WO2014132809A1 - Carbon black dispersion and use thereof - Google Patents

Carbon black dispersion and use thereof Download PDF

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Publication number
WO2014132809A1
WO2014132809A1 PCT/JP2014/053403 JP2014053403W WO2014132809A1 WO 2014132809 A1 WO2014132809 A1 WO 2014132809A1 JP 2014053403 W JP2014053403 W JP 2014053403W WO 2014132809 A1 WO2014132809 A1 WO 2014132809A1
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Prior art keywords
carbon black
polyvinyl alcohol
weight
parts
black dispersion
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PCT/JP2014/053403
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French (fr)
Japanese (ja)
Inventor
康平 高橋
真木　伸一郎
尚久 廣田
昌洋 寺澤
Original Assignee
東洋インキＳｃホールディングス株式会社
トーヨーカラー株式会社
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Priority claimed from JP2013125306A external-priority patent/JP5454725B1/en
Priority claimed from JP2013241746A external-priority patent/JP5601416B1/en
Application filed by 東洋インキＳｃホールディングス株式会社, トーヨーカラー株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to KR1020157024135A priority Critical patent/KR102217137B1/en
Priority to CN201480010467.2A priority patent/CN105073915B/en
Publication of WO2014132809A1 publication Critical patent/WO2014132809A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • H01B1/122—Ionic conductors
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a carbon black dispersion excellent in dispersibility and storage stability.
  • the present invention also relates to a battery electrode mixture layer and a lithium ion secondary battery using the dispersion.
  • carbon black is widely used as a conductive additive, but when forming a battery electrode mixture layer, in order to shorten the production process in an efficient manner, the carbon black can be increased in a solvent. It is important to make it possible to easily disperse in concentration and uniformly.
  • N-methyl-2-pyrrolidone used in non-aqueous secondary batteries is more expensive than common solvents and has a very high boiling point of 200 ° C. or higher. Since energy is required, reduction of the amount of solvent used in the dispersion is strongly demanded.
  • Patent Documents 1 and 2 carbon black is dispersed while adsorbing an acidic or basic organic dye derivative to the carbon black, thereby achieving dispersion stabilization without impairing the conductivity of the carbon black.
  • a battery composition is described.
  • a carbon black dispersion liquid containing an electrode active material hereinafter referred to as an electrode mixture liquid
  • an organic pigment derivative as a dispersant
  • the electrode mixture layer and the coating layer are coated.
  • the adhesion of the film substrate may be insufficient, and the electrode mixture layer may unintentionally peel from the coating film substrate.
  • a dispersant for dispersing carbon black a pigment derivative type dispersant and a polymer polymer type dispersant (hereinafter referred to as a resin type dispersant) are used. It is described that, when used in combination, a positive electrode plate having good adhesion can be produced while utilizing the performance as a dispersant possessed by the pigment derivative type dispersant.
  • a resin type dispersant a polymer polymer type dispersant
  • resin-type dispersants such as polyvinyl acetal, which are known as dispersants for dispersing carbon black using N-methyl-2-pyrrolidone as a solvent, do not have sufficient performance as dispersants.
  • resin-type dispersants such as polyvinyl acetal
  • dispersants for dispersing carbon black using N-methyl-2-pyrrolidone as a solvent do not have sufficient performance as dispersants.
  • a pigment derivative type dispersant as a dispersant.
  • polyvinyl acetal has a problem of low resistance to non-aqueous electrolytes such as ethylene carbonate and propylene carbonate.
  • Patent Documents 5 and 6 describe coating liquids containing carbon black, unmodified or modified polyvinyl alcohol, and N-methyl-2-pyrrolidone, and Patent Document 5 describes this coating liquid. It describes that a positive electrode active material or a negative electrode active material is added to a working solution to produce an electrode plate of a lithium ion secondary battery.
  • the polyvinyl alcohols in Patent Documents 5 and 6 are used in large amounts as binders (resin binders), and there is no technical idea of using polyvinyl alcohols as a dispersant.
  • Patent Documents 3 and 4 suggest the possibility of using polyvinyl alcohol as one of the dispersants and N-methyl-2-pyrrolidone as one of the solvents.
  • the physical and chemical properties of the carbon black, solvent type, and dispersant used are closely related to each other, what kind of physical properties are required when a specific solvent called N-methyl-2-pyrrolidone is used.
  • polyvinyl alcohols having chemical properties can function well as a dispersant, and the molecular structure, functional group ratio, The relationship between molecular weight and the conditions for functioning as a resin-type dispersant was still unclear.
  • the dispersibility of the carbon black is deteriorated when the amount of the dispersant is extremely reduced, and on the contrary, the dispersibility is improved when the amount of the dispersant is extremely increased.
  • the resin-type dispersant does not have sufficient resistance to the non-aqueous electrolyte, and the dispersant functions as an insulating component, resulting in a high resistance value and poor conductivity. It is expected to have a negative effect on battery characteristics.
  • the selection of the type of carbon black itself may be important.
  • carbon black with a small primary particle size and high specific surface area or carbon black with a small volume density and high specific surface area it is known that a coating film with good conductivity and low surface resistance can be obtained. ing.
  • these carbon blacks have a high specific surface area, it has been difficult to stably disperse and to improve the storage stability.
  • the solvent used for preparing the electrode mixture liquid is determined by the polymer material used for the binder in the battery.
  • polyvinylidene fluoride is generally used as a particularly suitable binder for forming an electrode
  • N-methyl-2-pyrrolidone is generally used as a solvent for dissolving polyvinylidene fluoride. It is used. Since N-methyl-2-pyrrolidone has a very high boiling point of 202 ° C., it is necessary to spend a large amount of energy and time for drying the electrode mixture liquid.
  • the resulting carbon black dispersion is significantly reduced in viscosity compared to conventionally known resin-type dispersants, that is, the carbon black concentration that can be achieved is significantly higher, and carbon
  • a carbon black dispersion using N-methyl-2-pyrrolidone as a solvent which is excellent in black dispersibility and storage stability of the dispersion.
  • the battery electrode compound-material layer which has a uniform and favorable coating-film physical property and low surface resistance.
  • (1) 1st invention The present inventors paid attention to the physical and chemical properties of carbon black, solvent species, and a dispersant, and as a result of examining the quantitative relationship thereof in detail, the specific surface area of carbon black was determined. And a use amount of polyvinyl alcohol having a specific degree of saponification, there is a critical range that greatly contributes to dispersibility, and when these are within a certain range, high concentration, low viscosity, and long-term It has been found that a carbon black dispersion having good storage stability can be produced, and the present invention has been completed.
  • an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is When the BET specific surface area of carbon black is Xm 2 / g and the amount of polyvinyl alcohol added to 1 g of carbon black is aXg, a is in the range of 0.00017 ⁇ a ⁇ 0.00256.
  • the present invention relates to a carbon black dispersion.
  • an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.65 parts by weight to 15 parts by weight with respect to 100 parts by weight of the carbon black.
  • an embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol is 2 to 8 parts by weight with respect to 100 parts by weight of the carbon black.
  • an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
  • an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
  • An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
  • an embodiment of the present invention is a carbon black dispersion containing carbon black, polyvinyl alcohol and a triazine derivative or polyvinyl alcohol and an organic dye derivative as a dispersant, and N-methyl-2-pyrrolidone as a solvent.
  • the total amount of the dispersant is 50 parts by weight or less based on 100 parts by weight of carbon black
  • the polyvinyl alcohol contains 50 to 95 mol% of repeating units represented by the following general formula (A) in the polymer chain.
  • the present invention relates to a carbon black dispersion characterized by containing. Formula (A)
  • an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol and a triazine derivative or polyvinyl alcohol and an organic dye derivative as a dispersant, and N-methyl-2-pyrrolidone as a solvent. Liquid, When the total amount of the dispersant with respect to 100 parts by weight of carbon black is 50 parts by weight or less, the BET specific surface area of carbon black is Xm 2 / g, and the amount of polyvinyl alcohol added to 1 g of carbon black is aXg.
  • the polyvinyl alcohol contains 50 to 95 mol%, preferably 60 to 85 mol%, of the repeating unit represented by the general formula (A) in the polymer chain. And a carbon black dispersion.
  • an embodiment of the present invention relates to the above carbon black dispersion, wherein the dispersant is polyvinyl alcohol and a triazine derivative.
  • An embodiment of the present invention also relates to the carbon black dispersion, wherein the polyvinyl alcohol contains 55 to 85 mol% of a repeating unit represented by the general formula (A) in a polymer chain. .
  • an embodiment of the present invention relates to the above carbon black dispersion, wherein the total amount of the dispersant with respect to 100 parts by weight of carbon black is 0.5 part by weight or more and 40 parts by weight or less.
  • an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the carbon black.
  • an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.2 parts by weight to 8 parts by weight with respect to 100 parts by weight of the carbon black.
  • an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
  • an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
  • An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
  • an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is 60 to 85 mol%, the BET specific surface area of carbon black is 30 to 1500 m 2 / g, and the polyvinyl alcohol with respect to 100 parts by weight of carbon black is more than 8 parts by weight and 40 parts by weight or less, It relates to a carbon black dispersion.
  • an embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol is more than 8 parts by weight and 25 parts by weight or less based on 100 parts by weight of the carbon black.
  • An embodiment of the present invention also relates to the carbon black dispersion, wherein the carbon black has a BET specific surface area of 200 to 1500 m 2 / g.
  • an embodiment of the present invention relates to the carbon black dispersion, wherein the carbon black has a BET specific surface area of 500 to 1500 m 2 / g.
  • an embodiment of the present invention relates to the carbon black dispersion, wherein the carbon black is a hollow carbon black.
  • the embodiment of the present invention is characterized in that the content of polyvinyl alcohol is 0.05 parts by weight or more and less than 2 parts by weight with respect to 100 parts by weight of the total solid components contained in the dispersion liquid. It relates to a carbon black dispersion.
  • an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
  • an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
  • An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
  • the second invention it is possible to obtain a coating film having better adhesion to the coating substrate than when a conventionally known pigment derivative type dispersing agent is used alone, and a conventionally known resin type dispersing agent A carbon black dispersion having a remarkably low viscosity can be obtained as compared with the case where it is used alone or in combination with a pigment derivative, and the carbon black concentration can be increased while maintaining adhesion.
  • the second invention, and the third invention it becomes possible to provide a carbon black dispersion having a higher concentration than before, and the amount of N-methyl-2-pyrrolidone solvent used is greatly reduced.
  • the drying process of the coated film can be greatly shortened.
  • an electrode mixture solution for a secondary battery is prepared using the dispersion, it is easy to add and knead electrode active material powder because of its low viscosity, and each electrode component has a high concentration.
  • carbon black dispersion and “carbon black dispersion for battery” are referred to as “dispersion”, “organic dye derivative or triazine derivative” as “pigment derivative”, “polyvinyl alcohol” (first (Invention and third invention) or “polyvinyl alcohol and pigment derivative” (second invention) may be abbreviated as “dispersant”, and “N-methyl-2-pyrrolidone” may be abbreviated as “NMP”.
  • Carbon black As carbon black, various types such as commercially available hollow carbon black, furnace black, channel black, thermal black, acetylene black, ketjen black, etc., and commonly used oxidized carbon black, graphitized treatment Carbon black, carbon nanotubes and carbon nanofibers can also be used. Moreover, carbon black which has high electroconductivity, such as acetylene black and furnace black, and is produced industrially is used suitably.
  • the oxidation treatment of carbon black is performed by treating the carbon black at a high temperature in the air or by treating it with nitric acid, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group.
  • This is a treatment for directly introducing (covalently bonding) such an oxygen-containing polar functional group to the surface of carbon black, and is generally performed to improve the dispersibility of carbon black.
  • the average primary particle diameter of the carbon black used for the production of the dispersion is preferably 0.01 to 1 ⁇ m, particularly in the range of the average primary particle diameter of the carbon black used for general dispersions and paints. Is preferably 0.2 ⁇ m, more preferably 0.01 ⁇ m to 0.1 ⁇ m.
  • the average primary particle size referred to here indicates an arithmetic average particle size measured with an electron microscope, and this physical property value is generally used to represent the physical characteristics of carbon black.
  • BET specific surface area and pH are known as other physical property values representing the physical characteristics of carbon black.
  • the BET specific surface area refers to a specific surface area (hereinafter simply referred to as a specific surface area) measured by the BET method by nitrogen adsorption, and this specific surface area corresponds to the surface area of carbon black. The amount you need also increases.
  • the pH changes under the influence of functional groups on the carbon black surface and impurities contained therein.
  • the carbon black used in the first and second inventions preferably has a BET specific surface area of 20 to 1500 m 2 / g, more preferably 20 to 1000 m 2 / g, and more preferably 20 to 500 m 2 / g. preferably, more preferably those of 20 ⁇ 250m 2 / g, more preferably those of 30 ⁇ 150m 2 / g, particularly preferably from 30 ⁇ 75m 2 / g.
  • various commercially available products and synthetic products can be used alone, or two or more carbon blacks can be used in combination.
  • the carbon black used in the first and second inventions is not particularly limited as long as it has the above specific surface area, but is high such as acetylene black, furnace black, hollow carbon black and graphitized carbon black. Carbon black having electrical conductivity and industrially produced is preferably used. Among these carbon blacks, acetylene black is particularly preferably used. Examples of acetylene black include Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.), and various grades can be obtained as commercial products.
  • the carbon black used in the third invention preferably has a BET specific surface area of 30 to 1500 m 2 / g, more preferably 200 to 1500 m 2 / g, still more preferably 500 to 1500 m 2 / g, Particularly preferred are those of up to 1000 m 2 / g.
  • various commercially available products and synthetic products can be used alone, or two or more carbon blacks can be used in combination.
  • the BET specific surface area of the carbon black prepared by mixing two or more kinds of carbon black is in the total carbon black G i
  • the BET specific surface area of a carbon black i S i is in the total carbon black G i
  • (BET specific surface area of mixed carbon black) ⁇ (S i ⁇ G i )
  • the specific surface area of carbon black prepared by mixing carbon black having a BET specific surface area of 800 m 2 / g and carbon black of 1200 m 2 / g in a weight ratio of 1: 1 is 1000 m 2 / g.
  • the carbon black used in the third invention is not particularly limited as long as it has the above specific surface area, but has high conductivity such as acetylene black, furnace black, hollow carbon black and graphitized carbon black. Carbon black produced and industrially produced is preferably used. Among these carbon blacks, hollow carbon black having excellent conductivity per weight is particularly preferably used. Examples of the hollow carbon black include ketjen black (manufactured by Akzo Corporation), and various grades can be obtained as commercial products.
  • Polyvinyl alcohol is used as a dispersant. That is, polyvinyl alcohol is used as a dispersant rather than as a binder.
  • polyvinyl alcohol obtained by using polyvinyl acetate as a raw material and saponifying this is described.
  • polyvinyl alcohol is obtained by using polyvinyl acetate obtained by polymerizing vinyl acetate as a raw material, saponifying the polyvinyl acetate, and substituting the acetyl group with a hydroxyl group. Due to this synthesis process, polyvinyl alcohol has an acetyl group and a hydroxyl group, and the ratio is expressed as the degree of saponification.
  • the saponification degree is the same as the definition of saponification degree known in the industry, and is based on the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification.
  • the ratio (mol%) occupied by the number of moles of the vinyl alcohol unit in other words, the ratio (mol%) of the repeating unit represented by the general formula (A) contained in the polyvinyl alcohol).
  • the number of hydroxyl groups derived from the vinyl alcohol skeleton contained in the polyvinyl alcohol is divided by the sum of the number of acetyl groups derived from the vinyl acetate skeleton and the number of hydroxyl groups derived from the vinyl alcohol skeleton. Mean value.
  • polyvinyl alcohol polyvinyl alcohol, particularly those obtained by saponifying polyvinyl acetate, are mainly used, but are not limited thereto.
  • the saponification degree is preferably 50 to 95 mol%, more preferably 55 to 92 mol%, still more preferably 55 to 85 mol%, and particularly preferably 60 to 85 mol%. If it is the polyvinyl alcohol of the said saponification degree, various commercial products and synthetic products can be used individually or in combination of 2 or more types.
  • a functional group other than a hydroxyl group and an acetic acid group for example, an acetoacetyl group, a sulfonic acid group, a carboxyl group, a carbonyl group, an amino group, an isocyanate group introduced, Modified with various salts, other anion or cation modified, unsaturated modified, acetal modified (butyral modified, acetoacetal modified, formal modified, etc.) with aldehydes, diol structure introduced
  • these are also included in the range of usable polyvinyl alcohol, and these can be used alone or in combination of two or more.
  • the polyvinyl alcohol preferably has an average degree of polymerization of 50 to 4000, then preferably 50 to 3000, more preferably 100 to 3000, particularly preferably 100 to 2000, and particularly preferably 100 to 1500. Further preferred. If it is polyvinyl alcohol of the said polymerization degree, various commercial products and synthetic products can be used individually or in combination of 2 or more types.
  • the polyvinyl alcohol preferably has a 4% aqueous solution viscosity of 2.0 to 25 mPa ⁇ s, more preferably 2.0 to 20.0 mPa ⁇ s, according to JIS K6726.
  • those having a saponification degree of less than 50 mol% to 60 mol% have very good solubility in NMP, but are considered to be ineffective for dispersion due to poor adsorptivity to carbon black.
  • Those larger than 95 mol% hardly dissolve or swell in NMP, so even if adsorbed to carbon black, the polymer chain cannot be extended to the NMP side, and therefore, the steric repulsion cannot be effectively performed. Inferred.
  • those having a saponification degree within these ranges have a good balance between the solubility or swelling in NMP and the adsorptivity to carbon black and the steric repulsion effect after adsorption. It is considered to function particularly effectively.
  • Examples of commercially available polyvinyl alcohols included in the saponification degree range include Kuraray Poval (polyvinyl alcohol manufactured by Kuraray Co., Ltd.), Gohsenol (polyvinyl alcohol manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), Denkapoval (manufactured by Denki Kagaku Kogyo Co., Ltd.), -Various grades can be obtained from the market under trade names such as POVAL (manufactured by Nippon Vinegar-Poval).
  • Kuraray Poval's PVA-403 (saponification degree: 78.5 to 81.5 mol%, average polymerization degree: 300, viscosity of 4% aqueous solution at a liquid temperature of 20 ° C. according to JIS K6726: 2.8 to 3.3 mPa ⁇ s) s), PVA-505 (saponification degree 72.5-74.5 mol%, average polymerization degree 500, 4% aqueous solution viscosity 4.2-5.0 mPa ⁇ s), L-8 (saponification degree 69.5-72.
  • NMP is used for manufacturing electrodes of lithium ion secondary batteries.
  • one or more other solvents may be used in combination as long as the performance as a dispersant (mainly polyvinyl alcohol alone or a combination of polyvinyl alcohol and a pigment derivative) and battery performance are not impaired. From the industrial applicability assumed by the invention, it is preferable to use NMP alone.
  • the pigment derivative is an organic dye derivative having an acidic or basic functional group, or a triazine derivative having an acidic or basic functional group.
  • a triazine derivative having an acidic functional group represented by the following general formula (1) or an organic dye derivative having an acidic functional group represented by the following general formula (4) is particularly preferable.
  • [X 1 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 3 -Y-X 4 - represents, X 2 and X 4, each independently, represent -NH- or -O-, X 3 is, -CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - and represent , Y represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, and Z represents —SO 3 M, —COOM, Represents —P (O) (— OM) 2 or —O—P (O) (— OM) 2 , M represents one equivalent of a monovalent to trivalent cation, and Q represents —O—R 2
  • X 5 represents -NH- or -O-
  • X 6 and X 7 are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH- or Represents —CH 2 NHCOCH 2 NH—
  • R 3 and R 4 each independently represents an organic dye residue, an optionally substituted heterocyclic residue, or an optionally substituted aromatic group. Represents a group ring residue or —YZ, and Y and Z have the same meanings as Y and Z in formula (1).
  • organic dye residues in R 1 , R 3 and R 4 include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, anthraquinones, diaminodianthraquinones, anthrapyrimidines, and flavans
  • Anthraquinone dyes such as Throne, Antanthrone, Indanthrone, Pyrantron, Biolantron, Quinacridone dyes, Dioxazine dyes, Perinone dyes, Perylene dyes, Thioindigo dyes, Isoindolin dyes, Isoindolinone dyes, Residues such as quinophthalone dyes, selenium dyes, metal complex dyes and the like can be mentioned.
  • an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, Quinacridone dyes and dioxazine dye residues are preferred because they exhibit excellent dispersibility.
  • heterocyclic residue and aromatic ring residue in R 1 , R 3 , and R 4 include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, and benzine.
  • heterocyclic residues such as thiazole, benztriazole, indole, quinoline, carbazole and acridine, and aromatic ring residues such as benzene, naphthalene, anthracene, fluorene, phenanthrene and anthraquinone.
  • a heterocyclic residue containing any one of S, N, and O heteroatoms is preferable because it exhibits an effect of excellent dispersibility.
  • Y in general formula (1) and general formula (2) represents an alkylene group, alkenylene group or arylene group which may have a substituent, but preferably has 20 or less carbon atoms, more preferably 10 or less carbon atoms.
  • Particularly preferred embodiments include an optionally substituted phenylene group, biphenylene group, naphthylene group or an alkylene group which may have a side chain having 10 or less carbon atoms.
  • a preferred embodiment of the alkenyl group which may have an alkyl group and a substituted group which may have a substituent in R 2 are those having 20 or less carbon atoms. More preferably, an alkyl group which may have a side chain having 10 or less carbon atoms is exemplified.
  • the alkyl group having a substituent and the alkenyl group having a substituent are a group in which a hydrogen atom of an alkyl group or an alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group or a mercapto group. Can be mentioned.
  • M represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen ion (proton), a metal cation, or a quaternary ammonium cation.
  • M may be only one kind of a proton, a metal cation, and a quaternary ammonium cation, and may be a combination of two or more kinds.
  • the metal cation include metal cations such as lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.
  • the quaternary ammonium cation is a single compound having a structure represented by the general formula (3) or a mixture.
  • R 5 , R 6 , R 7 and R 8 each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a good aryl group.
  • R 5 , R 6 , R 7 and R 8 may be the same or different. Further, when R 5 , R 6 , R 7 , and R 8 have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20.
  • quaternary ammonium cation examples include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, stearylammonium and the like. However, it is not limited to these.
  • [X 8 is a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH -, - X 9 -Y- or -X 9 -Y-X 10 - represents, X 9 is, -CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 10 is, -NH- or -O Y represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, and Z represents —SO 3 M, -COOM, -P (O) (-OM) 2 or -O-P (O) (-OM) 2 , M represents one equivalent of a monovalent to trivalent cation, and R 9 represents an organic dye residue Represent
  • the organic dye residue of R 9 has the same meaning as the organic dye residue in R 1 , R 3 , and R 4 .
  • an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, Quinacridone dyes and dioxazine dye residues are preferred because they exhibit excellent dispersibility.
  • M in the general formula (4) has the same meaning as M in the general formula (1).
  • the method for synthesizing the acidic pigment derivative to be used is not particularly limited.
  • Japanese Patent Publication No. 39-28884, Japanese Patent Publication No. 45-11026, Japanese Patent Publication No. 45-29755, Japanese Patent Publication No. 64- They can be synthesized by the methods described in JP 5070, JP 2004-217842 A, and the like.
  • a triazine derivative having a basic functional group represented by the following general formula (101) or an organic dye derivative having a basic functional group represented by the following general formula (106) is particularly preferable.
  • X 101 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 102 -Y 1 -X 103 - represents, X 102, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 103 is, -NH- or -O- and Y 1 represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, each having 1 to 20 carbon atoms.
  • P represents a group represented by any one of the general formula (102), the general formula (103), and the general formula (104).
  • Q 101 represents —O—R 102 , —NH—R 102 , a halogen group, —X 101 —R 101, or a group represented by any one of the general formula (102), the general formula (103), and the general formula (104).
  • R 102 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
  • o represents an integer of 1 to 4.
  • X 104 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or -X 105 -Y 1 -X 106 - represents a.
  • X 105 represents -NH- or -O-
  • X 106 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 - represents a .
  • v 1 represents an integer of 1 to 10.
  • R 103 and R 104 represent respectively independently, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a heterocyclic residue, R 103 And R 104 may combine to form a ring.
  • R 105 , R 106 , R 107 and R 108 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
  • R 109 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • R 101 represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (105). .
  • General formula (105) is an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (105). .
  • General formula (105) is an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (105).
  • T represents -X 108 -R 110 or W 1
  • U represents -X 109 -R 111 or W 2
  • W 1 and W 2 are each independently —O—R 102 , —NH—R 102 , a halogen group or a group represented by any one of the general formula (102), the general formula (103), and the general formula (104).
  • X 107 represents -NH- or -O-
  • X 108 and X 109 each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH- or - CH 2 NHCOCH 2 NH— is represented.
  • R 110 and R 111 each independently represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent.
  • Examples of the organic dye residue in R 101 of the general formula (101) and R 110 and R 111 of the general formula (105) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, and phthalocyanine dyes.
  • Examples of the heterocyclic residue and the aromatic ring residue in R 101 of the general formula (101) and R 110 and R 111 of the general formula (105) include thiophene, furan, pyridine, pyrazine, triazine, pyrazine, pyrrole, Examples include imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, acridone and the like.
  • heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups.
  • hydroxyl group alkoxyl group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.)
  • a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
  • R 103 and R 104 represent respectively independently, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a heterocyclic residue, R 103 And R 104 may combine to form a ring.
  • a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high.
  • Y 1 in the general formula (101) and the general formula (105) represents an alkylene group, an alkenylene group or an arylene group which may have a substituent having 20 or less carbon atoms, and preferably has a substituent. Examples thereof include a phenylene group, a biphenylene group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.
  • Z101 is a group represented by the following general formula (107), general formula (108), or general formula (109).
  • m represents an integer of 1 to 4.
  • General formula (107) Formula (108)
  • X 24 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or -X 25 -Y 2 -X 26 - represents a.
  • X 25 represents -NH- or -O-
  • X 26 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 - represents a .
  • Y 2 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, having 1 to 20 carbon atoms.
  • v 2 represents an integer of 1 to 10.
  • R 23 and R 24 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group or a heterocyclic residue, R 23 And R 24 may combine to form a ring.
  • a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high.
  • R 25 , R 26 , R 27 and R 28 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
  • R 29 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • R 22 represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent.
  • the organic dye residue in R 22 include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, indanthrone, Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, Examples include residues of metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not
  • heterocyclic residue and aromatic ring residue in R 22 examples include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, and indole. , Quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, acridone and the like.
  • heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups.
  • hydroxyl group alkoxyl group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.)
  • a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
  • Examples of the amine component used for forming the substituents represented by the general formulas (102) to (104) and the general formulas (107) to (109) include dimethylamine, diethylamine, methylethylamine, N, N -Ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethyl) Hexyl) amine Dioctylamine, N,
  • the method for synthesizing the organic dye derivative having a basic functional group or the triazine derivative having a basic functional group to be used is not particularly limited, but JP-A-54-62227 and JP-A-56- 118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3-2676, JP 11-199796, and the like. It can be synthesized by the method.
  • an organic dye derivative having a basic functional group includes a substituent represented by the formula (110) to the formula (113) in an organic dye, a heterocyclic compound (eg, acridone) or an aromatic ring compound (eg, anthraquinone).
  • these substituents and amine components for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1 , 3,5-triazin-2-ylamino] aniline and the like) can be synthesized.
  • an organic dye having a carboxyl group, a heterocyclic compound (for example, acridone) or an aromatic ring compound (for example, anthraquinone) is synthesized by a known method. Then, a method of reacting a chlorinating agent such as thionyl chloride in an aromatic solvent such as benzene is exemplified.
  • the substituent represented by the formula (110) is a sulfonic acid group
  • the substituent represented by the formula (111) is a carboxylic acid group.
  • a metal or a salt of the above amine may be formed.
  • organic dye is an azo dye
  • a substituent represented by the formula (107) to the formula (109) or the following general formula (114) is previously introduced into the diazo component or the coupling component, and then the coupling is performed.
  • An azo organic dye derivative can also be produced by carrying out the reaction.
  • X 101 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 102 -Y 1 -X 103 - represents, X 102, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 103 each independently -NH- or -O Y 1 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms, Represents.
  • P represents a substituent represented by any one of the general formulas (102), (103) and the general formula (104).
  • Q 101 represents —O—R 102 , —NH—R 102 , a halogen group, —X 101 —R 101, or a substitution represented by any of the general formula (102), (103), or the general formula (104)
  • R 102 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
  • the triazine derivative having a basic functional group is, for example, a substituent represented by formula (107) to formula (109) or general formula (114) in at least one chlorine of cyanuric chloride using cyanuric chloride as a starting material. It is obtained by reacting an amine component (for example, N, N-dimethylaminopropylamine or N-methylpiperazine etc.) to form, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.
  • an amine component for example, N, N-dimethylaminopropylamine or N-methylpiperazine etc.
  • the pigment derivative to be used is preferably an organic dye derivative having an acidic or basic functional group or a triazine derivative having an acidic or basic functional group, and is a triazine derivative having an acidic or basic functional group. More preferably, it is more preferably a triazine derivative having an acidic functional group, and particularly preferably a triazine derivative having no azo bond and having an acidic functional group.
  • the pigment derivative may be used alone or in combination of two or more. It is considered that the pigment derivative mainly functions as a dispersant and plays a role for creating an electrode film state suitable for improving battery performance.
  • the dispersion liquid of the present invention mainly comprises carbon black using polyvinyl alcohol as a dispersant (first invention and third invention) or using polyvinyl alcohol and a pigment derivative as a dispersant (second invention). Dispersed in NMP. In this case, the dispersant and carbon black are added simultaneously or sequentially and mixed to disperse the dispersant while acting (adsorbing) on the carbon black. However, in order to more easily produce a carbon black dispersion, the dispersant is dissolved, swollen, or dispersed in NMP, and then the carbon black is added to the liquid and mixed to disperse the dispersant in carbon. It is more preferable to act (adsorb) on black.
  • a powder other than carbon black for example, when an electrode active material for a secondary battery is added and used as an electrode mixture liquid, a dispersing agent, carbon black and an electrode active material are simultaneously charged and dispersed in NMP. Processing may be performed.
  • a dispersing device usually used for pigment dispersion or the like can be used.
  • mixers such as dispersers, homomixers, planetary mixers, homogenizers (such as “Clearmix” manufactured by M Technique, “Fillmix” manufactured by PRIMIX, “Abramix” manufactured by Silverson, etc.), paint conditioners ( Red Devil Co.), colloid mill ("PUC Colloid Mill” manufactured by PUC, “Colloid Mill MK” manufactured by IKA), cone mill (“Cone Mill MKO” manufactured by IKA, etc.), ball mill, sand mill (Shinmaru Enterprises) “Dynomill”, etc.), Attritor, Pearl Mill (“DCP Mill” manufactured by Eirich), Coball Mill and other media type dispersers, Wet Jet Mill (“Genus PY” manufactured by Genus, “Starburst” manufactured by Sugino Machine) "Nanomizer” manufactured by Nanomizer ), M Technique Co., Ltd. "Claire SS-5", Nara Machinery
  • a carbon black dispersion can be obtained by adding and mixing a mixture of carbon black and dispersant obtained by the following dry treatment in NMP.
  • Examples of a method for obtaining carbon black surface-treated with a dispersant include a dry treatment method.
  • Dry processing is to make the dispersant act (adsorb) on the surface of the carbon black while mixing, pulverizing, and the like of the carbon black and the dispersant with a dry processing apparatus at room temperature or under heating.
  • the dispersant it is not necessary for the dispersant to be completely adsorbed on the carbon black surface, and there may be no practical problem as long as it can be mixed homogeneously to some extent.
  • the equipment to be used is not particularly limited.
  • Media type dispersers such as paint conditioner (manufactured by Red Devil), ball mill, attritor, vibration mill, kneader, roller mill, stone mill, planetary mixer, fen Dispersing and kneading machines such as Shell Mixer, Hybridizer (Nara Machinery Co., Ltd.), Mechano Micros (Nara Machinery Co., Ltd.), Mechano Fusion System AMS (Hosokawa Micron Co., Ltd.) can be used. Therefore, it is more preferable to use a medialess dispersion / kneading machine.
  • paint conditioner manufactured by Red Devil
  • ball mill ball mill
  • attritor vibration mill
  • kneader roller mill
  • stone mill stone mill
  • planetary mixer fen Dispersing and kneading machines
  • fen Dispersing and kneading machines such as Shell Mixer, Hybridizer (Nara Machinery Co., Ltd.), Mechano Micros (Nara Machinery Co.
  • an organic solvent may be added as long as the treated product does not become a gel. It is expected that the interaction between the carbon black and the dispersing agent is promoted by improving the wetting or (partly) dissolution of the dispersing agent by the addition of the solvent and the wetting of the carbon black with respect to the dispersing agent.
  • the solvent used at this time is not particularly limited. However, when a solvent other than NMP is used, it is desirable to dry after the treatment.
  • the amount of organic solvent added varies depending on the material used, but is 0.5 to 100% by weight based on the amount of dispersant added. Further, the inside of the dry processing apparatus may be treated as a deoxygenated atmosphere by flowing nitrogen gas or the like as necessary.
  • the dry treatment time can be arbitrarily set depending on the apparatus used and the desired degree of kneading. By performing these dry treatments, a powdery or lump treated product can be obtained. The obtained processed product may be further dried and pulverized.
  • the amount of dispersant added to carbon black is preferably 0.65 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of carbon black. 0.65 parts by weight or more and 10 parts by weight or less are more preferable, 1 part by weight or more and 10 parts by weight or less are more preferable, 1 part by weight or more and 8 parts by weight or less are more preferable, 2 parts by weight or more and 8 parts by weight or less.
  • the amount is preferably 50 parts by weight or less, more than 0.5 parts by weight and 40 parts by weight with respect to 100 parts by weight of carbon black. Parts by weight or less, preferably 0.5 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less, still more preferably 1 part by weight or more and 10 parts by weight or less. As mentioned above, 8 weight part or less is especially preferable.
  • the amount is more than 8 parts by weight, preferably 40 parts by weight or less, more than 8 parts by weight, 30 parts by weight with respect to 100 parts by weight of carbon black. Is more preferably 8 parts by weight or more, more preferably 25 parts by weight or less, more preferably 8 parts by weight, further preferably 20 parts by weight or less, particularly preferably 8 parts by weight or more and 15 parts by weight or less.
  • the amount of polyvinyl alcohol added as a dispersant to carbon black is 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of carbon black.
  • 0.15 parts by weight or more and 10 parts by weight or less are more preferable, 0.2 parts by weight or more and 8 parts by weight or less are more preferable, 0.2 parts by weight or more and 4 parts by weight or less are more preferable, 0.4 Part by weight or more and 4 parts by weight or less are particularly preferable.
  • the proportion of polyvinyl alcohol in the dispersant is preferably 10 parts by weight or more and 90 parts by weight or less, and 20 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the dispersant. More preferred is 25 parts by weight or less, and particularly preferred is 25 parts by weight or more and 75 parts by weight or less.
  • the amount of the dispersant added to the carbon black dispersion is determined by the specific surface area of the carbon black to be added, the average particle diameter after dispersion of the carbon black particles, the amount of the dispersant adsorbed on the carbon black, and the like.
  • the amount of polyvinyl alcohol added relative to the specific surface area of carbon black is important.
  • the saponification degree of polyvinyl alcohol is 50 to 95 mol% (preferably 60 to 85 mol%)
  • the BET specific surface area of carbon black is Xm 2 / g.
  • the addition amount of polyvinyl alcohol to 1 g of carbon black is aXg, a carbon black dispersion having a high concentration, low viscosity and good long-term storage stability when a is in the range of 0.00017 ⁇ a ⁇ 0.00256 It has been found that there is a critical range in which can be produced.
