WO2023218872A1 - ポリマー型導電性ペースト、導電膜、及び、固体電解コンデンサ素子 - Google Patents

ポリマー型導電性ペースト、導電膜、及び、固体電解コンデンサ素子 Download PDF

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WO2023218872A1
WO2023218872A1 PCT/JP2023/015416 JP2023015416W WO2023218872A1 WO 2023218872 A1 WO2023218872 A1 WO 2023218872A1 JP 2023015416 W JP2023015416 W JP 2023015416W WO 2023218872 A1 WO2023218872 A1 WO 2023218872A1
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conductive paste
polymer
type conductive
mass
acid
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French (fr)
Japanese (ja)
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WO2023218872A9 (ja
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恵 河原
将平 荒木
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Shoei Chemical Inc
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Shoei Chemical Inc
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Priority to US18/864,316 priority Critical patent/US12384925B2/en
Priority to CN202380039037.2A priority patent/CN119096318B/zh
Priority to KR1020247037809A priority patent/KR102847696B1/ko
Publication of WO2023218872A1 publication Critical patent/WO2023218872A1/ja
Publication of WO2023218872A9 publication Critical patent/WO2023218872A9/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F116/38—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a acetal or ketal radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G2009/05—Electrodes or formation of dielectric layers thereon characterised by their structure consisting of tantalum, niobium, or sintered material; Combinations of such electrodes with solid semiconductive electrolytes, e.g. manganese dioxide

