JP4930873B2 - Fine carbon dispersion - Google Patents

Description

  The present invention manufactures fine carbon dispersions (eg, gels and dried gels, fibers, membranes, molded articles) and articles as composite materials in which nano to micro-sized fine carbons (eg, carbon nanotubes) are uniformly dispersed. The present invention relates to a fine carbon dispersion as a mediating material for dispersing the fine carbon in the article, a production method thereof, and use thereof.

  Nano to micro-sized carbon has recently attracted attention in various fields. In particular, nanocarbon is a new material that is attracting attention in various fields such as energy, electronics, chemistry, pharmaceuticals, optical components, materials and machines, represented by carbon nanotubes (CNT). Among them, CNT, which is one of the representative materials of nanotechnology, is a light and strong new material, and applied research such as electron emitter materials for displays, hydrogen storage materials, and atomic force microscope probes is being promoted. ing. Here, there are single-layer / multi-layer types and cup-stacked types of CNT, and single-layer / multi-layer types are acicular carbon molecules with a diameter of nanometer order, and graphene is rolled into a cylindrical shape. have. A graphene cylinder having a concentric multi-layer structure is called a multi-wall carbon nanotube (MWCNT), and is used for applications such as FED emitters, ultra-high strength materials, and composite materials. Moreover, what consists only of a single layer graphene cylinder is called single wall carbon nanotube (SWCNT), and is utilized for uses, such as a fuel cell and a lithium secondary battery negative electrode. In particular, the development of composite materials using carbon nanotubes as fillers has been vigorously conducted.

By the way, since CNTs have excellent electrical conduction characteristics and mechanical strength, researches in the field of electronic materials such as electron-emitting devices and the field of high-strength materials have been mainly conducted. For example, the technique of Patent Document 1 is a method of manufacturing a CNT thin film for obtaining an electron-emitting device. In this method, the dispersed particles are deposited on the electrode particles to form a thin film. That is, in this technique, CNTs are aggregated at a high density in order to ensure high electron emission ability. Moreover, the technique of patent document 2 is a thermoplastic resin composition used for a heat insulating material etc. containing a thermoplastic resin, a foaming agent, a crosslinking agent, and CNT. The composition containing CNTs is melt-kneaded and molded, and then subjected to a crosslinking / foaming reaction to form a crosslinked thermoplastic resin in which CNTs are dispersed.
JP 2001-48511 JP 2004-75707 A

  Here, when manufacturing the composite material, in the prior art, a composite material obtained by mixing with a resin is generally used. However, according to this method, if the carbon nanotubes to be mixed have a complicated intertwined shape, a lump of carbon nanotubes remains and uniform dispersibility cannot be ensured. Specifically, the CNT material as an electronic material is not sufficiently provided with properties such as air permeability, permeability, and adsorptivity because CNTs are aggregated at high density. Further, the CNT material as a high-strength material also has air permeability with respect to the pores resulting from foaming, but there are few gaps between the crosslinked structures of the thermoplastic resin, and the internal air permeability is extremely poor. Therefore, even if these materials are used as an adsorbent, the ability to absorb CNT existing on the surface or inside cannot be sufficiently exhibited. Then, an object of this invention is to provide the means for ensuring the uniform dispersibility of a carbon nanotube in a composite material.

  As a result of intensive studies by the inventors in view of the above problems, the inventors have found that the above problems can be solved by using a fine carbon dispersion in the production of a composite material, thereby completing the present invention. At the same time, the present inventors also found a novel dispersion that can be applied to other uses. After all, the present invention is as follows.

  In the present invention (1), a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon is applied to a hydrophobic smooth body and then dried when the liquid medium is aqueous. On the other hand, when the liquid medium is non-aqueous, it is a network-like nanocarbon aggregate obtained by drying after applying to a hydrophilic smooth body and, optionally, washing the dispersant after the drying.

  The present invention (2) is a conductive material containing the network-like nanocarbon aggregate of the above invention (1).

  The present invention (3) is an electrical product including the conductive material of the invention (2).

  Here, in the above inventions (1) to (3), the “smooth body” is a concept including not only a case where the surface is planar, but also a case where the surface is spherical, for example. In addition, examples of “application” include application and immersion, and specific examples include means such as dip coating, spray coating, roll coating, and flow coating. The definitions of other terms will be described as appropriate below.

  Next, the invention disclosed in the present specification other than the above-described inventions (1) to (3) according to the claim for rights will be described.

  The present invention (4-1) is a fine carbon dispersion produced using a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon.

Here, "fine carbon micro-sized nano" size ¹⁰ -6 ^{to 10-9} m order, length ¹⁰ -4 ^{to 10 -9} m (preferably ¹⁰ -6 ^{to 10 -9} m) refers to carbon in the order of, for example, nanocarbon. “Nanocarbon” refers to carbon having an order of 10 ⁻⁹ m, preferably carbon nanotubes (single-layer / double-layer / multi-layer type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite or fullerene. Can be mentioned. Here, “micro carbon from nano to micro size” means containing at least one kind of carbon corresponding to nano to micro size carbon, for example, containing all sizes from nano to micro size. It does not mean that carbon other than nano to micro size is not contained. Further, the “carbon nanotube” includes single-walled and multi-walled (two or more layers), and also includes carbon nanofibers with a disordered graphite layer. In addition, since it becomes difficult to disperse | distribute, so that there are many layers, the significance of this invention increases, so that there are many layers. The term is not limited to the present invention (4-1), and is applied to all the inventions to be described later unless otherwise specified. The same applies to each term appearing in the following description of each invention other than the present term.

  “Dispersant” refers to a reagent for dispersing fine carbon in a liquid medium. Preferably, it is a reagent that disperses the fine carbon without modifying the surface of the fine carbon so as not to impair the properties of the fine carbon. Here, “dispersion” means dispersion in a broad sense including suspension and dissolution. For example, a mode in which all microcarbons are dissolved, a mode in which all are suspended, a mode in which some are dissolved (the others are in other forms such as suspension), a mode in which some are suspended (other May exist in other forms such as dissolution). From a visual point of view, for example, a fine carbon is dispersed in a liquid and floats, and it looks as if it looks uniform. Particularly preferably, the fine carbon is present up to the upper layer part of the liquid part even after standing for more than one day.

  The “fine carbon dispersion” refers to the target object in a state where the fine carbon is dispersed in the target object. Here, it is preferable that the minute carbon is uniformly dispersed in the object. For example, a composite material (for example, a fiber, a film, or a molded body) in which carbon nanotubes are uniformly dispersed. “Uniformly dispersed” means a state in which the physical properties of the obtained composite material do not vary from place to place (for example, about ± 20%). Specifically, when observing with an electron microscope, it can be visually confirmed that it is uniformly dispersed as compared with the conventional lump-like case. Applicable.

  The “liquid medium” in the “carbon-dispersed liquid medium” is not particularly limited as long as it can disperse the carbon in combination with a dispersant. For example, an aqueous solvent such as water, alcohol, or a combination thereof And non-aqueous solvents (oil-based solvents) such as silicon oil, carbon tetrachloride, chloroform, toluene, and combinations thereof.

  In the present invention (4-2), the fine carbon dispersion is a surface dispersion type in which the fine carbon is dispersed on the surface of the object, or the inside in which the fine carbon is dispersed in the object. It is a fine carbon dispersion of the said invention (4-1) which is a dispersion type.

  In the invention (4-3), the internal dispersion type fine carbon dispersion is a gel obtained by gelling the fine carbon liquid medium or a dry product thereof or the dry product thereof (4- 2) The fine carbon dispersion.

  The “micro carbon liquid medium” according to the present invention needs to be gelable. Here, “gelable” means that the carbon-dispersed liquid medium contains a gelling material having a crosslinking group that can be crosslinked by some means. Preferably, the dispersant is a gelling material.

  The “dried product” refers to a dried product of “the carbon dispersion liquid medium”, and the degree of drying is not particularly limited. In this state, it is understood that the carbon is present in the gelled material {eg, dispersant (eg, surfactant)} with high uniformity while maintaining a very small particle size.

  “The dried material is gelled” means that the dried material is gelled by any means in a wet form in which a liquid medium is present. For example, a mode in which the gelling agent-containing liquid medium is applied to the dried product, a mode in which the liquid medium is applied to the dried product, and then light / radiation crosslinking is performed.

  “The resulting gel” is understood to be encapsulated in the gel with a high degree of uniformity while the carbon maintains a very small particle size. Here, the “encapsulation” is a concept in which the gel film encloses the carbon in the liquid medium or the carbon in a dry form depending on the case in addition to the inclusion of the carbon in the network structure of the gel. is there. For example, in the case of a bead-like or fiber-like gel enclosing a liquid medium, the carbon is present only in the gel network, the carbon is present in the gel network, and the carbon medium is also present in the internal liquid medium. An embodiment in which carbon is dissolved and dispersed can be mentioned. Further, in the case of a film-like, plate-like gel or bulk gel, an embodiment in which nanocarbon is present in the gel network can be exemplified. Furthermore, since it is not “the obtained gel” but “the obtained gel”, it is not limited to the gel obtained by the production method limitation as long as it is the same as the product.

  Here, the “gel” is a three-dimensional network structure formed by chemical crosslinking or physical crosslinking between polymers, or a three-dimensional network structure formed by crosslinking simultaneously with polymerization of monomers. In this structure, a solvent is retained, and the “solvent” is a liquid contained in the network structure that swells the network structure. Therefore, it can be read simply as “liquid”. In addition, the said solvent is not specifically limited, It selects suitably in relation to a specific use. Therefore, it is not necessarily the same as the “liquid medium” in the “gelable carbon-dispersed liquid medium” that is the raw material of the gel, and when the solvent is exchanged after the raw material is gelled, The new solvent becomes the solvent of the “obtained gel”. Specific examples include aqueous solvents such as water, alcohol, combinations thereof, and oily solvents such as silicon oil, carbon tetrachloride, chloroform, toluene, and combinations thereof. For example, when the liquid medium is water, it can be used as a separation resin for applications requiring biosafety such as use in a water purifier or for chromatography using an aqueous solution as an eluent.

  In the present invention (4-4), the fine carbon dispersion has a double structure of an inner layer and an outer layer, the inner layer is the carbon-dispersed liquid medium, and the outer layer is a gel of the fine carbon-dispersed liquid medium. It is a fine carbon dispersion of the said invention (4-3) which is a chemical compound.

  In addition, as long as the double structure of an inner layer and an outer layer is taken, the aspect which coat | covered the gel, the polymer, etc. further on the further outer side of the said outer layer is also within the scope of the present invention.

  Here, when the mode of the gel or dried gel of the above inventions (4-2) to (4-4) is set as group A, the preferable group A invention is as follows.

  The preferred embodiment (A-1) is a gel obtained by gelling the gelable carbon dispersion liquid medium containing nano to micro-sized carbon and a dispersant for the carbon, or a dried product thereof.

  Preferred embodiment (A-2) is the gel of preferred embodiment (1), wherein the carbon-dispersed liquid medium is the carbon solution or suspension. Here, the term “or” in “the carbon solution or suspension” does not exclude the other as long as only one of them is essential. This also applies to other parts unless otherwise specified. That is, for example, in the carbon-dispersed liquid medium, all the carbon is dissolved, all suspended, some partially dissolved (the others exist in other forms such as suspended), one An embodiment in which the part is suspended (the others are present in other forms such as dissolution) can be mentioned. A solution form is preferable because it has a smaller particle size and high uniformity.

  A preferred embodiment (A-3) is the gel of the preferred embodiment (A-1) or (A-2), which is gelled by crosslinking of the dispersant.

  A preferred embodiment (A-4) is the gel according to any one of the preferred embodiments (A-1) to (A-3), in which the dispersant is a surfactant. Specific examples of the surfactant will be described in detail in the “Best Mode for Invention” section below.

In a preferred embodiment (A-5), the carbon is a carbon nanotube (single-layer / double-layer / multi-layer type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, or microcarbon filter. The gel is any one of the preferred embodiments (A-1) to (A-4). Here, “graphite” as referred to in the present preferred embodiment refers to a powder that has been pulverized to a particle size of 10 ⁻⁶ m or less.

  The preferred embodiment (A-6) is a gel according to any one of the preferred embodiments (A-1) to (A-5), wherein the shape is a bead shape, a fiber shape, a membrane shape, a plate shape, or a bulk shape. It is.

  Here, “bead shape” may be referred to as “parcel” and means a substantially spherical shape, the particle size is not particularly limited, and the preferred range varies depending on the application and the like. Further, “fibrous” means linear, and the length and diameter are not particularly limited and are determined depending on the application. For example, anything as thin as a thread or as thick as a toad egg is also included in the “fiber form”. Next, regarding the “film shape” and “plate shape”, the surface area and shape are not particularly limited, and are determined according to the application. The volume and shape of the “bulk shape” are not particularly limited and are determined depending on the application. As for other preferred embodiments described below {for example, preferred embodiment (A-7)}, for example, a bead-like or fibrous gel may have a double structure of an inner layer and an outer layer. About aspect (A-6), it does not specifically limit, The double structure is not taken and the thing which all gelatinized is also included.

  In a preferred embodiment (A-7), the bead-like gel or the fiber-like gel has a double structure of an inner layer and an outer layer, the inner layer is the carbon dispersion liquid medium, and the outer layer is the carbon dispersion liquid. The gel according to the preferred embodiment (A-6), which is a gelled product of the medium.

  In a preferred embodiment (A-8), the beaded gel or the fibrous gel is obtained by dropping or flowing down the carbon-dispersed liquid medium in a liquid medium containing a gelling agent. It is a gel of preferred embodiment (A-7).

  Here, the “gelling agent” is not particularly limited as long as it is a gelling agent capable of crosslinking a gel material (for example, a dispersing agent) in the carbon dispersion liquid medium. The “liquid medium” of the “liquid medium containing the gelling agent” is not particularly limited as long as it is a liquid medium that can disperse (eg, dissolve or suspend) the gelling agent. Examples thereof include the same “liquid medium” as the “nanocarbon dispersion liquid medium” described in the section A-1). Since the purpose is to gel the gelling material (for example, a dispersant) in the nanocarbon-dispersed liquid medium with a gelling agent, it is preferable that the “liquid medium” of “the liquid medium containing the gelling agent” be used. It is preferable that at least one of “medium” and “liquid medium” of “nanocarbon-dispersed liquid medium” has a property of dispersing both the gelling material and the gelling agent.

  Further, “dropping” refers to applying the “carbon dispersion liquid medium” to the “liquid medium containing a gelling agent” discontinuously with respect to time. Moreover, “flowing down” means that “the carbon dispersion liquid medium” is continuously applied to “a liquid medium containing a gelling agent” with respect to time. In both cases, not only free fall but also acceleration and dropping into a “liquid medium containing a gelling agent” (for example, dropping by applying pressure with a syringe or the like), decelerating and “gelling agent” (For example, a tube or a guide member and slowly drop into a “liquid medium containing a gelling agent”). The direction to be applied is preferably the downward direction, but may be another direction.

  In a preferred embodiment (A-9), the film-form gel, the plate-form gel, or the bulk gel is formed by crosslinking the carbon-dispersed liquid medium applied in a film form or placed in a mold, or The gel according to the preferred embodiment (A-6), which is obtained by applying a liquid medium containing a gelling agent to the dried product.

  Here, regarding the former, as for the former, crosslinking using a gelling agent (such as applying a gelling agent-containing liquid or applying a solid gelling agent) and crosslinking without using a gelling agent (for example, , Radiation cross-linking), and the latter means cross-linking using a gelling agent in the form of a gelling agent-containing liquid.

  The “type” may be an open type or a closed type, and the size and shape are not particularly limited, and are determined in relation to the application. “Apply” means that the carbon-dispersed liquid medium or the dried product including adding, being applied, or being applied, and a gelling agent or a liquid medium containing the gelling agent. Means any concept that fits together.

