WO2020194380A1 - Liquide de dispersion de nanocarbone, son procédé de production et agent de dispersion de nanocarbone - Google Patents

Liquide de dispersion de nanocarbone, son procédé de production et agent de dispersion de nanocarbone Download PDF

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WO2020194380A1
WO2020194380A1 PCT/JP2019/012112 JP2019012112W WO2020194380A1 WO 2020194380 A1 WO2020194380 A1 WO 2020194380A1 JP 2019012112 W JP2019012112 W JP 2019012112W WO 2020194380 A1 WO2020194380 A1 WO 2020194380A1
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nanocarbon
dispersion
mass
cnc
dispersion liquid
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PCT/JP2019/012112
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English (en)
Japanese (ja)
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篤 田村
彰太 福島
英秋 込山
光次 田中
純司 根本
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北越コーポレーション株式会社
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Priority to PCT/JP2019/012112 priority Critical patent/WO2020194380A1/fr
Priority to PCT/JP2020/011197 priority patent/WO2020195974A1/fr
Priority to JP2021509058A priority patent/JP7177912B2/ja
Publication of WO2020194380A1 publication Critical patent/WO2020194380A1/fr

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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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • 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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose

Definitions

  • the present disclosure relates to a nanocarbon dispersion liquid containing nanocarbon and cellulose nanocrystals, a method for producing the same, and a nanocarbon dispersant containing cellulose nanocrystals.
  • nanocarbons such as carbon nanotubes and nanographenes have high surface energy, a strong van der Waals force acts on the surface of the nanocarbons even if the nanocarbons are dispersed in the medium. Therefore, nanocarbons tend to aggregate. Therefore, it is required to stably disperse nanocarbon.
  • a method for dispersing nanocarbons a method for dispersing carbon nanotubes in which water is added to a crushed mixture obtained by crushing monosaccharide or low sugar crystals, carbon nanotubes, and a nonionic or anionic surfactant is disclosed. (See, for example, Patent Document 1). Further, a method for dispersing carbon nanotubes using carboxymethyl cellulose as a dispersant is disclosed (see, for example, Patent Document 2). Further, a method for dispersing carbon nanotubes using cellulose nanofibers as a dispersant is disclosed (see, for example, Patent Document 3). Further, a method of dispersing multi-walled carbon nanotubes having an average fiber outer diameter in the range of 50 to 110 nm with sodium carboxymethyl cellulose is disclosed (see, for example, Patent Document 4).
  • Patent Document 1 has a problem that only a low-concentration carbon nanotube dispersion liquid having an upper limit value of about 5 g / L can be obtained.
  • a surfactant since a surfactant is used, the dispersion liquid tends to have a problem of foaming.
  • the viscosity of the dispersion tends to be high, and when it is attempted to be produced using a disperser, there is a problem that the disperser is blocked by the viscous dispersion.
  • Patent Document 3 since cellulose nanofibers are used, the viscosity of the dispersion tends to be high, and the concentration of carbon nanotubes in the examples is only 0.05% by mass at the maximum.
  • the method disclosed in Patent Document 4 can be applied only to multi-walled carbon nanotubes having a specific fiber diameter, and it is difficult to stably disperse carbon nanotubes having a fiber diameter of 50 nm or less and a small fiber diameter (large specific surface area). Met.
  • the present disclosure describes a dispersion liquid in which nanocarbons such as carbon nanotubes are stably dispersed and has fluidity, a method for producing the dispersion liquid, and nanocarbon added to obtain the dispersion liquid. It is intended to provide a dispersant.
  • the nanocarbon dispersion liquid according to the present invention is characterized by containing nanocarbon, cellulose nanocrystals, and a dispersion medium.
  • the concentration of the nanocarbon is preferably 1% by mass or more. Even if the concentration of nanocarbon is 1% by mass or more, the stability and fluidity of the nanocarbon dispersion can be improved.
  • the mass-based content ratio (nanocarbon: cellulose nanocrystal) of the nanocarbon and the cellulose nanocrystal is preferably 1: 0.1 to 1:10.
