JP2007224182A - Electrically conductive polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically conductive polymer composition that comprises a π-conjugated polymer and a dopant agent imparting high electrical conductivity to the π-conjugated polymer and maintaining the high electrical conductivity even under a high-temperature and high-humidity environment. <P>SOLUTION: The electrically conductive polymer composition comprises a π-conjugated polymer and a solid acid having a sulfonic acid group wherein the solid acid having a sulfonic acid group is a polycondensation compound having a sulfonic acid group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

In recent years, with the development of electronics, new electronic materials have been developed. In particular, remarkable technological innovations have progressed in the field of functional organic materials, and even when limited to conductive materials, electron-donating compounds are doped with π-conjugated polymers such as polyacetylene, polyaniline, polyparaphenyl, polypyrrole, and polythiophene. Conductive polymer materials have been developed, such as solid electrolytes in aluminum and tantalum solid electrolytic capacitors, which are component parts of PCs and mobile phones, as well as EL hole injection layers, semiconductor charge-up prevention agents, and metal protection. Rust agent, antistatic / antistatic agent, electromagnetic shielding agent, battery, electrode material, lithium secondary battery, solar cell, fuel cell, sensor, gas sensor, biosensor, temperature sensor, humidity sensor, pressure / strain sensor, electrochromism , Optical switching element, optical recording element, electro Minence element, nonlinear optical material, coating modified electrode, catalytic function, permeation control film, ion permeable film, amino acid permeable film, actuator, filler, through-hole plating of printed wiring board, photo-induced electrochromism (photoelectrochromism), electrochromic The use is expanding in various fields such as devices, bringing business opportunities to many companies.
However, in order to expand the practicality of these conductive polymer substances, further improvement in electrical conductivity and environmental stability such as heat resistance and moisture resistance are major issues.
With respect to these problems for practical application, in particular, regarding environmental stability, in Patent Document 1, a π-conjugated polymer compound using m-sulfobenzamides as a dopant agent and in Patent Document 2, m-fluorobenzenesulfone The use of acid derivatives as dopant agents is stated.
However, when moisture coexists in addition to high temperature (for example, in the air at 150 ° C.), there are problems that conductivity is lowered and sulfonic acid groups of the dopant agent are eliminated.
Therefore, it can be said that improving the stability at high humidity and high temperature is indispensable for expanding the practicality of the conductive polymer.

JP 2000-204074 A JP 2003-40856 A

An object of the present invention is to provide a conductive polymer composition containing a π-conjugated polymer and a dopant agent capable of maintaining high conductivity in a high-temperature / high-humidity environment together with the π-conjugated polymer. The purpose is to provide.

  The present invention relates to a conductive polymer composition comprising a π-conjugated polymer and a solid acid having a sulfonic acid group as a result of earnest research to solve the above problems.

  The present invention also relates to the above conductive polymer composition, wherein the solid acid having a sulfonic acid group is a polycondensation compound having a sulfonic acid group.

The present invention also relates to the above conductive polymer composition, wherein the π-conjugated polymer is polyaniline, polythiophene, or polypyrrole.

The conductive polymer composition of the present invention contains a π-conjugated polymer and a solid acid having a sulfonic acid group, and the solid acid having a sulfonic acid group is a sulfonic acid. It is a polycondensation compound having a group. Since the solid acid having a sulfonic acid group is a polycondensation compound having a sulfonic acid group obtained by sulfonating a compound obtained by cyclocondensation of an aromatic compound, the sulfonic acid group is hardly released and has excellent heat resistance. Yes. Moreover, since the said solid acid is a super strong acid body and its acid dissociation constant is high, it is estimated that it becomes an excellent dopant agent. The conductive polymer composition containing a π-conjugated polymer and a solid acid having a sulfonic acid group has a remarkable effect that it can maintain high conductivity even in a high temperature / high humidity environment as well as high conductivity. Play.
Further, the present invention is characterized in that the π-conjugated polymer of the conductive polymer composition is polyaniline, polythiophene or polypyrrole, and has high conductivity in a high temperature / high humidity environment. Furthermore, there is a further remarkable effect that high conductivity can be maintained.

