Conductive polymer compound, conductive polymer composition, and electronic component

Abstract

This conductive polymer compound contains, as a repeating unit, a pyrrole having a substituent at the 3-position, wherein the substituent is one kind selected from among a halogenated alkyl group, a formyl group, and a formamide group, and the halogenated alkyl group is CnH2n+1-mXm. Here, n is an integer of 1 or more, m is an integer satisfying 1≤m≤2n+1, and X is a fluorine element, a chlorine atom, a bromine element, or an iodine element.

Description

Conductive polymer compound, conductive polymer composition, and electronic component

[0001] The present disclosure relates to a conductive polymer compound, a conductive polymer composition, and an electronic component.

[0002] It has been known for some time that the conductivity of an electrolyte in an electrolytic capacitor can be improved by using a conductive polymer layer (solid electrolyte layer) formed from a conductive polymer instead of a liquid component (such as an electrolytic solution) (see, for example, Patent Document 1 below). In an electrolytic capacitor, improving the conductivity of the electrolyte as described above can reduce the equivalent series resistance (ESR). An electrolytic capacitor having such a solid electrolyte layer typically has a capacitor element including an anode body, a dielectric layer covering the anode body, a solid electrolyte layer covering the dielectric layer, and a cathode extraction layer formed on the solid electrolyte layer.

[0003] The following Patent Document 1 describes an electrolytic capacitor having a solid electrolyte layer formed of two layers: a first solid electrolyte layer covering a dielectric layer and a second solid electrolyte layer covering the first solid electrolyte layer. More specifically, the following Patent Document 1 describes a first solid electrolyte layer containing a first conductive polymer compound having a polythiophene skeleton and exhibiting a conductivity of 2 S / cm or less. Furthermore, the following Patent Document 1 describes a second solid electrolyte layer containing a second conductive polymer compound having a polypyrrole skeleton. The following Patent Document 1 also describes that by forming the first and second solid electrolyte layers as described above, the conductivity of the solid electrolyte layer is improved and the equivalent series resistance (ESR) of the electrolytic capacitor is reduced. In other words, the following Patent Document 1 describes a solid electrolyte layer containing two types of conductive polymer compounds with different properties, thereby improving the conductivity of the solid electrolyte layer and reducing the equivalent series resistance (ESR) of the electrolytic capacitor.

[0004] Patent Document 2 below describes obtaining a monomer of a specific structure by bonding 2 to 10 3-alkyl heterocyclic five-membered compounds having a specific structure at the 2- and 5-positions of the heterocyclic five-membered ring while restricting the alkyl groups head-to-tail. It also describes obtaining a conductive polymer by polymerizing the monomer of the specific structure. Patent Document 2 below also describes that by including such a conductive polymer in the solid electrolyte layer of an electrolytic capacitor, the conductivity of the solid electrolyte layer is improved and the equivalent series resistance (ESR) of the electrolytic capacitor is reduced.

[0005] International Publication No. 2022 / 017574 Japanese Patent Application Laid-Open No. 2009-209259

[0006] One aspect of the present invention relates to a conductive polymer compound. The conductive polymer compound contains, as a repeating unit, a pyrrole having a substituent at the 3-position, the substituent being one selected from a halogenated alkyl group, a formyl group, and a formamide group, and the halogenated alkyl group is C ｎ H ２ｎ＋１－ｍ X ｍ where n is an integer of 1 or more, m is an integer satisfying 1≦m≦2n+1, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0007] Another aspect of the present invention relates to a conductive polymer composition, which contains the conductive polymer compound described above.

[0008] Yet another aspect of the present invention relates to an electronic component, the electronic component including a solid electrolyte layer formed from the conductive polymer composition.

[0009] According to the present disclosure, it is possible to provide a conductive polymer compound capable of sufficiently improving the conductivity of a solid electrolyte layer, a conductive polymer composition containing the conductive polymer compound, and an electronic component including a solid electrolyte layer formed from the conductive polymer composition.

[0010] 4 is a diagram showing a synthetic route for pyrrole having a formamide group at the 3-position; FIG. 5 is a diagram showing a synthetic route for pyrrole having a formyl group at the 3-position; FIG. 6 is a diagram showing a first synthetic route for pyrrole having a halogenated methyl group at the 3-position; FIG. 7 is a diagram showing a second synthetic route for pyrrole having a halogenated methyl group at the 3-position; FIG. 8 is a schematic cross-sectional view of an electrolytic capacitor according to an embodiment of the present disclosure; FIG. 9 is an enlarged cross-sectional view schematically showing region V in FIG. 4;

[0011] The problems in the prior art will be briefly described below.

[0012] In the electrolytic capacitors described in Patent Documents 1 and 2, various studies have been conducted on the conductive polymer compounds to be contained in the solid electrolyte layer in order to improve the conductivity of the solid electrolyte layer, but it cannot be said that the studies have been conducted sufficiently.

[0013] Furthermore, although improving the conductivity of the solid electrolyte layer is also desired in other electronic components (e.g., solid-state batteries) that include a solid electrolyte layer, it cannot be said that sufficient research has been conducted on this issue.

[0014] The present disclosure provides a conductive polymer compound capable of sufficiently improving the conductivity of a solid electrolyte layer, a conductive polymer composition containing the conductive polymer compound, and an electronic component including a solid electrolyte layer formed from the conductive polymer composition.

[0015] The present inventors have discovered that in a polymer compound obtained by bonding multiple substituted pyrroles (hereinafter also referred to as substituted pyrroles), the energy level of the molecular orbital of the main chain (the chain portion obtained by bonding multiple substituted pyrroles) of the polymer compound changes depending on the type of substituent. Furthermore, as the energy level of the molecular orbital of the polymer compound increases, electronic transitions in the polymer compound become more likely, resulting in improved conductivity in a solid electrolyte layer (conductive polymer layer) formed using such a polymer compound. On the other hand, as the energy level of the molecular orbital decreases, electronic transitions in the polymer compound become less likely, resulting in reduced conductivity in a solid electrolyte layer (conductive polymer layer) formed using such a polymer compound. Therefore, the present inventors focused on substituents that can increase the energy level of the molecular orbital in a polymer compound obtained by bonding multiple substituted pyrroles. The present inventors conducted extensive research into such substituents, leading to the completion of the present invention.

[0016] Below, embodiments of the present disclosure will be described using examples, but the present disclosure is not limited to the examples described below. In the following description, specific numerical values ​​and materials may be exemplified, but other numerical values, materials, etc. may be applied as long as the effects of the present disclosure are obtained. Note that known components may be applied to components characteristic of the present disclosure. In this specification, when a "range from numerical value A to numerical value B" is mentioned, the range includes numerical value A and numerical value B.

[0017] In the following description, when lower and upper limits of numerical values ​​relating to specific physical properties, conditions, etc. are exemplified, any of the exemplified lower limits and any of the exemplified upper limits can be arbitrarily combined, as long as the lower limit is not equal to or greater than the upper limit. When multiple materials are exemplified, one of them can be selected and used alone, or two or more can be used in combination, unless otherwise specified.

[0018] The present disclosure also encompasses combinations of two or more features arbitrarily selected from the appended claims, i.e., two or more features arbitrarily selected from the appended claims can be combined unless a technical contradiction arises.

