WO2020129872A1 - Carbon nanotube dispersion liquid and method for producing same - Google Patents

Carbon nanotube dispersion liquid and method for producing same Download PDF

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Publication number
WO2020129872A1
WO2020129872A1 PCT/JP2019/049082 JP2019049082W WO2020129872A1 WO 2020129872 A1 WO2020129872 A1 WO 2020129872A1 JP 2019049082 W JP2019049082 W JP 2019049082W WO 2020129872 A1 WO2020129872 A1 WO 2020129872A1
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Prior art keywords
dispersion liquid
carbon nanotubes
carbon nanotube
walled carbon
polymer dispersant
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PCT/JP2019/049082
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French (fr)
Japanese (ja)
Inventor
寿始 高橋
兼司 近藤
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レジノカラー工業株式会社
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Priority to JP2020561393A priority Critical patent/JP7301881B2/en
Publication of WO2020129872A1 publication Critical patent/WO2020129872A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/159—Carbon nanotubes single-walled
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising 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
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a carbon nanotube dispersion liquid and a method for producing the same. More specifically, the present invention relates to a dispersion of single-walled carbon nanotubes having excellent dispersibility of carbon nanotubes, good stability over time, hard to reaggregate, and low viscosity, and a method for producing the same.
  • Carbon-based materials such as carbon black, graphite, and carbon nanotubes are known as one of industrial materials having excellent conductivity. Among them, carbon nanotubes are also very excellent in mechanical properties and thermal conductivity, and have recently attracted attention as industrial materials. Examples of the carbon nanotubes include multi-wall carbon nanotubes (also referred to as “MWCNT (Multi Wall Carbon Nanotube)”) and single-wall carbon nanotubes (also referred to as “SWCNT (Single Wall Carbon Nanotube)”).
  • MWCNT Multi Wall Carbon Nanotube
  • SWCNT Single Wall Carbon Nanotube
  • the single-walled carbon nanotube has a large specific surface area per unit mass as compared with the multi-walled carbon nanotube, and thus is excellent in that high conductivity can be imparted with a small addition amount.
  • Patent Document 1 discloses a carbon nanotube aggregate having a swelling ratio of 5 or more, and a dispersant having both an amine value and an acid value in a specific range. Is dispersed in a dispersion medium to obtain a dispersion of carbon nanotubes.
  • the dispersion liquid of single-walled carbon nanotubes is inferior in stability over time to the dispersion liquid of multi-walled carbon nanotubes, and particularly at high temperatures (40° C., etc.), it is easy to re-aggregate even once, so that the low temperature It had to be stored.
  • the dispersion liquid of carbon nanotubes has a low viscosity.
  • the present invention has excellent dispersibility of single-walled carbon nanotubes, good stability over time, and low viscosity that does not easily re-aggregate, an organic solvent dispersion liquid containing single-walled carbon nanotubes, and a method for producing the same.
  • the purpose is to provide.
  • the present inventor has conducted various studies on methods of dispersing carbon nanotubes containing single-walled carbon nanotubes in a dispersion medium.
  • an ultrasonic wave irradiation step is performed using at least single-walled carbon nanotubes, a polymer dispersant, and an organic solvent.
  • a dispersion is produced by a predetermined method including a dispersion step using a disperser that does not use a crushing medium, it has excellent dispersibility, good stability over time, is hard to re-aggregate, has low viscosity, and is an organic single-walled carbon nanotube. It has been found that a solvent dispersion can be easily produced.
  • a coating film excellent in both transparency and conductivity can be obtained by using a dispersion of single-walled carbon nanotubes obtained by the above-mentioned production method, and the present invention has been completed.
  • the present invention provides a dispersion liquid of carbon nanotubes containing at least carbon nanotubes, a polymer dispersant, and an organic solvent, wherein the dispersion liquid contains 0.01 to 10% by mass of carbon nanotubes. Is 75% by mass or more of single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, and the dispersion liquid is adjusted so that the content of the carbon nanotubes is 0.2% by mass.
  • the viscosity of the prepared liquid prepared in 1. is less than 500 mPa ⁇ s, which is a carbon nanotube dispersion liquid.
  • the particle diameter D50 of the carbon nanotubes is preferably less than 5 ⁇ m.
  • the particle diameter D90 of the carbon nanotubes is preferably less than 10 ⁇ m.
  • the dispersion liquid further contains a dispersion aid.
  • the polymer dispersant is preferably a cationic polymer dispersant.
  • the organic solvent is preferably at least one selected from the group consisting of an ester solvent, a ketone solvent, a glycol solvent, an alcohol solvent, and a nitrogen-containing polar solvent.
  • the coating film formed by the following method using the above dispersion has a total light transmittance of 90% or more and a surface resistance value of less than 1.0 ⁇ 10 9 ⁇ / ⁇ .
  • Method for forming coating film A resin composition having a solid content of 1% by mass, which is prepared by mixing the dispersion liquid, the butyl methacrylate resin and the organic solvent so that the concentration of the carbon nanotubes in the coating film is 8% by mass. Is prepared, and the above resin composition is applied onto a polyethylene terephthalate film using a bar coater having a wire diameter of 0.27 mil, and the applied material is dried to form a coating film.
  • the present invention also provides a step (1) of mixing at least a single-walled carbon nanotube having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent, and the above step ( A step (2) of irradiating the mixture obtained in 1) with ultrasonic waves, a step (3) of dispersing the ultrasonic irradiation product obtained in the step (2) by a disperser which does not use grinding media, and A method for producing a single-walled carbon nanotube dispersion, which comprises the step (4) of adding a polymer dispersant to the dispersion obtained in the above step (3) and irradiating the obtained mixture with ultrasonic waves. Is.
  • the method for producing a dispersion liquid preferably includes a step of washing the single-walled carbon nanotube with an inorganic acid or a solution containing an inorganic acid before the step (1).
  • step (1) it is preferable to further mix a dispersion aid.
  • the polymer dispersant is preferably a cationic polymer dispersant.
  • the organic solvent is preferably at least one selected from the group consisting of an ester solvent, a ketone solvent, a glycol solvent, an alcohol solvent, and a nitrogen-containing polar solvent. ..
  • the present invention it is possible to obtain a low-viscosity carbon nanotube dispersion having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes, good stability over time, and less likely to re-aggregate. Further, when the dispersion liquid of the present invention is used, high conductivity can be imparted with a small amount of addition, so that a coating film or the like excellent in both conductivity and transparency can be formed.
  • the dispersion liquid of the present invention can be preferably used as a conductive material.
  • Dispersion liquid The present invention is a dispersion liquid of carbon nanotubes containing at least carbon nanotubes, a polymer dispersant, and an organic solvent, wherein the dispersion liquid contains 0.01 to 10% by mass of carbon nanotubes. Is 75% by mass or more of single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, and the dispersion liquid is adjusted so that the content of the carbon nanotubes is 0.2% by mass.
  • the viscosity of the prepared liquid prepared in 1. is less than 500 mPa ⁇ s, which is a carbon nanotube dispersion liquid.
  • the dispersion liquid of the present invention is a low-viscosity organic solvent dispersion liquid of single-walled carbon nanotubes having excellent dispersibility, good stability over time, and hardly re-aggregated.
  • the dispersion of the present invention is an organic solvent dispersion of low-viscosity single-walled carbon nanotubes, which has excellent dispersibility, good stability over time, is difficult to re-aggregate, and has a short diameter and an aspect ratio within a predetermined range. This is because the single-walled carbon nanotubes are contained in a predetermined range amount and have a viscosity in a predetermined range.
  • the dispersion liquid of the present invention when used, a coating film having excellent conductivity and transparency can be formed.
  • the dispersion of the present invention can form a coating film excellent in conductivity and transparency by using a single-walled carbon nanotube as the carbon nanotube, which contains 75% by mass or more of the carbon nanotube, Compared with multi-walled carbon nanotubes, excellent conductivity can be obtained with a smaller amount of use, and very strong van der Waals force acts between particles, and while using single-walled carbon nanotubes with a large aspect ratio, low This is due to the fact that it is possible to stably maintain a good dispersed state in which there are few aggregates of carbon nanotubes due to viscosity.
  • Such a dispersion of the present invention can be produced by a specific production method described below, and the concentration of carbon nanotubes including single-walled carbon nanotubes is relatively high at 0.2% by mass in the dispersion.
  • concentration of carbon nanotubes including single-walled carbon nanotubes is relatively high at 0.2% by mass in the dispersion.
  • a dispersion having a relatively low viscosity which has excellent dispersibility of carbon nanotubes, good stability over time, and is less likely to re-aggregate.
  • a dispersion having a carbon nanotube content of 0.2% by mass has excellent dispersibility, good stability over time, is difficult to re-aggregate, and has a low viscosity, so that it can be widely mixed with other binder components. Can be prescribed. Further, it is possible to reduce the amount of solvent volatilized in the solvent volatilization step.
  • the dispersion of the present invention has a viscosity of 500 mPa ⁇ s prepared by preparing the dispersion so that the content of the carbon nanotubes (preferably single-walled carbon nanotubes) is 0.2% by mass. Is less than.
  • the viscosity is in the above range, the dispersibility of the carbon nanotubes is good, the stability over time is excellent, re-aggregation is difficult, and a low viscosity dispersion liquid can be obtained.
  • the filtration recovery rate of the dispersion liquid by its own weight can be increased. When the recovery rate is high, the dispersion liquid can be easily handled.
  • the viscosity of the prepared liquid is preferably 300 mPa ⁇ s or less, and more preferably 100 mPa ⁇ s or less, from the viewpoint of further increasing the filtration recovery rate by its own weight.
  • the viscosity of the dispersion liquid of the present invention is usually 5 mPa ⁇ s or more.
  • the same organic solvent as the organic solvent contained in the dispersion may be added to the dispersion, or the organic solvent may be partially removed. Then, a method of appropriately adjusting the concentration of carbon nanotubes to a predetermined value (0.2% by mass) can be given.
  • the method for removing the organic solvent is not particularly limited, and a known method such as vacuum distillation may be used.
  • the viscosity is a value obtained by measuring with a BII type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25° C. and a rotation speed of 60 rpm.
  • the recovery rate is preferably 75% or more, more preferably 80% or more, and further preferably 90% or more. If the recovery rate is low, there is a possibility that uniform mixing with another binder, increase in working time due to difficulty in accurate measurement, and increase in pressure resistance of the apparatus may result in reduction in production efficiency.
  • the dispersion liquid of the present invention contains at least carbon nanotubes, a polymer dispersant, and an organic solvent. Each component contained in the dispersion liquid of the present invention will be described below.
  • the carbon nanotubes used in the dispersion of the present invention include single-walled carbon nanotubes having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more.
  • the single-walled carbon nanotube is a seamless cylindrical material formed of single-walled graphene.
  • the short diameter of the single-walled carbon nanotube is the diameter of the cylindrical single-walled carbon nanotube.
  • the minor axis is preferably 0.1 to 40 nm, more preferably 0.3 to 20 nm, and further preferably 0.5 to 10 nm.
  • the single-walled carbon nanotube has an aspect ratio of 100 or more.
  • the aspect ratio is the ratio of (B)/(A) when the diameter (minor axis) of the cylindrical single-walled carbon nanotube is A (nm) and the length (major axis) is B (nm). It is a value.
  • the aspect ratio is preferably 500 or more, more preferably 1500 or more.
  • the upper limit of the aspect ratio is preferably 200,000 or less, more preferably 10,000 or less.
  • the major axis is preferably 100 to 1,000,000 nm, more preferably 500 to 500,000 nm, further preferably 1,000 to 100,000 nm.
  • the major axis is the length of the single-walled carbon nanotube having a cylindrical shape.
  • the minor axis and major axis can be measured by an atomic force microscope (AFM), Raman spectroscopy (Raman), a transmission electron microscope (TEM), or the like.
  • AFM atomic force microscope
  • Raman spectroscopy Raman
  • TEM transmission electron microscope
  • a commercially available product may be used as the single-walled carbon nanotube.
  • Specific examples of commercially available single-walled carbon nanotubes that can be used in the present invention include TUBALL (registered trademark) (manufactured by OCSiAl) and ZEONANO (registered trademark) SG101 (manufactured by ZEON Nano Technology Co., Ltd.). Can be mentioned. Among them, TUBALL (registered trademark) (manufactured by OCSiAl) is preferable because the dispersibility of the dispersion liquid of the present invention can be further improved.
  • the single-walled carbon nanotubes may be used alone or in combination of two or more.
  • the carbon nanotubes used in the dispersion of the present invention may contain carbon nanotubes other than the above single-walled carbon nanotubes, for example, other carbon nanotubes such as multi-walled carbon nanotubes. Including the above.
  • the single-walled carbon nanotubes By containing the single-walled carbon nanotubes in an amount of 75% by mass or more, high conductivity can be imparted by adding a small amount of the dispersion liquid of the present invention to a resin and the like, and a coating film having both excellent transparency and conductivity Can be formed.
  • the multi-walled carbon nanotube is a carbon nanotube in which two or more single-walled carbon nanotubes having different diameters are coaxially stacked in a multi-layer.
  • the carbon nanotubes preferably contain 80% by mass or more of the single-walled carbon nanotubes, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.
  • one kind of carbon nanotube may be used, or two or more kinds thereof may be used in combination.
  • the dispersion liquid of the present invention contains 0.01 to 10% by mass of carbon nanotubes.
  • the content of carbon nanotubes in the dispersion is preferably 0.01 to 1% by mass, and more preferably 0.01 to 0.5% by mass.
  • the particle diameter D50 of the carbon nanotubes is preferably less than 5 ⁇ m.
  • the particle diameter D50 is more preferably less than 4 ⁇ m, further preferably less than 3 ⁇ m.
  • the lower limit of the particle diameter D50 is not particularly limited, but is preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more in order to prevent insufficient conductivity due to fiber breakage.
  • the particle diameter D90 of the carbon nanotubes is preferably less than 10 ⁇ m.
  • the particle diameter D90 is more preferably less than 8 ⁇ m, further preferably less than 5 ⁇ m.
  • the lower limit of the particle diameter D90 is not particularly limited, but is preferably 1.5 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 3 ⁇ m or more, in order to prevent that excellent conductivity due to fiber breakage cannot be obtained. It is particularly preferably 3.5 ⁇ m or more.
  • the particle diameters D50 and D90 are measured by a laser diffraction/scattering particle diameter distribution analyzer such as LA-950V2 (manufactured by Horiba, Ltd.) by appropriately diluting the dispersion liquid to a concentration at which particle size distribution can be measured. This is the value obtained.
  • LA-950V2 manufactured by Horiba, Ltd.
  • the polymer dispersant used in the present invention is not particularly limited as long as it can improve the dispersibility of carbon nanotubes, and includes nonionic polymer dispersants, anion polymer dispersants, and cationic high dispersants. Examples thereof include molecular dispersants, and among them, cationic polymer dispersants are preferable from the viewpoint that the dispersibility of carbon nanotubes can be further improved.
  • Examples of the cationic polymer dispersant include polymers having a basic functional group such as an amine group, and the like, for example, a basic functional group-containing copolymer; a high molecular weight unsaturated acid ester having a basic functional group.
  • Modified polyurethane, modified polyester, modified poly(meth)acrylate, modified polyacrylic acid salt, or (meth)acrylic copolymer polyethyleneimine; polyoxyethylenealkylamine; alkanolamine; alkylammonium salt or alkylacetalization Examples thereof include polyvinyl alcohol and the like.
  • the cationic polymer dispersant is a copolymer having a basic functional group, a (meth)acrylic resin having a basic functional group, in that the dispersibility of the single-walled carbon nanotube can be further improved. It is preferably a copolymer or an alkyl acetalized polyvinyl alcohol.
  • the polymer dispersant may be a linear, terminal-modified, block-type, or graft-type polymer.
  • the amine value of the polymer dispersant is preferably 0 mgKOH/g or more, more preferably 5 mgKOH/g or more, and 100 mgKOH/g from the viewpoint that the dispersibility of carbon nanotubes can be further improved. It is preferably not more than 75 mgKOH/g, more preferably not more than 50 mgKOH/g.
  • the amine value is preferably 0 to 100 mgKOH/g, more preferably 5 to 100 mgKOH/g, further preferably 5 to 75 mgKOH/g, and particularly preferably 5 to 50 mgKOH/g. preferable.
  • a commercially available product may be used as the polymer dispersant.
  • Specific examples of commercially available polymer dispersants that can be used in the present invention include Azisper PB821, PB822, PB824, PB881 (all manufactured by Ajinomoto Fine-Techno Co., Inc.), Efka (registered trademark) PX4320, PX4310, PX4300, PX4330, PX4340, PX4700, PX4701, PX4731, PX4732, PU4063, PA4400, PA4401, PA4403 (all manufactured by BASF), BYK-9077 (manufactured by BYK Chemie), S-REC BL-1, BL-2, BL-.
  • BL-10 BL-S (all manufactured by Sekisui Chemical Co., Ltd.) and the like.
  • Azisper PB821, Efka (registered trademark) PX4320, S-REC BL-10, and S-REC BL-S are preferable because the dispersibility of the dispersion liquid can be further improved.
  • the above polymer dispersants may be used alone or in combination of two or more.
  • the content of the polymer dispersant in the dispersion liquid of the present invention is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and further preferably 1 to 3% by mass. ..
  • Organic solvent used in the present invention is not particularly limited, and examples thereof include alcohol solvents (methanol, ethanol, butanol, isopropanol, phenol, etc.), amine solvents (triethylamine, trimethanolamine, etc.), ether solvents ( Dioxane, tetrahydrofuran, etc.), ether alcohol solvent (2-methoxyethanol, ethoxyethanol, methoxyethoxyethanol, phenylethanol, etc.), glycol solvent (ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, etc.), ester solvents (methyl acetate, ethyl acetate, normal butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene carbonate, etc
  • the ester solvent, the ketone solvent, the glycol solvent, the alcohol solvent, or the nitrogen-containing polar solvent is preferable in that the dispersibility of the single-walled carbon nanotube can be further improved, and the ester is preferably used.
  • a system solvent, a glycol solvent, or a ketone solvent is more preferable, and normal butyl acetate, propylene glycol monomethyl ether acetate, or methyl ethyl ketone is further preferable.
  • the above organic solvents may be used alone or in combination of two or more.
  • the content of the organic solvent in the dispersion liquid of the present invention is preferably 89 to 98% by mass, more preferably 93 to 98% by mass, and further preferably 95 to 98% by mass.
  • the dispersion liquid of the present invention may contain water or the like as a dispersion medium in addition to the above organic solvent, but the organic solvent is preferably contained in the dispersion medium in an amount of 95% by mass or more, and 98% by mass. % Or more is more preferable, and 100% by mass is further preferable.
  • the dispersion liquid of the present invention contains at least the above carbon nanotubes, a polymer dispersant, and an organic solvent, but may further contain other components.
  • the other components include a dispersion aid, a pH adjusting agent, a surface adjusting agent, and the like.
  • the above-mentioned dispersion liquid further contains a dispersion aid in that the wettability of the single-walled carbon nanotube can be further enhanced and the dispersibility (improvement of stability over time, suppression of re-aggregation, reduction of viscosity) can be improved. It is preferable.
  • the types and contents of the other components described above can be appropriately selected from known ones according to the purpose and application of the dispersion.
  • dispersion aid examples include phthalocyanine derivatives such as SOLSPERSE 5000 and SOLSPERSE 12000 (manufactured by Lubrizol), and azo derivatives such as SOLSPERSE 22000 (manufactured by Lubrizol).
