JP2907131B2 - Conductive polymer, solid electrolytic capacitor using the same, and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be widely used for various electronic parts, electrodes, etc., and is a stable conductive polymer which is hard to be dedoped even in water or under high temperature and high humidity. The present invention relates to a solid electrolytic capacitor having excellent moisture resistance and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, technological innovation has progressed in the field of functional organic materials, and even in the field of conductive polymers, electrons are donated to electron conjugated polymers such as polyacetylene, polyparaphenylene, polypyrrole, polythiophene, and polyaniline. A conductive polymer material to which a dopant having an electron-accepting or electron-accepting compound is added has been developed, and has been partially used as an electrode material or a conductive thin film. Among these conductive polymers,
It is known that polyaniline and polypyrrole have high electrical conductivity and are superior in stability in air as compared with other conductive polymers. Polyaniline is imino-p
-Phenylene, polypyrrole is a linear polymer compound having a pyrrole ring as a main repeating unit,
The doping changes the absorption spectrum and also increases the conductivity from a few nS / cm to more than 10 S / cm. In general, the properties of conductive polymers such as polyaniline and polypyrrole change depending on the type of dopant and its content (dopant concentration). Therefore, various dopants have been studied for the purpose of applying conductive polymers to electronic devices. For example, JP-A-3-62451 discloses benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonyl chloride, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, 1-butanesulfonic acid, modified Nafion, An electrode made of polyaniline using 3,5-trichlorobenzenesulfonic acid or biphenylsulfonic acid as a dopant is disclosed. Japanese Patent Publication No. 8-13873 discloses carboxylic acid, sulfonic acid,
A water-soluble self-doping conductive polymer in which a Bronsted acid group containing phosphoric acid is covalently bonded to the main chain of a homopolymer or copolymer such as polypyrrole, polythiophene, or polyisothianaphthene is disclosed.

On the other hand, a solid electrolytic capacitor uses a porous formed body of a film-forming metal such as tantalum or aluminum as a first electrode (anode), and uses a surface oxide film as a dielectric, manganese dioxide, 7,7,8,8. -Has a structure in which a tetracyanoquinodimethane complex salt, a conductive polymer, or the like is used as the second electrode (cathode), that is, a solid electrolyte. Among them, since the conductivity of the solid electrolyte has a large effect on the internal resistance and leakage current of the capacitor, loss in the high frequency region, etc., the development of a capacitor using a conductive polymer, which is a highly conductive material, as the electrolyte has been developed. I'm advancing. For example, "Tokuhei 4-5644
No. 5 "discloses a solid electrolytic capacitor using doped polypyrrole or an alkyl-substituted product thereof as an electrolyte. A method for forming an electrolyte by electrolytic polymerization of pyrrole and immersion of a metal on which a dielectric film is formed in a polypyrrole solution is disclosed. Are listed. Also, Japanese Patent Application Laid-Open No. 61-2396
In Japanese Patent Application Laid-Open No. Sho 62 (1987), a solid electrolytic capacitor using an oxidized polymer containing a dopant of an aniline derivative as an electrolyte is disclosed.
Japanese Patent Publication No. 29124 discloses a solid electrolytic capacitor using polyaniline as an electrolyte with arylsulfonic acid as a dopant.

[0004] However, these publications do not disclose a method for improving stability under a high temperature or a steam atmosphere, which is important for using polypyrrole or polyaniline for an electronic device, conditions of a dopant, and the like.

[0005]

The conductive polymer is expected as a material for various electronic parts and electrodes, but is a stable conductive polymer which is highly conductive and hard to be dedoped even in water or under high temperature and high humidity. In addition, there has been a problem that a solid electrolytic capacitor using a stable conductive polymer, having a low internal resistance and having excellent heat resistance and moisture resistance, and a simple manufacturing method thereof have not been obtained.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems. As a result, a conductive polymer having an electron accepting substituent and dopant, or
One is superior in stability to hardly dedoping also conjugated conductive polymer comprising a polymer compound under wet water or high-temperature and high at high electrical conductivity, also the conductive having an electron-accepting substituent high A solid electrolytic capacitor using a molecule as a dopant and a conductive polymer composed of a conjugated polymer compound as an electrolyte has a low internal resistance and excellent heat resistance and moisture resistance, and a valve with an enlarged capacitor. The present invention has been found to be possible by introducing a monomer capable of forming a conjugated polymer compound with a conductive polymer having an electron-accepting substituent on a dielectric film of a working metal and bringing the monomer into contact with an oxidizing agent solution. Was. That is, the present invention is a solid electrolytic capacitor and its manufacturing method of the electron-accepting substituent conductive polymer conductive polymer composed of a conjugated polymer compound and a dopant having, and it an electrolyte.

