TW201302854A - Conductive polymer precursor, conductive polymer, method for producing aniline conductive polymer, conductive composition, conductor and solid electrolytic capacitor - Google Patents

Abstract

This invention relates to a conductive polymer precursor represented by the following formula (1): In the formula (1), R1 to R4 each independently are selected from the group consisting of a hydrogen atom, straight or branched C1 to C24 alkyl group, straight or branched C1 to C24 alkoxy group, an acid group or its salt, a hydroxy group, a nitro group, and a halogen atom, A represents an acid group or its salt, and n represents an integer from 1 to 20.

Description

導電性聚合物前驅物、導電性聚合物及固體電解電容器 Conductive polymer precursor, conductive polymer and solid electrolytic capacitor

本申請案主張基於2011年6月14日於日本提出申請的日本專利申請2011-132184號、及2012年5月14日於日本提出申請的日本專利申請2012-110285號的優先權，並在此引用其內容。 The present application claims priority based on Japanese Patent Application No. 2011-132184, filed on Jan. Quote its content.

本發明是有關於一種導電性聚合物前驅物、導電性聚合物及固體電解電容器，上述導電性聚合物前驅物適合作為導電性聚合物的前驅物，上述導電性聚合物是使上述導電性聚合物前驅物聚合而獲得，上述固體電解電容器具備含有導電性聚合物的固體電解質層。 The present invention relates to a conductive polymer precursor, a conductive polymer, and a solid electrolytic capacitor, wherein the conductive polymer precursor is suitable as a precursor of a conductive polymer, and the conductive polymer is a conductive polymer. The solid electrolytic capacitor is obtained by polymerizing a precursor, and the solid electrolytic capacitor includes a solid electrolyte layer containing a conductive polymer.

作為可用於多種用途中的導電性聚合物，已知有聚苯胺系、聚噻吩系、聚吡咯系等的導電性聚合物。 Conductive polymers such as polyaniline, polythiophene, and polypyrrole are known as conductive polymers that can be used in various applications.

通常，導電性聚合物的導電性(σ)依存於載體的電荷(q)、載體的個數(n)以及載體的分子鏈間及分子鏈內的可動度(μ)，是由下述式(I)所導出。 Generally, the conductivity (σ) of the conductive polymer depends on the charge (q) of the carrier, the number of carriers (n), and the mobility (μ) between the molecular chains of the carrier and the molecular chain. (I) is derived.

σ=qnμ………(I) σ=qnμ.........(I)

於聚苯胺系導電性聚合物的情況下，載體的電荷(q)成為由載體的種類所決定的固有值，故為了提高導電性，重要的是增大載體的個數(n)及可動度(μ)。 In the case of a polyaniline-based conductive polymer, since the charge (q) of the carrier is a deterministic value determined by the type of the carrier, it is important to increase the number (n) of the carrier and the mobility in order to improve the conductivity. (μ).

為了增大可動度(μ)，一般認為有效的是提高導電性 聚合物的分子量，或減少導電性聚合物中所含的雜質的比例等。 In order to increase the mobility (μ), it is generally considered to be effective to improve conductivity. The molecular weight of the polymer, or the ratio of impurities contained in the conductive polymer, and the like.

另一方面，為了增大載體的個數(n)，一般認為有效的是導入磺酸基、羧基等酸性基，將妨礙摻雜的鹼去除等。 On the other hand, in order to increase the number (n) of the carriers, it is considered to be effective to introduce an acidic group such as a sulfonic acid group or a carboxyl group, and to remove the alkali which hinders the doping.

導入有酸性基的聚苯胺系導電性聚合物例如已提出有以下的導電性聚合物：使下述所示的化合物(II)2-胺基苯甲醚-4-磺酸作為前驅物進行聚合而成的導電性聚合物(參照專利文獻1)。 A polyaniline-based conductive polymer having an acidic group introduced thereto is, for example, a conductive polymer obtained by polymerizing the compound (II) 2-aminoanisole-4-sulfonic acid shown below as a precursor. A conductive polymer (see Patent Document 1).

另外，具備含有導電性聚合物的固體電解質層的固體電解電容器為以下的電容器：於鋁、鉭或鈮等閥作用金屬的金屬箔或金屬燒結體的表面形成多孔質成形體的陽極氧化被膜，並將上述陽極氧化被膜作為介電質而構成的電容器。電解質與上述陽極氧化被膜接觸，該電解質作為自上述陽極氧化被膜拉出電極的陰極而發揮功能。 In addition, the solid electrolytic capacitor including the solid electrolyte layer containing the conductive polymer is a capacitor in which a porous molded body is formed on the surface of a metal foil or a metal sintered body of a valve action metal such as aluminum, tantalum or niobium. A capacitor formed by using the above anodized film as a dielectric material. The electrolyte is in contact with the anodized film, and the electrolyte functions as a cathode for pulling out the electrode from the anodized film.

作為陰極的電解質對電解電容器的電氣特性造成大的影響，因此先前以來，提出了採用各種電解質的電解電容器。於固體電解電容器中，廣泛使用作為導電性聚合物的 聚乙烯二氧噻吩(Polyethylenedioxythiophene，PEDOT)等來作為固體電解質。進而已知以下方法：將電容器元件浸漬於氧化劑溶液與單體溶液的混合溶液中，藉此使電容器元件含浸氧化劑及單體，於電容器元件的絕緣膜上促進氧化劑與單體的聚合反應，形成固體電解質。 The electrolyte as the cathode has a large influence on the electrical characteristics of the electrolytic capacitor, and therefore, an electrolytic capacitor using various electrolytes has been proposed. Widely used as a conductive polymer in solid electrolytic capacitors Polyethylenedioxythiophene (PEDOT) or the like is used as a solid electrolyte. Further, a method is known in which a capacitor element is immersed in a mixed solution of an oxidizing agent solution and a monomer solution, whereby a capacitor element is impregnated with an oxidizing agent and a monomer, and a polymerization reaction of the oxidizing agent and the monomer is promoted on the insulating film of the capacitor element to form a capacitor element. Solid electrolyte.

另外，作為提高電解質的導電性能的方法，一直使用以下的化學氧化聚合法：於單體中添加氧化劑及摻雜物(導電助劑)，使單體與氧化劑於陽極氧化被膜上直接反應，形成固體電解質層(導電性聚合物層)。作為該製法，提出有以下的化學氧化聚合法：使3,4-乙烯二氧噻吩(EDOT)與氧化劑及摻雜物溶解於有機溶劑中，使其於陽極氧化被膜上反應而形成導電性聚合物層(專利文獻2)。 Further, as a method of improving the conductivity of the electrolyte, the following chemical oxidation polymerization method has been used: an oxidizing agent and a dopant (conductive auxiliary agent) are added to the monomer, and the monomer and the oxidizing agent are directly reacted on the anodized film to form Solid electrolyte layer (conductive polymer layer). As a method of the production, there is proposed a chemical oxidation polymerization method in which 3,4-ethylenedioxythiophene (EDOT), an oxidizing agent and a dopant are dissolved in an organic solvent, and reacted on an anodic oxide film to form a conductive polymerization. Physical layer (Patent Document 2).

另外，作為降低等效串聯電阻(Equivalent Series Resistance，以下簡稱為ESR)的電解電容器的製造方法，已提出有依序經由以下操作而於電容器元件內形成固體電解質層的方法：將電容器元件浸漬於含有摻雜劑的溶液中後，使其乾燥，滴加藉由氧化聚合而成為導電性聚合物的單體，將該電容器元件含浸於氧化劑的水溶液中(專利文獻3)；或提出有一種含有導電率高的摻雜劑的含浸有導電性聚合物及電解液的電解電容器(專利文獻4)。 Further, as a method of manufacturing an electrolytic capacitor which reduces Equivalent Series Resistance (hereinafter referred to as ESR), a method of forming a solid electrolyte layer in a capacitor element in sequence by immersing a capacitor element in a method has been proposed. After the solution containing the dopant is dried, a monomer which becomes a conductive polymer by oxidative polymerization is added dropwise, and the capacitor element is impregnated into an aqueous solution of an oxidizing agent (Patent Document 3); An electrolytic capacitor in which a dopant having a high conductivity is impregnated with a conductive polymer and an electrolytic solution (Patent Document 4).

另外，提出有以下方法：製備導電性聚合物的溶液，使陽極氧化被膜含浸該溶液，進行乾燥並塗膜化，藉此形成固體電解質層(專利文獻5)。 Further, there has been proposed a method of preparing a solution of a conductive polymer, impregnating the solution with an anodic oxide film, drying and coating the film to form a solid electrolyte layer (Patent Document 5).

另外，提出有以下方法：於導電性聚合物的溶液中添 加鹼性化合物，藉此提高耐熱性(專利文獻6)。 In addition, the following method is proposed: adding a solution of a conductive polymer The basic compound is added to improve heat resistance (Patent Document 6).

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平7-196791號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-196791

[專利文獻2]日本專利特開平02-15611號公報 [Patent Document 2] Japanese Patent Laid-Open No. 02-15611

[專利文獻3]日本專利特開2000-223364號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-223364

[專利文獻4]日本專利特開平11-186110號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 11-186110

[專利文獻5]日本專利特開平09-22833號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 09-22833

[專利文獻6]日本專利特開2010-116441號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-116441

再者，導電性聚合物被用於電容器等各種用途。例如於用於電容器中的情形時，通常於金屬電極上塗佈導電性聚合物，於預定的溫度下進行加熱處理而形成導電性聚合物層(電解質層)。 Further, the conductive polymer is used for various purposes such as capacitors. For example, in the case of being used in a capacitor, a conductive polymer is usually applied to a metal electrode, and heat treatment is performed at a predetermined temperature to form a conductive polymer layer (electrolyte layer).

然而，專利文獻1所記載的導電性聚合物雖然具有優異的導電性，但不滿足熱穩定性。因此，若用於在製造過程中含有加熱處理步驟的電容器等用途，則無法發揮充分的導電性。 However, the conductive polymer described in Patent Document 1 has excellent conductivity, but does not satisfy thermal stability. Therefore, if it is used for a capacitor or the like which contains a heat treatment step in the manufacturing process, sufficient conductivity cannot be exhibited.

另外，關於固體電解質層，於陽極氧化被膜上使固體電解質聚合的上述方法有以下問題：難以使導電性聚合物層充分地形成至陽極氧化被膜的微細的凹凸部分為止，進而，含有摻雜劑的固體電解質層容易產生於電解液中摻雜物劑自固體電解質層中脫出(脫摻雜)的現象，故固體電解質層的導電率下降，ESR逐漸變高。 In addition, the above-described method of polymerizing the solid electrolyte on the anodic oxide film in the solid electrolyte layer has a problem that it is difficult to sufficiently form the conductive polymer layer to the fine uneven portion of the anodic oxide film, and further contains a dopant. The solid electrolyte layer is liable to be desorbed (de-doped) from the solid electrolyte layer in the electrolyte solution, so that the conductivity of the solid electrolyte layer is lowered and the ESR is gradually increased.

另一方面，對於預先製備成為摻雜物的於分子內具有 酸性基的導電性聚合物溶液並加以塗膜化的方法而言，雖然與於陽極氧化被膜上進行聚合的方法相比較為更簡便的製造方法，但導電性聚合物的性能不可謂充分，具有同樣的問題。 On the other hand, there is a molecule in the molecule prepared in advance as a dopant. The method of coating an acid-based conductive polymer solution and coating it is a simpler method than the method of performing polymerization on an anodized film, but the performance of the conductive polymer is not sufficient. same question.

另外，於導電性聚合物中添加鹼性化合物的方法亦於用於電容器等用途時耐熱性不可謂充分，具有同樣的問題。 Further, a method of adding a basic compound to a conductive polymer is also insufficient in heat resistance when used for a capacitor or the like, and has the same problem.

本發明是鑒於上述情況而成，其目的在於提供一種導電性聚合物前驅物、導電性聚合物及導電性組成物，上述導電性聚合物前驅物適合作為具有高的導電性、且熱穩定性優異的導電性聚合物的前驅物，上述導電性聚合物具有高的導電性、且熱穩定性優異，上述導電性組成物含有該導電性聚合物。另外，本發明的目的在於提供一種耐熱性優異、且等效串聯電阻低的固體電解電容器。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a conductive polymer precursor, a conductive polymer, and a conductive composition, and the conductive polymer precursor is suitable as a high conductivity and thermal stability. The precursor of the excellent conductive polymer has high conductivity and excellent thermal stability, and the conductive composition contains the conductive polymer. Further, an object of the present invention is to provide a solid electrolytic capacitor which is excellent in heat resistance and has a low equivalent series resistance.

本發明者等人進行了潛心研究，結果發現：若對導入有酸性基的導電性聚合物進行加熱，則酸性基脫離而導致導電性下降。 As a result of intensive studies, the inventors of the present invention have found that when the conductive polymer into which the acidic group is introduced is heated, the acidic group is desorbed and the conductivity is lowered.

因此發現，藉由製成以下的可溶性苯胺系導電性聚合物，可維持導電性、並且提高導電性聚合物的熱穩定性，從而完成了本發明，上述可溶性苯胺系導電性聚合物具有經由特定碳數的伸烷基而導入有酸性基的重複單元(亦稱為導電性聚合物前驅物)。 Therefore, it has been found that the present invention can be maintained by providing the following soluble aniline-based conductive polymer, and the heat-stable stability of the conductive polymer can be improved, and the above-described soluble aniline-based conductive polymer has specific properties. A repeating unit (also referred to as a conductive polymer precursor) having an acid group introduced into an alkyl group.

進而發現，藉由使用具有上述重複單元的可溶性的苯胺系導電性聚合物，可獲得耐熱性優異、且等效串聯電阻 低的固體電解電容器。 Further, it has been found that by using a soluble aniline-based conductive polymer having the above repeating unit, excellent heat resistance and equivalent series resistance can be obtained. Low solid electrolytic capacitors.

另外，本發明的可溶性苯胺系導電性聚合物於水、有機溶劑及含水有機溶劑中的溶解性高，另外無需製膜後的摻雜步驟，故將電容器的製造方法簡化。 Further, the soluble aniline-based conductive polymer of the present invention has high solubility in water, an organic solvent, and an aqueous organic solvent, and does not require a doping step after film formation, so that the method for producing a capacitor is simplified.

本發明具有以下態樣。 The present invention has the following aspects.

本發明的第1態樣是一種導電性聚合物前驅物，其是以下述通式(1)所表示， A first aspect of the present invention is a conductive polymer precursor which is represented by the following general formula (1).

式(1)中，R¹~R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 In the formula (1), R ¹ to R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group or In the group consisting of a salt, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.

本發明的第2態樣如上述第1態樣所述之導電性聚合物前驅物，其中上述R²為氫原子，R¹、R³、R⁴中的至少一個為碳數1~24的直鏈或分支的烷氧基。 According to a second aspect of the invention, the conductive polymer precursor according to the first aspect, wherein the R ² is a hydrogen atom, and at least one of R ¹ , R ³ and R ⁴ is a carbon number of 1 to 24. Linear or branched alkoxy group.