  • the coating film formed by the method described below using the dispersion liquid of the present invention has a total light transmittance of 90% or more and a surface resistance value of less than 1.0 ⁇ 10 9 ⁇ / ⁇ . Is preferred.
  • the total light transmittance is preferably 93% or more, more preferably 95% or more.
  • the total light transmittance is measured using a haze meter such as Haze Meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.) by a method according to the total light transmittance standard (ISO 13468-1, JIS K 7361). It is the value obtained by
  • the surface resistance value is preferably less than 5.0 ⁇ 10 8 ⁇ / ⁇ , and more preferably less than 1.0 ⁇ 10 7 ⁇ / ⁇ .
  • the surface resistance value is a value obtained by measuring the current value flowing on the coating film surface at 20° C. using a resistivity meter such as Hiresta MCP-HT450 (manufactured by Mitsubishi Chemical Corporation).
  • the coating film for measuring the total light transmittance and the surface resistance value was prepared by mixing the dispersion liquid of the present invention, butyl methacrylate resin and an organic solvent so that the concentration of carbon nanotubes in the coating film was 8% by mass. Then, a resin composition having a solid content of 1% by mass is prepared, and the resin composition is applied onto a polyethylene terephthalate film using a bar coater having a wire diameter of 0.27 mil, and the applied material is dried. Can be formed.
  • the organic solvent include the same organic solvents as those contained in the dispersion of the present invention.
  • the method for drying the coating material is not particularly limited as long as the organic solvent in the coating material is sufficiently distilled off to form a coating film, depending on the type of the organic solvent used, heat drying, etc. It can be performed by appropriately selecting from known methods. The drying conditions can also be appropriately selected according to the type of organic solvent used and the like.
  • the dispersion of the present invention is not particularly limited as long as the dispersion satisfying the requirements of the above-mentioned dispersion of the present invention is manufactured, but for example, the following step (1 The method including (1) to (4) is preferable.
  • Step (1) At least a step of mixing single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent.
  • Step (2) Step ( Step of irradiating the mixture obtained in 1) with ultrasonic waves
  • Step (3) Step of dispersing the ultrasonic irradiation object obtained in Step (2) by a disperser which does not use grinding media
  • Step (4) Step A step of adding a polymer dispersant to the dispersion obtained in (3) and irradiating the obtained mixture with ultrasonic waves.
  • the single-walled carbon nanotube, the polymer dispersant, and the organic solvent are mixed in the step (1), and then the single-walled carbon is subjected to the ultrasonic treatment in the step (2).
  • Wetting the nanotubes sufficiently with an organic solvent and a polymeric dispersant makes the carbon nanotubes easier to disperse, and the dispersion using a disperser that does not use the grinding media in step (3) causes the fiber structure of the single-walled carbon nanotubes to change.
  • the single-walled carbon nanotubes are dispersed and stabilized by breaking them without breaking them, and further adding the polymer dispersant in the step (4) and performing ultrasonic treatment.
  • a single-walled carbon nanotube having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more first, at least a single-walled carbon nanotube having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent are mixed. ..
  • At least the method for mixing the single-walled carbon nanotubes, the polymer dispersant, and the organic solvent is not particularly limited, and known mixing means such as using a stirring and mixing device such as a mixer or a dissolver can be used. Also, these components can be mixed in any order. For example, a solution in which a polymer dispersant is dissolved in an organic solvent may be prepared in advance, and this solution may be mixed with the single-walled carbon nanotube.
  • step (1) is a step of mixing the single-walled carbon nanotubes, the polymer dispersant, and the organic solvent, it does not mean that only these components are mixed, and the single-walled carbon nanotubes are not mixed.
  • multi-walled carbon nanotubes may be mixed.
  • Dispersion As the above-mentioned single-walled carbon nanotube, polymer dispersant, and organic solvent, the same ones as described in the above “1. Dispersion” can be mentioned.
  • the respective components are preferably mixed so as to have the content ratios described in the above "1. Dispersion”.
  • multi-walled carbon nanotubes are also mixed in addition to the single-walled carbon nanotubes, it is preferable to mix them so that the content ratio is as described in “1. Dispersion” above.
  • the step (1) it is preferable to further mix a dispersion aid in addition to the components described above.
  • a dispersion aid By further mixing the dispersion aid, the wettability of the single-walled carbon nanotube in the step (2) can be further enhanced, and a dispersion liquid having further excellent dispersibility can be produced.
  • the dispersion aid include the same as those described in "1. Dispersion" above.
  • the amount of the dispersion aid added is not particularly limited, but is preferably 10 to 100 parts by mass, more preferably 10 to 60 parts by mass, and 20 to 20 parts by mass with respect to 100 parts by mass of the single-walled carbon nanotube. It is more preferably 40 parts by mass.
  • the method for producing a dispersion liquid of the present invention preferably also includes a step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid before the step (1).
  • impurities such as iron contained in the single-walled carbon nanotubes can be removed and the purity of the single-walled carbon nanotubes can be increased.
  • the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrogen peroxide and the like.
  • the solution containing the inorganic acid include a solution obtained by mixing the inorganic acid with water.
  • the above-mentioned washing step may be performed on the entire carbon nanotubes including multi-walled carbon nanotubes. preferable.
  • the method for washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid is not particularly limited, and a known method can be used.
  • the mixture obtained in the above step (1) is irradiated with ultrasonic waves.
  • the ultrasonic irradiation method is not particularly limited, and it can be performed by a known method using an ultrasonic device or the like.
  • the amplitude is preferably 10 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and further preferably 10 to 40 ⁇ m.
  • the output is preferably 10 to 5000 W, more preferably 100 to 3000 W, and further preferably 200 to 1500 W.
  • the irradiation time is preferably 30 seconds or more, more preferably 60 seconds or more, further preferably 300 seconds or more, and the upper limit is not particularly limited, but it is preferably 600 seconds or less and 480 seconds or less. Is more preferable.
  • the temperature of the dispersion liquid during irradiation is not particularly limited, but is usually 20 to 80° C., preferably 30 to 70° C., and more preferably 40 to 60° C.
  • the ultrasonic irradiation is a process for the purpose of sufficiently wetting the carbon nanotubes with the organic solvent. Therefore, in the step (2), referring to the ultrasonic irradiation conditions, the carbon nanotubes are treated with an organic solvent. Can be set by appropriately setting the conditions for sufficiently wetting.
  • the ultrasonic irradiation product obtained in the above step (2) is dispersed by a disperser which does not use a grinding medium.
  • the disperser that does not use the grinding media include a mixer, a homogenizer, a dissolver, a roll mill, a kneader, a jet mill, and a nanomizer.
  • the jet mill is preferable, and the wet jet mill is more preferable.
  • the wet jet mill include a table-top type wet ultrahigh pressure atomization experimental device NVL-ES008-D manufactured by Yoshida Kikai Co., Ltd.
  • the processing pressure is preferably 50 to 300 MPa, more preferably 100 to 250 MPa, further preferably 150 to 200 MPa.
  • the shape of the gauge may be cross or straight, but is preferably cross.
  • Dispersion in the step (3) using a disperser that does not use the grinding media is preferably completed after confirming that the viscosity of the dispersion becomes higher than that of the dispersion immediately after the step (2).
  • a polymer dispersant is further added to the dispersion obtained in the above step (3), and the resulting mixture is irradiated with ultrasonic waves.
  • the polymer dispersant those similar to the polymer dispersants described in the above “1. Dispersion” are preferably mentioned, and the same as the polymer dispersants used in the step (1). It is preferable.
  • the amount of the polymer dispersant added may be appropriately adjusted so that the content of the polymer dispersant in the obtained dispersion becomes the content of the polymer dispersant described in “1. Dispersion”. However, it is preferable to add half each amount in step (1) and step (4).
  • the conditions for ultrasonic irradiation in step (4) are preferably the same as the conditions for ultrasonic irradiation in step (1) above, but the irradiation time may be set longer than in step (1).
  • the irradiation time in the step (4) is preferably 60 seconds or more, more preferably 120 seconds or more, further preferably 600 seconds or more, and the upper limit is not particularly limited, but it is preferably 1800 seconds or less. It is more preferably 1200 seconds or less.
  • the deposit is not attached to the side surface of the beaker when the obtained dispersion liquid is left for about 30 minutes.
  • the method for producing a dispersion liquid of the present invention may include steps other than the steps (1) to (4) and the step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid.
  • steps other than the steps (1) to (4) and the step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid examples include a cooling step using a heat exchanger.
  • the dispersion liquid of the present invention is a low-viscosity dispersion liquid having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes and hardly reaggregating. It also has excellent stability over time.
  • Use of the dispersion liquid of the present invention makes it possible to easily mix carbon nanotubes, including single-walled carbon nanotubes, with a resin, and to impart high conductivity to the resin with a small amount of addition, which is excellent.
  • a coating film or the like having transparency and conductivity can be formed.
  • Such a dispersion liquid of the present invention can be suitably used for applications where conductivity and transparency are required at the same time, and examples of the applications include semiconductors, primary batteries, secondary batteries, fuel cells, and optical devices. , Communication devices, conductive paints, transparent conductive films, and the like.
  • the dispersion liquid of the present invention is a dispersion liquid having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes, good stability over time, and being hard to reaggregate the carbon nanotubes.
  • the dispersion liquid of the present invention it is possible to produce a coating film having excellent conductivity and transparency.
  • the method for producing a dispersion of the present invention even when the concentration of the single-walled carbon nanotube is relatively high, the dispersion has excellent dispersibility, good stability over time, and low viscosity that does not easily re-aggregate. Can be suitably manufactured.
  • the dispersion liquid and the method for producing the same according to the present invention are very useful in semiconductors, primary batteries, secondary batteries, fuel cells, optical and electronic fields such as optical devices and communication devices, optical fields, conductive paints, transparent conductive films and the like. is there.
  • part means “part by mass”
  • % means “% by mass” unless otherwise specified.
  • Example 1 Preparation Example 1> Preparation of polymer dispersant solution 1
  • Polymer dispersant 1 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) in a 500 cc stainless tank.
  • Ajinomoto Fine Techno Co., Ltd. and normal butyl acetate were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) in the following compounding ratio, and a polymer dispersant solution 1 having a solid content of 20% by mass was prepared.
  • TK Homo Disper 2.5 type manufactured by PRIMIX
  • ⁇ Production Example 1 Production of dispersion 1 (first step) In a 500 cc stainless tank different from the stainless tank used in Preparation Example 1, a single-walled carbon nanotube (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6 ⁇ 0.4 nm, major axis) was used.
  • TABALL registered trademark
  • (Third step) Disperse the intermediate dispersion liquid 1-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultra-high pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 1-2 was obtained. Dispersion conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, cross nozzle used
  • Example 2 Preparation Example 2 Preparation of Polymer Dispersant Solution 2
  • Polymer dispersant 2 (trade name: Efka (registered trademark) PX 4320, solid content 50 mass%, acrylic block copolymer polymer, amine value 30 mgKOH/in a 500 cc stainless tank. g, manufactured by BASF) and normal butyl acetate are mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following compounding ratio, and 100 g of a polymer dispersant solution 2 having a solid content of 20% by mass. Obtained.
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 2-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • the intermediate dispersion liquid 2-2 obtained in the third step and the polymer dispersant solution 2 prepared in Preparation Example 2 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 2-3. Further, the intermediate dispersion liquid 2-3 is irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, whereby the single-walled carbon nanotube dispersion liquid 2 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
  • Mixing ratio (mass ratio): Intermediate dispersion 2-2/polymer dispersant solution 2 95/5 Ultrasonic irradiation conditions: amplitude 30 ⁇ m, output 650 W, time 1 min
  • Example 3 Preparation Example 3 Preparation of Polymer Dispersant Solution 3
  • Polymer dispersant 3 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was prepared in a 500 cc stainless tank.
  • MEK methyl ethyl ketone
  • MEK methyl ethyl ketone
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 3-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • Example 4 Preparation Example 4 Preparation of Polymer Dispersant Solution 4
  • Polymer dispersant 4 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was placed in a 500 cc stainless tank.
  • Ajinomoto Fine Techno Co., Ltd. and propylene glycol monomethyl ether acetate (hereinafter, also referred to as “PMA”) are mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) at the following mixing ratio, 100 g of a polymer dispersant solution 4 having a solid content of 20 mass% was obtained.
  • Mixing ratio (mass ratio): Polymer dispersant 4/PMA 20/80
  • ⁇ Production Example 4 Production of dispersion liquid 4 (first step) In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 4, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6 ⁇ 0.4 nm, major axis) 5 ⁇ m or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 4, and PMA are described below.
  • TABALL registered trademark
  • SWCNT 93% manufactured by OCSiAl
  • purity 93% manufactured by OCSiAl
  • minor axis 1.6 ⁇ 0.4 nm, major axis
  • aspect ratio 2500 or more aspect ratio 2500 or more
  • specific surface area 1070 m 2 /g BET method
  • dispersion aid trade name
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 4-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • Example 5 Preparation Example 5 Preparation of Polymer Dispersant Solution 5
  • Polymer dispersant 5 (trade name: S-REC BL-10, solid content 100% by mass, alkyl acetalized polyvinyl alcohol, amine value 0 mgKOH/g, was added to a 500 cc stainless tank. Sekisui Chemical Co., Ltd.) and isopropanol (hereinafter, also referred to as “IPA”) were mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following mixing ratio, and solid content was 20% by mass. 100 g of the polymer dispersant solution 5 of was obtained.
  • ⁇ Production Example 5 Production of dispersion liquid 5 (first step) In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 5, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6 ⁇ 0.4 nm, major axis) 5 ⁇ m or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 5, and IPA are described below.
  • TABALL registered trademark
  • SWCNT 93% manufactured by OCSiAl
  • purity 93% 1.6 ⁇ 0.4 nm, major axis
  • aspect ratio 2500 or more aspect ratio 2500 or more
  • specific surface area 1070 m 2 /g BET method
  • dispersion aid trade name: SOLSPERSE 5000, phthalocyanine
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 5-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • Example 6 Preparation Example 6 Preparation of Polymer Dispersant Solution 6
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 6-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • Example 7 Preparation Example 7 Preparation of Polymer Dispersant Solution 7
  • Polymer dispersant 7 (trade name: S-REC BL-S, solid content 100 mass %, alkyl acetalized polyvinyl alcohol, amine value 0 mgKOH/g, was added to a 500 cc stainless tank. Sekisui Chemical Co., Ltd.) and normal butyl acetate were mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following compounding ratio to obtain a polymer dispersant solution 7 having a solid content of 20% by mass. 100 g was obtained.
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 7-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • (Third step) Disperse the intermediate dispersion liquid 7-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 7-2 was obtained. Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
  • TABALL registered trademark
  • ⁇ Production Example 9 Production of dispersion 9 (first step) In a 225 cc glass bottle, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6 ⁇ 0.4 nm, major axis 5 ⁇ m or more, aspect ratio 2500 or more, specific surface area 1070 m 2 / g (BET method)), a dispersion aid (trade name: SOLSPERSE 5000, a phthalocyanine derivative, manufactured by Lubrizol), a polymer dispersant solution 9, and normal butyl acetate are weighed at the following compounding ratio, and then 0.3 mm ⁇ zirconia 95 g of an intermediate dispersion liquid 9-1 of single-walled carbon nanotubes was obtained by adding beads and dispersing with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 10 hours.
  • the mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 100 g of Intermediate Dispersion Liquid 11-1.
  • Ultrasonic irradiation conditions amplitude 30 ⁇ m, output 650 W, time 1 min
  • ⁇ Viscosity> The obtained dispersion of single-walled carbon nanotubes was adjusted to 25° C., the viscosity at a rotation speed of 60 rpm was measured with a BII type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the evaluation was performed according to the following criteria. It was Evaluation criteria ⁇ ⁇ : Less than 100 mPa ⁇ s ⁇ : 100 mPa ⁇ s or more, less than 300 mPa ⁇ s ⁇ : 300 mPa ⁇ s or more, less than 500 mPa ⁇ s ⁇ : 500 mPa ⁇ s or more
  • ⁇ Particle size> The obtained single-walled carbon nanotube dispersion is set with carbon black particles and various solvents with a laser diffraction/scattering particle size distribution measuring device (device name: LA-950V2, manufactured by Horiba, Ltd.). Then, the sample was diluted with various solvents to a concentration (about 100 to 500 times) at which the particle size distribution could be measured, and then measured, and evaluated according to the following criteria.
  • the various solvents are normal butyl acetate in Examples 1, 2, 7 and Comparative Examples 1 to 4, MEK in Example 3, and PMA in Example 4. In the case of Example 5, it is IPA, and in the case of Example 6, it is NMP.
  • Recovery rate 100 g of the obtained dispersion liquid of single-walled carbon nanotubes was dropped on a polyester mesh (10 cm ⁇ 10 cm) having an opening of 53 ⁇ m, the passing amount of the polyester mesh under its own weight was measured for 1 minute, and the recovery rate was calculated based on the following formula. It calculated and evaluated based on the following criteria.
  • Recovery rate (%) passing amount (g)/100 (g) ⁇ 100 Evaluation criteria ⁇ ⁇ : 90% or more ⁇ : 80% or more, less than 90% ⁇ : 75% or more, less than 80% ⁇ : less than 75%
  • the butyl methacrylate resin used was a resin solution that was mixed and dissolved in advance with various solvents to a solid content of 40% by mass.
  • Blending ratio (mass ratio): Single-walled carbon nanotube dispersion/resin solution (solid content 40%)/various solvents 40.0/0.24/59.76
  • the above-mentioned various solvents are normal butyl acetate in the case of Examples 1, 2, 7 and Comparative Examples 1 to 4, MEK in the case of Example 3, and PMA in the case of Example 4.
  • MEK in the case of Example 3
  • PMA in the case of Example 4.
  • it it is IPA
  • NMP NMP.
  • the physical properties of the used butyl methacrylate resin are as follows. Diinal BR-115: Molecular weight 55000, Tg 50°C Diinal BR-116: Molecular weight 45,000, Tg 50°C
  • a haze meter (device name: haze meter HZ-2, manufactured by Suga Test Instruments Co., Ltd.) was used to measure according to the total light transmittance standard (ISO 13468-1, JIS K7361) (single beam method, light source D65). The following criteria were evaluated.
  • At least single-walled carbon nanotubes, a polymeric dispersant and an organic solvent are mixed, and the resulting mixture is irradiated with ultrasonic waves to disperse, and then dispersed by a disperser without using grinding media. It was confirmed that by adding a dispersant and performing ultrasonic irradiation to disperse it, it is possible to produce a low-viscosity organic solvent dispersion of single-walled carbon nanotubes having excellent dispersibility and hardly re-aggregating. It was also confirmed that a coating film having excellent conductivity and transparency can be formed by using the dispersion liquid of the example produced by the method.
  • the dispersions of Examples have a low viscosity even after standing at 40° C. for 1 month, and single-walled carbon nanotubes are less likely to aggregate, forming a coating film excellent in transparency and conductivity. It was confirmed that it was possible to do so and that it was excellent in stability over time.