[0019] [Conductive Polymer Compound] The conductive polymer compound according to an embodiment of the present disclosure contains a pyrrole having a substituent at the 3-position as a repeating unit. The pyrrole having a substituent at the 3-position has a structure represented by the following formula (1). In the following formula (1), R is a substituent. The substituent R is a halogenated alkyl group, a formyl group (CHO), or a formamide group (NHCHO).

[0020]

[0021] The conductive polymer compound according to an embodiment of the present disclosure may have a structure in which a plurality of pyrroles having a substituent at the 3-position are bonded so that the substituents R are aligned in the same direction (see formula (2a) below), or may have a structure in which a plurality of pyrroles having a substituent at the 3-position are bonded so that the substituents R are not aligned in the same direction (see formula (2b) below). When the conductive polymer compound according to an embodiment of the present disclosure has a structure represented by formula (2b) below, the ratio (molar ratio) of the first constitutional unit represented by formula (1) above to the second constitutional unit in which the substituent R exists in a position that is linearly symmetrical to the first constitutional unit with respect to the line segment connecting N (nitrogen atom) and H (hydrogen atom) directly bonded to the N may be first constitutional unit:second constitutional unit = 1:1 to 1:10. Note that the conductive polymer compound according to an embodiment of the present disclosure usually has a structure represented by formula (2b) below.

[0022]

[0023] The halogenated alkyl group is C ｎ H ２ｎ＋１－ｍ X ｍ(where n is an integer of 1 or more, m is an integer satisfying 1≦m≦2n+1, and X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). The upper limit of n is 9. The halogenated alkyl group is CH ２ X, CHX ２ , or CX ３ That is, in the conductive polymer compound according to the embodiment of the present disclosure, the substituent R is preferably CH ２ X, CHX ２ , CX ３ , CHO, and NHCHO.

[0024] The substituent R is CH ２ X, CHX ２ , CX ３ , and CHO, these substituents R are bonded to the 3-position of the pyrrole via a carbon atom. In these substituents R, the positive charge of the carbon atom at the 3-position of the pyrrole is reduced by the influence of X (a halogen element) or O (an oxygen atom). Similarly, when the substituent R is NHCHO, the positive charge of the carbon atom at the 3-position of the pyrrole is reduced by the influence of a nitrogen atom. Thus, since the substituent R is bonded to the 3-position of the pyrrole, it is believed that electron transition is more likely to occur in the main chain of a conductive polymer compound containing such pyrrole as a repeating unit due to the reduced positive charge of the main chain. In other words, it is believed that the energy level is more likely to rise in the main chain of a conductive polymer compound containing the above-described pyrrole as a repeating unit. For the reasons described above, it is believed that the conductive polymer compound according to the embodiment of the present disclosure has high conductivity.

[0025] A pyrrole having a formamide group (NHCHO) at the 3-position can be obtained by carrying out a formylation reaction on the amino group using a pyrrole having an amino group at the 3-position and formic acid (HCOOH), as shown in Figure 1. To promote the formylation reaction on the amino group, a formylating reagent (e.g., N-formylsaccharin) may be used.

[0026] Pyrroles having a formyl group (CHO) at the 3-position can be synthesized by the reaction of dichloromethane (CH ２ Cl ２ ) in which a hydroxymethyl group (CH ２ The hydroxymethyl group in pyrrole having a hydroxymethyl group (OH) can be oxidized to an aldehyde with pyridinium chlorochromate (PCC).

[0027] Next, the synthesis of pyrrole having a halogenated methyl group at the 3-position will be described with reference to FIGS. 3A and 3B.

[0028] CH in third place ２ The pyrrole having X1 has a methyl group (CH ３ ) and pyrrole having X1 ２ It can be obtained by irradiating light in the presence of X1 molecules (in the gas phase). ２ The molecule is photocleaved to obtain an X1 radical, which converts the methyl group (CH ３ ) by abstracting one hydrogen atom (H) (Reaction 1A in FIG. 3A). The light irradiation can be carried out, for example, by irradiating ultraviolet light using a UV lamp as a light source. The wavelength of the irradiated ultraviolet light can be, for example, 200 nm or more and 430 nm or less, and the integrated light amount can be, for example, 100 mJ or more and 1000 mJ or less. In FIG. 3A, hν means light irradiation. Here, X1 is a fluorine (F) element, a chlorine (Cl) element, or a boron (Br) element.

[0029] CHX1 in third place ２ Pyrrole having CH at the 3-position ２ Pyrrole having X1 and X1 ２ Specifically, the X1 radical obtained by light irradiation can be converted into CH ２ It can be obtained by abstracting one hydrogen atom (H) from X1 (Reaction 2A in FIG. 3A). The light irradiation can be carried out under the above-mentioned conditions. ２ X １The pyrrole having the formula (I) can be obtained by reaction 1A in FIG. 3A.

[0030] CX1 in third place ３ Pyrrole having CHX1 at the 3-position ２ Pyrrole having X1 ２ Specifically, the X1 radical obtained by light irradiation can be converted into CHX1 ２ It can be obtained by abstracting one hydrogen atom (H) from (Reaction 3A in FIG. 3A). The light irradiation can be carried out under the conditions described above. ２ The pyrrole having the formula: can be obtained by reaction 2A in FIG. 3A.

[0031] The reactions 1A to 3A in FIG. 3A proceed continuously due to the presence of radical species such as the X1 radical. ２ Pyrrole having X1, CHX1 at the 3-position ２ and a pyrrole having CX1 at the 3-position. ３ The pyrroles having the formula (I) can be obtained in high purity by classification by silica gel chromatography after the radical termination reaction. The classification by silica gel chromatography can be carried out using a solvent containing at least one of hexane and ethyl acetate as the mobile phase. In this specification, classification refers to a series of operations for extracting a specific substance.

[0032] On the other hand, when the halogen element X of the halogenated methyl group is iodine (I), the compound can be synthesized by a route different from the above.

[0033] CH in third place ２ Pyrrole having I has CH at the 3-position ２ It can be obtained by reacting pyrrole having Cl with sodium iodide (NaI) in acetone (liquid phase). ２ It can be obtained by substituting the chlorine atom of Cl with the iodine atom (I) of sodium iodide (NaI) (Reaction 1B in FIG. 3B). After Reaction 1B, there is no CH at the 3-position.２ Therefore, after the first reaction, the product is separated by silica gel chromatography to remove the unreacted pyrrole having a Cl group at the 3-position. ２ Pyrroles having I can be obtained with high purity. As explained above, the classification by silica gel chromatography can be carried out using a solvent containing at least one of hexane and ethyl acetate as the mobile phase. ２ The pyrrole having Cl can be obtained by reaction 1A in FIG. 3A.

[0034] CHI in third place ２ Pyrrole having CHCl at the 3-position ２ It can be obtained by reacting pyrrole having the formula (I) with sodium iodide (NaI) in acetone (liquid phase). ２ It can be obtained by substituting two chlorine atoms of with iodine atoms (I) of sodium iodide (NaI) (Reaction 2B in Figure 3B). ２ The pyrrole having the formula (I) can be obtained in high purity by classification by silica gel chromatography, as in the case of the reaction of step 1B. As explained above, the classification by silica gel chromatography can be carried out using a solvent containing at least one of hexane and ethyl acetate as the mobile phase. ２ The pyrrole having the formula: can be obtained by reaction 2A in FIG. 3A.