Definitions

  • the present invention relates to a polymer-type conductive paste, a conductive film, and a solid electrolytic capacitor element that can be suitably used for forming conductor layers in solid electrolytic capacitor elements such as tantalum capacitors and electrodes of multilayer ceramic electronic components.
  • the polymer type conductive paste of the present invention is used, for example, in a method for manufacturing a solid electrolyte capacitor element.
  • Solid electrolytic capacitor elements generally have a dielectric layer formed by chemical conversion treatment on the surface of an anode body made of a metal that has a valve action, and an electrolyte layer made of a conductive polymer or the like, a carbon layer, and a conductive layer on the surface. It has a structure in which cathode layers made of paste are successively formed. Then, the cathode layer is adhered to the cathode lead terminal using a conductive adhesive, the anode body is joined to the anode lead terminal by welding, and a molding resin is applied to the outside of these to form a capacitor component.
  • FIG. 1 shows an example of the structure of a solid electrolytic capacitor element.
  • the solid electrolytic capacitor element 1 includes a valve metal sintered body 11 obtained by sintering a valve metal such as tantalum, niobium, titanium, aluminum, etc., an oxide film layer 12 formed on the surface of the sintered body 11, and the oxide film layer 12 formed on the surface of the sintered body 11. It has a structure including a solid electrolyte layer 13, a carbon layer 14, and a conductor layer 15 formed thereon.
  • the sintered body 11 is used as an anode body
  • the oxide film layer 12 is used as a dielectric layer
  • the carbon layer 14 and conductor layer 15 on the solid electrolyte layer 13 are used as a cathode body.
  • the oxide film layer 12 is preferably made of an oxidized sintered body, but may be made of other oxides.
  • manganese dioxide, conductive polymers, and the like are widely used.
  • the carbon layer 14 is formed by applying and drying a carbon paste in which carbon powder is dispersed in an organic vehicle. It is believed that this carbon layer 14 can lower the contact resistance between the solid electrolyte layer 13 and the conductor layer 15, and lower the ESR (equivalent series resistance).
  • the conductor layer 15 is usually formed by applying, drying, and/or curing a conductive paste in which metal powder such as silver is dispersed in an organic vehicle.
  • a conductive paste in which metal powder such as silver is dispersed in an organic vehicle.
  • Such solid electrolytic capacitor elements have been widely known as described in Patent Document 1 and Patent Document 2.
  • Patent Document 1 discloses a solid electrolytic capacitor including, on the surface of an anode body, at least a dielectric layer, a solid electrolyte layer, a carbon layer containing a first resin component, and a conductor layer containing a second resin component.
  • ESR deterioration is small and ESR changes over time for each product are minimized. It is described that the solid electrolytic capacitor element has suppressed variations.
  • Patent Document 2 attempts to solve the above problem by dispersing conductive polymer particles in a solid electrolyte layer and using a polymer with a controlled water content as a resin component in the conductor layer. Specifically, by dispersing thiophene polymer particles in the solid electrolyte layer to prevent the movement of silver ions, and by using vinyl acetal polymer with a small amount of residual hydroxyl groups in the polymer as the resin component of the conductor layer, It is said that the water content of the conductor layer can be lowered.
  • the residual amount of hydroxyl groups is 35 mol% or less, preferably 10 mol% or more and 25 mol% or less, and as an example of such a polymer, " BH-S" (polyvinyl butyral resin) is exemplified.
  • Moisture resistance can be improved by using, for example, an epoxy resin that provides a dense cured film instead of polyvinyl butyral resin.
  • an epoxy resin that provides a dense cured film instead of polyvinyl butyral resin.
  • the cured film of epoxy resin is very hard, it is not suitable for use depending on the purpose. Therefore, there are many requests for improvement in the moisture resistance of paste using polyvinyl butyral resin.
  • moisture resistance can be improved to some extent by adding compounds such as 5-amino-2hydroxybenzoic acid, naphthol, cresol, and salicylic acid to a conductive paste using polyvinyl butyral resin. could be improved, but not necessarily enough.
  • an object of the present invention is to provide a polymer type conductive paste that can provide a highly reliable conductive layer even in a high humidity environment.
  • the present invention which solves the above problems, relates to the following polymer-type conductive paste, conductive film, and solid electrolytic capacitor element.
  • a polymer-type conductive paste containing conductive metal powder, binder resin, organic solvent, and specific additives The binder resin is polyvinyl butyral resin,
  • the specific additive is selected from the group consisting of stearic acid, lauric acid, octadecylbutanedioic acid, benzoic acid, acetamidophenol, aminophenol, catechol, and N,N-bis(2-hydroxyethyl)cocoalkylamine.
  • the specific additive is octadecyl butanedioic acid.
  • a solid electrolytic capacitor element comprising at least a dielectric layer, a solid electrolyte layer, a carbon layer, and a conductor layer on the surface of the anode body, A solid electrolytic capacitor element, wherein the conductive layer is made of the conductive film described in (6) above.
  • the conductor layer formed by the polymer-type conductive paste of the present invention has low moisture permeability even in a high-humidity environment, and therefore ionization of silver in the conductor layer is suppressed, resulting in a highly reliable conductor layer. can be obtained.
  • FIG. 1 is a diagram showing an example of a solid electrolytic capacitor element.
  • polymer-type conductive paste refers to a "fired-type conductive paste” in which organic components in the coating film are scattered by firing, leaving only inorganic components in the resulting conductive film.
  • This term refers to a type of paste in which organic components including a binder resin remain in the conductive film obtained by drying and/or curing the coating film.
  • the use of the polymer-type conductive paste of the present invention is not limited, and it can be used to form electrodes for general electric circuit wiring and electronic components, such as multilayer ceramic electronic components, but it can also be used for solid electrolytic capacitor elements such as tantalum capacitors. It is particularly preferable to use it for forming a conductive layer in , since the effects of the present invention can be fully enjoyed.
  • the polymer-type conductive paste of the present invention is applied to the solid electrolytic capacitor element shown in FIG. 1 will be explained.
  • the conductor layer 15 mainly consists of conductive metal powder and polyvinyl butyral resin. After applying the polymer-type conductive paste of the present invention on the carbon layer 14, it is heated to about 120° C. or more and 220° C. or less, and an organic solvent is removed. Obtained by removing and drying.
  • the polymer type conductive paste of the present invention contains at least conductive metal powder, polyvinyl butyral resin as a binder resin, an organic solvent capable of dissolving the binder resin, and specific additives.
  • the conductive metal powder contained in the polymer type conductive paste is not particularly limited, but metal powders commonly used in conductive pastes such as silver, copper, nickel, palladium, aluminum, etc. can be used.
  • silver powder is particularly preferred, and in addition to pure silver powder, silver coated powder in which the surface of metal powder other than silver is coated with silver, composite silver powder in which the surface of silver powder is coated with inorganic and/or organic matter, and even A silver alloy powder obtained by alloying silver with a metal other than silver may also be used.