  A preferred embodiment (A-10) is a dried gel obtained by drying any one of the preferred embodiments (A-1) to (A-9).

  Here, the “dry gel” is a gel obtained by drying the original gel containing the solvent, and the degree of drying (the degree of the amount of solvent in the gel) is not particularly limited, and is determined in relation to the use. Is done. For example, a gel from which X% solvent of the original gel has been removed and a completely dry gel (resin) from which 100% of the solvent has been removed can be mentioned.

  In the present invention (4-5), the fine carbon dispersion of the internal dispersion type disperses the raw material monomer in the fine carbon dispersed liquid medium, and then polymerizes the raw material monomer to remove the liquid medium. This is a fine carbon dispersion according to the invention (4-2), which is manufactured by the method described above. Here, “dispersing the monomer” includes dissolution, suspension, and emulsion.

  In the present invention (4-6), the fine carbon dispersion of the internal dispersion type is produced by dispersing the raw polymer in the fine carbon-dispersed liquid medium and then removing the liquid medium. The fine carbon dispersion of the invention (4-2). Here, “dispersing the polymer” includes dissolution, suspension, and emulsion.

  According to the present invention (4-7), the surface-dispersion type fine carbon dispersion is obtained by immersing a raw material in the fine carbon-dispersed liquid medium, and optionally unraveling the raw material and then removing the liquid medium. The fine carbon dispersion according to the invention (4-2) to be manufactured. An example of the “unraveling” process is an ultrasonic process.

  According to the present invention (4-8), the object constituting the fine carbon dispersion is obtained by subjecting the fine carbon dispersed in the surface and / or the inside thereof to a predetermined condition. It is the fine carbon dispersion of the said invention (4-1) or (4-2) comprised by the raw material which can be released below.

  Here, “free” means, for example, that the object is decomposed, evaporated, melted and dissolved by chemical treatment (acid, alkali, enzyme, etc.), physical treatment (heat, electricity, etc.), precipitation, etc. This means that it is separated from the supported fine carbon.

  In the present invention (4-9), the fine carbon dispersion moves the fine carbon from the liquid medium side to the object side after adding the object to the fine carbon dispersion liquid medium. The fine carbon dispersion according to the invention (4-8), which is produced by carrying out a transfer treatment.

  Here, the “triggered phase transfer process” is a process that separates the fine carbon from the dispersant in a state in which the fine carbon is dispersed and moves the fine carbon from the dispersion to another phase. Without being limited thereto, for example, heat treatment (for example, electromagnetic wave treatment) for increasing molecular motion of fine carbon, treatment for imparting vibration energy (for example, ultrasonic treatment), treatment for applying pressure, and the like can be given.

  The present invention (4-10) is the fine carbon dispersion according to the invention (4-9), wherein the induced phase transfer treatment is electromagnetic wave treatment or ultrasonic treatment.

  The present invention (4-11) is the fine carbon dispersion according to any one of the inventions (4-8) to (4-10), wherein the object is an ultrafine fiber or higher paraffin.

  Here, “extra fine fiber” refers to a fiber having a diameter of 1000 μm or less, preferably a fiber having a diameter of 100 μm or less, and more preferably a fiber having a diameter of 10 μm or less. “Higher paraffin” refers to paraffins having a melting point of 40 ° C. or higher. For example, a polyester fiber and a urethane foam fiber can be mentioned.

  The present invention (4-12) includes the inventions (4-8) to (4-11), wherein the fine carbon dispersion is an intermediate material for dispersing the fine carbon in the article when the article is produced. 1) a fine carbon dispersion.

  Here, the object constituting the “mediating material” is one that remains in the finally manufactured article, for example, functions as one material constituting the article after liberating the minute carbon. Alternatively, it may be one that does not remain in the finally manufactured article, such as functioning as a simple carrier only for dispersing the fine carbon in the article.

  The present invention (4-13) includes a step of crosslinking a crosslinkable component contained in a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon or a dried product thereof. This is a method for producing a fine carbon dispersion in which the fine carbon is dispersed inside a gel or a dried product thereof.

Here, “crosslinking” includes both chemical crosslinking and physical crosslinking. “Chemical crosslinking” means covalent crosslinking, and includes crosslinking using a crosslinking agent and crosslinking by radical polymerization (radiation crosslinking, photocrosslinking, plasma crosslinking). This chemical cross-linking is generally characterized in that the formed cross-linking is strong. Specific examples of the former include a polymer / dialdehyde compound in which the chemical crosslinking dispersant / crosslinking agent has an amino group or a hydroxyl group; a polymer having a halogen-based polymer, a carboxy polymer ester, an isocyanate, an epoxy group, or a methylol group / Amine compound; polymer having carboxyl group / aziridine compound; polymer / di- or polymethylolphenol resin having nitrile group, mercapto group, carboxyl group, etc .; amine, diene-based polymer / halide system; —OH, —SH, NH _2, polymer / di- and polyisocyanate compounds with active hydrogen of -COOH and the like; chlorosulfonic group, a polymer having an isocyanate group, cellulose / diols, polyols, alcohols such as bisphenol; carboxyl group, a hydroxyl group, Mercapto group, a polymer / diepoxy compound having a chlorosulfonated group. Specific examples of the latter include radiation-induced crosslinking such as polyvinyl alcohol, polymethyl vinyl ether, polyethylene, polystyrene, polyacrylate, and natural rubber as those that are crosslinked in water by irradiating γ rays. As for photocrosslinking, water-soluble polymers such as polyvinyl alcohol and N-vinylpyrrolidone can be exemplified as those crosslinked with a photocrosslinking agent such as diazo resin, bisazide, dichromate, and plasma crosslinking. With regard to the above, polyethylene, polytetrafluoroethylene, and nylon can be exemplified as those that are cross-linked by contact with an inert gas excited using high-frequency discharge.

Next, “physical crosslinking” refers to physical cross-linking by ionic bonds (Coulomb force bonds), hydrogen bonds, coordination bonds, helix formation or hydrophobic bonds. This physical crosslinking is generally characterized by causing a sol-gel transition due to changes in heat, solution species, ionic strength, and pH. Specific examples include polyvinylbenzyltrimethylammonium chloride and sodium chloride-polymethacrylate that can be cross-linked by mixing with respect to ionic bonds, and polyacrylic acid that can be cross-linked by freeze-drying with respect to hydrogen bonds. Polyacrylic acid-polyvinyl alcohol which can be cross-linked by acid, freeze-thaw method, polymethacrylic acid-polyethylene glycol can be exemplified as those which can be cross-linked by freezing and low-temperature crystallization method, and for coordination bond, chelate reaction Polyvinyl alcohol-Cu ²⁺ , polyacrylic acid-Fe ³⁺ can be mentioned as those that can be cross-linked by the above, and with respect to helix formation, agar, gelatin can be cross-linked by forming a helix between polymer chains. , Carrageenan, Can be mentioned alginic acid, for hydrophobic bonding, as can be crosslinked by hydrophobic interactions, mention may be made of ovalbumin, serum albumin.

  This invention (4-14) is a manufacturing method of the said invention (4-13) whose said crosslinkable component is a dispersing agent.

  The present invention (4-15) is a gelation capable of gelling a fine carbon-dispersed liquid medium containing nano- to micro-sized fine carbon and a dispersant for the fine carbon and containing a crosslinkable component. A double structure of an inner layer and an outer layer, including a step of adding to a liquid medium containing an agent, the inner layer is the fine carbon-dispersed liquid medium, and the outer layer is a gelled product of the fine carbon-dispersed liquid medium This is a method for producing a fine carbon dispersion in which the fine carbon is dispersed inside the gel.

  Here, when the aspect of the manufacturing method of the said invention (4-13)-(4-15) is made into B group, the invention of the suitable B group is as follows.

  A preferred embodiment (B-1) comprises a gelable carbon dispersion liquid medium containing nano to micro size carbon and a dispersant for the carbon, and a gelling agent capable of gelling the carbon dispersion liquid medium. Including a step of adding to the liquid medium, the inner layer and the outer layer having a dual structure, the inner layer is the carbon-dispersed liquid medium, and the outer layer is a gelled product of the carbon-dispersed liquid medium. This is a method for producing a bead-like or fiber-like gel containing micro-sized carbon or a dried gel thereof.

  Here, the “addition” in the “adding step” is not particularly limited as long as it is an addition mode that can obtain a bead-like or fiber-like gel. If it is in a state, the above-mentioned “flowing down” can be mentioned. In addition, a process other than the process may be included, for example, a process for producing the carbon (for example, nanocarbon), a purification process for the carbon, a process for producing the carbon-dispersed liquid medium, and a process for producing the gelling agent-containing liquid medium. And a gel drying step.

  A preferred embodiment (B-2) is the production method of the preferred embodiment (B-1), wherein the carbon dispersion liquid medium is the carbon solution or suspension.

  A preferred embodiment (B-3) is the production method of the preferred embodiment (B-1) or (B-2), wherein the dispersant can be crosslinked by the gelling agent.

  A preferred embodiment (B-4) is the production method of any one of the preferred embodiments (B-1) to (B-3), in which the dispersant is a surfactant.

  In the preferred embodiment (B-5), the carbon is a carbon nanotube (single-layer / multi-layer type, cup-stacked type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, or microcarbon filter. It is any one manufacturing method of aspect (B-1)-(B-4).

  A preferred embodiment (B-6) is: (1) the carbon-dispersed liquid medium after coating the gelable carbon-dispersed liquid medium containing nano to micro-sized carbon and the carbon dispersant into a film. Or (2) coating the gel-capable carbon-dispersed liquid medium containing nano to micro-sized carbon and the carbon dispersant into a film. And then drying to obtain a membranous dried product, and then applying to the membranous dried product a liquid medium containing a gelling agent that can be gelled when the membranous dried product returns to a wet state again. Or a step of obtaining a film-like gel by (3) or a step of obtaining a plate-like gel or a bulk gel by repeating the step (1) and / or the step (2). Carbon inside To a film form, a method for producing a plate-like or bulk gel or the dry gel.

  Here, “coating” includes not only the case where the liquid medium is applied by a coater or the like, but also the case where the liquid medium is sprayed. In addition, a process other than the process may be included, for example, a process for producing the carbon (for example, nanocarbon), a purification process for the carbon, a process for producing the carbon-dispersed liquid medium, and a process for producing the gelling agent-containing liquid medium. And a gel drying step.

  With respect to the above step (1), for example, after the carbon dispersion liquid medium is coated in a film shape, the gelling agent is directly sprayed or irradiated with light or radiation in the film liquid medium. The aspect which gelatinizes a carbon dispersion liquid medium can be mentioned. With regard to the above step (2), for example, by applying a liquid medium in which a gelling agent is dispersed to the film-shaped dried material, the film-shaped dried material absorbs the liquid medium, and the absorber is gelled. An embodiment in which gelation occurs with an agent can be given. Regarding the step (3), for example, after forming a film gel, the liquid medium is applied again on the gel and the operation of applying the gelling agent is performed several times. it can.

  Preferred embodiment (B-7) is the production method of preferred embodiment (B-6), wherein the carbon-dispersed liquid medium is the carbon solution or suspension.

  Preferred embodiment (B-8) is the production method of preferred embodiment (B-6) or (B-7), wherein the dispersant is capable of crosslinking.

  A preferred embodiment (B-9) is the production method according to any one of the preferred embodiments (B-6) to (B-9), in which the dispersant is a surfactant.

  In the preferred embodiment (B-10), the carbon is a carbon nanotube (single-layer / multi-layer type, cup-stacked type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, or microcarbon filter. It is a manufacturing method in any one of aspect (B-16)-(B-19).

  In a preferred embodiment (B-11), (1) the gelable carbon dispersion liquid medium containing nano to microsize carbon and the carbon dispersant is placed in a mold, and then the carbon dispersion liquid medium is gelled. Or a step (2) of obtaining a gel having a shape corresponding to the mold, or (2) the gelable carbon-dispersed liquid medium containing nano to micro-sized carbon and the carbon dispersant. A liquid medium containing a gelling agent which can be dried after being put in a mold to obtain a dried product having a shape corresponding to the mold, and then gelled when the dried product returns to a wet state again. A method for producing a gel having a shape corresponding to the mold encapsulating nano to micro-sized carbon or a dried gel thereof, including a step of obtaining a gel having a shape corresponding to the mold by applying to the mold.

  With regard to (1) above, for example, after the step of casting a mold, a gelling agent is directly sprayed into the carbon-dispersed liquid medium that has entered the mold, a liquid medium containing the gelling agent is poured, or light -The aspect which gelatinizes this carbon dispersion liquid medium by irradiating a radiation etc. can be mentioned. Regarding the above step (2), for example, by applying a liquid medium in which a gelling agent is dispersed to the dried product, the dried product absorbs the liquid medium, and the absorber is gelled by the gelling agent. Can be mentioned.

  The shape, size, and the like of the “mold” are not particularly limited, and are determined according to the application. In addition, the “shape corresponding to the mold” does not necessarily mean that the shape is completely the same as the mold. For example, the gel obtained using the mold expands after being removed from the mold. Thus, it is a concept including all shapes as a result of being manufactured using the mold, including embodiments that are larger than the mold.

  In a preferred embodiment (B-12), the mold is a circular container, a polygonal container, a spherical container, or a rectangular parallelepiped container, and the gels corresponding to the mold are a circular plate gel and a polygonal plate shape, respectively. It is a manufacturing method of the said suitable aspect (B-11) which is a gel, a spherical gel, and a rectangular parallelepiped gel.

  A preferred embodiment (B-13) is the production method of the preferred embodiment (B-11) or (B-12), wherein the carbon dispersion liquid medium is the carbon solution or suspension.

  A preferred embodiment (B-14) is the production method of any one of the preferred embodiments (B-11) to (B-13), wherein the dispersant is capable of crosslinking.

  A preferred embodiment (B-15) is the production method according to any one of the preferred embodiments (B-11) to (B-14), wherein the dispersant is a surfactant.

  In the preferred embodiment (B-16), the carbon is a carbon nanotube (single-layer / multi-layer type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, or microcarbon filter. It is any one manufacturing method of aspect (B-11)-(B-15).

  The present invention (4-16) comprises a step of dispersing a target raw material monomer in a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon, and polymerizing the target raw material monomer. A method for producing a fine carbon dispersion in which the fine carbon is dispersed inside an object, including a step and a step of removing the liquid medium. Here, “dispersing the monomer” includes dissolution, suspension, and emulsion.

  The present invention (4-17) includes a step of dispersing a target material polymer in a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon, and a step of removing the liquid medium. And a method for producing a fine carbon dispersion in which the fine carbon is dispersed inside the object. Here, “dispersing the polymer” includes dissolution, suspension, and emulsion.

  The present invention (4-18) includes a step of immersing an object in a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon, and a step of removing the liquid medium. This is a method for producing a fine carbon dispersion in which the fine carbon is dispersed on the surface of an object.

  The present invention (4-19) is the production method according to the invention (4-18), further comprising an induced interphase transfer treatment step of moving the minute carbon from the liquid medium side to the object side.

  This invention (4-20) is an adsorptive material containing the fine carbon dispersion any one of this invention (4-1)-(4-12).

  Here, the substance to be adsorbed is not particularly limited, and may be any substance contained in liquid or gas. For example, in the case of liquid phase treatment, petroleum fractions (solvents, fuel oils, lubricants, waxes) decolorization, dehydration or degumming, odors from tap water, removal of unpleasant taste and color, decolorization of animal and vegetable oils, Decolorization of crude sugar mitsu, clarification of beverages and medicinal beverages, recovery of vitamins and other products from fermentation broth, purification of process wastewater (including ion exchange) to prevent water contamination, salt or ash from process water Removal (including ion exchange, ion lag, deionization by ion exclusion), separation of aromatic hydrocarbons from aliphatic hydrocarbons, in the case of gas phase treatment, paint drying, newspaper printing, dry cleaning of clothes or Solvent recovery from air exhausted from evaporation processes such as rayon spinning, gas dehydration (including package drying), and removal of malodors in ventilation systems or exhaust gases to prevent air pollution And toxic gas removal, separation of noble gases (krypton, xenon) at low temperature, removal of impurities from raw air to cryogenic separation, removal of malodor from city lighting gas, gas of low molecular weight hydrocarbon gas Examples include adsorption of substances that cause problems in phase separation (adsorption with reflux or an alternative to cryogenic separation). Further, it can be used for dyeing fibers and the like. That is, minute carbon (for example, CNT) functions as an “adsorption field” and can be dyed in various colors.

