JP2003268082A - Conductive composition and method of manufacturing the same, capacitor using conductive composition and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition containing a conjugated double bond polymer having excellent mechanical strength and heat resistance, and to have excellent leakage current characteristics and heat resistance using this conductive composition. It is intended to provide a capacitor. SOLUTION: By using a conductive composition comprising a conjugated double bond polymer as a composite dopant comprising a high molecular anion and a low molecular anion represented by (Chemical Formula 1),
A conductive composition having high conductivity and excellent in mechanical strength and heat resistance can be obtained. In addition, by providing a capacitor using the conductive composition with at least one of the pair of electrodes provided with a dielectric and a pair of electrodes via the dielectric, high heat resistance and high leakage current characteristics are obtained. In addition, a material excellent in ESR characteristics can be obtained. Embedded image

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive composition having excellent mechanical strength and heat resistance, and a method for producing the same.

The present invention also relates to a capacitor using the above conductive composition as an electrode and having excellent leakage current characteristics and heat resistance, and a method for manufacturing the same.

[0003]

2. Description of the Related Art Generally, a conductive composition containing a conjugated double bond polymer represented by polyaniline, polypyrrole or polythiophene can be prepared by chemical oxidative polymerization and electrolytic polymerization.

In the chemical oxidative polymerization, the oxidant anion is incorporated as a dopant, and in the electrolytic polymerization, the supporting electrolyte anion is incorporated as a dopant, thereby exhibiting conductivity.

Further, it is known that a powdery conductive composition is formed by chemical oxidative polymerization, and a film-shaped conductive polymer is formed on an anode by electrolytic polymerization.

The above conductive composition is used for the cathode conductive layer of a solid electrolytic capacitor.

In this solid electrolytic capacitor, the electric conductivity of the conductive composition is orders of magnitude higher than that of the conventional cathode conductive layer of metal oxide or the like, so that a solid electrolytic capacitor having excellent high frequency characteristics can be realized. Are known.

[0008]

However, in the conductive composition containing the conjugated double bond polymer, the characteristics such as electric conductivity and heat resistance are greatly changed depending on the incorporated dopant.

In particular, in the case of a conductive composition obtained by electrolytic polymerization, there is a problem that mechanical strength is easily influenced in addition to characteristics such as electric conductivity and heat resistance.

To improve the heat resistance, doping with a dopant having a sublime molecular structure such as an aromatic sulfonate ion suppresses dedoping, so that the heat resistance can be improved. It is said to be possible. This effect is further improved in heat resistance because ions having a condensed aromatic ring such as naphthalene sulfonic acid and anthraquinone sulfonic acid have a molecular structure that is more subtle than that of a benzene ring, and dedoping does not easily occur.

However, even when such a conductive composition doped with an aromatic sulfonate ion is prepared by electrolytic polymerization, the conjugated double bond polymer is polyethylenedioxythiophene (hereinafter abbreviated as PEDOT). In addition, when the naphthalene sulfonate ion which is an aromatic sulfonate ion is doped, there is a problem that the self-supporting film cannot be separated from the electrode because it is very brittle.

This makes it difficult to analyze and evaluate the conductive composition in the film, and when applied to the electrodes of the capacitor, mechanical stress easily causes defects such as cracks, resulting in a large leakage current. It was the cause.

On the other hand, in order to improve the mechanical strength,
The mechanical strength can be improved by using PEDOT doped with a polymer dopant in which a hydroxyl group contained in a polyhydroxypolyether (phenoxy resin) synthesized from bisphenol-A and epichlorohydrone is partially sulfated. It has been reported (H. Yama
To et al., Synthetic Metals magazine (Elsevier 1996) 83: 125-130).

However, even in such a case, PEDOT doped with the above-mentioned polymer dopant has a low heat resistance because the sulfate ester group of the polymer dopant is easily thermally decomposed at a high temperature, particularly at a temperature of 200 ° C. or higher. Have a

Further, in the solid electrolytic capacitor using the conductive composition containing the above-mentioned polymer dopant in the cathode conductive layer, when exposed to a solder reflow temperature of 250 ° C. or higher during mounting, the equivalent series resistance (hereinafter, The phenomenon that the ESR (abbreviated as ESR) becomes large was observed, and there was a practically large problem.

