JP2000239361A - Conductive polymer, solid electrolytic capacitor and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid electrolytic capacitor useful as a solid electrolyte for solid electrolytic capacitor elements by forming a solid electrolytic layer comprising a polymer having a fibril structure on a porous metal conductor foil having a valve action. SOLUTION: This solid electrolytic capacitor is obtained by forming a solid electrolytic layer comprising a polymer having a fibril structure on a porous metal conductor foil having a value action. The polymer preferably contains thiophene skeleton structure units of formula I [R1, R2 are each H, a 1-10C alkyl or the like; (δ) is 0, 1; Z is an anion; (j) is 1 or 2 which is the valency of Z], condensed polycyclic skeleton structure units of formula II (R3 to R8 are each H, a 1-10C alkyl or the like), pyrrole skeleton structure units of formula III (R9, R10 are each H, a 1-10C alkyl or the like), furan skeleton structure units of formula IV (R11, R12 are each H, a 1-10C alkyl or the like), or the like as repeating units, and has a fibril structure. The solid polymer electrolytic layer preferably has a conductivity of 0.1-200 S/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polymer, a solid electrolytic capacitor equipped with the polymer, and a method for producing the same. More specifically, a compact, high-capacity, low-impedance, good moisture-resistant load characteristic, and excellent heat resistance solid electrolytic capacitor, its manufacturing method, a highly conductive polymer having a novel fibril structure used for the capacitor, And a method for producing the highly conductive polymer.

[0002]

2. Description of the Related Art In a solid electrolytic capacitor, a dielectric oxide film layer is generally formed on an anode substrate made of a metal foil having a large specific surface area which has been subjected to an etching treatment, and a solid semiconductor layer (a solid semiconductive layer) is formed as an electrode facing the outside. Hereinafter, the element will be referred to as a solid electrolyte), and a conductor layer such as a conductive paste is desirably formed on the outer surface thereof, and a lead wire is connected to the element. Actual elements are entirely sealed with epoxy resin or the like, and are widely used in electrical products as capacitor parts.

In recent years, in order to meet the demands for digitization of electric equipment and speeding-up of personal computers, it has been required that capacitors used for these devices have characteristics such as small size, large capacity, and low impedance in a high frequency range. Have been. Examples of small and large-capacity capacitors include solid electrolytic capacitors such as aluminum electrolytic capacitors and tantalum electrolytic capacitors. However, since the aluminum electrolytic capacitor uses an ion-conductive liquid electrolyte as the electrolytic solution, it has a problem that the impedance in a high frequency region is high and the temperature characteristics are poor. On the other hand, a tantalum electrolytic capacitor uses manganese oxide as an electrolyte, but has a problem that the impedance in a high frequency region is high because the manganese oxide has a relatively high specific resistance.

To meet these demands, it has been proposed to use a conductive polymer having electron conductivity as a solid electrolyte, and to use a conductive organic polyaniline containing a π-conjugated polymer (Japanese Patent Application Laid-Open JP-A 61-239617), polypyrrole (JP-A 61-240625), and polythiophene derivatives (JP-A 2-15611 (US Pat. No. 490)
No. 1645)), polyisothianaphthene containing no dopant (JP-A-62-118509), doped polyisothianaphthene (JP-A-62-118511), and a conductivity of 1
Use of an intrinsically conductive polymer having a range of 0 ⁻³ to 10 ³ S / cm (Japanese Patent Application Laid-Open No. 1-169914 (US Pat. No. 4,803,596)) has been proposed.

That is, generally, aniline, pyrrole,
Polymers with conjugated double bonds represented by polymers such as thiophene have a unique conductivity, and various research and development have been conducted. Attention has been focused on electronic, magnetic and optical properties. These conductive polymers are mainly produced by an electrolytic polymerization method and a chemical oxidation polymerization method.

However, in the conventional manufacturing method, if the adhesion between the low molecular weight polymer obtained by the oxidation-reduction reaction performed on the electrode surface and the electrode surface is poor, the low molecular weight polymer dissolves or deposits in the electrolyte solution. Will be. Further, when an article having a large area is to be obtained, an electrode or the like having a size corresponding to the article is required, which has a serious problem in manufacturing cost.

On the other hand, when the chemical oxidative polymerization method is used, a conductive polymer can be easily obtained by mixing a polymerizable monomer and an appropriate oxidizing agent. Attention has been paid to a simple polymerization method, and research and development have been carried out. However, a major problem with the chemical oxidation polymerization method is that a highly active oxidizing agent is required because the polymerization rate is proportional to the activity of the oxidizing agent. That is, when polymerization is performed using an oxidizing agent having high activity, undesirable side reactions are likely to occur, and only a polymer having low structural regularity and low conductivity can be obtained. This is because the generated conductive polymer having a conjugated double bond stays in the reaction system for a long time, and the polymer skeleton having the conjugated double bond is partially affected by an extra oxidizing agent in the reaction system. It is considered that the conductive film is destroyed as a result, and as a result, the conductivity is reduced.

Further, the conductive polymer obtained by electrolytic polymerization or chemical oxidation polymerization is generally insoluble and infusible, and has an operational problem that post-processing is particularly difficult. Therefore, various efforts have been made to solve these problems. For example, Japanese Patent Application Laid-Open No. Hei 7-130579 (US Pat. No. 5,567,209) discloses that an oxide film is formed on a valve metal and used as a dielectric layer, and a conductive polymer layer is formed on the dielectric layer. In a method for manufacturing a solid electrolytic capacitor using the same as a solid electrolyte, a monomer compound solution is applied to the surface of the oxide film and dried to form a solid monomer compound, and then oxidized to the solid monomer compound. There has been disclosed a technique of forming a conductive polymer layer by contacting an agent solution to obtain a solid electrolytic capacitor having a high capacitance appearance rate and good high-frequency characteristics. JP-A-6-
340754 discloses that after attaching or impregnating a polycyclic aromatic amine compound to an insulating substrate, the substrate is contacted with a solution containing an oxidizing agent to bring the polycyclic aromatic amine compound into the interior or surface of the substrate. A technique of oxidatively polymerizing with a polymer has been disclosed.

Further, as an application of a conductive polymer to a solid electrolytic capacitor, a method for manufacturing a solid electrolytic capacitor in which a capacitor element having an anode member formed with a chemical conversion film is impregnated with a conductive polymer as a cathode electrolyte, A technique is known in which a capacitor element is immersed in a solution obtained by dissolving an oxidizing agent in a monomer that becomes a conductive polymer by oxidative polymerization to form a conductive polymer layer in the capacitor element, thereby forming a small, large-capacity capacitor. Kaiping
It is disclosed in Japanese Patent Publication No. 10-50558.

Further, as an application of a conductive polymer to a solid electrolytic capacitor, after immersing a capacitor element in a solution of an oxidizing agent and evaporating a solvent component, an oxide is precipitated in the capacitor element. A technique for improving high-temperature load characteristics by immersing the capacitor element in a solution containing a monomer that becomes a conductive polymer by oxidative polymerization and allowing the oxidizing agent to act on the monomer is disclosed in Japanese Unexamined Patent Publication (Kokai) No. Heisei 9 (1999).
It is disclosed in Japanese Patent Publication No. 10-50559.

Further, Japanese Patent Application Laid-Open No. 9-289141 (EPA 8038)
No. 85) in the manufacturing method of solid electrolytic capacitors,
A solid capacitor in which an electrode porous body is immersed in a monomer salt solution maintained at a temperature equal to or higher than the dissolution temperature, cooled to precipitate a monomer salt on the surface thereof, and the porous body is immersed in a solution containing an oxidizing agent. Has been proposed.

As a solid electrolyte formed on a dielectric film, conductive metal oxides, conductive polymers, etc., which are basically expected to improve electric conductivity sufficiently, have been attracting attention. If the electric conductivity is higher than the appropriate range, the leakage current value rises significantly, resulting in a short circuit. The control of the appropriate range of the degree and the thermal stability of the solid electrolyte are the development issues.

A conventional capacitor using a conductive polymer such as polypyrrole has a problem that the capacitor characteristics greatly fluctuate due to a moisture-proof load. Also related,
There is a great demand for heat resistance. For example, solder heat resistance (reflow property) when molding a capacitor element into a capacitor component is regarded as important, and a capacitor element having high heat resistance is required. That is, the prior art has a problem in a solid electrolyte produced on an oxide film and a method for producing the solid electrolyte.

Specifically, in the technique disclosed in Japanese Patent Application Laid-Open No. Hei 7-130579 (US Pat. No. 5,567,209), a monomer compound solution is dried into a solid monomer, but the degree of polymerization of the polymer composition is large. As the monomer phase is a solid, the diffusion of the monomer is suppressed, and there is a concern that the polymerization rate may be reduced.

Japanese Patent Application Laid-Open No. 6-340754 relates to a method for producing a transparent conductive thin film on an insulator,
No mention is made of the form or performance of a highly conductive polymer having a fibril structure due to active polymerization at the interface. The technique disclosed in JP-A-10-50558 is a technique of forming a conductive polymer thin film on a chemical conversion film, but is prepared by directly dissolving an oxidizing agent in a monomer that becomes a conductive polymer by oxidative polymerization. Even in the monomer solution, oxidative polymerization proceeds before and during use to form a polymer, and it is difficult to maintain a uniform monomer solution at all times. This is an unstable production method that cannot exhibit stable performance.