Abstract

The purpose of the present invention is to provide: an organic solvent dispersion liquid containing single walled carbon nanotubes, which exhibits excellent dispersibility of the single walled carbon nanotubes and good stability over time, is unlikely to undergo re-aggregation, and has a low viscosity; and a method for producing same. The present invention is a carbon nanotube dispersion liquid which contains at least carbon nanotubes, a polymer dispersing agent and an organic solvent, and is characterized in that the dispersion liquid contains 0.01-10 mass% of carbon nanotubes, the carbon nanotubes include 75 mass% or more of single walled carbon nanotubes having a short axis length of 0.1-50 nm and an aspect ratio of 100 or more, and the viscosity of a preparation liquid, which is obtained by preparing the dispersion liquid so that the content of the carbon nanotubes is 0.2 mass%, is less than 500 mPa·s.

Description

カーボンナノチューブ分散液、及びその製造方法Carbon nanotube dispersion liquid and method for producing the same
本発明は、カーボンナノチューブ分散液、及びその製造方法に関する。より詳しくは、カーボンナノチューブの分散性に優れ、経時安定性が良く、再凝集しにくく、低粘度である単層カーボンナノチューブの分散液、及びその製造方法に関する。 The present invention relates to a carbon nanotube dispersion liquid and a method for producing the same. More specifically, the present invention relates to a dispersion of single-walled carbon nanotubes having excellent dispersibility of carbon nanotubes, good stability over time, hard to reaggregate, and low viscosity, and a method for producing the same.
導電性に優れた工業的材料の一つとして、カーボンブラック、グラファイト、カーボンナノチューブ等のカーボン系材料が知られている。なかでも、カーボンナノチューブは、機械的性質や熱伝導性にも非常に優れ、工業的材料として、近年注目が高まっている。
カーボンナノチューブには、多層カーボンナノチューブ（「ＭＷＣＮＴ（Ｍｕｌｔｉ　Ｗａｌｌ　Ｃａｒｂｏｎ　Ｎａｎｏｔｕｂｅ）」とも称する。）や、単層カーボンナノチューブ（「ＳＷＣＮＴ（Ｓｉｎｇｌｅ　Ｗａｌｌ　Ｃａｒｂｏｎ　Ｎａｎｏｔｕｂｅ）」とも称する。）等がある。 Carbon-based materials such as carbon black, graphite, and carbon nanotubes are known as one of industrial materials having excellent conductivity. Among them, carbon nanotubes are also very excellent in mechanical properties and thermal conductivity, and have recently attracted attention as industrial materials.
Examples of the carbon nanotubes include multi-wall carbon nanotubes (also referred to as “MWCNT (Multi Wall Carbon Nanotube)”) and single-wall carbon nanotubes (also referred to as “SWCNT (Single Wall Carbon Nanotube)”).
カーボンブラックや多層カーボンナノチューブを使用して樹脂等に導電性を付与するためには、これらを多量に添加する必要がある。しかしながら、カーボンブラックやカーボンナノチューブの添加量を多くすると、透明性が低下してしまうという問題がある。一方、単層カーボンナノチューブは、多層カーボンナノチューブと比較して、単位質量当たりの比表面積が大きいため、少ない添加量で高い導電性を付与することができる点で優れている。 In order to impart conductivity to a resin or the like using carbon black or multi-walled carbon nanotubes, it is necessary to add a large amount of them. However, if the addition amount of carbon black or carbon nanotubes is increased, there is a problem that transparency is lowered. On the other hand, the single-walled carbon nanotube has a large specific surface area per unit mass as compared with the multi-walled carbon nanotube, and thus is excellent in that high conductivity can be imparted with a small addition amount.
カーボンナノチューブを樹脂と混合して使用する場合、分散媒中にカーボンナノチューブを分散させる必要がある。カーボンナノチューブを分散媒中に安定して分散させる方法として、例えば、特許文献１には、膨潤率が５以上のカーボンナノチューブ集合体と、特定範囲のアミン価と酸価の両方を有する分散剤とを、分散媒に分散させてカーボンナノチューブの分散体を得ることが記載されている。 When using the carbon nanotubes mixed with a resin, it is necessary to disperse the carbon nanotubes in a dispersion medium. As a method for stably dispersing carbon nanotubes in a dispersion medium, for example, Patent Document 1 discloses a carbon nanotube aggregate having a swelling ratio of 5 or more, and a dispersant having both an amine value and an acid value in a specific range. Is dispersed in a dispersion medium to obtain a dispersion of carbon nanotubes.
特開２０１４－１０８３号公報JP, 2014-1083, A
上記のとおり、導電性に優れたカーボンナノチューブを分散媒中に分散させる方法が知られているが、単層カーボンナノチューブは、微細な粒子であり、粒子間で非常に強いファンデルワールス力が働き、かつ、大きいアスペクト比を有する。このため、多層カーボンナノチューブよりも分散媒中に分散させるのが困難であり、従来のカーボンナノチューブの分散方法では、単層カーボンナノチューブを分散媒中に十分に分散させることは困難である。特に、分散媒として有機溶媒を使用する場合、単層カーボンナノチューブを十分に分散させるのは非常に困難であり、分散方法については未だ検討の余地があった。
また、単層カーボンナノチューブの分散液は、多層カーボンナノチューブの分散液と比較して、経時安定性に劣り、特に、高温下（４０℃等）では一度分散しても再凝集しやすいため、低温保管する必要があった。 As described above, a method of dispersing carbon nanotubes having excellent conductivity in a dispersion medium is known, but single-walled carbon nanotubes are fine particles, and a very strong Van der Waals force works between particles. And has a large aspect ratio. Therefore, it is more difficult to disperse the single-walled carbon nanotubes in the dispersion medium than the multi-walled carbon nanotubes, and it is difficult to sufficiently disperse the single-walled carbon nanotubes in the dispersion medium by the conventional carbon nanotube dispersion method. In particular, when an organic solvent is used as the dispersion medium, it is extremely difficult to sufficiently disperse the single-walled carbon nanotubes, and there is still room for study on the dispersion method.
In addition, the dispersion liquid of single-walled carbon nanotubes is inferior in stability over time to the dispersion liquid of multi-walled carbon nanotubes, and particularly at high temperatures (40° C., etc.), it is easy to re-aggregate even once, so that the low temperature It had to be stored.
また、分散液中のカーボンナノチューブ含有量が高くなると、分散液の粘度が高くなって、分散液の流動性が低下する。そうすると、分散液を他のバインダー成分等と混合した際に均一に混合させることが困難になったり、分散液自体の正確な計量も困難になったりするため、当該混合液を調製するのに非常に時間がかかるという問題がある。また、上記混合液を用いて均一な塗工層を得ることも困難になる。また、高粘度の分散液を用いて製品を加工する際には、装置の耐圧化を高めることが必要になり、それが生産効率の低下を招くことになる。このような問題を避けるために、カーボンナノチューブの分散液は低粘度であることが好ましい。 Further, when the content of carbon nanotubes in the dispersion is high, the viscosity of the dispersion is high and the fluidity of the dispersion is low. This makes it difficult to uniformly mix the dispersion with other binder components and the like, and also makes it difficult to accurately measure the dispersion itself, which is extremely difficult to prepare the mixture. There is a problem that it takes time. Further, it becomes difficult to obtain a uniform coating layer using the above mixed solution. Further, when processing a product using a high-viscosity dispersion liquid, it is necessary to increase the pressure resistance of the device, which leads to a reduction in production efficiency. In order to avoid such a problem, it is preferable that the dispersion liquid of carbon nanotubes has a low viscosity.
しかしながら、現時点では、分散性に優れ、経時安定性が良く、再凝集しにくい、低粘度な単層カーボンナノチューブの有機溶媒分散液を得る方法については未だ充分に検討されていない。 However, at present, a method for obtaining a low-viscosity organic solvent dispersion liquid of single-walled carbon nanotubes, which has excellent dispersibility, good stability over time, is hard to re-aggregate, has not yet been sufficiently studied.
本発明は、上記現状に鑑みて、単層カーボンナノチューブの分散性に優れ、経時安定性が良く、再凝集しにくい低粘度の、単層カーボンナノチューブを含む有機溶媒分散液、及びその製造方法を提供することを目的とする。 In view of the above situation, the present invention has excellent dispersibility of single-walled carbon nanotubes, good stability over time, and low viscosity that does not easily re-aggregate, an organic solvent dispersion liquid containing single-walled carbon nanotubes, and a method for producing the same. The purpose is to provide.
本発明者は、単層カーボンナノチューブを含むカーボンナノチューブの分散媒への分散方法について種々検討したところ、少なくとも、単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを用い、超音波照射工程と粉砕メディアを使用しない分散機による分散工程とを含む所定の方法により分散液を製造すると、分散性に優れ、経時安定性がよく、再凝集しにくい、低粘度な、単層カーボンナノチューブの有機溶媒分散液を容易に製造できることを見いだした。また、上記製造方法により得られる単層カーボンナノチューブの分散液を用いれば、透明性と導電性の両方に優れた塗膜が得られることも見いだし、本発明を完成するに至った。 The present inventor has conducted various studies on methods of dispersing carbon nanotubes containing single-walled carbon nanotubes in a dispersion medium. As a result, an ultrasonic wave irradiation step is performed using at least single-walled carbon nanotubes, a polymer dispersant, and an organic solvent. When a dispersion is produced by a predetermined method including a dispersion step using a disperser that does not use a crushing medium, it has excellent dispersibility, good stability over time, is hard to re-aggregate, has low viscosity, and is an organic single-walled carbon nanotube. It has been found that a solvent dispersion can be easily produced. Moreover, it was also found that a coating film excellent in both transparency and conductivity can be obtained by using a dispersion of single-walled carbon nanotubes obtained by the above-mentioned production method, and the present invention has been completed.
すなわち、本発明は、少なくとも、カーボンナノチューブ、高分子分散剤、及び有機溶媒を含むカーボンナノチューブの分散液であって、上記分散液は、カーボンナノチューブを０．０１～１０質量％含み、上記カーボンナノチューブは、短径が０．１～５０ｎｍであり、アスペクト比が１００以上である単層カーボンナノチューブを７５質量％以上含み、上記カーボンナノチューブの含有量が０．２質量％となるように上記分散液を調製した調製液の粘度が、５００ｍＰａ・ｓ未満であることを特徴とするカーボンナノチューブ分散液である。 That is, the present invention provides a dispersion liquid of carbon nanotubes containing at least carbon nanotubes, a polymer dispersant, and an organic solvent, wherein the dispersion liquid contains 0.01 to 10% by mass of carbon nanotubes. Is 75% by mass or more of single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, and the dispersion liquid is adjusted so that the content of the carbon nanotubes is 0.2% by mass. The viscosity of the prepared liquid prepared in 1. is less than 500 mPa·s, which is a carbon nanotube dispersion liquid.
上記分散液において、上記カーボンナノチューブの粒子径Ｄ５０が、５μｍ未満であることが好ましい。 In the dispersion liquid, the particle diameter D50 of the carbon nanotubes is preferably less than 5 μm.
上記分散液において、上記カーボンナノチューブの粒子径Ｄ９０が、１０μｍ未満であることが好ましい。 In the dispersion liquid, the particle diameter D90 of the carbon nanotubes is preferably less than 10 μm.
上記分散液において、更に、分散助剤を含むことが好ましい。 It is preferable that the dispersion liquid further contains a dispersion aid.
上記分散液において、上記高分子分散剤は、カチオン系高分子分散剤であることが好ましい。 In the dispersion liquid, the polymer dispersant is preferably a cationic polymer dispersant.
上記分散液において、上記有機溶媒は、エステル系溶媒、ケトン系溶媒、グリコール系溶媒、アルコール系溶媒、及び、窒素含有極性溶媒からなる群より選択される少なくとも１種であることが好ましい。 In the dispersion liquid, the organic solvent is preferably at least one selected from the group consisting of an ester solvent, a ketone solvent, a glycol solvent, an alcohol solvent, and a nitrogen-containing polar solvent.
上記分散液を使用して下記の方法で形成された塗膜の全光線透過率が９０％以上であり、かつ、表面抵抗値が１．０×１０９Ω／□未満であることが好ましい。
塗膜の形成方法：塗膜中の上記カーボンナノチューブの濃度が８質量％となるように、上記分散液とメタクリル酸ブチル樹脂と上記有機溶媒を混合して、固形分１質量％の樹脂組成物を調製し、上記樹脂組成物を、ワイヤー径が０．２７ミルであるバーコーターを用いてポリエチレンテレフタレートフィルム上に塗布し、塗布物を乾燥させて塗膜を形成する。 It is preferable that the coating film formed by the following method using the above dispersion has a total light transmittance of 90% or more and a surface resistance value of less than 1.0×10 9 Ω/□.
Method for forming coating film: A resin composition having a solid content of 1% by mass, which is prepared by mixing the dispersion liquid, the butyl methacrylate resin and the organic solvent so that the concentration of the carbon nanotubes in the coating film is 8% by mass. Is prepared, and the above resin composition is applied onto a polyethylene terephthalate film using a bar coater having a wire diameter of 0.27 mil, and the applied material is dried to form a coating film.
本発明はまた、少なくとも、短径が０．１～５０ｎｍでありアスペクト比が１００以上である単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する工程（１）、上記工程（１）で得られた混合物に超音波を照射する工程（２）、上記工程（２）で得られた超音波照射物を、粉砕メディアを使用しない分散機により分散する工程（３）、及び、上記工程（３）で得られた分散物に高分子分散剤を添加し、得られた混合物に超音波を照射する工程（４）を含むことを特徴とする単層カーボンナノチューブ分散液の製造方法である。 The present invention also provides a step (1) of mixing at least a single-walled carbon nanotube having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent, and the above step ( A step (2) of irradiating the mixture obtained in 1) with ultrasonic waves, a step (3) of dispersing the ultrasonic irradiation product obtained in the step (2) by a disperser which does not use grinding media, and A method for producing a single-walled carbon nanotube dispersion, which comprises the step (4) of adding a polymer dispersant to the dispersion obtained in the above step (3) and irradiating the obtained mixture with ultrasonic waves. Is.
上記分散液の製造方法において、上記工程（１）の前に、上記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄する工程を含むことが好ましい。 The method for producing a dispersion liquid preferably includes a step of washing the single-walled carbon nanotube with an inorganic acid or a solution containing an inorganic acid before the step (1).
上記工程（１）において、更に分散助剤を混合することが好ましい。 In the step (1), it is preferable to further mix a dispersion aid.
上記分散液の製造方法において、上記高分子分散剤は、カチオン系高分子分散剤であることが好ましい。 In the method for producing the dispersion liquid, the polymer dispersant is preferably a cationic polymer dispersant.
上記分散液の製造方法において、上記有機溶媒は、エステル系溶媒、ケトン系溶媒、グリコール系溶媒、アルコール系溶媒、及び、窒素含有極性溶媒からなる群より選択される少なくとも１種であることが好ましい。 In the method for producing a dispersion liquid, the organic solvent is preferably at least one selected from the group consisting of an ester solvent, a ketone solvent, a glycol solvent, an alcohol solvent, and a nitrogen-containing polar solvent. ..
本発明によれば、単層カーボンナノチューブを含むカーボンナノチューブの分散性に優れ、経時安定性が良く、再凝集しにくい、低粘度なカーボンナノチューブ分散液を得ることができる。また、本発明の分散液を使用すると、少量の添加で高い導電性を付与することができるので、導電性及び透明性の両方に優れた塗膜等を形成することができる。本発明の分散液は、導電性材料として、好適に使用することができる。 According to the present invention, it is possible to obtain a low-viscosity carbon nanotube dispersion having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes, good stability over time, and less likely to re-aggregate. Further, when the dispersion liquid of the present invention is used, high conductivity can be imparted with a small amount of addition, so that a coating film or the like excellent in both conductivity and transparency can be formed. The dispersion liquid of the present invention can be preferably used as a conductive material.
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。 The present invention is described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
１．分散液
本発明は、少なくとも、カーボンナノチューブ、高分子分散剤、及び有機溶媒を含むカーボンナノチューブの分散液であって、上記分散液は、カーボンナノチューブを０．０１～１０質量％含み、上記カーボンナノチューブは、短径が０．１～５０ｎｍであり、アスペクト比が１００以上である単層カーボンナノチューブを７５質量％以上含み、上記カーボンナノチューブの含有量が０．２質量％となるように上記分散液を調製した調製液の粘度が、５００ｍＰａ・ｓ未満であることを特徴とするカーボンナノチューブ分散液である。 1. Dispersion liquid The present invention is a dispersion liquid of carbon nanotubes containing at least carbon nanotubes, a polymer dispersant, and an organic solvent, wherein the dispersion liquid contains 0.01 to 10% by mass of carbon nanotubes. Is 75% by mass or more of single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, and the dispersion liquid is adjusted so that the content of the carbon nanotubes is 0.2% by mass. The viscosity of the prepared liquid prepared in 1. is less than 500 mPa·s, which is a carbon nanotube dispersion liquid.
本発明の分散液は、分散性に優れ、経時安定性が良く、再凝集しにくい、低粘度の単層カーボンナノチューブの有機溶媒分散液である。本発明の分散液が分散性に優れ、経時安定性が良く、再凝集しにくい、低粘度の単層カーボンナノチューブの有機溶媒分散液であるのは、所定範囲の短径とアスペクト比を有する単層カーボンナノチューブを所定範囲量で含み、所定範囲の粘度を有することによる。 The dispersion liquid of the present invention is a low-viscosity organic solvent dispersion liquid of single-walled carbon nanotubes having excellent dispersibility, good stability over time, and hardly re-aggregated. The dispersion of the present invention is an organic solvent dispersion of low-viscosity single-walled carbon nanotubes, which has excellent dispersibility, good stability over time, is difficult to re-aggregate, and has a short diameter and an aspect ratio within a predetermined range. This is because the single-walled carbon nanotubes are contained in a predetermined range amount and have a viscosity in a predetermined range.
また、本発明の分散液を用いると、導電性及び透明性に優れた塗膜を形成することができる。
本発明の分散液が、導電性及び透明性に優れた塗膜を形成することができるのは、カーボンナノチューブとして、単層カーボンナノチューブを、カーボンナノチューブ中７５質量％以上含むものを用いることで、多層カーボンナノチューブに比べて少ない使用量で優れた導電性を得ることができること、及び、粒子間で非常に強いファンデルワールス力が働き、またアスペクト比が大きい単層カーボンナノチューブを使用しながら、低粘度でカーボンナノチューブの凝集物が少ない良好な分散状態を安定的に維持できていることによる。 Further, when the dispersion liquid of the present invention is used, a coating film having excellent conductivity and transparency can be formed.
The dispersion of the present invention can form a coating film excellent in conductivity and transparency by using a single-walled carbon nanotube as the carbon nanotube, which contains 75% by mass or more of the carbon nanotube, Compared with multi-walled carbon nanotubes, excellent conductivity can be obtained with a smaller amount of use, and very strong van der Waals force acts between particles, and while using single-walled carbon nanotubes with a large aspect ratio, low This is due to the fact that it is possible to stably maintain a good dispersed state in which there are few aggregates of carbon nanotubes due to viscosity.
このような本発明の分散液は、後述する特定の製造方法により製造することができ、単層カーボンナノチューブを含むカーボンナノチューブの濃度が、分散液中０．２質量％と比較的高い状態であっても、カーボンナノチューブの分散性に優れ、経時安定性が良く、再凝集しにくい比較的低粘度の分散液を得ることができる。
カーボンナノチューブの含有量が０．２質量％である分散液が、分散性に優れ、経時安定性が良く、再凝集しにくく、低粘度であると、他のバインダー成分等と混合する際に広範囲の処方が可能である。また、溶媒揮発工程での溶媒の揮発量を減らすことが可能である。 Such a dispersion of the present invention can be produced by a specific production method described below, and the concentration of carbon nanotubes including single-walled carbon nanotubes is relatively high at 0.2% by mass in the dispersion. However, it is possible to obtain a dispersion having a relatively low viscosity, which has excellent dispersibility of carbon nanotubes, good stability over time, and is less likely to re-aggregate.
