Conductive polymer compound, conductive polymer composition, and electronic component

Abstract

To provide a conductive polymer compound or the like capable of satisfactorily improving the conductivity of a solid electrolyte layer.SOLUTION: A conductive polymer compound contains a repeating unit of pyrrole having a substituent at the 3-position. The substituent is a halogenated alkyl group, a formyl group, or a formamide group. The halogenated alkyl group is CnH2n+1-mXm (wherein 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.)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, in an electrolytic capacitor, it is known to improve the conductivity of an electrolyte by using a conductive polymer layer (solid electrolyte layer) formed of a conductive polymer instead of a liquid component (such as an electrolytic solution) (for example, Patent Document 1 below). In an electrolytic capacitor, by improving the conductivity of the electrolyte as described above, the equivalent series resistance (ESR) can be reduced. An electrolytic capacitor having the solid electrolyte layer as described above usually 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 lead-out layer formed on the solid electrolyte layer.

[0003] Patent Document 1 below describes that in an electrolytic capacitor, the solid electrolyte layer is constituted by two layers, a first solid electrolyte layer covering the dielectric layer and a second solid electrolyte layer covering the first solid electrolyte layer. More specifically, Patent Document 1 below describes that the first solid electrolyte layer is constituted to include a first conductive polymer compound having a polythiophene as a basic skeleton and to exhibit a conductivity of 2 S / cm or less, and the second solid electrolyte layer is constituted to include a second conductive polymer compound having a polypyrrole as a basic skeleton. And Patent Document 1 below describes that by constituting the first solid electrolyte layer and the second solid electrolyte layer 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, Patent Document 1 below describes that by making the solid electrolyte layer include two types of conductive polymer compounds having different characteristics, the conductivity of the solid electrolyte layer is improved and the equivalent series resistance (ESR) of the electrolytic capacitor is reduced.

[0004] Patent Document 2 below describes obtaining a monomer with a specific structure by bonding 2 to 10 3-alkyl heterocyclic five-membered ring compounds having a specific structure, while regulating the head-to-tail of the alkyl group and bonding the 2-position and 5-position of the heterocyclic five-membered ring, and polymerizing the monomer with the specific structure to obtain a conductive polymer compound. Further, Patent Document 2 below describes improving the conductivity of the solid electrolyte layer of an electrolytic capacitor by using a conductive polymer compound as described above, thereby reducing the equivalent series resistance (ESR) of the electrolytic capacitor.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] As described above, in electrolytic capacitors, various studies have been conducted on the conductive polymer compounds to be included in the solid electrolyte layer in order to improve the conductivity of the solid electrolyte layer, but it is hard to say that the studies have been sufficiently made.

[0007] Also, as described above, improving the conductivity of the solid electrolyte layer is desired in other electronic components (such as solid-state batteries) provided with the solid electrolyte layer, but it is hard to say that the studies on this have been sufficiently made.

[0008] Therefore, 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 provided with a solid electrolyte layer formed by the conductive polymer composition.

Means for Solving the Problems

[0009] One aspect of the present invention contains a pyrrole having a substituent at the 3-position as a repeating unit, the substituent being a halogenated alkyl group, a formyl group, or a formamide group, and the halogenated alkyl group being 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 element, a chlorine atom, a bromine element, or an iodine element.) It relates to a conductive polymer compound.

[0010] Another aspect of the present invention relates to a conductive polymer composition containing the above conductive polymer compound.

[0011] Still another aspect of the present invention relates to an electronic component provided with a solid electrolyte layer formed by the above conductive polymer composition.

Advantages of the Invention

[0012] 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 provided with a solid electrolyte layer formed by the conductive polymer composition.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 4

Figure 5

Best Mode for Carrying Out the Invention

[0014] The inventors have found that in a polymer compound obtained by bonding a plurality of pyrroles having substituents (hereinafter also referred to as substituent-containing pyrroles), the energy level of the molecular orbit of the main chain of the polymer compound (the chain portion obtained by bonding a plurality of substituent-containing pyrroles) changes depending on the type of substituent. And since an electron transfer is likely to occur in the polymer compound when the energy level of the molecular orbit of the polymer compound rises, the conductivity improves in the solid electrolyte layer (conductive polymer layer) formed using such a polymer compound. On the other hand, since an electron transfer is less likely to occur in the polymer compound when the energy level of the molecular orbit decreases, it is considered that the conductivity decreases in the solid electrolyte layer (conductive polymer layer) formed using such a polymer compound. Therefore, the inventors focused on substituents capable of raising the energy level of the molecular orbit in a polymer compound obtained by bonding a plurality of substituent-containing pyrroles. And the inventors completed the present invention by earnestly studying such substituents.

[0015] Hereinafter, embodiments of the present disclosure will be described with 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 can be obtained. In addition, known components may be applied to the components characteristic of the present disclosure. In this specification, when referring to "the range of numerical value A to numerical value B", the range includes numerical value A and numerical value B.

[0016] In the following description, when the lower limit and the upper limit of a numerical value regarding a specific physical property or condition are exemplified, any combination of 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 greater than the upper limit. When a plurality of materials are exemplified, unless otherwise specified, one of them may be selected and used alone, or two or more of them may be used in combination.

[0017] The present disclosure also includes combinations of matters described in two or more claims arbitrarily selected from a plurality of claims described in the appended claims. That is, as long as no technical contradiction occurs, matters described in two or more claims arbitrarily selected from a plurality of claims described in the appended claims can be combined.

[0018] [Conductive polymer compound] The conductive polymer compound according to an embodiment of the present disclosure contains pyrrole having a substituent at the 3-position as a repeating unit. 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).

