WO2005110594A1 - 微小カーボン分散物 - Google Patents
微小カーボン分散物 Download PDFInfo
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- WO2005110594A1 WO2005110594A1 PCT/JP2005/008795 JP2005008795W WO2005110594A1 WO 2005110594 A1 WO2005110594 A1 WO 2005110594A1 JP 2005008795 W JP2005008795 W JP 2005008795W WO 2005110594 A1 WO2005110594 A1 WO 2005110594A1
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- carbon
- liquid medium
- dispersion
- fine carbon
- micro
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Definitions
- the present invention relates to a fine carbon dispersion (eg, a gel and its dried gel, fiber, film, molded product) as a composite material in which micro carbon (eg, carbon nanotube) having a nano force and micro size is uniformly dispersed, and
- a fine carbon dispersion as an intermediary material for dispersing the fine carbon in the article when manufacturing the article, a method for producing the same, and uses thereof.
- Nano-sized and micro-sized carbon has recently attracted attention in various fields.
- nanocarbon is a new material that has attracted attention in various fields such as energy, electronics, chemistry, pharmaceuticals, optical components, and materials and machinery, such as carbon nanotubes (CNT).
- CNT carbon nanotubes
- one of the representative materials of nanotechnology is a light and strong new material, and applied research such as electron emitter materials such as displays, hydrogen storage materials, and tips of atomic force microscopes. Is underway.
- there are two types of CNTs single-layered multilayer type and cup-stacked type.Single-layered multilayer type is a needle-shaped carbon molecule with a diameter on the order of nanometers. have.
- Multi-wall carbon nanotubes with a concentric multilayered Dalafen cylinder are used for applications such as emitters for FEDs, ultra-high strength materials, and composite materials.
- a single-walled dalaphen cylinder that produces only a force is called a single-walled carbon nanotube (SWCNT), which is used for fuel cells and negative electrodes for lithium secondary batteries.
- SWCNT single-walled carbon nanotube
- Patent Document 1 is a method of manufacturing a CNT thin film for obtaining an electron-emitting device.
- the dispersed particles are deposited on the electrode particles, and a thin film is formed. That is, this technology
- the CNTs are aggregated at high density to ensure high electron emission ability.
- Patent Document 2 is a thermoplastic resin composition containing a thermoplastic resin, a foaming agent, a cross-linking agent, and CNT and used for a heat insulating material or the like.
- the composition containing CNT is
- the mixture After melt-kneading and molding, the mixture is subjected to a crosslinking / foaming reaction to form a crosslinked thermoplastic resin in which CNTs are dispersed.
- Patent Document 1 JP 2001-48511
- Patent Document 2 JP 2004-75707
- the composite material in the prior art, a composite material is generally obtained by mixing with a resin.
- the carbon nanotubes to be mixed are intricately entangled with each other, there is a problem that a lump of carbon nanotubes remains and uniform dispersibility cannot be secured.
- the CNT material as an electronic material cannot be said to have sufficient properties such as air permeability, permeability, and adsorptivity because the CNTs are aggregated at a high density.
- the CNT material as a high-strength material also has air permeability with respect to pores resulting from foaming, but has only a small gap between crosslinked structures of thermoplastic resin, and has extremely poor internal air permeability.
- an object of the present invention is to provide a means for ensuring uniform dispersibility of carbon nanotubes in a composite material.
- the present invention (1) is a fine carbon dispersion produced using a fine carbon dispersed liquid medium containing nano force micro-sized fine carbon and a dispersant for the fine carbon.
- micro carbon of nano to micro size refers to a carbon having a diameter of 10 to 10 m and a length of 10 _4 to 10 _9 m (preferably 10 _6 to 10 _9 m). Carbon on order, for example, nanocarbon.
- nanocarbon 10 _9 refers to the order in which force one Bonn m, preferably, carbon nanotubes (single-walled 'bilayer' multilayer type, Kappusuta click type), carbon nanofiber, carbon nanohorn, graphite Or fullerene.
- ⁇ nano force and micro-sized minute carbon '' means that nano force also contains at least one type of carbon that corresponds to micro-sized carbon, for example, containing all sizes from nano to micro size. It does not mean that it does not contain carbon other than nano to micro size.
- carbon nanotube includes a single layer and a multilayer (two or more layers), and also includes a carbon nanofiber having a disordered graphite layer.
- dispersion becomes difficult as the number of layers increases, the significance of the present invention increases as the number of layers increases. Note that this term is not limited to the present invention (1), and applies to all inventions described hereinafter, unless otherwise specified. The same applies to each term other than this term, which appears in the description of each invention below.
- 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.
- dispersion means dispersion in a broad sense including suspension and dissolution. For example, an embodiment in which all of the fine carbon is dissolved, an embodiment in which all of them are suspended, an embodiment in which some are dissolved (others exist in other forms such as suspension), and an embodiment in which some are suspended (other Exist in other forms such as dissolution).
- a state in which fine carbon is dispersed and suspended in a liquid looks uniform in appearance.
- fine carbon is present even in the upper part of the liquid part.
- fine carbon dispersion refers to an object in which minute carbon is dispersed in the object.
- the fine carbon is uniformly dispersed in the object.
- a composite material eg, fiber, film, molded product
- uniformly dispersed means a state where the physical properties of the obtained composite material do not vary from place to place (for example, about ⁇ 20%). Specifically, If it can be visually confirmed that the particles are uniformly dispersed as compared with a conventional lump when observed with a microscopic microscope, this corresponds to “uniformly dispersed” in the present invention.
- 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, and examples thereof include aqueous solvents such as water and alcohol.
- aqueous solvents such as water and alcohol.
- a non-aqueous solvent oil-based solvent
- silicon dioxide silicon dioxide
- carbon tetrachloride carbon tetrachloride
- chloroform toluene
- the fine carbon dispersion is a surface dispersion type in which the fine carbon is dispersed on the surface of the object, or the fine carbon is dispersed inside the object.
- the fine carbon dispersion of the invention (1) which is an internal dispersion type.
- the present invention (3) is the above-mentioned invention (2), wherein the fine carbon dispersion of the internal dispersion type is a gel obtained by gelling the fine carbon liquid medium or a dried product thereof or a dried product thereof. ) Is a fine carbon dispersion.
- the "fine carbon liquid medium" according to the present invention needs to be capable of gelling.
- “capable of gelling” means that the carbon-dispersed liquid medium contains a gelling material having a crosslinkable group that can be crosslinked by some means.
- the dispersant is a gelling material.
- the dried product refers to a dried product of the “carbon-dispersed liquid medium”, and the degree of drying is not particularly limited.
- the carbon is present in the gelling material ⁇ eg, a dispersant (eg, a surfactant) ⁇ with high uniformity while maintaining a very small particle size! Is understood.
- the dried product is gelled means that the dried product is gelled in a wet state in which a liquid medium is present by any means.
- a mode in which a liquid medium containing a gelling agent is applied to the dried product, a mode in which a light medium is applied to the dried product, and then light and radiation are cross-linked can be exemplified.
- the carbon is included in the gel with high and uniformity while maintaining the particle size very small!
- the term “encapsulation” means not only that the carbon is included in the network structure of the gel but also that the carbon or the dry form is contained in a liquid medium.
- This is a concept in which a gel film wraps the carbon in a state.
- a bead-like or fiber-like gel enclosing a liquid medium an embodiment in which the carbon exists only in the gel network, the carbon exists in the gel network, and the carbon exists in the internal liquid medium
- the gel is not limited to the gel obtained by the production method limitation as long as the product is the same.
- the “gel” refers to a three-dimensional network formed by chemically or physically cross-linking polymers or a three-dimensional network formed by cross-linking simultaneously with polymerization of a monomer.
- solvent refers to a liquid that swells the network structure, which is contained in the network structure. Therefore, it can be read simply as "liquid”.
- the solvent is not particularly limited, and is appropriately selected in relation to the specific use. Therefore, when the solvent is exchanged after gelling the raw material, which need not necessarily be the same as the “liquid medium” in the “gelled carbon-dispersible liquid medium” that is the raw material of the gel, The new solvent becomes the solvent for the “obtained gel”.
- aqueous solvents for example, water, alcohols, combinations thereof, and oily solvents, for example, silicon oil, carbon tetrachloride, chloroform, toluene, and combinations thereof.
- oily solvents for example, silicon oil, carbon tetrachloride, chloroform, toluene, and combinations thereof.
- the liquid medium when it is water, it can be used for applications requiring biosafety such as use in a water purifier, or as a separation resin for mouth chromatography using an aqueous solution as an eluent.
- the fine carbon dispersion has a double structure of an inner layer and an outer layer, wherein the inner layer is the carbon dispersion liquid medium, and the outer layer is the fine carbon dispersion liquid medium.
- the fine carbon dispersion according to the invention (3) which is a gel.
- the outer layer is further covered with a gel, a polymer, or the like is also within the scope of the present invention.
- carbon having a nano force and micro size and a dispersant for the carbon are used. It is a gel obtained by gelling the gelled carbon-dispersed liquid medium or the dried product thereof.
- a preferred embodiment (A-2) is the gel according to the preferred embodiment (1), wherein the carbon dispersion liquid medium is the carbon solution or suspension.
- the term “or” in the "carbon solution or suspension” does not exclude the other as long as only one is essential. This also applies to other parts unless otherwise stated. That is, for example, in the carbon-dispersed liquid medium, an embodiment in which the carbon is completely dissolved, an embodiment in which all of the carbon is suspended, an embodiment in which a part of the carbon is dissolved (others exist in other forms such as suspension), In this case, there may be mentioned an embodiment in which a part is suspended (others are present in other forms such as dissolution).
- the solution state is preferable because the particle size is smaller and the uniformity is higher.
- the preferred embodiment (A) is such that the dispersant is gelled by crosslinking.
- the carbon is a carbon nanotube (single-wall / double-wall / multilayer type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn,
- graphite refers to one that has been pulverized to a particle size of 10 to 6 m or less.
- the preferred embodiment (A-6) is the same as the preferred embodiment (A-1) to (A-5), wherein the shape is bead, fiber, membrane, plate, or barta. , One of the gels.
- the term “beads”, as well as “package”, means a substantially spherical shape, the particle size is not particularly limited, and the preferred range varies depending on the application and the like.
- the term “fiber-shaped” means a linear shape, and the length and diameter are not particularly limited, and are determined by the application. For example, everything as thin as a thread or as thick as a toad egg is included in the “fiber form”.
- film shape and “plate shape” the surface area and shape are not particularly limited, and are determined depending on the application.
- the volume and shape of “Balta” are not particularly limited, and are determined by the application. .
- a bead-like or fibrous gel force has a double structure of an inner layer and an outer layer.
- A-6) is not particularly limited, and includes those without a double structure, all of which are gelled.
- the bead-like gel or the fibrous gel has a double structure of an inner layer and an outer layer, the inner layer being the carbon-dispersed liquid medium, and the outer layer being the carbohydrate.
- a preferred embodiment (A-8) is that the bead-like gel or the fiber-like gel is obtained by dropping or flowing the carbon-dispersed liquid medium into a liquid medium containing a gelling agent.
- the “gelling agent” is not particularly limited as long as it is a gelling agent capable of crosslinking a gel material (eg, a dispersing agent) in the carbon-dispersed 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 capable of dispersing (for example, dissolving and suspending) the gelling agent.