  The present invention (4-21) is the adsorbent material according to the invention (4-20), which is for adsorbing pollutants and harmful substances in liquid or gas.

  For example, the pollutants and harmful substances include hydrogen chloride, vinyl chloride, sodium hydroxide, tetrachloroethylene (solvent), BDBPP compound (flameproofing agent), tributyltin compound (antibacterial and antifungal agent), formaldehyde (resin Processing agents), organic mercury compounds (antibacterial and fungicides), dieldrin (insect repellents), sulfuric acid (cleaning agents), DTTB (insect repellents), potassium hydroxide (cleaning agents), trichlorethylene (solvent), APO (Flameproofing agent), TDBPP, methanol (solvent), triphenyltin compound and the like.

  The present invention (4-22) is for industrial water / beverage water filtration equipment, for pure water equipment, for various chromatography, for adsorbing human harmful substances such as carcinogens, for air purifiers, for exhaust gas purification equipment, The adsorptive material according to the invention (4-20) or (4-21), which is used for a conductive material.

  For drinking water filtration equipment, the substance to be adsorbed is not particularly limited, but free residual chlorine, turbidity, trihalomethane, soluble lead, pesticide (CAT), tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, mold Odor (2-MIB) can be mentioned. Further, regarding the adsorption of harmful substances such as carcinogens, carcinogens that are one of the objects of adsorption are not particularly limited, and examples include ethidium bromide, trihalomethanes, and various environmental hormones (for example, nonylphenol). . Regarding the air cleaner, the substance to be adsorbed is not particularly limited, and examples thereof include house dust such as pollen in the room, cigarette smoke, and dead mites. Furthermore, specific applications for “conductive material” include, for example, various fields such as the electronics field, electrical products, machine parts, vehicles, and the like. In particular, when used in combination with a gel having heat resistance, a suitable example is a material for a fuel cell separator.

  The present invention (4-23) is a conductive material containing the fine carbon dispersion according to any one of the inventions (4-1) to (4-12).

  Here, specific applications of the “conductive material” according to the present invention include, for example, various fields such as the electronics field, electrical products, machine parts, vehicles, and the like. In particular, when used in combination with a gel having heat resistance, a suitable example is a material for a fuel cell separator.

  The present invention (4-24) includes an adsorbent material according to the invention (4-20), an industrial water / beverage water filtration device, a pure water device, various chromatographs, an adsorbing device for harmful substances such as carcinogens, and air. It is a purifier, an exhaust gas purification device or an electrical product.

  The present invention (4-25) is a system in which an article or an article raw material is present, and any one of the fine carbon dispersions of the inventions (4-1) to (4-12) is dry-type or wet-type. This is a method for producing an article in which fine carbon is dispersed, including an adding step.

  Here, the present invention is a technique for fusing highly dispersed fine carbon to a target substance in a dry or wet manner. Conventionally, the method adopted when introducing highly dispersed fine carbon into fibers, glass, metal and organic / inorganic crystals or amorphous thereof is a dry introduction method, that is, adding powdery fine carbon. Is the method. Here, for example, the carbon nanotubes are usually present in a form called a bundle. Therefore, there has been a problem that it is extremely difficult to obtain a composite material in which carbon nanotubes are highly fused, that is, a material in which carbon nanotubes are dispersed one by one. In the above invention, for example, first, a solution of carbon nanotubes in which the bundled carbon nanotubes are highly dispersed is prepared using a dispersant. Next, a substance called “mediating material” or “mediating medium” is added to the dispersion solution, and the carbon nanotubes are dispersed and transferred to the “mediating medium”. A target material is prepared using a “mediating medium” carrying highly dispersed carbon nanotubes as a starting material. Thereafter, if necessary, processing such as decomposition of the “mediating material” is performed to remove the “mediating medium”. As the “mediating medium”, a material that decomposes with acid, alkali, or heat, or a material that undergoes a phase transition such as a solid / liquid according to a change in temperature is suitable. Here, “dry” means an aspect of addition to the solid phase, and “wet” means an aspect of addition to the liquid phase.

  The present invention (4-26) is a system in which an article or an article raw material is present and satisfies the predetermined condition of the invention (4-8), and the inventions (4-8) to (4-12) A method for producing an article in which fine carbon is dispersed, including the step of adding any one of the fine carbon.

  The present invention (4-27) is the manufacturing method of the invention (4-26), wherein the article is an aramid fiber and the object is a concentrated sulfuric acid-soluble material.

  The present invention (4-28) is a carbon nanotube non-aqueous dispersion using fullerene as a carbon nanotube dispersant.

  The present invention (4-29) is a carbon nanotube aqueous dispersion using cyclodextrin and fullerene as a carbon nanotube dispersant.

  The present invention (4-30) is a liquid medium in which the fine carbon is dispersed with a nano- to micro-size fine carbon dispersant, and the fine carbon-producing dispersion liquid in which the fine carbon is dispersed on the surface and / or inside thereof. It is.

  A preferred embodiment of the invention is a carbon nanotube dispersion for producing a composite material in which carbon nanotubes are uniformly dispersed, which is a liquid medium in which carbon nanotubes are dispersed by a carbon nanotube dispersant. The following inventions (4-31) to (4-33) relate to the preferred embodiment.

  The present invention (4-31) is the dispersion according to the invention (4-30), wherein the liquid medium is a non-aqueous liquid medium, the fine carbon is a carbon nanotube, and the dispersant is fullerene.

  Here, “non-aqueous” means that the base liquid medium is a water-insoluble solvent. The “water-insoluble solvent” means a solvent having a solubility in water at 23.5 ° C. of 0.2% by weight or less. The “fullerene” is a concept including, for example, fullerene dimers in addition to fullerenes such as C60, C70, and C82. Preferred examples of the non-aqueous solvent include non-aqueous solvents having an aromatic ring, such as toluene, anthracene and naphthalene (dissolved in acetonitrile).

  In the present invention (4-32), the liquid medium is an aqueous liquid medium, the fine carbon is a carbon nanotube, and the dispersant can form spherical micelles having a diameter of 50 to 2000 nm in the liquid medium. The dispersion of the invention (4-30), which is a water-soluble polymer having an agent or a weight average molecular weight of 10,000 to 50 million.

  Here, “aqueous” means that the base liquid medium is a water-soluble solvent (aqueous solvent). Here, the “water-soluble solvent” means a solvent having a solubility in water at 23.5 ° C. of 20% by weight or more, and is a concept including water.

  “Spherical micelle” (“endoplasmic reticulum”) refers to a micelle formed of a surfactant and having a spherical storage space. For example, in the case of a phospholipid surfactant, the endoplasmic reticulum is referred to as a liposome. Here, the diameter of the spherical micelle (endoplasmic reticulum) refers to a value measured by a light scattering method (20 ° C. pH-unadjusted aqueous solution).

  “Water-soluble polymer” (pseudo micelle type) refers to a polymer having a weight average molecular weight of 10,000 to 50 million (preferably 10,000 to 5 million). Here, the weight average molecular weight is based on a value measured by gel filtration high performance liquid chromatography using pullulan as a standard.

  The present invention (4-33) is the dispersion according to the invention (4-30), wherein the liquid medium is an aqueous liquid medium, the fine carbon is a carbon nanotube, and the dispersant is cyclodextrin and fullerene. .

  Here, “cyclodextrin” is a cyclic oligosaccharide obtained by allowing an enzyme (cyclodextrin glucanotransferase) to act on starch, and may be any of α, β and γ types.

  The present invention (4-34) is a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon, and as one of the dispersants, an unbundled state promoting substance for fine carbon And / or a fine carbon-dispersed liquid medium characterized by containing an unbundled state maintaining substance.

  Here, as the unbundled state promoting substance, for example, a charged substance {anion or cation (such as an anion or a cation) that causes a repulsive force between the minute carbons by adhering to or entering the minute carbons or intervening between the minute carbons. For example, NaI)}. Examples of the unbundled state maintaining substance include an obstacle substance {for example, a polymer compound (for example, κ-carrageenan, for example) that physically intervenes between the separated minute carbons to prevent the two from being bonded or approached. )}.

  The present invention (4-35) is the fine carbon-dispersed liquid medium according to the invention (4-34) for producing fine carbon in which the fine carbon is dispersed on the surface and / or inside thereof.

  The present invention (4-36) is a fine carbon dispersant having an attachment portion from nano to micro size fine carbon and an electric attractive force inducing group, and the electric power of the dispersant attached to one of the fine carbons. Micro-carbon dispersant that promotes the unbundled state of the micro-carbon by attracting the attractive attraction-inducing group with the electrical attraction-inducing group of the dispersant attached to another micro-carbon It is.

  Here, the “electric attraction induction group” is an anionic group or a cationic group. Incidentally, even if the above-mentioned micro carbon dispersant is a compound having both electrical properties in one molecule (for example, a zwitterionic surfactant having an anionic group and a cationic group), It may be a mixture of a compound having a property (for example, a cationic surfactant) and a compound having the other electrical property in one molecule (for example, an anionic surfactant). Further, the “attachment portion” means a portion having an affinity for fine carbon. For example, when the fine carbon is hydrophobic, it is a hydrophobic portion (for example, an alkylene group).

  In the present invention (4-37), the dispersant is a fine carbon dispersant having an anionic group and a cationic group, and the anionic group and the cationic group of the dispersant attached to one of the fine carbons are different from each other. The invention (4), wherein the fine carbon dispersant promotes an unbundled state of the fine carbon by attracting each with an electric attractive force generated between a cation group and an anion group of the dispersant attached to the fine carbon. -36) a fine carbon dispersant.

  The present invention (4-38) is the dispersant according to the invention (4-37), wherein the dispersant is a zwitterionic surfactant.

  The present invention (4-39) is produced using a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and the dispersant according to any one of the inventions (4-36) to (4-38). A fine carbon dispersion.

  According to the present invention (4-1) and (4-2), the fine carbon of the fine carbon dispersion is present in the dispersion (surface and / or inside) with extremely high uniformity. Has an effect that the physical properties (for example, strength, adsorptivity, conductivity) unique to the fine carbon can be uniformly maintained regardless of the site.

  According to the present invention (4-3), nano- to micro-sized fine carbon-dispersed liquid medium is gelled, so that it can enjoy the characteristics of gel with excellent permeability and nano particles with extremely small particle size. From the above, since micro-sized micro carbon is present in the network structure of the gel with extremely high uniformity, there is an effect of having very high adsorptivity.

  In the present invention (4-4), since the outer layer gel is obtained by gelling the inner layer liquid medium, the affinity between the outer layer gel and the inner layer liquid medium is increased. -The effect that adsorption property can be improved is produced. Furthermore, because the outer layer gel wraps the inner layer nano to micro-sized micro carbon dispersion liquid medium, the inconvenient liquid can be handled in the same way as the solid, and the outer layer is a gel. In addition to excellent permeability, the inner layer is a nano- to micro-sized carbon-dispersed liquid medium, so that it can exhibit high adsorption performance, especially when adsorbing substances with high affinity to the liquid medium. Play.

  Here, effects of preferred embodiments (A-1) to (A-10) relating to the gels or dry gels of the inventions (4-2) to (4-4) will be described.

  The preferred embodiment (A-1) is obtained by gelling a nano- to micro-sized carbon-dispersed liquid medium, so that it can enjoy the properties of a gel excellent in permeability and has a very small particle size from nano- to micro-size. This carbon is considered to exist in the network structure of the gel with extremely high homogeneity, and therefore has an effect of having very high adsorptivity.

  In the preferred embodiment (A-2), in addition to the effects of the preferred embodiment (A-1), the carbon dispersion liquid medium as a raw material is a solution or a suspension. It is understood that the carbon exists in a state where the particle size is smaller, and as a result, there is an effect that the carbon has higher adsorptivity.

  In the preferred embodiment (A-3), in addition to the effects of the preferred embodiment (A-1) or (A-2), since the dispersant dissolved in the liquid medium is gelled, a more uniform network A structure is formed, and carbon having a very small particle diameter is included in the network structure. As a result, the adsorption performance is further improved.

  In preferred embodiment (A-4), in addition to the effects of preferred embodiments (A-1) to (A-3), a crosslinkable surfactant is used, so that the carbon is held at the hydrophobic site, There is an effect that the solvent (hydrophilic solvent) can be held at the hydrophilic portion.

  A preferred embodiment (A-5) includes, in addition to the effects of the inventions (A-1) to (A-4), carbon nanotubes (single wall / multilayer type, cup stack type), carbon nanofibers, carbon nanohorns, graphite, There is an effect that nano- to micro-sized carbons of various forms suitable for various uses such as fullerene, carbon microhorn, and microcarbon filter can be used.

  The preferred embodiment (A-6) has an effect that a shape suitable for various applications such as a bead shape, a fiber shape, a film shape, a plate shape, or a bulk shape can be taken.

  In the preferred embodiment (A-7), in addition to the effect of the preferred embodiment (A-6), the outer layer gel is obtained by gelling the inner layer liquid medium. As a result of the increased affinity, there is an effect that the permeability, permeability and adsorptivity can be further enhanced. In addition, the outer layer gel wraps the nano- to micro-sized carbon dispersion liquid medium in the inner layer, so that the inconvenient liquid can be handled in the same way as the solid, and the outer layer is a gel. In addition to being excellent in performance, the inner layer is a nano- to micro-sized carbon-dispersed liquid medium, so that it has the effect of exhibiting high adsorption performance particularly when adsorbing a substance having a high affinity with the liquid medium. .

  In the preferred embodiment (A-8), in addition to the effect of the preferred embodiment (A-7), by adopting the technique of dripping, the gel surface shape becomes closer to a sphere, resulting in a larger gel surface area per unit weight. As a result, the adsorbing properties are further improved. Further, by adopting the technique of flowing down, the gel becomes a desired length and thickness. As a result, there is an effect that the optimum size can be obtained in relation to the application.

  In addition to the effects of the preferred embodiment (A-6), the preferred embodiment (A-9) can be applied to various applications where the shape is required because the shape is a film, plate or bulk. There is an effect that there is.

  Since the preferred embodiment (A-10) is a dry gel, it is excellent in air permeability, and since nano to micro size carbon having a very small particle size is uniformly dispersed in the network structure of the dry gel, There is an effect that a substance contained in a gas such as air can be adsorbed with extremely high efficiency.

  According to the present invention (4-5), since the polymerization is performed in a state where the raw material monomer is dispersed in the fine carbon liquid medium, there is an effect that high internal dispersibility of the fine carbon in the obtained polymer is ensured.

  According to the present invention (4-6), since the liquid medium is removed in a state where the raw material polymer is dispersed in the fine carbon liquid medium, the effect that the high internal dispersibility of the fine carbon in the obtained removed product is ensured. Play.

  According to the present invention (4-7), since the raw material is immersed in the fine carbon liquid medium, there is an effect that the high surface dispersibility of the fine carbon in the obtained immersion treatment product is secured.

  According to the present invention (4-8) to (4-12), since the object constituting the fine carbon dispersion is composed of a material that liberates fine carbon under a predetermined condition, the predetermined condition By adding the fine carbon dispersion to the underlying liquid medium, the fine carbon and the object are separated. As a result, the fine carbon is dispersed in the liquid medium. In such a state, for example, the product in which the fine carbon is uniformly dispersed can be produced by dissolving the raw material monomer or raw material polymer of the product and performing polymerization or solvent removal. With respect to a certain type of liquid medium, it is difficult to disperse the fine carbon from the beginning, and in such a case, it is extremely useful as a material for dispersing the fine carbon in the liquid medium.