The present invention solves the above-mentioned problems of the prior art, provides a highly conductive conductive composition having both high heat resistance and mechanical strength, and a method for producing the same, and at the same time, provides the above conductive composition. It is an object of the present invention to provide a capacitor having excellent heat resistance, low leakage current and small ESR, and a method for manufacturing the same.

[0017]

In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention provides a conjugated double bond containing a polymer anion and a low-molecular anion represented by the formula (5) as a dopant. Since it is made of a polymer, it has a function of having high conductivity and being able to obtain a conductive composition having excellent mechanical strength and heat resistance.

[0018]

[Chemical 5]

The invention described in claim 2 is particularly
Sulfate esterification rate n / (m
+ N) is in the range of 0.1 to 0.9 and has the effect of maintaining high conductivity and excellent mechanical strength.

It should be noted that the sulfuric acid esterification rate of the above-mentioned polymer anion can quantify the remaining hydroxyl groups, but if the sulfuric acid esterification rate is lower than 0.1, a conductive composition cannot be obtained substantially. . Further, it is not possible to obtain a compound having a sulfuric acid esterification rate of more than 0.9 in terms of chemical equilibrium.

In the invention according to claim 3, the low-molecular anion is an aromatic sulfonate ion, and in the invention according to claim 4, the aromatic sulfonate ion is a naphthalene sulfonate ion or anthraquinone. It is composed of a sulfonate ion, has excellent electrical conductivity and stability, and has an effect of maintaining mechanical strength and excellent heat resistance.

According to the fifth aspect of the present invention, in particular, the conjugated double bond polymer is made of polyethylenedioxythiophene, and has the action of having high conductivity.

The invention according to claim 6 comprises a step of dispersing a polymer electrolyte of a polymer anion represented by (Chemical Formula 6), a low molecular electrolyte of a low molecular anion and a conjugated double bond polymer monomer in an organic solvent. And a method for producing the conjugated double bond polymer monomer dispersed in the above organic solvent, which comprises a step of electrolytically polymerizing, and has a high electrical conductivity, and an electrical conductivity excellent in mechanical strength and heat resistance. It has the effect that a composition can be obtained.

[0024]

[Chemical 6]

Any organic solvent can be used as long as it can dissolve the polymer anion polymer electrolyte, the low molecule anion low molecule electrolyte, and the conjugated double bond polymer monomer. Polycarbonate or the like can be used, and water can also be added and used.

The invention described in claim 7 is particularly
Sulfate esterification rate n / (m
+ N) is in the range of 0.1 to 0.9, and has the action of maintaining a high conductivity and obtaining a conductive composition excellent in mechanical strength.

The sulfuric acid esterification rate of the above-mentioned polymer anion can quantify the residual hydroxyl group, but if the sulfuric acid esterification rate is lower than 0.1, a conductive composition cannot be obtained substantially. . Further, it is not possible to obtain a compound having a sulfuric acid esterification rate of more than 0.9 in terms of chemical equilibrium.

The invention according to claim 8 is a method for producing, in particular, the low molecular weight anion is an aromatic sulfonate ion, and the invention according to claim 9 is that the aromatic sulfonate ion is naphthalene. This is a method for producing a sulfonate ion or an anthraquinone sulfonate ion, and has an effect of being able to obtain a conductive composition excellent in heat resistance while maintaining mechanical strength.

The invention described in claim 10 is particularly directed to a production method in which the conjugated double bond polymer monomer is ethylenedioxythiophene, and a conductive composition having high conductivity can be obtained. Have an effect.

The eleventh aspect of the present invention is a manufacturing method in which the concentration ratio of the low molecular weight electrolyte and the high molecular weight electrolyte is in the range of 1: 9 to 9: 1. It has the action and effect that an excellent conductive composition is obtained.

According to a twelfth aspect of the present invention, a dielectric and a pair of electrodes via the dielectric are provided, and at least one of the pair of electrodes has a polymer anion and a low molecular anion represented by the chemical formula A capacitor using a conductive composition composed of a conjugated double bond polymer containing as a dopant, which has high heat resistance and excellent leakage current characteristics and ESR characteristics.

[0032]

[Chemical 7]

The thirteenth aspect of the present invention is, in particular, the sulfuric acid esterification rate n / of the polymer anion represented by the chemical formula (7).
(M + n) is in the range of 0.1 to 0.9, and since it is possible to form a conductive composition having high conductivity and excellent mechanical strength, leakage current characteristics and It has the effect that a capacitor having excellent ESR characteristics can be obtained.

