JP2019192752A - Conductive polymer composition, conductive polymer film, and electrolytic capacitor - Google Patents

Abstract

To provide a conductive composition which gives a conductive polymer film and an electrolytic capacitor excellent in heat resistance.SOLUTION: The conductive polymer composition is obtained by mixing: a conductive polymer (B) which contains, as a dopant, a polymer (A) comprising a monomer having an anionic group as an essential constituent monomer; and a quaternary ammonium carbonate (C). There are also provided: a conductive polymer film containing the conductive polymer composition; and an electrolytic capacitor having an anode, a solid electrolyte layer and a cathode, the solid electrolyte layer having the conductive polymer film.SELECTED DRAWING: None

Description

  The present invention relates to a conductive polymer composition, a conductive polymer film, and an electrolytic capacitor.

  In recent years, conductive polymer materials that develop high conductivity by adding a dopant to a conjugated polymer have been developed and are widely used in electrolytic capacitors, antistatic agents, transparent electrodes, and electromagnetic shielding materials. In particular, solid capacitors and hybrid capacitors using conductive polymers in electrolytic capacitors have low equivalent series resistance (ESR) and excellent frequency characteristics, and the small and large capacity recently required with downsizing of electronic products. A high frequency capacitor can be achieved.

  Solid electrolytic capacitors and hybrid capacitors are superior in terms of low ESR compared to general capacitors using an electrolytic solution, but have a problem that their lifespan in a high temperature environment is insufficient.

  In order to solve this problem, Patent Document 1 discloses a technique in which film-forming properties are improved and heat resistance is improved by using a polyvalent hydroxy compound and an amine having hydroxy together. Patent Document 2 discloses a technique for improving heat resistance by using an amine compound and a polyvalent carboxylic acid in combination. However, these techniques have insufficient heat resistance.

International Publication No. 2011/115011 JP 2017-216317 A

  An object of the present invention is to provide a conductive polymer composition that provides a conductive polymer film or an electrolytic capacitor excellent in heat resistance.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a conductive polymer (B) containing, as a dopant, a polymer (A) having an anionic group-containing monomer as an essential constituent monomer, a quaternary ammonium carbonate (C), Is a conductive polymer composition obtained by mixing.

  The conductive polymer composition of the present invention has the effect of enhancing the heat resistance of the conductive polymer film and the electrolytic capacitor.

The polymer (A) having an anionic group-containing monomer of the present invention as an essential constituent monomer uses an anionic group-containing monomer as an essential constituent monomer. The polymer (A) may be a homopolymer of a monomer having an anionic group or two or more types of copolymers having an anionic group. Moreover, the copolymer of the monomer which has an anion group, and the monomer which does not have an anion group may be sufficient. The polymer (A) functions to increase conductivity by doping the conductive polymer.
The anionic group is preferably a sulfonic acid group or a carboxylic acid group, more preferably a sulfonic acid group, from the viewpoint of conductivity.

Examples of the polymer (A) having a monomer having an anionic group as an essential constituent monomer include a polymer of a monomer having a sulfonic acid group and a polymer of a monomer having a carboxylic acid group. It is done.
Polymers of monomers having sulfonic acid groups include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid) , Polymers having a sulfonic acid group such as polyisoprene sulfonic acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), and polymethacryloxybenzene sulfonic acid.

  Polymers of monomers having a carboxylic acid group include polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid). And polymers having a carboxylic acid group such as polyisoprene carboxylic acid and polyacrylic acid.

Of these polymers (A), from the viewpoint of conductivity and heat resistance, a polymer of a monomer having a sulfonic acid group is preferred, and polystyrene sulfonic acid is more preferred.
The mass average molecular weight of the polymer (A) is preferably from 20,000 to 1,000,000, more preferably from 100,000 to 500,000.
The mass average molecular weight in this specification is a value obtained by measuring gel permeation chromatography under the following conditions.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSYRENE) manufactured by Tosoh (weight average molecular weight: 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

The conductive polymer (B) of the present invention is a conductive polymer containing, as a dopant, a polymer (A) having an anionic group-containing monomer as an essential constituent monomer.
The polymer constituting the conductive polymer is an organic polymer having a main chain composed of a π-conjugated system and exhibiting conductivity. There is no particular limitation as long as it exhibits conductivity and has the effect of the present invention. For example, polypyrrole conductive polymer, polythiophene conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline Examples thereof include conductive polymers, polyacene conductive polymers, polythiophene vinylene conductive polymers, and copolymers thereof.