A dispersion having a carbon nanotube content of 0.2% by mass has excellent dispersibility, good stability over time, is difficult to re-aggregate, and has a low viscosity, so that it can be widely mixed with other binder components. Can be prescribed. Further, it is possible to reduce the amount of solvent volatilized in the solvent volatilization step.
本発明の分散液は、上記カーボンナノチューブ（好ましくは、単層カーボンナノチューブである。）の含有量が０．２質量％となるように上記分散液を調製した調製液の粘度が、５００ｍＰａ・ｓ未満である。
上記粘度が上記範囲であると、カーボンナノチューブの分散性が良好になり、経時安定性に優れ、再凝集しにくく、低粘度の分散液となりうる。また、分散液の自重での濾過回収率を高めることができる。上記回収率が高いと分散液の取り扱いが容易になる。上記調製液の粘度は、自重での濾過回収率がより一層高くなる点で、３００ｍＰａ・ｓ以下であることが好ましく、１００ｍＰａ・ｓ以下であることがより好ましい。なお、本発明の分散液の粘度は、通常、５ｍＰａ・ｓ以上である。 The dispersion of the present invention has a viscosity of 500 mPa·s prepared by preparing the dispersion so that the content of the carbon nanotubes (preferably single-walled carbon nanotubes) is 0.2% by mass. Is less than.
When the viscosity is in the above range, the dispersibility of the carbon nanotubes is good, the stability over time is excellent, re-aggregation is difficult, and a low viscosity dispersion liquid can be obtained. In addition, the filtration recovery rate of the dispersion liquid by its own weight can be increased. When the recovery rate is high, the dispersion liquid can be easily handled. The viscosity of the prepared liquid is preferably 300 mPa·s or less, and more preferably 100 mPa·s or less, from the viewpoint of further increasing the filtration recovery rate by its own weight. The viscosity of the dispersion liquid of the present invention is usually 5 mPa·s or more.
上記分散液を調製して調製液を作製する方法としては、上記分散液に、上記分散液に含まれる有機溶媒と同様の有機溶媒を添加したり、又は、上記有機溶媒を一部除去したりして、所定のカーボンナノチューブの濃度（０．２質量％）となるよう適宜調製する方法が挙げられる。上記有機溶媒を除去する方法としては、特に限定されず、減圧蒸留等の公知の方法が挙げられる。 As a method for preparing the dispersion by preparing the dispersion, the same organic solvent as the organic solvent contained in the dispersion may be added to the dispersion, or the organic solvent may be partially removed. Then, a method of appropriately adjusting the concentration of carbon nanotubes to a predetermined value (0.2% by mass) can be given. The method for removing the organic solvent is not particularly limited, and a known method such as vacuum distillation may be used.
上記粘度は、ＢＩＩ型粘度計（東機産業株式会社製）を用いて、２５℃、回転数６０ｒｐｍの条件下で測定することにより得られる値である。 The viscosity is a value obtained by measuring with a BII type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25° C. and a rotation speed of 60 rpm.
上記自重での濾過回収率は、単層カーボンナノチューブ分散液１００ｇを、目開き５３μｍのポリエステルメッシュ（１０ｃｍ×１０ｃｍ）に滴下し、１分間での、自重でのポリエステルメッシュ通過量を測定し、下記の式に基づいて算出することにより求めることができる。
自重での濾過回収率（％）＝〔１分間のポリエステルメッシュ通過量（ｇ）／１００（ｇ）〕×１００ The filtration recovery rate by the above self-weight is obtained by dropping 100 g of the single-walled carbon nanotube dispersion liquid onto a polyester mesh (10 cm×10 cm) having an opening of 53 μm, and measuring the amount of the self-weight passing through the polyester mesh for 1 minute. It can be obtained by calculating based on the equation.
Filtration and recovery rate (%) by own weight=[amount of polyester mesh per minute (g)/100 (g)]×100
上記回収率は、７５％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。
上記回収率が低いと、他のバインダーとの均一混合や、正確な計量が困難になることによる作業時間の増加、装置の耐圧化を高めることによる生産効率の低下を招くおそれがある。 The recovery rate is preferably 75% or more, more preferably 80% or more, and further preferably 90% or more.
If the recovery rate is low, there is a possibility that uniform mixing with another binder, increase in working time due to difficulty in accurate measurement, and increase in pressure resistance of the apparatus may result in reduction in production efficiency.
本発明の分散液は、少なくとも、カーボンナノチューブ、高分子分散剤、及び有機溶媒を含む。以下に、本発明の分散液に含まれる各成分について説明する。 The dispersion liquid of the present invention contains at least carbon nanotubes, a polymer dispersant, and an organic solvent. Each component contained in the dispersion liquid of the present invention will be described below.
（カーボンナノチューブ）
本発明の分散液において使用されるカーボンナノチューブは、短径が０．１～５０ｎｍであり、アスペクト比が１００以上である単層カーボンナノチューブを含む。
上記単層カーボンナノチューブは、単層のグラフェンから形成される継ぎ目のない円筒状物質である。
上記単層カーボンナノチューブの短径とは、円筒状である単層カーボンナノチューブの直径である。上記短径は、好ましくは０．１～４０ｎｍであり、より好ましくは０．３～２０ｎｍであり、更に好ましくは、０．５～１０ｎｍである。 (carbon nanotube)
The carbon nanotubes used in the dispersion of the present invention include single-walled carbon nanotubes having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more.
The single-walled carbon nanotube is a seamless cylindrical material formed of single-walled graphene.
The short diameter of the single-walled carbon nanotube is the diameter of the cylindrical single-walled carbon nanotube. The minor axis is preferably 0.1 to 40 nm, more preferably 0.3 to 20 nm, and further preferably 0.5 to 10 nm.
また、上記単層カーボンナノチューブは、アスペクト比が１００以上である。上記アスペクト比とは、円筒状である単層カーボンナノチューブの直径（短径）をＡ（ｎｍ）とし、長さ（長径）をＢ（ｎｍ）とした場合の、（Ｂ）／（Ａ）の値である。
上記アスペクト比は、５００以上が好ましく、１５００以上がより好ましい。上記アスペクト比の上限としては、２０００００以下が好ましく、１００００以下がより好ましい。 Further, the single-walled carbon nanotube has an aspect ratio of 100 or more. The aspect ratio is the ratio of (B)/(A) when the diameter (minor axis) of the cylindrical single-walled carbon nanotube is A (nm) and the length (major axis) is B (nm). It is a value.
The aspect ratio is preferably 500 or more, more preferably 1500 or more. The upper limit of the aspect ratio is preferably 200,000 or less, more preferably 10,000 or less.
上記長径は、１００～１００００００ｎｍであることが好ましく、５００～５０００００ｎｍであることがより好ましく、１０００～１０００００ｎｍであることが更に好ましい。上記長径とは、円筒状である単層カーボンナノチューブの長さである。 The major axis is preferably 100 to 1,000,000 nm, more preferably 500 to 500,000 nm, further preferably 1,000 to 100,000 nm. The major axis is the length of the single-walled carbon nanotube having a cylindrical shape.
上記短径及び長径は、原子間力顕微鏡（ＡＦＭ）、ラマン分光法（Ｒａｍａｎ）、透過型電子顕微鏡（ＴＥＭ）等により測定することができる。 The minor axis and major axis can be measured by an atomic force microscope (AFM), Raman spectroscopy (Raman), a transmission electron microscope (TEM), or the like.
本発明においては、上記単層カーボンナノチューブとして、市販品を用いてもよい。本発明において使用することができる単層カーボンナノチューブの市販品の具体例としては、例えば、ＴＵＢＡＬＬ（登録商標）（ＯＣＳｉＡｌ社製）、ＺＥＯＮＡＮＯ（登録商標）ＳＧ１０１（ゼオンナノテクノロジー株式会社製）等を挙げることができる。なかでも、本発明の分散液の分散性をより一層向上させることができる点で、ＴＵＢＡＬＬ（登録商標）（ＯＣＳｉＡｌ社製）が好ましい。
上記単層カーボンナノチューブは、１種のみ使用してもよいし、２種以上組み合わせて使用してもよい。 In the present invention, a commercially available product may be used as the single-walled carbon nanotube. Specific examples of commercially available single-walled carbon nanotubes that can be used in the present invention include TUBALL (registered trademark) (manufactured by OCSiAl) and ZEONANO (registered trademark) SG101 (manufactured by ZEON Nano Technology Co., Ltd.). Can be mentioned. Among them, TUBALL (registered trademark) (manufactured by OCSiAl) is preferable because the dispersibility of the dispersion liquid of the present invention can be further improved.
The single-walled carbon nanotubes may be used alone or in combination of two or more.
本発明の分散液において使用するカーボンナノチューブは、上記単層カーボンナノチューブ以外のカーボンナノチューブ、例えば、多層カーボンナノチューブ等の他のカーボンナノチューブを含んでいてもよいが、上記単層カーボンナノチューブを７５質量％以上含む。単層カーボンナノチューブを７５質量％以上含むことにより、樹脂等に本発明の分散液を少量添加するだけで高い導電性を付与することができ、優れた透明性と導電性を兼ね備えた塗膜等を形成することができる。
上記多層カーボンナノチューブは、直径の異なる２本以上の単層カーボンナノチューブが同軸で多層に重なったカーボンナノチューブである。
上記カーボンナノチューブは、上記単層カーボンナノチューブを８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、９５質量％以上含むことが更に好ましく、１００質量％含むことが特に好ましい。 The carbon nanotubes used in the dispersion of the present invention may contain carbon nanotubes other than the above single-walled carbon nanotubes, for example, other carbon nanotubes such as multi-walled carbon nanotubes. Including the above. By containing the single-walled carbon nanotubes in an amount of 75% by mass or more, high conductivity can be imparted by adding a small amount of the dispersion liquid of the present invention to a resin and the like, and a coating film having both excellent transparency and conductivity Can be formed.
The multi-walled carbon nanotube is a carbon nanotube in which two or more single-walled carbon nanotubes having different diameters are coaxially stacked in a multi-layer.
The carbon nanotubes preferably contain 80% by mass or more of the single-walled carbon nanotubes, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.
本発明の分散液において、カーボンナノチューブは、１種のみ使用してもよいし、２種以上を組み合わせて使用してもよい。 In the dispersion liquid of the present invention, one kind of carbon nanotube may be used, or two or more kinds thereof may be used in combination.
本発明の分散液は、カーボンナノチューブを０．０１～１０質量％含む。上記分散液におけるカーボンナノチューブの含有量は、０．０１～１質量％であることが好ましく、０．０１～０．５質量％であることがより好ましい。 The dispersion liquid of the present invention contains 0.01 to 10% by mass of carbon nanotubes. The content of carbon nanotubes in the dispersion is preferably 0.01 to 1% by mass, and more preferably 0.01 to 0.5% by mass.
本発明の分散液において、上記カーボンナノチューブの粒子径Ｄ５０は、５μｍ未満であることが好ましい。上記カーボンナノチューブの粒子径Ｄ５０が上記範囲であると、カーボンナノチューブの分散性がより一層良好になり、再凝集しにくい低粘度な分散液となりうる。上記粒子径Ｄ５０は、４μｍ未満であることがより好ましく、３μｍ未満であることが更に好ましい。上記粒子径Ｄ５０の下限値は、特に限定されないが、繊維破断により充分な導電性が得られないことを防ぐ為には０．５μｍ以上が好ましく、１μｍ以上がより好ましい。 In the dispersion liquid of the present invention, the particle diameter D50 of the carbon nanotubes is preferably less than 5 μm. When the particle diameter D50 of the carbon nanotubes is in the above range, the dispersibility of the carbon nanotubes is further improved, and a low-viscosity dispersion liquid that is unlikely to re-aggregate can be obtained. The particle diameter D50 is more preferably less than 4 μm, further preferably less than 3 μm. The lower limit of the particle diameter D50 is not particularly limited, but is preferably 0.5 μm or more, and more preferably 1 μm or more in order to prevent insufficient conductivity due to fiber breakage.
また、上記カーボンナノチューブの粒子径Ｄ９０は、１０μｍ未満であることが好ましい。上記カーボンナノチューブの粒子径Ｄ９０が１０μｍ未満であると、カーボンナノチューブの分散性がより一層良好になり、再凝集しにくい低粘度の分散液となりうる。上記粒子径Ｄ９０は、８μｍ未満であることがより好ましく、５μｍ未満であることが更に好ましい。上記粒子径Ｄ９０の下限値は、特に限定されないが、繊維破断により優れた導電性が得られないことを防ぐ為には１．５μｍ以上が好ましく、２μｍ以上がより好ましく、３μｍ以上が更に好ましく、３．５μｍ以上が特に好ましい。 The particle diameter D90 of the carbon nanotubes is preferably less than 10 μm. When the particle diameter D90 of the carbon nanotubes is less than 10 μm, the dispersibility of the carbon nanotubes is further improved, and a low-viscosity dispersion liquid that hardly re-aggregates can be obtained. The particle diameter D90 is more preferably less than 8 μm, further preferably less than 5 μm. The lower limit of the particle diameter D90 is not particularly limited, but is preferably 1.5 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, in order to prevent that excellent conductivity due to fiber breakage cannot be obtained. It is particularly preferably 3.5 μm or more.
上記粒子径Ｄ５０及びＤ９０は、上記分散液を粒度分布測定可能な濃度に適宜希釈して、ＬＡ－９５０Ｖ２（株式会社堀場製作所製）等のレーザー回折／散乱式粒子径分布定装置により測定して得られる値である。 The particle diameters D50 and D90 are measured by a laser diffraction/scattering particle diameter distribution analyzer such as LA-950V2 (manufactured by Horiba, Ltd.) by appropriately diluting the dispersion liquid to a concentration at which particle size distribution can be measured. This is the value obtained.
（高分子分散剤）
本発明において使用される高分子分散剤としては、カーボンナノチューブの分散性を向上させることができるものであれば特に限定されず、ノニオン系高分子分散剤、アニオン系高分子分散剤、カチオン系高分子分散剤等が挙げられるが、なかでもカーボンナノチューブの分散性をより一層向上させることができる点で、カチオン系高分子分散剤であることが好ましい。 (Polymer dispersant)
The polymer dispersant used in the present invention is not particularly limited as long as it can improve the dispersibility of carbon nanotubes, and includes nonionic polymer dispersants, anion polymer dispersants, and cationic high dispersants. Examples thereof include molecular dispersants, and among them, cationic polymer dispersants are preferable from the viewpoint that the dispersibility of carbon nanotubes can be further improved.
上記カチオン系高分子分散剤としては、アミン基等の塩基性官能基を有する高分子等が挙げられ、例えば、塩基性官能基含有共重合体；塩基性官能基を有する高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、変性ポリアクリル酸塩、又は（メタ）アクリル系共重合体；ポリエチレンイミン；ポリオキシエチレンアルキルアミン；アルカノールアミン；アルキルアンモニウム塩、又はアルキルアセタール化ポリビニルアルコール等が挙げられる。
なかでも、単層カーボンナノチューブの分散性をより一層向させることができる点で、上記カチオン系高分子分散剤は、塩基性官能基含有共重合体、塩基性官能基を有する（メタ）アクリル系共重合体、又は、アルキルアセタール化ポリビニルアルコールであることが好ましい。 Examples of the cationic polymer dispersant include polymers having a basic functional group such as an amine group, and the like, for example, a basic functional group-containing copolymer; a high molecular weight unsaturated acid ester having a basic functional group. , Modified polyurethane, modified polyester, modified poly(meth)acrylate, modified polyacrylic acid salt, or (meth)acrylic copolymer; polyethyleneimine; polyoxyethylenealkylamine; alkanolamine; alkylammonium salt or alkylacetalization Examples thereof include polyvinyl alcohol and the like.
Among them, the cationic polymer dispersant is a copolymer having a basic functional group, a (meth)acrylic resin having a basic functional group, in that the dispersibility of the single-walled carbon nanotube can be further improved. It is preferably a copolymer or an alkyl acetalized polyvinyl alcohol.
上記高分子分散剤は、直鎖状、末端変性型、ブロック型、又はグラフト型の高分子であってもよい。 The polymer dispersant may be a linear, terminal-modified, block-type, or graft-type polymer.
上記高分子分散剤のアミン価は、カーボンナノチューブの分散性をより一層向上させることができる点で、０ｍｇＫＯＨ／ｇ以上であることが好ましく、５ｍｇＫＯＨ／ｇ以上であることがより好ましく、１００ｍｇＫＯＨ／ｇ以下であることが好ましく、７５ｍｇＫＯＨ／ｇ以下であることがより好ましく、５０ｍｇＫＯＨ／ｇ以下であることが更に好ましい。上記アミン価は、０～１００ｍｇＫＯＨ／ｇであることが好ましく、５～１００ｍｇＫＯＨ／ｇであることがより好ましく、５～７５ｍｇＫＯＨ／ｇであることが更に好ましく、５～５０ｍｇＫＯＨ／ｇであることが特に好ましい。 The amine value of the polymer dispersant is preferably 0 mgKOH/g or more, more preferably 5 mgKOH/g or more, and 100 mgKOH/g from the viewpoint that the dispersibility of carbon nanotubes can be further improved. It is preferably not more than 75 mgKOH/g, more preferably not more than 50 mgKOH/g. The amine value is preferably 0 to 100 mgKOH/g, more preferably 5 to 100 mgKOH/g, further preferably 5 to 75 mgKOH/g, and particularly preferably 5 to 50 mgKOH/g. preferable.
本発明においては、上記高分子分散剤として、市販品を用いてもよい。本発明において使用することができる高分子分散剤の市販品の具体例としては、アジスパー　ＰＢ８２１、ＰＢ８２２、ＰＢ８２４、ＰＢ８８１（いずれも、味の素ファインテクノ株式会社製）、Ｅｆｋａ（登録商標）ＰＸ４３２０、ＰＸ４３１０、ＰＸ４３００、ＰＸ４３３０、ＰＸ４３４０、ＰＸ４７００、ＰＸ４７０１、ＰＸ４７３１、ＰＸ４７３２、ＰＵ４０６３、ＰＡ４４００、ＰＡ４４０１、ＰＡ４４０３（いずれも、ＢＡＳＦ社製）、ＢＹＫ－９０７７（ビックケミー社製）、エスレックＢＬ－１、ＢＬ－２、ＢＬ－５、ＢＬ－１０、ＢＬ－Ｓ（いずれも、積水化学工業株式会社製）等が挙げられる。
なかでも、上記分散液の分散性をより一層向上させることができる点で、アジスパー　ＰＢ８２１、Ｅｆｋａ（登録商標）ＰＸ４３２０、エスレックＢＬ－１０、エスレックＢＬ－Ｓが好ましい。 In the present invention, a commercially available product may be used as the polymer dispersant. Specific examples of commercially available polymer dispersants that can be used in the present invention include Azisper PB821, PB822, PB824, PB881 (all manufactured by Ajinomoto Fine-Techno Co., Inc.), Efka (registered trademark) PX4320, PX4310, PX4300, PX4330, PX4340, PX4700, PX4701, PX4731, PX4732, PU4063, PA4400, PA4401, PA4403 (all manufactured by BASF), BYK-9077 (manufactured by BYK Chemie), S-REC BL-1, BL-2, BL-. 5, BL-10, BL-S (all manufactured by Sekisui Chemical Co., Ltd.) and the like.
