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WO2009131011A1 - Dispersion de composition électroconductrice, composition électroconductrice et utilisation de celles-ci - Google Patents

Dispersion de composition électroconductrice, composition électroconductrice et utilisation de celles-ci Download PDF

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Publication number
WO2009131011A1
WO2009131011A1 PCT/JP2009/057241 JP2009057241W WO2009131011A1 WO 2009131011 A1 WO2009131011 A1 WO 2009131011A1 JP 2009057241 W JP2009057241 W JP 2009057241W WO 2009131011 A1 WO2009131011 A1 WO 2009131011A1
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Prior art keywords
conductive composition
dispersion
acid
conductive
solid electrolytic
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English (en)
Japanese (ja)
Inventor
良介 杉原
兄 廣田
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Tayca Corp
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Tayca Corp
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Priority to CN200980103893XA priority Critical patent/CN101932628B/zh
Priority to JP2009528934A priority patent/JP4454041B2/ja
Publication of WO2009131011A1 publication Critical patent/WO2009131011A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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

Definitions

  • the present invention relates to a dispersion of a conductive composition, a conductive composition obtained by drying the dispersion of the conductive composition, an antistatic film and an antistatic sheet using the conductive composition as a conductor
  • the present invention also relates to a solid electrolytic capacitor using the conductive composition as a solid electrolyte.
  • the conductive polymer is used as a solid electrolyte of a solid electrolytic capacitor such as a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, or an aluminum solid electrolytic capacitor because of its high conductivity.
  • conductive polymer in this application for example, those synthesized by oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof are used.
  • organic sulfonic acid is mainly used, and among them, aromatic sulfonic acid is said to be suitable.
  • Transition metals are used as oxidants, among which ferric iron is said to be suitable.
  • ferric salts of aromatic sulfonic acids are chemically oxidative polymerization of polymerizable monomers such as thiophene or its derivatives. It is used as an oxidizing agent / dopant agent.
  • ferric salts of aromatic sulfonic acids it is said that ferric salts of toluene sulfonic acid and ferric salts of methoxybenzene sulfonic acid are particularly useful, and conductive polymers using them. It can be synthesized by mixing those oxidizing agent / dopant with a polymerizable monomer such as thiophene or a derivative thereof, and is reported to be simple and suitable for industrialization (Patent Document 1, Patent Document) 2).
  • the conductive polymer obtained using ferric toluenesulfonate as an oxidizing agent and dopant does not have sufficiently satisfactory characteristics in terms of initial resistance and heat resistance, and methoxybenzenesulfonic acid.
  • the conductive polymer obtained using ferric salt as an oxidant and dopant has lower initial resistance and excellent heat resistance than the conductive polymer using ferric toluenesulfonate. Even so, satisfactory characteristics were not obtained.
  • toluene sulfonic acid ferric salt and methoxybenzene sulfonic acid ferric salt are solid, so they are generally used in a state of being dissolved in alcohol, but these solutions are precipitated during storage. This is because.
  • the conductive polymer synthesized by a chemical oxidation polymerization method is usually not soluble in a solvent, so tantalum, niobium, aluminum, etc. It is necessary to form a conductive polymer layer directly on an element having an anode made of a porous body of the valve metal and a dielectric layer made of an oxide film of the valve metal.
  • Patent Document 3 solubilized conductive polymers have been actively studied.
  • Patent Document 3 it is reported that a dispersion of a conductive polymer can be obtained by mixing and reacting polystyrene sulfonic acid, ammonium persulfate, iron salt, ethylenedioxythiophene, and the like.
  • the conductive polymer obtained thereby cannot be said to have sufficiently high conductivity, and further improvement in conductivity is necessary for use as a solid electrolyte of a solid electrolytic capacitor.
  • Patent Documents 6 to 7 studies have been made on solubilized conductive polymers by electrolytic oxidation polymerization.
  • Patent Documents 6 to 7 there is a problem that it is difficult to use industrially because it requires a process of taking out and solubilizing the insoluble conductive polymer formed on the electrode.
  • the present invention provides a conductive composition having high conductivity and excellent heat resistance, and using the conductive composition as a conductor, having high conductivity,
  • An object of the present invention is to provide an antistatic film having excellent heat resistance, and to provide a solid electrolytic capacitor having low ESR and high reliability under high temperature conditions using the conductive composition as a solid electrolyte. To do.
  • the present invention provides thiophene or a derivative thereof in water or water miscibility in the presence of a phenolsulfonic acid novolak resin having a repeating unit represented by the above general formula (I), sulfonated polyester or polystyrenesulfonic acid.
  • Dispersion of a conductive composition comprising a conductive polymer obtained by electrolytic oxidative polymerization in an aqueous liquid composed of a mixture with a solvent, and a high-boiling solvent or an organic acid having a cyclic structure Regarding liquids.
