WO2005070825A1 - Composite matriciel secondaire contenant un nanotube de carbone - Google Patents

Composite matriciel secondaire contenant un nanotube de carbone Download PDF

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Publication number
WO2005070825A1
WO2005070825A1 PCT/JP2005/000331 JP2005000331W WO2005070825A1 WO 2005070825 A1 WO2005070825 A1 WO 2005070825A1 JP 2005000331 W JP2005000331 W JP 2005000331W WO 2005070825 A1 WO2005070825 A1 WO 2005070825A1
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Prior art keywords
composite element
weight
primary composite
fiber
matrix
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PCT/JP2005/000331
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English (en)
Japanese (ja)
Inventor
Yoshikatsu Mizukami
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Sanc Salaam Coproration
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Priority to JP2005517224A priority Critical patent/JPWO2005070825A1/ja
Publication of WO2005070825A1 publication Critical patent/WO2005070825A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • the present invention relates to abrasives, friction materials such as brake materials or clutch materials, wear-resistant material molded products such as coatings, and rubber molded products such as tires, which exhibit high elasticity and high hardness characteristics.
  • carbon nanotubes have a large aspect ratio, if they can be oriented, the properties of rigidity and hardness, which are characteristics thereof, can be sufficiently exhibited.
  • a method for orienting the fiber perpendicular to the surface a method of charging a dielectric fiber with static electricity and orienting the fiber by placing it in an electric field is generally used as flocking and is known.
  • this method it is possible to adhere the film to a uniform thickness without much influence on the shape of the surface.
  • it has been industrially used as a powder coating electrodeposition coating on the same principle.
  • carbon nanotubes are conductive, they cannot be charged with static electricity and cannot be oriented by this method.
  • the abrasive material needs to have the same hardness or higher hardness as the object to be polished, and generally has a higher hardness.
  • the purpose of polishing is achieved by the fact that the object to be polished is worn out by the action of friction and collision between the abrasive and the object to be polished.
  • the material with the highest hardness is diamond.
  • natural diamonds as well as artificial diamonds are significantly more expensive.
  • carbon nanotube as a high hardness material. 1S
  • the diameter is extremely small, 2-50 nm.
  • the aspect ratio is extremely large, 100 or more. It is difficult to handle as it is.
  • the advantage of this method is that the carbon nanotubes are dispersed in a plane on a plane in a 'plane' orientation and are stacked in multiple layers, so that the contact between the carbon nanotubes is increased.
  • a large number of contact points is an advantage in imparting conductivity, a large number of entanglements results in a poor polymer flow and poor moldability.
  • static electricity cannot be used for orientation.
  • Patent Document 5 describes "a method for producing a molten fiber containing carbon nanotubes". This method consists of (a) mixing carbon nanotubes with a polymer, (b) melt-spinning, and (c) stretching at a temperature equal to or higher than the glass transition temperature. A three-step force is required, and a post-stretching step is essential to obtain high strength. It has been. However, this document did not propose a new mixing method for mixing the carbon nanotubes with the molten polymer while preventing secondary aggregation. Further, there is no description regarding the conductivity or the dielectric property of the obtained fiber. In addition, high-strength fibers are unlikely to cause stress concentration where crystallinity is extremely large.
  • High-strength fibers can exhibit their performance sufficiently when stress is applied uniformly and simultaneously.
  • the constituent polymers are oriented in the fiber axis direction by stretching, and at the same time, a microcrystalline network is formed, contributing to the strength.
  • the microcrystalline network does not apply stress to the fibrous reinforcement, but results in stress being applied to the microcrystalline network. Can't be obtained. Again, no such considerations are made in this document.
  • Asbestos was conventionally used as a powder having high hardness and easy to fibrillate for brake or clutch materials.
  • carcinogenicity was pointed out with asbestos powder of 3 microns or less, and damage due to dust generation during collection was noted. Use in Europe, the United States and Japan was banned.
  • Aramide pulp is also used as a substitute for asbestos in the friction material described in Patent Document 6, but Midpulp is expensive and economically unfavorable.
  • the aramide fiber has a drawback that the tensile elastic modulus is large but the compressive elastic modulus is not so large. When a compressive load is applied in parallel to the aramide fiber, it is inappropriate to use the aramide fiber as a highly elastic material.
  • Document 8 describes a method of increasing the surface unevenness of carbon black, processing the carbon black into a porous form, and using the same in order to prevent the compound from falling off.
  • the shape of the compound was still a powder, and did not reach a basic solution, which was insufficient to effectively prevent the compound from falling off.
  • An inorganic compound having a higher elasticity than carbon black that is, a hardness higher than carbon black
  • an inorganic compound surface-treated with carbon black was blended with a rubber component containing 2070 parts by mass of natural rubber and 3080 parts by mass of polybutadiene rubber.