Hereinafter, the present invention will be described in more detail.
The π-conjugated polymer in the present invention can be obtained by oxidative polymerization of monomers that are raw materials such as polyaniline, polythiophene, or polypyrrole.
The oxidative polymerization can be performed by a known method such as chemical oxidative polymerization, electrolytic polymerization, or photochemical oxidative polymerization.

  The oxidizing agent used for the oxidative polymerization in the present invention includes a metallic type and a nonmetallic type, and is not particularly limited as long as it can be oxidized. In the electrolytic oxidation polymerization, an oxidizing agent having an oxidation potential comparable to that of the electrolytic oxidation polymerization method for producing a highly conductive polymer in the reaction medium is suitable.

  Examples of the metal oxidant include iron (III) salt, molybdate (V) salt, ruthenium (III) salt and the like. Examples of non-metallic oxidants include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, peroxides such as benzoyl peroxide and hydrogen peroxide, sodium peroxyborate, peroxyboric acid, and peroxysulfuric acid. , Peroxy acids such as ammonium peroxysulfate, peroxysulfuric acid, potassium peroxysulfate, perchloric acids such as perchloric acid, copper perchlorate, chloric acids such as hypochlorous acid, sodium hypochlorite, potassium hypochlorite Can be mentioned.

  In addition, the addition of a compound serving as a catalyst for these oxidizing agents is performed as necessary. Examples of these oxidation catalysts include transition metal ions such as iron ions (II) and iron ions (III), organic transition metal complex compounds such as iron salen compounds, and peroxidases such as horseradish peroxidase.

Examples of the monomer that is a raw material of polythiophene in the present invention include a compound having a thiophene skeleton and a compound having a polycyclic sulfide skeleton.
Examples of the compound having a thiophene skeleton include 3-methylthiophene, 3-ethylthiophene, 3-n-propylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3- n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3-n-dodecylthiophene, 3-n-octadodecylthiophene, 3 -Methoxythiophene, 3-phenylthiophene, 3-thiophenecarboxylic acid, 3-thiophene aldehyde, thiophene-3-acetic acid, 3-thiopheneethanol, 3-thiophenmalonic acid, 3-thiophenemethanol, 3-fluorothiophene, 3-bromo Thiophene, 3-iodothiophene, -Cyanothiophene, 3-bromo-4-methylthiophene, 3,4-dimethylthiophene, 3,4-diethylthiophene, 3,4-butylenethiophene, 3,4-methylenedioxythiophene, 3,4-ethylenedioxy Although derivatives, such as thiophene, can be mentioned, it is not limited to these. These compounds are generally commercially available compounds, or can be prepared by known methods (for example, Synthetic Metals, 1986, Vol. 15, p.169). Polythiophene can be produced by oxidative polymerization of these alone or in combination of two or more.

  Examples of the compound having a polycyclic sulfide skeleton include a compound having a 1,3-dihydropolycyclic sulfide (also known as 1,3-dihydrobenzo [c] thiophene) skeleton, 1,3-dihydronaphtho [2,3- c) a compound having a thiophene skeleton, a compound having a 1,3-dihydroanthra [2,3-c] thiophene skeleton, and a compound having a 1,3-dihydronaphthaceno [2,3-c] thiophene skeleton. it can. These can be adjusted by known methods such as those described in JP-A-8-3156.

  Further, for example, a compound having a 1,3-dihydronaphtho [1,2-c] thiophene skeleton, a 1,3-dihydrophenanthra [2,3-c] thiophene derivative, a 1,3-dihydrotriphenylo [2 , 3-c] thiophene skeleton, 1,3-dihydrobenzo [a] anthraceno [7,8-c] thiophene derivatives, and the like can also be used.

  The condensed ring may optionally contain nitrogen or N-oxide, such as 1,3-dihydrothieno [3,4-b] quinoxaline, 1,3-dihydrothieno [3,4-b] quinoxaline-4-oxide 1,3-dihydrothieno [3,4-b] quinoxaline-4,9-dioxide, and the like, but is not limited thereto.