According to the technique disclosed in Japanese Patent Application Laid-Open No. H10-50559, an oxidizing agent is introduced into pores as a solution, and then the solvent is evaporated to precipitate oxidizing agent crystals, followed by oxidative polymerization. The process of precipitating the oxidizing agent in the pores of the metal foil subjected to the chemical conversion treatment is indispensable, and the contact area between the oxidizing agent solid and the monomer is very small, so the polymerization reaction is slow and inefficient. I have to say that it is industrially unsuitable for production. Further, the technique disclosed in JP-A-9-289141 (EPA 803885) discloses that the polymerizable monomer is a solid,
There is the same problem as in the technique of the '0559 publication.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly conductive polymer having a conjugated double bond (π electron conjugated system) which is preferably used as a solid electrolyte of a solid electrolytic capacitor element. . Another object of the present invention is to provide a method for producing the above novel polymer having a conjugated double bond (π-electron conjugated system) which has higher conductivity while having the same chemical composition by an oxidative polymerization method. Is to do. Furthermore, an object of the present invention is to provide a solid electrolytic capacitor using the highly conductive polymer as a solid electrolyte, which is excellent not only in initial characteristics but also in long-term reliability such as durability under high temperature and high humidity, and a method for manufacturing the same. Is to provide.

[0018]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned problems, and as a result, have found that a polymerizable monomer alone or a solution in which a polymerizable monomer is dissolved and an electrolyte having doping ability are polymerized. It is possible to obtain a highly conductive polymer having a flaky fibril structure by slowly contacting a solution of an oxidizing agent having an initiating ability at the interface to polymerize, and this polymerization method is carried out on a dielectric film. By using the obtained film-like composition having a fibril structure as a solid electrolyte, initial characteristics (loss coefficient, leakage current, heat resistance, equivalent series resistance and low impedance in a high frequency region, etc.), long-term reliability It has been found that a capacitor excellent in (eg, durability under high temperature and high humidity) can be obtained, and the present invention has been completed.

That is, the present invention relates to the following solid electrolytic capacitor, a method for producing the same, a conductive polymer, and a method for producing the same. [1] A solid electrolytic capacitor in which a solid electrolyte layer made of a polymer having a fibril structure is formed on a porous dielectric film of a metal having a valve action. [2] The polymer has the following general formula (1)

Embedded image (Wherein, R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, Nitro group, cyano group, 1
Represents a monovalent group selected from the group consisting of primary, secondary or tertiary amino groups, CF ₃ groups, phenyl groups and substituted phenyl groups. Further, the hydrocarbon chains of R ¹ and R ² are bonded to each other at an arbitrary position to form a 3- to 7-membered saturated or unsaturated hydrocarbon cyclic structure together with the carbon atom substituted by such a group. A bivalent chain may be formed. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. Δ is in the range of 0 to 1. Z represents an anion; j represents the valence of Z;
Or 2. (2) The solid electrolytic capacitor according to the above (1), which is a conductive polymer having a fibril structure containing a thiophene skeleton structure as a repeating unit. [3] The polymer has the following general formula (2)

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms) , An alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ³ , R ⁴ , R ⁵ ,
The hydrocarbon chains of R ⁶ , R ⁷ or R ⁸ may be bonded to each other at any position to form at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain forming a cyclic structure of The cyclic bond chain includes carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl,
An imino bond may be included at any position. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is 0 or an integer of 1 to 3.
The fused ring in the formula may contain any number of nitrogens or N-oxides, but the number of substituents R ^{3 to} R ⁸ will be reduced by that number. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. )
2. The solid electrolytic capacitor according to the above item 1, which is a conductive polymer having a fibril structure containing a condensed polycyclic skeleton structure represented by the following formula as a repeating unit. [4] The polymer has the following general formula (3)

Embedded image (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. Z represents an anion, j represents the valence of Z, and is 1 or 2. (2) The solid electrolytic capacitor according to the above (1), which is a conductive polymer having a fibril structure containing a pyrrole skeleton structure as a repeating unit. [5] The polymer has the following general formula (4)

Embedded image (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.
δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. (2) The solid electrolytic capacitor according to the above (1), which is a conductive polymer having a fibril structure containing a furan skeleton structure as a repeating unit. [6] The polymer has the following general formula (5)

Embedded image (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one divalent chain forming a cyclic structure of a saturated or unsaturated hydrocarbon of one or more 3- to 7-membered rings may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. z represents an anion, j represents the valence of z, and is 1 or 2. 2.) The solid electrolytic capacitor according to item 1, which is a conductive polymer having a fibril structure containing an aniline skeleton structure as a repeating unit. [7] The conductivity of the solid electrolyte layer of the polymer is 0.1 to
7. The solid electrolytic capacitor according to any one of the above items 2 to 6, which is 200 S / cm.

[8] In a method for manufacturing a solid electrolytic capacitor in which a solid electrolyte layer made of a polymer is provided on a porous dielectric film of a metal having a valve action, a polymerizable monomer may be formed on the dielectric film. A polymer film having a fibril structure on the dielectric film by contacting a single solution of an oxidizing agent having a polymerization initiating ability or a mixed solution of the oxidizing agent and an electrolyte having a doping ability while maintaining a saturated or supersaturated state. A method for producing a solid electrolytic capacitor having a solid electrolyte layer formed of a polymer having a fibril structure, comprising a step of forming a liquid composition. [9] In a method for manufacturing a solid electrolytic capacitor in which a solid electrolyte layer made of a polymer is provided on a porous dielectric film of a metal having a valve action, a polymerizable monomer solution or a polymerizable A solution in which a monomer and an electrolyte having a doping ability are dissolved, and a single solution of an oxidizing agent having a polymerization initiating ability maintaining a saturated or supersaturated state or a mixed solution of the oxidizing agent and an electrolyte having a doping ability are brought into contact with each other. Forming a film composition of a polymer having a fibril structure on the dielectric film. A method for producing a solid electrolytic capacitor having a solid electrolyte layer formed of a polymer having a fibril structure. [10] On the dielectric film, the following general formula (6)

Embedded image (Wherein the substituents R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom) atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a trihalomethyl group, a hydrocarbon chain of .R ¹ and R ² represent a monovalent group selected from a phenyl group and a group consisting of substituted phenyl groups May be bonded to each other at any position to form a divalent chain which forms a cyclic structure of a 3- to 7-membered saturated or unsaturated hydrocarbon with a carbon atom substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.) The method for producing a solid electrolytic capacitor according to item 8 or 9 to form a film-like composition of a polymer having a fibril structure in contact with a solution containing an oxidizing agent to the dielectric film having a Hajimeno. On the dielectric film, the following general formula (7)

Embedded image(Wherein the substituent R^Three, R^Four, R^Five, R⁶, R⁷And R⁸Is
Each independently represents a hydrogen atom, a straight chain having 1 to 10 carbon atoms.
Or branched saturated or unsaturated alkyl group, alcohol
Xy group or alkyl ester group, or halogen source
Nitro, cyano, primary, secondary or tertiary amine
No group, CF_ThreeGroup, phenyl group and substituted phenyl group.
Represents a monovalent group selected from the group consisting of Also, R^Three, R^Four, R
^Five, R⁶, R ⁷Or R⁸Hydrocarbon chains are in any position relative to each other
And the carbon atom which is substituted by such a group
Together with at least one saturated or unsaturated 3- to 7-membered ring
Even if a divalent chain forming a cyclic structure of a saturated hydrocarbon is formed
Good. The cyclic bond chain includes carbonyl, ether, S
Ter, amide, sulfide, sulfinyl, sulfoni
And an imino bond may be included at any position. k is j
Offen ring and substituent R^ThreeOr R⁶Surrounded by a benzene ring
Represents an integer of 0 or 1 to 3
You. Nitrogen or an N-oxide may be added to the fused ring in the formula.
May contain a number of substituents R^ThreeOr R⁸Decreases
Will do. ) And the polymerizable monomer
Contacting with a solution containing an oxidizing agent having initiating ability,
Film-like set of polymer having fibril structure on dielectric film
10. The solid electrolytic capacitor according to item 8 or 9 above, which forms a product.
Sensor manufacturing method. On the dielectric film, the following general formula
(8)

Embedded image (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. The above-mentioned item 8 or 10), wherein a polymerizable monomer having a fibril structure is formed on the dielectric film by contacting the polymerizable monomer represented by 10. The method for manufacturing a solid electrolytic capacitor according to item 9. On the dielectric film, the following general formula (9)

Embedded image (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.) The solid electrolyte according to the above item 8 or 9, wherein a monomer and a solution containing an oxidizing agent having a polymerization initiation ability are brought into contact with each other to form a polymer film composition having a fibril structure on the dielectric film. Manufacturing method of capacitor. On the dielectric film, the following general formula (10)

Embedded image (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one or more divalent chains forming a cyclic structure of one or more 3- or 1-membered saturated or unsaturated hydrocarbons may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. The above-mentioned item 8 or 10), wherein a polymerizable monomer having a fibril structure is formed on the dielectric film by contacting the polymerizable monomer represented by 10. The method for manufacturing a solid electrolytic capacitor according to item 9. [15] The method for producing a solid electrolytic capacitor according to item 9, wherein the concentration of the polymerizable monomer is 0.01 to 5 mol / L. [16] The concentration of the doping electrolyte is 0.001.
10. The method for producing a solid electrolytic capacitor according to the above item 8 or 9, which is in a range of from mol / L to 2.5 mol / L. [17] At least one oxidizing agent having a polymerization initiating ability selected from persulfates, dichromates, and trivalent iron salts.
10. The method for producing a solid electrolytic capacitor according to the above item 8 or 9, which is a kind of compound. [18] The method for producing a solid electrolytic capacitor as described in the above item 8 or 9, wherein the concentration of the oxidizing agent having a polymerization initiation ability is 0.01 to 5 times the concentration of the polymerizable monomer. [19] The method for producing a solid electrolytic capacitor according to any one of items 8 to 14, wherein the step of forming a polymer solid electrolyte is repeated 2 to 30 times to form a film-like composition.