[0035] CI in third place ３ Pyrroles having CCl at the 3-position ３ It can be obtained by reacting pyrrole having the formula: with sodium iodide (NaI) in acetone (liquid phase). ３ It can be obtained by replacing three chlorine atoms with iodine atoms (I) of sodium iodide (NaI) (Reaction 3B in Figure 3B). ３The pyrrole having the formula (I) can be obtained in high purity by classification by silica gel chromatography, as in the case of the reaction of step 1B. As explained above, the classification by silica gel chromatography can be carried out using a solvent containing at least one of hexane and ethyl acetate as the mobile phase. ３ The pyrrole having the formula: can be obtained by reaction 3A in FIG. 3A.

[0036] The conductive polymer compound according to the embodiment of the present disclosure preferably contains, as a repeating unit, a pyrrole having a formamide group (NHCHO) as a substituent at the 3-position. By having such a substituent, the conductive polymer compound according to the embodiment of the present disclosure exhibits particularly high conductivity. Furthermore, a solid electrolyte layer containing such a conductive polymer compound also exhibits particularly high conductivity. As a result, an electrolytic capacitor including such a solid electrolyte layer exhibits particularly low equivalent series resistance (ESR).

[0037] The degree of polymerization of the conductive polymer compound according to an embodiment of the present disclosure may be 6 or more and 1100 or less. The degree of polymerization may be 10 or more, 50 or more, or 100 or more. The degree of polymerization may be 800 or less, 500 or less, or 300 or less. The degree of polymerization can be determined by dividing the weight-average molecular weight Mw of the conductive polymer compound by the formula weight of the monomer that is a constituent unit of the basic structure of the conductive polymer compound. The weight-average molecular weight Mw of the conductive polymer compound can be measured by the method described below.

[0038] The weight average molecular weight Mw of the conductive polymer compound according to this embodiment is 5.6 × 10 ２ The above is 4.6 x 10 ５ The weight average molecular weight Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC). The GPC measurement is carried out using a column consisting of two connected Shodex OHpak SB804HQ and SB8025HQ columns, and is preferably carried out using LiBr or NaOH. ３This can be carried out using a 50 mM dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) solution as the eluent. Furthermore, a differential refractive index detector (RI detector) can be used, and the column temperature can be set to 40°C to 120°C, the eluent flow rate to 0.2 mL / min, and the analysis time to 40 min. Furthermore, the measurement sample can be prepared by dissolving a conductive polymer compound in the eluent to a concentration of 1.0 g / L.

[0039] Each of the conductive polymer compounds having each substituent preferably has a weight average molecular weight Mw within the range shown in Table 1 below.

[0040]

[0041] The conductive polymer compound according to an embodiment of the present disclosure can be obtained by chemical oxidative polymerization or electrolytic polymerization of a pyrrole having a substituent at the 3-position. Hereinafter, a pyrrole having a substituent at the 3-position will be referred to as a 3-substituted pyrrole.

[0042] A method for chemically oxidatively polymerizing a 3-substituted pyrrole (hereinafter also referred to as a chemical oxidative polymerization method) will be described below. First, as the reaction solvent, a solvent capable of dissolving the 3-substituted pyrrole and the oxidizing agent used may be used alone, or a solvent capable of dissolving the 3-substituted pyrrole and a solvent capable of dissolving the oxidizing agent used may be used in combination. That is, the chemical oxidative polymerization may be carried out in a heterogeneous system. Examples of such solvents include water, sulfuric acid, methanol, ethanol, propanol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, chloroform, dichloromethane, carbon tetrachloride, benzene, toluene, xylene, tetrahydrofuran, N-methyl-2-pyrrolidone, and propylene carbonate.

[0043] Examples of the oxidizing agent include ferric oxide, iron(III) tri(p-toluenesulfonate), sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, and potassium permanganate.

[0044] In the chemical oxidative polymerization method, a dopant compound may be used. Examples of the dopant compound include sulfuric acid, alkyl sulfuric acid (e.g., heptyl sulfuric acid, octyl sulfuric acid), alkyl benzene sulfonic acid (e.g., benzene sulfonic acid, toluene sulfonic acid, ethyl benzene sulfonic acid), naphthalene sulfonic acid, alkyl naphthalene sulfonic acid (e.g., methyl naphthalene sulfonic acid), naphthalene disulfonic acid, and alkyl naphthalene disulfonic acid (e.g., methyl naphthalene disulfonic acid). The dopant compound may also be a salt of the various acids described above. Examples of the salts of the various acids include sodium salts and ammonium salts. In an embodiment of the present disclosure, naphthalene sulfonic acid or a salt thereof is preferably used as the dopant compound in the chemical oxidative polymerization method. The salt of naphthalene sulfonic acid is preferably a sodium salt (sodium naphthalene sulfonate).

[0045] The 3-substituted pyrrole is chemically oxidatively polymerized using the solvent, the oxidizing agent, and, if necessary, the dopant compound. An example of chemically oxidatively polymerizing the 3-substituted pyrrole using a dopant compound in a heterogeneous system (hereinafter simply referred to as a heterogeneous system) will be described below. In the heterogeneous system, a first solution obtained by dissolving the 3-substituted pyrrole in a solvent and a second solution obtained by dissolving the oxidizing agent and the dopant compound in a solvent are used. In the heterogeneous system, the second solution is added dropwise to the first solution to chemically oxidatively polymerize the 3-substituted pyrrole. The concentration of the 3-substituted pyrrole in the first solution is preferably 1 mmol / L or more and 1000 mmol / L or less, and more preferably 10 mmol / L or more and 200 mmol / L or less. In the second solution, the concentration of the oxidizing agent is preferably 1 mmol / L or more and 1,000 mmol / L or less, and preferably 10 mmol / L or more and 200 mmol / L or less, and the concentration of the dopant compound is preferably 5 mmol / L or more and 5,000 mmol / L or less, and more preferably 50 mmol / L or more and 1,000 mmol / L or less. By ensuring that the concentrations of the 3-substituted pyrrole, the oxidizing agent, and the dopant compound are each within the above ranges, side reactions are suppressed, thereby preventing a decrease in the conductivity of the resulting conductive polymer compound. Furthermore, the chemical oxidative polymerization of the 3-substituted pyrrole can be sufficiently promoted. The reaction temperature is preferably −40°C or more and 110°C or less, more preferably −20°C or more and 40°C or less, and even more preferably −20°C or more and 10°C or less. By ensuring that the reaction temperature is within the above range, side reactions are suppressed, thereby preventing a decrease in the conductivity of the resulting conductive polymer compound. The reaction temperature is preferably selected from a range from a temperature at which the solvent used does not freeze to the boiling point of the solvent. In order to allow the reaction to proceed slowly, it is preferable to carry out the reaction at as low a temperature as possible so that the solvent does not freeze and the viscosity does not increase. The reaction time is preferably from 0.1 to 72 hours, more preferably from 0.1 to 10 hours.

[0046] A method for electropolymerizing 3-substituted pyrrole (hereinafter also referred to as electropolymerization method) will be described below. In the electropolymerization method, 3-substituted pyrrole is polymerized in a polymerization solvent. In the electropolymerization method, it is preferable to use a dopant compound. As the polymerization solvent, it is preferable to use a solvent capable of dissolving 3-substituted pyrrole and the dopant compound. Examples of such solvents include water, sulfuric acid, methanol, ethanol, propanol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, and propylene carbonate.

