WO2013147087A1 - Composition de dispersion de carbone fin et composite polyimide/carbone fin l'utilisant - Google Patents

Composition de dispersion de carbone fin et composite polyimide/carbone fin l'utilisant Download PDF

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WO2013147087A1
WO2013147087A1 PCT/JP2013/059386 JP2013059386W WO2013147087A1 WO 2013147087 A1 WO2013147087 A1 WO 2013147087A1 JP 2013059386 W JP2013059386 W JP 2013059386W WO 2013147087 A1 WO2013147087 A1 WO 2013147087A1
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fine carbon
dispersion composition
composition according
dispersant
polyimide
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PCT/JP2013/059386
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English (en)
Japanese (ja)
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健 川岸
福永　謙二
範 高崎
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宇部興産株式会社
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Priority to JP2014508062A priority Critical patent/JP6156363B2/ja
Publication of WO2013147087A1 publication Critical patent/WO2013147087A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • 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 fine carbon dispersion composition obtained using a fine carbon dispersant containing a polyimide precursor. Furthermore, the present invention relates to a polyimide-fine carbon composite and a conductive binder resin composition obtained from the fine carbon dispersion composition.
  • Fine carbon materials such as carbon blacks, ketjen black, fullerene, graphene and carbon nanotubes are used in a wide range of fields such as electronics and energy due to their unique electrical properties and thermal conductivity.
  • carbon nanotubes are tube-like carbon having a diameter of 1 ⁇ m or less, and are expected to be further expanded to various applications due to high conductivity, tensile strength, heat resistance and the like based on their unique structure.
  • the fine carbon is uniformly dispersed without agglomeration.
  • fine carbon materials generally tend to form aggregates due to their small size and surface area, and uniform dispersion in a solution is difficult.
  • carbon nanotubes are obtained as aggregates (also referred to as bundles) that are entangled with each other, and because of their cohesive force (van der Waals force), they become bundles and ropes. Since a smooth surface reduces the affinity for the solvent, it is difficult to disperse in both polar and nonpolar solvents.
  • Patent Document 1 a method of dispersing carbon nanotubes in acetone while applying ultrasonic waves.
  • Patent Document 1 a method of dispersing carbon nanotubes in acetone while applying ultrasonic waves.
  • the carbon nanotubes start to aggregate when the irradiation ends, and when the concentration of the carbon nanotubes increases, they aggregate.
  • Non-Patent Documents 1 and 2 Ultrasonic treatment in anionic surfactant sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate aqueous solution adsorbs the hydrophobicity of the surface of the carbon nanotubes and the hydrophobic part of the surfactant, and the hydrophilic part on the outside. It has also been reported that it is formed and dispersed in an aqueous solution (Non-Patent Documents 1 and 2).
  • Non-patent Document 3 ultrasonic treatment in water or N-methyl-2-pyrrolidone (NMP) using Triton (trademark) -X-100, which is a nonionic surfactant, has been proposed (Non-patent Document 3).
  • Patent Document 2 In addition, dispersion in water and NMP using a water-soluble polymer polyvinylpyrrolidone (PVP) instead of a surfactant has been proposed (Non-patent Documents 4 and 3).
  • PVP water-soluble polymer polyvinylpyrrolidone
  • an ionic impurity such as a metal salt is mixed in the surfactant, which may adversely affect the electrical characteristics, and the heat resistance of the surfactant and the polymer dispersant itself.
  • the thermal decomposition of the dispersant is concerned in use at low temperatures.
  • a method has been proposed in which a carbon nanotube dispersion is produced using a nonionic surfactant or polyvinylpyrrolidone (PVP) as a dispersant, and this is mixed with soluble polyimide or polyamic acid to improve dispersibility (patent)
  • PVP polyvinylpyrrolidone
  • Patent Document 7 As a general system that does not use a dispersant, solubilization of carbon nanotubes using a polyimide having a specific structure has been proposed (Patent Document 7). However, since this polyimide introduces a functional group such as sulfonic acid or sulfonate in the side chain in order to impart solubility to a solvent, high heat resistance as a polyimide cannot be expected.
  • the present invention relates to the following matters.
  • a fine carbon dispersion composition comprising:
  • B is a tetravalent unit derived from a tetracarboxylic acid component
  • A is a divalent unit derived from a diamine component.
  • the structure represented by A includes at least one structure selected from the structures represented by the following chemical formulas (3), (4), and (5): The fine carbon dispersion composition as described.
  • the basic compound contains at least one selected from the group consisting of imidazoles, alkylamines, piperazines, guanidine and guanidine salts, carboxyl-substituted alkylamines, piperidines and pyrrolidines; 4.
  • the fine carbon dispersion composition according to any one of 3 above.
  • the imidazoles are 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1 6.
  • the alkylamine is at least one compound selected from the group consisting of trimethylamine, diethylamine, dimethylethylamine, triethylamine, N-propylethylamine, N-butylethylamine, N, N-dimethylcyclohexylamine, and tributylamine.
  • the fine carbon dispersion composition according to any one of claims 4 to 6, wherein:
  • Fine carbon comprising a polyimide precursor having a repeating unit represented by the general formula (1) and a basic compound having a pKa of 7.5 times or more with respect to the carboxyl group of the polyimide precursor of 7.5 or more
  • a first step of preparing a fine carbon dispersant solution in which the dispersant is dissolved in a polar solvent A second step of mixing the fine carbon dispersant solution and fine carbon, and dispersing and mixing the fine carbon;
  • the manufacturing method of the fine carbon dispersion composition characterized by including.
  • a polyimide-fine carbon composite obtained by heat-treating the fine carbon dispersion composition according to any one of 1 to 12 above.
  • a film of a polyimide-fine carbon composite obtained by heat-treating the fine carbon dispersion composition according to any one of 1 to 12 above.
  • a conductive binder resin composition comprising the fine carbon dispersion composition according to any one of 1 to 12 above.
  • a method for producing a polyimide-fine carbon composite comprising a step of mixing and heating the fine carbon dispersion composition according to any one of 1 to 12 above, a tetracarboxylic acid component, and a diamine component.
  • a method for producing a polyimide-fine carbon composite comprising a step of mixing the fine carbon dispersion composition according to any one of 1 to 12 above and a polyimide precursor having a repeating unit represented by the general formula (1). .
  • the present invention makes it possible to uniformly disperse fine carbon, which has been difficult to disperse in a solvent, without using a low heat-resistant dispersant such as a surfactant or polyvinylpyrrolidone.
  • the dispersant for fine carbon in the present invention can be converted to a polyimide having high heat resistance by imidization, and functions as a dispersant having high heat resistance. Further, by imidizing the fine carbon dispersion composition of the present invention, a polyimide-fine carbon composite can be easily obtained.
  • the fine carbon dispersion composition of the present invention comprises fine carbon having good conductivity and a polyimide precursor having excellent heat resistance, mechanical properties, and solvent resistance, it can be used as a binder for various battery electrodes. It can be used suitably.
  • the polyimide precursor having the repeating unit represented by the general formula (1) and a pKa of 0.7 times equivalent or more with respect to the carboxyl group of the polyimide precursor is 7.5.