[20] The following general formula (1)

Embedded image (Wherein the substituents R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom) atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹ and R ² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups May combine with each other at any position to form a divalent chain that forms a cyclic structure of a 3- to 7-membered saturated or unsaturated hydrocarbon with a carbon atom substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position, and δ is in the range of 0 to 1.
Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the thiophene skeleton structure as a repeating unit. [21] The following general formula (2)

Embedded image (Wherein, the substituents R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated C 1-10 carbon atom, An alkyl group, an alkoxy group or an alkyl ester group, or a monovalent group selected from the group consisting of a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group And R ³ , R ⁴ ,
The hydrocarbon chains of R ⁵ , R ⁶ , R ⁷ or R ⁸ may be bonded to each other at any position to form a saturated or unsaturated at least one or more 3- to 7-membered ring together with the carbon atom substituted by such groups. A divalent chain that forms a cyclic structure of a saturated hydrocarbon may be formed. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is 0 or an integer of 1 to 3. The fused ring in the formula may optionally contain nitrogen or N-oxide, but will not have the same number of substituents R ^{3 to} R ⁸ . δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the condensed polycyclic skeleton structure represented by the formula (1) as a repeating unit. [22] The following general formula (3)

Embedded image (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the pyrrole skeleton structure as a repeating unit. [23] The following general formula (4)

Embedded image (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.
δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing a furan skeleton structure represented by the following formula as a repeating unit. [24] The following general formula (5)

Embedded image (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one or more divalent chains forming a cyclic structure of one or more 3- or 1-membered saturated or unsaturated hydrocarbons may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. z represents an anion, j represents the valence of z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the aniline skeleton structure as a repeating unit.

[25] The following general formula (6)

Embedded image (Wherein, R ¹ and R ² represent the same meaning as described in the above item 10), and the general formula (7)

Embedded image (Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those in the preceding item 11)
Has the same meaning as described above. ), General formula (8)

Embedded image (In the formula, R ⁹ and R ¹⁰ have the same meanings as described in the above item 12.)

Embedded image (Wherein, the substituents R ¹¹ and R ¹² have the same meaning as described in the above item 13), and the general formula (10)

Embedded image (Wherein, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meaning as described in the above item ¹⁴ ) and an oxidizing agent having a polymerization initiation ability. A method for producing a highly conductive polymer having a fibril structure, comprising: contacting a solution to be formed with the solution so as to form an interface, and performing polymerization at the interface. [26] The general formulas (6), (7) described in the preceding item 25,
(8) A solution obtained by dissolving at least one of the polymerizable monomers represented by (9) and (10) in a solvent, and a solution containing an oxidizing agent having a polymerization initiating ability have both interfaces. 26. The method for producing a highly conductive polymer having a fibril structure according to the above item 25, wherein the polymer is brought into contact so as to form a polymer at the interface. [27] The method for producing a highly conductive polymer having a fibril structure according to the above item 25 or 26, wherein the solution containing an oxidizing agent having a polymerization initiation ability contains an electrolyte having a doping ability. [28] The method for producing a highly conductive polymer having a fibril structure according to any one of the above items 25 to 27, wherein the solution containing an oxidizing agent having a polymerization initiation ability is a saturated solution or a supersaturated solution. [29] A saturated solution of an oxidizing agent having a polymerization initiating ability is prepared, and the oxidizing agent solution and the polymerizable monomer are brought into contact with each other at a temperature lower than the saturated solution preparing temperature so as to form an interface. 27. The method for producing a highly conductive polymer having a fibril structure according to the above item 25 or 26, wherein [30] The method for producing a highly conductive polymer having a fibril structure according to the above item 25 or 26, wherein at least one of a persulfate, a dichromate and a trivalent iron salt is used as the oxidizing agent having a polymerization initiation ability. . [31] The method for producing a highly conductive polymer having a fibril structure according to the above item 26, wherein a hydrophilic organic solvent capable of dissolving the polymerizable monomer is used as the solvent. [32] The method for producing a highly conductive polymer having a fibril structure according to the above item 25, wherein the polymerizable monomer is brought into contact with a solution containing an oxidizing agent to produce a highly conductive polymer having a fibril structure. The method for producing a highly conductive polymer having a fibril structure according to the above item 25 on the surface of the highly conductive polymer having a fibril structure, which is washed or not washed, is further performed a plurality of times, A method for producing a highly conductive polymer having a fibril structure, comprising laminating a polymer composition. [33] The method for producing a highly conductive polymer having a fibril structure according to the above item 26, wherein the polymerizable monomer is brought into contact with a solution containing an oxidizing agent to produce a highly conductive polymer having a fibril structure. The method for manufacturing a highly conductive polymer having a fibril structure according to the above item 26 on the surface of the highly conductive polymer having a fibril structure without washing or without washing, is further performed a plurality of times, A method for producing a highly conductive polymer having a fibril structure, comprising laminating a polymer composition.

The highly conductive polymer having a fibril structure containing the chemical structure represented by the general formulas (1) to (5) as a repeating unit according to the present invention has not existed before. This means that the polymer produced under stirring conditions using the polymerizable monomers represented by the general formulas (6) to (10) and an oxidizing agent having a polymerization initiating ability is shown in FIGS. 7 and FIGS. 5 and 9 showing no fibril structure are apparent from the difference. In particular, Examples 12, 13, 15, 16 and Comparative Examples 2, 3,
As is clear from 4, 5 and 6, there is a great difference in conductivity between those having a fibril structure and those having no fibril structure.

The detailed reason why the polymer having a fibril structure according to the present invention exhibits high conductivity is unknown, but in the present invention, a solution containing an oxidizing agent having a polymerization initiating ability,
Preferably, a high-concentration solution, more preferably a saturated solution or a supersaturated solution (hereinafter, both of them are simply referred to as a “saturated solution or the like”) and a polymerizable monomer or a solution containing a polymerizable monomer are interfaced ( In the present invention, the term "interface" means that the oxidizing agent solution layer and the polymerizable monomer layer or the solution layer containing the polymerizable monomer are partially mutually dissolved on a contact surface, and the concentration gradient layer is formed. Even if they are present, they are in a state where each layer is present) .Since they are gently brought into contact to form a polymer and polymerized at the interface, excess conductive polymer is generated. It is thought that this is due to the fact that the structural regularity is not destroyed without being affected by the oxidizing agent.

Another reason is that the oxidizing agent is used as a high-concentration solution or a saturated solution. At this time, the oxidizing agent is considered to exist in the form of extremely small crystal nuclei. It is considered that the polymerization of the polymerizable monomer proceeds in a limited reaction field, so that the polymer is a highly conductive polymer having high stereoregularity. For these reasons, a polymer having the same composition obtained from the same polymerizable monomer but having a high conductivity of 10 to 1000 times is produced,
It is considered that it appears as a fibril structure in the electron microscope.

Examples of the thiophene derivative represented by the general formula (6) as a raw material of the highly conductive polymer include 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, and 3-pentylthiophene. 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene,
3-decylthiophene, 3-fluorothiophene, 3-
Chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-methylenedioxythiophene,
Examples thereof include 3,4-ethylenedioxythiophene and 3,4-propylenedioxythiophene, but are not limited thereto.

As the condensed heteropolycyclic compound represented by the general formula (7) as a raw material of the highly conductive polymer, specifically, 1,3-dihydroisothianaphthene with k = 0 (also called 1 , 3-dihydrobenzo [c] thiophene) skeleton and a compound having a k = 1,3-dihydronaphtho [2,3-c] thiophene skeleton. Furthermore, 1,3-dihydroanthra [2,3-c]
Examples include a compound having a thiophene skeleton and a compound having a 1,3-dihydronaphthaseno [2,3-c] thiophene skeleton, but are not limited thereto.

Among the substituents R ³ , R ⁴ , R ⁵ and R ⁶ of the condensed heteropolycyclic compound represented by the general formula (7),
Two substituents are bonded to each other by an unsaturated bond to form a condensation system 6
Also included are compounds that form a membered ring (ortho substitution), for example, 1,3-dihydronaphtho [1,2-c] thiophene derivative with k = 0, and 1,3-dihydrophenanthate with k = 1 La [2,3-c] thiophene derivative, 1,
3-Dihydrotriphenylo [2,3-c] thiophene derivatives, and when k = 2, 1,3-dihydrobenzo [a] anthraceno [7,8-c] thiophene derivatives, etc. However, the present invention is not limited to this.

The condensed ring may optionally contain nitrogen or N-oxide, and when k = 0, 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 are not limited thereto.

Examples of the pyrrole derivative represented by the general formula (8) which is a raw material of the highly conductive polymer include 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, and 3-pentylpyrrole. , 3-
Hexylpyrrole, 3-heptylpyrrole, 3-octylpyrrole, 3-nonylpyrrole, 3-decylpyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-
Bromopyrrole, 3-cyanopyrrole, 3,4-methylenedioxypyrrole, 3,4-ethylenedioxypyrrole, 3,4-propylenedioxypyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole and the like Derivatives can be mentioned.

Examples of the furan derivative represented by the general formula (9) as a raw material of the highly conductive polymer include 3-methylfuran, 3-ethylfuran, 3-propylfuran, 3-butylfuran, and 3-pentylfuran. 3-hexylfuran, 3-heptylfuran, 3-octylfuran, 3-nonylfuran, 3-decylfuran, 3-fluorofuran,
Derivatives such as 3-chlorofuran, 3-bromofuran, 3-cyanofuran, 3,4-methylenedioxyfuran, 3,4-ethylenedioxyfuran, and 3,4-propylenedioxyfuran can be given.

Examples of the aniline derivative represented by the general formula (10) as a raw material of the highly conductive polymer include 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, and 2-pentylaniline. , 2-
Hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decylaniline, 2-fluoroaniline, 2-chloroaniline, 2-chloroaniline
Derivatives such as bromoaniline and 2-cyanoaniline can be exemplified, but not limited thereto.