  • the range of 0.00019 ⁇ a ⁇ 0.00217 is more preferable, the range of 0.00026 ⁇ a ⁇ 0.00145 is more preferable, and 0 Particularly preferred is a range of .00051 ⁇ a ⁇ 0.00145.
  • the viscosity of the carbon black dispersion can be lowered, and it becomes easy to obtain a dispersion having a high concentration and excellent dispersibility and storage stability.
  • a positive electrode active material or a negative electrode active material can be further contained.
  • the positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to. Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc.
  • lithium and transition metals examples include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, transition metal sulfide powders such as TiS 2 and FeS, and the like.
  • conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used.
  • the negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions.
  • metal Li alloys thereof such as tin alloys, silicon alloys, lead alloys, etc., Li X Fe 2 O 3 , Li X Fe 3 O 4 , Li X WO 2 , lithium titanate, lithium vanadate, silicon
  • Metal oxides such as lithium oxide, conductive polymer such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers.
  • These negative electrode active materials can be used alone or in combination.
  • These active materials preferably have an average particle diameter in the range of 0.05 to 100 ⁇ m, and more preferably in the range of 0.1 to 50 ⁇ m.
  • the average particle diameter of the active material as used herein is an average value of particle diameters of the active material measured with an electron microscope.
  • the addition amount of the polyvinyl alcohol as a dispersing agent is 0.05 weight part or more with respect to 100 weight part of the amount of all the solid components contained in the carbon black dispersion liquid containing an electrode active material, Less than 2 parts by weight is preferable, 0.05 part by weight or more and less than 1.5 parts by weight are more preferable, 0.05 part by weight or more and less than 1.25 parts by weight are further preferable, 0.05 part by weight or more and 1 part by weight Less than 1 part by weight is more preferable, and 0.1 part by weight or more and less than 1 part by weight is particularly preferable.
  • ⁇ Other additives Conventionally known dispersants, resins, additives, and the like may be used in combination for the purpose of adjusting the physical properties of the coating film and the like as long as the object of the present invention is not affected.
  • a dispersant include a polyvinyl acetal resin (such as polyvinyl butyral resin), a polyvinyl pyrrolidone resin, a conventionally known dye derivative, and a low molecular weight surfactant.
  • the resin examples include polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyacrylamide, and polyurethane.
  • Polydimethylsiloxane epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, styrene butadiene rubber and other rubbers, lignin, pectin, gelatin, xanthan gum, welan gum, succinoglycan, cellulosic resin, polyalkylene oxide,
  • Examples include polyvinyl ether, chitins, chitosans, starch and the like.
  • the additive include phosphorus compounds, sulfur compounds, organic acids, amine compounds and amide compounds, organic esters, various silane-based, titanium-based, and aluminum-based coupling agents. These conventionally known dispersants, resins, additives and the like can be used alone or in combination of two or more.
  • the field of application of the carbon black dispersion is not particularly limited, but is a field that requires light-shielding properties, electrical conductivity, durability, jetness, etc., such as gravure ink, offset ink, back coat for magnetic recording media, static It is possible to provide a stable and uniform composition in electric toner, ink jet, automobile paint, fiber / plastic forming material, battery electrode, and electrophotographic seamless belt.
  • the use of NMP compatibility with polyvinylidene fluoride, polyimide precursors, and the like, and the strength and flexibility of the formed coating film and molded product, the electrode for lithium ion secondary battery, It is suitably used for electric double layer capacitor electrodes, lithium ion capacitor electrodes, electrophotographic seamless belts, and the like.
  • the electrode layer of the electrode for double layer capacitors and the electrode for lithium ion capacitors can be manufactured.
  • the electrophotographic seamless belt can be produced by a conventionally known method using a carbon black dispersion, a polyimide, a polyamideimide, or the like as a conductive material and a precursor thereof as components.
  • a battery electrode mixture layer By coating and drying a carbon black dispersion containing a positive electrode active material or a negative electrode active material on a current collector, a battery electrode mixture layer can be formed and an electrode can be obtained.
  • the material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries can be appropriately selected.
  • examples of the material for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel.
  • a flat foil is used as the shape, but a roughened surface, a perforated foil, or a mesh current collector can also be used.
  • Battery electrode mixture layer There is no restriction
  • the thickness of the battery electrode mixture layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
  • a secondary battery can be obtained by using an electrode for at least one of the positive electrode and the negative electrode.
  • Secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, etc.
  • conventionally known electrolytes, separators, and the like can be used as appropriate.
  • Electrode A case of a lithium ion secondary battery will be described as an example.
  • an electrolyte containing lithium dissolved in a non-aqueous solvent is used.
  • the electrolyte LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, or LiBPh 4, but are not limited thereto.
  • the non-aqueous solvent is not particularly limited.
  • carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1, Glymes such as 2-dibutoxyethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. And the like.
  • These solvents may be used alone or in combination of two or more.
  • separator examples include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.
  • the structure of the lithium ion secondary battery is not particularly limited, it is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary.
  • a separator provided as necessary.
  • a paper type such as a paper type, a cylindrical type, a button type, and a laminated type. Various shapes can be obtained.
  • carbon black sometimes abbreviated as “CB”
  • polyvinyl alcohol sometimes abbreviated as “PVA”
  • binder sometimes abbreviated as “NMP”
  • NMP N-methyl-2-pyrrolidone
  • Denka black HS-100 (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 48 nm, specific surface area 39 m 2 / g. Hereinafter, it is abbreviated as HS-100.
  • Denka black granular product (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 35 nm, specific surface area 69 m 2 / g. Hereinafter, it is abbreviated as a granular product.
  • EC-300J (manufactured by Akzo): Ketjen black, average primary particle size 40 nm, specific surface area 800 m 2 / g. Hereinafter, it is abbreviated as 300J.
  • the average primary particle size (MV) of carbon black was measured (calculated) by the method shown below.
  • a sample for measurement was prepared by adding propylene glycol monomethyl ether acetate to a carbon black powder, adding a small amount of Disperbyk-161 as a resin-type dispersant, and dispersing in a water bath of an ultrasonic cleaner for 1 minute. This sample was applied to a measurement target, dried, and photographed with a transmission electron microscope (Transmission Electron Microscope H-7650, manufactured by Hitachi High-Technologies Corporation) to observe 100 or more primary particles of carbon black.
  • Kuraray Poval L-8 (manufactured by Kuraray): polyvinyl alcohol, saponification degree 71 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 5.5 mPa ⁇ s.
  • L-8 Kuraray Poval L-10 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree 1000 or less.
  • L-10 abbreviated as L-10.
  • Kuraray Poval C-506 (manufactured by Kuraray Co., Ltd.): cation-modified polyvinyl alcohol, saponification degree 76 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.1 mPa ⁇ s.
  • C-506 Kuraray Poval KL-506 (manufactured by Kuraray Co., Ltd.): anion-modified polyvinyl alcohol, saponification degree 77 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.6 mPa ⁇ s.
  • KL-506 anion-modified polyvinyl alcohol, saponification degree 77 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.6 mPa ⁇ s.
  • KL-506 anion-modified polyvinyl alcohol, saponification degree 77 mol%, average polymerization degree 600, 4% aqueous solution
  • KL-05 Japanese Chemical Industry: polyvinyl alcohol, saponification degree 82 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.4 mPa ⁇ s.
  • KL-05 Kuraray Poval PVA-205 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 88 mol%, average polymerization degree 500, 4% aqueous solution viscosity 5.0 mPa ⁇ s.
  • PVA-205 Japanese Patent Application Laid by Kuraray Co., Ltd.
  • Goosephimer LL-02 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): polyvinyl alcohol, saponification degree 50 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 7.7 mPa ⁇ s.
  • LL-02. Synthetic product 1: polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.2 mPa ⁇ s.
  • Synthetic product 2 polyvinyl alcohol, saponification degree 85 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.7 mPa ⁇ s.
  • Synthetic product 3 polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100, 4% aqueous solution viscosity 2.0 mPa ⁇ s.
  • Synthetic product 4 polyvinyl alcohol, saponification degree 70 mol%, average polymerization degree about 1500, 4% aqueous solution viscosity 19.8 mPa ⁇ s.
  • the synthetic product 1, the synthetic product 2, the synthetic product 3, and the synthetic product 4 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
  • KF polymer W1100 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as PVDF.
  • PVDF polyvinylidene fluoride
  • -KF polymer W7300 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as # 7300.
  • HLC-22 Hyjo Chemical Co., Ltd.
  • positive electrode active material lithium cobaltate (LiCoO 2 ) positive electrode active material lithium cobaltate (LiCoO 2 ), average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g.
  • LCO positive electrode active material lithium cobaltate
  • MCMB6-28 manufactured by Osaka Gas Chemical Co.
  • MFC mesophase carbon
  • the viscosity value was measured using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.), and the dispersion was sufficiently stirred with a spatula at a dispersion temperature of 25 ° C. and a B-type viscometer rotor rotation speed of 60 rpm. Then went immediately.
  • the rotor used for the measurement is No. when the viscosity value is less than 100 mPa ⁇ s. No. 1 is 100 or more and less than 500 mPa ⁇ s. 2 is 500 or more and less than 2000 mPa ⁇ s. 3 is 2000 or more and less than 10,000 mPa ⁇ s. Four of each were used.
  • the storage stability was evaluated from the change in viscosity value after the carbon black dispersion was stored at 50 ° C. for 30 days. The smaller the change, the better the stability.
  • the average particle size after dispersion is measured by diluting the carbon black dispersion to an appropriate concentration with NMP, and then using the ultrasonically treated liquid as a measurement sample.
  • the measurement was carried out by measuring the average particle diameter (D50 value) using “Nanotrack UPA-EX” manufactured by Nikkiso Co., Ltd., light source wavelength 780 nm).
  • the loading index value of the dispersion diluted with NMP by the above method was 0.7 or more and 1.3 or less
  • the particle conditions were absorbent particles, particle shape non-spherical, density 1.80
  • the solvent conditions were The solvent refractive index was 1.47
  • the solvent viscosity was 1.80 mPa ⁇ s at a liquid temperature of 20 ° C.
  • the solvent viscosity was 1.65 mPa ⁇ s at a liquid temperature of 25 ° C.
  • the obtained median diameter was expressed as a D50 value.
  • the measurement result is obtained by measuring the background value of the NMP solvent at a liquid temperature of 25 ° C., filling a sample with the liquid temperature of 25 ° C.
  • the storage stability was evaluated from the change in D50 value after storing the carbon black dispersion at 50 ° C. for 30 days. The smaller the change, the better the stability.
  • Example 1-8 to Example 1-24 (Different types of carbon black and carbon black dispersions with different polyvinyl alcohol content) [Example 1-8 to Example 1-24]
  • NMP and polyvinyl alcohol are charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks are added, and 1.25 mm ⁇ zirconia beads are used as a medium and dispersed for 2 hours in a paint shaker. Each carbon black dispersion was obtained. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good.
  • Example 2-1 to Example 2-16 ⁇ Preparation of carbon black dispersion containing binder>
  • Example 2-1 to Example 2-16 In accordance with the composition shown in Table 1-2, NMP, various polyvinyl alcohols, and various binders are charged into a glass bottle, and after thoroughly mixing, dissolving, or dispersing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. A liquid was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 2-17 According to the composition shown in Table 1-2, NMP and polyvinyl alcohol were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to an NMP solution of polyvinyl alcohol prepared in advance. Then, it disperse
  • Example 2-18 According to the composition shown in Table 1-2, 60 parts of the carbon black dispersion of Example 1-2, 6 parts of PVDF and 34 parts of NMP were added to a glass bottle and dispersed for 1 hour with a homogenizer to obtain each carbon black dispersion. It was. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 3-1 to Example 3-3, Example 3-5 to Example 3-14 According to the composition shown in Table 1-3, the positive electrode active material was used for the carbon black dispersions containing the binders obtained in Examples 2-1 to 2-3 and Example 2-5 to Example 2-14. A certain LCO was charged and thoroughly mixed with a disper to obtain each liquid mixture. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
  • Example 3-4 After preparing a powder mixture in which 2.67 parts of granular product, 1.33 parts of PVDF, 0.13 part of L-8, and 62.7 parts of LCO are homogeneously mixed, 33.17 parts of NMP are prepared. Half of the total amount of the powder mixture was added and treated for 30 minutes with a planetary mixer. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 3-2.
  • Example 3-15 to Example 3-18 In accordance with the composition shown in Table 1-3, MFC, which is a negative electrode active material, was charged into the carbon black dispersion containing the binder obtained in Examples 2-1 to 2-3 and Example 2-9. The mixture was sufficiently mixed with a disper to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of MFC could be added, and the resulting mixture was also in a low viscosity state.
  • ⁇ Preparation of battery electrode composite layer> After applying the carbon black dispersion containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid on a polyethylene terephthalate (PET) film using a doctor blade Then, the film was dried at 120 ° C. under reduced pressure for 30 minutes, and a coating film (battery electrode mixture layer) having a film thickness of 100 ⁇ m was produced after drying. Evaluation of the obtained battery electrode mixture layer was performed by surface resistance and coating film appearance. The surface resistance was measured using Loresta-GP (manufactured by Mitsubishi Chemical Analytech) according to JIS K7194. The smaller the numerical value, the better the surface resistance. Further, the appearance of the coating film was visually evaluated as ⁇ : no problem (good), ⁇ : spotted pattern (bad), and x: coarse-grained stripes (very bad).
  • Example 4-1 to Example 4-11, Comparative Example 4-1 to Comparative Example 4-3 As the positive electrode mixture liquid, the battery electrode mixture liquids obtained in Examples 3-1 to 3-3, Example 3-5 to Example 3-12, and Comparative Example 3-1 to Comparative Example 3-3 were used. The positive electrode composite material layer (battery electrode composite material layer) was produced by using it. The evaluation results are shown in Table 1-4.
  • Example 4-12 to Example 4-15 Comparative Example 4-4 to Comparative Example 4-5
  • the battery electrode mixture liquids obtained in Examples 3-15 to 3-18 and Comparative Examples 3-4 to 3-5 were used.
  • a composite layer) was prepared.
  • the evaluation results are shown in Table 1-4. From Table 1-4, the battery electrode composite layers of Examples 4-1 to 4-15 have coating film appearances that are compared with the battery electrode composite layers of Comparative Examples 4-1 to 4-5. It was clear that the surface resistance of the coating film was excellent. In Comparative Examples 4-1 to 4-5, coating is difficult because the viscosity of the electrode mixture solution used is too high. Further, as a result of the large amount of polyvinyl alcohol functioning as an insulating component, It is considered that the resistance value has increased.
  • Example 5-1 to Example 5-11, Comparative Example 5-1 to Comparative Example 5-3 The battery electrode mixture solutions prepared previously (the positive electrode mixture solutions of Examples 3-1 to 3-3 and 3-5 to 3-12 and Comparative Examples 3-1 to 3-3) ) Is applied onto a 20 ⁇ m thick aluminum foil as a current collector using a doctor blade, dried at 120 ° C. under reduced pressure, and then rolled with a roller press to obtain a positive electrode composite having a thickness of 100 ⁇ m. A material layer was prepared.
  • the prepared positive electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 1.0 C using a charge / discharge device (SM-8 manufactured by Hokuto Denko) at 25 ° C.
  • the charge / discharge for discharging to the discharge lower limit voltage of 3.0 V at a constant current at the same rate as the charge was defined as one cycle (charge / discharge interval pause time 30 minutes), and this cycle was performed for a total of 50 cycles to perform charge / discharge.
  • the cell after evaluation was disassembled in a glove box substituted with argon gas, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was visually confirmed.
  • the evaluation criteria for the appearance of the coating film are ⁇ (very good) when no peeling from the current collector is observed and no change in the appearance, ⁇ (good) when no change is observed in the appearance.
  • ⁇ very good
  • ⁇ good
  • x defective
  • the capacity retention ratio is a percentage of the discharge capacity at the 50th cycle with respect to the discharge capacity at the 1st cycle, and the closer the value is to 100%, the better.
  • the prepared negative electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 0.5 V) at a charge rate of 1.0 C using a charging / discharging device (SM-8 manufactured by Hokuto Denko) at 25 ° C. Charging / discharging is performed at a constant current at the same rate as during charging until the voltage reaches 1.5 V, and one cycle (charging / discharging interval pause time 30 minutes) is performed, and this cycle is performed for a total of 50 cycles. It was.
  • the cell after evaluation was disassembled in a glove box substituted with argon gas, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was evaluated based on the same criteria as the positive electrode characteristic evaluation. The evaluation results are shown in Table 1-5.
  • Example 5-1 to Example 5-11 and Example 5-12 to Example 5-15 using the electrode of the present invention are shown in Comparative Example 5-1 to Comparative Example 5-3 and Compared with Comparative Examples 5-4 to 5-5, the appearance of the coating film was good, and the capacity retention rate after 50 cycles was also good.
  • Carbon black (sometimes abbreviated as “CB”), polyvinyl alcohol (sometimes abbreviated as “PVA”), organic dye derivative or triazine derivative (abbreviated as “pigment derivative”) used in Examples and Comparative Examples.
  • the binder, the electrode active material, etc. are shown below. In each table, only the composition of each raw material is described, but the remaining components not specifically described are all N-methyl-2-pyrrolidone (NMP).
  • Kuraray Poval PVA-505 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 73 mol%, average polymerization degree 500.
  • Kuraray Poval PVA-105 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 98 mol%, average polymerization degree 500.
  • Kuraray Poval LM-20 manufactured by Kuraray
  • Synthetic product 1 polyvinyl alcohol, saponification degree 55 mol%, average polymerization degree about 500.
  • Synthetic product 2 polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500.
  • Synthetic product 3 amino group-modified polyvinyl alcohol, saponification degree 76 mol%, modified group amount 10 mol%, average polymerization degree about 500.
  • Synthetic product 4 polyvinyl alcohol, saponification degree of 85 mol%, average polymerization degree of about 500.
  • -Synthetic product 5 Polyvinyl alcohol, saponification degree 92 mol%, average degree of polymerization about 100.
  • Synthetic product 6 polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100.
  • -Synthetic product 7 Polyvinyl alcohol, saponification degree 70 mol%, average degree of polymerization about 1500. Synthetic products 1 to 7 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
  • ESREC BH-3 (manufactured by Sekisui Chemical Co., Ltd.): polyvinyl butyral resin, hydroxyl group 34 mol%, butyralization degree 65 mol%, calculated molecular weight 110000.
  • BH-3 polyvinyl butyral resin, hydroxyl group 34 mol%, butyralization degree 65 mol%, calculated molecular weight 110000.
  • ESREC KS-1 (manufactured by Sekisui Chemical Co., Ltd.): polyvinyl acetoacetal resin, hydroxyl group 25 mol%, acetalization degree 74 mol%, calculated molecular weight 27000.
  • KS-1 Polyvinyl acetoacetal resin
  • Vinylec H (manufactured by JNC): polyvinyl formal resin, hydroxyl group of about 13 mol%, average molecular weight of 73,000.
  • vinylec polyvinyl formal resin
  • hydroxyl group (mol%) contained in the polymer chain of polyvinyl acetal represents the molar ratio of the repeating unit represented by the general formula (A) contained in the polymer chain of polyvinyl acetal.
  • ⁇ Other compounds > 1,2,3,4-benzenetetracarboxylic acid.
  • D-01 1,2,3,4-benzenetetracarboxylic acid
  • HLC-22 Hydrophil Chemical Co., Ltd.
  • average particle size 6.6 ⁇ m specific surface area 0.62 m 2 / g.
  • LCO positive electrode active material lithium cobaltate
  • Artificial graphite negative electrode active material, average particle size 18 ⁇ m.
  • graphite it is abbreviated as graphite.
  • the carbon black dispersions obtained in the examples and comparative examples are evaluated by measuring the viscosity (its storage stability) and the average particle size after dispersion (its storage stability) according to the method described in the first invention. It went by.
  • the storage stability of the viscosity was evaluated from the change in viscosity value after the carbon black dispersion was stored at 60 ° C. for 10 days. The smaller the change, the better the stability.
  • the storage stability of the average particle diameter after dispersion was evaluated from the change in D50 value after the carbon black dispersion was stored at 60 ° C. for 10 days. The smaller the change, the better the stability.
  • Example 2-16 According to the composition shown in Table 2-6, NMP, polyvinyl alcohol, and a pigment derivative were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to the NMP solution of the dispersant prepared in advance. Then, it disperse
  • Example 2-17 to Example 2-18 According to the composition shown in Table 2-6, 65 parts of the carbon black dispersion of Example 1-2, 6 parts of PVDF or 3 parts of # 7300, and 29 parts or 32 parts of NMP were added to a glass bottle and dispersed with a homogenizer for 1 hour. Each carbon black dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 2-19 to Example 2-20 In accordance with the composition shown in Table 2-6, NMP, polyvinyl alcohol, pigment derivative and # 7300 were charged in a glass bottle, mixed and dissolved or mixed and dispersed sufficiently, and then carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 2-9 to Example 2-13 Carbon black dispersion using different types of carbon black
  • NMP, polyvinyl alcohol, pigment derivative and PVDF were charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks were added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 3-1 to Example 3-20 Carbon black dispersion using different types of pigment derivatives
  • NMP, polyvinyl alcohol, various pigment derivatives, and PVDF were charged into a glass bottle, mixed and dissolved, or mixed and dispersed. Carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability. Further, among these, it was found that a particularly good dispersion can be obtained when a triazine derivative is used.
  • Example 4-1 to Example 4-9 Carbon black dispersions with different polyvinyl alcohol contents
  • NMP NMP, polyvinyl alcohol, various pigment derivatives, and PVDF were charged into a glass bottle, mixed and dissolved, or mixed and dispersed. Carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 5-1 to Example 5-23 According to the composition shown in Table 2-9, Example 2-1 to Example 2-6, Example 2-11, Example 3-1, Example 3-6 to Example 3-10, Example 3-16 To the carbon black dispersions containing the binders obtained in Example 3-17, Example 4-1 to Example 4-7, and Example 4-9, LCO as the positive electrode active material was charged and dispersed with a disper. Mix well to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
  • Example 5-24 According to the composition shown in Table 2-9, 2.7 parts of HS-100, 1.25 parts of PVDF, 0.011 part of polyvinyl alcohol, 0.043 part of pigment derivative, and 63 parts of LCO were mixed homogeneously. After preparing the powder mixture, half of the total amount of the powder mixture was added to 32.996 parts of NMP, and the mixture was processed with a planetary mixer for 30 minutes. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 5-23.
  • Examples 5-25 to 5-28 In accordance with the composition shown in Table 2-9, graphite as a negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Example 2-2 to Example 2-5, and thoroughly mixed with a disper. Each liquid mixture was obtained. Since the carbon black dispersion used had a low viscosity, a large amount of graphite could be added, and the resulting mixture was also in a low viscosity state.
  • a battery electrode mixture layer was prepared according to the method described in the first invention. The evaluation was performed. When the surface resistance is not measurable, no value is given ( ⁇ ), and “ ⁇ ” in the appearance of the coating means “spotted (possible)”.
  • Example 6-1 to Example 6-21 Comparative Example 6-1 to Comparative Example 6-3
  • the positive electrode mixture liquid As the positive electrode mixture liquid, Examples 5-1 to 5-6, Examples 5-8 to 5-14, Examples 5-16 to 5-23, Comparative Example 5-2, and Comparison Using the battery electrode mixture liquid obtained in Examples 5-4 to 5-5, a positive electrode mixture layer (battery electrode mixture layer) was produced. The evaluation results are shown in Table 2-10.
  • Example 6-22 to Example 6-24, Comparative Example 6-4 to Comparative Example 6-5 As the negative electrode mixture liquid, using the battery electrode mixture liquid obtained in Example 5-25 to Example 5-26, Example 5-28, and Comparative Example 5-7 to Comparative Example 5-8, A negative electrode mixture layer (battery electrode mixture layer) was produced.
  • the evaluation results are shown in Table 2-10.
  • the battery electrode composite layers of Examples 6-1 to 6-24 have a coating film appearance as compared with the battery electrode composite layers of Comparative Examples 6-1 to 6-5. It was clear that the surface resistance of the coating film was excellent.
  • Comparative Examples 6-1 to 6-5 coating is difficult because the viscosity of the electrode mixture solution used is too high. Further, in Comparative Examples 6-3 and 6-5, a large amount is used. As a result of the contained dispersant functioning as an insulating component, the surface resistance value is considered to have increased.
  • Example 7-1 to Example 7-21, Comparative Example 7-1 to Comparative Example 7-3 The previously prepared battery electrode mixture liquids (Examples 5-1 to 5-6, Examples 5-8 to 5-14, Examples 5-16 to 5-23, Comparative Example 5) 2 and the positive electrode mixture liquids of Comparative Examples 5-4 to 5-5) were assembled according to the method described in the first invention.
  • Example 7-1 to Example 7-21 and Example 7-22 to Example 7-24 using the electrode of the present invention are shown in Comparative Example 7-1 to Comparative Example 7-3 and Compared with Comparative Examples 7-4 to 7-5, the coating film appearance was good, there was no peeling from the current collector, and the adhesion was also good. Furthermore, the capacity retention rate after 50 cycles was also a good result.
  • carbon black sometimes abbreviated as “CB”
  • polyvinyl alcohol sometimes abbreviated as “PVA”
  • binder sometimes abbreviated as “NMP”
  • NMP N-methyl-2-pyrrolidone
  • Ketjen black EC-600JD manufactured by Akzo: hollow carbon black, average primary particle size 34 nm, specific surface area 1270 m 2 / g. Hereinafter, it is abbreviated as 600 JD.
  • the measurement of the average primary particle diameter of carbon black was performed by the same method as the method demonstrated in the Example regarding 1st invention.
  • Kuraray Poval PVA-505 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 73 mol%, average polymerization degree 500.
  • Kuraray Poval PVA-205 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 88 mol%, average polymerization degree 500.
  • Goosephimer LL-02 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • Synthetic product 1 polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500.
  • Synthetic product 2 polyvinyl alcohol, saponification degree 85 mol%, average polymerization degree about 500.
  • Synthetic product 3 polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100.
  • -Synthetic product 4 Polyvinyl alcohol, saponification degree 70 mol%, average degree of polymerization about 1500.
  • the synthetic product 1, the synthetic product 2, the synthetic product 3, and the synthetic product 4 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
  • HLC-22 Hydrophil Chemical Co., Ltd.
  • average particle size 6.6 ⁇ m specific surface area 0.62 m 2 / g.
  • LCO positive electrode active material lithium cobaltate
  • Artificial graphite negative electrode active material, average particle size 12 ⁇ m.
  • graphite it is abbreviated as graphite.
  • the carbon black dispersions obtained in the examples and comparative examples are evaluated by measuring the viscosity (its storage stability) and the average particle size after dispersion (its storage stability) according to the method described in the first invention. It went by.
  • the storage stability of the viscosity was evaluated from the change in viscosity value after the carbon black dispersion was stored at 60 ° C. for 10 days or at 50 ° C. for 15 days. The smaller the change, the better the stability.
  • the storage stability of the average particle diameter after dispersion was evaluated from the change in D50 value after the carbon black dispersion was stored at 60 ° C. for 10 days or at 50 ° C. for 15 days. . The smaller the change, the better the stability.
  • Example 2-1 to Example 2-15 ⁇ Preparation of carbon black dispersion containing binder>
  • Example 2-1 to Example 2-15 In accordance with the composition shown in Table 3-2, NMP, various polyvinyl alcohols and various binders are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. A liquid was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 2-16, Example 2-17 According to the composition shown in Table 3-2, NMP, polyvinyl alcohol, and PVDF were charged into a glass bottle and mixed and dissolved or dispersed sufficiently. Thereafter, carbon black obtained by mixing # 850 and 300J at a weight ratio of 1: 1, or carbon black obtained by mixing 300J and 600JD at a weight ratio of 1: 1, was added, and dispersed with a homogenizer for 1 hour. Each carbon black dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 2-18 According to the composition shown in Table 3-2, NMP and polyvinyl alcohol were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to an NMP solution of polyvinyl alcohol prepared in advance. Then, it disperse
  • Example 2-19 According to the composition shown in Table 3-2, 57 parts of the carbon black dispersion liquid of Example 1-2, 6 parts of PVDF and 37 parts of NMP were added to a glass bottle and dispersed with a homogenizer for 1 hour to obtain each carbon black dispersion liquid. It was. All of them had no coarse particles, had a low viscosity, and had good storage stability.
  • Example 3-1 to Example 3-14 ⁇ Preparation of carbon black dispersion containing positive electrode active material or negative electrode active material>
  • the carbon black dispersion containing the binder obtained in Example 2-1 to Example 2-14 was charged with LCO as the positive electrode active material and thoroughly mixed with a disper, Each mixture was obtained. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
  • Example 3-15 After preparing a powder mixture with 1.71 parts of granular product, 2.56 parts of PVDF, 0.26 part of PVA-505, 56.7 parts of LCO and homogeneously mixed, 38.77 parts of NMP Half of the total amount of the powder mixture was added and treated for 30 minutes with a planetary mixer. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 3-2.
  • Example 3-16 to Example 3-20 In accordance with the composition shown in Table 3-3, graphite as a negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Examples 2-1 to 2-4 and Example 2-7. The mixture was sufficiently mixed with a disper to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of graphite could be added, and the resulting mixture was also in a low viscosity state.
  • ⁇ Preparation of battery electrode composite layer> Using the carbon black dispersion liquid containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid, a battery electrode mixture layer was prepared according to the method described in the first invention. The evaluation was performed. In the appearance of the coating film, “ ⁇ ” means “with spotted pattern (possible)”. When the appearance of the coating film was extremely poor and could not be measured, no value was given ( ⁇ ).
  • Example 4-1 to Example 4-14 Comparative Example 4-1 to Comparative Example 4-3
  • the positive electrode mixture layer battery electrode A composite layer
  • the evaluation results are shown in Table 3-4.
  • Example 4-15 to Example 4-19, Comparative Example 4-4 to Comparative Example 4-6 Using the battery electrode mixture liquids obtained in Examples 3-16 to 3-20 and Comparative Examples 3-5 to 3-7 as the negative electrode mixture liquid, the negative electrode mixture layer (battery electrode) A composite layer) was prepared. The evaluation results are shown in Table 3-4.
  • the battery electrode composite layers of Examples 4-1 to 4-19 have an appearance of the coating film as compared with the battery electrode composite layers of Comparative Examples 4-1 to 4-6. It was clear that the surface resistance of the coating film was excellent. In Comparative Examples 4-1 to 4-6, the viscosity of the electrode mixture solution used was too high to be applied, and in Comparative Examples 4-3 and 4-6, a large amount As a result of the contained polyvinyl alcohol functioning as an insulating component, the surface resistance value is considered to have increased.
  • Example 5-1 to Example 5-14 and Example 5-15 to Example 5-19 using the electrode of the present invention are shown in Comparative Example 5-1 to Comparative Example 5-3 and As compared with Comparative Examples 5-4 to 5-6, it was found that the appearance of the coating film was good, there was no peeling from the current collector, and the adhesion was good. Furthermore, the capacity retention rate after 50 cycles was also a good result. On the other hand, Comparative Example 5-1 to Comparative Example 5-6 were unable to obtain a good coating film, so that the positive electrode characteristics and the negative electrode characteristics could not be evaluated.

Abstract

Provided is a carbon black dispersion in which N-methyl-2-pyrrolidone that can achieve dispersibility at a lower viscosity and a higher concentration and can also achieve superior storage stability compared with conventional resin-type dispersants is used as a solvent. Also provided are: a battery electrode mix layer which is homogeneous and has good coating film properties and low surface resistance; and a lithium ion secondary battery equipped with the battery electrode mix layer. The problems can be solved by, for example, a carbon black dispersion comprising carbon black, polyvinyl alcohol (or a combination of polyvinyl alcohol with a pigment derivative) that serves as a dispersant, and N-methyl-2-pyrrolidone that serves as a solvent, said carbon black dispersion being characterized in that the degree of saponification of polyvinyl alcohol is 60 to 85 mol% and the value (a) falls within the range from 0.00017 to 0.00256 inclusive wherein X (m2/g) represents the BET specific surface area of carbon black and aX (g) represents the addition amount of polyvinyl alcohol relative to 1 g of carbon black.

Description

カーボンブラック分散液およびその利用Carbon black dispersion and use thereof
　本発明は、分散性、貯蔵安定性に優れたカーボンブラック分散液に関する。また、該分散液を使用した電池電極合材層およびリチウムイオン二次電池に関する。 The present invention relates to a carbon black dispersion excellent in dispersibility and storage stability. The present invention also relates to a battery electrode mixture layer and a lithium ion secondary battery using the dispersion.
　電池分野において、カーボンブラックは、導電助剤として広く用いられているが、電池電極合材層を形成する際、生産プロセスを効率化して短縮するためには、カーボンブラックを溶剤中に、いかに高濃度かつ均一に分散して、容易に塗工可能とするかが重要である。 In the battery field, carbon black is widely used as a conductive additive, but when forming a battery electrode mixture layer, in order to shorten the production process in an efficient manner, the carbon black can be increased in a solvent. It is important to make it possible to easily disperse in concentration and uniformly.
　近年、特に環境や生産コストへの配慮から、従来よりも、より高濃度かつ均一に分散されたカーボンブラック分散液を作製することによって、溶剤使用量を低減することや乾燥時の使用エネルギーを低減することが求められている。 In recent years, especially in consideration of the environment and production costs, the amount of solvent used and the energy used during drying have been reduced by producing a carbon black dispersion with a higher concentration and uniformity than before. It is requested to do.
　これらの要求は、溶剤のコストや乾燥時の使用エネルギーに大きな影響があることから、使用する溶剤が高価であるほど、または、使用する溶剤が高沸点であるほど重要になる。非水系二次電池で使用されるＮ－メチル－２－ピロリドンは、一般的な溶剤と比較して高価であり、さらに２００℃以上と沸点が非常に高いため、溶剤を回収する際に多くのエネルギーを必要とすることから、分散液における溶剤使用量の低減が強く求められている。 These requirements have a great influence on the cost of the solvent and the energy used during drying. Therefore, the more expensive the solvent used or the higher the solvent used, the more important. N-methyl-2-pyrrolidone used in non-aqueous secondary batteries is more expensive than common solvents and has a very high boiling point of 200 ° C. or higher. Since energy is required, reduction of the amount of solvent used in the dispersion is strongly demanded.
　多量のカーボンブラックを溶剤中に分散するためには、カーボンブラックの表面に分散剤を吸着処理して分散安定な状態にすることが、特に有効な方法であり、様々な分散剤を用いたカーボンブラック分散液が提案されている。 In order to disperse a large amount of carbon black in a solvent, it is particularly effective to adsorb a dispersant on the surface of the carbon black so that the dispersion is in a stable state. Carbon using various dispersants Black dispersions have been proposed.
　例えば、特許文献１、２には、カーボンブラックに対して酸性または塩基性の有機色素誘導体を吸着させつつカーボンブラックを分散させることで、カーボンブラックの導電性を阻害せずに分散安定化を図った電池用組成物が記載されている。しかしながら、分散剤として有機色素誘導体を用いて得た、電極活物質を含有するカーボンブラック分散液（以下、電極合材液と呼ぶ）を塗膜基板に塗工した場合、電極合材層と塗膜基板の密着性が不十分な場合があり、電極合材層が塗膜基板から意図せずに剥離する恐れがあるという問題があった。 For example, in Patent Documents 1 and 2, carbon black is dispersed while adsorbing an acidic or basic organic dye derivative to the carbon black, thereby achieving dispersion stabilization without impairing the conductivity of the carbon black. A battery composition is described. However, when a carbon black dispersion liquid containing an electrode active material (hereinafter referred to as an electrode mixture liquid) obtained using an organic pigment derivative as a dispersant is applied to a coating film substrate, the electrode mixture layer and the coating layer are coated. In some cases, the adhesion of the film substrate may be insufficient, and the electrode mixture layer may unintentionally peel from the coating film substrate.