[0019] [Chemical formula]

[0020] 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 directions of the substituents R are aligned in the same direction (see the following formula (2a)), or may have a structure in which a plurality of pyrroles having a substituent at the 3-position are bonded so that the directions of the substituents R are not aligned in the same direction (see the following formula (2b)). When the conductive polymer compound according to an embodiment of the present disclosure has a structure represented by the following formula (2b), the ratio (molar ratio) of the first structural unit represented by the above formula (1) to the second structural unit in which the substituent R is present at a position line-symmetric to the first structural unit with respect to the line segment connecting N (nitrogen atom) and H (hydrogen atom) directly bonded to the N may be 1:1 to 1:10 for the first structural unit: the second structural unit. In general, the conductive polymer compound according to an embodiment of the present disclosure often has a structure represented by the following formula (2b).

[0021] [Chemical formula]

[0022] The alkyl halide 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 element, a chlorine atom, a bromine element, or an iodine element). Note that the upper limit value of n is 9. The alkyl halide group is preferably CH2X, CHX2, or CX3. That is, in the conductive polymer compound according to the embodiment of the present disclosure, the substituent R is preferably one selected from the group consisting of CH2X, CHX2, CX3, CHO, and NHCHO).

[0023] When the substituent R is CH2X, CHX2, CX3, or CHO, these substituents R are bonded to the 3-position of pyrrole via a carbon atom. And in these substituents R, due to the influence of X (halogen element) or O (oxygen atom), the positive charge amount of the carbon atom at the 3-position of pyrrole decreases. Similarly, when the substituent R is NHCHO, due to the influence of the nitrogen atom, the positive charge amount of the carbon atom at the 3-position of pyrrole decreases. Thus, since the substituent R is bonded to the 3-position of pyrrole, in the main chain of the conductive polymer compound containing such pyrrole as a repeating unit, it is considered that electron transfer is likely to occur due to the influence of the decrease in the positive charge amount of the main chain. That is, in the main chain of the conductive polymer compound containing such pyrrole as a repeating unit, it is considered that the energy level is likely to rise. For the above reasons, it is considered that the conductive polymer compound according to the embodiment of the present disclosure has a high conductivity.

[0024] Pyrrole having a formamide group (NHCHO) at the 3-position can be obtained by allowing a formylation reaction to proceed on an amino group using pyrrole having an amino group at the 3-position and formic acid (HCOOH) as shown in FIG. 1. In order to promote the progress of the formylation reaction on the amino group, a formylating reagent (for example, N-formyl saccharin, etc.) may be used.

[0025] Pyrrole having a formyl group (CHO) at the 3-position can be obtained by oxidizing the hydroxymethyl group in pyrrole having a hydroxymethyl group (CH2OH) at the 3-position to an aldehyde with pyridinium chlorochromate (PCC) in dichloromethane (CH2Cl2) as shown in Figure 2.

[0026] Next, the synthesis of pyrrole having a methyl halide group at the 3-position will be described with reference to Figures 3A and 3B.

[0027] Pyrrole having CH2X1 at the 3-position can be obtained by irradiating light in the coexistence of pyrrole having a methyl group (CH3) at the 3-position and X12 molecules (in the gas phase). Specifically, it can be obtained by photo-cleaving the X12 molecules by light irradiation to obtain X1 radicals, and the X1 radicals extracting one hydrogen atom (H) from the methyl group (CH3) (the first A reaction in Figure 3A). The light irradiation can be carried out, for example, by irradiating ultraviolet rays using a UV lamp as a light source. Examples of the wavelength of the irradiated ultraviolet rays include 200 nm or more and 430 nm or less, and examples of the integrated light amount include 100 mJ or more and 1000 mJ or less. In Figure 3A, hν means light irradiation. Here, X1 is a fluorine (F) element, a chlorine (Cl) element, or a bromine (Br) element.

[0028] Pyrrole having CHX12 at the 3-position can be obtained by irradiating light in the coexistence of pyrrole having CH2X1 at the 3-position and X12 molecules (in the gas phase). Specifically, it can be obtained by the X1 radicals obtained by light irradiation extracting one hydrogen atom (H) from CH2X1 (the second A reaction in Figure 3A). The light irradiation can be carried out under the above-described conditions. Note that pyrrole having CH2X1 at the 3-position obtained by the first A reaction in Figure 3A can be used.

[0029] Pyrrole having CX13 at the 3-position can be obtained by irradiating light in the coexistence (in the gas phase) of pyrrole having CHX12 at the 3-position and the X12 molecule. Specifically, it can be obtained by extracting one hydrogen atom (H) from CHX12 by the X1 radical obtained by light irradiation (Reaction 3A in Figure 3A). The light irradiation can be carried out under the conditions described above. In addition, as the pyrrole having CHX12 at the 3-position, that obtained by Reaction 2A in Figure 3A can be used.

[0030] In addition, Reaction 1A to Reaction 3A in Figure 3A proceed continuously due to the presence of radical species such as the X1 radical. Therefore, pyrrole having CH2X1 at the 3-position, pyrrole having CHX12 at the 3-position, and pyrrole having CX13 at the 3-position can be obtained with high purity by classifying them by silica gel column 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 means a series of operations for extracting a specific substance.

[0031] On the other hand, when the halogen element X of the halogenated methyl group is the iodine (I) element, it can be synthesized by a different route from the above.

[0032] Pyrrole having CH2I at the 3-position can be obtained by reacting pyrrole having CH2Cl at the 3-position with sodium iodide (NaI) in acetone (in the liquid phase). Specifically, it can be obtained by substituting the chlorine atom of CH2Cl with the iodine atom (I) of sodium iodide (NaI) (the 1B reaction in Figure 3B). Here, after the 1B reaction, unreacted pyrrole having CH2Cl at the 3-position remains. Therefore, by classifying with silica gel chromatography after the 1B reaction, pyrrole having CH2I at the 3-position can be obtained with high purity. 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, as described above. Note that pyrrole having CH2Cl at the 3-position can be obtained by the 1A reaction in Figure 3A.