Preferred examples of the substituted phenyl group described in the general formulas (1) to (10) include a CF ₃ group, Br and C
l, F, at least one group selected from the group consisting of a methyl group, an ethyl group, a cyano group and a nitro group is represented by o-, m
And phenyl groups optionally substituted at the p-position.

The metal having a valve action that can be used in the solid electrolytic capacitor of the present invention is a simple metal such as aluminum, tantalum, niobium, titanium, zirconium, magnesium, silicon, or an alloy thereof. As for the form, any form may be used as long as it is a form of a porous formed body such as an etched rolled foil or a fine powder sintered body.

Used in the production of the conductive polymer of the present invention
The oxidizing agent is used for the dehydrogenative four-electron oxidation reaction.
Any oxidizing agent that can be sufficiently used may be used, and it is industrially inexpensive.
And a compound which is easy to handle in production is preferred.
Specifically, for example, FeCl _Three, Fe (ClO_Four)_Three, F
e (organic acid anion) salts and other Fe (III) compounds,
Or anhydrous aluminum chloride / cuprous chloride, alkali metal
Persulfates, ammonium persulfates, peroxides, peroxides
Manganese such as potassium manganate, 2,3-dichloro
-5,6-dicyano-1,4-benzoquinone (DD
Q), tetrachloro-1,4-benzoquinone, tetracy
Quinones such as ano-1,4-benzoquinone, iodine, bromine
Such as halogens, peracid, sulfuric acid, fuming sulfuric acid, sulfur trioxide,
Sulfone such as chlorosulfuric acid, fluorosulfuric acid and amidosulfuric acid
Acids, ozone, etc. and combinations of these oxidizing agents are listed.
I can do it.

Among them, the organic acid anion iron (III)
Examples of the basic compound of the organic acid anion that forms a salt include organic sulfonic acids or organic carboxylic acids, organic phosphoric acids, and organic boric acids. Specific examples of organic sulfonic acids include
Benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfo-naphthalene, β-sulfo-naphthalene, naphthalenedisulfonic acid, alkylnaphthalenesulfonic acid (alkyl groups such as butyl, triisopropyl, di- t-butyl and the like are used.

On the other hand, specific examples of the organic carboxylic acid include:
Acetic acid, propionic acid, benzoic acid, oxalic acid and the like can be mentioned.
Further, in the present invention, polyelectrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfate, poly-α-methyl sulfonic acid, polyethylene sulfonic acid, and polyphosphoric acid are also used. Examples of these organic sulfonic acids or organic carboxylic acids are merely examples, and are not limiting.

The counter cation of the anion is H ⁺ ,
An alkali metal ion such as Na ⁺ and K ⁺ or an ammonium ion substituted with a hydrogen atom, a tetramethyl group, a tetraethyl group, a tetrabutyl group, a tetraphenyl group or the like is not particularly limited in the present invention. Among the oxidizing agents described above, particularly preferably, an oxidizing agent containing a trivalent Fe-based compound, or a cuprous chloride-based compound, an alkali salt of persulfate, an ammonium persulfate, a manganic acid, or a quinone is preferably used.

The concentration of the solution of the oxidizing agent having a polymerization initiating ability may be sufficient as long as it allows the polymerization to be carried out, but it is preferably a high concentration, and more preferably a saturated solution or a supersaturated solution. Methods using such saturated or supersaturated solutions include slightly higher temperatures depending on the reaction temperature,
Depending on the temperature dependence of the thermal solubility of the oxidizing agent, the temperature difference is small when the temperature dependence is large, and the temperature difference is large when the temperature dependence is small. For example, at a temperature several degrees to about 20 ° C. higher than the polymerization temperature, the oxidizing agent is dissolved in a solvent such as water or alcohol under strong stirring. Take out the supernatant oxidant solution, put it in the reactor, and set it to a predetermined temperature lower than the time of dissolution. And contact them so as to form an interface.

The reaction proceeds at the interface between the two to form a highly conductive polymer, which is separated from the reaction solution by evaporation or decantation, and washed to produce a macroscopic scale-like highly conductive polymer. Can be obtained. The product may be sufficiently washed to obtain a highly conductive polymer, or the solution of an oxidizing agent capable of initiating polymerization and a polymerizable monomer or polymerizable polymer may be washed or not washed on the upper surface of the resulting polymer. It is also possible to laminate a highly conductive polymer by bringing the solution into contact with a solution containing a monomer and carrying out the procedure several times. Also in this case, the concentration of the oxidizing agent solution may be a concentration sufficient to cause polymerization, but it is preferably a high concentration, and more preferably a saturated solution or a supersaturated solution.

The method for preparing a saturated or supersaturated state of the oxidizing agent having a polymerization initiating ability on the derivative film is not particularly limited. Alternatively, a low-concentration solution may be introduced in advance so that the pores can be sufficiently impregnated, and the foil pores may be saturated or supersaturated by drying such as standing or heating.

In the method for producing a highly conductive polymer of the present invention, since the oxidant anion (reduced form of the oxidant) produced from the oxidant serves as a dopant, the doping step can be omitted. It is preferable that an electrolyte having another doping ability is present during the polymerization, and both are used in combination. Examples of the electrolyte having doping ability to coexist as necessary include an electrolyte compound having an oxidizing agent anion (a reduced form of the oxidizing agent) produced from the oxidizing agent as a counter ion or another anionic electrolyte.

Specifically, for example, PF₆ ^-, SbF₆ ^-, A
sF₆ ^-A halide anion of a group 5B element such as
_Four ^-A halide anion of a Group 3B element such as^-(I_Three
^-), Br^-, Cl^-Halogen anion such as, ClO_Four ^-
Halogen anion such as, AlCl_Four ^-And FeCl_Four ^-,
SnCl_Five ^-Lewis acid anion such as
O _Three ^-, SO_Four ^2-Or an inorganic acid anion such as
Enesulfonic acid or naphthalenesulfonic acid, having 1 to carbon atoms
5, alkyl-substituted naphthalenesulfonic acid, anthraquino
Sulfonic acid, CF_ThreeSO_Three ^-, CH_ThreeSO_Three ^-Organics like
Sulfonate anion, or CF_ThreeCOO^-, C₆H_FiveCOO
^-Proton acid anions such as carboxylate anions
Can be mentioned.

Similarly, polymer electrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, polyvinylsulfuric acid, poly-α-methylsulfonic acid, polyethylenesulfonic acid, and polyphosphoric acid. It is possible, but not necessarily limited to these. Among these, a high molecular weight or low molecular weight organic sulfonic acid compound or polyphosphoric acid is preferable, and an aromatic sulfonic acid compound is preferably used.

The concentration of the polymerizable monomer represented by the general formulas (6) to (10) used in the method for producing a highly conductive polymer of the present invention depends on the type of the substituent of the compound, the solvent and the like. Although it depends on the type or the type and amount of other monomers to be copolymerized, it is generally preferably in the range of 10 ^-3 to 10 mol / l, more preferably in the range of 10 ^{-2 to} 5 mol / l. .

The reaction temperature is not particularly limited since it varies depending on the type of the monomer, the solvent, the oxidizing agent, and the reaction method, but is preferably a temperature at which the saturated state of the oxidizing agent can be maintained at the start of the polymerization. In addition, even after the solvent evaporates after the initiation of the polymerization and the solid of the oxidizing agent precipitates, when the polymerizable monomer is present in the liquid phase, the interface of the main polymerization system is maintained, and the polymerization continues. . Generally -70 ° C to 2
It is selected from a temperature range of 50 ° C. Desirably 0 ° C to 15
The temperature is 0 ° C., and it is more preferably performed in a temperature range of 15 ° C. to 100 ° C.

The reaction solvent used in the production method of the present invention may be any solvent capable of dissolving a monomer, an oxidizing agent, and an electrolyte having a doping ability simultaneously or individually, for example, tetrahydrofuran (THF).
Or dioxane, ethers such as diethyl ether, or aprotic polar solvents such as dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO); esters such as ethyl acetate and butyl acetate; Non-aromatic chlorine solvents such as chloroform and methylene chloride, nitro compounds such as nitromethane, nitroethane, and nitrobenzene;
Alternatively, alcohols such as methanol, ethanol, and propanol, or organic acids such as formic acid, acetic acid, and propionic acid or acid anhydrides of the organic acids (eg, acetic anhydride and the like), water,
Alternatively, a mixed solvent thereof can be used. Further, the oxidizing agent and / or the electrolyte having the doping ability and the monomer may be handled in a solvent system in which they are individually dissolved, that is, a two-liquid system or a three-liquid system.

From the polymerizable monomers represented by the general formulas (6) to (10), a highly conductive polymer having a fibril structure containing the chemical structures represented by the general formulas (1) to (5) as repeating units, respectively. A polymer is obtained. The electric conductivity of the conductive polymer produced in this manner is extremely high, and as shown in Examples and Comparative Examples, it is produced by stirring in a reaction system comprising an oxidizing agent having a polymerization initiation ability and a polymerizable monomer. Compared to the electrical conductivity of the conductive polymer obtained by, 10 to 1000
Twice as high and its electrical conductivity ranges from 0.1 to 200 S / cm. Under desirable conditions, a highly conductive polymer in the range of 1 to 100 S / cm, more preferably 10 to 100 S / cm is obtained.

The thickness of the conductive polymer layer produced in this manner is usually such that the solid electrolyte layer of the solid electrolytic capacitor has a thickness of only about 0.1 to 0.3 μm in one polymerization step. The polymerizable monomer is contacted with an oxidizing agent capable of initiating polymerization to produce a conductive polymer having a fibril structure, and the fibril structure obtained by polymerization with or without washing is obtained. It is preferred to synthesize the solid polymer at least about three times, practically five or more times, on the surface (on the porous valve metal) of the conductive polymer having However, it is not preferable that the solid electrolyte layer has an unnecessarily thick thickness, so that about 20 to 25 times is usually sufficient. Preferably, the required thickness of the solid electrolyte layer can be ensured in about 7 to 25 times.

