JP2009164187A - Method of manufacturing conductive polymer capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a conductive polymer electrolytic capacitor that uses pyrrole and a pyrrole derivative by a chemical polymerization method, obtains an electrolyte having high conductivity, and has a low impedance and a large capacity. <P>SOLUTION: An organic base, which has a polymerization delay effect and a conductivity improvement effect of an obtained polymer is added in the polymerization of the pyrrole and the pyrrole derivative to delay polymerization speed, thus obtaining the electrolyte, having high conductivity and manufacturing a conductive polymer electrolytic capacitor which includes an electrolyte and an electrode having both a low impedance and a large capacity. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive polymer capacitor, and more particularly, by polymerizing pyrrole and a pyrrole derivative, by adding an organic base having a polymerization delay effect and an effect of improving the conductivity of the obtained polymer, The present invention relates to a method for producing a conductive polymer capacitor having both low impedance and large capacity by obtaining an electrolyte and delaying the polymerization rate.

In recent years, electrolytic capacitors using a conductive polymer as an electrolyte are expanding the market due to their excellent impedance characteristics. A conductive polymer electrolytic capacitor typically uses a solid conductive polymer such as polypyrrole or a polythiophene derivative as an electrolyte. In general, these conductive polymers are prepared by electrolytic polymerization in which conductive polymer monomers are dissolved in a solvent and polymerized by anodic oxidation, or chemical polymerization methods in which conductive polymer monomers are oxidatively polymerized in the presence of an oxidizing agent. Formed by. The electrolytic polymerization method is a useful method for producing capacitor elements because it can form a dense film of conductive polymer, but it requires advanced technology and equipment, so it is chemical in terms of manufacturing cost. It is desirable to form a conductive polymer by a polymerization method. On the other hand, polypyrrole has not only high conductivity comparable to that of poly (3,4-ethylenedioxythiophene) (Patent Document 1), but is also inexpensive and is very useful as an electrolyte for capacitors. However, there is a problem that the capacitor element cannot be produced by chemical polymerization because the polymerization rate is too high. In order to solve this problem, a method is disclosed in which an organic compound such as sulfoxides or amides can be added as a polymerization control agent to delay the polymerization rate (Patent Document 2), but the polymerization rate is delayed. Even if it was possible, the impedance and capacitance of the capacitor element produced were not satisfactory. In particular, regarding the impedance characteristics, since the conductivity of the polymer is lowered by adding a polymerization control agent that is an insulator, deterioration of the characteristics is inevitable. Thus, a technique for producing a low-impedance, large-capacity capacitor by chemical polymerization using pyrrole as a conductive polymer monomer is awaited.
Japanese Patent Application No. 2004-355020 JP 2006-165288 A

  In view of the above, the object of the present invention is to obtain an electrolyte having a high conductivity by adding an organic base having a polymerization retardation effect and a conductivity improvement effect of the obtained polymer during polymerization of pyrrole and a pyrrole derivative, An object of the present invention is to provide a method for producing a conductive polymer capacitor having both a low impedance and a large capacity by slowing the polymerization rate to such an extent that the chemical polymerization rate advantage over the electropolymerization is not lost.

  As a result of intensive studies in view of the above problems, the present inventors have found that imidazole and pyridine have a pyrrole polymerization retardation effect, and not only can capacitor elements be produced by chemical polymerization methods, but also low The inventors have found that an impedance and a large capacity can be realized, and have completed the present invention.

  That is, the present invention relates to the general formula (1);

(Here, X and Y each independently represent any of H, C, O, N, and S, R ¹ and R ² are present when X and Y are not H, and H or C _{1 to} C _20. A hydrocarbon group, which may be linear or branched and may have a cyclic structure, and R ³ represents a protective group for H or amine). General formula (2) and / or general formula (3) having a polymerization delay effect and an effect of improving the conductivity of the obtained polymer;

  The present invention relates to a method for producing a conductive polymer capacitor, characterized in that chemical polymerization is performed using an oxidizing agent in the presence of an organic base.