本發明的第3態樣如上述第2態樣所述之導電性聚合物前驅物，其中上述R²為氫原子，R¹、R³、R⁴中的一個為碳數1~24的直鏈或分支的烷氧基，其餘為氫原子。 According to a third aspect of the invention, the conductive polymer precursor according to the second aspect, wherein the R ² is a hydrogen atom, and one of R ¹ , R ³ and R ⁴ is a straight one having a carbon number of 1 to 24. Alkoxy groups of a chain or branch, the remainder being a hydrogen atom.

本發明的第4態樣是一種導電性聚合物，其是使如上 述第1態樣至第3態樣中任一態樣所述之導電性聚合物前驅物聚合而獲得。 A fourth aspect of the invention is a conductive polymer which is made as above The conductive polymer precursor described in any one of the first aspect to the third aspect is obtained by polymerization.

本發明的第5態樣是一種導電性組成物，其含有苯胺系導電性聚合物(a)及溶劑(b)，上述苯胺系導電性聚合物(a)具有下述通式(1-A)所表示的重複單元。 According to a fifth aspect of the invention, there is provided a conductive composition comprising an aniline-based conductive polymer (a) and a solvent (b), wherein the aniline-based conductive polymer (a) has the following formula (1-A) ) the repeating unit represented.

式(1)中，R¹、R³及R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 In the formula (1), R ¹ , R ³ and R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, In the group consisting of an acidic group or a salt thereof, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.

本發明的第6態樣如上述第5態樣所述之導電性組成物，其中R¹、R³、R⁴中的至少一個為碳數1~24的直鏈或分支的烷氧基。 According to a sixth aspect of the invention, the conductive composition according to the fifth aspect, wherein at least one of R ¹ , R ³ and R ⁴ is a linear or branched alkoxy group having 1 to 24 carbon atoms.

本發明的第7態樣如上述第5態樣所述之導電性組成物，其中R¹、R³、R⁴中的一個為碳數1~24的直鏈或分支的烷氧基，其餘為氫原子。 According to a seventh aspect of the invention, the conductive composition according to the fifth aspect, wherein one of R ¹ , R ³ , and R ⁴ is a linear or branched alkoxy group having 1 to 24 carbon atoms, and the rest It is a hydrogen atom.

本發明的第8態樣如上述第5態樣至第7態樣中任一態樣所述之導電性組成物，其更含有鹼性化合物(c)。 According to an eighth aspect of the invention, the conductive composition according to any one of the fifth aspect to the seventh aspect, further comprising the basic compound (c).

本發明的第9態樣是一種導電體，其具有由如上述第4態樣所述之導電性聚合物所形成的塗膜。 According to a ninth aspect of the invention, there is provided a conductor comprising a coating film formed of the conductive polymer according to the fourth aspect.

本發明的第10態樣是一種導電體，其具有由如上述第5態樣至第7態樣中任一態樣所述之導電性組成物所形成的塗膜。 A tenth aspect of the invention is the electric conductor comprising the coating film formed of the electroconductive composition as described in any one of the fifth aspect to the seventh aspect.

本發明的第11態樣是一種導電體，其具有由如上述第8態樣所述之導電性組成物所形成的塗膜。 An eleventh aspect of the invention is the electric conductor comprising the coating film formed of the electroconductive composition as described in the eighth aspect.

本發明的第12態樣是一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具備含有如上述第4態樣所述之導電性聚合物的固體電解質層。 According to a twelfth aspect of the invention, there is provided a solid electrolytic capacitor comprising a solid electrolyte layer containing the conductive polymer according to the fourth aspect described above, on the anodized film formed on the valve action metal body.

本發明的第13態樣是一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具備由如上述第5態樣至第7態樣中任一態樣所述之導電性組成物所形成的固體電解層。 According to a thirteenth aspect of the present invention, there is provided a solid electrolytic capacitor comprising an electrically conductive film formed on a valve-acting metal body and having a conductivity as described in any one of the fifth aspect to the seventh aspect. A solid electrolyte layer formed by a composition.

本發明的第14態樣是一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具備由如上述第8態樣所述之導電性組成物所形成的固體電解質層。 According to a fourteenth aspect of the invention, there is provided a solid electrolytic capacitor comprising: a solid electrolyte layer formed of the conductive composition according to the eighth aspect of the invention, formed on the anodized film formed on the valve action metal body.

本發明的第15態樣是一種下述通式(1)所表示的化合物作為導電性聚合物前驅物的用途：[化4] The fifteenth aspect of the invention is the use of a compound represented by the following formula (1) as a conductive polymer precursor: [Chemical 4]

(式(1)中，R¹~R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數)。 (In the formula (1), R ¹ to R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, and an acidic group. In the group consisting of a salt, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20).

本發明的第16態樣是一種製造方法：其於氧化劑的存在下使上述第1態樣至第3態樣中任一態樣所述之導電性聚合物前驅物聚合，製造具有下述通式(1-A)所表示的重複單元的苯胺系導電性聚合物(a)。 According to a sixteenth aspect of the present invention, there is provided a method of producing a conductive polymer precursor according to any one of the first aspect to the third aspect in the presence of an oxidizing agent, which has the following properties. An aniline-based conductive polymer (a) of a repeating unit represented by the formula (1-A).

式(1-A)中，R¹、R³及R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分 支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 In the formula (1-A), R ¹ , R ³ and R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a linear or branched alkoxy group having 1 to 24 carbon atoms. In the group consisting of a group, an acidic group or a salt thereof, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.

式(1)及式(1-A)中的R¹較佳為氫原子、碳數1~10的直鏈或分支的烷基，更佳為氫原子、碳數1~3的直鏈或分支的烷基，特佳為氫原子。 R ¹ in the formula (1) and the formula (1-A) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a linear chain having 1 to 3 carbon atoms or Branched alkyl groups, particularly preferably hydrogen atoms.

式(1)及式(1-A)中的R²較佳為氫原子、碳數1~10的直鏈或分支的烷基，更佳為氫原子、碳數1~3的直鏈或分支的烷基，特佳為氫原子。 R ² in the formula (1) and the formula (1-A) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a linear chain having 1 to 3 carbon atoms or Branched alkyl groups, particularly preferably hydrogen atoms.

式(1)及式(1-A)中的R³較佳為氫原子、碳數1~10的直鏈或分支的烷基，更佳為氫原子、碳數1~3的直鏈或分支的烷基，特佳為氫原子。 R ³ in the formula (1) and the formula (1-A) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a linear chain having 1 to 3 carbon atoms or Branched alkyl groups, particularly preferably hydrogen atoms.

式(1)及式(1-A)中的R⁴較佳為氫原子、碳數1~24的直鏈或分支的烷基、碳數1~10的直鏈或分支的烷氧基，更佳為碳數1~10的直鏈或分支的烷氧基，特佳為碳數1~5的直鏈或分支的烷氧基。 R ⁴ in the formula (1) and the formula (1-A) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. More preferably, it is a linear or branched alkoxy group having 1 to 10 carbon atoms, particularly preferably a linear or branched alkoxy group having 1 to 5 carbon atoms.

式(1)及式(1-A)中的A為酸性基或其鹽，較佳為羧基、磺酸基或其鹽，更佳為磺酸基或其鹽。 A in the formula (1) and the formula (1-A) is an acidic group or a salt thereof, preferably a carboxyl group, a sulfonic acid group or a salt thereof, more preferably a sulfonic acid group or a salt thereof.

式(1)及式(1-A)中的n較佳為1~10，更佳為1~6，進而佳為1~3，特佳為1或2。 The n in the formula (1) and the formula (1-A) is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 3, particularly preferably from 1 or 2.

本發明的導電性聚合物前驅物適合作為具有高的導電性、且熱穩定性優異的導電性聚合物的前驅物。 The conductive polymer precursor of the present invention is suitable as a precursor of a conductive polymer having high conductivity and excellent thermal stability.

另外，本發明的導電性聚合物具有高的導電性，且熱穩定性優異。 Further, the conductive polymer of the present invention has high conductivity and is excellent in thermal stability.

另外，藉由使用本發明的導電性聚合物、導電性組成物，可製造具備等效串聯電阻低、耐熱性優異的高導電率的固體電解層的固體電解電容器。 In addition, by using the conductive polymer or the conductive composition of the present invention, a solid electrolytic capacitor having a solid electrolytic layer having a low equivalent series resistance and high heat resistance and excellent in electrical conductivity can be produced.

以下，對本發明加以詳細說明。 Hereinafter, the present invention will be described in detail.

[導電性聚合物前驅物] [conductive polymer precursor]

本發明的導電性聚合物前驅物為下述通式(1)所表示的化合物(以下稱為「化合物(1)」)。 The conductive polymer precursor of the present invention is a compound represented by the following formula (1) (hereinafter referred to as "compound (1)").

再者，於本發明中所謂「導電性」，是指膜厚為約0.1 μm的塗膜具有10¹⁴ Ω/□以下的表面電阻值。 In the present invention, the term "electrical conductivity" means that the coating film having a film thickness of about 0.1 μm has a surface resistance value of 10 ¹⁴ Ω/□ or less.

式(1)中，R¹~R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中。 In the formula (1), R ¹ to R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group or It is a group consisting of a salt, a hydroxyl group, a nitro group and a halogen atom.

烷基例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基等。 Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like.

烷氧基例如可列舉：甲氧基、乙氧基、正丙氧基、異 丙氧基、正丁氧基、第二丁氧基、第三丁氧基、戊氧基、己氧基等。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, and a different group. Propyloxy, n-butoxy, second butoxy, tert-butoxy, pentyloxy, hexyloxy and the like.

酸性基可列舉磺酸基、羧基等。 The acidic group may, for example, be a sulfonic acid group or a carboxyl group.

該些基分別能以酸的狀態(-SO₃H、-COOH)而含有，亦能以離子的狀態而含有。 These groups can be contained in an acid state (-SO ₃ H, -COOH), and can also be contained in an ion state.

該些基中，特別就可提高對水的親和性、且製成導電性聚合物時可表現出更高的導電性的觀點而言，較佳為磺酸基或羧基，更佳為磺酸基。 Among these, in particular, a sulfonic acid group or a carboxyl group, more preferably a sulfonic acid, is preferred from the viewpoint of improving the affinity for water and exhibiting higher conductivity when the conductive polymer is formed. base.

酸性基的鹽表示酸性基的鹼金屬鹽、鹼土金屬鹽、銨鹽、經取代銨鹽的至少一種。 The acid group salt means at least one of an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and a substituted ammonium salt of an acidic group.

鹼金屬例如可列舉鋰、鈉、鉀等。 Examples of the alkali metal include lithium, sodium, potassium, and the like.

鹼土金屬例如可列舉鎂、鈣等。 Examples of the alkaline earth metal include magnesium, calcium, and the like.

經取代銨例如可列舉脂式銨類、環式飽和銨類、環式不飽和銨類等。 Examples of the substituted ammonium include aliphatic ammonium salts, cyclic saturated ammonium compounds, and cyclic unsaturated ammonium compounds.

上述脂式銨類可列舉下式通式(III)所表示的銨。 The above-mentioned aliphatic ammonium compound can be exemplified by the ammonium represented by the following formula (III).

式(III)中，R⁵~R⁸分別獨立為氫原子或碳數1~4的烷基。 In the formula (III), R ⁵ to R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

此種脂式銨類具體可例示：甲基銨、二甲基銨、三甲基銨、乙基銨、二乙基銨、三乙基銨、甲基乙基銨、二乙基甲基銨、二甲基乙基銨、丙基銨、二丙基銨、異丙基銨、二異丙基銨、丁基銨、二丁基銨、甲基丙基銨、乙基丙基銨、甲基異丙基銨、乙基異丙基銨、甲基丁基銨、乙基丁基銨、四甲基銨、四羥甲基銨、四乙基銨、四正丁基銨、四第二丁基銨、四第三丁基銨等。該些脂式銨中，就溶解性的觀點而言，最佳為R⁵~R⁸中的一個為氫原子、其餘三個為碳數1~4的烷基的情形，其次較佳為R⁵~R⁸中的兩個為氫原子、其餘兩個為碳數1~4的烷基的情形。 Specific examples of such aliphatic ammonium salts include methyl ammonium, dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methyl ethyl ammonium, and diethyl methyl ammonium. , dimethylethyl ammonium, propyl ammonium, dipropyl ammonium, isopropyl ammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium, methylpropyl ammonium, ethylpropyl ammonium, A Isopropylammonium, ethyl isopropylammonium, methylbutylammonium, ethylbutylammonium, tetramethylammonium, tetrahydroxymethylammonium, tetraethylammonium, tetra-n-butylammonium, tetra-second Butyl ammonium, tetra-tert-butyl ammonium, and the like. Among the above-mentioned aliphatic ammonium, from the viewpoint of solubility, it is preferred that one of R ⁵ to R ⁸ is a hydrogen atom and the other three are an alkyl group having 1 to 4 carbon atoms, and secondarily, R is preferable. Two of ⁵ to R ⁸ are hydrogen atoms, and the other two are alkyl groups having 1 to 4 carbon atoms.

環式飽和銨類例如可列舉：哌啶鎓、吡咯啶鎓、嗎啉鎓、哌嗪鎓及具有該些骨架的衍生物等。 Examples of the cyclic saturated ammonium compound include piperidinium, pyrrolidinium, morpholinium, piperazinium, and derivatives having such skeletons.

環式不飽和銨類例如可列舉：吡啶鎓、α-甲基吡啶鎓、β-甲基吡啶鎓、γ-甲基吡啶鎓、喹啉鎓、異喹啉鎓、吡咯啉鎓及具有該些骨架的衍生物等。 Examples of the cyclic unsaturated ammonium compound include pyridinium, α-methylpyridinium, β-methylpyridinium, γ-methylpyridinium, quinolinium, isoquinolinium, pyrroline and some of these. Derivatives of the skeleton, etc.

鹵素原子可列舉氟原子、氯原子、溴原子、碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

另外，式(1)中，A為酸性基或其鹽。 Further, in the formula (1), A is an acidic group or a salt thereof.

此處，所謂「酸性基」，是指磺酸基、羧基。 Here, the "acid group" means a sulfonic acid group or a carboxyl group.

酸性基及酸性基的鹽可列舉上文R¹~R⁴的說明中例示的酸性基及酸性基的鹽。其中，特別就提高對水的親和性、且製成導電性聚合物可表現出更高的導電性的觀點而言，A較佳為磺酸基或其鹽。 Examples of the acidic group and the acidic group include the acidic group and the acidic group exemplified in the above description of R ¹ to R ⁴ . Among them, A is preferably a sulfonic acid group or a salt thereof from the viewpoint of improving the affinity for water and producing a conductive polymer which exhibits higher conductivity.