It is preferable that a conductive layer is provided on the conductive polymer solid electrolyte layer thus formed in order to improve electrical contact with the cathode lead terminal. Solid or plating, metal deposition, formation of a conductive resin film, and the like are performed. Next, by connecting the cathode lead terminals and applying an exterior by, for example, a resin mold, a resin case, a metal exterior case, or a resin dipping, a solid electrolytic capacitor for various uses can be obtained.

In the solid electrolytic capacitor of the present invention,
As a solid electrolyte on the electrode, a highly conductive polymer in the form of fibrils covers the oxide film in the pores of a porous valve-acting metal foil that has been subjected to chemical conversion treatment. Since a fibril layered structure is formed and has a space in a part between adjacent layers, it is possible to effectively relieve the thermal stress above and below the temperature. In addition, since fine pores are also formed on the surface of the conductive polymer composition, the conductive paste layer for connection can enter the fine pores on the outer surface, thereby ensuring good adhesion. Furthermore, the presence of the conductive polymer form in the fibril state also in the micropores, and the space portion is formed by a plurality of laminating steps, so the supply of oxygen is ensured,
The ability to repair the dielectric oxide film during conduction is improved.

The shape of the polymer having a fibril structure formed on the dielectric film of the solid electrolytic capacitor preferably has an outer diameter of about 3 nm to about 100 nm, more preferably about 5 nm to about 50 nm.

[0053]

The present invention will be described in detail below with reference to examples and comparative examples, but these do not limit the scope of the present invention.

Example 1: In the middle of the 10 mm surface of the etched aluminum chemical conversion foil cut into 3 mm × 10 mm,
A polyimide solution was applied to a width of 1 mm on both sides so as to divide the surface into 4 mm and 5 mm portions, and dried to form a mask. 3m of this etched aluminum conversion foil
A portion of m × 4 mm was subjected to a chemical conversion treatment with a 10% by weight aqueous solution of ammonium adipate by applying a voltage of 13 V to form a dielectric oxide film.

Next, 3 mm × 4 m
The part m was immersed in a 2 mol / L ammonium persulfate aqueous solution (referred to as solution 1), pulled up, and dried at room temperature for 3 minutes. Then, 3 of this aluminum foil
A portion of a size of 4 mm × 4 mm was treated with a 1 mol / L solution of 3,4-ethylenedioxythiophene in isopropanol (solution 2).
And ) And then lifted up and placed in an atmosphere of 40 ° C.
Oxidative polymerization was carried out by allowing to stand for 0 minutes. Then, the operation from immersion in the solution 1 to immersion in the solution 2 to perform oxidative polymerization was repeated 20 times, and then 10 minutes with 50 ° C. warm water.
After washing for 1 minute, the resultant was dried at 100 ° C. for 30 minutes to form a conductive polymer layer.

FIG. 1 shows a scanning electron micrograph (cross-sectional view of aluminum foil) of the conductive polymer layer obtained here, magnified 50,000 times. FIG. 2 shows a scanning electron micrograph (a cross-sectional view of the aluminum foil) of the chemically treated aluminum foil magnified 50,000 times. FIG. 1 also shows a comparison between FIG. 2 and FIG. 1 showing an aluminum metal portion (a), an oxidized alumina dielectric portion (b), and a fibril-like conductive polymer deposited on the alumina dielectric surface. (In Fig. 1, the fibrils are seen as a network-like film.)
Are gathered into a tuft-like portion (c), which indicates that the conductive polymer film is formed to a thickness of about 0.06 μm. From the observation of FIG. 1, the approximate outer diameter of the fibrils was 5 to 50 nm. The structure of the fibril-shaped conductive polymer (film-like) portion (c) is shown in Example 14
And that a structure similar to the highly conductive polymer obtained by reacting "3,4-ethylenedioxythiophene" and "polymerization initiator (containing oxidizing agent)" at the interface described in 15 and 15 I understand.

Next, a carbon paste and a silver paste were applied to the portion of the aluminum foil where the conductive polymer layer was formed, four aluminum foils were laminated, a cathode lead terminal was connected, and a conductive polymer layer was formed. An anode lead terminal was connected by welding to the aluminum foil portion where no was formed. After sealing this element with epoxy resin,
Aging was performed for 2 hours by applying a rated voltage at ℃ to complete a total of 30 capacitors.

For these 30 capacitor elements,
As an initial characteristic, the capacity and the loss coefficient at 120 Hz (t
anδ), the impedance at the resonance frequency, and the leakage current were measured. The leakage current was measured one minute after applying the rated voltage. Table 1 shows the average value of these measured values, the defective rate when the leakage current of 0.16 μA (0.002 CV) or more was regarded as a defective product, and the number of short products.

Here, the average value of the leakage current is a value calculated excluding defective products. Table 2 shows the results of the reflow test and the subsequent moisture resistance test. However, the leakage current value in the moisture resistance test was 3.2 μA (0.04C
V) The above was regarded as defective. Here, the reflow test (also referred to as a solder heat resistance test) was evaluated by the following method. That is, 30 capacitor elements are prepared, and the
It was passed for 30 seconds at a temperature of 0 ° C., the leakage current was measured one minute after the application of the rated voltage, and the measured value was 0.04 CV (μm).
A) The above elements were regarded as defective. The moisture resistance test was 85
The test was performed by leaving the device under high temperature and high humidity of 85 ° C. and 85% RH for 500 hours.

Example 2 Example 2 was repeated except that ferric sulfate was used instead of ammonium persulfate, dihydroisothianaphthene was used instead of 3,4-ethylenedioxythiophene, and the polymerization temperature was changed to 60 ° C. Completed 30 capacitors in the same manner as in Example 1. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 3 Thirty capacitor elements were completed in the same manner as in Example 1 except that pyrrole was used instead of 3,4-ethylenedioxythiophene. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 4 Thirty capacitor elements were completed in the same manner as in Example 1 except that aniline was used instead of 3,4-ethylenedioxythiophene. The results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1 are shown in Tables 1 and 2.

Example 5: In Example 1, 2 mol / mol
Thirty capacitor elements were completed in the same manner as in Example 1, except that sodium anthraquinone-2-sulfonate was added as a compound having a doping ability to the L aqueous ammonium persulfate solution at a concentration of 0.07 mol / L.
The results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1 are shown in Tables 1 and 2.

Example 6 Thirty capacitor elements were completed in the same manner as in Example 1, except that the concentration of the 3,4-ethylenedioxythiophene solution in isopropanol was changed to 5 mol / L. . Tables 1 and 2 show the evaluation results of these capacitor elements in the same manner as in Example 1.

Example 7 Thirty capacitor elements were completed in the same manner as in Example 1 except that the concentration of the 3,4-ethylenedioxythiophene solution in isopropanol was changed to 0.01 mol / L. Was. Table 1 shows the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.
And Table 2.

Example 8: In Example 5, 0.07 mol
3 in the same manner as in Example 1 except that 0.07 mol / L of sodium 6-methoxynaphthalenesulfonate was used instead of 1 / L of sodium anthraquinone-2-sulfonate.
Zero capacitor elements were completed. Tables 1 and 2 show the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.

Example 9 Thirty capacitor elements were completed in the same manner as in Example 1 except that the aqueous solution of ammonium persulfate was changed to 0.01 mol / L.
Tables 1 and 2 show the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.

Example 10 Thirty capacitor elements were completed in the same manner as in Example 1, except that the aqueous solution of ammonium persulfate was changed to 4 mol / L.
Tables 1 and 2 show the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.

Example 11 Thirty capacitor elements were completed in the same manner as in Example 1 except that the operation from immersion in the solution 1 to oxidative polymerization was repeated twice. . Tables 1 and 2 show the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.

Example 12: In Example 1, 3,4-
Replace ethylenedioxythiophene with furan, 2 mol
/ L ammonium persulfate was replaced by 1.4 mol / L iron (III) paratoluenesulfonate hexahydrate,
In the same manner as in Example 1, 30 capacitor elements were completed. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. When the obtained conductive polymer layer was observed with a scanning electron micrograph under the same conditions as in Example 1, a morphology similar to that of FIG. 1 was observed.

Comparative Example 1: Referring to JP-A-10-50558, 2.87 g (0.02 g) of 3,4-ethylenedioxythiophene
mol), 29.8 g (0.044 mol) of iron (III) paratoluenesulfonate hexahydrate was dissolved together in the chemical polymerization liquid, and then the aluminum foil was immersed once at 100 ° C.
To form a polymer in the foil. Then, a conductive paste (carbon and silver powder) was applied to the portion where the conductive polymer layer was formed.
Zero capacitor elements were completed. Tables 1 and 2 show the results of evaluating the characteristics of these capacitor elements in the same manner as in Example 1.

[0072]

[Table 1]

[0073]

[Table 2]

Example 13: 6.49 g (0.04 mol) of ferric chloride was weighed into a 30 ml sample tube, and 8 ml of water was added thereto to prepare an aqueous ferric chloride solution. To this, 1.68 g (0.02 mol) of thiophene as a polymerizable monomer was gently poured. Thiophene became the upper layer of the aqueous solution, creating an interface between them. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. Water 1
After stirring for 1 hour, the mixture was filtered to dissolve and remove excess ferric chloride.
After stirring for an hour, the mixture was filtered to remove unreacted thiophene and soluble low polymer, and then purified. Vacuum dried overnight at room temperature. The obtained polymer was weighed to 10 tons (t) under vacuum.
While maintaining the pressure for 3 minutes to produce pellets having a radius of 1 cm. The surface resistivity of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 16 S / cm.

