ELECTRIC CONDUCTIVE POLYMER SUSPENSION AND METHOD FOR PRODUCING THE SAME, ELECTRIC CONDUCTIVE POLYMER MATERIAL, AND ELECTROLYTIC CAPACITOR AND METHOD FOR PRODUCING THE SAME

• US 20140211372A1
• Filed: 05/17/2012
• Published: 07/31/2014
• Est. Priority Date: 05/17/2011
• Status: Active Grant

• Current Assignee: Tokin Corporation (Yageo Corporation)
• Original Assignee: NEC Tokin Corporation (Yageo Corporation)
• Inventors: Sugawara, Yasuhisa, Nobuta, Tomoki, Suzuki, Satoshi, Tomioka, Yasuhiro
• Granted Patent: US 9,455,092 B2
• Time in Patent Office: Days
• US Class Current: 361/525
• CPC Class Codes: C08G 2261/3221 containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/794 with polymeric dopants
• CPC Class Codes: C08G 73/0266 Polyanilines or derivatives thereof
• CPC Class Codes: C08K 5/053 Polyhydroxylic alcohols
• CPC Class Codes: C08L 101/12 characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity liquid crystal materials or compositions C09K19/00
• CPC Class Codes: C08L 25/18 Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 125/18 Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01B 1/20 Conductive material dispersed in non-conductive organic material organic macromolecular compounds or compositions C08
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 9/0036 Formation of the solid electrolyte layer
• CPC Class Codes: H01G 9/028 Organic semiconducting electrolytes, e.g. TCNQ
• CPC Class Codes: H01G 9/15 Solid electrolytic capacitors H01G11/00 takes precedence
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

An electric conductive polymer suspension is produced by performing chemical oxidative polymerization of a monomer for providing an electric conductive polymer by using an oxidant in a solvent containing an organic acid or a salt thereof as a dopant to form an electric conductive polymer, recovering the electric conductive polymer, allowing an oxidant to act on the electric conductive polymer in an aqueous solvent containing a polyacid, and further mixing a dispersant with a branched structure and then pulverizing the electric conductive polymer. According to the electric conductive polymer suspension, an organic material high in conductivity, and excellent in adhesiveness to a substrate and water resistance, and a method for producing the material, as well as an electrolytic capacitor and a method for producing the capacitor can be provided.

Claims

1-35. -35. (canceled)

36. An electric conductive polymer suspension comprising an electric conductive polymer, at least one polyanion, and at least one dispersant with a branched structure.

37. The electric conductive polymer suspension according to claim 36, wherein the electric conductive polymer comprises an electric conductive polymer with a particle size of 100 nm or less.

38. The electric conductive polymer suspension according to claim 36, wherein the particle size of the electric conductive polymer is 100 nm or less.

39. The electric conductive polymer suspension according to claim 36, wherein the dispersant with a branched structure comprises a structure bearing an adsorption group for adsorption to the electric conductive polymer in a main chain, and bearing one or more hydrophilic and/or hydrophobic side chains.

40. The electric conductive polymer suspension according to claim 36, wherein the amount of the polyanion is 10 to 200 parts by weight, and the amount of the dispersant with a branched structure is 1 to 120 parts by weight, with respect to 100 parts by weight of the electric conductive polymer.

41. The electric conductive polymer suspension according to claim 36, wherein the electric conductive polymer is a polymer including at least one of pyrrole, thiophene, and derivatives thereof.

42. The electric conductive polymer suspension according to claim 36, containing polystyrene sulfonic acid as the polyanion.

43. The electric conductive polymer suspension according to claim 42, wherein the weight average molecular weight of the polystyrene sulfonic acid is 2,000 to 500,000.

44. The electric conductive polymer suspension according to claim 36, comprising at least one water-soluble binder.

45. The electric conductive polymer suspension according to claim 44, wherein the water-soluble binder is at least one of polyester and polyamide.

46. The electric conductive polymer suspension according to claim 44, wherein the amount of the at least one water-soluble binder is 10 to 400 parts by weight with respect to 100 parts by weight of the electric conductive polymer.

47. The electric conductive polymer suspension according to claim 36, comprising erythritol and/or pentaerythritol.

64. An electric conductive polymer material formed by drying the electric conductive polymer suspension according to claim 36 to remove the solvent.

66. An electrolytic capacitor comprising an electrolyte layer comprising the electric conductive polymer material according to claim 64.

68. The electrolytic capacitor according to claim 66, comprising an anode conductor comprising a valve metal, and a dielectric layer formed on the surface of the anode conductor, wherein the electrolyte layer is formed on the dielectric layer.

69. A method for producing an electrolytic capacitor, comprising a step of forming a dielectric layer on the surface of an anode conductor including a valve metal, and

a step of coating or impregnating the dielectric layer with the electric conductive polymer suspension according to claim 36 to form an electrolyte layer on the dielectric layer.

71. A method for producing an electrolytic capacitor, comprising

a step of forming a dielectric layer on the surface of an anode conductor including a valve metal,

a step of performing chemical oxidative polymerization or electropolymerization of a monomer for providing a first electric conductive polymer compound to form a first electric conductive polymer compound layer on the dielectric layer, and

a step of coating or impregnating the first electric conductive polymer compound layer with the electric conductive polymer suspension according to claim 36 to form a second electric conductive polymer compound layer on the first electric conductive polymer compound layer.