  According to the present invention, a conductive polymer capacitor in which an electrolyte is formed by inexpensive chemical polymerization of pyrrole can be produced. Further, since the electrolyte has high conductivity, a conductive polymer capacitor having both low impedance and large capacity can be obtained.

  Hereinafter, the present invention will be described in detail.

  First, the conductive polymer capacitor of the present invention includes at least an electrolyte layer, and an anode and a cathode arranged so as to face each other with the electrolyte layer interposed therebetween. The conductive polymer capacitor of the present invention can be formed in either a chip type or a wound type. A chip-type electrolytic capacitor typically has a capacitor element in which an electrolyte layer and a cathode are laminated in this order on the dielectric film of an anode made of an anode metal having a dielectric film formed on the surface thereof. A connection terminal electrically connected to the capacitor element is provided. On the other hand, a wound-type electrolytic capacitor typically has an electrolyte layer, a separator, a cathode, and a separator on the dielectric film of an anode made of an anode metal having a dielectric film formed on the surface thereof from the radially inner side. Are arranged so as to be arranged in this order, and the capacitor element is laminated and wound, and a connection terminal electrically connected to the capacitor element. In the separator, usually, a separator material made of, for example, polyolefin or cellulose fiber and a conductive polymer are combined.

  As the anode of the conductive polymer capacitor of the present invention, a conventionally known one can be preferably used in the conductive polymer capacitor. For example, as the anode metal, etching is performed on the surface of an electrode foil such as aluminum to form an etching hole. Using a powder electrode made of tantalum or the like, and combining a dielectric film made of an oxide film formed by a method such as anodic oxidation on the surface of the anode metal, it is made of an anode metal and a dielectric film An anode can be formed. The above anodic oxidation can be performed by immersing the anode metal in an aqueous solution of ammonium adipate, for example, and applying a chemical voltage.

  As the cathode, for example, a carbon paste and a silver paste can be formed by a conventionally known method. The anode and cathode are each connected to a terminal. In this way, a conductive polymer denser having at least an anode, an electrolyte membrane, and a cathode can be formed.

  Next, general formula (1);

The conductive polymer monomer used in the present invention represented by In the general formula (1), X and Y each independently represent any of a hydrogen atom (H), a carbon atom (C), an oxygen atom (O), a nitrogen atom (N), and a sulfur atom (S). It is preferable that both X and Y are H from the viewpoint of easy availability of raw materials. R ¹ and R ² are present when X and Y are not H, are H or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, and may be linear or branched, In addition, it may have a ring structure. In the present invention, “may have a substituent” means that it may be substituted with another atom or substituent. The “substituent” is not particularly limited as long as it does not adversely affect the reaction. Specifically, the hydroxyl group, alkyl group, alkoxy group, alkylthio group, nitro group, amino group, cyano group, carboxyl group, A halogen atom etc. are mentioned. Examples of the hydrocarbon group optionally _C 1 _{-C 20} which may have a substituent, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, t- Butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, n-icosyl group, phenyl Examples thereof include, but are not limited to, a naphthyl group. From the viewpoints of the reactivity of the polymerization reaction, the conductivity of the obtained polymer and the solubility of the obtained polymer in a solvent, a methyl group, an ethyl group and an n-hexyl group are preferred. R ³ represents a protecting group for H or amine, and examples thereof include a methyl group, an ethyl group, a phenyl group, a 4-nitrophenyl group, a benzyl group, and a t-butyloxycarbonyl group. Otherwise, H is preferred because it is not necessary to deprotect after polymerization.