[0033] Pyrrole having CHI2 at the 3-position can be obtained by reacting pyrrole having CHCl2 at the 3-position with sodium iodide (NaI) in acetone (in the liquid phase). Specifically, it can be obtained by substituting two chlorine atoms of CHCl2 with the iodine atom (I) of sodium iodide (NaI) (the 2B reaction in Figure 3B). Pyrrole having CHI2 at the 3-position can also be obtained with high purity by classification with silica gel chromatography. 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, as described above. Note that pyrrole having CHCl2 at the 3-position can be obtained by the 2A reaction in Figure 3A.

[0034] Pyrrole having CI3 at the 3-position can be obtained by reacting pyrrole having CCl3 at the 3-position with sodium iodide (NaI) in acetone (in the liquid phase). Specifically, it can be obtained by substituting three chlorine atoms of CCl3 with iodine atoms (I) of sodium iodide (NaI) (the 3B reaction in Fig. 3B). Pyrrole having CI3 at the 3-position can also be obtained with high purity by classification using silica gel chromatography. 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, as described above. Note that pyrrole having CCl3 at the 3-position obtained by the 3A reaction in Fig. 3A can be used.

[0035] The conductive polymer compound according to an embodiment of the present disclosure preferably contains pyrrole having a formamide group (NHCHO) as a substituent at the 3-position as a repeating unit. By having such a substituent, the conductive polymer compound according to an embodiment of the present disclosure exhibits a particularly high conductivity. And a solid electrolyte layer containing such a conductive polymer compound also exhibits a particularly high conductivity. Thereby, an electrolytic capacitor provided with such a solid electrolyte layer exhibits a particularly low equivalent series resistance (ESR).

[0036] 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, or 50 or more, or 100 or more. Also, the degree of polymerization may be 800 or less, or 500 or less, or 300 or less. The degree of polymerization can be obtained by dividing the weight average molecular weight Mw of the conductive polymer compound by the formula weight of the monomer which is the structural unit of the basic structure in the conductive polymer compound. Note that the weight average molecular weight Mw of the conductive polymer compound can be measured by the method described later.

[0037] The weight average molecular weight Mw of the conductive polymer compound according to the present embodiment is 5.6×10 2 or more and 4.6×10 5The following are preferred. The weight average molecular weight Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC). The GPC measurement is carried out using two columns connected in series, Shodex OHpak SB804HQ and SB8025HQ, with a dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) solution in which LiBr or NaOH3 is dissolved at 50 mM as the eluent, using an RI detector, setting the column temperature from 40°C to 120°C, the flow rate of the eluent to 0.2 mL / min, and the analysis time to 40 min. The measurement sample can be prepared by dissolving the conductive polymer compound in the above eluent to a concentration of 1.0 g / L.

[0038] The conductive polymer compounds having respective substituents preferably have a weight average molecular weight Mw within the range shown in Table 1 below.

[0039] [Table 1]

[0040] The conductive polymer compound according to the embodiment of the present disclosure can be obtained by chemically oxidizing or electrolytically polymerizing pyrrole having a substituent at the 3-position. Hereinafter, pyrrole having a substituent at the 3-position is referred to as 3-position substituted pyrrole.

[0041] A method for chemically oxidatively polymerizing 3-substituted pyrrole (hereinafter also referred to as the chemical oxidative polymerization method) will be described below. First, as the reaction solvent, a solvent capable of dissolving 3-substituted pyrrole and the oxidizing agent to be used may be used alone, or a solvent capable of dissolving 3-substituted pyrrole and a solvent capable of dissolving the oxidizing agent to be used may be combined and used. 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, propylene carbonate, and the like.

[0042] Examples of the oxidizing agent include ferric oxide, iron(III) tris(p-toluenesulfonate), sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, potassium permanganate, and the like.

[0043] In the chemical oxidative polymerization method, a dopant compound may be used. Examples of the dopant compound include sulfuric acid, alkyl sulfuric acid (such as heptyl sulfuric acid, octyl sulfuric acid), alkyl benzene sulfonic acid (such as benzene sulfonic acid, toluene sulfonic acid, ethyl benzene sulfonic acid), naphthalene sulfonic acid, alkyl naphthalene sulfonic acid (such as methyl naphthalene sulfonic acid), naphthalene disulfonic acid, alkyl naphthalene disulfonic acid (such as methyl naphthalene disulfonic acid), and the like. Further, the dopant compound may be a salt of various acids described above. Examples of the salts of various acids include sodium salts and ammonium salts. In the embodiments of the present disclosure, it is preferable to use naphthalene sulfonic acid or a salt thereof as the dopant compound in the chemical oxidative polymerization method. Further, the salt of naphthalene sulfonic acid is preferably a sodium salt (sodium naphthalene sulfonate).

[0044] Using the solvent, the oxidizing agent, and, if necessary, the dopant compound, 3-substituted pyrrole is chemically oxidative polymerized. Hereinafter, an example of chemically oxidative polymerizing 3-substituted pyrrole in a heterogeneous system (hereinafter simply referred to as a heterogeneous system) using a dopant compound will be described. In the heterogeneous system, a first solution obtained by dissolving 3-substituted pyrrole in a solvent and a second solution obtained by dissolving an oxidizing agent and a dopant compound in a solvent are used. In the heterogeneous system, the second solution is dropped into the first solution to chemically oxidative polymerize 3-substituted pyrrole. In the first solution, the concentration of 3-substituted pyrrole 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 1000 mmol / L or less, and preferably 10 mmol / L or more and 200 mmol / L or less. The concentration of the dopant compound is preferably 5 mmol / L or more and 5000 mmol / L or less, and more preferably 50 mmol / L or more and 1000 mmol / L or less. When each of the 3-substituted pyrrole, the oxidizing agent, and the dopant compound is within the above concentration range, side reactions are suppressed, and it is possible to suppress a decrease in the conductivity of the resulting conductive polymer compound. In addition, the chemical oxidative polymerization of 3-substituted pyrrole can proceed sufficiently. 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. When the reaction temperature is within the above range, side reactions are suppressed, and it is possible to suppress a decrease in the conductivity of the resulting conductive polymer compound. The reaction temperature is preferably selected from the range from the temperature at which the solvent used does not freeze to the boiling point of the solvent. In order to allow the reaction to proceed gently, it is preferably carried out at as low a temperature as possible such that the solvent does not freeze and the viscosity does not increase. The reaction time is preferably 0.1 hour or more and 72 hours or less, and more preferably 0.1 hour or more and 10 hours or less.

