JPS63313412A - Conductive compound film - Google Patents

Abstract

PURPOSE:To obtain a new compound film which is especially excellent in the uniformity of conductivity by forming a conductive macromolecular compound layer in a macromolecular film containing fine particles of inorganic compound in a dispersed state. CONSTITUTION:A conductive macromolecular compound layer is formed in a macromolecular film containing inorganic fine particles in a dispersed state. Fine particles of nonconducting inorganic substance and macromolecular substance are kneaded together and molded to form a film. As a nonconducting inorganic substance, there are silicon oxide, calcium carbonate or basic magnesium carbonate. According to a purpose, one of these inorganic substance is selected and mixed uniformly with a macromolecular substance, and a film of a characteristic corresponding to the kind of an inorganic substance is obtained. The film has high uniform conductivity on the whole area; therefore it can be applied to a wide range of usage as a conductive film.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a conductive composite film, and particularly aims to provide a novel composite film with excellent uniformity of conductivity. be.

The conductive composite film according to the present invention can be used widely as a conductive material such as in switches, switches, A1G materials, etc., as an electrode material in power storage systems, batteries, etc., as a semiconductor element, or as a photoelectric conversion element such as a solar cell. It is used in many technical fields.

[Prior art] Conventionally, as conductive polymer compounds, polyacetylene,
A large number of these polymers are known, including polyparaphenylene, polyparaphenylene vinylene, polyparaphenylene sulfide, polypyrrole, polythenylene, polythiophene, and polypyridazine.

When reduced), it usually exhibits a conductivity activity of 1 to 1,0 OOs/ca+. These conductive polymer compounds can be easily synthesized by various known methods.

For example, in the case of polypyrrole, BF'', AsF-1AsF6-1SbF are added to the organic solvent solution of the roll.
-1SbCJ-1PF”, Cρo4-1) (SO
When electrolysis is performed by adding a salt containing 7 ions such as ``, So4'-, such as tetrabutylammonium barchlorate, Cj04- ions are doped into the pyrrole polymer and formed in a film form on the anode. do.

On the other hand, “Polymer Preprints, Jap
an” magazine, Vol. 33, No. 4, pp. 844-845 (1
A paper published in 1998 (1984) has attracted attention as it discloses that when pyrrole is electrolytically polymerized on an electrode substrate coated with a polymer, a II composite film of the used polymer and polypyrrole can be obtained. Ta.

[Problems to be Solved by the Invention] As described above, the 112 polymer compound can be easily obtained by various methods. This does not result in a composite film, and there is a problem that, for example, the electric power differs by several times locally or on the front and back sides.

[Means and effects for solving the problems] The present inventors have conducted extensive research to solve the above-mentioned problems in the prior art, and as a result of various studies on conductive polymer compounds, have selected the electrolyte to be used. The inventors have discovered that it is possible to always form a conductive polymer compound layer with uniform gi conductivity over the entire surface, leading to the present invention. That is, the present invention is a conductive composite film characterized by forming an electroconductive polymer compound layer on a polymer film containing fine particles of an inorganic compound in a dispersed state.

The present invention will be explained in detail below.

Materials for the polymer film in the present invention include polyethylene, boria [cobylene, polybutylene, polymethylpentene, polyamide resins, polyether resins such as polyoxymethylene, polyethylene terephthalate,
Polyester resins such as polyethylene naphthalate and polyethylene oxide, cellulose resins such as cellulose diacetate, cellulose triacetate, and cellulose nitroacetate,
Ethylene-acrylic acid ionomer, polystyrene, ethylene-ethyl acrylate copolymer, polymethyl methacrylate, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl acetal, polycarbonate, silicone resin, Plastics such as epoxy resin, polyamide, polyimide, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, butyl rubber, ethylene-vinyl acetate elastomer, styrene-
Butadiene rubber, butadiene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, silicone rubber, epichlorohydrin rubber, tetrafluoroethylene-propylene rubber, urethane rubber, natural rubber, isoprene rubber, polysulfide rubber, nitrile-isoprene rubber, etc. There are many natural and synthetic rubbers. Two or more types of these may be blended as appropriate, and various compounding agents may be added.

One of the most distinctive features of the present invention is the use of these polymeric substances mixed with finely divided non-conductive inorganic substances and molded into a film-like body.

Examples of the non-conductive inorganic substance include silicon oxide, calcium carbonate, basic magnesium carbonate, aluminum silicate, aluminum oxide, hydrated alumina, magnesium hydroxide,
These include talc, calcium sulfate, barium sulfate, etc. By selecting these inorganic substances as desired and uniformly mixing them, materials with various characteristics can be obtained.

