JP6900329B2 - Capacitor and its manufacturing method, and conductive polymer dispersion - Google Patents

Description

The present invention relates to a capacitor provided with a solid electrolyte layer containing a π-conjugated conductive polymer, a method for producing the same, and a conductive polymer dispersion.

For the purpose of reducing the equivalent series resistance of the capacitor, a solid electrolyte layer formed from a conductive polymer dispersion containing poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is formed between the dielectric layer and the cathode. Capacitors arranged between them are known (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-67749

Conventional capacitors manufactured using a conductive polymer dispersion are required to further reduce their equivalent series resistance. It is also desired to improve the heat resistance of the capacitor.
The present invention provides a capacitor having a smaller equivalent series resistance than the conventional one and excellent heat resistance, a method for producing the same, and a conductive polymer dispersion suitable for producing the capacitor.

[1] A conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (11), a compound represented by the following chemical formula (2), and a compound represented by the following chemical formula (13). A conductive polymer dispersion liquid containing one or more compounds selected from the group of compounds represented by the following chemical formula (14) and a dispersion medium.
[2] A conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (1), a compound represented by the following chemical formula (2), and a compound represented by the following chemical formula (3). A conductive polymer dispersion liquid containing one or more compounds selected from the group of compounds represented by the following chemical formula (4) and a dispersion medium.
[3] The conductive polymer dispersion according to [1] or [2], which further contains a nitrogen-containing aromatic cyclic compound.
[4] The conductive polymer dispersion liquid according to [3], wherein the nitrogen-containing aromatic cyclic compound is imidazole.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[6] The conductive polymer dispersion liquid according to any one of [1] to [5], wherein the polyanion is polystyrene sulfonic acid.
[7] An anode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode made of a conductive substance provided on the opposite side of the dielectric layer to the anode, and the above. It is provided with a dielectric layer and a solid electrolyte layer formed between the cathodes, and the solid electrolyte layer is represented by the following chemical formula (11) with a conductive composite containing a π-conjugated conductive polymer and a polyanion. It has one or more compounds selected from the group of the compound represented by the following chemical formula (2), the compound represented by the following chemical formula (13), and the compound represented by the following chemical formula (14). Dielectric.
[8] An anode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode made of a conductive substance provided on the opposite side of the dielectric layer to the anode, and the above. It is provided with a dielectric layer and a solid electrolyte layer formed between the cathodes, and the solid electrolyte layer is represented by the following chemical formula (1) with a conductive composite containing a π-conjugated conductive polymer and a polyanion. It has one or more compounds selected from the group of the compound represented by the following chemical formula (2), the compound represented by the following chemical formula (3), and the compound represented by the following chemical formula (4). Dielectric.
[9] The capacitor according to [7] or [8], wherein the solid electrolyte layer further contains a nitrogen-containing aromatic cyclic compound.
[10] The capacitor according to [9], wherein the nitrogen-containing aromatic cyclic compound is imidazole.
[11] The capacitor according to any one of [7] to [10], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[12] The capacitor according to any one of [7] to [11], wherein the polyanion is polystyrene sulfonic acid.
[13] A step of forming a dielectric layer by oxidizing the surface of an anode made of a porous body of a valve metal, a step of arranging a cathode at a position facing the dielectric layer, and a step of arranging a cathode on the surface of the dielectric layer. A method for producing a capacitor, which comprises a step of applying the conductive polymer dispersion liquid according to any one of [1] to [6] and drying it to form a solid electrolyte layer.

［式（１１）中、ｌ、ｍ、ｎは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＜３０ １１０を満たし、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基であり、Ｒ１は水素原子又は炭素数１〜６の直鎖状又は分岐鎖状アルキル基である。
式（２）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。
式（１３ ）中、ｌ、ｍ、ｎは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＜３０を満たし、１〜４の整数を表し、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基である。
式（１４）中、ｌ、ｍ、ｎ、ｋは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＋ｋ ＜５ ０を満たし、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。］

[In the formula (11), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30 110, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms. Yes, R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (13), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, represent an integer of 1 to 4, and A1, A2, and A3 each independently represent 2 carbon atoms. ~ 4 alkylene groups.
In formula (14), l, m, n, and k each independently represent an integer of 1 or more, satisfy l + m + n + k <50, and A1, A2, A3, and A4 each independently have 2 to 4 carbon atoms. It is an alkylene group. ]

［式（１）中、ｌ、ｍ、ｎは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基であり、Ｒ^１は水素原子又は炭素数１〜６の直鎖状又は分岐鎖状アルキル基である。
式（２）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。
式（３）中、ｌ、ｍ、ｎは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基である。
式（４）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。］

[In the formula (1), l, m, and n each independently represent an integer of 1 to 4, A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms, and R ¹ is hydrogen. It is a linear or branched alkyl group having 1 to 6 atoms or carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (3), l, m, and n each independently represent an integer of 1 to 4, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (4), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms. ]

Since the capacitor of the present invention has excellent heat resistance and the equivalent series resistance is smaller than that of the conventional one, it contributes to high performance of electronic devices.
According to the capacitor manufacturing method of the present invention, a capacitor having excellent heat resistance and a small equivalent series resistance can be easily manufactured.
The conductive polymer dispersion of the present invention is suitable for forming a solid electrolyte layer of a capacitor having excellent heat resistance and a small equivalent series resistance.

It is sectional drawing which shows one Embodiment of the capacitor of this invention.

《Capacitor》
An embodiment of the capacitor of the present invention will be described. As shown in FIG. 1, the capacitor 10 of the present embodiment is formed on the surfaces of the anode 11 made of a porous body of a valve metal, the dielectric layer 12 made of an oxide of a valve metal, and the dielectric layer 12. It includes a solid electrolyte layer 14 and a cathode 13 provided on the outermost side.

Examples of the valve metal constituting the anode 11 include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Of these, aluminum, tantalum, and niobium are preferable.
Specific examples of the anode 11 include etching an aluminum foil to increase the surface area and then oxidizing the surface thereof, and oxidizing the surface of a sintered body of tantalum particles and niobium particles to form pellets. Can be mentioned. The product treated in this way becomes a porous body having irregularities formed on its surface.

The dielectric layer 12 in the present embodiment is a layer formed by oxidizing the surface of the anode 11, and anodizes the surface of the anode 11 of the metal body in an electrolytic solution such as an aqueous solution of ammonium adipate. It was formed by that. Therefore, as shown in FIG. 1, unevenness is formed in the dielectric layer 12 as well as the anode 11.

As the cathode 13 in the present embodiment, a metal layer made of a conductive substance such as a conductive layer formed from a conductive paste or an aluminum foil can be used.