  According to the present invention (4-13), since the crosslinkable component contained in the nano to micro size fine carbon dispersion liquid medium or the dried product thereof is crosslinked, it is possible to enjoy the properties of the gel having excellent permeability. The nano- to micro-sized fine carbon having a very small particle diameter has an effect that a fine carbon dispersion existing in the network structure of the gel can be produced with extremely high uniformity.

  In the present invention (4-14), in addition to the effects of the invention (4-13), the dispersant dissolved in the liquid medium is gelled, so that a more uniform network structure is formed. In addition to being able to obtain a gel or dry gel with higher adsorption performance as a result of inclusion of carbon with a very small particle size in the structure, there is no need to add another gelling material separately, so cost performance It also has the effect of being excellent.

  In the present invention (4-15), an inner layer and an outer layer exhibit the above effects by a very simple technique of adding a nano to micro size carbon dispersion liquid medium into a liquid medium containing a gelling agent of the medium. A bead-like or fiber-like gel containing nano- to micro-sized carbon, wherein the inner layer is the carbon-dispersed liquid medium and the outer layer is a gelled product of the carbon-dispersed liquid medium, or There exists an effect that the dried gel can be obtained. In addition, by changing the addition method such as dripping or flowing, it is possible to easily obtain gels or dry gels of various shapes and sizes according to the application.

  Here, effects of preferred embodiments (B-1) to (B-16) relating to the gels or dried gels of the inventions (4-13) to (4-15) will be described.

  A preferred embodiment (B-1) is an inner layer and an outer layer that exhibit the above effects by a very simple method of adding a nano to micro size carbon dispersion liquid medium into a liquid medium containing the gelling agent of the medium. A bead-like or fiber-like gel containing nano- to micro-sized carbon, wherein the inner layer is the carbon-dispersed liquid medium and the outer layer is a gelled product of the carbon-dispersed liquid medium, or There exists an effect that the dried gel can be obtained. In addition, by changing the addition method such as dripping or flowing, it is possible to easily obtain gels or dry gels of various shapes and sizes according to the application.

  In a preferred embodiment (B-2), since the carbon dispersion liquid medium as a raw material is a solution or a suspension, the carbon has a smaller particle size in the network structure of the obtained gel. As a result, it is understood that a gel having a higher adsorptivity or a dried gel can be obtained.

  In the preferred embodiment (B-3), since the dispersant dissolved in the liquid medium is gelled, a more uniform network structure is formed, and carbon having a very small particle diameter is included in the network structure. As a result, in addition to being able to obtain a gel or dried gel having a higher adsorption performance, it is not necessary to add another gelling material separately, so that the cost performance is excellent.

  In the preferred embodiment (B-4), since a crosslinkable surfactant is used, it is possible to obtain a gel capable of holding the carbon at the hydrophobic site and holding the solvent (hydrophilic solvent) at the hydrophilic site. There is an effect that can be done.

  The preferred embodiment (B-5) is a variety of carbon nanotubes (single-layer / multi-layer type, cup-stacked type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, and microcarbon filter. There is an effect that a gel or dry gel containing micro-sized carbon is obtained from nano in the form.

  A preferred embodiment (B-6) is a very simple gel or dry gel having excellent permeability and air permeability in which nano to micro size carbon having a very small particle size is present in the network structure with extremely high uniformity. In addition to being able to be obtained by operation, there is also an effect that the gel or the dried gel can be made into a shape (film shape, plate shape or bulk shape) according to the application. Further, after the liquid medium in the carbon-dispersed liquid medium is volatilized before the gelation step in the step (2) or the step (3), the gelling agent is applied in a form in which the liquid is present in the liquid medium. As a result, the dried material absorbs the liquid medium, and as a result, the gel is formed uniformly in a short time.

  In a preferred embodiment (B-7), since the carbon dispersion liquid medium as a raw material is a solution or a suspension, the carbon has a smaller particle size in the network structure of the obtained gel. As a result, it is understood that a gel having a higher adsorptivity or a dried gel can be obtained.

  In the preferred embodiment (B-8), since the dispersant dissolved in the liquid medium is gelled, a more uniform network structure is formed, and carbon having a very small particle diameter is included in the network structure. As a result, in addition to being able to obtain a gel or dried gel having a higher adsorption performance, it is not necessary to add another gelling material separately, so that the cost performance is excellent.

  In the preferred embodiment (B-9), since a crosslinkable surfactant is used, a gel capable of holding the carbon at the hydrophobic site and holding the solvent (hydrophilic solvent) at the hydrophilic site is obtained. There is an effect.

  The preferred embodiment (B-10) is a variety of carbon nanotubes (single-layer / multi-layer type, cup-stacked type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, and microcarbon filter. There is an effect that a gel or dry gel containing micro-sized carbon is obtained from nano in the form.

  In a preferred embodiment (B-11), a nano- or micro-sized carbon having a very small particle size is present in a network structure with extremely high uniformity, and a gel having excellent permeability and air permeability or a dry gel is very simple. Since it can be obtained by an operation and manufactured using a mold, there is also an effect that it is possible to make a gel or a dried gel into a shape according to the application.

  The preferred embodiment (B-12) has an effect that a circular plate gel, a polygon plate gel, a spherical gel, a rectangular parallelepiped gel or a dried gel thereof can be obtained by a simple operation.

  In a preferred embodiment (B-13), since the carbon dispersion liquid medium as a raw material is a solution or a suspension, the carbon has a smaller particle size in the network structure of the obtained gel. As a result, it is understood that a gel having a higher adsorptivity or a dried gel can be obtained.

  In the preferred embodiment (B-14), since the dispersant dissolved in the liquid medium is gelled, a more uniform network structure is formed, and carbon having a very small particle diameter is included in the network structure. As a result, in addition to being able to obtain a gel or dried gel having a higher adsorption performance, it is not necessary to add another gelling material separately, so that the cost performance is excellent.

  In a preferred embodiment (B-15), since a crosslinkable surfactant is used, it is possible to obtain a gel capable of holding the carbon at the hydrophobic site and holding the solvent (hydrophilic solvent) at the hydrophilic site. There is an effect that can be done.

  The preferred embodiment (B-16) is a variety of carbon nanotubes (single wall / multilayer type, cup stack type), carbon nanofibers, carbon nanohorns, graphite, fullerenes, carbon microhorns, and microcarbon filters. There is an effect that a gel or dry gel containing micro-sized carbon is obtained from nano in the form.

  According to the present invention (4-16), since the polymerization is performed in a state where the raw material monomer is dispersed in the fine carbon liquid medium, there is an effect that high internal dispersibility of the fine carbon in the obtained polymer can be ensured. .

  According to the present invention (4-17), since the liquid medium is removed in a state where the raw polymer is dispersed in the fine carbon liquid medium, it is possible to ensure high internal dispersibility of the fine carbon in the obtained removed product. There is an effect.

  According to the present invention (4-18), since the raw material is immersed in the fine carbon liquid medium, there is an effect that high surface dispersibility of the fine carbon in the obtained immersion treatment product can be ensured.

  According to the present invention (4-19), there is an effect that the minute carbon can be reliably moved from the liquid medium side to the object side by performing the induction type interphase transfer treatment step.

  In the present invention (4-20), for example, in an adsorption test of ethidium bromide known as a DNA contaminant, other adsorptive materials (for example, Compared with activated carbon), the adsorbing ability is remarkably high.

  This invention (4-21) can adsorb | suck the pollutant and harmful substance in a liquid or gas using the high adsorption capacity, and there exists an effect that the influence to the human body by the said substance is suppressed.

  The present invention (4-22) is used for industrial water / beverage water filtration equipment, for pure water equipment, for various chromatography, for adsorption of harmful substances such as carcinogens, for air purifiers, and for exhaust gas purification equipment. Then, since it has a much higher adsorption capacity than the existing adsorbent (for example, activated carbon) in the said use, there exists an effect that the target harmful | toxic substance can be removed beyond the expectation so far. Further, since nano- to micro-sized carbon having conductor / semiconductor characteristics is used, there is an effect that it is useful as a special electronic material that requires adsorptivity. Since the present invention is excellent not only in adsorptivity but also in permeability and air permeability, it is also useful for electronic materials that require these properties.

  According to the present invention (4-23), when nano- to micro-sized carbon having conductor / semiconductor characteristics is applied to an article, the conductivity of the soot inherent to the carbon cannot be fully or fully exhibited. This is an epoch-making point in that the important problem is solved for the first time by making the carbon present in a dispersed state. That is, although the reason is not clear, the present inventor has newly found that the carbon, which has been present in the form of a lump, is present in a dispersed state, and thereby has a remarkable effect of improving conductivity.

  Since this invention (4-24) contains the adsorbent material which has the said effect, compared with the conventional adsorbent material (for example, activated carbon), a target substance can be adsorb | sucked efficiently and the performance of each apparatus and apparatus is improved. There is an effect. Further, since the electrical product or the like includes the conductive material having the above-described effect, the electrical product or the like has an effect of being able to enjoy excellent characteristics such as conductivity and mechanical strength based on the presence of the carbon.

  According to the present invention (4-25), for example, there is an effect that carbon nanotubes that are usually present in a form called a bundle can be present in a state of being dispersed one by one.

  According to the present invention (4-26), since the object constituting the fine carbon dispersion is made of a material that liberates the fine carbon under a predetermined condition, the material is present in the final article. If this is inconvenient, the material can be prevented from being included in the final article. Furthermore, with respect to a certain type of liquid medium, it is difficult to disperse the fine carbon from the beginning, and in such a case, it is extremely useful as a material for dispersing the fine carbon in the liquid medium.

  According to the present invention (4-27), it is possible to produce an aramid fiber excellent in heat resistance and strength in which fine carbon is uniformly dispersed in the fiber.

  According to the present invention (4-28) and (4-31), since carbon nanotubes that are particularly useful among the minute carbons are dispersed in the non-aqueous solvent, the use of the non-aqueous solvent in the manufacturing process of the target object Is essential, it is extremely useful when dispersing the carbon nanotubes in the object.

  According to the present invention (4-29), (4-32), and (4-33), since carbon nanotubes that are particularly useful among fine carbons are dispersed in an aqueous solvent, When the use of an aqueous solvent is indispensable, there is an effect that it is extremely useful when carbon nanotubes are dispersed in the object.

  According to the present invention (4-30), there is an effect that it is very useful as a raw material for dispersing fine carbon in an object.

  According to the present invention (4-34) and (4-35), since the unbundled state promoting substance and / or the unbundled state maintaining substance of fine carbon are contained, a dispersing agent or Even when a dispersing agent that is easy to bind is used, there is an effect that these problems do not occur.

  According to the present invention (4-36) to (4-39), since the minute carbons in the bundle state are peeled apart by the electric attractive force, there is an effect that a higher dispersion state can be secured.

  In the following, the best mode of the present invention will be described. In the following description, first, as a first best mode, a gel-like fine carbon dispersion obtained by crosslinking the fine carbon dispersion itself is described. Next, as a second best mode, a fine carbon dispersion obtained using a fine carbon dispersion will be described. Finally, a fine carbon dispersion article obtained by using a fine carbon dispersion (mediator) will be described. The present invention is not limited to these best modes.

In the first best mode and below, the fine carbon dispersion according to the first best mode will be described first by taking the use of an adsorbent for harmful substances in water as an example. First, in the application, it is best that the solvent in the gel is water. Moreover, in the production of the gel, it is more efficient to use water as the “liquid medium” of the carbon-dispersed liquid medium from the beginning than to perform solvent exchange in a later step. Furthermore, the case where a carbon nanotube (CNT) is used as nano to micro size carbon is assumed. Under this premise, the best mode will be described for each component of the best mode.

  First, the dispersant contained in the CNT aqueous solution will be described. A suitable dispersing agent for dissolving CNTs is a surfactant (solubilizing agent). The surfactant is a surfactant (micelle type) capable of forming spherical micelles having a diameter of 50 to 2000 nm in a CNT aqueous solution and / or a water-soluble polymer (pseudo-) having a weight average molecular weight of 10,000 to 50 million. Micelle type). The pseudo micelle type is also included in the concept of “surfactant” in this specification.

  Here, “surfactant (micelle type)” refers to those capable of forming spherical micelles having a diameter of 50 to 2000 nm (preferably 50 to 300 nm) in an aqueous solution. The reason why spherical micelles (endoplasmic reticulum) of this size are suitable is not clear, but at present, it is presumed that the reason is as follows. For example, in the case of carbon nanotubes, the length is usually in the range of 100 to 1000 nm. In the surfactant (micelle type) aqueous solution, the carbon nanotubes are folded to a length of about a few (for example, about a quarter). As a result, in the solution, the carbon nanotube is several tens nm to several hundreds. The length is nm. Perhaps it is understood that the above-mentioned size is just good for accommodating the folded carbon nanotubes in the endoplasmic reticulum, and as a result, the carbon nanotubes can be efficiently solubilized. In addition, it is estimated that other nanocarbons are also stored in micelles by the same mechanism of action.

  Incidentally, there is a conventional technique for adding a surfactant (Japanese Patent Laid-Open No. 2002-255528), but the micelle formed thereby is as small as about 0.1 nm, and carbon nanotubes are formed on the surface of the micelle. It is the principle of adhering. This best mode is based on a novel idea of storing nanocarbon (for example, carbon nanotube) inside the micelle (endoplasmic reticulum) instead of the micelle surface.

  Here, “spherical micelle” (“endoplasmic reticulum”) refers to a micelle formed of a surfactant and having a spherical storage space. For example, in the case of a phospholipid surfactant, the endoplasmic reticulum is referred to as a liposome. Moreover, the diameter of this spherical micelle (endoplasmic reticulum) refers to the value (20 degreeC pH unadjusted aqueous solution) measured according to the light-scattering method.

  The type of the surfactant is not particularly limited as long as it has the above-mentioned properties. For example, any of a phospholipid surfactant and a non-phospholipid surfactant can be used. Particularly preferred surfactants are zwitterionic surfactants. FIG. 13 conceptually shows the CNT separation mechanism when a zwitterionic surfactant is used. First, as shown in FIG. 13A, the zwitterionic surfactant adheres to the CNT. Then, as shown in FIG. 13B, the anion and cation of the zwitterionic surfactant attached to the CNT attract each other by the attractive force with the cation and anion of the zwitterionic surfactant attached to another CNT ( As a result of the double force), the CNTs are pulled, resulting in an unbundled state separated from the bundled state one by one. In addition, although illustrated about the aspect which used the zwitterionic surfactant which has an anion and a cation in a molecule | numerator as a dispersing agent here, CNT liquid (1st liquid) and anionic surfactant which added the anionic surfactant An unbundled state can also be formed based on the electric attractive force by mixing with the CNT liquid (second liquid) to which is added.

  Here, the “phospholipid surfactant” is an anionic surfactant / zwitterionic surfactant having a phosphate group as a functional group, and includes both phospholipid (glycerophospholipid and sphingophospholipid). ) And modified phospholipids (for example, hydrogenated phospholipids, lysophospholipids, enzyme-converted phospholipids, lysophosphatidylglycerol, complexes with other substances). Such phospholipids are present in various membrane systems of the cells that make up organisms, such as the plasma membrane, nuclear membrane, endoplasmic reticulum membrane, mitochondrial membrane, Golgi membrane, lysosomal membrane, chloroplast membrane, and bacterial cell membrane. Preferably, phospholipids used for preparing liposomes are suitable. Specifically, for example, phosphatidylcholine {for example, distearoylphosphatidylcholine (DSPC), dimyristoylphosphatidylcholine (DMPC), dipalmitrylphosphatidylcholine (DPPC)}, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylglycerol, diphosphatidylglycerol Lysophosphatidylcholine and sphingomyelin.