  • the fine carbon dispersant in the present invention contains a polyimide precursor (polyamic acid) having a repeating unit represented by the general formula (1) and a basic compound having a pKa of 7.5 or more.
  • a polyimide precursor polyamic acid
  • containing may mean that a polyimide or the like reacts with a basic compound to form a salt or the like.
  • the polyimide precursor having the repeating unit represented by the general formula (1) may be simply referred to as “polyimide precursor” or “polyamic acid”.
  • B is a tetravalent unit resulting from the tetracarboxylic acid component.
  • A is a divalent unit derived from the diamine component. The units constituting the polyimide precursor will be described in detail below.
  • Unit B is a tetravalent unit resulting from the tetracarboxylic acid component.
  • the tetracarboxylic acid component is not particularly limited as long as it can produce a polyimide precursor and exhibits good fine carbon dispersibility, but is preferably a tetracarboxylic dianhydride, for example, 3, 3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), 2,2 ', 3 3'-biphenyltetracarboxylic dianhydride (i-BPDA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2 ', 3,3
  • s-BPDA 4,4'-biphenyltetracarboxylic dian
  • Unit A is a divalent unit resulting from the diamine component.
  • the structure represented by A includes at least one structure selected from the structures represented by the chemical formulas (3), (4), and (5).
  • the diamine component is not particularly limited as long as it can produce a polyimide precursor and exhibits good fine carbon dispersibility. For example, p-phenylenediamine (PPD), m-phenylenediamine (MPD), etc.
  • PPD PPD
  • ODA organic light-sensitive diamine
  • DAPBI DAPBI
  • the alicyclic diamine isophorone diamine, cyclohexane diamine, or the like can be appropriately used as long as the polymerization property and dispersibility are not hindered.
  • the basic compound used in the present invention may be an organic compound or an inorganic compound as long as it has a pKa of about 7.5 or more.
  • a basic compound having a pKa of 7.5 or more may be simply referred to as “basic compound”.
  • an ionic impurity such as a metal salt is mixed into the product, so it may not be preferred depending on the application. Therefore, an organic compound is preferable, and a nitrogen-containing organic compound is particularly preferable.
  • Examples of usable nitrogen-containing organic compounds having a pKa of 7.5 or more include imidazoles, alkylamines, piperazines, guanidine and guanidine salts, carboxyl-substituted alkylamines, piperidines, pyrrolidines and the like. .
  • imidazoles and alkylamines are particularly preferable from the viewpoints of dispersibility of fine carbon, solubility of a dispersant for fine carbon when used as an aqueous solution, and contribution to catalytic action during imidization described later.
  • the amino group-containing alcohol is a basic compound having a pKa of 7.5 or more and is effective in improving dispersibility.
  • the hydrolysis of the polyimide precursor is accelerated and the stability of the dispersion is deteriorated. Therefore, it is preferable not to use it.
  • the basic compound used in the present invention has a pKa of 7.5 or more.
  • the dispersibility of fine carbon is insufficient only with a mixture of a compound having a small pKa such as N-methyl-2-pyrrolidone and a polyamic acid (polyimide precursor).
  • the basic compound used in the present invention also contributes to the solubility of the polyimide precursor when the fine carbon dispersant is used in an aqueous solvent. This is presumably because the solubility in water is enhanced by forming a salt with a carboxyl group of polyamic acid (polyimide precursor).
  • a compound having a small pKa such as N-methyl-2-pyrrolidone described above has insufficient solubility in water, and an aqueous dispersant for fine carbon cannot be obtained. Therefore, it is considered important to have a pKa of about 7.5 or more.
  • imidazoles examples include 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1 Specific examples include -methyl-4-ethylimidazole and 5-methylbenzimidazole, and 1,2-dimethylimidazole can be particularly preferably used.
  • the imidazoles may be one kind of compound selected from the above compound group or a mixture of plural kinds of compounds.
  • a compound represented by the following chemical formula (10) can be preferably exemplified.
  • X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least two of X 1 to X 4
  • imidazoles which are alkyl groups having 1 to 5 carbon atoms that is, imidazoles having two or more alkyl groups as substituents are more preferable.
  • the existing alkyl groups are independently of each other a branched or straight chain alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, or an alicyclic ring having 3 to 6 carbon atoms, particularly 6 carbon atoms.
  • a primary to tertiary amine having a formula group is preferred, and an alkyl group is more preferred so that the total number of carbon atoms in the molecule is 9 or less.
  • alkylamines include trimethylamine, diethylamine, dimethylethylamine, triethylamine, N-propylethylamine, N-butylethylamine, N, N-dimethylcyclohexylamine, tributylamine, and a mixture of two or more thereof.
  • triethylamine can be preferably used.
  • alkyl group may be substituted with an amino group, and in that case, it contains two or more primary to tertiary amino groups, and examples thereof include di- or triamines such as ethylenediamine and diethylenediaminetriamine.
  • the piperazine is preferably piperazine which is unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further comprises an amino group. You may have.
  • the substitution position of the alkyl group may be any position in the piperazine ring, and may be on a nitrogen atom or on a carbon atom.
  • piperazine 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 2-methylpiperazine, 2 -Ethylpiperazine, 3-propylpiperazine, 2,6-dimethylpiperazine, 2,6-diethylpiperazine, 2,6-dipropylpiperazine, 2,5-dimethylpiperazine, 2,5-diethylpiperazine, 2,5-di And propylpiperazine.
  • Piperazine substituted with an aminoalkyl group such as 1-aminoethylpiperazine is also preferred.
  • guanidine and guanidine salts examples include guanidine, salts of weak acids and guanidine carbonate, guanidine oxalate, and guanidine acetate.
  • carboxyl-substituted alkylamines include compounds in which the hydrogen of the alkyl group in the above alkylamine is substituted with COOH, such as ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid.
  • 1,3-diamino-2-hydroxypropanetetraacetic acid glycol etherdiaminetetraacetic acid, trans 1,2-cyclohexanediaminetetraacetic acid, hexamethylenediaminetetraacetic acid, dicarboxymethylglutamic acid, dicarboxymethylaspartic acid, S, S -Ethylenediamine disuccinic acid, ethylenediamine di (o-hydroxyphenyl) acetic acid, hydroxyethyliminodiacetic acid, ethylenediaminediacetic acid, iminodiacetic acid, ethylenediaminedipropionic acid, nitrilotriacetic acid, hydroxyethylenediamy Triacetate, nitrilotriacetate propionate, methyl glycine diacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the like.
  • a part or all of the carboxyl group may be
  • the piperidine is preferably piperidine which is unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further comprises an amino group. You may have.
  • the substitution position of the alkyl group may be any position in the piperidine ring, and may be on a nitrogen atom or on a carbon atom.
  • piperidine 1-methylpiperidine, 1-ethylpiperidine, 1-propylpiperidine, 2, 3 or 4-methylpiperidine, 2, 3 or 4-ethylpiperidine, 2,6-dimethylpiperidine, 2,6 -Diethylpiperidine, 2,6-dipropylpiperidine, 2,4-dimethylpiperidine, 2,4-diethylpiperidine and the like.