It should be noted that the sulfuric acid esterification rate of the above-mentioned polymer anion can quantify the residual hydroxyl groups, but if the sulfuric acid esterification rate is lower than 0.1, a conductive composition cannot be obtained substantially. . Further, it is not possible to obtain a compound having a sulfuric acid esterification rate of more than 0.9 in terms of chemical equilibrium.

The invention according to claim 14 is particularly directed to the case where the sulfonate ion is an aromatic sulfonate ion, and the invention according to claim 15 is that the aromatic sulfonate ion is naphthalene sulfonate. Since it is an ion or anthraquinone sulfonate ion and can form a conductive composition excellent in heat resistance while maintaining mechanical strength, it is possible to obtain a capacitor excellent in leakage current characteristics and ESR characteristics. It has the effect of being able to.

According to the sixteenth aspect of the present invention, in particular, the conjugated double bond polymer is polyethylenedioxythiophene, and since a conductive composition having high conductivity can be obtained, It has an effect that a high capacitor can be obtained.

The invention according to claim 17 is a capacitor in which the dielectric is an anodized film of a valve metal, and the invention according to claim 18 is that the valve metal is made of aluminum, tantalum or niobium. It shall be chosen.

It is optimum to use a valve metal whose surface area has been expanded by etching or sintering.

The invention according to claim 19 is the process of forming a dielectric, the process of forming a pair of electrodes via the dielectric, and the chemical formula (8) on at least one of the pair of electrodes. A method for producing a conductive composition by electropolymerizing a polyelectrolyte of a polyanion, a low molecular electrolyte of a low molecular anion, and an organic solvent in which a conjugated double bond polymer monomer is dispersed to form a conductive composition Therefore, there is an effect that a capacitor having high heat resistance and excellent leakage current characteristics and ESR characteristics can be easily obtained.

[0040]

[Chemical 8]

Any organic solvent can be used as long as it can dissolve the polymer anion polymer electrolyte, the low molecular anion low molecule electrolyte, and the conjugated double bond polymer monomer. For example, polycarbonate or the like can be used, and water can also be added and used.

When forming a conductive composition by the above-mentioned electrolytic polymerization, it is necessary to provide a conductive precoat layer on the surface of the dielectric, but a soluble or dispersible conductive polymer and an organic solvent are used. It can be provided by applying the mixture and then removing the organic solvent.

Further, before forming the conductive composition, the conductive composition may be formed by chemical polymerization or the metal oxide semiconductor layer may be formed and used as the conductive precoat layer.

The invention described in claim 20 is, in particular, that the ratio of sulfuric acid esterification of the polymeric anion represented by the chemical formula (8) is n /
(M + n) is in the range of 0.1 to 0.9, and since it is possible to form a conductive composition having high conductivity and excellent mechanical strength, leakage current characteristics and It has the effect that a capacitor having excellent ESR characteristics can be obtained.

The sulfate esterification rate of the above-mentioned polymer anion can quantify the residual hydroxyl group, but if the sulfate esterification rate is lower than 0.1, a conductive composition cannot be obtained substantially. . Further, it is not possible to obtain a compound having a sulfuric acid esterification rate of more than 0.9 in terms of chemical equilibrium.

In the invention described in claim 21, particularly, the low molecular weight anion is an aromatic sulfonate ion,
Further, the invention according to claim 22 is a manufacturing method in which the aromatic sulfonate ion is a naphthalene sulfonate ion or an anthraquinone sulfonate ion, and a conductive material excellent in heat resistance while maintaining mechanical strength. Since a conductive composition can be formed, leakage current characteristics and ES
It has an effect that a capacitor having excellent R characteristics and high heat resistance can be obtained.

The invention as set forth in claim 23 is particularly directed to a production method in which the conjugated double bond polymer monomer is ethylenedioxythiophene, and a highly electrically conductive composition can be obtained. , And has the effect that a capacitor having excellent ESR characteristics can be obtained.

The invention as set forth in claim 24 provides a manufacturing method in which the concentration ratio of the low molecular weight electrolyte and the high molecular weight electrolyte is in the range of 1: 9 to 9: 1. Since an excellent conductive composition can be obtained, it has an effect of obtaining a capacitor having excellent heat resistance and excellent leakage current characteristics.

According to a twenty-fifth aspect of the invention, there is provided a manufacturing method in which the dielectric is an anodized film of a valve metal, and the twenty-sixth aspect of the invention is that the valve metal is aluminum. The production method is tantalum, niobium, titanium or zirconium.