When both X and Y are not H, R ¹ and R ² may be combined to form a cyclic structure. Examples of this include general formula (8);

The pyrrole derivative represented by these is mentioned. In the formula, A ¹ and A ² each independently represent any of C, O, N, and S, n is an integer of 1 to 20, and the viewpoint of the reactivity of the polymerization reaction and the conductivity of the obtained polymer To preferably 1 to 5, particularly preferably 2 or 3. R ³ represents the same meaning as described above. Moreover, general formula (9);

A compound having a branched structure at the cross-linked part of A ¹ and A ² is also exemplified. R ^{15, R 16} represents an alkyl group having each independently H or optionally substituted _C 1 _{-C 20,} a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, Isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n -An octadecyl group, n-icosyl group, a phenyl group, and a naphthyl group are illustrated, Preferably they are a methyl group and n-hexyl group. R ³ represents the same meaning as described above. The general formula (9) is an example when n = 2 in the general formula (8), but the same can be said for compounds having n = 1 and n = 3 to 20. That is, in the general formula (8), an alkyl group corresponding to R ¹⁵ and R ¹⁶ may be bonded to each carbon of the alkyl chain forming the cyclic structure. Furthermore, general formula (10);

As described above, the alkyl chain forming the cross-linked portion of A ¹ and A ² may have an unsaturated bond. In the formula, R ³ , A ¹ , A ² , R ¹⁵ and R ¹⁶ represent the same meaning as described above. The general formula (10) is an example having an unsaturated bond in the general formula (9), but the same can be said for a compound with n = 1 and n = 3 to 20, and a cyclic structure is formed. Unsaturated bonds may be present everywhere in the alkyl chain.

  Next, the organic base will be described. The organic base contained in the electrolyte of the present invention has the effect of delaying the polymerization rate of the monomer constituting the conductive polymer represented by the general formula (1) and the effect of improving the conductivity of the resulting polymer. It is speculated that, during the polymerization, the organic base forms a complex with the cation component of the oxidant, and as a result, the oxidation potential of the oxidant decreases, thereby slowing the chemical (oxidation) polymerization of the monomer. thinking. Due to this polymerization rate retarding effect, polymerization starts after the monomer and oxidizer solution containing the organic base are sufficiently immersed in the etching holes of aluminum, so that the capacitor element of polypyrrole can be obtained by the conventional chemical polymerization method. In addition to solving the problem that it is not possible to form the conductive polymer layer, it is possible to form the conductive polymer layer uniformly in the etching hole, thereby realizing a large-capacity capacitor. In addition, since the oxidation potential of the oxidizing agent is lowered, for example, even in the case of pyrrole having a very high reactivity, the polymerization does not proceed at random, but is selectively polymerized at the preferred 2nd and 5th positions on the pyrrole ring. It is considered that a polymer having a long conjugated chain and a high structural regularity can be obtained. Furthermore, the organic base also has an effect of controlling the morphology of the resulting polymer, and the two effects of lowering the oxidation potential are factors that give a polymer having very high conductivity. I think that. As a result, we believe that a low impedance capacitor could be realized.

  Next, the general formula (2)

And general formula (3)

The organic base used in the present invention represented by In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H (hydrogen atom) or a C _{1 to} C ₂₀ hydrocarbon group, and may be linear or branched. In addition, it may have a ring structure. From the viewpoint of easy availability of raw materials, it is preferable that R ⁴ , R ⁵ , R ⁶ and R ⁷ are all H (hydrogen atom). In the general formula (3), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are each independently H (hydrogen atom) or a C ₁ -C ₂₀ hydrocarbon group, linear or branched And may have a ring structure. From the viewpoint of easy availability of raw materials, it is preferable that R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are all H (hydrogen atom). Examples of the organic base represented by the general formula (2) include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2,4,5-trimethylimidazole, 1 , 2,4,5-tetramethylimidazole, 1-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, 1,2-diethylimidazole, 2,4,5-triethylimidazole, 1,2,4,5- Tetraethylimidazole, 2-methyl-4-ethylimidazole, 2-isopropylimidazole, 1-butylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4,5-diphenylimidazole, 4-methyl-2-phenylimidazole, 1- Benzyl-2-methylimida Lumpur, 1-acetyl imidazole, benzimidazole, 1H-imidazole-4,5-like dicarboxylate including without being limited thereto. From the viewpoint of the effect of delaying the polymerization rate, imidazole is preferable. Examples of the organic base represented by the general formula (3) include pyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, Lutidines such as 3,5-lutidine, picolines such as 2-picoline, 3-picoline, 4-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-n-propylpyridine, 2- Isopropylpyridine, 3-n-propylpyridine, 3-isopropylpyridine, 4-n-propylpyridine, 4-isopropylpyridine, 4-t-butylpyridine, 2,6-di-t-butylpyridine, 2,6-di -T-butyl-4-methylpyridine, 5-ethyl-2-picoline, 3-methyl-2-phenylpyridine, 2-methoxy-6-methylpyridine, 2,4, - collidine, 4-dimethylaminopyridine, picolinate, but like ethyl picolinic acid, but it is not limited thereto. From the viewpoint of the effect of delaying the polymerization rate, pyridine is preferable.