  Examples of the monomer that is a raw material for polyaniline in the present invention include compounds having an aniline skeleton. For example, 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline, 2-hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decyl Aniline, 2-fluoroaniline, 2-chloroaniline, 2-bromoaniline, 2-cyanoaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2,3-butyleneaniline, 2,3-methylenedi Examples thereof include compounds such as oxyaniline and 2,3-ethylenedioxyaniline. These compounds are commercially available and can be produced by known methods. Polyaniline can be produced by oxidative polymerization of these alone or in combination of two or more.

Examples of the monomer that is a raw material for polypyrrole in the present invention include compounds having a pyrrole skeleton. For example, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-pentylpyrrole, 3-hexylpyrrole, 3-heptylpyrrole, 3-octylpyrrole, 3-nonylpyrrole, 3-decyl Pyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-cyanopyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-butylenepyrrole, 3,4-methylenedioxy Examples of the compound include pyrrole and 3,4-ethylenedioxypyrrole. These compounds are commercially available and can be produced by known methods. Polyaniline can be produced by oxidative polymerization of these alone or in combination of two or more.
It is possible to produce a π-conjugated polymer by oxidative polymerization of a monomer that is a raw material of the polythiophene, a monomer that is a raw material of polyaniline, or a monomer that is a raw material of polypyrrole, alone or in combination of two or more.

Examples of the solid acid having a sulfonic acid group in the present invention include a polycyclic aromatic hydrocarbon in which two or more aromatic rings are condensed, or an aromatic polycyclic compound in which aromatic rings such as calixarene are assembled to sulfonic acid. The thing which has group is mentioned.
As the polycondensation compound having a sulfonic acid group in the present invention, an aromatic compound is heat-treated in the presence of a polycondensation agent under normal pressure, and the resulting polycondensation compound is sulfonated with a sulfonated agent. The heat treatment temperature is preferably 50 ° C. to 220 ° C., more preferably the heat treatment temperature is 90 ° C. to 150 ° C., and the aromatic compound is It is preferably in a liquid state at 50 ° C. to 220 ° C. under normal pressure, heat-treated in the presence of a polycondensation agent under normal pressure, and the resulting polycondensation compound is sulfonated with a sulfonated agent. .
More preferably, the aromatic compound is in a liquid state at 90 ° C. to 150 ° C. under normal pressure, and heat-treated at 90 ° C. to 150 ° C. in the presence of a polycondensation agent under normal pressure. Sulfonated with a sulfonating agent. The liquid state here means a state in which the reaction temperature is not lower than the melting point and not higher than the boiling point, or in a state where there is a liquid part dissolved in another liquid substance at the reaction temperature, for example, at a heat treatment temperature of 100 ° C. 80.2 ° C., boiling point 218 ° C.) means that coronene (melting point: 438 to 440 ° C.) exists.

  As the aromatic compound used in the present invention, any compound containing one or more aromatic rings can be used, and two or more of these compounds can be used in combination.

  Among them, when an aromatic compound that is in a liquid state at 50 ° C. to 220 ° C. under normal pressure is used as a raw material, it has higher protonic conductivity and excellent heat resistance, and excellent ion exchange capacity, catalyst performance, etc. It can be preferably used because it has a high degree of freedom in work safety, yield, and molecular design, is often reproducible and can be easily manufactured.

  Specific examples of the aromatic compound used in the present invention include benzene and substituent-containing benzene. Examples of the substituent include halogen group, phenyl group, alkoxyl group, amino group, hydroxyl group, N-oxide group, phenyl oxide group, amino group, hydrazyl group, ferdazyl group, nitro group, nitroso group, hydroxyl group, phosphate group, disulfide Group, mercaptan group, amide group, imide group, isocyanate group, vinyl group, (meth) acrylyl group, cyano group, carboxylic acid, aldehyde group, hydrocarbon group. The hydrocarbon group may be linear or cyclic, and the cyclic hydrocarbon may be aliphatic or aromatic, and may be monocyclic, polycyclic, or heterocyclic. It may be a ring. The hydrocarbon group may contain a substituent.