The solid electrolyte layer 14 in the present embodiment is formed on the surface of the dielectric layer 12. The solid electrolyte layer 14 covers at least a part of the surface of the dielectric layer 12, and may cover the entire surface of the dielectric layer 12.
The thickness of the solid electrolyte layer 14 may or may not be constant, and examples thereof include a thickness of 1 μm or more and 100 μm or less.

The solid electrolyte layer 14 is a compound represented by the following chemical formula (1), a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (3), and a compound represented by the following chemical formula (4). It contains one or more compounds selected from the above group and a conductive composite containing a π-conjugated conductive polymer and a polyanion, which will be described in detail later.

［式（１）中、ｌ、ｍ、ｎは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基であり、Ｒ^１は水素原子又は炭素数１〜６の直鎖状又は分岐鎖状アルキル基である。
式（２）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。
式（３）中、ｌ、ｍ、ｎは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基である。
式（４）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。］

[In the formula (1), l, m, and n each independently represent an integer of 1 to 4, A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms, and R ¹ is hydrogen. It is a linear or branched alkyl group having 1 to 6 atoms or carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (3), l, m, and n each independently represent an integer of 1 to 4, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (4), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms. ]

From the viewpoint of reducing the equivalent series resistance (ESR) of the capacitor of the present embodiment, in the above equations (1), (2), (3) and (4), l, m, n, k Is appropriately set according to the hydroxyl value or the average molecular weight of each compound. The hydroxyl value of each compound is preferably 250 to 700, for example.
The above hydroxyl value is measured by JIS K 1557 or JIS K 0070. The above average molecular weight is measured by a chromatographic method using a standard substance.

In the formulas (1) to (4), the alkylene groups having 2 to 4 carbon atoms of A1 to A4 are independently ethylene group, propylene group (-CH (CH ₃ ) -CH _2- ) or trimethylene group (-CH (CH 3) -CH 2-). -CH _2- CH _2- CH _2- ) is preferable. Here, the orientation of the left end and the right end of the propylene group is not distinguished.

In the formula (1), R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
As a specific example of the compound represented by the formula (1), for example, TMP-30 (hydroxyl value 612-633, A1 to A3 are ethylene groups, which is a trimethylol propantripolyoxyethylene ether manufactured by Nippon Emulsifier Co., Ltd., R ¹ is an ethyl group), TMP-60 (hydroxyl value 410-435, A1 to A3 are ethylene groups, R ¹ is an ethyl group), TMP-90 (hydroxyl values 300 to 320, A1 to A3 are ethylene groups, R ^1). ethyl groups), TMP-F32 (hydroxyl value five hundred and seventeen to five hundred and thirty-six , A1 to A3 is an alkylene group having 3 carbon atoms, ^{R 1} is include ethyl group).

As a specific example of the compound represented by the formula (2), for example, PNT-40 (hydroxyl value 650 to 710, A1 to A4 are ethylene groups), which is a pentaerythritol polyoxyethylene ether manufactured by Nippon Emulsifier Co., Ltd., PNT-60U (hydroxyl value 535-565, A1 to A4 are ethylene groups) and the like can be mentioned.

Specific examples of the compound represented by the formula (3) include Uniox G-450 (average molecular weight 450, A1 to A3 are ethylene groups), which is a polyethylene glycol / glyceryl ether manufactured by Nichiyu Co., Ltd. Examples thereof include Ox G-750 (average molecular weight 750, A1 to A3 are ethylene groups) and Uniol TG-330 (average molecular weight 330, A1 to A3 are alkylene groups having 3 carbon atoms).

As a specific example of the compound represented by the formula (4), for example, Unilube DGP-700 (average molecular weight 700, A1 to A4 are alkylenes having 3 carbon atoms), which is a polypropylene glycol / diglyceryl ether manufactured by Nichiyu Co., Ltd. Group), Unilube DGP-700F (average molecular weight 700, A1 to A4 are alkylene groups having 3 carbon atoms) and the like.

The total content of the compounds represented by the formulas (1) to (4) with respect to the total mass of the solid electrolyte layer 14 is preferably 50% by mass or more and 99.9% by mass or less, and 60% by mass or more and 99% by mass or less. Is more preferable, and 70% by mass or more and 95% by mass or less is further preferable. The above range is preferable because the equivalent series resistance of the capacitor is more likely to decrease.
The type of the compound represented by the formulas (1) to (4) contained in the solid electrolyte layer 14 may be one type or two or more types.

The solid electrolyte layer 14 is a compound represented by the following chemical formula (11), a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (13), and a compound represented by the following chemical formula (14). It may contain one or more compounds selected from the above group and a conductive composite containing a π-conjugated conductive polymer and a polyanion, which will be described in detail later.

［式（１１）中、ｌ、ｍ、ｎは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＜３０ １１０を満たし、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基であり、Ｒ１は水素原子又は炭素数１〜６の直鎖状又は分岐鎖状アルキル基である。
式（２）中、ｌ、ｍ、ｎ、ｋは各々独立して１〜４の整数を表し、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。
式（１３ ）中、ｌ、ｍ、ｎは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＜３０を満たし、Ａ１，Ａ２，Ａ３は各々独立して炭素数２〜４のアルキレン基である。
式（１４）中、ｌ、ｍ、ｎ、ｋは各々独立して１以上の整数を表し、ｌ＋ｍ＋ｎ＋ｋ ＜５ ０を満たし、Ａ１，Ａ２，Ａ３，Ａ４は各々独立して炭素数２〜４のアルキレン基である。］

[In the formula (11), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30 110, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms. Yes, R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (13), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (14), l, m, n, and k each independently represent an integer of 1 or more, satisfy l + m + n + k <50, and A1, A2, A3, and A4 each independently have 2 to 4 carbon atoms. It is an alkylene group. ]

From the viewpoint of reducing the equivalent series resistance (ESR) of the capacitor of the present embodiment, in the above formula (11), the above formula (2), the above formula (13) and the above formula (14), l, m, n, k Is appropriately set according to the hydroxyl value or the average molecular weight of each compound. The hydroxyl value of each compound is preferably 100 to 700, for example. The unit of hydroxyl value is mgKOH / g.
The above hydroxyl value is measured by JIS K 1557 or JIS K 0070. The above average molecular weight is measured by a chromatographic method using a standard substance.

In the formulas (11), (2), (13), and (14), the alkylene groups having 2 to 4 carbon atoms of A1 to A4 are independently ethylene group and propylene group (-CH (CH ₃ )-. It is preferably CH _2- ) or a trimethylene group (-CH _2- CH _2- CH _2-). Here, the orientation of the left end and the right end of the propylene group is not distinguished.