　密着性の問題を解決するために、例えば特許文献３では、カーボンブラックを分散するための分散剤として色素誘導体型分散剤と高分子ポリマー型分散剤（以下、樹脂型分散剤と呼ぶ）とを併用して用いることで、色素誘導体型分散剤が有する分散剤としての性能を利用しつつ密着性が良好な正極板を作製できることが記載されている。特に、色素誘導体型分散剤としてオキサジン誘導体を、樹脂型分散剤としてポリビニルブチラールを、特定の比率範囲で併用して用いた場合に、正極合材液の粘度と密着性のバランスについて両立できることが記載されている。 In order to solve the adhesion problem, for example, in Patent Document 3, as a dispersant for dispersing carbon black, a pigment derivative type dispersant and a polymer polymer type dispersant (hereinafter referred to as a resin type dispersant) are used. It is described that, when used in combination, a positive electrode plate having good adhesion can be produced while utilizing the performance as a dispersant possessed by the pigment derivative type dispersant. In particular, when using an oxazine derivative as a pigment derivative-type dispersant and polyvinyl butyral as a resin-type dispersant in combination in a specific ratio range, it is described that the balance between the viscosity and adhesion of the positive electrode mixture liquid can be achieved. Has been.
　しかしながら、Ｎ－メチル－２－ピロリドンを溶剤としてカーボンブラックを分散するための分散剤として公知であるポリビニルアセタール等の樹脂型分散剤は、分散剤としての性能が充分ではなく、カーボンブラック分散液の濃度を向上させ、かつその貯蔵安定性を良好にするためには、分散剤として多量の色素誘導体型分散剤を添加する必要があった。さらに、例えば特許文献５に記載されているように、ポリビニルアセタールはエチレンカーボネートやプロピレンカーボネート等の非水電解液に対する耐性が低いという問題があった。 However, resin-type dispersants such as polyvinyl acetal, which are known as dispersants for dispersing carbon black using N-methyl-2-pyrrolidone as a solvent, do not have sufficient performance as dispersants. In order to improve the concentration and improve the storage stability, it is necessary to add a large amount of a pigment derivative type dispersant as a dispersant. Furthermore, as described in Patent Document 5, for example, polyvinyl acetal has a problem of low resistance to non-aqueous electrolytes such as ethylene carbonate and propylene carbonate.
　ポリビニルアセタール等の非水電解液に対して溶解しやすい高分子を分散剤として用いた場合、二次電池に使用する非水電解液の種類や組成次第では、分散剤の非水電解液に対する耐性が充分では無く塗膜性状が安定しない懸念があるため、非水電解液に対する耐性がより高く、得られる塗膜の塗膜物性が安定であり、かつ、Ｎ－メチル－２－ピロリドン溶剤中での分散剤としての能力がより優れた樹脂型分散剤の開発が求められていた。 When polymers that are easily soluble in non-aqueous electrolytes such as polyvinyl acetal are used as dispersants, depending on the type and composition of the non-aqueous electrolyte used in the secondary battery, the resistance of the dispersant to non-aqueous electrolytes Is not sufficient, and there is a concern that the properties of the coating film will not be stable. Therefore, the resistance to non-aqueous electrolyte is higher, the coating film properties of the resulting coating film are stable, and in a N-methyl-2-pyrrolidone solvent. There has been a demand for the development of a resin-type dispersant having more excellent ability as a dispersant.
　一方、特許文献５、６には、カーボンブラック、未変性又は変性ポリビニルアルコール、及びＮ－メチル－２－ピロリドンを含有する塗工液が記載されており、また、特許文献５には、この塗工液に正極活物質又は負極活物質を添加して、リチウムイオン二次電池の電極板を製造することが記載されている。しかしながら、これら特許文献５、６におけるポリビニルアルコール類は、結合剤（樹脂バインダー）として多量に使用されており、ポリビニルアルコール類を分散剤として使用するという技術的思想はない。 On the other hand, Patent Documents 5 and 6 describe coating liquids containing carbon black, unmodified or modified polyvinyl alcohol, and N-methyl-2-pyrrolidone, and Patent Document 5 describes this coating liquid. It describes that a positive electrode active material or a negative electrode active material is added to a working solution to produce an electrode plate of a lithium ion secondary battery. However, the polyvinyl alcohols in Patent Documents 5 and 6 are used in large amounts as binders (resin binders), and there is no technical idea of using polyvinyl alcohols as a dispersant.
　また、特許文献３、４では、ポリビニルアルコールを分散剤の１つとして、Ｎ－メチル－２－ピロリドンを溶剤の１つとして用いる可能性が示唆されている。しかし、使用するカーボンブラック、溶剤種、分散剤の物理的、化学的性質は互いに密接な関係にあるが、Ｎ－メチル－２－ピロリドンという特定の溶剤を使用した場合において、どのような物理的、化学的性質を有するポリビニルアルコール類が分散剤として良好に機能し得るのかということについては何ら言及されておらず、また、本来高分子を特徴付けるパラメータであるはずの、分子構造、官能基比率や分子量などと、樹脂型分散剤として機能するための条件との関連性は依然として不明であった。 Patent Documents 3 and 4 suggest the possibility of using polyvinyl alcohol as one of the dispersants and N-methyl-2-pyrrolidone as one of the solvents. However, although the physical and chemical properties of the carbon black, solvent type, and dispersant used are closely related to each other, what kind of physical properties are required when a specific solvent called N-methyl-2-pyrrolidone is used. However, no mention is made as to whether polyvinyl alcohols having chemical properties can function well as a dispersant, and the molecular structure, functional group ratio, The relationship between molecular weight and the conditions for functioning as a resin-type dispersant was still unclear.
　一般的な完全けん化型ポリビニルアルコールはＮ－メチル－２－ピロリドンに対して不溶であり、かつ分散剤として機能せず、さらに、その前駆体原料であるポリ酢酸ビニル等のポリビニルエステルについても同様に分散剤として充分に機能しないことを発明者は見出した。 General fully saponified polyvinyl alcohol is insoluble in N-methyl-2-pyrrolidone, does not function as a dispersant, and also applies to polyvinyl esters such as polyvinyl acetate as a precursor material. The inventors have found that it does not function well as a dispersant.
　一般に、分散剤を使用してカーボンブラックを分散する場合、分散剤の量が極端に少なくなるとカーボンブラックの分散性は悪化し、逆に分散剤の量が非常に多くなると分散性は良好になるものの、電池用途で使用する場合には、樹脂型分散剤の非水電解液に対する耐性が充分ではない、および、分散剤が絶縁成分として機能して抵抗値が高くなり導電性が悪化する、といった悪影響を電池特性に及ぼすことが予想される。 In general, when carbon black is dispersed using a dispersant, the dispersibility of the carbon black is deteriorated when the amount of the dispersant is extremely reduced, and on the contrary, the dispersibility is improved when the amount of the dispersant is extremely increased. However, when used in battery applications, the resin-type dispersant does not have sufficient resistance to the non-aqueous electrolyte, and the dispersant functions as an insulating component, resulting in a high resistance value and poor conductivity. It is expected to have a negative effect on battery characteristics.
　しかしながら、高濃度かつ均一に分散されたカーボンブラック分散液を得るために、使用するカーボンブラック、溶剤種、分散剤の物理的、化学的性質はもとより、それらの量的関係についてまで詳細に検討された例は報告されていない。特定の溶剤としてＮ－メチル－２－ピロリドンと分散剤として主にポリビニルアルコール類とを使用する場合や、特定の溶剤としてＮ－メチル－２－ピロリドンと、分散剤としてポリビニルアルコール類および顔料誘導体（有機色素誘導体またはトリアジン誘導体）とを使用する場合に、カーボンブラックと分散剤の物理的、化学的性質、さらには、それらの量的関係が、カーボンブラック分散液や電池電極合材層、電池特性へどのように影響するのかについては何ら検討されていないのが実状であった。 However, in order to obtain a highly concentrated and uniformly dispersed carbon black dispersion, not only the physical and chemical properties of the carbon black used, the solvent type, and the dispersant, but also their quantitative relationships have been studied in detail. No examples have been reported. When N-methyl-2-pyrrolidone is used as a specific solvent and polyvinyl alcohols are mainly used as a dispersant, or N-methyl-2-pyrrolidone is used as a specific solvent, and polyvinyl alcohols and pigment derivatives ( When using organic dye derivatives or triazine derivatives), the physical and chemical properties of carbon black and the dispersant, and their quantitative relationship, are determined by the carbon black dispersion, the battery electrode mixture layer, and the battery characteristics. The actual situation is that no consideration has been given to how the impact is affected.
　また、塗膜中に含まれる導電材料の比率を抑えつつも導電性が良好な塗膜を作製するためには、カーボンブラックの種類そのものの選定が重要になる場合がある。一般に、一次粒子径が小さく高比表面積なカーボンブラックや、体積密度が小さく高比表面積なカーボンブラックを用いたときに、導電性が良好で表面抵抗値が低い塗膜を得られることが知られている。しかし、これらのカーボンブラックは高比表面積であるために、安定に分散することや貯蔵安定性を良好にすることが難しかった。 Also, in order to produce a coating film with good conductivity while suppressing the ratio of the conductive material contained in the coating film, the selection of the type of carbon black itself may be important. In general, when carbon black with a small primary particle size and high specific surface area or carbon black with a small volume density and high specific surface area is used, it is known that a coating film with good conductivity and low surface resistance can be obtained. ing. However, since these carbon blacks have a high specific surface area, it has been difficult to stably disperse and to improve the storage stability.
　また、一般に、リチウムイオン二次電池用電極を製造する際には、電池中の結合剤に用いる高分子材料によって電極合材液の作製に用いる溶剤が決定される。現在、リチウムイオン二次電池用電極の生産においては、電極を形成するために特に好適な結合剤としてポリフッ化ビニリデンが、ポリフッ化ビニリデンを溶かすための溶剤としてＮ－メチル－２－ピロリドンが、一般に用いられている。Ｎ－メチル－２－ピロリドンは沸点が２０２℃と非常に高く、そのために、電極合材液の乾燥には多量のエネルギーと時間を費やす必要があった。この問題を解決するために、Ｎ－メチル－２－ピロリドンを溶剤とした、できるだけ高濃度な電極合材液を得る試みが行われてきた。リチウムイオン二次電池の電極合材液用のカーボンブラック分散液に求められるもう１つの性能として、分散剤添加量は極力少ない方が望ましいことが挙げられる。これは、分散剤を添加した分だけ、電極膜における他の電極構成成分の比率が下がるためである。 In general, when manufacturing an electrode for a lithium ion secondary battery, the solvent used for preparing the electrode mixture liquid is determined by the polymer material used for the binder in the battery. Currently, in the production of electrodes for lithium ion secondary batteries, polyvinylidene fluoride is generally used as a particularly suitable binder for forming an electrode, and N-methyl-2-pyrrolidone is generally used as a solvent for dissolving polyvinylidene fluoride. It is used. Since N-methyl-2-pyrrolidone has a very high boiling point of 202 ° C., it is necessary to spend a large amount of energy and time for drying the electrode mixture liquid. In order to solve this problem, attempts have been made to obtain an electrode mixture solution having a concentration as high as possible using N-methyl-2-pyrrolidone as a solvent. Another performance required for the carbon black dispersion liquid for the electrode mixture liquid of the lithium ion secondary battery is that it is desirable that the amount of the dispersant added is as small as possible. This is because the ratio of the other electrode constituent components in the electrode film decreases by the amount of the dispersant added.
国際公開第２００８／１０８３６０号International Publication No. 2008/108360 特開２００９－２６７４４号公報JP 2009-26744 A 特開２０１３－８９４８５号公報JP 2013-89485 A 特開２０１１－７０９０８号公報JP 2011-70908 A 国際公開第２００９／１４７９８９号International Publication No. 2009/147789 国際公開第２０１１／０２４７９９号International Publication No. 2011/024799
　以上の状況を鑑み、本発明では、従来公知の樹脂型分散剤と比較して、得られるカーボンブラック分散液を顕著に低粘度化すること、すなわち、達成できるカーボンブラック濃度が顕著に高く、カーボンブラックの分散性と分散液の貯蔵安定性に優れた、Ｎ－メチル－２－ピロリドンを溶剤とするカーボンブラック分散液を提供することが課題である。また、均質で良好な塗膜物性と低い表面抵抗を有する電池電極合材層を提供することが課題である。さらに、均質で良好な塗膜物性と低い表面抵抗を有し、かつ非水電解液に対する樹脂型分散剤の耐性が良好で安定した塗膜物性を有する電池電極合材層を提供することが課題である。 In view of the above situation, in the present invention, the resulting carbon black dispersion is significantly reduced in viscosity compared to conventionally known resin-type dispersants, that is, the carbon black concentration that can be achieved is significantly higher, and carbon It is an object to provide a carbon black dispersion using N-methyl-2-pyrrolidone as a solvent, which is excellent in black dispersibility and storage stability of the dispersion. Moreover, it is a subject to provide the battery electrode compound-material layer which has a uniform and favorable coating-film physical property and low surface resistance. Furthermore, it is a problem to provide a battery electrode mixture layer having uniform and good coating film properties and low surface resistance, and having good and stable coating film properties with good resistance of the resin-type dispersant to the non-aqueous electrolyte. It is.
（１）第１の発明
　本発明者らは、カーボンブラック、溶剤種、分散剤の物理的、化学的性質に着目し、それらの量的関係についてまで詳細に検討した結果、カーボンブラックの比表面積と、特定のけん化度を有するポリビニルアルコールの使用量との間に分散性に大きく寄与する臨界的範囲があることを見出し、これらが一定の範囲内である場合に高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造できることを見出し、本発明の完成に至った。 (1) 1st invention The present inventors paid attention to the physical and chemical properties of carbon black, solvent species, and a dispersant, and as a result of examining the quantitative relationship thereof in detail, the specific surface area of carbon black was determined. And a use amount of polyvinyl alcohol having a specific degree of saponification, there is a critical range that greatly contributes to dispersibility, and when these are within a certain range, high concentration, low viscosity, and long-term It has been found that a carbon black dispersion having good storage stability can be produced, and the present invention has been completed.
　即ち、本発明の実施態様は、カーボンブラックと、分散剤としてのポリビニルアルコールと、溶剤としてのＮ－メチル－２－ピロリドンとを含んでなるカーボンブラック分散液であって、ポリビニルアルコールのけん化度が６０～８５ｍｏｌ％であり、カーボンブラックのＢＥＴ比表面積をＸｍ２／ｇ、カーボンブラック１ｇに対するポリビニルアルコールの添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲であることを特徴とする、カーボンブラック分散液に関する。 That is, an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is When the BET specific surface area of carbon black is Xm 2 / g and the amount of polyvinyl alcohol added to 1 g of carbon black is aXg, a is in the range of 0.00017 ≦ a ≦ 0.00256. The present invention relates to a carbon black dispersion.
　また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコールが０．６５重量部以上、１５重量部以下であることを特徴とする上記カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.65 parts by weight to 15 parts by weight with respect to 100 parts by weight of the carbon black.
　また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコールが２重量部以上、８重量部以下であることを特徴とする上記カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol is 2 to 8 parts by weight with respect to 100 parts by weight of the carbon black.
　また、本発明の実施態様は、上記カーボンブラック分散液に、さらに、正極活物質または負極活物質を含有してなる電池用カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
　また、本発明の実施態様は、上記カーボンブラック分散液または上記電池用カーボンブラック分散液を塗布してなる電池電極合材層に関する。 Also, an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
　また、本発明の実施態様は、集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウムイオン二次電池であって、正極および負極の少なくとも一方が、上記電池電極合材層を具備してなるリチウムイオン二次電池に関する。 An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
（２）第２の発明
　また、本発明者らは、カーボンブラック、溶剤種、分散剤の物理的、化学的性質に着目し、それらの量的関係についてまで詳細に検討した結果、カーボンブラックと、有機色素誘導体またはトリアジン誘導体と、下記一般式（Ａ）で表される繰り返し単位を重合体鎖中に特定の比率で有するポリビニルアルコールの使用量との間に、分散性に大きく寄与する臨界的範囲があること、および、これらが一定の範囲内である場合に高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造でき、さらに、表面抵抗値が低く、分散剤の非水電解液への耐性が良好な電池電極合材層が得られることを見出し、本発明の完成に至った。 (2) Second invention Further, the present inventors paid attention to the physical and chemical properties of carbon black, solvent species, and a dispersant, and as a result of detailed examination of their quantitative relationship, A critical contribution greatly contributing to dispersibility between the organic dye derivative or the triazine derivative and the amount of polyvinyl alcohol having a repeating unit represented by the following general formula (A) in a specific ratio in the polymer chain A carbon black dispersion having a high concentration, a low viscosity, and a good long-term storage stability when these are within a certain range, and having a low surface resistance, The present inventors have found that a battery electrode mixture layer having good resistance to a non-aqueous electrolyte can be obtained, and have completed the present invention.
　即ち、本発明の実施態様は、カーボンブラックと、分散剤としての、ポリビニルアルコールおよびトリアジン誘導体、またはポリビニルアルコールおよび有機色素誘導体と、溶剤としてのＮ－メチル－２－ピロリドンとを含有するカーボンブラック分散液であって、カーボンブラック１００重量部に対する分散剤の合計量が５０重量部以下であり、ポリビニルアルコールが、下記一般式（Ａ）で表される繰り返し単位を重合体鎖中に５０～９５ｍｏｌ％含有することを特徴とするカーボンブラック分散液に関する。
　一般式（Ａ）
Figure JPOXMLDOC01-appb-C000002
 That is, an embodiment of the present invention is a carbon black dispersion containing carbon black, polyvinyl alcohol and a triazine derivative or polyvinyl alcohol and an organic dye derivative as a dispersant, and N-methyl-2-pyrrolidone as a solvent. The total amount of the dispersant is 50 parts by weight or less based on 100 parts by weight of carbon black, and the polyvinyl alcohol contains 50 to 95 mol% of repeating units represented by the following general formula (A) in the polymer chain. The present invention relates to a carbon black dispersion characterized by containing.
Formula (A)
Figure JPOXMLDOC01-appb-C000002
　また、本発明の実施態様は、カーボンブラックと、分散剤としての、ポリビニルアルコールおよびトリアジン誘導体、またはポリビニルアルコールおよび有機色素誘導体と、溶剤としてのＮ－メチル－２－ピロリドンとを含有するカーボンブラック分散液であって、
　カーボンブラック１００重量部に対する分散剤の合計量が５０重量部以下であり、カーボンブラックのＢＥＴ比表面積をＸｍ２／ｇ、カーボンブラック１ｇに対するポリビニルアルコールの添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲であり、ポリビニルアルコールが上記一般式（Ａ）で表される繰り返し単位を重合体鎖中に５０～９５ｍｏｌ％、好ましくは６０～８５ｍｏｌ％含有することを特徴とする、カーボンブラック分散液に関する。 Further, an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol and a triazine derivative or polyvinyl alcohol and an organic dye derivative as a dispersant, and N-methyl-2-pyrrolidone as a solvent. Liquid,
When the total amount of the dispersant with respect to 100 parts by weight of carbon black is 50 parts by weight or less, the BET specific surface area of carbon black is Xm 2 / g, and the amount of polyvinyl alcohol added to 1 g of carbon black is aXg. 0.00000 ≦ a ≦ 0.00256, and the polyvinyl alcohol contains 50 to 95 mol%, preferably 60 to 85 mol%, of the repeating unit represented by the general formula (A) in the polymer chain. And a carbon black dispersion.
　また、本発明の実施態様は、上記分散剤が、ポリビニルアルコールおよびトリアジン誘導体であることを特徴とする、上記カーボンブラック分散液に関する。 Also, an embodiment of the present invention relates to the above carbon black dispersion, wherein the dispersant is polyvinyl alcohol and a triazine derivative.
　また、本発明の実施態様は、上記ポリビニルアルコールが、上記一般式（Ａ）で表される繰り返し単位を重合体鎖中に５５～８５ｍｏｌ％含有することを特徴とする、上記カーボンブラック分散液に関する。 An embodiment of the present invention also relates to the carbon black dispersion, wherein the polyvinyl alcohol contains 55 to 85 mol% of a repeating unit represented by the general formula (A) in a polymer chain. .
　また、本発明の実施態様は、カーボンブラック１００重量部に対する分散剤の合計量が０．５重量部以上、４０重量部以下であることを特徴とする、上記カーボンブラック分散液に関する。 In addition, an embodiment of the present invention relates to the above carbon black dispersion, wherein the total amount of the dispersant with respect to 100 parts by weight of carbon black is 0.5 part by weight or more and 40 parts by weight or less.
　また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコールが０．２重量部以上、２０重量部以下であることを特徴とする、上記カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the carbon black.
　また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコールが０．２重量部以上、８重量部以下であることを特徴とする、上記カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to the above carbon black dispersion, wherein the polyvinyl alcohol is from 0.2 parts by weight to 8 parts by weight with respect to 100 parts by weight of the carbon black.
　また、本発明の実施態様は、上記カーボンブラック分散液に、さらに、正極活物質または負極活物質を含有してなる電池用カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
　また、本発明の実施態様は、上記カーボンブラック分散液または上記電池用カーボンブラック分散液を塗布してなる電池電極合材層に関する。 Also, an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
　また、本発明の実施態様は、集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウムイオン二次電池であって、正極および負極の少なくとも一方が、上記電池電極合材層を具備してなるリチウムイオン二次電池に関する。 An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
（３）第３の発明
　また、本発明者らは、カーボンブラック、溶剤種、分散剤の物理的、化学的性質に着目し、それらの量的関係についてまで詳細に検討した結果、カーボンブラックの比表面積と、特定のけん化度を有するポリビニルアルコールの使用量との間に分散性に大きく寄与する臨界的範囲があることを見出し、これらが一定の範囲内である場合に高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造できることを見出し、本発明の完成に至った。 (3) Third invention Further, the present inventors paid attention to the physical and chemical properties of carbon black, solvent species, and a dispersant, and as a result of detailed examination of their quantitative relationship, It is found that there is a critical range that greatly contributes to dispersibility between the specific surface area and the amount of polyvinyl alcohol having a specific degree of saponification, and when these are within a certain range, high concentration, low viscosity, And it discovered that the carbon black dispersion liquid with favorable long-term storage stability could be manufactured, and came to completion of this invention.
　即ち、本発明の実施態様は、カーボンブラックと、分散剤としてのポリビニルアルコールと、溶剤としてのＮ－メチル－２－ピロリドンとを含んでなるカーボンブラック分散液であって、ポリビニルアルコールのけん化度が６０～８５ｍｏｌ％であり、カーボンブラックのＢＥＴ比表面積が３０～１５００ｍ２／ｇであり、カーボンブラック１００重量部に対するポリビニルアルコールが８重量部を超え、４０重量部以下であることを特徴とする、カーボンブラック分散液に関する。 That is, an embodiment of the present invention is a carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is 60 to 85 mol%, the BET specific surface area of carbon black is 30 to 1500 m 2 / g, and the polyvinyl alcohol with respect to 100 parts by weight of carbon black is more than 8 parts by weight and 40 parts by weight or less, It relates to a carbon black dispersion.
　また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコールが８重量部を超え、２５重量部以下であることを特徴とする、上記カーボンブラック分散液に関する。 Also, an embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol is more than 8 parts by weight and 25 parts by weight or less based on 100 parts by weight of the carbon black.
　また、本発明の実施態様は、上記カーボンブラックのＢＥＴ比表面積が２００～１５００ｍ２／ｇであることを特徴とする、上記カーボンブラック分散液に関する。 An embodiment of the present invention also relates to the carbon black dispersion, wherein the carbon black has a BET specific surface area of 200 to 1500 m 2 / g.
　また、本発明の実施態様は、上記カーボンブラックのＢＥＴ比表面積が５００～１５００ｍ２／ｇであることを特徴とする、上記カーボンブラック分散液に関する。 In addition, an embodiment of the present invention relates to the carbon black dispersion, wherein the carbon black has a BET specific surface area of 500 to 1500 m 2 / g.
　また、本発明の実施態様は、上記カーボンブラックが中空カーボンブラックであることを特徴とする、上記カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to the carbon black dispersion, wherein the carbon black is a hollow carbon black.
　また、本発明の実施態様は、分散液中に含まれる全固形成分の量１００重量部に対するポリビニルアルコールの含有量が０．０５重量部以上、２重量部未満であることを特徴とする、上記カーボンブラック分散液に関する。 The embodiment of the present invention is characterized in that the content of polyvinyl alcohol is 0.05 parts by weight or more and less than 2 parts by weight with respect to 100 parts by weight of the total solid components contained in the dispersion liquid. It relates to a carbon black dispersion.
　また、本発明の実施態様は、上記カーボンブラック分散液に、さらに、正極活物質または負極活物質を含有してなる電池用カーボンブラック分散液に関する。 Further, an embodiment of the present invention relates to a carbon black dispersion for a battery, which further contains a positive electrode active material or a negative electrode active material in the carbon black dispersion.
　また、本発明の実施態様は、上記カーボンブラック分散液または上記電池用カーボンブラック分散液を塗布してなる電池電極合材層に関する。 Also, an embodiment of the present invention relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
　また、本発明の実施態様は、集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウムイオン二次電池であって、正極および負極の少なくとも一方が、上記電池電極合材層を具備してなるリチウムイオン二次電池に関する。 An embodiment of the present invention is a lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
　第１の発明および第３の発明により、従来公知の樹脂型分散剤を用いた場合よりも、顕著に低粘度なカーボンブラック分散液を得ることができ、カーボンブラック濃度を高くすることが可能となる。 According to the first and third inventions, it is possible to obtain a carbon black dispersion having a significantly lower viscosity than when a conventionally known resin-type dispersant is used, and to increase the carbon black concentration. Become.
　第２の発明により、従来公知の顔料誘導体型分散剤を単独で用いた場合よりも、塗膜基板に対する密着性が良好な塗膜を得ることができ、かつ、従来公知の樹脂型分散剤を単独または顔料誘導体を併用して用いた場合よりも、顕著に低粘度なカーボンブラック分散液を得ることができ、密着性を維持しつつカーボンブラック濃度を高くすることが可能となる。 According to the second invention, it is possible to obtain a coating film having better adhesion to the coating substrate than when a conventionally known pigment derivative type dispersing agent is used alone, and a conventionally known resin type dispersing agent A carbon black dispersion having a remarkably low viscosity can be obtained as compared with the case where it is used alone or in combination with a pigment derivative, and the carbon black concentration can be increased while maintaining adhesion.
　さらに、第１の発明、第２の発明および第３の発明により、従来よりも高濃度なカーボンブラック分散液を提供できるようになり、Ｎ－メチル－２－ピロリドン溶剤の使用量を大幅に低減できると共に、塗工した塗膜の乾燥プロセスも大幅に短縮することができるようになる。また、カーボンブラックの分散性と分散液の貯蔵安定性に優れた、Ｎ－メチル－２－ピロリドンを溶剤とするカーボンブラック分散液を提供することが可能となる。
　また、該分散液を用いて二次電池用電極合材液を調製した場合、低粘度であることから電極活物質粉体の添加や混練が容易になり、さらに、各電極成分が高濃度な電極合材液を用いても、均質で良好な塗膜を得ることができるため、表面抵抗値の低い電池電極合材層を得る事が可能となる。さらに、該分散液を用いて電池電極合材層を作製した場合、非水電解液に対する耐性が良好となり、より塗膜物性が安定した電池電極合材層を得ることが可能となる。 Furthermore, according to the first invention, the second invention, and the third invention, it becomes possible to provide a carbon black dispersion having a higher concentration than before, and the amount of N-methyl-2-pyrrolidone solvent used is greatly reduced. In addition, the drying process of the coated film can be greatly shortened. Further, it is possible to provide a carbon black dispersion liquid using N-methyl-2-pyrrolidone as a solvent, which is excellent in carbon black dispersibility and dispersion storage stability.
In addition, when an electrode mixture solution for a secondary battery is prepared using the dispersion, it is easy to add and knead electrode active material powder because of its low viscosity, and each electrode component has a high concentration. Even when an electrode mixture solution is used, a uniform and good coating film can be obtained, and therefore a battery electrode mixture layer having a low surface resistance value can be obtained. Furthermore, when a battery electrode mixture layer is produced using the dispersion, it becomes possible to obtain a battery electrode mixture layer with good resistance to non-aqueous electrolyte and more stable coating film properties.
　以下、本発明（第１の発明、第２の発明および第３の発明）の詳細を説明する。尚、本明細書では、「カーボンブラック分散液」および「電池用カーボンブラック分散液」を「分散液」、「有機色素誘導体またはトリアジン誘導体」を「顔料誘導体」、「ポリビニルアルコール」（第１の発明および第３の発明）または「ポリビニルアルコールおよび顔料誘導体」（第２の発明）を「分散剤」、「Ｎ－メチル－２－ピロリドン」を「ＮＭＰ」と略記することがある。 Hereinafter, the details of the present invention (first invention, second invention and third invention) will be described. In this specification, “carbon black dispersion” and “carbon black dispersion for battery” are referred to as “dispersion”, “organic dye derivative or triazine derivative” as “pigment derivative”, “polyvinyl alcohol” (first (Invention and third invention) or “polyvinyl alcohol and pigment derivative” (second invention) may be abbreviated as “dispersant”, and “N-methyl-2-pyrrolidone” may be abbreviated as “NMP”.
＜カーボンブラック＞
　カーボンブラックとしては、市販の中空カーボンブラック、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック、ケッチェンブラックなど各種のものや、また、通常行われている酸化処理されたカーボンブラック、、黒鉛化処理されたカーボンブラック、カーボンナノチューブやカーボンナノファイバーなども使用できる。また、アセチレンブラックやファーネスブラックなどの高い導電性を有し、かつ工業的に生産されるカーボンブラックが好適に用いられる。 <Carbon black>
As carbon black, various types such as commercially available hollow carbon black, furnace black, channel black, thermal black, acetylene black, ketjen black, etc., and commonly used oxidized carbon black, graphitized treatment Carbon black, carbon nanotubes and carbon nanofibers can also be used. Moreover, carbon black which has high electroconductivity, such as acetylene black and furnace black, and is produced industrially is used suitably.
　カーボンブラックの酸化処理は、カーボンブラックを空気中で高温処理したり、硝酸や二酸化窒素、オゾン等で二次的に処理したりすることによって、例えばフェノール基、キノン基、カルボキシル基、カルボニル基のような酸素含有極性官能基をカーボンブラック表面に直接導入（共有結合）する処理であり、カーボンブラックの分散性を向上させるために一般的に行われている。 The oxidation treatment of carbon black is performed by treating the carbon black at a high temperature in the air or by treating it with nitric acid, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) such an oxygen-containing polar functional group to the surface of carbon black, and is generally performed to improve the dispersibility of carbon black.
　分散液の製造に用いるカーボンブラックの平均一次粒子径としては、一般的な分散液や塗料に用いられるカーボンブラックの平均一次粒子径範囲と同様に０．０１～１μｍが好ましく、特に、０．０１～０．２μｍが好ましく、０．０１～０．１μｍがさらに好ましい。ここでいう平均一次粒子径とは、電子顕微鏡で測定された算術平均粒子径を示し、この物性値は一般にカーボンブラックの物理的特性を表すのに用いられている。 The average primary particle diameter of the carbon black used for the production of the dispersion is preferably 0.01 to 1 μm, particularly in the range of the average primary particle diameter of the carbon black used for general dispersions and paints. Is preferably 0.2 μm, more preferably 0.01 μm to 0.1 μm. The average primary particle size referred to here indicates an arithmetic average particle size measured with an electron microscope, and this physical property value is generally used to represent the physical characteristics of carbon black.
　カーボンブラックの物理的特性を表すその他の物性値としては、ＢＥＴ比表面積やｐＨが知られている。ＢＥＴ比表面積は、窒素吸着によりＢＥＴ法で測定された比表面積（以下、単に比表面積と記載）を指し、この比表面積はカーボンブラックの表面積に対応しており、比表面積が大きいほど分散剤を必要とする量も多くなる。ｐＨはカーボンブラック表面の官能基や含有不純物の影響を受けて変化する。 BET specific surface area and pH are known as other physical property values representing the physical characteristics of carbon black. The BET specific surface area refers to a specific surface area (hereinafter simply referred to as a specific surface area) measured by the BET method by nitrogen adsorption, and this specific surface area corresponds to the surface area of carbon black. The amount you need also increases. The pH changes under the influence of functional groups on the carbon black surface and impurities contained therein.
　第１および第２の発明で用いるカーボンブラックは、ＢＥＴ比表面積が２０～１５００ｍ２／ｇのものが好ましく、２０～１０００ｍ２／ｇのものがより好ましく、２０～５００ｍ２／ｇのものがさらに好ましく、２０～２５０ｍ２／ｇのものがさらに好ましく、３０～１５０ｍ２／ｇのものがさらに好ましく、３０～７５ｍ２／ｇのものが特に好ましい。上記ＢＥＴ比表面積のカーボンブラックであれば、各種の市販品、合成品を単独で、もしくは２種以上のカーボンブラックを併せて使用することができる。 The carbon black used in the first and second inventions preferably has a BET specific surface area of 20 to 1500 m 2 / g, more preferably 20 to 1000 m 2 / g, and more preferably 20 to 500 m 2 / g. preferably, more preferably those of 20 ~ 250m 2 / g, more preferably those of 30 ~ 150m 2 / g, particularly preferably from 30 ~ 75m 2 / g. As long as the carbon black has the BET specific surface area, various commercially available products and synthetic products can be used alone, or two or more carbon blacks can be used in combination.
　第１および第２の発明で用いるカーボンブラックは、上記比表面積のものであれば特に限定されるものではないが、アセチレンブラック、ファーネスブラック、中空カーボンブラックや黒鉛化処理されたカーボンブラックなど、高い導電性を有し、かつ工業的に生産されるカーボンブラックが好適に用いられる。これらのカーボンブラックの中でも、アセチレンブラックが特に好適に用いられる。アセチレンブラックとしては、例えば、デンカブラック（電気化学工業社製）等が挙げられ、種々のグレードを市販品として入手することができる。 The carbon black used in the first and second inventions is not particularly limited as long as it has the above specific surface area, but is high such as acetylene black, furnace black, hollow carbon black and graphitized carbon black. Carbon black having electrical conductivity and industrially produced is preferably used. Among these carbon blacks, acetylene black is particularly preferably used. Examples of acetylene black include Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.), and various grades can be obtained as commercial products.
　第３の発明で用いるカーボンブラックは、ＢＥＴ比表面積が３０～１５００ｍ２／ｇのものが好ましく、２００～１５００ｍ２／ｇのものがより好ましく、５００～１５００ｍ２／ｇのものがさらに好ましく、５００～１０００ｍ２／ｇのものが特に好ましい。上記ＢＥＴ比表面積のカーボンブラックであれば、各種の市販品、合成品を単独で、もしくは２種以上のカーボンブラックを併せて使用することができる。 The carbon black used in the third invention preferably has a BET specific surface area of 30 to 1500 m 2 / g, more preferably 200 to 1500 m 2 / g, still more preferably 500 to 1500 m 2 / g, Particularly preferred are those of up to 1000 m 2 / g. As long as the carbon black has the BET specific surface area, various commercially available products and synthetic products can be used alone, or two or more carbon blacks can be used in combination.
　また、２種以上のカーボンブラックを混合して調製されたカーボンブラックのＢＥＴ比表面積は、あるカーボンブラックｉのＢＥＴ比表面積をＳｉ、あるカーボンブラックｉが全カーボンブラック中に占める比率をＧｉとしたときの、各カーボンブラック種のＢＥＴ比表面積とその比率の積の総和として、下記式に基づいて算出することができる。
　　　（混合カーボンブラックのＢＥＴ比表面積）＝Σ（Ｓｉ・Ｇｉ）
　例えば、ＢＥＴ比表面積８００ｍ２／ｇのカーボンブラックと、１２００ｍ２／ｇのカーボンブラックとを、重量比１対１で混合して調製したカーボンブラックの比表面積は、１０００ｍ２／ｇである。 Further, the BET specific surface area of the carbon black prepared by mixing two or more kinds of carbon black, the BET specific surface area of a carbon black i S i, a certain percentage of carbon black i is in the total carbon black G i As the sum of the product of the BET specific surface area of each carbon black type and the ratio, it can be calculated based on the following formula.
