes more active. These conductive polymer compounds can be easily synthesized by various known methods. For example, U.S. Pat. No. 3,574,072 or r
J, C, S, Chem, Co1n+, J magazine (197
In the case of polypyrrole, BF -1AsF -1AsF6-1SbF5
-1SbCj-1PF6-1CJO4-1H8O-,S
When electrolysis is performed by adding a conductive salt containing an anion such as O2, such as tetrabutyl ammonium perchlorate, for example, CfJO4- ions are doped into the pyrrole polymer and formed in the form of a film on the anode member. In the synthesis of this polymer, the anion of the 41 salt acts as a complexing agent, and the system consisting of the pyrrole polymer and complexing agent accelerates electrical conductivity. Electrochemical polymerization of pyrrole is usually carried out by placing pyrrole in an electrolytic solution in an electrolytic cell containing an electrode member made of a noble metal such as platinum, and applying electricity to perform anodic oxidation.
Pyrrole polymer is deposited on the anode part/material and formed into a film-like material. However, in this prior art, the size of the film of the pyrrole polymer "polypyrrole" obtained is limited by the size of the electrode member surface, and it is difficult to use a fixed electrode surface with a specific size. With the J type electrode member, it is virtually impossible to manufacture a large or long film. Therefore, after that, for example, Japanese Patent Application Laid-Open No. 59-2388
As described in Publication No. 9, in the above-mentioned polypyrrole polymerization reaction apparatus, an anode such as a drum or an endless belt that rotates continuously and constantly forms a new anode surface in the electrolyte solution is used as an anode member. The development of methods using components made it possible for the first time to produce large or long polymeric films. [Problems to be Solved by the Invention] However, if the T1 manufacturing operation is continued for a long time in the above method, the cathode member that has been immersed in the reaction tank for a long time will lose its cathode activity, and the problem will often occur. There was a problem in that the pole members had to be replaced. Therefore, in practice, large or long films could not be produced continuously for a long period of time.

[Means and effects for solving the problems] The present invention solves the problem of 12% 1ff 1 in the above-mentioned conventional technology, and provides a novel method that can easily and continuously mass-produce pyrrole polymer films of any size. The purpose is to provide a method for That is, the present invention enables pyrrole polymerization by electrochemically polymerizing pyrrole or pyrrole and a comonomer in an electrolyte solution, and depositing the resulting polymer in the form of a film on the surface of an anode member placed in the solution. In the method of producing a composite film, in the solution, 1li14i members and ll! This is a continuous method for producing a pyrrole polymer film, characterized by moving the ViA member in parallel and continuously, and further including pyrrole or pyrrole and a comonomer between the anode member and the cathode member that move in parallel as described above. This is a method for producing a film-like polymer of pyrrole, which is characterized by passing an electrolyte solution containing the polymer. The present invention will be explained in detail below. As mentioned above, the invention is based on the electrochemical polymerization of pyrrole or pyrrole and a comonomer in an electrolyte solution. The pyrrole used in the present invention includes pyrrole, N-alkylpyrrole, N-arylpyrrole, pyrrole in which a carbon atom is substituted with monoalkyl or dialkyl, and pyrrole in which a carbon atom is substituted with monohalogen or dihalogen. pyrrole, etc. For example, the substituted pyrrole is 3.4
-dialkylpyrrole, 3,4-diarylpyrrole,
3-alkyl-4-arylpyrrole, 3-aryl-
4-alkylpyrroles include alkyl groups having 1 to 4 carbon atoms, aryl groups such as phenyl, tolyl, and xylyl groups, and chlorine-substituted 3,4-tylpyrrole. This is a preferable example. Comonomers to be mixed and copolymerized with the above-mentioned various pyrroles include alkynes such as acetylene, polynuclear aromatic compounds such as oligophenylene, acenaphthene, phenanthrene, or tetralene, and other 5- and/or 6-membered heterocyclic aromatics. and also other heteroaromatic ring compounds, in particular those containing 1 to 3 heteroatoms in the ring system, and in which the heteroatoms or ring carbon atoms contain e.g. alkyl groups, especially those having 1 to 6 carbon atoms. A heteroaromatic ring compound optionally substituted with an alkyl group having a carbon atom (preferably at least two so that anodization can be carried out easily)
ring carbon atoms are unsubstituted. ) etc. And heteroaromatic ring compounds as suitable comonomers include furan, thiophene, thiazole, oxazole,
Examples include thiadiazole, imidazole, pyridine, 3,5-dimethylpyridine, pyrazine, and 3,5-dimethylpyrazine. Particularly preferred are 5-membered heteroaromatic ring compounds such as furan, thiophene, deazole, and thiadiazole. In the present invention, when pyrrole is used together with other comonomers, the preferred mixing ratio of both is:
It can be within a wide range, specifically within the range of 1:99 to 99:1 (juki ratio). To produce film-like polymers, the pyrrole or the pyrrole and the comonomer are anodized in an electrolyte solution in the presence of a suitable electrically conductive salt and polymerized in the process. In this case, the monomer concentration is usually about 0 per gram of electrolyte solution.