  • the stability and fluidity of the nanocarbon dispersion can be improved.
  • the concentration of the nanocarbon is 1% by mass or more and 4% by mass or less, and the total concentration of the nanocarbon and the cellulose nanocrystal exceeds 1% by mass and 15% by mass.
  • the following is preferable. Even if the concentration of nanocarbon is high, the stability and fluidity of the nanocarbon dispersion can be improved.
  • the dispersion medium is a polar solvent.
  • a nanocarbon dispersion having higher dispersibility can be obtained.
  • the polar solvent is alcohols, ketones, water, or a mixture thereof.
  • a nanocarbon dispersion having even higher dispersibility can be obtained.
  • the method for producing a nanocarbon dispersion according to the present invention is characterized in that a mixed solution containing nanocarbon, cellulose nanocrystals, and a dispersion medium is dispersed by a disperser.
  • the mixed solution is a mixed solution prepared by adding the cellulose nanocrystals to the dispersion medium, stirring the mixture, and then adding the nanocarbons.
  • the compatibility between the dispersion medium and the nanocarbon is less likely to be impaired, and the nanocarbon is less likely to float on the dispersion medium.
  • the cellulose nanocrystal is a spray-dried product. It is possible to easily adjust the concentration of cellulose nanocrystals.
  • the disperser is a homogenizer. A nanocarbon dispersion with more stable dispersibility can be obtained.
  • the nanocarbon dispersant according to the present invention is characterized by containing cellulose nanocrystals.
  • a dispersion liquid in which nanocarbons such as carbon nanotubes are stably dispersed and have fluidity a method for producing the dispersion liquid, and a nanocarbon dispersant added to obtain the dispersion liquid. be able to.
  • Nanocarbon dispersion liquid contains nanocarbon, cellulose nanocrystals, and a dispersion medium.
  • the nanocarbon refers to nanocarbon such as carbon nanotubes (hereinafter, also referred to as CNT), fullerenes, graphene nanoplatelets by a CVD method or a mechanical peeling method.
  • CNT carbon nanotubes
  • These nanocarbons may have a single layer or a structure having two or more layers.
  • these nanocarbon dispersions will be described, but the CNT dispersion will be described in detail below as a representative example.
  • CNT Since CNT has an intermediate conductivity between that of fullerene and that of graphene, it has a feature that it is easy to use industrially.
  • the CNT those having different fiber lengths, fiber diameters and BET specific surface areas are used depending on the application.
  • the fiber length range is 1 ⁇ m to 500 ⁇ m
  • the fiber diameter range is 0.4 nm to 150 nm.
  • the range of BET specific surface area is 10 m 2 / g to 2500 m 2 / g.
  • those having a small specific surface area have a large fiber diameter and are relatively easy to disperse, but as the specific surface area increases (as the fiber diameter decreases), dispersion tends to become difficult.
  • Some CNTs have a functional group such as a carboxyl group introduced on the surface in order to improve dispersibility, but even in such a CNT, as the specific surface area increases (as the fiber diameter decreases), the CNTs disperse. Tends to be difficult. Specifically, when the BET specific surface area of the CNT into which a functional group such as a carboxyl group has been introduced exceeds 100 m 2 / g, it may be difficult to sufficiently disperse the CNT with a conventional dispersant such as carboxymethyl cellulose. In particular, it has become difficult to obtain a dispersion having a high concentration, and it has been difficult to obtain a dispersion having a CNT concentration of more than 1% by mass.
  • a functional group such as a carboxyl group introduced on the surface in order to improve dispersibility, but even in such a CNT, as the specific surface area increases (as the fiber diameter decreases), the CNTs disperse. Tends to be difficult. Specifically, when the B
  • CNTs are dispersed by using cellulose nanocrystals (hereinafter, also referred to as CNC) as a dispersant.
  • the CNC is an acicular crystal obtained by subjecting a plant-derived cellulose fiber, particularly a wood-derived cellulose fiber, to a chemical treatment such as acid hydrolysis.