[0047] The dopant compound is dissolved in a polymerization solvent before use. Examples of the dopant compound include sulfuric acid, alkyl sulfuric acid (heptyl sulfuric acid, octyl sulfuric acid, etc.), benzenesulfonic acid, alkyl benzenesulfonic acid (toluenesulfonic acid, ethylbenzenesulfonic acid, etc.), naphthalenesulfonic acid, alkyl naphthalenesulfonic acid (methyl naphthalenesulfonic acid, etc.), naphthalenesulfonic acid, and alkyl naphthalenedisulfonic acid (methyl naphthalenesulfonic acid, etc.). In an embodiment of the present disclosure, it is preferable to use naphthalenesulfonic acid or a salt thereof as the dopant compound in the electrolytic polymerization. Furthermore, it is preferable that the salt of naphthalenesulfonic acid be a sodium salt (sodium naphthalenesulfonate).

[0048] Examples of electrolytic polymerization methods include a method in which a 3-substituted pyrrole and a dopant compound are dissolved in a polymerization solvent (hereinafter referred to as a pyrrole-containing polymerization solvent) by applying a potential sweep method or a constant voltage method using a potentiostat to polymerize the 3-substituted pyrrole, and a method in which a constant current method is applied to a pyrrole-containing polymerization solvent by using a galvanostat to polymerize the 3-substituted pyrrole. In the electrolytic polymerization method, the concentrations of the 3-substituted pyrrole and the dopant compound can be within the above-mentioned ranges. The dopant compound functions as an electrolyte in the pyrrole-containing polymerization solvent.

[0049] When the electropolymerization method is carried out by a potential sweep method, the potential is preferably swept in the range of −500 mV to 2500 mV relative to a standard hydrogen electrode, and more preferably in the range of 0 mV to 2000 mV. Sweeping the potential within the above range can prevent the 3-substituted pyrrole from decomposing due to peroxidation. The reaction time is preferably 0.1 hours to 72 hours, and more preferably 0.1 hours to 10 hours. By keeping the reaction time within the above range, the polymerization product can be obtained in the form of a film rather than a powder. A film-like polymerization product has the advantage of being easy to handle and exhibiting high conductivity.

[0050] When electropolymerization is carried out by a constant voltage method, a voltage in the range of 0 mV to 2500 mV relative to a standard hydrogen electrode is preferably used, and a voltage in the range of 500 mV to 2000 mV is more preferably used. By using a voltage within this range, decomposition of the 3-substituted pyrrole due to peroxidation can be suppressed. The reaction time is preferably 0.1 hours to 72 hours, and more preferably 0.1 hours to 10 hours. By keeping the reaction time within the above range, the polymerization product can be obtained in the form of a film rather than a powder. A film-like polymerization product has the advantage of being easy to handle and exhibiting high conductivity.

[0051] When electropolymerization is performed by a constant current method, the current is 0.1 mA / cm relative to the area of ​​the working electrode used. ２ 50mA / cm or more ２ It is preferable to use a current in the range of 0.1 mA / cm ２ 10mA / cm or more ２ It is more preferable to adopt a current within the following range. The reaction time is preferably 0.1 hours or more and 72 hours or less, and more preferably 0.1 hours or more and 10 hours or less. When the reaction time is within the above range, the polymerized product can be obtained in a film form rather than a powder form. A film-like polymerized product has the advantage of being easy to handle and exhibiting high electrical conductivity.

[0052] [Conductive Polymer Composition] The conductive polymer composition according to an embodiment of the present disclosure includes a conductive polymer compound according to an embodiment of the present disclosure. That is, the conductive polymer composition according to an embodiment of the present disclosure includes a conductive polymer compound containing a pyrrole having a substituent at the 3-position as a repeating unit, and the substituent is a halogenated alkyl group, a formyl group, or a formamide group. Specifically, the conductive polymer composition according to an embodiment of the present disclosure includes a conductive polymer compound having a structure represented by the above formula (2a) or (2b). The halogenated alkyl group is a C ｎ H ２ｎ X, C ｎ H ｎ X ２ , or C ｎ X ３ (wherein n is an integer of 1 or more, and X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) Since the conductive polymer composition of the present disclosure contains the conductive polymer compound as described above, it has high conductivity.

[0053] The conductive polymer composition according to an embodiment of the present disclosure may contain two or more of the above conductive polymer compounds.

[0054] The conductive polymer composition according to the embodiment of the present disclosure may contain a conductive polymer compound other than those described above. Examples of the conductive polymer compound other than those described above include a conductive polymer compound containing a pyrrole compound without a substituent as a repeating unit, and a conductive polymer compound containing a pyrrole having an alkyl group as a substituent as a repeating unit. The conductive polymer composition according to the embodiment of the present disclosure preferably contains 50% by mass or more of the conductive polymer compound according to the embodiment of the present disclosure, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. Furthermore, the conductive polymer composition according to the embodiment of the present disclosure may contain only the conductive polymer compound of the present disclosure.

[0055] The conductive polymer composition according to the embodiment of the present disclosure preferably contains a dopant compound. As described above, by incorporating a conductive polymer compound obtained by polymerizing a 3-substituted pyrrole in the presence of a dopant compound into the conductive polymer composition, the conductive polymer composition contains the dopant compound.

[0056] [Electronic Component] An electronic component according to an embodiment of the present disclosure includes a solid electrolyte layer formed from the conductive polymer composition according to an embodiment of the present disclosure. Examples of the electronic component include an electrolytic capacitor and a solid-state battery. Examples of the electrolytic capacitor include a tantalum electrolytic capacitor and an aluminum electrolytic capacitor. That is, the electronic component according to an embodiment of the present disclosure is preferably one selected from the group consisting of a tantalum electrolytic capacitor, an aluminum electrolytic capacitor, and a solid-state battery. Note that a tantalum electrolytic capacitor is a capacitor in which an anode body, which will be described later, contains tantalum as a valve metal, and a Ta electrolytic capacitor is formed on the surface of the anode body as a dielectric layer. ２ O ５ In a tantalum electrolytic capacitor, the anode body is usually made of a sintered body of tantalum particles. In an aluminum electrolytic capacitor, the anode body contains aluminum as a valve metal, and an aluminum electrolytic capacitor is provided on the surface of the anode body as a dielectric layer. ２ O ３ In an aluminum electrolytic capacitor, the anode body is usually made of aluminum foil.

[0057] (Electrolytic Capacitor) An electrolytic capacitor according to an embodiment of the present disclosure includes a capacitor element. The capacitor element includes an anode body, a dielectric layer covering the anode body, and a cathode section covering the dielectric layer. The cathode section includes a solid electrolyte layer covering the dielectric layer and a cathode extraction layer covering the solid electrolyte layer.

[0058] <Anode Body> The anode body may contain a valve metal, an alloy containing a valve metal, a compound containing a valve metal, or the like. These materials may be used alone or in combination of two or more. Examples of the valve metal that are preferably used include aluminum, tantalum, niobium, and titanium. The anode body may have a porous portion formed from the surface toward the center. The porous portion can be formed by roughening the surface of a substrate (such as a foil-shaped or plate-shaped substrate) containing a valve metal by etching or the like. The anode body may be a compact of particles containing a valve metal or a sintered body thereof. The sintered body has a porous structure. Therefore, a sintered body having a porous structure may have a porous portion throughout its entirety.