[0045] A method for electrochemically polymerizing 3-substituted pyrrole (hereinafter also referred to as the electrochemical polymerization method) will be described below. In the electrochemical polymerization method, 3-substituted pyrrole is polymerized in a polymerization solvent. In the electrochemical polymerization 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, propylene carbonate, and the like.

[0046] The dopant compound is used by dissolving it in the polymerization solvent. Examples of the dopant compound include sulfuric acid, alkyl sulfuric acid (such as heptyl sulfuric acid and octyl sulfuric acid), benzenesulfonic acid, alkylbenzenesulfonic acid (such as toluenesulfonic acid and ethylbenzenesulfonic acid), naphthalenesulfonic acid, alkylnaphthalenesulfonic acid (such as methylnaphthalenesulfonic acid), naphthalenesulfonic acid, alkylnaphthalenedisulfonic acid (such as methylnaphthalenedisulfonic acid). In the embodiments of the present disclosure, in the electrochemical polymerization, it is preferable to use naphthalenesulfonic acid or a salt thereof as the dopant compound. Further, the salt of naphthalenesulfonic acid is preferably a sodium salt (sodium naphthalenesulfonate).

[0047] Examples of the electrochemical polymerization method include a method of polymerizing 3-substituted pyrrole by applying a potential sweep method or a constant voltage method using a potentiostat to a polymerization solvent (hereinafter referred to as a pyrrole-containing polymerization solvent) in which 3-substituted pyrrole and a dopant compound are dissolved, and a method of polymerizing 3-substituted pyrrole by applying a constant current method using a galvanostat to the pyrrole-containing polymerization solvent. In the electrochemical polymerization method, the above ranges can be adopted for the concentration of 3-substituted pyrrole and the concentration of the dopant compound. Note that the dopant compound functions as an electrolyte in the pyrrole-containing polymerization solvent.

[0048] When the electrolytic polymerization method is carried out by the potential sweep method, it is preferable to sweep the potential in the range of -500 mV or more and 2500 mV or less with respect to the standard hydrogen electrode, and more preferably in the range of 0 mV or more and 2000 mV or less. By sweeping the potential within the above range, it is possible to suppress the decomposition of the 3-substituted pyrrole due to peroxidation. The reaction time is preferably 0.1 hour or more and 72 hours or less, and more preferably 0.1 hour or more and 10 hours or less. When the reaction time is within the above range, the polymerization product can be obtained in the form of a film rather than a powder. The film-like polymerization product has the advantage of excellent handleability in addition to showing a high conductivity.

[0049] When the electrolytic polymerization method is carried out by the constant voltage method, it is preferable to adopt a voltage within the range of 0 mV or more and 2500 mV or less with respect to the standard hydrogen electrode, and more preferably within the range of 500 mV or more and 2000 mV or less. By adopting the voltage within the above range, it is possible to suppress the decomposition of the 3-substituted pyrrole due to peroxidation. The reaction time is preferably 0.1 hour or more and 72 hours or less, and more preferably 0.1 hour or more and 10 hours or less. When the reaction time is within the above range, the polymerization product can be obtained in the form of a film rather than a powder. The film-like polymerization product has the advantage of excellent handleability in addition to showing a high conductivity.

[0050] When the electrolytic polymerization method is carried out by the constant current method, with respect to the area of the working electrode used, a current within the range of 0.1 mA / cm 2 or more and 50 mA / cm 2 or less is preferably adopted, and a current within the range of 0.1 mA / cm 2 or more and 10 mA / cm 2 or less is more preferably adopted. The reaction time is preferably 0.1 hour or more and 72 hours or less, and more preferably 0.1 hour or more and 10 hours or less. When the reaction time is within the above range, the polymerization product can be obtained in the form of a film rather than a powder. The film-like polymerization product has the advantage of excellent handleability in addition to showing a high conductivity.

[0051] [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 contains 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 C n H 2n X, C n H n X2, or C n X3 (where n is an integer of 1 or more, and X represents a fluorine element, a chlorine atom, a bromine element, or an iodine element). Since the conductive polymer composition of the present disclosure contains the conductive polymer compound as described above, it has a high conductivity.

[0052] The conductive polymer composition according to an embodiment of the present disclosure may contain two or more of the above conductive polymer compounds.

[0053] The conductive polymer composition according to an embodiment of the present disclosure may contain a conductive polymer compound other than the above. Examples of the conductive polymer compound other than the above include a conductive polymer compound containing a pyrrole compound having no substituent as a repeating unit, a conductive polymer compound containing pyrrole having an alkyl group as a substituent as a repeating unit, and the like. The conductive polymer composition according to an embodiment of the present disclosure preferably contains 50% by mass or more of the conductive polymer compound according to an embodiment of the present disclosure, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more. Further, the conductive polymer composition according to an embodiment of the present disclosure may contain only the conductive polymer compound of the present disclosure.

[0054] The conductive polymer composition according to an embodiment of the present disclosure preferably contains a dopant compound. As described above, by including a conductive polymer compound obtained by polymerizing 3-substituted pyrrole in the presence of a dopant compound in the conductive polymer composition, the conductive polymer composition comes to contain the dopant compound.