  • the number average fiber diameter of CNC is 4 nm to 70 nm
  • the number average fiber length is 25 nm to 1000 nm
  • the BET specific surface area is 100 m 2 / g to 500 m 2 / g
  • the aspect ratio is less than 50. is there.
  • the aspect ratio is a dimensionless number obtained by dividing the number average fiber length by the number average fiber diameter.
  • CNF Cellulose nanocrystals are also called cellulose nanowhiskers.
  • CNC cellulose nanofibers
  • CNF has a number average fiber diameter equivalent to that of CNC, but has a fiber length longer than that of CNC. It refers to a fibrous material having a fiber length of 10 times or more, generally 5 ⁇ m or more, and a CNC aspect ratio of more than 100.
  • CNC is an acicular crystal and does not have a large aspect ratio like a fibrous material such as CNF.
  • the major axis of CNC is also referred to as fiber length
  • the minor axis is also referred to as fiber diameter.
  • CNC having a fiber length shorter than that of CNF is suitable.
  • the number average fiber length of the CNC is preferably 25 nm to 500 nm, more preferably 100 nm to 400 nm, and most preferably 200 nm to 300 nm. If the average fiber length is less than 25 nm, the CNCs may aggregate with each other. If the number average fiber length exceeds 500 nm, the viscosity of the dispersion liquid tends to increase, and the fluidity of the dispersion liquid tends to be impaired when the concentration of CNTs is increased.
  • the viscosity measured with a B-type viscometer (20 ° C., 60 rpm, rotation time 1 minute) is 100 mPa ⁇ s or less in the case of a 2% by mass aqueous solution of CNC, and the fluidity is good, but CNF 2
  • the mass% aqueous solution often exceeds 10,000 mPa ⁇ s, resulting in impaired fluidity.
  • the number average fiber diameter of the CNC is preferably 5 nm to 60 nm, more preferably 10 nm to 50 nm, and most preferably 20 nm to 30 nm. If the average fiber diameter is less than 5 nm, the CNCs may aggregate with each other. If the number average fiber diameter exceeds 60 nm, the viscosity of the dispersion liquid may increase and the fluidity may decrease.
  • BET specific surface area of the CNC is preferably 120m 2 / g ⁇ 400m 2 / g, more preferably 150m 2 / g ⁇ 300m 2 / g, and most preferably 175m 2 / g ⁇ 250m 2 / g. If the BET specific surface area is less than 120 m 2 / g, the viscosity of the dispersion may increase and the fluidity may decrease. If the BET specific surface area exceeds 400 m 2 / g, the viscosity of the dispersion becomes high, and CNCs may aggregate with each other.
  • the aspect ratio of the CNC is preferably 5 to 40, more preferably 10 to 30, and most preferably 15 to 25. If the aspect ratio is less than 5, the CNCs may aggregate with each other. If the aspect ratio exceeds 40, the fluidity of the dispersion liquid when the CNT concentration is increased may decrease.
  • the number average fiber diameter and number average fiber length of CNC can be calculated according to the following. Using a transmission electron microscope (TEM, Transmission Electron Microscope) or a scanning electron microscope (SEM, Scanning Electron Microscope) on the surface of the CNC, at least three images of the CNC surface where the fields of view do not overlap are taken. To do. For the obtained image, two random axes are drawn vertically and horizontally for each image, and the fiber diameter and fiber length of the fibers intersecting the axes are visually read. At this time, the magnification is 5,000 times, 10,000 times, or 50,000 times depending on the size of the constituent fibers. The condition for the number of fibers intersecting the two axes is 20 or more.
  • TEM Transmission Electron Microscope
  • SEM Scanning Electron Microscope
  • CNC prepared by a chemical method such as acid hydrolysis using a strong acid with sulfuric acid, hydrochloric acid, hydrobromic acid or the like can be used for an aqueous suspension or slurry of cellulose fibers.
  • the strong acid is preferably sulfuric acid.