  Examples of the polythiophene conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), 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-dibutylthiophene), Poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3 Ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), 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-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxy) Thiophene), 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-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene) and the like.

  Examples of the polypyrrole 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-hydroxypyrrole), Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyl) Kishipiroru), poly (3-methyl-4-hexyloxy-pyrrole) and the like.

  Examples of the polyaniline conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.

Of these, from the viewpoint of stability in air and heat resistance, polypyrrole conductive polymer, polythiophene and polyaniline conductive polymer are preferable, and polythiophene conductive polymer is more preferable. From the viewpoint, poly (3,4-ethylenedioxythiophene) is particularly preferable.
The said conductive polymer may be used individually by 1 type, and may use 2 or more types together.

  The content of the polymer (A) with respect to the weight of the conductive polymer (B) is preferably 110 to 500% by weight, more preferably 200 to 300% by weight, from the viewpoint of conductivity and dispersion stability. It is.

  Preferred examples of the conductive polymer (B) containing the polymer (A) as a dopant include thiophene-based conductive polymers (also referred to as PEDOT / PSS), and poly (3,4-ethylenedioxythiophene). And a mixture of polystyrene sulfonic acid and the like. The conductive polymer (B) can be obtained by a known method, as well as a reagent available from Merck and the like and a commercially available product available from Heures and the like.

The quaternary ammonium carbonate (C) used in the present invention is a salt of quaternary ammonium and a carbonate ion and / or an anion represented by the following general formula (1).
ROCOO ^- (1)
[R is an alkyl group having 1 to 4 carbon atoms]

Examples of R include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, from the viewpoint of heat resistance, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.
Examples of the anion represented by the general formula (1) include methoxy formate ion and ethoxy formate ion.
These anions which are anionic components may be used alone or in combination.

  Examples of the quaternary ammonium that is a cation component of the quaternary ammonium carbonate (C) include heterocyclic ammonium, aromatic quaternary ammonium, and alkyl ammonium.

  1,2,3-trimethyl-2-imidazolinium, 1,2,3,4-tetramethylimidazolinium, 1-ethyl-1-methylprolidinium, 5-azoniaspiro [4, as heterocyclic ammonium 4] Nonane, 1-butyl-1-methylpyrrolidinium, 1,1-dimethylpiperidinium, 4-ethyl-4-methylmorpholinium, N, N, N, N-tetramethylpiperazinium It is done.

  Aromatic ammonium includes N, N, N-trimethylphenylammonium, N-ethyl-N, N-dimethylphenylammonium, N, N, N-trimethylnaphthylammonium, N, N, N-trimethylbenzylammonium and the like.

  As alkylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, triethylmethylammonium, diethyldimethylammonium, tributylmethylammonium, ethyltriethylammonium, N, N, N, N, N, N-hexamethylethylenediammonium, N, N, N, N, N-pentamethylethyleneaminoammonium, N, N, N-trimethylmethanolammonium, N, N, N-trimethylhexylammonium and the like can be mentioned.

Among these quaternary ammoniums, heterocyclic ammonium and alkylammonium are preferable from the viewpoint of conductivity and heat resistance, and imidazolium, pyrrolidinium and alkylammonium are more preferable.
These quaternary ammoniums may be used alone or in combination.

  The quaternary ammonium carbonate (C) may be used alone or in combination of two or more.

  The amount of the quaternary ammonium carbonate (C) is preferably 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the weight of the polymer (A), from the viewpoints of conductivity and heat resistance. Is more preferable.

  The quaternary ammonium carbonate (C) can be synthesized by using a known method (method described in JP-A-63-284148). For example, an amine and dialkyl carbonate can be synthesized in a solvent (such as methanol).

  The reaction between the polymer (A) and the quaternary ammonium carbonate (C) is a salt exchange between the anionic group of the polymer (A) and the carbonate ion which is an anion of the quaternary ammonium carbonate (C). Presumed to be a reaction. The reaction product is presumed to be a salt in which part or all of the anionic group of the polymer (A) is neutralized with quaternary ammonium.