  • the present invention also provides a conductive composition obtained by drying a dispersion of the conductive composition, an antistatic film and an antistatic sheet using the conductive composition as a conductor, and the conductive composition.
  • the present invention relates to a solid electrolytic capacitor using as a solid electrolyte.
  • the conductive composition of the present invention has high transparency, high conductivity, and excellent heat resistance. Further, the conductive composition of the present invention is highly transparent, and since the conductive polymer is synthesized by electrolytic oxidation polymerization, it can be seen in the conductive polymer synthesized by chemical oxidation polymerization. The content of sulfate radicals based on an oxidizing agent is small, and there is little decrease in conductivity or transparency due to residual sulfate radicals.
  • the conductive composition of the present invention by using it as a conductor, an antistatic film, an antistatic resin having high transparency, high conductivity, and excellent heat resistance, An antistatic sheet or the like can be obtained.
  • the conductive composition of the present invention having such high conductivity and excellent heat resistance as a solid electrolyte, a solid electrolytic capacitor having low ESR and high reliability under high temperature conditions can be obtained. Can do.
  • a phenol sulfonic acid novolak resin, sulfonated polyester or polystyrene sulfonic acid having a repeating unit represented by the general formula (I) is used for the synthesis of the conductive polymer. It functions as an excellent dispersing agent during the synthesis of thiophene as a polymerizable monomer or a derivative thereof, and a catalyst to be added as necessary, uniformly in water or an aqueous liquid, and a dopant in the synthesized polymer. To make the conductive polymer highly conductive. And it is thought that it is a factor which can synthesize
  • phenolsulfonic acid novolak resin represented by the general formula (I) those having a number average molecular weight of 5,000 to 500,000 are preferable. This is based on the following reason.
  • the resulting conductive polymer has low conductivity and may have poor transparency.
  • the number average molecular weight of the said phenolsulfonic acid novolak resin is larger than 500,000, there exists a possibility that the viscosity of the dispersion liquid of an electroconductive composition may become high, and it may become difficult to use it for manufacture of a solid electrolytic capacitor etc.
  • the phenol sulfonic acid novolak resin has a number average molecular weight of preferably 10,000 or more, more preferably 400,000 or less, and more preferably 80,000 or less within the above range. .
  • the sulfonated polyester is a mixture of dicarboxybenzene sulfonic acid such as sulfoisophthalic acid and sulfoterephthalic acid or dicarboxybenzene sulfonic acid diester such as sulfoisophthalic acid ester and sulfoterephthalic acid ester and alkylene glycol.
  • a mixture of the above dicarboxybenzene sulfonic acid or dicarboxybenzene sulfonic acid diester, alkylene glycol, and terephthalic acid or dimethyl terephthalate is oxidized with antimony oxide or oxidized
  • This is a polycondensation polymer in the presence of a catalyst such as zinc, and the sulfonated polyester preferably has a number average molecular weight of 5,000 to 300,000.
  • the sulfonated polyester preferably has a number average molecular weight within the above range of 10,000 or more, more preferably 20,000 or more, and preferably 100,000 or less. More preferable is 1,000 or less.
  • the polystyrene sulfonic acid preferably has a number average molecular weight of 10,000 to 1,000,000.
  • the polystyrene sulfonic acid has a number average molecular weight within the above range, preferably 20,000 or more, more preferably 40,000 or more, and more preferably 800,000 or less. More preferably, 300,000 or less.
  • the dispersion of the present invention contains a high-boiling solvent or an organic acid having a cyclic structure, but such a high-boiling solvent improves the film-forming property of the resulting conductive composition. This is to improve the conductivity.
  • the reason why the conductivity of the conductive polymer is improved by including the high boiling point solvent in this way is not necessarily clear at present, but, for example, a dispersion of the conductive composition is applied to the substrate, When the high boiling point solvent escapes when dried, the layer density in the thickness direction is increased, thereby reducing the spacing between the conductive polymers and increasing the conductivity of the conductive polymers. Conceivable.
  • the high boiling point solvent preferably has a boiling point of 150 ° C. or higher.
  • a high boiling point solvent include dimethyl sulfoxide (boiling point 189 ° C.), ⁇ -butyrolactone (boiling point 204 ° C.), sulfolane ( Examples include boiling point 285 ° C., N-methylpyrrolidone (boiling point 202 ° C.), dimethyl sulfone (boiling point 233 ° C.), ethylene glycol (boiling point 198 ° C.), diethylene glycol (boiling point 244 ° C.), and dimethyl sulfoxide is particularly preferred.
  • the content of the high-boiling solvent is 5 to 3,000% on a mass basis with respect to the conductive polymer in the dispersion (that is, the high-boiling solvent is 5% with respect to 100 parts by mass of the conductive polymer). To 3,000 parts by mass), particularly 20 to 700%.