  • Negative charge is given by adding a sulfate ester group to the surface by hydrodispersing with sulfuric acid, and since the sulfate ester group has a large molecular weight, it also causes steric hindrance and has a large ability to disperse CNT. It is presumed that it will be.
  • the degree of polymerization of CNC is not particularly limited, but is preferably 100 to 500, and more preferably 200 to 400. If the degree of polymerization is less than 100, the dispersibility of CNTs may decrease. If the degree of polymerization exceeds 500, the viscosity of the dispersion liquid may increase and the fluidity may decrease.
  • CNT dispersion The details of the CNT dispersion have been described as a typical example of the nanocarbon dispersion, but even if the nanocarbon is another nanocarbon such as fullerene or graphene nanoplatelet, it is as good as the case of CNT. Nanocarbon dispersion can be obtained.
  • nanocarbons such as CNTs are stably dispersed in a dispersion medium.
  • CNTs having a BET specific surface area of 100 m 2 / g or more for example, CNTs having a BET specific surface area of 100 to 1000 m 2 / g can be stably dispersed.
  • the fiber diameter of CNTs having a BET specific surface area of 100 to 1000 m 2 / g is 30 nm or less, and many CNTs having such a fiber diameter are flexible and have excellent conductivity.
  • the concentration of nanocarbon is preferably 1% by mass or more. Even if the concentration of nanocarbon is 1% by mass or more, the stability and fluidity of the dispersion liquid of nanocarbon can be improved.
  • the content ratio contains more CNC than 1:10
  • the amount of nanocarbon is relatively small with respect to CNC, so that the effect of improving the dispersibility and stability of the nanocarbon dispersion has reached a plateau.
  • the upper limit of the concentration of nanocarbon is, for example, 4% by mass from the viewpoint of dispersibility.
  • the total concentration of nanocarbon and cellulose nanocrystals is preferably more than 1% by mass and 15% by mass or less. More preferably, it is 1.5% by mass or more and 13% by mass or less. Most preferably, it is 1.8% by mass or more and 5% by mass or less. If this total concentration is 1% by mass or less, nanocarbon may not be dispersed. If this total concentration exceeds 15% by mass, the viscosity of the dispersion liquid may increase and the fluidity may decrease.
  • the concentration of nanocarbon is 1% by mass or more and 4% by mass or less, and the total concentration of nanocarbon and cellulose nanocrystals is more than 1% by mass and 15% by mass or less. It is preferable to have. More preferably, the concentration of nanocarbon is 1% by mass or more and 3.5% by mass or less, and the total concentration of nanocarbon and cellulose nanocrystal is 1.5% by mass or more and 13% by mass or less. Most preferably, the concentration of nanocarbon is 1% by mass or more and 3% by mass or less, and the total concentration of nanocarbon and cellulose nanocrystal is 1.8% by mass or more and 5% by mass or less. Even if the concentration of nanocarbon is high, the stability and fluidity of the nanocarbon dispersion can be improved.
  • the dispersion medium can be arbitrarily selected depending on the intended use, but in order to fully exert the dispersion effect of CNC, it is preferable that the dispersion medium is a polar solvent in the nanocarbon dispersion liquid according to the present embodiment. ..
  • the polar solvent is preferably alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone, water, or a mixture thereof. Water is particularly preferable. A nanocarbon dispersion having even higher dispersibility can be obtained.
  • the nanocarbon dispersion can contain various additives as long as the desired effect of the present invention is not impaired.
  • Additives include, for example, antioxidants, heat stabilizers, light stabilizers, UV absorbers, pigments, colorants, foaming agents, antistatic agents, flame retardants, lubricants, softeners, tackifiers, plasticizers, mold release agents. Agents, deodorants, fragrances or combinations thereof. Care must be taken when adding these additives, as they can affect the properties of nanocarbons.
  • the nanocarbon dispersion liquid according to the present embodiment can be applied to a substrate such as a film, dried and formed into a film, and the solvent can be directly removed from the dispersion liquid or put into a poor solvent.