- the same “liquid medium” as the “nanocarbon-dispersed liquid medium” described in the section of the embodiment (A-1) can be used.
- the “liquid medium containing the gelling agent” is set to “ At least one of the ⁇ liquid medium '' of the ⁇ liquid medium '' and the ⁇ liquid medium '' of the ⁇ nanocarbon-dispersed liquid medium '' must have a property of dispersing both the gelling material and the gelling agent. It is suitable.
- the term “dropping” means that the "carbon-dispersed liquid medium” is applied discontinuously with respect to time to the "liquid medium containing the gelling agent”. Further, “flowing down” means that the “carbon-dispersed liquid medium” is continuously applied to the “liquid medium containing a gelling agent” with respect to time. In each case, not only free-falling, but also accelerating and dropping into a “liquid medium containing a gelling agent” (for example, dropping by applying pressure with a syringe-like device) The liquid may be dropped into a “liquid medium containing a gelling agent” (for example, slowly dropped into a “liquid medium containing a gelling agent” by means of a tube or a guide member). The direction of application is preferably downward, but may be other directions.
- the film gel, the plate gel or the barta gel is coated in a film form.
- the above-mentioned preferred embodiment which is obtained by crosslinking the carbon dispersion liquid medium obtained or put into a mold, or by applying a liquid medium containing a gelling agent to the dried product ( It is the gel of A-6).
- crosslinking using a gelling agent such as applying a gelling agent-containing liquid or applying a solid gelling agent
- a gelling agent such as applying a gelling agent-containing liquid or applying a solid gelling agent
- a gelling agent such as applying a gelling agent-containing liquid or applying a solid gelling agent
- / ⁇ means both crosslinking (eg, radiation crosslinking)
- the latter means crosslinking using a gelling agent in the form of a gelling agent-containing solution.
- the "mold” may be an open type or a closed type, and its size and shape are not particularly limited, and are determined in relation to the application.
- “Applying” refers to a process of adding the carbon-dispersed liquid medium or the dried product thereof, including the addition and the addition, the application and the like, and the gelling agent or the liquid medium containing the gelling agent. It means any concept that fits together.
- the preferred embodiment (A-10) is a dried gel obtained by drying any one of the gels of the preferred embodiments (A-1) to (A-9).
- the "dry gel” is not particularly limited as long as it is a gel obtained by drying an original gel containing a solvent, and the degree of drying (the amount of the solvent in the gel) is not particularly limited. Determined by the relationship. For example, a gel from which X% of the solvent of the original gel has been removed or a completely dried gel (resin) from which 100% of the solvent has been removed can be mentioned.
- the fine carbon dispersion of the internal dispersion type disperses a raw material monomer in the fine carbon dispersion liquid medium, and then polymerizes the raw material monomer to remove the liquid medium.
- the fine carbon dispersion according to the invention (2) which is produced by the above method.
- “dispersing the monomer” includes dissolution, suspension, and emulsion.
- the present invention (6) is produced by dispersing the raw polymer in the fine carbon dispersion liquid medium, and then removing the liquid medium, in which the fine carbon dispersion of the internal dispersion type is dispersed.
- the fine carbon dispersion of the invention (2) includes dissolution, suspension, and emulsion.
- the fine carbon dispersion of the surface-dispersed type may be used to immerse a raw material in the fine carbon dispersed liquid medium, and in some cases to unravel the raw material, and then remove the liquid medium.
- the present invention (8) is characterized in that the object constituting the minute carbon dispersion is the minute carbon in which the object constituting the minute carbon dispersion is dispersed on the surface, Z or inside.
- the fine carbon dispersion according to the invention (1) or (2) which is composed of a material that can be released under predetermined conditions.
- free means, for example, that the object is decomposed, evaporated, melted, and dissolved by chemical treatment (acid, alkali, enzyme, etc.) or physical treatment (heat, electricity, etc.). , Precipitation, etc., to separate it from the supported fine carbon.
- the fine carbon dispersion may include moving the fine carbon from the liquid medium side to the target object side after adding the target to the fine carbon dispersed liquid medium.
- the fine carbon dispersion according to the invention (8) which is produced by performing an induced phase transfer treatment.
- the “induced phase transfer process” is a process in which fine carbon is separated from a dispersant while fine carbon is dispersed, and fine carbon is transferred from the dispersion to another phase.
- a heat treatment for example, electromagnetic wave treatment
- vibration energy for example, ultrasonic treatment
- a treatment for applying pressure for example, a pressure
- the present invention (10) is the fine carbon dispersion of the above-mentioned invention (9), wherein the induced phase transfer treatment is an electromagnetic wave or an ultrasonic treatment.
- the present invention (11) is the fine carbon dispersion of any one of the inventions (8;) to (10), wherein the object is an ultrafine fiber or a higher paraffin.
- the “extremely fine fiber” refers to a fiber having a diameter of 1000 ⁇ m or less, preferably a fiber having a diameter of 100 m or less, and more preferably a fiber having a diameter of 10 m or less.
- “Higher paraffin” refers to paraffins with a melting point of 40 ° C or higher.
- polyester fibers and urethane foam fibers can be mentioned.
- the present invention (12) is any of the inventions (8) to (11), wherein the fine carbon dispersion is an intermediary material for dispersing the fine carbon in the article when the article is manufactured. It is one fine carbon dispersion.
- the object constituting the "intermediate material" remains in the finally manufactured article after releasing the fine carbon, for example, functions as one material constituting the article. It may be one that does not remain in the finally manufactured article, such as functioning as a mere carrier only for dispersing the fine carbon in the article.
- the present invention (13) includes a step of cross-linking a cross-linkable component contained in a micro carbon-dispersed liquid medium containing a micro carbon having a nano force and a micro size and a dispersant for the micro carbon, or a dried product thereof.
- 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 cross-links formed are strong. Specific examples of the former include a chemically crosslinkable dispersant Z, a polymer having an amino group and a hydroxyl group, and a dialdehyde compound; a nitrogen peroxide polymer, a carboxy polymer ester, an isocyanate, an epoxy group, and a methylol group.
- Polymer z amine conjugated product polymer having carboxyl group 1 Z aziridine conjugated product; polymer Z having nitrile group, mercapto group, carboxyl group, etc. di or polymethylolphenol resin; OH, one SH, NH, one COOH and other polymers with active hydrogen
- Insects that can be crosslinked include polyethylene, polytetrafluoroethylene, and nylon.
- physical cross-linking refers to physical bridging by ionic bonding (Coulomb force bonding), hydrogen bonding, coordination bonding, helium formation, or hydrophobic bonding.
- This physical cross-linking is generally characterized by a sol-gel transition caused by changes in heat, solution type, ionic strength, and pH.
- Specific examples include, for ionic bonds, those which can be crosslinked by mixing, such as polybutylbenzyltrimethylammonium and sodium chloride-polymethacrylate.
- Polyacrylic acid, poly (vinyl alcohol) that can be crosslinked by freeze-thawing method, and poly (ethylene glycol methacrylate) that can be cross-linked by freezing and low-temperature crystallization method can be mentioned.
- cross-linking can be performed by forming a helix between polymer chains.
- Agar, gelatin, carrageenan, algin Can be mentioned, for hydrophobic bonding, as can be crosslinked by hydrophobic interactions, Ru can be given ovalbumin, serum albumin.
- the present invention (14) is the method according to the above invention (13), wherein the crosslinkable component is a dispersant.
- the present invention can gel a fine carbon-dispersed liquid medium containing a crosslinkable component containing a microcarbon having a nano force and a microsize and a dispersant of the microcarbon, and the component. It has a double structure of an inner layer and an outer layer, including a step of adding it to a liquid medium containing a gelling agent, wherein the inner layer is the fine carbon dispersed liquid medium, and the outer layer is the fine carbon dispersed liquid medium.
- This is a method for producing a fine carbon dispersion, which is a gely dagger, in which the fine carbon is dispersed inside the gel.
- the gel-dispersible carbon-dispersed liquid medium containing carbon having a nano force and a microsize and a dispersant for the carbon are used as the gel-dispersed liquid medium.
- the “addition” in the “adding step” is not particularly limited as long as it is an addition mode in which a bead-like or fiber-like gel can be obtained. If it is in the form of a fiber, the above-mentioned “downflow” can be exemplified.
- the method may include a step other than the above step, for example, a step of producing the carbon (for example, a nanocarbon), a step of purifying the carbon, a step of producing the carbon-dispersed liquid medium, and a step of producing a liquid medium containing a gelling agent.
- a production step, a gel drying step and the like can be mentioned.
- a preferred embodiment (B-2) is the method for producing the preferred embodiment (B-1), wherein the carbon dispersion liquid medium is the carbon solution or suspension.
- a preferred embodiment (B-3) is the method for producing the preferred embodiment (B-1) or (B-2), wherein the dispersant is capable of being crosslinked by the gelling agent.
- Preferred embodiments (B-4) are the preferred embodiments (B-1) to (B-1), wherein the dispersant is a surfactant.
- the carbon is a carbon nanotube (single-walled 'multi-layered type, cup-stacked type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, or microcarbon filter.
- Certain of the preferred embodiments (B-1) to (B4) are production methods.
- a preferred embodiment (B-6) is as follows: (1) Nano-force The gel-like carbon-dispersed liquid medium containing micro-sized carbon and a dispersant for the carbon is applied in a film form, and then the car Or (2) nano-forced carbon-dispersed liquid medium containing micro-sized carbon and a dispersant of the carbon. Is applied in the form of a film and dried to obtain a dried film, and then the liquid medium containing a gelling agent capable of gelling when the dried film returns to a wet state again is applied to the film.
- step (3) repeating step (1) and step Z or step (2) to obtain a plate-like gel or barta
- This is a method for producing a film-like, plate-like or barta-like gel containing nano- to micro-size carbon or a dry gel thereof, including a step of obtaining a gel.
- coating includes not only a case where the liquid medium is applied with a coater or the like but also a case where the liquid medium is sprayed.
- the method may include a step other than the above step, for example, a step of producing the carbon (for example, nanocarbon), a step of purifying the carbon, a step of producing a carbon dispersed liquid medium, and a step of producing a gelling agent-containing liquid medium. And a step of drying the gel.
- the gelling agent is directly sprayed into the film-shaped liquid medium or light irradiation is performed.
- the carbon dispersed liquid medium is gelled.
- the step (2) for example, by applying a liquid medium in which a gelling agent is dispersed to the dried film, the dried film absorbs the liquid medium, and An embodiment in which the gel is formed by a gelling agent can be given.
- the step (3) for example, after forming a film gel, the liquid medium is applied again on the gel, and the operation is performed several times when the gelling agent is applied. Can be.
- a preferred embodiment (B-7) is the method for producing the preferred embodiment (B-6), wherein the carbon dispersion liquid medium is the carbon solution or suspension.
- a preferred embodiment (B-8) is the process according to the preferred embodiment (B-6) or (B-7), wherein the dispersant is crosslinkable.
- the carbon is a carbon nanotube (single-walled 'multi-layered type, power stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, power micro-horn, micro carbon filter ⁇ of the preferred embodiments (B-16) to (B-19).
- the carbon dispersion liquid medium capable of gelling containing carbon having a nano force and micro size and a dispersant for the carbon is placed in a mold and then dispersed in the carbon.