  • Piperidine substituted with an aminoalkyl group such as 1-aminoethylpiperidine is also preferred.
  • a compound in which —CH 2 — not adjacent to N is replaced by O, such as morpholine, is also preferable.
  • the pyrrolidines are preferably pyrrolidines that are unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further includes an amino group. You may have.
  • the substitution position of the alkyl group may be any position in the pyrrolidine ring, and may be on a nitrogen atom or a carbon atom.
  • pyrrolidine 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-propylpyrrolidine, 2 or 3-methylpyrrolidine, 2 or 3-ethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, Examples include 2,5-dipropylpyrrolidine, 2,4-dimethylpyrrolidine, 2,4-diethylpyrrolidine and the like.
  • Pyrrolidine substituted with an aminoalkyl group such as 1-aminoethylpyrrolidine is also preferable.
  • the metal salt having a pKa of 7.5 or more a salt of an alkali metal and a weak acid is preferable, and the alkali metal is preferably Na or K.
  • the weak acid includes carbonic acid, oxalic acid, acetic acid, phosphoric acid, An acid is preferable, and carbonic acid, oxalic acid, acetic acid, and phosphoric acid are particularly preferable.
  • sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium oxalate, potassium oxalate, sodium acetate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, etc. Can be mentioned.
  • any basic compound having a pKa of 7.5 or more can be used.
  • all pKa values have 7.5 or more. It is preferable.
  • the value of pKa can be easily searched by SciFinder (registered trademark) known as a search service based on a database such as chemical abstract.
  • SciFinder registered trademark
  • the values calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) were adopted.
  • the basic compound to be used may be one kind or a mixture of plural kinds.
  • the amount of the basic compound used in the present invention is preferably 0.7 times equivalent or more, more preferably 1 with respect to the carboxyl group of the polyamic acid produced by the reaction of the raw material tetracarboxylic dianhydride and diamine. It is 0.0 times equivalent or more, More preferably, it is 1.2 times equivalent or more. When the amount of the basic compound used is less than 0.7 times equivalent to the carboxyl group of the polyamic acid, the fine carbon dispersibility may not be sufficient. In addition, when the fine carbon dispersant is used in an aqueous solvent, it may not be easy to obtain a uniformly dissolved fine carbon dispersant.
  • the upper limit of the usage-amount of a basic compound is not specifically limited, Usually, it is less than 10 times equivalent with respect to the carboxyl group of polyamic acid, Preferably it is less than 5 times equivalent, More preferably, it is less than 3 times equivalent.
  • the amount of the basic compound used is too large, it becomes uneconomical and the storage stability of the fine carbon dispersant may be deteriorated.
  • regulates the quantity of a basic compound represents how many (how many molecules) a basic compound is used with respect to one carboxyl group of a polyamic acid.
  • the number of carboxyl groups in the polyamic acid is calculated as forming two carboxyl groups per molecule of the starting tetracarboxylic acid component.
  • the amount of the basic compound used in the present invention is preferably 1.4 times mol or more, more preferably, relative to the tetracarboxylic dianhydride of the raw material (relative to the tetracarboxylic acid component of the polyamic acid). It is 2.0 times mol or more, More preferably, it is 2.4 times mol or more.
  • the basic compound used in the present invention only improves the dispersibility of fine carbon by forming a salt with a carboxyl group of a polyamic acid (polyimide precursor) produced by a reaction between a raw material tetracarboxylic dianhydride and a diamine.
  • polyimide precursor polyamic acid
  • the polyimide precursor is imidized (dehydrated ring-closing) into a polyimide, it has a very high catalytic action.
  • the dispersant for fine carbon used in the present invention can provide a polyimide having high physical properties even when subjected to a heat treatment at a lower temperature and for a shorter time, and in particular, elongation and end tear resistance may be improved. Therefore, a good polyimide-fine carbon composite or conductive binder resin composition can be obtained.
  • the fine carbon dispersant of the present invention can suitably disperse fine carbon in a medium.
  • the medium include polar solvents. Specific examples include a protic polar solvent, an aprotic polar organic solvent, and a mixture of two or more thereof.
  • the polar solvent used in the present invention may be simply referred to as “solvent”.
  • the protic polar solvent is not particularly limited as long as the dispersant for fine carbon dissolves, but examples thereof include aliphatic alcohols such as water, methanol, ethanol, and propanol, phenol, m-cresol, 4-chlorophenol, and the like. Examples include phenols.
  • water is particularly preferable from the viewpoint of the solubility of the dispersant for fine carbon and environmental adaptability.
  • the aprotic polar organic solvent is not particularly limited as long as the dispersant for fine carbon dissolves.
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • Amide organic solvents such as dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphorotriamide, 1,2- Dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethylsulfoxide, Diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurine , Ani
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • mixtures thereof are particularly preferred from the viewpoint of environmental adaptability.
  • the fine carbon in the present invention means fine carbon powder containing carbon blacks such as furnace black, acetylene black, channel black and thermal black, ketjen black, fullerene, graphene and carbon nanotubes.
  • the size of the fine carbon is largely different from the shape of the fine carbon, and there are things that form secondary agglomerates, so it cannot be specified unconditionally, but it is about several nanometers to several hundred ⁇ m (that is, 1 nm)
  • the particle size is preferably 3 nm or more and 1 mm or less, preferably 800 ⁇ m or less, more preferably about 500 ⁇ m or less.
  • Carbon nanotubes are particularly preferred from the viewpoint of improving characteristics such as conductivity and thermal conductivity.
  • Carbon nanotubes means vapor grown carbon fiber (VGCF (registered trademark) -H), single-walled carbon nanotube (SWNT), multi-walled carbon nanotube (MWNT), etc. I can do it.
  • the method for producing carbon nanotubes is not particularly limited, and any conventionally known production method such as a thermal decomposition method using a catalyst, an arc discharge method, a laser evaporation method, and a CVD method such as HiPco method and CoMoCAT method, etc. A method may be adopted.
  • a thermal decomposition method using a catalyst such as a thermal decomposition method using a catalyst, an arc discharge method, a laser evaporation method, and a CVD method such as HiPco method and CoMoCAT method, etc.
  • a method may be adopted.
  • single-walled carbon nanotubes sold as reagents and commercially available multi-walled carbon nanotubes can also be used.
  • Examples of commercially available multi-wall carbon nanotubes include BN-1100 (Hyperion Catalysis International), NC7000 (Nanosil), C100 (Arkema), VGCF (registered trademark) -X (Showa Denko) ), Flotube 9000 (manufactured by Sea Nano Technology), AMC (registered trademark) (manufactured by Ube Industries), and the like.
  • the method for producing a fine carbon dispersion composition comprising the fine carbon dispersant of the present invention, fine carbon and a polar solvent is not particularly limited as long as the fine carbon is uniformly dispersed in the polar solvent.
  • the manufacturing method containing these is preferable.