(BET specific surface area of mixed carbon black) = Σ (S i · G i )
For example, the specific surface area of carbon black prepared by mixing carbon black having a BET specific surface area of 800 m 2 / g and carbon black of 1200 m 2 / g in a weight ratio of 1: 1 is 1000 m 2 / g.
　第３の発明で用いるカーボンブラックは、上記比表面積のものであれば特に限定されるものではないが、アセチレンブラック、ファーネスブラック、中空カーボンブラックや黒鉛化処理されたカーボンブラックなど、高い導電性を有し、かつ工業的に生産されるカーボンブラックが好適に用いられる。これらのカーボンブラックの中でも、重量当たりの導電性が優れる、中空カーボンブラックが特に好適に用いられる。中空カーボンブラックとしては、例えば、ケッチェンブラック（アクゾ社製）等が挙げられ、種々のグレードを市販品として入手することができる。 The carbon black used in the third invention is not particularly limited as long as it has the above specific surface area, but has high conductivity such as acetylene black, furnace black, hollow carbon black and graphitized carbon black. Carbon black produced and industrially produced is preferably used. Among these carbon blacks, hollow carbon black having excellent conductivity per weight is particularly preferably used. Examples of the hollow carbon black include ketjen black (manufactured by Akzo Corporation), and various grades can be obtained as commercial products.
＜ポリビニルアルコール＞
　ポリビニルアルコールは分散剤として用いられる。すなわちポリビニルアルコールをバインダーとしてではなく分散剤として使用する。ポリビニルアルコールの製造方法については特に制限はないが、以下、ポリ酢酸ビニルを原料とし、これをけん化することによって得られたポリビニルアルコールについて記述する。 <Polyvinyl alcohol>
Polyvinyl alcohol is used as a dispersant. That is, polyvinyl alcohol is used as a dispersant rather than as a binder. Although there is no restriction | limiting in particular about the manufacturing method of polyvinyl alcohol, Hereinafter, polyvinyl alcohol obtained by using polyvinyl acetate as a raw material and saponifying this is described.
　一般に、ポリビニルアルコールは、酢酸ビニルを重合させて得られたポリ酢酸ビニルを原料とし、このポリ酢酸ビニルをけん化して、アセチル基を水酸基に置換することによって得られる。この合成プロセスのために、ポリビニルアルコールはアセチル基と水酸基を有し、その比率はけん化度として表される。 Generally, polyvinyl alcohol is obtained by using polyvinyl acetate obtained by polymerizing vinyl acetate as a raw material, saponifying the polyvinyl acetate, and substituting the acetyl group with a hydroxyl group. Due to this synthesis process, polyvinyl alcohol has an acetyl group and a hydroxyl group, and the ratio is expressed as the degree of saponification.
　なお、けん化度とは、業界公知のけん化度の定義と同一であり、けん化によりビニルアルコール単位に変換され得る構造単位（典型的にはビニルエステル単位）とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合（モル％）（言い換えれば、ポリビニルアルコール中に含まれる一般式（Ａ）で表される繰り返し単位の割合（モル％））をいう。特に、ポリ酢酸ビニルを原料として用いた場合、ポリビニルアルコール中に含まれるビニルアルコール骨格に由来した水酸基数を、酢酸ビニル骨格に由来したアセチル基数とビニルアルコール骨格に由来した水酸基数の和で除した値を意味する。 The saponification degree is the same as the definition of saponification degree known in the industry, and is based on the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) occupied by the number of moles of the vinyl alcohol unit (in other words, the ratio (mol%) of the repeating unit represented by the general formula (A) contained in the polyvinyl alcohol). In particular, when polyvinyl acetate is used as a raw material, the number of hydroxyl groups derived from the vinyl alcohol skeleton contained in the polyvinyl alcohol is divided by the sum of the number of acetyl groups derived from the vinyl acetate skeleton and the number of hydroxyl groups derived from the vinyl alcohol skeleton. Mean value.
　ポリビニルアルコールとしては、ポリビニルエステル、特にポリ酢酸ビニルをけん化することによって得られるものが主に使用されるが、これに限定されない。また、けん化度は５０～９５ｍｏｌ％のものが好ましく、５５～９２ｍｏｌ％のものがより好ましく、５５～８５ｍｏｌ％のものがさらに好ましく、６０～８５ｍｏｌ％のものが特に好ましく使用される。上記けん化度のポリビニルアルコールであれば、各種の市販品、合成品を単独で、もしくは２種類以上併せて使用することができる。 As polyvinyl alcohol, polyvinyl alcohol, particularly those obtained by saponifying polyvinyl acetate, are mainly used, but are not limited thereto. The saponification degree is preferably 50 to 95 mol%, more preferably 55 to 92 mol%, still more preferably 55 to 85 mol%, and particularly preferably 60 to 85 mol%. If it is the polyvinyl alcohol of the said saponification degree, various commercial products and synthetic products can be used individually or in combination of 2 or more types.
　また、上記けん化度の範囲内であれば、水酸基、酢酸基以外の官能基として、例えば、アセトアセチル基、スルホン酸基、カルボキシル基、カルボニル基、アミノ基、イソシアネート基を導入されたものや、各種の塩によって変性されたもの、その他アニオンあるいはカチオン変性されたもの、不飽和変性されたもの、アルデヒド類によってアセタール変性（ブチラール変性、アセトアセタール変性、ホルマール変性等）されたもの、ジオール構造を導入されたものなども、使用可能なポリビニルアルコールの範囲に含まれ、これらは、単独もしくは２種類以上併せて使用することができる。 In addition, within the above saponification degree range, as a functional group other than a hydroxyl group and an acetic acid group, for example, an acetoacetyl group, a sulfonic acid group, a carboxyl group, a carbonyl group, an amino group, an isocyanate group introduced, Modified with various salts, other anion or cation modified, unsaturated modified, acetal modified (butyral modified, acetoacetal modified, formal modified, etc.) with aldehydes, diol structure introduced These are also included in the range of usable polyvinyl alcohol, and these can be used alone or in combination of two or more.
　ポリビニルアルコールは、平均重合度が５０～４０００のものが好ましく、次に５０～３０００のものが好ましく、１００～３０００のものがより好ましく、１００～２０００のものが特に好ましく、１００～１５００のものがさらに好ましい。上記重合度のポリビニルアルコールであれば、各種の市販品、合成品を単独で、もしくは２種類以上併せて使用することができる。 The polyvinyl alcohol preferably has an average degree of polymerization of 50 to 4000, then preferably 50 to 3000, more preferably 100 to 3000, particularly preferably 100 to 2000, and particularly preferably 100 to 1500. Further preferred. If it is polyvinyl alcohol of the said polymerization degree, various commercial products and synthetic products can be used individually or in combination of 2 or more types.
　ポリビニルアルコールは、第１の発明においては、ＪＩＳ　Ｋ６７２６に準ずる４％水溶液粘度が２．０～２５ｍＰａ・ｓのものが好ましく、２．０～２０．０ｍＰａ・ｓのものがさらに好ましい。 In the first invention, the polyvinyl alcohol preferably has a 4% aqueous solution viscosity of 2.0 to 25 mPa · s, more preferably 2.0 to 20.0 mPa · s, according to JIS K6726.
　けん化度が５０ｍｏｌ％～６０ｍｏｌ％より小さいものは、ＮＭＰに対する溶解性は非常に良好だが、カーボンブラックに対する吸着性が乏しいために分散には有効ではないと考えられ、また、けん化度が８５ｍｏｌ％～９５ｍｏｌ％より大きいものは、ＮＭＰに対してほとんど溶解、膨潤しないことから、たとえカーボンブラックに吸着されたとしても、ＮＭＰ側に高分子鎖を伸ばすことができず、そのために効果的に立体反発できないものと推察される。これに対して、けん化度がこれらの範囲に含まれるものは、ＮＭＰに対する溶解、または膨潤性と、カーボンブラックに対する吸着性や吸着後の立体反発効果の兼合いが良好であることから、分散剤として特に有効に機能するものと考えられる。 Those having a saponification degree of less than 50 mol% to 60 mol% have very good solubility in NMP, but are considered to be ineffective for dispersion due to poor adsorptivity to carbon black. Those larger than 95 mol% hardly dissolve or swell in NMP, so even if adsorbed to carbon black, the polymer chain cannot be extended to the NMP side, and therefore, the steric repulsion cannot be effectively performed. Inferred. On the other hand, those having a saponification degree within these ranges have a good balance between the solubility or swelling in NMP and the adsorptivity to carbon black and the steric repulsion effect after adsorption. It is considered to function particularly effectively.
　上記けん化度範囲に含まれる市販のポリビニルアルコールとしては、例えば、クラレポバール（クラレ社製ポリビニルアルコール）や、ゴーセノール（日本合成化学工業社製ポリビニルアルコール）、デンカポバール（電気化学工業社製）、Ｊ－ポバール（日本酢ビ・ポバール社製）などの商品名で、種々のグレードを市場より入手することができる。 Examples of commercially available polyvinyl alcohols included in the saponification degree range include Kuraray Poval (polyvinyl alcohol manufactured by Kuraray Co., Ltd.), Gohsenol (polyvinyl alcohol manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), Denkapoval (manufactured by Denki Kagaku Kogyo Co., Ltd.), -Various grades can be obtained from the market under trade names such as POVAL (manufactured by Nippon Vinegar-Poval).
　より具体的には、クラレポバールのＰＶＡ－４０３（けん化度７８．５～８１．５ｍｏｌ％、平均重合度３００、ＪＩＳ　Ｋ６７２６に準ずる液温２０℃における４％水溶液粘度２．８～３．３ｍＰａ・ｓ）、ＰＶＡ－５０５（けん化度７２．５～７４．５ｍｏｌ％、平均重合度５００、４％水溶液粘度４．２～５．０ｍＰａ・ｓ）、Ｌ－８（けん化度６９．５～７２．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度５．０～５．８ｍＰａ・ｓ）、Ｌ－９（けん化度６９．５～７２．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０～６．５ｍＰａ・ｓ）、Ｌ－９－７８（けん化度７６．５～７９．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０～６．７ｍＰａ・ｓ）、Ｌ－１０（けん化度７１．５～７３．５ｍｏｌ％、平均重合度１０００以下）、Ｃ－５０６（けん化度７４．０～７９．０ｍｏｌ％、平均重合度６００、４％水溶液粘度４．０～６．０ｍＰａ・ｓ）、ＫＬ－５０６（けん化度７４．０～８０．０ｍｏｌ％、平均重合度６００、４％水溶液粘度５．２～６．２ｍＰａ・ｓ）や、ゴーセノールのＫＬ－０３（けん化度７８．５～８２．０ｍｏｌ％、平均重合度５００以下、４％水溶液粘度２．８～３．４ｍＰａ・ｓ）、ＫＬ－０５（けん化度７８．５～８２．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度４．０～５．０ｍＰａ・ｓ）、ＮＫ－０５Ｒ（同７１．０～７５．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度４．５～５．５ｍＰａ・ｓ）、ＫＰ－０８Ｒ（同７１．０～７３．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０～８．０ｍＰａ・ｓ）等が挙げられるが、これらに限定されるものではない。 More specifically, Kuraray Poval's PVA-403 (saponification degree: 78.5 to 81.5 mol%, average polymerization degree: 300, viscosity of 4% aqueous solution at a liquid temperature of 20 ° C. according to JIS K6726: 2.8 to 3.3 mPa · s) s), PVA-505 (saponification degree 72.5-74.5 mol%, average polymerization degree 500, 4% aqueous solution viscosity 4.2-5.0 mPa · s), L-8 (saponification degree 69.5-72. 5 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 5.0 to 5.8 mPa · s), L-9 (saponification degree 69.5 to 72.5 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 6 0.0-6.5 mPa · s), L-9-78 (degree of saponification 76.5-79.0 mol%, average degree of polymerization 1000 or less, 4% aqueous solution viscosity 6.0-6.7 mPa · s), L- 10 (saponification degree 71.5 ~ 3.5 mol%, average polymerization degree 1000 or less), C-506 (saponification degree 74.0-79.0 mol%, average polymerization degree 600, 4% aqueous solution viscosity 4.0-6.0 mPa · s), KL-506 (Saponification degree 74.0 to 80.0 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.2 to 6.2 mPa · s), Gohsenol KL-03 (saponification degree 78.5 to 82.0 mol%), Average polymerization degree 500 or less, 4% aqueous solution viscosity 2.8 to 3.4 mPa · s), KL-05 (saponification degree 78.5 to 82.0 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.0 to 5.0 mPa · s), NK-05R (71.0-75.0 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.5-5.5 mPa · s), KP-08R (71.0 ~ 73.5 mol%, average polymerization 1000, 4% although aqueous viscosity 6.0 ~ 8.0mPa · s), and the like, but is not limited thereto.
＜Ｎ－メチル－２－ピロリドン＞
　ＮＭＰは、リチウムイオン二次電池の電極製造に用いられている。本発明では、分散剤（主にポリビニルアルコール単独、またはポリビニルアルコールと顔料誘導体との併用）としての性能、電池性能を損なわない範囲で、他の溶剤を１種類以上併用しても良いが、本発明の想定する産業上の利用可能性から、ＮＭＰを単独で用いることが好ましい。 <N-methyl-2-pyrrolidone>
NMP is used for manufacturing electrodes of lithium ion secondary batteries. In the present invention, one or more other solvents may be used in combination as long as the performance as a dispersant (mainly polyvinyl alcohol alone or a combination of polyvinyl alcohol and a pigment derivative) and battery performance are not impaired. From the industrial applicability assumed by the invention, it is preferable to use NMP alone.
＜顔料誘導体＞
　顔料誘導体は、酸性または塩基性の官能基を有する有機色素誘導体、または、酸性または塩基性の官能基を有するトリアジン誘導体である。 <Pigment derivative>
The pigment derivative is an organic dye derivative having an acidic or basic functional group, or a triazine derivative having an acidic or basic functional group.
＜酸性顔料誘導体＞
　酸性顔料誘導体の中でも、とりわけ、下記一般式（１）で示される酸性官能基を有するトリアジン誘導体、または下記一般式（４）で示される酸性官能基を有する有機色素誘導体が好ましい。 <Acid pigment derivative>
Among the acidic pigment derivatives, a triazine derivative having an acidic functional group represented by the following general formula (1) or an organic dye derivative having an acidic functional group represented by the following general formula (4) is particularly preferable.
　まず、一般式（１）で示される酸性官能基を有するトリアジン誘導体について説明する。
Figure JPOXMLDOC01-appb-C000003
 　　一般式（１） First, the triazine derivative having an acidic functional group represented by the general formula (1) will be described.
Figure JPOXMLDOC01-appb-C000003
 General formula (1)
　［Ｘ１は、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－または－Ｘ３－Ｙ－Ｘ４－を表し、Ｘ２及びＸ４は、それぞれ独立に、－ＮＨ－または－Ｏ－を表し、Ｘ３は、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＮＨＣＯ－または－ＮＨＳＯ２－を表し、Ｙは、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または置換基を有してもよいアリーレン基を表し、Ｚは、－ＳＯ３Ｍ、－ＣＯＯＭ、－Ｐ（Ｏ）（－ＯＭ）２または－Ｏ－Ｐ（Ｏ）（－ＯＭ）２を表し、Ｍは、１～３価のカチオンの一当量を表し、Ｑは、－Ｏ－Ｒ２、－ＮＨ－Ｒ２、ハロゲン基、－Ｘ１－Ｒ１または－Ｘ２－Ｙ－Ｚを表し、Ｒ２は、水素原子、置換基を有してもよいアルキル基または置換基を有してもよいアルケニル基を表す。ｎは、１～４の整数を表す。Ｒ１は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基または、下記一般式（２）で表される基を表す。］ [X 1 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 3 -Y-X 4 - represents, X 2 and X 4, each independently, represent -NH- or -O-, X 3 is, -CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - and represent , Y represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, and Z represents —SO 3 M, —COOM, Represents —P (O) (— OM) 2 or —O—P (O) (— OM) 2 , M represents one equivalent of a monovalent to trivalent cation, and Q represents —O—R 2 , -NH-R 2, a halogen group, -X 1 -R 1 or -X 2 -Y-Z, R 2 is a hydrogen atom, Have an alkyl group or a substituted group may have a substituent represents an alkenyl group. n represents an integer of 1 to 4. R 1 represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (2) Represents. ]
Figure JPOXMLDOC01-appb-C000004
 　　一般式（２）
Figure JPOXMLDOC01-appb-C000004
 General formula (2)
　［Ｘ５は、－ＮＨ－または－Ｏ－を表し、Ｘ６及びＸ７は、それぞれ独立に、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－または－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－を表し、Ｒ３及びＲ４は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基または－Ｙ－Ｚを表し、Ｙ及びＺは、一般式（１）におけるＹ及びＺと同義である。］ [X 5 represents -NH- or -O-, X 6 and X 7 are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH- or Represents —CH 2 NHCOCH 2 NH—, and R 3 and R 4 each independently represents an organic dye residue, an optionally substituted heterocyclic residue, or an optionally substituted aromatic group. Represents a group ring residue or —YZ, and Y and Z have the same meanings as Y and Z in formula (1). ]
　Ｒ１、Ｒ３、Ｒ４における有機色素残基としては、例えば、ジケトピロロピロール系色素、アゾ、ジスアゾ、ポリアゾ等のアゾ系色素、フタロシアニン系色素、アントラキノン、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、ぺリノン系色素、ぺリレン系色素、チオインジゴ系色素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素等の残基が挙げられる。とりわけ、金属による電池の短絡を抑制する効果を高めるためには、金属錯体系色素ではない有機色素残基の使用が好ましく、中でもアゾ系色素、ジケトピロロピロール系色素、無金属フタロシアニン系色素、キナクリドン系色素、ジオキサジン系色素の残基が、分散性に優れた効果を発揮するため好ましい。 Examples of organic dye residues in R 1 , R 3 and R 4 include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, anthraquinones, diaminodianthraquinones, anthrapyrimidines, and flavans Anthraquinone dyes such as Throne, Antanthrone, Indanthrone, Pyrantron, Biolantron, Quinacridone dyes, Dioxazine dyes, Perinone dyes, Perylene dyes, Thioindigo dyes, Isoindolin dyes, Isoindolinone dyes, Residues such as quinophthalone dyes, selenium dyes, metal complex dyes and the like can be mentioned. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, Quinacridone dyes and dioxazine dye residues are preferred because they exhibit excellent dispersibility.
　また、Ｒ１、Ｒ３、Ｒ４における複素環残基および芳香族環残基としては、例えば、チオフェン、フラン、ピリジン、ピラゾール、ピロール、イミダゾール、イソインドリン、イソインドリノン、ベンズイミダゾロン、ベンズチアゾール、ベンズトリアゾール、インドール、キノリン、カルバゾール、アクリジン等の複素環残基、ベンゼン、ナフタレン、アントラセン、フルオレン、フェナントレン、アントラキノン等の芳香族環残基が挙げられる。とりわけ、Ｓ、Ｎ、Ｏのヘテロ原子のいずれかを含む複素環残基が、分散性に優れた効果を発揮するため好ましい。 Examples of the heterocyclic residue and aromatic ring residue in R 1 , R 3 , and R 4 include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, and benzine. Examples include heterocyclic residues such as thiazole, benztriazole, indole, quinoline, carbazole and acridine, and aromatic ring residues such as benzene, naphthalene, anthracene, fluorene, phenanthrene and anthraquinone. In particular, a heterocyclic residue containing any one of S, N, and O heteroatoms is preferable because it exhibits an effect of excellent dispersibility.
　一般式（１）及び一般式（２）のＹは、置換基を有していてもよいアルキレン基、アルケニレン基またはアリーレン基を表すが、炭素数２０以下が好ましく、炭素数１０以下がより好ましい。特に好ましい態様としては、置換されていてもよいフェニレン基、ビフェニレン基、ナフチレン基または炭素数が１０以下の側鎖を有していてもよいアルキレン基が挙げられる。 Y in general formula (1) and general formula (2) represents an alkylene group, alkenylene group or arylene group which may have a substituent, but preferably has 20 or less carbon atoms, more preferably 10 or less carbon atoms. . Particularly preferred embodiments include an optionally substituted phenylene group, biphenylene group, naphthylene group or an alkylene group which may have a side chain having 10 or less carbon atoms.
　Ｒ２における置換基を有してもよいアルキル基および置換基を有してもよいアルケニル基の好ましい態様は、炭素数２０以下のものである。更に好ましくは、炭素数が１０以下の側鎖を有していてもよいアルキル基が挙げられる。ここで、置換基を有するアルキル基および置換基を有するアルケニル基とは、アルキル基またはアルケニル基の水素原子が、フッ素原子、塩素原子、臭素原子等のハロゲン基、水酸基、メルカプト基等に置換されたものを挙げることができる。 A preferred embodiment of the alkenyl group which may have an alkyl group and a substituted group which may have a substituent in R 2 are those having 20 or less carbon atoms. More preferably, an alkyl group which may have a side chain having 10 or less carbon atoms is exemplified. Here, the alkyl group having a substituent and the alkenyl group having a substituent are a group in which a hydrogen atom of an alkyl group or an alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group or a mercapto group. Can be mentioned.
　Ｍは、１～３価のカチオンの一当量を表し、例えば、水素イオン（プロトン）、金属カチオン、４級アンモニウムカチオンのいずれかを表す。また、分散剤の構造（一分子）中にＭを２つ以上有する場合、Ｍは、プロトン、金属カチオン、４級アンモニウムカチオンのいずれか一種のみでも良いし、二種以上の組み合わせでも良い。金属カチオンとしては、リチウム、ナトリウム、カリウム、カルシウム、バリウム、マグネシウム、アルミニウム、ニッケル、コバルト等の金属のカチオンが挙げられる。４級アンモニウムカチオンとしては、一般式（３）で示される構造を有する単一化合物または、混合物である。 M represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen ion (proton), a metal cation, or a quaternary ammonium cation. Moreover, when it has two or more M in the structure (one molecule) of a dispersing agent, M may be only one kind of a proton, a metal cation, and a quaternary ammonium cation, and may be a combination of two or more kinds. Examples of the metal cation include metal cations such as lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt. The quaternary ammonium cation is a single compound having a structure represented by the general formula (3) or a mixture.
Figure JPOXMLDOC01-appb-C000005
 　　一般式（３）
Figure JPOXMLDOC01-appb-C000005
 General formula (3)
　［Ｒ５、Ｒ６、Ｒ７、Ｒ８は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、または置換基を有してもよいアリール基を表す。］ [R 5 , R 6 , R 7 and R 8 each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a good aryl group. ]
　Ｒ５、Ｒ６、Ｒ７、Ｒ８は、それぞれ同一でもよいし、異なっていてもよい。また、Ｒ５、Ｒ６、Ｒ７、Ｒ８が炭素原子を有する場合、炭素数は１～４０、好ましくは１～３０、更に好ましくは１～２０である。 R 5 , R 6 , R 7 and R 8 may be the same or different. Further, when R 5 , R 6 , R 7 , and R 8 have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20.
　４級アンモニウムカチオンの具体例としては、ジメチルアンモニウム、トリメチルアンモニウム、ジエチルアンモニウム、トリエチルアンモニウム、ヒドロキシエチルアンモニウム、ジヒドロキシエチルアンモニウム、２－エチルヘキシルアンモニウム、ジメチルアミノプロピルアンモニウム、ラウリルアンモニウム、ステアリルアンモニウム等が挙げられるが、これらに限定されない。 Specific examples of the quaternary ammonium cation include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, stearylammonium and the like. However, it is not limited to these.
　次いで、一般式（４）で示される酸性官能基を有する有機色素誘導体について説明する。
Figure JPOXMLDOC01-appb-C000006
 　　一般式（４） Next, the organic dye derivative having an acidic functional group represented by the general formula (4) will be described.
Figure JPOXMLDOC01-appb-C000006
 General formula (4)
　［Ｘ８は、直接結合、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－、－Ｘ９－Ｙ－または－Ｘ９－Ｙ－Ｘ１０－を表し、Ｘ９は、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＮＨＣＯ－または－ＮＨＳＯ２－を表し、Ｘ１０は、－ＮＨ－または－Ｏ－を表し、Ｙは、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または置換基を有してもよいアリーレン基を表し、Ｚは、－ＳＯ３Ｍ、－ＣＯＯＭ、－Ｐ（Ｏ）（－ＯＭ）２または－Ｏ－Ｐ（Ｏ）（－ＯＭ）２を表し、Ｍは１～３価のカチオンの一当量を表し、Ｒ９は、有機色素残基を表し、ｎは、１～４の整数を表す。］ [X 8 is a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH -, - X 9 -Y- or -X 9 -Y-X 10 - represents, X 9 is, -CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 10 is, -NH- or -O Y represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, and Z represents —SO 3 M, -COOM, -P (O) (-OM) 2 or -O-P (O) (-OM) 2 , M represents one equivalent of a monovalent to trivalent cation, and R 9 represents an organic dye residue Represents a group, and n represents an integer of 1 to 4. ]
　Ｒ９の有機色素残基としては、Ｒ１、Ｒ３、Ｒ４における有機色素残基と同義である。とりわけ、金属による電池の短絡を抑制する効果を高めるためには、金属錯体系色素ではない有機色素残基の使用が好ましく、中でもアゾ系色素、ジケトピロロピロール系色素、無金属フタロシアニン系色素、キナクリドン系色素、ジオキサジン系色素の残基が、分散性に優れた効果を発揮するため好ましい。 The organic dye residue of R 9 has the same meaning as the organic dye residue in R 1 , R 3 , and R 4 . In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, Quinacridone dyes and dioxazine dye residues are preferred because they exhibit excellent dispersibility.
　一般式（４）におけるＭは、一般式（１）におけるＭと同義である。 M in the general formula (4) has the same meaning as M in the general formula (1).
　使用する酸性顔料誘導体の合成方法としては、特に限定されるものではないが、例えば、特公昭３９－２８８８４号公報、特公昭４５－１１０２６号公報、特公昭４５－２９７５５号公報、特公昭６４－５０７０号公報、特開２００４－２１７８４２号公報等に記載されている方法で合成することができる。 The method for synthesizing the acidic pigment derivative to be used is not particularly limited. For example, Japanese Patent Publication No. 39-28884, Japanese Patent Publication No. 45-11026, Japanese Patent Publication No. 45-29755, Japanese Patent Publication No. 64- They can be synthesized by the methods described in JP 5070, JP 2004-217842 A, and the like.
＜塩基性顔料誘導体＞
　塩基性顔料誘導体の中でも、とりわけ、下記一般式（１０１）で示される塩基性官能基を有するトリアジン誘導体、または下記一般式（１０６）で示される塩基性官能基を有する有機色素誘導体が好ましい。 <Basic pigment derivative>
Among the basic pigment derivatives, a triazine derivative having a basic functional group represented by the following general formula (101) or an organic dye derivative having a basic functional group represented by the following general formula (106) is particularly preferable.
　まず、一般式（１０１）で示される塩基性官能基を有するトリアジン誘導体について説明する。
Figure JPOXMLDOC01-appb-C000007
 　　一般式（１０１） First, the triazine derivative having a basic functional group represented by the general formula (101) will be described.
Figure JPOXMLDOC01-appb-C000007
 Formula (101)
　Ｘ１０１は、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－または－Ｘ１０２－Ｙ１－Ｘ１０３－を表し、Ｘ１０２は、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＮＨＣＯ－または－ＮＨＳＯ２－を表し、Ｘ１０３は、－ＮＨ－または－Ｏ－を表し、Ｙ１は、炭素数１～２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または置換基を有してもよいアリーレン基を表す。
　Ｐは、一般式（１０２）、一般式（１０３）または一般式（１０４）のいずれかで示される基を表す。
　Ｑ１０１は、－Ｏ－Ｒ１０２、－ＮＨ－Ｒ１０２、ハロゲン基、－Ｘ１０１－Ｒ１０１または一般式（１０２）、一般式（１０３）もしくは一般式（１０４）のいずれかで示される基を表す。
　Ｒ１０２は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基または置換基を有してもよいアリール基を表す。
　ｏは、１～４の整数を表す。 X 101 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 102 -Y 1 -X 103 - represents, X 102, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 103 is, -NH- or -O- and Y 1 represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an arylene group that may have a substituent, each having 1 to 20 carbon atoms. .
P represents a group represented by any one of the general formula (102), the general formula (103), and the general formula (104).
Q 101 represents —O—R 102 , —NH—R 102 , a halogen group, —X 101 —R 101, or a group represented by any one of the general formula (102), the general formula (103), and the general formula (104). Represents.
R 102 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
o represents an integer of 1 to 4.
Figure JPOXMLDOC01-appb-C000008
 　　一般式（１０２）
Figure JPOXMLDOC01-appb-I000009
　　一般式（１０３）
Figure JPOXMLDOC01-appb-I000010
　　一般式（１０４）
Figure JPOXMLDOC01-appb-C000008
 General formula (102)
Figure JPOXMLDOC01-appb-I000009
General formula (103)
Figure JPOXMLDOC01-appb-I000010
General formula (104)
　Ｘ１０４は、直接結合、－ＳＯ２－、－ＣＯ－、－ＣＨ２ＮＨＣＯＣＨ２－、－ＣＨ２ＮＨＣＯＮＨＣＨ２－、－ＣＨ２－または－Ｘ１０５－Ｙ１－Ｘ１０６－を表す。Ｘ１０５は、－ＮＨ－または－Ｏ－を表し、Ｘ１０６は、直接結合、－ＳＯ２－、－ＣＯ－、－ＣＨ２ＮＨＣＯＣＨ２－、－ＣＨ２ＮＨＣＯＮＨＣＨ２－または－ＣＨ２－を表す。
　ｖ１は、１～１０の整数を表す。
　Ｒ１０３およびＲ１０４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアリール基または複素環残基を表し、Ｒ１０３とＲ１０４が結合して環を形成しても良い。
　Ｒ１０５、Ｒ１０６、Ｒ１０７およびＲ１０８は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
　Ｒ１０９は、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。 X 104 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or -X 105 -Y 1 -X 106 - represents a. X 105 represents -NH- or -O-, X 106 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 - represents a .
v 1 represents an integer of 1 to 10.
R 103 and R 104 represent respectively independently, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a heterocyclic residue, R 103 And R 104 may combine to form a ring.
R 105 , R 106 , R 107 and R 108 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
R 109 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
　Ｒ１０１は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基または下記一般式（１０５）で示される基を表す。
Figure JPOXMLDOC01-appb-C000011
 　　一般式（１０５） R 101 represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (105). .
Figure JPOXMLDOC01-appb-C000011
 General formula (105)
　Ｔは、－Ｘ１０８－Ｒ１１０またはＷ１を表し、Ｕは、－Ｘ１０９－Ｒ１１１またはＷ２を表す。
　Ｗ１およびＷ２は、それぞれ独立に、－Ｏ－Ｒ１０２、－ＮＨ－Ｒ１０２、ハロゲン基または一般式（１０２）、一般式（１０３）もしくは一般式（１０４）のいずれかで示される基を表す。
　Ｘ１０７は、－ＮＨ－または－Ｏ－を表し、Ｘ１０８およびＸ１０９は、それぞれ独立に、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－または－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－を表す。
　Ｒ１１０およびＲ１１１は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基または置換基を有していてもよい芳香族環残基を表す。 T represents -X 108 -R 110 or W 1 , and U represents -X 109 -R 111 or W 2 .
W 1 and W 2 are each independently —O—R 102 , —NH—R 102 , a halogen group or a group represented by any one of the general formula (102), the general formula (103), and the general formula (104). Represents.
X 107 represents -NH- or -O-, X 108 and X 109 each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH- or - CH 2 NHCOCH 2 NH— is represented.
R 110 and R 111 each independently represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent.
　一般式（１０１）のＲ１０１および一般式（１０５）のＲ１１０、Ｒ１１１における有機色素残基としては、例えば、ジケトピロロピロール系色素、アゾ、ジスアゾ、ポリアゾ等のアゾ系色素、フタロシアニン系色素、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、ぺリノン系色素、ぺリレン系色素、チオインジゴ系色素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素等の残基が挙げられる。とりわけ、金属による電池の短絡を抑制する効果を高めるためには、金属錯体系色素ではない有機色素残基の使用が好ましい。 Examples of the organic dye residue in R 101 of the general formula (101) and R 110 and R 111 of the general formula (105) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, and phthalocyanine dyes. Dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrones, indantrons, pyranthrones, violanthrones, anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, iso Examples include residues such as indoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complex dyes, and the like. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.
　一般式（１０１）のＲ１０１および一般式（１０５）のＲ１１０、Ｒ１１１における複素環残基および芳香族環残基としては、例えば、チオフェン、フラン、ピリジン、ピラジン、トリアジン、ピラゾール、ピロール、イミダゾール、イソインドリン、イソインドリノン、ベンズイミダゾロン、ベンズチアゾール、ベンズトリアゾール、インドール、キノリン、カルバゾール、アクリジン、ベンゼン、ナフタリン、アントラセン、フルオレン、フェナントレン、アントラキノン、アクリドン等の残基が挙げられる。これらの複素環残基および芳香族環残基は、アルキル基（メチル基、エチル基、ブチル基等）、アミノ基、アルキルアミノ基（ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基等）、ニトロ基、水酸基、アルコキシル基（メトキシ基、エトキシ基、ブトキシ基等）、ハロゲン（塩素、臭素、フッ素等）、フェニル基（アルキル基、アミノ基、アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン等で置換されていてもよい）、およびフェニルアミノ基（アルキル基、アミノ基、アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン等で置換されていてもよい）等の置換基を有していてもよい。 Examples of the heterocyclic residue and the aromatic ring residue in R 101 of the general formula (101) and R 110 and R 111 of the general formula (105) include thiophene, furan, pyridine, pyrazine, triazine, pyrazine, pyrrole, Examples include imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, acridone and the like. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups. Hydroxyl group, alkoxyl group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
　Ｒ１０３およびＲ１０４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアリール基または複素環残基を表し、Ｒ１０３とＲ１０４が結合して環を形成しても良い。とりわけ、水素原子であることが、電池内での金属析出を抑える効果が高いと思われ好ましい。一般式（１０１）および一般式（１０５）のＹ１は、炭素数２０以下の置換基を有してもよいアルキレン基、アルケニレン基またはアリーレン基を表すが、好ましくは、置換基を有してもよいフェニレン基、ビフェニレン基、ナフチレン基または炭素数が１０以下の側鎖を有していてもよいアルキレン基が挙げられる。 R 103 and R 104 represent respectively independently, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a heterocyclic residue, R 103 And R 104 may combine to form a ring. In particular, a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high. Y 1 in the general formula (101) and the general formula (105) represents an alkylene group, an alkenylene group or an arylene group which may have a substituent having 20 or less carbon atoms, and preferably has a substituent. Examples thereof include a phenylene group, a biphenylene group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.
　次いで、一般式（１０６）で示される塩基性官能基を有する有機色素誘導体について説明する。
Figure JPOXMLDOC01-appb-C000012
 　　一般式（１０６） Next, an organic dye derivative having a basic functional group represented by the general formula (106) will be described.
Figure JPOXMLDOC01-appb-C000012
 Formula (106)
　Ｚ１０１は、下記一般式（１０７）、一般式（１０８）または一般式（１０９）で示される基である。ｍは、１～４の整数を表す。
Figure JPOXMLDOC01-appb-C000013
 　　一般式（１０７）
Figure JPOXMLDOC01-appb-I000014
　　一般式（１０８）
Figure JPOXMLDOC01-appb-I000015
　　一般式（１０９） Z101 is a group represented by the following general formula (107), general formula (108), or general formula (109). m represents an integer of 1 to 4.