In the present invention, the electron-accepting substituent is a substituent capable of forming a Bronsted acid anion, such as a sulfonyl group, a carboxyl group, and a phosphonyl group. In addition, the conductive polymer is an electronic conjugated polymer compound such as polyaniline, polypyrrole, polythiophene, polyethylenedioxythiophene, polyacetylene, polyparaphenylene, polyparaphenylenevinylene, polyazulene, polyisothianaphthene, or a monomer unit thereof. a configured copolymer compound, a conductive polymer having an electron-accepting substituent is a polymer compound is an electron-accepting substituent covalently bound to the conductive polymer. In the present invention,
The conductive polymer having an electron-accepting substituent is not particularly limited as long as it is an electron conjugated polymer compound in which a substituent capable of becoming a Bronsted acid anion is covalently bonded. However, from the viewpoint of high conductivity, a sulfonated product of polyaniline ( Hereinafter referred to as polysulfoaniline ) and its derivatives, polypillow
(Hereinafter referred to as polysulfopyrrole)
That) is preferable. Examples of the polysulfoaniline derivative include polymers such as m-aminobenzenesulfonic acid and 5-amino-2-naphthalenesulfonic acid.

In the present invention, the method for synthesizing the conductive polymer having an electron-accepting substituent is not particularly limited. For example, the conductive polymer is directly sulfonated by contacting it with sulfuric acid or fuming sulfuric acid, It is obtained by polymerizing a compound obtained by sulfonating or carboxylating a monomer that can become a polymer by an electrochemical anodic oxidation method or a chemical oxidation method using an oxidizing cationizing agent. At this time, the electron-accepting substituent can be inactivated by esterification. In addition, when the conductive polymer is directly contacted with sulfuric acid, the main chain is cut at the same time as the sulfonation, and the degree of polymerization may be reduced. Lost.

In the present invention, the amount of the electron-accepting substituent for the monomer unit of the conductive polymer is not particularly limited, but is preferably larger from the viewpoint of the doping ability to the conjugated compound and the higher conductivity.

Although the conductive polymer having an electron-accepting substituent of the present invention exhibits conductivity itself, the conductivity is higher than that of the original conductive polymer having no electron-accepting substituent. Small, at most 0.1 S / cm or less.
The reason why the conductive polymer having an electron-accepting substituent exhibits conductivity is considered to be that the electron-accepting substituent acts as an intramolecular dopant in a charge-transfer-type interaction with other parts of the conjugated polymer. Can be The reason why the conductivity of such a compound is relatively low is considered to be that the conjugated system of the polymer main chain skeleton is cut or the carrier is localized by the electron-accepting substituent. Therefore, a conductive polymer having an electron-accepting substituent, that is, a self-doping conductive polymer has low conductivity, and its use as a conductor for an electrode or the like is limited. In addition, a conductive polymer having an electron-accepting substituent is generally water-soluble because the polarity of the electron-accepting substituent is high, and a molded product such as a film changes its shape and properties due to water and humidity. This also limits the use of self-doping conductive polymers for electronic device materials.