- (2) Nano force The gellable carbon-dispersed liquid medium containing micro-sized carbon and the carbon dispersant is placed in a mold and then dried to form a shape corresponding to the mold.
- a gelling agent is directly sprayed into the carbon-dispersed liquid medium in the mold, or a liquid medium containing a gelling agent is charged.
- the carbon dispersion liquid medium may be gelled by irradiating light or radiation.
- step (2) for example, by applying a liquid medium in which a gelling agent is dispersed to the dried substance, the dried substance absorbs the liquid medium, and the absorber is gelled by the gelling agent. There can be mentioned a mode of being ridden.
- the shape, size, and the like of the "mold” are not particularly limited, and are determined according to the application. Further, the term “shape corresponding to the mold” does not necessarily mean that the shape is completely the same as the mold. For example, a gel obtained using the mold expands after being removed from the mold. This is a concept that includes all shapes resulting from the use of the mold, including an embodiment that is larger than the mold.
- the mold is a circular container, a polygonal container, a spherical container, or a rectangular parallelepiped container, and the gel having a shape corresponding to the mold is a circular plate-like gel or polygonal gel, respectively.
- a preferred embodiment (B-13) is the method for producing 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 any one of the above-mentioned preferred embodiments (B-11;) to (B-13), wherein the dispersant is crosslinkable.
- a preferred embodiment (B-15) is any one of the above-mentioned preferred embodiments (B-11) to (B-14), wherein the dispersant is a surfactant.
- the carbon is a carbon nanotube (single-walled / multi-layered type, power stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, power
- the present invention (16) includes a step of dispersing the target material monomer in a fine carbon dispersion liquid medium containing fine carbon having a nano force and a micro size and a dispersant for the fine carbon, and polymerizing the target material monomer. And a step of removing the liquid medium.
- “dispersing the monomer” includes dissolution, suspension, and emulsion.
- the present invention (17) comprises a step of dispersing the target raw material polymer in a fine carbon dispersion liquid medium containing fine carbon having a nano force and a micro size and a dispersant for the fine carbon, and removing the liquid medium.
- This is a method for producing a fine carbon dispersion in which the fine carbon is dispersed inside an object, including a step.
- “dispersing the polymer” includes dissolution, suspension, and emulsion.
- the present invention (18) includes a step of immersing the object in a fine carbon-dispersed liquid medium containing fine carbon having a nano force and a micro size 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 on the surface of the object.
- the present invention (19) is the manufacturing method according to the invention (18), further comprising an induced phase transfer treatment step of moving the fine carbon from the liquid medium side to the object side.
- the present invention (20) is an adsorptive material containing the fine carbon dispersion of any one of the present inventions (1) to (12).
- the substance to be adsorbed is not particularly limited, and may be any substance contained in a liquid or a gas.
- the present invention (21) is the adsorptive material according to the invention (20), which is used for adsorbing pollutants in liquids or gases.
- the contaminants "harmful substances” include hydrogen chloride, butyl chloride, sodium hydroxide, tetrachloroethylene (solvent), BDBPP compound (flameproofing agent), and tributyltin compound (antibacterial and fungicide).
- Examples include trichloroethylene (solvent), APO (flameproofing agent), TDBPP, methanol (solvent), and triphenyltin compounds.
- the present invention (22) is intended for industrial water and drinking water filtration equipment, for pure water equipment, for various chromatographies, for adsorption equipment for human harmful substances such as carcinogens, for air cleaners, and for exhaust gas purification.
- the substances to be adsorbed for drinking water filtration equipment are not particularly limited, but free residual chlorine, turbidity, trihalomethane, soluble lead, pesticides (CAT), tetrachloroethylene, trifluoroethylene, 1,1,1 —Trichloroethane, musty odor (2-MIB).
- the carcinogen to be adsorbed is not particularly limited, but, for example, bromides, trihalomethanes, and various environmental forms (for example, nonylphenol) may be used. Can be mentioned.
- the substance to be adsorbed is not particularly limited, and examples thereof include house dust such as pollen in a room, cigarette smoke, and dead mites.
- house dust such as pollen in a room, cigarette smoke, and dead mites.
- for conductive material for example, various parts such as electronics field, electric products, mechanical parts, and vehicles are used. Can be mentioned.
- a material for a fuel cell separator can be mentioned as a preferred example.
- the present invention (23) is the conductive material according to any one of the above inventions (1) to (12), containing at least one fine carbon dispersion.
- conductive material includes, for example, various fields such as electronics, electric products, mechanical parts, and vehicles.
- a material for a fuel cell separator can be mentioned as a preferred example.
- the present invention (24) is directed to an industrial water / drinking water filtration device, a pure water device, various types of chromatography, a device for adsorbing harmful substances such as carcinogens, and air containing the adsorbent material of the invention (20). It is a purifier, an exhaust gas purification device or an electric product.
- the present invention (25) is a system in which an article or an article raw material is present, and wherein the fine carbon dispersion according to any one of the inventions (1) to (12) is dry- or wet-added. including
- the present invention is a technique for fusing highly dispersed fine carbon to a target substance in a dry or wet manner.
- the method used to introduce highly dispersed fine carbon in fibers, glass, metals, organic or inorganic crystals or amorphous materials thereof is a dry introduction method, that is, powdered fine carbon is added.
- carbon nanotubes usually exist in a form called a bundle. For this reason, there is 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.
- a solution of carbon nanotubes in which bundles of carbon nanotubes are highly dispersed is prepared using a dispersant.
- a substance called “mediation material” or “mediation medium” is added to this dispersion solution, and the carbon nanotubes are transferred to the “mediation medium” in a dispersed state.
- the target material is prepared using the “mediation medium” carrying highly dispersed carbon nanotubes as the starting material.
- processing such as decomposition of the “mediation material” is performed to remove the “mediation medium”.
- Mediators include materials that decompose with acids, alkalis, or heat, and solid Materials that undergo a phase transition, such as z liquids, are preferred.
- dry means an addition mode to a solid phase
- “wet” means an addition mode to a liquid phase.
- the present invention (26) is a system in which an article or an article raw material is present, and a system that satisfies the predetermined conditions of the invention (8) is one of the systems of the inventions (8) to (12).
- This is a method for producing an article in which fine carbon is dispersed, including a step of adding two fine carbons.
- the present invention (27) is the method for producing the invention (26), wherein the article is an aramide fiber and the object is a concentrated sulfuric acid-soluble material.
- the present invention (28) is a non-aqueous carbon nanotube dispersion liquid using fullerene as a carbon nanotube dispersant.
- the present invention (29) is an aqueous carbon nanotube dispersion using cyclodextrin and fullerene as carbon nanotube dispersants.
- the present invention (30) provides a liquid medium in which the fine carbon is dispersed by a dispersing agent for the fine carbon having a nano force and a micro size, wherein the fine carbon is dispersed on the surface and Z or inside. It is a dispersion for use.
- a preferred embodiment of the invention is a carbon nanotube dispersion liquid for producing a composite material in which carbon nanotubes are uniformly dispersed, which is a liquid medium in which carbon nanotubes are dispersed with a carbon nanotube dispersant.
- the following inventions (31) to (33) relate to the preferred embodiment.
- the present invention (31) is the dispersion according to the invention (30), wherein the liquid medium is a non-aqueous liquid medium, the fine carbon is a carbon nanotube, and the dispersant is fullerene.
- non-aqueous means that the base liquid medium is a non-aqueous solvent.
- water-insoluble solvent means a solvent having a solubility in water at 23.5 ° C of 0.2% by weight or less.
- fullerene is a concept that includes, for example, fullerenes such as C60, C70, and C82, as well as fullerene dimers.
- the non-aqueous solvent preferably includes a non-aqueous solvent having an aromatic ring, such as toluene, anthracene, and naphthalene (dissolved in acetonitrile).
- the liquid medium is an aqueous liquid medium
- the fine carbon is carbon
- the dispersant is a surfactant capable of forming spherical micelles having a diameter of 50 to 2000 nm in the liquid medium or a water-soluble polymer having a weight average molecular weight of 10,000 to 50 million.
- aqueous means that the base liquid medium is a water-soluble solvent (aqueous solvent).
- water-soluble solvent means a solvent having a solubility in water at 23.5 ° C. of 20% by weight or more and includes water.
- Spherical micelles refer to micelles formed by a surfactant and having a spherical storage space.
- the endoplasmic reticulum is called a ribosome.
- the diameter of the spherical micelles (vesicles) refers to a value measured according to a light scattering method (a 20 ° C. pH-unadjusted aqueous solution).
- the "water-soluble polymer” refers to a polymer having a weight average molecular weight of 10,000 to 50 million (preferably 10,000 to 5 million).
- 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 (33) is the dispersion according to the invention (30), wherein the liquid medium is an aqueous liquid medium, the fine carbon is a carbon nanotube, and the dispersants are cyclodextrin and fullerene. is there.
- cyclodextrin is a cyclic oligosaccharide obtained by allowing an enzyme (cyclodextrin glucanotransferase) to act on starch, and may be any of
- the present invention (34) is directed to a fine carbon-dispersed liquid medium containing nano-sized micro carbon and a dispersant for the fine carbon, wherein one of the dispersants is used to promote the unbundled state of the fine carbon. It is a fine carbon-dispersed liquid medium containing a substance and a ⁇ or unbundled state maintaining substance.
- the unbundled state promoting substance for example, a charged substance that adheres to or penetrates the fine carbon or generates a repulsive force between the fine carbons by being interposed between the fine carbons ⁇ A-one cation (eg, Nal) ⁇ .
- the unbundled state maintaining substance for example, an interfering substance that intervenes between separated fine carbons to physically prevent the two from binding or approaching each other (e.g., For example, a high molecular compound (for example, ⁇ -lactate lagenan) can be used.
- the present invention (35) is the fine carbon-dispersed liquid medium according to the invention (34), which is used for producing a fine carbon in which the fine carbon is dispersed on the surface, Z or inside.
- the present invention (36) is a fine carbon dispersant having a portion that adheres to micro carbon having a nano force and a micro force and an electric attractive force inducing group.
- the agent's electric attraction inducing group promotes the unbundled state of the fine carbon by attracting with the electric attraction generated between the electric attraction inducing group of the dispersing agent and the dispersing agent attached to another of the micro carbons. It is a fine carbon dispersant.
- the "electric attraction inducing group” is an ion group or a cationic group.
- the above-mentioned fine carbon dispersant is a compound having both electric properties in one molecule (for example, a zwitterionic surfactant having an ion group and a cationic group), it may be one compound in one molecule. It may be a mixture of a compound having the same electrical properties (for example, a cationic surfactant) and a compound having another electrical property in one molecule (for example, an anionic surfactant).
- the “attached portion” means a portion having an affinity for the fine carbon. For example, when the fine carbon is hydrophobic, it is a hydrophobic portion (for example, an alkylene group).
- the present invention provides a method according to the present invention, wherein the dispersant is a fine carbon dispersant having an a-on group and a cationic group, wherein the dispersant has an a-on group and a cation attached to one of the fine carbons.
- the fine carbon dispersion promotes the unbundled state of the fine carbon by attracting each of the on groups by an electric attraction generated between the cationic group and the aon group of the dispersant attached to another fine carbon.
- the fine carbon dispersant according to the invention (36) which is a dispersant.
- the present invention (38) is the dispersant of the above invention (37), wherein the dispersant is a zwitterionic surfactant.
