WO2019093360A1 - Liquide de dispersion de nanofils de carbone et sa méthode de production - Google Patents

Liquide de dispersion de nanofils de carbone et sa méthode de production Download PDF

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WO2019093360A1
WO2019093360A1 PCT/JP2018/041299 JP2018041299W WO2019093360A1 WO 2019093360 A1 WO2019093360 A1 WO 2019093360A1 JP 2018041299 W JP2018041299 W JP 2018041299W WO 2019093360 A1 WO2019093360 A1 WO 2019093360A1
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carbon
dispersion liquid
less
nanowire dispersion
carbon nanowire
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PCT/JP2018/041299
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English (en)
Japanese (ja)
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成久 秋澤
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Ａｃａ株式会社
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    • 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
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • 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
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof

Definitions

  • the present invention relates to a dispersion in which carbon nanowires having a specific shape are dispersed, a method for producing the same, and a paint or ink obtained from the dispersion.
  • CFRP carbon fiber reinforced plastics
  • the shortest carbon fiber is also referred to as milled fiber, and in general, the average fiber length is 70 ⁇ m or more and 200 ⁇ m or less, and the average fiber diameter is about 10 ⁇ m. It is often used.
  • CFRP and so-called "carbon fibers” are considered to be less useful because their processability becomes more difficult and they tend to aggregate as they become shorter, and there are documents in which the fiber diameter and aspect ratio of carbon fibers are described.
  • nano-sized carbon fibers having a smaller size than milled fibers are not in reality. That is, at present, the demand and utilization of nano-sized carbon fibers are extremely low, particularly nano-sized carbon fibers having a large aspect ratio are not (commercially) present in the market, and at least such carbon fibers are stable. There are no known dispersions in dispersion.
  • nano-sized carbon fibers were not present for conductivity because nanoparticles such as carbon nanotubes, silver, copper, etc. are on the market and are generally available. Be In addition, although it is considered that nano-sized carbon fibers can be used for various applications requiring conductivity etc., dispersions of carbon fibers having a small average fiber diameter and an extremely large aspect ratio The fluid was unknown.
  • JP 7-118440 A Japanese Patent Laid-Open No. 2000-254919 JP 2001-030245 A JP, 2009-138143, A JP 2012-188790 A Unexamined-Japanese-Patent No. 2017-066546
  • the present invention has been made in view of the above background art, and the problem is that, in carbon fibers having an average fiber diameter of nanosize, the average fiber length is longer as compared to the fineness of the average fiber diameter, that is, the aspect ratio It is an object of the present invention to provide a carbon nanowire dispersion liquid which is easy to be easily crushed and dispersed in the dispersion medium and hardly reaggregated, and a method for producing the same.
  • CFRP carbon fiber reinforced plastic
  • the present invention is a carbon nanowire dispersion liquid characterized in that a carbon nanowire having an average fiber diameter of 300 nm or less and an average aspect ratio of 30 to 200 is dispersed in a dispersion medium.
  • the present invention is also a method for producing the above-mentioned carbon nanowire dispersion liquid, A carbon nanowire dispersion liquid in which carbon fibers are dispersed in the dispersion medium by pulverizing the carbon fibers in a dry state or preparing a dry-ground carbon fiber and then grinding the carbon fibers in the dispersion medium by wet grinding.
  • a manufacturing method In the wet grinding, the dry ground carbon fiber is contained in the dispersion medium, and the carbon fiber is subjected to bead milling in the presence of an anionic surfactant, whereby the carbon fiber has an average fiber diameter of 300 nm or less and an average
  • the present invention provides a method for producing a carbon nanowire dispersion liquid, which has an aspect ratio of 30 or more and 200 or less.
  • the present invention provides a method for producing the above-mentioned carbon nanowire dispersion liquid, wherein the above-mentioned anionic surfactant is an alkali metal salt or alkylol ammonium salt of a (co) polymer having an acid group. It is.
  • the present invention provides a method for producing a carbon nanowire dispersion as described above, wherein the dispersion medium is water or "2-pyrrolidone in which the nitrogen atom may be substituted with a hydrocarbon group". is there.
  • the present invention also provides a carbon nanowire dispersion liquid, which is characterized by being manufactured by the above method of manufacturing a carbon nanowire dispersion liquid.
  • the present invention provides a paint or ink characterized in that the dispersion medium of the carbon nanowire dispersion described above is water, and further containing at least a water-soluble polymer therein. is there.
  • the dispersion medium of the above-mentioned carbon nanowire dispersion liquid is “2-pyrrolidone in which a nitrogen atom may be substituted with a hydrocarbon group”, and at least polyimide is further contained therein. It provides a paint or ink characterized by a certain thing.
  • a carbon nanowire dispersion liquid in which carbon nanowires having an average fiber diameter of 300 nm or less and an average aspect ratio of 30 or more and 200 or less are dispersed in a dispersion medium has not been known so far and is novel It is.
  • the method for producing a carbon nanowire dispersion liquid of the present invention it is possible to preferably grind to a specific nano-sized shape having a large average aspect ratio, and more preferably to disperse it in a dispersion medium, The obtained dispersion is also extremely excellent in dispersion stability.
  • the carbon nanowires dispersed in the carbon nanowire dispersion liquid of the present invention are closer in shape to so-called silver nanowires and carbon nanotubes than so-called carbon nanofibers (CNF). Therefore, the carbon nanowires in the present invention are chemically structurally graphite, but are close to silver nanowires in shape, so they are suitably used in applications similar to those where silver nanowires are currently used. Be done. Moreover, the carbon nanowires in the carbon nanowire dispersion liquid of the present invention are extremely inexpensive (can be manufactured inexpensively) than silver nanowires (150,000 yen / g).
  • the carbon nanowire in the present invention has a small average diameter to the extent that light does not scatter and has a low electrical resistivity, it is expected to be used for transparent conductive films and the like. Further, since it is a dispersion, it can be suitably used not only for applications (fields) by vapor deposition, CVD, etc., but for applications (fields) where it is applied as a dispersion to form films, layers, wires, etc. That is, it can be suitably used as, for example, “various paints, various printing inks, etc.” of conductivity, heat conductivity, heat dissipation, rust prevention, jet blackness.
  • the dispersion is in the form of wires instead of particles, that is, the average fiber diameter is nano size and the aspect ratio is large, a substrate having micro-sized voids (paper; substrate such as polyimide film; etc.)