[0055] [Electronic component] The electronic component according to an embodiment of the present disclosure includes a solid electrolyte layer formed of 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 the tantalum electrolytic capacitor is an electrolytic capacitor in which an anode body described later contains tantalum as a valve metal and has Ta2O5 as a dielectric layer on the surface of the anode body. In a tantalum electrolytic capacitor, the anode body is usually composed of a sintered body of tantalum particles. The aluminum electrolytic capacitor is an electrolytic capacitor in which an anode body described later contains aluminum as a valve metal and has Al2O3 as a dielectric layer on the surface of the anode body. In an aluminum electrolytic capacitor, the anode body is usually composed of an aluminum foil.

[0056] (Electrolytic capacitor) The 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 portion covering the dielectric layer. The cathode portion includes a solid electrolyte layer covering the dielectric layer and a cathode lead-out layer covering the solid electrolyte layer.

[0057] <Anode body> The anode body can include valve-acting metals, alloys containing valve-acting metals, compounds containing valve-acting metals, etc. These materials may be used alone or in combination of two or more. As the valve-acting metal, for example, aluminum, tantalum, niobium, titanium, etc. are preferably used. In the anode body, a porous portion may be formed from the surface toward the central portion. The porous portion can be formed by roughening the surface of a base material (such as a foil-shaped or plate-shaped base material) containing a valve-acting metal by etching or the like. The anode body may be a molded body of particles containing a valve-acting metal or a sintered body thereof. The sintered body has a porous structure. Therefore, the sintered body having a porous structure can be entirely a porous portion.

[0058] <Dielectric layer> The dielectric layer is formed, for example, by subjecting an anode body containing a valve-acting metal to a forming treatment (anodic oxidation treatment). The dielectric layer only needs to be formed so as to cover at least a part of the anode body. The dielectric layer is usually formed at least on the surface (main surface) of the anode body. In the case where a porous portion is formed from the surface toward the central portion in the anode body, it is preferable that the dielectric layer is formed on at least a part of the porous portion. The dielectric layer is preferably formed on the surface (outer surface) of the porous portion and also penetrate into the inside of the pores (pits).

[0059] The dielectric layer contains an oxide of the valve-acting metal. For example, when tantalum is used as the valve-acting metal, the dielectric layer contains Ta2O5, and when aluminum is used as the valve-acting metal, the dielectric layer contains Al2O3. Note that the dielectric layer is not limited to the above, and any material that functions as a dielectric can be used.

[0060] <Cathode portion> The cathode portion only needs to be formed so as to cover at least a part of the dielectric layer. As described above, the cathode portion includes a solid electrolyte layer covering the dielectric layer and a cathode lead-out layer covering the solid electrolyte layer. That is, the cathode portion only needs to cover at least a part of the dielectric layer with the solid electrolyte layer. Further, the cathode lead-out layer only needs to be formed so as to cover at least a part of the solid electrolyte layer.

[0061] As described above, the solid electrolyte layer only needs to cover at least a part of the dielectric layer. The solid electrolyte layer may cover the entire dielectric layer (the entire surface). As described above, the solid electrolyte layer is formed of the conductive polymer composition according to the embodiment of the present disclosure. As described above, since the conductive polymer composition according to the embodiment of the present disclosure has a high conductivity, the solid electrolyte layer formed of such a conductive polymer composition also has a high conductivity. For example, as shown in the examples described later, it has a high conductivity exceeding 65 S / cm. Therefore, in an electrolytic capacitor provided with such a solid electrolyte layer, the equivalent series resistance (ESR) can be sufficiently reduced.

[0062] The cathode lead-out layer has a carbon layer covering the solid electrolyte layer and a silver paste layer covering the carbon layer. The carbon layer does not necessarily need to be formed so as to cover the entire solid electrolyte layer (the entire surface), and only needs to be formed so as to cover at least a part of the solid electrolyte layer. Further, the silver paste layer does not necessarily need to be formed so as to cover the entire carbon layer (the entire surface), and only needs to be formed so as to cover at least a part of the carbon layer. The carbon layer only needs to have conductivity, and for example, it can be configured using a conductive carbon material (such as graphite). The silver paste layer can be configured, for example, by a composition containing silver powder and a binder resin (such as an epoxy resin). The configuration of the cathode lead-out layer is not limited to the above, and any configuration may be used as long as it has a current collecting function.

[0063] Hereinafter, with reference to FIGS. 4 and 5, the specific configuration of the solid electrolytic capacitor according to an embodiment of the present disclosure will be described. FIG. 4 is a schematic cross-sectional view of the solid electrolytic capacitor according to an embodiment of the present disclosure, and FIG. 5 is an enlarged cross-sectional view schematically showing region V of FIG. 4.

[0064] As shown in FIG. 4, the solid electrolytic capacitor 1 includes a capacitor element 2, a resin exterior 3 that seals the capacitor element 2, and an anode terminal 4 and a cathode terminal 5, at least a part of which is exposed outside the resin exterior 3. The anode terminal 4 and the cathode terminal 5 can be made of a metal such as copper or a copper alloy, for example. The resin exterior 3 has a substantially rectangular parallelepiped outer shape, and the solid electrolytic capacitor 1 also has a substantially rectangular parallelepiped outer shape. As the material of the resin exterior 3, for example, an epoxy resin can be used.

[0065] The capacitor element 2 includes an anode body 6, a dielectric layer 7 that covers the anode body 6, and a cathode portion 8 that covers the dielectric layer 7. The cathode portion 8 includes a solid electrolyte layer 9 that covers the dielectric layer 7 and a cathode lead-out layer 10 that covers the solid electrolyte layer 9. In the illustrated example, the cathode lead-out layer 10 has a carbon layer 11 as the first layer and a silver paste layer 12 as the second layer. In the solid electrolytic capacitor 1, the solid electrolyte layer 9 is a conductive polymer layer formed of a conductive composition, and the conductive polymer layer contains the conductive polymer compound according to an embodiment of the present disclosure described above.

[0066] 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). Among the non-facing regions, an insulating separation layer 13 is formed on one end side adjacent to the cathode portion 8 so as to cover the surface (exposed surface) of the anode body 6 in a band shape, and the contact between the cathode portion 8 and the anode body 6 is restricted. Among the non-facing regions, the 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.