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION (Embodiment 1) Hereinafter, the invention described in claims 1 to 11 of the present invention will be described with reference to Embodiment 1.

A phenoxy resin synthesized from bisphenol A and epichlorohydrin as a polymer electrolyte (trade name "Phenotote YP-50" manufactured by Tohto Kasei Co., Ltd.)
Using a known method (US Pat. No. 50614).
No. 01) to obtain a tetrabutylammonium salt. The sulfate esterification rate obtained from the analysis of the residual hydroxyl groups of this polymer electrolyte was 0.73. 0.65 g of this polymer electrolyte, 1 g of sodium triisopropylnaphthalene sulfonate as a low molecular electrolyte, 50 g of propylene carbonate as an organic solvent and 0.5 of water.
Then, 1.42 g of ethylenedioxythiophene (EDOT) was dissolved to prepare a polymerization solution.

The concentration of the above-mentioned polymer electrolyte (repeating unit basis) and the concentration of the low-molecular electrolyte are each 0.025 mol.
/ L.

Next, as an anode, a lead was attached to one end of a 20 mm × 30 mm stainless steel foil in the longitudinal direction, immersed in the above polymerization solution to a depth of 20 mm, and separated from the anode so as to surround the anode. And a DC voltage of 4 V was applied for 40 minutes to form a black electropolymerized film on the surface of the anode.

After washing this electropolymerized film with ethanol and water, lift off with water to peel off the thin film from the anode,
It was dried at room temperature to obtain a conductive composition.

(Comparative Example 1) In the first embodiment,
A conductive composition was obtained in the same manner as in Embodiment 1 except that a polymer electrolyte having a concentration of 0.05 mol / l was used instead of mixing the polymer electrolyte and the low molecular electrolyte.

(Comparative Example 2) In the first embodiment,
A conductive composition was obtained in the same manner as in Embodiment 1 except that a low molecular electrolyte having a concentration of 0.05 mol / l was used instead of mixing the high molecular electrolyte and the low molecular electrolyte.

A black electropolymerized film was formed on the surface of the anode with this conductive composition, but it was very brittle and could not be peeled from the anode onto the thin film.

With respect to the conductive compositions of Embodiment 1 and Comparative Examples 1 and 2, mechanical strength (180 degree bending test) and heat resistance test (initial and after heating in nitrogen at 260 ° C. for 10 minutes). The electrical conductivity was measured by the four-terminal method). The results are shown in (Table 1).

[0059]

[Table 1]

As is clear from Table 1, the mechanical strength of the conductive composition of Comparative Example 2 was brittle.
It was confirmed that the conductive compositions of Embodiment 1 and Comparative Example 1 did not break even when bent 180 degrees and returned to the original state.

Further, in the heat resistance test, the conductive composition of Comparative Example 1 was compared with the conductive composition of the first embodiment.
It can be seen that the decrease in electrical conductivity after heating at 260 ° C. is large.

Therefore, it can be seen that the conductive composition of the first embodiment has both excellent mechanical strength and high heat resistance. This is doped with both a polymeric anion containing a sulfate ester group and a low molecular anion containing an aromatic sulfonate ion, giving the former strong mechanical strength, and the latter imparting high heat resistance. This is the effect of

(Embodiment 2) Hereinafter, the invention according to claim 2 will be described with reference to Embodiment 2.

In the first embodiment, the sulfuric acid esterification rate of the polymer electrolyte is (a) 0.098, (b) 0.
No. 21, (c) 0.43, and (d) 0.91 were changed to obtain the conductive composition in the same manner as in the first embodiment.

All of the conductive compositions could be peeled off from the anode and were not broken even by bending 180 degrees.

Further, in order to evaluate the heat resistance, the electrical conductivity was measured at the initial stage and after holding in nitrogen at 260 ° C. for 10 minutes, and the results are shown in (Table 1).

It can be seen that the conductive composition of Embodiment 2 has both excellent mechanical strength and high heat resistance.

(Third Embodiment) Hereinafter, the invention according to claim 4 will be described with reference to the third embodiment.

In the first embodiment, the anthraquinone-2,6-disulfonic acid 2 is used instead of the low molecular electrolyte sodium triisopropylnaphthalene sulfonate.
A conductive composition was obtained in the same manner as in Embodiment 1 except that 0.013 mol / l of sodium was used.