  The amount of the organic base added is 0.05 to 10 molar equivalents with respect to the cation component constituting the oxidizing agent when chemically (oxidizing) polymerizing the conductive polymer monomer, 1 to 5 molar equivalents. If the equivalent amount of the organic base is too small, the polymerization retarding effect is too weak and chemical polymerization proceeds rapidly. Moreover, when there are too many equivalents of an organic base, the polymerization delay effect will become strong too much and chemical polymerization will become difficult.

  The polymerization step in the present invention, that is, a method for forming an electrolyte by chemical (oxidation) polymerization using a composition containing a conductive polymer monomer, an oxidizing agent and an organic base will be described. The chemical polymerization method is a method of synthesizing by conducting oxidative polymerization of a conductive polymer monomer as a raw material in the presence of an appropriate oxidizing agent.

  Examples of the oxidizing agent include iron salts such as ferric paratoluene sulfonate, ferric naphthalene sulfonate, ferric n-butyl naphthalene sulfonate, ferric triisopropyl naphthalene sulfonate, persulfate, and peroxidation. Hydrogen, diazonium salts, halogens and halides, or transition metal salts such as copper and manganese can be used. The conductive polymer synthesized by chemical polymerization can obtain a polymer having conductivity in a one-step reaction by incorporating an anion of an oxidant into the polymer as a dopant in the polymerization process. It is preferable to use ferric paratoluenesulfonate containing paratoluenesulfonate ions having high mobility as an oxidizing agent.

  In the polymerization step, the polymerization conditions may be known polymerization conditions. An electrolyte is formed by chemical polymerization using a composition containing a monomer, an oxidant, and an organic base constituting the conductive polymer represented by the above general formula (1). Even if an oxidizing agent is added to the solution containing a base, an oxidizing agent solution containing an organic base may be added to the monomer, and the viscosity and concentration may be adjusted as appropriate by adding a solvent. The polymerization solvent used in the polymerization may be a known solvent such as water, alcohol, ether, nitrile, ketone, amide, carbonate, ester, lactone, sulfur-containing solvent, halogenated carbonization. Examples thereof include hydrogen and hydrocarbon solvents, and two or more of these solvents may be used.

  Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, 1-butanol and the like, but are not limited thereto. Examples of ether solvents include, but are not limited to, diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, and the like. Examples of the nitrile solvent include acetonitrile, propionitrile, benzonitrile, and the like, but are not limited thereto. Examples of the ketone solvent include, but are not limited to, acetone and methyl ethyl ketone. Examples of the amide solvent include, but are not limited to, formamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone and the like. Examples of the carbonate-based solvent include, but are not limited to, ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate. Examples of ester solvents include, but are not limited to, methyl acetate, ethyl acetate, butyl acetate and the like. Examples of the lactone solvent include butyrolactones, valerolactones, caprolactones, and the like, but are not limited thereto. Examples of the sulfur-containing solvent include, but are not limited to, sulfur disulfide, dimethyl sulfoxide, diethyl sulfoxide and the like. Examples of the halogen solvent include, but are not limited to, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and the like. Examples of the hydrocarbon solvent include, but are not limited to, pentane, hexane, cyclohexane, benzene, and toluene.