  • a carbon nanotube / cellulose nanocrystal composite material can also be obtained by precipitating the solid content, filtering and drying.
  • the surfactant include a surfactant having a defoaming effect, a surfactant having a dispersing effect, and a surfactant having a viscosity adjusting effect.
  • the surfactant having a dispersing effect is used. It is preferable not to contain it. Surfactants with a dispersing effect can cause foaming.
  • the method for producing a nanocarbon dispersion liquid according to the present embodiment is characterized in that a mixed liquid containing nanocarbon, cellulose nanocrystals, and a dispersion medium is dispersed by a disperser.
  • CNC includes, for example, a slurry product dispersed in water and a spray-dried product obtained by drying the slurry product, both of which can be used.
  • the CNC is a spray-dried product.
  • CNC can be dispersed in water relatively easily even if it is a dried product, so that the concentration can be easily adjusted by using the dried product.
  • the order of addition of nanocarbon and CNC to the dispersion medium is not particularly limited, but in the method for producing a nanocarbon dispersion liquid according to the present embodiment, the mixed liquid simultaneously adds nanocarbon and CNC to the dispersion medium. It is preferable that the mixture is prepared by adding CNC to a dispersion medium and stirring, and then adding nanocarbon. Since nanocarbon has strong hydrophobicity, when the dispersion medium is water, if it is first added to the dispersion medium alone, it may float on the dispersion medium and easily impair compatibility.
  • the disperser used for the dispersion treatment is not particularly limited, and various known mechanical dispersion treatment machines can be used.
  • a stirrer equipped with an agitator, an ultrasonic disperser, a high shear stirrer, a biomixer or a homogenizer can be used.
  • Two or more kinds of these dispersers may be used in combination.
  • the mixed solution is pre-dispersed with an ultrasonic disperser and then dispersed with a homogenizer
  • the mixed solution is pre-dispersed with a biomixer, and then dispersed with a homogenizer. Dispersion processing of steps or more may be performed.
  • the disperser is a homogenizer.
  • the homogenizer includes, for example, an ultrasonic type, a stirring type, and a high pressure type, and a high pressure type, and a high pressure type homogenizer (high pressure homogenizer) is preferable.
  • the water jet method is preferable.
  • a water jet type high pressure homogenizer for example, there is Starburst (registered trademark) manufactured by Sugino Machine Limited.
  • the pressure homogenized dispersion treatment condition is preferably a pressure of 100 to 250 MPa and 1 to 10 passes. A nanocarbon dispersion cannot be obtained without dispersion treatment. If the pressure is less than 100 MPa, the dispersion may be insufficient. If the pressure exceeds 250 MPa or the number of passes exceeds 10, the dispersion does not proceed and the high temperature of the dispersion liquid may rise.
  • the nanocarbon dispersant is an agent for dispersing nanocarbon.
  • the nanocarbon dispersant according to the present embodiment contains cellulose nanocrystals.
  • Examples of the form of the nanocarbon dispersant include a slurry product in which cellulose nanocrystals are dispersed in water (hereinafter referred to as Form L), and a spray-dried product of cellulose nanocrystals obtained by drying the slurry product (hereinafter referred to as Form L).
  • Form L a slurry product in which cellulose nanocrystals are dispersed in water
  • Form L a spray-dried product of cellulose nanocrystals obtained by drying the slurry product
  • the nanocarbon dispersion liquid in which the dispersion medium is water can be easily prepared by adding the nanocarbon to the slurry product in the form L.
  • the form of use is, for example, adding nanocarbon and the nanocarbon dispersant to the dispersion medium at the same time, or in a liquid in which the nanocarbon is dispersed in the dispersion medium.
  • Nanocarbon dispersants may be added.
  • the dispersion medium is water, it is preferable to add the nanocarbon and the nanocarbon dispersant to the dispersion medium at the same time from the viewpoint of the hydrophobicity of the nanocarbon.