All the conductive compositions could be peeled off from the anode and were not broken even by bending 180 degrees.

Further, the electric conductivity of the above conductive composition was evaluated in the same manner as in the first embodiment, and the results are shown in (Table 1).

It can be seen that the conductive composition of the above-mentioned Embodiment 3 has both excellent mechanical strength and high heat resistance.

(Embodiment 4) Hereinafter, the invention according to claim 11 will be described with reference to Embodiment 4.

In the first embodiment, the total concentration of the polymer electrolyte and the low molecular electrolyte is kept constant at 0.05 mol / l, and the ratio of the two is (a) 1: 9, (b) 2.5: 7. ．
5, (c) 7.5: 2.5 and (d) 9: 1, respectively, except that the conductive composition was obtained by electrolytic polymerization in the same manner as in the first embodiment.

All of the conductive compositions could be peeled off from the anode and were not broken even by bending 180 degrees.

The electric conductivity of the above-mentioned conductive composition was evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 1).

It can be seen that the conductive composition of Embodiment 4 has both excellent mechanical strength and high heat resistance.

(Fifth Embodiment) In the following, the invention described in claims 12 to 26 will be described with reference to the fifth embodiment.

FIG. 1 (a) shows an external view of a capacitor element according to the fifth embodiment, and FIG. 1 (b) shows a sectional view of a capacitor using the capacitor element.

The above capacitor element has a length of 8 mm and a width of 3.
Aluminum etched foil 1 of 3mm, 4mm in the vertical direction
A polyimide adhesive tape 2 having a width of 1 mm was attached over the screen so as to be divided into a 3 mm portion and a 2 mm portion.

Next, the anode lead 6 was attached to a portion of the aluminum etched foil 1 in the vertical direction of 3 mm, and the vertical direction was set to 4 mm.
Using a 3% ammonium adipate aqueous solution at 70 ° C., a constant voltage of 3 V was applied to the portion to form a barrier type anodic oxide film 3. Then, it was washed with deionized water and dried at 105 ° C.

The capacity of the anodized film 3 at this time was measured in the chemical conversion solution, and it was 20 μF.

Next, the longitudinal 4 mm portion of the aluminum etched foil 1 was immersed in a 30% aqueous solution of manganese sulfate, and then 2
Manganese sulfate was thermally decomposed by heating at 50 ° C. to form a manganese dioxide layer (not shown) on the surface of the anodic oxide coating 3.

Then, a polymerization initiation electrode made of stainless steel was brought into contact with the polyimide adhesive tape 2, immersed in the polymerization solution used in the first embodiment, and separated from the cathode separately provided in the polymerization solution. Then, a direct current voltage of 4 V was applied to carry out electrolytic polymerization.

After that, the capacitor element whose longitudinal portion of 4 mm was covered with the conductive composition 4 was washed and dried, and then a collector layer 5 consisting of a carbon layer and a silver paint layer was formed and the cathode lead 7 was attached. It was

Further, an aging process was performed after packaging (not shown) using an epoxy resin, and 10 capacitors were manufactured.

(Comparative Example 3) In the above fifth embodiment,
The polymerization solution used was (a) a polymerization solution having the same material and composition as the polymerization solution used in Comparative Example 1 above, and (b) a polymerization solution having the same material and composition as the polymerization solution used in Comparative Example 2 above was used. Ten capacitors were manufactured in the same manner as in Embodiment 5 except for the above.

With respect to the capacitors of the fifth embodiment and the comparative example 3, the leakage current and the equivalent series resistance of 400 kHz after applying a capacitance of 1 kHz, a loss coefficient and a voltage of 2 V for 2 minutes were measured. Further, after holding in a thermostat at 260 ° C. for 10 minutes, the above characteristics were measured. The average values thereof are shown in (Table 2) below.

[0089]

[Table 2]

As is clear from Table 2, Comparative Example 3
Since the conductive composition of the capacitor obtained in (a) contains only the sulfated esterified polymer anion as a dopant, the deterioration after the isothermal heat treatment is large, which causes the loss of the capacitor. The coefficient and equivalent series resistance are large.

On the other hand, since the conductive composition of the capacitor obtained in Comparative Example 3 (b) was not in the form of a homogeneous film, the current collector layer was in contact with the anode, resulting in a large leakage current. I understand.