  • paper substrate such as polyimide film; etc.
  • the dispersion goes into the voids and does not show sufficient conductivity. That is, since the average fiber length is sufficiently long, a network of carbon nanowires is formed on the substrate without flowing into the void.
  • a film, a layer, a wiring or the like formed by, for example, coating, printing or the like using the carbon nanowire dispersion liquid of the present invention has high conductivity even if the thickness is thin.
  • the aspect ratio is large even when the substrate is bent or bent, the network of carbon nanowires is less likely to be broken, and the conductivity can be maintained. Therefore, it can apply especially suitably to deformable substrates, such as a flexible substrate.
  • the coated surface is turned to the outside by 180 °, for example, conductivity, heat conductivity, heat dissipation, rust prevention, and jet blackness can be secured on the entire surface.
  • the conductivity since the conductivity is ensured even at the bent portion, it is possible to produce a "structured body made of folded origami or flexible film" which is entirely conductive.
  • the carbon nanowire dispersion liquid of the present invention is particularly useful as a material of the wiring of the wiring substrate.
  • the wiring formed by printing etc. using the carbon nanowire dispersion liquid of this invention has electroconductivity, it can use this wiring as a cathode and can apply electrolytic metal plating further on that, By doing this, a printed wiring board having a normal conductor thickness (wiring thickness) can be produced.
  • a printed wiring board having a normal conductor thickness (wiring thickness) can be produced.
  • an electrolytic copper plating solution is used as the electrolytic metal plating solution, it is possible to produce a copper wiring with an arbitrary thickness on a substrate.
  • the conductive circuit forming ink using the carbon nanowire dispersion liquid of the present invention can not only be printed on a substrate as described above, but can also be filled in through holes and via holes, so that it can be applied to various multilayer wiring boards It is.
  • the method for producing a carbon nanowire dispersion liquid of the present invention uses carbon fiber, sized carbon fiber, or CFRP as a raw material, and first performs "dry grinding” or “dry grinding” as a raw material Although “used", wastes and unnecessary things can also be used as the CFRP. Alternatively, commercially available CFRP products can be used, and optionally after coarse grinding, dry grinding (used as a raw material). By grinding and dispersion treatment under the specific conditions of the present invention, plastics other than the carbon fiber itself are substantially removed from the obtained dispersion, and they are substantially the same regardless of the starting materials.
  • the dispersion stability of the carbon nanowire dispersion liquid of the present invention can be further enhanced by using a water-soluble polymer as a dispersion medium, and can be suitably used as, for example, various water-based paint for conductor formation. It is.
  • the dispersion medium is “2-pyrrolidone in which the nitrogen atom may be substituted with a hydrocarbon group”, and further contains polyimide in the dispersion stability.
  • it can be suitably used as various organic solvent paints and inks for forming conductive circuits.
  • the present invention is a carbon nanowire dispersion liquid characterized in that a carbon nanowire having an average fiber diameter of 300 nm or less and an average aspect ratio of 30 to 200 is dispersed in a dispersion medium. .
  • the average fiber diameter, average fiber length, average aspect ratio and particle size distribution of carbon fibers and carbon nanowires are measured by the method described in the Examples, and defined as such measurements.
  • carbon nanowire has a chemical structure of graphite (graphite) and a chemical structure of carbon fiber, and has an average fiber diameter of 300 nm or less and an average aspect ratio of 30 or more.
  • the average fiber length is short and the average fiber diameter is also thin.
  • the average fiber length and the average fiber diameter are smaller.
  • a carbonaceous material such as graphite
  • a plastic derived from CFRP etc.
  • the average fiber diameter of the carbon nanowires is 300 nm or less, preferably 200 nm or less, more preferably 130 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less. If the upper limit is less than or equal to the above, dispersibility and dispersion stability are improved, and the “structure such as a coating film or circuit” obtained by applying and printing the obtained dispersion (paint or ink having the same) Conductivity, thermal conductivity, heat dissipation, rust prevention, jet blackness, uniformity, etc. are improved. In addition, the effects of the present invention described above can be achieved.
  • the lower limit of the average fiber diameter of carbon nanowires is not particularly limited, but is preferably 20 nm or more, particularly preferably 30 nm or more, from the viewpoint of easiness of production including pulverization, dispersion and the like.
  • the average fiber length of carbon nanowire 60 micrometers or less are preferable, as for the average fiber length of carbon nanowire, 40 micrometers or less are more preferable, 25 micrometers or less are still more preferable, and 15 micrometers or less are especially preferable. If the upper limit is less than or equal to the above, dispersibility and dispersion stability are improved, and the above-described effects of the present invention are exhibited. On the other hand, the lower limit of the average fiber length of the carbon nanowire is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 3 ⁇ m or more, and particularly preferably 4 ⁇ m or more.
  • the lower limit is at least the above, when the obtained dispersion liquid (paint or ink having the same) is applied and printed, it hardly enters the minute depressions of the substrate and becomes isolated, and obtained by application and printing Conductivity, thermal conductivity, heat dissipation, rust resistance, jet blackness, etc. of a structure such as a coating film or a circuit are improved. In addition, manufacturing including pulverization, dispersion and the like is facilitated, and the above-described effects of the present invention can be achieved.
  • the average aspect ratio of the carbon nanowires is 30 or more and 200 or less, preferably 40 or more and 180 or less, more preferably 50 or more and 170 or less, and particularly preferably 60 or more and 150 or less.
  • the above-mentioned “effect similar to the effect that the upper limit of the average fiber diameter is below or above and the effect that the lower limit of the average fiber length is above” is exhibited.
  • the upper limit of the average aspect ratio of the carbon nanowires is equal to or less than the above, the above-mentioned "effect similar to the effect that the lower limit of the average fiber diameter is more than the above or the effect that the upper limit of the average fiber length is the following" is exhibited.
  • the particle size distribution measured by the method described in the examples is, for example, as shown in FIG. 3, in which 95% is distributed in the range of less than two digits in particle diameter (horizontal axis), for example, FIG. As shown in 4, when the particle diameter (horizontal axis) is 95% distributed in the range of 2 digits or more, the average fiber length is maintained longer and the average aspect ratio becomes larger. So preferred. Excessive wet grinding may reduce the average fiber length too much and may reduce the average aspect ratio.
  • the dispersion medium of the carbon nanowire dispersion liquid of the present invention is used as a solvent or dispersion medium for paints, inks, etc., or as a solvent or dispersion medium for masterbatches when producing paints, inks, etc.