In the formula (11), R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
In the above formula (11), the sum of l + m + n is 3 or more and less than 30, preferably 9 or more and 30 or less, more preferably 9 or more and 25 or less, and further preferably 9 or more and 20 or less.
As a specific example of the compound represented by the formula (11), for example, TMP-30 (hydroxyl value 612-633, A1 to A3 are ethylene groups, which are trimethylolpropantripolyoxyethylene ether manufactured by Nippon Emulsifier Co., Ltd., R ¹ is an ethyl group), TMP-60 (hydroxyl value 410-435, A1 to A3 are ethylene groups, R ¹ is an ethyl group), TMP-90 (hydroxyl values 300 to 320, A1 to A3 are ethylene groups, R ^1). ethyl group), TMP-F32 (hydroxyl value from 517 to 536 is, A1 to A3 is an alkylene group having 3 carbon atoms, ^{R 1} is ethyl group), trimethylolpropane Tripoli polyoxyethylene ethers manufactured by Aoki oil industrial Co., Buraunon TMP-20 (hydroxyl value approximately 160, A1 to A3 is an ethylene group, ^{R 1} is an ethyl group).

Specific examples of the compound represented by the formula (2) include those described above.
In the formula (13), the sum of l + m + n is 3 or more and less than 30, preferably 10 or more and less than 30, more preferably 20 or more and less than 30, and further preferably 20 or more and 26 or less.
Specific examples of the compound represented by the formula (13) include Braunon GL-20 (hydroxyl value of about 170, A1 to A3 are ethylene groups) and Braunon GL, which are polyoxyethylene glyceryl ethers manufactured by Aoki Oil & Fat Industry Co., Ltd. -26 (hydroxyl value is about 130, A1 to A3 are ethylene groups) and the like.

In the above formula (14), the sum of l + m + n + k is 4 or more and less than 50, preferably 8 or more and 45 or less, more preferably 10 or more and 35 or less, and further preferably 10 or more and 20 or less.
As a specific example of the compound represented by the formula (14), for example, Unilube DGP-700 (average molecular weight 700, A1 to A4 are alkylenes having 3 carbon atoms), which is a polyoxypropylene diglyceryl ether manufactured by Nichiyu Co., Ltd. Group), Unilube DGP-700F (average molecular weight 700, A1 to A4 are alkylene groups with 3 carbon atoms), SC-E750 (average molecular weight 750, hydroxyl value) which is a polyoxyethylene diglyceryl ether manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. Approximately 300, A1 to A4 are ethylene groups), SC-E1000 (average molecular weight 1000, hydroxyl value approximately 220, A1 to A4 are ethylene groups), SC-E1500 (average molecular weight 1500, hydroxyl value approximately 150, A1 to A4 are ethylene) Groups), SC-E2000 (average molecular weight 2000, hydroxyl value about 110, A1 to A4 are ethylene groups) and the like.

The total content of the compounds represented by the formulas (11), (2), (13) and (14) with respect to the total mass of the solid electrolyte layer 14 is preferably 50% by mass or more and 99.9% by mass or less. It is more preferably 60% by mass or more and 99% by mass or less, and further preferably 70% by mass or more and 95% by mass or less. The above range is preferable because the equivalent series resistance of the capacitor is more likely to decrease.
The type of the compound represented by the formulas (11), (2), (13) and (14) contained in the solid electrolyte layer 14 may be one kind or two or more kinds.

Next, a conductive composite containing a π-conjugated conductive polymer and a polyanion contained in the solid electrolyte layer 14 will be described.
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, and a polyacetylene-based polymer are used. Conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophenine-based conductive polymer, and copolymers thereof, etc. Can be mentioned. From the viewpoint of stability in air, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, and a polyaniline-based conductive polymer are preferable, and a polythiophene-based conductive polymer is more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexyl). Thiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) , Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxy) Thiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxy) Thiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), Poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-methoxythiophene) 3-Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4) -Carboxybutylthiophene).

Examples of the polypyrrole-based conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3). -Butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxy) Pyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole). Be done.

Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among the π-conjugated conductive polymers exemplified above, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity and heat resistance.
One type of π-conjugated conductive polymer may be used alone, or two or more types may be used in combination.

The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer, and can improve the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of the polyanion include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylsulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, and poly. Polymers with sulfonic acid groups such as sulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinylcarboxylic acid, polystyrenecarboxylic acid, polyallylcarboxylic acid, polyacryliccarboxylic acid, polymethacryl Examples thereof include polymers having a carboxylic acid group such as carboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, and polyacrylic acid. These homopolymers may be used, or two or more kinds of copolymers may be used.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
One type of polyanion may be used alone, or two or more types may be used in combination.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less.
The mass average molecular weight in the present specification is a value measured by gel permeation chromatography and determined as polystyrene as a standard substance.

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass. The range is more preferably 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is equal to or higher than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be strong, sufficient conductivity can be easily obtained, and the conductivity in the conductive polymer dispersion is further increased. The dispersibility of the complex is increased. Further, when the content of the polyanion is not more than the upper limit value, the relative content of the π-conjugated conductive polymer increases, and sufficient conductivity can be easily obtained.

A conductive composite is formed by coordinating and doping a π-conjugated conductive polymer with a polyanion. From the viewpoint of improving the conductivity and dispersibility of the conductive composite, it is preferable that all the anion groups have a surplus anion group that does not contribute to the doping, rather than doping the π-conjugated conductive polymer.

The content of the conductive composite with respect to the total mass of the solid electrolyte layer 14 is preferably 1% by mass or more and 90% by mass or less, more preferably 3% by mass or more and 50% by mass or less, and further preferably 5% by mass or more and 30% by mass or less. preferable. The above range is preferable because the equivalent series resistance of the capacitor is more likely to decrease.

The solid electrolyte layer 14 may contain one or more nitrogen-containing compounds. By including the nitrogen-containing compound in the solid electrolyte layer 14, the equivalent series resistance of the capacitor can be further reduced.