In addition, as the aromatic compound used in the present invention, polycyclic aromatic carbonization in which at least two or more aromatic rings such as naphthalene, pyrene, benzo (α) pyrene, benzoanthracene, anthracene, phenanthrene, coronene, and ketrene are condensed. Examples thereof include hydrogen or a substituent-containing polycyclic aromatic hydrocarbon.
Examples of the substituent include the above-described substituents.

In addition, as an aromatic compound used in the present invention, two or more aromatic rings such as biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexualphenyl, septiphenyl, octiphenyl, nobiphenyl, deciphenyl, hexaphenylbenzene are aggregated. Examples thereof include polyphenyl and substituent-containing polyphenyl.
Examples of the substituent include the above-described substituents.

In addition, as the aromatic compound used in the present invention, the benzene, the substituent-containing benzene, the polycyclic aromatic hydrocarbon, the substituent-containing polycyclic aromatic hydrocarbon, polyphenyl, the substituent-containing polyphenyl is an amide bond. , An aromatic ring containing one or more aromatic rings bonded by ester bond, ether bond, sulfone bond, imide bond, urethane group, urea bond, ketone bond, carbon-carbon double bond, carbon-carbon triple bond, etc. An aromatic compound containing an aromatic ring formed by combining one or more kinds of contained compounds or one or more of these bonds.
For example, polyaromatic sulfones, polystyrenes, polyphenols, polyimides, polyalkyds, polyamic acids, polymelamines, benzoguanamines, polybenzoguanamines, polybismaleimide-triazines, polyallyls, polyepoxies, polyamides , Polyamideimides, polyarylates, polyallyl sulfones, polybenzimidazoles, polycarbonates, polyether ether ketones, polyether imides, polyether ketones, polyether nitriles, polyether sulfones, poly Thioether sulfones, polyethylene terephthalates, polyamino bismaleimides, polyketones, polyphenyl ethers, polyphenyl sulfides, SAN resins, polyurethanes, polyxylates And the like can be mentioned synthetic polymers such as kind, but is not limited thereto.
More preferably, examples of the aromatic compound that is in a liquid state at 50 ° C. to 220 ° C. under normal pressure include benzene, benzoic acid, toluene, xylene, naphthalene, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-naphthol, Examples include, but are not limited to, 2-naphthol, biphenyl, pyrene, anthracene, benzoanthracene, and bis (N, N-dimethylaniline).
The heat treatment temperature range of the present invention may be any temperature at which a polycondensation reaction occurs, and is preferably 50 ° C to 220 ° C, more preferably 90 ° C to 150 ° C.

In addition, if the aromatic compound is in a liquid state at 50 ° C. to 220 ° C. under normal pressure, contact with the polycondensation agent is further improved, and thus it is presumed that the polycondensation reaction is facilitated to be effective. It is to be done.
Examples of the polycondensation agent used in the present invention include antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, iron chloride, and the like such as AlCl ₃ , FeCl ₃ , SbCl ₅ , BF ₃ , ZnCl ₂ , TiCl ₄ , HF, H ₃ PO ₄ , P ₂ O ₅ , Lewis acid catalyst such as polyphosphoric acid, ferric chloride, potassium ferricyanide, manganese dioxide, hydrogen peroxide, persulfuric acid, iodine, selenium oxide And various oxidizing agents such as organic peracids, condensing agents used in Scholl reaction, solid acids and general dehydrogenation catalysts, but are not limited thereto.
These addition methods may be added at once, or may be added separately.
In order to promote polycondensation, a Lewis acid catalyst and an oxidizing agent may be combined.
In order to promote polycondensation, a combination of alkali metal salts such as potassium chloride, sodium chloride, potassium iodide, sodium bromide, sodium iodide, potassium bromide, etc. that lowers the melting temperature of the polycondensation agent is combined. Is also effective.