[0059] <Dielectric Layer> The dielectric layer is formed, for example, by subjecting an anode body containing a valve metal to chemical conversion treatment (anodizing treatment). The dielectric layer may be formed so as to cover at least a portion of the anode body. The dielectric layer is usually formed at least on the surface (main surface) of the anode body. When a porous portion is formed in the anode body from the surface toward the center, the dielectric layer is preferably formed on at least a portion of the porous portion. The dielectric layer is preferably formed on the surface (outer surface) of the porous portion and also penetrates into the pores (pits).

[0060] The dielectric layer includes an oxide of the valve metal. For example, if tantalum is used as the valve metal, the dielectric layer may include an oxide of Ta. ２ O ５ When aluminum is used as the valve metal, the dielectric layer contains Al ２ O ３ The dielectric layer is not limited to the above, and any material that functions as a dielectric can be used.

[0061] <Cathode section> The cathode section may be formed so as to cover at least a portion of the dielectric layer. As described above, the cathode section includes a solid electrolyte layer covering the dielectric layer and a cathode extraction layer covering the solid electrolyte layer. That is, the cathode section may be formed so as to cover at least a portion of the dielectric layer with the solid electrolyte layer. Furthermore, the cathode extraction layer may be formed so as to cover at least a portion of the solid electrolyte layer.

[0062] As described above, the solid electrolyte layer may cover at least a portion of the dielectric layer. The solid electrolyte layer may cover the entire dielectric layer (entire surface). As described above, the solid electrolyte layer is formed from a conductive polymer composition according to an embodiment of the present disclosure. As described above, the conductive polymer composition according to an embodiment of the present disclosure has high conductivity, and therefore, a solid electrolyte layer formed from such a conductive polymer composition also has high conductivity. For example, as shown in the examples described below, the solid electrolyte layer has high conductivity exceeding 65 S / cm. Therefore, an electrolytic capacitor including such a solid electrolyte layer can have a sufficiently reduced equivalent series resistance (ESR).

[0063] The cathode extraction layer includes a carbon layer covering the solid electrolyte layer and a silver paste layer covering the carbon layer. The carbon layer does not necessarily have to be formed so as to cover the entire solid electrolyte layer (entire surface), but only needs to be formed so as to cover at least a portion of the solid electrolyte layer. The silver paste layer does not necessarily have to be formed so as to cover the entire carbon layer (entire surface), but only needs to be formed so as to cover at least a portion of the carbon layer. The carbon layer may be formed using, for example, a conductive carbon material (such as graphite). The silver paste layer may be formed, for example, using a composition containing silver powder and a binder resin (such as an epoxy resin). The configuration of the cathode extraction layer is not limited to the above and may be any configuration that has a current collecting function.

[0064] A specific configuration of an electrolytic capacitor according to an embodiment of the present disclosure will be described below with reference to Figures 4 and 5. Figure 4 is a schematic cross-sectional view of an electrolytic capacitor according to an embodiment of the present disclosure, and Figure 5 is an enlarged cross-sectional view schematically showing region V in Figure 4.

[0065] As shown in Figure 4, electrolytic capacitor 1 includes capacitor element 2, resin outer casing 3 that seals capacitor element 2, and anode terminal 4 and cathode terminal 5, at least a portion of which is exposed to the outside of resin outer casing 3. Anode terminal 4 and cathode terminal 5 may be made of a metal such as copper or a copper alloy. Resin outer casing 3 has a substantially rectangular parallelepiped outer shape, and electrolytic capacitor 1 also has a substantially rectangular parallelepiped outer shape. The resin outer casing 3 may be made of, for example, epoxy resin.

[0066] Capacitor element 2 includes an anode body 6, a dielectric layer 7 covering anode body 6, and a cathode portion 8 covering dielectric layer 7. Cathode portion 8 includes a solid electrolyte layer 9 covering dielectric layer 7, and a cathode extraction layer 10 covering solid electrolyte layer 9. In the illustrated example, cathode extraction layer 10 has a carbon layer 11 as a first layer and a silver paste layer 12 as a second layer. In electrolytic capacitor 1, solid electrolyte layer 9 is a conductive polymer layer formed from a conductive composition, and the conductive polymer layer includes the conductive polymer compound according to one embodiment of the present disclosure described above.

[0067] The anode body 6 includes a region facing the cathode portion 8 (hereinafter simply referred to as the facing region) and a region not facing the cathode portion 8 (hereinafter simply referred to as the non-facing region). In the non-facing region, an insulating separation layer 13 is formed in a strip shape on one end side adjacent to the cathode portion 8 so as to cover the surface (exposed surface) of the anode body 6, thereby restricting contact between the cathode portion 8 and the anode body 6. In the non-facing region, an anode terminal 4 is electrically connected by welding to the other end side not adjacent to the cathode portion 8. The cathode terminal 5 is electrically connected to the cathode portion 8 via an adhesive layer 14 formed of a conductive adhesive.

[0068] The main surface 4S of the anode terminal 4 and the main surface 5S of the cathode terminal 5 are exposed on the same side of the resin outer casing 3. That is, the main surface 4S of the anode terminal 4 and the main surface 5S of the cathode terminal 5 constitute exposed surfaces. These exposed surfaces are used for soldering to a substrate (not shown) on which the electrolytic capacitor 1 is to be mounted, for example.

[0069] Carbon layer 11 may be made of any material as long as it is conductive, such as a conductive carbon material (such as graphite). Silver paste layer 12 may be made of a composition containing silver powder and a binder resin (such as an epoxy resin). The configuration of cathode extraction layer 10 is not limited to this, and may be any material that has a current collecting function.

[0070] The solid electrolyte layer 9 is formed so as to cover the dielectric layer 7. Specifically, as shown in FIG. 5 , the dielectric layer 7 is formed along the surface of the anode body 6 (the outer surface S of the porous portion 6 a and the inner wall surfaces of the holes P). The surface of the dielectric layer 7 has an uneven shape corresponding to the shape of the surface of the anode body 6 (see FIG. 5 ). The solid electrolyte layer 9 is preferably formed so as to fill in these unevennesses of the dielectric layer 7.

[0071] The electrolytic capacitor according to the embodiment of the present disclosure is not limited to the electrolytic capacitor having the above structure, but can be applied to electrolytic capacitors having various structures. Specifically, the electrolytic capacitor according to the embodiment of the present disclosure can also be applied to wound electrolytic capacitors. The electrolytic capacitor according to the embodiment of the present disclosure can also be applied to hybrid electrolytic capacitors that contain a liquid component (such as an electrolyte solution) in addition to a solid polymer layer (conductive polymer layer). The anode body may be a porous body in which a portion of the anode lead is embedded. In the anode body, the anode terminal and the anode lead may be electrically connected.

[0072] (Solid-state battery) A solid-state battery according to an embodiment of the present disclosure includes a positive electrode, a negative electrode, and a solid electrolyte layer provided between the positive electrode and the negative electrode. The solid electrolyte layer is formed from the conductive polymer composition according to an embodiment of the present disclosure. Therefore, the solid electrolyte layer also has high conductivity.

[0073] (Wound Electrolytic Capacitor) A wound electrolytic capacitor according to an embodiment of the present disclosure includes an anode, a dielectric layer covering the anode, a cathode, and an electrolyte layer disposed between the dielectric layer and the cathode. The electrolyte layer is composed of a separator member and a solid electrolyte contained in the separator member. The solid electrolyte constituting the electrolyte layer is formed from a conductive polymer composition according to an embodiment of the present disclosure. Therefore, the electrolyte layer also has high conductivity.