另外，式(1)中，n為1~20的整數。若n為1以上，則可獲得熱穩定性優異的導電性聚合物。 Further, in the formula (1), n is an integer of 1 to 20. When n is 1 or more, a conductive polymer excellent in thermal stability can be obtained.

n較佳為1~10，更佳為1~6，進而佳為1~3，特佳為1或2。 n is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 3, and particularly preferably from 1 or 2.

作為化合物(1)，就導電性聚合物的熱穩定性提高、且化合物(1)的製造容易的觀點而言，較佳為R²為氫原子，R¹、R³、R⁴中的至少一個為碳數1~24的直鏈或分支的烷氧基，其中特佳為R²為氫原子，R¹、R³、R⁴中的一個為碳數1~24的直鏈或分支的烷氧基，其餘為氫原子。 From the viewpoint of improving the thermal stability of the conductive polymer and facilitating the production of the compound (1), the compound (1) preferably has R ² as a hydrogen atom and at least R ¹ , R ³ and R ⁴ . a linear or branched alkoxy group having a carbon number of 1 to 24, wherein particularly preferably R ² is a hydrogen atom, and one of R ¹ , R ³ and R ⁴ is a linear or branched carbon number of 1 to 24. Alkoxy, the remainder being a hydrogen atom.

化合物(1)例如可藉由以下所示的(a)步驟及(b)步驟來製造。 The compound (1) can be produced, for example, by the steps (a) and (b) shown below.

(a)步驟：將下述通式(2)所表示的化合物(以下稱為「化合物(2)」)磺化或羧化，獲得下述通式(3)所表示的化合物(以下稱為「化合物(3)」)的步驟。 (a) Step: Sulfonated or carboxylated a compound represented by the following formula (2) (hereinafter referred to as "compound (2)") to obtain a compound represented by the following formula (3) (hereinafter referred to as The procedure of "compound (3)").

(b)步驟：將化合物(3)還原，獲得化合物(1)的步驟。 (b) Step: a step of reducing the compound (3) to obtain the compound (1).

通式(3)中，R¹~R⁴、A及n與通式(1)中的R¹~R⁴、A及n相同。另外，通式(2)中的D為具有脫離性的取代基，只要為藉由(a)步驟的反應而轉化為A的基即可，具體而言，例如可列舉：氯原子、溴原子、碘原 子等鹵素原子，甲磺醯基，甲苯磺醯基等。 Formula (3), R ¹ ~ R ^4, A and n in the general formula (1) R ¹ ~ R ^4, A and n are the same. In addition, D in the general formula (2) is a substituent having a detachment property, and may be a group which is converted into A by the reaction of the step (a), and specific examples thereof include a chlorine atom and a bromine atom. A halogen atom such as an iodine atom, a methanesulfonyl group or a toluenesulfonyl group.

以下，對各步驟加以詳細說明。再者，以下所示的方法為製造化合物(1)中A為磺酸基的鹼金屬鹽、銨鹽或經取代銨鹽的化合物(以下稱為「化合物(1-1)」)或者A為磺酸基的化合物(以下稱為「化合物(1-2)」)的方法。 Hereinafter, each step will be described in detail. Further, the method shown below is a method for producing an alkali metal salt, an ammonium salt or a substituted ammonium salt of a compound (1) in which A is a sulfonic acid group (hereinafter referred to as "compound (1-1)") or A is A method of a sulfonic acid group compound (hereinafter referred to as "compound (1-2)").

另外，以下所示的反應式中，M為鹼金屬、銨或經取代銨。 Further, in the reaction formula shown below, M is an alkali metal, ammonium or substituted ammonium.

<化合物(1-1)的製造> <Manufacture of Compound (1-1)>

((a)步驟) ((a) step)

(a)步驟具有以下所示的(a-1)步驟。 The step (a) has the step (a-1) shown below.

(a-1)步驟：於溶劑中使化合物(2)與磺化劑(M₂SO₃)反應，獲得下述通式(3-1)所表示的化合物(以下稱為「化合物(3-1)」)的步驟。 (a-1) Step: reacting the compound (2) with a sulfonating agent (M ₂ SO ₃ ) in a solvent to obtain a compound represented by the following formula (3-1) (hereinafter referred to as "compound (3- 1)") steps.

化合物(2)與磺化劑的反應比例(mol比)較佳為1：0.5~1：5。若磺化劑過少，則反應難以完成。若磺化劑過多，則必須將未反應的磺化劑去除，費工或耗費製造成本。 The reaction ratio (mol ratio) of the compound (2) to the sulfonating agent is preferably from 1:0.5 to 1:5. If the sulfonating agent is too small, the reaction is difficult to complete. If the sulfonating agent is too much, the unreacted sulfonating agent must be removed, labor or cost.

反應溫度較佳為0℃以上，反應時間較佳為0.5小時 ~12小時。 The reaction temperature is preferably 0 ° C or more, and the reaction time is preferably 0.5 hour. ~12 hours.

磺化劑可列舉：亞硫酸鈉、亞硫酸鉀、亞硫酸鋰、亞硫酸銨、亞硫酸氫鈉、亞硫酸氫鉀等。 Examples of the sulfonating agent include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, and the like.

溶劑可列舉：水；甲醇、乙醇、丙醇等醇類；四氫呋喃、1,4-二噁烷、1,2-二甲氧基乙烷、二異丙醚等醚類；二甲基甲醯胺、二甲基乙醯胺等醯胺類等。該些溶劑可單獨使用一種，或亦可混合使用兩種以上。 Examples of the solvent include water; alcohols such as methanol, ethanol, and propanol; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and diisopropyl ether; and dimethylformamidine; Amidoxime such as amine or dimethylacetamide. These solvents may be used alone or in combination of two or more.

((b)步驟) ((b) steps)

於(b)步驟中，將化合物(3-1)還原而獲得化合物(1-1)。 In the step (b), the compound (3-1) is reduced to obtain the compound (1-1).

(b)步驟中的反應條件只要為對硝基的通常的還原條件，則並無特別限定。具體可列舉：使用鈀碳、雷氏鎳等還原劑的催化氫化，或於酸性條件下使用鋅粉或錫等還原劑的還原等方法。 The reaction conditions in the step (b) are not particularly limited as long as they are normal reducing conditions for the nitro group. Specific examples thereof include catalytic hydrogenation using a reducing agent such as palladium carbon or Raney nickel, or reduction using a reducing agent such as zinc powder or tin under acidic conditions.

<化合物(1-2)的製造> <Manufacture of Compound (1-2)>

((a)步驟) ((a) step)

(a)步驟具有以下所示的(a-1)步驟及(a-2)步驟。 The step (a) has the steps (a-1) and (a-2) shown below.

(a-1)步驟：於溶劑中使化合物(2)與磺化劑反應，獲得化合物(3-1)的步驟。 (a-1) Step: a step of reacting the compound (2) with a sulfonating agent in a solvent to obtain a compound (3-1).

(a-2)步驟：將化合物(3-1)質子化，獲得下述通式(3-2)所表示的化合物(以下稱為「化合物(3-2)」)的步驟。 (a-2) Step: The step of protonating the compound (3-1) to obtain a compound represented by the following formula (3-2) (hereinafter referred to as "compound (3-2)").

(a-1)步驟：(a-1)步驟與化合物(1-1)的製造步驟中所含有的(a-1)步驟相同。 (a-1) Step: The step (a-1) is the same as the step (a-1) contained in the production step of the compound (1-1).

(a-2)步驟：(a-2)步驟為將化合物(3-1)中的磺酸基的鹽質子化而成為磺酸基的步驟，(a-2)步驟中的質子化條件只要為通常的質子化條件，則並無特別限定，化合物(3-1)與用於質子化的試劑(質子化劑)的反應比例(mol比)較佳為1：0.5~1：10。若質子化劑過少，則反應難以完成。若質子化劑過多，則必須將未反應的質子化劑去除，費工 或耗費製造成本。 (a-2) Step: The step (a-2) is a step of protonating a salt of a sulfonic acid group in the compound (3-1) to form a sulfonic acid group, and the protonation conditions in the step (a-2) are as long as The normal protonation conditions are not particularly limited, and the reaction ratio (mol ratio) of the compound (3-1) to the reagent (protonating agent) for protonation is preferably 1:0.5 to 1:10. If the amount of the protonating agent is too small, the reaction is difficult to complete. If there are too many protonating agents, the unreacted protonating agent must be removed, and labor is required. Or cost of manufacturing.

反應溫度較佳為0℃以上，反應時間較佳為0.5小時~12小時。 The reaction temperature is preferably 0 ° C or more, and the reaction time is preferably 0.5 hour to 12 hours.

質子化劑可列舉：硫酸、鹽酸、硝酸、磷酸等無機酸；甲磺酸、三氟甲磺酸等有機酸等。 Examples of the protonating agent include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; and organic acids such as methanesulfonic acid and trifluoromethanesulfonic acid.

((b)步驟) ((b) steps)

於(b)步驟中，將化合物(3-2)還原而獲得化合物(1-2)。 In the step (b), the compound (3-2) is reduced to obtain a compound (1-2).

(b)步驟與化合物(1-1)的製造步驟所含的(b)步驟相同。 The step (b) is the same as the step (b) contained in the production step of the compound (1-1).

再者，(a)步驟中所用的化合物(2)可使用市售品，亦可使用合成品。於使用合成品作為化合物(2)的情形時，化合物(2)例如是經由以下所示的(c)步驟而獲得。 Further, as the compound (2) used in the step (a), a commercially available product may be used, or a synthetic product may be used. When a synthetic product is used as the compound (2), the compound (2) is obtained, for example, via the step (c) shown below.

(c)步驟：將下述通式(4)所表示的化合物(以下稱為「化合物(4)」)鹵化、甲磺醯化或甲苯磺醯化等，獲得化合物(2)的步驟。 (c) Step: a step of obtaining a compound (2) by halogenating a compound represented by the following formula (4) (hereinafter referred to as "the compound (4)"), methanesulfonation or toluenesulfonation.

[化13] [Chemistry 13]

(c)步驟為將化合物(4)中的羥基(醇)取代為取代基(D)的步驟，(c)步驟中的反應條件只要為對醇的通常的鹵化條件、甲磺醯化條件或甲苯磺醯化條件，則並無特別限定。 The step (c) is a step of substituting a hydroxyl group (alcohol) in the compound (4) into the substituent (D), and the reaction conditions in the step (c) are as long as the usual halogenation conditions for the alcohol, the methanesulfonation conditions or The toluene sulfonation conditions are not particularly limited.

另外，作為(c)步驟中所用的試劑，於將醇鹵化的情形時，可列舉：亞硫醯氯、磺醯氯、三氯化磷、五氯化磷、三溴化磷、五溴化磷、氯化氫、溴化氫、碘化氫、N-氯琥珀醯亞胺、N-溴琥珀醯亞胺等。另外，於將醇甲磺醯化的情形時，可列舉甲磺醯氯等。另外，於將醇甲苯磺醯化的情形時，可列舉對甲苯磺醯氯等。 Further, as the reagent used in the step (c), in the case of halogenating the alcohol, sulfinium chloride, sulfonium chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, pentabromide may be mentioned. Phosphorus, hydrogen chloride, hydrogen bromide, hydrogen iodide, N-chlorosuccinimide, N-bromosuccinimide, and the like. Further, in the case of the methanesulfonyl group, methanesulfonyl chloride or the like can be mentioned. Further, in the case where the alcohol toluene is sulfonated, p-toluenesulfonyl chloride or the like is exemplified.

再者，化合物(2)中R⁴為R^4'(烷氧基)、R¹~R³為氫原子且D為D²(鹵素原子)的化合物(以下稱為「化合物(2-1)」)例如亦可藉由以下方式獲得：將下述通式(5)所表示的化合物(以下稱為「化合物(5)」)鹵烷基化。 Further, in the compound (2), R ⁴ is a compound of R ^{4 '} (alkoxy group), R ¹ to R ³ are a hydrogen atom, and D is D ² (halogen atom) (hereinafter referred to as "compound (2-1)" For example, it can be obtained by halogenating a compound represented by the following formula (5) (hereinafter referred to as "compound (5)").

[化14] [Chemistry 14]

化合物(5)與用於鹵烷基化的試劑(鹵烷基化劑)的反應比例(mol比)較佳為1：0.5~1：10。若鹵烷基化劑過少，則反應難以完成。若鹵烷基化劑過多，則容易生成副產物，必須於反應後將副產物去除，費工或耗費製造成本。 The reaction ratio (mol ratio) of the compound (5) to the reagent (halogen alkylating agent) for haloalkylation is preferably from 1:0.5 to 1:10. If the amount of the haloalkylating agent is too small, the reaction is difficult to complete. If the amount of the haloalkylating agent is too large, by-products are easily formed, and by-products must be removed after the reaction, which is labor-intensive or costly to produce.

反應溫度較佳為-10℃以上，反應時間較佳為0.5小時~24小時。 The reaction temperature is preferably -10 ° C or more, and the reaction time is preferably 0.5 to 24 hours.

鹵烷基化劑例如可列舉：氯甲氧基甲烷、氯甲氧基乙烷、氯甲氧基丙烷、氯化氫與福馬林的混合物等。 Examples of the haloalkylating agent include chloromethoxymethane, chloromethoxyethane, chloromethoxypropane, a mixture of hydrogen chloride and formalin, and the like.

如此而獲得的本發明的導電性聚合物前驅物中，酸性基或其鹽(相當於化合物(1)中的A)經由特定碳數的伸烷基而鍵結於芳香環。 In the conductive polymer precursor of the present invention thus obtained, an acidic group or a salt thereof (corresponding to A in the compound (1)) is bonded to the aromatic ring via a specific alkyl group alkyl group.

再者，由於酸性基具有吸電子性，故與酸性基鍵結的不飽和碳原子上的電子密度下降，結果若進行加熱，則酸性基與碳原子的鍵結容易被切斷。 Further, since the acidic group has an electron-withdrawing property, the electron density on the unsaturated carbon atom bonded to the acidic group decreases, and as a result, when heated, the bond between the acidic group and the carbon atom is easily cut.

因此一般認為，於如上述2-胺基苯甲醚-4-磺酸般將酸性基直接鍵結於芳香環的化合物進行聚合所得的導電性聚合物的情形時，若進行加熱處理，則酸性基與碳原子的鍵結被切斷而酸性基脫離，導電性下降。 Therefore, in the case of a conductive polymer obtained by polymerizing a compound in which an acidic group is directly bonded to an aromatic ring as in the above 2-aminoanisole-4-sulfonic acid, it is considered to be acidic when subjected to heat treatment. The bond between the group and the carbon atom is cleaved and the acidic group is detached, and the conductivity is lowered.