The addition amount of the polycondensation agent of the present invention may be an amount that causes a polycondensation reaction, but is more preferably 50 to 2000 parts by weight with respect to 100 parts by weight of the aromatic compound. Preferably, it is 100-500 weight part.
In the present invention, the ratio by the combination of the Lewis acid catalyst and the oxidizing agent is 0.01 to 100 parts by weight of the oxidizing agent with respect to 100 parts by weight of the Lewis acid catalyst.
The addition amount of the alkali metal halide in the present invention is 1 to 100 parts by weight of the metal halide with respect to 100 parts by weight of the Lewis acid catalyst. More preferably, it is 5 to 60 parts by weight.

The polycondensation reaction can be performed in the absence of a solvent, but can also be performed in the presence of a solvent.
As this solvent, a solvent generally used for Friedel-Crafts reaction or cationic polymerization, such as nitromethane, nitropropane, nitrobenzene and carbon disulfide, can be used.

The polycondensation compound obtained by this polycondensation reaction can be obtained by hydrolysis with an acidic aqueous solution such as dilute hydrochloric acid or dilute sulfuric acid as a method for removing excess Lewis acid.
Hydrolysis can be performed by a method of adding the polycondensation reaction solution to an acidic aqueous solution, a method of adding an acidic aqueous solution to the polycondensation reaction solution in a reaction vessel, or the like. After hydrolysis, it can be obtained by a method of taking out by filtration, a method of adding a solvent that dissolves the polycondensation reaction product and taking out it as a solution, removing the solvent from this solution, a method of obtaining by a reprecipitation method, and the like.

  In the polycondensation compound having a sulfonic acid group in the present invention, the aromatic compound is subjected to heat treatment in the presence of a polycondensation agent under normal pressure, that is, polycondensation, that is, two or more aromatic rings are newly added. The formation of fused rings with one or more atoms in common, the formation of complex polycondensed polycyclic aromatic hydrocarbons with advanced condensation, generally condensed As the number of aromatic rings increases, its properties become close to that of graphite, and this polycondensed aromatic hydrocarbon, which has undergone condensation, has been designed in terms of structure and molecular weight by IR, NMR, GPC, etc. It is obtained by applying the knowledge that cyclic aromatic hydrocarbons are sulfonated with a sulfonating agent, retaining the previous properties without breaking the bond due to oxidation, and optionally introducing sulfonic acid groups. It is a solid acid.

  When the present inventors heat-treat at 50 ° C. to 220 ° C. in the presence of a polycondensation agent under normal pressure, and sulfonated the resulting polycondensation compound with a sulfonated agent, carbonization proceeds and is greatly increased. The result of heat treatment under normal pressure in anticipation of the development of a developed hydrophobic polycyclic aromatic hydrocarbon, which is sulfonated with a sulfonating agent to form a solid acid insoluble in water. And achieved the goal.

Examples of the sulfonating agent used in the present invention include, but are not limited to, sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, amidosulfuric acid and the like.
The addition amount of the sulfonating agent of the present invention varies depending on the kind of sulfonating agent and the amount of introduction of sulfonation, but any amount that causes sulfonation to the polycondensation compound may be used, and preferably 100 wt. 0.1 to 2000 parts by weight with respect to parts.
The reaction temperature at this time is suitably -20 ° C to 250 ° C, although the reaction temperature varies appropriately depending on the type of the sulfonating agent and the amount of sulfone group introduced.

  The sulfonation reaction can be performed in the absence of a solvent, but can also be performed in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as pentane, hexane, benzene, toluene and xylene; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, trichlorofluoromethane, 1,1,2-trichloro-1,2, Halogenated hydrocarbon solvents such as 2-trifluoroethane; nitrogen-containing solvents such as nitromethane, nitroethane, nitropropane, and nitrobenzene. In addition, a solvent generally used for Friedel-Crafts reaction, cationic polymerization and the like can be appropriately selected and used suitably. These solvents may be used alone or in combination of two or more.