  The polymer (A) and the quaternary ammonium carbonate (C) can be mixed by stirring the polymer (A) and the quaternary ammonium carbonate (C) in a solution. The reaction solution may contain a polymer used for the conductive polymer (B). The reaction temperature is preferably 0 to 25 ° C. from the viewpoint of dispersion stability.

  The conductive polymer composition includes a conductive polymer (B) containing as a dopant a polymer (A) having a monomer having an anionic group as an essential constituent monomer, and a quaternary ammonium carbonate (C). In addition, a dispersion medium can be included. When the dispersion medium is included, the solid content concentration of the conductive polymer composition is preferably 0.1 to 10% by weight based on the total weight of the conductive polymer composition from the viewpoint of conductivity and dispersion stability. Preferably it is 0.5 to 5 weight%, Most preferably, it is 1 to 3 weight%.

Examples of the dispersion medium include water and organic solvents.
From the viewpoint of dispersion stability, it is preferable to contain water. The content of water contained in the dispersion medium is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 85% by mass or more.

As an organic solvent that can be used for the dispersion medium, an organic solvent such as an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, a sulfoxide solvent, or a sulfone solvent can be used in combination. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
Examples of the alcohol solvent include methanol, ethanol, 2-propanol, t-butanol, ethylene glycol, propylene glycol, diethylene glycol and the like.
Examples of the ether solvent include diethyl ether and dimethyl ether.
Examples of the ketone solvent include 2-butanone and acetone.
Examples of the ester solvent include ethyl acetate.
Examples of the sulfoxide solvent include dimethyl sulfoxide.
Examples of the sulfone solvent include sulfolane and ethyl methyl sulfone.
Among these organic solvents, from the viewpoint of conductivity, preferred are high-boiling solvents such as ethylene glycol, propylene glycol, diethylene glycol, dimethyl sulfoxide, sulfolane, ethyl methyl sulfone, and more preferred are ethylene glycol, diethylene glycol, and dimethyl sulfoxide. Particularly preferred is diethylene glycol.

The conductive polymer composition includes a conductive polymer (B) containing a polymer (A) having an anionic group-containing monomer as an essential constituent monomer as a dopant, and a quaternary ammonium carbonate (C ) And a dispersion medium.
Examples of the additive include polyether and surfactant. From the viewpoint of electrical conductivity, polyether is preferable, and from the viewpoint of film formability, a surfactant is preferable.

  As the polyether, polyethylene glycol [trade name “PEG-400”, manufactured by Sanyo Chemical Industries, Mn = 400], polyethylene glycol [trade name “PEG-600”, manufactured by Sanyo Chemical Industries, Ltd., Mn = 600] and the like.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Of these surfactants, nonionic surfactants are preferred from the viewpoint of storage stability.

The conductive polymer film of the present invention is a conductive polymer film containing a conductive polymer composition.
When the conductive polymer composition is a liquid containing a dispersion medium, the conductive polymer film can be obtained by distilling off the dispersion medium. As a method for applying the composition, for example, dipping (that is, dip coating), application coating using a bar coater or an applicator, comma coating, reverse coating, lip coating, microgravure coating, and the like can be applied.
Examples of the drying method include known methods such as room temperature drying, hot air drying, and far-infrared drying.
On the other hand, when the conductive polymer composition does not contain a dispersion medium, the conductive polymer film can be obtained by molding the composition in the same manner as in the above coating method or in the form of a film.

  The electrolytic capacitor of the present invention is an electrolytic capacitor having an anode, a solid electrolyte layer, and a cathode, wherein the solid electrolyte layer has a conductive polymer film. Examples of the electrolytic capacitor include a capacitor configured by disposing a cathode foil through a separator (manila hemp, kraft paper, etc.) facing an anode foil including a dielectric layer and a solid electrolyte layer.

As the anode foil, a conductive material can be used.
Examples of the conductive material include aluminum, titanium, tantalum, niobium, and alloys thereof.
The anode foil preferably has a larger surface area by a method such as making it porous by etching.

Since the dielectric layer is formed by anodizing the surface of the anode foil by chemical conversion or the like, an oxide of a conductive material used for the anode foil can be used.
For example, when aluminum is used as the anode foil, the dielectric layer formed on the surface of the anode foil is aluminum oxide generated by chemical conversion.

  The solid electrolyte layer in contact with the surface of the dielectric layer is a layer having the conductive polymer film described above. The solid electrolyte layer is a layer containing boric acid, boric acid ester and polyether as necessary.