In the present invention, such a conductive polymer having an electron-accepting substituent is used as a dopant for a conjugated polymer compound. In the present invention, the conjugated polymer compound may be the same repeating unit as the original conductive polymer having no electron-accepting substituent of the conductive polymer having an electron-accepting substituent, or may be a different repeating unit. It can also be. The conjugated polymer compound of the present invention is not particularly limited as long as it is an electron conjugated polymer compound. For example, polyaniline,
Electronic conjugated polymer compounds such as polypyrrole, polyethylenedioxythiophene, polythiophene, polyacetylene, polyparaphenylene, polyparaphenylenevinylene, polyazulene, polyisothianaphthene, and copolymer compounds composed of these monomer units, and the like. However, those having a high oxidation potential have a low conductivity because of a small interaction with a dopant formed of a conductive polymer having an electron-accepting substituent. For this reason, polypyrrole, polyaniline, and polyethylenedioxythiophene are particularly preferable as the conjugated polymer compound. Further, in the present invention, a method for producing a conductive polymer comprising a conjugated polymer compound using a conductive polymer having an electron-accepting substituent as a dopant is not particularly limited, and the conjugated polymer compound is formed in advance. After doping and re-doping the conductive polymer having an electron-accepting substituent, or polymerizing and doping a monomer that can become a conjugated polymer compound in the presence of the conductive polymer having an electron-accepting substituent Or manufactured. Further, if necessary, further doping can be performed with an electron-accepting dopant such as a halogen compound, a metal halide, or alkylbenzene sulfonic acid.

In the present invention, the composition ratio of the conductive polymer having an electron-accepting substituent to the conjugated polymer compound is not particularly limited, but the conductive polymer having an electron-accepting substituent is preferred from the viewpoint of high conductivity. Is preferably 0.1 to 0.7 with respect to that of the conjugated polymer compound.

Although the conductive polymer of the present invention can be produced in a powder state, the conductive polymer having an electron-accepting substituent is water-soluble, and thus, for example, ammonium peroxodisulfate is used in the presence of polysulfoaniline. When aniline is polymerized as an oxidizing agent, an aqueous solution of polyaniline using polysulfoaniline as a dopant is obtained. The solution is spread on a smooth surface and dried to obtain a film. The film does not dissolve upon contact with water again. This is considered to be because once dried, the hydrophilic electron-accepting substituent interacts with the conjugated polymer compound to lose the solubility. In addition, when polyaniline is doped with a small molecular weight dopant such as chlorine or benzenesulfonic acid, the dopant is eliminated in an aqueous solution to lower the conductivity , but the conductive polymer of the present invention is a doped conjugated polymer compound. And a dopant having conductivity, the conductivity is high, and since the dopant substantially has a skeleton of a conductive polymer, the dopant is also excellent in environmental stability such as heat resistance.

The solid electrolytic capacitor of the present invention is tantalum,
An electrolytic capacitor with a film-forming metal such as aluminum as the anode and a surface oxide film of the film-forming metal as the dielectric, and a conjugated polymer compound in which the solid electrolyte is a conductive polymer having an electron-accepting substituent as a dopant. A conductive polymer compound comprising:

In the solid electrolytic capacitor of the present invention, the kind of the film-forming metal is not limited, and any conventionally known base metal of the electrolytic capacitor such as tantalum or aluminum can be used. The shape and the method of forming the dielectric film are not particularly limited, and a conventionally known material such as a fine powder sintered body pellet or a rolled foil etched by a known method such as anodic oxidation in an electrolytic solution. Used after forming a metal oxide film.

In the solid electrolytic capacitor of the present invention, there is no particular limitation on the method for producing a conductive polymer compound comprising a conjugated polymer compound having a conductive polymer having an electron-accepting substituent as an electrolyte as a dopant. A method for forming a conductive polymer by a conventionally known method, for example, a method of growing a conductive polymer from a polymerization electrode by an electrolytic polymerization method, or a method of introducing a reaction solution for forming a conductive polymer on a dielectric surface to cause a reaction. Method, a method of introducing a solution of a conductive polymer, a method of dedoping a conductive polymer having another dopant synthesized in advance, and then a method of doping a conductive polymer having an electron-accepting substituent But it can be manufactured,
Preferably, a monomer capable of forming a conjugated polymer compound with a conductive polymer having an electron-accepting substituent is introduced onto the enlarged dielectric film of the valve action metal, and the resultant is brought into contact with an oxidizing agent solution. You. In the method for producing the solid electrolytic capacitor of the present invention, the type of the conductive polymer having an electron-accepting substituent is not particularly limited as long as the substituent capable of being a Bronsted acid anion is a covalently bonded electron conjugated polymer. Polysulfoaniline and polysulfopyrrole are particularly preferred from the viewpoint of high conductivity and moisture resistance of the electrolyte. The conjugated polymer compound is not particularly limited, but polyaniline and polypyrrole are particularly preferred from the viewpoint of heat resistance.