  • the fine carbon dispersant can be obtained, for example, by mixing and reacting a polyimide precursor obtained by a known synthesis method with a basic compound having a pKa of 7.5 or more. Moreover, the dispersing agent for fine carbon can be directly synthesize
  • the synthesis of the polyimide precursor is performed by, for example, mixing an approximately equimolar aromatic tetracarboxylic dianhydride and an aromatic diamine in the amide organic solvent and polymerizing the polyimide precursor to the amide solvent.
  • a polyimide precursor solution in which is dissolved can be obtained.
  • it combines the two or more polyimide precursors in which either component is excessive, after combining each polyimide precursor solution, to obtain a polyimide precursor solution by mixing under reaction conditions You can also.
  • the polyimide precursor can be deposited by putting the polyimide precursor solution into a non-solvent or poor solvent of polyimide.
  • a fine carbon dispersant solution can be obtained by directly adding a predetermined amount of a basic compound to the polyimide precursor solution obtained by the above synthesis method and mixing them.
  • the dispersing agent solution for fine carbon can be obtained by adding a basic compound to the polyimide precursor solution which melt
  • the polyimide precursor and the basic compound are put into a solvent (for example, water), and mixed and dissolved to obtain a fine carbon dispersant solution. Can be obtained.
  • a solvent for example, water
  • a dispersant for fine carbon is produced very simply and directly by reacting a tetracarboxylic acid component and a diamine component in the presence of a basic compound in a solvent. It is also possible.
  • the dispersant for fine carbon is directly produced (polymerized) in water with low solubility of polyamic acid, the basic compound is previously present in water, so that the generated amic acid forms a salt and dissolves in water. Therefore, this method is particularly preferable.
  • the amount of the basic compound added at this time is less than 0.7 times equivalent to the carboxyl group of the polyamic acid, dissolution due to salt formation does not proceed, and a uniformly dissolved fine carbon dispersant is obtained. May not be easy.
  • This reaction is carried out at a relatively low temperature of 100 ° C. or less, preferably 80 ° C. or less in order to suppress the imidization reaction, using a tetracarboxylic acid component (tetracarboxylic dianhydride) and a diamine component in approximately equimolar amounts. .
  • the reaction temperature is usually 25 ° C. to 100 ° C.
  • reaction when the reaction is carried out in water, it is preferably 40 ° C to 80 ° C, more preferably 50 ° C to 80 ° C.
  • the reaction time is about 0.1 to 24 hours, preferably about 2 to 12 hours.
  • the reaction can be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas atmosphere, preferably in a nitrogen gas atmosphere.
  • tetracarboxylic acid component tetracarboxylic dianhydride
  • diamine component tetracarboxylic dianhydride
  • tetracarboxylic acid component / diamine component Preferably, it is about 0.95 to 1.05.
  • the fine carbon dispersant solution obtained by any of the above methods can be used for the dispersion and mixing of fine carbon by diluting and concentrating as necessary. Further, after the fine carbon dispersant and the solvent are separated, they may be dissolved in a predetermined solvent.
  • the method for dispersing and mixing fine carbon in the fine carbon dispersant solution is not particularly limited.
  • the fine carbon can be dispersed and mixed by performing treatments such as ultrasonic treatment and stirring / dispersion treatment after the fine carbon is introduced into the dispersant solution for fine carbon.
  • ultrasonic treatment a bus type or probe type sonicator can be used.
  • stirring / dispersing method high-speed stirring such as a homomixer or a homogenizer, a media type wet dispersing device such as an attritor, a bead mill, a sand mill, or a planetary mill, or a high-pressure dispersion processing device such as a wet jet mill can be used. .
  • ultrasonic treatment is particularly suitable.
  • the treatment time of the ultrasonic treatment is appropriately determined depending on the treatment method, the kind and addition amount of fine carbon, and the kind and addition amount of the fine carbon dispersant to be used, and the treatment is preferably about 10 minutes to 5 hours, preferably 10 minutes to A treatment for 3 hours is more preferable.
  • treatment with a media-type wet dispersion device such as an attritor, a bead mill, a sand mill, or a planetary mill is particularly suitable. .
  • the treatment time by the media-type wet dispersion apparatus is appropriately determined depending on the treatment method, the type and addition amount of fine carbon, and the type and addition amount of fine carbon dispersant, but a treatment of about 30 minutes to 50 hours is preferable. If the treatment time is too short, the fine carbon dispersion may be insufficient. If the treatment time is too long, fine carbon may be damaged by excessive energy. In particular, when carbon nanotubes or the like are used, it is known that the tube breaks with the lapse of processing time, and caution is required.
  • the fine carbon dispersion composition of the present invention it is preferable to remove a coarse product remaining without being partially dispersed after the fine carbon dispersion treatment.
  • a method for removing the remaining coarse material is not particularly limited, and examples thereof include centrifugation and filter treatment.
  • the filter used in the filter treatment is not particularly limited, and a glass fiber filter, a membrane filter, or the like can be used.
  • the retained particle diameter of the filter can be appropriately determined according to the purpose.
  • the retained particle size of the filter can be obtained from the leaked particle size when barium sulfate or the like defined in JIS 3801 is naturally filtered. For example, when applied to applications requiring transparency, the smaller the retained particle diameter of the filter, the better, but generally a retained particle diameter of 0.1 to 5.0 ⁇ m can be used.
  • the amount of fine carbon is not particularly limited as long as the fine carbon is uniformly dispersed.
  • SWNT is used as fine carbon and dispersed in water or an aprotic polar organic solvent, depending on the dispersibility and application in the range of 0.005 wt% to 1 wt% with respect to the weight of the solvent.
  • MWNT is used as the fine carbon, it is appropriately selected depending on the dispersibility and application within the range of 0.005 wt% to 20 wt% with respect to the weight of the solvent.
  • the amount of the fine carbon dispersant added can be appropriately determined according to the type, blending amount, and use of the fine carbon, but is generally 20 wt. % Carbon (which may be 100% by weight or more) and 20% by weight or less based on the weight of the solvent can sufficiently disperse the fine carbon. If the dispersant for fine carbon is less than 20% by weight based on the weight of fine carbon, the amount of fine carbon dispersant that acts as a dispersant is insufficient because it adsorbs on the surface of fine carbon. There is a risk that the carbon aggregates and many precipitates are formed.
  • the amount exceeds 20% by weight with respect to the weight of the solvent, molecular movement in the solvent of the fine carbon dispersant becomes difficult, so that a sufficient amount of the dispersant is present on the surface of the fine carbon such as carbon nanotubes. Adsorption is difficult, and the viscosity of the solution is too high, making mechanical dispersion difficult.
  • a conductive auxiliary agent, or another polymer as a dispersion for imparting conductivity it is preferable to reduce the amount of fine carbon dispersant added within a range that maintains dispersibility.
  • the concentration of the fine carbon dispersant (the polyimide precursor in the fine carbon dispersant) It is also possible to increase the concentration).
  • fine carbon after fine carbon is dispersed in a dispersant solution for fine carbon having a low concentration (low viscosity), it may be mixed with a polyimide precursor or a polyimide precursor solution.
  • a basic compound may or may not be added together.