  From the viewpoint of the solubility of the monomer and the oxidizing agent, the viscosity of the solution, and the polymerization rate, it is preferable to use an alcohol system, and particularly preferably 1-butanol. The polymerization temperature range may be −78 ° C. to 200 ° C., more preferably −60 ° C. to 100 ° C., particularly preferably −40 ° C. to 25 ° C. The polymerization temperature range is preferably the above range from the viewpoint of suppressing the substantial reaction rate and excessive chain reaction or side reaction. The polymerization time is 30 seconds to 12 hours, more preferably 1 minute to 6 hours, and particularly preferably 3 minutes to 2 hours. By polymerizing for a long time by slowing the polymerization rate, it is considered that the polymerization proceeds slowly and a polymer having good structure regularity can be obtained. The polymerization may be repeated a plurality of times.

  Hereinafter, an example of a typical capacitor manufacturing method using the electrolyte forming method of the present invention will be described. The components of the capacitor not specifically mentioned in the electrolytic capacitor of the present invention are not particularly limited, and conventionally known components can be appropriately applied.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited thereto, and the embodiments and examples disclosed herein are illustrative and restrictive in all respects. It should be considered not. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

<Initial capacity measurement>
The initial capacity of the electrolytic capacitor used in the examples of the present invention was calculated from the slope of a graph obtained in a constant current charge / discharge test of 50 μA between 0 and 4 V using solartron, model number “1480” manufactured by Toyo Technica.

<Impedance measurement>
After the initial capacity measurement, impedance was measured using the mercury cell shown in FIG. As a device, solartron manufactured by Toyo Technica, model number “1480” was used, and measurement was performed in the range of 1 Hz to 1 MHz under the conditions of DC Potential = 0V and AC Amplitude 100V. The impedance value of 100 kHz was defined as the electrode impedance.

<Conductivity measurement>
The conductivity measured by the present invention was measured by putting 100 mg of the obtained polymer powder into a 13 mm Evacuable Pellet Die and pressing it with a high pressure jack to produce a pellet, and then determining the sheet resistance of the resulting pellet as HIKI 3522- It was measured by 50 LCR HiTESTER and calculated from this and the film thickness of the pellet.

Example 1
A conductive polymer aluminum electrolytic capacitor was produced by forming a conductive polymer obtained by chemical polymerization of pyrrole on an aluminum oxide film. That is, an aluminum etched foil having an effective area of 10 mm × 10 mm is dipped in a 1% ammonium adipate aqueous solution, first raised from 0 to 45 V at a rate of 20 mV / sec, and then a constant voltage of 45 V is applied for 40 minutes, A dielectric film was formed on the surface of the aluminum etched foil. Next, this foil was washed with running deionized water for 3 minutes and then dried at 120 ° C. for 1 hour. The in-liquid capacity of the aluminum etched foil obtained at this time was 25 μF. Then, the chemical polymerization composition used for electrolyte formation was prepared with the following compounding ratios. As the conductive polymer monomer, 1.0 g of pyrrole, 4.2 g of paratoluenesulfonic acid ferric acid as the oxidizing agent, 6.4 g of 1-butanol as the solvent, and 0.50 g of imidazole were used. These compounds are in a molar ratio of monomer: oxidant: imidazole = 1: 0.5: 0.5. Pyrrole and imidazole were mixed in a well-dried beaker and cooled to −20 ° C., and then an oxidizing agent was added to the solution and stirred for 3 minutes. Next, the aluminum etched foil was immersed in the polymerization solution in the polymerization solution, and after being pulled up, heat treatment was performed at 120 ° C. for 1 hour. The initial capacity and impedance of the foil thus obtained were measured using the mercury cell shown in FIG. Table 1 shows the characteristics of the obtained electrode. All the results in Table 1 are average values of 10 electrodes.

(Example 2)
As Example 2, a conductive polymer aluminum electrolytic capacitor was produced under the same conditions as in Example 1 except that 0.58 g of pyridine was added instead of imidazole. These compounds have a molar ratio of monomer: oxidant: pyridine = 1: 0.5: 0.5.