  • the content of the high-boiling solvent is less than the above, the film-forming property of the conductive composition is lowered, and as a result, the action of improving the conductivity of the conductive composition may be reduced.
  • the content is higher than the above, it takes time to dry the dispersion, and on the contrary, there is a risk of causing a decrease in conductivity.
  • the dispersion of the present invention may contain an organic acid having a cyclic structure instead of the high boiling point solvent.
  • an organic acid is contained in the resulting conductive composition. This is to improve the film property and thereby improve the conductivity.
  • the reason why the conductivity of the conductive polymer is improved by including an organic acid having such a cyclic structure is not necessarily clear at present, but, for example, a dispersion of a conductive composition is applied to a substrate.
  • the organic acid having a cyclic structure may enter the conductive polymer layer to facilitate the transfer of holes between the conductive polymer layers. .
  • organic acid having the cyclic structure examples include phthalic acid, phthalaldehyde, carboxyphenol, carboxycresol, carboxynaphthalene, dicarboxynaphthalene, thiophenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, and naphthalenesulfonic acid.
  • Naphthalene disulfonic acid, naphthalene trisulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid and the like, and aromatic organic acids such as phenol sulfonic acid, naphthalene sulfonic acid and anthraquinone sulfonic acid are particularly preferable.
  • the content of the organic acid having a cyclic structure is 5 to 500% on a mass basis with respect to the conductive polymer in the dispersion (that is, the cyclic structure has a cyclic structure with respect to 100 parts by mass of the conductive polymer).
  • the organic acid is preferably 5 to 500 parts by mass), more preferably 20 to 150%.
  • the film-forming property of the conductive composition is lowered, and as a result, the effect of improving the conductivity of the conductive composition may be lowered.
  • the film-forming property of the conductive composition is lowered by acting as an impurity, and there is a possibility that the conductivity is lowered.
  • the content of the conductive polymer in the dispersion affects the workability when the dispersion of the conductive composition is dried to form a film or the like, and is usually about 1 to 10% by mass. preferable. In other words, when the content of the conductive polymer is less than the above, it takes time to dry, and when the content of the conductive polymer is more than the above, the viscosity becomes high and the coating is performed. Workability may be reduced.
  • the dried product obtained by drying a dispersion containing a conductive polymer and a high-boiling point solvent is considered to contain a high-boiling point solvent and a conductive polymer as the main component.
  • What is obtained by drying a dispersion of the product is expressed as a conductive composition.
  • the high boiling point solvent is also a solvent, if it is dried at a higher temperature, it may almost evaporate, but in the present invention, the conductive composition containing the conductive polymer and the high boiling point solvent is dried.
  • the dried product thus obtained is expressed as a conductive composition even if it contains almost no high-boiling solvent.
  • a dried product obtained by drying a dispersion containing an organic acid is usually a conductive composition containing a conductive polymer and an organic acid having a cyclic structure.
  • the conductive polymer dispersion of the present invention may contain a high-boiling solvent and an organic acid having a cyclic structure in combination.
  • thiophene or a derivative thereof is used as a polymerizable monomer for synthesizing a conductive polymer by electrolytic oxidation polymerization.
  • the thiophene or derivative thereof include, for example, 3,4-ethylene. Examples include dioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-alkylthiophene, 3,4-alkoxythiophene, etc.
  • the carbon number of the alkyl group or alkoxy group 1 to 16 is preferable, and 1 to 4 is particularly suitable, and 3,4-ethylenedioxythiophene having 2 carbon atoms is particularly preferable.
  • Electrolytic oxidation polymerization in the synthesis of the conductive polymer is carried out by using a phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (I) as a dopant, a sulfonated polyester, polystyrene sulfonic acid (hereinafter referred to as “dopant”).
  • dopant a phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (I) as a dopant, a sulfonated polyester, polystyrene sulfonic acid (hereinafter referred to as “dopant”).
  • dopant polystyrene sulfonic acid
  • water-miscible solvent constituting the aqueous liquid examples include methanol, ethanol, propanol, acetone, acetonitrile, and the like.
  • the mixing ratio of these water-miscible solvents with water is 50 in the entire aqueous liquid. The mass% or less is preferable.
  • the amount of the dopant and polymerizable monomer used in the electrolytic oxidation polymerization is not particularly limited.
  • a phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (I) is used as a dopant.
  • 3,4-ethylenedioxythiophene, which is a derivative of thiophene, is used as a polymerizable monomer will be described as an example.
  • the use ratio thereof is, as a mass ratio, phenolsulfonic acid novolak resin: 3,4-ethylene.
  • Electrolytic oxidation polymerization is be carried out even at a constant voltage at a constant current, for example, when performing electrolytic oxidation polymerization at a constant current, preferably 0.05mA / cm 2 ⁇ 10mA / cm 2 as the current value, 0.2 mA / cm 2 to 4 mA / cm 2 is more preferable.