Of these, Azisper PB821, Efka (registered trademark) PX4320, S-REC BL-10, and S-REC BL-S are preferable because the dispersibility of the dispersion liquid can be further improved.
上記高分子分散剤は、１種のみ使用してもよいし、２種以上を組み合わせて使用してもよい。 The above polymer dispersants may be used alone or in combination of two or more.
本発明の分散液における上記高分子分散剤の含有量は、１～１０質量％であることが好ましく、１～５質量％であることがより好ましく、１～３質量％であることが更に好ましい。 The content of the polymer dispersant in the dispersion liquid of the present invention is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and further preferably 1 to 3% by mass. ..
（有機溶媒）
本発明において使用される有機溶媒としては、特に限定されず、例えば、アルコール系溶媒（メタノール、エタノール、ブタノール、イソプロパノール、フェノール等）、アミン系溶媒（トリエチルアミン、トリメタノールアミン等）、エーテル系溶媒（ジオキサン、テトラヒドロフラン等）、エーテルアルコール系溶媒（２－メトキシエタノール、エトキシエタノール、メトキシエトキシエタノール、フェニルエタノール等）、グリコール系溶媒（エチレングリコール、エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル等）、エステル系溶媒（酢酸メチル、酢酸エチル、酢酸ノルマルブチル等）、カーボネート系溶媒（エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、ブチレンカーボネート等）、ケトン系溶媒（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等）、炭化水素系溶媒（トルエン、ベンゼン、キシレン、ヘキサン、シクロヘキサン等）、塩素含有炭化水素系溶媒（クロロホルム、ジクロロメタン、クロロベンゼン等）、低級カルボン酸（酢酸等）、窒素含有極性溶媒（Ｎ，Ｎ－ジメチルホルムアミド、ニトロメタン、Ｎ－メチルピロリドン等）、硫黄化合物系溶媒（ジメチルスルホキシド等）等を用いることができる。 (Organic solvent)
The organic solvent used in the present invention is not particularly limited, and examples thereof include alcohol solvents (methanol, ethanol, butanol, isopropanol, phenol, etc.), amine solvents (triethylamine, trimethanolamine, etc.), ether solvents ( Dioxane, tetrahydrofuran, etc.), ether alcohol solvent (2-methoxyethanol, ethoxyethanol, methoxyethoxyethanol, phenylethanol, etc.), glycol solvent (ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, etc.), ester solvents (methyl acetate, ethyl acetate, normal butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene carbonate, etc.), ketone solvents Solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), hydrocarbon solvents (toluene, benzene, xylene, hexane, cyclohexane, etc.), chlorine-containing hydrocarbon solvents (chloroform, dichloromethane, chlorobenzene, etc.), lower carboxylic acids ( Acetic acid and the like), nitrogen-containing polar solvent (N,N-dimethylformamide, nitromethane, N-methylpyrrolidone and the like), sulfur compound-based solvent (dimethyl sulfoxide and the like) and the like can be used.
なかでも、単層カーボンナノチューブの分散性をより一層向上させることができる点で、エステル系溶媒、ケトン系溶媒、グリコール系溶媒、アルコール系溶媒、又は、窒素含有極性溶媒であることが好ましく、エステル系溶媒、グリコール系溶媒、又は、ケトン系溶媒であることがより好ましく、酢酸ノルマルブチル、プロピレングリコールモノメチルエーテルアセテート、又は、メチルエチルケトンであることが更に好ましい。
上記有機溶媒は、１種のみ使用してもよいし、２種以上を混合して使用してもよい。 Among them, the ester solvent, the ketone solvent, the glycol solvent, the alcohol solvent, or the nitrogen-containing polar solvent is preferable in that the dispersibility of the single-walled carbon nanotube can be further improved, and the ester is preferably used. A system solvent, a glycol solvent, or a ketone solvent is more preferable, and normal butyl acetate, propylene glycol monomethyl ether acetate, or methyl ethyl ketone is further preferable.
The above organic solvents may be used alone or in combination of two or more.
本発明の分散液における上記有機溶媒の含有量は、８９～９８質量％であることが好ましく、９３～９８質量％であることがより好ましく、９５～９８質量％であることが更に好ましい。 The content of the organic solvent in the dispersion liquid of the present invention is preferably 89 to 98% by mass, more preferably 93 to 98% by mass, and further preferably 95 to 98% by mass.
本発明の分散液は、分散媒として、上記有機溶媒の他に水等を含んでいてもよいが、上記有機溶媒は、分散媒中に９５質量％以上含まれているのが好ましく、９８質量％以上含まれているのがより好ましく、１００質量％含まれているのが更に好ましい。 The dispersion liquid of the present invention may contain water or the like as a dispersion medium in addition to the above organic solvent, but the organic solvent is preferably contained in the dispersion medium in an amount of 95% by mass or more, and 98% by mass. % Or more is more preferable, and 100% by mass is further preferable.
（他の成分）
本発明の分散液は、少なくとも、上記のカーボンナノチューブ、高分子分散剤、及び有機溶媒を含むものであるが、他の成分を更に含んでいてもよい。
上記他の成分としては、例えば、分散助剤、ｐＨ調整剤、表面調整剤等が挙げられる。なかでも、単層カーボンナノチューブの濡れをより一層高め、分散性（経時安定性の向上、再凝集抑制、低粘度化）を向上させることができる点で、上記分散液は分散助剤を更に含むことが好ましい。
上記他の成分の種類や含有量は、上記分散液の目的、用途に応じて、公知のものから適宜選択することができる。 (Other ingredients)
The dispersion liquid of the present invention contains at least the above carbon nanotubes, a polymer dispersant, and an organic solvent, but may further contain other components.
Examples of the other components include a dispersion aid, a pH adjusting agent, a surface adjusting agent, and the like. Among them, the above-mentioned dispersion liquid further contains a dispersion aid in that the wettability of the single-walled carbon nanotube can be further enhanced and the dispersibility (improvement of stability over time, suppression of re-aggregation, reduction of viscosity) can be improved. It is preferable.
The types and contents of the other components described above can be appropriately selected from known ones according to the purpose and application of the dispersion.
上記分散助剤としては、例えば、ＳＯＬＳＰＥＲＳＥ　５０００、ＳＯＬＳＰＥＲＳＥ　１２０００（Ｌｕｂｒｉｚｏｌ社製）等のフタロシアニン誘導体、ＳＯＬＳＰＥＲＳＥ　２２０００（Ｌｕｂｒｉｚｏｌ社製）等のアゾ誘導体等が挙げられる。 Examples of the dispersion aid include phthalocyanine derivatives such as SOLSPERSE 5000 and SOLSPERSE 12000 (manufactured by Lubrizol), and azo derivatives such as SOLSPERSE 22000 (manufactured by Lubrizol).
本発明の分散液を使用すれば、透明性及び導電性に優れた塗膜を形成することができる。
本発明の分散液を使用して後述する方法で形成された塗膜は、全光線透過率が９０％以上であり、かつ、表面抵抗値が１．０×１０９Ω／□未満であることが好ましい。
上記全光線透過率は、９３％以上であることが好ましく、９５％以上であることがより好ましい。
上記全光線透過率は、ヘイズメーターＨＺ－２（スガ試験機株式会社製）等のヘイズメーターを用いて、全光線透過率規格（ＩＳＯ　１３４６８－１、ＪＩＳ　Ｋ　７３６１）に準じた方法により測定して得られる値である。 By using the dispersion of the present invention, a coating film having excellent transparency and conductivity can be formed.
The coating film formed by the method described below using the dispersion liquid of the present invention has a total light transmittance of 90% or more and a surface resistance value of less than 1.0×10 9 Ω/□. Is preferred.
The total light transmittance is preferably 93% or more, more preferably 95% or more.
The total light transmittance is measured using a haze meter such as Haze Meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.) by a method according to the total light transmittance standard (ISO 13468-1, JIS K 7361). It is the value obtained by
上記表面抵抗値は、５．０×１０８Ω／□未満であることが好ましく、１．０×１０７Ω／□未満であることがより好ましい。
上記表面抵抗値は、ハイレスタＭＣＰ－ＨＴ４５０（三菱化学株式会社製）等の抵抗率計を用いて、２０℃で、塗膜表面を流れる電流値を測定することにより得られる値である。 The surface resistance value is preferably less than 5.0×10 8 Ω/□, and more preferably less than 1.0×10 7 Ω/□.
The surface resistance value is a value obtained by measuring the current value flowing on the coating film surface at 20° C. using a resistivity meter such as Hiresta MCP-HT450 (manufactured by Mitsubishi Chemical Corporation).
上記全光線透過率と表面抵抗値を測定するための塗膜は、塗膜中のカーボンナノチューブの濃度が８質量％となるように、本発明の分散液とメタクリル酸ブチル樹脂と有機溶媒を混合して、固形分１質量％の樹脂組成物を調製し、上記樹脂組成物を、ワイヤー径が０．２７ミルであるバーコーターを用いてポリエチレンテレフタレートフィルム上に塗布し、塗布物を乾燥させることにより、形成することができる。
上記有機溶媒としては、本発明の分散液に含まれる有機溶媒と同じ有機溶媒が挙げられる。 The coating film for measuring the total light transmittance and the surface resistance value was prepared by mixing the dispersion liquid of the present invention, butyl methacrylate resin and an organic solvent so that the concentration of carbon nanotubes in the coating film was 8% by mass. Then, a resin composition having a solid content of 1% by mass is prepared, and the resin composition is applied onto a polyethylene terephthalate film using a bar coater having a wire diameter of 0.27 mil, and the applied material is dried. Can be formed.
Examples of the organic solvent include the same organic solvents as those contained in the dispersion of the present invention.
上記塗布物の乾燥方法は、塗布物中の有機溶媒が十分に留去されて塗膜が形成される方法であれば、特に限定されず、使用する有機溶媒の種類に応じて、加熱乾燥等の公知の方法から適宜選択して行うことができる。乾燥条件も、使用する有機溶媒の種類等に応じて適宜選択することができる。 The method for drying the coating material is not particularly limited as long as the organic solvent in the coating material is sufficiently distilled off to form a coating film, depending on the type of the organic solvent used, heat drying, etc. It can be performed by appropriately selecting from known methods. The drying conditions can also be appropriately selected according to the type of organic solvent used and the like.
２．分散液の製造方法
本発明の分散液は、上述した本発明の分散液の要件を満たす分散液が製造されることになる限り、その製造方法は特に制限されないが、例えば、下記の工程（１）～（４）を含む方法が好ましく挙げられる。
工程（１）：少なくとも、短径が０．１～５０ｎｍでありアスペクト比が１００以上である単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する工程
工程（２）：工程（１）で得られた混合物に超音波を照射する工程
工程（３）：工程（２）で得られた超音波照射物を、粉砕メディアを使用しない分散機により分散する工程
工程（４）：工程（３）で得られた分散物に高分子分散剤を添加し、得られた混合物に超音波を照射する工程。 2. Manufacturing Method of Dispersion The dispersion of the present invention is not particularly limited as long as the dispersion satisfying the requirements of the above-mentioned dispersion of the present invention is manufactured, but for example, the following step (1 The method including (1) to (4) is preferable.
Step (1): At least a step of mixing single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent. Step (2): Step ( Step of irradiating the mixture obtained in 1) with ultrasonic waves Step (3): Step of dispersing the ultrasonic irradiation object obtained in Step (2) by a disperser which does not use grinding media Step (4): Step A step of adding a polymer dispersant to the dispersion obtained in (3) and irradiating the obtained mixture with ultrasonic waves.
上記の工程（１）～（４）を含むことにより、分散性に優れ、経時安定性が良好で、再凝集しにくい低粘度な単層カーボンナノチューブを含む分散液を好適に製造することができる。このような、少なくとも、短径が０．１～５０ｎｍでありアスペクト比が１００以上である単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する工程（１）、上記工程（１）で得られた混合物に超音波を照射する工程（２）、上記工程（２）で得られた超音波照射物を、粉砕メディアを使用しない分散機により分散する工程（３）、及び、上記工程（３）で得られた分散物に高分子分散剤を添加し、得られた混合物に超音波を照射する工程（４）を含むことを特徴とする単層カーボンナノチューブ分散液の製造方法もまた、本発明の一つである。 By including the above steps (1) to (4), it is possible to favorably produce a dispersion containing a low-viscosity single-walled carbon nanotube having excellent dispersibility, good stability over time, and less likely to re-aggregate. .. Such a step (1) of mixing the single-walled carbon nanotubes having a minor axis of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent, and the above step (1). ) A step (2) of irradiating the mixture obtained in (1) with ultrasonic waves, a step (3) of dispersing the ultrasonic wave obtained in the above step (2) by a disperser which does not use grinding media, and A method for producing a single-walled carbon nanotube dispersion, which comprises the step (4) of adding a polymer dispersant to the dispersion obtained in the step (3) and irradiating the obtained mixture with ultrasonic waves. It is also one of the present invention.
本発明の分散液の製造方法は、工程（１）で少なくとも、単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合した後、工程（２）の超音波処理により、単層カーボンナノチューブを有機溶媒と高分子分散剤で十分に濡らすことでカーボンナノチューブが分散しやすい状態にし、工程（３）の粉砕メディアを使用しない分散機を用いた分散により、単層カーボンナノチューブの繊維構造を破壊せずに解し、更に、工程（４）の高分子分散剤を添加して超音波処理することで、単層カーボンナノチューブを分散安定化させる方法である。
以下、各工程について、詳細に説明する。 In the method for producing a dispersion liquid of the present invention, at least the single-walled carbon nanotube, the polymer dispersant, and the organic solvent are mixed in the step (1), and then the single-walled carbon is subjected to the ultrasonic treatment in the step (2). Wetting the nanotubes sufficiently with an organic solvent and a polymeric dispersant makes the carbon nanotubes easier to disperse, and the dispersion using a disperser that does not use the grinding media in step (3) causes the fiber structure of the single-walled carbon nanotubes to change. In this method, the single-walled carbon nanotubes are dispersed and stabilized by breaking them without breaking them, and further adding the polymer dispersant in the step (4) and performing ultrasonic treatment.
Hereinafter, each step will be described in detail.
工程（１）
本発明の分散液の製造方法においては、まず、少なくとも、短径が０．１～５０ｎｍでありアスペクト比が１００以上である単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する。
少なくとも、上記単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する方法としては、特に限定されず、ミキサー、ディゾルバー等の攪拌混合装置を用いる等の公知の混合手段が挙げられる。また、これらの成分は、任意の順で混合することができる。例えば、高分子分散剤を有機溶媒に溶解させた溶液を予め調製し、この溶液と、単層カーボンナノチューブとを混合してもよい。
なお、工程（１）は、単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する工程であるが、これらの成分のみを混合することを意味するものではなく、カーボンナノチューブとして単層カーボンナノチューブに加えて多層カーボンナノチューブを混合してもよい。また、後述する分散助剤等の他の成分を混合してもよい。 Process (1)
In the method for producing a dispersion liquid of the present invention, first, at least a single-walled carbon nanotube having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent are mixed. ..
At least the method for mixing the single-walled carbon nanotubes, the polymer dispersant, and the organic solvent is not particularly limited, and known mixing means such as using a stirring and mixing device such as a mixer or a dissolver can be used. Also, these components can be mixed in any order. For example, a solution in which a polymer dispersant is dissolved in an organic solvent may be prepared in advance, and this solution may be mixed with the single-walled carbon nanotube.
Although step (1) is a step of mixing the single-walled carbon nanotubes, the polymer dispersant, and the organic solvent, it does not mean that only these components are mixed, and the single-walled carbon nanotubes are not mixed. In addition to the multi-walled carbon nanotubes, multi-walled carbon nanotubes may be mixed. Moreover, you may mix other components, such as a dispersion auxiliary agent mentioned later.
上記単層カーボンナノチューブ、高分子分散剤、有機溶媒としては、いずれも上述の「１．分散液」において記載したものと同様のものが挙げられる。各成分は、上述の「１．分散液」において記載される含有割合となるように混合されることが好ましい。また、単層カーボンナノチューブに加えて多層カーボンナノチューブも混合する場合は、上述の「１．分散液」に記載される含有割合となるように混合することが好ましい。 As the above-mentioned single-walled carbon nanotube, polymer dispersant, and organic solvent, the same ones as described in the above "1. Dispersion" can be mentioned. The respective components are preferably mixed so as to have the content ratios described in the above "1. Dispersion". When multi-walled carbon nanotubes are also mixed in addition to the single-walled carbon nanotubes, it is preferable to mix them so that the content ratio is as described in “1. Dispersion” above.
また、上記工程（１）において、上述した成分に加えて、分散助剤を更に混合することが好ましい。分散助剤を更に混合することにより、工程（２）での単層カーボンナノチューブの濡れをより一層高め、分散性がより一層優れた分散液を製造することができる。
上記分散助剤としては、上述の「１．分散液」において記載したものと同様のものが挙げられる。
上記分散助剤の添加量としては、特に限定されないが、単層カーボンナノチューブ１００質量部に対して１０～１００質量部であることが好ましく、１０～６０質量部であることがより好ましく、２０～４０質量部であることが更に好ましい。 In addition, in the step (1), it is preferable to further mix a dispersion aid in addition to the components described above. By further mixing the dispersion aid, the wettability of the single-walled carbon nanotube in the step (2) can be further enhanced, and a dispersion liquid having further excellent dispersibility can be produced.
Examples of the dispersion aid include the same as those described in "1. Dispersion" above.
The amount of the dispersion aid added is not particularly limited, but is preferably 10 to 100 parts by mass, more preferably 10 to 60 parts by mass, and 20 to 20 parts by mass with respect to 100 parts by mass of the single-walled carbon nanotube. It is more preferably 40 parts by mass.
本発明の分散液の製造方法においてはまた、上記工程（１）の前に、上記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄する工程を含むことが好ましい。
上記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄することにより、単層カーボンナノチューブに含まれる鉄等の不純物質を除去し、単層カーボンナノチューブの純度を高めることができる。
上記無機酸としては、塩酸、硫酸、硝酸、リン酸、過酸化水素等が挙げられる。
上記無機酸を含む溶液としては、上記無機酸と、水を混合した溶液等が挙げられる。
なお、本発明の分散液の製造方法において、原料として単層カーボンナノチューブに加えて多層カーボンナノチューブも使用される場合には、多層カーボンナノチューブも含んだカーボンナノチューブ全体について、上記洗浄工程を行うことが好ましい。 The method for producing a dispersion liquid of the present invention preferably also includes a step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid before the step (1).
By washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid, impurities such as iron contained in the single-walled carbon nanotubes can be removed and the purity of the single-walled carbon nanotubes can be increased.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrogen peroxide and the like.
Examples of the solution containing the inorganic acid include a solution obtained by mixing the inorganic acid with water.
In the method for producing a dispersion of the present invention, when multi-walled carbon nanotubes are used as a raw material in addition to single-walled carbon nanotubes, the above-mentioned washing step may be performed on the entire carbon nanotubes including multi-walled carbon nanotubes. preferable.
上記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄する方法としては、特に限定されず、公知の方法で行うことができる。 The method for washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid is not particularly limited, and a known method can be used.