(Comparative Example 1)
For comparison, a conductive polymer aluminum electrolytic capacitor was produced under the same conditions as in Example 1 except that imidazole was not added as Comparative Example 1, but the capacitor was produced because the polymerization rate of pyrrole was too high. I could not.

(Comparative Example 2)
For comparison, a conductive polymer aluminum electrolytic capacitor was produced under the same conditions as in Example 1 except that 0.58 g of dimethyl sulfoxide was added instead of imidazole as Comparative Example 2. These compounds have a molar ratio of monomer: oxidizer: dimethyl sulfoxide = 1: 0.5: 0.5. Unlike Comparative Example 1, although the polymerization rate of pyrrole was slow and a capacitor could be produced, the initial capacity and impedance were inferior compared with Example 1.

(Example 3)
The polymerization solution obtained in the same polymerization step as in Example 1 was transferred to a petri dish and heat-treated at 120 ° C. for 1 hour. The polymer prepared in this manner was ground in a mortar, and the resulting powder was pelleted and the conductivity was measured (before washing). Furthermore, this powder was added into well-stirred water and washed for 30 minutes. The washing water was filtered and the powder obtained by filtration was dried at room temperature for 1 day under vacuum. The powder thus obtained was pelleted and the conductivity was measured (after washing with water). The measured conductivity is shown in Table 2. The results in Table 2 are average values for 10 pellets.

Example 4
In Example 4, except that pyridine was added instead of imidazole, pellets were prepared under the same conditions as in Example 3, and the conductivity before and after washing was measured.

(Comparative Example 3)
For comparison, pellets were produced under the same conditions as in Example 3 except that imidazole was not added as Comparative Example 3. Compared with Example 3 and Example 4, the electrical conductivity before water washing was inferior, and the electrical conductivity after water washing was greatly inferior.

(Comparative Example 4)
For comparison, pellets were produced under the same conditions as in Example 3 except that dimethyl sulfoxide was added instead of imidazole as Comparative Example 4. Compared with Example 3 and Example 4, both the electrical conductivity before and after washing was significantly inferior.

Schematic diagram of mercury cell

Claims (7)

General formula (1);
A monomer constituting a conductive polymer represented by the formula (where X and Y each independently represent any of H, C, O, N and S, R ¹ and R ² are not X and Y is H) Is present, and is H or a C _{1 to} C ₂₀ hydrocarbon group, may be linear or branched, and may have a cyclic structure, R ³ is a protecting group for H or amine Represents general formula (2) and / or general formula (3);
(Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H or a C _{1 to} C ₂₀ hydrocarbon group, which may be linear or branched, and has a cyclic structure. May be)
(Here, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are each independently H or a C _{1 to} C ₂₀ hydrocarbon group, which may be linear or branched, together with a cyclic structure. And a method for producing a conductive polymer capacitor, wherein the polymerization is performed using an oxidizing agent in the presence of an organic base represented by formula (1). The method for producing a conductive polymer capacitor according to claim 1, wherein the substituent R ³ in the monomer constituting the conductive polymer represented by the general formula (1) is H. The monomer constituting the conductive polymer is represented by general formula (4), general formula (5), general formula (6), and general formula (7);
(Here, R ¹³ and R ¹⁴ are C _{1 to} C ₂₀ hydrocarbon groups, which may be linear or branched, and may have a cyclic structure together). The method for producing a conductive polymer capacitor according to claim 1, wherein the at least one monomer is selected.   The method for producing a conductive polymer capacitor according to claim 3, wherein the monomer constituting the conductive polymer is pyrrole.   The method for producing a conductive polymer capacitor according to any one of claims 1 to 4, wherein the organic base is imidazole or pyridine.   The method for producing a conductive polymer capacitor according to any one of claims 1 to 5, wherein the chemical polymerization of the monomer constituting the conductive polymer is performed at -40 ° C to 25 ° C.   A conductive polymer capacitor produced by the method according to claim 1.