The electrolytic capacitor of the present invention is stable because the conductive polymer as the electrolyte is highly conductive and hardly dedoped even in water or under high temperature and high humidity. Are better. The solid electrolytic capacitor of the present invention draws out lead electrodes using a conductive paste such as a carbon paste or a silver paste like a normal solid electrolytic capacitor, and is sealed with a resin or a metal case.
Completed as a capacitor.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0019]

【Example】

Example 1 40 ml of pure water, 33 mmol of paratoluenesulfonic acid, 1.023 g of aniline were placed in a glass reaction vessel.
And mixed at 0 ° C. To this solution, an aqueous solution containing 0.88 g of ammonium bichromate and 24 mmol of paratoluenesulfonic acid was added dropwise, and the mixture was stirred at 0 ° C. for 2 hours. As a result, a dark green reaction product was obtained, and after washing and drying, a polyaniline powder using p-toluenesulfonic acid as a dopant was obtained. This polyaniline powder was added to 10
wt. % Ammonia water, undoped for 30 minutes, washed and dried to obtain neutral polyaniline.

Next, neutral polyaniline was dissolved by stirring at room temperature with 10 ml of sulfuric acid, and a deep blue solution was obtained. This solution was neutralized with calcium hydroxide, and the precipitated calcium sulfate was removed by filtration. The obtained filtrate was dried and the infrared absorption spectrum was measured. As a result, a phenyl ring substituted with a sulfonyl group was found. When the conductivity was measured, it was found to be 3.5 × 10 ⁻⁷ S / at room temperature.
cm. The obtained filtrate was passed through an ion exchange resin (Duolite C-20, manufactured by Wako Pure Chemical Industries) column to obtain an aqueous solution. The aqueous solution was concentrated and dried, and the conductivity was measured. As a result, it was 8 × 10 ⁻³ S / cm at room temperature. As a result, a conductive polysulfoaniline having a sulfonyl group as an electron-accepting substituent was obtained.

In a glass reactor, the amount of sulfonyl groups is 3
An aqueous solution of polysulfoaniline was added so as to be 3 mmol, and the mixture was stirred at 1.0C with 1.023 g of aniline. 0.88 g of ammonium bichromate and 24 mm
An aqueous solution of polysulfoaniline containing a sulphonyl group was added dropwise and stirred at 0 ° C. for 2 hours. As a result, a dark green reaction product was obtained, which was reprecipitated in methanol and dried to obtain a dark green solid. This solid was pulverized, and the infrared absorption spectrum was measured by the KBr method. As a result, a phenyl ring substituted with a sulfonyl group was recognized, and polyaniline using polysulfoaniline as a dopant was obtained. This polyaniline was molded under pressure, cut out to a length of 10 mm, a width of 1.5 mm, and a thickness of 0.1 mm, and the conductivity was measured by a four-terminal method. The result was 1.3 S / cm. It could be used as a conductive material.
Further, the obtained polyaniline was insoluble in water, methanol, dimethyl sulfoxide, N-methylpyrrolidone, and m-cresol.
The heat resistance did not change until the thermogravimetry.

Example 2 Example 1 was applied to a glass reaction vessel.
The aqueous solution of the polysulfoaniline obtained in the above was added so that the amount of the sulfonyl group was 33 mmol, 2.6 g of ferric nitrate was added and dissolved, and 0.73 g of pyrrole was added dropwise, followed by stirring at 0 ° C. . As a result, a dark blue reaction product was obtained, which was reprecipitated in methanol and dried to obtain a solid. This solid was pulverized, and the infrared absorption spectrum was measured by the KBr method. As a result, a phenyl ring and a pyrrole ring substituted with a sulfonyl group were recognized, and polypyrrole using polysulfoaniline as a dopant was obtained. When the conductivity of this polypyrrole was measured by the same method as in Example 1, it was 25 S / cm, and it was usable as a conductive material for various electronic components and electrodes. Further, the obtained polypyrrole was insoluble in water, methanol, dimethylsulfoxide, N-methylpyrrolidone, and m-cresol, and when subjected to thermogravimetric analysis, had excellent heat resistance that did not change thermogravimetrically up to 260 ° C. .