．． It is 1 mole. However, this concentration may be significantly lower or significantly higher. In the method of the invention, the concentration of monomers and conductive salts in the electrolyte solution gradually decreases if the electrolysis time is very long, so that if desired they can be replenished fresh during the electrolysis. This operation is most preferably carried out in such a way that the electrolyte solution is circulated by a pump and the monomer and/or conductive salt is prepared at the desired W outside the electrolyzer body. However, when producing monolithic, homogeneous polymer films by the continuous process of the present invention, it is not necessary to force a constant concentration of monomer and/or conductive salt in the electrolyte solution, and therefore the above-described operation is not necessary. It can be carried out in a simple closed electrolytic cell without circulating the electrolyte solution. In the method of the invention, the monomers and/or conductive salts mentioned above are dissolved in an electrolyte solvent. As this electrolyte solvent, any known and commonly used polar organic solvent can be used. If a water-miscible organic solvent is used, water can be added to increase the conductivity, generally up to 1% by weight relative to the organic solvent. Preferred electrolyte organic solvents include, for example, alcohols, ethers, such as 1,2-methoxyethane, dioxane, tetrahydrofuran and methyltetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, methylene chloride, N-methoxyridone,
and pyrene carbonate, as well as mixtures of these solvents or polyglycols derived from ethylene glycol, propylene glycol or tetrahydrofuran, or ethylene oxide/
Examples include propylene oxide copolymers. Additionally, aqueous electrolyte systems such as those described in U.S. Pat. No. 3,574,072 may also be used. Further, as the conductive salt, an ionic or ionizable compound, especially one having an anion of an aromatic compound having a strong oxidizing acid or an acidic group and optionally substituted with W1 by an alkyl group and/or a nitro group, is used. can be used. Preferred conductive salts include alkali metal ions as cations, especially Ll, Na, N,
o and cations such as NO2+, or in particular nitrogen and phosphorous, such as the RN type or the R2H type, in which the radicals R are independently hydrogen atoms, lower alkyl groups, 1- to
having 6 carbon atoms, cycloaliphatic radicals, advantageously 6 to
with 14 carbon atoms, or an aromatic radical, preferably with 6 to 14 carbon atoms. ), for example, compounds containing onium cations such as tetramethylammonium cation, buteraethylammonium cation, tri-n-butylammonium cation, tetra-n-butylammonium cation, triphinylbosphonium cation, etc. be. On the other hand, as an anion of conductive salt, BF -1AsF4-1AsF
-SbF -5bCjl-1PF6''', e!JO
Anions such as -, H3O-, So, furthermore, for example, a C6H5C00- anion, an anion of an aromatic sulfonic acid optionally substituted with an alkyl group, and particularly preferably an anion of pembene sulfonate or a tosylate anion. There are anions of aromatic compounds with groups. Other embodiments of the anion include nitro group-substituted acidic nido-O aromatic compounds, such as nitrophenol, nitro group-substituted aromatic carboxylic acids, and nitro group-substituted aromatic sulfonic acids. Conductive salts such as nido-O-, dinitro-D-, trinitro-phenol, nitro-, dinitro-, trinitro-benzoic acid, and nido-O-, dinitro-, trinitro-benzenesulfonic acid are particularly preferred. The conductive salt concentration used in the method of the present invention is generally from o, ooi to 1 mol per 1.1 liter.