[0067] 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 exterior body 3. That is, the main surface 4S of the anode terminal 4 and the main surface 5S of the cathode terminal 5 constitute the exposed surface. These exposed surfaces are used for soldering connection with a substrate (not shown) on which the solid electrolytic capacitor 1 is to be mounted and the like.

[0068] The carbon layer 11 only needs to have conductivity, and for example, it can be formed using a conductive carbon material (such as graphite). For the silver paste layer 12, for example, a composition containing silver powder and a binder resin (such as an epoxy resin) can be used. Note that the configuration of the cathode lead-out layer 10 is not limited to this, and any configuration having a current collecting function may be used.

[0069] 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 6a and the inner wall surface of the hole P). On the surface of the dielectric layer 7, an uneven shape corresponding to the shape of the surface of the anode body 6 is formed (see FIG. 5). The solid electrolyte layer 9 is preferably formed so as to fill the unevenness of such a dielectric layer 7.

[0070] The electrolytic capacitor according to the embodiment of the present disclosure is not limited to the electrolytic capacitor having the above structure, and 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 a wound type electrolytic capacitor or the like. Further, the electrolytic capacitor according to the embodiment of the present disclosure can also be applied to a hybrid type electrolytic capacitor containing a liquid component (such as an electrolytic solution) in addition to a solid polymer layer (conductive polymer layer). The anode body may be a porous body in which a part of the anode lead is embedded. In the anode body, the anode terminal and the anode lead may be electrically connected.

[0071] (Solid battery) The 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. And the solid electrolyte layer is formed of the conductive polymer composition according to the embodiment of the present disclosure. Therefore, this solid electrolyte layer also has a high conductivity.

[0072] (Appendix) The following techniques are disclosed by the above description. (Technique 1) Containing pyrrole having a substituent at the 3-position as a repeating unit, wherein the substituent is a halogenated alkyl group, a formyl group, or a formamide group, the halogenated alkyl group is C n H 2n+1-m X m (However, n is an integer of 1 or more, m is an integer satisfying 1 ≦ m ≦ 2n + 1, and X represents a fluorine element, a chlorine atom, a bromine element, or an iodine element.) Conductive polymer compound. (Technique 2) The substituent is one selected from the group consisting of CH2X, CHX2, CX3, CHO, and NHCHO, The conductive polymer compound according to Technique 1. (Technique 3) Containing the conductive polymer compound according to Technique 1 or 2, Conductive polymer composition. (Technique 4) Containing two or more kinds of the conductive polymer compounds, The conductive polymer composition according to Technique 3. (Technique 5) Further containing a dopant compound, The conductive polymer composition according to Technique 3 or 4. (Technique 6) The dopant compound is naphthalenesulfonic acid or a salt thereof, The conductive polymer composition according to Technique 5. (Technique 7) Comprising a solid electrolyte layer formed of the conductive polymer composition according to any one of Techniques 3 to 6, Electronic component. (Technology 8) The electronic component is one selected from the group consisting of a tantalum electrolytic capacitor, an aluminum electrolytic capacitor, and a solid battery.

[0073] Although the present invention has been described with respect to preferred embodiments at the present time, such disclosure should not be construed in a limiting sense. Various modifications and alterations will undoubtedly become apparent to those skilled in the art in the technical field to which the present invention pertains upon reading the above disclosure. Accordingly, the appended claims should be construed to encompass all modifications and alterations without departing from the true spirit and scope of the present invention.

Example

[0074] 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.

[0075] [Example 1A] (1) Fabrication of anode body As the anode body, a tantalum sintered body (porous body) in which a part of the anode lead was embedded was prepared. The tantalum sintered body had a rectangular parallelepiped shape. A part of the anode lead was embedded on one end face side of the tantalum sintered body. That is, the anode lead was provided so as to protrude outward from one end face of the tantalum sintered body. Anodic oxidation was carried out on the anode body in an aqueous phosphoric acid solution (the concentration of phosphoric acid was 0.010 mass%) to form a dielectric layer containing tantalum oxide (Ta2O5) on the surface of the anode body. The anodic oxidation was carried out under the condition of applying a DC voltage of 70 V for 20 minutes.

[0076] (2) Formation of solid electrolyte layer A water dispersion containing pyrrole having a formamide group (NHCHO) at the 3-position (hereinafter referred to as 3-position formamide group-containing pyrrole) and a dopant compound (sulfonate having a naphthalene skeleton) was prepared. In the water dispersion, the concentration of the 3-position formamide group-containing pyrrole was 0.5 mol / L, and the concentration of the dopant compound was 0.3 mol / L. The 3-position formamide group-containing pyrrole was synthesized by the method described in the above embodiment section.

[0077] The anode body with the dielectric layer formed and the counter electrode were immersed, and the formamide group-containing pyrrole was electrolytically polymerized under the conditions of a liquid temperature of 25 °C and a polymerization voltage of 3 V (polymerization potential with respect to the silver reference electrode). Thereby, a solid electrolyte layer was formed on the dielectric layer. The thickness of the solid electrolyte layer was 100 nm. The conductivity value (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 liquid having the same composition as the above water dispersion, immersing the sample liquid in a metal substrate, passing an electric current through the metal substrate, and electrolytically polymerizing the 3-position formamide group-containing pyrrole. For measuring the conductivity of the sample film, Loresta-GX and PSP probes manufactured by Nitto Seiko Analytic Co., Ltd. can be used.

[0078] (3) Formation of the cathode lead-out layer A dispersion liquid in which graphite particles were dispersed in water was applied to the surface of the solid electrolyte layer and then dried to form a carbon layer. The 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 then the binder resin was thermally cured to form a silver paste layer. The thermal curing of the binder resin was carried out at 150 to 200 °C for 10 to 60 minutes. Thereby, a cathode lead-out layer composed of a carbon layer and a silver paste layer was formed on the surface of the solid electrolyte. In this way, the capacitor element according to Example 1A was obtained.