(Example 3) A butyl alcohol solution of polysulfoaniline was placed in a glass reaction vessel such that the amount of sulfonyl groups became 33 mmol, and 2.6 g of nitric acid nitrate was added.
Iron was added and dissolved, and 1.5 g of ethylenedioxythiophene was added dropwise, followed by stirring at room temperature. As a result, a dark blue reaction product precipitated, and was filtered, washed with methanol and dried to obtain a solid. This was crushed, and the infrared absorption spectrum was measured by the KBr method. As a result, a phenyl ring and a thiophene ring substituted with a sulfonyl group were recognized, and polyethylenedioxythiophene using polysulfoaniline as a dopant was obtained. When the conductivity of the polyethylene dioxythiophene was measured in the same manner as in Example 1, it was 2.2 S.
/ Cm, and could be used as a conductive material for various electronic components, electrodes and the like. Further, the obtained polyethylene dioxythiophene is insoluble in water, methanol, dimethyl sulfoxide, N-methylpyrrolidone, and m-cresol, and when subjected to thermogravimetric analysis, has excellent heat resistance which does not change thermogravimetrically up to 250 ° C. Met.

(Example 4) 10 mm was placed in a glass reaction vessel.
ol of 5-amino-2-naphthalenesulfonic acid,
40 ml of pure water was added and cooled to 0 ° C. 1 in this solution
40 containing 0 mmol ammonium peroxodisulfate
When the aqueous solution of ml was dropped, the solution turned black.
After reacting for 2 hours, the mixture was filtered, the filtrate was put in methanol, the precipitate was taken out, washed and dried. The infrared absorption spectrum of the product was measured by the KBr method. As a result, a naphthalene ring substituted with a sulfonyl group was recognized, and formation of polysulfonaphthylamine was confirmed. The product was water soluble and had a conductivity of 10 ^-4 S / cm at room temperature.

Next, an aqueous solution of polysulfonaphthylamine was placed in a glass reaction vessel so that the amount of sulfonyl groups became 33 mmol, and stirred at 0 ° C. with 1.023 g of aniline. Add 0.88 ammonium dichromate to this solution.
g and 24 mmol of an aqueous solution of polysulfonaphthylamine containing a sulfonyl group were added dropwise, and the mixture was stirred at 0 ° C. for 2 hours.
As a result, a dark green reaction product was obtained, which was reprecipitated in methanol and dried to obtain a dark green solid. This solid was crushed, and the infrared absorption spectrum was measured. As a result, absorption peaks attributed to polysulfonaphthylamine and polyaniline were observed, and formation of polyaniline using polysulfonaphthylamine as a dopant was recognized. When the electric conductivity was measured by the method of Example 1, it was found that the electric conductivity was 0.
It was 7 S / cm, and could be used as a conductive material for various electronic components, electrodes, and the like. Further, the obtained polyaniline was insoluble in water, methanol, dimethyl sulfoxide, N-methylpyrrolidone, and m-cresol, and was subjected to thermogravimetric analysis. .

Example 5 A glass reaction vessel was charged with 10 mmol of ferric p-toluenesulfonate and 50 mm of pyrrole.
was dissolved in 50 ml of methanol, and polypyrrole powder having p-toluenesulfonic acid as a dopant was obtained. 10 wt. % Of aqueous ammonia solution, undoped for 30 minutes and washed to obtain neutral polypyrrole powder.

Next, the above-mentioned polypyrrole was stirred at room temperature with 10 ml of sulfuric acid to dissolve, and a dark blue solution was obtained. This solution was neutralized with calcium hydroxide, and the precipitated calcium sulfate was removed by filtration. The obtained filtrate was dried and the infrared absorption spectrum was measured. As a result, a pyrrole ring substituted with a sulfonyl group was found. When the conductivity was measured, it was found to be 4.1 × 10 ^-8 S / at room temperature.
cm. The obtained filtrate was passed through an ion exchange resin (manufactured by Wako Pure Chemical Industries, Duolite C-20) column to obtain an aqueous solution. The aqueous solution was concentrated and dried, and the conductivity was measured. As a result, it was 2 × 10 ⁻³ S / cm at room temperature. As a result, a conductive polysulfopyrrole having a sulfonyl group as an electron-accepting substituent was obtained.

