Method for manufacturing solid electrolytic capacitor

A method of producing a solid electrolytic capacitor comprising a step of preparing valve-acting metal having fine pores, a step of forming a dielectric film on the surface of the valve-acting metal, a step of attaching a polymerization reaction solution containing monomers of a conductive polymer on the dielectric film, and a step of polymerizing the monomers of the conductive polymer to thereby form a solid electrolyte layer containing the conductive polymer on the dielectric film;

• wherein the solid electrolyte layer containing the conductive polymer is formed on the dielectric film by polymerizing at least one compound (A1) represented by the following formula (1) without using an oxidizing agent in the presence of a compound (B) having a sulfo group:
• in the formula, R1, R2, R3, R4, R5, and R6 independently represent a monovalent substituent selected from a group consisting of (1) a hydrogen atom, (2) linear or branched alkyl group having 1 to 20 carbon atoms, linear or branched alkoxy group having 1 to 20 carbon atoms, or linear or branched alkyl ester group (alkylcarbonyloxy group or alkoxycarbonyl group) having 1 to 20 carbon atoms, (3) SO2M, (4) a halogen atom, (5) carboxy group, (6) phosphonyl group, (7) nitro group, (8) cyano group, (9) primary, secondary or tertiary amino group, (10) trihalomethyl group, (11) phenyl group, and (12) phenyl group substituted with at least one member selected from alkyl group, hydroxy group, alkoxy group, alkyl ester group, carbonyl group and a halogen atom. Hydrocarbon chains in the substituent represented by R1, R2, R3, R4, R5, and R6 are bound to one another at an arbitrary position and may form at least one bivalent chain that forms at least one three- to seven-membered ring structure of saturated or unsaturated hydrocarbon chain with the carbon atoms to which the substituent is bound;
• the alkyl group, alkoxy group, or alkyl ester group represented by R1, R2, R3, R4, R5, and R6, or a cyclic hydrocarbon chain constituted thereof may contain at least one bond selected from a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond, sulphonyl bond, and an imino bond;
• M represents OH;
• alkali metal alkoxide selected from O−Na+, O−Li+, and O−K+;
• ammonium alkoxide represented by O−NH4+;
• linear or branched alkoxy group having 1 to 20 carbon atoms;
• or a halogen atom selected from chlorine, fluorine, bromine, and iodine;
• and k represents the number of condensed rings surrounded by a hetero ring and a benzene ring having substituents of R1 to R4, which is an integer from 0 to 3.

A method of producing a solid electrolytic capacitor, comprising a step of preparing valve-acting metal having fine pores, a step of forming a dielectric film on the surface of the valve-acting metal, a step of attaching a polymerization reaction solution containing monomers of a conductive polymer on the dielectric film, and a step of polymerizing the monomers of the conductive polymer to thereby form a solid electrolyte layer containing the conductive polymer on the dielectric film;

• wherein the solid electrolyte layer containing the conductive polymer is formed on the dielectric film by polymerizing at least one compound (A2) represented by the following formula (2) without using an oxidizing agent:
• in the formula, R7 is sulfo group;
• R2, R3, R4, R5, and R6 independently represent a monovalent substituent selected from a group consisting of (1) a hydrogen atom, (2) linear or branched alkyl group having 1 to 20 carbon atoms, linear or branched alkoxy group having 1 to 20 carbon atoms, or linear or branched alkyl ester group (alkylcarbonyloxy group or alkoxycarbonyl group) having 1 to 20 carbon atoms, (3) SO2M, (4) a halogen atom, (5) carboxy group, (6) phosphonyl group, (7) nitro group, (8) cyano group, (9) primary, secondary or tertiary amino group, (10) trihalomethyl group, (11) phenyl group, and (12) phenyl group substituted with at least one member selected from alkyl group, hydroxy group, alkoxy group, alkyl ester group, carbonyl group, sulfo group and a halogen atom;
• hydrocarbon chains in the substituent represented by R2, R3, R4, R5, and R6 are bound to one another at an arbitrary position and may form at least one bivalent chain that forms at least one three- to seven-membered ring structure of saturated or unsaturated hydrocarbon chain with the carbon atoms to which the substituent is bound;
• the alkyl group, alkoxy group, or alkyl ester group represented by R2, R3, R4, R5, and R6, or a cyclic hydrocarbon chain constituted thereof may contain at least one bond selected from a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond, sulphonyl bond, and an imino bond;
• M represents OH;
• alkali metal alkoxide selected from O−Na+, O−Li+, and O−K+;
• ammonium alkoxide represented by O−NW;
• linear or branched alkoxy group having 1 to 20 carbon atoms;
• or a halogen atom selected from chlorine, fluorine, bromine, and iodine;
• and k represents the number of condensed rings surrounded by a hetero ring and a benzene ring having substituents of R2 to R4, which is an integer from 0 to 3.