Comparative Example 2: Ferrous chloride (6.49 g, 0.04 mol) was weighed into a 100 ml round bottom flask containing a stirrer.
Then, 16 ml of water was added to completely dissolve the solution, and the product was immersed in a warm bath at 40 ° C. 1.68 g of thiophene (0.
02mol) is heated to 30 ° C and isopropanol 24m
and stirred into the reaction system. During the polymerization reaction, stirring was always maintained. Stop heating after 2 hours,
The sample tube was taken out, and the polymer was taken out by filtration.
100 ml of water was added to the solid content, and the mixture was stirred for 1 hour and filtered to dissolve and remove excess ferric chloride.
After stirring for 1 hour, the mixture was filtered, and purified through a step of removing unreacted thiophene and soluble low polymer.

Next, the purified polymer was dried in a vacuum at room temperature overnight. The obtained polymer was in the form of fine powder. The polymer was molded under vacuum while applying a pressure of 10 t for 3 minutes to produce pellets having a radius of 1 cm. Lorest
a Using an IP MCP-250 (manufactured by Mitsubishi Yuka), the surface resistance of the pellet was measured, and the electrical conductivity was calculated to be 0.0054.
S / cm.

Example 14: 6.85 g (0.03 mol) of ammonium persulfate was weighed and placed in a 30 ml sample tube, and 8 ml of water was added thereto to prepare a solution. To this, 2.87 g of 3,4-ethylenedioxythiophene (0.02
mol) was gently poured. An interface was created between 3,4-ethylenedioxythiophene and the aqueous solution. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. It was confirmed that the polymerization proceeded at the interface between the aqueous solution containing the oxidizing agent and 3,4-ethylenedioxythiophene. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. 100 ml of water was added to the solid content, and the mixture was stirred for 1 hour and then filtered to dissolve and remove excess ammonium persulfate. Then, 100 ml of acetone was added and the mixture was stirred for 1 hour and filtered, and unreacted 3,4-ethylenedioxythiophene and Purification was performed through a step of removing a soluble low polymer.

FIG. 3 shows an SEM photograph of the purified polymer obtained at a magnification of 5,100 times. FIG. 4 shows a SEM photograph of the fibril structure portion of FIG. 3 at a magnification of 50,000 times. FIG.
Clearly show the fibril structure. From the observation of FIG. 4, the approximate outer diameter of the fibrils is 10 to 60 nm.
Met.

Next, the purified polymer was vacuum-dried at room temperature all day and night, and the obtained polymer was molded under vacuum while continuously applying a pressure of 10 t for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 20 S / cm.

Comparative Example 3: 2.87 g (0.02 mol) of 3,4-ethylenedioxythiophene as a polymerizable monomer, and 6.85 g (0.03 mol) of ammonium persulfate as a polymerization oxidizing agent
A polymer was prepared according to Comparative Example 2 except that was used.
FIG. 5 shows an SEM photograph of the obtained purified polymer magnified 50,000 times, but no fibril structure was observed.

Next, the purified polymer was vacuum-dried at room temperature all day and night, and the obtained polymer was molded under vacuum while continuously applying a pressure of 10 t for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 0.064 S / cm.

Example 15 Ammonium persulfate (6.85 g, 0.03 mol) was weighed into a 30 ml sample tube, and 1 ml of water was added thereto to prepare a saturated solution containing undissolved ammonium persulfate. To this, 2.87 g (0.02 mol) of 3,4-ethylenedioxythiophene as a polymerizable monomer was gently poured. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization in an open system. After 2 hours, heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. 100 ml of water was added to this solid, and the mixture was stirred for 1 hour and filtered to dissolve and remove excess ammonium persulfate.
After stirring for 1 hour, the mixture was filtered, and purified through a step of removing unreacted 3,4-ethylenedioxythiophene and a soluble low polymer.

FIG. 6 shows a SEM photograph of the obtained purified polymer at 2,000-fold magnification. FIG. 7 shows an enlarged SEM photograph of the fibril structure shown in FIG. 6 at a magnification of 20,000 times. The fibril structure is clearly shown. Next, the purified polymer was vacuum-dried at room temperature all day and night, and the polymer obtained after the drying was molded under vacuum at a pressure of 10 t for 3 minutes to form a pellet having a radius of 1 cm. Lore
The surface resistance of the pellets was measured using sta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated.
S / cm.

Example 16: 6.85 g (0.03 mol) of ammonium persulfate was weighed and placed in a 30 ml sample tube, and 8 ml of water was added thereto to prepare a solution. 1.86 g (0.014 mol) of 1,3-dihydroisothianaphthene as a polymerizable monomer
l) was warmed to 30 ° C. and gently poured in to create an interface with the oxidant solution. Next, heat the sample tube to 40 ° C.
In a warm bath to initiate polymerization. The heating was stopped after 6 hours, and then left at room temperature for 7 days to complete the polymerization reaction.
The sample tube was taken out, and the polymer was taken out by filtration.
After adding 100 ml of water to the solid content and stirring for 1 hour, filtration was performed to dissolve and remove excess ammonium persulfate. Then, 100 ml of acetone was added and the mixture was stirred for 1 hour and filtered. Purification was performed through a step of removing naphthenes and soluble low polymers.

FIG. 8 shows a photograph of the obtained purified polymer magnified 50,000 times with a scanning electron microscope (SEM). The fibril structure is clearly shown. From the observation in FIG.
The approximate outer diameter of the fibrils was 10-50 nm. The purified polymer is then vacuum dried at room temperature all day and night,
The obtained polymer was molded under vacuum while continuously applying a pressure of 10 t for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 14 S / cm.

Comparative Example 4 A polymer was prepared according to Comparative Example 2 except that 1.86 g (0.014 mol) of 1,3-dihydroisothianaphthene was used as a polymerizable monomer and the polymerization time was changed to 2 hours. The polymer obtained after drying was molded under vacuum while continuously applying a pressure of 10 t for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka),
The calculated electrical conductivity was 0.0033 S / cm. FIG. 9 shows a SEM photograph of the obtained polymer at a magnification of 50,000 times. It did not show a fibril structure.

Example 17: 6.85 g (0.03 mol) of ammonium persulfate was weighed into a 30-ml sample tube, and the mixture was weighed with 0.1%.
A solution was prepared by adding 8 ml of 1N-HCl aqueous solution. 1.86 g (0.02 mol) of aniline as a polymerizable monomer
Was poured gently. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. To this solid was added 100 ml of water, stirred for 1 hour, and filtered to dissolve and remove excess ammonium persulfate.
Then, the mixture was stirred for 1 hour, filtered, and purified through a step of removing unreacted aniline and soluble low polymer. Vacuum dried at room temperature all day and night, and the obtained polymer was molded under vacuum while applying a pressure of 10 t for 3 minutes to obtain a polymer having a radius of 1c.
m pellets were prepared. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 10 S / cm.

Comparative Example 5: As the polymerizable monomer, aniline 1.
A polymer was prepared according to Comparative Example 3 except that 86 g (0.02 mol) was used. The polymer obtained after drying was molded under vacuum while continuously applying a pressure of 10 t for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using LorestaIP MCP-250 (manufactured by Mitsubishi Yuka),
The calculated electric conductivity was 0.0024 S / cm.

Example 18: 6.85 g (0.03 mol) of ammonium persulfate and 0.46 g (0.0014 mol) of sodium anthraquinone-2-sulfonate were weighed into a 30 ml sample tube, and 8 ml of water was added thereto to prepare a solution. . To this, 2.87 g (0.02 mol) of 3,4-ethylenedioxythiophene as a polymerizable monomer was gently poured. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. 100 ml of water was added to the solid content, and the mixture was stirred for 1 hour and filtered to dissolve and remove excess ammonium persulfate and sodium anthraquinone-2-sulfonate. Then, 100 ml of acetone was added, and the mixture was stirred for 1 hour and filtered. , 4-ethylenedioxythiophene and a soluble low polymer were removed. Vacuum dried at room temperature all day and night, and the obtained polymer was dried under vacuum for 10 hours.
Molding was performed while pressing at t was continued for 3 minutes to produce pellets having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 26 S / cm.

Example 19: 6.85 g (0.03 mol) of ammonium persulfate was weighed and placed in a 30 ml sample tube, and 8 ml of water was added thereto to prepare a solution. To this, 2.87 g of 3,4-ethylenedioxythiophene (0.02
mol) was gently poured. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. Stop heating after 2 hours,
The sample tube was taken out, and the polymer was taken out by filtration.
Again, add 6.85 ammonium persulfate to the 30 ml sample tube.
g (0.03 mol) was weighed, and 8 ml of water was added thereto to prepare a solution. To this, gently pour 2.87 g (0.02 mol) of 3,4-ethylenedioxythiophene as a polymerizable monomer, put the removed polymer into the system, and immerse the sample tube in a warm bath at 40 ° C for polymerization. Was started. This step was performed three times to laminate the polymer. Water 1
Add 100 ml, stir for 1 hour, and filter to dissolve and remove excess ammonium persulfate. Then, add 100 ml of acetone, stir for 1 hour, and filter to remove unreacted 3,4-ethylenedioxythiophene and soluble low polymer. And purified. The polymer was dried under vacuum at room temperature for 24 hours, and the polymer obtained after drying was molded under vacuum while applying a pressure of 10 t for 3 minutes to form a pellet having a radius of 1 cm. Lo
The surface resistance of these pellets was measured using resta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated.
It was 9 S / cm.