- the present invention (39) is manufactured using a fine carbon-dispersed liquid medium containing nano force micro-sized fine carbon and the dispersant V of any of the above-mentioned inventions (36) to (38). Is a fine carbon dispersion.
- the fine carbon in the fine carbon dispersion is present in the dispersion with extremely high uniformity (surface and Z or inside). Has an effect that physical properties (for example, strength, adsorptivity, and conductivity) inherent in the fine carbon can be uniformly retained regardless of the site.
- the nano force micro-sized fine carbon dispersed liquid medium is gelled, the properties of a gel having excellent permeability can be enjoyed and the particle size can be extremely high. It is very small, and has a very high nano- to micro-sized micro carbon force. It is very uniform and exists in the network of the gel, so that it has an effect of having a very high adsorptivity.
- the nano-force of the inner layer also adopts a configuration in which the gel of the outer layer wraps the micro-sized micro carbon dispersion liquid medium, so that it is possible to treat liquids that are inconvenient to handle in the same way as solids, and to achieve the effect that the outer layer is formed of gel. Therefore, in addition to having excellent permeability, the inner layer is a nano-sized micro-sized carbon dispersion liquid medium, so it has high adsorption performance especially when adsorbing substances having high affinity with the liquid medium. If you can show it!
- the carbon-dispersed liquid medium as a raw material is a solution or a suspension
- the network of the obtained gel is It is understood that the carbon is present in the structure in a state of a smaller particle size, and as a result, the effect is obtained if the carbon has a higher adsorptivity.
- the dispersant dissolved in the liquid medium is gelled.
- a more uniform network structure is formed
- carbon having an extremely small particle size is included in the network structure, and as a result, the effect of further improving the adsorption performance is exhibited.
- a crosslinkable surfactant is used. If it can be retained and the solvent (hydrophilic solvent) can be retained at its hydrophilic site, it will have an effect.
- a carbon nanotube in addition to the effects of the inventions (A-1) to (A-4), a carbon nanotube (single-layered multilayer type, cup-stacked type), carbon nanofiber, carbon nanofiber
- the preferred embodiment (A-6) has an effect that it can take a shape suitable for various uses, such as a bead shape, a fiber shape, a film shape, a plate shape, or a barta shape.
- the gel force of the outer layer is obtained by gelling the liquid medium of the inner layer.
- the inner layer has a nano force in which the gel of the outer layer wraps the micro-sized carbon-dispersed liquid medium, an inconvenient liquid can be treated in the same manner as a solid.
- the inner layer is a nano-sized micro-sized carbon-dispersed liquid medium, so it has high affinity especially for liquid medium and exhibits high adsorption performance when adsorbing substances. When it is obtained, it has an effect.
- the shape in addition to the effect of the preferred embodiment (A-6), the shape is a film shape, a plate shape, or a barta shape.
- the preferred embodiment (A-10) is a dry gel, which is excellent in air permeability, and in which the nano- to micro-sized carbon having an extremely small particle size is uniformly dispersed in the network structure of the dry gel. Therefore, there is an effect that a substance contained in a gas such as air can be adsorbed with extremely high efficiency.
- the object constituting the fine carbon dispersion is composed of a material capable of releasing fine carbon under predetermined conditions.
- the fine carbon is separated from the object, so that the fine carbon is dispersed in the liquid medium.
- the product in which the fine carbon is uniformly dispersed can be manufactured by dissolving the raw material monomer and the raw material polymer of the product and performing polymerization, solvent removal, and the like.
- it is difficult to disperse the fine carbon with an initial force and in such a case, it is extremely useful as a material for dispersing the fine carbon in the liquid medium.
- the crosslinkable component contained in the nano- to micro-sized fine carbon-dispersed liquid medium or its dried product is cross-linked, the properties of a gel having excellent permeability can be enjoyed.
- the nano-sized micro carbon having an extremely small particle diameter has an effect that a micro carbon dispersion existing in the network structure of the gel can be manufactured with extremely high uniformity.
- the present invention (14) has the effect of the above-mentioned invention (13) and further comprises a dispersant dissolved in a liquid medium. Since the gelling is performed, a more uniform network structure is formed, and carbon having an extremely small particle size is included in the network structure. As a result, a gel or a dried gel having higher adsorption performance can be obtained. In addition to this, it is not necessary to add another gelling material separately, so that it is excellent in cost performance!
- the present invention exhibits the above-mentioned effects by a very simple method, which comprises adding a nano-sized micro-sized carbon dispersed liquid medium to a liquid medium containing a gelling agent of the medium. It has a double structure of an inner layer and an outer layer, wherein the inner layer is the carbon-dispersed liquid medium, and the outer layer is a gel-like product of the carbon-dispersed liquid medium.
- the effect is that a fibrous gel or a dried gel thereof can be obtained.
- by changing the addition method such as dropping or flowing down, there is also an effect that a gel or a dried gel having various shapes and sizes according to the application can be easily obtained.
- a carbon dispersion liquid medium of nano to micro size is added to a liquid medium containing a gelling agent for the medium. It has a double structure of an inner layer and an outer layer, in which the inner layer is the carbon-dispersed liquid medium, and the outer layer contains carbon of the nanocapsule size, which is a gel of the carbon-dispersed liquid medium.
- This is advantageous in that a bead-like or fiber-like gel or a dried gel thereof can be obtained.
- the addition method such as dropping or flowing down, there is also an effect that a gel or a dried gel having various shapes and sizes depending on the application can be easily obtained.
- the preferred embodiment (B-2) is a solution or suspension of the carbon-dispersed liquid medium as the raw material, the carbon is further reduced in the network structure of the obtained gel in the network structure. It is understood that the gel exists in a state, and as a result, there is an effect that a gel or a dried gel having higher adsorptivity can be obtained.
- the dispersant dissolved in the liquid medium is gelled, a more uniform network structure is formed, and the particle size in the network structure is extremely small. carbon Is contained, and as a result, it is possible to obtain a gel or a dried gel having higher adsorption performance, and it is not necessary to separately add another gelling material, so that there is also an effect that the cost performance is excellent. .
- the preferred embodiment (B-4) uses a crosslinkable surfactant, a gel capable of holding the carbon at its hydrophobic site and holding a solvent (hydrophilic solvent) at its hydrophilic site. This has the effect of being able to obtain
- the preferred embodiment (B-5) is used for various applications such as carbon nanotubes (single-wall / multi-wall type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, and microcarbon filter. This has the effect of obtaining gels or dry gels containing various suitable forms of nano- to micro-sized carbon.
- a gel or a dry gel having excellent permeability and gas permeability in which nano- to micro-sized carbon having an extremely small particle size is present in a network structure with extremely high uniformity, is used. It can be obtained by a very simple operation, and also has the effect that the gel or dried gel can be formed into a shape (film, plate, or barta) according to the application.
- the liquid medium in the carbon-dispersed liquid medium is volatilized before the gelation step, and the gelling agent is applied in a form in which the gelling agent is present in the liquid medium.
- the dried product absorbs the liquid medium, and as a result, an effect is obtained that a gel is formed uniformly in a short time.
- the dispersing agent dissolved in the liquid medium is gelled, a more uniform network structure is formed, and the particle size in the network structure is extremely small. Carbon is included, and as a result, a gel or a dried gel having higher adsorption performance can be obtained, and it is not necessary to separately add another gelling material, so that the cost performance is also excellent. Play.
- the preferred embodiment (B-9) uses a crosslinkable surfactant, a gel capable of holding the carbon at its hydrophobic site and holding a solvent (hydrophilic solvent) at its hydrophilic site. This has the effect of obtaining
- the preferred embodiment (B-10) is suitable for various uses such as carbon nanotube (single-wall / multi-wall type, cup-stack type), carbon nanofiber, carbon nanohorn, graphite, fullerene, carbon microhorn, and microcarbon filter.
- carbon nanotube single-wall / multi-wall type, cup-stack type
- carbon nanofiber carbon nanohorn
- graphite fullerene
- carbon microhorn and microcarbon filter.
- gels or dry gels containing various forms of nano to micro carbon can be obtained.
- a gel or a dried gel having excellent permeability and gas permeability, in which nano- to micro-sized carbon having an extremely small particle size is present in the network structure with extremely high uniformity since the gel can be obtained by a very simple operation and is manufactured using a mold, the gel or the dried gel can be formed into a shape suitable for the application.
- the preferred embodiment (B-12) has an effect that a circular plate-like gel, a polygonal plate-like gel, a spherical gel, a rectangular parallelepiped gel, or a dry gel thereof can be obtained by a simple operation.
- the raw material is a carbon-dispersed liquid medium solution or suspension
- the carbon is further reduced in the network structure of the obtained gel. It is understood that it exists in a state, and as a result, it is possible to obtain a gel or a dry gel having higher adsorptivity.
- the preferred embodiment (B-15) uses a crosslinkable surfactant, a gel capable of holding the carbon at its hydrophobic site and holding a solvent (hydrophilic solvent) at its hydrophilic site. This has the effect of being able to obtain
- Preferred embodiments (B-16) include carbon nanotubes (single-walled 'multi-layered type, cup-stacked type), carbon nanofibers, carbon nanohorns, graphite, fullerenes, and carbon micros. It is effective in that a gel or a dry gel containing carbon of nano to micro size in various forms suitable for various uses such as a horn and a micro carbon filter can be obtained.
- the liquid medium is removed in a state where the raw material 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 material. It has the effect of being able to do it.
- the present invention (21) has an effect that a pollutant in a liquid or gas can be adsorbed by utilizing its high adsorptivity, and the influence of the substance on the human body is suppressed. .
- the present invention (22) is directed to an industrial water / drinking water filtration apparatus, a pure water apparatus, various chromatographies, an adsorption of carcinogens and other human harmful substances, an air purifier, and an exhaust gas purification apparatus.
- adsorbents eg, activated carbon
- it has a much higher adsorptive capacity than existing adsorbents (eg, activated carbon) in this application, and thus has the effect of removing target harmful substances more than expected.
- nano- to micro-sized carbon having electrical conductor's semiconductor properties is used, it is effective when used as a special electronic material that requires adsorptivity.
- the present invention is excellent not only in adsorptivity but also in permeability and air permeability, and is therefore useful for electronic materials that require these properties.
- the carbon when nano- to micro-sized carbon having a conductor's semiconductor property is applied to an article, the carbon inherently exhibits the conductivity of the answer originally or completely. This is an epoch-making point in that the important problem that cannot be achieved is solved for the first time by making the carbon exist in a dispersed state. That is, although the reason is not clear, the present inventor has newly found that the existence of the carbon, which had conventionally existed in a lump, in a dispersed state has a remarkable effect of improving the conductivity.
- the present invention (24) includes an adsorptive material having the above-mentioned effects, and therefore can adsorb the target substance more efficiently than a conventional adsorptive material (for example, activated carbon), and improve the performance of each device or device. It has the effect of increasing. Further, since the electric product or the like contains the conductive material having the above-mentioned effect, it has an effect of being able to enjoy characteristics such as excellent conductivity and mechanical strength based on the presence of the carbon.