A method of producing a solid electrolytic capacitor, comprising a step of preparing valve-acting metal having fine pores, a step of forming a dielectric film on the surface of the valve-acting metal, a step of attaching a polymerization reaction solution containing monomers of a conductive polymer on the dielectric film, and a step of polymerizing the monomers of the conductive polymer to thereby form a solid electrolyte layer containing the conductive polymer on the dielectric film;

• wherein the solid electrolyte layer containing the conductive polymer is formed on the dielectric film by copolymerizing at least one of compounds (A1) represented by the following formula (1) and at least one of compounds (A2) represented by the following formula (2) without using an oxidizing agent:
• in the formula, R1, R2, R3, R4, R5, and R6 independently represent a monovalent substituent selected from a group consisting of (1) a hydrogen atom, (2) linear or branched alkyl group having 1 to 20 carbon atoms, linear or branched alkoxy group having 1 to 20 carbon atoms, or linear or branched alkyl ester group (alkylcarbonyloxy group or alkoxycarbonyl group) having 1 to 20 carbon atoms, (3) SO2M, (4) a halogen atom, (5) carboxy group, (6) phosphonyl group, (7) nitro group, (8) cyano group, (9) primary, secondary or tertiary amino group, (10) trihalomethyl group, (11) phenyl group, and (12) phenyl group substituted with at least one member selected from alkyl group, hydroxy group, alkoxy group, alkyl ester group, carbonyl group and a halogen atom. Hydrocarbon chains in the substituent represented by R1, R2, R3, R4, R5, and R6 are bound to one another at an arbitrary position and may form at least one bivalent chain that forms at least one three- to seven-membered ring structure of saturated or unsaturated hydrocarbon chain with the carbon atoms to which the substituent is bound;
• the alkyl group, alkoxy group, or alkyl ester group represented by R1, R2, R3, R4, R5, and R6, or a cyclic hydrocarbon chain constituted thereof may contain at least one bond selected from a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond, sulphonyl bond, and an imino bond;
• M represents OH;
• alkali metal alkoxide selected from O−Na+, O−Li+, and O−K+;
• ammonium alkoxide represented by O−NH4+;
• linear or branched alkoxy group having 1 to 20 carbon atoms;
• or a halogen atom selected from chlorine, fluorine, bromine, and iodine;
• and k represents the number of condensed rings surrounded by a hetero ring and a benzene ring having substituents of R1 to R4, which is an integer from 0 to 3;
• in the formula, R7 is sulfo group;
• R2, R3, R4, R5, and R6 independently represent a monovalent substituent selected from a group consisting of (1) a hydrogen atom, (2) linear or branched alkyl group having 1 to 20 carbon atoms, linear or branched alkoxy group having 1 to 20 carbon atoms, or linear or branched alkyl ester group (alkylcarbonyloxy group or alkoxycarbonyl group) having 1 to 20 carbon atoms, (3) SO2M, (4) a halogen atom, (5) carboxy group, (6) phosphonyl group, (7) nitro group, (8) cyano group, (9) primary, secondary or tertiary amino group, (10) trihalomethyl group, (11) phenyl group, and (12) phenyl group substituted with at least one member selected from alkyl group, hydroxy group, alkoxy group, alkyl ester group, carbonyl group, sulfo group and a halogen atom;
• hydrocarbon chains in the substituent represented by R2, R3, R4, R5, and R6 are bound to one another at an arbitrary position and may form at least one bivalent chain that forms at least one three- to seven-membered ring structure of saturated or unsaturated hydrocarbon chain with the carbon atoms to which the substituent is bound;
• the alkyl group, alkoxy group, or alkyl ester group represented by R2, R3, R4, R5, and R6, or a cyclic hydrocarbon chain constituted thereof may contain at least one bond selected from a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond, sulphonyl bond, and an imino bond;
• M represents OH;
• alkali metal alkoxide selected from O−Na+, O−Li+, and O−K+;
• ammonium alkoxide represented by O−NH4+;
• linear or branched alkoxy group having 1 to 20 carbon atoms;
• or a halogen atom selected from chlorine, fluorine, bromine, and iodine;
• and k represents the number of condensed rings surrounded by a hetero ring and a benzene ring having substituents of R2 to R4, which is an integer from 0 to 3.