然而，若為本發明的導電性聚合物前驅物，則如上述般酸性基或其鹽經由伸烷基而鍵結於芳香環。因此一般認為，與酸性基直接鍵結於芳香環的情形相比較，與伸烷基鍵結的芳香環上的碳原子不易受到吸電子性的影響，減輕電子密度的下降。因此，使用本發明的導電性聚合物前驅物的導電性聚合物即便進行加熱處理，酸性基亦不易脫離，可維持導電性。特別是若為上述通式(1)中R²為氫原子且R¹、R³、R⁴中的至少一個為烷氧基的導電性聚合物前驅物，更佳為R²為氫原子並且R¹、R³、R⁴中的一個為烷氧基且其餘為氫原子的導電性聚合物前驅物，則可獲得能表現出更高的導電性的導電性聚合物。 However, in the case of the conductive polymer precursor of the present invention, the acidic group or a salt thereof is bonded to the aromatic ring via an alkyl group as described above. Therefore, it is considered that, compared with the case where the acidic group is directly bonded to the aromatic ring, the carbon atom on the aromatic ring bonded to the alkyl group is less susceptible to electron-withdrawing properties, and the decrease in electron density is reduced. Therefore, even if the conductive polymer using the conductive polymer precursor of the present invention is subjected to heat treatment, the acidic group is not easily detached, and conductivity can be maintained. In particular, in the case of the conductive polymer precursor in which R ² in the above formula (1) is a hydrogen atom and at least one of R ¹ , R ³ and R ⁴ is an alkoxy group, it is more preferred that R ² is a hydrogen atom and When a conductive polymer precursor in which one of R ¹ , R ³ and R ⁴ is an alkoxy group and the balance is a hydrogen atom, a conductive polymer which exhibits higher conductivity can be obtained.

因此，本發明的導電性聚合物前驅物適合作為具有高的導電性、且熱穩定性優異的導電性聚合物的前驅物(原料)。 Therefore, the conductive polymer precursor of the present invention is suitable as a precursor (raw material) of a conductive polymer having high conductivity and excellent thermal stability.

[導電性聚合物(苯胺系導電性聚合物(a))] [Electroconductive polymer (aniline-based conductive polymer (a))]

本發明的導電性聚合物(亦稱為苯胺系導電性聚合物(a))是使含有本發明的導電性聚合物前驅物的苯胺系單體成分聚合而獲得，具有下述通式(1-A)所表示的重複單元。 The conductive polymer (also referred to as an aniline-based conductive polymer (a)) of the present invention is obtained by polymerizing an aniline-based monomer component containing the conductive polymer precursor of the present invention, and has the following general formula (1) -A) Representation of the repeating unit.

[化15] [化15]

式(1-A)中，R¹、R³及R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 In the formula (1-A), R ¹ , R ³ and R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a linear or branched alkoxy group having 1 to 24 carbon atoms. In the group consisting of a group, an acidic group or a salt thereof, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.

特別就導電性或可溶性的觀點而言，n較佳為1~10，更佳為1~5，特佳為1~3。 Particularly, from the viewpoint of conductivity or solubility, n is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3.

一般認為其原因在於：藉由在酸性基與芳香環之間***間隔物，可抑制由加熱導致的酸性基的脫離。 The reason for this is considered to be that the detachment of the acidic group due to heating can be suppressed by inserting a spacer between the acidic group and the aromatic ring.

苯胺系導電性聚合物含有本發明的導電性聚合物前驅物作為必需成分，作為上述通式(1-A)所表示的以外的結構單元(單體成分)，只要不對可溶性、導電性及特性造成影響，則亦可含有選自由經取代或未經取代的苯胺(其他苯胺系單體)、噻吩、吡咯、伸苯基、伸乙烯基、其他二價不飽和基及二價飽和基所組成的組群中的至少一種結構單元(單體成分)。 The aniline-based conductive polymer contains the conductive polymer precursor of the present invention as an essential component, and the structural unit (monomer component) other than the above-described general formula (1-A) is not soluble, conductive, or characteristic. The effect may also be selected from the group consisting of substituted or unsubstituted aniline (other aniline monomers), thiophene, pyrrole, phenylene, vinyl, other divalent unsaturated groups and divalent saturated groups. At least one structural unit (monomer component) in the group.

於苯胺系單體成分100質量%中，導電性聚合物前驅物的含量較佳為1質量%~100質量%，更佳為10質量% ~100質量%，容易獲得具有高的導電性、且熱穩定性優異的導電性聚合物。 The content of the conductive polymer precursor is preferably from 1% by mass to 100% by mass, more preferably 10% by mass, based on 100% by mass of the aniline monomer component. ~100% by mass, a conductive polymer having high conductivity and excellent thermal stability can be easily obtained.

於本發明的苯胺系導電性聚合物中，就提高可溶性的觀點而言，較佳為含有70%以上的上述通式(1-A)的重複單元，即酸性基相對於芳香環的含有率為70%以上，更佳為含有80%以上，特佳為含有90%以上。此處，酸性基相對於芳香環的含有率為70%以下者於水中的溶解性不充分而欠佳。另外，酸性基相對於芳香環的含有率越高，溶解性越提高而越適於製造電容器。 In the aniline-based conductive polymer of the present invention, in order to improve the solubility, it is preferred to contain 70% or more of the repeating unit of the above formula (1-A), that is, the content ratio of the acidic group to the aromatic ring. It is 70% or more, more preferably 80% or more, and particularly preferably 90% or more. Here, the solubility of the acidic group with respect to the aromatic ring is 70% or less, and the solubility in water is insufficient and it is unpreferable. Further, the higher the content of the acidic group relative to the aromatic ring, the more the solubility is improved, and the more suitable the capacitor is.

再者，導電性聚合物前驅物可單獨使用一種，亦可於相當於通式(1-A)的範圍內以任意比例將不同的兩種以上混合使用。 Further, the conductive polymer precursor may be used singly or in combination of two or more kinds in any ratio corresponding to the formula (1-A).

關於上述苯胺系導電性聚合物的重量平均分子量，就導電性、成膜性及膜強度的觀點而言，以聚苯乙烯磺酸鈉換算計較佳為3000~50萬，更佳為5000~20萬，特佳為7000~10萬。 The weight average molecular weight of the aniline-based conductive polymer is preferably from 3,000 to 500,000, more preferably from 5,000 to 20,000, in terms of conductivity, film formability, and film strength, in terms of sodium polystyrene sulfonate. Ten thousand, especially good for 7,000 to 100,000.

此處，於重量平均分子量為3000以下的情形時，雖然溶解性優異但成膜性及導電性不足，於為50萬以上的情形時，溶解性及向多孔質成形體中的含浸性不充分。 When the weight average molecular weight is 3,000 or less, the solubility is excellent, but the film formability and the conductivity are insufficient. When the weight average molecular weight is 500,000 or less, the solubility and the impregnation property in the porous molded body are insufficient. .

另外，固體電解電容器的導電率越良好，則頻率特性等性能越良好，故可使用導電率為0.01 S/cm以上、較佳為0.05 S/cm以上的可溶性導電性聚合物。 Further, the better the conductivity of the solid electrolytic capacitor, the better the performance such as frequency characteristics, and therefore a soluble conductive polymer having a conductivity of 0.01 S/cm or more, preferably 0.05 S/cm or more can be used.

其他苯胺系單體只要為可與本發明的導電性聚合物前驅物共聚合的苯胺系單體，則並無特別限定，例如可列舉： 苯胺、甲基苯胺、二甲基苯胺、三甲基苯胺、四甲基苯胺、乙基苯胺、二乙基苯胺、三乙基苯胺、四乙基苯胺、丙基苯胺、二丙基苯胺、三丙基苯胺、四丙基苯胺、丁基苯胺、二丁基苯胺、三丁基苯胺、四丁基苯胺、甲氧基苯胺、二甲氧基苯胺、三甲氧基苯胺、四甲氧基苯胺、乙氧基苯胺、二乙氧基苯胺、三乙氧基苯胺、四乙氧基苯胺、溴苯胺、氯苯胺、氟苯胺、氰基苯胺、羥基苯胺、硝基苯胺、二溴苯胺、二氯苯胺、二氟苯胺、二氰基苯胺、二羥基苯胺、二硝基苯胺、二胺基苯、N-甲基苯胺、N-乙基苯胺、N-正丙基苯胺、N-異丙基苯胺、N-丁基苯胺、胺基苯磺酸、胺基苯二磺酸、胺基苯酚磺酸、胺基苯酚二磺酸、甲氧基苯胺磺酸、胺基安息香酸、胺基苯二羧酸、胺基苯磷酸、胺基苯二磷酸、胺基苯磺醯胺、胺基苯硫醇、胺基苯甲醯胺、乙醯甲苯胺、胺基苯乙酮、胺基苯硫醇、胺基氯苯酚、胺基萘、胺基萘磺酸、胺基萘羧酸、胺基萘磷酸、胺基硝基苯酚、胺基苯、胺基苯基苯酚、、胺基三氟甲基苯、胺基苄醇、胺基苯基硼酸、胺基甲酚、胺基吲哚、發光胺(luminol)等。 The other aniline-based monomer is not particularly limited as long as it is an aniline-based monomer copolymerizable with the conductive polymer precursor of the present invention, and examples thereof include aniline, methylaniline, dimethylaniline, and trimethyl. Aniline, tetramethylaniline, ethylaniline, diethylaniline, triethylaniline, tetraethylaniline, propylaniline, dipropylaniline, tripropylaniline, tetrapropylaniline, butylaniline, two Butylaniline, tributylaniline, tetrabutylaniline, methoxyaniline, dimethoxyaniline, trimethoxyaniline, tetramethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxy Aniline, tetraethoxyaniline, bromoaniline, chloroaniline, fluoroaniline, cyanoaniline, hydroxyaniline, nitroaniline, dibromoaniline, dichloroaniline, difluoroaniline, dicyanoaniline, dihydroxyaniline, Dinitroaniline, diaminobenzene, N-methylaniline, N-ethylaniline, N-n-propylaniline, N-isopropylaniline, N-butylaniline, aminobenzenesulfonic acid, amine Phenyl disulfonic acid, aminophenol sulfonic acid, aminophenol phenol disulfonic acid, methoxyaniline sulfonic acid, amine ketone Aromatic acid, amino benzene dicarboxylic acid, amino phenyl phosphonic acid, amino benzene diphosphate, amino benzene sulfonamide, amino phenyl thiol, amino benzamide, acetamidine, amino phenyl Ketone, amino phenyl thiol, amino chlorophenol, amino naphthalene, amino naphthalene sulfonic acid, amino naphthalene carboxylic acid, amino naphthyl phosphate, amino nitrophenol, amino benzene, amino phenyl phenol, Aminotrifluoromethylbenzene, aminobenzyl alcohol, aminophenylboronic acid, aminocresol, aminoguanidine, luminol, and the like.

於苯胺系單體成分100質量%中，其他苯胺系單體的含量較佳為0質量%~99質量%，更佳為0質量%~90質量%，容易獲得具有高的導電性、且熱穩定性優異的導電性聚合物。 In 100% by mass of the aniline monomer component, the content of the other aniline monomer is preferably from 0% by mass to 99% by mass, more preferably from 0% by mass to 90% by mass, and it is easy to obtain high conductivity and heat. A conductive polymer excellent in stability.

本發明的導電性聚合物的製造方法並無特別限定，可使用利用氧化劑的化學聚合法或電解聚合法等公知的製造 方法。 The method for producing the conductive polymer of the present invention is not particularly limited, and a known production such as a chemical polymerization method or an electrolytic polymerization method using an oxidizing agent can be used. method.

以下，對本發明的導電性聚合物的製造方法的一例加以具體說明。 Hereinafter, an example of the method for producing the conductive polymer of the present invention will be specifically described.

本發明的導電性聚合物例如是於聚合溶劑中藉由氧化劑使上述苯胺系單體成分聚合所得。 The conductive polymer of the present invention is obtained, for example, by polymerizing the above aniline monomer component with an oxidizing agent in a polymerization solvent.

本發明中所用的苯胺系單體具有磺醯基及/或羧基，此種經酸性基取代苯胺系單體較佳為選自由經酸性基取代苯胺、其鹼金屬鹽、鹼土金屬鹽、銨鹽及經取代銨鹽所組成的組群中的化合物。 The aniline monomer used in the present invention has a sulfonyl group and/or a carboxyl group, and the acid group-substituted aniline monomer is preferably selected from the group consisting of an acid group-substituted aniline, an alkali metal salt thereof, an alkaline earth metal salt, and an ammonium salt. And a compound in the group consisting of substituted ammonium salts.

另外，作為酸性基取代苯胺系單體，若考慮到表現出優異的導電性、且提高水溶性的方面，則較佳為通式(1)所表示的化合物。 In addition, the acid group-substituted aniline monomer is preferably a compound represented by the formula (1) in view of exhibiting excellent conductivity and improving water solubility.

<氧化劑> <oxidant>

氧化劑例如可列舉：過氧二硫酸、過氧二硫酸銨、過氧二硫酸鈉、過氧二硫酸鉀等過氧二硫酸類；過氧化氫等。 Examples of the oxidizing agent include peroxydisulfuric acid such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxydisulfate; and hydrogen peroxide.

該些氧化劑可單獨使用一種，亦能以任意比例混合使用兩種以上。 These oxidizing agents may be used alone or in combination of two or more kinds in any ratio.

相對於苯胺系單體成分1 mol，氧化劑的使用量較佳為1 mol~5 mol，更佳為1 mol~3 mol。若氧化劑的使用量為上述範圍內，則可充分進行導電性聚合物的高分子量化或主鏈的氧化。 The amount of the oxidizing agent is preferably from 1 mol to 5 mol, more preferably from 1 mol to 3 mol, based on 1 mol of the aniline monomer component. When the amount of the oxidizing agent used is within the above range, the polymerizable polymer can be sufficiently polymerized or the main chain can be oxidized.

再者，將作為觸媒的鐵、銅等過渡金屬化合物與氧化劑併用亦有效。 Further, it is also effective to use a transition metal compound such as iron or copper as a catalyst in combination with an oxidizing agent.

<聚合溶劑> <Polymer solvent>

聚合溶劑可列舉水或有機溶劑。有機溶劑例如可列舉：甲醇、乙醇、異丙醇、丙醇、丁醇等醇類；丙酮、乙基異丁基酮等酮類；乙二醇、乙二醇甲醚等乙二醇類；丙二醇、丙二醇甲醚、丙二醇***、丙二醇丁醚、丙二醇丙醚等丙二醇類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；N-甲基吡咯烷酮、N-乙基吡咯烷酮等吡咯烷酮類等。 The polymerization solvent may, for example, be water or an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, propanol, and butanol; ketones such as acetone and ethyl isobutyl ketone; and ethylene glycols such as ethylene glycol and ethylene glycol methyl ether; Propylene glycol such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether; amides such as N,N-dimethylformamide, N,N-dimethylacetamide; N-methyl Pyrrolidone such as pyrrolidone or N-ethylpyrrolidone.