  • silver-based powder By using silver-based powder, the effects of the present invention can be further enjoyed, and it is also advantageous from the viewpoints of conductivity and cost.
  • a mixed powder obtained by mixing these silver-based powders with other conductive metal powders such as palladium, platinum, copper, or metal oxides may be used. In either case, the content of the silver component relative to the entire conductive metal powder is preferably 10% by mass or more.
  • the shape of the conductive metal powder can be conventionally used, such as spherical, flaky, or dendritic, and differs in one or more of the properties such as average particle size, particle size distribution, and shape. Two or more types may be mixed and used. In the present invention, it is particularly preferable to use a mixture of spherical silver-based powder and flaky silver-based powder because it facilitates control of conductivity, moisture resistance, etc.
  • Polyvinyl butyral resin is used as the binder resin contained in the polymer-type conductive paste of the present invention.
  • the content of polyvinyl butyral resin is not particularly limited and may be determined as appropriate depending on the properties required for the paste.
  • the solid component of the polyvinyl butyral resin is in the range of 1.0 parts by mass or more and 20 parts by mass or less.
  • the binder resin may contain resins other than polyvinyl butyral resin as long as they do not impede the effects of the present invention, examples of which include cellulose resin, acrylic resin, methacrylic resin, epoxy resin, phenol resin, rosin acrylic resin, etc. can be mentioned.
  • the amount of residual hydroxyl groups in the polyvinyl butyral resin used in the present invention is not particularly limited, but is preferably 35 mol % or less since it increases moisture resistance. More preferably, the residual amount of hydroxyl groups is 30 mol% or less, particularly preferably 25 mol% or less.
  • Any organic solvent may be used as long as it shows solubility in the binder resin used.
  • alcohol-based, ether-based, ester-based, or hydrocarbon-based organic solvents may be used, and two types may be used as necessary.
  • the above organic solvents and mixed solvents with water can also be used.
  • the polymer-type conductive paste of the present invention contains stearic acid, lauric acid, octadecylbutanedioic acid, benzoic acid, acetamidophenol, aminophenol, catechol, and N,N-bis(2-hydroxyethyl)cocoalkyl as specific additives. It is characterized by containing one or more selected from the group consisting of amines. Since these specific additives function as moisture permeability regulators in the paste of the present invention, they may also be referred to as moisture permeability regulators in this specification.
  • moisture permeability modifiers when a predetermined amount of these moisture permeability modifiers is blended into a paste containing polyvinyl butyral resin as a binder, there is almost no adverse effect on conductivity, printability (thixotropy), etc.
  • the moisture permeability (moisture permeability) of the film obtained by applying and drying the paste is significantly reduced, and as a result, the moisture resistance of the film can be improved.
  • octadecyl butanedioic acid is particularly preferred because it can be expected to have the effect of increasing membrane density and lowering ESR.
  • the content of these moisture permeability modifiers based on 100 parts by mass of the conductive metal powder is within the range of 0.01 parts by mass or more and 3.0 parts by mass or less. If the content of the moisture permeability modifier is outside the range, moisture resistance will deteriorate and other properties (eg, conductivity) may be adversely affected.
  • the content of the moisture permeability regulator is preferably in the range of 0.1 parts by mass or more and 1.5 parts by mass or less.
  • polymer type conductive paste of the present invention may contain general additives such as surfactants, antifoaming agents, plasticizers, dispersants, etc., and organic or inorganic fillers, etc., which are appropriately blended as necessary. May be added.
  • Sample 1 was a silver paste prepared by stirring and diluting with butyl acetate so that the viscosity was 1 Pa ⁇ s as measured with a Brookfield viscometer HA type at 25°C and a shear rate of 9.3 s -1 . .
  • Sample 3 The composition of Sample 2 was the same as Sample 2, except that 0.5 parts by mass of p-acetamidophenol ("3-hydroxyacetanilide" manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 parts by mass of silver powder. The obtained silver paste was designated as Sample 3.
  • Sample 4 was a silver paste obtained in the same manner as Sample 3 except that stearic acid ("Stearic Acid 90" manufactured by Miyoshi Oil Co., Ltd.) was used in place of acetamidophenol.
  • stearic acid (“Stearic Acid 90" manufactured by Miyoshi Oil Co., Ltd.) was used in place of acetamidophenol.
  • Sample 5 was a silver paste obtained in the same manner as Sample 3 except that lauric acid ("Lauric acid” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used in place of acetamidophenol.
  • lauric acid manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • Sample 6 was a silver paste obtained in the same manner as Sample 3 except that octadecyl butanedioic acid (dicarboxylic acid "Hypermer KD-16" manufactured by Croda Japan) was used in place of acetamidophenol.
  • octadecyl butanedioic acid dicarboxylic acid "Hypermer KD-16" manufactured by Croda Japan
  • Sample 7 was a silver paste obtained in the same manner as Sample 3 except that benzoic acid ("Benzoic Acid” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used in place of acetamidophenol.
  • benzoic acid (“Benzoic Acid” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used in place of acetamidophenol.
  • Sample 8 was a silver paste obtained in the same manner as Sample 3 except that aminophenol ("p-aminophenol” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used in place of acetamidophenol.
  • Sample 9 was a silver paste obtained in the same manner as Sample 3 except that catechol ("Pyrocatechol” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used in place of acetamidophenol.
  • Sample 10 Silver paste obtained in the same manner as Sample 3 except that N,N-bis(2-hydroxyethyl)coconutylamine (Esomin "Liponol C/12" manufactured by Lion Specialty Chemicals) was used in place of acetamidophenol. was designated as sample 10.
  • Sample 11 was a silver paste obtained in the same manner as Sample 3 except that stearylamine ("Fermin 80" manufactured by Kao Corporation) was used in place of acetamidophenol.
  • Samples 12-21 were silver pastes obtained in the same manner as Sample 3 except that the amounts of conductive metal powder, polyvinyl butyral resin, and acetamidophenol were set as shown in Table 2.
  • Samples 22 to 25 were silver pastes obtained in the same manner as Sample 6, except that the amounts of conductive metal powder, polyvinyl butyral resin, and octadecyl butanedioic acid were set as shown in Table 3.
  • ⁇ Moisture permeability test> Each sample silver paste was applied onto a PET film, heated at 150° C. for 60 minutes, and then peeled off from the PET film to produce a sample dry film having a thickness of 20 ⁇ 2 ⁇ m.
  • plastic container B After container A was placed in plastic container B, the opening of plastic container B was completely sealed. Thereafter, the plastic container B containing the glass container A was heated to raise the temperature from room temperature to 65° C., and then held as it was for 15 hours. After the holding time had elapsed, the slowly cooled plastic container B was opened, the glass container A inside was taken out, the total mass of the glass container A was weighed again, and the increase was taken as the amount of moisture permeation (mg). In this example, samples with a moisture permeation amount of less than 20 mg were accepted.
  • the present invention can be applied to solid electrolytic capacitor elements and multilayer ceramic electronic components.