工程（２）
本発明の分散液の製造方法においては、次に、上記工程（１）で得られた混合物に超音波を照射する。
超音波照射の方法は、特に限定されず、超音波装置等を用いて公知の方法により行うことができる。
超音波照射の条件として、振幅は１０～１００μｍであることが好ましく、１０～６０μｍであることがより好ましく、１０～４０μｍであることが更に好ましい。
出力は、１０～５０００Ｗであることが好ましく、１００～３０００Ｗであることがより好ましく、２００～１５００Ｗであることが更に好ましい。
照射時間は、３０秒以上であることが好ましく、より好ましくは６０秒以上、更に好ましくは３００秒以上であり、上限は特に限定されないが、６００秒以下であることが好ましく、４８０秒以下であることが更に好ましい。
照射時の分散液の温度は、特に限定されないが、通常２０～８０℃、好ましくは３０～７０℃、より好ましくは４０～６０℃である。
上述のとおり、超音波照射は、カーボンナノチューブを有機溶媒で十分に濡らすことを目的とする工程であるため、工程（２）は、上記超音波照射の条件を参考にして、カーボンナノチューブが有機溶媒で十分に濡れる条件を適宜設定して行うことができる。 Process (2)
In the method for producing a dispersion liquid of the present invention, next, the mixture obtained in the above step (1) is irradiated with ultrasonic waves.
The ultrasonic irradiation method is not particularly limited, and it can be performed by a known method using an ultrasonic device or the like.
As conditions for ultrasonic irradiation, the amplitude is preferably 10 to 100 μm, more preferably 10 to 60 μm, and further preferably 10 to 40 μm.
The output is preferably 10 to 5000 W, more preferably 100 to 3000 W, and further preferably 200 to 1500 W.
The irradiation time is preferably 30 seconds or more, more preferably 60 seconds or more, further preferably 300 seconds or more, and the upper limit is not particularly limited, but it is preferably 600 seconds or less and 480 seconds or less. Is more preferable.
The temperature of the dispersion liquid during irradiation is not particularly limited, but is usually 20 to 80° C., preferably 30 to 70° C., and more preferably 40 to 60° C.
As described above, the ultrasonic irradiation is a process for the purpose of sufficiently wetting the carbon nanotubes with the organic solvent. Therefore, in the step (2), referring to the ultrasonic irradiation conditions, the carbon nanotubes are treated with an organic solvent. Can be set by appropriately setting the conditions for sufficiently wetting.
工程（３）
本発明の分散液の製造方法においては、次いで、上記工程（２）で得られた超音波照射物を、粉砕メディアを使用しない分散機により分散する。
上記粉砕メディアを使用しない分散機としては、例えば、ミキサー、ホモジナイザー、ディソルバー、ロールミル、混練機、ジェットミル、ナノマイザー等が挙げられる。なかでも、ジェットミルが好ましく、湿式ジェットミルがより好ましい。
上記湿式ジェットミルとしては、例えば、吉田機械興業株式会社製の卓上型湿式超高圧微粒化実験装置ＮＶＬ－ＥＳ００８－Ｄ等が挙げられる。 Process (3)
In the method for producing a dispersion liquid of the present invention, next, the ultrasonic irradiation product obtained in the above step (2) is dispersed by a disperser which does not use a grinding medium.
Examples of the disperser that does not use the grinding media include a mixer, a homogenizer, a dissolver, a roll mill, a kneader, a jet mill, and a nanomizer. Among them, the jet mill is preferable, and the wet jet mill is more preferable.
Examples of the wet jet mill include a table-top type wet ultrahigh pressure atomization experimental device NVL-ES008-D manufactured by Yoshida Kikai Co., Ltd.
工程（３）の分散において湿式ジェットミルを使用する場合、処理圧力は５０～３００ＭＰａであることが好ましく、１００～２５０ＭＰａであることがより好ましく、１５０～２００ＭＰａであることが更に好ましい。
また、ゲージの形状としては、クロス又はストレートが挙げられるが、クロスであることが好ましい。 When a wet jet mill is used in the dispersion in the step (3), the processing pressure is preferably 50 to 300 MPa, more preferably 100 to 250 MPa, further preferably 150 to 200 MPa.
The shape of the gauge may be cross or straight, but is preferably cross.
工程（３）における上記粉砕メディアを使用しない分散機による分散は、分散液の粘度が、工程（２）直後の分散液の粘度よりも大きくなるのを確認した後、終了することが好ましい。 Dispersion in the step (3) using a disperser that does not use the grinding media is preferably completed after confirming that the viscosity of the dispersion becomes higher than that of the dispersion immediately after the step (2).
工程（４）
本発明の分散液の製造方法においては、更に、上記工程（３）で得られた分散物に、高分子分散剤を添加し、得られた混合物に超音波を照射する。
上記高分子分散剤としては、上述の「１．分散液」において記載した高分子分散剤と同様のものが好ましく挙げられ、上記工程（１）で使用する高分子分散剤と同様のものであることが好ましい。
上記高分子分散剤の添加量としては、得られる分散液における上記高分子分散剤の含有量が、「１．分散液」において記載した高分子分散剤の含有量となるよう適宜調製すればよいが、工程（１）と工程（４）で半分量ずつ添加することが好ましい。 Process (4)
In the method for producing a dispersion liquid of the present invention, a polymer dispersant is further added to the dispersion obtained in the above step (3), and the resulting mixture is irradiated with ultrasonic waves.
As the polymer dispersant, those similar to the polymer dispersants described in the above “1. Dispersion” are preferably mentioned, and the same as the polymer dispersants used in the step (1). It is preferable.
The amount of the polymer dispersant added may be appropriately adjusted so that the content of the polymer dispersant in the obtained dispersion becomes the content of the polymer dispersant described in “1. Dispersion”. However, it is preferable to add half each amount in step (1) and step (4).
工程（４）における超音波照射の条件としては、上記工程（１）における超音波照射の条件と同様の条件が好ましく挙げられるが、工程（１）よりも照射時間を長く設定してもよい。
工程（４）における上記照射時間は、６０秒以上であることが好ましく、より好ましくは１２０秒以上、更に好ましくは６００秒以上であり、上限は特に限定されないが、１８００秒以下であることが好ましく、１２００秒以下であることがより好ましい。 The conditions for ultrasonic irradiation in step (4) are preferably the same as the conditions for ultrasonic irradiation in step (1) above, but the irradiation time may be set longer than in step (1).
The irradiation time in the step (4) is preferably 60 seconds or more, more preferably 120 seconds or more, further preferably 600 seconds or more, and the upper limit is not particularly limited, but it is preferably 1800 seconds or less. It is more preferably 1200 seconds or less.
また、工程（４）における超音波照射終了後は、得られた分散液を３０分程放置した場合、ビーカー側面に析出物が付着しないことが好ましい。 Further, after the ultrasonic wave irradiation in the step (4) is finished, it is preferable that the deposit is not attached to the side surface of the beaker when the obtained dispersion liquid is left for about 30 minutes.
以上の工程（１）～（４）を行うことにより、単層カーボンナノチューブの分散性に優れ、低粘度で、経時安定性が良く、単層カーボンナノチューブが再凝集しにくい分散液を容易に製造することができる。 By performing the above steps (1) to (4), it is possible to easily produce a dispersion liquid having excellent dispersibility of single-walled carbon nanotubes, low viscosity, good stability over time, and less likely to reaggregate single-walled carbon nanotubes. can do.
本発明の分散液の製造方法は、上記工程（１）～（４）及び上記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄する工程以外の他の工程を含んでいてもよい。上記他の工程としては、熱交換器による冷却工程等が挙げられる。 The method for producing a dispersion liquid of the present invention may include steps other than the steps (1) to (4) and the step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid. Examples of the other steps include a cooling step using a heat exchanger.
３．用途
本発明の分散液は、上述のように、単層カーボンナノチューブを含むカーボンナノチューブの分散性に優れ、再凝集しにくい低粘度の分散液である。また、経時安定性にも優れる。本発明の分散液を用いれば、単層カーボンナノチューブを含むカーボンナノチューブを樹脂等に容易に混合させることができ、しかも少量の添加で樹脂等に高い導電性を付与することができるので、優れた透明性と導電性を有する塗膜等を形成することができる。
このような本発明の分散液は、導電性と透明性が同時に求められる用途に好適に使用することができ、上記用途としては、例えば、半導体、一次電池、二次電池、燃料電池、光学機器、通信機器、導電性塗料、透明導電膜等が挙げられる。 3. Applications As described above, the dispersion liquid of the present invention is a low-viscosity dispersion liquid having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes and hardly reaggregating. It also has excellent stability over time. Use of the dispersion liquid of the present invention makes it possible to easily mix carbon nanotubes, including single-walled carbon nanotubes, with a resin, and to impart high conductivity to the resin with a small amount of addition, which is excellent. A coating film or the like having transparency and conductivity can be formed.
Such a dispersion liquid of the present invention can be suitably used for applications where conductivity and transparency are required at the same time, and examples of the applications include semiconductors, primary batteries, secondary batteries, fuel cells, and optical devices. , Communication devices, conductive paints, transparent conductive films, and the like.
以上のとおり、本発明の分散液は、単層カーボンナノチューブを含むカーボンナノチューブの分散性に優れ、経時安定性が良く、上記カーボンナノチューブが再凝集しにくい低粘度な分散液である。本発明の分散液を使用すれば、導電性と透明性に優れた塗膜等を製造することができる。また、本発明の分散液の製造方法によれば、単層カーボンナノチューブの濃度が比較的高濃度であっても、分散性に優れ、経時安定性が良く、再凝集しにくい低粘度な分散液を好適に製造することができる。本発明の分散液及びその製造方法は、半導体、一次電池、二次電池、燃料電池、光学機器、通信機器等の電子・電気や光学分野、導電性塗料、透明導電膜等において非常に有用である。 As described above, the dispersion liquid of the present invention is a dispersion liquid having excellent dispersibility of carbon nanotubes including single-walled carbon nanotubes, good stability over time, and being hard to reaggregate the carbon nanotubes. By using the dispersion liquid of the present invention, it is possible to produce a coating film having excellent conductivity and transparency. Further, according to the method for producing a dispersion of the present invention, even when the concentration of the single-walled carbon nanotube is relatively high, the dispersion has excellent dispersibility, good stability over time, and low viscosity that does not easily re-aggregate. Can be suitably manufactured. INDUSTRIAL APPLICABILITY The dispersion liquid and the method for producing the same according to the present invention are very useful in semiconductors, primary batteries, secondary batteries, fuel cells, optical and electronic fields such as optical devices and communication devices, optical fields, conductive paints, transparent conductive films and the like. is there.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.
実施例１
＜調製例１＞　高分子分散剤溶液１の調製
５００ｃｃステンレスタンクに高分子分散剤１（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）と酢酸ノルマルブチルを、下記の配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液１を１００ｇ得た。
配合比（質量比）：高分子分散剤１／酢酸ノルマルブチル＝２０／８０ Example 1
<Preparation Example 1> Preparation of polymer dispersant solution 1 Polymer dispersant 1 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) in a 500 cc stainless tank. Ajinomoto Fine Techno Co., Ltd.) and normal butyl acetate were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) in the following compounding ratio, and a polymer dispersant solution 1 having a solid content of 20% by mass was prepared. Was obtained.
Mixing ratio (mass ratio): Polymer dispersant 1/Normal butyl acetate=20/80
＜製造例１＞　分散液１の製造
（第１工程）
調製例１で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））と、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）と、調製例１で調製した高分子分散剤溶液１と、酢酸ノルマルブチルとを、下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液１／酢酸ノルマルブチル＝０．２／０．０６／５／８９．７４ <Production Example 1> Production of dispersion 1 (first step)
In a 500 cc stainless tank different from the stainless tank used in Preparation Example 1, a single-walled carbon nanotube (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) was used. 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), and polymer dispersant prepared in Preparation Example 1 Solution 1 and normal butyl acetate were weighed and mixed in the following mixing ratio, and stirred with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed liquid.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 1/normal butyl acetate=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射して、中間分散液１－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed solution obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion 1-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液１－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させて、中間分散液１－２を９５ｇ得た。
分散条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 1-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultra-high pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 1-2 was obtained.
Dispersion conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, cross nozzle used
（第４工程）
第３工程で得られた中間分散液１－２と調製例１で作製した高分子分散剤溶液１を、下記配合比にて混合し、中間分散液１－３を１００ｇ得た。更に中間分散液１－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液１（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散液１－２／高分子分散剤溶液１＝９５／５
超音波照射条件：振幅３０μｍ、出力：６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 1-2 obtained in the third step and the polymer dispersant solution 1 prepared in Preparation Example 1 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 1-3. Further, the intermediate dispersion liquid 1-3 is irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, whereby the single-walled carbon nanotube dispersion liquid 1 (single-walled carbon nanotubes) is irradiated. 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion liquid 1-2/polymer dispersant solution 1=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output: 650 W, time 1 min
実施例２
＜調製例２＞　高分子分散剤溶液２の調製
５００ｃｃステンレスタンクに高分子分散剤２（商品名：Ｅｆｋａ（登録商標）ＰＸ　４３２０、固形分５０質量％、アクリルブロックコポリマー高分子、アミン価３０ｍｇＫＯＨ／ｇ、ＢＡＳＦ社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液２を１００ｇ得た。
配合比（質量比）：高分子分散剤２／酢酸ノルマルブチル＝４０／６０ Example 2
Preparation Example 2 Preparation of Polymer Dispersant Solution 2 Polymer dispersant 2 (trade name: Efka (registered trademark) PX 4320, solid content 50 mass%, acrylic block copolymer polymer, amine value 30 mgKOH/in a 500 cc stainless tank. g, manufactured by BASF) and normal butyl acetate are mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following compounding ratio, and 100 g of a polymer dispersant solution 2 having a solid content of 20% by mass. Obtained.
Mixing ratio (mass ratio): Polymer dispersant 2/Normal butyl acetate=40/60
＜製造例２＞　分散液２の製造
（第１工程）
調製例２で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、上記高分子分散剤溶液２、及び、酢酸ノルマルブチルを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液２／酢酸ノルマルブチル＝０．２／０．０６／５／８９．７４ <Production Example 2> Production of dispersion 2 (first step)
In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 2, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), the above polymer dispersant solution 2, and normal acetate normal Butyl was weighed and mixed in the following mixing ratio, and stirred with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 2/normal butyl acetate=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射して、中間分散液２－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 2-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液２－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させて、中間分散液２－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 2-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 2-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液２－２と調製例２で作製した高分子分散剤溶液２を、下記配合比にて混合し、中間分散液２－３を１００ｇ得た。更に中間分散液２－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液２（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体２－２／高分子分散剤溶液２＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 2-2 obtained in the third step and the polymer dispersant solution 2 prepared in Preparation Example 2 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 2-3. Further, the intermediate dispersion liquid 2-3 is irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, whereby the single-walled carbon nanotube dispersion liquid 2 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 2-2/polymer dispersant solution 2=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
実施例３
＜調製例３＞　高分子分散剤溶液３の調製
５００ｃｃステンレスタンクに、高分子分散剤３（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）とメチルエチルケトン（以下、「ＭＥＫ」とも称する。）を、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液３を１００ｇ得た。
配合比（質量比）：高分子分散剤３／ＭＥＫ＝２０／８０ Example 3
Preparation Example 3 Preparation of Polymer Dispersant Solution 3 Polymer dispersant 3 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was prepared in a 500 cc stainless tank. , Ajinomoto Fine Techno Co., Ltd. and methyl ethyl ketone (hereinafter, also referred to as “MEK”) were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) at the following mixing ratio, and a solid content of 20 mass. % Of the polymer dispersant solution 3 was obtained.
Mixing ratio (mass ratio): Polymer dispersant 3/MEK=20/80
＜製造例３＞　分散液３の製造
（第１工程）
調製例３で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液３、及び、メチルエチルケトンを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液３／メチルエチルケトン＝０．２／０．０６／５／８９．７４ <Production Example 3> Production of dispersion 3 (first step)
In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 3, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 3, and methyl ethyl ketone are described below. The mixture was weighed and mixed at a compounding ratio, and stirred with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 3/methyl ethyl ketone=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液３－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 3-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液３－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液３－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 3-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultra-high pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Kogyo Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 3-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液３－２と調製例３で作製した高分子分散剤溶液３を、下記配合比にて混合し、中間分散液３－３を１００ｇ得た。更に中間分散液３－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液３（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体３－２／高分子分散剤溶液３＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 3-2 obtained in the third step and the polymer dispersant solution 3 prepared in Preparation Example 3 were mixed in the following mixing ratio to obtain 100 g of the intermediate dispersion liquid 3-3. Further, by irradiating the intermediate dispersion liquid 3-3 with ultrasonic waves with an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, the single-walled carbon nanotube dispersion liquid 3 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 3-2/polymer dispersant solution 3=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
実施例４
＜調製例４＞　高分子分散剤溶液４の調製
５００ｃｃステンレスタンクに、高分子分散剤４（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）とプロピレングリコールモノメチルエーテルアセテート（以下、「ＰＭＡ」とも称する。）を、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液４を１００ｇ得た。
配合比（質量比）：高分子分散剤４／ＰＭＡ＝２０／８０ Example 4
Preparation Example 4 Preparation of Polymer Dispersant Solution 4 Polymer dispersant 4 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was placed in a 500 cc stainless tank. , Ajinomoto Fine Techno Co., Ltd. and propylene glycol monomethyl ether acetate (hereinafter, also referred to as “PMA”) are mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) at the following mixing ratio, 100 g of a polymer dispersant solution 4 having a solid content of 20 mass% was obtained.
Mixing ratio (mass ratio): Polymer dispersant 4/PMA=20/80
＜製造例４＞　分散液４の製造
（第１工程）
調製例４で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液４、及び、ＰＭＡを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液４／ＰＭＡ＝０．２／０．０６／５／８９．７４ <Production Example 4> Production of dispersion liquid 4 (first step)
In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 4, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 4, and PMA are described below. The mixture was weighed and mixed at a compounding ratio, and stirred with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 4/PMA=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液４－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 4-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液４－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液４－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 4-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultra-high pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 4-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液４－２と調製例４で作製した高分子分散剤溶液４を、下記配合比にて混合し、中間分散液４－３を１００ｇ得た。更に中間分散液４－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液４（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体４－２／高分子分散剤溶液４＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 4-2 obtained in the third step and the polymer dispersant solution 4 prepared in Preparation Example 4 were mixed in the following mixing ratio to obtain 100 g of the intermediate dispersion liquid 4-3. Further, by irradiating the intermediate dispersion liquid 4-3 with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, the single-walled carbon nanotube dispersion liquid 4 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 4-2/polymer dispersant solution 4=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
実施例５
＜調製例５＞　高分子分散剤溶液５の調製
５００ｃｃステンレスタンクに、高分子分散剤５（商品名：エスレックＢＬ－１０、固形分１００質量％、アルキルアセタール化ポリビニルアルコール、アミン価０ｍｇＫＯＨ／ｇ、積水化学工業株式会社製）とイソプロパノール（以下、「ＩＰＡ」とも称する。）を、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液５を１００ｇ得た。
配合比（質量比）：高分子分散剤５／ＩＰＡ＝２０／８０ Example 5
Preparation Example 5 Preparation of Polymer Dispersant Solution 5 Polymer dispersant 5 (trade name: S-REC BL-10, solid content 100% by mass, alkyl acetalized polyvinyl alcohol, amine value 0 mgKOH/g, was added to a 500 cc stainless tank. Sekisui Chemical Co., Ltd.) and isopropanol (hereinafter, also referred to as “IPA”) were mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following mixing ratio, and solid content was 20% by mass. 100 g of the polymer dispersant solution 5 of was obtained.