  • a tetracarboxylic acid component tetracarboxylic dianhydride
  • a diamine component tetracarboxylic dianhydride
  • the components may be polymerized to synthesize a polyimide precursor, and the polyimide-fine carbon composite may be synthesized by increasing the concentration of the polyimide precursor in the fine carbon dispersant solution and then imidizing.
  • the solution viscosity of the fine carbon dispersion composition of the present invention is not particularly limited, but is preferably as low as possible when used for dispersion in other resins. If the solution viscosity is high, the dispersion may be insufficient when mixed with other resins or active materials to obtain a conductive binder resin composition or electrode mixture paste, or the conductive binder resin composition or electrode mixture.
  • the viscosity of the agent paste is high, and there is a concern of adversely affecting the molding.
  • the fine carbon dispersion composition of the present invention may contain other additive components depending on the use of the obtained polyimide.
  • a polyimide-fine carbon composite can be suitably obtained by removing water and an aprotic polar organic solvent by heat treatment and imidizing (dehydrating cyclization).
  • the heat treatment conditions are not particularly limited, but are generally 100 ° C. or higher, preferably 120 ° C. to 600 ° C., more preferably 150 ° C. to 500 ° C., still more preferably 150 ° C. to 350 ° C., preferably in steps. It is preferable to perform heat treatment for 0.01 to 30 hours, preferably 0.01 to 10 hours while increasing the temperature.
  • This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove water and amide-based organic solvents. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur.
  • the fine carbon dispersion composition of the present invention is excellent in that, for example, it has high adhesiveness to metals, etc. only by heat treatment at a relatively low temperature (eg, 150 ° C. to 300 ° C., preferably 200 ° C. to 280 ° C.).
  • a relatively low temperature eg, 150 ° C. to 300 ° C., preferably 200 ° C. to 280 ° C.
  • a polyimide-fine carbon composite having the above characteristics can be easily obtained.
  • a coating film comprising a fine carbon dispersion composition layer applied or sprayed on the surface of a support.
  • the fine carbon dispersion composition is heat-treated to obtain a polyimide-fine carbon composite film.
  • a coating film made of a fine carbon dispersion composition is formed on a support, heat-treated at a relatively low temperature to remove the solvent, and a self-supporting film (in a state where no film flows)
  • the polymerization and partial imidization reaction are proceeding with the removal, and then the self-supporting membrane is dehydrated and imidized by heat treatment in the state as it is or peeled off from the support as necessary
  • a film can be suitably obtained.
  • solvent removal or “dehydration / imidization” does not mean that only solvent removal or only dehydration / imidation proceeds in the step. A considerable degree of dehydration and imidization also proceeds in the solvent removal step, and removal of the residual solvent proceeds in the dehydration and imidization step.
  • the thickness of the polyimide-fine carbon composite film can be appropriately selected depending on the purpose, but it is preferably 1 to 20 ⁇ m for a flexible device substrate, and usually 20 to 200 ⁇ m for a seamless belt. is there.
  • the fine carbon dispersion composition of the present invention is excellent in strength, elongation, elastic modulus, and volume resistance because fine carbon is uniformly dispersed due to the high dispersibility of the dispersant for fine carbon.
  • a polyimide-fine carbon composite film can be obtained.
  • the fine carbon dispersion composition of the present invention is a polyimide resin in which fine carbon is uniformly dispersed by the high dispersibility of the fine carbon dispersant, and exhibits excellent physical properties by imidization only by heat treatment of the fine carbon dispersant. Therefore, it can be suitably used as a conductive binder resin composition. Furthermore, it can be suitably used as an electrode mixture paste containing the conductive binder resin composition and an electrode active material.
  • the electrode active material that can be used for the electrode mixture paste of the present invention is not particularly limited, but the electrode mixture paste is preferably prepared by mixing preferably in the temperature range of 10 ° C to 60 ° C. be able to.
  • Electrode active materials can be preferably used, but lithium-containing metal composite oxides, carbon powders, silicon powders, tin powders, or alloy powders containing silicon or tin are preferable.
  • the amount of the electrode active material in the electrode mixture paste is not particularly limited, but is usually 0.1 to 1000 times, preferably 1 to 1000 times on a mass basis with respect to the solid content mass caused by the fine carbon dispersant. Times, more preferably 5 to 1000 times, and still more preferably 10 to 1000 times. When the amount of the active material is too small, an inactive portion is increased in the active material layer formed on the current collector, and the function as an electrode may be insufficient. If the amount of the active material is too large, the active material is not sufficiently bound to the current collector and easily falls off. In the electrode mixture paste, additives such as surfactants, viscosity modifiers, and other binders can be added as necessary.
  • An electrode mixture paste comprising the conductive binder resin composition of the present invention and an electrode active material such as a lithium-containing metal composite oxide capable of reversibly inserting and releasing lithium ions by charge and discharge is used as a conductive material such as aluminum.
  • Cast or coat on a conductive current collector to remove the solvent and heat the imidation reaction at a temperature of 80 to 400 ° C., more preferably 120 to 380 ° C., particularly preferably 150 to 350 ° C. By doing so, an electrode can be obtained.
  • the heat treatment temperature is outside the above range, the imidization reaction may not proceed sufficiently, or the physical properties of the electrode molded body may be deteriorated.
  • the heat treatment may be performed in multiple stages to prevent foaming or powdering.
  • the heat treatment time is preferably in the range of 3 minutes to 48 hours.
  • the heat treatment time exceeding 48 hours is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction and solvent removal may be insufficient, which is not preferable.
  • the electrode thus obtained can be particularly suitably used as the positive electrode of a lithium ion secondary battery.
  • the conductive binder resin composition of the present invention and an electrode active material such as carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin capable of reversibly inserting and releasing lithium ions by charging and discharging.
  • An electrode mixture paste containing is cast or coated on a conductive current collector such as copper, and a temperature range of 80 to 300 ° C., more preferably 120 to 280 ° C., particularly preferably 150 to 250 ° C.
  • the electrode can be obtained by heat treatment to remove the solvent and imidization reaction. When the heat treatment temperature is lower than 80 ° C., the imidization reaction does not proceed sufficiently and the physical properties of the electrode molded body may be lowered.
  • heat treatment is performed at a temperature higher than 300 ° C., copper may be deformed and cannot be used as an electrode. Also in this case, the heat treatment may be performed in multiple stages in order to prevent foaming or powdering.
  • the heat treatment time is preferably in the range of 3 minutes to 48 hours. The heat treatment time exceeding 48 hours is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction and solvent removal may be insufficient, which is not preferable.
  • the electrode thus obtained can be used particularly suitably as a negative electrode for a lithium ion secondary battery.
  • the acid dianhydrides, diamines, basic compounds, aprotic polar organic solvents and fine carbons used in the following examples, and the measurement methods are as follows.