[0074] (Method for forming a wound electrolytic capacitor) An aluminum foil (thickness: 100 μm) having both surfaces (both main surfaces) roughened is prepared as an anode body. The aluminum foil can be roughened by etching. The anode body is anodized in a phosphoric acid aqueous solution (phosphoric acid concentration: 0.010 mass %) to form aluminum oxide (Al ２ O ３ The anodic oxidation is carried out under the condition that a direct current voltage of 70 V is applied for 20 minutes.

[0075] An aluminum foil (thickness: 100 μm) having both surfaces (main surfaces) roughened is prepared as the cathode body. The aluminum foil can be roughened by etching. A layer containing titanium or carbon may be formed on the surface of the cathode body.

[0076] The anode body, separator, and cathode body are stacked in this order and wound up to form a wound body.

[0077] The wound body is immersed in the solution, and the substituted pyrrole of the present disclosure is electrolytically polymerized at a solution temperature of 25° C. and a polymerization voltage of 3 V (polymerization potential relative to a silver reference electrode). This forms a conductive polymer from the surface of the dielectric layer to the inside of the separator and the cathode.

[0078] The wound body with the conductive polymer formed is housed in an aluminum case with a bottom, and the open end is crimped and curled with a sealing member. A seat plate is placed on this curled portion to complete the hybrid electrolytic capacitor.

[0079] (Hybrid Electrolytic Capacitor) A hybrid electrolytic capacitor according to an embodiment of the present disclosure includes an anode, a dielectric layer covering the anode, a cathode, and an electrolyte layer disposed between the dielectric layer and the cathode. The electrolyte layer is composed of a separator member, a solid electrolyte contained in the separator member, and an electrolytic solution. The solid electrolyte constituting the electrolyte layer is formed from a conductive polymer composition according to an embodiment of the present disclosure. Therefore, the electrolyte layer also has high conductivity.

[0080] (Method of Forming a Hybrid Electrolytic Capacitor) An aluminum foil (thickness: 100 μm) having both surfaces (both main surfaces) roughened was prepared as an anode body. The aluminum foil can be roughened by etching. The anode body was anodized in a phosphoric acid aqueous solution (phosphoric acid concentration: 0.010 mass %) to form aluminum oxide (Al ２ O ３ The anodic oxidation is carried out under the condition that a direct current voltage of 70 V is applied for 20 minutes.

[0081] An aluminum foil (thickness: 100 μm) having both surfaces (main surfaces) roughened was prepared as the cathode body. The aluminum foil can be roughened by etching. A layer containing titanium or carbon may be formed on the surface of the cathode body.

[0082] The anode body, separator, and cathode body are stacked in this order and wound up to form a wound body.

[0083] The wound body is immersed in the electrolytic solution, and the substituted pyrrole of the present disclosure is electrolytically polymerized at a solution temperature of 25° C. and a polymerization voltage (polymerization potential relative to a silver reference electrode) of 3 V. This allows a conductive polymer to be formed from the surface of the dielectric layer to the inside of the separator and the cathode.

[0084] The wound body with the conductive polymer formed is immersed in an electrolyte. It is then housed in an aluminum case with a bottom, and the open end is crimped and curled with a sealing material. A seat plate is placed on this curled portion to complete the hybrid electrolytic capacitor.

[0085] (Additional Note) The above description discloses the following techniques.

[0086] (Technology 1) A compound containing a pyrrole having a substituent at the 3-position as a repeating unit, wherein the substituent is one selected from a halogenated alkyl group, a formyl group, and a formamide group, and the halogenated alkyl group is C ｎ H ２ｎ＋１－ｍ X ｍ wherein n is an integer of 1 or more, m is an integer satisfying 1≦m≦2n+1, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0087] (Technology 2) The substituent is CH ２ X, CHX ２ , CX ３ 2. The conductive polymer compound according to claim 1, wherein the compound is one selected from the group consisting of , CHO, and NHCHO.

[0088] (Technology 3) A conductive polymer composition comprising the conductive polymer compound according to Technology 1 or 2.

[0089] (Technology 4) The conductive polymer composition according to Technology 3, comprising two or more conductive polymer compounds including the conductive polymer compound.

[0090] (Technology 5) The conductive polymer composition according to Technology 3 or 4, further comprising a dopant compound.

[0091] (Technology 6) The conductive polymer composition according to Technology 5, wherein the dopant compound includes at least one of naphthalenesulfonic acid and a salt of naphthalenesulfonic acid.

[0092] (Technology 7) An electronic component comprising a solid electrolyte layer formed from the conductive polymer composition according to any one of Technologies 3 to 6.

[0093] (Technology 8) The electronic component is one selected from the group consisting of a tantalum electrolytic capacitor, an aluminum electrolytic capacitor, and a solid-state battery.

[0094] While the present invention has been described with respect to presently preferred embodiments, such disclosure should not be interpreted as limiting. Various variations and modifications will no doubt become apparent to those skilled in the art to which the present invention pertains upon reading the above disclosure. It is therefore intended that the appended claims be interpreted to cover all variations and modifications that do not depart from the true spirit and scope of the invention.

[0095] Hereinafter, the present disclosure will be specifically described based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0096] [Example 1A] (1) Preparation of Anode Body A tantalum sintered body (porous body) in which a part of an anode lead was embedded was prepared as an anode body. The tantalum sintered body had a rectangular parallelepiped shape. A part of the anode lead was embedded in one end face of the tantalum sintered body. In other words, the anode lead was provided so as to protrude outward from one end face of the tantalum sintered body. The anode body was anodized in an aqueous phosphoric acid solution (phosphoric acid concentration: 0.010% by mass) to form a tantalum oxide (TaO) film on the surface of the anode body. ２ O ５ The anodization was carried out under the condition that a direct current voltage of 70 V was applied for 20 minutes.

[0097] (2) Formation of Solid Electrolyte Layer An aqueous dispersion containing pyrrole having a formamide group (NHCHO) at the 3-position (hereinafter referred to as 3-formamide group-containing pyrrole) and a dopant compound (sulfonate salt having a naphthalene skeleton) was prepared. In the aqueous dispersion, the concentration of the 3-formamide group-containing pyrrole was 0.5 mol / L, and the concentration of the dopant compound was 0.3 mol / L. The 3-formamide group-containing pyrrole was synthesized by the method described in the embodiment section above.

[0098] The anode body with the dielectric layer formed thereon and the counter electrode were immersed in the solution, and the formamide group-containing pyrrole was electropolymerized at a solution temperature of 25°C and a polymerization voltage of 3 V (polymerization potential relative to a silver reference electrode). This resulted in a solid electrolyte layer being formed on the dielectric layer. The thickness of the solid electrolyte layer was 100 nm. The conductivity (unit: S / cm) of the solid electrolyte layer is shown in Table 2 below. The conductivity of the solid electrolyte layer can be obtained by measuring the conductivity of a sample film formed on a metal substrate so as to have the same composition as the solid electrolyte layer. The sample film can be formed by preparing a sample solution having the same composition as the aqueous dispersion, immersing the sample solution on a metal substrate, and passing a current through the metal substrate to electropolymerize the 3-formamide group-containing pyrrole. The conductivity of the sample film can be measured using a Loresta GX and PSP probe manufactured by Nitto Seiko Analytech Co., Ltd.