聚合溶劑較佳為水、或水與有機溶劑的混合溶劑。 The polymerization solvent is preferably water or a mixed solvent of water and an organic solvent.

<聚合步驟> <polymerization step>

藉由氧化劑將上述苯胺系單體成分於聚合溶劑中進行化學氧化聚合，藉此獲得導電性聚合物(聚合步驟)。 The aniline monomer component is subjected to chemical oxidative polymerization in a polymerization solvent by an oxidizing agent to obtain a conductive polymer (polymerization step).

具體而言，可藉由以下各種方法獲得導電性聚合物：於氧化劑溶液中滴加苯胺系單體成分溶液(前驅物溶液)的方法；於苯胺系單體成分溶液中滴加氧化劑溶液的方法；於反應容器等中同時滴加苯胺系單體成分溶液與氧化劑溶液的方法；於反應容器等中連續供給苯胺系單體成分溶液及氧化劑溶液，藉由推流(plug flow)使其聚合的方法等。 Specifically, a conductive polymer can be obtained by various methods: a method of dropping an aniline monomer component solution (precursor solution) into an oxidizing agent solution; and a method of dropping an oxidizing agent solution into an aniline monomer component solution a method of simultaneously adding an aniline monomer component solution and an oxidizing agent solution to a reaction container or the like; continuously supplying an aniline monomer component solution and an oxidizing agent solution to a reaction container or the like, and polymerizing the mixture by a plug flow; Method, etc.

聚合時，可使用上述聚合溶劑。 In the polymerization, the above polymerization solvent can be used.

另外，聚合時，亦可於反應系內添加質子酸。 Further, a protic acid may be added to the reaction system during the polymerization.

質子酸例如可列舉：鹽酸、硝酸、硫酸、氟硼酸等無機酸類；三氟甲磺酸等超強酸類；甲磺酸、十二烷基苯磺酸、甲苯磺酸、樟腦磺酸等有機磺酸類；及聚苯乙烯磺酸、聚丙烯酸、聚乙烯磺酸、聚-2-甲基丙烷-2-丙烯醯胺磺酸等 高分子酸類等。 Examples of the protic acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and fluoroboric acid; super acids such as trifluoromethanesulfonic acid; and organic sulfonates such as methanesulfonic acid, dodecylbenzenesulfonic acid, toluenesulfonic acid, and camphorsulfonic acid; Acids; and polystyrene sulfonic acid, polyacrylic acid, polyvinyl sulfonic acid, poly-2-methylpropane-2-propene decyl sulfonic acid, etc. Polymer acids and the like.

聚合反應的內溫較佳為50℃以下，更佳為-15℃~50℃，進而佳為-10℃~20℃。特別是若聚合反應的內溫為20℃以下，則可抑制副反應的進行、或由主鏈的氧化還原結構的變化導致的導電性下降。另外，若聚合反應的內溫為-15℃以上，則可維持充分的反應速度，可縮短反應時間。 The internal temperature of the polymerization reaction is preferably 50 ° C or lower, more preferably -15 ° C to 50 ° C, and further preferably -10 ° C to 20 ° C. In particular, when the internal temperature of the polymerization reaction is 20 ° C or lower, the progress of the side reaction or the decrease in conductivity due to the change of the redox structure of the main chain can be suppressed. Further, when the internal temperature of the polymerization reaction is -15 ° C or higher, a sufficient reaction rate can be maintained, and the reaction time can be shortened.

<純化步驟> <Purification step>

導電性聚合物是以溶解或分散於溶劑中的聚合物溶液的狀態而獲得。導電性聚合物可於去除溶劑後直接用於各種用途，但有時聚合物溶液中含有未反應的單體(苯胺系單體成分)、低聚物、雜質等。因此，較佳為將導電性聚合物純化後使用(純化步驟)。 The conductive polymer is obtained in a state of a polymer solution dissolved or dispersed in a solvent. The conductive polymer can be directly used for various purposes after removing the solvent, but the polymer solution may contain an unreacted monomer (aniline monomer component), an oligomer, an impurity, or the like. Therefore, it is preferred to use the conductive polymer after purification (purification step).

將導電性聚合物純化的方法可列舉使用溶劑的清洗法、膜過濾法、陽離子交換法等。 The method of purifying the conductive polymer includes a washing method using a solvent, a membrane filtration method, a cation exchange method, and the like.

如此而獲得的導電性聚合物是將含有本發明的導電性聚合物前驅物的苯胺系單體成分聚合而獲得。如上所述，本發明的導電性聚合物前驅物為酸性基或其鹽經由碳數1~20的伸烷基而鍵結於芳香環的單體，即便進行加熱處理，酸性基或其鹽亦不易脫離。因此，本發明的導電性聚合物具有高的導電性，且熱穩定性優異。因此，即便進行加熱處理亦可維持導電性。 The conductive polymer obtained in this manner is obtained by polymerizing an aniline monomer component containing the conductive polymer precursor of the present invention. As described above, the conductive polymer precursor of the present invention is a monomer in which an acidic group or a salt thereof is bonded to an aromatic ring via an alkyl group having 1 to 20 carbon atoms, and even if it is subjected to heat treatment, the acidic group or its salt is also Not easy to get rid of. Therefore, the conductive polymer of the present invention has high conductivity and is excellent in thermal stability. Therefore, the conductivity can be maintained even by heat treatment.

再者，一般認為，本發明的導電性聚合物具有下述通式(6)所表示的苯二胺結構(還原型)及苯醌二亞胺結構(氧化型)。 In addition, it is considered that the conductive polymer of the present invention has a phenylenediamine structure (reduced type) represented by the following formula (6) and a benzoquinone diimine structure (oxidized type).

式(6)中，R⁹~R²⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子(氟原子、氯原子、溴原子、碘原子)所組成的組群中，且R¹¹、R¹⁵、R¹⁹、R²³中的至少一個為-(CH₂)_n-A。此處，A為酸性基或其鹽，n為1~20的整數。另外，y表示聚合度。 In the formula (6), R ⁹ to R ²⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group or a group consisting of a salt, a hydroxyl group, a nitro group, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and at least one of R ¹¹ , R ¹⁵ , R ¹⁹ , and R ²³ is -(CH) ₂ ) _n -A. Here, A is an acidic group or a salt thereof, and n is an integer of 1 to 20. In addition, y represents the degree of polymerization.

該苯二胺結構(還原型)與苯醌二亞胺結構(氧化型)可藉由氧化或還原而以任意的比率可逆地轉化。苯二胺結構與苯醌二亞胺結構的比率(x)就導電性及溶解性的方面而言，較佳為0.2<x<0.8的範圍，更佳為0.3<x<0.7。 The phenylenediamine structure (reduced form) and the benzoquinone diimine structure (oxidized form) can be reversibly converted in an arbitrary ratio by oxidation or reduction. The ratio (x) of the phenylenediamine structure to the benzoquinone diimine structure is preferably in the range of 0.2 < x < 0.8, more preferably 0.3 < x < 0.7 in terms of conductivity and solubility.

再者，本發明的導電性聚合物可溶解於單純的水、含有鹼及鹼性鹽的水、含有酸的水或甲醇、乙醇、異丙醇等溶劑或該等的混合物中，加工性亦優異。 Further, the conductive polymer of the present invention can be dissolved in simple water, water containing an alkali and an alkali salt, water containing an acid, or a solvent such as methanol, ethanol or isopropyl alcohol or a mixture thereof, and the processability is also Excellent.

本發明的導電性聚合物可藉由噴霧塗佈法、浸漬塗佈法、輥塗佈法、凹版塗佈法、反向塗佈法、輥式刷塗法、氣刀塗佈法、簾幕式塗佈法等簡便的方法而形成導電體。 The conductive polymer of the present invention can be spray coated, dip coated, roll coated, gravure coated, reverse coated, roll brushed, air knife coated, curtain A conductor is formed by a simple method such as a coating method.

另外，以本發明的導電性聚合物作為主成分的組成物 可適應於各種防靜電劑、電容器、電池、電磁干擾(Electromagnetic Interference，EMI)遮罩、化學感測器、顯示元件、非線性材料、防蝕、接著劑、纖維、防靜電塗料、防蝕塗料、電鍍塗料、鍍敷底材、靜電塗佈的底層、電氣防蝕、電池的蓄電能力提高等。 Further, a composition containing the conductive polymer of the present invention as a main component Can be applied to various antistatic agents, capacitors, batteries, electromagnetic interference (EMI) masks, chemical sensors, display components, nonlinear materials, corrosion, adhesives, fibers, antistatic coatings, anti-corrosion coatings, electroplating Coatings, plating substrates, electrostatically applied underlayers, electrical corrosion protection, and improved battery storage capacity.

該些用途中，本發明的導電性聚合物由於熱穩定性優異，即便進行加熱處理亦可維持導電性，故適於製造過程中含有加熱處理步驟的電容器等用途。 Among these uses, the conductive polymer of the present invention is excellent in thermal stability, and can maintain conductivity even by heat treatment. Therefore, it is suitable for use in a capacitor including a heat treatment step in a production process.

藉由上述製造方法所得的苯胺系導電性聚合物(a)有時與陽離子形成鹽，成為妨礙導電性的要因，故較理想為將該些陽離子去除。 The aniline-based conductive polymer (a) obtained by the above production method may form a salt with a cation, which may cause a problem of hindering conductivity. Therefore, it is preferred to remove the cation.

為了將陽離子等雜質去除，較佳為使上述導電性聚合物的分散液或溶解液與陽離子交換樹脂接觸的方法。於對上述導電性聚合物藉由陽離子交換樹脂進行雜質去除的情形時，以分散或溶解於溶劑中的狀態使用。 In order to remove impurities such as cations, a method of bringing the dispersion or solution of the above conductive polymer into contact with the cation exchange resin is preferred. When the conductive polymer is removed by impurities using a cation exchange resin, it is used in a state of being dispersed or dissolved in a solvent.

溶劑較佳為：水；甲醇、乙醇、異丙醇、丙醇、丁醇等醇類；丙酮、甲基乙基酮、乙基異丁基酮、甲基異丁基酮等酮類；乙二醇、乙二醇甲醚、乙二醇單正丙醚等乙二醇類；丙二醇、丙二醇甲醚、丙二醇***、丙二醇丁醚、丙二醇丙醚等丙二醇類；二甲基甲醯胺、二甲基乙醯胺等醯胺類；N-甲基吡咯烷酮、N-乙基吡咯烷酮等吡咯烷酮類；乳酸甲酯、乳酸乙酯、β-甲氧基異丁酸甲酯、α-羥基異丁酸甲酯等羥基酯類；及該些溶劑的混合物。 The solvent is preferably: water; alcohols such as methanol, ethanol, isopropanol, propanol, butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone; Ethylene glycols such as diol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether; propylene glycol such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether; dimethylformamide, two Amidoxime such as methyl acetamide; pyrrolidone such as N-methylpyrrolidone or N-ethylpyrrolidone; methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate, α-hydroxyisobutyric acid a hydroxy ester such as a methyl ester; and a mixture of such solvents.

使上述導電性聚合物分散或溶解於上述溶劑中時的濃 度就工業性或純化效率的觀點而言，較佳為0.1質量%~20質量%，更佳為0.1質量%~10質量%。 Concentration when the above conductive polymer is dispersed or dissolved in the above solvent The degree is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass, from the viewpoint of industrial property or purification efficiency.

陽離子交換樹脂可使用市售品，例如較佳為奧璐佳瑙(Organo)股份有限公司製造的「Amber Light」等強酸型的陽離子交換樹脂。 As the cation exchange resin, a commercially available product can be used, and for example, a strong acid type cation exchange resin such as "Amber Light" manufactured by Organo Co., Ltd. is preferable.

陽離子交換樹脂的形態並無特別限定，可使用各種形態者，例如可列舉球狀細粒、膜狀或纖維狀等。 The form of the cation exchange resin is not particularly limited, and various forms can be used, and examples thereof include spherical fine particles, film forms, and fibers.

關於陽離子交換樹脂相對於導電性聚合物的量，就工業性或純化效率的觀點而言，相對於導電性聚合物1質量份，較佳為1質量份~20質量份，更佳為5質量份~15質量份。 The amount of the cation exchange resin relative to the conductive polymer is preferably from 1 part by mass to 20 parts by mass, more preferably from 5 parts by mass, per part by mass of the conductive polymer, from the viewpoint of industrial property or purification efficiency. ~15 parts by mass.

導電性聚合物的分散液或溶解液與陽離子交換樹脂的接觸方法可列舉以下方法：於容器中放入導電性聚合物的分散液或溶解液與陽離子交換樹脂，進行攪拌或旋轉，藉此與陽離子交換樹脂接觸。 The contact method of the dispersion or the solution of the conductive polymer and the cation exchange resin may be a method in which a dispersion or a solution of a conductive polymer and a cation exchange resin are placed in a container, and stirred or rotated, thereby The cation exchange resin is in contact.

另外，亦可為以下方法：將陽離子交換樹脂填充至管柱中，使導電性聚合物的分散液或溶解液以較佳為SV=0.01~20、更佳為SV=0.2~5的流量通過，進行陽離子交換處理。 Alternatively, the method may be such that the cation exchange resin is filled into the column, and the dispersion or solution of the conductive polymer is passed through a flow rate of preferably SV = 0.01 to 20, more preferably SV = 0.2 to 5. , cation exchange treatment.

此處，空間速度SV(1/hr)=流量(m³/hr)/濾材量(體積：m³)。 Here, the space velocity SV (1/hr) = flow rate (m ³ /hr) / amount of filter material (volume: m ³ ).

關於使導電性聚合物的分散液或溶解液與陽離子交換樹脂接觸的時間，就純化效率的觀點而言，較佳為0.1小時以上，更佳為0.5小時以上。 The time for bringing the dispersion or the solution of the conductive polymer into contact with the cation exchange resin is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, from the viewpoint of purification efficiency.

再者，接觸時間的上限值並無特別限制，只要與導電性聚合物的分散液或溶離液的濃度、陽離子交換樹脂的量、後述的接觸溫度等條件一併適當設定即可。 In addition, the upper limit of the contact time is not particularly limited, and may be appropriately set together with conditions such as the concentration of the dispersion or the solution of the conductive polymer, the amount of the cation exchange resin, and the contact temperature to be described later.

關於使導電性聚合物的分散液或溶解液與陽離子交換樹脂接觸時的溫度，就工業觀點而言，較佳為10℃~50℃，更佳為10℃~30℃。 The temperature at which the dispersion or the solution of the conductive polymer is brought into contact with the cation exchange resin is preferably from 10 ° C to 50 ° C, more preferably from 10 ° C to 30 ° C from the industrial viewpoint.

如此般經純化的導電性聚合物由於低聚物或單體等低分子量體、或陽離子等雜質被充分去除，故表現出更優異的導電性。 The conductive polymer thus purified exhibits more excellent conductivity because the low molecular weight such as an oligomer or a monomer or an impurity such as a cation is sufficiently removed.