Examples of the nitrogen-containing compound include the following amine compounds and nitrogen-containing aromatic cyclic compounds. When at least one of these amine compounds and nitrogen-containing aromatic cyclic compounds is contained in the solid electrolyte layer 14, the equivalent series resistance of the capacitor may be further reduced.
Amine compounds are compounds that have an amino group, and the amino group reacts with the anion group of the polyanion.
The amine compound may be any of a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt. In addition, one type of amine compound may be used alone, or two or more types may be used in combination.
The amine compound is a linear or branched alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an alkylene group having 2 to 12 carbon atoms. , It may have a substituent selected from an arylene group having 6 or more and 12 or less carbon atoms, an aralkylene group having 7 or more and 12 or less carbon atoms, and an oxyalkylene group having 2 or more and 12 or less carbon atoms.
Specific primary amines include, for example, aniline, toluidine, benzylamine, ethanolamine and the like.
Specific examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Specific examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Specific examples of the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, tetranaphthylammonium salt and the like. Hydroxide ions are examples of anions that are paired with ammonium.
Of these amine compounds, tertiary amines are preferable, and triethylamine and tripropylamine are more preferable.
Examples of the nitrogen-containing aromatic cyclic compound (an aromatic compound in which at least one nitrogen atom forms a ring structure) include pyrrole, imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, and N. -Propyl imidazole, N-butyl imidazole, 1- (2-hydroxyethyl) imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, 1-benzyl-2-methyl imidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2 -Hydroxybenzimidazole, 2- (2-pyridyl) benzimidazole, pyridine and the like can be mentioned.
Of these nitrogen-containing aromatic cyclic compounds, imidazole is more preferable.

The solid electrolyte layer 14 may contain an electrolytic solution in which an electrolyte is dissolved in a solvent for an electrolytic solution. The higher the electrical conductivity of the electrolytic solution, the more preferable.
Examples of the solvent for the electrolytic solution include alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol and glycerin, and lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone. Examples thereof include amide solvents such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N-methylpyrrolidinone, nitrile solvents such as acetonitrile and 3-methoxypropionitrile, and water.
Examples of the electrolyte include adipic acid, glutaric acid, succinic acid, benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, maleic acid, toluic acid, enanthic acid, ammonium acid, formic acid, 1,6-decandicarboxylic acid, and 5 , Decandycarboxylic acid such as 6-decandicarboxylic acid, octanedicarboxylic acid such as 1,7-octanedicarboxylic acid, organic acid such as azelaic acid, sebacic acid; or a large amount of boric acid obtained from boric acid, boric acid and polyvalent alcohol. Hyvalent alcohol complex compounds; primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc.) and secondary amines (dimethylamine, diethylamine, diamine, etc.) with inorganic acids such as phosphoric acid, carbonic acid, and silicic acid as anionic components. Propylamine, methylethylamine, diphenylamine, etc.), tertiary amine (trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, etc.), tetraalkylammonium (tetraalkylammonium) An electrolyte containing methylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, etc.) as a cation component; and the like.

<Effect>
The solid electrolyte layer of the capacitor of the present invention is one or more selected from the compounds represented by the formulas (1) to (4) or the formulas (11), (2), (13) and (14). By containing the above compound, the equivalent series resistance of the capacitor can be reduced as compared with the conventional case without lowering the capacitance. Although this mechanism has not been elucidated, it is speculated that the equivalent series resistance of the compound was reduced by improving the conductivity of the solid electrolyte layer.
Further, the solid electrolyte layer of the capacitor of the present invention is selected from the compound group represented by the above formulas (1) to (4) or the above formulas (11), (2), (13) and (14) 1 By containing more than one kind of compound, the heat resistance of the capacitor can be improved. Although this mechanism has not been elucidated, it is presumed that the heat resistance of the compound is improved by improving the stability of the conductive complex contained in the solid electrolyte layer.

<< Capacitor manufacturing method, conductive polymer dispersion >>
The capacitor according to the present invention has a step of forming a dielectric layer by oxidizing the surface of an anode made of a porous body of a valve metal (dielectric forming step) and a step of arranging a cathode at a position facing the dielectric layer. It can be produced by a step (cathode forming step) and a step of applying a conductive polymer dispersion liquid to at least a part of the surface of the dielectric layer and drying it to form a solid electrolyte layer.

The conductive polymer dispersion liquid is one or more selected from the compound group represented by the formulas (1) to (4) or the formulas (11), (2), (13) and (14). It is a dispersion liquid containing a compound and further dispersed with a conductive composite containing a π-conjugated conductive polymer and a polyanion.
The conductive polymer dispersion may contain the nitrogen-containing compound, an additive described later, and the like.

The dielectric layer forming step is a step of oxidizing the surface of the anode 11 made of the porous body of the valve metal to form the dielectric layer 12.
Examples of the method for forming the dielectric layer 12 include a method of anodizing the surface of the anode 11 in an electrolytic solution for chemical conversion treatment such as an aqueous solution of ammonium adipate, an aqueous solution of ammonium borate, and an aqueous solution of ammonium phosphate. ..

The cathode forming step is a step of arranging the cathode 13 at a position facing the dielectric layer 12.
Examples of the method of arranging the cathode 13 include a method of forming the cathode 13 using a conductive paste such as carbon paste and silver paste, and a method of arranging a metal foil such as aluminum foil facing the dielectric layer 12. Be done.

The solid electrolyte layer forming step is a step of applying the conductive polymer dispersion liquid to at least a part of the surface of the dielectric layer 12 and drying it to form the solid electrolyte layer 14.

The dispersion medium constituting the conductive polymer dispersion is not particularly limited as long as it is a liquid capable of dispersing the conductive composite, and examples thereof include water, an organic solvent, or a mixed solution of water and an organic solvent. Be done.
Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents and the like. One of these organic solvents may be used alone, or two or more of them may be used in combination.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ether solvent include propylene glycol monoalkyl ethers such as diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, and propylene glycol dialkyl ethers.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.

Examples of the additive include a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like. However, the additive is the conductive complex, the compound group represented by the formulas (1) to (4), the formula (11), the formula (13) and the formula (14), and the nitrogen-containing compound. Compounds other than.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinyl alcohol or polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group, an amino group, an epoxy group and the like.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.

The content of the conductive complex with respect to the total mass of the conductive polymer dispersion is not particularly limited, and a content having a viscosity that makes it easy to apply is preferable. Specifically, for example, 0.1% by mass or more and 10% by mass or less is preferable, 0.5% by mass or more and 5% by mass or less is more preferable, and 1% by mass or more and 2% by mass or less is further preferable.

The total content of one or more compounds selected from the group of compounds represented by the above formulas (1) to (4) with respect to the total mass of the conductive polymer dispersion is not particularly limited and is easy to apply. The content having a high viscosity is preferable. Specifically, for example, 1% by mass or more and 45% by mass or less is preferable, 2% by mass or more and 35% by mass or less is more preferable, and 3% by mass or more and 25% by mass or less is further preferable.
The total content of one or more compounds selected from the group of compounds represented by the above formulas (11), (2), (13) and (14) with respect to the total mass of the conductive polymer dispersion is particularly limited. It is preferable that the content has a viscosity that is easy to apply. Specifically, for example, 1% by mass or more and 45% by mass or less is preferable, 2% by mass or more and 35% by mass or less is more preferable, and 3% by mass or more and 25% by mass or less is further preferable.