In configuring this polycondensation reaction system, there are no particular restrictions on the order and method of blending the aromatic compound and the polycondensation agent, and each can be blended simultaneously or stepwise in various orders and manners. It is.
In addition, there are no particular restrictions on the order and method of blending the polycondensation compound and the sulphonating agent, etc. in configuring this sulphonation reaction system, and they may be blended simultaneously or stepwise in various orders and manners. Is possible.
The solid acid obtained by sulfonating with the sulfonating agent of the present invention is obtained by diluting the reaction solution with ion-exchanged water, and decanting or performing general filtration, microfiltration, ultrafiltration, reverse osmosis filtration, etc. Wash until is neutralized.

  As a drying method, natural drying, hot air drying, external heating drying, spray drying, drying using microwaves, infrared rays, far infrared rays, freeze drying, or the like can be performed.

  The counter cation of the sulfonic acid group of the solid acid having a sulfonic acid group in the present invention is selected from the group consisting of hydrogen ions, alkali metal ions, alkaline earth metal ions, and transition metal ions of Group VIII of the periodic table. It is preferable that it is an ion. In particular, the counter ion of the sulfonic acid group is preferably an ion selected from the group consisting of hydrogen ion, sodium ion, potassium ion, and iron (III). This is in order to obtain a suitable polymerization rate by maintaining pH in a neutral region in the subsequent electrolytic oxidation polymerization method, and sodium ions and potassium ions are particularly preferable. In addition, since the chemical oxidative polymerization method described later utilizes oxidation and reduction of transition metals, iron (III) ions are particularly preferable as metal ions that can be easily oxidized.

The conductive polymer composition in the present invention is formed, for example, by blending or doping a solid acid having a sulfonic acid group to a π-conjugated polymer.
Examples of the blending method in the present invention include a dry method, a wet method, and a melt method.
As the dry method, the solid acid and the π-conjugated polymer are in powder form, and can be blended using, for example, various mixers and kneaders. Among them, a Henschel mixer and a super mixer, which are agitating mixers, are preferable in that the mixture can be swirled, vertically and circumferentially drawn at once.
As the wet method, for example, the state of a solvent slurry (the solvent can be adjusted by mixing the solid acid and / or the π-conjugated polymer. The type of the solvent used here is not particularly limited, and particularly impurities. Any solvent can be used as long as it does not contain a large amount of.), And the mixing method is not particularly limited, and any stirrer usually used for liquid mixing can be used. Moreover, it is also possible to carry out a dispersion process with a disperser such as a sand mill, if necessary. When the mixture containing the π-conjugated polymer and a solid acid having a sulfonic acid group is finally obtained as a slurry when it is produced, it may be used as it is without being dried. Also, it can be used after drying and pulverizing by a usual method.
As the melting method, for example, blending can be performed by melt kneading using a kneader such as a twin screw extruder such as a kneader, a heat roll, or an extruder. Further, it can be used after being pulverized by an ordinary method. For example, the fine particles may be obtained with a jet mill.

The conductive polymer composition in the present invention may use additives as necessary.

The doping method in the present invention includes a method of immersing a π-conjugated polymer in a solution of a solid acid having a sulfonic acid group, a method of electrolytic oxidation polymerization using the solid acid as a supporting electrolyte, and a chemical method using the solid acid. General methods such as a method of oxidative polymerization, a method of chemical oxidative polymerization using the transition metal salt of the solid acid, and a method of chemical oxidative polymerization using the solid acid and an oxidizing agent can be used.

As a solvent for dissolving or dispersing a solid acid having a sulfonic acid group in doping by immersion, any solvent having a dissolving power or a dispersing power can be used. For example, water, acetonitrile, methanol, ethanol, isopropyl alcohol, n-butanol, nitrobenzene, propylene carbonate, ethylene glycol and the like can be used.
In the doping by dipping according to the present invention, it is desirable to thoroughly wash the π-conjugated polymer former after oxidative polymerization of the monomer, and remove the remaining oxidizing agent and its reduced form. At this time, the same solvent as that used in the oxidation polymerization step can be used as the solvent. Furthermore, it is desirable that after the washing, the polymer formed body is well dried to remove the remaining solvent. If the oxidant or its reduced form or solvent remains in the resulting conductive polymer former, it may cause the surface conductive film to be altered by heat during secondary molding, or it may be gas during use. May be caused. If necessary, the solution may be stirred.