73. The method for producing an electrolytic capacitor according to claim 71, wherein the first electric conductive polymer compound is a polymer of at least one selected from pyrrole, thiophene, aniline, and derivatives thereof.

75. The method for producing an electrolytic capacitor according to any one of claims 69, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.

78. The method for producing an electrolytic capacitor according to any one of claims 71, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.

80. The method for producing an electrolytic capacitor according to any one of claims 73, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.

48. A method for producing an electric conductive polymer suspension, comprising:

a first step of performing chemical oxidative polymerization of a monomer for providing an electric conductive polymer by using an oxidant in a solvent containing an organic acid or a salt thereof as a dopant to provide an electric conductive polymer-containing mixture,

a second step of recovering the electric conductive polymer from the mixture,

a third step of mixing an oxidant with the electric conductive polymer in an aqueous solvent containing a polyanion, and

a fourth step of mixing a dispersant with a branched structure and then, pulverizing the electric conductive polymer.

49. The method for producing an electric conductive polymer suspension according to claim 48, wherein the monomer for providing an electric conductive polymer is at least one selected from pyrrole, thiophene, and derivatives thereof.

50. The method for producing an electric conductive polymer suspension according to claim 48, wherein the dopant is at least one selected from benzenesulfonic acid, naphthalenesulfonic acid, camphorsulfonic acid and derivatives thereof, and salts thereof.

51. The method for producing an electric conductive polymer suspension according to claim 48, wherein the first step is performed in the presence of a substance with a surface-active action.

52. The method for producing an electric conductive polymer suspension according to claim 48, wherein in the second step, the electric conductive polymer is washed with a solvent capable of dissolving the monomer and/or the oxidant.

53. The method for producing an electric conductive polymer suspension according to claim 48, wherein in the third step, polystyrene sulfonic acid is used as the polyanion.

54. The method for producing an electric conductive polymer suspension according to claim 53, wherein the weight average molecular weight of the polystyrene sulfonic acid is 2,000 to 500,000.

55. The method for producing an electric conductive polymer suspension according to claim 48, wherein in the fourth step, the electric conductive polymer is pulverized so that the electric conductive polymer includes an electric conductive polymer particles having a particle size of 100 nm or less.

56. The method for producing an electric conductive polymer suspension according to claim 48, wherein in the fourth step, the electric conductive polymer is pulverized so that the particle size thereof is 100 nm or less.

57. The method for producing an electric conductive polymer suspension according to claim 48, wherein the dispersant with a branched structure is provided with a structure bearing an adsorption group for adsorption to the electric conductive polymer in a main chain, and bearing one or more hydrophilic and/or hydrophobic side chains.

58. The method for producing an electric conductive polymer suspension according to claim 48, wherein the amount of the polyanion is 10 to 200 parts by weight, and the amount of the dispersant with a branched structure is 1 to 120 parts by weight, with respect to 100 parts by weight of the electric conductive polymer.

59. The method for producing an electric conductive polymer suspension according to claim 48, wherein at least one water-soluble binder is mixed during or after the fourth step.

60. The method for producing an electric conductive polymer suspension according to claim 59, wherein the water-soluble binder is at least one of polyester and polyamide.

61. The method for producing an electric conductive polymer suspension according to claim 59, wherein the at least one water-soluble binder is mixed in an amount of 10 to 400 parts by weight with respect to 100 parts by weight of the electric conductive polymer.

62. The method for producing an electric conductive polymer suspension according to claim 48, wherein erythritol and/or pentaerythritol are/is mixed during or after the fourth step.

63. An electric conductive polymer suspension obtained by the method according to claim 48.

65. An electric conductive polymer material formed by drying the electric conductive polymer suspension according to claim 63 to remove the solvent.

67. n electrolytic capacitor comprising an electrolyte layer comprising the electric conductive polymer material according to claim 65.

70. A method for producing an electrolytic capacitor, comprising

a step of forming a dielectric layer on the surface of an anode conductor including a valve metal, and

a step of coating or impregnating the dielectric layer with the electric conductive polymer suspension according to claim 63 to form an electrolyte layer on the dielectric layer.

72. A method for producing an electrolytic capacitor, comprising

a step of forming a dielectric layer on the surface of an anode conductor including a valve metal,

a step of performing chemical oxidative polymerization or electropolymerization of a monomer for providing a first electric conductive polymer compound to form a first electric conductive polymer compound layer on the dielectric layer, and

a step of coating or impregnating the first electric conductive polymer compound layer with the electric conductive polymer suspension according to claim 63 to form a second electric conductive polymer compound layer on the first electric conductive polymer compound layer.

74. The method for producing an electrolytic capacitor according to claim 72, wherein the first electric conductive polymer compound is a polymer of at least one selected from pyrrole, thiophene, aniline, and derivatives thereof.

76. The electrolytic capacitor according to claim 67, comprising an anode conductor comprising a valve metal, and a dielectric layer formed on the surface of the anode conductor, wherein the electrolyte layer is formed on the dielectric layer.

77. The method for producing an electrolytic capacitor according to any one of claims 70, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.

79. The method for producing an electrolytic capacitor according to any one of claims 72, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.

81. The method for producing an electrolytic capacitor according to any one of claims 74, wherein the valve metal is at least one selected from aluminum, tantalum, and niobium.