  • the voltage is preferably 0.5 V to 10 V, more preferably 1.5 V to 5 V.
  • the temperature during the electrolytic oxidation polymerization is preferably 5 ° C to 95 ° C, particularly preferably 10 ° C to 30 ° C.
  • the polymerization time is preferably 1 hour to 72 hours, particularly preferably 8 hours to 24 hours.
  • ferrous sulfate or ferric sulfate may be added as a catalyst.
  • electrolytic oxidation polymerization is carried out in water or an aqueous liquid containing the iron ions of these catalysts, polymerization of thiophene or a derivative thereof is promoted.
  • the conductive polymer obtained as described above is obtained in a state of being dispersed in water or an aqueous liquid immediately after polymerization, and contains an iron sulfate salt used as a catalyst or a decomposition product thereof. Therefore, it is preferable to remove the metal component with a cation exchange resin after dispersing the impurities by dispersing the conductive polymer dispersion containing the impurities in a dispersing machine such as an ultrasonic homogenizer or a planetary ball mill.
  • the particle size of the conductive polymer at this time is preferably 100 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • sulfuric acid generated by decomposition of the catalyst is removed by an ethanol precipitation method, an ultrafiltration method, an anion exchange resin, or the like, and a high boiling point solvent or an organic acid having a cyclic structure is added.
  • the conductive composition of the present invention Since the conductive composition of the present invention has high conductivity, excellent heat resistance, and excellent transparency, it is suitable as a conductor of an antistatic material such as an antistatic film, an antistatic cloth, or an antistatic resin. Can be used.
  • an antistatic material such as an antistatic film, an antistatic cloth, or an antistatic resin.
  • the conductive composition of the present invention has high conductivity and excellent heat resistance, solid electrolytes for solid electrolytic capacitors such as aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, niobium solid electrolytic capacitors, etc. And a solid electrolytic capacitor having a low ESR and high reliability under high-temperature conditions can be provided.
  • the conductive composition of the present invention utilizes the property that the electrical conductivity is high and the heat resistance is excellent, in addition to the solid electrolyte of the solid electrolytic capacitor and the conductor of the antistatic material, It can also be suitably used as a positive electrode active material for batteries, a base resin for anti-corrosion paints, and the like.
  • the conductive composition of the present invention when used as a conductor of an antistatic material or a solid electrolyte of a solid electrolytic capacitor, it can be used as it is, but the conductive composition is water or aqueous. It is suitable to use the conductive composition obtained by dispersing in a liquid and then drying it as a conductor or a solid electrolyte.
  • a dispersion of the conductive composition is applied to the base sheet, or the base sheet is dispersed in the conductive composition. It is sufficient to immerse it in a liquid, pull it up, and then dry it to form an antistatic film and peel the film from the base sheet. Rather, the antistatic film formed on one or both sides of the base sheet May be suitable for use as an antistatic sheet using the base sheet as a support material without peeling off the base sheet from the base sheet.
  • a dispersion of the conductive composition is applied to the cloth or the cloth is dispersed in a conductive composition.
  • the binder resin is added to the dispersion liquid of the conductive composition, the adhesion of the conductive composition to the base sheet or the cloth is determined. Can be improved. It is also preferable to add a binder to the dispersion liquid of the conductive composition as described above even when the conductive composition is used as a solid electrolyte of a solid electrolytic capacitor.
  • binder resin examples include polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, novolac resin, silane coupling agent, and the like. Polyester, polyurethane, acrylic resin and the like are particularly preferable. Moreover, since the electroconductivity of an electroconductive composition can be improved when the sulfone group is added like sulfonated polyallyl, sulfonated polyvinyl, and sulfonated polystyrene, it is more preferable.
  • a solid electrolytic capacitor when using an electroconductive composition as a solid electrolytic capacitor, can be produced as follows.
  • the conductive composition of the present invention when used as a solid electrolyte such as a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, or an aluminum laminated solid electrolytic capacitor, an anode made of a porous body of a valve metal such as tantalum, niobium, or aluminum
  • a valve metal such as tantalum, niobium, or aluminum
  • the capacitor element having a dielectric layer made of an oxide film of the valve metal is immersed in the dispersion liquid of the conductive composition of the present invention, taken out, and then dried, by repeating the drying process.
  • a carbon paste and a silver paste are applied, dried, and then packaged to produce a solid electrolytic capacitor such as a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, or an aluminum laminated solid electrolytic capacitor. be able to.
  • the capacitor element is immersed in a liquid containing a polymerizable monomer and an oxidizing agent, and after taking out, polymerized at room temperature, immersed in water, After the conductive polymer is synthesized by taking out, washing, and drying, the whole is immersed in the dispersion of the conductive composition of the present invention, and the process of taking out and drying is repeated to conduct the conductive composition of the present invention.
  • a solid electrolyte layer made of a material may be formed, or vice versa.