In the present invention, in order to impart conductivity to the substrate, the thickness of the conductive film formed on the surface is ^{0.02 × 10 -6 m~200 × 10 -6} m. Preferably, a ^{0.02 × 10 -6 m~20 × 10 -6} m. More preferably ^{0.05 × 10 -6 m~10 × 10 -6} m. If the thickness of the coating is less than 0.02 × 10 ⁻⁶ m, sufficient conductivity cannot be obtained, and if it exceeds 200 × 10 ⁻⁶ m, the coating is cut or peeled off during formation, and the conductivity is impaired. Problems such as facilitation arise.

In the electrolytic oxidation polymerization method, doping is performed by applying a predetermined current or potential to a solution comprising a solid acid having a sulfonic acid group as a supporting electrolyte and a monomer of the π-conjugated polymer. If necessary, the solution may be stirred.

The solvent used in the electrolytic oxidation polymerization reaction may be any solvent that dissolves or disperses a solid acid having a sulfonic acid group and dissolves the monomer of the conductive polymer. For example, water, dimethylformamide , Acetonitrile, propylene carbonate, ethylene glycol, nitrobenzene, methanol, ethanol, isopropyl alcohol, n-butanol and the like. The electrolytic oxidation polymerization can be usually performed in a temperature range of −100 to 200 ° C., preferably in a temperature range of 0 to 100 ° C., and may be either a constant current electrolysis method or a constant potential electrolysis method. The electrolytic oxidation polymerization is desirably performed in an atmosphere of an inert gas such as nitrogen or argon.

In doping by chemical oxidative polymerization, a transition metal complex that coordinates a conjugated base of a solid acid having a sulfonic acid group, a monomer of a conductive polymer that forms a polymer compound having a molecular structure of an electron conjugated system, and Is contacted in a solvent to perform doping together with polymerization. Examples of the central metal constituting the transition metal complex include iron, cobalt, ruthenium and the like, and iron is particularly preferable among these. The transition metal complex is usually used in an amount of 1 to 100 mol with respect to 1 mol of the monomer. The solvent used in the reaction may be any solvent that dissolves the transition metal complex and the monomer, and examples thereof include water, dimethylformamide, acetonitrile, tetrahydrofuran, propylene carbonate, and ethylene glycol. The polymerization temperature is preferably 0 to 50 ° C., and the reaction time is preferably 1 to 48 hours. The polymerization is desirably performed in an inert gas atmosphere such as nitrogen or argon.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not interpreted limitedly by this illustration.

(Production of solid acid 1)
A 300 ml four-necked flask was charged with 50 g of anhydrous aluminum chloride, 10 g of sodium chloride and 20 g of naphthalene while flowing nitrogen at 60 ml / min, and gently stirred for 30 minutes. Nitrogen was turned off as soon as heating was started, heated to 90 ° C., held at 90 ° C. for 30 minutes, and then heated to 100 ° C. The reaction was carried out at 100 ° C. to 105 ° C. for 4 hours. In order to cool to room temperature and deactivate excess aluminum chloride, 150 ml of dilute hydrochloric acid was added.
The supernatant was discarded and 200 ml of toluene was added to dissolve the precipitate. The resulting solution was filtered through filter paper and gradually added to 1000 ml of heptane. The obtained precipitate was filtered, and the obtained precipitate was dried at 80 ° C. overnight to obtain 17.1 g of polycondensation reaction compound 1.
A 300 ml four-necked flask was charged with 17.1 g of polycondensation reaction compound 1 and 171 ml of 97% sulfuric acid, heated to 180 ° C. while allowing nitrogen to flow at 80 ml / min, and reacted for 5 hours. This solution was poured into 340 ml of ion-exchanged water with stirring and stirred for 1 hour. This was subjected to suction filtration and further washed with 300 ml of ion-exchanged water. Again, the precipitate was dispersed in 300 ml of ion-exchanged water, stirred for 1 hour, suction filtered, washed with ion-exchanged water until the filtrate became neutral, and then dried overnight at 80 ° C. in a hot air drying oven. 23.1 g of solid acid 1 was obtained.
The acid value was measured by washing the solid acid 1 with pure water. Next, it was reacted with solid acid 1 in 2N aqueous sodium nitrate solution for 48 hours, and solid acid 1 was filtered with a filter. A sodium hydroxide solution was dropped into the acidic solution from which the solid acid 1 was removed, and the neutralization point was measured in a nitrogen stream. The acid value was calculated from the amount dropped. The acid value of the solid acid 1 was 4.5 meq / g.