The particle size of the particulate inorganic substance is relatively small, for example 1 to 5 μm, more preferably 0.02 to 0.5 μm.
A certain degree is used.

The ratio of mixing the particulate inorganic substance with these polymeric substances is 3 to 2004 parts by weight per 100 parts by weight of the polymeric substance,
Preferably it is 5 to 100 parts by weight. Further, processing aids, stabilizers, cross-linking agents, etc. may be added to the composition consisting of the above-mentioned polymeric substance and inorganic substance, as desired, in order to improve the formability into a film and the electrical properties of the conductive film. be able to.

Next, some of the compositions will be illustrated.

Composition Example 1 Polyvinyl acetate (100 parts by weight) and barium sulfate (50 parts by weight)
parts by weight).

Composition Example 2 Calcium carbonate (4 parts by weight) in polyvinyl chloride (100 parts by weight)
0@ffi parts), tribasic barium sulfate (10 parts by weight)
and plasticizer DOP (20 Juumaibu).

Chlorinated polyethylene (chlorine 140%> (100 parts by weight)
Contains calcium ViA acid (50 parts by weight).

There are various known methods for forming a composition prepared in this way into a film, such as a solution casting method, a spin cord method, and a melt compression method. It can be used as a polymer film in accordance with the present invention.

Among the above methods, when using an organic solvent, examples of the organic solvent include alcohol solvents such as methanol, ethanol, and propatool, ester solvents such as ethyl acetate and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, There are various solvents such as ketone solvents such as acetone and cyclohexanone, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. More than one species can be used in combination.

Then, the thickness of the film obtained during this molding is determined,
The thickness depends on the use of each composite film, but it is usually about 0.05 to 1.01 IIm thick.

Next, a layer of a conductive polymer compound is electrochemically generated on the polymer film obtained as described above, that is, a monomer that generates a conductive polymer compound is electrochemically added to the polymer film in an electrolyte solution. The polymer is polymerized and deposited in layers on a polymer film. This is one of the other features of the invention.

Examples of this monomer include virol, N-alkylvirol, N-arylvirol, virol in which the carbon atom is substituted with monoalkyl 6 or dialkyl,
There are virols in which carbon atoms are substituted with monohalogen or dihalogen, and examples of substituted virols include 3.4-dialkylvirol, 3.4-diarylvirol, 3-alkyl-4-arylvirol, etc. rubirol, 3-7-aryl-4-alkylvirol, especially alkyl groups having 1 to 4 carbon atoms, aryl groups such as phenyl, tolyl, and xylyl groups, and 3,4-dichlorovirol substituted with In addition, comonomers to be copolymerized with the various virols mentioned above include alkynes such as acetylene, polynuclear aromatic compounds such as oligophenylene, acenaphthene, phenanthrene, or tetracene, and other 5- and/or 6-membered heterocycles. Aromatic compounds of the formula Aromatic compounds, and also other heteroaromatic ring compounds, in particular contain 1 to 3 heteroatoms in the ring system, and at said heteroatoms or ring carbon atoms, e.g. These include heteroaromatic ring compounds substituted with an alkyl group having 6 carbon atoms. Examples of heteroaromatic ring compounds particularly suitable as comonomers are furan, thiophene, thiazole, oxazole, thiadiazole, imidazole, pyridine, 3,5-dimethylpyridine, pyrazine, and 3,5-dimethylpyrazine.

Particularly preferred comonomers are 5-membered heteroaromatic compounds, such as furan, thiophene, thiazole, thiadiazole. If virol is used together with other comonomers, the ratio of virol to other comonomers can be varied within wide limits, for example in the range from 1:99 to 99:1. Preferably such a comonomer mixture contains at most 2
0-90fi1% and other comonomers 80-10% by weight
Contains.

In order to deposit these conductive polymeric compounds on polymeric films, virol and optionally virol and comonomer are anodized in an electrolyte solution in the presence of a suitable conductive salt and polymerized during this process. It is then deposited in a layered manner. In this case, the monomer concentration is usually about 0.1 mol per 1j of solvent. As this electrolyte solvent, a polar organic solvent capable of dissolving the monomer and/or the conductive salt can be used. When using an organic solvent that is miscible with water, a small amount of water, generally 1% by weight of water relative to the organic solvent, can be added to increase the conductivity. Useful electrolyte organic solvents are, for example, alcohols, ethers such as 1,2-methoxyethane, dioxane, tetrahydrofuran and methyltetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, methylene chloride, N-methylpyrrolidone, and propylene carbonate, Likewise mixtures of these solvents or also polyglycols derived from ethylene glycol, propylene glycol or tetrahydrofuran, polybutylene glycol, or ethylene oxide/propylene oxide copolymers, and as described in U.S. Pat. No. 3,574,072. It can be an aqueous electrolyte system such as