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PCT/JP2023/015416 2022-05-09 2023-04-18 ポリマー型導電性ペースト、導電膜、及び、固体電解コンデンサ素子 Ceased WO2023218872A1 (ja)

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US18/864,316 US12384925B2 (en) 2022-05-09 2023-04-18 Polymer-type conductive paste, conductive film, and solid electrolytic capacitor element
CN202380039037.2A CN119096318B (zh) 2022-05-09 2023-04-18 聚合物型导电性糊剂、导电膜和固体电解电容器元件
KR1020247037809A KR102847696B1 (ko) 2022-05-09 2023-04-18 폴리머형 도전성 페이스트, 도전막 및 고체 전해 콘덴서 소자

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JPH10162646A (ja) * 1996-11-28 1998-06-19 Asahi Chem Ind Co Ltd 導電性樹脂組成物
WO2013111438A1 (ja) * 2012-01-27 2013-08-01 昭栄化学工業株式会社 固体電解コンデンサ素子、その製造方法及び導電ペースト
JP2020500427A (ja) * 2016-11-15 2020-01-09 エイブイエックス コーポレイション 高湿度雰囲気中で用いるための固体電解キャパシタ

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JP2008124030A (ja) * 2007-11-30 2008-05-29 Jsr Corp 導電性ペースト組成物、転写フィルムおよびプラズマディスプレイパネル
JP6247015B2 (ja) * 2013-04-04 2017-12-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ ポリマー型導電性ペースト、及びポリマー型導電性ペーストを用いた電極の製造方法
EP3010870A1 (de) * 2013-06-05 2016-04-27 CeramTec GmbH Metallisierung auf keramischen substraten
CN105405490A (zh) * 2015-12-23 2016-03-16 东洋油墨Sc控股株式会社 激光加工用导电性糊、导电性片材、信号布线的制造方法及电子设备
JP6635186B2 (ja) * 2016-02-29 2020-01-22 住友金属鉱山株式会社 導電性ペースト、電子部品及び積層セラミックコンデンサ
WO2018062220A1 (ja) * 2016-09-30 2018-04-05 Ｄｏｗａエレクトロニクス株式会社 接合材およびそれを用いた接合方法
EP3648115A4 (en) * 2017-06-30 2021-03-24 Sekisui Chemical Co., Ltd. CONDUCTIVE PASTE
MY209180A (en) * 2018-12-25 2025-06-26 Sumitomo Metal Mining Co Conductive paste, electronic component, and laminated ceramic capacitor

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JPH10162646A (ja) * 1996-11-28 1998-06-19 Asahi Chem Ind Co Ltd 導電性樹脂組成物
WO2013111438A1 (ja) * 2012-01-27 2013-08-01 昭栄化学工業株式会社 固体電解コンデンサ素子、その製造方法及び導電ペースト
JP2020500427A (ja) * 2016-11-15 2020-01-09 エイブイエックス コーポレイション 高湿度雰囲気中で用いるための固体電解キャパシタ

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CN119096318B (zh) 2026-01-02
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CN119096318A (zh) 2024-12-06
CZ2024429A3 (cs) 2024-12-11
CZ310405B6 (cs) 2025-05-14
KR20240167095A (ko) 2024-11-26
TWI906615B (zh) 2025-12-01
WO2023218872A9 (ja) 2024-07-04
TW202402975A (zh) 2024-01-16
JP2023166098A (ja) 2023-11-21
JP7540459B2 (ja) 2024-08-27

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