  • s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • ODA 4,4′-diaminodiphenyl ether
  • PPD paraphenylenediamine
  • DAPBI 5 (6) -amino-2- (4-amino Phenyl) -benzimidazole
  • 1,2-DMz 1,2-dimethylimidazole
  • TEA Triethylamine NMP: 1-methyl-2-pyrrolidone single-walled carbon nanotube (SWNT): SWENT (registered trademark) GC-100 manufactured by ALDRICH Multi-walled carbon nanotube (MWNT): AMC (registered trademark) average diameter 10-15 nm manufactured by Ube Industries, Ltd.
  • the particle size of fine carbon in the obtained dispersion composition was measured by a laser diffraction method.
  • LA-950V2 manufactured by Horiba Ltd. was used, and the median diameter (D50) was used as an evaluation index.
  • Example A1 In a reaction vessel equipped with a stirrer and a nitrogen introduction tube, 1.23 g (6.14 mmol) of ODA and 27.00 g of ion-exchanged water were added, and 1.45 g (15.35 mmol) of 1,2-DMz was added. The mixture was further stirred at 70 ° C. for 1 hour. Further, 1.77 g (6.02 mmol) of s-BPDA was added and stirred at 70 ° C. for 4 hours to synthesize a fine carbon dispersant aqueous solution having a dispersant concentration of about 14 wt%.
  • concentration used here shows weight% (wt%) with respect to the solution of acid dianhydride + diamine + basic compound.
  • Ion exchanged water was added to the obtained fine carbon dispersant aqueous solution for dilution to obtain a fine carbon dispersant aqueous solution having a dispersant concentration of 1 wt%.
  • the temperature of the solution is maintained at 30 ° C. or lower using an ultrasonic cleaner (BRANSON 1510: 42 kHz / 90 W). The mixture was sonicated for 2 hours while cooling to obtain a fine carbon dispersion composition.
  • Examples A2, A3 The same operation as in Example A1 was performed except that the dispersant was diluted to the concentration shown in Table 1. When the dispersion composition after sonication was allowed to stand for 1 day and observed, a slight aggregated precipitate was observed, but the supernatant was a black solution. Moreover, the filtrate which filtered the dispersion composition was black transparent, and SWNT which is fine carbon was disperse
  • Examples A4 and A5 The same operation as in Example A2 was performed except that the acid dianhydride, diamine, and basic compound shown in Table 1 were used in the molar ratio shown in Table 1.
  • the dispersion composition after sonication was allowed to stand for 1 day and observed, a slight aggregated precipitate was observed, but the supernatant was a black solution.
  • the filtrate which filtered the dispersion composition was black transparent, and SWNT which is fine carbon was disperse
  • Example A6 The same operation as in Example A2 was performed except that MWNT was used instead of SWNT as the fine carbon.
  • MWNT was used instead of SWNT as the fine carbon.
  • the dispersion composition after sonication was allowed to stand for 1 day and observed, a slight aggregated precipitate was observed, but the supernatant was a black solution.
  • the filtrate which filtered the dispersion composition was black transparent, and MWNT which is fine carbon was disperse
  • Examples A7 and A8 The same operation as in Example A6 was carried out except that the acid dianhydride, diamine and basic compound shown in Table 1 were used in the molar ratio shown in Table 1.
  • the dispersion composition after sonication was allowed to stand for 1 day and observed, a slight aggregated precipitate was observed, but the supernatant was a black solution.
  • the filtrate which filtered the dispersion composition was black transparent, and MWNT which is fine carbon was disperse
  • Example A9 The same operation as in Example A2 was performed except that acetylene black was used instead of SWNT as the fine carbon.
  • acetylene black was used instead of SWNT as the fine carbon.
  • Example A10 The same operation as in Example A2 was performed except that VGCF-H was used instead of SWNT as the fine carbon.
  • VGCF-H was used instead of SWNT as the fine carbon.
  • the filtrate was colorless and transparent.
  • SWNT is not sufficiently dispersed, SWNT is agglomerated in the dispersion composition and cannot pass through the filter, and a solution in which SWNT, which is fine carbon, is uniformly dispersed cannot be obtained. It was.
  • Example A3 Dispersion treatment was performed in the same manner as in Example A2, except that only 1,2-DMz was used as the dispersant at the concentrations shown in Table 1.
  • the dispersion composition after the ultrasonic treatment most of the SWNTs were precipitated at the bottom after being left for 1 day, and when only 1,2-DMz was added, it was difficult to disperse the SWNTs.
  • the filtrate obtained by filtering the dispersion composition was colorless and transparent, and could not pass through the filter due to insufficient dispersion of SWNT, so that a solution in which SWNT as fine carbon was dispersed could not be obtained.
  • Example A4 The same dispersion treatment as in Example A9 was performed except that the fine carbon dispersant was not added.
  • the dispersion composition after ultrasonic treatment most of the acetylene black was precipitated at the bottom after being left for 1 day, and it was difficult to disperse the acetylene black when no dispersant was added.
  • the solution after filtration was colorless and transparent, and was unable to pass through the filter due to insufficient dispersion of acetylene black, and a solution in which acetylene black, which is fine carbon, was uniformly dispersed could not be obtained. .
  • Example A5 The same dispersion treatment as in Example A10 was performed, except that the fine carbon dispersant was not added.
  • the dispersion composition after the ultrasonic treatment most of the vapor-grown carbon fibers were precipitated at the bottom after being left for 1 day, and it was difficult to disperse the vapor-grown carbon fibers when no dispersant was added.
  • the filtrate after filtration is colorless and transparent and cannot pass through the filter due to insufficient dispersion of the vapor grown carbon fiber, and the vapor grown carbon fiber, which is fine carbon, is uniformly dispersed. The obtained solution could not be obtained.
  • Examples B1 to B5 The same operation as in Example A7 was carried out except that the compounds shown in Table 2 were used as the basic compound in the fine carbon dispersant.
  • the compounds used in Examples B1 to B5 are all basic compounds having a pKa of 7.5 or more.
  • the dispersion composition after sonication was observed after standing for 1 day. As a result, although a slight aggregated precipitate was observed, the supernatant was a black solution.
  • the filtrate which filtered the dispersion composition was black transparent, and MWNT which is fine carbon was disperse
  • Examples B6 and B7 The same operations as in Example A7 were carried out except that the compounds shown in Table 2 were used as the basic compounds in the fine carbon dispersant and NMP was used as the solvent for the dispersant solution.
  • a basic compound having a pKa of 7.5 or more was used in the fine carbon dispersants of Examples B6 and B7.
  • the dispersion composition after ultrasonic treatment was observed after standing for 1 day. As a result, although a slight aggregated precipitate was observed, the supernatant was a black solution.
  • the filtrate which filtered the dispersion composition was black transparent, and MWNT which is fine carbon was disperse
  • Comparative Examples B1, B2 The same operation as in Example A7 was performed except that the compounds listed in Table 2 were used as the compound to be mixed in the dispersant.
  • the compounds used in Comparative Examples B1 and B2 are both compounds having a pKa of less than 7.5. However, since the reaction product was not uniformly dissolved in water, an aqueous solution could not be obtained.