[0099] (3) Formation of Cathode Extraction Layer A carbon layer was formed by applying a dispersion of graphite particles in water to the surface of the solid electrolyte layer and then drying. Drying was carried out at 130 to 180°C for 10 to 30 minutes. Next, a silver paste containing silver particles and a binder resin (epoxy resin) was applied to the surface of the carbon layer, and the binder resin was then thermally cured to form a silver paste layer. The binder resin was thermally cured at 150 to 200°C for 10 to 60 minutes. This resulted in a cathode extraction layer composed of a carbon layer and a silver paste layer being formed on the surface of the solid electrolyte. In this way, a capacitor element according to Example 1A was obtained.

[0100] (4) Fabrication of Electrolytic Capacitor After attaching an anode terminal (anode lead frame) and a cathode terminal (cathode lead frame) to the capacitor element, the remaining portions of the capacitor element, anode terminal, and cathode terminal were sealed with a resin sealant so that a portion of each of the anode terminal and cathode terminal was exposed. In this manner, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 1A was obtained. Specifically, an electrolytic capacitor such as that shown in FIG. 4 was obtained. The anode terminal was attached by welding the anode terminal to the anode lead of the capacitor element, and the cathode terminal was attached by connecting the cathode terminal to the cathode extraction layer of the capacitor element with a conductive adhesive.

[0101] [Example 2A] An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 2A was obtained in the same manner as in Example 1A, except that a pyrrole having a formyl group (CHO) at the 3-position (hereinafter referred to as a 3-formyl group-containing pyrrole) was used when forming the solid electrolyte layer. The measurement results of the conductivity of the solid electrolyte layer for Example 2A are also shown in Table 2 below. The 3-formyl group-containing pyrrole was synthesized according to the method described in the embodiment section above.

[0102] [Example 3A] When forming a solid electrolyte layer, CH ２ Pyrrole having F (hereinafter, 3-CH ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 3A was obtained in the same manner as in Example 1A, except that a tantalum electrolytic capacitor containing fluorine (hereinafter referred to as F-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer of Example 3A are also shown in Table 2 below. ２ The F-containing pyrroles were synthesized according to the method described in the Examples section above.

[0103] [Example 4A] When forming a solid electrolyte layer, CHF was added to the 3-position. ２ Pyrrole having 3-CHF ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 4A was obtained in the same manner as in Example 1A, except that a 3-substituted CHF was used. The measurement results of the conductivity of the solid electrolyte layer of Example 4A are also shown in Table 2 below. ２ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0104] [Example 5A] When forming a solid electrolyte layer, CF was added to the 3-position. ３ Pyrrole having CF at the 3-position (hereinafter, ３ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 5A was obtained in the same manner as in Example 1A, except that a 3-position CF was used. The measurement results of the conductivity of the solid electrolyte layer of Example 5A are also shown in Table 2 below. ３ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0105] [Example 6A] When forming a solid electrolyte layer, CH ２ Pyrrole having Cl (hereinafter, 3-CH ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 6A was obtained in the same manner as in Example 1A, except that a tantalum electrolytic capacitor containing Cl was used. The measurement results of the conductivity of the solid electrolyte layer of Example 6A are also shown in Table 2 below. ２ The Cl-containing pyrroles were synthesized according to the method described in the Examples section above.

[0106] [Example 7A] When forming a solid electrolyte layer, CHCl was added to the 3-position. ２ Pyrrole having a structure in which the 3-position is CHCl ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 7A was obtained in the same manner as in Example 1A, except that a tantalum-containing pyrrole (hereinafter referred to as a pyrrole-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer of Example 7A are also shown in Table 2 below. ２ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0107] [Example 8A] When forming a solid electrolyte layer, CCl was added to the 3-position. ３ Pyrrole having a CCl ３ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 8A was obtained in the same manner as in Example 1A, except that a ternary CCl-containing pyrrole was used. The measurement results of the conductivity of the solid electrolyte layer of Example 8A are also shown in Table 2 below. ３ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0108] [Example 9A] When forming a solid electrolyte layer, CH ２ Pyrrole having Br (hereinafter, 3-CH ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 9A was obtained in the same manner as in Example 1A, except that a tantalum electrolytic capacitor containing Br was used. The measurement results of the conductivity of the solid electrolyte layer of Example 9A are also shown in Table 2 below. ２ The Br-containing pyrroles were synthesized according to the method described in the Examples section above.

[0109] [Example 10A] When forming a solid electrolyte layer, CHBr was added to the 3-position. ２ Pyrrole having 3-CHBr ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 10A was obtained in the same manner as in Example 1A, except that a tantalum-containing pyrrole (hereinafter referred to as a pyrrole-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer of Example 10A are also shown in Table 2 below. ２ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0110] [Example 11A] When forming a solid electrolyte layer, CBr was added to the 3-position. ３ Pyrrole having CBr at the 3-position ３ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 11A was obtained in the same manner as in Example 1A, except that a 3-position CBr was used. The measurement results of the conductivity of the solid electrolyte layer of Example 11A are also shown in Table 2 below. ３ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0111] [Example 12A] When forming a solid electrolyte layer, CH ２ Pyrrole having I (hereinafter, 3-CH ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 12A was obtained in the same manner as in Example 1A, except that a tantalum electrolytic capacitor containing 1,000 I-containing pyrrole (hereinafter referred to as "I-containing pyrrole") was used. The measurement results of the conductivity of the solid electrolyte layer of Example 12A are also shown in Table 2 below. ２ I-containing pyrroles were synthesized according to the method described in the Examples section above.

[0112] [Example 13A] When forming a solid electrolyte layer, CHI was added to the 3-position. ２ Pyrrole having 3-CH ２ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 13A was obtained in the same manner as in Example 1A, except that a tantalum-containing pyrrole was used. The measurement results of the conductivity of the solid electrolyte layer of Example 13A are also shown in Table 2 below. ２The containing pyrrole was synthesized according to the method described in the Examples section above.

[0113] [Example 14A] When forming a solid electrolyte layer, CI was added to the 3-position. ３ Pyrroles having 3-position CI ３ An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 14A was obtained in the same manner as in Example 1A, except that a pyrrole-containing compound (hereinafter referred to as "pyrrole-containing compound") was used. The measurement results of the conductivity of the solid electrolyte layer of Example 14A are also shown in Table 2 below. ３ The containing pyrrole was synthesized according to the method described in the Examples section above.

[0114] Comparative Example 1: A heptyl group ((CH ２ ) ６ CH ３ A conductive polymer compound according to Comparative Example 1 was obtained by chemically oxidatively polymerizing pyrrole having a heptyl group at the 3-position (hereinafter referred to as pyrrole having a heptyl group at the 3-position). The chemical oxidative polymerization was carried out using acetonitrile as the solvent, ferric chloride as the oxidizing agent, and a sulfonate having a naphthalene skeleton as the dopant compound. That is, the chemical oxidative polymerization was carried out in a mixed solution containing pyrrole having a heptyl group at the 3-position, an oxidizing agent, and a dopant compound in acetonitrile. The concentration of pyrrole having a heptyl group at the 3-position was 50 mmol / L, the concentration of the oxidizing agent was 100 mmol / L, and the concentration of the dopant compound was 300 mmol / L. The reaction time was 1 hour, and the reaction temperature was 25°C. The mixed solution containing the conductive polymer compound according to Comparative Example 1 was dropped onto a glass substrate and dried. This formed a coating of the conductive polymer compound (hereinafter also referred to as a conductive polymer coating) on ​​the glass plate. The conductivity of the conductive polymer coating according to Comparative Example 1 was then measured in the same manner as described above. The measurement results are shown in Table 2 below.