  The “non-phospholipid surfactant” is a nonionic surfactant / zwitterionic surfactant that does not contain a phosphate group as a functional group, and is represented by 3-[(3-colamidopropyl) dimethyl. Amino] -2-hydroxy-1-propanesulfonic acid (CHAPSO), 3-[(3-colamidopropyl) dimethylamino] -propanesulfonic acid (CHAP) and N, N-bis (3-D-gluconamide Mention may be made of propyl) -colamide.

  For reference, amphoteric surfactants are listed. In addition, the following table is, in order, quaternary ammonium base / sulfonic acid group type, quaternary ammonium base / phosphate group type (soluble in water), quaternary ammonium base / phosphate group type (insoluble in water). ), Quaternary ammonium base / carboxyl group type names and sources.

  Next, “water-soluble polymer (pseudo micelle type)” refers to those having a weight average molecular weight of 10,000 to 50 million (preferably 10,000 to 5 million). Here, the weight average molecular weight is based on a value measured by gel filtration high performance liquid chromatography using pullulan as a standard.

  The water-soluble polymer is not particularly limited as long as it has the molecular weight described above. For example, various plant surfactants, water-soluble polysaccharides such as alginic acids such as alginic acid, propylene glycol alginate, Arabian gum, xanthan gum, hyaluronic acid, chondroitin sulfate, water-soluble celluloses such as cellulose acetate, hydroxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, chitosan, chitin; water-soluble proteins such as gelatin, collagen; polyoxyethylene polyoxy Examples include propylene block polymers; compounds selected from DNA.

  Here, “class” in alginic acids and water-soluble celluloses refers to those derivatives (for example, salts, esters, ethers) that share the basic skeleton with alginic acid and cellulose and exhibit water solubility.

  Next, the CNT aqueous solution in the best mode will be described. Regarding the content of the surfactant in the aqueous solution, in the case of the micelle type, the content of the surfactant needs to be equal to or higher than the critical micelle concentration for forming the endoplasmic reticulum. Usually 0.2 to 10 mmol per liter of aqueous solution for 1 g of crude product. In the case of the pseudo micelle type, the content of the water-soluble polymer is not particularly limited, but is usually 5 to 50 g per liter of an aqueous solution for 1 g of the crude product. As for the solubilization conditions, in the case of the micelle type, in order to completely dissolve the nanocarbon (for example, carbon nanotube), for example, first, the ultrasonic wave is loosened for about 5 minutes. After that, when it is heated to 60 ° C. for about 6 hours at room temperature, it completely dissolves in about several minutes. In the case of the pseudo micelle type, for example, with a homogenizer, a pseudo micelle forming substance (for example, sodium alginate), a permeating agent (for example, lithium hydroxide), an oxidizing agent (for example, sodium persulfate), nanocarbon and deionized After sufficiently diffusing and dispersing the mixture containing water, the mixture is allowed to stand at 40 ° C. for about one day. In the case of not using a permeating agent or an oxidizing agent, for example, it is allowed to stand at 40 ° C. for about one week.

  Next, the crosslinking agent in the best mode will be described. In this best mode, the surfactant has a crosslinking group. For example, alginic acids have a carboxylic acid group in the molecule, and this carboxylic acid group forms a gel by crosslinking with a polyvalent cation to form a chelate structure. Here, the polyvalent cation means a divalent or higher cation, preferably a divalent or higher metal ion, more preferably a divalent metal ion such as barium ion, calcium ion, Examples include magnesium ions, lead ions, copper ions, strontium ions, cadmium ions, zinc ions, nickel ions, cobalt ions, manganese ions, and iron ions. In addition, it is reported that the tendency that multivalent ions cause gelation is the order of barium <lead <copper <strontium <cadmium <calcium <zinc <nickel <cobalt <manganese <iron <magnesium. In addition, ion exchange increases with an increase in valence of exchange ions in one step. Therefore, if an aqueous solution containing a polyvalent cation (eg, barium ion) is added to an aqueous solution of alginic acid (eg, sodium alginate), ion exchange occurs rapidly, and a gel of alginic acid and a polyvalent cation forms a gel. Generate.

  Below, two types of surfactant more suitable in the best form are explained in full detail. The first form is a bead-like and fiber-like gel using alginic acid as a surfactant (+ gelling material). The second form is a membranous gel using methylcellulose as a surfactant (+ gelling material).

  The first form has a double structure of an inner layer and an outer layer, the inner layer is an aqueous solution of carbon nanotubes, and the outer layer is a hydrogel that encloses carbon nanotubes in a network structure. It is. The best mode will be described in detail below.

  First, the carbon nanotube aqueous solution present in the inner layer will be described. The aqueous solution contains a carbon nanotube and a surfactant as a dispersant thereof. Each will be described in detail below.

The carbon nanotube that can be used in the best mode is not particularly limited, and any synthesis method such as an electric discharge method (C. Journet et al., Nature 388, 756 (1997) and DS
Bethune et al., Nature 363, 605 (1993)), laser deposition (RESmally
et al., Science 273, 483 (1996)), gas phase synthesis (R. Andrews et al.,
Chem. Phys. Lett., 303,468, 1999), thermal chemical vapor deposition (WZLi et
al., Science, 274, 1701 (1996), Shinohara et al.,
Jpn.J.Appl.Phys. 37, 1257 (1998)), plasma enhanced chemical vapor deposition (ZFRen et al.
al., Science, 282, 1105 (1998)).

  In addition, about the crude product in which the metal catalyst was used in the synthesis | combination, it is suitable to process with an acid and to remove a metal catalyst. Regarding acid treatment, for example, as disclosed in JP-A-2001-26410, a nitric acid solution or a hydrochloric acid solution is used as an aqueous acid solution. For example, a nitric acid solution is diluted 50 times with water, and a hydrochloric acid solution is also 50 times. A method using a solution diluted in water can be mentioned. And after acid-treating in this way, it wash | cleans and filters and it is set as carbon nanotube aqueous solution.

  Surfactants that can be used in this embodiment are the above-described micelle type and pseudo micelle type, and alginic acids are particularly preferred. Although suitable content of alginic acid in this aqueous solution is not specifically limited, Usually, it is 5-50g per liter of aqueous solution for 1g of crude products.

  Furthermore, the carbon nanotube aqueous solution that can be used in this embodiment is preferably initially in the form of an alkaline aqueous solution that further contains a carbon nanotube permeable substance and an oxidizing agent. Here, “in the beginning” means that these components and states are not essential when finally becoming beads or fibers. That is, these components and states are added and adjusted in order to remove unnecessary components present in the system when the above crude product is used as the carbon nanotube source. These will be described below.

  First, the “nanocarbon permeable substance” means a substance having a diameter smaller than the CC lattice size of the carbon nanotube. For example, nanotube permeable cations having such a diameter (ion diameter), specifically, lithium ions can be mentioned. However, although the hydrogen ions are smaller than the lattice size, they are deprived of water in the form of oxonium ions, so that they are inappropriate as carbon nanotube permeable cations. Although the role of carbon nanotube permeable substances has not been elucidated at present, for example, in the case of carbon nanotube permeable cations, by entering the carbon nanotubes, the charge state inside the carbon nanotubes is changed and the carbon nanotubes are changed. It is assumed that it plays a role of extruding the internal surface and internal impurities. In the case of an aqueous solution for 1 g of the carbon nanotube crude product, the content of the carbon nanotube-permeable substance is preferably 0.1 to 1 mol per liter of the aqueous solution.

  Next, the oxidizing agent will be described. Although the oxidizing agent which can be used is not specifically limited, persulfate (persulfate ion in a liquid) is suitable. This is because persulfate is alkaline and highly active, and after oxidation, itself becomes sulfuric acid, so that post-treatment is easy.

  Next, pH will be described. The pH is preferably in the range of 6 to 14 (preferably alkaline). The reason why it is preferable that the liquid is in this range is not clear, but in addition to changing the electronic state of the nanocarbon surface, in the case of carbon nanotubes, the role of softening the carbon surface and folding the carbon nanotubes It is inferred that he is responsible. In the case of the micelle type, the range of 10 to 14 is suitable, and in the case of the pseudo micelle type, the range of 6 to 12 is suitable.

  Furthermore, it is important to keep the pH alkaline at the beginning for another reason. Alginic acid, which is a solubilizer for carbon nanotubes, is insoluble in water in the neutral and acidic regions, but becomes a highly viscous aqueous solution under alkaline conditions. Therefore, when it is necessary to contain more alginic acid in the carbon nanotube aqueous solution, alkalinity is preferable as the liquid property.

  Depending on the application, metal and other impurities that are residues in the production of carbon nanotubes, and carbon nanotube permeable substances for removing these, oxidizing agents, reduced products of oxidizing agents remain, Since the pH may be alkaline, in these cases, the carbon nanotube aqueous solution in the bead-like or fiber-like gel that is the final product has a pH even if the above components remain as they are. May be alkaline.

  Next, a hydrogel that includes carbon nanotubes in a network structure, which is an outer layer, will be described. The network structure is not particularly limited as long as water and carbon nanotubes are included, but from the viewpoint of ease of production and affinity with the carbon nanotube aqueous solution in the inner layer, the solubilizer of the carbon nanotube aqueous solution in the inner layer is crosslinked. It is preferable that A specific preferred example is a cross-linked product of alginic acid. In this case, the crosslinking is preferably chelate crosslinking, and examples of the crosslinking agent for chelate crosslinking include polyvalent cations (for example, barium ions and calcium ions).

  The outer layer hydrogel preferably contains carbon nanotubes. However, since the hydrogel is excellent in permeability even if the carbon nanotube is not included in the outer layer, for example, when the bead gel according to the best mode is used as an adsorbent, the substance existing outside Osmose | permeates an inside (inner layer) by the said property of a hydrogel, and is adsorb | sucked by the inner layer carbon nanotube.

  The bead-like / fibrous gel having the above two-layer structure can be produced by the following procedure. First, an aqueous solution containing a gelling agent (divalent metal ion such as barium ion) of the gelling material (alginic acid) is prepared. At this time, the gelling agent is set to a concentration sufficient to allow all the crosslinking groups of the alginic acid used to be crosslinked. And the said carbon nanotube aqueous solution is dripped or flowed down to this gelatinizer aqueous solution, for example using the dripping apparatus used when manufacturing a chemical | medical agent, a syringe, etc. As a result, the carbon nanotube aqueous solution portion in contact with the gelling agent aqueous solution immediately undergoes a crosslinking reaction to gel, and a bead-like or fiber-like gel is obtained in which the carbon nanotube aqueous solution not in contact is confined.

  Next, a dried form of a film-like gel in which carbon nanotubes are encapsulated in a network structure (dry gel, resin, dry sheet-like material), which is a second form, will be described. Since usable carbon nanotubes and the like are the same as those in the first embodiment, the description of overlapping portions is omitted.

  As the pseudo micelle type surfactant constituting the membranous gel, water-soluble celluloses such as hydroxymethylcellulose and methylcellulose are suitable from the viewpoint of ensuring sufficient strength even in a thin shape such as a membranous dry gel. The crosslinking is preferably chelate crosslinking or hydrogen bond crosslinking. For example, when methylcellulose is used as the gelling material, a polyvalent cation (eg, barium ion) is preferred as the crosslinking agent.

  The dry gel of this embodiment is obtained by drying the gel. Here, although the degree of drying (solvent content) is not limited, for example, when used for an air filter, a lower solvent content is preferable. Further, the thickness also varies depending on the use, but in the case of the use, it is typically about 0.1 to 3 mm.

  The above membranous dry gel can be produced by the following procedure. First, an aqueous solution containing a gelling agent (divalent metal ion such as barium ion) of the gelling material (methylcellulose) is prepared. At this time, for example, the gelling agent is set to a concentration sufficient to allow all the crosslinking groups of methylcellulose to be used to be crosslinked. Then, a carbon nanotube solution containing methylcellulose is applied on a plate and formed into a film with a coater, and then the film-like solution is dried. Subsequently, when the gelling agent aqueous solution is evenly applied to the film-like dried product, the dried product absorbs the aqueous solution and simultaneously undergoes a crosslinking reaction, thereby obtaining a methylcellulose hydrogel including carbon nanotubes. Thereafter, the gel-like dried gel is obtained by drying the gel by a well-known method.

Second best mode is described in detail below second best mode. In the following description, a carbon nanotube dispersion for producing a composite material in which carbon nanotubes are uniformly dispersed (hereinafter referred to as “dispersion for producing a composite material”) will be described first. In particular, the novel ones will be described in detail. Next, a method of using the dispersion for producing the composite material (in other words, a method of producing “a composite material in which carbon nanotubes are uniformly dispersed”) will be described, and finally the composite material will be described.

  The dispersion for producing a composite material is a liquid medium in which carbon nanotubes are dispersed with a carbon nanotube dispersant.

Here, usable CNTs are not particularly limited, and any synthesis method such as an electric discharge method (C. Journet et al.
al., Nature 388, 756 (1997) and DS Bethune et al., Nature
363, 605 (1993)), laser deposition (RESmally et al., Science 273,
483 (1996)), gas phase synthesis (R. Andrews et al., Chem. Phys. Lett., 303,
468, 1999), thermal chemical vapor deposition (WZLi et al., Science, 274,
1701 (1996), Shinohara et al., Jpn.J.Appl.Phys. 37,
1257 (1998)), plasma chemical vapor deposition (ZFRen et al., Science, 282, 1105 (1998)) or the like.

  In addition, about the crude product in which the metal catalyst was used in the synthesis | combination, it is suitable to process with an acid and to remove a metal catalyst. Regarding acid treatment, for example, as disclosed in JP-A-2001-26410, a nitric acid solution or a hydrochloric acid solution is used as an aqueous acid solution. For example, a nitric acid solution is diluted 50 times with water, and a hydrochloric acid solution is also 50 times. A method using a solution diluted in water can be mentioned. And after acid-treating in this way, it wash | cleans and filters and obtains CNT which does not contain a metal catalyst substantially.

  Next, the liquid medium will be selected according to the application. For example, as the non-aqueous liquid medium, aliphatic or aromatic hydrocarbons such as aliphatic or aromatic hydrocarbons having 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane, decane, Examples include dodecane, isooctane, benzene, toluene, xylene, cyclopentane, cyclohexane, and methylcyclopentane. In addition to single use, it may be used as a mixture of two or more. Further, for example, the aqueous liquid medium includes water, a water-miscible organic solvent, or a mixed solvent thereof. Examples of the water-miscible organic solvent include alcohol, ether, ester, ketone, and various carbonyl compounds such as methanol, ethanol, propanol, dioxane, dimethylformamide, acetone, methyl ethyl ketone, and methyl acetate.

  When a non-aqueous liquid medium is selected as the liquid medium, the preferred CNT dispersant is fullerene. In a non-aqueous liquid medium, a structure in which fullerene is sandwiched between openings of two CNTs has been confirmed. By adopting such a structure, it is considered that CNT can be stably dispersed in the liquid. In addition, it is suitable that the addition amount of fullerene is 15 to 30% with respect to the total weight of CNT to add.

  When an aqueous liquid medium is selected as the liquid medium, the first suitable CNT dispersant is a surfactant capable of forming spherical micelles having a diameter of 50 to 2000 nm in the liquid medium or a weight average molecular weight of 10,000 to 5 It is a 10 million water-soluble polymer. The reason why spherical micelles (endoplasmic reticulum) of this size are suitable is not clear, but at present, it is presumed that the reason is as follows. For example, in the case of CNT, the length is usually in the range of 100 to 1000 nm. In the surfactant (micelle type) aqueous solution, the CNTs are folded to a length of about a fraction (for example, about a quarter), and as a result, in the solution, tens to hundreds of nm. It becomes the length of. Perhaps it is understood that the above-mentioned size is just good for storing the folded CNTs in the endoplasmic reticulum, and as a result, the CNTs can be efficiently solubilized.