When the conductive polymer dispersion contains the nitrogen-containing compound, the content ratio thereof is appropriately determined according to the type of the nitrogen-containing compound. For example, with respect to 100 parts by mass of the solid content of the conductive composite, the content ratio thereof is appropriately determined. For example, it is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less.

When the conductive polymer dispersion liquid contains the additive, the content ratio thereof is appropriately determined depending on the type of the additive. For example, with respect to 100 parts by mass of the solid content of the conductive composite, for example, It can be in the range of 1 part by mass or more and 1000 parts by mass or less.

Examples of the method for preparing the conductive polymer dispersion include a method of oxidatively polymerizing a precursor monomer forming a π-conjugated conductive polymer in the presence of a polyanion and a dispersion medium.
The obtained conductive polymer dispersion is selected from the group of compounds represented by the formulas (1) to (4) or the formulas (11), (2), (13) and (14). More than a kind of compound can be added, and if necessary, the nitrogen-containing compound, additives and the like can be added.
For the purpose of improving the dispersibility of each material contained in the conductive polymer dispersion, it is preferable to perform a known high dispersion treatment in which the conductive polymer dispersion is dispersed while applying a shearing force before coating.

As a method for applying the conductive polymer dispersion liquid, for example, dipping (dip coating), comma coating, reverse coating, lip coating, microgravure coating and the like can be applied. Among these, immersion is preferable from the viewpoint that the solid electrolyte layer 14 can be easily formed between the dielectric layer 12 and the cathode 13.
Examples of the drying method include room temperature drying, hot air drying, far infrared drying and the like.

The capacitor of the present invention and the method for producing the same are not limited to the examples of the above embodiments.
In the capacitor of the present invention, a separator may be provided between the dielectric layer and the cathode.
As a capacitor in which a separator is provided between the dielectric layer and the cathode, a winding type capacitor can be mentioned.
Examples of the separator include a sheet (including a non-woven fabric) made of cellulose, polyvinyl alcohol, polyester, polyethylene, polystyrene, polypropylene, polyimide, polyamide, polyvinylidene fluoride and the like, a non-woven fabric of glass fiber, and the like.
The density of the separator ^{is preferably in the range of 0.1 g / cm 3} or more and 1.0 g / cm ³ or less, and more preferably in the range of 0.2 g / cm ³ or more and 0.8 g / cm ³ or less.
When the separator is provided, a method of impregnating the separator with carbon paste or silver paste to form a cathode can also be applied.

(Manufacturing Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added dropwise for 20 minutes while stirring at 80 ° C., and this solution was added dropwise for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium styrene sulfonate-containing solution, and about 1000 ml of the solvent of the polystyrene sulfonic acid-containing solution was removed by an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Manufacturing Example 2)
14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 were dissolved in 2000 ml of ion-exchanged water and mixed at 20 ° C. The obtained mixed solution was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added, and the mixture was slowly added for 3 hours. The mixture was stirred and reacted.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This operation was repeated 3 times.
200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) was washed with water. After repeating this washing operation 8 times, dispersion treatment was performed at a pressure of 140 MPa using a high-pressure disperser to carry out a 1.6 mass% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (3,4-ethylenedioxythiophene). PEDOT-PSS aqueous dispersion) was obtained.

(Manufacturing Example 3)
After connecting the anode lead terminal to the etched aluminum foil (anode foil), a voltage of 130 V is applied in a 10 mass% aqueous solution of ammonium adipate and chemical conversion (oxidation treatment) is performed to form dielectric layers on both sides of the aluminum foil. It was formed to obtain an anode foil.
Next, an opposed aluminum cathode foil in which cathode lead terminals were welded was laminated on both sides of the anode foil via a cellulose separator, and this was wound into a cylindrical shape to obtain a capacitor element.

(Manufacturing Example 4)
100 g of γ-butyrolactone, 10 g of sulfolane, and 25 g of tetramethylammonium phthalate were mixed and dissolved to obtain a driving electrolyte.

(Example 1)
0.3 parts by mass of imidazole and 5.0 parts by mass of TMP-30 (manufactured by Nippon Emulsifier Co., Ltd.) were added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was stirred at room temperature and then subjected to high pressure. A dispersion treatment was carried out at a pressure of 140 MPa using a disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, the process of drying with a hot air dryer at 125 ° C. for 20 minutes was repeated twice to conduct conductivity on the surface of the dielectric layer. A solid electrolyte layer containing the sex complex was formed.
Next, the capacitor element on which the solid electrolyte layer was formed was loaded into an aluminum case and sealed with a sealing rubber to obtain a capacitor.

(Example 2)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that the amount of TMP-30 added was changed to 25.0 parts by mass.

(Example 3)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to TMP-60 (manufactured by Nippon Emulsifier Co., Ltd.).

(Example 4)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to TMP-60 and the amount added was changed to 10.0 parts by mass.

(Example 5)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to TMP-60 and the amount added was changed to 25.0 parts by mass.

(Example 6)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to TMP-F32 (manufactured by Nippon Emulsifier Co., Ltd.).

(Example 7)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to TMP-F32 and the amount added was changed to 25.0 parts by mass.

(Example 8)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to PNT-40 (manufactured by Nippon Emulsifier Co., Ltd.).
(Example 9)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to PNT-40 and the amount added was changed to 25.0 parts by mass.
(Example 10)
Conductive polymer dispersion and capacitor in the same manner as in Example 1 except that TMP-30 was changed to Uniox G-750 (manufactured by NOF CORPORATION) and the amount added was changed to 25.0 parts by mass. Got

(Comparative Example 1)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that imidazole and TMP-30 were not added.

(Comparative Example 2)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was not added.

(Comparative Example 3)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to trimethylolpropane (described as TMP in the table).

(Comparative Example 4)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 1 except that TMP-30 was changed to 3.0 g of pentaerythritol.

<Evaluation>
For each of the obtained capacitors, the capacitance (C) at 120 Hz and the equivalent series resistance (ESR) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 1.

The capacitors of Examples 1 to 10 provided with the solid electrolyte layer containing the compounds represented by the formulas (1) to (3) had a sufficient capacitance, and the equivalent series resistance was greatly reduced.
The capacitors of Comparative Examples 1 to 4 provided with the solid electrolyte layer containing no compounds represented by the formulas (1) to (3) have the same capacitance as that of the examples, but have equivalent series resistance. It was bigger than the example.