  • the thing is mentioned. Specific examples include, but are not limited to, the following.
  • ethylene glycol ethylene glycol condensates such as diethylene glycol and triethylene glycol; diacetates thereof; ethylene glycol monoalkyl (or phenyl) ethers such as ethylene glycol monoethyl ether and ethylene glycol monophenyl ether; monoacetates thereof Ethylene glycol dialkyl (or diphenyl) ethers such as ethylene glycol diethyl ether, ethylene glycol diphenyl ether; solvents obtained by replacing the above "ethylene glycol” with "diethylene glycol” or "triethylene glycol”;"propyleneglycol” above And the like.
  • alcohols such as 3,5,5-trimethylhexanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol; carboxylic acid esters thereof; cyclic esters such as ⁇ -butyl lactone Carbonates such as propylene carbonate, butylene carbonate, vinyl carbonate, etc .; "pyrrolidones whose nitrogen atoms may be substituted by hydrocarbon groups” such as pyrrolidone, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone etc. (“pyrrolidone” And “2-pyrrolidone” is preferable); and the like.
  • acetic acid tetrahydrofuran
  • hydrocarbons such as benzene, cyclohexane and xylene
  • esters such as methyl acetate, ethyl acetate, dioctyl phthalate and aromatic esters
  • ketones such as acetophenone, methyl ethyl ketone (MEK), cyclohexanone and acetone
  • carbon tetrachloride Chlorine-containing solvents such as chloroform, trichloroethylene and dichloromethane
  • alcohols such as octylene glycol, acetone alcohol and isopropyl alcohol
  • carbon disulfide nitrogen-containing solvents such as pyridine, nitroethane and acetonitrile
  • dioxane ⁇ -caprolactone, ⁇ -butyrolactone ( And lactones such as GBL).
  • the dispersion media may be used alone or in combination of two or more.
  • carbon nanowire dispersions have a wide range of uses such as paints and inks, etc., that they have good crushability and dispersibility, that a specific surfactant suitably functions, and that their dispersion stability is good, Water is preferred from the viewpoint of safe and easy handling.
  • the water is more preferably pure water such as demineralized water or distilled water.
  • the particularly suitable use of the carbon nanowire dispersion liquid of the present invention is a conductive paint or a conductive ink, so that it is matched to a polymer substrate such as polyimide or polyepoxy as the substrate; bead mill treatment
  • a polymer substrate such as polyimide or polyepoxy as the substrate
  • bead mill treatment The compatibility with the pulverization by carbon dioxide is good; the dispersibility of carbon nanowires is particularly suitable; a specific surfactant functions suitably; and so on, such as pyrrolidone, N-methyl pyrrolidone, N-ethyl pyrrolidone etc.
  • ketone such as methyl ethyl ketone (MEK): lactone such as ⁇ -butyrolactone (GBL); etc. are preferable, and “nitrogen atom is substituted with a hydrocarbon group
  • 2-pyrrolidone "methyl ethyl ketone (MEK), ⁇ -butyrolactone (GBL), etc.
  • NMP methyl-2-pyrrolidone
  • the content ratio of the carbon nanowires dispersed in the carbon nanowire dispersion liquid of the present invention is not particularly limited, but preferably 0.01% by mass or more and 20% by mass or less with respect to the whole carbon nanowire dispersion liquid. 0.1 mass% or more and 15 mass% or less are more preferable, 0.3 mass% or more and 10 mass% or less are more preferable, and 1 mass% or more and 6 mass% or less are particularly preferable.
  • the dispersion liquid When the content ratio is at least the above lower limit, the dispersion liquid is not too thin and the dispersion medium is not wasted; the volume of the dispersion liquid is not increased more than necessary; the dispersion liquid is excessive when used in the production of paints, inks, etc. Since the dispersion medium of (1) is not contained, the use is expanded; On the other hand, the dispersibility and the dispersion stability of the carbon nanowires are improved when the content ratio is not more than the above upper limit; the dispersibility is improved without the viscosity and the concentration of the dispersion becoming too high at the time of grinding such as bead milling And the dispersion time is shortened; carbon nanowires with a large aspect ratio can be obtained; and so on.
  • the “method for producing a carbon nanowire dispersion” of the present invention is a method for producing the “carbon nanowire dispersion described above”, and A method of dry-pulverizing carbon fibers or preparing dry-pulverized carbon fibers and thereafter dispersing the carbon fibers in the dispersion medium while grinding the carbon fibers by wet-pulverizing in the dispersion medium, In the wet grinding, the dry ground carbon fiber is contained in the dispersion medium, and the carbon fiber is subjected to bead milling in the presence of an anionic surfactant, whereby the carbon fiber has an average fiber diameter of 300 nm or less and an average It is characterized in that the aspect ratio is 30 or more and 200 or less.
  • Carbon fiber as raw material includes carbon fibers subjected to sizing treatment; carbon fiber reinforced plastics (hereinafter abbreviated as "CFRP"); carbon fiber reinforced carbon composite material 90% by mass or more according to the JIS standard is a carbonaceous material; carbon fiber alone or carbon material single; so-called carbon fibers; and the like.
  • CFRP carbon fiber reinforced plastics
  • the CFRP may be a prepreg obtained by causing carbon fiber to be contained in a matrix resin in a matrix resin, which is heated under pressure in an autoclave, or a molded by heating using a microwave or the like.
  • CFRP carbon fibers
  • “carbon fibers” such as CFRP are longitudinally unwound by bead milling in the presence of an anionic surfactant, and the average fiber length relative to the average fiber length It is particularly preferable to use CFRP as the above-mentioned "carbon fiber” as a raw material because the diameter can be specifically narrowed, in order to take advantage of the features of the present invention.
  • the present invention does not exclude the case where the substance remains or adheres to the carbon nanowires.
  • the above “transfer into the dispersion medium” may be, for example, when it is dissolved in the dispersion medium; when it is finely dispersed or lumped and dispersed; when it is suspended or separated in the dispersion medium;
  • carbon fiber is dry-ground or dry-ground carbon fiber is prepared. That is, carbon fibers may be dry-ground (renewed), or carbon fibers which have already been dry-ground may be obtained and used, but dry-grinding carbon fibers before bead mill processing described later Is preferred.