  Examples of boric acid esters include alkyl borate (such as triethyl borate) and aryl borate (such as triphenyl borate).

  As the polyether, polyethylene glycol [trade name “PEG-400”, manufactured by Sanyo Chemical Industries, Mn = 400], polyethylene glycol [trade name “PEG-600”, manufactured by Sanyo Chemical Industries, Ltd., Mn = 600] and the like.

The solid electrolyte layer can be formed by the method described below.
The anode foil having a dielectric layer and an electrolytic capacitor element having a cathode opposed to the anode through a separator are impregnated with a dispersion of the conductive polymer composition, and then dried. A conductive polymer film in contact with the body layer can be formed as a solid electrolyte layer.

In the solid electrolyte layer forming method, the above operation may be performed a plurality of times to form a plurality of conductive polymer films.
Moreover, the conductive polymer film of the present invention may be formed in a plurality of layers, or may be used in combination with another conductive polymer film.

  In the present invention, it may be used as a solid electrolytic capacitor having only the conductive polymer film, or may be used as a hybrid electrolytic capacitor in combination with an electrolytic solution.

The electrolyte contained in the electrolytic solution for a hybrid electrolytic capacitor is composed of a cation component and an anion component. As the cation component, ammonia, triethylamine, dimethylethylamine, diethylmethylamine, dimethylamine, diethylamine, 1-methylimidazole, 1, 2,3,4-Tetramethylimidazolinium, 1-ethyl-3-methylimidazolinium and the like can be mentioned. Among them, ammonia, dimethylethylamine, diethylamine, triethylamine and more preferably dimethylethylamine are preferable from the viewpoint of ESR. .
On the other hand, examples of the anionic component include adipic acid, azelaic acid, 1,6-decanedicarboxylic acid, phthalic acid, maleic acid, benzoic acid, phosphoric acid and derivatives thereof, and boric acid and derivatives thereof. Preferred is phthalic acid.
An electrolyte may be used individually by 1 type, or may use 2 or more types together.

As a dispersion medium contained in the electrolytic solution for a hybrid electrolytic capacitor, alcohol (methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol, ethylene glycol monobutyl ether, propylene glycol and polyethylene glycol (Mn: 600 or less)), Amides (such as N-methylformamide and N, N-dimethylformamide), lactones (such as α-acetyl-γ-butyrolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone and δ-valerolactone), nitriles (acetonitrile, Propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, benzonitrile, etc.) sulfoxide (dimethyl sulfoxide, methyl ethyl sulfoxide and diethyl sulfo) Sid) and sulfone (sulfolane and ethyl methyl sulfone) and the like.
Of these dispersion media, alcohols and lactones are preferable from the viewpoint of solubility and heat resistance of the electrolyte, and ethylene glycol, propylene glycol, and γ-butyrolactone are more preferable.
A dispersion medium may be used individually by 1 type, or may use 2 or more types together.

  The conductive polymer composition of the present invention and the conductive polymer film containing the conductive polymer composition can be suitably used as a conductive polymer material that exhibits high conductivity. As an application, it can be widely used for an electrolytic capacitor, an antistatic agent, a transparent electrode, and an electromagnetic wave shielding material, and can be particularly suitably used as an electrolytic capacitor.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Synthesis of quaternary ammonium carbonate (C)>
<Production Example 1: Synthesis of tetramethylammonium methyl carbonate (C-1)>
In a stirring autoclave, 17.8 parts by weight of dimethyl carbonate [Tokyo Chemical Industry Co., Ltd.], 20.0 parts by weight of triethylamine [Tokyo Chemical Industry Co., Ltd.] and 20.0 parts by weight of methanol [Tokyo Chemical Industry Co., Ltd.] as a solvent The reaction was carried out at a reaction temperature of 115 ° C. and a reaction pressure of 6.0 atm for 12 hours. After the reaction, the autoclave was cooled, and unreacted substances and the solvent were distilled off to obtain tetramethylammonium methyl carbonate (C-1).

<Production Example 2: Synthesis of 1,2,3-trimethyl-2-imidazolinium methyl carbonate (C-2)>
In Production Example 1, 16.5 parts by weight of 2-methyl-2-imidazoline [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of triethylamine, and the reaction pressure was changed to 4.0 atm. 1,2,3-trimethyl-2-imidazolinium methyl carbonate (C-2) was synthesized.