Example 20 27.10 g (0.04 g) of iron (III) paratoluenesulfonate hexahydrate was placed in a 30 ml sample tube.
mol), and 8 ml of water was added thereto to prepare an oxidizing agent aqueous solution. 1.36 g of furan as a polymerizable monomer
(0.02 mol) was poured in gently. Furan became the upper layer of the aqueous solution, creating an interface between them. 40 sample tubes
It was immersed in a warm bath at ℃ to initiate polymerization. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. After adding 100 ml of water to this solid content and stirring for 1 hour,
Filtration and extra iron (III) paratoluenesulfonate ・ 6
The hydrate was dissolved and removed. Then, 100 ml of acetone was added, and the mixture was stirred for 1 hour and then filtered to remove unreacted furan and a soluble low polymer, followed by purification. Vacuum dried overnight at room temperature. The obtained polymer was molded under vacuum while continuously applying a pressure of 10 tons (t) for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 13 S / cm. Further, when the obtained conductive polymer layer was observed with a scanning electron microscope photograph under the same conditions as in Example 14, fibril shapes similar to those in FIGS. 3 and 4 were observed.

Example 21: To a 30 ml sample tube, 6.49 g (0.04 mol) of ferric chloride was weighed, and 8 ml of water was added thereto to prepare an aqueous ferric chloride solution. To this, 1.34 g (0.02 mol) of pyrrole as a polymerizable monomer was gently poured. Pyrrole became the upper layer of the aqueous solution, creating an interface between them. The sample tube was immersed in a warm bath at 40 ° C. to initiate polymerization. After 2 hours, the heating was stopped, the sample tube was taken out, and the polymer was taken out by filtration. This solid is added to water 10
After adding 0 ml and stirring for 1 hour, filtration was performed to dissolve and remove excess ferric chloride, and then 100 ml of acetone was added to add 1 ml of acetone.
After stirring for an hour, the mixture was filtered to remove unreacted pyrrole and a soluble low polymer, and then purified. Vacuum dried overnight at room temperature.
The obtained polymer was molded under vacuum while continuously applying a pressure of 10 tons (t) for 3 minutes to produce a pellet having a radius of 1 cm. The surface resistance of the pellet was measured using Loresta IP MCP-250 (manufactured by Mitsubishi Yuka) and the electrical conductivity was calculated to be 21 S / cm. Further, when the obtained conductive polymer layer was observed with a scanning electron microscope photograph under the same conditions as in Example 14, fibril shapes similar to those in FIGS. 3 and 4 were observed.

[0093]

According to the present invention, general formulas (6) to (1)
The polymerizable monomer represented by 0) alone or together with the polymerizable monomer and an electrolyte having a doping ability is brought into contact with a solution containing an oxidizing agent having a polymerization initiating ability to polymerize at an interface formed. By a simple chemical oxidation polymerization technique, a highly conductive film-like polymer composition having a fibril structure, excellent anisotropy and excellent film properties, containing a repeating unit represented by formulas (1) to (5) Things are obtained. Such a highly conductive polymer composition, as a highly conductive solid electrolyte,
It can be used for various industrial applications such as a solid electrolytic capacitor, a conductive material such as an antistatic material and a radio wave absorbing material.

Further, according to the present invention, there is provided a solid electrolytic capacitor using a conductive polymer as a solid electrolyte, having the above-mentioned fibril structure, excellent anisotropy and excellent film properties. ) By forming a polymer solid electrolyte containing a repeating unit represented by
A solid electrolyte layer having excellent thermal stress relaxation ability and excellent adhesion to the paste layer can be obtained.

Furthermore, the present invention provides a solid electrolyte which is excellent in the ability to repair a film during conduction by covering with a film-like solid electrolyte having highly conductive fibrils so that a space remains in the fine pores of the anode. Layers can be obtained. As a result, not only initial characteristics (loss coefficient, leakage current, heat resistance, equivalent series resistance and impedance in high frequency range, etc.) but also long-term reliability (durability under high temperature and high humidity) are excellent. A capacitor element can be provided.

[Brief description of the drawings]

FIG. 1 is a scanning electron micrograph (× 50,000) of a cross section of an anode aluminum foil having a conductive polymer layer formed thereon in Example 1 of the present invention.

FIG. 2 is a scanning electron micrograph (× 50,000) of a chemically treated aluminum foil.

FIG. 3 is a scanning electron micrograph (× 5,100) of a 3,4-ethylenedioxythiophene highly conductive polymer obtained in Example 14.

FIG. 4 is an enlarged scanning electron micrograph (× 50,000) of a fibril structure portion of the highly conductive polymer in FIG.

FIG. 5 is a scanning electron micrograph (× 50,0) of a 3,4-ethylenedioxythiophene polymer obtained in Comparative Example 3.
00).

FIG. 6 is a scanning electron micrograph (× 2,000) of the 3,4-ethylenedioxythiophene highly conductive polymer obtained in Example 15.

7 is an enlarged scanning electron micrograph (× 20,000) of the fibril structure portion of the highly conductive polymer in FIG. 6.

FIG. 8 is a scanning electron micrograph (× 50,000) showing the fibril structure of the 1,3-dihydroisothianaphthene highly conductive polymer obtained in Example 16.

FIG. 9 is a scanning electron micrograph (× 50,00) of a 1,3-dihydroisothianaphthene polymer obtained in Comparative Example 4.
0).

Continued on the front page (72) Inventor Ryuji Kadota 6850 Omachi Omachi, Omachi City, Nagano Prefecture Showa Denko Omachi Plant Co., Ltd. (Reference) 4J032 BA03 BA04 BA08 BA09 BA13 BA14 BB01 BC03 BC24 BC26 BC32 CG01 4J043 PA01 PC016 PC066 PC076 PC116 PC136 PC146 PC166 PC186 QB02 RA08 SA05 SB01 UA121 VA041 XA03 XA13 XA19 XA28 YB05 ZA44 ZB11 ZB49 ZB60

Claims (33)