  • the "carbon fiber” which is a raw material before dry grinding may be a chopped fiber, a milled fiber, etc. crushed to some extent or the like, or it may be roughly crushed if a large CFRP etc. is required. In addition, it may be a waste material or CFRP (which is roughly crushed) which has become unnecessary.
  • CFRPs that are no longer needed include those that are no longer needed for commonly used and sold CFRPs, CFRPs that are wastes, and CFRPs that have come out as prototypes (including failed products) by manufacturers etc. Be Specifically, but not limited to, for example, golf club shafts; tennis racquet frame materials; fishing rods; car frames and various parts; plane wings and various parts; Parts; cases of musical instruments, portable items, etc .;
  • the “carbon fiber” as a raw material a pitch-based (PITCH-based) carbon obtained by carbonizing a pitch at a high temperature
  • PAN-based bread-based
  • PITCH-based pitch-based carbon obtained by carbonizing a pitch at a high temperature
  • it may be a fiber, it is preferably a pitch-based (PITCH-based) carbon fiber from the viewpoint of excellent conductivity and the ease with which a carbon nanowire with a large aspect ratio can be obtained.
  • dry grinding is first performed, and as the dry grinding, pneumatic grinding using "air flow grinding machine such as cyclone mill; jet mill; etc.”;”crusher mill, pin mill, cutter mill, hammer” Mills, axial flow mills, etc. “rotational impact grinding, roll grinding, medium grinding, stone grinding, cutter grinding” and the like can be mentioned.
  • pneumatic pulverization using a cyclone mill, jet mill or the like is particularly preferable as the dry pulverization in the present invention.
  • an air flow is generated by rotation of an impeller (rotor blade), and an object placed in the air flow is dryly crushed to produce fine particles.
  • the target is made to collide with the collision plate, and the target is dry ground to produce fine particles.
  • An apparatus marketed can also be used conveniently as a cyclone mill.
  • Cyclone mill manufactured by Shizuoka Plant Co., Ltd. Cyclone mill manufactured by Shizuoka Machine Co., Ltd., super powder mill manufactured by Nishimura Machinery Co., Ltd., tornado mill manufactured by Mitaka Industry Co., Ltd., Furukawa Sangyo Co., Ltd.
  • a Dream Mill manufactured by Systems Co., Ltd. may, for example, be mentioned.
  • the structure of the above-mentioned cyclone mill is not particularly limited, but it has one or more impellers, and it is mainly intended that the objects to be crushed are collided and crushed by the swirling air flow generated by the impellers. It is particularly preferable from the viewpoint of easily achieving the effects by using the air flow crusher; very little metal contamination; and the like.
  • the impellers may be rotated in the same direction or in opposite directions, respectively.
  • the air flow crusher has a classification function inside, and the classified coarse powder can be crushed again inside and the classified fine powder can be taken out. Particularly preferred in view of obtaining a narrow distribution for removing coarse powder.
  • the classification function is not particularly limited, but is preferably a cyclone classification function from the viewpoint of high classification ability.
  • the ambient temperature or setting temperature in the case of using a cyclone mill is not particularly limited and may be in accordance with the use of the apparatus used, but is preferably 0 ° C. to 50 ° C., particularly preferably 5 ° C. to 35 ° C. .
  • the impeller rotational speed in the case of using a cyclone mill may be in accordance with the method of use of the apparatus used, but is preferably 4000 rpm or more and 20000 rpm or less, and particularly preferably 8000 rpm or more and 15000 rpm or less.
  • a commercially available apparatus can also be suitably used as a jet mill.
  • Examples of commercially available manufacturers include Seishin Enterprise Co., Ltd., Hosokawa Micron Corporation, Nippon Pneumatic Mfg Co., Ltd., Nisshin Engineering Co., Ltd., and the like.
  • the ambient temperature or setting temperature in the case of using a jet mill is not particularly limited and may be in accordance with the method of use of the apparatus used, but is preferably 0 ° C. or more and 50 ° C. or less, particularly preferably 5 ° C. or more and 35 ° C. or less .
  • the jet injection pressure or injection speed may be in accordance with the method of use of the apparatus used, but most preferably, compressed air at 20 ° C. and 6 bar (0.6 MPaG) is used as a grinding gas, and a 500 m / s nozzle The spouting speed is most preferred.
  • the preferred range is ⁇ 20% of the above value, and particularly preferred is ⁇ 10% of the above value.
  • carbon fiber which is a raw material in the present invention
  • dry grinding By carrying out dry grinding until the average fiber length becomes 70 ⁇ m or less and then carrying out wet grinding, the required range of the average fiber diameter, average fiber length, shape distribution, etc. of carbon nanowires in the carbon nanowire dispersion liquid or It becomes easy to be included in the suitable range.
  • the average fiber length is preferably 70 ⁇ m or less by dry grinding, more preferably 5 ⁇ m to 60 ⁇ m, still more preferably 10 ⁇ m to 50 ⁇ m, and particularly preferably 15 ⁇ m to 40 ⁇ m.
  • the upper limit is larger than the above, even if the average fiber diameter of the carbon nanowires hardly reaches 300 nm or less finally even if the conditions of the wet grinding are adjusted by wet grinding using a bead mill which is the next step, or In some cases, the average fiber diameter of the above-described (more preferable or particularly preferable) carbon nanowires is difficult to be achieved.
  • the average fiber length and average aspect ratio of the carbon nanowires may hardly fall in the above-mentioned ("more preferable" or "particularly preferable") range. .
  • the average fiber length of the carbon nanowires can not exceed the lower limit after wet grinding, so finally the average fiber length and average aspect ratio of the carbon nanowires are described above (" There is a case where it is difficult to be in the range of “preferred” or “particularly preferred”. In particular, the average aspect ratio of the final carbon nanowire may be too small.
  • the average fiber diameter after dry grinding is preferably 3000 nm or more, and particularly preferably 5000 nm or more and 15000 nm or less.
  • the average aspect ratio after dry pulverization is not particularly limited, but is preferably 10 or less, more preferably 7 or less, and particularly preferably 0.5 or more and 5 or less.
  • the present invention can be finally achieved by dry-grinding, even with a relatively large average fiber diameter or relatively small average aspect ratio, or by specific wet-grinding later on. It has been found that suitable "small average fiber diameter and large average aspect ratio" can be obtained.
  • the average fiber diameter of "the above-mentioned dry-ground carbon fiber" before wet grinding is 3000 nm or more and the average aspect ratio is 10 or less preferable.