On the other hand, in the capacitor of the fifth embodiment, the conductive composition doped with the composite dopant consisting of the high molecular anion and the low molecular anion is used, and it is in the form of a mechanically tough thin film. It has been found that a capacitor having excellent leakage current characteristics and heat resistance can be obtained because of its excellent heat resistance.

(Embodiment 6) First, 1.3 × 2.1 ×
A solution of 5 ml of phosphoric acid dissolved in 1000 ml of water was applied to an electrode made of a tantalum sintered body with a 1.6 mm tantalum wire anode lead, and 18 V was applied at about 90 ° C.
An anodized film was formed by anodization.

Then, the substrate is washed with deionized water and washed with 10
Drying was performed at 5 ° C.

The capacity of the anodized film at this time was measured in the chemical conversion solution, and it was 121 μF.

Next, this sintered body was immersed in a solution of ethylenedioxythiophene: ferric p-toluenesulfonate: ferric acid: n-butanol: water = 1: 8: 10: 10 (weight ratio), and then 80 The polyethylene dioxythiophene layer was formed inside the sintered body by heating at 0 ° C. for 1 hour, and then washed with ethanol. This operation was repeated several times.

Next, a polymerization initiation electrode made of stainless steel was brought into contact with the sintered body, dipped in a polymerization solution containing the same material composition as that described in the first embodiment, and separately provided in the system. A DC voltage of 4 V was applied between the cathode and the cathode, and electrolytic polymerization was performed until the entire surface of the sintered body was covered with the conductive composition.

Thereafter, 1 is performed in the same manner as in the fifth embodiment.
Zero capacitors were made.

(Comparative Example 4) In the sixth embodiment,
The polymerization solution used was (a) a polymerization solution having the same material and composition as the polymerization solution used in Comparative Example 1, and (b) a polymerization solution having the same material and composition as the polymerization solution used in Comparative Example 2. Ten capacitors were manufactured in the same manner as in the sixth embodiment.

The capacitors of the sixth embodiment and the comparative example 4 were evaluated in the same manner as the fifth embodiment. Their average values are shown in (Table 2).

As can be seen from this (Table 2), Comparative Example 4
Since the conductive composition of the capacitor obtained in (a) contains only the sulfuric acid esterified polymer anion as a dopant, the deterioration after the high temperature heat treatment is large, which causes the loss factor of the capacitor. And the equivalent series resistance is large.

On the other hand, the conductive composition of the capacitor obtained in Comparative Example 4 (b) caused cracks due to the low mechanical strength of the conductive composition, and the current collector layer was in contact with the anode to leak. It is considered that the current is increasing.

On the other hand, it was shown that the capacitor of the sixth embodiment had a small leakage current and was excellent in heat resistance, and thus the conductive composition containing a polymer anion and a low molecule anion as dopants was used. The effect of the present invention used for the cathode conductive layer is clear.

In the embodiment of the present invention, only the case where aluminum and tantalum are used for the anode and the conductive composition is used for the cathode conductive layer has been described. However, the capacitor of another valve metal such as niobium is used. It can be used as a cathode conductive layer, and can also be applied to a film capacitor whose dielectric is composed of, for example, a polymer film.

Further, only the case where an alkylated naphthalene sulfonate ion is used as the low molecular weight anion has been described, but it is also possible to use one having no alkyl group, and the anthraquinone sulfonate ion can also be used as the disulfonate ion. Other than that, the same effect can be obtained by using monosulfonate ion, and the present invention is not limited to the sulfonation number of the low molecular anion.

Although only the case of using propylene carbonate and water as the organic solvent has been described, another solvent may be used as long as it is a solvent that substantially dissolves the polymer electrolyte, the low molecular electrolyte and the conjugated double bond polymer monomer. You may use.

[0107]

As described above, according to the present invention, the polymer is composed of a conjugated double bond polymer containing a polymer anion and a low molecular anion as a dopant, and has high conductivity,
A conductive composition having excellent mechanical strength and heat resistance can be obtained.

Further, by providing a dielectric and a pair of electrodes via the dielectric and using the conductive composition in at least one of the pair of electrodes, the heat resistance is high and the leakage current is high. The effect is that it is possible to obtain a material having excellent characteristics and ESR characteristics.

[Brief description of drawings]

1A is a front view showing the appearance of a capacitor element according to a fifth embodiment of the present invention, and FIG. 1B is a sectional view of a capacitor using the same capacitor element.