  The type of the surfactant is not particularly limited as long as it has the above-mentioned properties. For example, any of a phospholipid surfactant and a non-phospholipid surfactant can be used.

  Here, the “phospholipid surfactant” is an anionic surfactant / zwitterionic surfactant having a phosphate group as a functional group, and includes both phospholipid (glycerophospholipid and sphingophospholipid). ) And modified phospholipids (for example, hydrogenated phospholipids, lysophospholipids, enzyme-converted phospholipids, lysophosphatidylglycerol, complexes with other substances). Such phospholipids are present in various membrane systems of the cells that make up organisms, such as the plasma membrane, nuclear membrane, endoplasmic reticulum membrane, mitochondrial membrane, Golgi membrane, lysosomal membrane, chloroplast membrane, and bacterial cell membrane. Preferably, phospholipids used for preparing liposomes are suitable. Specifically, for example, phosphatidylcholine {for example, distearoylphosphatidylcholine (DSPC), dimyristoylphosphatidylcholine (DMPC), dipalmitrylphosphatidylcholine (DPPC)}, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylglycerol, diphosphatidylglycerol Lysophosphatidylcholine and sphingomyelin.

  The “non-phospholipid surfactant” is a nonionic surfactant / zwitterionic surfactant that does not contain a phosphate group as a functional group, and is represented by 3-[(3-colamidopropyl) dimethyl. Amino] -2-hydroxy-1-propanesulfonic acid (CHAPSO), 3-[(3-colamidopropyl) dimethylamino] -propanesulfonic acid (CHAP) and N, N-bis (3-D-gluconamide Mention may be made of propyl) -colamide.

  Further, examples of the water-soluble polymer include various plant surfactants, water-soluble polysaccharides such as alginic acids such as alginic acid, propylene glycol alginate, arabian gum, xanthan gum, hyaluronic acid, chondroitin sulfate, water-soluble Examples include celluloses such as cellulose acetate, hydroxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, chitosan, chitin; water-soluble proteins such as gelatin, collagen; polyoxyethylene / polyoxypropylene block polymers; and compounds selected from DNA. it can.

  Here, “class” in alginic acids and water-soluble celluloses refers to those derivatives (for example, salts, esters, ethers) that share the same basic skeleton as alginic acid and cellulose, and exhibit water solubility. .

  In addition, regarding the content of the surfactant in the aqueous solution, in the case of the micelle type, the content of the surfactant needs to be equal to or higher than the critical micelle concentration that forms the endoplasmic reticulum. Usually 0.2 to 10 mmol per liter of aqueous solution for 1 g of crude product. In the case of the pseudo micelle type, the content of the water-soluble polymer is not particularly limited, but is usually 5 to 50 g per liter of an aqueous solution for 1 g of the crude product. As for the solubilization conditions, in the case of the micelle type, in order to completely dissolve the CNTs, for example, first, loosen with an ultrasonic wave for about 5 minutes. After that, when it is heated to 60 ° C. for about 6 hours at room temperature, it completely dissolves in about several minutes. In the case of the pseudo micelle type, for example, with a homogenizer, a pseudo micelle forming substance (for example, sodium alginate), a permeating agent (for example, lithium hydroxide), an oxidizing agent (for example, sodium persulfate), CNT, and deionized water After fully diffusing and dispersing the mixture containing, the mixture is allowed to stand at 40 ° C. for about a day. In the case of not using a permeating agent or an oxidizing agent, for example, it is allowed to stand at 40 ° C. for about one week.

  Of the first preferred CNT dispersants, particularly preferred are alginic acids. Although suitable content of alginic acid in this dispersion liquid is not specifically limited, Usually, it is 5-50g per liter of aqueous solution for 1g of crude products.

  Further, it is preferable that the micelle type CNT dispersion further contains a CNT permeable substance and an oxidizing agent, and is in the form of an alkaline aqueous solution. Here, the “CNT permeable substance” means a substance having a diameter smaller than the CC lattice size of the CNT. For example, CNT permeable cations having such a diameter (ion diameter), specifically, lithium ions can be mentioned. However, although hydrogen ions are smaller than the lattice size, they are deprived of water in the form of oxonium ions, so that they are inappropriate as CNT-permeable cations. Although the role of the CNT-permeable substance has not been elucidated at the present time, for example, in the case of a CNT-permeable cation, by entering the CNT, the charge state inside the CNT is changed, and the surface and inside of the CNT are changed. It is presumed to play a role of pushing out impurities. In the case of an aqueous solution for 1 g of CNT crude product, the content of the CNT permeable substance is preferably 0.1 to 1 mol per liter of the aqueous solution. Moreover, the oxidizing agent which can be used is not particularly limited, but persulfate (persulfate ion in the liquid) is preferable. This is because persulfate is alkaline and highly active, and after oxidation, itself becomes sulfuric acid, so that post-treatment is easy. Furthermore, the pH is preferably in the range of 6 to 14 (preferably alkaline). The reason why it is preferable that the liquid is in this range is not clear, but in addition to changing the electronic state of the CNT surface, it is presumed to play a role of softening the CNT surface and folding the CNT. In the case of the micelle type, the range of 10 to 14 is suitable, and in the case of the pseudo micelle type, the range of 6 to 12 is suitable. In addition, it is important to keep pH initially alkaline for another reason. Alginic acid, which is a CNT dispersant, is insoluble in water in the neutral and acidic regions, but becomes a highly viscous aqueous solution under alkaline conditions. Therefore, when it is necessary to contain more alginic acid in the CNT aqueous solution, the liquidity is preferably alkaline.

  When an aqueous liquid medium is selected as the liquid medium, the second preferred CNT dispersant is cyclodextrin and fullerene. Here, the usable cyclodextrins may be any of α-type, 7 β-types, and 8 γ-type cyclodextrins having 6 glucose residues. In addition, maltosyl cyclodextrin, dimethyl cyclodextrin may be used. Branched cyclodextrins such as dextrin, modified cyclodextrins, or cyclodextrin polymers can also be used. The mechanism by which these dispersants solubilize CNTs is that cyclodextrins first include hydrophobic fullerenes, and then fullerenes (hydrophobic) on the surface of the inclusions have an affinity for CNTs (hydrophobic). It is thought that it is based on the combination. The addition amount of cyclodextrin is preferably 150 to 300% with respect to the total weight of CNT to be added, and the addition amount of fullerene is 15 to 30 with respect to the total weight of CNT to be added. % Is preferred.

  Next, a method for using the dispersion for producing a composite material (in other words, a method for producing a “composite material in which carbon nanotubes are uniformly dispersed”) will be described. There are roughly three types of usage. First, in the first method, the raw material monomer of the composite material is dispersed in the dispersion for producing the composite material, and then, the raw material monomer is polymerized by a well-known method (and may be cross-linked in some cases), and finally, the liquid medium It is a method of removing. This method is suitable for producing a film or a molded composite material.

  The second method is a method of removing the liquid medium after dispersing a raw material polymer in a dispersion for producing a composite material. This method is suitable for producing a film or a molded composite material.

  A third method is a method of removing the liquid medium after immersing the raw material in a dispersion for producing a composite material, unraveling the raw material. Here, examples of the method for unraveling the raw material include heat treatment and ultrasonic treatment. This method is suitable for producing a fibrous composite material.

  Finally, a composite material in which carbon nanotubes are uniformly dispersed will be described. The composite material can be used in various applications. For example, an adsorbing material can be mentioned. Here, the substance to be adsorbed is not particularly limited, and may be any substance contained in liquid or gas. For example, in the case of liquid phase treatment, petroleum fractions (solvents, fuel oils, lubricants, waxes) decolorization, dehydration or degumming, odors from tap water, removal of unpleasant taste and color, decolorization of animal and vegetable oils, Decolorization of crude sugar mitsu, clarification of beverages and medicinal beverages, recovery of vitamins and other products from fermentation broth, purification of process wastewater (including ion exchange) to prevent water contamination, salt or ash from process water Removal (including ion exchange, ion lag, deionization by ion exclusion), separation of aromatic hydrocarbons from aliphatic hydrocarbons, in the case of gas phase treatment, paint drying, newspaper printing, dry cleaning of clothes or Solvent recovery from air exhausted from evaporation processes such as rayon spinning, gas dehydration (including package drying), and removal of malodors in ventilation systems or exhaust gases to prevent air pollution And toxic gas removal, separation of noble gases (krypton, xenon) at low temperature, removal of impurities from raw air to cryogenic separation, removal of malodor from city lighting gas, gas of low molecular weight hydrocarbon gas Examples include adsorption of substances that cause problems in phase separation (adsorption with reflux or an alternative to cryogenic separation). It is particularly useful as a material for adsorbing pollutants and harmful substances in liquids, gases, and gases. Here, for example, the pollutants and harmful substances include hydrogen chloride, vinyl chloride, sodium hydroxide, tetrachloroethylene (solvent), BDBPP compound (flameproofing agent), tributyltin compound (antibacterial and antifungal agent), Formaldehyde (resin processing agent), organic mercury compounds (antibacterial and antifungal agent), dieldrin (insect repellent processing agent), sulfuric acid (cleaning agent), DTTB (insect repellent processing agent), potassium hydroxide (cleaning agent), trichlorethylene (solvent) ), APO (flameproofing agent), TDBPP, methanol (solvent), triphenyltin compound and the like. Furthermore, it is useful as an absorptive material for industrial water / beverage water filtration equipment, for pure water equipment, for various chromatography, for adsorbing human harmful substances such as carcinogens, for air purifiers, and for exhaust gas purification equipment. is there. Furthermore, it is also useful as a conductive material. For example, various parts such as the electronics field, electrical products, mechanical parts, vehicles and the like can be mentioned. In particular, when used in combination with a gel having heat resistance, a suitable example is a material for a fuel cell separator. Furthermore, it is useful as a reinforced composite material. For example, it is useful to use for reinforcing fibers, particularly heat resistant / reinforced fibers.

Third Best Mode Hereinafter, the third best mode will be described in detail. In the following description, a carbon nanotube dispersion for manufacturing articles in which carbon nanotubes are uniformly dispersed will be described first, and then a method of using the CNT dispersion for manufacturing articles (in other words, “carbon nanotubes are uniformly distributed” will be described. A method for producing a “dispersed article” will be described.

  First, the CNT dispersion for manufacturing articles is a product in which CNTs are uniformly dispersed on the surface of an object. Here, the object is not particularly limited as long as it is a material capable of releasing CNT under a predetermined condition as described above.

  Next, the manufacturing method of this fine carbon dispersion is demonstrated. First, the object is added to the fine carbon-dispersed liquid medium. Next, it can be manufactured by performing an induced phase transfer process in which the minute carbon is moved from the liquid medium side to the object side.

  Next, a method for using the present fine carbon dispersion will be described by taking an example of a method for producing an aramid fiber. First, in the aramid fiber manufacturing process, since there is a process of dissolving the aramid fiber raw material in concentrated sulfuric acid, a material for the object that uniformly disperses CNT in the liquid is selected by dissolving in the concentrated sulfuric acid. There is a need. As such an object, it is preferable to use ultrafine fibers or higher paraffin. And if the target object in which CNT was uniformly disperse | distributed to the concentrated sulfuric acid which the said aramid fiber raw material melt | dissolved, the said target object will melt | dissolve and CNT will disperse | distribute in a concentrated sulfuric acid. From this state, when fibers are produced by a known method, aramid fibers in which CNTs are uniformly dispersed can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the following examples.

CNF Synthesis Carbon nanofibers (CNF) according to this example were synthesized by the following procedure by using chemical vapor deposition (CVD) {NM Rodriguez, J. Mater. Res., 8, 3233 (1996) }. After the powder Ni catalyst was placed on an Al ₂ O ₃ plate, this Ni / Al ₂ O ₃ plate was placed in a quartz tube placed in a horizontal tube furnace and reduced at 873 K in 10% hydrogen / helium vapor for about 2 hours. . CNF growth was achieved by decomposition of ethylene (C ₂ H ₄ / H ₂ = 4: 1) in a 4 hour reaction at 873 K under atmospheric pressure. To dissolve the metal catalyst, soot, a thermal CVD product, was treated with 6.0 M HCl for about 12 hours at 373 K in reflux attached to the flask. Using a high pressure vesicle extruder, the suspension was passed through two polycarbonate filters superimposed with a pore size of 0.1 μm. The solid cake was thoroughly washed with deionized water and then dried at 333 K for at least 24 hours. It was found that the purity of the obtained CNF exceeded 90%. The diameter and length ranged from 50 to 300 nm and 2 to 15 μm, respectively. FIG. 1 shows an SEM image (FIG. 1A) and a TEM image (FIG. 1B) of the obtained CNF. A plate-like CNF with the 002 plane stacked in the fiber axis direction and a herringbone-like CNF with the 002 plane distributed obliquely with respect to the fiber axis on both sides were observed.

Preparation of CNF / alginate colloid aqueous solution Sodium alginate according to this example (viscosity and pH of an aqueous solution containing 20 mg / ml sodium alginate is 20 to 400 cP and 6.0 to 8.0, respectively) Obtained from Chemical Industries (Osaka). Sodium alginate (Na-ALG) was dissolved in deionized water to prepare an aqueous Na-ALG solution. CNF was added to the Na-ALG aqueous solution and then mixed well by a combination of high shear mixing and sufficient sonication. The aqueous CNF / Na-ALG colloid solution was centrifuged at 4000 rpm for 30 minutes, and a very small amount of black precipitate separated from the aqueous solution was taken out from the aqueous colloid solution. FIG. 2 shows a photograph of a 100 ml vial containing an aqueous CNF / Na-ALG colloid solution containing 0.5 mg / ml CNF and 20 mg / ml Na-ALG. During the observation period of 3 weeks, no precipitation from this aqueous colloid was observed. By using an aqueous solution containing 20 mg / ml sodium alginate as a dispersion solution, a highly uniform CNF / alginate colloidal solution having a CNF concentration of 1.0 mg / ml could be obtained.

Uniformity / Stability Test UV-vis is used as a detection system to measure the uniformity of CNF / Na-ALG colloidal solution by calculating the linearity of the CNF calibration curve in the CNF / Na-ALG colloid solution. did. A characteristic absorption mainly derived from the CNF dispersion is observed in the vicinity of the wavelength range of 220 to 500 nm (FIG. 3). The linearity r ² of the calibration curve of CNF in the CNF / Na-ALG colloid aqueous solution at 260 nm was found to be higher than 0.9989, indicating the high uniformity of the CNF / Na-ALG colloid solution. The samples used for deriving the calibration curve were CNF of 0, 0.1, 0.2, 0.3, 0.4 with the concentration of Na-ALG in each sample fixed at 20 mg / ml, respectively. And an aqueous Na-ALG solution containing 0.5 mg / ml. Reported by Jiang et al. [L. Jiang, L. Gao, J.
Sun, J. Colloid and Interface Sci., 260, 89 (2003)], the stability of CNF / Na-ALG colloid was measured by calculating the CNF concentration with respect to sedimentation time. The change in CNF concentration was found to be less than 0.4% even after long-term measurement at room temperature for 3 weeks. The zeta potential of the CNF / Na-ALG colloid is another essential parameter that determines the stability of the colloidal solution. A CNF / Na-ALG colloidal solution containing 0.5 mg / ml CNF and 20 mg / ml Na-ALG was prepared and an electrophoretic light scattering spectrophotometer (ELS-8000, Otsuka Electronics) was used for zeta potential measurement. analyzed. The zeta potential value ζ is calculated from the particle velocity based on the Helmholtz-Smolkovsky equation ζ = 4πμη / D (where μ, η, and D represent the electrophoretic mobility, viscosity, and dielectric constant of the boundary layer, respectively) [HE Ries, Nature (London), 226,72 (1970)]. As can be seen from the plot of ζ vs. pH (FIG. 4), the maximum ζ value of CNF / Na-ALG colloid was found to be −58.03 mV, which is also high for CNF / Na-ALG colloid. It shows stability (repulsive force). The ζ vs. pH plot of CNF / Na-ALG colloid (FIG. 4) and the ζ vs. pH plot of an aqueous solution containing only Na-ALG (20 mg / ml) are substantially identical, and the CNF / Na-ALG colloid It was shown that the zeta potential of was determined by alginate ions. For both samples, the decrease in absolute value of ζ is seen as a decrease in pH in all pH value tests (sample pH was adjusted using 1.0 M HCl). This implies that alginic acid molecules have been adsorbed by CNF throughout the entire pH range. The electrostatic repulsion generated between carboxyl groups of alginate ions (mainly adsorbed on the surface of CNF) weakens the van der Waals attraction generated between CNFs, resulting in CNF / Na-ALG colloids. Highly stabilized.