  • the nanocarbon dispersant is of form N, by adding nanocarbon to the dispersion of form N, a nanocarbon dispersion in which the dispersion medium is a dispersion medium other than water can be easily prepared.
  • the obtained suspension was concentrated by centrifugation, and then ion-exchanged water was added to adjust the solid content concentration to 2% by mass to obtain a second suspension.
  • the second suspension was defibrated by an ultrasonic homogenizer (US300E, manufactured by Nippon Seiki Seisakusho), and then water was removed by a spray dry method to obtain a powdery CNC.
  • CNT Carbon nanotube
  • A Carbon nanotube (trade name: K-nanos100P, multi-walled CNT, manufactured by Kumho Petrochemical, fiber length (Bundle Diameter) 3 ⁇ m, fiber diameter 8 to 15 nm, specific surface area 220 m 2 / g)
  • B Carbon nanotube (trade name: nanocil-7000, multi-walled CNT, manufactured by nanocil, number average fiber length 1.5 ⁇ m, number average fiber diameter 9.5 nm, specific surface area 250 to 300 m 2 / g)
  • Example 1 The obtained CNC was added to ion-exchanged water as a dispersant and stirred, and then CNT (A) was gradually added together with ion-exchanged water to obtain a mixed solution.
  • the concentration of CNC in the mixed solution was 2% by mass, and the concentration of CNT (A) was 2% by mass.
  • the obtained mixed solution was dispersed for 30 minutes using a biomixer (BM-2 type, Nissei Tokyo Office), filtered through a 60-mesh sieve, and then a high-pressure homogenizer (trade name: Ultimizer, manufactured by Sugino Machine Limited).
  • a carbon nanotube dispersion was obtained by passing the mixture 10 times at a pressure of 200 MPa.
  • Example 2 A carbon nanotube dispersion was obtained in the same manner as in Example 1 except that CNC was added so that the concentration of CNC in the mixed solution was 0.2% by mass.
  • Example 3 A carbon nanotube dispersion was obtained in the same manner as in Example 1 except that CNC was added so that the concentration of CNC in the mixed solution was 10% by mass.
  • Example 4 Same as in Example 1 except that CNT (A) was added so that the concentration of CNT (A) in the mixed solution was 1% by mass, and CNC was added so that the concentration of CNC was 1% by mass. A carbon nanotube dispersion was obtained.
  • Example 5 Same as in Example 1 except that CNT (A) was added so that the concentration of CNT (A) in the mixed solution was 1% by mass, and CNC was added so that the concentration of CNC was 0.1% by mass. A carbon nanotube dispersion was obtained.
  • Example 6 Same as in Example 1 except that CNT (A) was added so that the concentration of CNT (A) in the mixed solution was 1% by mass, and CNC was added so that the concentration of CNC was 10% by mass. A carbon nanotube dispersion was obtained.
  • Example 7 Change CNT (A) to CNT (B), add CNT (A) so that the concentration of CNT (B) in the mixed solution is 1.5% by mass, and the concentration of CNC is 1.5% by mass.
  • a carbon nanotube dispersion was obtained in the same manner as in Example 1 except that CNC was added so as to become.
  • Example 1 Carbon nanotubes in the same manner as in Example 1 except that the CNC was changed to cellulose nanofibers obtained by mechanically defibrating hardwood kraft pulp (processing machine: Super Mascoroider, manufactured by Masuko Sangyo Co., Ltd.). A dispersion was obtained.
  • Example 2 The treatment was carried out in the same manner as in Example 1 except that the CNC was changed to carboxymethyl cellulose (CMC, cellogen PR, manufactured by Dai-ichi Kogyo Seiyaku), but the viscosity increased during the high-pressure homogenizer treatment, and the inside of the high-pressure homogenizer was blocked for the purpose. It was not possible to obtain the carbon nanotube dispersion liquid.
  • CMC carboxymethyl cellulose
  • CNC was changed to carboxymethyl cellulose (CMC, cellogen WS-C, manufactured by Dai-ichi Kogyo Seiyaku), and CNT (A) was added so that the concentration of CNT (A) in the mixed solution was 1.5% by mass.