<溶劑(b)> <Solvent (b)>

上述導電性組成物中所用的溶劑(b)只要為將上述導電性聚合物(a)溶解的溶劑，則並無特別限定，較佳為水及/或水溶性有機溶劑等。 The solvent (b) to be used in the above-mentioned conductive composition is not particularly limited as long as it is a solvent for dissolving the above-mentioned conductive polymer (a), and is preferably water or a water-soluble organic solvent.

水溶性有機溶劑具體可列舉：乙腈；甲醇、乙醇、異丙醇、正丙醇、正丁醇等醇類；丙酮、甲基乙基酮、乙基異丁基酮、甲基異丁基酮等酮類；乙二醇、乙二醇甲醚等乙二醇類；丙二醇、丙二醇甲醚等丙二醇類；二甲基甲醯胺、二甲基乙醯胺等醯胺類；N-甲基吡咯烷酮、N-乙基吡咯烷酮等吡咯烷酮類；而且可列舉乳酸甲酯、乳酸乙酯、β-甲氧基異丁酸甲酯、α-羥基異丁酸甲酯等羥基酯類等。 Specific examples of the water-soluble organic solvent include acetonitrile; alcohols such as methanol, ethanol, isopropanol, n-propanol and n-butanol; acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; Ketones; glycols such as ethylene glycol and ethylene glycol methyl ether; propylene glycols such as propylene glycol and propylene glycol methyl ether; guanamines such as dimethylformamide and dimethylacetamide; N-methyl Pyrrolidone such as pyrrolidone or N-ethylpyrrolidone; and examples thereof include a hydroxy ester such as methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate or methyl α-hydroxyisobutyrate.

該些溶劑中，就工業觀點而言，較佳為醇類、丙酮、乙腈、二甲基甲醯胺、二甲基乙醯胺等。 Among these solvents, from the industrial viewpoint, an alcohol, acetone, acetonitrile, dimethylformamide, dimethylacetamide or the like is preferable.

關於導電性組成物的濃度，就工業性或純化效率的觀點而言，較佳為0.1質量%~20質量%，更佳為0.5質量% ~10質量%。濃度越高越可形成充分膜厚的固體電解質層。另一方面，濃度越低越可抑制溶液中的導電性聚合物及化合物凝聚，不易高黏度化，容易含浸至陽極氧化被膜的微細凹凸的內部。 The concentration of the conductive composition is preferably from 0.1% by mass to 20% by mass, more preferably 0.5% by mass, from the viewpoint of industrial efficiency or purification efficiency. ~10% by mass. The higher the concentration, the more the solid electrolyte layer of sufficient film thickness can be formed. On the other hand, the lower the concentration, the more the conductive polymer and the compound in the solution are inhibited from agglomerating, the high viscosity is not easily formed, and the inside of the fine unevenness of the anodized film is easily impregnated.

<鹼性化合物(c)> <basic compound (c)>

藉由使本發明的導電性組成物中含有鹼性化合物(c)，耐熱性提高。作為其理由，一般認為其原因在於：鹼性化合物(c)抑制導電性聚合物(a)的分解。鹼性化合物(c)可列舉：氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鈣等無機鹼；氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨等有機氫氧化物；甲胺、乙胺、丙胺、丁胺、戊胺、己胺等一級烷基胺類；苄胺、苯胺等一級胺；二甲胺、二乙胺、二丙胺、二丁胺、二戊胺、二己胺等二級烷基胺類；甲基苯胺等二級胺；三甲胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺等三級烷基胺類；二甲基苯胺等三級胺；2-胺基乙醇、二乙醇胺、三乙醇胺等醇胺類；α-甲基吡啶、β-甲基吡啶、γ-甲基吡啶、吡啶、等雜環式胺水；苄胺、甲氧基乙胺、胺基吡啶、羥基甲基吡啶、吡啶醇、伸乙基二胺、氨等。其中，較佳為氫氧化鈉或氨。該些鹼性化合物可單獨使用任一種，亦可混合使用兩種以上。 The heat resistance is improved by including the basic compound (c) in the conductive composition of the present invention. The reason for this is considered to be that the basic compound (c) suppresses decomposition of the conductive polymer (a). Examples of the basic compound (c) include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydrogen. An organic hydroxide such as tetrabutylammonium oxide; a primary alkylamine such as methylamine, ethylamine, propylamine, butylamine, pentylamine or hexylamine; a primary amine such as benzylamine or aniline; dimethylamine, diethylamine, Secondary alkylamines such as dipropylamine, dibutylamine, diamylamine, and dihexylamine; secondary amines such as methylaniline; trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, and trihexyl Tertiary alkylamines such as amines; tertiary amines such as dimethylaniline; alcohol amines such as 2-aminoethanol, diethanolamine and triethanolamine; α-methylpyridine, β-methylpyridine, γ-methyl Pyridine, pyridine, Heterocyclic amine water; benzylamine, methoxyethylamine, aminopyridine, hydroxymethylpyridine, pyridinol, ethylidene diamine, ammonia, and the like. Among them, sodium hydroxide or ammonia is preferred. These basic compounds may be used alone or in combination of two or more.

關於鹼性化合物(c)，可使將經酸性基取代苯胺等成為導電性聚合物(a)的原料的單體於溶液中進行氧化聚合時所使用者殘存，而含有於導電性組成物中，除此以外， 亦可將與其為相同種類或不同種類的鹼性化合物添加至導電性組成物中。 In the case of the basic compound (c), a monomer which is a raw material of the conductive polymer (a) such as an acid-substituted aniline may be left in the solution during oxidative polymerization in a solution, and may be contained in the conductive composition. Other than that, A basic compound of the same kind or a different kind may be added to the conductive composition.

另外，關於鹼性化合物(c)的添加量，就導電性及/或耐熱性的觀點而言，相對於導電性聚合物(a)的重複單元1 mol，較佳為0.01 mol~2.0 mol，更佳為0.1 mol~1.5 mol，進而佳為0.15 mol~1.0 mol，特佳為0.2 mol~0.65 mol。 In addition, the amount of the basic compound (c) to be added is preferably 0.01 mol to 2.0 mol with respect to 1 mol of the repeating unit of the conductive polymer (a) from the viewpoint of conductivity and/or heat resistance. More preferably 0.1 mol to 1.5 mol, and further preferably 0.15 mol to 1.0 mol, particularly preferably 0.2 mol to 0.65 mol.

<固體電解質層(導電性聚合物層)> <Solid electrolyte layer (conductive polymer layer)>

於本發明中，固體電解質層是由將上述苯胺系導電性聚合物與溶劑混合所得的導電性組成物所形成。 In the present invention, the solid electrolyte layer is formed of a conductive composition obtained by mixing the above-described aniline-based conductive polymer and a solvent.

固體電解質層的形成方法可列舉：浸漬塗佈法、毛刷塗佈法、旋轉塗佈法、澆鑄法、微凹版塗佈法、凹版塗佈法、棒塗佈法、輥塗佈法、線棒塗佈法、噴霧塗佈法、流式塗佈法、網版印刷法、柔版印刷法、套版印刷法、噴墨印刷法等。其中，就操作容易的方面而言，較佳為浸漬塗佈法。 Examples of the method for forming the solid electrolyte layer include a dip coating method, a brush coating method, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, and a line. Bar coating method, spray coating method, flow coating method, screen printing method, flexographic printing method, plate printing method, inkjet printing method, and the like. Among them, in terms of ease of handling, a dip coating method is preferred.

於藉由浸漬塗佈法來塗佈導電性組成物的情形時，就作業性的觀點而言，於導電性組成物中的浸漬時間較佳為1分鐘~30分鐘。另外，於浸漬塗佈時，於減壓時浸漬後回到常壓、或於浸漬時加壓等方法亦有效。 In the case where the conductive composition is applied by the dip coating method, the immersion time in the conductive composition is preferably from 1 minute to 30 minutes from the viewpoint of workability. Further, in the case of dip coating, it is also effective to return to normal pressure after immersion under reduced pressure or to pressurize during immersion.

形成固體電解質層後的乾燥方法較佳為加熱乾燥，例如亦可使用風乾或使其旋轉而加以物理乾燥的方法等。 The drying method after forming the solid electrolyte layer is preferably heat drying, and for example, a method of air drying or physical drying by rotating it may be used.

另外，乾燥條件是根據上述導電性聚合物(a)或上述溶劑(b)的種類而決定，通常，乾燥溫度就乾燥性的觀點 而言較佳為50℃~190℃，乾燥時間較佳為1分鐘~120分鐘。 Further, the drying conditions are determined depending on the type of the conductive polymer (a) or the solvent (b), and usually, the drying temperature is dry. Preferably, it is 50 ° C to 190 ° C, and the drying time is preferably from 1 minute to 120 minutes.

<捲繞型固體電解電容器的製造方法> <Method of Manufacturing Winding Solid Electrolytic Capacitor>

於本發明的實施形態中，除了固體電解質層的形成步驟以外，捲繞型固體電解電容器是藉由公知的技術而製造。 In the embodiment of the present invention, the wound solid electrolytic capacitor is manufactured by a known technique in addition to the step of forming the solid electrolyte layer.

例如，可藉由蝕刻將鋁箔的表層附近形成多孔質體後，藉由陽極氧化而形成陽極氧化被膜，並且形成含有本實施形態的固體電解質層的固體電荷質後，形成陰極部，對陽極部及陰極部連接外部端子並實施外包裝，獲得本實施形態的捲繞型固體電解電容器。 For example, after forming a porous body in the vicinity of the surface layer of the aluminum foil by etching, an anodized film is formed by anodization, and a solid charge containing the solid electrolyte layer of the present embodiment is formed, and then a cathode portion is formed, and the anode portion is formed. The external terminal is connected to the cathode portion and the outer package is applied to obtain the wound solid electrolytic capacitor of the present embodiment.

上述陽極氧化被膜是對包含鋁、鉭、鈮、鎳等金屬材料(被膜形成金屬)的電極(閥作用金屬體)進行陽極氧化而形成。對多孔質的閥作用金屬體進行陽極氧化所形成的陽極氧化被膜反映出閥作用金屬體的表面狀態，表面成為微細的凹凸結構。該凹凸的週期依存於閥作用金屬體的種類等，通常為200 nm以下左右。 The anodized film is formed by anodizing an electrode (valve-action metal body) containing a metal material (film-forming metal) such as aluminum, tantalum, niobium, or nickel. The anodized film formed by anodizing the porous valve action metal body reflects the surface state of the valve action metal body, and the surface has a fine uneven structure. The period of the unevenness depends on the type of the valve action metal body, etc., and is usually about 200 nm or less.

另外，形成凹凸的凹部(孔隙部)的深度特別容易依存於閥作用金屬體的種類等，故不可一概而定，例如於使用鋁的情形時，凹部的深度為數十nm~1 μm左右。 In addition, the depth of the concave portion (pore portion) in which the unevenness is formed is particularly likely to depend on the type of the valve action metal body, etc., and therefore it is not always possible. For example, when aluminum is used, the depth of the concave portion is about several tens nm to 1 μm.

<積層型固體電解電容器的製造方法> <Method of Manufacturing Multilayer Type Solid Electrolytic Capacitor>

於本發明的實施形態中，除了固體電解質層的形成步驟以外，積層型固體電解電容器是藉由公知的技術而製造。 In the embodiment of the present invention, in addition to the step of forming the solid electrolyte layer, the laminated solid electrolytic capacitor is produced by a known technique.

例如藉由蝕刻將鋁箔等閥作用金屬體的表層附近多孔質體化後，藉由陽極氧化而形成陽極氧化被膜。繼而，於 陽極氧化被膜上形成固體電解質層後，使其浸漬於石墨液中，或塗佈石墨液而於固體電解質層上形成石墨層，並進而於石墨層上形成金屬層。進而，對陰極部及陽極部連接外部端子並進行外包裝，藉此可獲得本實施形態的積層型固體電解電容器。 For example, the vicinity of the surface layer of the valve-acting metal body such as aluminum foil is porous by etching, and then anodized film is formed by anodization. Then After forming a solid electrolyte layer on the anodized film, it is immersed in a graphite liquid, or a graphite liquid is applied to form a graphite layer on the solid electrolyte layer, and a metal layer is further formed on the graphite layer. Further, the external terminal is connected to the cathode portion and the anode portion and externally packaged, whereby the laminated solid electrolytic capacitor of the present embodiment can be obtained.

[實例] [Example]

以下，藉由實例對本發明加以具體說明，但本發明不限定於該些實例。 Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples.

再者，實例及比較例中的測定、評價方法如下。 Further, the measurement and evaluation methods in the examples and comparative examples are as follows.

(核磁共振(Nuclear Magnetic Resonance，NMR)的測定) (Measurement of Nuclear Magnetic Resonance (NMR))

藉由¹H-NMR光譜的測定來進行化合物的鑑定。該測定中，使用傅立葉變換核磁共振儀(Fourier Transform-Nuclear Magnetic Resonance，FT-NMR)(日本電子股份有限公司製造，「JNM-GX270」)，將於氘代二甲基亞碸中以濃度成為約5質量%的方式溶解測定樣品所得的溶液放入至直徑為5 mmΦ的試管中，以25℃的測定溫度、270 MHz的測定頻率於單脈波模式下以64次的累計次數進行。 The identification of the compound was carried out by measurement of ¹ H-NMR spectrum. In this measurement, a Fourier Transform-Nuclear Magnetic Resonance (FT-NMR) ("JNM-GX270" manufactured by JEOL Ltd.) was used, and the concentration in the deuterated dimethyl hydrazine was The solution obtained by dissolving the measurement sample in a manner of about 5 mass% was placed in a test tube having a diameter of 5 mmφ, and was carried out in a single pulse mode at a cumulative number of times of 64 times at a measurement temperature of 25 ° C and a measurement frequency of 270 MHz.

(導電性聚合物的質量平均分子量的測定) (Measurement of mass average molecular weight of conductive polymer)

首先，於將水(超純水)與甲醇以容積比成為水：甲醇=8：2的方式混合而成的混合溶劑中，以各自的固體成分濃度成為20 mmol/L、30 mmol/L的方式添加碳酸鈉與碳酸氫鈉，製備溶離液。所得的溶離液於25℃下的pH值為 10.8。於該溶離液中使導電性聚合物以固體成分濃度成為0.1質量%的方式溶解，製備試驗溶液。 First, in a mixed solvent in which water (ultra-pure water) and methanol are mixed in a volume ratio of water: methanol = 8:2, the respective solid content concentrations are 20 mmol/L and 30 mmol/L. The sodium carbonate and sodium hydrogencarbonate were added in a manner to prepare a solution. The pH of the resulting solution at 25 ° C 10.8. The conductive polymer was dissolved in the solution to have a solid content concentration of 0.1% by mass to prepare a test solution.