Figure JPOXMLDOC01-appb-C000013
 General formula (107)
Figure JPOXMLDOC01-appb-I000014
Formula (108)
Figure JPOXMLDOC01-appb-I000015
General formula (109)
　Ｘ２４は、直接結合、－ＳＯ２－、－ＣＯ－、－ＣＨ２ＮＨＣＯＣＨ２－、－ＣＨ２ＮＨＣＯＮＨＣＨ２－、－ＣＨ２－または－Ｘ２５－Ｙ２－Ｘ２６－を表す。Ｘ２５は、－ＮＨ－または－Ｏ－を表し、Ｘ２６は、直接結合、－ＳＯ２－、－ＣＯ－、－ＣＨ２ＮＨＣＯＣＨ２－、－ＣＨ２ＮＨＣＯＮＨＣＨ２－または－ＣＨ２－を表す。Ｙ２は、炭素数１～２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または置換基を有してもよいアリーレン基を表す。
　ｖ２は、１～１０の整数を表す。 X 24 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or -X 25 -Y 2 -X 26 - represents a. X 25 represents -NH- or -O-, X 26 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 - represents a . Y 2 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, having 1 to 20 carbon atoms.
v 2 represents an integer of 1 to 10.
　Ｒ２３およびＲ２４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基または複素環残基を表し、Ｒ２３とＲ２４が結合して環を形成しても良い。とりわけ、水素原子であることが、電池内での金属析出を抑える効果が高いと思われ好ましい。
　Ｒ２５、Ｒ２６、Ｒ２７およびＲ２８は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
　Ｒ２９は、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。 R 23 and R 24 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group or a heterocyclic residue, R 23 And R 24 may combine to form a ring. In particular, a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high.
R 25 , R 26 , R 27 and R 28 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
R 29 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
　Ｒ２２は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基を表す。
　Ｒ２２における有機色素残基としては、例えば、ジケトピロロピロール系色素、アゾ、ジスアゾ、ポリアゾ等のアゾ系色素、フタロシアニン系色素、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、ぺリノン系色素、ぺリレン系色素、チオインジゴ系色素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素の残基が挙げられる。とりわけ、金属による電池の短絡を抑制する効果を高めるためには、金属錯体系色素ではない有機色素残基の使用が好ましい。 R 22 represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent.
Examples of the organic dye residue in R 22 include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, indanthrone, Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, Examples include residues of metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.
　また、Ｒ２２における複素環残基および芳香族環残基としては、例えば、チオフェン、フラン、ピリジン、ピラゾール、ピロール、イミダゾール、イソインドリン、イソインドリノン、ベンズイミダゾロン、ベンズチアゾール、ベンズトリアゾール、インドール、キノリン、カルバゾール、アクリジン、ベンゼン、ナフタリン、アントラセン、フルオレン、フェナントレン、アントラキノン、アクリドン等の残基が挙げられる。これらの複素環残基および芳香族環残基は、アルキル基（メチル基、エチル基、ブチル基等）、アミノ基、アルキルアミノ基（ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基等）、ニトロ基、水酸基、アルコキシル基（メトキシ基、エトキシ基、ブトキシ基等）、ハロゲン（塩素、臭素、フッ素等）、フェニル基（アルキル基、アミノ基、アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン等で置換されていてもよい）、およびフェニルアミノ基（アルキル基、アミノ基、アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン等で置換されていてもよい）等の置換基を有していてもよい。 Examples of the heterocyclic residue and aromatic ring residue in R 22 include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, and indole. , Quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, acridone and the like. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups. Hydroxyl group, alkoxyl group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
　一般式（１０２）～（１０４）および一般式（１０７）～（１０９）で示される置換基を形成するために使用されるアミン成分としては、例えば、ジメチルアミン、ジエチルアミン、メチルエチルアミン、Ｎ，Ｎ－エチルイソプロピルアミン、Ｎ，Ｎ－エチルプロピルアミン、Ｎ，Ｎ－メチルブチルアミン、Ｎ，Ｎ－メチルイソブチルアミン、Ｎ，Ｎ－ブチルエチルアミン、Ｎ，Ｎ－ｔｅｒｔ－ブチルエチルアミン、ジイソプロピルアミン、ジプロピルアミン、Ｎ，Ｎ－ｓｅｃ－ブチルプロピルアミン、ジブチルアミン、ジ－ｓｅｃ－ブチルアミン、ジイソブチルアミン、Ｎ，Ｎ－イソブチル－ｓｅｃ－ブチルアミン、ジアミルアミン、ジイソアミルアミン、ジヘキシルアミン、ジシクロヘキシルアミン、ジ（２－エチルへキシル）アミン、ジオクチルアミン、Ｎ，Ｎ－メチルオクタデシルアミン、ジデシルアミン、ジアリルアミン、Ｎ，Ｎ－エチル－１，２－ジメチルプロピルアミン、Ｎ，Ｎ－メチルヘキシルアミン、ジオレイルアミン、ジステアリルアミン、Ｎ，Ｎ－ジメチルアミノメチルアミン、Ｎ，Ｎ－ジメチルアミノエチルアミン、Ｎ，Ｎ－ジメチルアミノアミルアミン、Ｎ，Ｎ－ジメチルアミノブチルアミン、Ｎ，Ｎ－ジエチルアミノエチルアミン、Ｎ，Ｎ－ジエチルアミノプロピルアミン、Ｎ，Ｎ－ジエチルアミノヘキシルアミン、Ｎ，Ｎ－ジエチルアミノブチルアミン、Ｎ，Ｎ－ジエチルアミノペンチルアミン、Ｎ，Ｎ－ジプロピルアミノブチルアミン、Ｎ，Ｎ－ジブチルアミノプロピルアミン、Ｎ，Ｎ－ジブチルアミノエチルアミン、Ｎ，Ｎ－ジブチルアミノブチルアミン、Ｎ，Ｎ－ジイソブチルアミノペンチルアミン、Ｎ，Ｎ－メチルーラウリルアミノプロピルアミン、Ｎ，Ｎ－エチルーヘキシルアミノエチルアミン、Ｎ，Ｎ－ジステアリルアミノエチルアミン、Ｎ，Ｎ－ジオレイルアミノエチルアミン、Ｎ，Ｎ－ジステアリルアミノブチルアミン、ピペリジン、２－ピペコリン、３－ピペコリン、４－ピペコリン、２，４－ルペチジン、２，６－ルペチジン、３，５－ルペチジン、３－ピペリジンメタノール、ピペコリン酸、イソニペコチン酸、イソニコペチン酸メチル、イソニコペチン酸エチル、２－ピペリジンエタノール、ピロリジン、３－ヒドロキシピロリジン、Ｎ－アミノエチルピペリジン、Ｎ－アミノエチル－４－ピペコリン、Ｎ－アミノエチルモルホリン、Ｎ－アミノプロピルピペリジン、Ｎ－アミノプロピル－２－ピペコリン、Ｎ－アミノプロピル－４－ピペコリン、Ｎ－アミノプロピルモルホリン、Ｎ－メチルピペラジン、Ｎ－ブチルピペラジン、Ｎ－メチルホモピペラジン、１－シクロペンチルピペラジン、１－アミノ－４－メチルピペラジン、１－シクロペンチルピペラジン等が挙げられる。 Examples of the amine component used for forming the substituents represented by the general formulas (102) to (104) and the general formulas (107) to (109) include dimethylamine, diethylamine, methylethylamine, N, N -Ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethyl) Hexyl) amine Dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylamino Methylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylamino Tylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotine Acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperi Gin, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino -4-methylpiperazine, 1-cyclopentylpiperazine and the like.
　使用する、塩基性官能基を有する有機色素誘導体または塩基性官能基を有するトリアジン誘導体の合成方法としては、特に限定されるものではないが、特開昭５４－６２２２７号公報、特開昭５６－１１８４６２号公報、特開昭５６－１６６２６６号公報、特開昭６０－８８１８５号公報、特開昭６３－３０５１７３号公報、特開平３－２６７６号公報、特開平１１－１９９７９６号公報等に記載されている方法で合成することができる。 The method for synthesizing the organic dye derivative having a basic functional group or the triazine derivative having a basic functional group to be used is not particularly limited, but JP-A-54-62227 and JP-A-56- 118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3-2676, JP 11-199796, and the like. It can be synthesized by the method.
　例えば、塩基性官能基を有する有機色素誘導体は、有機色素、複素環化合物（例えば、アクリドン）または芳香族環化合物（例えば、アントラキノン）に式（１１０）～式（１１３）で示される置換基を導入した後、これら置換機とアミン成分（例えば、Ｎ，Ｎ－ジメチルアミノプロピルアミン、Ｎ－メチルピペラジン、ジエチルアミンまたは４－［４－ヒドロキシ－６－［３－（ジブチルアミノ）プロピルアミノ］－１，３，５－トリアジン－２－イルアミノ］アニリン等）を反応させることによって、合成することができる。
　式（１１０）　－ＳＯ２Ｃｌ
　式（１１１）　－ＣＯＣｌ
　式（１１２）　－ＣＨ２ＮＨＣＯＣＨ２Ｃｌ
　式（１１３）　－ＣＨ２Ｃｌ
　また、例えば、式（１１０）で示される置換基を導入する場合には、有機色素、複素環化合物（例えば、アクリドン）または芳香族環化合物（例えば、アントラキノン）をクロロスルホン酸に溶解して、塩化チオニル等の塩素化剤を反応させるが、このときの反応温度、反応時間等の条件により、有機色素、複素環化合物（例えば、アクリドン）または芳香族環化合物（例えば、アントラキノン）に導入する式（１１０）で示される置換基数をコントロールすることができる。 For example, an organic dye derivative having a basic functional group includes a substituent represented by the formula (110) to the formula (113) in an organic dye, a heterocyclic compound (eg, acridone) or an aromatic ring compound (eg, anthraquinone). After the introduction, these substituents and amine components (for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1 , 3,5-triazin-2-ylamino] aniline and the like) can be synthesized.
Formula (110) -SO 2 Cl
Formula (111) -COCl
Formula (112) -CH 2 NHCOCH 2 Cl
Formula (113) -CH 2 Cl
In addition, for example, when a substituent represented by the formula (110) is introduced, an organic dye, a heterocyclic compound (for example, acridone) or an aromatic ring compound (for example, anthraquinone) is dissolved in chlorosulfonic acid, A chlorinating agent such as thionyl chloride is reacted, but depending on conditions such as reaction temperature and reaction time, a formula to be introduced into an organic dye, a heterocyclic compound (eg, acridone) or an aromatic ring compound (eg, anthraquinone) The number of substituents represented by (110) can be controlled.
　また、式（１１１）で示される置換基を導入する場合には、まずカルボキシル基を有する有機色素、複素環化合物（例えば、アクリドン）または芳香族環化合物（例えば、アントラキノン）を公知の方法で合成した後、ベンゼン等の芳香族溶媒中で塩化チオニル等の塩素化剤を反応させる方法等が挙げられる。 When introducing the substituent represented by the formula (111), first, an organic dye having a carboxyl group, a heterocyclic compound (for example, acridone) or an aromatic ring compound (for example, anthraquinone) is synthesized by a known method. Then, a method of reacting a chlorinating agent such as thionyl chloride in an aromatic solvent such as benzene is exemplified.
　式（１１０）～式（１１３）で示される置換基とアミン成分との反応時には、式（１１０）～式（１１３）で示される置換基の一部が加水分解して、塩素が水酸基に置換することがある。その場合、式（１１０）で示される置換基はスルホン酸基となり、式（１１１）で示される置換基はカルボン酸基となるが、いずれも遊離酸のままでもよく、また、１～３価の金属もしくは、上記のアミンと塩を形成していてもよい。 During the reaction of the substituents represented by the formulas (110) to (113) with the amine component, some of the substituents represented by the formulas (110) to (113) are hydrolyzed to replace chlorine with hydroxyl groups. There are things to do. In that case, the substituent represented by the formula (110) is a sulfonic acid group, and the substituent represented by the formula (111) is a carboxylic acid group. A metal or a salt of the above amine may be formed.
　また、有機色素がアゾ系色素である場合は、式（１０７）～式（１０９）または、下記一般式（１１４）で示される置換基をあらかじめジアゾ成分またはカップリング成分に導入し、その後カップリング反応を行うことによってアゾ系有機色素誘導体を製造することもできる。
Figure JPOXMLDOC01-appb-C000016
 　　一般式（１１４） When the organic dye is an azo dye, a substituent represented by the formula (107) to the formula (109) or the following general formula (114) is previously introduced into the diazo component or the coupling component, and then the coupling is performed. An azo organic dye derivative can also be produced by carrying out the reaction.
Figure JPOXMLDOC01-appb-C000016
 Formula (114)
　Ｘ１０１は、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＣＨ２ＮＨＣＯＣＨ２ＮＨ－または－Ｘ１０２－Ｙ１－Ｘ１０３－を表し、Ｘ１０２は、－ＮＨ－、－Ｏ－、－ＣＯＮＨ－、－ＳＯ２ＮＨ－、－ＣＨ２ＮＨ－、－ＮＨＣＯ－または－ＮＨＳＯ２－を表し、Ｘ１０３はそれぞれ独立に－ＮＨ－または－Ｏ－を表し、Ｙ１は炭素数１～２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または、置換基を有してもよいアリーレン基を表す。
　Ｐは、一般式（１０２）、（１０３）または、一般式（１０４）のいずれかで示される置換基を表す。
　Ｑ１０１は、－Ｏ－Ｒ１０２、－ＮＨ－Ｒ１０２、ハロゲン基、－Ｘ１０１－Ｒ１０１または、一般式（１０２）、（１０３）もしくは、一般式（１０４）のいずれかで示される置換基を表す。
　Ｒ１０２は、水素原子、置換基を有してもよいアルキル基または、置換基を有してもよいアルケニル基もしくは、置換基を有してもよいアリール基を表す。 X 101 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 102 -Y 1 -X 103 - represents, X 102, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 103 each independently -NH- or -O Y 1 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms, Represents.
P represents a substituent represented by any one of the general formulas (102), (103) and the general formula (104).
Q 101 represents —O—R 102 , —NH—R 102 , a halogen group, —X 101 —R 101, or a substitution represented by any of the general formula (102), (103), or the general formula (104) Represents a group.
R 102 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
　また、塩基性官能基を有するトリアジン誘導体は、例えば、塩化シアヌルを出発原料とし、塩化シアヌルの少なくとも１つの塩素に式（１０７）～式（１０９）または、一般式（１１４）で示される置換基を形成するアミン成分（例えば、Ｎ，Ｎ－ジメチルアミノプロピルアミンまたはＮ－メチルピペラジン等）を反応させ、次いで塩化シアヌルの残りの塩素と種々のアミンまたはアルコール等を反応させることによって得られる。 The triazine derivative having a basic functional group is, for example, a substituent represented by formula (107) to formula (109) or general formula (114) in at least one chlorine of cyanuric chloride using cyanuric chloride as a starting material. It is obtained by reacting an amine component (for example, N, N-dimethylaminopropylamine or N-methylpiperazine etc.) to form, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.
　使用する顔料誘導体は、酸性または塩基性の官能基を有する有機色素誘導体、または、酸性または塩基性の官能基を有するトリアジン誘導体であることが好ましく、酸性または塩基性の官能基を有するトリアジン誘導体であることがより好ましく、酸性の官能基を有するトリアジン誘導体であることさらに好ましく、アゾ結合を有さず、かつ酸性の官能基を有するトリアジン誘導体であることが特に好ましい。 The pigment derivative to be used is preferably an organic dye derivative having an acidic or basic functional group or a triazine derivative having an acidic or basic functional group, and is a triazine derivative having an acidic or basic functional group. More preferably, it is more preferably a triazine derivative having an acidic functional group, and particularly preferably a triazine derivative having no azo bond and having an acidic functional group.
　顔料誘導体は、１種または２種以上を任意の割合で混合して使用しても良い。顔料誘導体は主に分散剤として機能するとともに、電池性能を向上させるに適した電極膜状態を作り出すための役割も担っているものと考えられる。 The pigment derivative may be used alone or in combination of two or more. It is considered that the pigment derivative mainly functions as a dispersant and plays a role for creating an electrode film state suitable for improving battery performance.
＜カーボンブラック分散液の製造方法＞
　本発明の分散液は、主にポリビニルアルコールを分散剤として（第１の発明および第３の発明）、または、ポリビニルアルコールと顔料誘導体とを分散剤として（第２の発明）用いてカーボンブラックをＮＭＰ中に分散したものである。この場合、分散剤とカーボンブラックを同時、または順次添加し、混合することで、分散剤をカーボンブラックに作用（吸着）させつつ分散する。但し、カーボンブラック分散液の製造をより容易に行うためには、分散剤をＮＭＰ中に溶解、膨潤、または分散させ、その後、液中にカーボンブラックを添加し、混合することで分散剤をカーボンブラックに作用（吸着）させることが、より好ましい。また、カーボンブラック以外の粉体として、例えば二次電池用電極活物質等を添加して、電極合材液として使用する場合、ＮＭＰ中に分散剤とカーボンブラックと電極活物質とを同時に仕込み分散処理を行っても良い。 <Method for producing carbon black dispersion>
The dispersion liquid of the present invention mainly comprises carbon black using polyvinyl alcohol as a dispersant (first invention and third invention) or using polyvinyl alcohol and a pigment derivative as a dispersant (second invention). Dispersed in NMP. In this case, the dispersant and carbon black are added simultaneously or sequentially and mixed to disperse the dispersant while acting (adsorbing) on the carbon black. However, in order to more easily produce a carbon black dispersion, the dispersant is dissolved, swollen, or dispersed in NMP, and then the carbon black is added to the liquid and mixed to disperse the dispersant in carbon. It is more preferable to act (adsorb) on black. In addition, as a powder other than carbon black, for example, when an electrode active material for a secondary battery is added and used as an electrode mixture liquid, a dispersing agent, carbon black and an electrode active material are simultaneously charged and dispersed in NMP. Processing may be performed.
　分散装置としては、顔料分散等に通常用いられている分散機を使用することができる。例えば、ディスパー、ホモミキサー、プラネタリーミキサー等のミキサー類、ホモジナイザー（エム・テクニック社製「クレアミックス」、ＰＲＩＭＩＸ社「フィルミックス」等、シルバーソン社製「アブラミックス」等）類、ペイントコンディショナー（レッドデビル社製）、コロイドミル（ＰＵＣ社製「ＰＵＣコロイドミル」、ＩＫＡ社製「コロイドミルＭＫ」）類、コーンミル（ＩＫＡ社製「コーンミルＭＫＯ」等）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル等のメディア型分散機、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ－５」、奈良機械社製「ＭＩＣＲＯＳ」等のメディアレス分散機、その他ロールミル等が挙げられるが、これらに限定されるものではない。 As the dispersing device, a dispersing device usually used for pigment dispersion or the like can be used. For example, mixers such as dispersers, homomixers, planetary mixers, homogenizers (such as “Clearmix” manufactured by M Technique, “Fillmix” manufactured by PRIMIX, “Abramix” manufactured by Silverson, etc.), paint conditioners ( Red Devil Co.), colloid mill ("PUC Colloid Mill" manufactured by PUC, "Colloid Mill MK" manufactured by IKA), cone mill ("Cone Mill MKO" manufactured by IKA, etc.), ball mill, sand mill (Shinmaru Enterprises) “Dynomill”, etc.), Attritor, Pearl Mill (“DCP Mill” manufactured by Eirich), Coball Mill and other media type dispersers, Wet Jet Mill (“Genus PY” manufactured by Genus, “Starburst” manufactured by Sugino Machine) "Nanomizer" manufactured by Nanomizer ), M Technique Co., Ltd. "Claire SS-5", Nara Machinery Co., Ltd. "MICROS" media-less dispersing machine such as, but other roll mill, and the like, but is not limited to these.
　次に、乾式処理により、カーボンブラックを分散剤で表面処理した後、分散液を製造する場合について説明する。ＮＭＰ中に、下記乾式処理により得たカーボンブラックと分散剤の混合物を添加、混合する事により、カーボンブラック分散液を得ることができる。分散剤により表面処理されたカーボンブラックを得る方法としては、乾式処理による方法が挙げられる。 Next, the case where a dispersion is produced after the surface treatment of carbon black with a dispersant by dry treatment will be described. A carbon black dispersion can be obtained by adding and mixing a mixture of carbon black and dispersant obtained by the following dry treatment in NMP. Examples of a method for obtaining carbon black surface-treated with a dispersant include a dry treatment method.
　乾式処理は、常温もしくは加熱下で乾式処理装置により、カーボンブラックおよび分散剤の混合、粉砕等を行いながら、カーボンブラック表面に分散剤を作用（吸着）させるものである。但し、カーボンブラック表面に分散剤が完全に吸着されている必要はなく、ある程度均質に混合できていれば、実用上は問題無い場合もある。使用する装置は、特に限定されるものではく、ペイントコンディショナー（レッドデビル社製）、ボールミル、アトライター、振動ミル等のメディア型分散機、ニーダー、ローラーミル、石臼式ミル、プラネタリーミキサー、フェンシェルミキサー、ハイブリダイザー（（株）奈良機械製作所）、メカノマイクロス（（株）奈良機械製作所）、メカノフュージョンシステムＡＭＳ（ホソカワミクロン（株））等の分散・混錬機が使用できるが、コンタミ等を考慮し、メディアレスの分散・混錬機を使用するのがより好ましい。 Dry processing is to make the dispersant act (adsorb) on the surface of the carbon black while mixing, pulverizing, and the like of the carbon black and the dispersant with a dry processing apparatus at room temperature or under heating. However, it is not necessary for the dispersant to be completely adsorbed on the carbon black surface, and there may be no practical problem as long as it can be mixed homogeneously to some extent. The equipment to be used is not particularly limited. Media type dispersers such as paint conditioner (manufactured by Red Devil), ball mill, attritor, vibration mill, kneader, roller mill, stone mill, planetary mixer, fen Dispersing and kneading machines such as Shell Mixer, Hybridizer (Nara Machinery Co., Ltd.), Mechano Micros (Nara Machinery Co., Ltd.), Mechano Fusion System AMS (Hosokawa Micron Co., Ltd.) can be used. Therefore, it is more preferable to use a medialess dispersion / kneading machine.
　また、このとき処理物がゲル状にならない範囲で有機溶剤を添加してもよい。溶剤の添加による分散剤の濡れ、または（一部）溶解、およびカーボンブラックの分散剤に対する濡れが向上することで、カーボンブラックと分散剤との相互作用の促進が期待される。このとき用いる溶剤は特に限定されるものではないが、ＮＭＰ以外を使用する場合は処理後に乾燥することが望ましい。また、有機溶剤の添加量は用いる材料により異なるが、分散剤の添加量に対して０．５～１００重量％である。さらに、必要に応じて窒素ガスなどを流すことで、乾式処理装置内部を脱酸素雰囲気として処理を行っても良い。 Further, at this time, an organic solvent may be added as long as the treated product does not become a gel. It is expected that the interaction between the carbon black and the dispersing agent is promoted by improving the wetting or (partly) dissolution of the dispersing agent by the addition of the solvent and the wetting of the carbon black with respect to the dispersing agent. The solvent used at this time is not particularly limited. However, when a solvent other than NMP is used, it is desirable to dry after the treatment. The amount of organic solvent added varies depending on the material used, but is 0.5 to 100% by weight based on the amount of dispersant added. Further, the inside of the dry processing apparatus may be treated as a deoxygenated atmosphere by flowing nitrogen gas or the like as necessary.
　乾式処理時間は、用いる装置によって、また希望とする混練度に応じて任意に設定できる。これらの乾式処理を行うことにより、粉状もしくは塊状の処理物を得ることができる。得られた処理物については、その後さらに、乾燥、粉砕しても良い。 The dry treatment time can be arbitrarily set depending on the apparatus used and the desired degree of kneading. By performing these dry treatments, a powdery or lump treated product can be obtained. The obtained processed product may be further dried and pulverized.
　カーボンブラックに対する分散剤の添加量は、第１の発明（分散剤が主にポリビニルアルコール単独）の場合は、カーボンブラック１００重量部に対して、０．６５重量部以上、１５重量部以下が好ましく、０．６５重量部以上、１０重量部以下がより好ましく、１重量部以上、１０重量部以下がさらに好ましく、１重量部以上、８重量部以下がさらに好ましく、２重量部以上、８重量部以下が特に好ましい。また、第２の発明（分散剤がポリビニルアルコールと顔料誘導体との併用）の場合は、カーボンブラック１００重量部に対して、５０重量部以下であることが好ましく、０．５重量部以上、４０重量部以下が好ましく、０．５重量部以上、２０重量部以下がより好ましく、１重量部以上、１５重量部以下がさらに好ましく、１重量部以上、１０重量部以下がさらに好ましく、１重量部以上、８重量部以下が特に好ましい。また、第３の発明（分散剤が主にポリビニルアルコール単独）の場合は、カーボンブラック１００重量部に対して、８重量部を超え、４０重量部以下が好ましく、８重量部を超え、３０重量部以下がより好ましく、８重量部を超え、２５重量部以下がさらに好ましく、８重量部を超え、２０重量部以下がさらに好ましく、８重量部を超え、１５重量部以下が特に好ましい。 In the case of the first invention (dispersant is mainly polyvinyl alcohol alone), the amount of dispersant added to carbon black is preferably 0.65 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of carbon black. 0.65 parts by weight or more and 10 parts by weight or less are more preferable, 1 part by weight or more and 10 parts by weight or less are more preferable, 1 part by weight or more and 8 parts by weight or less are more preferable, 2 parts by weight or more and 8 parts by weight or less. The following are particularly preferred: In the case of the second invention (the dispersant is a combination of polyvinyl alcohol and a pigment derivative), the amount is preferably 50 parts by weight or less, more than 0.5 parts by weight and 40 parts by weight with respect to 100 parts by weight of carbon black. Parts by weight or less, preferably 0.5 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less, still more preferably 1 part by weight or more and 10 parts by weight or less. As mentioned above, 8 weight part or less is especially preferable. In the case of the third invention (dispersant is mainly polyvinyl alcohol alone), the amount is more than 8 parts by weight, preferably 40 parts by weight or less, more than 8 parts by weight, 30 parts by weight with respect to 100 parts by weight of carbon black. Is more preferably 8 parts by weight or more, more preferably 25 parts by weight or less, more preferably 8 parts by weight, further preferably 20 parts by weight or less, particularly preferably 8 parts by weight or more and 15 parts by weight or less.
　分散剤がポリビニルアルコールと顔料誘導体との併用の場合は、カーボンブラックに対する分散剤としてのポリビニルアルコールの添加量は、カーボンブラック１００重量部に対して、０．１重量部以上、２０重量部以下が好ましく、０．１５重量部以上、１０重量部以下がより好ましく、０．２重量部以上、８重量部以下がさらに好ましく、０．２重量部以上、４重量部以下がさらに好ましく、０．４重量部以上、４重量部以下が特に好ましい。 When the dispersant is a combination of polyvinyl alcohol and a pigment derivative, the amount of polyvinyl alcohol added as a dispersant to carbon black is 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of carbon black. Preferably, 0.15 parts by weight or more and 10 parts by weight or less are more preferable, 0.2 parts by weight or more and 8 parts by weight or less are more preferable, 0.2 parts by weight or more and 4 parts by weight or less are more preferable, 0.4 Part by weight or more and 4 parts by weight or less are particularly preferable.
　分散剤がポリビニルアルコールと顔料誘導体との併用の場合は、分散剤中におけるポリビニルアルコールの比率は、分散剤１００重量部に対して、１０重量部以上９０重量部以下が好ましく、２０重量部以上８０重量部以下がより好ましく、２５重量部以上７５重量部以下が特に好ましい。 When the dispersant is a combination of polyvinyl alcohol and a pigment derivative, the proportion of polyvinyl alcohol in the dispersant is preferably 10 parts by weight or more and 90 parts by weight or less, and 20 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the dispersant. More preferred is 25 parts by weight or less, and particularly preferred is 25 parts by weight or more and 75 parts by weight or less.
　カーボンブラック分散液における分散剤の添加量は、添加するカーボンブラックの比表面積やカーボンブラック粒子の分散後の平均粒子径、カーボンブラックへの分散剤の吸着量等により決定される。 The amount of the dispersant added to the carbon black dispersion is determined by the specific surface area of the carbon black to be added, the average particle diameter after dispersion of the carbon black particles, the amount of the dispersant adsorbed on the carbon black, and the like.
　特にカーボンブラックの比表面積に対するポリビニルアルコールの添加量は重要であり、ポリビニルアルコールのけん化度が５０～９５ｍｏｌ％（好ましくは６０～８５ｍｏｌ％）である場合、カーボンブラックのＢＥＴ比表面積をＸｍ２／ｇ、カーボンブラック１ｇに対するポリビニルアルコールの添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲で、高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造できる臨界的範囲があることが見出された。 In particular, the amount of polyvinyl alcohol added relative to the specific surface area of carbon black is important. When the saponification degree of polyvinyl alcohol is 50 to 95 mol% (preferably 60 to 85 mol%), the BET specific surface area of carbon black is Xm 2 / g. When the addition amount of polyvinyl alcohol to 1 g of carbon black is aXg, a carbon black dispersion having a high concentration, low viscosity and good long-term storage stability when a is in the range of 0.00017 ≦ a ≦ 0.00256 It has been found that there is a critical range in which can be produced.
　更に良好な分散液や電池特性を得る観点から、０．０００１９≦ａ≦０．００２１７の範囲であることがより好ましく、０．０００２６≦ａ≦０．００１４５の範囲であることがさらに好ましく、０．０００５１≦ａ≦０．００１４５の範囲であることが特に好ましい。 From the viewpoint of obtaining better dispersion and battery characteristics, the range of 0.00019 ≦ a ≦ 0.00217 is more preferable, the range of 0.00026 ≦ a ≦ 0.00145 is more preferable, and 0 Particularly preferred is a range of .00051 ≦ a ≦ 0.00145.
　上記のような比率で配合することにより、カーボンブラック分散液の低粘度化が可能となり、高濃度で分散性と貯蔵安定性に優れた分散液を得ることが容易となる。 By blending at the above ratio, the viscosity of the carbon black dispersion can be lowered, and it becomes easy to obtain a dispersion having a high concentration and excellent dispersibility and storage stability.
＜活物質＞
　分散液を電池電極合材層に用いる場合は、さらに、正極活物質または負極活物質を含有させることができる。 <Active material>
When the dispersion is used for the battery electrode mixture layer, a positive electrode active material or a negative electrode active material can be further contained.
　リチウムイオン二次電池用の正極活物質としては、特に限定はされないが、リチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物等の金属化合物、および導電性高分子等を使用することができる。例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ等の遷移金属の酸化物、リチウムとの複合酸化物、遷移金属硫化物等の無機化合物等が挙げられる。具体的には、ＭｎＯ、Ｖ２Ｏ５、Ｖ６Ｏ１３、ＴｉＯ２等の遷移金属酸化物粉末、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウムなどのリチウムと遷移金属との複合酸化物粉末、オリビン構造のリン酸化合物であるリン酸鉄リチウム系材料、ＴｉＳ２、ＦｅＳなどの遷移金属硫化物粉末等が挙げられる。また、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン等の導電性高分子を使用することもできる。また、上記の無機化合物や有機化合物を混合して用いてもよい。 The positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to. Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc. Examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, transition metal sulfide powders such as TiS 2 and FeS, and the like. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.
　リチウムイオン二次電池用の負極活物質としては、リチウムイオンをドーピングまたはインターカレーション可能なものであれば特に限定されない。例えば、金属Ｌｉ、その合金であるスズ合金、シリコン合金、鉛合金等の合金系、ＬｉＸＦｅ２Ｏ３、ＬｉＸＦｅ３Ｏ４、ＬｉＸＷＯ２、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物系、ポリアセチレン、ポリ－ｐ－フェニレン等の導電性高分子系、ソフトカーボンやハードカーボンといった、アモルファス系炭素質材料や、高黒鉛化炭素材料等の人造黒鉛、あるいは天然黒鉛等の炭素質粉末、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維などの炭素系材料が挙げられる。これら負極活物質は、１種または複数を組み合わせて使用することもできる。 The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloys thereof such as tin alloys, silicon alloys, lead alloys, etc., Li X Fe 2 O 3 , Li X Fe 3 O 4 , Li X WO 2 , lithium titanate, lithium vanadate, silicon Metal oxides such as lithium oxide, conductive polymer such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers. These negative electrode active materials can be used alone or in combination.
　これらの活物質は、平均粒子径が０．０５～１００μｍの範囲内であることが好ましく、さらに好ましくは、０．１～５０μｍの範囲内である。本明細書でいう活物質の平均粒子径とは、活物質を電子顕微鏡で測定した粒子径の平均値である。 These active materials preferably have an average particle diameter in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. The average particle diameter of the active material as used herein is an average value of particle diameters of the active material measured with an electron microscope.
　第３の発明において、分散剤としてのポリビニルアルコールの添加量は、電極活物質を含有するカーボンブラック分散液中に含まれる全固形成分の量１００重量部に対して、０．０５重量部以上、２重量部未満が好ましく、０．０５重量部以上、１．５重量部未満がより好ましく、０．０５重量部以上、１．２５重量部未満がさらに好ましく、０．０５重量部以上、１重量部未満がさらに好ましく、０．１重量部以上、１重量部未満が特に好ましい。 In 3rd invention, the addition amount of the polyvinyl alcohol as a dispersing agent is 0.05 weight part or more with respect to 100 weight part of the amount of all the solid components contained in the carbon black dispersion liquid containing an electrode active material, Less than 2 parts by weight is preferable, 0.05 part by weight or more and less than 1.5 parts by weight are more preferable, 0.05 part by weight or more and less than 1.25 parts by weight are further preferable, 0.05 part by weight or more and 1 part by weight Less than 1 part by weight is more preferable, and 0.1 part by weight or more and less than 1 part by weight is particularly preferable.
＜その他の添加剤＞
　本発明の課題に支障を及ぼさない範囲で、塗膜物性等の調整等の目的で、従来公知の分散剤や樹脂、添加剤等を併用しても良い。そのような分散剤としては、例えば、ポリビニルアセタール樹脂（ポリビニルブチラール樹脂など）やポリビニルピロリドン樹脂、従来公知の色素誘導体、低分子量の界面活性剤等が挙げられる。また樹脂としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリエチレン、ポリプロピレン、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸、ポリアクリルアミド、ポリウレタン、ポリジメチルシロキサン、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、スチレンブタジエンゴムなどの各種ゴム、リグニン、ペクチン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、セルロース系樹脂、ポリアルキレンオキサイド、ポリビニルエーテル、キチン類、キトサン類、デンプン等が挙げられる。また添加剤としては、リン化合物、硫黄化合物、有機酸、アミン化合物やアミド化合物、有機エステル、各種シラン系やチタン系、アルミニウム系のカップリング剤等が挙げられる。これらの従来公知の分散剤や樹脂、添加剤等は、単独または２種類以上併用して用いることができる。 <Other additives>
Conventionally known dispersants, resins, additives, and the like may be used in combination for the purpose of adjusting the physical properties of the coating film and the like as long as the object of the present invention is not affected. Examples of such a dispersant include a polyvinyl acetal resin (such as polyvinyl butyral resin), a polyvinyl pyrrolidone resin, a conventionally known dye derivative, and a low molecular weight surfactant. Examples of the resin include polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyacrylamide, and polyurethane. , Polydimethylsiloxane, epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, styrene butadiene rubber and other rubbers, lignin, pectin, gelatin, xanthan gum, welan gum, succinoglycan, cellulosic resin, polyalkylene oxide, Examples include polyvinyl ether, chitins, chitosans, starch and the like. Examples of the additive include phosphorus compounds, sulfur compounds, organic acids, amine compounds and amide compounds, organic esters, various silane-based, titanium-based, and aluminum-based coupling agents. These conventionally known dispersants, resins, additives and the like can be used alone or in combination of two or more.