Mixing ratio (mass ratio): Polymer dispersant 5/IPA=20/80
＜製造例５＞　分散液５の製造
（第１工程）
調製例５で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液５、及び、ＩＰＡを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液５／ＩＰＡ＝０．２／０．０６／５／８９．７４ <Production Example 5> Production of dispersion liquid 5 (first step)
In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 5, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 5, and IPA are described below. The mixture was weighed and mixed at a compounding ratio, and stirred with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 5/IPA=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液５－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 5-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液５－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液５－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 5-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 5-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液５－２と調製例５で作製した高分子分散剤溶液５を、下記配合比にて混合し、中間分散液５－３を１００ｇ得た。更に中間分散液５－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液５（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体５－２／高分子分散剤溶液５＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 5-2 obtained in the third step and the polymer dispersant solution 5 prepared in Preparation Example 5 were mixed in the following mixing ratio to obtain 100 g of the intermediate dispersion liquid 5-3. Further, by irradiating the intermediate dispersion liquid 5-3 with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, the single-walled carbon nanotube dispersion liquid 5 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 5-2/polymer dispersant solution 5=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
実施例６
＜調製例６＞　高分子分散剤溶液６の調製
５００ｃｃステンレスタンクに、高分子分散剤６（商品名：エスレックＢＬ－１０、固形分１００質量％、アルキルアセタール化ポリビニルアルコール、アミン価０ｍｇＫＯＨ／ｇ、積水化学工業株式会社製）とＮ－メチルピロリドン（以下、「ＮＭＰ」とも称する。）を、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液６を１００ｇ得た。
配合比（質量比）：高分子分散剤６／ＮＭＰ＝２０／８０ Example 6
Preparation Example 6 Preparation of Polymer Dispersant Solution 6 A polymer dispersant 6 (trade name: S-REC BL-10, solid content 100% by mass, alkyl acetalized polyvinyl alcohol, amine value 0 mgKOH/g, was added to a 500 cc stainless tank. Sekisui Chemical Co., Ltd.) and N-methylpyrrolidone (hereinafter, also referred to as “NMP”) were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) in the following mixing ratio to obtain a solid content. 100 g of a 20% by mass polymer dispersant solution 6 was obtained.
Mixing ratio (mass ratio): Polymer dispersant 6/NMP=20/80
＜製造例６＞　分散液６の製造
（第１工程）
調製例６で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液６、及び、ＮＭＰを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液６／ＮＭＰ＝０．２／０．０６／５／８９．７４ <Production Example 6> Production of dispersion liquid 6 (first step)
In a 500 cc stainless steel tank different from the stainless steel tank used in Preparation Example 6, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 6, and NMP are described below. The mixture was weighed and mixed at a compounding ratio, and stirred with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 6/NMP=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液６－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 6-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液６－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液６－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 6-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of Intermediate Dispersion Liquid 6-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液６－２と調製例６で作製した高分子分散剤溶液６を、下記配合比にて混合し、中間分散液６－３を１００ｇ得た。更に中間分散液６－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液６（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体６－２／高分子分散剤溶液６＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 6-2 obtained in the third step and the polymer dispersant solution 6 prepared in Preparation Example 6 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 6-3. Further, by irradiating the intermediate dispersion liquid 6-3 with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, the single-walled carbon nanotube dispersion liquid 6 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 6-2/polymer dispersant solution 6=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
実施例７
＜調製例７＞　高分子分散剤溶液７の調製
５００ｃｃステンレスタンクに、高分子分散剤７（商品名：エスレックＢＬ－Ｓ、固形分１００質量％、アルキルアセタール化ポリビニルアルコール、アミン価０ｍｇＫＯＨ／ｇ、積水化学工業株式会社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液７を１００ｇ得た。
配合比（質量比）：高分子分散剤７／酢酸ノルマルブチル＝２０／８０ Example 7
Preparation Example 7 Preparation of Polymer Dispersant Solution 7 Polymer dispersant 7 (trade name: S-REC BL-S, solid content 100 mass %, alkyl acetalized polyvinyl alcohol, amine value 0 mgKOH/g, was added to a 500 cc stainless tank. Sekisui Chemical Co., Ltd.) and normal butyl acetate were mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following compounding ratio to obtain a polymer dispersant solution 7 having a solid content of 20% by mass. 100 g was obtained.
Mixing ratio (mass ratio): Polymer dispersant 7/Normal butyl acetate=20/80
＜製造例７＞　分散液７の製造
（第１工程）
調製例７で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液７、及び、酢酸ノルマルブチルを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液７／酢酸ノルマルブチル＝０．２／０．０６／５／８９．７４ <Production Example 7> Production of dispersion 7 (first step)
In a 500 cc stainless tank different from the stainless tank used in Preparation Example 7, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis) 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 7, and normal butyl acetate Were weighed and mixed in the following mixing ratio, and stirred with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): single-walled carbon nanotube/dispersion aid/polymer dispersant solution 7/normal butyl acetate=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液７－１を９５ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 95 g of Intermediate Dispersion Liquid 7-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液７－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液７－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 7-1 obtained in the second step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 7-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液７－２と調製例７で作製した高分子分散剤溶液７を、下記配合比にて混合し、中間分散液７－３を１００ｇ得た。更に中間分散液７－３に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液７（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体７－２／高分子分散剤溶液７＝９５／５
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
The intermediate dispersion liquid 7-2 obtained in the third step and the polymer dispersant solution 7 prepared in Preparation Example 7 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 7-3. Further, by irradiating the intermediate dispersion liquid 7-3 with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, the single-walled carbon nanotube dispersion liquid 7 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 7-2/polymer dispersant solution 7=95/5
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
比較例１
＜調製例８＞　高分子分散剤溶液８の調製
５００ｃｃステンレスタンクに、高分子分散剤８（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液８を１００ｇ得た。
配合比（質量比）：高分子分散剤８／酢酸ノルマルブチル＝２０／８０ Comparative Example 1
Preparation Example 8 Preparation of Polymer Dispersant Solution 8 Polymer dispersant 8 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was prepared in a 500 cc stainless tank. , Ajinomoto Fine Techno Co., Ltd.) and normal butyl acetate were mixed and dissolved by a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) at the following compounding ratio, and a polymer dispersant solution 8 having a solid content of 20% by mass was prepared. Was obtained.
Mixing ratio (mass ratio): Polymer dispersant 8/Normal butyl acetate=20/80
＜製造例８＞　分散液８の製造
２２５ｃｃガラス瓶に、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液８、及び、酢酸ノルマルブチルを下記配合比にて秤量後、０．３ｍｍφジルコニアビーズを加えてペイントシェイカー（株式会社東洋精機製作所製）で１０時間分散することにより、単層カーボンナノチューブの分散液８（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液８／酢酸ノルマルブチル＝０．２／０．０６／１０／８９．７４ <Production Example 8> Production of Dispersion 8 In a 225 cc glass bottle, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6 ± 0.4 nm, major axis 5 μm or more, Aspect ratio 2,500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 8, and normal butyl acetate are blended below. After being weighed with a ratio, 0.3 mmφ zirconia beads were added and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 10 hours to obtain a single-walled carbon nanotube dispersion 8 (single-walled carbon nanotube concentration 0.2 mass). %) was obtained.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 8/normal butyl acetate=0.2/0.06/10/89.74
比較例２
＜調製例９＞　高分子分散剤溶液９の調製
５００ｃｃステンレスタンクに、高分子分散剤９（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液９を１００ｇ得た。
配合比（質量比）：高分子分散剤９／酢酸ノルマルブチル＝２０／８０ Comparative example 2
Preparation Example 9 Preparation of Polymer Dispersant Solution 9 Polymer dispersant 9 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was placed in a 500 cc stainless tank. , Ajinomoto Fine Techno Co., Ltd.) and normal butyl acetate were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) at the following compounding ratio to obtain a polymer dispersant solution 9 having a solid content of 20% by mass. Was obtained.
Mixing ratio (mass ratio): Polymer dispersant 9/Normal butyl acetate=20/80
＜製造例９＞　分散液９の製造
（第１工程）
２２５ｃｃガラス瓶に、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液９、及び、酢酸ノルマルブチルを下記配合比にて秤量後、０．３ｍｍφジルコニアビーズを加えてペイントシェイカー（株式会社東洋精機製作所製）で１０時間分散することにより、単層カーボンナノチューブの中間分散液９－１を９５ｇ得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液９／酢酸ノルマルブチル＝０．２／０．０６／５／８９．７４ <Production Example 9> Production of dispersion 9 (first step)
In a 225 cc glass bottle, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 / g (BET method)), a dispersion aid (trade name: SOLSPERSE 5000, a phthalocyanine derivative, manufactured by Lubrizol), a polymer dispersant solution 9, and normal butyl acetate are weighed at the following compounding ratio, and then 0.3 mmφ zirconia 95 g of an intermediate dispersion liquid 9-1 of single-walled carbon nanotubes was obtained by adding beads and dispersing with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 10 hours.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 9/normal butyl acetate=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた中間分散液９－１と調製例９で作製した高分子分散剤溶液９を下記配合比にて混合し、中間分散液９－２を１００ｇ得た。更に中間分散液９－２に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することにより、単層カーボンナノチューブ分散液９（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散液９－１／高分子分散剤溶液９＝９５／５
条件　振幅：３０［μｍ］、出力：６５０［Ｗ］、時間：１［ｍｉｎ］ (Second step)
The intermediate dispersion liquid 9-1 obtained in the first step and the polymer dispersant solution 9 prepared in Preparation Example 9 were mixed at the following compounding ratio to obtain 100 g of the intermediate dispersion liquid 9-2. Further, the intermediate dispersion liquid 9-2 is irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, whereby the single-walled carbon nanotube dispersion liquid 9 (single-walled carbon nanotubes) 100 g of a concentration of 0.2% by mass) was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 9-1/polymer dispersant solution 9=95/5
Conditions Amplitude: 30 [μm], Output: 650 [W], Time: 1 [min]
比較例３
＜調製例１０＞　高分子分散剤溶液１０の調製
５００ｃｃステンレスタンクに、高分子分散剤１０（商品名：アジスパー　ＰＢ８２１、アミン価１０ｍｇＫＯＨ／ｇ、固形分１００質量％、味の素ファインテクノ株式会社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液１０を１００ｇ得た。
配合比（質量比）：高分子分散剤１０／酢酸ノルマルブチル＝２０／８０ Comparative Example 3
Preparation Example 10 Preparation of Polymer Dispersant Solution 10 Polymer dispersant 10 (trade name: ADISPER PB821, amine value 10 mgKOH/g, solid content 100% by mass, manufactured by Ajinomoto Fine-Techno Co., Inc.) was placed in a 500 cc stainless tank. Normal butyl acetate was mixed and dissolved with a dissolver (TK homodisper 2.5 type: manufactured by PRIMIX) in the following mixing ratio to obtain 100 g of a polymer dispersant solution 10 having a solid content of 20% by mass.
Mixing ratio (mass ratio): Polymer dispersant 10/Normal butyl acetate=20/80
＜製造例１０＞　分散液１０の製造
（第１工程）
２２５ｃｃガラス瓶に、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液１０、及び、酢酸ノルマルブチルを下記配合比にて秤量後、０．３ｍｍφジルコニアビーズを加えてペイントシェイカー（株式会社東洋精機製作所製）で１０時間分散し、単層カーボンナノチューブの中間分散液１０－１を９５ｇ得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液１０／酢酸ノルマルブチル＝０．２／０．０６／５／８９．７４ <Production Example 10> Production of Dispersion Liquid 10 (First Step)
In a 225 cc glass bottle, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 / g (BET method)), a dispersion aid (trade name: SOLSPERSE 5000, a phthalocyanine derivative, manufactured by Lubrizol), a polymer dispersant solution 10, and normal butyl acetate are weighed at the following compounding ratio, and then 0.3 mmφ zirconia Beads were added and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 10 hours to obtain 95 g of an intermediate dispersion 10-1 of single-walled carbon nanotubes.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 10/normal butyl acetate=0.2/0.06/5/89.74
（第２工程）
第１工程で得られた中間分散液１０－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液１０－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Second step)
Disperse the intermediate dispersion liquid 10-1 obtained in the first step in a wet jet mill (device name: desktop type wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion liquid 10-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第３工程）
第２工程で得られた中間分散液１０－２と調製例１０で作製した高分子分散剤溶液１０を、下記配合比にて混合し、単層カーボンナノチューブ分散液１０（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
配合比（質量比）：中間分散体１０－２／高分子分散剤溶液１０＝９５／５ (Third step)
The intermediate dispersion 10-2 obtained in the second step and the polymer dispersant solution 10 prepared in Preparation Example 10 were mixed in the following mixing ratio to obtain a single-wall carbon nanotube dispersion 10 (single-wall carbon nanotube concentration 0 100% of 0.2 mass% was obtained.
Mixing ratio (mass ratio): Intermediate dispersion 10-2/polymer dispersant solution 10=95/5
比較例４
＜調製例１１＞　高分子分散剤溶液１１の調製
５００ｃｃステンレスタンクに、高分子分散剤１１（商品名：アジスパー　ＰＢ８２１、固形分１００質量％、塩基性官能基含有共重合物、アミン価１０ｍｇＫＯＨ／ｇ、味の素ファインテクノ株式会社製）と酢酸ノルマルブチルを、下記配合比にてディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で混合溶解し、固形分２０質量％の高分子分散剤溶液１１を１００ｇ得た。
配合比（質量比）：高分子分散剤１１／酢酸ノルマルブチル＝２０／８０ Comparative Example 4
Preparation Example 11 Preparation of Polymer Dispersant Solution 11 Polymer dispersant 11 (trade name: ADISPER PB821, solid content 100% by mass, basic functional group-containing copolymer, amine value 10 mgKOH/g) was placed in a 500 cc stainless tank. , Ajinomoto Fine-Techno Co., Ltd.) and normal butyl acetate were mixed and dissolved with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) at the following compounding ratio to obtain a polymer dispersant solution 11 having a solid content of 20% by mass. Was obtained.
Mixing ratio (mass ratio): Polymer dispersant 11/Normal butyl acetate=20/80
＜製造例１１＞　分散液１１の製造
（第１工程）
調製例１１で使用のステンレスタンクとは別の５００ｃｃステンレスタンクに、単層カーボンナノチューブ（ＴＵＢＡＬＬ（登録商標）ＳＷＣＮＴ　９３％、ＯＣＳｉＡｌ社製、純度９３％、短径１．６±０．４ｎｍ、長径５μｍ以上、アスペクト比２５００以上、比表面積１０７０ｍ２／ｇ（ＢＥＴ法））、分散助剤（商品名：ＳＯＬＳＰＥＲＳＥ　５０００、フタロシアニン誘導体、Ｌｕｂｒｉｚｏｌ社製）、高分子分散剤溶液１１、及び、酢酸ノルマルブチルを下記配合比にて秤量混合し、ディゾルバー（ＴＫホモディスパー２．５型：ＰＲＩＭＩＸ社製）で攪拌して、９５ｇの混合液を得た。
配合比（質量比）：単層カーボンナノチューブ／分散助剤／高分子分散剤溶液１１／酢酸ノルマルブチル＝０．２／０．０６／１０／８９．７４ <Production Example 11> Production of dispersion 11 (first step)
In a 500 cc stainless tank different from the stainless tank used in Preparation Example 11, single-walled carbon nanotubes (TUBALL (registered trademark) SWCNT 93%, manufactured by OCSiAl, purity 93%, minor axis 1.6±0.4 nm, major axis). 5 μm or more, aspect ratio 2500 or more, specific surface area 1070 m 2 /g (BET method), dispersion aid (trade name: SOLSPERSE 5000, phthalocyanine derivative, manufactured by Lubrizol), polymer dispersant solution 11, and normal butyl acetate Were weighed and mixed in the following mixing ratio, and stirred with a dissolver (TK Homo Disper 2.5 type: manufactured by PRIMIX) to obtain 95 g of a mixed solution.
Mixing ratio (mass ratio): Single-walled carbon nanotube/dispersion aid/polymer dispersant solution 11/normal butyl acetate=0.2/0.06/10/89.74
（第２工程）
第１工程で得られた混合液に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射し、中間分散液１１－１を１００ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Second step)
The mixed liquid obtained in the first step was irradiated with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions to obtain 100 g of Intermediate Dispersion Liquid 11-1.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
（第３工程）
第２工程で得られた中間分散液１１－１を、下記条件で湿式ジェットミル（装置名：卓上型湿式超高圧微粒化実験装置　ＮＶＬ－ＥＳ００８－Ｄ、吉田機械興業株式会社製）にて分散させ、中間分散液１１－２を９５ｇ得た。
条件：吸込み速度３００％、吐出速度２３５％、処理圧力１５０ＭＰａ、クロスノズル使用 (Third step)
Disperse the intermediate dispersion liquid 11-1 obtained in the second step in a wet jet mill (device name: tabletop wet ultrahigh pressure atomization experimental device NVL-ES008-D, manufactured by Yoshida Kikai Co., Ltd.) under the following conditions. Thus, 95 g of the intermediate dispersion 11-2 was obtained.
Conditions: suction rate 300%, discharge rate 235%, processing pressure 150 MPa, use cross nozzle
（第４工程）
第３工程で得られた中間分散液１１－２に、下記条件で超音波分散機（装置名：ＧＳＤ１２００ＡＴ、株式会社ソニックテクノロジー製）にて超音波を照射することで、単層カーボンナノチューブ分散液１１（単層カーボンナノチューブ濃度０．２質量％）を１００ｇ得た。
超音波照射条件：振幅３０μｍ、出力６５０Ｗ、時間１ｍｉｎ (Fourth step)
By irradiating the intermediate dispersion liquid 11-2 obtained in the third step with ultrasonic waves using an ultrasonic disperser (device name: GSD1200AT, manufactured by Sonic Technology Co., Ltd.) under the following conditions, single-walled carbon nanotube dispersion liquid is obtained. 100 g of 11 (single-walled carbon nanotube concentration: 0.2% by mass) was obtained.
Ultrasonic irradiation conditions: amplitude 30 μm, output 650 W, time 1 min
上記の実施例１～７及び比較例１～４で得られた分散液１～１１の粘度、分散液中の単層カーボンナノチューブの粒子径、回収率、分散液を用いて形成した塗膜の全光線透過率及び表面抵抗値について、下記の方法にて評価を行った。結果を表１に示す。 The viscosities of the dispersions 1 to 11 obtained in Examples 1 to 7 and Comparative Examples 1 to 4 described above, the particle size of the single-walled carbon nanotubes in the dispersions, the recovery rate, and the coating films formed using the dispersions The total light transmittance and the surface resistance value were evaluated by the following methods. The results are shown in Table 1.