  • the device covered with the conductive composition is covered with carbon paste and silver paste, and then packaged to produce a tantalum solid electrolytic capacitor, niobium solid electrolytic capacitor, aluminum laminated solid electrolytic capacitor, etc. You can also
  • the lead terminal is connected to the anode on which the dielectric layer is formed by performing a chemical treatment after etching the surface of the aluminum foil.
  • a lead terminal is attached to a cathode made of aluminum foil, and a capacitor element is produced by winding the anode and cathode with the lead terminal through a separator, and the capacitor element is made of the conductive composition of the present invention.
  • an aluminum wound solid electrolytic capacitor can be produced by packaging with an exterior material.
  • Example 1 Contains 600 g of a 4% aqueous solution of a phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (I) [LotEW00130 (trade name) manufactured by Konishi Chemical Industry Co., Ltd., number average molecular weight 60,000, R is hydrogen]
  • a 1 L stainless steel container 0.3 g of ferrous sulfate heptahydrate was added, and 4 mL of 3,4-ethylenedioxythiophene was slowly added dropwise thereto.
  • the mixture was stirred with a stainless steel stirring blade, an anode was attached to the container, a cathode was attached to the base of the stirring blade, and electrolytic oxidation polymerization was performed at a constant current of 1 mA / cm 2 for 18 hours.
  • electrolytic oxidation polymerization it was diluted 6-fold with water, and then subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T300 (trade name)]. Thereafter, 100 g of Cation Exchange Resin Amberlite 120B (trade name) manufactured by Organo Corporation was added and stirred with a stirrer for 1 hour.
  • the mixture was filtered through 131, and the treatment with this cation exchange resin and filtration were repeated three times to remove all cation components such as iron ions in the liquid.
  • the ratio of the phenolsulfonic acid novolak resin as a dopant in the electrolytic oxidation polymerization to the polymerizable monomer 3,4-ethylenedioxythiophene is a mass ratio of phenolsulfonic acid novolak resin: 3,4-ethylenediene.
  • Oxythiophene 1: 0.2.
  • the treated liquid is passed through a filter having a pore size of 1 ⁇ m, and the passing liquid is treated with an ultrafiltration apparatus (Vivaflow 200 (trade name), molecular weight fraction 50,000, manufactured by Sartorius Co., Ltd.). Ingredients were removed.
  • the liquid after this treatment is diluted with water to adjust the concentration to 3%, and 4 g of dimethyl sulfoxide as a high boiling point solvent (about 330% of dimethyl sulfoxide with respect to the conductive polymer) is added to 40 g of the 3% liquid. Then, a dispersion liquid of the conductive composition was obtained.
  • the content of sulfuric acid in this dispersion was measured with an ion chromatograph DX120 (trade name) manufactured by Dionex, and the content of sulfuric acid was 25 ppm.
  • Example 2 Except for adding 0.05 g of ferrous sulfate heptahydrate to 600 g of a 3% aqueous solution of sulfonated polyester [Plus Coat Z-561 (trade name), number average molecular weight 27,000, manufactured by Kyoyo Chemical Co., Ltd.] The same operation as in Example 1 such as addition of dimethyl sulfoxide was performed to obtain a dispersion liquid of the conductive composition. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 22 ppm.
  • Example 3 A dispersion of the electrically conductive composition was carried out in the same manner as in Example 1 except that dimethyl sulfoxide was added, except that 600 g of a 4% aqueous solution of polystyrene sulfonic acid (manufactured by Teica, number average molecular weight 100,000) was used. Got. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 26 ppm.
  • Example 4 4% aqueous solution of a phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (I) [lotEG0727 (trade name) manufactured by Konishi Chemical Industries, number average molecular weight 20,000, R in the formula is hydrogen] Except for using 600 g, the same operations as in Example 1 were carried out, such as addition of dimethyl sulfoxide, to obtain a dispersion of a conductive composition. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 27 ppm.
  • the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 27 ppm.
  • Example 5 The same operation as in Example 3 except that 0.4 g of naphthalenesulfonic acid (33% naphthalenesulfonic acid with respect to the conductive polymer) was added as an organic acid having a cyclic structure instead of dimethylsulfoxide as a high boiling point solvent. To obtain a dispersion of the conductive composition. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 26 ppm.
  • naphthalenesulfonic acid 33% naphthalenesulfonic acid with respect to the conductive polymer
  • Example 6 The same operation as in Example 3 except that 0.5 g of anthraquinone sulfonic acid (42% of anthraquinone sulfonic acid relative to the conductive polymer) was added as an organic acid having a cyclic structure instead of dimethyl sulfoxide as a high boiling point solvent. To obtain a dispersion of the conductive composition. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 26 ppm.