  • Wet grinding is carried out after dry grinding, wherein the wet grinding contains the dry ground carbon fiber in the dispersion medium and is subjected to bead milling by bead milling in the presence of an anionic surfactant.
  • the shape (average fiber diameter, average fiber length, average aspect ratio) and particle size distribution of carbon nanowires are used. That is, finally, carbon fibers are formed into carbon nanowires having an average fiber diameter of 300 nm or less and an average aspect ratio of 30 or more and 200 or less, and the above-described ⁇ carbon nanowire dispersion> ⁇ carbon nanowires >> Particularly preferred is the formation of carbon nanowires in a range of shapes and particle size distributions. It goes without saying that another process may be interposed between dry grinding and wet grinding. Examples of the "other processing" include pre-mixing, pre-mixing, and the like.
  • bead milling is performed using a bead mill.
  • carbon nanowires of the specific shape and particle size distribution as described above and a carbon nanowire dispersion liquid are obtained for the first time.
  • the conditions for bead milling are adjusted so as to obtain the above-mentioned specific mean fiber diameter, mean fiber length, mean aspect ratio, and particle size distribution of carbon nanowire and carbon nanowire dispersion liquid.
  • the conditions for bead milling described below are extremely important in order to obtain carbon nanowires of the above-described shape by finally pulverizing carbon fibers after dry pulverization, and the combination of the respective conditions in bead milling can be easily selected. It is not a natural range.
  • Examples of the material of the beads used in the bead mill include glass, alumina, zircon (zirconia-silica ceramic), zirconia, metal (steel) and the like, with zirconia and the like being preferable and zirconia being particularly preferable from the viewpoint of hardness and the like.
  • the bead diameter of the beads used in the bead mill is preferably 0.1 mm or more and 1.5 mm or less, more preferably 0.3 mm or more and 1 mm or less, and particularly preferably 0.5 mm or more and 0.8 mm or less. If the bead diameter is too large, the number of beads in the bead mill container will decrease and the contact point will decrease, and if it can not be suitably dispersed, the average fiber diameter etc. may not be reduced sufficiently. On the other hand, when the bead diameter is too small, when it can not be suitably dispersed, pulverization may take too long.
  • bead packing factor used for a bead mill 45% or more and 85% or less are preferable, 55% or more and 80% or less are more preferable, and 65% or more and 75% or less are particularly preferable.
  • the bead filling rate is too small, it is difficult for the carbon fiber to be vertically cracked, and it may be difficult to produce a carbon nanowire with a large aspect ratio.
  • the stirring blade of the bead mill may not be easily rotated.
  • the shape of the stirring blade used in the bead mill processing is a propeller type, and since the dispersion has extremely high structural viscosity and thixotropy, the shear rate is increased (the viscosity is not increased), and the stirring property and the grinding property In order to keep the dispersibility properly.
  • the number of rotations of the stirring blade depends on the length of the stirring blade, it is preferably 500 rpm or more and 2000 rpm or less, more preferably 700 rpm or more and 1500 rpm or less, and particularly preferably 1000 rpm or more and 1200 rpm or less.
  • the peripheral speed of the tip of the agitating blade (agitator) depends on the length of the agitating blade, but is preferably in the range which can be calculated from the above-mentioned rotational speed as a diameter of 20 cm.
  • 5 m / s or more and 20 m / s or less are preferable, 7 m / s or more and 16 m / s or less are more preferable, and 9 m / s or more and 13 m / s or less are particularly preferable.
  • the operation mode of the grinding and dispersion of the bead mill may be either a circulation system or a batch system, but the circulation system is preferred.
  • the circulation type since it is not delivered to the container as in the batch type, reagglomeration does not proceed at that time.
  • the circulation method is used, the degree of miniaturization changes with the number of passes. For example, when the residence time per pass is increased to 60 minutes at 5000 mL, the particle size distribution becomes sharp due to the absence of the short path of the treated product, but the aspect ratio of the carbon nanowire itself also decreases. Therefore, for example, it is desirable that the circulation speed per pass is preferably 10 minutes to 40 minutes, particularly preferably 15 minutes to 30 minutes, preferably 2 passes or more, particularly preferably 3 passes or more.
  • the time per pass (continuous operation time), the number of passes, and the total time depend on the device structure, concentration, grinding dispersion conditions, type of carbon fiber (CFRP), type of anionic surfactant, etc. Since there are cases, the dispersion after wet-pulverization is appropriately adjusted by observing one by one with a particle size distribution measuring device, a scanning electron microscope (SEM) or the like.
  • SEM scanning electron microscope
  • the time per one pass is preferably 7 minutes to less than 45 minutes, more preferably 10 minutes to 40 minutes, and particularly preferably 15 minutes to 30 minutes.
  • the upper limit is set to the above or less, the average aspect ratio can be increased.
  • 20 minutes or more and 180 minutes or less are preferable, and, as for the total time of wet grinding and dispersion
  • the temperature of the dispersion and carbon fibers (carbon nanowires) in bead milling is preferably 0 ° C. or more and 50 ° C. or less, particularly preferably 5 ° C. or more and 35 ° C. or less.
  • the bead mill in the present invention is a wet bead mill, but may be vertical or horizontal. Moreover, a bead mill can also use a commercially available apparatus. As a commercially available apparatus, for example, a bead mill manufactured by Ashizawa Finetech Co., Ltd., a Dino Mill of Willie E. Bachkofen (WAB), a bead mill of Imex Co., Ltd., a bead mill of Netti (US) and the like can be mentioned.
  • a commercially available apparatus for example, a bead mill manufactured by Ashizawa Finetech Co., Ltd., a Dino Mill of Willie E. Bachkofen (WAB), a bead mill of Imex Co., Ltd., a bead mill of Netti (US) and the like can be mentioned.
  • the wet grinding is preferably performed by bead milling in the presence of an anionic surfactant to disperse simultaneously with the grinding.
  • the anionic surfactant is preferably a polymeric anionic surfactant ("polymer” also includes an oligomer), and an alkali metal salt of a (co) polymer having an acid group, More preferably, they are ammonium salts, alkyl ammonium salts, alkylol ammonium salts and the like.
  • the (co) polymer having an acid group is a (co) polymer of (meth) acrylic acid, a (co) polymer of (anhydride) phthalic acid, and a (co) polymer of vinyl benzene sulfonic acid And at least one (co) polymer selected from the group consisting of (co) condensates of naphthalenesulfonic acid is particularly preferable.