[Explanation of symbols]

1 Aluminum Etched Foil 2 Polyimide adhesive tape 3 Anodized film 4 Conductive composition 5 Current collector layer 6 Anode lead 7 Cathode lead

Claims (26)

[Claims] 1. A conductive composition comprising a conjugated double bond polymer containing a polymer anion represented by (Chemical formula 1) and a low molecular anion as dopants. [Chemical 1] 2. The conductive composition according to claim 1, wherein the sulfuric acid esterification rate n / (m + n) of the polymer anion represented by (Chemical formula 1) is in the range of 0.1 to 0.9. 3. The conductive composition according to claim 1, wherein the low molecular weight anion is an aromatic sulfonate ion. 4. The conductive composition according to claim 3, wherein the aromatic sulfonate ion is a naphthalene sulfonate ion or an anthraquinone sulfonate ion. 5. The conductive composition according to claim 1, wherein the conjugated double bond polymer is polyethylenedioxythiophene. 6. A step of dispersing a polymer electrolyte of a polymer anion represented by (Chemical Formula 2), a low molecular electrolyte of a low molecular anion, and a conjugated double bond polymer monomer in an organic solvent; And a step of electrolytically polymerizing the conjugated double bond polymer monomer. [Chemical 2] 7. The method for producing a conductive composition according to claim 6, wherein the sulfuric acid esterification rate n / (m + n) of the polymer anion represented by (Chemical Formula 2) is in the range of 0.1 to 0.9. . 8. The method for producing a conductive composition according to claim 6, wherein the low molecular weight anion is an aromatic sulfonate ion. 9. The method for producing a conductive composition according to claim 8, wherein the aromatic sulfonate ion is a naphthalene sulfonate ion or an anthraquinone sulfonate ion. 10. The method for producing a conductive composition according to claim 6, wherein the conjugated double bond polymer monomer is ethylenedioxythiophene. 11. The method for producing a conductive composition according to claim 6, wherein the concentration ratio of the low molecular weight electrolyte and the high molecular weight electrolyte is in the range of 1: 9 to 9: 1. 12. A conjugated double layer comprising a dielectric and a pair of electrodes via the dielectric, wherein at least one of the pair of electrodes contains a polymer anion and a low molecular anion represented by the formula (3) as dopants. A capacitor using a conductive composition composed of a binding polymer. [Chemical 3] 13. The capacitor according to claim 12, wherein the sulfuric acid esterification rate n / (m + n) of the polymer anion represented by (Chemical Formula 3) is in the range of 0.1 to 0.9. 14. The capacitor according to claim 12, wherein the low molecular weight anion is an aromatic sulfonate ion. 15. The capacitor according to claim 14, wherein the aromatic sulfonate ion is a naphthalene sulfonate ion or an anthraquinone sulfonate ion. 16. The capacitor according to claim 12, wherein the conjugated double bond polymer is polyethylenedioxythiophene. 17. The capacitor according to claim 12, wherein the dielectric is a valve metal anodized film. 18. The capacitor according to claim 17, wherein the valve metal is selected from aluminum, tantalum and niobium. 19. A step of forming a dielectric, a step of forming a pair of electrodes via the dielectric, and a polymer electrolyte of a polymer anion represented by the formula (4) on at least one of the pair of electrodes. And a step of electrolytically polymerizing an organic solvent in which a low molecular weight electrolyte of a low molecular weight anion and a conjugated double bond polymer monomer are dispersed to form a conductive composition. [Chemical 4] 20. The method for producing a capacitor according to claim 19, wherein the sulfuric acid esterification rate n / (m + n) of the polymer anion represented by (Chemical Formula 4) is in the range of 0.1 to 0.9. 21. The method for producing a capacitor according to claim 19, wherein the low molecular weight anion is an aromatic sulfonate ion. 22. The method for producing a capacitor according to claim 21, wherein the aromatic sulfonate ion is a naphthalene sulfonate ion or an anthraquinone sulfonate ion. 23. The method for producing a capacitor according to claim 19, wherein the conjugated double bond polymer monomer is ethylenedioxythiophene. 24. The method for producing a capacitor according to claim 19, wherein the concentration ratio of the low molecular weight electrolyte and the high molecular weight electrolyte is in the range of 1: 9 to 9: 1. 25. The method of manufacturing a capacitor according to claim 19, wherein the dielectric is a valve metal anodized film. 26. The method of manufacturing a capacitor according to claim 25, wherein the valve metal is selected from aluminum, tantalum and niobium.