[0079] (4) Fabrication of the 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, the anode terminal, and the cathode terminal were sealed with a resin encapsulant so that a part of each of the anode terminal and the cathode terminal was exposed. In this way, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 1A was obtained. Specifically, an electrolytic capacitor as shown in FIG. 4 was obtained. Note that 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.

[0080] [Example 2A] An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 2A was obtained in the same manner as in Example 1A, except that pyrrole having a formyl group (CHO) at the 3-position (hereinafter referred to as 3-position formyl group-containing pyrrole) was used when forming the solid electrolyte layer. Note that the measurement results of the conductivity of the solid electrolyte layer for Example 2A are also shown in Table 2 below. The 3-position formyl group-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0081] [Example 3A] An electrolytic capacitor (tantalum electrolytic capacitor) according to Example 3A was obtained in the same manner as in Example 1A, except that pyrrole having CH2F at the 3-position (hereinafter referred to as 3-position CH2F-containing pyrrole) was used when forming the solid electrolyte layer. The measurement results of the conductivity of the solid electrolyte layer for Example 3A are also shown in Table 2 below. The 3-position CH2F-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0082] [Example 4A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 4A was obtained in the same manner as in Example 1A, except that pyrrole having CHF₂ at the 3-position (hereinafter referred to as 3-position CHF₂-containing pyrrole) was used. For Example 4A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CHF₂-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0083] [Example 5A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 5A was obtained in the same manner as in Example 1A, except that pyrrole having CF₃ at the 3-position (hereinafter referred to as 3-position CF₃-containing pyrrole) was used. For Example 5A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CF₃-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0084] [Example 6A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 6A was obtained in the same manner as in Example 1A, except that pyrrole having CH₂Cl at the 3-position (hereinafter referred to as 3-position CH₂Cl-containing pyrrole) was used. For Example 6A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CH₂Cl-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0085] [Example 7A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 7A was obtained in the same manner as in Example 1A, except that pyrrole having CHCl₂ at the 3-position (hereinafter referred to as 3-position CHCl₂-containing pyrrole) was used. For Example 7A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CHCl₂-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0086] [Example 8A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 8A was obtained in the same manner as in Example 1A, except that pyrrole having CCl3 at the 3-position (hereinafter referred to as 3-position CCl3-containing pyrrole) was used. For Example 8A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CCl3-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0087] [Example 9A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 9A was obtained in the same manner as in Example 1A, except that pyrrole having CH2Br at the 3-position (hereinafter referred to as 3-position CH2Br-containing pyrrole) was used. For Example 9A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CH2Br-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0088] [Example 10A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 10A was obtained in the same manner as in Example 1A, except that pyrrole having CHBr2 at the 3-position (hereinafter referred to as 3-position CHBr2-containing pyrrole) was used. For Example 10A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CHBr2-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0089] [Example 11A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 11A was obtained in the same manner as in Example 1A, except that pyrrole having CBr3 at the 3-position (3-position CBr3-containing pyrrole) was used. For Example 11A as well, the measurement results of the conductivity of the solid electrolyte layer are shown in Table 2 below. The 3-position CBr3-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0090] [Example 12A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 12A was obtained in the same manner as in Example 1A, except that pyrrole having CH2I at the 3-position (hereinafter referred to as 3-position CH2I-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer for Example 12A are also shown in Table 2 below. The 3-position CH2I-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0091] [Example 13A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 13A was obtained in the same manner as in Example 1A, except that pyrrole having CHI2 at the 3-position (hereinafter referred to as 3-position CHI2-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer for Example 13A are also shown in Table 2 below. The 3-position CHI2-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0092] [Example 14A] When forming the solid electrolyte layer, an electrolytic capacitor (tantalum electrolytic capacitor) according to Example 14A was obtained in the same manner as in Example 1A, except that pyrrole having CI3 at the 3-position (hereinafter referred to as 3-position CI3-containing pyrrole) was used. The measurement results of the conductivity of the solid electrolyte layer for Example 14A are also shown in Table 2 below. The 3-position CI3-containing pyrrole was synthesized according to the method described in the above embodiment section.

[0093] [Comparative Example 1] Pyrrole having a heptyl group ((CH2)6CH3) at the 3-position (hereinafter referred to as 3-position heptyl group-containing pyrrole) was chemically oxidative polymerized to obtain a conductive polymer compound according to Comparative Example 1. The chemical oxidative polymerization was carried out using acetonitrile as a solvent, ferric chloride as an oxidizing agent, and a sulfonate having a naphthalene skeleton as a dopant compound. That is, the chemical oxidative polymerization was carried out in a mixed solution in which 3-position heptyl group-containing pyrrole, an oxidizing agent, and a dopant compound were contained in acetonitrile. The concentration of 3-position heptyl group-containing pyrrole 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. A mixed solution containing the conductive polymer compound according to Comparative Example 1 was dropped onto a glass substrate and dried. Thereby, a film of the conductive polymer compound (hereinafter also referred to as a conductive polymer film) was formed on the glass plate. Then, the conductivity of the conductive polymer film according to Comparative Example 1 was measured in the same manner as described above. The measurement results are shown in Table 2 below.

[0094] <Evaluation> Regarding the electrolytic capacitors (tantalum electrolytic capacitors) according to Examples 1A to 14A, using an LCR meter for four-terminal measurement, in an environment of 20 °C, the initial ESR (unit: mΩ) at a frequency of 100 kHz was measured. Also, using an LCR meter for four-terminal measurement, in an environment of 20 °C, the initial capacitance (unit: μF) at a frequency of 120 kHz was measured. For each example, the initial ESR and the initial capacitance were carried out for 10 specimens, and the arithmetic mean value of each was calculated. The results are shown in Table 2 below.