- a conventional adsorptive material for example, activated carbon
- the object constituting the fine carbon dispersion since the object constituting the fine carbon dispersion also has a material force for releasing the fine carbon under predetermined conditions, the material is contained in the final article. When the presence of the material is inconvenient, the material can be prevented from being included in the final product. Furthermore, it is difficult to disperse fine carbon from the beginning with respect to a certain liquid medium, and in such a case, it is extremely useful as a material for dispersing fine carbon in the liquid medium.
- aramide fibers excellent in heat resistance and strength, in which fine carbon is uniformly dispersed in the fibers, can be produced.
- carbon nanotubes which are particularly useful among the fine carbons, are dispersed in a non-aqueous solvent.
- aqueous solvent When the use of an aqueous solvent is indispensable, it is extremely useful when dispersing the carbon nanotubes in the target object.
- carbon nanotubes which are particularly useful among the fine carbons, are dispersed in an aqueous solvent, so that they can be used in a process for producing an object.
- an aqueous solvent is indispensable, the carbon nanotube is extremely useful when dispersing the carbon nanotubes in the target object.
- the minute carbons in the bundle state are peeled off from each other by the electric attractive force, so that an effect that a higher dispersion state can be ensured can be obtained.
- the fine carbon dispersion according to the first best mode will be described first taking an example of an application relating to an adsorbent for harmful substances in water.
- the solvent in the gel be water.
- carbon nanotubes (CNT) are used as nano- to micro-sized carbon. Under this assumption, the best mode will be described for each component of the present best mode.
- a suitable dispersant for dissolving CNTs is a surfactant (solubiliser).
- the surfactant is a surfactant capable of forming spherical micelles having a diameter of 50 to 2000 nm in an aqueous CNT solution (micelle type).
- Z or a water-soluble polymer having a weight average molecular weight of 10,000 to 50 million pseudo micelle type.
- the pseudo micelle type is also included in the concept of “surfactant” in this specification.
- surfactant refers to a surfactant capable of forming spherical micelles having a diameter of 50 to 2000 nm (preferably 50 to 300 nm) in an aqueous solution.
- spherical micelles (vesicles) of this size are suitable is not clear, but at present, it is speculated that the reasons may be as follows.
- carbon nanotubes their length is usually in the range of 100-1 OOO nm.
- the carbon nanotube is folded to a length of about one-fourth (for example, about one-fourth). It will be the length of one hundred years.
- spherical micelles are micelles formed by a surfactant and have a spherical storage space.
- the endoplasmic reticulum is called a ribosome.
- the diameter of the spherical micelles (vesicles) refers to the value measured according to the light scattering method (20 ° C. pH-unadjusted aqueous solution).
- the type of the surfactant is not particularly limited as long as it has the above-mentioned properties.
- both 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. 13 (A), a zwitterionic surfactant is attached to the CNT. Then, as shown in Fig. 13 (B), the zwitterionic surfactant afon attached to CNT and the cationic force attached to another CNT.
- the cations and aions of the zwitterionic surfactant are attracted to each other by an attractive force (double force), so that the CNTs are pulled, resulting in an unbundled state separated from the bundle state one by one.
- double force double force
- an amphoteric surfactant having an a-on and a cation in one molecule as a dispersant has been described as an example, but a CNT solution containing an a-on surfactant ( The unbundled state can also be formed by mixing the first liquid) and the CNT liquid (second liquid) to which the cationic surfactant has been added, based on the electric attraction.
- phospholipid surfactant refers to an anionic surfactant or a zwitterionic surfactant having a phosphate group as a functional group, and is a phospholipid (glycemic phospholipid, sphingoline). Both lipids (including both lipids) and modified phospholipids (eg, hydrogenated phospholipids, lysophospholipids, enzyme-modified phospholipids, lysophosphatidylglycerol, and complexes with other substances) may be used.
- modified phospholipids eg, hydrogenated phospholipids, lysophospholipids, enzyme-modified phospholipids, lysophosphatidylglycerol, and complexes with other substances
- Such phospholipids are present in various membrane systems of cells constituting living organisms, such as plasma membrane, nuclear membrane, endoplasmic reticulum membrane, mitochondrial membrane, Golgi membrane, lysosomal membrane, chloroplast membrane, and bacterial cell membrane.
- phospholipids used for the preparation of ribosomes are suitable.
- phosphatidylcholine for example, distearoyl phosphatidylcholine (DSPC), dimyristoyl phosphatidylcholine (DMPC), dipalmitrile phosphatidylcholine (DPPC) ⁇ , phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylglycerol, Examples include phosphatidylglycerol, lysophosphatidylcholine, and sphingomyelin.
- non-phospholipid surfactant refers to a non-phospholipid surfactant which does not contain a phosphate group as a functional group! / ⁇
- Non-ionic surfactant / Zwitterionic surfactant —Cholamidopropyl) dimethylamino] —2-Hydroxy-1-propanesulfonic acid (CHAPSO), 3-[(3-Cholamidopropyl) dimethylamino] -propanesulfonic acid (CHAP) and N, N-bis (3-D —Gluconamide propyl) monocollamide.
- amphoteric surfactant is given for reference.
- the following table shows the quaternary ammonium base Z sulfonic acid group type, quaternary ammonium base Z phosphate group (soluble in water), quaternary ammonium base Z phosphate group type ( (Insoluble in water), quaternary ammonium base Z-force Shows the name and source of the ropoxyl group type.
- the "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).
- the weight average molecular weight is based on a value measured by gel filtration high performance liquid chromatography using pullulan as a standard.
- the above-mentioned water-soluble polymer is not particularly limited as long as it has the above-mentioned molecular weight.
- various vegetable surfactants water-soluble polysaccharides, for example, alginic acids, for example, alginic acid, propylene Glycol alginate, arabic gum, xanthan gum, hyaluronic acid, chondroitin sulfate, water-soluble celluloses such as cellulose acetate, hydric xymethinoresenololose, methinoresenololose, hydroxypropinolemethinoresenololose, chitosan, chitin Water-soluble proteins such as gelatin and collagen; polyoxyethylene 'polyoxypropylene block polymers; and compounds whose DNA power is also selected.
- alginic acids and water-soluble celluloses are a derivative thereof (for example, salts, esters, ethers) which shares a basic skeleton with alginic acid cellulose and exhibits water solubility. ).
- the content of the surfactant in the aqueous solution in the case of the micelle type, the content of the surfactant must be equal to or higher than the critical micelle concentration for forming vesicles. Usually, from 0.2 to: LO mmol per liter of aqueous solution for the crude product lg.
- the content of the water-soluble polymer is not particularly limited, but is usually 5 to 50 g per liter of the aqueous solution for the crude product lg.
- the nanocarbon for example, carbon nanotubes
- the nanocarbon is completely dissolved with ultrasonic waves for about 5 minutes in order to completely dissolve it. After that, it is completely dissolved in about 6 hours at room temperature and about several minutes when heated to 60 ° C.
- a homogenizer may be used to form 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 the like. After thoroughly diffusing and dispersing the mixture containing deionized water, leave it at 40 ° C for about one day. When a permeating agent or an oxidizing agent is not used, it is allowed to stand at 40 ° C. for about one week, for example.
- the activator has a crosslinking group.
- alginic acids have a carboxylic acid group in the molecule, and the carboxylic acid group crosslinks by forming a chelate structure with a polyvalent cation to form a gel.
- the polyvalent cation means a divalent or higher cation, preferably a divalent or higher metal ion, more preferably a divalent metal ion, for example, a norium ion or a calcium ion.
- an aqueous solution containing polyvalent cations for example, norium ion
- an aqueous solution of alginic acids for example, sodium alginate
- the first form is a bead-like or fiber-like gel using alginic acid as a surfactant (+ Geri-dori material).
- the second form is a film-like gel using methylcellulose as a surfactant (+ Gellyfish material).
- the first mode has a double structure of an inner layer and an outer layer, wherein the inner layer is an aqueous solution of carbon nanotubes, and the outer layer is a hydrogel in which a carbon nanotube is included in a network structure. It is a fibrous gel.
- the best mode will be described in detail.
- the aqueous solution of carbon nanotubes present in the inner layer contains carbon nanotubes and a surfactant as a dispersant thereof.
- a surfactant as a dispersant thereof.
- the carbon nanotubes that can be used in the present best mode are not particularly limited, and any synthesis method, for example, an electric discharge method (C. Journet et al., Nature 388, 756 (1997) and DS Bethune et al. Nature 363, 605 (1993), laser vapor deposition (RESmally et al, Science 273, 483 (1996)), gas phase synthesis (R. Andrews et al "Chem. Phys. Lett., 303,468, 1999), thermochemistry Vapor deposition (WZ ⁇ i et al., Science, 274, 1701 (1996), Shinohara et al., Jpn. J. Appl. Phys. 37, 1257 (1998)), and plasma chemical vapor deposition (ZFRen et al., Science. 282, 1105 (1998)).
- an electric discharge method C. Journet et al., Nature 388, 756 (1997) and DS Bethune et al. Nature 363, 605 (1993
- a crude product using a metal catalyst in the synthesis is treated with an acid to remove the metal catalyst.
- an acid treatment for example, as described in JP-A-2001-26410, a nitric acid solution or a hydrochloric acid solution is used as the acid aqueous solution.
- the nitric acid solution is a 50-fold diluted solution of water, and the hydrochloric acid solution is 50 times.
- An example is a technique using a solution diluted in double water. Then, after the acid treatment as described above, the resultant is washed and filtered to obtain a carbon nanotube aqueous solution.
- Surfactants that can be used in the present embodiment are the above micelle type and pseudo micelle type, and particularly preferable ones are alginic acids.
- the preferred content of alginic acids in the aqueous solution is not particularly limited, but is usually 5 to 50 g per liter of the aqueous solution for the crude product lg.
- the aqueous solution of carbon nanotubes usable in the present embodiment initially contains a carbon nanotube-permeable substance and an oxidizing agent, and is in the form of an alkaline aqueous solution.
- “initially” means that these components and states are not essential when finally becoming beads or fibers. That is, these components and states are adjusted to remove unnecessary components existing in the system when the above crude product is used as a carbon nanotube source.
- these components and states are adjusted to remove unnecessary components existing in the system when the above crude product is used as a carbon nanotube source.
- a “nanocarbon-permeable substance” means a substance having a diameter smaller than the CC lattice size of carbon nanotubes.
- a nanotube-permeable cation having such a diameter (ion diameter) specifically, a lithium ion can be mentioned.
- hydrogen ions although smaller than the lattice size, are deprived of water in the form of oxo-pum ions, making them unsuitable as carbon nanotube-permeable cations.
- the role of the carbon nanotube-permeable substance has not been elucidated at present, for example, in the case of a carbon nanotube-permeable cation, the charge state inside the carbon nanotube is changed by penetrating the carbon nanotube. It is presumed to play a role in pushing out impurities inside and inside the carbon nanotube.
- the content of the nanotube-permeable substance is preferably 0.1 to: Lmol per liter of the aqueous solution for the carbon nanotube crude product lg.
- the oxidizing agent that can be used is not particularly limited, but is preferably a persulfate (persulfate ion in the liquid).
- the reason is that the persulfate is alkaline and has a high activity and, after acidification, becomes sulfuric acid itself, so that post-treatment is easy.
- the pH is preferably in the range 6-14 (preferably alkaline). It is not clear why the liquid is preferably in this range, but it is necessary to change the electronic state of the surface of the nanocarbon, and in the case of carbon nanotubes, the surface of the carbon is softened and the carbon nanotube is strengthened. It is presumed that it plays the role of folding.