  • Example 7 The same operation as in Example 3 except that 0.5 g of phenolsulfonic acid (42% of phenolsulfonic acid with respect to the conductive polymer) was added as an organic acid having a cyclic structure instead of dimethylsulfoxide as a high boiling point solvent. To obtain a dispersion of the conductive composition. When the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 26 ppm.
  • phenolsulfonic acid 42% of phenolsulfonic acid with respect to the conductive polymer
  • Comparative Example 1 200 g of a 4% aqueous solution of phenolsulfonic acid novolak resin (number average molecular weight 60,000) similar to that used in Example 1 was placed in a 1 L container, 2 g of ammonium persulfate was added, and the mixture was stirred with a stirrer. Dissolved. Next, 3 mL of 3,4-ethylenedioxythiophene was slowly dropped into the mixture while stirring, and chemical oxidation polymerization of 3,4-ethylenedioxythiophene was performed over 24 hours.
  • phenolsulfonic acid novolak resin number average molecular weight 60,000
  • the mixture was diluted 4 times with water, and then subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T300 (trade name)]. Thereafter, 100 g of Cation Exchange Resin Amberlite 120B (trade name) manufactured by Organo Corporation was added and stirred with a stirrer for 1 hour. Subsequently, filter paper No. manufactured by Toyo Filter Paper Co., Ltd. The mixture was filtered through 131, and the treatment with this cation exchange resin and filtration were repeated three times to remove all cation components in the liquid.
  • the treated liquid is passed through a filter having a pore size of 1 ⁇ m, and the passing liquid is treated with an ultrafiltration apparatus (Vivaflow 200 (trade name), molecular weight fraction 50,000, manufactured by Sartorius Co., Ltd.). Ingredients were removed.
  • the liquid after this treatment was diluted with water to adjust the concentration to 3%, and 4 g of dimethyl sulfoxide was added to 40 g of the 3% liquid to obtain a dispersion of a conductive composition.
  • the sulfuric acid content in this dispersion was measured in the same manner as in Example 1, the sulfuric acid content was 123 ppm.
  • Comparative Example 2 Except not adding 4 g of dimethyl sulfoxide, operation similar to Example 1 was performed and the dispersion liquid of the electrically conductive composition was obtained. In addition, since this dispersion liquid does not add dimethyl sulfoxide as a high boiling point solvent, it should be expressed accurately as a dispersion liquid of a conductive polymer. In accordance with the conductive composition dispersions of Examples 1 to 7 and Comparative Example 1, they are expressed as conductive composition dispersions. And when content of the sulfuric acid in this dispersion liquid was measured like Example 1, content of sulfuric acid was 22 ppm.
  • Examples 1 to 7 had higher electrical conductivity and superior electrical conductivity than Comparative Examples 1 and 2. That is, Examples 1 to 7 in which conductive polymers were synthesized by electrolytic oxidation polymerization method had higher conductivity and superior conductivity than Comparative Example 1 in which conductive polymers were synthesized by chemical oxidation polymerization method. Moreover, the electrical conductivity was higher and the electrical conductivity was superior than Comparative Example 2 in which a high boiling point solvent or an organic acid having a cyclic structure was not added.
  • each sheet was left in a thermostatic bath at 150 ° C. for 100 hours, and then taken out.
  • Each conductivity was measured in the same manner as described above. The results are shown in Table 2. However, the conductivity is shown by the retention rate of the conductivity after standing at 150 ° C. for 100 hours.
  • the conductivity retention is obtained by dividing the conductivity after 100 hours at 150 ° C. by the initial conductivity (conductivity described in Table 1) and expressing it as a percentage (%). This can be expressed as follows. The higher the retention rate, the lower the electrical conductivity with respect to heat, and the better the heat resistance.
  • Examples 1 to 7 had higher conductivity retention after storage at high temperatures and superior heat resistance than Comparative Examples 1 and 2.
  • Examples 8-12 and Comparative Examples 3-4 For the dispersions of the conductive compositions of Examples 1 to 4, Example 7 and Comparative Examples 1 and 2, a sulfonated polyester resin [Plus Coat Z-561 (trade name) manufactured by Kyoyo Chemical Industry Co., Ltd.] was made conductive. After adding the polymer so that the resin content is about 150% with respect to the polymer, stirring, 50 ⁇ L of the dispersion containing the sulfonated polyester resin is dropped on a 2.8 cm ⁇ 4.8 cm polyethylene sheet, . After uniformizing with an 8 bar coater, the film was dried at 60 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to produce an antistatic film using each conductive composition as a conductor.