＜カーボンブラック分散液の用途＞
　カーボンブラック分散液の利用分野としては、特に制限はないが、遮光性、導電性、耐久性、漆黒性等が要求される分野、例えば、グラビアインキ、オフセットインキ、磁気記録媒体用バックコート、静電トナー、インクジェット、自動車塗料、繊維・プラスチック形成材料、電池用電極、電子写真用シームレスベルトにおいて、安定かつ均一な組成物を提供し得るものである。中でも、ＮＭＰを使用すること、ポリフッ化ビニリデンやポリイミド前駆体などと相溶すること、および形成される塗膜や成型物の強度、柔軟性が良好なことから、リチウムイオン二次電池用電極、電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極、電子写真用シームレスベルトなどに好適に用いられる。 <Uses of carbon black dispersion>
The field of application of the carbon black dispersion is not particularly limited, but is a field that requires light-shielding properties, electrical conductivity, durability, jetness, etc., such as gravure ink, offset ink, back coat for magnetic recording media, static It is possible to provide a stable and uniform composition in electric toner, ink jet, automobile paint, fiber / plastic forming material, battery electrode, and electrophotographic seamless belt. Among them, the use of NMP, compatibility with polyvinylidene fluoride, polyimide precursors, and the like, and the strength and flexibility of the formed coating film and molded product, the electrode for lithium ion secondary battery, It is suitably used for electric double layer capacitor electrodes, lithium ion capacitor electrodes, electrophotographic seamless belts, and the like.
　カーボンブラック分散液を用いて、更にはポリフッ化ビニリデン、ポリテトラフルオロエチレン等のバインダーを添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極のプライマー層、更にコバルト酸リチウム、マンガン酸リチウム等のリチウム遷移金属複合酸化物、黒鉛、活性炭、グラファイト、カーボンナノチューブやカーボンナノファイバーなどの正極活物質や負極活物質を添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極の電極層を製造することができる。また、電子写真用シームレスベルトは、導電材としてのカーボンブラック分散液、ポリイミド、ポリアミドイミド等およびその前駆体を成分として用いて、従来公知の方法によって製造することができる。 Using a carbon black dispersion, and further adding a binder such as polyvinylidene fluoride and polytetrafluoroethylene, an electrode for a lithium ion secondary battery, an electrode for an electric double layer capacitor, a primer layer for an electrode for a lithium ion capacitor, Lithium ion rechargeable battery electrodes and electricity by adding positive and negative active materials such as lithium transition metal composite oxides such as lithium cobaltate and lithium manganate, graphite, activated carbon, graphite, carbon nanotubes and carbon nanofibers The electrode layer of the electrode for double layer capacitors and the electrode for lithium ion capacitors can be manufactured. The electrophotographic seamless belt can be produced by a conventionally known method using a carbon black dispersion, a polyimide, a polyamideimide, or the like as a conductive material and a precursor thereof as components.
＜電極＞
　正極活物質または負極活物質を含有するカーボンブラック分散液を、集電体上に塗工・乾燥することで、電池電極合材層を形成し、電極を得ることができる。 <Electrode>
By coating and drying a carbon black dispersion containing a positive electrode active material or a negative electrode active material on a current collector, a battery electrode mixture layer can be formed and an electrode can be obtained.
（集電体）
　電極に使用する集電体の材質や形状は特に限定されず、各種二次電池にあったものを適宜選択することができる。例えば、集電体の材質としては、アルミニウム、銅、ニッケル、チタン、又はステンレス等の金属や合金が挙げられる。また、形状としては、一般的には平板上の箔が用いられるが、表面を粗面化したものや、穴あき箔状のもの、及びメッシュ状の集電体も使用できる。 (Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries can be appropriately selected. For example, examples of the material for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. In general, a flat foil is used as the shape, but a roughened surface, a perforated foil, or a mesh current collector can also be used.
（電池電極合材層）
　集電体上に合材スラリーや下地層形成用組成物を塗工する方法としては、特に制限はなく公知の方法を用いることができる。具体的には、ダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法または静電塗装法等が挙げる事ができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できるが、特にこれらに限定されるものではない。 (Battery electrode mixture layer)
There is no restriction | limiting in particular as a method of apply | coating a mixture slurry and the composition for base layer formation on a collector, A well-known method can be used. Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto.
　また、塗布後に平版プレスやカレンダーロール等による圧延処理を行っても良い。電池電極合材層の厚みは、一般的には１μｍ以上、５００μｍ以下であり、好ましくは１０μｍ以上、３００μｍ以下である。 Further, after the application, a rolling process using a lithographic press or a calendar roll may be performed. The thickness of the battery electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.
＜二次電池＞
　正極もしくは負極の少なくとも一方に電極を用い、二次電池を得ることができる。二次電池としては、リチウムイオン二次電池の他、ナトリウムイオン二次電池、マグネシウム二次電池、アルカリ二次電池、鉛蓄電池、ナトリウム硫黄二次電池、リチウム空気二次電池等が挙げられ、それぞれの二次電池において、従来から知られている電解液やセパレーター等を適宜用いることができる。 <Secondary battery>
A secondary battery can be obtained by using an electrode for at least one of the positive electrode and the negative electrode. Secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, etc. In the secondary battery, conventionally known electrolytes, separators, and the like can be used as appropriate.
（電解液）
　リチウムイオン二次電池の場合を例にとって説明する。電解液としては、リチウムを含んだ電解質を非水系の溶媒に溶解したものを用いる。電解質としては、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、ＬｉＣ４Ｆ９ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ２、ＬｉＳＣＮ、又はＬｉＢＰｈ４等が挙げられるが、これらに限定されない。 (Electrolyte)
A case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, an electrolyte containing lithium dissolved in a non-aqueous solvent is used. As the electrolyte, LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, or LiBPh 4, but are not limited thereto.
　非水系の溶媒としては、特に限定はされないが、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、及びジエチルカーボネート等のカーボネート類；γ－ブチロラクトン、γ－バレロラクトン、及びγ－オクタノイックラクトン等のラクトン類；テトラヒドロフラン、２－メチルテトラヒドロフラン、１，３－ジオキソラン、４－メチル－１，３－ジオキソラン、１，２－メトキシエタン、１，２－エトキシエタン、及び１，２－ジブトキシエタン等のグライム類；メチルフォルメート、メチルアセテート、及びメチルプロピオネート等のエステル類；ジメチルスルホキシド、及びスルホラン等のスルホキシド類；並びに、アセトニトリル等のニトリル類等が挙げられる。これらの溶媒は、それぞれ単独で使用しても良いが、２種以上を混合して使用しても良い。 The non-aqueous solvent is not particularly limited. For example, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1, Glymes such as 2-dibutoxyethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. And the like. These solvents may be used alone or in combination of two or more.
（セパレーター）
　セパレーターとしては、例えば、ポリエチレン不織布、ポリプロピレン不織布、ポリアミド不織布及びこれらに親水性処理を施したものが挙げられるが、特にこれらに限定されるものではない。 (separator)
Examples of the separator include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.
（電池構造・構成）
　リチウムイオン二次電池の構造については特に限定されないが、通常、正極及び負極と、必要に応じて設けられるセパレーターとから構成され、ペーパー型、円筒型、ボタン型、積層型等、使用する目的に応じた種々の形状とすることができる。 (Battery structure / configuration)
Although the structure of the lithium ion secondary battery is not particularly limited, it is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary. For the purpose of use, such as a paper type, a cylindrical type, a button type, and a laminated type. Various shapes can be obtained.
＜第１の発明に関する実施例＞
　以下、実施例に基づき主に第１の発明を詳細に説明するが、下記実施例は必ずしも第１の発明だけに関するものではなく、第２の発明や第３の発明の範囲内に入るものであればこれらの発明の実施例としても参照することができる。また、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。本実施例中、部は重量部を、％は重量％を、それぞれ表す。 <Example relating to the first invention>
Hereinafter, the first invention will be mainly described in detail based on examples. However, the following examples are not necessarily related only to the first invention, but fall within the scope of the second invention and the third invention. If any, it can be referred to as an embodiment of these inventions. Moreover, this invention is not limited to a following example, unless the summary is exceeded. In this example, “part” represents “part by weight” and “%” represents “% by weight”.
　実施例及び比較例で使用したカーボンブラック（「ＣＢ」と略記することがある）、ポリビニルアルコール（「ＰＶＡ」と略記することがある）、バインダー、電極活物質等を以下に示す。また、各表には、各原料の組成のみを記載しているが、特に記載のない残りの成分は、全てＮ－メチル－２－ピロリドン（ＮＭＰ）である。 The carbon black (sometimes abbreviated as “CB”), polyvinyl alcohol (sometimes abbreviated as “PVA”), binder, electrode active material, and the like used in Examples and Comparative Examples are shown below. In each table, only the composition of each raw material is described, but the remaining components not specifically described are all N-methyl-2-pyrrolidone (NMP).
＜カーボンブラック＞
・＃３０（三菱化学社製）：ファーネスブラック、平均一次粒子径３０ｎｍ、比表面積７４ｍ２／ｇ。以下、＃３０と略記する。
・＃５（三菱化学社製）：ファーネスブラック、平均一次粒子径７６ｎｍ、比表面積２９ｍ２／ｇ。以下、＃５と略記する。
・ＭＡ７７（三菱化学社製）：酸化処理カーボンブラック、平均一次粒子径２３ｎｍ、比表面積１３０ｍ２／ｇ。以下、ＭＡ７７と略記する。
・デンカブラックＨＳ－１００（電気化学工業社製）：アセチレンブラック、平均一次粒子径４８ｎｍ、比表面積３９ｍ２／ｇ。以下、ＨＳ－１００と略記する。
・デンカブラック粒状品（電気化学工業社製）：アセチレンブラック、平均一次粒子径３５ｎｍ、比表面積６９ｍ２／ｇ。以下、粒状品と略記する。
・ＥＣ－３００Ｊ（アクゾ社製）：ケッチェンブラック、平均一次粒子径４０ｎｍ、比表面積８００ｍ２／ｇ。以下、３００Ｊと略記する。 <Carbon black>
# 30 (manufactured by Mitsubishi Chemical Corporation): furnace black, average primary particle size 30 nm, specific surface area 74 m 2 / g. Hereinafter, it is abbreviated as # 30.
# 5 (Mitsubishi Chemical Co., Ltd.): Furnace black, average primary particle size 76 nm, specific surface area 29 m 2 / g. Hereinafter, it is abbreviated as # 5.
MA77 (manufactured by Mitsubishi Chemical Corporation): oxidized carbon black, average primary particle size of 23 nm, specific surface area of 130 m 2 / g. Hereinafter, it is abbreviated as MA77.
Denka black HS-100 (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 48 nm, specific surface area 39 m 2 / g. Hereinafter, it is abbreviated as HS-100.
Denka black granular product (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 35 nm, specific surface area 69 m 2 / g. Hereinafter, it is abbreviated as a granular product.
EC-300J (manufactured by Akzo): Ketjen black, average primary particle size 40 nm, specific surface area 800 m 2 / g. Hereinafter, it is abbreviated as 300J.
（カーボンブラックの平均一次粒子径の測定方法）
　カーボンブラックの平均一次粒子径（ＭＶ）は、以下に示す方法により測定（算出）した。カーボンブラックの粉末にプロピレングリコールモノメチルエーテルアセテートを加え、樹脂型分散剤としてＤｉｓｐｅｒｂｙｋ－１６１を少量添加し、超音波洗浄機の水浴中で１分間分散処理して測定用試料を調製した。この試料を測定用ターゲットに塗布、乾燥し、透過型電子顕微鏡（日立ハイテクノロジーズ社製透過型電子顕微鏡Ｈ－７６５０）により、１００個以上のカーボンブラックの一次粒子が観察できる写真を撮影した。撮影された画像にて、カーボンブラック粒子の任意の１００個を選び、その一次粒子の短軸径と長軸径の平均値を粒子径（ｄ）とし、次いで個々のカーボンブラックを、求めた粒子径（ｄ）を有する球とみなして、それぞれの粒子の体積（Ｖ）を求め、この作業を１００個のカーボンブラック粒子について行い、そこから下記式（１）を用いて算出した。
　　式（１）　　　　　　　ＭＶ＝Σ（Ｖ・ｄ）／Σ（Ｖ） (Measurement method of average primary particle size of carbon black)
The average primary particle size (MV) of carbon black was measured (calculated) by the method shown below. A sample for measurement was prepared by adding propylene glycol monomethyl ether acetate to a carbon black powder, adding a small amount of Disperbyk-161 as a resin-type dispersant, and dispersing in a water bath of an ultrasonic cleaner for 1 minute. This sample was applied to a measurement target, dried, and photographed with a transmission electron microscope (Transmission Electron Microscope H-7650, manufactured by Hitachi High-Technologies Corporation) to observe 100 or more primary particles of carbon black. In the photographed image, an arbitrary 100 carbon black particles are selected, the average value of the minor axis diameter and major axis diameter of the primary particles is defined as the particle diameter (d), and then the individual carbon blacks are obtained. Considering it as a sphere having a diameter (d), the volume (V) of each particle was determined, and this operation was performed on 100 carbon black particles, and the calculation was performed using the following equation (1).
Formula (1) MV = Σ (V · d) / Σ (V)
＜ポリビニルアルコール＞
・クラレポバール　Ｌ－８（クラレ社製）：ポリビニルアルコール、けん化度７１ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度５．５ｍＰａ・ｓ。以下、Ｌ－８と略記する。
・クラレポバール　Ｌ－１０（クラレ社製）：ポリビニルアルコール、けん化度７２ｍｏｌ％、平均重合度１０００以下。以下、Ｌ－１０と略記する。
・クラレポバール　Ｃ－５０６（クラレ社製）：カチオン変性ポリビニルアルコール、けん化度７６ｍｏｌ％、平均重合度６００、４％水溶液粘度５．１ｍＰａ・ｓ。以下、Ｃ－５０６と略記する。
・クラレポバール　ＫＬ－５０６（クラレ社製）：アニオン変性ポリビニルアルコール、けん化度７７ｍｏｌ％、平均重合度６００、４％水溶液粘度５．６ｍＰａ・ｓ。以下、ＫＬ－５０６と略記する。
・ゴーセノール　ＫＬ－０５（日本合成化学工業社製）：ポリビニルアルコール、けん化度８２ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度４．４ｍＰａ・ｓ。以下、ＫＬ－０５と略記する。
・クラレポバール　ＰＶＡ－２０５（クラレ社製）：ポリビニルアルコール、けん化度８８ｍｏｌ％、平均重合度５００、４％水溶液粘度５．０ｍＰａ・ｓ。以下、ＰＶＡ－２０５と略記する。
・ゴーセファイマー　ＬＬ－０２（日本合成化学工業社製）：ポリビニルアルコール、けん化度５０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度７．７ｍＰａ・ｓ。以下、ＬＬ－０２と略記する。
・合成品１：ポリビニルアルコール、けん化度６０ｍｏｌ％、平均重合度約５００、４％水溶液粘度５．２ｍＰａ・ｓ。
・合成品２：ポリビニルアルコール、けん化度８５ｍｏｌ％、平均重合度約５００、４％水溶液粘度５．７ｍＰａ・ｓ。
・合成品３：ポリビニルアルコール、けん化度７２ｍｏｌ％、平均重合度約１００、４％水溶液粘度２．０ｍＰａ・ｓ。
・合成品４：ポリビニルアルコール、けん化度７０ｍｏｌ％、平均重合度約１５００、４％水溶液粘度１９．８ｍＰａ・ｓ。
　尚、合成品１、合成品２、合成品３、合成品４は、業界公知の方法により、ポリ酢酸ビニルを水酸化ナトリウムでけん化することで得たものである。 <Polyvinyl alcohol>
Kuraray Poval L-8 (manufactured by Kuraray): polyvinyl alcohol, saponification degree 71 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 5.5 mPa · s. Hereinafter, it is abbreviated as L-8.
Kuraray Poval L-10 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree 1000 or less. Hereinafter, abbreviated as L-10.
Kuraray Poval C-506 (manufactured by Kuraray Co., Ltd.): cation-modified polyvinyl alcohol, saponification degree 76 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.1 mPa · s. Hereinafter, this is abbreviated as C-506.
Kuraray Poval KL-506 (manufactured by Kuraray Co., Ltd.): anion-modified polyvinyl alcohol, saponification degree 77 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.6 mPa · s. Hereinafter, it is abbreviated as KL-506.
-Gohsenol KL-05 (manufactured by Nippon Synthetic Chemical Industry): polyvinyl alcohol, saponification degree 82 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.4 mPa · s. Hereinafter, it is abbreviated as KL-05.
Kuraray Poval PVA-205 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 88 mol%, average polymerization degree 500, 4% aqueous solution viscosity 5.0 mPa · s. Hereinafter, it is abbreviated as PVA-205.
Goosephimer LL-02 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): polyvinyl alcohol, saponification degree 50 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 7.7 mPa · s. Hereinafter, abbreviated as LL-02.
Synthetic product 1: polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.2 mPa · s.
Synthetic product 2: polyvinyl alcohol, saponification degree 85 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.7 mPa · s.
Synthetic product 3: polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100, 4% aqueous solution viscosity 2.0 mPa · s.
Synthetic product 4: polyvinyl alcohol, saponification degree 70 mol%, average polymerization degree about 1500, 4% aqueous solution viscosity 19.8 mPa · s.
The synthetic product 1, the synthetic product 2, the synthetic product 3, and the synthetic product 4 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
＜バインダー＞
・ＫＦポリマーＷ１１００（クレハ社製）：ポリフッ化ビニリデン（ＰＶＤＦ）、以下、ＰＶＤＦと略記する。
・ＫＦポリマーＷ７３００（クレハ社製）：ポリフッ化ビニリデン（ＰＶＤＦ）、以下、＃７３００と略記する。 <Binder>
KF polymer W1100 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as PVDF.
-KF polymer W7300 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as # 7300.
＜活物質＞
・ＨＬＣ－２２（本荘ケミカル社製）：正極活物質コバルト酸リチウム（ＬｉＣｏＯ２）、平均粒径６．６μｍ、比表面積０．６２ｍ２／ｇ。以下、ＬＣＯと略記する。
・ＭＣＭＢ６－２８（大阪ガスケミカル社製）：負極活物質メソフェーズカーボン（ＭＦＣ）、平均粒径５～７μｍ、比表面積４ｍ２／ｇ。以下、ＭＦＣと略記する。 <Active material>
HLC-22 (Honjo Chemical Co., Ltd.): positive electrode active material lithium cobaltate (LiCoO 2 ), average particle size 6.6 μm, specific surface area 0.62 m 2 / g. Hereinafter, abbreviated as LCO.
MCMB6-28 (manufactured by Osaka Gas Chemical Co.): negative electrode active material mesophase carbon (MFC), average particle size 5-7 μm, specific surface area 4 m 2 / g. Hereinafter, abbreviated as MFC.
＜カーボンブラック分散液の評価＞
　実施例、比較例で得られたカーボンブラック分散液の評価は、粘度（その貯蔵安定性）、分散後平均粒子径（その貯蔵安定性）を測定することにより行った。 <Evaluation of carbon black dispersion>
The carbon black dispersions obtained in Examples and Comparative Examples were evaluated by measuring the viscosity (its storage stability) and the average particle diameter after dispersion (its storage stability).
　粘度値の測定は、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、分散液温度２５℃、Ｂ型粘度計ローター回転速度６０ｒｐｍにて、分散液をヘラで充分に撹拌した後、直ちに行った。測定に使用したローターは、粘度値が１００ｍＰａ・ｓ未満の場合はＮｏ．１を、１００以上５００ｍＰａ・ｓ未満の場合はＮｏ．２を、５００以上２０００ｍＰａ・ｓ未満の場合はＮｏ．３を、２０００以上１００００ｍＰａ・ｓ未満の場合はＮｏ．４のものをそれぞれ用いた。得られた粘度値が１００００ｍＰａ・ｓ以上の場合については、「＞１００００」と記載したが、これは評価に用いたＢ型粘度計では評価不可能なほどに高粘度であったことを表す。低粘度であるほど分散性が良好であり、高粘度であるほど分散性が不良である。貯蔵安定性の評価は、カーボンブラック分散液を５０℃にて、３０日間静置して保存した後の、粘度値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。 The viscosity value was measured using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.), and the dispersion was sufficiently stirred with a spatula at a dispersion temperature of 25 ° C. and a B-type viscometer rotor rotation speed of 60 rpm. Then went immediately. The rotor used for the measurement is No. when the viscosity value is less than 100 mPa · s. No. 1 is 100 or more and less than 500 mPa · s. 2 is 500 or more and less than 2000 mPa · s. 3 is 2000 or more and less than 10,000 mPa · s. Four of each were used. The case where the obtained viscosity value was 10,000 mPa · s or more was described as “> 10000”, but this indicates that the viscosity was so high that it could not be evaluated with the B-type viscometer used for the evaluation. The lower the viscosity, the better the dispersibility, and the higher the viscosity, the poor the dispersibility. The storage stability was evaluated from the change in viscosity value after the carbon black dispersion was stored at 50 ° C. for 30 days. The smaller the change, the better the stability.
　また、分散後平均粒子径の測定は、カーボンブラック分散液をＮＭＰにより適切な濃度に希釈した後に、超音波処理を施した液を測定サンプルとして用い、動的光散乱法方式の粒度分布計（日機装社製「ナノトラックＵＰＡ－ＥＸ」、光源波長７８０ｎｍ）を用いて平均粒子径（Ｄ５０値）を測定することにより行った。各種測定条件は、上記方法によりＮＭＰ希釈した分散液のローディングインデックス値を０．７以上１．３以下に、粒子条件を、吸収性粒子、粒子形状非球形、密度１．８０とし、溶媒条件を、溶媒屈折率１．４７、液温２０℃における溶媒粘度１．８０ｍＰａ・ｓ、液温２５℃における溶媒粘度１．６５ｍＰａ・ｓと設定し、得られたメジアン径をＤ５０値として表記した。測定結果は、液温２５℃のＮＭＰ溶剤についてバックグラウンド値を測定した後、上記方法にて調製した液温２５℃のサンプルを測定容器に充填し、上記測定条件にて測定を行うことにより得た。同じカーボンブラックを使用して同じ分散処理をした場合、Ｄ５０値が小さいほど分散性が良好であり、大きいほど分散性が不良であることを示す。貯蔵安定性の評価は、カーボンブラック分散液を５０℃にて、３０日間静置して保存した後のＤ５０値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。 In addition, the average particle size after dispersion is measured by diluting the carbon black dispersion to an appropriate concentration with NMP, and then using the ultrasonically treated liquid as a measurement sample. The measurement was carried out by measuring the average particle diameter (D50 value) using “Nanotrack UPA-EX” manufactured by Nikkiso Co., Ltd., light source wavelength 780 nm). Various measurement conditions were such that the loading index value of the dispersion diluted with NMP by the above method was 0.7 or more and 1.3 or less, the particle conditions were absorbent particles, particle shape non-spherical, density 1.80, and the solvent conditions were The solvent refractive index was 1.47, the solvent viscosity was 1.80 mPa · s at a liquid temperature of 20 ° C., the solvent viscosity was 1.65 mPa · s at a liquid temperature of 25 ° C., and the obtained median diameter was expressed as a D50 value. The measurement result is obtained by measuring the background value of the NMP solvent at a liquid temperature of 25 ° C., filling a sample with the liquid temperature of 25 ° C. prepared by the above method into a measurement container, and performing the measurement under the measurement conditions. It was. When the same dispersion treatment is performed using the same carbon black, the smaller the D50 value, the better the dispersibility, and the greater the value, the poorer the dispersibility. The storage stability was evaluated from the change in D50 value after storing the carbon black dispersion at 50 ° C. for 30 days. The smaller the change, the better the stability.
＜カーボンブラック分散液の調製＞
（けん化度の異なるポリビニルアルコールを用いたカーボンブラック分散液）
［実施例１－１～実施例１－７］
　表１－１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。また、ポリビニルアルコールの変性の有無は、分散剤としての性能には大きな影響を与えないことが明らかとなった。 <Preparation of carbon black dispersion>
(Carbon black dispersion using polyvinyl alcohol with different saponification degrees)
[Example 1-1 to Example 1-7]
In accordance with the composition shown in Table 1-1, NMP and various polyvinyl alcohols were charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks were added, and 1.25 mmφ zirconia beads were used as media for 2 hours with a paint shaker. Each carbon black dispersion was obtained by dispersing. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good. Moreover, it became clear that the presence or absence of the modification | denaturation of polyvinyl alcohol does not have big influence on the performance as a dispersing agent.
［比較例１－１～比較例１－２］
　表１－１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールとを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散した。しかし、得られた分散液は、いずれも著しく高粘度な状態であり、Ｄ５０値が大きいことから、カーボンブラックを十分に分散できていないことがわかる。この結果から、カーボンブラックの比表面積に対するポリビニルアルコールの添加量より算出されるａ値が、０．０００１７≦ａ≦０．００２５６の範囲内であっても、けん化度が６０ｍｏｌ％未満または８５ｍｏｌ％を越えるポリビニルアルコールを使用した場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。 [Comparative Example 1-1 to Comparative Example 1-2]
In accordance with the composition shown in Table 1-1, NMP and various polyvinyl alcohols were charged into a glass bottle, mixed and dissolved, or mixed and dispersed. Then, various carbon blacks were added, and 1.25 mmφ zirconia beads were used as media, and 2 on a paint shaker. Time dispersed. However, all of the obtained dispersions are in a state of extremely high viscosity and have a large D50 value, which indicates that carbon black cannot be sufficiently dispersed. From this result, even if the a value calculated from the addition amount of polyvinyl alcohol relative to the specific surface area of carbon black is within the range of 0.00017 ≦ a ≦ 0.00256, the degree of saponification is less than 60 mol% or 85 mol%. It was clarified that a carbon black dispersion liquid having a desired high concentration and low viscosity could not be obtained when exceeding the polyvinyl alcohol was used.
（種類の異なるカーボンブラックとポリビニルアルコール含有量の異なるカーボンブラック分散液）
［実施例１－８～実施例１－２４］
　表１－１に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。 (Different types of carbon black and carbon black dispersions with different polyvinyl alcohol content)
[Example 1-8 to Example 1-24]
In accordance with the composition shown in Table 1-1, NMP and polyvinyl alcohol are charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks are added, and 1.25 mmφ zirconia beads are used as a medium and dispersed for 2 hours in a paint shaker. Each carbon black dispersion was obtained. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good.
［比較例１－３、参考例１－１］
　表１－１に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。得られた分散液は、いずれも著しく高粘度な状態であり、Ｄ５０値が大きいことから、カーボンブラックを十分に分散できていない状態であった。この結果から、けん化度が６０～８５ｍｏｌ％のポリビニルアルコールを使用しても、カーボンブラックの比表面積に対するポリビニルアルコールの添加量より算出されるａ値が、０．０００１７≦ａ≦０．００２５６の範囲以外の場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。 [Comparative Example 1-3, Reference Example 1-1]
In accordance with the composition shown in Table 1-1, NMP and polyvinyl alcohol are charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks are added, and 1.25 mmφ zirconia beads are used as a medium and dispersed for 2 hours in a paint shaker. Each carbon black dispersion was obtained. All of the obtained dispersions were in a state of extremely high viscosity and the D50 value was large, so that the carbon black could not be sufficiently dispersed. From this result, even when polyvinyl alcohol having a saponification degree of 60 to 85 mol% is used, the a value calculated from the addition amount of polyvinyl alcohol with respect to the specific surface area of carbon black is in the range of 0.00017 ≦ a ≦ 0.00256. In other cases, it became clear that a desired high concentration and low viscosity carbon black dispersion could not be obtained.
＜バインダーを含むカーボンブラック分散液の調製＞
［実施例２－１～実施例２－１６］
　表１－２に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールと各種バインダーを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 <Preparation of carbon black dispersion containing binder>
[Example 2-1 to Example 2-16]
In accordance with the composition shown in Table 1-2, NMP, various polyvinyl alcohols, and various binders are charged into a glass bottle, and after thoroughly mixing, dissolving, or dispersing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. A liquid was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［実施例２－１７］
　表１－２に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールを仕込み、充分に混合溶解した。次いで、カーボンブラックとＰＶＤＦとを均質に混合した粉体混合品を調製し、これを事前に調製したポリビニルアルコールのＮＭＰ溶液に添加した。その後、ホモジナイザーで１時間分散し、カーボンブラック分散液を得た。粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-17]
According to the composition shown in Table 1-2, NMP and polyvinyl alcohol were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to an NMP solution of polyvinyl alcohol prepared in advance. Then, it disperse | distributed for 1 hour with the homogenizer, and obtained the carbon black dispersion liquid. There were no coarse particles, the viscosity was low, and the storage stability was good.
［実施例２－１８］
　表１－２に示す組成に従い、ガラス瓶に実施例１－２のカーボンブラック分散液を６０部、ＰＶＤＦを６部、ＮＭＰを３４部加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-18]
According to the composition shown in Table 1-2, 60 parts of the carbon black dispersion of Example 1-2, 6 parts of PVDF and 34 parts of NMP were added to a glass bottle and dispersed for 1 hour with a homogenizer to obtain each carbon black dispersion. It was. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［比較例２－１～比較例２－５］
　表１－２に示す組成に従い、ガラス瓶にＮＭＰと、各種ポリビニルアルコールとＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。しかし、得られた分散液の粘度は、バインダーを添加せずに調製した場合と同様に高粘度であり、カーボンブラックおよびバインダー濃度のさらなる向上はできないことが明らかとなった。 [Comparative Examples 2-1 to 2-5]
In accordance with the composition shown in Table 1-2, NMP, various polyvinyl alcohols and PVDF are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. A liquid was obtained. However, it was revealed that the viscosity of the obtained dispersion was as high as that prepared without adding a binder, and the carbon black and binder concentrations could not be further improved.
　表１－２より、ＮＭＰに溶解、または分散可能な樹脂をバインダーとして用いた場合、得られるカーボンブラック分散液の性状は、表１－１のバインダーを添加せずに分散液を調製した場合と同様に、高濃度かつ低粘度であり、貯蔵安定性も良好な分散液を得られることが分かる。 From Table 1-2, when a resin that can be dissolved or dispersed in NMP is used as a binder, the properties of the resulting carbon black dispersion are as follows when the dispersion is prepared without adding the binder of Table 1-1. Similarly, it can be seen that a dispersion having high concentration and low viscosity and good storage stability can be obtained.
＜正極活物質または負極活物質を含むカーボンブラック分散液の調製＞
［実施例３－１～実施例３－３、実施例３－５～実施例３－１４］
　表１－３に示す組成に従い、実施例２－１～実施例２－３および実施例２－５～実施例２－１４で得たバインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＬＣＯを多量に添加することができ、また、得られた混合液も低粘度な状態であった。 <Preparation of carbon black dispersion containing positive electrode active material or negative electrode active material>
[Example 3-1 to Example 3-3, Example 3-5 to Example 3-14]
According to the composition shown in Table 1-3, the positive electrode active material was used for the carbon black dispersions containing the binders obtained in Examples 2-1 to 2-3 and Example 2-5 to Example 2-14. A certain LCO was charged and thoroughly mixed with a disper to obtain each liquid mixture. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
［実施例３－４］
　粒状品を２．６７部、ＰＶＤＦを１．３３部、Ｌ－８を０．１３部、ＬＣＯを６２．７部を均質に混合した粉体混合品を調製後、ＮＭＰ３３．１７部に対して粉体混合品全量の半分を添加し、プラネタリーミキサーにて３０分間処理を行った。次いで、残った粉体混合品の半分を添加してプラネタリーミキサーにて３０分間処理し、その後、残った粉体混合品を全て添加してプラネタリーミキサーにて１時間処理することにより、正極活物質であるＬＣＯを含有したカーボンブラック分散液を得た。得られた液は、実施例３－２の場合と同様、低粘度な状態であった。 [Example 3-4]
After preparing a powder mixture in which 2.67 parts of granular product, 1.33 parts of PVDF, 0.13 part of L-8, and 62.7 parts of LCO are homogeneously mixed, 33.17 parts of NMP are prepared. Half of the total amount of the powder mixture was added and treated for 30 minutes with a planetary mixer. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 3-2.
［実施例３－１５～実施例３－１８］
　表１－３に示す組成に従い、実施例２－１～実施例２－３および実施例２－９で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質であるＭＦＣを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＭＦＣを多量に添加することができ、また、得られた混合液も低粘度な状態であった。 [Example 3-15 to Example 3-18]
In accordance with the composition shown in Table 1-3, MFC, which is a negative electrode active material, was charged into the carbon black dispersion containing the binder obtained in Examples 2-1 to 2-3 and Example 2-9. The mixture was sufficiently mixed with a disper to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of MFC could be added, and the resulting mixture was also in a low viscosity state.
［比較例３－１～比較例３－３］
　表１－３に示す組成に従い、比較例２－３～比較例２－５で得た、バインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３－１～実施例３－１４と比較して、ＬＣＯを添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。 [Comparative Examples 3-1 to 3-3]
In accordance with the composition shown in Table 1-3, LCO as the positive electrode active material was charged into the carbon black dispersion containing the binder obtained in Comparative Examples 2-3 to 2-5 and mixed well with a disper. Each liquid mixture was obtained. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when LCO is added is larger than in Examples 3-1 to 3-14, and the stability is increased. The increase in viscosity in the evaluation test was also large.
［比較例３－４～比較例３－６］
　表１－３に示す組成に従い、比較例２－３～比較例２－５で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質であるＭＦＣを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３－１５～実施例３－１８と比較して、ＭＦＣを添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。 [Comparative Examples 3-4 to 3-6]
According to the composition shown in Table 1-3, the carbon black dispersion containing the binder obtained in Comparative Examples 2-3 to 2-5 was charged with MFC as a negative electrode active material, and thoroughly mixed with a disper. Each liquid mixture was obtained. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when MFC is added is larger than that in Examples 3-15 to 3-18, and the stability is increased. The increase in viscosity in the evaluation test was also large.
＜電池電極合材層の作製＞
　上記の各実施例、比較例で得られた正極活物質または負極活物質を含むカーボンブラック分散液を電池電極合材液として、ポリエチレンテレフタレート（ＰＥＴ）フィルム上にドクターブレードを用いて塗工した後、減圧下１２０℃で３０分間乾燥し、乾燥後膜厚１００μｍの塗膜（電池電極合材層）を作製した。
　得られた電池電極合材層の評価は、表面抵抗と塗膜外観により行った。表面抵抗の測定にはロレスタ－ＧＰ（三菱化学アナリテック社製）を用い、ＪＩＳ　Ｋ７１９４に準じて測定した。
　表面抵抗は、数値が小さい程、良好であることを示す。また、塗膜外観は、目視で、○：問題なし（良好）、△：斑模様あり（不良）、×：粗粒の筋引きあり（極めて不良）、とした。 <Preparation of battery electrode composite layer>
After applying the carbon black dispersion containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid on a polyethylene terephthalate (PET) film using a doctor blade Then, the film was dried at 120 ° C. under reduced pressure for 30 minutes, and a coating film (battery electrode mixture layer) having a film thickness of 100 μm was produced after drying.
Evaluation of the obtained battery electrode mixture layer was performed by surface resistance and coating film appearance. The surface resistance was measured using Loresta-GP (manufactured by Mitsubishi Chemical Analytech) according to JIS K7194.
The smaller the numerical value, the better the surface resistance. Further, the appearance of the coating film was visually evaluated as ◯: no problem (good), Δ: spotted pattern (bad), and x: coarse-grained stripes (very bad).