- the range is preferably 10 to 14, and in the case of the pseudo micelle type, the range is preferably 6 to 12.
- Alginic acid a solubilizing agent for carbon nanotubes
- the liquidity is preferably alkaline.
- metals and other impurities that are residues in the production of carbon nanotubes, and a carbon nanotube-permeable substance, an oxidizing agent, and a reduced product of the oxidizing agent for removing these are removed.
- the above components and the like may remain in the final product, that is, the aqueous solution of carbon nanotubes in a bead-like or fiber-like gel, because they may remain or the pH may be alkaline. It may remain and the pH may be alkaline.
- an outer layer a hydrated gel in which a carbon nanotube is included in a network structure.
- the network structure is not particularly limited as long as the carbon nanotubes are included in the water.However, from the viewpoint of ease of production and affinity with the aqueous solution of carbon nanotubes in the inner layer, the solubilizer of the aqueous solution of carbon nanotubes in the inner layer is crosslinked. It is preferred that they are.
- a specific preferred example is a crosslinked product of alginic acid.
- the bridge is preferably a chelate crosslink, and examples of the crosslinker for the chelate crosslink include polyvalent cations (for example, norium ions and calcium ions).
- the hide opening gel of the outer layer contains carbon nanotubes.
- the nodule gel is excellent in permeability.
- the bead-shaped gel according to the best mode is used as an adsorbent, The substance existing in the inner layer penetrates into the inside (inner layer) and is adsorbed by the carbon nanotubes in the inner layer due to the above-mentioned property of the hide mouth gel.
- the above-mentioned beaded'fibrous gel having a two-layer structure can be produced by the following procedure.
- a gelling agent a divalent metal ion, for example, a barium ion
- the gelling agent is set at a concentration sufficient to crosslink all the crosslinking groups of the arginic acid used.
- the above-mentioned aqueous solution of carbon nanotubes is dropped or allowed to flow into the aqueous solution of the gelling agent using, for example, a dropping device or a syringe used for producing a drug.
- the portion of the aqueous solution of carbon nanotubes that has come into contact with the aqueous solution of the gelling agent immediately undergoes a cross-linking reaction and undergoes gelling, whereby a bead-like or fiber-like gel containing the aqueous solution of carbon nanotubes that has not contacted is obtained.
- the second embodiment is a dried film gel (a dried gel, a resin, a dried sheet) in which carbon nanotubes are included in a network structure.
- a dried film gel a dried gel, a resin, a dried sheet
- carbon nanotubes are included in a network structure.
- usable carbon nanotubes and the like are the same as those in the first embodiment, and a description of overlapping parts will be omitted.
- the pseudo micelle type surfactant constituting the film gel is preferably a water-soluble cellulose, for example, a hydrogel.
- Xymethylcellulose and methylcellulose are preferred.
- the crosslinking is preferably chelate crosslinking or hydrogen bond crosslinking.
- a polyvalent cation for example, norion ion is suitable as the crosslinking agent.
- the dried gel of the present embodiment is obtained by drying the gel.
- the degree of drying is not limited, but for example, when used for an air filter, a lower solvent content is preferred.
- the thickness varies depending on the application, In the case of the above-mentioned application, it is typically about 0.1 to 3 mm.
- the above film-shaped dry gel can be produced by the following procedure. First, the gelled material
- aqueous solution containing a gelling agent (divalent metal ion, for example, barium ion) for (methylcellulose) is prepared.
- the concentration of the gelling agent is set, for example, to a concentration sufficient to allow all the crosslinking groups of the methylcellulose to be used to crosslink.
- a carbon nanotube solution containing methylcellulose is applied on a plate, and formed into a film by a coater, and then the film solution is dried.
- the aqueous solution of the gelling agent is evenly applied to the dried film, the dried product absorbs the aqueous solution and simultaneously undergoes a cross-linking reaction to obtain a methylcellulose hydrate mouth gel containing the carbon nanotubes.
- the gel is dried by a known method to obtain the above-mentioned film-shaped dry gel.
- a carbon nanotube dispersion liquid for producing a composite material in which carbon nanotubes are uniformly dispersed (hereinafter, referred to as a “dispersion liquid for producing a composite material”) will be described first. New liquids will be described in detail. Next, a method of using the dispersion for producing a 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.
- CNTs that can be used are not particularly limited.
- V such a synthesis method, for example, 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 It may be produced by the method (ZFRen et al., Science. 282, 1105 (1998)) or the like.
- a nitric acid solution or a hydrochloric acid solution is used as the acid aqueous solution.
- a method in which a nitric acid solution is diluted 50 times with water, and a hydrochloric acid solution is also diluted 50 times with water. can be mentioned.
- non-aqueous liquid media include aliphatic or aromatic hydrocarbons, for example, aliphatic or aromatic hydrocarbons having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, octane, Examples thereof include nonane, decane, dodecane, isooctane, benzene, toluene, xylene, cyclopentane, cyclohexane, and methylcyclopentane.
- a mixture of two or more kinds may be used.
- the aqueous liquid medium includes water, a water-miscible organic solvent, or a mixed solvent thereof.
- water-miscible organic solvent include alcohols, ethers, esters, ketones, and various carbon compounds, for example, methanol, ethanol, propanol, dioxane, dimethylformamide, acetone, methylethylketone, and methyl acetate.
- a suitable CNT dispersant is fullerene.
- a structure in which fullerene is sandwiched between the openings of two CNTs has been confirmed.
- the added amount of fullerene is 15 to 30% based on the total weight of CNT to be added.
- the first suitable CNT dispersant is a surfactant or a weight-average surfactant capable of forming spherical micelles having a diameter of 50 to 2,000 in the liquid medium. It is a water-soluble polymer with a molecular weight of 10,000 to 50 million.
- spherical micelles (vesicles) of this size are suitable is not clear, but at present, it is speculated that the reasons may be as follows. For example, in the case of CNT, its length is usually in the range of 100 to 1000 nm.
- the CNTs are folded to a length of about a few (for example, about a quarter), and as a result, in the solution, several tens of ⁇ ! ⁇ Several hundred ohms long. It is understood that the above-mentioned size is probably good for storing the folded CNT in the endoplasmic reticulum, so that the CNT can be efficiently dissolved.
- the type of the surfactant is not particularly limited as long as it has the above-mentioned properties. For example,! / ⁇ of a phospholipid surfactant and a non-phospholipid surfactant can be used.
- phospholipid surfactant refers to an anionic surfactant or a zwitterionic surfactant having a phosphate group as a functional group, and is a phospholipid (glycemic phospholipid, sphingoline). Both lipids (including both lipids) and modified phospholipids (eg, hydrogenated phospholipids, lysophospholipids, enzyme-modified phospholipids, lysophosphatidylglycerol, and complexes with other substances) may be used.
- modified phospholipids eg, hydrogenated phospholipids, lysophospholipids, enzyme-modified phospholipids, lysophosphatidylglycerol, and complexes with other substances
- Such phospholipids are present in various membrane systems of cells constituting living organisms, such as plasma membrane, nuclear membrane, endoplasmic reticulum membrane, mitochondrial membrane, Golgi membrane, lysosomal membrane, chloroplast membrane, and bacterial cell membrane.
- phospholipids used for the preparation of ribosomes are suitable.
- phosphatidylcholine for example, distearoyl phosphatidylcholine (DSPC), dimyristoyl phosphatidylcholine (DMPC), dipalmitrile phosphatidylcholine (DPPC) ⁇ , phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylglycerol, Examples include phosphatidylglycerol, lysophosphatidylcholine, and sphingomyelin.
- non-phospholipid surfactant refers to a nonionic surfactant containing no phosphate group as a functional group! / ⁇ a nonionic surfactant or a zwitterionic surfactant.
- CHAPSO 2-Hydroxy-1-propanesulfonic acid
- CHP 3-[(3-Cholamidopropyl) dimethylamino] -propanesulfonic acid
- water-soluble polymer examples include, for example, various vegetable surfactants, water-soluble polysaccharides, for example, alginic acids, for example, alginic acid, propylene glycol alginate, Arabian gum, xanthan gum, hyaluronic acid, chondroitin sulfate
- water-soluble celluloses for example, cellulose acetate, hydroxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, chitosan, chitin
- water-soluble proteins for example, gelatin, collagen; polyoxyethylene / polyoxypropylene block polymers; and DNA.
- alginic acids and water-soluble celluloses is a derivative of alginic acid-cellulose having a common basic skeleton and exhibiting water solubility (for example, , Salts, esters, ethers).
- the content of the surfactant in the aqueous solution in the case of the micelle type, the content of the surfactant must be equal to or higher than the critical micelle concentration for forming vesicles. Usually, from 0.2 to: LO mmol per liter of aqueous solution for the crude product lg.
- the content of the water-soluble polymer is not particularly limited, but is usually 5 to 50 g per liter of the aqueous solution for the crude product lg.
- the fusible conditions in the case of the micelle type, for example, first dissolve the ultrasonic waves for about 5 minutes in order to completely dissolve the CNTs.
- a homogenizer may be used to form 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 CNT.
- a permeating agent or an oxidizing agent is not used, it is allowed to stand at 40 ° C. for about one week, for example.
- alginic acids particularly preferred are alginic acids.
- the suitable content of alginic acids in the dispersion is not particularly limited, but is usually 5 to 50 g per liter of the aqueous solution for the crude product lg.
- the micelle type CNT dispersion liquid preferably further contains a CNT permeable substance and an oxidizing agent, and is preferably in the form of an alkaline aqueous solution.
- CNT-permeable substance means a substance having a diameter smaller than the C—C lattice size of CNT.
- a CNT-permeable cation having such a diameter (ion diameter) specifically, a lithium ion can be given.
- hydrogen ions are smaller than the lattice size, they are deprived of water in the form of oxo-ion, which is inappropriate as a CNT-permeable cation.
- the content of the CNT-permeable substance is preferably 0.1 to 1 mol per liter of the aqueous solution for CNT crude product lg.
- the oxidizing agent that can be used is not particularly limited, but a persulfate (persulfate ion in the liquid) is preferable.
- ⁇ is preferably in the range of 6 to 14 (preferably alkaline). It is not clear why the liquid is preferably in this range, but it is presumed that in addition to changing the electronic state of the CNT surface, it plays a role in softening the CNT surface and folding the CNT. In the case of micelle type, the range is preferably 10 to 14, and in the case of pseudo micelle type, the range is preferably 6 to 12. Power! ] And for another reason, it is important to keep the pH initially alkaline.
- Alginic acid a CNT dispersant
- Alginic acid a CNT dispersant
- the liquid property is preferably alkaline.
- the second suitable CNT dispersants are cyclodextrin and fullerene.
- the cyclodextrin that can be used may be an at-type, seven-type 13, or eight-gamma-type cyclodextrins having six dalcosid residues, or may be maltosyl cyclodextrin.
- a branched cyclodextrin such as dimethyl cyclodextrin, a modified cyclodextrin, a cyclodextrin polymer, or the like can be used.
- the mechanism by which the CNTs are soluble by these dispersants is that cyclodextrin firstly covers the hydrophobic fullerene, and then the fullerene (hydrophobic) on the surface of the clathrate becomes CNT (hydrophobic). It is considered that they bind based on affinity.