The shifted alginic acid in the FT-IR spectrum is a linear water-soluble 1,4-linked copolymer of β-D-mannuronic acid (M) and α-L-guluronic acid (G). As shown in FIG. 5, M and G are homopolymer [poly (β-D-mannosyluronate), MMMM)] and poly (α-L-grosyluronate, GGG) blocks. Can be arranged in heteropolymer (MGM) blocks [NP Chandia, B. Matushiro, AEVasquez, Carbohydrate Polymers, 46,
81 (2001)]. In an attempt to elucidate the mechanism of formation of alginic acid / CNF complex in aqueous solution, FT-IR spectra of alginic acid (reference sample) and CNF / alginic acid complex were measured. Characteristic bands typical for alginate are (i) 1627 and 1419 cm ^-1 (characteristic bands typical for carboxylic acids), (ii) 808 cm ^-1 (characteristic bands for mannuronic acid) and / or 787 cm ^-1 (guluronic acid). (Iii) 940 cm ⁻¹ (characteristic band of α1 → 4 bond) and (iv) 904 cm ⁻¹ (characteristic band of α-L-gropyranuron ring) [NP Chandia, B. Matushiro, AEVasquez, Carbohydrate Polymers, 46,
81 (2001), H. Ronghua, D. Yumin, Y. Jianhong,
Carbohydrate Polymers, 52, 19 (2003)]. CNF / Na-ALG characteristic bands of the carboxylic acids of alginic acid samples from 1627.63 and 1419.35Cm ^-1 in the reference alginate samples are respectively shifted to 1613.16 and 1413.57Cm ^-1 in CNF / Na alginate samples . The characteristic band of α1 → 4 bond of alginic acid and the characteristic band of α-L-gropyranuron ring of CNF / Na-ALG sample are from 947.84 and 890.95 cm ⁻¹ in the reference alginate sample, and 943 in the CNF / Na alginate sample. Shift to .98 and 887.8 cm ⁻¹ , respectively. These shifts in the characteristic bands of CNF / Na-ALG samples are an indication that alginate is interacting with CNF. On the other hand, characteristic bands of mannuronic acid CNF / Na-ALG sample shifts from 811.88Cm ^-1 to 814.77Cm ^-1 in the reference alginate sample. This increase in the mannuronic acid band is a sign suggesting that the alginate sugar skeleton is a key site governing the formation of the alginate / CNF complex. A characteristic band of guluronic acid (also about an increase of about 3 cm ⁻¹ ) was observed, indicating that the alginic acid used in this study was constructed by both M and G units.

Biocompatibility studies Normal human fibroblasts (HF) were used as typical cells and obtained from BioWhitteker. The MTS cell proliferation assay kit was purchased from Promega. Dulbecco's Modified Eagle Minimum Essential Medium (D-MEM), L-glutamine and fetal bovine serum (FBS) were purchased from Sigma. CNF / Na-ALG colloidal solution containing 1.0 mg / ml of CNF and 20 mg / ml of Na-ALG was reduced to 1/10, 1/100 and 1/1000 with D-MEM containing 5% FBS and 50 μg / ml kanamycin. Diluted. Also, an aqueous solution (control medium) containing only Na-ALG (20 mg / ml) was diluted to the same extent in the same medium as in CNF / Na-ALG. HF was seeded in 96 multiwell plates at 2 × 3 ¹⁰ cells / well and maintained at 37 ° C. for 3 days in 200 μl D-MEM containing 10% FBS and 50 μg / ml kanamycin. The medium was replaced with medium containing CNF / Na-ALG or control medium and HF was further incubated at 37 ° C. for 1-7 days. Following incubation, cell proliferation was assessed by MTS assay. For MTS assay, it was replaced with 100 μl Eagle's minimum essential medium (no phenol red) containing 333 μg / ml MTS and 25 μM phenazine methosulfate solution. After incubating at 37 ° C. for 2 hours, the absorbance at 485 nm of each well was measured. Cell growth was calculated from the _A485 value 2 hours after MTS treatment. Relative cell growth rate (RCG,%) was calculated by dividing the mean value of treated cells by the mean value of untreated cells (cultured with 5% FBS). The RCG of cells incubated in medium containing CNF and / or Na-ALG was 100% ± 5% 1 and 2 days after administration. Even 7 days after dosing, the RCG was over 85%.

Eight week old male Jcl: SD rats were purchased from Clea Japan. These rats were isolated for 6 days and acclimated. One was used without administration and the other rats were administered orally once using a gastric tube. Dose values were 10 mg CNF and 200 mg Na-ALG per kg body weight. Macroscopic observations and body weight were recorded once a week. At the end of the observation, rats were starved for 16 hours and anesthetized before blood and serum samples were collected. An autopsy was performed to observe changes in the glandular stomach. One to two weeks after dosing, white blood cells (WBC) increased from 5100 in untreated rats to 7700 and 8100 in rats given vehicle control. A similar situation (WBC increased from 5100 to 7900 and 8400) was observed for rats given CNF / Na-ALG colloid. The β-globulin fraction increased from 16.2% in untreated rats to 21.7% and 21.5% in rats treated with Na-ALG and CNF / Na-ALG. One week after dosing, deep folds of the glandular stomach were observed for rats given Na-ALG and / or CNF / Na-ALG. No other parameter changes were observed (deviation <10%). Three weeks after administration, all hematological and biochemical data returned to normal values.
Both in vitro and in vivo experiments show the fact that sodium alginate and aqueous CNF / Na-ALG colloids have little or no deleterious effect on the cells / animals studied in this experiment.

Large scale production of Ba ²⁺ -alginic acid-coated vesicles containing highly dispersed CNF Using a CNF / Na-ALG colloidal solution, Ba ²⁺ -alginate coated with highly dispersed CNF was coated by encapsulation method. Vesicles were produced. Encapsulator Research IER-20 was purchased from InoTech. (I) an aqueous solution containing only 20 mg / ml sodium alginate, (ii) an aqueous solution containing 0.5 mg / ml CNF highly dispersed in a 20 mg / ml Na-ALG solution, and (iii) 20 mg / ml Na- Prepare aqueous solutions containing 0.5 mg / ml of CNF (mixed for 5 minutes by sonication) easily dispersed in ALG solution, each containing standard vesicles (without CNF) and small amounts containing highly dispersed CNF. Used for the preparation of vesicles and vesicles containing low dispersion CNF. A gelatinized solution (also known as a hardening solution) was prepared by dissolving BaCl ₂ in deionized water to a concentration of 100 mM. Using this encapsulation technique, adjustable size vesicles were obtained in volume. Vesicles having a diameter range of 400-800 micrometers were obtained by activating electrostatic charge tension at 1100 V and vibration frequency of 900 Hz using a 300 micrometer diameter nozzle. A typical microscopic observation of a vesicle containing highly dispersed CNF is shown in FIG. Using this encapsulation method, kilogram vesicles can be produced in a matter of hours. Ba ²⁺ ions are more gelatinized ions than Ca ²⁺ ions [P. Grohn, Exp. Clin. Endocrinol., 102, 380 (1994)] and were used throughout this study. Ba ²⁺ -alginic acid coated CNF vesicles are chemically and mechanically stable and much heavier than water (easy to separate from the aqueous phase).

CNF / Ba ²⁺ -alginic acid vesicle reference vesicles (without CNF) and vesicles containing CNF as adsorbents to remove ethidium ions from aqueous solution , thoroughly with deionized water using a sieve Was washed. The screen mesh was 100 micrometers. Two 45 ml tubes with conical bottoms containing 10 ml each of reference vesicles and vesicles containing highly dispersed CNF were held vertically using a tube stand. Next, 15 ml of 30 μM ethidium bromide aqueous solution was added to each tube. Approximately 5 minutes after the ethidium solution was mixed with the vesicles, the aggregated phase solution was collected and measured using a UV-vis spectrometer (Jasco UV-550). FIG. 8 shows the result. The absorption value at 480 nm of the 30 μM ethidium bromide aqueous solution was found to be 0.142. However, when this solution was mixed with highly dispersed CNF-containing vesicles, it decreased to 4.9 × 10 ⁻³ .

FIG. 9 shows the change in the concentration of ethidium ions in the aqueous solution as a function of contact time (15 ml of 30 μM ethidium bromide aqueous solution mixed with 10 ml of highly dispersed CNF-containing vesicles). As the contact time increased, the concentration of ethidium ions in the aqueous solution decreased rapidly. About 8 minutes after the solution was mixed with CNF / Ba ²⁺ -alginate vesicles, 0.98 μM was reached, after which there was no change. The ability of 10 ml of vesicles obtained using an aqueous CNF / Na-ALG colloid solution containing 0.5 mg / ml CNF and 20 mg / ml Na-ALG as a gelling solution is 0.43 μm to remove ethidium ions from the aqueous solution. It was found to be mol / ml. This number is calculated by dividing the amount of ethidium ions removed by the vesicles by the amount of vesicles used as an adsorbent, approximately 10 minutes after mixing the aqueous ethidium bromide with CNF / Ba ²⁺ -alginate vesicles. Calculated by

The same experiment was also performed by using Ba ²⁺ -alginate coated vesicles containing highly dispersed multi-walled carbon nanotubes (MWCNT) as adsorbent. MWCNT (diameter 20-40 nm, length 5-20 μm, purity> 80%, manufacturer recommended) was purchased from Nano Lab and used as it was. The method for preparing aqueous MWCNT / Na-ALG colloid, MWCNT / Ba ²⁺ -alginate vesicles and testing the ability to remove ethidium ions was the same as for CNF. The ability to adsorb ethidium ions is 10 ml of MWCNT / Ba ²⁺ -ALG vesicles obtained using an aqueous solution containing 0.5 mg / ml MWCNT and 20 mg / ml Na-ALG as the gelling solution, It was found to be 0.42 μmol / ml. This ability value is in fact substantially the same as that of CNF / Ba2 ⁺ -ALG vesicles.

Sodium alginate (Na-ALG) of this example was obtained from Wako Pure Chemical Industries (Osaka). MWCNT (CVD product: outer diameter 15 nm ± 5 nm, length 1-5 μm, purity> 90%, published by the manufacturer) was purchased from Nanolab (Massachusetts, USA) and used as it was. Na-ALG was dissolved in deionized water to prepare a Na-ALG aqueous solution having a concentration of 15 mg / ml. MWCNT was dispersed in this Na-ALG aqueous solution at a concentration of 1.0 mg / ml by a combination of high shear mixing and sonication. A semi-automated instrument IER-20® system (Inotech, Dottikon, Switzerland) was used to encapsulate MWCNTs to form microbeads coated with Ba ²⁺ -alginic acid. The IER-20® system consisted of an injector, injector pump, pulsation chamber, vibration system, nozzle, electrode, ultrasonic vibration system and electrostatic supply system and O-ring electrode. An injector pump was used to pump the aqueous Na-ALG / MWCNT colloid solution into the pulsation chamber. Then, this colloidal aqueous solution was passed through a sapphire nozzle (nozzle diameter 300 μm) having been precisely perforated and separated into droplets of equal size when exiting the nozzle. These droplets were passed through an electrostatic field between the nozzle and the ring electrode, causing the surface of the droplets to have an electrostatic charge. When the droplets dropped into the curing solution (crosslinker-containing solution), that is, an aqueous barium chloride solution (Ba ²⁺ ions 100 mM), the electrostatic repulsion force dispersed the droplets. For more information on the working principle of the IER-20® system, see the related references [H. Brandenberger,
D. Nussli, V. Piech, F. Widmer, J. Electrostatics, 1999, 45, 227, D. Serp, E. Cantana, C. Heinzen, U. von Stockar, IW Marson,
Biotech. & Bioeng., 2000, 70, 41]. The resulting Ba ²⁺ -ALG / MWCNT composite beads were thoroughly rinsed with deionized water using a 100 μm mesh sieve. FIG. 10 shows typical microscopic observations of Ba ²⁺ -ALG / MWCNT composite beads. Beads with diameters ranging from 400 to 900 micrometers were produced. The size of the beads can be adjusted by changing the ultrasonic vibration frequency, electrostatic charge tension, nozzle diameter and flow rate of the aqueous Na-ALG / MWCNT colloidal solution. Using this encapsulation method, kilogram quantities of Ba ²⁺ -ALG / MWCNT composite beads can be produced in a matter of hours. Ba ²⁺ ion is a more cohesive ion than Ca ²⁺ ion [P. Grohn, Exp. Clin. Endocrinol., 1994, 102, 380] and was therefore used as a curable ion in this study. Ba ²⁺ -ALG / MWCNT composite microbeads are chemically and mechanically stable and much heavier than water. Therefore, it is easy to separate from the aqueous phase.

An open glass column (length 20 cm, diameter 5.0 cm) was packed with about 200 ml of Ba ²⁺ -ALG / MWCNT composite microbeads. Two liters of an aqueous solution containing three model compounds, namely dibenzo-p-dioxin (DD), dibenzofuran (DF) and biphenyl (BP), each at a concentration of 2.0 μM, was supplied at a constant flow rate of 10 ml / min by a peristaltic pump. Pumped into the column. The concentration of the model compound in the effluent was measured using GC-MS. Target species, namely DD, DF and BP, were extracted from 50 ml of effluent with 10 ml of hexane. The hexane phase was separated from the aqueous phase, reduced to 1.0 ml and then analyzed by GC-MS (Shimadzu GC-MS-QP5050A). An aqueous solution containing 2.0 μM of each model compound was prepared by diluting a stock solution of DD, DF and BP (each 2.0 mM, dissolved in methanol) with deionized water.

  It was found that the concentrations of DD, DF and BP in the effluent after passing through the column once were 0.014 μM, 0.015 μM and 0.018 μM, respectively. However, when the effluent was passed through the column once more, these model compounds were no longer detected and the concentration had decreased below the detection capability of the GC-MS system. After passing contaminated water once, the model compound was eluted from the column using 40 ml of hexane. The hexane phase was separated from the aqueous phase and analyzed directly using the same GC-MS analytical conditions. The concentrations of DD, DF and BP in the hexane sample were found to be 99.12 μM, 99.03 μM and 98.86 μM, respectively. FIG. 11 shows a typical total ion chromatogram (TIC) and a mass spectrum corresponding to each peak. First, BP was eluted from the GC column, and then DF and then DD were eluted. The removal efficiency of DD, DF, and BP when passed once through the removal column was 99.12%, 99.03%, and 98.89%, respectively. These values were calculated by dividing the total amount of each model compound retained in the column by the total amount of each model compound fed to the column. Higher removal efficiency can also be obtained by returning the effluent from the first circulation to the removal column for the second treatment.