Preferably it is 0.01 to 0.1 mol. The method of the invention comprises a tank with or without a diaphragm;
It can be carried out using an electrolytic cell or an electrolytic device consisting of a cathode member, an anode member, and an external DC power source. The main feature of the present invention is that the electrochemical polymerization of pyrrole
An anode member and a cathode member that are continuously movable and are configured to form a plane in succession are moved in an electrolyte solution, or further between an anode member and a cathode member that move in parallel as described above. This is carried out while passing an electrolyte solution containing pyrrole or pyrrole or a comonomer. A simple and very advantageous embodiment of the method of the present invention is to use a cylindrical body whose surface is coated with the thread material of the anode member or whose surface is formed of the material of the anode member, and a cylinder whose surface is coated with the thread material of the anode member, and a cylinder whose surface is coated with the thread material of the anode member, and a cylinder whose surface is coated with the thread material of the anode member. The cylindrical body on which the material is applied or the cylindrical body whose surface is formed by the material of the cathode member is immersed in an electrolyte solution and rotated. In this case, the cylindrical body may be in the form of a drum, a simple drum jacket, ie, a hollow cylindrical body, or the like. Furthermore, instead of the cylindrical body, an endless belt whose surface contains the material for the anode member and an endless belt whose surface contains the material for the cathode member are used, which circulate and run around the O-ra arranged in the electrolyzer. You can also do that. Within the electrolyzer, these drums or endless belts are run at a speed that deposits a desired thickness of polymer film on the anode member under each electrolysis condition. after that,
The formed film-like polymer is peeled off from the surface of a drum that rotates continuously in the electrolyte solution or from the surface of an endless belt that is continuously conveyed through the electrolyte solution, and in some cases, the conductive material that adheres to the surface is removed. After washing with a solvent to remove salts and drying, it can be rolled up. The endless belt that circulates and runs around the drum or roll in the J5 embodiment of the present invention may be completely immersed in the electrolytic solution. In this case, the polymer film that forms in the electrolyte solution has to be drawn off and peeled off from the surface of the anode element, for which purpose a suitable peeling device, e.g. a scraper, a doctor knife or a periodically running Lunar or double-sided adhesive films can be used. However, in general, only a portion of the endless belt that circulates and runs around a rotating drum or roll is immersed in an electrolyte solution, whereby the film-like polymer deposited on the anode member in the electrolyte solution is carried out from the electrolyte solution. It can be stripped from the surface of the drum or endless belt outside the solution, optionally using a suitable stripping device as described above, and then the anode member with the surface exposed by stripping is run back into the electrolyte solution. Uru. Immersing only a portion of the endless belt that circulates around the rotating drum or roll in the electrolyte solution is a convenient method in terms of operation, particularly for peeling off the film-like polymer from the anode member. . In the method of the invention, it is possible in principle to use any and all known electrode materials as the anode component. If the anode member is the surface of a drum or endless belt, the surface should be treated in such a way that it can be peeled off without difficulty from the film-like polymer formed. In this case, the anode member is preferably made of a noble metal, such as platinum, molybdenum, tungsten, or stainless steel, especially nickel or titanium, and it is desirable that the surface of the anode member be as smooth as possible. When the anode member is, for example, a finite strip that is drawn into the electrolyte solution from a roll, the film-like polymer obtained as the anode member in addition to the above-mentioned metal will stick to the anode member and therefore will not peel off from the anode member. It is also possible to use materials for which it is impossible or extremely difficult to do so. In such a case, for example, the anode member may be a 1m polymer, such as p-
This is the case when using conductive polyacetylene or p-conductive polyphenylene. In this case, the electrically conductive polymer can be used directly in film form or applied in a suitable manner to the support. In this case, pyrrole and optionally used in combination ``mono! - chemically bonds and polymerizes on the conductive polymer used as the anode member. This method therefore allows the production of layered copolymer films with high electrical conductivity of arbitrary length and size. For example, when a formed film-like polymer is peeled off from an anode member using a belt that circulates around a rotating drum or roll, a non-3911 It is extremely advantageous if the material is coated with a synthetic material. For this coating, for example polyethylene,
These include polymers such as polypropylene, borisdylene and especially polytetrafluoroethylene. This type of coating at the edges facilitates peeling off the polymeric film of the anode member. This is because the polymer is deposited only between the coated edges on the anode member, and the polymer film is easily peeled off at these edges. Similarly, when using an endless belt that circulates and runs around the []-ru,