- the amount of cyclodextrin added is preferably 150 to 300% based on the total weight of CNT added, and the amount of added fullerene added to CNT is the total weight of CNT added. On the other hand, it is preferably 15 to 30%.
- the first method involves dispersing the raw material monomer of the composite material in the dispersion for producing a composite material, then polymerizing the raw material monomer by a well-known method (and possibly crosslinking), and finally, This is a method for removing a liquid medium. This method is suitable for producing a film or a shaped composite material.
- a second method is to disperse a raw material polymer in a dispersion for producing a composite material, and then prepare the liquid This is a method for removing the medium. This method is suitable for producing a composite material in the form of a film or a molded body.
- a third method is a method in which the raw material is immersed in the dispersion for producing a composite material, the raw material is unraveled, and then the liquid medium is removed.
- a method of unraveling the raw material for example, heat treatment or ultrasonic treatment can be mentioned. This method is suitable for producing a fibrous composite material.
- the composite material can be used for various purposes.
- an adsorption material can be mentioned.
- the substance to be adsorbed is not particularly limited, and may be any substance contained in a liquid or a gas.
- the contaminants and harmful substances include hydrogen chloride, vinyl chloride, sodium hydroxide, tetrachloroethylene (solvent), BDBPP compound (flameproofing agent), tributyltin compound (antibacterial and fungicide), Formaldehyde (resin processing agent), organic mercury diversion compound (antibacterial and fungicide), dieldrin (insect repellent), sulfuric acid (cleaning agent), DTTB (insect repellent), potassium hydroxide (cleaning agent) , Trichloride ethylene (solvent), APO (flame retardant), TDBPP, methanol (solvent), triphenyltin And the like.
- the adsorptivity for industrial water, drinking water filtration equipment, pure water equipment, various types of chromatography, adsorption equipment for human harmful substances such as carcinogens, air purification equipment, and exhaust gas purification equipment Useful as a material.
- various parts such as electronics field, electric products, mechanical parts, vehicles and the like can be mentioned.
- a material for a fuel cell separator can be mentioned as a preferred example.
- the CNT dispersion for article production is one in which CNTs are uniformly dispersed on the surface of an object.
- the target is not particularly limited as long as it is a material capable of releasing CNTs under predetermined conditions as described above.
- the object is added to the microcarbon-dispersed liquid medium.
- it can be manufactured by performing an induced phase transfer process in which the fine carbon is moved from the liquid medium side to the object side.
- the carbon nanofiber (CNF) according to this example was synthesized by the following procedure by using chemical vapor deposition (CVD) ⁇ N.M. Rodriguez, J. Mater. Res., 8, 3233 (1996) ⁇ . After the powdered Ni catalyst was placed on the Al O plate, the Ni ZAl O plate was placed in a horizontal tube furnace.
- CVD chemical vapor deposition
- FIG. 1 shows an SEM image (FIG. 1A) and a black image (FIG. 1B) of the obtained CNF.
- Sodium alginate according to this example (viscosity and pH of a 20 ° C. aqueous solution containing 20 mg / ml sodium alginate are 300-400 cP and 6.0-8.0, respectively) was obtained from Wako Chemical Industries (Osaka). Obtained. Sodium alginate (Na-ALG) was dissolved in deionized water to prepare an aqueous solution of Na-ALG. Add CNF to Na—ALG solution Thereafter, the mixture was sufficiently mixed by a combination of high shear mixing and sufficient sonication.
- 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 three-week observation period, sedimentation from this aqueous colloid solution was unrecognizable.
- aqueous solution containing 20 mg / ml sodium alginate as a dispersion solution, a highly uniform aqueous colloidal CNFZ alginate solution having a CNF concentration of about 1.0 mg / m could be obtained.
- the uniformity of the CNFZNa-ALG colloid aqueous solution was measured by calculating the linearity of the calibration curve of CNF in the CNFZNa-ALG colloid solution using UV-vis as a detection system. Characteristic absorption mainly derived from the CNF dispersion is observed in the wavelength range of 220 to 500 (Fig. 3).
- the linearity r 2 of the calibration curve of CNF in the aqueous CNFZNa-ALG colloid solution at 260 nm was found to be higher than 0.9998, indicating high uniformity of the CNFZNa-ALG colloid solution.
- the samples used to derive the calibration curve consisted of CNF of 0, 0.1, 0.2, 0.3, 0.3 with the concentration of Na-ALG in each sample fixed at 20 mg / ml. It was an aqueous solution of Na-ALG containing 4 and 0.5 mg / ml.
- Calculate CNF concentration with respect to sedimentation time by a method similar to that reported by Jiang et al. [L. Jiang, L. Gao, J. Sun, J. Colloid and Interface Sci "260, 89 (2003)]
- the stability of the CNF ZNa-ALG colloid was measured, and the change in the CNF concentration was found to be less than 0.4% even in a long-term measurement at room temperature for 3 weeks.
- CNFZNa-ALG The maximum ⁇ value of the Lloyd was found to be 58.03 mV, which also indicates the high stability (repulsion) of the CNFZNa-ALG colloid.
- the NF vs ⁇ plot of CNFZNa-ALG colloid ( Figure 4) and the ⁇ vs ⁇ plot of an aqueous solution containing only Na-ALG (20 mg / ml) are virtually identical, and the CNFZNa-ALG colloid zeta It indicated that the potential was determined by the alginate ion.
- Alginic acid is a linear, water-soluble 1,4-linked copolymer of 13-D-mannuronic acid (M) and aL-guluronic acid (G).
- M 13-D-mannuronic acid
- G aL-guluronic acid
- ⁇ and G are, as shown in FIG. 5, a homopolymer [poly (j8-D-mannosyl laurate), ⁇ - ⁇ - ⁇ )] and poly (a-L-glossyl lone, G-G-G). They can be arranged in blocks or in heteropolymer (M—G—M) blocks [NP Chandia, B. Matushiro, AEVasquez, Carbohydrate Polymers, 46, 81 (2001)].
- FT-IR spectra of alginate (reference sample) and CNFZ alginate complex were measured.
- Typical characteristic bands for alginic acid are (i) 1627 and 1419 cm- 1 (characteristic bands typical for carboxylic acids), (ii) 808 cm “ 1 (characteristic band for mannuronic acid) and Z or 787 cm- 1 (gluronic acid). Acid band), (iii) 940 cm “ 1 (character band of a 1 ⁇ 4 bond) and (iv) 904 cm” 1 (character band of a-L-glopyranuron ring) [NP Chandia, B.
- CNFZNa- ALG support The characteristic band of ⁇ 1 ⁇ 4 bond of alginate and the characteristic band of aL-glopyranurone ring were 947.84 and 890.95 cm- 1 in standard alginic acid sample, and 943 in CNF / Na alginate sample. 98 and 887.8 shift to 8cm- 1 respectively. These shifts in the characteristic bands of the CNFZNa-ALG sample are an indication that alginic acid is interacting with CNF. On the other hand, CNFZNa-ALG characteristic bands of Man'nuro phosphate sample is shifted to 811. 88cm- 1 Power et al. 814. 77 cm- 1 in the reference alginate sample.
- HF normal human fibroblasts
- D-MEM Dulbecco's Modified Eagle Minimum Essential Medium
- FBS Fetal Fetal Serum
- CNF1 CNFZNa-ALG colloid aqueous solution containing Omg / ml and Na-ALG 20 mg / ml was reduced to 1/10, 1/100 and 1/1000 with D-MEM containing 5% FBS and 50 ⁇ g / ml kanamycin. Diluted.
- an aqueous solution containing only Na-ALG (20 mg / ml) (control medium) was diluted to the same extent in the same medium as in the case of CNFZNa-ALG. 2 x 3 1 HF in a 96 multiwell plate.
- the cells were inoculated in a Z-well and maintained at 37 ° C. for 3 days in 200 1 D-MEM containing 10% FBS and 50 g / ml kanamycin.
- the medium containing CNFZNa-ALG or control medium was changed and HF was further incubated at 37 ° C for 1-7 days. After incubation, cell proliferation was assessed by the MTS assay.
- the medium was replaced with 100 ⁇ l Eagle's minimum essential medium (without phenolic red) containing 333 ⁇ g / ml MTS and 25 ⁇ phenazine methosulfate solution. After incubation at 37 ° C for 2 hours, the absorbance at 485 nm of each well was measured. Cell proliferation was calculated from the value of A two hours after MTS treatment.
- the relative cell growth rate (RCG,%) was calculated by dividing the mean of the isolated cells by the mean of untreated cells (cultured in 5% FBS). In medium containing CNF and Z or Na-ALG The RCG of the incubated cells was 100% ⁇ 5% one and two days after administration. Even 7 days after dosing, RCG was over 85%.
- 8-week-old Os Jcl SD rats were purchased from Clea Japan. The rats were 6 days apart and acclimated. One animal was used without administration and the other rat was given a single oral dose using a gastric tube. Dose values were 10 mg CNF and 20 mg Na-ALG per kg body weight. Macroscopic observations and body weights were recorded weekly. At the end of the observation, the rats were starved for 16 hours, anesthetized, and blood and serum samples were collected. Necropsy was also performed to observe changes in the glandular stomach. One to two weeks after dosing, leukocyte (WBC) power increased from 5100 in untreated rats to 7700 and 8100 in rats given vehicle control! /.
- WBC leukocyte
- Ba 21 alginic acid-coated vesicles containing highly dispersed CNF were manufactured by ffi.
- Encapsulator Research IER-20 was purchased from InoTech. (I) an aqueous solution containing only sodium alginate at 20 mg / ml, (ii) an aqueous solution containing 0.5 mg / ml of CNF highly dispersed in an ALG solution, and (iii) an aqueous solution containing 0.5 mg / ml of CNF.
- aqueous solution containing 0.5 mg / ml of CNF (mixed by sonication for 5 minutes) easily dispersed in the ALG solution, and prepare standard vesicles (without CNF) and small solutions containing highly dispersed CNF, respectively. Vesicles and vesicles containing low dispersed CNF were used. Dissolve BaCl in deionized water and add lOOmM A gelatinization solution (also known as a hardening solution) was prepared by adjusting the concentration. Using this encapsulation technique, vesicles of adjustable size were obtained in production.
- Vesicles having a diameter range of 400 to 800 micrometers were obtained by activating electrostatic charge tension at 1100 V and a vibration frequency of 900 Hz using a nozzle having a diameter of 300 micrometers.
- Figure 7 shows a typical microscopic observation of vesicles containing highly dispersed CNF. Using this encapsulation method, kilogram vesicles can be produced in a matter of hours.
- Ba 2+ ion is a stronger gelatinized ion than Ca 2+ ion [P. Grohn, Exp. Clin. Endocrinol, 102, 380 (1994)] and was used throughout this study.
- Ba 2+ —alginate-coated CNF vesicles are chemically and mechanically stable and are much heavier than water (easy to separate from the aqueous phase).
- CNF / Ba 21 alginate vesicles as adsorbent for removal of ethidium ions from aqueous solution
- Figure 9 shows the change in the concentration of ethidium ion in aqueous solution as a function of contact time (15 ml of 30 ⁇ m bromide solution of aqueous bromide mixed with 10 ml of highly dispersed CNF-containing vesicles). As the contact time increased, the concentration of ethidium ion in the aqueous solution decreased rapidly. Approximately 8 minutes after the solution was mixed with CNFZBa 2+ -alginate vesicles, it reached 0 and remained unchanged.