  • Example C1 A fine carbon dispersant aqueous solution (dispersant concentration 14 wt%) was synthesized in the same manner as in Example A1. 28.5 g of an aqueous solution obtained by diluting the obtained aqueous dispersant for fine carbon to a dispersant concentration of 1.25 wt% and 1.5 g (5 wt% with respect to the solution) of MWNT were mixed with zirconia (ZrO) having an average particle diameter of 1 mm.
  • ZrO zirconia
  • the mixture was put into a zirconia container of a planetary mill (P-5 manufactured by Fritsch) together with 50 g of beads and dispersed at room temperature for 24 hours at a pot rotation speed of 350 rpm to obtain a MWNT dispersion composition.
  • the resulting dispersion composition was a black solution.
  • the particle size of fine carbon (MWNT) in the dispersion composition was measured by the above method, the average particle size was small and the dispersibility was good.
  • the obtained dispersion composition was applied onto a PET film and dried at 80 ° C. for 1 hour, the coating film showed gloss and it was found that the dispersibility of MWNT in water was good.
  • Examples C2, C3 A MWNT dispersion composition was obtained in the same manner as in Example C1, except that the acid dianhydride, diamine, and basic compound shown in Table 3 were used.
  • the obtained dispersion composition was a black solution, and the average particle diameter of the fine carbon in the dispersion composition was small and the dispersibility was good.
  • the coating film showed gloss and it was found that the dispersibility of MWNT in water was good.
  • Example C4 In a reaction vessel equipped with a stirrer and a nitrogen introduction tube, 0.82 g (7.56 mmol) of PPD and 27.00 g of NMP were charged, and 2.18 g (7.42 mmol) of s-BPDA was charged. Then, a polyimide precursor NMP solution having a solid content of 10 wt% was synthesized by stirring at room temperature for 4 hours. To the obtained polyimide precursor solution, 1.78 g (1.25 times equivalent to the carboxyl group of the polyimide precursor) 1,2-DMz as a basic compound was added to obtain a fine carbon dispersant NMP solution.
  • Examples C5 and C6 The same operation as in Example C4, except that a fine carbon dispersant was prepared using the acid dianhydride, diamine, and basic compound shown in Table 3, and the dispersant was used at the concentration shown in Table 3.
  • a MWNT dispersion composition was a black solution, and the average particle diameter of the fine carbon in the dispersion composition was small and the dispersibility was good.
  • the coating film showed gloss and it was found that the dispersibility of MWNT in NMP was good.
  • Example C1 An MWNT dispersion composition was obtained in the same manner as in Example C1, except that the fine carbon dispersant was not used. It was found that the obtained dispersion composition had a large average particle size of fine carbon (MWNT) and was aggregated visually to separate from the solvent. It was coated on a PET film and dried at 80 ° C. for 1 hour, but the coating film was not rough and glossy, and it was shown that the dispersibility of MWNT in water was poor when a fine carbon dispersant was not used. It was.
  • MWNT fine carbon
  • Example C2 A MWNT dispersion composition was obtained in the same manner as in Example C1, except that only 1,2-DMz was used as the fine carbon dispersant at the concentrations shown in Table 3. It was found that the obtained dispersion composition had a large average particle size of fine carbon (MWNT) and was aggregated visually to separate from the solvent. Although it was coated on a PET film and dried at 80 ° C. for 1 hour, the coating film was not rough and glossy, and when only 1,2-DMz was used, the dispersibility of MWNT in water was poor. It was done.
  • 1,2-DMz fine carbon
  • Example C3 A MWNT dispersion composition was obtained in the same manner as in Example C4 except that only 1,2-DMz was used as a fine carbon dispersant at the concentrations shown in Table 3. It was found that the obtained dispersion composition had a large average particle size of fine carbon (MWNT) and was aggregated visually to separate from the solvent. It was coated on a PET film and dried at 80 ° C. for 1 hour, but the coating film was not rough and glossy, and when only 1,2-DMz was used, the dispersibility of MWNT in NMP was poor. It was done.
  • 1,2-DMz fine carbon
  • Example C4 A dispersion composition was obtained in the same manner as in Example C4, except that a polyimide precursor containing no 1,2-DMz was used as the fine carbon dispersant. It was found that the obtained dispersion composition had a large average particle size of fine carbon (MWNT) and was aggregated visually to separate from the solvent. It was coated on a PET film and dried at 80 ° C. for 1 hour, but the coating film was not rough and glossy, and when only a polyimide precursor containing no basic compound was used, MWNT was dispersible in NMP. It was shown to be bad.
  • MWNT fine carbon
  • Example D1 1 g of the MWNT dispersion composition obtained in Example C1 was added to 5 g of a 10 wt% polyimide precursor aqueous solution obtained from s-BPDA, ODA and 1,2-DMz, and stirred at 40 ° C. for 1 hour.
  • the obtained black transparent solution was cast on a glass support, heated at 50 ° C. for 30 minutes, and then heated from 100 ° C. to 350 ° C. over 1 hour to obtain a black transparent polyimide-MWNT composite.
  • aggregates having a size of 10 ⁇ m or more were not observed, and it was confirmed that MWNT was uniformly dispersed in the polyimide.
  • Example D2 1 g of the MWNT dispersion composition obtained in Example C4 was added to 5 g of a 10 wt% polyimide precursor NMP solution obtained from s-BPDA and PPD, and the mixture was stirred at 40 ° C. for 1 hour.
  • the obtained black transparent solution was cast on a glass support, heated at 50 ° C. for 30 minutes, and then heated from 100 ° C. to 350 ° C. over 1 hour to obtain a black transparent polyimide-MWNT composite.
  • aggregates having a size of 10 ⁇ m or more were not observed, and it was confirmed that MWNTs were uniformly dispersed.
  • Comparative Example D1 1 g of the MWNT dispersion composition obtained in Comparative Example C1 was added to 5 g of a 10 wt% polyimide precursor aqueous solution obtained from s-BPDA, ODA and 1,2-DMz, and stirred at 40 ° C. for 1 hour. The resulting black solution was cast on a glass support, heated at 50 ° C. for 30 minutes, and then heated from 100 ° C. to 350 ° C. over 1 hour to obtain a black polyimide-MWNT composite. When the obtained composite was observed with an optical microscope, many aggregates having a size of 10 ⁇ m or more were observed, and it was confirmed that MWNTs were not uniformly dispersed.
  • Comparative Example D2 1 g of the MWNT dispersion composition obtained in Comparative Example C3 was added to 5 g of a 10 wt% polyimide precursor NMP solution obtained from s-BPDA and PPD, and the mixture was stirred at 40 ° C. for 1 hour. The resulting black solution was cast on a glass support, heated at 50 ° C. for 30 minutes, and then heated from 100 ° C. to 350 ° C. over 1 hour to obtain a black polyimide-MWNT composite. When the obtained composite was observed with an optical microscope, many aggregates having a size of 10 ⁇ m or more were observed, and it was confirmed that MWNTs were not uniformly dispersed.
  • the measurement method performed in the following example is as follows.
  • volume resistance was measured by a four-terminal method using a low resistivity meter (Loresta GP manufactured by Mitsubishi Chemical Corporation) based on JISK7194.