<Production Example 3: Synthesis of 1-ethyl-1-methylpyrrolidinium ethyl carbonate (C-3)>
In Production Example 2, diethyl carbonate [manufactured by Tokyo Chemical Industry Co., Ltd.] 23.3 parts instead of dimethyl carbonate, 1-methylpyrrolidine [manufactured by Tokyo Chemical Industry Co., Ltd.] 16 instead of 2-methyl-2-imidazoline 1-Ethyl-1-methylpyrrolidinium ethyl carbonate (C-3) was synthesized in the same manner as in Production Example 2, except that .6 parts by weight was used.

<Production Example 4: Synthesis of trimethylhexylammonium methyl carbonate (C-4)>
In Production Example 2, the same procedure as in Production Example 2 was conducted except that 25.1 parts by weight of N, N-dimethylhexylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 2-methyl-2-imidazoline. Trimethylhexyl ammonium methyl carbonate (C-4) was synthesized.

<Production Example 5: Synthesis of 2-hydroxyethyltrimethylammonium methyl carbonate (C-5)>
2-hydroxyethyltrimethylammonium was prepared in the same manner as in Production Example 1 except that 16.8 parts by weight of N, N-dimethylethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of triethylamine in Production Example 1. Methyl carbonate (C-5) was synthesized.

<Examples 1-8, Comparative Examples 1-2>
<Preparation of conductive polymer composition>
In the examples of the present application, the conductive polymer (B) containing the polymer (A) as a dopant, and the conductive material being poly (3,4-ethylenedioxythiophene) containing polystyrenesulfonic acid (A-1) as a dopant. Water dispersion of a functional polymer (B-1) [trade name: pH-500, manufactured by Heraeus Co., Ltd., solid content concentration: 1.2% by weight, poly (3,4-ethylenedioxythiophene): polystyrenesulfonic acid ( Weight ratio) = 1: 2.5].
An aqueous dispersion containing the conductive polymer (B-1) in the number of parts shown in Table 1, quaternary ammonium carbonates (C-1) to (C-5), 1-butyl-1-methylpyrrolidinium Chloride (C′-1) [manufactured by Tokyo Chemical Industry Co., Ltd.], ammonium carbonate ((C′-2) [manufactured by Tokyo Chemical Industry Co., Ltd.]) and a dispersion medium are mixed and mixed at 20 ° C. for 10 minutes. The conductive polymer compositions (D-1) to (D-8) of Examples 1 to 8 and the comparative conductive polymer compositions (RD-1) to (RD-2) of Comparative Examples 1 and 2 Was prepared.

<Creation of conductive polymer film>
The conductive polymer compositions (D-1) to (D-8) and the comparative conductive polymer compositions (RD-1) to (RD-2) were respectively coated on glass using a bar coater, A conductive coating film is formed by drying for 10 minutes in a 170 ° C. normal air dryer to form conductive polymer films (E-1) to (E-8) and (RE-1) to (RE-1) RE-2) was obtained.

<Surface resistance of conductive polymer film>
The electrical conductivity surface resistance values (Ω / □) of the conductive polymer films (E-1) to (E-8) and the comparative conductive polymer films (RE-1) to (RE-2) According to K 7194: 1994, the measurement was performed by a four-probe method using Loresta-GX MCP-T700 (manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1. In addition, it shows that electroconductivity is so high that a surface resistance value is low.

<Surface resistance change rate of conductive polymer film>
After the conductive polymer membranes (E-1) to (E-8) and the comparative conductive polymer membranes (RE-1) to (RE-2) are stored for 1000 hours in a 125 ° C. normal air dryer, the surface resistance (R ₁₀₀₀ ) was measured, and the maintenance ratio when compared with the initial surface resistance (R ₀ ) was calculated by the following calculation formula.
Surface resistance change rate (%) = (R ₁₀₀₀ −d ₀ ) / R ₀ × 100 (1)
The results are shown in Table 1. The smaller the change rate, the higher the heat resistance.

The conductive polymer film of the example of the present invention exhibits a low surface resistance, and the increase in the surface resistance is small even under a high temperature environment.
In Comparative Example 1, since the conductive polymer composition contains chlorine ions, the surface resistance is greatly increased under a high environment. In Comparative Example 2, since the cation portion of ammonium carbonate is not quaternary ammonium, the dedoping of the conductive polymer is promoted, and the initial surface resistance is large.