  • a sulfonated polyester resin [Plus Coat Z-561 (trade name) manufactured by Kyoyo Chemical Industry Co., Ltd.] was made conductive. After adding the polymer so that the resin content is about 150% with respect to the polymer, stirring,
  • the surface resistance of the obtained antistatic films of Examples 8 to 12 and Comparative Examples 3 to 4 was measured at room temperature (about 25 ° C.) in accordance with JIS K 7194. MCP-T600 (trade name)], and visible light transmittance at a wavelength of 400 nm to 700 nm was measured using UV-VIS-NIR RECORDING SPECTROTOPOMETER [Shimadzu Corporation UV3100 (trade name)]. It shows in Table 3 with the kind of electrically conductive composition which used the result. In addition, measurement is performed for each sample for five points, and the numerical values shown in Table 3 are obtained by calculating an average value of the five points and rounding off the decimals.
  • the antistatic films of Examples 8 to 12 have a lower surface resistance than the antistatic films of Comparative Examples 3 to 4, and as a result, the conductivity is high and the antistatic function is excellent. I was able to guess. In addition, it was clear that the antistatic films of Examples 8 to 12 had high visible light transmittance equivalent to that of Comparative Examples 3 to 4 and excellent transparency.
  • Example 13 In a state where the tantalum sintered body is immersed in a phosphoric acid solution having a concentration of 0.1%, chemical conversion treatment is performed by applying a voltage of 20 V, and an oxide film is formed on the surface of the tantalum sintered body to form a dielectric layer. Configured. Next, the tantalum sintered body was immersed in an ethanol solution of 3,4-ethylenedioxythiophene having a concentration of 35%, taken out after 1 minute, and left for 5 minutes.
  • an oxidizer / dopant solution consisting of a mixture prepared by mixing a 50% phenol butylamine sulfonate aqueous solution (pH 5) and a 30% ammonium persulfate aqueous solution prepared in advance at a mass ratio of 1: 1. It was immersed, taken out after 30 seconds, allowed to stand at room temperature for 30 minutes, and then heated at 50 ° C. for 10 minutes for polymerization. Thereafter, the tantalum sintered body was immersed in water and allowed to stand for 30 minutes, then taken out and dried at 70 ° C. for 30 minutes. These operations were repeated 6 times, and then immersed in the dispersion liquid of the conductive composition of Example 1, taken out after 30 seconds, and dried at 70 ° C.
  • Example 14 A tantalum solid electrolytic capacitor was produced in the same manner as in Example 13, except that the conductive composition dispersion of Example 2 was used instead of the conductive composition dispersion of Example 1. .
  • Example 15 A tantalum solid electrolytic capacitor was produced in the same manner as in Example 13, except that the conductive composition dispersion of Example 3 was used instead of the conductive composition dispersion of Example 1. .
  • Example 16 A tantalum solid electrolytic capacitor was produced in the same manner as in Example 13 except that the conductive composition dispersion of Example 4 was used instead of the conductive composition dispersion of Example 1. .
  • Comparative Example 5 A tantalum solid electrolytic capacitor was produced in the same manner as in Example 13, except that the conductive composition dispersion of Comparative Example 1 was used instead of the conductive composition dispersion of Example 1. .
  • Comparative Example 6 A tantalum solid electrolytic capacitor was produced in the same manner as in Example 13, except that the conductive composition dispersion of Comparative Example 2 was used instead of the conductive composition dispersion of Example 1. .
  • the tantalum solid electrolytic capacitors of Examples 13 to 16 and Comparative Examples 5 to 6 manufactured as described above were measured for ESR and capacitance. The results are shown in Table 4.
  • the measuring method of ESR and an electrostatic capacitance is as showing below.
  • the ESR is measured using an LCR meter (4284A) manufactured by HEWLETT PACKARD at 25 ° C. and 100 kHz, and the ESR is measured at 25 ° C. using an LCR meter (4284A) manufactured by HEWLETT PACKARD.
  • the electrostatic capacity was measured at 120 Hz.
  • the tantalum solid electrolytic capacitors of Examples 13 to 16 are smaller in ESR, larger in capacitance and superior in function as a capacitor than the tantalum solid electrolytic capacitors of Comparative Examples 5 to 6. It was clear that
  • the tantalum solid electrolytic capacitors of Examples 13 to 16 have lower ESR and higher capacitance even after storage at a higher temperature than the tantalum solid electrolytic capacitors of Comparative Examples 5 to 6, High reliability under high temperature conditions.
  • Example 17 After etching the surface of the aluminum foil, a lead terminal is attached to the anode on which the dielectric layer is formed by performing a chemical conversion treatment, and the lead terminal is attached to the cathode made of aluminum foil. Was wound through a separator to produce a capacitor element.
  • the dispersion liquid of the conductive composition obtained in Example 3 was neutralized with butylamine to pH 5.5, the capacitor element was immersed in this liquid, taken out after 120 seconds, and dried at 150 ° C. for 30 minutes. This operation was repeated 4 times, and then dried at 150 ° C. for 120 minutes to form a solid electrolyte layer made of a conductive composition. Thereafter, the capacitor element after the formation of the solid electrolyte layer was put in an aluminum outer case and sealed, and then subjected to aging while applying a rated voltage of 25 V at 130 ° C. to produce an aluminum wound solid electrolytic capacitor.