When the amount of sulfonyl groups is 3
An aqueous solution of polysulfopyrrole was added so as to have a concentration of 3 mmol, and the mixture was stirred at 1.0C with 1.023 g of aniline. 0.88 g of ammonium bichromate and 24 mm
ol of an aqueous solution of polysulfopyrrol containing a sulfonyl group was added dropwise and stirred at 0 ° C. for 2 hours. As a result, a dark green reaction product was obtained, which was reprecipitated in methanol and dried to obtain a dark green solid. This solid was pulverized, and an infrared absorption spectrum was measured by a KBr method. As a result, a peak derived from a pyrrole ring substituted with a sulfonyl group was recognized, and polyaniline using polysulfopyrrole as a dopant was obtained. The conductivity measured by the method of Example 1 was 0.7 S / cm, and it was usable as a conductive material for various electronic components and electrodes. Further, the obtained polyaniline was insoluble in water, methanol, dimethyl sulfoxide, N-methylpyrrolidone, and m-cresol, and was subjected to thermogravimetric analysis. .

(Example 6) 0.25 in a glass reaction vessel
A mol / l nitromethane solution of 3-thiophene carboxylic acid was put therein, and two platinum electrodes were immersed therein, and a voltage of 12 V was applied. As a result, a blue film was deposited on the surface of the anode, and a part of the solution was dissolved and the solution turned black. After reacting for 3 hours, replace the electrode with a new one for another 0.25 m.
When a voltage of 3.5 V was applied by adding pyrrole so as to be ol / l, a blue film was deposited on the anode surface. When the infrared absorption spectrum of this film was measured, a pyrrole ring and a thiophene ring substituted with a sulfonyl group were recognized, and polypyrrole using polysulfothiophene as a dopant was obtained. The conductivity measured by the method of Example 1 was 6.7 S / cm, and it was usable as a conductive material for various electronic components and electrodes. Also,
The obtained polypyrrole was insoluble in water, methanol, dimethylsulfoxide, N-methylpyrrolidone, and m-cresol, and was found to be excellent in heat resistance without thermogravimetric change up to 280 ° C. by thermogravimetric analysis.

(Example 7) 2 m in diameter with anode lead
m, a columnar tantalum fine powder pellet having a height of 2 mm is immersed in a 0.05% by weight aqueous solution of phosphoric acid, anodized at 48 V with a stainless steel plate as a counter electrode, washed and dried to remove the metal oxide film. A sintered tantalum pellet having a dielectric film was obtained. The pellet was immersed in a 0.1 N aqueous sulfuric acid solution, and the capacitance was measured.

Next, a concentration of 13 wt. % Of the polysulfoaniline obtained in Example 1 and 5 wt. % Of aniline was prepared, and the tantalum sintered body pellet was immersed and taken out. Put this in air at room temperature
After drying for 0 min. % Ammonium bichromate and 13 wt. % Of polysulfoaniline, and taken out and kept in the air for another 20 minutes to polymerize aniline. Then, it was washed with water and methanol and dried at 80 ° C. When this operation was repeated four times, a pellet whose dielectric surface was coated with polyaniline using polysulfoaniline as a dopant was obtained.

A negative electrode lead was attached to the pellet using a silver paste to complete a capacitor. The resulting capacitor has a capacitance measured at 120 Hz of 10 μF, 100 μF.
The equivalent series resistance at kHz was 0.2Ω, and the capacitor had good properties with little change in capacitance up to the resonance frequency range. In addition, even in a solder bath immersion test at 260 ° C. for 25 seconds and a humidity resistance test at a relative humidity of 95% and 85 ° C. for 8 hours, the performance was not changed and the heat resistance was excellent.

(Embodiment 8) Concentration of 10 w in a glass container
t. % Of the polysulfopyrrole obtained in Example 5 and 5 w
t. % Of aniline was prepared, and a tantalum sintered body pellet on which a dielectric film was formed by the method of Example 7 was immersed and taken out. This was dried in the air at room temperature for 30 minutes, and then the pellet was dried at 10 wt. % Ammonium bichromate and 10 wt. % Of polysulfopyrrole, taken out, and kept in the air for another 20 minutes to polymerize aniline. Then, it was washed with water and methanol and dried at 80 ° C. When this operation was repeated four times, a pellet whose dielectric surface was coated with polyaniline using polysulfopyrrole as a dopant was obtained.