［実施例４－１～実施例４－１１、比較例４－１～比較例４－３］
　正極合材液として、実施例３－１～実施例３－３および実施例３－５～実施例３－１２、比較例３－１～比較例３－３で得た電池電極合材液を使用して、正極合材層（電池電極合材層）を作製した。評価結果を表１－４に示した。 [Example 4-1 to Example 4-11, Comparative Example 4-1 to Comparative Example 4-3]
As the positive electrode mixture liquid, the battery electrode mixture liquids obtained in Examples 3-1 to 3-3, Example 3-5 to Example 3-12, and Comparative Example 3-1 to Comparative Example 3-3 were used. The positive electrode composite material layer (battery electrode composite material layer) was produced by using it. The evaluation results are shown in Table 1-4.
［実施例４－１２～実施例４－１５、比較例４－４～比較例４－５］
　負極合材液としては、実施例３－１５～実施例３－１８、比較例３－４～比較例３－５で得た電池電極合材液を使用して、負極合材層（電池電極合材層）を作製した。評価結果を表１－４に示した。
　表１－４より、実施例４－１～実施例４－１５の電池電極合材層は、比較例４－１～比較例４－５の電池電極合材層と比較して塗膜外観が良好であり、さらに、塗膜の表面抵抗が優れていることが明らかとなった。比較例４－１～比較例４－５では、使用した電極合材液の粘度が高すぎるために塗工が困難であり、さらに、多量に含まれるポリビニルアルコールが絶縁成分として機能した結果、表面抵抗値が高くなったものと考えられる。 [Example 4-12 to Example 4-15, Comparative Example 4-4 to Comparative Example 4-5]
As the negative electrode mixture liquid, the battery electrode mixture liquids obtained in Examples 3-15 to 3-18 and Comparative Examples 3-4 to 3-5 were used. A composite layer) was prepared. The evaluation results are shown in Table 1-4.
From Table 1-4, the battery electrode composite layers of Examples 4-1 to 4-15 have coating film appearances that are compared with the battery electrode composite layers of Comparative Examples 4-1 to 4-5. It was clear that the surface resistance of the coating film was excellent. In Comparative Examples 4-1 to 4-5, coating is difficult because the viscosity of the electrode mixture solution used is too high. Further, as a result of the large amount of polyvinyl alcohol functioning as an insulating component, It is considered that the resistance value has increased.
＜リチウムイオン二次電池正極評価用セルの組み立て＞
［実施例５－１～実施例５－１１、比較例５－１～比較例５－３］
　先に調製した電池電極合材液（実施例３－１～実施例３－３および実施例３－５～実施例３－１２、比較例３－１～比較例３－３の正極合材液）を、集電体となる厚さ２０μｍのアルミ箔上にドクターブレードを用いて塗布した後、減圧下１２０℃で加熱乾燥した後、ローラープレス機にて圧延処理し、厚さ１００μｍの正極合材層を作製した。これを直径９ｍｍに打ち抜き作用極とし、金属リチウム箔（厚さ０．１５ｍｍ）を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター（セルガード社製＃２４００）を挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを容量比１：１で混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝泉社製ＨＳフラットセル）を組み立てた。セルの組み立ては、アルゴンガス置換したグローブボックス内で行った。 <Assembly of lithium ion secondary battery positive electrode evaluation cell>
[Example 5-1 to Example 5-11, Comparative Example 5-1 to Comparative Example 5-3]
The battery electrode mixture solutions prepared previously (the positive electrode mixture solutions of Examples 3-1 to 3-3 and 3-5 to 3-12 and Comparative Examples 3-1 to 3-3) ) Is applied onto a 20 μm thick aluminum foil as a current collector using a doctor blade, dried at 120 ° C. under reduced pressure, and then rolled with a roller press to obtain a positive electrode composite having a thickness of 100 μm. A material layer was prepared. This is a punching working electrode with a diameter of 9 mm, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator made of a porous polypropylene film (# 2400 manufactured by Celgard) is inserted and laminated between the working electrode and the counter electrode, An electrolyte solution (nonaqueous electrolyte solution in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1) was filled, and a bipolar electrode type metal cell (HS manufactured by Hosen Co., Ltd.) Flat cell). The cell was assembled in a glove box substituted with argon gas.
＜リチウムイオン二次電池負極評価用セルの組み立て＞
［実施例５－１２～実施例５－１５、比較例５－４～比較例５－５］
　先に調製した電池電極合材液（実施例３－１５～実施例３－１８、比較例３－４～比較例３－５の負極合材液）を、集電体となる厚さ２０μｍのアルミ箔上にドクターブレードを用いて塗布した後、減圧下１２０℃で加熱乾燥した後、ローラープレス機にて圧延処理し、厚さ１００μｍの負極合材層を作製した。これを直径９ｍｍに打ち抜き作用極とし、金属リチウム箔（厚さ０．１５ｍｍ）を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター（セルガード社製＃２４００）を挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを容量比１：１で混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝泉社製ＨＳフラットセル）を組み立てた。セルの組み立ては、アルゴンガス置換したグローブボックス内で行った。 <Assembly of lithium ion secondary battery negative electrode evaluation cell>
[Examples 5-12 to 5-15, Comparative Example 5-4 to Comparative Example 5-5]
The previously prepared battery electrode mixture liquids (negative electrode mixture liquids of Example 3-15 to Example 3-18 and Comparative Example 3-4 to Comparative Example 3-5) having a thickness of 20 μm serving as a current collector After apply | coating using a doctor blade on aluminum foil, after heat-drying at 120 degreeC under pressure reduction, it rolled by the roller press machine and produced the negative mix layer of thickness 100 micrometers. This is a punching working electrode with a diameter of 9 mm, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator made of a porous polypropylene film (# 2400 manufactured by Celgard) is inserted and laminated between the working electrode and the counter electrode, An electrolyte solution (nonaqueous electrolyte solution in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1) was filled, and a bipolar electrode type metal cell (HS manufactured by Hosen Co., Ltd.) Flat cell). The cell was assembled in a glove box substituted with argon gas.
＜リチウムイオン二次電池正極特性評価＞
　作製した正極評価用セルを２５℃で、充放電装置（北斗電工社製ＳＭ－８）を使用して、充電レート１．０Ｃの定電流定電圧充電（上限電圧４．２Ｖ）で満充電とし、充電時と同じレートの定電流で、放電下限電圧３．０Ｖまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計５０サイクル行い、充放電を行った。アルゴンガス置換したグローブボックス内で評価後のセルを分解し、電極塗膜の外観（５０サイクル後の塗膜外観）を目視にて確認した。塗膜外観の評価基準は、集電体からの剥がれが認められず外観に全く変化が無い場合を○（極めて良好）、剥がれてはいないが外観に変化が認められる場合を△（良好）、部分的に集電体からの合材の剥がれが認められる場合を×（不良）とした。また、容量維持率は、１サイクル目の放電容量に対する５０サイクル目の放電容量の百分率であり、数値が１００％に近いものほど良好であることを示す。評価結果を表１－５に示した。 <Characteristic evaluation of lithium ion secondary battery positive electrode>
The prepared positive electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 1.0 C using a charge / discharge device (SM-8 manufactured by Hokuto Denko) at 25 ° C. The charge / discharge for discharging to the discharge lower limit voltage of 3.0 V at a constant current at the same rate as the charge was defined as one cycle (charge / discharge interval pause time 30 minutes), and this cycle was performed for a total of 50 cycles to perform charge / discharge. . The cell after evaluation was disassembled in a glove box substituted with argon gas, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was visually confirmed. The evaluation criteria for the appearance of the coating film are ○ (very good) when no peeling from the current collector is observed and no change in the appearance, △ (good) when no change is observed in the appearance. A case where peeling of the composite material from the current collector was partially recognized was defined as x (defective). Further, the capacity retention ratio is a percentage of the discharge capacity at the 50th cycle with respect to the discharge capacity at the 1st cycle, and the closer the value is to 100%, the better. The evaluation results are shown in Table 1-5.
＜リチウムイオン二次電池負極特性評価＞
　作製した負極評価用セルを２５℃で、充放電装置（北斗電工社製ＳＭ－８）を使用して、充電レート１．０Ｃの定電流定電圧充電（上限電圧０．５Ｖ）で満充電とし、充電時と同じレートの定電流で電圧が１．５Ｖになるまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計５０サイクル行い、充放電サイクルを行った。アルゴンガス置換したグローブボックス内で評価後のセルを分解し、電極塗膜の外観（５０サイクル後の塗膜外観）について、正極特性評価と同じ基準で評価した。評価結果を表１－５に示した。 <Evaluation of lithium ion secondary battery negative electrode characteristics>
The prepared negative electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 0.5 V) at a charge rate of 1.0 C using a charging / discharging device (SM-8 manufactured by Hokuto Denko) at 25 ° C. Charging / discharging is performed at a constant current at the same rate as during charging until the voltage reaches 1.5 V, and one cycle (charging / discharging interval pause time 30 minutes) is performed, and this cycle is performed for a total of 50 cycles. It was. The cell after evaluation was disassembled in a glove box substituted with argon gas, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was evaluated based on the same criteria as the positive electrode characteristic evaluation. The evaluation results are shown in Table 1-5.
　表１－５より、本発明の電極を使用した実施例５－１～実施例５－１１および実施例５－１２～実施例５－１５は、比較例５－１～比較例５－３および比較例５－４～比較例５－５と比較して、塗膜外観が良好であり、かつ、５０サイクル後の容量維持率についても、良好な結果であった。 From Table 1-5, Example 5-1 to Example 5-11 and Example 5-12 to Example 5-15 using the electrode of the present invention are shown in Comparative Example 5-1 to Comparative Example 5-3 and Compared with Comparative Examples 5-4 to 5-5, the appearance of the coating film was good, and the capacity retention rate after 50 cycles was also good.
　表１－５より、実施例５－１～実施例５－１５は５０サイクルの充放電サイクル後も、塗膜外観が良好で、かつ容量維持率も良好であることが判明した。一方、比較例５－１～比較例５－５は、良好な塗膜を得ることができなかったため、正極特性および負極特性を評価することができなかった。 From Table 1-5, it was found that Examples 5-1 to 5-15 had good coating film appearance and good capacity retention even after 50 charge / discharge cycles. On the other hand, Comparative Example 5-1 to Comparative Example 5-5 could not evaluate the positive electrode characteristics and the negative electrode characteristics because a good coating film could not be obtained.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
＜第２の発明に関する実施例＞
　以下、実施例に基づき主に第２の発明を詳細に説明するが、下記実施例は必ずしも第２の発明だけに関するものではなく、第１の発明や第３の発明の範囲内に入るものであればこれらの発明の実施例としても参照することができる。また、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。本実施例中、部は重量部を、％は重量％を、それぞれ表す。 <Examples relating to the second invention>
Hereinafter, the second invention will be mainly described in detail based on examples. However, the following examples are not necessarily related only to the second invention, but fall within the scope of the first invention and the third invention. If any, it can be referred to as an embodiment of these inventions. Moreover, this invention is not limited to a following example, unless the summary is exceeded. In this example, “part” represents “part by weight” and “%” represents “% by weight”.
　実施例及び比較例で使用したカーボンブラック（「ＣＢ」と略記することがある）、ポリビニルアルコール（「ＰＶＡ」と略記することがある）、有機色素誘導体またはトリアジン誘導体（「顔料誘導体」と略記することがある）、バインダー、電極活物質等を以下に示す。また、各表には、各原料の組成のみを記載しているが、特に記載のない残りの成分は、全てＮ－メチル－２－ピロリドン（ＮＭＰ）である。 Carbon black (sometimes abbreviated as “CB”), polyvinyl alcohol (sometimes abbreviated as “PVA”), organic dye derivative or triazine derivative (abbreviated as “pigment derivative”) used in Examples and Comparative Examples. The binder, the electrode active material, etc. are shown below. In each table, only the composition of each raw material is described, but the remaining components not specifically described are all N-methyl-2-pyrrolidone (NMP).
＜カーボンブラック＞
　カーボンブラックは、第１の発明に関する実施例で用いたものと同じものを使用した。また、カーボンブラックの平均一次粒子径の測定は、第１の発明に関する実施例で説明した方法と同じ方法で行った。 <Carbon black>
The same carbon black as that used in the examples relating to the first invention was used. Moreover, the measurement of the average primary particle diameter of carbon black was performed by the same method as the method demonstrated in the Example regarding 1st invention.
＜ポリビニルアルコール（一般式（Ａ）を含有する樹脂）＞
・クラレポバール　ＰＶＡ－５０５（クラレ社製）：ポリビニルアルコール、けん化度７３ｍｏｌ％、平均重合度５００。以下、ＰＶＡ－５０５と略記する。
・クラレポバール　ＰＶＡ－１０５（クラレ社製）：ポリビニルアルコール、けん化度９８ｍｏｌ％、平均重合度５００。以下、ＰＶＡ－１０５と略記する。
・クラレポバール　ＬＭ－２０（クラレ社製）：ポリビニルアルコール、けん化度４０ｍｏｌ％、平均重合度２００。以下、ＬＭ－２０と略記する。
・合成品１：ポリビニルアルコール、けん化度５５ｍｏｌ％、平均重合度約５００。
・合成品２：ポリビニルアルコール、けん化度６０ｍｏｌ％、平均重合度約５００。
・合成品３：アミノ基変性ポリビニルアルコール、けん化度７６ｍｏｌ％、変性基量１０ｍｏｌ％、平均重合度約５００。
・合成品４：ポリビニルアルコール、けん化度８５ｍｏｌ％、平均重合度約５００。
・合成品５：ポリビニルアルコール、けん化度９２ｍｏｌ％、平均重合度約１００。
・合成品６：ポリビニルアルコール、けん化度７２ｍｏｌ％、平均重合度約１００。
・合成品７：ポリビニルアルコール、けん化度７０ｍｏｌ％、平均重合度約１５００。
　尚、合成品１から合成品７は、業界公知の方法により、ポリ酢酸ビニルを水酸化ナトリウムでけん化することで得たものである。 <Polyvinyl alcohol (resin containing general formula (A))>
Kuraray Poval PVA-505 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 73 mol%, average polymerization degree 500. Hereinafter, it is abbreviated as PVA-505.
Kuraray Poval PVA-105 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 98 mol%, average polymerization degree 500. Hereinafter, it is abbreviated as PVA-105.
Kuraray Poval LM-20 (manufactured by Kuraray): polyvinyl alcohol, saponification degree 40 mol%, average polymerization degree 200. Hereinafter, it is abbreviated as LM-20.
Synthetic product 1: polyvinyl alcohol, saponification degree 55 mol%, average polymerization degree about 500.
Synthetic product 2: polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500.
Synthetic product 3: amino group-modified polyvinyl alcohol, saponification degree 76 mol%, modified group amount 10 mol%, average polymerization degree about 500.
Synthetic product 4: polyvinyl alcohol, saponification degree of 85 mol%, average polymerization degree of about 500.
-Synthetic product 5: Polyvinyl alcohol, saponification degree 92 mol%, average degree of polymerization about 100.
Synthetic product 6: polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100.
-Synthetic product 7: Polyvinyl alcohol, saponification degree 70 mol%, average degree of polymerization about 1500.
Synthetic products 1 to 7 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
＜ポリビニルアセタール＞
・エスレックＢＨ－３（積水化学工業社製）：ポリビニルブチラール樹脂、水酸基３４ｍｏｌ％、ブチラール化度６５ｍｏｌ％、計算分子量１１００００。以下、ＢＨ－３と略記する。
・エスレックＫＳ－１（積水化学工業社製）：ポリビニルアセトアセタール樹脂、水酸基２５ｍｏｌ％、アセタール化度７４ｍｏｌ％、計算分子量２７０００。以下、ＫＳ－１と略記する。
・ビニレックＨ（ＪＮＣ社製）：ポリビニルホルマール樹脂、水酸基約１３ｍｏｌ％、平均分子量７３０００。以下、ビニレックと略記する。
　尚、ポリビニルアセタールの重合体鎖中に含まれる水酸基（ｍｏｌ％）は、ポリビニルアセタールの重合体鎖中に含まれる一般式（Ａ）で表される繰り返し単位のモル比率を表す。 <Polyvinyl acetal>
ESREC BH-3 (manufactured by Sekisui Chemical Co., Ltd.): polyvinyl butyral resin, hydroxyl group 34 mol%, butyralization degree 65 mol%, calculated molecular weight 110000. Hereinafter, it is abbreviated as BH-3.
ESREC KS-1 (manufactured by Sekisui Chemical Co., Ltd.): polyvinyl acetoacetal resin, hydroxyl group 25 mol%, acetalization degree 74 mol%, calculated molecular weight 27000. Hereinafter, it is abbreviated as KS-1.
Vinylec H (manufactured by JNC): polyvinyl formal resin, hydroxyl group of about 13 mol%, average molecular weight of 73,000. Hereinafter, it is abbreviated as vinylec.
In addition, the hydroxyl group (mol%) contained in the polymer chain of polyvinyl acetal represents the molar ratio of the repeating unit represented by the general formula (A) contained in the polymer chain of polyvinyl acetal.
＜酸性顔料誘導体＞
　酸性官能基を有する有機色素誘導体の構造を表２－１に示した。
Figure JPOXMLDOC01-appb-T000022
 <Acid pigment derivative>
The structures of organic dye derivatives having acidic functional groups are shown in Table 2-1.
Figure JPOXMLDOC01-appb-T000022
　酸性官能基を有するトリアジン誘導体の構造を表２－２に示した。
Figure JPOXMLDOC01-appb-T000023
 The structure of the triazine derivative having an acidic functional group is shown in Table 2-2.
Figure JPOXMLDOC01-appb-T000023
＜塩基性顔料誘導体＞
　塩基性官能基を有する有機色素誘導体の構造を表２－３に示した。
Figure JPOXMLDOC01-appb-T000024
 <Basic pigment derivative>
The structure of the organic dye derivative having a basic functional group is shown in Table 2-3.
Figure JPOXMLDOC01-appb-T000024
　塩基性官能基を有するトリアジン誘導体の構造を表２－４に示した。
Figure JPOXMLDOC01-appb-T000025
 The structures of triazine derivatives having basic functional groups are shown in Table 2-4.
Figure JPOXMLDOC01-appb-T000025
＜バインダー＞
　バインダーは、第１の発明に関する実施例で用いたものと同じものを使用した。 <Binder>
The binder used was the same as that used in the examples relating to the first invention.
＜その他化合物＞
・１，２，３，４－ベンゼンテトラカルボン酸。以下、Ｄ－０１と略記する。 <Other compounds>
1,2,3,4-benzenetetracarboxylic acid. Hereinafter, it is abbreviated as D-01.
＜活物質＞
・ＨＬＣ－２２（本荘ケミカル社製）：正極活物質コバルト酸リチウム（ＬｉＣｏＯ２）、平均粒子径６．６μｍ、比表面積０．６２ｍ２／ｇ。以下、ＬＣＯと略記する。
・人造黒鉛：負極活物質、平均粒子径１８μｍ。以下、黒鉛と略記する。 <Active material>
HLC-22 (Honjo Chemical Co., Ltd.): positive electrode active material lithium cobaltate (LiCoO 2 ), average particle size 6.6 μm, specific surface area 0.62 m 2 / g. Hereinafter, abbreviated as LCO.
Artificial graphite: negative electrode active material, average particle size 18 μm. Hereinafter, it is abbreviated as graphite.
＜カーボンブラック分散液の評価＞
　実施例、比較例で得られたカーボンブラック分散液の評価は、第１の発明で説明した方法に従って、粘度（その貯蔵安定性）、分散後平均粒子径（その貯蔵安定性）を測定することにより行った。ただし、粘度についての貯蔵安定性の評価は、カーボンブラック分散液を６０℃にて、１０日間静置して保存した後の、粘度値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。また、分散後平均粒子径についての貯蔵安定性の評価は、カーボンブラック分散液を６０℃にて、１０日間静置して保存した後のＤ５０値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。 <Evaluation of carbon black dispersion>
The carbon black dispersions obtained in the examples and comparative examples are evaluated by measuring the viscosity (its storage stability) and the average particle size after dispersion (its storage stability) according to the method described in the first invention. It went by. However, the storage stability of the viscosity was evaluated from the change in viscosity value after the carbon black dispersion was stored at 60 ° C. for 10 days. The smaller the change, the better the stability. The storage stability of the average particle diameter after dispersion was evaluated from the change in D50 value after the carbon black dispersion was stored at 60 ° C. for 10 days. The smaller the change, the better the stability.
＜メディア分散によるカーボンブラック分散液の調製＞
（けん化度の異なるポリビニルアルコールを用いたカーボンブラック分散液）
［実施例１－１～実施例１－３］
　表２－５に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールと各種顔料誘導体とを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントコンディショナーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。 <Preparation of carbon black dispersion by media dispersion>
(Carbon black dispersion using polyvinyl alcohol with different saponification degrees)
[Example 1-1 to Example 1-3]
In accordance with the composition shown in Table 2-5, NMP, various polyvinyl alcohols, and various pigment derivatives were charged into a glass bottle, mixed and dissolved or mixed and dispersed sufficiently, then carbon black was added, and 1.25 mmφ zirconia beads were used as a medium for painting. Each carbon black dispersion was obtained by dispersing for 2 hours with a conditioner. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
＜バインダーを含むカーボンブラック分散液の調製＞
（けん化度の異なるポリビニルアルコールを用いたカーボンブラック分散液）
［実施例２－１～実施例２－８、実施例２－１４～実施例２－１５］
　表２－６に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールと各種顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。また、ポリビニルアルコールの変性の有無は、分散剤としての性能には大きな影響を与えないことが明らかとなった。 <Preparation of carbon black dispersion containing binder>
(Carbon black dispersion using polyvinyl alcohol with different saponification degrees)
[Example 2-1 to Example 2-8, Example 2-14 to Example 2-15]
In accordance with the composition shown in Table 2-6, NMP, various polyvinyl alcohols, various pigment derivatives, and PVDF were charged into a glass bottle, mixed thoroughly, dissolved, or mixed and dispersed, then added with carbon black, and dispersed with a homogenizer for 1 hour. A black dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability. Moreover, it became clear that the presence or absence of the modification | denaturation of polyvinyl alcohol does not have big influence on the performance as a dispersing agent.
［実施例２－１６］
　表２－６に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと顔料誘導体とを仕込み、充分に混合溶解した。次いで、カーボンブラックとＰＶＤＦとを均質に混合した粉体混合品を調製し、これを事前に調製した分散剤のＮＭＰ溶液に添加した。その後、ホモジナイザーで１時間分散し、カーボンブラック分散液を得た。粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-16]
According to the composition shown in Table 2-6, NMP, polyvinyl alcohol, and a pigment derivative were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to the NMP solution of the dispersant prepared in advance. Then, it disperse | distributed for 1 hour with the homogenizer, and obtained the carbon black dispersion liquid. There were no coarse particles, the viscosity was low, and the storage stability was good.
［実施例２－１７～実施例２－１８］
　表２－６に示す組成に従い、ガラス瓶に実施例１－２のカーボンブラック分散液を６５部、ＰＶＤＦを６部または＃７３００を３部、ＮＭＰを２９部または３２部加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-17 to Example 2-18]
According to the composition shown in Table 2-6, 65 parts of the carbon black dispersion of Example 1-2, 6 parts of PVDF or 3 parts of # 7300, and 29 parts or 32 parts of NMP were added to a glass bottle and dispersed with a homogenizer for 1 hour. Each carbon black dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［実施例２－１９～実施例２－２０］
　表２－６に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと顔料誘導体と＃７３００を仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-19 to Example 2-20]
In accordance with the composition shown in Table 2-6, NMP, polyvinyl alcohol, pigment derivative and # 7300 were charged in a glass bottle, mixed and dissolved or mixed and dispersed sufficiently, and then carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［比較例２－１～比較例２－１０］
　表２－６に示す組成に従い、ガラス瓶にＮＭＰと、各種ポリビニルアルコールまたは各種ポリビニルアセタール樹脂と、各種顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。
　しかし、得られた分散液は、顔料誘導体の種類によらずいずれも高粘度な状態であり、カーボンブラックおよびバインダー濃度のさらなる向上はできないことが明らかとなった。
　さらに、比較例２－１～比較例２－２、および比較例２－６～比較例２－７では、いずれも著しく高粘度な状態であり、かつＤ５０値が大きいことから、カーボンブラックを十分に分散できていないことがわかった。また、これらの結果から、けん化度が５０ｍｏｌ％未満または９５ｍｏｌ％を越えるポリビニルアルコールと、顔料誘導体とを、合わせて分散剤として使用した場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。 [Comparative Examples 2-1 to 2-10]
In accordance with the composition shown in Table 2-6, NMP, various polyvinyl alcohols or various polyvinyl acetal resins, various pigment derivatives and PVDF were charged into a glass bottle, and thoroughly mixed, dissolved, or mixed, and then carbon black was added. Each carbon black dispersion was obtained by dispersing for 1 hour.
However, it was revealed that the obtained dispersion was in a high viscosity state regardless of the type of pigment derivative, and the carbon black and binder concentrations could not be further improved.
Further, in Comparative Examples 2-1 to 2-2 and Comparative Examples 2-6 to 2-7, all of them are in a significantly high viscosity state and have a large D50 value. It was found that they could not be dispersed. Further, from these results, when polyvinyl alcohol having a saponification degree of less than 50 mol% or more than 95 mol% and a pigment derivative are used as a dispersant, the desired high concentration and low viscosity carbon black dispersion is obtained. It became clear that the liquid could not be obtained.
　表２－６より、ＮＭＰに溶解、または分散可能な樹脂をバインダーとして用いた場合、得られるカーボンブラック分散液の性状は、表２－５のバインダーを添加せずに分散液を調製した場合と同様に、高濃度かつ低粘度であり、貯蔵安定性も良好な分散液を得られることが分かる。 From Table 2-6, when a resin that can be dissolved or dispersed in NMP is used as a binder, the properties of the obtained carbon black dispersion are as follows when the dispersion is prepared without adding the binder of Table 2-5. Similarly, it can be seen that a dispersion having high concentration and low viscosity and good storage stability can be obtained.
（種類の異なるカーボンブラックを用いたカーボンブラック分散液）
［実施例２－９～実施例２－１３］
　表２－６に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 (Carbon black dispersion using different types of carbon black)
[Example 2-9 to Example 2-13]
In accordance with the composition shown in Table 2-6, NMP, polyvinyl alcohol, pigment derivative and PVDF were charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks were added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
（種類の異なる顔料誘導体を用いたカーボンブラック分散液）
［実施例３－１～実施例３－２０］
　表２－７に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと各種顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。また、これらの中でも、トリアジン誘導体を用いた場合に特に良好な分散液を得ることができることが分かった。 (Carbon black dispersion using different types of pigment derivatives)
[Example 3-1 to Example 3-20]
In accordance with the composition shown in Table 2-7, NMP, polyvinyl alcohol, various pigment derivatives, and PVDF were charged into a glass bottle, mixed and dissolved, or mixed and dispersed. Carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability. Further, among these, it was found that a particularly good dispersion can be obtained when a triazine derivative is used.
［比較例３－１］
　表２－７に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと１，２，３，４－ベンゼンテトラカルボン酸（Ｄ－０１）とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。得られた液は著しく高粘度な状態であり、かつＤ５０値が大きいことから、カーボンブラックを十分に分散できていないことがわかった。 [Comparative Example 3-1]
In accordance with the composition shown in Table 2-7, NMP, polyvinyl alcohol, 1,2,3,4-benzenetetracarboxylic acid (D-01), and PVDF were charged into a glass bottle and thoroughly mixed and dissolved or mixed and dispersed. Black was added and dispersed with a homogenizer for 1 hour to obtain each carbon black dispersion. The obtained liquid was in a remarkably high viscosity state and had a large D50 value, indicating that carbon black could not be sufficiently dispersed.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
（ポリビニルアルコール含有量の異なるカーボンブラック分散液）
［実施例４－１～実施例４－９］
　表２－８に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと各種顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 (Carbon black dispersions with different polyvinyl alcohol contents)
[Example 4-1 to Example 4-9]
In accordance with the composition shown in Table 2-8, NMP, polyvinyl alcohol, various pigment derivatives, and PVDF were charged into a glass bottle, mixed and dissolved, or mixed and dispersed. Carbon black was added and dispersed with a homogenizer for 1 hour. A dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［比較例４－１］
　表２－８に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールと顔料誘導体とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。得られた液は著しく高粘度な状態であり、かつＤ５０値が大きいことから、カーボンブラックを十分に分散できていないことがわかった。 [Comparative Example 4-1]
In accordance with the composition shown in Table 2-8, NMP, polyvinyl alcohol, pigment derivative, and PVDF are charged into a glass bottle, mixed and dissolved or mixed and dispersed, and then carbon black is added and dispersed with a homogenizer for 1 hour. A liquid was obtained. The obtained liquid was in a remarkably high viscosity state and had a large D50 value, indicating that carbon black could not be sufficiently dispersed.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
＜正極活物質または負極活物質を含むカーボンブラック分散液の調製＞
［実施例５－１～実施例５－２３］
　表２－９に示す組成に従い、実施例２－１～実施例２－６、実施例２－１１、実施例３－１、実施例３－６～実施例３－１０、実施例３－１６～実施例３－１７、実施例４－１～実施例４－７、および実施例４－９で得たバインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＬＣＯを多量に添加することができ、また、得られた混合液も低粘度な状態であった。 <Preparation of carbon black dispersion containing positive electrode active material or negative electrode active material>
[Example 5-1 to Example 5-23]
According to the composition shown in Table 2-9, Example 2-1 to Example 2-6, Example 2-11, Example 3-1, Example 3-6 to Example 3-10, Example 3-16 To the carbon black dispersions containing the binders obtained in Example 3-17, Example 4-1 to Example 4-7, and Example 4-9, LCO as the positive electrode active material was charged and dispersed with a disper. Mix well to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
［実施例５－２４］
　表２－９に示す組成に従い、ＨＳ－１００を２．７部、ＰＶＤＦを１．２５部、ポリビニルアルコールを０．０１１部、顔料誘導体を０．０４３部、およびＬＣＯを６３部、均質に混合した粉体混合品を調製後、ＮＭＰ３２．９９６部に対して粉体混合品全量の半分を添加し、プラネタリーミキサーにて３０分間処理を行った。次いで、残った粉体混合品の半分を添加してプラネタリーミキサーにて３０分間処理し、その後、残った粉体混合品を全て添加してプラネタリーミキサーにて１時間処理することにより、正極活物質であるＬＣＯを含有したカーボンブラック分散液を得た。得られた液は、実施例５－２３の場合と同様、低粘度な状態であった。 [Example 5-24]
According to the composition shown in Table 2-9, 2.7 parts of HS-100, 1.25 parts of PVDF, 0.011 part of polyvinyl alcohol, 0.043 part of pigment derivative, and 63 parts of LCO were mixed homogeneously. After preparing the powder mixture, half of the total amount of the powder mixture was added to 32.996 parts of NMP, and the mixture was processed with a planetary mixer for 30 minutes. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 5-23.
［実施例５－２５～実施例５－２８］
　表２－９に示す組成に従い、実施例２－２～実施例２－５で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質である黒鉛を仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、黒鉛を多量に添加することができ、また、得られた混合液も低粘度な状態であった。 [Examples 5-25 to 5-28]
In accordance with the composition shown in Table 2-9, graphite as a negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Example 2-2 to Example 2-5, and thoroughly mixed with a disper. Each liquid mixture was obtained. Since the carbon black dispersion used had a low viscosity, a large amount of graphite could be added, and the resulting mixture was also in a low viscosity state.
［比較例５－１～比較例５－５］
　表２－９に示す組成に従い、比較例２－３、比較例２－５、比較例２－８、比較例２－１０、および比較例４－１で得た、バインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例５－１～実施例５－２３と比較して、ＬＣＯを添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。 [Comparative Examples 5-1 to 5-5]
According to the composition shown in Table 2-9, carbon black dispersion containing binders obtained in Comparative Example 2-3, Comparative Example 2-5, Comparative Example 2-8, Comparative Example 2-10, and Comparative Example 4-1. The liquid was charged with LCO as a positive electrode active material and mixed well with a disper to obtain each liquid mixture. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when LCO is added is larger than in Examples 5-1 to 5-23, and the stability is high. The increase in viscosity in the evaluation test was also large.
［比較例５－６～比較例５－８］
　表２－９に示す組成に従い、比較例２－８、比較例２－１０、および比較例４－１で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質である黒鉛を仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例５－２５～実施例５－２８と比較して、黒鉛を添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。 [Comparative Examples 5-6 to 5-8]
In accordance with the composition shown in Table 2-9, graphite as a negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Comparative Example 2-8, Comparative Example 2-10, and Comparative Example 4-1. The mixture was sufficiently mixed with a disper to obtain each mixture. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when graphite is added is larger than in Examples 5-25 to 5-28, and the stability is increased. The increase in viscosity in the evaluation test was also large.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
＜電池電極合材層の作製＞
　上記の各実施例、比較例で得られた正極活物質または負極活物質を含むカーボンブラック分散液を電池電極合材液として、第１の発明で説明した方法に従って電池電極合材層を作製し、その評価を行った。なお、表面抵抗が測定不可の場合は数値なし（－）とし、塗膜外観で「△」は、「斑模様あり（可）」を意味する。 <Preparation of battery electrode composite layer>
Using the carbon black dispersion liquid containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid, a battery electrode mixture layer was prepared according to the method described in the first invention. The evaluation was performed. When the surface resistance is not measurable, no value is given (−), and “△” in the appearance of the coating means “spotted (possible)”.
［実施例６－１～実施例６－２１、比較例６－１～比較例６－３］
　正極合材液として、実施例５－１～実施例５－６、実施例５－８～実施例５－１４、実施例５－１６～実施例５－２３、比較例５－２、および比較例５－４～比較例５－５で得た電池電極合材液を使用して、正極合材層（電池電極合材層）を作製した。評価結果を表２－１０に示した。 [Example 6-1 to Example 6-21, Comparative Example 6-1 to Comparative Example 6-3]
As the positive electrode mixture liquid, Examples 5-1 to 5-6, Examples 5-8 to 5-14, Examples 5-16 to 5-23, Comparative Example 5-2, and Comparison Using the battery electrode mixture liquid obtained in Examples 5-4 to 5-5, a positive electrode mixture layer (battery electrode mixture layer) was produced. The evaluation results are shown in Table 2-10.
［実施例６－２２～実施例６－２４、比較例６－４～比較例６－５］
　負極合材液としては、実施例５－２５～実施例５－２６、実施例５－２８、および比較例５－７～比較例５－８で得た電池電極合材液を使用して、負極合材層（電池電極合材層）を作製した。評価結果を表２－１０に示した。
　表２－１０より、実施例６－１～実施例６－２４の電池電極合材層は、比較例６－１～比較例６－５の電池電極合材層と比較して塗膜外観が良好であり、さらに、塗膜の表面抵抗が優れていることが明らかとなった。比較例６－１～比較例６－５では、使用した電極合材液の粘度が高すぎるために塗工が困難であり、さらに、比較例６－３および比較例６－５では、多量に含まれる分散剤が絶縁成分として機能した結果、表面抵抗値が高くなったものと考えられる。 [Example 6-22 to Example 6-24, Comparative Example 6-4 to Comparative Example 6-5]
As the negative electrode mixture liquid, using the battery electrode mixture liquid obtained in Example 5-25 to Example 5-26, Example 5-28, and Comparative Example 5-7 to Comparative Example 5-8, A negative electrode mixture layer (battery electrode mixture layer) was produced. The evaluation results are shown in Table 2-10.
As shown in Table 2-10, the battery electrode composite layers of Examples 6-1 to 6-24 have a coating film appearance as compared with the battery electrode composite layers of Comparative Examples 6-1 to 6-5. It was clear that the surface resistance of the coating film was excellent. In Comparative Examples 6-1 to 6-5, coating is difficult because the viscosity of the electrode mixture solution used is too high. Further, in Comparative Examples 6-3 and 6-5, a large amount is used. As a result of the contained dispersant functioning as an insulating component, the surface resistance value is considered to have increased.