＜粘度＞
得られた単層カーボンナノチューブの分散液を２５℃に調整し、ＢＩＩ形粘度計（東機産業株式会社製）にて回転数６０ｒｐｍの時の粘度を測定し、下記の基準にて評価を行った。
評価基準
◎◎：１００ｍＰａ・ｓ未満
◎：１００ｍＰａ・ｓ以上、３００ｍＰａ・ｓ未満
〇：３００ｍＰａ・ｓ以上、５００ｍＰａ・ｓ未満
×：５００ｍＰａ・ｓ以上 <Viscosity>
The obtained dispersion of single-walled carbon nanotubes was adjusted to 25° C., the viscosity at a rotation speed of 60 rpm was measured with a BII type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the evaluation was performed according to the following criteria. It was
Evaluation criteria ◎ ◎: Less than 100 mPa·s ◎: 100 mPa·s or more, less than 300 mPa·s ◯: 300 mPa·s or more, less than 500 mPa·s ×: 500 mPa·s or more
＜粒子径＞
得られた単層カーボンナノチューブの分散液を、レーザー回折／散乱式粒子径分布測定装置（装置名：ＬＡ－９５０Ｖ２、株式会社堀場製作所製）にて、粒子をカーボンブラック、溶媒を各種溶媒で設定し、各種溶媒で粒度分布測定可能な濃度（約１００～５００倍）に希釈したのち測定し、下記の基準にて評価を行った。なお、各種溶媒とは、実施例１、２、７及び比較例１～４の場合は、酢酸ノルマルブチルであり、実施例３の場合はＭＥＫであり、実施例４の場合はＰＭＡであり、実施例５の場合はＩＰＡであり、実施例６の場合はＮＭＰである。
評価基準
（Ｄ５０）
◎：３μｍ未満
〇：３μｍ以上、５μｍ未満
×：５μｍ以上
（Ｄ９０）
◎：８μｍ未満
〇：８μｍ以上、１０μｍ未満
×：１０μｍ以上 <Particle size>
The obtained single-walled carbon nanotube dispersion is set with carbon black particles and various solvents with a laser diffraction/scattering particle size distribution measuring device (device name: LA-950V2, manufactured by Horiba, Ltd.). Then, the sample was diluted with various solvents to a concentration (about 100 to 500 times) at which the particle size distribution could be measured, and then measured, and evaluated according to the following criteria. The various solvents are normal butyl acetate in Examples 1, 2, 7 and Comparative Examples 1 to 4, MEK in Example 3, and PMA in Example 4. In the case of Example 5, it is IPA, and in the case of Example 6, it is NMP.
Evaluation criteria (D50)
◎: Less than 3 μm ○: 3 μm or more, less than 5 μm ×: 5 μm or more (D90)
◎: Less than 8 μm ○: 8 μm or more, less than 10 μm ×: 10 μm or more
＜回収率＞
得られた単層カーボンナノチューブの分散液１００ｇを、目開き５３μｍのポリエステルメッシュ（１０ｃｍ×１０ｃｍ）に滴下し、自重でのポリエステルメッシュ通過量を１分間測定し、下記の式に基づいて回収率を算出し、下記の基準にて評価を行った。
回収率（％）＝通過量（ｇ）／１００（ｇ）×１００
評価基準
◎◎：９０％以上
◎：８０％以上、９０％未満
〇：７５％以上、８０％未満
×：７５％未満 <Recovery rate>
100 g of the obtained dispersion liquid of single-walled carbon nanotubes was dropped on a polyester mesh (10 cm×10 cm) having an opening of 53 μm, the passing amount of the polyester mesh under its own weight was measured for 1 minute, and the recovery rate was calculated based on the following formula. It calculated and evaluated based on the following criteria.
Recovery rate (%)=passing amount (g)/100 (g)×100
Evaluation criteria ◎ ◎: 90% or more ◎: 80% or more, less than 90% ◯: 75% or more, less than 80% ×: less than 75%
＜塗膜評価方法＞
（塗膜形成用塗料の調製）
塗膜中の単層カーボンナノチューブの濃度が８．０質量％となるように下記配合比で、得られた単層カーボンナノチューブ分散液とメタクリル酸ブチル樹脂（商品名：ダイヤナールＢＲ－１１５又はＢＲ－１１６、三菱ケミカル株式会社製）と各種溶媒とを、攪拌機（装置名：あわとり練太郎ＡＲＥ－３１０、株式会社シンキー製）にて混合し、塗膜形成用塗料（固形分１質量％）を調製した。
なお、メタクリル酸ブチル樹脂は、予め固形分４０質量％になるように各種溶媒と混合して溶解させた樹脂溶液を用いた。
配合比（質量比）：単層カーボンナノチューブ分散液／樹脂溶液（固形分４０％）／各種溶媒＝４０．０／０．２４／５９．７６
なお、上記各種溶媒とは、実施例１、２、７及び比較例１～４の場合は、酢酸ノルマルブチルであり、実施例３の場合はＭＥＫであり、実施例４の場合はＰＭＡであり、実施例５の場合はＩＰＡであり、実施例６の場合はＮＭＰである。
また、使用したメタクリル酸ブチル樹脂の物性は、下記のとおりである。
ダイヤナールＢＲ－１１５：分子量５５０００、Ｔｇ５０℃
ダイヤナールＢＲ－１１６：分子量４５０００、Ｔｇ５０℃ <Coating film evaluation method>
(Preparation of paint for film formation)
The obtained single-walled carbon nanotube dispersion liquid and butyl methacrylate resin (trade name: Dianal BR-115 or BR, in the following mixing ratio so that the concentration of the single-walled carbon nanotubes in the coating film will be 8.0% by mass). -116, manufactured by Mitsubishi Chemical Co., Ltd.) and various solvents are mixed by a stirrer (device name: Awatori Kentaro ARE-310, manufactured by Shinky Co., Ltd.) to form a coating film-forming coating material (solid content 1% by mass). Was prepared.
The butyl methacrylate resin used was a resin solution that was mixed and dissolved in advance with various solvents to a solid content of 40% by mass.
Blending ratio (mass ratio): Single-walled carbon nanotube dispersion/resin solution (solid content 40%)/various solvents=40.0/0.24/59.76
The above-mentioned various solvents are normal butyl acetate in the case of Examples 1, 2, 7 and Comparative Examples 1 to 4, MEK in the case of Example 3, and PMA in the case of Example 4. In the case of Example 5, it is IPA, and in the case of Example 6, it is NMP.
The physical properties of the used butyl methacrylate resin are as follows.
Diinal BR-115: Molecular weight 55000, Tg 50°C
Diinal BR-116: Molecular weight 45,000, Tg 50°C
（塗膜の形成方法）
厚み１００μｍのＰＥＴフィルムに上記塗料を適量垂らし、バーコーター＃３（太佑機材株式会社製）を用いて塗工後、その塗布フィルムを温度１２０℃のオーブンにて３分間乾燥させ、塗膜を作製した。 (Method of forming coating film)
An appropriate amount of the above coating composition is hung on a PET film having a thickness of 100 μm and coated using a bar coater #3 (manufactured by Taisuke Kikai Co., Ltd.), and then the coated film is dried in an oven at a temperature of 120° C. for 3 minutes to prepare a coating film. did.
＜全光線透過率の測定＞
ヘイズメーター（装置名：ヘイズメーターＨＺ－２、スガ試験機株式会社製）を用いて、全光線透過率規格（ＩＳＯ　１３４６８－１、ＪＩＳ　Ｋ７３６１）に準じて測定し（シングルビーム法、光源Ｄ６５）、下記の基準にて評価を行った。検出部位に何も塗布していない厚み１００μｍのＰＥＴフィルムをはさみ校正を行い、次いで、上記で得られた塗膜（塗布フィルム）を検出部位にはさみ測定した。
評価基準
◎：９５％以上
〇：９０％以上、９５％未満
×：９０％未満 <Measurement of total light transmittance>
A haze meter (device name: haze meter HZ-2, manufactured by Suga Test Instruments Co., Ltd.) was used to measure according to the total light transmittance standard (ISO 13468-1, JIS K7361) (single beam method, light source D65). The following criteria were evaluated. The PET film having a thickness of 100 μm, in which nothing was applied to the detection site, was sandwiched and calibrated, and then the coating film (coated film) obtained above was sandwiched at the detection site and measured.
Evaluation criteria ◎: 95% or more ◯: 90% or more, less than 95% ×: less than 90%
＜表面抵抗値の測定＞
抵抗率計（装置名：ハイレスタＭＣＰ－ＨＴ４５０、三菱化学株式会社製）を用いて、得られた塗膜の塗布表面に電極（プローブ）を押し当て、２０℃で、表面を流れる電流値を測定し、下記の基準にて評価を行った。
評価基準
◎：１．０×１０７Ω／□未満
〇：１．０×１０７Ω／□以上、１．０×１０９Ω／□未満
×：１．０×１０９Ω／□以上 <Measurement of surface resistance>
Using a resistivity meter (device name: Hiresta MCP-HT450, manufactured by Mitsubishi Chemical Co., Ltd.), an electrode (probe) is pressed against the coating surface of the obtained coating film, and the current value flowing on the surface is measured at 20°C. Then, the evaluation was performed according to the following criteria.
Evaluation criteria ◎: Less than 1.0×10 7 Ω/□ ◯: 1.0×10 7 Ω/□ or more, less than 1.0×10 9 Ω/□ ×: 1.0×10 9 Ω/□ or more
＜経時安定性＞
また、上記で得られた分散液１～１１を、４０℃で１ヶ月間静置させた後、上記と同じ方法により、粘度、分散液中の単層カーボンナノチューブの粒子径、回収率、分散液を用いて形成した塗膜の全光線透過率及び表面抵抗値について、評価を行った。結果を表２に示す。 <Stability over time>
The dispersions 1 to 11 obtained above were allowed to stand at 40° C. for 1 month, and then the viscosity, the particle size of single-walled carbon nanotubes in the dispersion, the recovery rate, and the dispersion were measured by the same method as described above. The total light transmittance and the surface resistance value of the coating film formed using the liquid were evaluated. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表１より、少なくとも、単層カーボンナノチューブと高分子分散剤と有機溶媒を混合し、得られた混合物を超音波照射して分散させ、次いで粉砕メディアを使用しない分散機により分散させ、更に高分子分散剤を添加して超音波照射して分散させることにより、分散性に優れ、再凝集しにくい低粘度な単層カーボンナノチューブの有機溶媒分散液を製造することができることが確認された。また、当該方法で製造された実施例の分散液を用いれば、導電性と透明性が共に優れた塗膜を形成することができることが確認された。
また、表２より、実施例の分散液は、４０℃で１ヶ月間静置した後も、粘度が低く、単層カーボンナノチューブが凝集しにくく、透明性及び導電性に優れた塗膜を形成することができ、経時安定性にも優れることが確認された。 From Table 1, at least single-walled carbon nanotubes, a polymeric dispersant and an organic solvent are mixed, and the resulting mixture is irradiated with ultrasonic waves to disperse, and then dispersed by a disperser without using grinding media. It was confirmed that by adding a dispersant and performing ultrasonic irradiation to disperse it, it is possible to produce a low-viscosity organic solvent dispersion of single-walled carbon nanotubes having excellent dispersibility and hardly re-aggregating. It was also confirmed that a coating film having excellent conductivity and transparency can be formed by using the dispersion liquid of the example produced by the method.
In addition, from Table 2, the dispersions of Examples have a low viscosity even after standing at 40° C. for 1 month, and single-walled carbon nanotubes are less likely to aggregate, forming a coating film excellent in transparency and conductivity. It was confirmed that it was possible to do so and that it was excellent in stability over time.

Claims (12)

  1. 少なくとも、カーボンナノチューブ、高分子分散剤、及び有機溶媒を含むカーボンナノチューブの分散液であって、
    該分散液は、カーボンナノチューブを０．０１～１０質量％含み、
    該カーボンナノチューブは、短径が０．１～５０ｎｍであり、アスペクト比が１００以上である単層カーボンナノチューブを７５質量％以上含み、
    該カーボンナノチューブの含有量が０．２質量％となるように該分散液を調製した調製液の粘度が、５００ｍＰａ・ｓ未満である
    ことを特徴とするカーボンナノチューブ分散液。     At least a carbon nanotube, a polymer dispersant, and a dispersion of carbon nanotubes containing an organic solvent,
    The dispersion contains 0.01 to 10% by mass of carbon nanotubes,
    The carbon nanotubes have a short diameter of 0.1 to 50 nm and include 75% by mass or more of single-walled carbon nanotubes having an aspect ratio of 100 or more,
    A carbon nanotube dispersion liquid, wherein the viscosity of the preparation liquid prepared by preparing the dispersion liquid such that the content of the carbon nanotubes is 0.2% by mass is less than 500 mPa·s.
  2. 前記カーボンナノチューブの粒子径Ｄ５０が、５μｍ未満であることを特徴とする請求項１に記載のカーボンナノチューブ分散液。 The carbon nanotube dispersion liquid according to claim 1, wherein the particle diameter D50 of the carbon nanotubes is less than 5 μm.
  3. 前記カーボンナノチューブの粒子径Ｄ９０が、１０μｍ未満であることを特徴とする請求項１又は２に記載のカーボンナノチューブ分散液。 The carbon nanotube dispersion liquid according to claim 1 or 2, wherein the particle diameter D90 of the carbon nanotubes is less than 10 µm.
  4. 更に、分散助剤を含むことを特徴とする請求項１～３のいずれかに記載のカーボンナノチューブ分散液。 The carbon nanotube dispersion liquid according to any one of claims 1 to 3, further comprising a dispersion aid.
  5. 前記高分子分散剤は、カチオン系高分子分散剤であることを特徴とする請求項１～４のいずれかに記載のカーボンナノチューブ分散液。 The carbon nanotube dispersion liquid according to any one of claims 1 to 4, wherein the polymer dispersant is a cationic polymer dispersant.
  6. 前記有機溶媒は、エステル系溶媒、ケトン系溶媒、グリコール系溶媒、アルコール系溶媒、及び、窒素含有極性溶媒からなる群より選択される少なくとも１種であることを特徴とする請求項１～５のいずれかに記載のカーボンナノチューブ分散液。 The organic solvent is at least one selected from the group consisting of an ester solvent, a ketone solvent, a glycol solvent, an alcohol solvent, and a nitrogen-containing polar solvent. The carbon nanotube dispersion liquid according to any one of the above.
  7. 前記カーボンナノチューブ分散液を使用して下記の方法で形成された塗膜の全光線透過率が９０％以上であり、かつ、表面抵抗値が１．０×１０９Ω／□未満であることを特徴とする請求項１～６のいずれかに記載のカーボンナノチューブ分散液。
    塗膜の形成方法：塗膜中の該カーボンナノチューブの濃度が８質量％となるように、該分散液とメタクリル酸ブチル樹脂と該有機溶媒を混合して、固形分１質量％の樹脂組成物を調製し、該樹脂組成物を、ワイヤー径が０．２７ミルであるバーコーターを用いてポリエチレンテレフタレートフィルム上に塗布し、塗布物を乾燥させて塗膜を形成する。     The coating film formed by the following method using the carbon nanotube dispersion has a total light transmittance of 90% or more and a surface resistance value of less than 1.0×10 9 Ω/□. 7. The carbon nanotube dispersion liquid according to any one of claims 1 to 6.
    Method for forming coating film: A resin composition having a solid content of 1% by mass, by mixing the dispersion liquid, butyl methacrylate resin and the organic solvent so that the concentration of the carbon nanotubes in the coating film is 8% by mass. Is prepared, and the resin composition is applied onto a polyethylene terephthalate film using a bar coater having a wire diameter of 0.27 mil, and the applied material is dried to form a coating film.
  8. 少なくとも、短径が０．１～５０ｎｍでありアスペクト比が１００以上である単層カーボンナノチューブと、高分子分散剤と、有機溶媒とを混合する工程（１）、
    該工程（１）で得られた混合物に超音波を照射する工程（２）、
    該工程（２）で得られた超音波照射物を、粉砕メディアを使用しない分散機により分散する工程（３）、及び、
    該工程（３）で得られた分散物に高分子分散剤を添加し、得られた混合物に超音波を照射する工程（４）を含む
    ことを特徴とする単層カーボンナノチューブ分散液の製造方法。     A step (1) of mixing at least a single-walled carbon nanotube having a short diameter of 0.1 to 50 nm and an aspect ratio of 100 or more, a polymer dispersant, and an organic solvent;
    Irradiating the mixture obtained in the step (1) with ultrasonic waves (2),
    A step (3) in which the ultrasonic irradiation product obtained in the step (2) is dispersed by a disperser which does not use grinding media, and
    A method for producing a single-walled carbon nanotube dispersion, which comprises the step (4) of adding a polymer dispersant to the dispersion obtained in the step (3) and irradiating the obtained mixture with ultrasonic waves. ..
  9. 前記工程（１）の前に、前記単層カーボンナノチューブを無機酸又は無機酸を含む溶液で洗浄する工程を含むことを特徴とする請求項８に記載の単層カーボンナノチューブ分散液の製造方法。 The method for producing a single-walled carbon nanotube dispersion liquid according to claim 8, comprising a step of washing the single-walled carbon nanotubes with an inorganic acid or a solution containing an inorganic acid before the step (1).
  10. 前記工程（１）において、更に分散助剤を混合することを特徴とする請求項８又は９に記載の単層カーボンナノチューブ分散液の製造方法。 The method for producing a single-walled carbon nanotube dispersion liquid according to claim 8 or 9, wherein a dispersion aid is further mixed in the step (1).
  11. 前記高分子分散剤は、カチオン系高分子分散剤であることを特徴とする請求項８～１０のいずれかに記載の単層カーボンナノチューブ分散液の製造方法。 The method for producing a single-walled carbon nanotube dispersion according to any one of claims 8 to 10, wherein the polymer dispersant is a cationic polymer dispersant.
  12. 前記有機溶媒は、エステル系溶媒、ケトン系溶媒、グリコール系溶媒、アルコール系溶媒、及び、窒素含有極性溶媒からなる群より選択される少なくとも１種であることを特徴とする請求項８～１１のいずれかに記載の単層カーボンナノチューブ分散液の製造方法。 12. The organic solvent is at least one selected from the group consisting of ester solvents, ketone solvents, glycol solvents, alcohol solvents, and nitrogen-containing polar solvents, according to claim 8-11. The method for producing a single-walled carbon nanotube dispersion liquid according to any one of claims.
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JP2021187701A (en) * 2020-05-28 2021-12-13 国立大学法人 奈良先端科学技術大学院大学 Carbon nanotube dispersion and its manufacturing method
JP7291351B2 (en) 2020-05-28 2023-06-15 国立大学法人 奈良先端科学技術大学院大学 CARBON NANOTUBE DISPERSION AND METHOD FOR MANUFACTURING SAME
CN111924826A (en) * 2020-07-22 2020-11-13 中国科学院金属研究所 Preparation method of narrow-diameter distribution and high-purity metallic single-walled carbon nanotube
CN111924826B (en) * 2020-07-22 2022-05-27 中国科学院金属研究所 Preparation method of narrow-diameter distribution and high-purity metallic single-walled carbon nanotube
KR20230029985A (en) 2020-10-21 2023-03-03 아사히 가세이 가부시키가이샤 Non-aqueous alkali metal storage element and positive electrode coating solution
WO2022250461A1 (en) * 2021-05-28 2022-12-01 주식회사 엘지에너지솔루션 Conductive material dispersion
CN113912876A (en) * 2021-11-03 2022-01-11 江西铜业技术研究院有限公司 Carbon nanotube mother solution for modified acrylic resin and preparation method thereof
CN114212776A (en) * 2021-12-29 2022-03-22 东莞瑞泰新材料科技有限公司 Modified carbon nano tube powder and preparation method and application thereof

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