  • the descriptions “(co)”, “(meth)”, and “(anhydrous)” indicate that parentheses may or may not be included.
  • copolymerization monomer in the case of a copolymer, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, styrene etc. are mentioned.
  • the (co) condensed product of naphthalenesulfonic acid includes one having a ring bonded by an aldehyde such as formaldehyde.
  • aldehyde such as formaldehyde.
  • co-condensation monomer in the case of co-condensate, phenol, cresol, naphthol and the like can be mentioned.
  • the counter cation of the (co) polymer having an acid group is more preferably an alkali metal salt, an ammonium salt, an alkyl ammonium salt or an alkylol ammonium salt, particularly preferably a sodium salt or an alkylol ammonium salt is there.
  • anionic surfactants may be used alone or in combination of two or more.
  • the carbon fiber can be longitudinally unwound to shorten the average fiber length. Without this, the average fiber diameter can be reduced, and carbon nanowires (dispersion liquid) having a large average aspect ratio can be obtained.
  • the amount of the anionic surfactant used is not particularly limited, but two or more anionic surfactants may be used with respect to 100 parts by mass of carbon fiber (the same applies to carbon nanowires) to be crushed and dispersed. When used in combination), preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, and particularly preferably 30 to 100 parts by weight is there. If the amount of the anionic surfactant used is too small, the effect of unraveling the carbon fiber is hardly exhibited, and it becomes difficult to narrow the average fiber diameter without shortening the average fiber length, and the average aspect ratio It may be difficult to obtain large carbon nanowires (dispersion liquid).
  • the carbon fibers may cause aggregation during melting in the longitudinal direction.
  • a dispersion liquid in a state in which the carbon nanowires are aggregated is obtained, and thus when applied to an object, the conductivity of the obtained material may be affected.
  • ⁇ dispersion medium >>>
  • the dispersion medium to be used and the preferable dispersion medium are as described above in the section of ⁇ dispersion medium >> in ⁇ carbon nanowire dispersion liquid>.
  • the content ratio of the carbon nanowires dispersed in the carbon nanowire dispersion liquid of the present invention is as described above, but in the production method, 2 parts by mass of dry pulverized carbon fiber in 100 parts by mass of dispersion medium is used. It is preferable to carry out wet grinding by containing it in an amount of 7 parts by mass or less. More preferably, it is 3 parts by mass or more and 6.5 parts by mass or less, and particularly preferably 4 parts by mass or more and 6 parts by mass or less. If the content ratio is too small, the viscosity of the dispersion may be too low and the efficiency of pulverization may decrease. On the other hand, if the content ratio is too large, the viscosity of the dispersion may be too high to make the stirring blade difficult to turn And the efficiency of grinding may decrease.
  • Carbon nanowire dispersion liquid is also a carbon nanowire dispersion characterized in that it is produced by the above-mentioned "Method of producing a carbon nanowire dispersion”.
  • the paint and the ink using the carbon nanowire dispersion liquid of the present invention can suitably impart conductivity, thermal conductivity, heat dissipation, rust resistance, jet blackness and the like to the surface of an object.
  • the present invention is also a paint or ink for imparting conductivity, heat conductivity, heat dissipation, rust resistance or jet-blackness to the surface of an object.
  • the carbon nanowire dispersion liquid of the present invention and a polymer dissolved therein, and the dispersion medium (solvent) being distilled off, "the carbon nanowire is encapsulated in the polymer", “coating film, circuit, structure Or “powder” is suitable as a functional thing with the said performance.
  • the method of printing the ink is not particularly limited, and examples thereof include inkjet printing, screen printing, electrophotographic printing, offset printing, relief printing, intaglio printing, gravure printing, tampo printing, handwriting printing, and the like.
  • the present invention is also a "paint or ink" characterized in that the dispersion medium of the carbon nanowire dispersion described above is water, and further contains at least a water-soluble polymer. Particularly preferably, the dispersion medium of the above-mentioned carbon nanowire dispersion liquid is water, and at least a water-soluble polymer is further contained therein. ".
  • water-soluble polymer those used for water-based paints and inks can be used, but polyvinyl alcohol, polyvinyl pyrrolidone, high molecular weight polyester, etc. have good adhesion by coating on film, paper, fiber, etc. It is preferable from the point of being able to adjust the hardness affecting the property.
  • the water-soluble polymer also includes a copolymer as long as the water solubility is maintained.
  • the dispersion medium of the carbon nanowire dispersion liquid of the present invention may be an organic solvent.
  • the organic solvent include those described above.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • MEK methyl ethyl ketone
  • a polymer is contained as a binder or a vehicle.
  • the polymer is not particularly limited, but polyimide, polyepoxy (precursor) and the like are mentioned as preferable. More preferably, they are aromatic polyimide, polyepoxy (precursor) and the like.
  • the polyimide those in a varnish state can be used.
  • the carbon nanowire dispersion can be blended on the main agent side or the curing agent side.
  • Aromatic polyimides have higher strength and higher heat resistance than ordinary polymers.
  • the coefficient of linear expansion is very low as an organic substance and close to metal, when forming an electronic circuit, distortion due to thermal expansion with metal (wiring) hardly occurs, and high-precision wiring processing is possible, In particular, aromatic polyimides are preferred.
  • the dispersion medium of the carbon nanowire dispersion described above is “2-pyrrolidone in which the nitrogen atom may be substituted with a hydrocarbon group”, and further contains at least a polyimide therein. It is also a "paint or ink” characterized by
  • the carbon nanowire dispersion liquid of the present invention is particularly preferably applied to a conductivity imparting material such as an ink for forming a conductive circuit, a conductive paint and the like.
  • paints or inks may further contain known compounding agents according to their use and "coating method or printing method".
  • the compounding agent for example, an antifoamer, a fluidity regulator, an organic or inorganic filler, a stabilizer, a dispersing (stabilizing) agent, a surfactant other than the above, a solvent other than the solvent of the dispersion, wettability
  • examples include modifiers, leveling agents, plasticizers, structural viscosity imparting agents, thixotropy imparting agents, and the like.
  • the present invention is a carbon nanowire dispersion, which is a “paint or ink” containing carbon nanowires in the dispersion, and a “coating film, circuit, structure or powder in which the carbon nanowire is contained. "
  • Measurement example 1 ⁇ Average fiber diameter, average fiber length, average aspect ratio, particle size distribution>
  • the average fiber diameter and the average fiber length in the present invention were measured using SEM (No. JSM 7000 series manufactured by Nippon Denshi Co., Ltd.).