In addition, an experiment was conducted using a removal column filled only with base material microbeads, that is, Ba ²⁺ -alginic acid microbeads not containing MWCNT. In the first circulation, it was found that the removal efficiency of DD and DF was 18.3%, and the removal efficiency of BP was 18.4%. The removal efficiency of the second circulation was substantially the same as the removal efficiency of the first circulation. These adsorption experimental data suggest that the removal of the target compound is mainly due to the presence of MWCNT. The high affinity binding between the target compound and MWCNT can be attributed to the unique structure and electronic properties of the carbon nanotubes. The hexagonal arrangement of carbon atoms in the MWCNT graphene sheet strongly interacts with the aromatic bonds of the model compound. As a result of these interactions, the target species, DD, DF and BP, were efficiently removed by MWCNT, a Ba ²⁺ -alginic acid / MWCNT composite adsorbent. In addition, the Ba ²⁺ -alginic acid / MWCNT composite adsorbent can be reused by regenerating the beads with hexane.

Production Example 1 Production Example of CNT Dispersion 1 (Aqueous Dispersion Using Zwitterionic Surfactant / Ionic Polymer as Dispersant) Single-Walled Carbon Nanotube (SWCNT, manufactured by Nano Lab) 100 mg, Surfactant (N-octadecyl) Using a mortar, a mixture of 1.68 g of -N, N'-dimethyl-3-amino-1-propanesulfonate, Zwitter-3-18, manufactured by Fluka) and 5 mL of glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) using a mortar After mixing for hours, 5 mL of deionized water was added and mixed for an additional 30 minutes. To this mixed colloid, 0.6 g NaI (manufactured by Wako Pure Chemical Industries) and 1.0 g κ-carrageenan (manufactured by Wako Pure Chemical Industries, Ltd.) were added, followed by further mixing for 30 minutes. A 10% aqueous methanol solution was added so that the mixture was 100 mL. The mixture was placed in an ice tray and mixed with a homogenizer for about 1 hour, and then centrifuged to remove insoluble components. The degree of dispersion and stability were evaluated by a previously reported method (for example, Environ. Sci. Technol., 38, 6890-6896, 2004). In this production example, I ⁻ functions to peel off each of the surfactant-attached SWCNTs in an aggregated form, and carrageenan recombines the detached surfactant-attached SWCNTs. Function to prevent. What functions as a dispersion aid in this way is also included in the concept of the “dispersant” in the present invention. 14 to 16 are AFM photographs using dispersions produced according to this production example and having SWCNT concentrations of 0.25, 0.25 / 10 and 0.25 / 30 mg / ml, respectively. Scanning microscope manufactured by Molecular Imaging, Yamato Science). Specifically, FIGS. 14 to 16 show that CNTs formed by aggregating these dispersions on a hydrophobic substrate (HOPG substrate) and then drying the applied product in a bundle shape. Shows a network of CNT aggregates connected to each other. The reason why such network-like CNT aggregates are formed is that the dispersion liquid is water-based, whereas the substrate is hydrophobic, and the liquid film thickness decreases with drying after the dispersion liquid is applied. This is because the dispersion repels water. As can be seen from these photographs, it is understood that an aggregate having extremely high dispersibility can be obtained by using the dispersant according to this production example. FIG. 17 is an AFM photograph when multi-walled carbon nanotubes (MWCNT, manufactured by Nano Lab) are used instead of SWCNT (MWCNT concentration is 10 μg / ml). From this photograph, it can be seen that the dispersant according to this production example gives the same result to the multi-walled carbon nanotube. Next, after the mesh-like CNT aggregate was washed to remove the dispersant and the electrical characteristics were examined, it was confirmed that all showed high conductivity. A similar test was performed using a hydrophilic substrate (mica substrate) instead of the HOPG substrate. However, the liquid did not repel water and no reticulated CNT aggregate was formed.

Production Example 2 Production Example of CNT Dispersion 2 (Aqueous Dispersion with Further Addition of Silicone Surfactant) Silicon used for producing polyurethane foam for 100 ml of the dispersion obtained in Production Example 1 50 ml of a system foam stabilizer was added, and the mixture was shaken with a shaker for about 1 hour. A SWCNT solution having a high degree of dispersion and stability was prepared.

Production Example 3 Production Example of CNT Dispersion 3 (Aqueous Dispersion Using Cyclodextrin Polymer as Dispersant) Single-Walled Carbon Nanotubes (SWCNT, manufactured by Nano Lab) 10 mg, C60 Fullerene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 mg Then, mix CD-polymer (Sigma) 500 mg and glycerol (Wako Pure Chemical Industries) 5 ml with a mortar for about 2 hours, then add 5 mL of deionized water and mix for another 30 minutes. It was. To this mixed colloid, 0.4 g CaCl ₂ (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then further mixed for 30 minutes. Deionized water was added so that the mixture was 100 ml. After placing in an ice tray and mixing with a homogenizer for about one hour, the mixture was centrifuged to remove insoluble components. The degree of dispersion and stability were evaluated by the above methods. In this production example, Ca ²⁺ functions to prevent the composite from adhering to the SWCNT / fullerene / CD composite and aggregating the composite.

Production Example 4 Production Example of CNT Dispersion 4 {Non-Aqueous Dispersion Using Low Molecular Compound (Lipid) as Dispersant} 100 mg lecithin (egg yolk-derived lecithin, Wako Pure Chemical Industries) was dissolved in 20 mL chloroform, and then added to an eggplant-shaped flask. And evaporated until the chloroform was completely removed. Next, 10 mL of sodium chloride added so that the concentration was 10 mM was added to the dispersion obtained in Production Example 1, and the lecithin thin film adhering to the flask was suspended with a vortex mixer. Next, the suspension was lyophilized, 10 ml deionized water and 10 ml hexane were added, and after sufficient vibration mixing, the hexane layer (lecithin / carbon nanotube complex) was recovered in a separatory funnel. . In this production example, sodium chloride functions to assist micelle formation.

Production Example 5 Production Example of CNT Dispersion 5 (Non-Aqueous Dispersion Using Paraffin as Dispersant) To the dispersant obtained in Production Example 1, 0.2% paraffin (melting point of the paraffin: 55 to 60 ° C.) was added. Ether was added 1: 1 and shaken for about 2 hours on a shaker. The paraffin layer (paraffin / carbon nanotube composite) was fractionated and collected, placed in an eggplant-shaped flask, and evaporated until the ether was completely removed. The paraffin / carbon nanotube composite (solid at room temperature) was recovered.

Production Example 6 Production Example of CNT Dispersion 6 (Non-Aqueous Dispersion Using Polymer Polymer as Dispersant) Single-Walled Carbon Nanotube (SWCNT, manufactured by Nano Lab) 100 mg, Surfactant (N-octadecyl-N, N ′ -After mixing a mixture of 1.68 g of dimethyl-3-amino-1-propanesulfonate, Zwitter-3-18, manufactured by Fluka) and 5 mL of glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) for about 2 hours using a mortar. 0.6 g NaI (manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed for another 30 minutes. Thereafter, 50 ml of a 1-methyl-pyrrolidone solution in which 1 g of polysulfone (Aldrich, MO 26000) was dissolved was added, and after mixing for about 2 hours using a mortar, insoluble components were removed by centrifugation.

Production Example 7 Production Example of CNT Dispersion 7 (Non-Aqueous Dispersion Using Fullerene as Dispersant ) After dissolving 0.5 g of C60 fullerene (Tokyo Chemical Industry Co., Ltd.) in 50 ml of toluene, single-walled carbon nanotubes (SWCNT, Nano Lab) 10 mg) was added and ground using a mortar for about 2 hours to obtain the title dispersion.

Production Example 8 Production Example of CNT-Dispersed Aramid Fiber Using Mediator After adding 5 g of ultrafine polyester fiber (diameter: 10 μm, manufactured by Unitika) to 100 mL of the dispersion obtained in Production Example 1, Then, it was placed in a tray filled with ice and heated in a microwave until just before the ice melted. In this process, the dispersant moved to the water phase, and the SWCNT moved to the ultrafine fibers that are the hydrophobic phase. Next, the ultrafine fibers carrying SWCNTs were thoroughly washed with deionized water and then treated with a 5% aqueous hydrogen peroxide solution to remove the remaining dispersant. Using a fully dried SWCNT / fiber composite, an aramid fiber fused with highly dispersed carbon nanotubes was prepared by the following procedure. As a production method, first, about 1 g of SWCNT / ultrafine fiber composite is added to 100 g of polyparaphenylene terephthalamide (PPTA, about 26%) solution dissolved in concentrated sulfuric acid, and then the ultrafine fibers are completely decomposed. Stir until FIG. 12 is an SEM photograph showing the situation. Next, an aramid yarn in which SWCNTs were fused from a PPTA / SWCNT solution was produced according to a liquid crystal spinning method. Here, as a result of conducting a conductivity test on the obtained aramid yarn, conductivity was confirmed.

Production Example 9 Production Example of CNT-dispersed hydroapatite using an intermediate substance About 1 g of SWCNT / ultrafine fiber obtained in Production Example 8 was added to 500 mL of 3.0 mM CaHPO ₄ .2H ₂ O and 7.0 mM Ca (OH) _2. After soaking in an aqueous solution containing for 7 days at room temperature, it was treated at 1000 ° C. under 120 MPa to produce hydroapatite fused with SWCNT.

Production Example 10 Production Example of CNT Dispersed Foam Polyurethane Using CNT Dispersion A catalytic amount of an amine catalyst (triethylenediamine) and water were added to and mixed with the CNT dispersion obtained in Production Example 2 {dispersion: water = 1: 4 (volume)} After that, the solution and toluene diisocyanate were mixed at a volume ratio of 1: 4 to obtain a CNT-dispersed urethane foam.

Production Example 11 Production Example of CNT Dispersion Dialysis Membrane Using CNT Dispersion The CNT dispersion obtained in Production Example 6 was cast on a Teflon (registered trademark) plate, and 1-methyl-2-pyrrolidone was slowly removed. Then, a dialysis membrane having carbon nanotubes dispersed therein was prepared.

Production Example 12 Production Example of CNT Dispersion Heat-Resistant Filter Using CNT Dispersion Dispersion obtained in Production Example 1 on a commercially available aluminum filter (Anodisc membrane, 20 to 500 nanometer wide porous is scattered) The solution was dropped and sandwiched by another aluminum filter, and then thoroughly washed with 10% ethanol / water and 5% hydrogen peroxide solution. Thereafter, heat-bonding was performed to produce a heat-resistant nanofilter having carbon nanotubes as the adsorption side.

Production Example 13 Production Example of CNT Dispersion Conductive Filter 1 Using CNT Dispersion After the dispersion obtained in Production Example 1 was uniformly immersed in foamed polyurethane (sponge), 10% ethanol / water, 5% It was thoroughly washed with hydrogen peroxide and dried. The sponge was immersed in 100 mM silver nitrate mercury ion and then reduced with a box-type electrode to produce a silver floc using the sponge as a mold. Thereafter, the sponge was pyrolyzed to prepare a CNT-dispersed conductive porous filter. Here, as a result of conducting a conductivity test on the obtained filter, conductivity was confirmed.

Production Example 14 Production Example of CNT Dispersion Conductive Filter 2 Using CNT Dispersion To 50 ml of the dispersion obtained in Production Example 1, sodium alginate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1.2% by weight. Thereafter, the film was cast and dried at room temperature to obtain a film. Next, a 1M silver nitrate aqueous solution was added to the film to obtain a film-like gel. Next, the gel was reduced with 1M ascorbic acid to obtain film-like silver in which SWCNTs were dispersed. Here, as a result of conducting a conductivity test on the obtained filter, conductivity was confirmed.

Production Example 15 Production Example of Fiber Filter in a Dry Type Using an Intermediate Material After mixing 1 g of polyester fiber (manufactured by Unitika) with 1 g of SWNT / extra fine fiber obtained in Production Example 8, the fiber filter was pressed at 150 ° C. Obtained. In order to confirm the performance of this filter, silicone oil was adsorbed. As a result, it was confirmed that the oil adsorption capacity was 30% by weight with respect to the weight of the filter.

FIG. 1 shows SEM images (FIG. 1A) and TEM images (FIG. 1B) of carbon nanofibers (CNF) synthesized by a CVD method. SEM (Hitachi 4800) was operated at 15 kV and TEM (Hitachi H-800) was operated at 200 kV. FIG. 2 is a photograph of an aqueous 100 ml vial containing an aqueous CNF / Na-ALG solution. The concentrations of CNF and Na-ALG were 0.5 mg / ml and 20 mg / ml, respectively. FIG. 3 shows the UV-vis spectrum (upper line) of an aqueous CNF / Na-ALG colloid solution (CNF 0.5 mg / ml, Na-ALG 20 mg / ml) and an aqueous solution containing only Na-ALG (Na-ALG 20 mg / ml). Is the UV-vis spectrum (bottom line). FIG. 4 shows the zeta potential (ζ) of an aqueous CNF / Na-ALG colloid solution (CNF 0.5 mg / ml, Na-ALG 20 mg / ml) and an aqueous solution containing only Na-ALG (Na-ALG 20 mg / ml) against pH. is there. FIG. 5 shows the three possible molecular forms of alginic acid, homopolymers MMM and GGG, and heteropolymers MGM linked alginic acid. FIG. 6 shows the FT-IR spectrum of Na-ALG in the solid state (upper line) and the FT-IR spectrum of the Na-ALG / CNF complex (lower line) using the potassium bromide (KBr) pellet method. It is. FIG. 7 is a microscopic result of Ba ²⁺ -alginate coated vesicles containing highly dispersed CNF. Vesicles, colloidal aqueous solution containing 0.5 mg / ml CNF and 20mg / ml Na-ALG used as the gelling solution and the aqueous solution containing 100 mM BaCl ₂ was prepared using as a gelatin solution. FIG. 8 shows an aqueous solution containing 30 μM ethidium bromide (line A), 15 ml of this 30 μM ethidium bromide solution mixed with Ba ²⁺ -alginate vesicles (reference vesicles, line B) and containing highly dispersed CNF. UV-vis absorption after 10 minutes of solution / vesicle mixing for vesicles (line C). FIG. 9 shows that after mixing 10 ml of an aqueous solution containing 30 μM ethidium bromide with 15 ml of reference (Ba ²⁺ -ALG) vesicles (top line) and with CNF / Ba ²⁺ -ALG vesicles ( The lower line) shows the change in ethidium ion concentration as a function of mixing time. FIG. 10 is a microscopic photograph of Ba ²⁺ -ALG / MWCNT composite beads. Beads with a diameter of 400-900 micrometers were observed. FIG. 11 is a GC-MS measurement / identification result of the target compound extracted from the removal column using hexane. The retention times for BP, DF, and DD were 4.12 minutes, 5.02 minutes, and 5.29 minutes, respectively. Column: DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm). The MS spectrum corresponds to the respective peaks of BP, DF and DD. FIG. 12 is an SEM photograph of an aramid fiber in which SWCNTs are dispersed in Production Example 8. FIG. 13 conceptually shows the CNT separation mechanism when a zwitterionic surfactant is used. FIG. 14 is an AFM photograph produced according to Production Example 1 and having a SWCNT concentration of 0.25 mg / ml. FIG. 15 is an AFM photograph produced according to Production Example 1 and having a SWCNT concentration of 0.25 / 10 mg / ml. FIG. 16 is an AFM photograph produced in accordance with Production Example 1 and having a SWCNT concentration of 0.25 / 30 mg / ml. FIG. 17 is an AFM photograph produced in accordance with Production Example 1 and having a MWCNT concentration of 10 μg / ml.

Claims (3)

When a fine carbon-dispersed liquid medium containing nano to micro-sized fine carbon and a dispersant for the fine carbon is applied to a hydrophobic smooth body when the liquid medium is aqueous, the liquid medium is dried. In the case of non-aqueous system, it is a method for producing a reticulated nanocarbon aggregate including a step of drying after applying to a hydrophilic smooth body ,
The minute carbon is a carbon nanofiber or a carbon nanotube,
The method for producing a reticulated nanocarbon aggregate, wherein the dispersant is a zwitterionic surfactant having an anion and a cation in one molecule. The method of claim 1, further comprising the step of washing the dispersant after the drying in the step.   The method according to claim 1, wherein the reticulated nanocarbon aggregate is a conductive material.