(Example 11)
0.3 parts by mass of imidazole and 5.0 parts by mass of TMP-30 (manufactured by Nippon Emulsifier Co., Ltd.) were added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was stirred at room temperature and then subjected to high pressure. A dispersion treatment was carried out at a pressure of 140 MPa using a disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, the process of drying with a hot air dryer at 125 ° C. for 20 minutes was repeated twice to conduct conductivity on the surface of the dielectric layer. A solid electrolyte layer containing the sex complex was formed.
Next, the aluminum case was loaded with the capacitor element on which the solid electrolyte layer was formed and the electrolytic solution obtained in Production Example 4, and sealed with a sealing rubber. A voltage of 65 V was applied for 30 minutes in an atmosphere of 125 ° C. to prepare a capacitor.

(Example 12)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that the amount of TMP-30 added was changed to 25.0 parts by mass.

(Example 13)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to TMP-60 (manufactured by Nippon Emulsifier Co., Ltd.).

(Example 14)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to TMP-60 and the amount added was changed to 10.0 parts by mass.

(Example 15)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to TMP-60 and the amount added was changed to 25.0 parts by mass.

(Example 16)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to TMP-F32 (manufactured by Nippon Emulsifier Co., Ltd.).

(Example 17)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to TMP-F32 and the amount added was changed to 25.0 parts by mass.

(Example 18)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to PNT-40 (manufactured by Nippon Emulsifier Co., Ltd.).

(Example 19)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to PNT-40 and the amount added was changed to 25.0 parts by mass.

(Example 20)
Conductive polymer dispersion and capacitor in the same manner as in Example 11, except that TMP-30 was changed to Uniox G-750 (manufactured by NOF CORPORATION) and the amount added was changed to 5.0 parts by mass. Got

(Example 21)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 11 except that TMP-30 was changed to Uniox G-750 and the amount added was changed to 25.0 parts by mass.

(Example 22)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 11 except that TMP-30 was changed to Uniol TG-330 (manufactured by NOF CORPORATION) and the amount added was changed to 5.0 parts by mass. Obtained.

(Example 23)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 11 except that TMP-30 was changed to Unilube DGP-700F (manufactured by NOF CORPORATION) and the amount added was changed to 5.0 parts by mass. Obtained.

(Comparative Example 5)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 10 except that imidazole and TMP-30 were not added.

(Comparative Example 6)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 10 except that TMP-30 was not added.

(Comparative Example 7)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 10 except that TMP-30 was changed to trimethylolpropane (described as TMP in the table).

(Comparative Example 8)
A conductive polymer dispersion and a capacitor were obtained in the same manner as in Example 10 except that TMP-30 was changed to 3.0 g of pentaerythritol.

<Evaluation>
[Capacitance / equivalent series resistance]
_{Capacitance at 120 Hz (C 0} ) and equivalent series resistance at 100 kHz using LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.) for the capacitors of Examples 11 to 23 and Comparative Examples 5 to 8. (ESR ₀ ) was measured. The measurement results are shown in Table 2.

[Heat resistance test]
The capacitors of Examples 11 to 23 and Comparative Examples 5 to 8 were allowed to stand in a hot air dryer at 135 ° C., taken out after 100 hours, and cooled at room temperature for 30 minutes. _{With respect to the cooled capacitor, the capacitance (C 1} ) at 120 Hz and the equivalent series resistance (ESR ₁ ) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 2.
_{Further, ΔC = C 1} / C ₀ and ΔESR = ESR ₁ / ESR ₀ were determined as the amount of change before and after the heat resistance test. Table 2 also shows ΔC and ΔESR.

The capacitors of Examples 11 to 23 provided with the solid electrolyte layer containing the compounds represented by the formulas (1) to (4) had a sufficient capacitance and a low equivalent series resistance. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also small.
The capacitors of Comparative Examples 5 to 8 provided with the solid electrolyte layer containing no compounds represented by the formulas (1) to (4) have the same capacitance as those of the examples, but the equivalent series resistance is the example. It was big compared to. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also large.

The ΔESR of Comparative Example 6 was equivalent to that of Example, but ESR ₀ and ESR ₁ were larger and inferior to those of Example. The result of Comparative Example 6 shows that imidazole can improve the heat resistance, but _{in order to substantially reduce ESR 0} and ESR ₁ , the presence of the compounds represented by the above formulas (1) to (4) is necessary. It shows that.
From the above results, it was confirmed that the capacitor of the example provided with the solid electrolyte layer containing one or more compounds selected from the group of compounds represented by the formulas (1) to (4) is also excellent in heat resistance. did it.

(Example 24)
0.3 parts by mass of imidazole and 1.0 part by mass of Blaunon TMP-20 (manufactured by Aoki Yushi Kogyo Co., Ltd.) were added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 and stirred at room temperature. After that, a dispersion treatment was performed at a pressure of 140 MPa using a high-pressure disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, the process of drying with a hot air dryer at 125 ° C. for 30 minutes was repeated twice to conduct conductivity on the surface of the dielectric layer. A solid electrolyte layer containing the sex complex was formed.
Next, the capacitor element on which the solid electrolyte layer was formed was loaded into an aluminum case and sealed with a sealing rubber to obtain a capacitor.

(Examples 25 to 46, Comparative Examples 9 to 11)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 24, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 3 and parts by weight. Obtained. In Table 3, "-" means that the corresponding compound was not added.

<Evaluation>
For each of the obtained capacitors, the capacitance (C) at 120 Hz and the equivalent series resistance (ESR) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 4.

The capacitors of Examples 24 to 46 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) have a sufficient capacitance, and the equivalent series resistance is greatly reduced. did.
The capacitors of Comparative Examples 9 to 11 provided with the solid electrolyte layer containing no compound represented by the formulas (11), (13), and (14) have the same capacitance as that of the examples, but are equivalent in series. The resistance was greater than in the examples.

(Example 47)
After adding 0.3 parts by mass of imidazole, 10.0 parts by mass of diethylene glycol and 3.0 parts by mass of Blaunon TMP-20 to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and stirring at room temperature. , The dispersion treatment was carried out at a pressure of 140 MPa using a high-pressure disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, a step of drying for 30 minutes with a hot air dryer at 125 ° C. is performed once, and the conductive polymer is conductive on the surface of the dielectric layer. A solid electrolyte layer containing the complex was formed.
Next, the capacitor element on which the solid electrolyte layer was formed was loaded into an aluminum case and sealed with a sealing rubber to obtain a capacitor.