[0095]

Table 2

[0096] As shown in Table 2, in the electrolytic capacitors (tantalum electrolytic capacitors) according to Examples 1A to 14A, the conductivity of the solid polymer layer showed a high value exceeding 65 S / cm. And in these electrolytic capacitors, the ESR value showed a low value of at most 6.02 mΩ. Also, in these electrolytic capacitors, the capacitance values all showed a high value of 453 μF. On the other hand, the conductivity of the conductive polymer film of Comparative Example 1 was 60 S / cm, which could not be said to be a sufficiently high value.

[0097] [Example 1B] (1) Fabrication of the anode body As the anode body, an aluminum foil (thickness 100 μm) with both surfaces (both main surfaces) roughened was prepared. The roughening of the aluminum foil was carried out by etching. Anodization was performed on the anode body in an aqueous phosphoric acid solution (the concentration of phosphoric acid was 0.010 mass%) to form a dielectric layer containing aluminum oxide (Al2O3) on the surface of the anode body. The anodization was carried out under the condition of applying a DC voltage of 70 V for 20 minutes.

[0098] (2) Formation of the solid electrolyte layer In the same manner as in Example 1A, a solid electrolyte layer was formed on the dielectric layer.

[0099] (3) Formation of the cathode lead-out layer In the same manner as in Example 1A, a cathode lead-out layer composed of a carbon layer and a silver paste layer was formed on the surface of the solid electrolyte layer. In this way, a capacitor element according to Example 1B was obtained.

[0100] (4) Fabrication of the 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. Also, in the same manner as in Example 1A, the remaining parts of the capacitor element, anode terminal, and cathode terminal were sealed with a resin encapsulant. In this way, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 1B was obtained.

[0101] [Example 2B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 2B was obtained in the same manner as in Example 1B, except that 3-formyl group-containing pyrrole was used when forming the solid electrolyte layer.

[0102] [Example 3B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 3B was obtained in the same manner as in Example 1B, except that 3-CH2F-containing pyrrole was used when forming the solid electrolyte layer.

[0103] [Example 4B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 4B was obtained in the same manner as in Example 1B, except that 3-CHF2-containing pyrrole was used when forming the solid electrolyte layer.

[0104] [Example 5B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 5B was obtained in the same manner as in Example 1B, except that 3-CF3-containing pyrrole was used when forming the solid electrolyte layer.

[0105] [Example 6B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 6B was obtained in the same manner as in Example 1B, except that 3-CH2Cl-containing pyrrole was used when forming the solid electrolyte layer.

[0106] [Example 7B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 7B was obtained in the same manner as in Example 1B, except that 3-CHCl2-containing pyrrole was used when forming the solid electrolyte layer.

[0107] [Example 8B] An electrolytic capacitor (aluminum electrolytic capacitor) according to Example 8B was obtained in the same manner as in Example 1B, except that 3-CCl3-containing pyrrole was used when forming the solid electrolyte layer.

[0108] [Example 9B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 9B was obtained in the same manner as in Example 1B, except that 3-position CH2Br-containing pyrrole was used.

[0109] [Example 10B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 10B was obtained in the same manner as in Example 1B, except that 3-position CHBr2-containing pyrrole was used.

[0110] [Example 11B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 11B was obtained in the same manner as in Example 1B, except that 3-position CBr3-containing pyrrole was used.

[0111] [Example 12B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 12B was obtained in the same manner as in Example 1B, except that 3-position CH2I-containing pyrrole was used.

[0112] [Example 13B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 13B was obtained in the same manner as in Example 1B, except that 3-position CHI2-containing pyrrole was used.

[0113] [Example 14B] When forming the solid electrolyte layer, an electrolytic capacitor (aluminum electrolytic capacitor) according to Example 14B was obtained in the same manner as in Example 1B, except that 3-position CI3-containing pyrrole was used.

[0114] [Evaluation] For the electrolytic capacitors (tantalum electrolytic capacitors) according to Examples 1B to 14B, the initial ESR and the initial capacitance were measured in the same manner as for the electrolytic capacitors according to Examples 1A to 14A. The results are shown in Table 3 below. Also shown in Table 3 below are the conductivity values of the solid electrolyte layers of Examples 1B to 14B.

[0115]

Table 3

[0116] As shown in Table 3, in the electrolytic capacitors (aluminum electrolytic capacitors) according to Examples 1B to 14B, the conductivity of the solid polymer layer also showed a high value exceeding 65 S / cm. And in these electrolytic capacitors, the ESR values showed low values of 2.05 mΩ to 2.07 mΩ. Also, in these electrolytic capacitors, the capacitance values all showed high values of 380 μF. On the other hand, the conductivity of the conductive polymer film of Comparative Example 1 was 60 S / cm, which could not be said to be a sufficiently high value.

Industrial Applicability

[0117] The conductive polymer compound according to the present disclosure can be used in applications where it is required to sufficiently improve the conductivity of the solid electrolyte layer.

Explanation of Reference Numerals

[0118] 1: Electrolytic capacitor, 2: Capacitor element, 3: Resin package, 4: Anode terminal, 4S: Main surface of the anode terminal, 5: Cathode terminal, 5S: Main surface of the cathode terminal, 6: Anode body, 7: Dielectric layer, 8: Cathode part, 9: Solid electrolyte layer, 10: Cathode lead-out layer, 11: Carbon layer, 12: Silver paste layer, 13: Separation layer, 14: Adhesive layer.

Claims

1. A conductive polymer compound containing a pyrrole having a substituent at the 3-position as a repeating unit, wherein the substituent is a halogenated alkyl group, a formyl group, or a formamide group. The alkyl halide 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 element, a chlorine atom, a bromine element, or an iodine element).

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

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

4. The conductive polymer composition according to Claim 3, containing two or more kinds of the conductive polymer compounds.

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 is naphthalenesulfonic acid or a salt thereof.

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

8. The electronic component according to Claim 7, which 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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