  • MWNT manufactured by Ube Industries, AMC
  • PCM-L manufactured by Asada Tekko Co., Ltd., 0.3 mm zirconia beads, peripheral speed 10 m / s
  • Example E1 The MWNT dispersion composition obtained in Reference Example E1 and NMP are added to a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and the mixture is stirred and mixed. An equimolar amount was added and mixed by stirring to synthesize a MWNT-dispersed polyimide precursor NMP solution having a polyamic acid solid content of 20 wt%. The amount of MWNT dispersion composition added was obtained from the solid content of the MWNT solid content of polyamic acid (polyamic acid in the MWNT dispersion composition produced in Reference Example E1, and PPD and s-BPDA added later. To 3 wt%, 5 wt%, 10 wt%, and 20 wt%, respectively.
  • the obtained MWNT-dispersed polyimide precursor NMP solution was filtered through a NASRON filter having a retention particle diameter of 5 ⁇ m, cast on glass, heated on a hot plate at 120 ° C. for 45 minutes, peeled off from the glass, and attached to a tenter. Then, it was cured in an oven at 150 ° C. for 30 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and 400 ° C. for 10 minutes to obtain a polyimide-MWNT composite having a film thickness of about 35 ⁇ m.
  • the properties of the obtained polyimide-MWNT composite are shown in Table 4.
  • the obtained polyimide-MWNT composite had good mechanical properties, and maintained a relatively high elongation even when the amount of MWNT added was large. In addition, the resistance value decreased well as the amount of MWNT added increased.
  • Example E2 Except for using the MWNT dispersion composition obtained in Reference Example E2, the same operation as in Example E1 was performed to obtain a polyimide-MWNT composite having a film thickness of about 35 ⁇ m.
  • the properties of the obtained polyimide-MWNT composite are shown in Table 4.
  • the obtained polyimide-MWNT composite had good mechanical properties, and maintained a relatively high elongation even when the amount of MWNT added was large. In addition, the resistance value decreased well as the amount of MWNT added increased.
  • Example E1 Except for using the MWNT dispersion composition obtained in Reference Example E3, the same operation as in Example E1 was performed to obtain a polyimide-MWNT composite having a film thickness of about 35 ⁇ m.
  • the properties of the obtained polyimide-MWNT composite are shown in Table 4. Since the obtained polyimide-MWNT composite had poor MWNT dispersibility, the elongation was greatly reduced even when the amount of MWNT added was small. Moreover, when there was much addition amount of MWNT, the filter obstruct
  • Reference Example E4 Dispersion treatment similar to that of Reference Example E1 was carried out using an NMP solution in which 2.5 wt% of polyvinylpyrrolidone (PVP: K25) was dissolved instead of the fine carbon dispersant (s-BPDA / PPD-TEA). A MWNT dispersion composition was obtained. The obtained dispersion composition was a black solution, and the average particle diameter of the fine carbon in the dispersion composition was small and the dispersibility was good.
  • PVP polyvinylpyrrolidone
  • s-BPDA / PPD-TEA fine carbon dispersant
  • Example E2 Except for using the MWNT dispersion composition obtained in Reference Example E4, the same operation as in Example E1 was performed to obtain a polyimide-MWNT composite having a film thickness of about 35 ⁇ m.
  • the properties of the obtained polyimide-MWNT composite are shown in Table 4. Even when the amount of MWNT added was small, the resulting polyimide-MWNT composite showed a significant decrease in elongation, suggesting a decrease in the mechanical properties of the composite due to thermal decomposition of the dispersant. Also, the resistance value was relatively large, suggesting an adverse effect on conductivity due to the presence of a dispersant other than the polyimide precursor.
  • the fine carbon dispersion composition using the fine carbon dispersant of the present invention is a solution in which fine carbon is uniformly dispersed by the excellent dispersibility of the fine carbon dispersant.
  • the fine carbon dispersion composition using the dispersant for fine carbon of the present invention preferably has excellent heat resistance, solvent resistance, and mechanical properties by removing polar solvent by heat treatment and imidization (dehydration ring closure). Since a polyimide-fine carbon composite can be obtained, it is suitable for use in fields where high temperature use and solvent resistance are required.
  • conductive pastes for electrodes such as lithium ion batteries, fuel cells, capacitors, hydrogen storage materials, LSI wiring, solar cells, transparent conductive films, applications for improving mechanical strength, applications for improving thermal conductivity, and the like.

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Abstract

L'invention concerne une composition de dispersion de carbone fin qui comprend : un agent de dispersion de carbone fin contenant un précurseur de polyimide ayant une unité de répétition représentée par la formule générale (1) et un composé basique de 0,7 fois équivalent ou plus au groupe carboxyle dans le précurseur de polyimide, ledit composé basique ayant un pKa de 7,5 ou plus ; du carbone fin ; et un solvant polaire. Dans la formule générale (1) : B représente une unité tétravalente issue d'un composant acide tétracarboxylique ; et A représente une unité divalente issue d'un composant diamine.
PCT/JP2013/059386 2012-03-28 2013-03-28 Composition de dispersion de carbone fin et composite polyimide/carbone fin l'utilisant WO2013147087A1 (fr)

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CN106165163A (zh) * 2014-01-28 2016-11-23 株式会社Lg化学 表面涂布的正极活性材料、其制备方法以及包含其的锂二次电池
JP2017076468A (ja) * 2015-10-13 2017-04-20 Jsr株式会社 蓄電デバイス電極用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極及び蓄電デバイスの製造方法
JP2019033094A (ja) * 2014-04-25 2019-02-28 サウス ダコタ ボード オブ リージェンツ 大容量電極
CN109535423A (zh) * 2013-11-27 2019-03-29 宇部兴产株式会社 聚酰亚胺前体组合物、聚酰亚胺的制造方法、聚酰亚胺、聚酰亚胺膜和基板
WO2019074109A1 (fr) 2017-10-12 2019-04-18 国立大学法人東京工業大学 Composite à particules inorganiques, sa méthode de production et dispersion de composite à particules inorganiques
WO2019107463A1 (fr) * 2017-11-30 2019-06-06 日本ゼオン株式会社 Pâte de matériau conducteur pour éléments électrochimiques, composition de bouillie pour électrodes positives d'élément électrochimique et son procédé de production, électrode positive pour éléments électrochimiques, et élément électrochimique
JP2020073305A (ja) * 2015-01-22 2020-05-14 ユニチカ株式会社 積層体およびその製造方法および使用方法ならびにガラス基板積層用ポリイミド前駆体溶液
JPWO2021085255A1 (fr) * 2019-10-28 2021-05-06
JP2021520040A (ja) * 2018-06-11 2021-08-12 エルジー・ケム・リミテッド 炭素ナノチューブ分散液及びこの製造方法
US11824189B2 (en) 2018-01-09 2023-11-21 South Dakota Board Of Regents Layered high capacity electrodes
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JP2022033182A (ja) * 2014-04-25 2022-02-28 サウス ダコタ ボード オブ リージェンツ 大容量電極
JP2019033094A (ja) * 2014-04-25 2019-02-28 サウス ダコタ ボード オブ リージェンツ 大容量電極
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