Example 1
6.00 g of solid acid and 1.34 g of pyrrole were dissolved in 200 ml of ion-exchanged water to prepare a reaction solution for electrolytic oxidation polymerization. After bubbling nitrogen gas in this solution for 15 minutes and replacing with nitrogen, two 4 cm square stainless steel (SUS304) plates were immersed at 1 cm intervals to form a working electrode and a counter electrode.
Using two immersed stainless steel electrodes, current was passed at a constant current (1.25 mA / cm ² ) for 40 minutes to perform electrolytic oxidation polymerization. The polypyrrole film produced on the electrode was washed with ion exchange water and acetone, then peeled off from the electrode, and dried in vacuum for 12 hours. It was 168 S / cm as a result of measuring the electrical conductivity of the obtained film by the four-point probe method.
After the produced polypyrrole film was kept in air at a high temperature of 150 ° C. for 6 hours, the electric conductivity was measured by a four-point probe method to be 133 S / cm.
On the other hand, the polypyrrole film obtained by polymerization was immersed in ion-exchanged water, the temperature of ion-exchanged water was set to 90 ° C., and held for 12 hours. Next, the polypyrrole film was taken out from the ion-exchanged water and dried in vacuum, and then the electrical conductivity was measured by a four-point probe method. As a result, it was 127 S / cm.

(Comparative Example 1)
A reaction liquid for electrolytic oxidation polymerization was prepared by dissolving 4.38 g of 4-fluoro-2-sulfobenzamide and 1.34 g of pyrrole in 200 ml of ion-exchanged water. After bubbling nitrogen gas in this solution for 15 minutes and replacing with nitrogen, two 4 cm square stainless steel (SUS304) plates were immersed at 1 cm intervals to form a working electrode and a counter electrode.
Using two immersed stainless steel electrodes, current was passed at a constant current (1.25 mA / cm ² ) for 40 minutes to perform electrolytic oxidation polymerization. The polypyrrole film produced on the electrode was washed with ion exchange water and acetone, then peeled off from the electrode, and dried in vacuum for 12 hours. It was 162 S / cm as a result of measuring the electrical conductivity of the obtained film by the four-point probe method.
After the produced polypyrrole film was kept in air at a high temperature of 150 ° C. for 6 hours, the electric conductivity was measured by a four-point probe method, and was 117 S / cm.
On the other hand, the polypyrrole film obtained by polymerization was immersed in ion-exchanged water, the temperature of ion-exchanged water was set to 90 ° C., and held for 12 hours. Next, the polypyrrole film was taken out from ion-exchanged water, dried in vacuum, and the electrical conductivity was measured by a four-probe method, which was 96 S / cm.

Since the conductive polymer composition containing the π-conjugated polymer in the present invention and the solid acid having a sulfonic acid group can maintain high conductivity in a high temperature / high humidity environment together with high conductivity, Since it can be suitably used for solid electrolytic capacitors, antistatic films, electromagnetic shielding materials, conductive adhesives, conductive paints, wiring materials, secondary battery electrode materials, display materials, overcurrent protection elements, semiconductor elements, etc. Industrial use value is high.

Claims (3)

  A conductive polymer composition comprising a π-conjugated polymer and a solid acid having a sulfonic acid group.   2. The conductive polymer composition according to claim 1, wherein the solid acid having a sulfonic acid group is a polycondensation compound having a sulfonic acid group. The conductive polymer composition according to claim 1 or 2, wherein the π-conjugated polymer is polyaniline, polythiophene, or polypyrrole.