[Claims] 1. A solid electrolytic capacitor in which a solid electrolyte layer made of a polymer having a fibril structure is formed on a porous dielectric film of a metal having a valve action. 2. The polymer is represented by the following general formula (1): (Wherein, R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, Nitro group, cyano group, 1
Represents a monovalent group selected from the group consisting of primary, secondary or tertiary amino groups, CF ₃ groups, phenyl groups and substituted phenyl groups. Further, the hydrocarbon chains of R ¹ and R ² are bonded to each other at an arbitrary position to form a 3- to 7-membered saturated or unsaturated hydrocarbon cyclic structure together with the carbon atom substituted by such a group. A bivalent chain may be formed. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. Δ is in the range of 0 to 1. Z represents an anion; j represents the valence of Z;
Or 2. The solid electrolytic capacitor according to claim 1, which is a conductive polymer having a fibril structure containing a thiophene skeleton structure represented by the formula (1) as a repeating unit. 3. The polymer is represented by the following general formula (2): (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms) , An alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ³ , R ⁴ , R ⁵ ,
The hydrocarbon chains of R ⁶ , R ⁷ or R ⁸ may be bonded to each other at any position to form at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain forming a cyclic structure of The cyclic bond chain includes carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl,
An imino bond may be included at any position. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is 0 or an integer of 1 to 3.
The fused ring in the formula may contain any number of nitrogens or N-oxides, but the number of substituents R ^{3 to} R ⁸ will be reduced by that number. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. )
2. A conductive polymer having a fibril structure containing a condensed polycyclic skeleton structure represented by the following formula as a repeating unit.
The solid electrolytic capacitor according to item 1. 4. The polymer is represented by the following general formula (3): (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. Z represents an anion, j represents the valence of Z, and is 1 or 2. The solid electrolytic capacitor according to claim 1, which is a conductive polymer having a fibril structure containing a pyrrole skeleton structure represented by the formula (1) as a repeating unit. 5. The polymer represented by the following general formula (4): (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.
δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. The solid electrolytic capacitor according to claim 1, which is a conductive polymer having a fibril structure containing a furan skeleton structure represented by the formula (1) as a repeating unit. 6. The polymer represented by the following general formula (5): (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one divalent chain forming a cyclic structure of a saturated or unsaturated hydrocarbon of one or more 3- to 7-membered rings may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. z represents an anion, j represents the valence of z, and is 1 or 2. The solid electrolytic capacitor according to claim 1, which is a conductive polymer having a fibril structure containing the aniline skeleton structure represented by the formula (1) as a repeating unit. 7. The conductivity of the solid electrolyte layer of the polymer,
The solid electrolytic capacitor according to any one of claims 2 to 6, which has a pressure of 0.1 to 200 S / cm. 8. A method for manufacturing a solid electrolytic capacitor comprising a solid electrolyte layer made of a polymer on a porous dielectric film of a metal having a valve action, wherein the polymerizable monomer is saturated on the dielectric film. Alternatively, by contacting a single solution of an oxidizing agent having a polymerization initiating ability or a mixed solution of the oxidizing agent and an electrolyte having a doping ability while maintaining a supersaturated state, a film of a polymer having a fibril structure on the dielectric film is formed. A method for producing a solid electrolytic capacitor having a solid electrolyte layer made of a polymer having a fibril structure, comprising a step of forming a composition. 9. A method for manufacturing a solid electrolytic capacitor comprising a solid electrolyte layer made of a polymer on a porous dielectric film of a metal having a valve action, wherein a polymerizable monomer solution or a polymerizable monomer solution is formed on the dielectric film. A solution in which a polymerizable monomer and an electrolyte having a doping ability are dissolved is brought into contact with a single solution of an oxidizing agent having a polymerization initiating ability in a saturated or supersaturated state or a mixed solution of the oxidizing agent and an electrolyte having a doping ability. Producing a solid electrolyte layer made of a polymer having a fibril structure, comprising the step of forming a film-like composition of a polymer having a fibril structure on the dielectric film. Method. 10. On the dielectric film, the following general formula (6): (Wherein the substituents R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom) atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a trihalomethyl group, a hydrocarbon chain of .R ¹ and R ² represent a monovalent group selected from a phenyl group and a group consisting of substituted phenyl groups May be bonded to each other at any position to form a divalent chain which forms a cyclic structure of a 3- to 7-membered saturated or unsaturated hydrocarbon with a carbon atom substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.) The method for producing a solid electrolytic capacitor according to claim 8 or 9 into contact with a solution containing an oxidizing agent to form a film-like composition of a polymer having a fibril structure on the dielectric film having a Hajimeno. 11. The following general formula on the dielectric film:
(7)(Wherein the substituent R^Three, R^Four, R^Five, R⁶, R⁷And R⁸Is
Each independently represents a hydrogen atom, a straight chain having 1 to 10 carbon atoms.
Or branched saturated or unsaturated alkyl group, alcohol
Xy group or alkyl ester group, or halogen source
Nitro, cyano, primary, secondary or tertiary amine
No group, CF_ThreeGroup, phenyl group and substituted phenyl group.
Represents a monovalent group selected from the group consisting of Also, R^Three, R^Four, R
^Five, R⁶, R ⁷Or R⁸Hydrocarbon chains are in any position relative to each other
And the carbon atom which is substituted by such a group
Together with at least one saturated or unsaturated 3- to 7-membered ring
Even if a divalent chain forming a cyclic structure of a saturated hydrocarbon is formed
Good. The cyclic bond chain includes carbonyl, ether, S
Ter, amide, sulfide, sulfinyl, sulfoni
And an imino bond may be included at any position. k is j
Offen ring and substituent R^ThreeOr R⁶Surrounded by a benzene ring
Represents an integer of 0 or 1 to 3
You. Nitrogen or an N-oxide may be added to the fused ring in the formula.
May contain a number of substituents R^ThreeOr R⁸Decreases
Will do. ) And the polymerizable monomer
Contacting with a solution containing an oxidizing agent having initiating ability,
Film-like set of polymer having fibril structure on dielectric film
10. The solid electrolytic capacitor according to claim 8, which forms a product.
Manufacturing method of DENSA. 12. On the dielectric film, the following general formula (8): (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. 9. A film-like composition of a polymer having a fibril structure is formed on the dielectric film by contacting the polymerizable monomer represented by the formula) with a solution containing an oxidizing agent having a polymerization initiating ability.
Or a method for manufacturing a solid electrolytic capacitor according to item 9. 13. On the dielectric film, the following general formula (9): (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.) The solid according to claim 8 or 9, wherein a monomer and a solution containing an oxidizing agent having a polymerization initiation ability are brought into contact with each other to form a polymer composition having a fibril structure on the dielectric film. Manufacturing method of electrolytic capacitor. 14. On the dielectric film, the following general formula (1)
0) (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one or more divalent chains forming a cyclic structure of one or more 3- or 1-membered saturated or unsaturated hydrocarbons may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. 9. A film-like composition of a polymer having a fibril structure is formed on the dielectric film by contacting the polymerizable monomer represented by the formula) with a solution containing an oxidizing agent having a polymerization initiating ability.
Or a method for manufacturing a solid electrolytic capacitor according to item 9. 15. The concentration of the polymerizable monomer is 0.01 to 5 mol.
/ L. The method for producing a solid electrolytic capacitor according to claim 9, wherein 16. The concentration of an electrolyte having doping ability is
9. The range of 0.001 mol / L to 2.5 mol / L.
Or a method for manufacturing a solid electrolytic capacitor according to item 9. 17. The method for producing a solid electrolytic capacitor according to claim 8, wherein the oxidizing agent having a polymerization initiation ability is at least one compound selected from persulfates, dichromates, and trivalent iron salts. Method. 18. The method according to claim 8, wherein the concentration of the oxidizing agent having the ability to initiate polymerization is 0.01 to 5 times the concentration of the polymerizable monomer.
3. The method for manufacturing a solid electrolytic capacitor according to item 1. 19. The method for producing a solid electrolytic capacitor according to claim 8, wherein the step of forming a solid electrolyte made of a polymer is repeated 2 to 30 times to form a film-like composition. 20. The following general formula (1): (Wherein the substituents R ¹ and R ² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom) atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹ and R ² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups May combine with each other at any position to form a divalent chain that forms a cyclic structure of a 3- to 7-membered saturated or unsaturated hydrocarbon with a carbon atom substituted by such a group. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position, and δ is in the range of 0 to 1.
Z represents an anion, j represents the valence of Z, and is 1 or 2. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. )
And a highly conductive polymer having a fibril structure containing a thiophene skeleton structure as a repeating unit. 21. The following general formula (2): (Wherein the substituents R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl having 1 to 10 carbon atoms) Group, an alkoxy group or an alkyl ester group, or a monovalent group selected from the group consisting of a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. R ³ , R ⁴ ,
The hydrocarbon chains of R ⁵ , R ⁶ , R ⁷ or R ⁸ may be bonded to each other at any position to form a saturated or unsaturated at least one or more 3- to 7-membered ring together with the carbon atom substituted by such groups. A divalent chain that forms a cyclic structure of a saturated hydrocarbon may be formed. The cyclic bond may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is 0 or an integer of 1 to 3. The fused ring in the formula may optionally contain nitrogen or N-oxide, but will not have the same number of substituents R ^{3 to} R ⁸ . δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the condensed polycyclic skeleton structure represented by the formula (1) as a repeating unit. 22. The following general formula (3): (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom,
A linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group,
Represents a monovalent group selected from the group consisting of a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ⁹ and R ¹⁰ are bonded to each other at any position to form a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the pyrrole skeleton structure as a repeating unit. 23. The following general formula (4): (Wherein the substituents R ¹¹ and R ¹² each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom; atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ and R ¹² represent a monovalent group selected from the group consisting of phenyl and substituted phenyl groups Are bonded to each other at any position to form a divalent chain which forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon with carbon atoms substituted by such a group. The cyclic bond may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position.
δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing a furan skeleton structure represented by the following formula as a repeating unit. 24. The following general formula (5): (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or Alkyl ester groups, or halogen atoms, nitro groups, cyano groups, primary, secondary or tertiary amino groups,
Represents a monovalent group selected from the group consisting of a CF ₃ group, a phenyl group and a substituted phenyl group. R ¹³ , R ¹⁴ , R ¹⁵ or R
^{The sixteen} hydrocarbon chains may be linked together at any position, with at least one carbon atom being substituted by such a group.
At least one or more divalent chains forming a cyclic structure of one or more 3- or 1-membered saturated or unsaturated hydrocarbons may be formed. The bonding chain may include a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino bond at any position. δ is 0
-1. z represents an anion, j represents the valence of z, and is 1 or 2. A) a highly conductive polymer having a fibril structure containing the aniline skeleton structure as a repeating unit. 25. The following general formula (6): (Wherein R ¹ and R ² have the same meanings as described in claim 10), and the general formula (7) (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as defined in claim 1)
It has the same meaning as described in 1. ), General formula (8) (Wherein R ⁹ and R ¹⁰ have the same meanings as described in claim 12). (Wherein, the substituents R ¹¹ and R ¹² have the same meanings as described in claim 13), and the general formula (10): (Wherein, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meaning as described in claim 14), and an oxidizing agent having a polymerization initiation ability. A method for producing a highly conductive polymer having a fibril structure, comprising contacting a solution containing the two with each other so as to form an interface, and causing polymerization at the interface. 26. The general formula (6) according to claim 25,
A solution obtained by dissolving at least one of the polymerizable monomers represented by (7), (8), (9) and (10) in a solvent and a solution containing an oxidizing agent having a polymerization initiation ability The method for producing a highly conductive polymer having a fibril structure according to claim 25, wherein both are brought into contact with each other to form an interface, and polymerization is carried out at the interface. 27. The method for producing a highly conductive polymer having a fibril structure according to claim 25, wherein the solution containing an oxidizing agent having a polymerization initiation ability contains an electrolyte having a doping ability. 28. The method for producing a highly conductive polymer having a fibril structure according to claim 25, wherein the solution containing an oxidizing agent having a polymerization initiation ability is a saturated solution or a supersaturated solution. 29. A saturated solution of an oxidizing agent having a polymerization initiating ability is prepared, and the oxidizing agent solution and the polymerizable monomer are contacted at a temperature lower than the saturated solution preparing temperature so as to form an interface, The method for producing a highly conductive polymer having a fibril structure according to claim 25 or 26, wherein the polymerization is performed thereafter. 30. The highly conductive polymer having a fibril structure according to claim 25, wherein at least one of a persulfate, a dichromate, and a trivalent iron salt is used as the oxidizing agent having a polymerization initiation ability. Manufacturing method. 31. The method for producing a highly conductive polymer having a fibril structure according to claim 26, wherein a hydrophilic organic solvent capable of dissolving a polymerizable monomer is used as the solvent. 32. The method for producing a highly conductive polymer having a fibril structure according to claim 25, wherein the polymerizable monomer is brought into contact with a solution containing an oxidizing agent to produce a highly conductive polymer having a fibril structure. A method for producing a highly conductive polymer having a fibril structure according to claim 25 on the surface of a highly conductive polymer having a fibril structure, which forms a coalescence and is washed or not washed, is further provided. A method for producing a highly conductive polymer having a fibril structure, wherein the method is repeated and a polymer composition is laminated. 33. The method for producing a highly conductive polymer having a fibril structure according to claim 26, wherein the polymerizable monomer is brought into contact with a solution containing an oxidizing agent to produce a highly conductive polymer having a fibril structure. A method for producing a highly conductive polymer having a fibril structure according to claim 26 on the surface of a highly conductive polymer having a fibril structure, which forms a coalescence and is washed or not washed, is further provided. A method for producing a highly conductive polymer having a fibril structure, wherein the method is repeated and a polymer composition is laminated.