(Examples 48 to 57, Comparative Example 12)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 47, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 5 and parts by weight. Obtained. In Table 5, "-" means that the corresponding compound was not added.

<Evaluation>
For each of the obtained capacitors, the capacitance (C) at 120 Hz and the equivalent series resistance (ESR) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 6.

前記式（１１）、（１３）、（１４）で表される化合物を含む固体電解質層を備えた実施例４７〜５７のキャパシタは、充分な静電容量を有し、等価直列抵抗が大きく低下した。
前記式（１１）、（１３）、（１４）で表される化合物を含有しない固体電解質層を備えた比較例１２のキャパシタは、実施例と同等の静電容量を有するが、等価直列抵抗が実施例と比べて大きかった。

The capacitors of Examples 47 to 57 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) have a sufficient capacitance, and the equivalent series resistance is greatly reduced. did.
The capacitor of Comparative Example 12 provided with the solid electrolyte layer containing no compound represented by the formulas (11), (13) and (14) has the same capacitance as that of the example, but has equivalent series resistance. It was larger than the examples.

(Example 58)
To 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 0.3 parts by mass of imidazole, 10.0 parts by mass of diethylene glycol, 3.0 parts by mass of pentaerythritol, and 5.0 parts by mass of Blaunon TMP-20 were added. After stirring at room temperature, dispersion treatment was performed at a pressure of 140 MPa using a high-pressure disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, a step of drying for 30 minutes with a hot air dryer at 125 ° C. is performed once, and the conductive polymer is conductive on the surface of the dielectric layer. A solid electrolyte layer containing the complex was formed.
Next, the capacitor element on which the solid electrolyte layer was formed was loaded into an aluminum case and sealed with a sealing rubber to obtain a capacitor.

(Examples 59 to 65, Comparative Example 13)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 58, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 7 and the part by weight. Obtained. In Table 7, "-" means that the corresponding compound was not added.

<Evaluation>
For each of the obtained capacitors, the capacitance (C) at 120 Hz and the equivalent series resistance (ESR) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 8.

The capacitors of Examples 58 to 65 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) have a sufficient capacitance, and the equivalent series resistance is greatly reduced. did.
The capacitor of Comparative Example 13 provided with the solid electrolyte layer containing no compounds represented by the formulas (11), (13) and (14) has a capacitance equivalent to that of the example, but has an equivalent series resistance. It was larger than the examples.

(Example 66)
0.3 parts by mass of imidazole and 1.0 part by mass of Blaunon TMP-20 were added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, stirred at room temperature, and then 140 MPa using a high-pressure disperser. The dispersion treatment was carried out at the same pressure as above to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, the process of drying with a hot air dryer at 125 ° C. for 30 minutes was repeated twice to conduct conductivity on the surface of the dielectric layer. A solid electrolyte layer containing the sex complex was formed.
Next, the aluminum case was loaded with the capacitor element on which the solid electrolyte layer was formed and the electrolytic solution obtained in Production Example 4, and sealed with a sealing rubber. A voltage of 65 V was applied for 30 minutes in an atmosphere of 125 ° C. to prepare a capacitor.

(Examples 67 to 88, Comparative Examples 14 to 16)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 67, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 9 and the part by weight. Obtained. In Table 9, "-" means that the corresponding compound was not added.

[Capacitance / equivalent series resistance]
_{Capacitance at 120 Hz (C 0} ) and equivalent series resistance at 100 kHz using LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.) for the capacitors of Examples 66 to 88 and Comparative Examples 14 to 16. (ESR ₀ ) was measured. The measurement results are shown in Table 10.

[Heat resistance test]
The capacitors of Examples 66 to 88 and Comparative Examples 14 to 16 were allowed to stand in a hot air dryer at 135 ° C., taken out after 1000 hours, and cooled at room temperature for 30 minutes. _{With respect to the cooled capacitor, the capacitance (C 1} ) at 120 Hz and the equivalent series resistance (ESR ₁ ) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 10.
_{Further, ΔC = C 1} / C ₀ and ΔESR = ESR ₁ / ESR ₀ were determined as the amount of change before and after the heat resistance test. Table 10 also shows ΔC and ΔESR.

The capacitors of Examples 66 to 88 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) had a sufficient capacitance and a low equivalent series resistance. .. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also small.
The capacitors of Comparative Examples 14 to 16 provided with the solid electrolyte layer containing no compound represented by the formulas (11), (13), and (14) have the same capacitance as that of the examples, but are equivalent in series. The resistance was greater than in the examples. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also large.

(Example 89)
After adding 0.3 parts by mass of imidazole, 10.0 parts by mass of diethylene glycol and 3.0 parts by mass of Blaunon TMP-20 to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and stirring at room temperature. , The dispersion treatment was carried out at a pressure of 140 MPa using a high-pressure disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, a step of drying for 30 minutes with a hot air dryer at 125 ° C. is performed once, and the conductive polymer is conductive on the surface of the dielectric layer. A solid electrolyte layer containing the complex was formed.
Next, the aluminum case was loaded with the capacitor element on which the solid electrolyte layer was formed and the electrolytic solution obtained in Production Example 4, and sealed with a sealing rubber. A voltage of 65 V was applied for 30 minutes in an atmosphere of 125 ° C. to prepare a capacitor.

(Examples 90 to 99, Comparative Example 17)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 89, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 11 and the part by weight. Obtained. In Table 11, "-" means that the corresponding compound was not added.

[Capacitance / equivalent series resistance]
_{For the capacitors of Examples 89 to 99 and Comparative Example 17, the capacitance (C 0} ) at 120 Hz and the equivalent series resistance (ESR) at 100 kHz were used using the LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). ₀ ) was measured. The measurement results are shown in Table 12.

[Heat resistance test]
The capacitors of Examples 89 to 99 and Comparative Example 17 were allowed to stand in a hot air dryer at 135 ° C., taken out after 1000 hours, and cooled at room temperature for 30 minutes. _{With respect to the cooled capacitor, the capacitance (C 1} ) at 120 Hz and the equivalent series resistance (ESR ₁ ) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 12.
_{Further, ΔC = C 1} / C ₀ and ΔESR = ESR ₁ / ESR ₀ were determined as the amount of change before and after the heat resistance test. Table 12 also shows ΔC and ΔESR.

The capacitors of Examples 89 to 99 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) had a sufficient capacitance and a low equivalent series resistance. .. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also small.
The capacitor of Comparative Example 17 provided with the solid electrolyte layer containing no compounds represented by the formulas (11), (13) and (14) has a capacitance equivalent to that of the example, but has an equivalent series resistance. It was larger than the examples. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also large.