A cathode lead was attached to the pellet using a silver paste to complete a capacitor. The resulting capacitor has a capacitance measured at 120 Hz of 10 μF, 100 μF.
The equivalent series resistance at kHz was 0.25Ω and the capacitor had good properties with little change in capacitance up to the resonance frequency range.
In addition, even in a solder bath immersion test at 260 ° C. for 25 seconds and a humidity resistance test at a relative humidity of 95% and 85 ° C. for 8 hours, the performance was not changed and the heat resistance was excellent.

(Embodiment 9) A thickness of 150 μm, an area of 10 mm × 5 in which the surface area is enlarged almost 50 times by etching.
mm aluminum foil of 5 wt. Anodized at 100 V in a 10% aqueous solution of ammonium borate, washed and dried to obtain an aluminum foil having a dielectric composed of a metal oxide film. This foil was immersed in a 0.1N sulfuric acid aqueous solution, and the capacitance was measured to be 1.5 μF.

Next, 13 wt. % Of the polysulfoaniline obtained in Example 1 and 5 wt. % Of aniline was prepared, and the aluminum foil was dipped and taken out. This was dried in air at room temperature for 30 minutes, and then dried at 10 wt. % Ammonium bichromate and 13%
wt. % Polysulfoaniline
The aniline was taken out and kept in the air for further 20 minutes to carry out the polymerization of aniline. Then, wash with water and methanol,
Dried at ° C. When this operation was repeated four times, an aluminum foil whose dielectric surface was coated with polyaniline using polysulfoaniline as a dopant was obtained.

A cathode lead was attached to the aluminum foil using a silver paste to complete a capacitor. The obtained capacitor has a capacitance of 1.2 μm measured at 120 Hz.
F, had an equivalent series resistance of 0.1Ω at 100 kHz, and had good properties with little change in capacitance up to the resonance frequency range. Also, a solder bath immersion test at 260 ° C. for 25 seconds,
In addition, the performance did not change even in a humidity resistance test at a relative humidity of 95%, 85 ° C. and 8 hours, and the heat resistance was excellent.

[0038]

As described above, according to the present invention, the present invention can be widely used for various electronic parts, electrodes, etc., is hard to be dedoped even in water or under high temperature and high humidity, and has a high conductivity having a stable electron accepting substituent. A conductive polymer comprising a molecule as a dopant , and a conjugated polymer compound, and a solid electrolytic capacitor having a low internal resistance and excellent heat resistance and moisture resistance using the same, and a method for producing the same can be provided. The effect is great.

Continuation of the front page (72) Inventor Hiroshi Yagada 5-7-1 Shiba, Minato-ku, Tokyo Within NEC Corporation (56) References JP-A-7-224207 (JP, A) JP-A-3- 56567 (JP, A) JP-A-1-190756 (JP, A) JP-A-63-135453 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101 / 14 H01B 1/00-1/24 H01G 9/022-9/028

Claims (5)

(57) [Claims] 1. A conductive polymer having an electron-accepting substituent as dopant, and a conjugated polymer compound this
And a conductive polymer . Wherein the conductive having an electron-accepting substituent polymer polyaniline sulfonated or polypyrrole
2. The conductive material according to claim 1, which is a sulfonated product.
Conductive polymer . 3. The method according to claim 1, wherein the conjugated polymer compound is one selected from the group consisting of polyaniline, polypyrrole, and polyethylenedioxythiophene.
Conductive polymer . 4. The conductive material according to claim 1,
A solid electrolytic capacitor comprising a polymer as a solid electrolyte. 5. Is contacted with enlarged surface with a valve action metal dielectric thin film on the introduced monomer capable of forming a conductive polymer compound and a conjugated polymer having an electron-accepting substituent oxidizing agent solution
The conductive polymer having an electron-accepting substituent.
Punt and conductive polymer consisting of conjugated polymer
5. The method for manufacturing a solid electrolytic capacitor according to claim 4, wherein the method comprises combining .