  • the average aspect ratio was determined by dividing the average fiber length determined by the above method by the average fiber diameter.
  • the particle size distribution is defined as a wet type measurement using a laser diffraction / scattering type particle size distribution measuring apparatus Nanotrac manufactured by Nikkiso Co., Ltd. and measurement using the measuring apparatus (method).
  • Measurement example 2 ⁇ Viscosity of dispersion> Using a B-type viscometer BM type, no. The # 4 rotor was rotated at 6 rpm and the viscosity at its shear rate was measured. The temperature was 25 ° C.
  • Measurement example 3 ⁇ Surface Resistivity of Surface Treated Film> The volume resistivity ( ⁇ ⁇ cm) was measured according to JlS L6911.
  • Example 1 ⁇ Raw material> CFRP milled fiber (70 ⁇ m to 150 ⁇ m in length, 11000 nm in diameter) was used as “carbon fiber” as a raw material. This carbon fiber was pitch based (PITCH based).
  • Dry grinding was performed on 500 g of the raw material under the following conditions.
  • a cyclone mill which is the following air flow grinder, was used.
  • the obtained product has an average fiber diameter of 8000 nm (a distribution width of 90% by volume, 5000 nm to 11000 nm), an average fiber length of 45 ⁇ m (a distribution width of 90% by volume, 20 ⁇ m to 70 ⁇ m), and an average aspect ratio was 5.6.
  • the above obtained by wet grinding has an average fiber diameter of 200 nm (90 nm by volume distribution, 100 nm to 300 nm), an average fiber length of 15 ⁇ m (90 volume% of distribution width, 10 ⁇ m to 20 ⁇ m), average aspect The ratio was 75.
  • the scanning electron micrograph (SEM photograph) of the carbon fiber after dry-pulverization of Example 1 before wet-pulverization is shown in FIG. 1, and the carbon nanowire dispersed in the carbon nanowire dispersion liquid after wet-pulverization
  • the scanning electron micrograph (SEM photograph) is shown in FIG.
  • Example 1 In Example 1, ⁇ dry grinding> and ⁇ premixing> are the same, and in ⁇ wet grinding and dispersing treatment>, the bead milling time (one pass time and the number of passes) is as follows. Wet pulverization and dispersion treatment were carried out in the same manner as in Example 1.
  • the wet-pulverized product had an average fiber diameter of 200 nm, an average fiber length of 0.67 ⁇ m, and an average aspect ratio of 3.4.
  • the particle size distribution is shown in FIG.
  • Example 2 In Example 1 and Reference Example 1, ⁇ dry grinding> and ⁇ premixing> were the same, and in ⁇ wet grinding and dispersing treatment>, bead milling time (one pass time and number of passes) was as follows. The wet grinding and the dispersion treatment were performed in the same manner as in Example 1 and Reference Example 1 except for the above.
  • the wet-pulverized product had an average fiber diameter of 200 nm, an average fiber length of 15 ⁇ m, and an average aspect ratio of 75.
  • the particle size distribution is shown in FIG.
  • Example 1 In Example 1 in which the time of one pass is short, the particle size distribution was not sharper than in Reference Example 1 in which the time of one pass was long, but the average fiber length remained long and the average aspect ratio was as large as 75. On the other hand, in Reference Example 1 in which the time of one pass is long, the particle size distribution is sharp, but the average fiber length is short and the average aspect ratio is as small as 3.4.
  • Example 3 50 g of the aqueous carbon nanowire dispersion obtained in Example 1 (containing 2.5 g of carbon nanowire), 50 g of polyvinyl alcohol, and 20 g of polymethyl methacrylate (PMMA) (copolymer) are mixed by stirring, The obtained paint was applied on a general-purpose copy paper at 120 g / m 2 using a bar coater and dried.
  • PMMA polymethyl methacrylate
  • the conductive coating film obtained had an extremely low electrical resistance, and the surface of the paper maintained conductivity even when it was strongly folded 180 ° with the coated surface outward (even if completely folded). Since the average fiber length is long, it is considered that the conductive property is not interrupted because the portions where wires having long fibers intervene are more in contact with each other than the nanoparticles having short fiber lengths. In addition, since the average fiber length is long, the particles do not fall off by being entangled in the fibers of the paper, and even when the paper is bent, the voids are in contact with the carbon nanowires. It is thought that
  • Example 4 In Example 1, ⁇ dry pulverization> was identical, and ⁇ premixing> and ⁇ wet pulverization and dispersion treatment> were performed as follows.
  • NMP N-methyl-2-pyrrolidone
  • the average fiber diameter of the product obtained by the above wet pulverization is finally 200 nm (distribution width of 90% by volume, 100 nm to 300 nm), average fiber length is 10 ⁇ m (distribution width of 90% by volume, 5 ⁇ m to 15 ⁇ m)
  • the average aspect ratio was 50.
  • Example 5 In Example 4, the same amount of the anionic surfactant as in Example 4 was introduced into the bead mill container in the middle of the wet pulverization and dispersion treatment of Example 4 and stirred in the same manner as in Example 4.
  • the transition of the average fiber diameter, the average fiber length, and the viscosity in the bead mill wet grinding process (time transition) was as follows.
  • the bead conditions, the stirring conditions, and the like were the same as in Example 4, and the conditions were always fixed even if time went by. As for the following, as it goes down, time has passed. The description of "average" is omitted.
  • an anionic surfactant is added, and the chemical dispersion start fiber diameter 1000 nm, fiber length 10 ⁇ m, aspect ratio 10, viscosity 700 MPa ⁇ s Fiber diameter: 200 nm, fiber length: 10 ⁇ m, aspect ratio: 50, viscosity: 700 MPa ⁇ s Finish of bead mill wet grinding
  • Example 6 In Example 4 and Example 5, 100 parts by mass of ⁇ -butyrolactone (GBL) or 100 parts by mass of methyl ethyl ketone (MEK) instead of 100 parts by mass of N-methyl-2-pyrrolidone (NMP) as a dispersion medium
  • GBL ⁇ -butyrolactone
  • MEK methyl ethyl ketone
  • NMP N-methyl-2-pyrrolidone
  • Example 7 The carbon nanowire dispersion obtained in Example 4 was added to a polyimide (varnish type).