[0115] <Evaluation> For the electrolytic capacitors (tantalum electrolytic capacitors) according to Examples 1A to 14A, the initial ESR (unit: mΩ) was measured at a frequency of 100 kHz in an environment of 20°C using a four-terminal LCR meter. The initial capacitance (unit: μF) was also measured at a frequency of 120 kHz in an environment of 20°C using a four-terminal LCR meter. For each example, the initial ESR and initial capacitance were measured for 10 samples, and the arithmetic mean values ​​for each were calculated. The results are shown in Table 2 below.

[0116]

[0117] As shown in Table 2, the electrolytic capacitors (tantalum electrolytic capacitors) according to Examples 1A to 14A had high electrical conductivity of the solid polymer layer exceeding 65 S / cm. Furthermore, these electrolytic capacitors had low ESR values, with a maximum of 6.02 mΩ. Furthermore, the capacitance values ​​of these electrolytic capacitors were all high, at 453 μF. On the other hand, the electrical conductivity of the conductive polymer coating of Comparative Example 1 was 60 S / cm, which was not sufficiently high.

[0118] [Example 1B] (1) Preparation of Anode Body An aluminum foil (thickness: 100 μm) having both surfaces (both main surfaces) roughened was prepared as an anode body. The aluminum foil was roughened by etching. The anode body was anodized in a phosphoric acid aqueous solution (phosphoric acid concentration: 0.010 mass %) to form aluminum oxide (Al ２ O ３ The anodization was carried out under the condition that a direct current voltage of 70 V was applied for 20 minutes.

[0119] (2) Formation of Solid Electrolyte Layer A solid electrolyte layer was formed on the dielectric layer in the same manner as in Example 1A.

[0120] (3) Formation of Cathode Extraction Layer A cathode extraction layer composed of a carbon layer and a silver paste layer was formed on the surface of the solid electrolyte layer in the same manner as in Example 1A, thereby obtaining a capacitor element according to Example 1B.

[0121] (4) Fabrication of Electrolytic Capacitor An anode terminal (anode lead frame) and a cathode terminal (cathode lead frame) were attached to the capacitor element in the same manner as in Example 1A, except that one end of the anode terminal (anode lead frame) was laser-welded to one end of the anode body protruding from the capacitor element. Furthermore, the remaining portions of the capacitor element, the anode terminal, and the cathode terminal were encapsulated with a resin encapsulant in the same manner as in Example 1A. In this manner, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 1B was obtained.

[0122] Example 2B An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 2B was obtained in the same manner as in Example 1B, except that a pyrrole containing a formyl group at the 3-position was used when forming the solid electrolyte layer.

[0123] Example 3B When forming a solid electrolyte layer, the 3-position CH ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 3B was obtained in the same manner as in Example 1B, except that F-containing pyrrole was used.

[0124] [Example 4B] When forming a solid electrolyte layer, 3-CHF ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 4B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0125] [Example 5B] When forming a solid electrolyte layer, 3-CF ３ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 5B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0126] [Example 6B] When forming a solid electrolyte layer, the 3-position CH ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 6B was obtained in the same manner as in Example 1B, except that Cl-containing pyrrole was used.

[0127] [Example 7B] When forming a solid electrolyte layer, 3-CHCl ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 7B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0128] [Example 8B] When forming a solid electrolyte layer, 3-position CCl ３ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 8B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0129] [Example 9B] When forming a solid electrolyte layer, the 3-position CH ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 9B was obtained in the same manner as in Example 1B, except that Br-containing pyrrole was used.

[0130] [Example 10B] When forming a solid electrolyte layer, 3-CHBr ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 10B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0131] [Example 11B] When forming a solid electrolyte layer, 3-CBr ３ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 11B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0132] [Example 12B] When forming a solid electrolyte layer, the 3-position CH ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 12B was obtained in the same manner as in Example 1B, except that I-containing pyrrole was used.

[0133] [Example 13B] When forming a solid electrolyte layer, 3-position CHI ２ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 13B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0134] [Example 14B] When forming a solid electrolyte layer, 3-position CI ３ An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 14B was obtained in the same manner as in Example 1B, except that pyrrole-containing compound was used.

[0135] <Evaluation> The initial ESR and initial capacitance of the electrolytic capacitors (tantalum electrolytic capacitors) of Examples 1B to 14B were measured in the same manner as the electrolytic capacitors of Examples 1A to 14A. The results are shown in Table 3 below. Table 3 also shows the electrical conductivity values ​​of the solid electrolyte layers of Examples 1B to 14B.

[0136]

[0137] As shown in Table 3, the electrolytic capacitors (aluminum electrolytic capacitors) according to Examples 1B to 14B also exhibited high electrical conductivity of the solid polymer layer exceeding 65 S / cm. Furthermore, these electrolytic capacitors exhibited low ESR values ​​of 2.05 mΩ to 2.07 mΩ. Furthermore, these electrolytic capacitors all exhibited high capacitance values ​​of 380 μF. On the other hand, the electrical conductivity of the conductive polymer coating of Comparative Example 1 was 60 S / cm, which was not sufficiently high.

[0138] The conductive polymer compound according to the present disclosure can be used in applications where sufficient improvement in the conductivity of a solid electrolyte layer is required.

[0139] 1: Electrolytic capacitor 2: Capacitor element 3: Resin exterior body 4: Anode terminal 4S: Main surface of anode terminal 5: Cathode terminal 5S: Main surface of cathode terminal 6: Anode body 7: Dielectric layer 8: Cathode portion 9: Solid electrolyte layer 10: Cathode lead layer 11: Carbon layer 12: Silver paste layer 13: Separation layer 14: Adhesive layer

Claims

1. A compound having a repeating unit of pyrrole having a substituent at the 3-position, the substituent being one selected from a halogenated alkyl group, a formyl group, and a formamide group, the halogenated alkyl group being C ｎ H ２ｎ＋１－ｍ X ｍ wherein n is an integer of 1 or more, m is an integer satisfying 1≦m≦2n+1, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

2. The substituent is CH ２ X, CHX ２ , C.X. ３ 2. The conductive polymer compound according to claim 1, wherein the compound is one selected from the group consisting of CHO and NHCHO.

3. A conductive polymer composition comprising the conductive polymer compound according to claim 1.

4. The conductive polymer composition according to claim 3, comprising two or more kinds of conductive polymer compounds including the conductive polymer compound.

5. The conductive polymer composition according to claim 3, further comprising a dopant compound.

6. The conductive polymer composition according to claim 5, wherein the dopant compound comprises at least one of naphthalenesulfonic acid and a salt of naphthalenesulfonic acid.

7. An electronic device comprising a solid electrolyte layer formed from the conductive polymer composition according to any one of claims 3 to 6.

8. The electronic component according to claim 7, wherein the electronic component is one selected from the group consisting of a tantalum electrolytic capacitor, an aluminum electrolytic capacitor, and a solid-state battery.

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