Furthermore, the above-mentioned conductive salts include known and customary ionic or ionizable compounds which lead to electrochemical polymerization of the monomers or comonomers used, in particular those containing strong oxidizing acids or acidic groups. An aromatic compound having an anion substituted with an alkyl group and/or a nitro group can be used. Useful conductive salts include alkali metal cations as cations, especially LI, Na+ or Ni+, NO and NO31,
or especially nitrogen and phosphorus, such as RN+ and R4R+ (
In this formula, each group R is a salt containing an onium cation (hydrogen atom, lower alkyl group, alicyclic group, aromatic group, etc.), and examples of this type of cation include tetramethylammonium cation. ion, tetraethylammonium cation, tri-n-butylammonium cation, tetra-n
-butylammonium cations, triphenylphosphonium cations, and tri-n-butylphosphonium cations. Other useful conductive salts are BF6-1AsF-1AsF-1SbF, especially as anions,
, -1SbCj-1PF -1CjO-1H3O4-
It is a salt containing an anion such as 1so4'. Still other conductive salts include anions of aromatic compounds having acidic groups, such as C6H5C00- anions and anions of aromatic sulfonic acids optionally substituted with alkyl groups. Particularly preferred is a 391 group containing a benzenesulfonic acid anion or a tosylate anion.

Further examples of conductive salts include aromatic compounds having acidic groups, which may be substituted with nitro groups (e.g., nitrophenol, nitro group-substituted aromatic carboxylic acids, and nitro group-substituted aromatic compounds). are substituted with aromatic sulfonic acids, especially nitro-, dinitro-, trinitro-phenol,
Examples include benzoic acid, nitro-, dinitro-, and trinitro-benzenesulfonic acid.

The amount of the conductive salt added is generally about 0.001 to 1 mol, particularly about 0.01 to 0.1 mol, per 1M of electrolyte solvent.

As described above, in order to deposit these conductive polymer compound layers on a polymer film, fine particles of a non-conductive inorganic substance are placed as a cathode and an anode in an electrolytic cell with or without a diaphragm. An electrolyte solution and the monomer or the monomer and the comonomer are dissolved and housed in a tank at a desired concentration, and an external DC power source is connected to the cathode and the anode. This can be carried out by performing anodic oxidation treatment. The conditions for the applied power can be determined as appropriate by the practitioner. As the anodic oxidation progresses, the monomer or the monomer and the comonomer polymerize and precipitate on the polymer film. Therefore, by performing this anodic oxidation while continuously moving the polymer film, it is possible to form a continuous conductive polymer compound layer on a long polymer film.

The composite film thus produced can be washed with fresh solvent, dried and then cut or rolled into a form suitable for the intended use. If desired, a polymer film such as plastic or rubber may be attached or coated on the conductive polymer compound layer of this composite film in order to stabilize the conductivity over a long period of time. Regardless of the form, an electrode material of any form can be appropriately bonded to the conductive polymer compound layer, and an electrode can be provided to serve as a power input section.

[Examples] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.

Tomo IL Nisilica “Aerosil” (product name Nippon Aerosil@manufactured,
Particle size: 30mμm) 10IC! After dissolving the polyvinyl chloride resin mixed and dispersed at 1% ff in tetrahydrofuran, it was applied to the Nesa glass electrode material using a spin cord.
A film with a thickness of 30 μm was formed.

The coated electrode material manufactured in this way was immersed in an electrolytic bath containing pyrrole with various electrolytes, and electrolytic oxidation polymerization was performed to form a polypyrrole layer with a thickness of 30 μm on the electrode material. At this time, a platinum electrode was used as the counter electrode, and the test was carried out under conditions of a voltage of 1 to 2.2 . The obtained composite film is referred to as a "sample".

Comparative Example 1 Example 1 except that a film of polyvinyl chloride resin containing no silica was formed on the platinum electrode.
A composite film was prepared in the same manner as in the case of . This composite film is referred to as a "comparative sample."

As above, g! The electrical conductivity of the front and back surfaces of each sample was measured by the four-probe method, and the results are shown in Table 1.

As shown in Table 1, it is clear that the sample according to the present invention exhibits uniformly high electrical conductivity on both the front and back sides compared to the comparative sample, which specifically demonstrates the effects of the present invention. .

[Effects of the Invention] As explained in detail above, the conductive composite film of the present invention has uniform high conductivity over the entire surface of the composite film even when various electrolytes are used, so it can be widely used as a conductive film. It can be applied to various uses, and its industrial value is extremely large.

Claims (1)

[Claims] (1) A conductive composite film characterized by forming a conductive polymer compound layer on a polymer film containing fine particles of an inorganic compound in a dispersed state.