(Example 100)
To 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 0.3 parts by mass of imidazole, 10.0 parts by mass of diethylene glycol, 3.0 parts by mass of pentaerythritol, and 5.0 parts by mass of Blaunon TMP-20 were added. After stirring at room temperature, dispersion treatment was performed at a pressure of 140 MPa using a high-pressure disperser to obtain a conductive polymer dispersion liquid.
After immersing the capacitor element obtained in Production Example 3 in the conductive polymer dispersion under reduced pressure, a step of drying for 30 minutes with a hot air dryer at 125 ° C. is performed once, and the conductive polymer is conductive on the surface of the dielectric layer. A solid electrolyte layer containing the complex was formed.
Next, the aluminum case was loaded with the capacitor element on which the solid electrolyte layer was formed and the electrolytic solution obtained in Production Example 4, and sealed with a sealing rubber. A voltage of 65 V was applied for 30 minutes in an atmosphere of 125 ° C. to prepare a capacitor.

(Examples 101-107, Comparative Example 18)
The conductive polymer dispersion and the capacitor were prepared in the same manner as in Example 100, except that the compound added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was changed to the compound shown in Table 13 and parts by weight. Obtained. In Table 13, "-" means that the corresponding compound was not added.

[Capacitance / equivalent series resistance]
For the capacitors of Examples 100 to 107 and Comparative Example 18, using the LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.), the capacitance at 120 Hz (C ₀ ) and the equivalent series resistance at 100 kHz (ESR). ₀ ) was measured. The measurement results are shown in Table 14.

[Heat resistance test]
The capacitors of Examples 100 to 107 and Comparative Example 18 were allowed to stand in a hot air dryer at 135 ° C., taken out after 1000 hours, and cooled at room temperature for 30 minutes. _{With respect to the cooled capacitor, the capacitance (C 1} ) at 120 Hz and the equivalent series resistance (ESR ₁ ) at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). The measurement results are shown in Table 14.
_{Further, ΔC = C 1} / C ₀ and ΔESR = ESR ₁ / ESR ₀ were determined as the amount of change before and after the heat resistance test. Table 14 also shows ΔC and ΔESR.

The capacitors of Examples 100 to 107 provided with the solid electrolyte layer containing the compounds represented by the formulas (11), (13) and (14) had a sufficient capacitance and a low equivalent series resistance. .. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also small.
The capacitor of Comparative Example 18 provided with the solid electrolyte layer containing no compounds represented by the formulas (11), (13) and (14) has a capacitance equivalent to that of the example, but has an equivalent series resistance. It was larger than the examples. Furthermore, the amount of change in equivalent series resistance (ΔESR) after the heat resistance test was also large.

10 Capacitor 11 Anode 12 Dielectric layer 13 Cathode 14 Solid electrolyte layer

Claims (11)

A conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (11), a compound represented by the following chemical formula (2), and a compound represented by the following chemical formula (13). A conductive polymer dispersion containing one or more compounds selected from the group of compounds represented by the following chemical formula (14), a dispersion medium, and a nitrogen-containing aromatic cyclic compound.

[In the formula (11), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms. , R ¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (13), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (14), l, m, n, and k each independently represent an integer of 1 or more, satisfy l + m + n + k <50, and A1, A2, A3, and A4 independently represent alkylenes having 2 to 4 carbon atoms. Is the basis. ] A conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (1), a compound represented by the following chemical formula (2), and a compound represented by the following chemical formula (3). A conductive polymer dispersion containing one or more compounds selected from the group of compounds represented by the following chemical formula (4), a dispersion medium, and a nitrogen-containing aromatic cyclic compound.

[In the formula (1), l, m, and n each independently represent an integer of 1 to 4, A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms, and R ¹ is hydrogen. It is a linear or branched alkyl group having 1 to 6 atoms or carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (3), l, m, and n each independently represent an integer of 1 to 4, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (4), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms. ] The conductive polymer dispersion liquid according to claim 1 or 2 , wherein the nitrogen-containing aromatic cyclic compound is imidazole. The conductive polymer dispersion according to any one of claims 1 to 3 , wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The conductive polymer dispersion liquid according to any one of claims 1 to 4 , wherein the polyanion is polystyrene sulfonic acid. An anode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode of the dielectric layer made of a conductive material provided on the opposite side of the anode, and the dielectric layer. And a solid electrolyte layer formed between the cathodes.
The solid electrolyte layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (11), a compound represented by the following chemical formula (2), and the following chemical formula (13). A capacitor having one or more compounds selected from the group of the compound represented by, the compound represented by the following chemical formula (14), and a nitrogen-containing aromatic cyclic compound.

[In the formula (11), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms. , R ¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (13), l, m, and n each independently represent an integer of 1 or more, satisfy l + m + n <30, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (14), l, m, n, and k each independently represent an integer of 1 or more, satisfy l + m + n + k <50, and A1, A2, A3, and A4 independently represent alkylenes having 2 to 4 carbon atoms. Is the basis. ] An anode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode of the dielectric layer made of a conductive material provided on the opposite side of the anode, and the dielectric layer. And a solid electrolyte layer formed between the cathodes.
The solid electrolyte layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a compound represented by the following chemical formula (1), a compound represented by the following chemical formula (2), and the following chemical formula (3). A capacitor having one or more compounds selected from the group of the compound represented by, the compound represented by the following chemical formula (4), and a nitrogen-containing aromatic cyclic compound.

[In the formula (1), l, m, and n each independently represent an integer of 1 to 4, A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms, and R ¹ is hydrogen. It is a linear or branched alkyl group having 1 to 6 atoms or carbon atoms.
In formula (2), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (3), l, m, and n each independently represent an integer of 1 to 4, and A1, A2, and A3 are independently alkylene groups having 2 to 4 carbon atoms.
In formula (4), l, m, n, and k each independently represent an integer of 1 to 4, and A1, A2, A3, and A4 are independently alkylene groups having 2 to 4 carbon atoms. ] The capacitor according to claim 6 or 7 , wherein the nitrogen-containing aromatic cyclic compound is imidazole. The capacitor according to any one of claims 6 to 8 , wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The capacitor according to any one of claims 6 to 9 , wherein the polyanion is polystyrene sulfonic acid. The process of oxidizing the surface of the anode made of the porous body of the valve metal to form a dielectric layer,
The step of arranging the cathode at a position facing the dielectric layer and
A method for producing a capacitor, which comprises a step of applying the conductive polymer dispersion liquid according to any one of claims 1 to 5 to the surface of the dielectric layer and drying the mixture to form a solid electrolyte layer.

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