- MWCNTs multi-walled carbon nanotubes
- the methods for preparing aqueous MWCNTZNa-ALG colloids, MWCNTZBa2 + -alginate vesicles, and for testing the ability to remove ethidium ions were the same as for CNF.
- the ability to adsorb ethidium ions is 0.42 for 10 ml of MWCNTZBa 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 ⁇ mol / ml. This ability is in fact substantially the same as that of CNF / Ba 2+ —ALG vesicles.
- Na-ALG sodium alginate
- MWCNT CVD product: outer diameter 15 nm ⁇ 5 nm, length 1-5 / ⁇ , purity> 90%, published by the manufacturer
- Na-ALG was dissolved in deionized water to produce a 15 mg / ml aqueous solution of Na-ALG.
- MWCNT was dispersed in this aqueous solution of Na-ALG at a concentration of 1. Omg / ml by a combination of high shear mixing and ultrasonic treatment.
- a semi-automated instrument IER-20® system (Inotech, Dottikon, Switzerland) was used for encapsulation of MWCNTs to form microbeads coated with Ba 2+ -alginic acid.
- the IER_20® system consisted of an injector, an injector pump, a pulsatile chamber, a vibrating system, a nozzle, an electrode, an ultrasonic vibrating system, as well as an electrostatic supply system and an O-ring type electrode car.
- An aqueous Na-ALGZMWCNT colloid was pumped into the pulsatile chamber using an injector pump.
- this colloid aqueous solution was passed through a precision-perforated sapphire nozzle (nozzle diameter: 300 ⁇ m) to separate into small droplets such as 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 carry an electrostatic charge. Droplets are cured solution When dropped into a bridging agent-containing solution), ie, an aqueous barium chloride solution (Ba 2+ ion lOOmM), the electrostatic repulsion force dispersed the droplets.
- a bridging agent-containing solution ie, an aqueous barium chloride solution (Ba 2+ ion lOOmM)
- FIG. 10 shows typical microscopic observation results of Ba 2+ —ALG / MWCNT composite beads. Beads with diameters ranging from 400 to 900 micrometers have been produced.
- the size of the beads can be adjusted by changing the ultrasonic vibration frequency, electrostatic charge tension, nozzle diameter and the flow rate of the aqueous Na-ALGZMWCNT colloid solution.
- kilogram quantities of Ba 2+ —ALG / MWCNT composite beads can be produced in a matter of hours.
- Ba 2+ ions are more aggregating ions than Ca 2+ ions [P.Grohn, Exp. Clin. Endocrinol, 1994, 102, 380], and were therefore used as curable ions in this study. .
- Ba 2+ — ALG / MWCNT composite microphone mouth beads are chemically and mechanically stable and are much heavier than water. Therefore, it is easy to separate from the aqueous phase.
- the target species, DD, DF and BP were extracted from 50 ml of effluent with 10 ml of hexane.
- the hexane phase was separated by aqueous phase separation, reduced to 1. Oml, and analyzed by GC-MS (Shimadzu GC-MS-QP5050A).
- Aqueous solutions containing 2.0 M of each model compound were prepared by diluting stock solutions of DD, DF and BP (2.0 mM each, dissolved in methanol) with deionized water.
- the concentration of DD, DF, and BP in the effluent after once passing through the column was 0.014 ⁇ M, 0.015 ⁇ M, and 0.018 ⁇ M, respectively. And remove this effluent again.
- these modeled conjugates were no longer detected and the concentration had fallen below the detectability of the GC-MS system.
- the modeled conjugate was eluted with 40 ml of hexane using column force. The hexane phase was separated by aqueous phase separation and analyzed directly using the same GC-MS analytical conditions.
- FIG. 11 shows a typical total ion chromatogram (TIC) and a mass spectrum corresponding to each peak.
- TIC total ion chromatogram
- the hexagonal arrangement of carbon atoms in the durafin sheet of the MWCNT interacts strongly with the aromatic bonds of the modeled conjugate.
- the target species, DD, DF and BP were efficiently removed by the Ba 2+ -alginate / MWCNT composite adsorbent MWCNT. Power!
- the Ba 2+ -alginate / MWCNT composite adsorbent can also be reused by regenerating the beads with hexane.
- Single-walled carbon nanotubes (SWCNT, manufactured by Nano Lab) 100mg, surfactant (N —Octadecyl- ⁇ , ⁇ '-dimethyl—3-amino-1-propanesulfonate, Zwitter—3—18, manufactured by Fluka 1.
- SWCNT Single-walled carbon nanotubes
- surfactant N —Octadecyl- ⁇ , ⁇ '-dimethyl—3-amino-1-propanesulfonate, Zwitter—3—18, manufactured by Fluka 1.
- 14 to 16 show the concentration strength of SWCNTs produced according to this production example of 0.25, 0.25 / 10, 0.25 / 30 mg / ml (AFM photograph (Molecular Imaging Co., Ltd.)). (Scanning microscope, Yamato Scientific Co., Ltd.) From these photographs, it can be seen that the dispersant according to the present production example has extremely high dispersibility.
- Single-walled carbon nanotubes SWCNT, manufactured by Nano Lab 100mg, surfactant (N-octadecyl- ⁇ , ⁇ '-dimethyl-3-amino-1-propanesulfonate, Zwitter-3-18, manufactured by Fluka) 1.68g and A mixture of 5 mL of glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) was ground and mixed for about 2 hours using a mortar, and then 0.6 g Nal (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by further 30 minutes of polishing. Then, polysulfone (Aldrich, MO 26000) lg was dissolved. After adding 50 ml of Chillup's lidone solution, the mixture was polished using a mortar for about 2 hours, and then centrifuged to remove insoluble components.
- surfactant N-octadecyl- ⁇ , ⁇ '-dimethyl-3-amino-1-propa
- SWCNTZ ultrafine fiber obtained in Production Example 8 was mixed with 500 mL of 3.OmM CaHPO
- the mixture was treated at ° C to produce a nodal apatite fused with SWCNT.
- the CNT dispersion obtained in Production Example 6 was cast on a Teflon plate, and 1-methyl-2-pyrrolidone was slowly removed to prepare a dialysis membrane in which carbon nanotubes were dispersed.
- Production Example 12 Production example of CNT-dispersed heat-resistant filter using CNT dispersion liquid
- the dispersion obtained in Production Example 1 was dropped onto a commercially available aluminum filter (anodisk membrane, 20 to 500 nanometer-wide porous), and sandwiched with another aluminum-film filter. Thereafter, the substrate was sufficiently washed with 10% ethanol Z water and 5% hydrogen peroxide solution. After that, heat bonding was performed to produce a heat-resistant nanofilter using carbon nanotubes as the adsorption side.
- Example 1 CNT dispersion using CNT dispersion Lightning filter ⁇ B ⁇ line
- Sodium alginate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 50 ml of the dispersion obtained in Production Example 1 so as to have a concentration of 1.2% by weight, then cast and dried at room temperature to obtain a film.
- a film-like gel was obtained by adding a 1 M aqueous solution of silver nitrate to the film.
- the gel was reduced with 1 M ascorbic acid to obtain SWCNT-dispersed film silver.
- a conductivity test was performed on the obtained filter, and as a result, conductivity was confirmed.
- Production Example 15 Production example of fiber filter in dry process using intermediary ⁇
- FIG. 1 shows an SEM image (FIG. 1A) and a TEM image (FIG. 1B) of a carbon nanofiber (CNF) synthesized by a CVD method.
- the SEM (Hitachi 4800) was operated at 15 kV and the TEM (Hitachi H-800) was operated at 200 kV.
- FIG. 2 is a photograph of a 100 mL vial of an aqueous solution containing a CNF / Na ALG aqueous solution.
- concentrations of CNF and Na-ALG were 0.5 mg / ml and 20 mg / ml, respectively.
- Fig. 3 shows the UV-vis spectrum of CNFZNa-ALG colloid aqueous solution (CNFO. 5mg / ml, Na-ALG20mg / ml) (upper line) and the aqueous solution containing only Na-ALG (Na-ALG20mg). / ml) UV-vis spectrum (lower line).
- FIG. 4 shows the zeta potential (pH vs. pH) of an aqueous solution of CNFZNa-ALG colloid (CNFO. 5 mg / ml, Na-ALG 20 mg / ml) and an aqueous solution containing only Na-ALG (Na-ALG 20 mg / ml) versus pH. ⁇ ).
- FIG. 5 shows three possible molecular forms for alginic acid, homopolymers ⁇ - ⁇ - ⁇ and G-GG and heteropolymer M-G- ⁇ -linked alginic acid.
- Fig. 6 shows the FT-IR spectrum of Na-ALG in the solid state using the potassium bromide (KBr) pellet method (upper line) and the FT-IR ⁇ -coefficient of the Na-ALGZCNF complex. Torr (lower line).
- FIG. 7 shows the results of microscopic observation of Ba 2+ alginate-coated vesicles containing highly dispersed CNF.
- the vesicles use a colloidal aqueous solution containing 0.5 mg / ml CNF and 20 mg / ml Na-ALG as a gelling solution, and an aqueous solution containing 100 mM BaCl.
- FIG. 8 shows an aqueous solution containing 30 / zM bromide solution (line A), and 15 ml of this 30 / zM bromide solution mixed with Ba 2+ -alginate vesicles (reference vesicles). UV-vis absorption of the vesicles containing high dispersion CNF, line B) and vesicles containing highly dispersed CNF (line C) 10 minutes after mixing the solution Z vesicles.
- FIG. 9 shows that after mixing 10 ml of an aqueous solution containing 30 M bromide medium with 15 ml of reference (Ba 2+ —ALG) vesicles (upper line) and CNF / Ba 2+ —ALG vesicles The change in ethidium ion concentration after mixing with (lower line) is shown as a function of mixing time.
- FIG. 10 is a microscopic photograph of Ba 2+ —ALG / MWCNT composite beads. Beads between 400 and 900 micrometers in diameter were observed.
- Fig. 11 shows the results of GC-MS measurement Z identification of the target compound from which the removal column power was also removed using hexane.
- the retention times of BP, DF and DD were 4.12 minutes, 5.02 minutes and 5.29 minutes, respectively.
- the MS spectrum corresponds to each peak of BP, DF and DD.
- FIG. 12 is an SEM photograph of an aramide fiber in which SWCNTs are dispersed in Production Example 8.
- FIG. 13 conceptually shows a 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 0.25Zl0 mg / ml.
- FIG. 16 is an AFM photograph of a SWCNT having a concentration of 0.25Z30 mg / ml manufactured according to Production Example 1.
- FIG. 17 is an AFM photograph of MWCNT produced in accordance with Production Example 1 and having a MWCNT concentration of gZml.
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Abstract
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US11/579,905 US20080023396A1 (en) | 2004-05-13 | 2005-05-13 | Fine Carbon Dispesion |
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Also Published As
Publication number | Publication date |
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US20080023396A1 (en) | 2008-01-31 |
CN101010137B (zh) | 2011-02-02 |
JP4805820B2 (ja) | 2011-11-02 |
CN101010137A (zh) | 2007-08-01 |
EP2113302A1 (en) | 2009-11-04 |
JPWO2005110594A1 (ja) | 2008-03-21 |
EP2113302A4 (en) | 2009-12-23 |
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