<Examples 9 to 16 and Comparative Examples 3 to 4>
<Creation of solid electrolytic capacitor>
Using the conductive polymer composition, a wound solid electrolytic capacitor having a rated voltage of 50 V and a capacitance of 30 μF was prepared by the following procedure.
(1) An anode foil having a dielectric layer of an aluminum oxide film on the surface (chemically formed aluminum foil: JHC, 115HC9-323Vf), a cathode foil (unformed aluminum foil: JCC, 80LJ11B), a separator ( (Manila paper) was cut into a certain width and length, and the lead wires were connected to the anode and cathode by caulking.
Thereafter, the product was wound into a roll shape to form a cylindrical shape, and the outer peripheral side surface thereof was fixed with an insulating tape to complete a capacitor element (no solid electrolyte layer). Next, in order to repair the cut surface and the defect, the element was subjected to repair conversion at a voltage of 90 V in an aqueous ammonium borate solution. Thereafter, the sealing rubber and the lead wire were passed through.
(2) Next, the conductive polymer compositions (D-1) to (D-8) and the comparative conductive polymer compositions of Comparative Examples 1 and 2 are used for the capacitor element (without the solid electrolyte layer). After impregnating the products (RD-1) to (RD-2), the capacitor element was dried in a constant temperature bath at 120 ° C. for 1 hour.
Finally, the capacitor element was stored in a case and crimped to complete solid electrolytic capacitors (F-1 to F-8) and comparative solid electrolytic capacitors (RF-1) to (RF-2).

<Characteristic evaluation of solid electrolytic capacitor>
As an initial evaluation, electrostatic capacity and ESR were measured using a 3532-50 LCR HiTester (manufactured by Hioki Electric Co., Ltd.) according to JIS C 5101-1: 2010.
The capacitance was measured at 25 ° C. and 120 Hz, and the ESR value was measured at 25 ° C. and 100 kHz.
Moreover, the current value after applying a rated voltage (50V) for 1 minute at 25 degreeC was measured, and this was made into the leakage current.
The results are shown in Table 2.

<Characteristic maintenance rate of solid electrolytic capacitor>
After storing the solid electrolytic capacitors (F-1) to (F-8) and the discharge electrolytic capacitors (RF-1) to (RF-2) for 1000 hours in a 125 ° C. normal air dryer, the capacitance (C ₁₀₀₀ ), ESR (ESR ₁₀₀₀ ) was measured, and the maintenance ratio when compared with the initial surface resistance (C ₀ ) and ESR (ESR ₀ ) was calculated by the following calculation formula.
Capacitance change rate (%) = (C ₁₀₀₀ −d ₀ ) / C ₀ × 100 (2)
ESR change rate (%) = (ESR ₁₀₀₀ −d ₀ ) / ESR ₀ × 100 (1)
The results are shown in Table 2. The smaller the change rate, the higher the heat resistance.

  The conductive polymer composition of the present invention and the conductive polymer film containing the conductive polymer composition can be suitably used as a conductive polymer material that exhibits high conductivity. As an application, it can be widely used for an electrolytic capacitor, an antistatic agent, a transparent electrode, and an electromagnetic wave shielding material, and can be particularly suitably used as an electrolytic capacitor.

Claims (5)

  Obtained by mixing a polymer (A) containing a monomer having an anionic group as an essential constituent monomer (A) as a dopant and a quaternary ammonium carbonate (C). Conductive polymer composition.   The conductive polymer composition according to claim 1, wherein the quaternary ammonium carbonate (C) is at least one quaternary ammonium carbonate selected from the group consisting of imidazolium, pyrrolidinium and alkylammonium. The conductive polymer according to claim 1 or 2, wherein the carbonate (C) of the quaternary ammonium is a salt of a quaternary ammonium ion and a carbonate ion and / or an anion represented by the following general formula (1). Composition.
ROCOO ^- (1)
[R is an alkyl group having 1 to 4 carbon atoms]   A conductive polymer film comprising the conductive polymer composition according to claim 1.   An electrolytic capacitor having an anode, a solid electrolyte layer, and a cathode, wherein the solid electrolyte layer has a conductive polymer film according to claim 4.