  • a polyimide varnish Ube Industries, Ltd. product Yupia (registered trademark) -AT (U-varnish-A) [for general heat resistance], and Yupia (registered trademark)-ST (U-varnish-S) [high heat resistance was used.
  • the carbon nanowire dispersion obtained in Example 4 was added to 100 parts by mass of each of the above-mentioned polyimide varnishes only in the following parts by mass. 5 parts by mass (0.25 parts by mass of carbon nanowires) 10 parts by mass (0.50 parts by mass of carbon nanowires) 20 parts by mass (1.0 parts by mass of carbon nanowires) 40 parts by mass (2.0 parts by mass of carbon nanowires) 50 parts by mass (2.5 parts by mass of carbon nanowires) 80 parts by mass (carbon nanowires 4.0 parts by mass)
  • a paint or an ink was obtained by using an automatic mixer AS100 manufactured by As One Co., Ltd. as a machine for mixing the above, and repeating this twice with a stirring time of 14 seconds.
  • the resulting paint or ink was coated on a 20 ⁇ m polyimide resin film.
  • the coater was coated at 12 ⁇ m using a bar coater. After coating, the film was baked by heating at 140 ° C. for 5 minutes in an oven to obtain a surface-treated film.
  • Each of the surface-treated films obtained by coating the polyimide resin film with the paint or ink obtained above and heating and baking it has a volume resistivity of 1.0 ⁇ 10 ⁇ 8 measured by the evaluation method 3 It was less than [ ⁇ ⁇ cm].
  • the paint or ink obtained above was able to impart conductivity, thermal conductivity, heat dissipation and jet blackness to the surface of the polyimide resin film as the object. If the object is a metal, it is considered to provide corrosion resistance.
  • Example 8 A paint or an ink was prepared in the same manner as in Example 7 using an epoxy resin and an acrylic resin instead of the polyimide of Example 7, to obtain a surface-treated film.
  • a dispersion medium NMP was used for all.
  • a conductive film, a heat conductive film, a heat dissipating film, an anticorrosive film, and a jet-black film were obtained.
  • the epoxy resin containing a curing agent the cured epoxy resin cured product formed a micro phase separation structure.
  • Example 9 The “paint or ink” obtained in Example 7 and Example 8 is placed in a glass bottle and heated in an oven at 120 ° C. for 1 hour to 1 hour and 20 minutes to evaporate the dispersion medium, and the dried product and Got a powder.
  • the powder was nano-sized powder. Although all were agglomerated, it was possible to be easily diffused in water, an acrylic monomer, and an epoxy resin main agent. The following was considered as the reason. That is, the anionic surfactant (for example, an alkylol ammonium salt of a copolymer containing an acid group) used in the wet grinding / dispersion step is attached to the surface of the carbon nanowire, and volatilizes even at a drying temperature of 120 ° C. It is considered that the dispersion is very good in the dispersion medium, the monomer, the binder, etc.
  • the anionic surfactant for example, an alkylol ammonium salt of a copolymer containing an acid group
  • the amount to be attached can be adjusted and changed depending on the amount and type of anionic surfactant added at the time of viscosity adjustment of bead mill wet grinding and dispersion, so application is possible depending on the amount and type of anionic surfactant The range spreads.
  • the carbon nanowire dispersion liquid of the present invention, and the paint or ink using the dispersion liquid contain carbon nanowires having a specific shape, and therefore, the surface has conductivity, heat conductivity, heat dissipation, prevention It can be made to have rustiness, jet-blackness, etc. Therefore, since "a film, a structure, etc.” having “a film, a layer, etc.” having the performance, and “powder, a circuit, a structure, etc.”, having the performance, such performance is required. It is widely used in various fields (required).

Abstract

La présente invention aborde le problème consistant à fournir : un liquide de dispersion de nanofils de carbone dans lequel des nanofibres de carbone ayant un diamètre de fibre moyen dans la plage de taille nanométrique ont une longueur de fibre moyenne longue par rapport à la finesse dudit diamètre de fibre moyen, sont faciles à broyer et se dispersent dans un milieu de dispersion, et sont peu susceptibles de s'agglomérer ; et un méthode de production du liquide de dispersion de nanofils de carbone. Le problème est résolu par un liquide de dispersion de nanofils de carbone dans lequel des nanofils de carbone ayant un diamètre de fibre moyen de 300 nm ou moins et un rapport d'aspect moyen de 30 à 200 sont dispersés dans un milieu de dispersion, et par une méthode de production du liquide de dispersion de nanofils de carbone dans laquelle des fibres de carbone sont soumises à un broyage à sec ou des fibres de carbone broyées à sec sont préparées, puis lesdites fibres de carbone sont broyées tout en étant dispersées dans un milieu de dispersion en effectuant un broyage humide à l'intérieur du milieu de dispersion. Lors de la réalisation du broyage humide, les fibres de carbone broyées à sec sont incorporées dans le milieu de dispersion, un traitement de broyeur à billes est effectué en présence d'un tensioactif anionique, et les fibres de carbone deviennent ainsi des fibres de carbone ayant un diamètre moyen de fibre de 300 nm ou moins et un rapport d'aspect moyen de 30 à 200.
PCT/JP2018/041299 2017-11-13 2018-11-07 Liquide de dispersion de nanofils de carbone et sa méthode de production WO2019093360A1 (fr)

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WO2016084697A1 (fr) * 2014-11-26 2016-06-02 昭和電工株式会社 Procédé de fabrication d'une pâte électroconductrice, et pâte électroconductrice
JP2017066546A (ja) * 2015-09-30 2017-04-06 帝人株式会社 ピッチ系極細炭素繊維、非水電解質二次電池用電極合剤層及び非水電解質二次電池用電極並びに非水電解質二次電池

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Publication number Priority date Publication date Assignee Title
JP2013217011A (ja) * 2003-05-09 2013-10-24 Showa Denko Kk 直線性微細炭素繊維
JP2005154200A (ja) * 2003-11-26 2005-06-16 Teijin Ltd カーボンナノチューブの製造方法
JP2009235650A (ja) * 2008-03-28 2009-10-15 Toyota Central R&D Labs Inc 繊維状炭素系材料絶縁物、それを含む樹脂複合材、および繊維状炭素系材料絶縁物の製造方法
JP2013534897A (ja) * 2010-06-22 2013-09-09 デザインド・ナノチューブス・リミテッド・ライアビリティ・カンパニー 修飾カーボンナノチューブ、それらの製造方法およびそれらから得られる製品
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