  • Example 18 An aluminum wound solid was obtained in the same manner as in Example 17 except that the dispersion of the electrically conductive composition obtained in Example 5 was neutralized with 2-methylimidazole to pH 5.5. An electrolytic capacitor was produced.
  • Example 19 The same procedure as in Example 17 was performed, except that the dispersion of the conductive composition obtained in Example 6 was neutralized with 2-methylimidazole to pH 5.5 to perform aluminum wound solid electrolytic. A capacitor was produced.
  • Example 20 The same procedure as in Example 17 was performed, except that the dispersion of the conductive composition obtained in Example 7 was neutralized with 4-methylimidazole to pH 5.5 to perform aluminum wound solid electrolytic. A capacitor was produced.
  • Comparative Example 7 An aluminum wound solid electrolytic capacitor was obtained by performing the same operation as in Example 17 except that the dispersion of the conductive composition obtained in Comparative Example 1 was neutralized with butylamine to pH 5.5. Produced.
  • the ESR and capacitance of the aluminum wound solid electrolytic capacitors of Examples 17 to 20 and Comparative Example 7 produced as described above were measured. The results are shown in Table 6.
  • the measuring method of ESR and an electrostatic capacitance is as showing below.
  • the ESR is measured using an LCR meter (4284A) manufactured by HEWLETT PACKARD at 25 ° C. and 100 kHz, and the ESR is measured at 25 ° C. using an LCR meter (4284A) manufactured by HEWLETT PACKARD.
  • the electrostatic capacity was measured at 120 Hz.
  • the aluminum-wound solid electrolytic capacitors of Examples 17 to 20 have smaller ESR and larger capacitance than the aluminum-wound solid electrolytic capacitor of Comparative Example 7, It was clear that the function was excellent.
  • the aluminum-wound solid electrolytic capacitors of Examples 17 to 20 have smaller ESR and higher electrostatic capacity after storage at a higher temperature than the aluminum-wound solid electrolytic capacitor of Comparative Example 7. Large capacity and high reliability under high temperature conditions.
  • the present invention it is possible to provide a conductive composition having high transparency, high conductivity, and excellent heat resistance.
  • the conductive composition of the present invention has high transparency, and since the conductive polymer is synthesized by electrolytic oxidation polymerization, it can be found in the conductive polymer synthesized by chemical oxidation polymerization. There is little content of sulfate groups based on such oxidizing agents, and there is little decrease in conductivity or transparency due to residual sulfate groups. Therefore, based on the characteristics of the conductive composition of the present invention, by using it as a conductor, an antistatic film, an antistatic resin having high transparency, high conductivity, and excellent heat resistance, An antistatic sheet or the like can be provided. In addition, by using the conductive composition of the present invention having such high conductivity and excellent heat resistance as a solid electrolyte, a solid electrolytic capacitor having low ESR and high reliability under high temperature conditions is provided. be able to.

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Abstract

L'invention concerne une composition électroconductrice qui présente une électroconductivité supérieure et une excellente résistance à la chaleur. L'invention concerne aussi un film antistatique qui utilise la composition électroconductrice et présente une électroconductivité supérieure et une excellente résistance à la chaleur, et un condensateur électrolytique solide utilisant la composition électroconductrice et qui présente une faible RPE et une fiabilité supérieure dans des conditions de température élevée. Une dispersion de la composition électroconductrice comprend: un polymère électroconducteur produit par la polymérisation par oxydation électrolytique de thiophène ou d'un dérivé de thiophène dans l'eau, ou dans un liquide aqueux formé d'un liquide mixte comprenant de l'eau et un solvant miscible avec l'eau, en présence d'une résine novolaque d'acide phénolsulfonique qui comprend des motifs de répétition représentés par la formule générale (I), R représentant hydrogène ou un groupe méthyle, un polyester sulfoné ou un acide polystyrène sulfonique; et un solvant à point d'ébullition élevé ou un acide organique comportant une structure cyclique. Le film antistatique utilise la composition électroconductrice comme conducteur électrique. Le condensateur électrolytique solide utilise la composition électroconductrice comme électrolyte solide.
PCT/JP2009/057241 2008-04-21 2009-04-09 Dispersion de composition électroconductrice, composition électroconductrice et utilisation de celles-ci Ceased WO2009131011A1 (fr)

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JP2012097209A (ja) * 2010-11-02 2012-05-24 Tokyo Univ Of Science 導電性高分子ナノ微粒子分散溶液、当該分散溶液を用いた導電薄膜及び導電薄膜の製造方法
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KR20160034431A (ko) 2011-09-06 2016-03-29 데이카 가부시키가이샤 도전성 고분자의 분산액, 도전성 고분자 및 그 용도
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TW200951993A (en) 2009-12-16
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TWI357083B (en) 2012-01-21
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