  • CMC carboxymethyl cellulose
  • A carboxymethyl cellulose
  • the treatment was carried out in the same manner as in Example 1 except that carboxymethyl cellulose was added so that the concentration of carboxymethyl cellulose became 1.5% by mass, but the viscosity increased during the high-pressure homogenizer treatment, and the inside of the high-pressure homogenizer was blocked for the purpose. It was not possible to obtain the carbon nanotube dispersion liquid.
  • Example 4 A carbon nanotube dispersion was obtained in the same manner as in Example 1 except that CNC was not added to the mixed solution.
  • Example 5 The same as in Example 1 except that the CNC was changed to a surfactant having a dispersing effect (sodium dodecyl sulfate, manufactured by Tokyo Chemical Industry Co., Ltd.), but a large amount of bubbles were generated at the stage of the dispersion treatment with the biomixer. , The treatment with the high pressure homogenizer could not be performed.
  • a surfactant having a dispersing effect sodium dodecyl sulfate, manufactured by Tokyo Chemical Industry Co., Ltd.
  • Table 1 shows the composition and evaluation of the nanocarbon dispersions obtained in each Example and Comparative Example. The following methods were used for the evaluation of the nanocarbon dispersion.
  • the nanocarbon dispersion obtained by the dispersion treatment was diluted with ion-exchanged water so that the CNT concentration was 0.05% by mass, left in a glass vial for 1 hour, and then evaluated by visual observation according to the following criteria. .. A: It is good because there is no sedimentation of aggregates and separation of CNT and water. B: There is no sedimentation of aggregates, and the separation between CNT and water is slight and good. C: There are fine aggregates, and a small separation between CNT and water can be confirmed (lower limit of practical use). D: Most of the agglomerates are large, and the separation from water is also large (not practical).
  • the viscosity of the nanocarbon dispersion obtained by the dispersion treatment was adjusted to 20 ° C. using a B-type viscometer (No. 1 to 4 rotor) (trade name: B-type viscometer, model: BM, manufactured by Tokyo Keiki Seisakusho). The viscosity was measured by rotating at a rotation speed of 60 rpm for 1 minute, and the value was evaluated according to the following criteria A to D.
  • B B-type viscosity is 1000 mPa ⁇ s or less, and the fluidity is good.
  • B-type viscosity is 2000 mPa ⁇ s or less, and fluidity can be confirmed (practical lower limit).
  • D B-type viscosity exceeds 5000 mPa ⁇ s and lacks fluidity (not practical).

Abstract

Le but de la présente invention est de fournir : un liquide de dispersion dans lequel du nanocarbone, tel que des nanotubes de carbone, est dispersé de façon stable et qui présente une bonne fluidité, et un procédé de production de celui-ci ; et un agent de dispersion de nanocarbone qui est ajouté afin d'obtenir le liquide de dispersion. Ce liquide de dispersion de nanocarbone contient du nanocarbone, des nanocristaux de cellulose et un milieu de dispersion.
PCT/JP2019/012112 2019-03-22 2019-03-22 Liquide de dispersion de nanocarbone, son procédé de production et agent de dispersion de nanocarbone WO2020194380A1 (fr)

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PCT/JP2019/012112 WO2020194380A1 (fr) 2019-03-22 2019-03-22 Liquide de dispersion de nanocarbone, son procédé de production et agent de dispersion de nanocarbone
PCT/JP2020/011197 WO2020195974A1 (fr) 2019-03-22 2020-03-13 Liquide de dispersion de nanocarbone, son procédé de production, agent de dispersion de nanocarbone, et matériau de protection contre les ondes électromagnétiques
JP2021509058A JP7177912B2 (ja) 2019-03-22 2020-03-13 ナノカーボン分散液の製造方法、ナノカーボン分散剤及び電磁波遮蔽材

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JPWO2021065432A1 (fr) * 2019-10-02 2021-04-08
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