使用具備凝膠滲透層析儀的高分子材料評價裝置，對所得的試驗溶液測定分子量分布。 The molecular weight distribution of the obtained test solution was measured using a polymer material evaluation apparatus equipped with a gel permeation chromatograph.

繼而，對所得的層析圖將保持時間換算成聚苯乙烯磺酸鈉換算的分子量(M)，求出導電性聚合物的質量平均分子量。 Then, the obtained chromatogram was converted into a molecular weight (M) in terms of sodium polystyrene sulfonate in terms of retention time, and the mass average molecular weight of the conductive polymer was determined.

(熱穩定性及導電性的評價) (Evaluation of thermal stability and electrical conductivity)

使用旋轉塗佈機將導電性聚合物溶液塗佈於玻璃基板上，於熱板上以預定溫度加熱5分鐘，獲得於玻璃基板上形成有塗膜(膜厚為約100 nm)的試片。 The conductive polymer solution was applied onto a glass substrate using a spin coater, and heated on a hot plate at a predetermined temperature for 5 minutes to obtain a test piece having a coating film (having a film thickness of about 100 nm) formed on the glass substrate.

於電阻率計(三菱化學分析技術(Mitsubishi Chemical Analytech)股份有限公司製造，「Hiresta IP」)上安裝2探針探頭，對所得的試片的表面電阻值進行測定。 A 2-probe probe was attached to a resistivity meter ("Hiresta IP" manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the surface resistance value of the obtained test piece was measured.

(電容測定、等效串聯電阻測定) (capacitance measurement, equivalent series resistance measurement)

關於電容及等效串聯電阻，使用電感電容電阻(Inductance Capacitance Resistance，LCR)計(安捷倫科技(Agilent Technology)股份有限公司製造，E4980A，精準LCR計)以120 Hz的頻率測定電容，以100 kHz的頻率測定等效串聯電阻。 For capacitance and equivalent series resistance, the capacitance is measured at 120 Hz using an Inductance Capacitance Resistance (LCR) meter (Agilent Technology, Inc., E4980A, precision LCR meter) at 100 kHz. The frequency is determined by the equivalent series resistance.

(導電性聚合物的重複單元(單體單元)[mol]) (Repeating unit (monomer unit) [mol] of conductive polymer)

對於導電性聚合物的粉末，將粉末的重量除以高分子的重複單元的分子量，求出導電性聚合物的重複單元(單體單元)[mol]。 The powder of the conductive polymer was obtained by dividing the weight of the powder by the molecular weight of the repeating unit of the polymer to obtain a repeating unit (monomer unit) [mol] of the conductive polymer.

於導電性聚合物的分散液或溶解液的情形時，將溶解液或分散液於100℃下乾燥1小時，將殘存的固體成分作為導電性聚合物的粉末，同樣地求出導電性聚合物的重複單元(單體單元)[mol]。 In the case of a dispersion or a solution of a conductive polymer, the solution or dispersion is dried at 100 ° C for 1 hour, and the remaining solid component is used as a powder of a conductive polymer, and a conductive polymer is obtained in the same manner. Repeat unit (monomer unit) [mol].

[實例1] [Example 1]

<導電性聚合物前驅物的合成> <Synthesis of Conductive Polymer Precursors>

(c)步驟：3-硝基-4-甲氧基苄基氯的合成 Step (c): Synthesis of 3-nitro-4-methoxybenzyl chloride

於將3-硝基-4-甲氧基苄醇(4-1)4.8 g(26.2 mmol)溶解於二氯甲烷48 mL的溶液中，添加亞硫醯氯6.2 g(52.4 mmol)。將該溶液於室溫下攪拌20小時後，添加甲苯30 mL，進行減壓濃縮。將所得的固體懸浮於己烷中後，將其過濾，將殘渣乾燥，藉此獲得3-硝基-4-甲氧基苄基氯(2-2)5.13 g(產率為97.2%)。 To a solution of 48 mL of dichloromethane, 3-nitro-4-methoxybenzyl alcohol (4-1) 4.8 g (26.2 mmol) was added, and 6.2 g (52.4 mmol) of sulfinium chloride was added. After the solution was stirred at room temperature for 20 hours, 30 mL of toluene was added and concentrated under reduced pressure. After the obtained solid was suspended in hexane, it was filtered, and the residue was dried, whereby 3-nitro-4-methoxybenzyl chloride (2-2) 5.13 g (yield: 97.2%) was obtained.

(a)步驟：3-硝基-4-甲氧基苯基甲磺酸的合成 Step (a): Synthesis of 3-nitro-4-methoxyphenyl methanesulfonic acid

於水6 mL中混合3-硝基-4-甲氧基苄基氯(2-2)3.00 g(14.9 mmol)、亞硫酸鈉3.48 g(9.21 mmol)，於100℃下加熱回流3小時((a-1)步驟)。 Mix 3-nitro-4-methoxybenzyl chloride (2-2) 3.00 g (14.9 mmol) and sodium sulfite 3.48 g (9.21 mmol) in 6 mL of water and heat to reflux at 100 ° C for 3 hours (a -1) Step).

將反應液冷卻後，於析出的固體(3-3)中添加水而使其溶解，於其中添加50質量%硫酸6.18 g。將該溶液減壓濃縮，進而添加乙醇80 mL並再次進行減壓濃縮。將所得的固體懸浮於甲醇中後，將其減壓過濾。將濾液減壓濃縮，藉此獲得3-硝基-4-甲氧基苯基甲磺酸(3-4)2.64 g((a-2)步驟)(產率為71.7%)。 After cooling the reaction liquid, water was added to the precipitated solid (3-3) to dissolve it, and 6.18 g of 50% by mass sulfuric acid was added thereto. The solution was concentrated under reduced pressure, and then 80 mL of ethanol was added and then concentrated under reduced pressure. After the obtained solid was suspended in methanol, it was filtered under reduced pressure. The filtrate was concentrated under reduced pressure, whereby 2-nitro-4-methoxyphenyl methanesulfonic acid (3-4) (2.6) g (yield (y-2)) (yield: 71.7%).

以下示出所得的3-硝基-4-甲氧基苯基甲磺酸(3-4)的¹H-NMR光譜的歸屬。 The assignment of the obtained ¹ H-NMR spectrum of 3-nitro-4-methoxyphenylmethanesulfonic acid (3-4) is shown below.

¹H-NMR(270 MHz下，於DMSO中)：δ7.79(s,1H),δ7.58(d,1H,J=8.37 Hz),δ7.27(d,1H,J=8.37 Hz),δ3.90(s,3H),δ3.73(s,2H). ¹ H-NMR (in DMSO at 270 MHz): δ 7.79 (s, 1H), δ 7.58 (d, 1H, J = 8.37 Hz), δ 7.27 (d, 1H, J = 8.37 Hz) , δ 3.90 (s, 3H), δ 3.73 (s, 2H).

(b)步驟：3-胺基-4-甲氧基苯基甲磺酸的合成 Step (b): Synthesis of 3-amino-4-methoxyphenyl methanesulfonic acid

將3-硝基-4-甲氧基苯基甲磺酸(3-4)2.2 g(8.9 mmol) 溶解於甲醇27.7 mL中，於其中添加鈀碳(Pd-C)0.22 g。對反應容器進行氫氣置換，於室溫(25℃)下攪拌3小時後，將反應液過濾，並將濾液減壓濃縮，藉此獲得3-胺基-4-甲氧基苯基甲磺酸(1-3)1.95 g(產率為90%)。 3-nitro-4-methoxyphenyl methanesulfonic acid (3-4) 2.2 g (8.9 mmol) It was dissolved in 27.7 mL of methanol, and palladium carbon (Pd-C) 0.22 g was added thereto. The reaction vessel was subjected to hydrogen displacement, and after stirring at room temperature (25 ° C) for 3 hours, the reaction liquid was filtered, and the filtrate was concentrated under reduced pressure to give 3-amino-4-methoxyphenyl methanesulfonic acid. (1-3) 1.95 g (yield 90%).

以下示出所得的3-胺基-4-甲氧基苯基甲磺酸(1-3)的¹H-NMR光譜的歸屬。 The assignment of the obtained 1-amino-4-methoxyphenylmethanesulfonic acid (1-3) to the ¹ H-NMR spectrum is shown below.

¹H-NMR(270 MHz下，於DMSO中)：δ6.65(d,1H,J=9.99 Hz),δ6.64(s,1H),δ6.44(d,1H,J=9.99 Hz),δ3.72(s,3H),δ3.51(s,2H). ¹ H-NMR (in DMSO at 270 MHz): δ 6.65 (d, 1H, J = 9.99 Hz), δ 6.64 (s, 1H), δ 6.44 (d, 1H, J = 9.99 Hz) , δ 3.72 (s, 3H), δ 3.51 (s, 2H).

[實例2] [Example 2]

<導電性聚合物(a)的製造> <Manufacture of Conductive Polymer (a)>

將過氧二硫酸銨(分子量為224.20)2.24 g(100 mmol)於25 g水中攪拌溶解，製備氧化劑溶液。 An oxidizing agent solution was prepared by stirring and dissolving 2.24 g (100 mmol) of ammonium peroxodisulfate (molecular weight: 224.20) in 25 g of water.

另外，將包含3-胺基-4-甲氧基苯基甲磺酸(分子量為217.24)2.17 g(100 mmol)的苯胺系單體成分溶解於水25 g中，製備苯胺系單體成分溶液(前驅物溶液)。 Further, an aniline monomer component containing 2-amino-4-methoxyphenyl methanesulfonic acid (molecular weight: 217.24) of 2.17 g (100 mmol) was dissolved in 25 g of water to prepare an aniline monomer component solution. (precursor solution).

一面將氧化劑溶液於冰浴中冷卻並加以攪拌，一面用 1小時滴加前驅物溶液，滴加結束後，於冰浴冷卻下繼續攪拌2小時。繼而，於室溫(25℃)下繼續攪拌2小時而進行聚合反應，獲得黑色沈澱物。 While cooling the oxidant solution in an ice bath and stirring it, use The precursor solution was added dropwise over 1 hour, and after completion of the dropwise addition, stirring was continued for 2 hours while cooling in an ice bath. Then, stirring was continued for 2 hours at room temperature (25 ° C) to carry out a polymerization reaction, and a black precipitate was obtained.

將所得的黑色沈澱過濾，以水將殘渣清洗後，進行減壓乾燥，獲得導電性聚合物(聚(3-胺基-4-甲氧基苯基甲磺酸))(a)1.5 g。所得的聚(3-胺基-4-甲氧基苯基甲磺酸)的質量平均分子量為25000。 The obtained black precipitate was filtered, and the residue was washed with water, and then dried under reduced pressure to obtain a conductive polymer (poly(3-amino-4-methoxyphenylmethanesulfonic acid)) (a) 1.5 g. The obtained poly(3-amino-4-methoxyphenylmethanesulfonic acid) had a mass average molecular weight of 25,000.

將所得的聚(3-胺基-4-甲氧基苯基甲磺酸)(a)溶解於0.2 mol/L的氨水中，製備導電性聚合物溶液。 The obtained poly(3-amino-4-methoxyphenylmethanesulfonic acid) (a) was dissolved in 0.2 mol/L of aqueous ammonia to prepare a conductive polymer solution.

使用該導電性聚合物溶液進行熱穩定性及導電性的評價。 The thermal conductivity and conductivity were evaluated using the conductive polymer solution.

再者，變更加熱溫度而製作合計7個試片，對各試片測定表面電阻值。根據所得的結果，製作於X軸上繪製加熱溫度(℃)、於Y軸上繪製試片的表面電阻值(Ω/□)的圖表。將該圖表示於圖1中。 Further, a total of seven test pieces were prepared by changing the heating temperature, and the surface resistance value was measured for each test piece. Based on the obtained results, a graph was prepared in which the heating temperature (° C.) was plotted on the X-axis and the surface resistance value (Ω/□) of the test piece was plotted on the Y-axis. This figure is shown in Fig. 1.

[比較例1] [Comparative Example 1]

<導電性聚合物前驅物(a')的合成> <Synthesis of Conductive Polymer Precursor (a')>

將過氧二硫酸銨(分子量為224.20)2.24 g(100 mmol)於10 g的水及乙腈的混合溶劑(體積比=1：1)中攪拌溶解，製備氧化劑溶液。 An oxidizing agent solution was prepared by stirring and dissolving 2.24 g (100 mmol) of ammonium peroxodisulfate (molecular weight: 224.20) in 10 g of a mixed solvent of water and acetonitrile (volume ratio = 1:1).

另外，將東京化成工業股份有限公司所市售的2-胺基苯甲醚-4-磺酸(分子量為203.22)2.03 g(100 mmol)及三乙胺1.1g溶解於10 g的水及乙腈的混合溶劑(體積比=1：1)中，製備前驅物溶液。 In addition, 2-aminoanisole-4-sulfonic acid (molecular weight: 203.22) 2.03 g (100 mmol) and triethylamine 1.1 g commercially available from Tokyo Chemical Industry Co., Ltd. were dissolved in 10 g of water and acetonitrile. A precursor solution was prepared in a mixed solvent (volume ratio = 1:1).

除了使用該些氧化劑溶液及前驅物溶液以外，與實例1同樣地進行聚合反應，將所得的黑色沈澱過濾，以水清洗殘渣後，進行減壓乾燥，而獲得導電性聚合物(聚(2-胺基苯甲醚-4-磺酸))(a')1.2 g。所得的聚(2-胺基苯甲醚-4-磺酸)的質量平均分子量為23000。 A polymerization reaction was carried out in the same manner as in Example 1 except that the oxidizing agent solution and the precursor solution were used, and the obtained black precipitate was filtered, and the residue was washed with water, followed by drying under reduced pressure to obtain a conductive polymer (poly(2-) Aminoanisole-4-sulfonic acid)) (a') 1.2 g. The obtained poly(2-aminoanisole-4-sulfonic acid) had a mass average molecular weight of 23,000.

將所得的聚(2-胺基苯甲醚-4-磺酸)於室溫(25℃)下溶解於水中，利用強酸性離子交換樹脂(奧璐佳瑙股份有限公司製造，「Amber Light IR-120B」)進行離子交換處理，而將其作為導電性聚合物溶液(a'-2)。 The obtained poly(2-aminoanisole-4-sulfonic acid) was dissolved in water at room temperature (25 ° C) using a strong acid ion exchange resin (Amber Light IR, manufactured by Aochengan Co., Ltd., "Amber Light IR -120B") An ion exchange treatment was carried out to obtain a conductive polymer solution (a'-2).

使用所得的導電性聚合物溶液，與實例2同樣地進行熱穩定性及導電性的評價。將結果示於圖1中。 The thermal conductivity and conductivity were evaluated in the same manner as in Example 2 using the obtained conductive polymer solution. The results are shown in Fig. 1.