The back side of the belt, ie the side running on the transport rolls, may be made of or coated with a non-conductive material, so that the polymer is deposited only on the surface side of the endless belt. As explained by Jun Rai, in the prior art, if a cathode member is fixed in a reaction solution system and the above manufacturing operation is continued for a long time while immersed, the cathode member may lose its cathode activity. However, in the present invention, the anode member and the cathode member in the electrolyte solution mentioned above are always kept clean. Therefore, it is desirable to wash the surface of the moving anode member and cathode member, particularly the cathode member, in a portion of the electrolyte solution or in the electrolyte solution. Namely 1. In the above-mentioned electrochemical reaction of the pyrrole-based composition of the present invention, not only a pyrrole polymer is produced by an oxidation reaction on the anode member, but also other reaction products are produced by a reduction reaction on the cathode member, and this reaction Product Il! When the concentration increases, the electrode action at the cathode deteriorates and the overall electrochemical reaction slows down, and at even higher concentrations, the electrochemical reaction may stop. Therefore, in the apparatus for carrying out the manufacturing method of the present invention, a cleaning mechanism such as a friction cloth or a brush is installed in the rotating or traveling process of the drum or endless belt constituting the electrode, and the anode member and The electrode surface of the cathode member is always kept clean by rubbing, polishing, etc. By doing so, it is possible to consistently produce old quality polymer films for long periods of time. According to the method for producing a conductive film of the present invention, self-supporting conductive films of various thicknesses can be produced. The thickness of the obtained film is generally 10 to 100 μm
is within the range of In this case, the thickness of the film can be varied and adjusted by the convection time of the anode active material in the electrolyte solution and, in particular, by the current density. The obtained film made of pyrrole polymer can be washed with a solvent to remove the attached conductive salt, dried at a temperature of 30 to 150°C, preferably under vacuum, and then cut and processed into any shape. It can be used for various purposes. The polymers of pyrrole produced according to the invention are highly conductive systems that contain, at least in part, the anions of the conductive salts used in the production process. Therefore, this polymer can also be referred to as a complex consisting of the cation and opposite ion of the pyrrole polymer. The electrical conductivity of pyrrole polymers is generally 100 as measured by the two-point or four-point method.
~102Ω-1cM-1. In other respects, the conductive film produced according to the present invention has the same properties as those produced by conventionally known methods, and can be used for various purposes. [Example 1] A conductive film of the present invention was prepared using the electrolysis apparatus shown in FIG. J construction method was implemented. In this electrolyzer, cathode belt rolls 5C-1, 5C-2, 5C-3, 5cm4 in the glass electrolytic cell 1,
etc., a stainless steel film belt with a width of 10α is used as the cathode member 3, and anode belt rolls 5a-1, 5a-
A platinum-plated nickel film belt having a width of 10 υ and having an insulating coating on the back side was suspended and arranged as an anode member 4 on 2, 5a-3, 5a-4, etc. The cathode belt 3 and the anode belt 4 are arranged substantially parallel within the electrolytic cell 1. 5. Acetonitrile in the electrolytic cell 1.
OOOmJl, containing electrolyte solution 2 consisting of pyrrole 25Q and 100 g of tetraethylammonium paratoluenesulfonate supporting salt, and running both belts 3.4 at a speed of 150
Run at α/min, current density 5 mA/cm2
The test was carried out by turning on the power. As a result, a polypyrrole film 6 with a thickness of 60 μm was formed on the anode belt 4. This film 6 is peeled off from the anode belt 4 by the rotation of the winding drum 7, and wound up.
Furthermore, the desired polypyrrole film was obtained by washing with acetonitrile and drying. When we measured the electrical conductivity of this polypyrrole film, we found that
It was 30 S/crtt. Electrolysis could be carried out continuously for 12 hours. [Effects of the Invention] According to the present invention, in an apparatus for carrying out a method for manufacturing a conductive film, without causing functional deterioration of the cathode member,
The extremely excellent effect that high-quality conductive polypyrrole films can be easily and continuously mass-produced economically can be achieved.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an outline of a continuous manufacturing apparatus for conductive films for carrying out the present invention. 1: Electrolytic tank, 2: Electrolyte solution, 3: Cathode member (belt), 4: Anode member (belt), 5 cm 1.5 cm 2.5 cm 3.5 cm 4: Cathode belt "1-ru, 5 a-1, 5 a- 2,5a-3,5a-4:
Roll for anode belt, 6: Polymer film, 7: Winding drum. 1: t# tank Sa: 1 for pongee belt 2:
Telephone condolence service Q -+,
3: Yin glaze grain 5c: Yinyu held m4:
Yang 8# Wood X Mouth -J
6: V to 6 fills 7: Winding drum

Claims (2)

[Claims] (1) Pyrrole polymers are produced by electrochemically polymerizing pyrrole or pyrrole and a comonomer in an electrolyte solution, and depositing the resulting polymer in the form of a film on the surface of an anode plate placed in the solution. 1. A continuous method for producing a pyrrole polymer film, which comprises moving an anode member and a cathode member in parallel and continuously in the solution. (2) A film of pyrrole according to claim 1, characterized in that an electrolyte solution containing pyrrole or pyrrole and a comonomer is passed between an anode member and a cathode member that move in parallel and continuously. Method for producing polymers.