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
＜リチウムイオン二次電池正極評価用セルの組み立て＞
［実施例７－１～実施例７－２１、比較例７－１～比較例７－３］
　先に調製した電池電極合材液（実施例５－１～実施例５－６、実施例５－８～実施例５－１４、実施例５－１６～実施例５－２３、比較例５－２、および比較例５－４～比較例５－５の正極合材液）を用いて、第１の発明で説明した方法に従って正極評価用セルを組み立てた。 <Assembly of lithium ion secondary battery positive electrode evaluation cell>
[Example 7-1 to Example 7-21, Comparative Example 7-1 to Comparative Example 7-3]
The previously prepared battery electrode mixture liquids (Examples 5-1 to 5-6, Examples 5-8 to 5-14, Examples 5-16 to 5-23, Comparative Example 5) 2 and the positive electrode mixture liquids of Comparative Examples 5-4 to 5-5) were assembled according to the method described in the first invention.
＜リチウムイオン二次電池負極評価用セルの組み立て＞
［実施例７－２２～実施例７－２４、比較例７－４～比較例７－５］
　先に調製した電池電極合材液（実施例５－２５～実施例５－２６、実施例５－２８、および比較例５－７～比較例５－８の負極合材液）を用いて、第１の発明で説明した方法に従って負極評価用セルを組み立てた。ただし、集電体としてアルミ箔の代わりに銅箔を使用した。 <Assembly of lithium ion secondary battery negative electrode evaluation cell>
[Examples 7-22 to 7-24, Comparative Examples 7-4 to 7-5]
Using the previously prepared battery electrode mixture liquids (negative electrode mixture liquids of Example 5-25 to Example 5-26, Example 5-28, and Comparative Example 5-7 to Comparative Example 5-8), A negative electrode evaluation cell was assembled according to the method described in the first invention. However, copper foil was used instead of aluminum foil as a current collector.
＜リチウムイオン二次電池正極特性評価＞
　第１の発明で説明した方法に従って、正極特性評価を行った。ただし、正極評価用セルの温度は２５℃ではなく、４０℃にした。集電体からの塗膜の剥離やショート等により正常な充放電曲線が得られず、容量が求められなかった場合は数値なし（－）とした。評価結果を表２－１１に示した。 <Characteristic evaluation of lithium ion secondary battery positive electrode>
The positive electrode characteristics were evaluated according to the method described in the first invention. However, the temperature of the positive electrode evaluation cell was set to 40 ° C. instead of 25 ° C. When a normal charge / discharge curve could not be obtained due to peeling or short-circuiting of the coating film from the current collector and the capacity could not be obtained, no value was given (−). The evaluation results are shown in Table 2-11.
＜リチウムイオン二次電池負極特性評価＞
　第１の発明で説明した方法に従って、負極特性評価を行った。ただし、負極評価用セルの温度は２５℃ではなく４０℃にして、定電流定電圧充電の上限電圧を０．５Ｖにするのではなく下限電圧を０．５Ｖにした。評価結果を表２－１１に示した。 <Evaluation of lithium ion secondary battery negative electrode characteristics>
According to the method described in the first invention, negative electrode characteristics were evaluated. However, the temperature of the negative electrode evaluation cell was set to 40 ° C. instead of 25 ° C., and the upper limit voltage for constant current and constant voltage charging was not set to 0.5V, but the lower limit voltage was set to 0.5V. The evaluation results are shown in Table 2-11.
　表２－１１より、本発明の電極を使用した実施例７－１～実施例７－２１および実施例７－２２～実施例７－２４は、比較例７－１～比較例７－３および比較例７－４～比較例７－５と比較して、塗膜外観が良好であり、かつ、集電体からの剥がれも無く、密着性も良好であった。さらに、５０サイクル後の容量維持率についても、良好な結果であった。 From Table 2-11, Example 7-1 to Example 7-21 and Example 7-22 to Example 7-24 using the electrode of the present invention are shown in Comparative Example 7-1 to Comparative Example 7-3 and Compared with Comparative Examples 7-4 to 7-5, the coating film appearance was good, there was no peeling from the current collector, and the adhesion was also good. Furthermore, the capacity retention rate after 50 cycles was also a good result.
　表２－１１より、実施例７－１～実施例７－２４は５０サイクルの充放電サイクル後も、塗膜外観が良好で、かつ容量維持率も良好であることが判明した。一方、比較例７－１～比較例７－５は、良好な塗膜を得ることができなかったため、正極特性および負極特性を評価することができなかった。 From Table 2-11, it was found that in Examples 7-1 to 7-24, the coating film appearance was good and the capacity retention rate was good even after 50 charge / discharge cycles. On the other hand, Comparative Examples 7-1 to 7-5 could not evaluate the positive electrode characteristics and the negative electrode characteristics because a good coating film could not be obtained.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
＜第３の発明に関する実施例＞
　以下、実施例に基づき第３の発明を詳細に説明するが、下記実施例は必ずしも第３の発明だけに関するものではなく、第１の発明や第２の発明の範囲内に入るものであればこれらの発明の実施例としても参照することができる。また、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。本実施例中、部は重量部を、％は重量％を、それぞれ表す。 <Examples relating to the third invention>
Hereinafter, the third invention will be described in detail based on examples. However, the following examples are not necessarily related only to the third invention, and may be within the scope of the first invention and the second invention. Reference can also be made to examples of these inventions. Moreover, this invention is not limited to a following example, unless the summary is exceeded. In this example, “part” represents “part by weight” and “%” represents “% by weight”.
　実施例及び比較例で使用したカーボンブラック（「ＣＢ」と略記することがある）、ポリビニルアルコール（「ＰＶＡ」と略記することがある）、バインダー、電極活物質等を以下に示す。また、各表には、各原料の組成のみを記載しているが、特に記載のなし残りの成分は、全てＮ－メチル－２－ピロリドン（ＮＭＰ）である。 The carbon black (sometimes abbreviated as “CB”), polyvinyl alcohol (sometimes abbreviated as “PVA”), binder, electrode active material, and the like used in Examples and Comparative Examples are shown below. In each table, only the composition of each raw material is described, but the remaining components not specifically described are all N-methyl-2-pyrrolidone (NMP).
＜カーボンブラック＞
・＃８５０（三菱化学社製）：ファーネスブラック、平均一次粒子径１７ｎｍ、比表面積２２０ｍ２／ｇ。以下、＃８５０と略記する。
・＃２６００（三菱化学社製）：ファーネスブラック、平均一次粒子径１３ｎｍ、比表面積３７０ｍ２／ｇ。以下、＃２６００と略記する。
・ケッチェンブラック　ＥＣ－３００Ｊ（アクゾ社製）：中空カーボンブラック、平均一次粒子径４０ｎｍ、比表面積８００ｍ２／ｇ。以下、３００Ｊと略記する。
・ケッチェンブラック　ＥＣ－６００ＪＤ（アクゾ社製）：中空カーボンブラック、平均一次粒子径３４ｎｍ、比表面積１２７０ｍ２／ｇ。以下、６００ＪＤと略記する。
　なお、カーボンブラックの平均一次粒子径の測定は、第１の発明に関する実施例で説明した方法と同じ方法で行った。 <Carbon black>
# 850 (manufactured by Mitsubishi Chemical Corporation): furnace black, average primary particle size 17 nm, specific surface area 220 m 2 / g. Hereinafter, it is abbreviated as # 850.
# 2600 (manufactured by Mitsubishi Chemical Corporation): furnace black, average primary particle size 13 nm, specific surface area 370 m 2 / g. Hereinafter, it is abbreviated as # 2600.
Ketjen black EC-300J (manufactured by Akzo): hollow carbon black, average primary particle size 40 nm, specific surface area 800 m 2 / g. Hereinafter, it is abbreviated as 300J.
Ketjen black EC-600JD (manufactured by Akzo): hollow carbon black, average primary particle size 34 nm, specific surface area 1270 m 2 / g. Hereinafter, it is abbreviated as 600 JD.
In addition, the measurement of the average primary particle diameter of carbon black was performed by the same method as the method demonstrated in the Example regarding 1st invention.
＜ポリビニルアルコール＞
・クラレポバール　ＰＶＡ－５０５（クラレ社製）：ポリビニルアルコール、けん化度７３ｍｏｌ％、平均重合度５００。以下、ＰＶＡ－５０５と略記する。
・クラレポバール　ＰＶＡ－２０５（クラレ社製）：ポリビニルアルコール、けん化度８８ｍｏｌ％、平均重合度５００。以下、ＰＶＡ－２０５と略記する。
・ゴーセファイマー　ＬＬ－０２（日本合成化学工業社製）：ポリビニルアルコール、けん化度５０ｍｏｌ％、平均重合度１０００以下。以下、ＬＬ－０２と略記する。
・合成品１：ポリビニルアルコール、けん化度６０ｍｏｌ％、平均重合度約５００。
・合成品２：ポリビニルアルコール、けん化度８５ｍｏｌ％、平均重合度約５００。
・合成品３：ポリビニルアルコール、けん化度７２ｍｏｌ％、平均重合度約１００。
・合成品４：ポリビニルアルコール、けん化度７０ｍｏｌ％、平均重合度約１５００。
　尚、合成品１、合成品２、合成品３、合成品４は、業界公知の方法により、ポリ酢酸ビニルを水酸化ナトリウムでけん化することで得たものである。 <Polyvinyl alcohol>
Kuraray Poval PVA-505 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 73 mol%, average polymerization degree 500. Hereinafter, it is abbreviated as PVA-505.
Kuraray Poval PVA-205 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 88 mol%, average polymerization degree 500. Hereinafter, it is abbreviated as PVA-205.
Goosephimer LL-02 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): polyvinyl alcohol, saponification degree 50 mol%, average polymerization degree 1000 or less. Hereinafter, abbreviated as LL-02.
Synthetic product 1: polyvinyl alcohol, saponification degree 60 mol%, average polymerization degree about 500.
Synthetic product 2: polyvinyl alcohol, saponification degree 85 mol%, average polymerization degree about 500.
Synthetic product 3: polyvinyl alcohol, saponification degree 72 mol%, average polymerization degree about 100.
-Synthetic product 4: Polyvinyl alcohol, saponification degree 70 mol%, average degree of polymerization about 1500.
The synthetic product 1, the synthetic product 2, the synthetic product 3, and the synthetic product 4 were obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
＜バインダー＞
　バインダーは、第１の発明に関する実施例で用いたものと同じものを使用した。 <Binder>
The binder used was the same as that used in the examples relating to the first invention.
＜活物質＞
・ＨＬＣ－２２（本荘ケミカル社製）：正極活物質コバルト酸リチウム（ＬｉＣｏＯ２）、平均粒子径６．６μｍ、比表面積０．６２ｍ２／ｇ。以下、ＬＣＯと略記する。
・人造黒鉛：負極活物質、平均粒子径１２μｍ。以下、黒鉛と略記する。 <Active material>
HLC-22 (Honjo Chemical Co., Ltd.): positive electrode active material lithium cobaltate (LiCoO 2 ), average particle size 6.6 μm, specific surface area 0.62 m 2 / g. Hereinafter, abbreviated as LCO.
Artificial graphite: negative electrode active material, average particle size 12 μm. Hereinafter, it is abbreviated as graphite.
＜カーボンブラック分散液の評価＞
　実施例、比較例で得られたカーボンブラック分散液の評価は、第１の発明で説明した方法に従って、粘度（その貯蔵安定性）、分散後平均粒子径（その貯蔵安定性）を測定することにより行った。ただし、粘度についての貯蔵安定性の評価は、カーボンブラック分散液を６０℃にて１０日間、または５０℃にて１５日間静置して保存した後の、粘度値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。また、分散後平均粒子径についての貯蔵安定性の評価は、カーボンブラック分散液を６０℃にて１０日間、または５０℃にて１５日間静置して保存した後のＤ５０値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。 <Evaluation of carbon black dispersion>
The carbon black dispersions obtained in the examples and comparative examples are evaluated by measuring the viscosity (its storage stability) and the average particle size after dispersion (its storage stability) according to the method described in the first invention. It went by. However, the storage stability of the viscosity was evaluated from the change in viscosity value after the carbon black dispersion was stored at 60 ° C. for 10 days or at 50 ° C. for 15 days. The smaller the change, the better the stability. The storage stability of the average particle diameter after dispersion was evaluated from the change in D50 value after the carbon black dispersion was stored at 60 ° C. for 10 days or at 50 ° C. for 15 days. . The smaller the change, the better the stability.
＜カーボンブラック分散液の調製＞
（けん化度の異なるポリビニルアルコールを用いたカーボンブラック分散液）
［実施例１－１～実施例１－８］
　表３－１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールとを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントコンディショナーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。 <Preparation of carbon black dispersion>
(Carbon black dispersion using polyvinyl alcohol with different saponification degrees)
[Example 1-1 to Example 1-8]
In accordance with the composition shown in Table 3-1, NMP and various polyvinyl alcohols were charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks were added, and 1.25 mmφ zirconia beads were used as media and 2 Each carbon black dispersion was obtained by time dispersion. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good.
［比較例１－１～比較例１－３、参考例１－１］
　表３－１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールとを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントコンディショナーで２時間分散した。しかし、得られた分散液はいずれも著しく高粘度な状態であり、Ｄ５０値が大きいことから、カーボンブラックを十分に分散できていないことがわかる。この結果から、けん化度が６０ｍｏｌ％未満または８５ｍｏｌ％を越えるポリビニルアルコールを使用した場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。また、分散剤としてのポリビニルアルコールの量が、カーボンブラックに対して大過剰または不足している場合も、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。 [Comparative Example 1-1 to Comparative Example 1-3, Reference Example 1-1]
In accordance with the composition shown in Table 3-1, NMP and various polyvinyl alcohols were charged into a glass bottle, mixed and dissolved or mixed and dispersed sufficiently, and then carbon black was added. Distributed. However, all of the obtained dispersions are in a very high viscosity state, and the D50 value is large, indicating that the carbon black cannot be sufficiently dispersed. From this result, it was revealed that when a polyvinyl alcohol having a saponification degree of less than 60 mol% or more than 85 mol% is used, a desired high concentration and low viscosity carbon black dispersion cannot be obtained. It is also clear that the desired high-concentration and low-viscosity carbon black dispersion cannot be obtained even when the amount of polyvinyl alcohol as a dispersant is excessively large or insufficient with respect to carbon black. It was.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
＜バインダーを含むカーボンブラック分散液の調製＞
［実施例２－１～実施例２－１５］
　表３－２に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコールと各種バインダーを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 <Preparation of carbon black dispersion containing binder>
[Example 2-1 to Example 2-15]
In accordance with the composition shown in Table 3-2, NMP, various polyvinyl alcohols and various binders are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. A liquid was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［実施例２－１６、実施例２－１７］
　表３－２に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールとＰＶＤＦを仕込み、充分に混合溶解、または混合分散した。その後、＃８５０と３００Ｊを重量比１対１で混合して得たカーボンブラック、または、３００Ｊと６００ＪＤを重量比１対１で混合して得たカーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-16, Example 2-17]
According to the composition shown in Table 3-2, NMP, polyvinyl alcohol, and PVDF were charged into a glass bottle and mixed and dissolved or dispersed sufficiently. Thereafter, carbon black obtained by mixing # 850 and 300J at a weight ratio of 1: 1, or carbon black obtained by mixing 300J and 600JD at a weight ratio of 1: 1, was added, and dispersed with a homogenizer for 1 hour. Each carbon black dispersion was obtained. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［実施例２－１８］
　表３－２に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコールを仕込み、充分に混合溶解した。次いで、カーボンブラックとＰＶＤＦとを均質に混合した粉体混合品を調製し、これを事前に調製したポリビニルアルコールのＮＭＰ溶液に添加した。その後、ホモジナイザーで１時間分散し、カーボンブラック分散液を得た。粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-18]
According to the composition shown in Table 3-2, NMP and polyvinyl alcohol were charged into a glass bottle and thoroughly mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to an NMP solution of polyvinyl alcohol prepared in advance. Then, it disperse | distributed for 1 hour with the homogenizer, and obtained the carbon black dispersion liquid. There were no coarse particles, the viscosity was low, and the storage stability was good.
［実施例２－１９］
　表３－２に示す組成に従い、ガラス瓶に実施例１－２のカーボンブラック分散液を５７部、ＰＶＤＦを６部、ＮＭＰを３７部加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。 [Example 2-19]
According to the composition shown in Table 3-2, 57 parts of the carbon black dispersion liquid of Example 1-2, 6 parts of PVDF and 37 parts of NMP were added to a glass bottle and dispersed with a homogenizer for 1 hour to obtain each carbon black dispersion liquid. It was. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［比較例２－１～比較例２－３、参考例２－１］
　表３－２に示す組成に従い、ガラス瓶にＮＭＰと、各種ポリビニルアルコールとＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。しかし、得られた分散液の粘度は、バインダーを添加せずに調製した場合と同様に高粘度であり、カーボンブラックおよびバインダー濃度のさらなる向上はできないことが明らかとなった。 [Comparative Examples 2-1 to 2-3, Reference Example 2-1]
In accordance with the composition shown in Table 3-2, NMP, various polyvinyl alcohols and PVDF are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, carbon black is added and dispersed for 1 hour with a homogenizer. Got. However, it was revealed that the viscosity of the obtained dispersion was as high as that prepared without adding a binder, and the carbon black and binder concentrations could not be further improved.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　表３－２より、ＮＭＰに溶解、または分散可能な樹脂をバインダーとして用いた場合、得られるカーボンブラック分散液の性状は、表１のバインダーを添加せずに分散液を調製した場合と同様に、高濃度かつ低粘度であり、貯蔵安定性も良好な分散液を得られることが分かる。 From Table 3-2, when a resin that can be dissolved or dispersed in NMP is used as a binder, the properties of the resulting carbon black dispersion are the same as in the case of preparing the dispersion without adding the binder in Table 1. It can be seen that a dispersion having high concentration and low viscosity and good storage stability can be obtained.
＜正極活物質または負極活物質を含むカーボンブラック分散液の調製＞
［実施例３－１～実施例３－１４］
　表３－３に示す組成に従い、実施例２－１～実施例２－１４で得たバインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＬＣＯを多量に添加することができ、また、得られた混合液も低粘度な状態であった。 <Preparation of carbon black dispersion containing positive electrode active material or negative electrode active material>
[Example 3-1 to Example 3-14]
In accordance with the composition shown in Table 3-3, the carbon black dispersion containing the binder obtained in Example 2-1 to Example 2-14 was charged with LCO as the positive electrode active material and thoroughly mixed with a disper, Each mixture was obtained. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
［実施例３－１５］
　粒状品を１．７１部、ＰＶＤＦを２．５６部、ＰＶＡ－５０５を０．２６部、ＬＣＯを５６．７部、均質に混合した粉体混合品を調製後、ＮＭＰ３８．７７部に対して粉体混合品全量の半分を添加し、プラネタリーミキサーにて３０分間処理を行った。次いで、残った粉体混合品の半分を添加してプラネタリーミキサーにて３０分間処理し、その後、残った粉体混合品を全て添加してプラネタリーミキサーにて１時間処理することにより、正極活物質であるＬＣＯを含有したカーボンブラック分散液を得た。得られた液は、実施例３－２の場合と同様、低粘度な状態であった。 [Example 3-15]
After preparing a powder mixture with 1.71 parts of granular product, 2.56 parts of PVDF, 0.26 part of PVA-505, 56.7 parts of LCO and homogeneously mixed, 38.77 parts of NMP Half of the total amount of the powder mixture was added and treated for 30 minutes with a planetary mixer. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 3-2.
［実施例３－１６～実施例３－２０］
　表３－３に示す組成に従い、実施例２－１～実施例２－４、および実施例２－７で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質である黒鉛を仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、黒鉛を多量に添加することができ、また、得られた混合液も低粘度な状態であった。 [Example 3-16 to Example 3-20]
In accordance with the composition shown in Table 3-3, graphite as a negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Examples 2-1 to 2-4 and Example 2-7. The mixture was sufficiently mixed with a disper to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of graphite could be added, and the resulting mixture was also in a low viscosity state.
［比較例３－１～比較例３－４］
　表３－３に示す組成に従い、比較例２－１～比較例２－３、および参考例２－１で得た、バインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３－１～実施例３－１４と比較して、ＬＣＯを添加した際の粘度値の上昇が大きく、また、著しく高粘度な状態であった。 [Comparative Examples 3-1 to 3-4]
In accordance with the composition shown in Table 3-3, LCO as a positive electrode active material was charged into the carbon black dispersion containing the binder obtained in Comparative Example 2-1 to Comparative Example 2-3 and Reference Example 2-1. The mixture was sufficiently mixed with a disper to obtain each mixture. In any case, since the viscosity value of the carbon black dispersion used was high, the increase in the viscosity value when LCO was added was larger than that in Examples 3-1 to 3-14, and the carbon black dispersion was remarkably high. It was in a viscous state.
［比較例３－５～比較例３－７］
　表３－３に示す組成に従い、比較例２－１～比較例２－３で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質である黒鉛を仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３－１６～実施例３－２０と比較して、黒鉛を添加した際の粘度値の上昇が大きく、また、著しく高粘度な状態であった。 [Comparative Examples 3-5 to 3-7]
In accordance with the composition shown in Table 3-3, graphite as the negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Comparative Examples 2-1 to 2-3, and thoroughly mixed with a disper. Each liquid mixture was obtained. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when graphite is added is larger than that in Examples 3-16 to 3-20, and it is remarkably high. It was in a viscous state.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
＜電池電極合材層の作製＞
　上記の各実施例、比較例で得られた正極活物質または負極活物質を含むカーボンブラック分散液を電池電極合材液として、第１の発明で説明した方法に従って電池電極合材層を作製し、その評価を行った。なお、塗膜外観で「△」は「斑模様あり（可）」を意味し、塗膜外観が著しく不良で測定不可の場合は数値なし（－）とした。 <Preparation of battery electrode composite layer>
Using the carbon black dispersion liquid containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid, a battery electrode mixture layer was prepared according to the method described in the first invention. The evaluation was performed. In the appearance of the coating film, “Δ” means “with spotted pattern (possible)”. When the appearance of the coating film was extremely poor and could not be measured, no value was given (−).
［実施例４－１～実施例４－１４、比較例４－１～比較例４－３］
　正極合材液として、実施例３－１～実施例３－１４、および比較例３－１～比較例３－３で得た電池電極合材液を使用して、正極合材層（電池電極合材層）を作製した。評価結果を表３－４に示した。 [Example 4-1 to Example 4-14, Comparative Example 4-1 to Comparative Example 4-3]
Using the battery electrode mixture liquids obtained in Examples 3-1 to 3-14 and Comparative Examples 3-1 to 3-3 as the positive electrode mixture liquid, the positive electrode mixture layer (battery electrode) A composite layer) was prepared. The evaluation results are shown in Table 3-4.
［実施例４－１５～実施例４－１９、比較例４－４～比較例４－６］
　負極合材液として、実施例３－１６～実施例３－２０、および比較例３－５～比較例３－７で得た電池電極合材液を使用して、負極合材層（電池電極合材層）を作製した。評価結果を表３－４に示した。 [Example 4-15 to Example 4-19, Comparative Example 4-4 to Comparative Example 4-6]
Using the battery electrode mixture liquids obtained in Examples 3-16 to 3-20 and Comparative Examples 3-5 to 3-7 as the negative electrode mixture liquid, the negative electrode mixture layer (battery electrode) A composite layer) was prepared. The evaluation results are shown in Table 3-4.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　表３－４より、実施例４－１～実施例４－１９の電池電極合材層は、比較例４－１～比較例４－６の電池電極合材層と比較して塗膜外観が良好であり、さらに、塗膜の表面抵抗が優れていることが明らかとなった。比較例４－１～比較例４－６では、使用した電極合材液の粘度が高すぎるために塗工が困難であり、さらに、比較例４－３および比較例４－６では、多量に含まれるポリビニルアルコールが絶縁成分として機能した結果、表面抵抗値が高くなったものと考えられる。 From Table 3-4, the battery electrode composite layers of Examples 4-1 to 4-19 have an appearance of the coating film as compared with the battery electrode composite layers of Comparative Examples 4-1 to 4-6. It was clear that the surface resistance of the coating film was excellent. In Comparative Examples 4-1 to 4-6, the viscosity of the electrode mixture solution used was too high to be applied, and in Comparative Examples 4-3 and 4-6, a large amount As a result of the contained polyvinyl alcohol functioning as an insulating component, the surface resistance value is considered to have increased.
＜リチウムイオン二次電池正極評価用セルの組み立て＞
［実施例５－１～実施例５－１４、比較例５－１～比較例５－３］
　先に調製した電池電極合材液（実施例３－１～実施例３－１４、および比較例３－１～比較例３－３の正極合材液）を用いて、第１の発明で説明した方法に従って正極評価用セルを組み立てた。 <Assembly of lithium ion secondary battery positive electrode evaluation cell>
[Example 5-1 to Example 5-14, Comparative Example 5-1 to Comparative Example 5-3]
Using the previously prepared battery electrode mixture liquids (the positive electrode mixture liquids of Examples 3-1 to 3-14 and Comparative Examples 3-1 to 3-3), the first invention will be described. A positive electrode evaluation cell was assembled according to the method described above.
＜リチウムイオン二次電池負極評価用セルの組み立て＞
［実施例５－１５～実施例５－１９、比較例５－４～比較例５－６］
　先に調製した電池電極合材液（実施例３－１６～実施例３－２０、および比較例３－５～比較例３－７の負極合材液）を用いて、第１の発明で説明した方法に従って負極評価用セルを組み立てた。ただし、集電体としてアルミ箔の代わりに銅箔を使用した。 <Assembly of lithium ion secondary battery negative electrode evaluation cell>
[Examples 5-15 to 5-19, Comparative Example 5-4 to Comparative Example 5-6]
Using the previously prepared battery electrode mixture liquids (negative electrode mixture liquids of Examples 3-16 to 3-20 and Comparative Examples 3-5 to 3-7), the first invention will explain A negative electrode evaluation cell was assembled according to the method described above. However, copper foil was used instead of aluminum foil as a current collector.
＜リチウムイオン二次電池正極特性評価＞
　第１の発明で説明した方法に従って、正極特性評価を行った。ただし、正極評価用セルの温度は２５℃ではなく、１５℃にした。集電体からの塗膜の剥離やショート等により正常な充放電曲線が得られず、容量が求められなかった場合は数値なし（－）とした。評価結果を表３－５に示した。 <Characteristic evaluation of lithium ion secondary battery positive electrode>
The positive electrode characteristics were evaluated according to the method described in the first invention. However, the temperature of the positive electrode evaluation cell was set to 15 ° C. instead of 25 ° C. When a normal charge / discharge curve could not be obtained due to peeling or short-circuiting of the coating film from the current collector and the capacity could not be obtained, no value was given (−). The evaluation results are shown in Table 3-5.
＜リチウムイオン二次電池負極特性評価＞
　第１の発明で説明した方法に従って、負極特性評価を行った。ただし、負極評価用セルの温度は２５℃ではなく１５℃にして、定電流定電圧充電の上限電圧を０．５Ｖにするのではなく下限電圧を０．５Ｖにした。評価結果を表３－５に示した。 <Evaluation of lithium ion secondary battery negative electrode characteristics>
According to the method described in the first invention, negative electrode characteristics were evaluated. However, the temperature of the negative electrode evaluation cell was set to 15 ° C. instead of 25 ° C., and the upper limit voltage for constant current and constant voltage charging was not set to 0.5V, but the lower limit voltage was set to 0.5V. The evaluation results are shown in Table 3-5.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　表３－５より、本発明の電極を使用した実施例５－１～実施例５－１４および実施例５－１５～実施例５－１９は、比較例５－１～比較例５－３および比較例５－４～比較例５－６と比較して、塗膜外観が良好であり、かつ、集電体からの剥がれも無く、密着性も良好であることが判明した。さらに、５０サイクル後の容量維持率についても、良好な結果であった。一方、比較例５－１～比較例５－６は、良好な塗膜を得ることができなかったため、正極特性および負極特性を評価することができなかった。 From Table 3-5, Example 5-1 to Example 5-14 and Example 5-15 to Example 5-19 using the electrode of the present invention are shown in Comparative Example 5-1 to Comparative Example 5-3 and As compared with Comparative Examples 5-4 to 5-6, it was found that the appearance of the coating film was good, there was no peeling from the current collector, and the adhesion was good. Furthermore, the capacity retention rate after 50 cycles was also a good result. On the other hand, Comparative Example 5-1 to Comparative Example 5-6 were unable to obtain a good coating film, so that the positive electrode characteristics and the negative electrode characteristics could not be evaluated.

Claims (16)

  1. 　カーボンブラックと、分散剤としてのポリビニルアルコールと、溶剤としてのＮ－メチル－２－ピロリドンとを含んでなるカーボンブラック分散液であって、ポリビニルアルコールのけん化度が６０～８５ｍｏｌ％であり、カーボンブラックのＢＥＴ比表面積をＸｍ２／ｇ、カーボンブラック１ｇに対するポリビニルアルコールの添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲であり、カーボンブラック１００重量部に対するポリビニルアルコールが０．６５重量部以上、１５重量部以下であることを特徴とする、カーボンブラック分散液。 A carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is 60 to 85 mol%, When the BET specific surface area of Xm 2 / g and the amount of polyvinyl alcohol added to 1 g of carbon black is aXg, a is in the range of 0.00017 ≦ a ≦ 0.00256, and polyvinyl alcohol relative to 100 parts by weight of carbon black The carbon black dispersion liquid is characterized in that is 0.65 parts by weight or more and 15 parts by weight or less.
  2. 　カーボンブラックと、分散剤としての、ポリビニルアルコールおよびトリアジン誘導体、またはポリビニルアルコールおよび有機色素誘導体と、溶剤としてのＮ－メチル－２－ピロリドンとを含有するカーボンブラック分散液であって、カーボンブラック１００重量部に対する分散剤の合計量が５０重量部以下であり、ポリビニルアルコールが、下記一般式（Ａ）で表される繰り返し単位を重合体鎖中に５０～９５ｍｏｌ％含有することを特徴とする、カーボンブラック分散液。
    　一般式（Ａ）
    Figure JPOXMLDOC01-appb-C000001
         A carbon black dispersion containing carbon black, polyvinyl alcohol and a triazine derivative, or polyvinyl alcohol and an organic dye derivative as a dispersant, and N-methyl-2-pyrrolidone as a solvent, and having a carbon black weight of 100 Carbon is characterized in that the total amount of the dispersant is 50 parts by weight or less with respect to parts, and the polyvinyl alcohol contains 50 to 95 mol% of repeating units represented by the following general formula (A) in the polymer chain. Black dispersion.
    Formula (A)
    Figure JPOXMLDOC01-appb-C000001
  3. 　上記分散剤が、ポリビニルアルコールおよびトリアジン誘導体であることを特徴とする、請求項２記載のカーボンブラック分散液。 3. The carbon black dispersion according to claim 2, wherein the dispersant is polyvinyl alcohol and a triazine derivative.
  4. 　上記ポリビニルアルコールが、上記一般式（Ａ）で表される繰り返し単位を重合体鎖中に５５～８５ｍｏｌ％含有することを特徴とする、請求項２または３記載のカーボンブラ
    ック分散液。     4. The carbon black dispersion according to claim 2, wherein the polyvinyl alcohol contains 55 to 85 mol% of the repeating unit represented by the general formula (A) in the polymer chain.
  5. 　カーボンブラック１００重量部に対する分散剤の合計量が０．５重量部以上、４０重量部以下であることを特徴とする、請求項２～４いずれか記載のカーボンブラック分散液。 The carbon black dispersion according to any one of claims 2 to 4, wherein the total amount of the dispersant is from 0.5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the carbon black.
  6. 　カーボンブラック１００重量部に対するポリビニルアルコールが０．２重量部以上、２０重量部以下であることを特徴とする、請求項２～５いずれか記載のカーボンブラック分散液。 The carbon black dispersion according to any one of claims 2 to 5, wherein the polyvinyl alcohol is from 0.2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the carbon black.
  7. 　カーボンブラック１００重量部に対するポリビニルアルコールが０．２重量部以上、８重量部以下であることを特徴とする、請求項２～５いずれか記載のカーボンブラック分散液。 The carbon black dispersion according to any one of claims 2 to 5, wherein the polyvinyl alcohol is 0.2 to 8 parts by weight with respect to 100 parts by weight of carbon black.
  8. 　カーボンブラックと、分散剤としてのポリビニルアルコールと、溶剤としてのＮ－メチル－２－ピロリドンとを含んでなるカーボンブラック分散液であって、ポリビニルアルコールのけん化度が６０～８５ｍｏｌ％であり、カーボンブラックのＢＥＴ比表面積が３０～１５００ｍ２／ｇであり、カーボンブラック１００重量部に対するポリビニルアルコールが８重量部を超え、４０重量部以下であることを特徴とする、カーボンブラック分散液。 A carbon black dispersion comprising carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the saponification degree of polyvinyl alcohol is 60 to 85 mol%, A carbon black dispersion characterized by having a BET specific surface area of 30 to 1500 m 2 / g and a polyvinyl alcohol content of more than 8 parts by weight and 40 parts by weight or less based on 100 parts by weight of carbon black.
  9. 　カーボンブラック１００重量部に対するポリビニルアルコールが８重量部を超え、２５重量部以下であることを特徴とする、請求項８記載のカーボンブラック分散液。 The carbon black dispersion according to claim 8, wherein the polyvinyl alcohol is more than 8 parts by weight and 25 parts by weight or less based on 100 parts by weight of carbon black.
  10. 　上記カーボンブラックのＢＥＴ比表面積が２００～１５００ｍ２／ｇであることを特徴とする、請求項８または９記載のカーボンブラック分散液。 The carbon black dispersion according to claim 8 or 9, wherein the carbon black has a BET specific surface area of 200 to 1500 m 2 / g.
  11. 　上記カーボンブラックのＢＥＴ比表面積が５００～１５００ｍ２／ｇであることを特徴とする、請求項８または９記載のカーボンブラック分散液。 The carbon black dispersion according to claim 8 or 9, wherein the carbon black has a BET specific surface area of 500 to 1500 m 2 / g.
  12. 　上記カーボンブラックが中空カーボンブラックであることを特徴とする、請求項８～１１いずれか記載のカーボンブラック分散液。 12. The carbon black dispersion according to claim 8, wherein the carbon black is hollow carbon black.
  13. 　分散液中に含まれる全固形成分の量１００重量部に対するポリビニルアルコールが０．０５重量部以上、２重量部未満であることを特徴とする、請求項８～１２いずれか記載のカーボンブラック分散液。 The carbon black dispersion according to any one of claims 8 to 12, wherein the polyvinyl alcohol is 0.05 parts by weight or more and less than 2 parts by weight with respect to 100 parts by weight of the total solid components contained in the dispersion. .
  14. 　請求項１～１３いずれか記載のカーボンブラック分散液に、さらに、正極活物質または負極活物質を含有してなる電池用カーボンブラック分散液。 A carbon black dispersion for a battery comprising the carbon black dispersion according to any one of claims 1 to 13 and further containing a positive electrode active material or a negative electrode active material.
  15. 　請求項１～１３いずれか記載のカーボンブラック分散液または請求項１４記載の電池用カーボンブラック分散液を塗布してなる電池電極合材層。 A battery electrode composite layer formed by applying the carbon black dispersion according to any one of claims 1 to 13 or the carbon black dispersion for batteries according to claim 14.
  16. 　集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウムイオン二次電池であって、正極および負極の少なくとも一方が、請求項１５記載の電池電極合材層を具備してなるリチウムイオン二次電池。 A lithium ion secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium, wherein the positive electrode and the negative electrode are at least A lithium ion secondary battery, one of which comprises the battery electrode mixture layer according to claim 15.
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US11469421B2 (en) 2020-09-03 2022-10-11 Toyo Ink Sc Holdings Co., Ltd. Conductive material dispersion, binder resin-containing conductive material dispersion, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery
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