由圖1表明，實例2中所得的導電性聚合物即便加熱溫度變高，表面電阻值亦穩定，可維持高的導電性。因此表示：由本發明的導電性聚合物前驅物所得的導電性聚合物即便於200℃以上的高溫下進行加熱處理，熱穩定性亦優異，並且具有高的導電性。 As shown in Fig. 1, the conductive polymer obtained in Example 2 was stable even when the heating temperature was high, and high conductivity was maintained. Therefore, it is shown that the conductive polymer obtained from the conductive polymer precursor of the present invention is heat-treated at a high temperature of 200 ° C or higher, is excellent in thermal stability, and has high conductivity.

另一方面，由酸性基或其鹽未經由伸烷基而鍵結於芳香環的單體所得的導電性聚合物(比較例1)隨著加熱溫度變高，表面電阻值變高，導電性下降。 On the other hand, the conductive polymer obtained by the monomer having an acidic group or a salt thereof bonded to the aromatic ring through the alkyl group (Comparative Example 1) becomes higher as the heating temperature becomes higher, and the surface resistance value becomes higher, and conductivity decline.

[實例3] [Example 3]

<導電性組成物的製造> <Manufacture of Conductive Composition>

使所得的導電性聚合物(a)5質量份於室溫下溶解於水95質量份中，獲得導電性聚合物溶液(a-1)。 5 parts by mass of the obtained conductive polymer (a) was dissolved in 95 parts by mass of water at room temperature to obtain a conductive polymer solution (a-1).

再者，所謂「室溫」，是指25℃。 In addition, "room temperature" means 25 °C.

以相對於所得的導電性聚合物水溶液(a-1)100質量份而成為50質量份的方式，將酸性陽離子交換樹脂(奧璐佳瑙股份有限公司製造，「Amber Light」)填充至管柱中，於該管柱中使導電性聚合物溶液(a-1)以SV=8的流量通過而進行陽離子交換處理，獲得經純化的導電性聚合物溶液(a-2)。 An acidic cation exchange resin ("Amber Light" manufactured by Aochengan Co., Ltd.) was filled into the column so as to be 50 parts by mass with respect to 100 parts by mass of the obtained conductive polymer aqueous solution (a-1). In the column, the conductive polymer solution (a-1) was passed at a flow rate of SV=8 to carry out a cation exchange treatment to obtain a purified conductive polymer solution (a-2).

於所得的導電性聚合物溶液(a-2)中，導電性聚合物的比例為4.5質量%(相對於溶劑100質量份而為4.7質量份)。另外，導電性聚合物溶液(a-2)中所含的形成鹽的鹼性化合物(三乙胺及氨)的含量為0.1質量%以下。 In the obtained conductive polymer solution (a-2), the ratio of the conductive polymer was 4.5% by mass (4.7 parts by mass based on 100 parts by mass of the solvent). In addition, the content of the salt-forming basic compound (triethylamine and ammonia) contained in the conductive polymer solution (a-2) is 0.1% by mass or less.

[實例4] [Example 4]

使用實例3中所得的導電性聚合物溶液(a-2)製備導電性組成物溶液。將鋁電容器的陽極氧化被膜浸漬於上述導電性組成物溶液2分鐘後，藉由熱風乾燥機於120℃下乾燥30分鐘，進而於180℃下進行120分鐘加熱處理，於陽極氧化被膜上形成固體電解質層。將所得的捲繞型固體電解電容器的等效串聯電阻一併示於表1中。 A conductive composition solution was prepared using the conductive polymer solution (a-2) obtained in Example 3. The anodized film of the aluminum capacitor was immersed in the above-mentioned conductive composition solution for 2 minutes, and then dried at 120 ° C for 30 minutes in a hot air dryer, and further heat-treated at 180 ° C for 120 minutes to form a solid on the anodized film. Electrolyte layer. The equivalent series resistance of the obtained wound solid electrolytic capacitor is shown together in Table 1.

[比較例2] [Comparative Example 2]

除了使用比較例1中所得的導電性聚合物溶液(a'-2)以外，與實例4同樣地進行操作，將所得的固體電解電容器的等效串聯電阻一併示於表1中。 Except that the conductive polymer solution (a'-2) obtained in Comparative Example 1 was used, the same operation as in Example 4 was carried out, and the equivalent series resistance of the obtained solid electrolytic capacitor was collectively shown in Table 1.

[實例5] [Example 5]

於實例3中所得的聚合物溶液(a-2)中，添加二乙醇胺作為鹼性化合物，除此以外，藉由與實例4相同的方法 形成固體電解質層，將所得的捲繞型固體電解電容器的等效串聯電阻一併示於表1中。 In the polymer solution (a-2) obtained in Example 3, diethanolamine was added as a basic compound, except that the same method as in Example 4 was carried out. A solid electrolyte layer was formed, and the equivalent series resistance of the obtained wound solid electrolytic capacitor was collectively shown in Table 1.

[實例6] [Example 6]

另外，於實例3中所得的聚合物溶液(a-2)中添加氫氧化鋰作為鹼性化合物，除此以外，藉由與實例4相同的方法形成固體電解質層，將所得的捲繞型固體電解電容器的等效串聯電阻一併示於表1中。 Further, a solid electrolyte layer was formed by the same method as in Example 4 except that lithium hydroxide was added as a basic compound to the polymer solution (a-2) obtained in Example 3, and the obtained wound solid was obtained. The equivalent series resistance of the electrolytic capacitor is shown together in Table 1.

表1中的耐熱性的評價是按下述基準進行。 The evaluation of the heat resistance in Table 1 was carried out in accordance with the following criteria.

A：與於120℃下加熱乾燥30分鐘時的等效串聯電阻值相比較，進一步於180℃下進行120分鐘加熱處理時的等效串聯電阻值的增加小於5倍。 A: Compared with the equivalent series resistance value at the time of heating and drying at 120 ° C for 30 minutes, the increase in the equivalent series resistance value at the time of heat treatment at 180 ° C for 120 minutes was less than 5 times.

B：與於120℃下加熱乾燥30分鐘時的等效串聯電阻值相比較，進一步於180℃下進行120分鐘加熱處理時的等效串聯電阻值的增加為5倍以上。 B: The increase in the equivalent series resistance value at the time of heat treatment at 180 ° C for 120 minutes was 5 times or more as compared with the equivalent series resistance value at the time of heating and drying at 120 ° C for 30 minutes.

根據表1，使用含有導電性聚合物(a)的導電性聚合物溶液(a-2)的實例4即便進行加熱處理，等效串聯電阻的增加亦得到抑制，加熱處理後表現出優異的耐熱性。 According to Table 1, in Example 4 using the conductive polymer solution (a-2) containing the conductive polymer (a), even if heat treatment was performed, the increase in the equivalent series resistance was suppressed, and the heat treatment showed excellent heat resistance. Sex.

另外，分別添加二乙醇胺、氫氧化鋰作為鹼性化合物(c)的實例5、實例6亦是即便進行加熱處理，等效串聯電阻的增加亦得到抑制。 Further, in Example 5 and Example 6 in which diethanolamine or lithium hydroxide was added as the basic compound (c), the increase in the equivalent series resistance was suppressed even by heat treatment.

另一方面，使用導電性聚合物溶液(a'-2)的比較例2加熱導致的等效串聯電阻明顯增加，加熱處理後耐熱性差，上述導電性聚合物溶液(a'-2)含有與導電性聚合物(a)不同而且酸性基直接鍵結於芳香環的導電性高聚合物(a')。 On the other hand, in Comparative Example 2 using the conductive polymer solution (a'-2), the equivalent series resistance caused by heating was remarkably increased, and heat resistance after heat treatment was poor, and the above-mentioned conductive polymer solution (a'-2) contained and The conductive polymer (a) is different and the acidic group is directly bonded to the highly conductive polymer (a') of the aromatic ring.

[產業上之可利用性] [Industrial availability]

本發明的導電性聚合物前驅物特別適合作為製造過程中含有加熱處理步驟的電容器等用途中所用的導電性聚合物的前驅物，於實用方面有用。 The conductive polymer precursor of the present invention is particularly suitable as a precursor of a conductive polymer used in applications such as capacitors containing a heat treatment step in a production process, and is useful in practical use.

另外，本發明的導電性聚合物亦可合適地用於製造過程中含有加熱處理步驟的電容器等用途。 Further, the conductive polymer of the present invention can also be suitably used for applications such as capacitors containing a heat treatment step in a manufacturing process.

20‧‧‧固體電解電容器 20‧‧‧Solid electrolytic capacitor

21‧‧‧陽極 21‧‧‧Anode

22‧‧‧陰極 22‧‧‧ cathode

23‧‧‧分隔物 23‧‧‧Separator

24‧‧‧外部端子 24‧‧‧External terminals

圖1為對實例2及比較例1於X軸上繪製加熱溫度(℃)、於Y軸上繪製試片的表面電阻值(Ω/□)而成的圖表。 1 is a graph in which the heating temperature (° C.) is plotted on the X-axis and the surface resistance value (Ω/□) of the test piece is plotted on the Y-axis for Example 2 and Comparative Example 1.

圖2為示意性地表示本發明的固體電解電容器的一例的剖面圖。 Fig. 2 is a cross-sectional view schematically showing an example of a solid electrolytic capacitor of the present invention.

20‧‧‧固體電解電容器 20‧‧‧Solid electrolytic capacitor

21‧‧‧陽極 21‧‧‧Anode

22‧‧‧陰極 22‧‧‧ cathode

23‧‧‧分隔物 23‧‧‧Separator

24‧‧‧外部端子 24‧‧‧External terminals

Claims (15)

一種導電性聚合物前驅物，其是以下述通式(1)所表示， 式(1)中，R¹~R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 A conductive polymer precursor represented by the following formula (1), In the formula (1), R ¹ to R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group or In the group consisting of a salt, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20. 如申請專利範圍第1項所述之導電性聚合物前驅物，其中上述R²為氫原子，R¹、R³、R⁴中的至少一個為碳數1~24的直鏈或分支的烷氧基。 The conductive polymer precursor according to claim 1, wherein the above R ² is a hydrogen atom, and at least one of R ¹ , R ³ and R ⁴ is a linear or branched alkane having 1 to 24 carbon atoms. Oxygen. 如申請專利範圍第2項所述之導電性聚合物前驅物，其中上述R²為氫原子，R¹、R³、R⁴中的一個為碳數1~24的直鏈或分支的烷氧基，其餘為氫原子。 The conductive polymer precursor according to claim 2, wherein the above R ² is a hydrogen atom, and one of R ¹ , R ³ and R ⁴ is a linear or branched alkoxy group having 1 to 24 carbon atoms. Base, the rest are hydrogen atoms. 一種導電性聚合物，其是使如申請專利範圍第1項至第3項中任一項所述之導電性聚合物前驅物聚合而獲得。 A conductive polymer obtained by polymerizing a conductive polymer precursor according to any one of claims 1 to 3. 一種導電性組成物，其含有苯胺系導電性聚合物 (a)及溶劑(b)，上述苯胺系導電性聚合物(a)具有下述通式(1-A)所表示的重複單元， 式(1)中，R¹、R³及R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 An electroconductive composition comprising an aniline-based conductive polymer (a) and a solvent (b), wherein the aniline-based conductive polymer (a) has a repeating unit represented by the following formula (1-A); In the formula (1), R ¹ , R ³ and R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, In the group consisting of an acidic group or a salt thereof, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20. 如申請專利範圍第5項所述之導電性組成物，其中上述R²為氫原子，上述R¹、R³、R⁴中的至少一個為碳數1~24的直鏈或分支的烷氧基。 The conductive composition according to claim 5, wherein the R ² is a hydrogen atom, and at least one of the above R ¹ , R ³ and R ⁴ is a linear or branched alkoxy group having 1 to 24 carbon atoms. base. 如申請專利範圍第5項所述之導電性組成物，其中上述R¹、R³、R⁴中的一個為碳數1~24的直鏈或分支的烷氧基，其餘為氫原子。 The conductive composition according to claim 5, wherein one of the above R ¹ , R ³ and R ⁴ is a linear or branched alkoxy group having 1 to 24 carbon atoms, and the remainder is a hydrogen atom. 如申請專利範圍第5項至第7項中任一項所述之導電性組成物，其中更含有鹼性化合物(c)。 The conductive composition according to any one of claims 5 to 7, which further contains a basic compound (c). 一種導電體，其具有由如申請專利範圍第4項所述 之導電性聚合物所形成的塗膜。 An electrical conductor having the same as described in item 4 of the scope of the patent application A coating film formed of a conductive polymer. 一種導電體，其具有由如申請專利範圍第5項至第7項中任一項所述之導電性組成物所形成的塗膜。 An electric conductor having a coating film formed of the electroconductive composition according to any one of claims 5 to 7. 一種導電體，其具有由如申請專利範圍第8項所述之導電性組成物所形成的塗膜。 An electric conductor having a coating film formed of the electroconductive composition as described in claim 8 of the patent application. 一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具備含有如申請專利範圍第4項所述之導電性聚合物的固體電解質層。 A solid electrolytic capacitor comprising a solid electrolyte layer containing the conductive polymer according to item 4 of claim 4, on an anodized film formed on a valve action metal body. 一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具有由如申請專利範圍第5項至第7項中任一項所述之導電性組成物所形成的固體電解質層。 A solid electrolytic capacitor having a solid electrolyte layer formed of the conductive composition according to any one of claims 5 to 7 on the anodized film formed on the metal body of the valve. . 一種固體電解電容器，其於形成於閥作用金屬體上的陽極氧化被膜上，具備由如申請專利範圍第8項所述之導電性組成物所形成的固體電解質層。 A solid electrolytic capacitor comprising a solid electrolyte layer formed of the conductive composition according to item 8 of the patent application of the anodic oxide film formed on the valve action metal body. 一種苯胺系導電性聚合物的製造方法，包括：於氧化劑的存在下使如申請專利範圍第1項至第3項中任一項所述之導電性聚合物前驅物聚合，而製造具有下述通式(1-A)所表示的重複單元的苯胺系導電性聚合物(a)，[化3] 式(1-A)中，R¹、R³及R⁴分別獨立選自由氫原子、碳數1~24的直鏈或分支的烷基、碳數1~24的直鏈或分支的烷氧基、酸性基或其鹽、羥基、硝基及鹵素原子所組成的組群中，A為酸性基或其鹽，n為1~20的整數。 A method for producing an aniline-based conductive polymer, comprising: polymerizing a conductive polymer precursor according to any one of claims 1 to 3 in the presence of an oxidizing agent, and having the following An aniline-based conductive polymer (a) of a repeating unit represented by the formula (1-A), [Chemical 3] In the formula (1-A), R ¹ , R ³ and R ⁴ are each independently selected from a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a linear or branched alkoxy group having 1 to 24 carbon atoms. In the group consisting of a group, an acidic group or a salt thereof, a hydroxyl group, a nitro group and a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.