  • a tread rubber composition for studless tires is described in Ref. Improvement of braking function effect by compounding with high hardness is recognized Force The shape was still a powder, which was insufficient to effectively prevent the compound from falling off.
  • Patent Document 1 US Pat. No. 5,234,045
  • Patent Document 2 US Patent No. 5,435,374
  • Patent Document 3 JP-A-10-88256
  • Patent Document 4 JP-A-2-235945
  • Patent Document 5 U.S. Patent No. 6,331,265
  • Patent Document 6 US Patent No. 6,670,408
  • Patent Document 7 Japanese Patent Application Laid-Open No. 5-2699884
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2004-27090
  • Patent Document 9 JP 2004-155807 A
  • An object of the present invention is to disperse carbon nanotubes which are difficult to handle due to their high hardness but extremely small diameter and extremely large aspect ratio, so that they are practically uniform and easy to handle, and at the same time, have an affinity with a matrix such as a metal.
  • a matrix such as a metal.
  • the inorganic composite element of the present invention is an inorganic primary composite element having carbon nanotubes as nuclei.
  • the primary composite element of the present invention is a dielectric primary composite element containing at least one kind of carbon nanotubes or inorganic primary composite elements dispersed uniformly in a matrix polymer in an amount of 0.1% by weight or more based on the total weight. It is an event.
  • the secondary matrix composite of the present invention contains at least 0.5% by weight of the dielectric primary composite element based on the total weight.
  • the primary composite element is granular or fibrous, for example, the secondary matrix composite molding is a metal, ceramic or glass matrix composite, such as an abrasive, a friction or coating material molding or a tire. Of the molded rubber composition.
  • the inorganic primary composite element of the present invention improves the hardness and modulus of metal, ceramic or glass, and can be oriented perpendicular to the coated surface by, for example, an electrostatic coating method by utilizing its dielectric properties. Therefore, the hardness of the painted surface of the present invention is improved, and the durability and abrasion resistance are improved. Further, by using the primary composite element of the present invention containing a carbon nanotube or a carbon nanotube inorganic primary composite element, a carbon nanotube or a carbon nanotube inorganic primary composite element in a molded article that is a secondary matrix composite is used. It is possible to easily improve the uniform dispersibility of the material, and it is possible to supply inexpensive molded articles suitable as a secondary matrix composite such as a coating material, an abrasive material, a friction material, and a tire.
  • the inorganic primary composite element of the present invention is an inorganic composite element having a carbon nanotube as a nucleus, and the carbon nanotube or inorganic primary element dispersed without unevenness in the matrix polymer of the secondary matrix composite molded article of the present invention.
  • the primary composite element is a granular or fibrous secondary matrix composite molded article, and more specifically, for example, the secondary matrix composite molded article is a metal, ceramic or glass matrix composite; It is a molded product of a friction material or a coating material or a rubber composition such as a tire.
  • the carbon nanotubes used in the present invention are produced by an arc discharge method (a torch arc discharge method, an arc jet plasma method, a vacuum cathodic arc discharge method), a laser deposition method, or the like.
  • the present invention is not limited thereto. Not something.
  • the carbon nanotubes may be in the form of a coil, in a straight line, in a single layer or in multiple layers.
  • the power of the present invention The carbon nanotube inorganic primary composite element uses carbon nanotubes as crystal nuclei, and deposits inorganic oxides such as silica, zeolite and alumina by a sol-gel method or the like, and deposits a dielectric inorganic substance around the carbon nanotubes. By coating Can build power S.
  • a sol-gel method for precipitating silica for example, a small seed crystal of silica is used in US Pat. No. 4,410,405, and a crystal is grown while maintaining a constant seed crystal concentration, whereby a uniform size of about 10 nm is obtained.
  • a process for obtaining a silica zonole is described.
  • carbon nanotubes serving as crystal nuclei are dispersed in water. The temperature is raised to a temperature at which no silica seed crystals are formed, and sodium is added with an acid while adding an appropriate amount of, for example, sodium silicate to the dispersed water.
  • silica is precipitated around the carbon nanotube to produce the dielectric inorganic composite element of the present invention.
  • the composition ratio of carbon nanotubes and silica in the inorganic composite element and the coating thickness by the precipitation of silica can be adjusted by the amount of precipitated silica and the charged amount of carbon nanotubes.
  • the inorganic coating material of the inorganic primary composite element of the present invention is not limited to the above oxides.
  • salts such as chloride, sulfate, carbonate, borate, and metal phosphide may be used.
  • Oxides are preferred in terms of hardness, affinity with the metal matrix and stability.
  • the inorganic primary composite element-containing metal matrix composite of the present invention can be produced by a known metal matrix composite production method as described in, for example, References 1 to 3.
  • the inorganic primary composite element and the matrix metal powder are pre-mixed at a predetermined ratio, sintered, pulverized, melted again in an inert gas or vacuum, and then die-cast. Mixing is uniform, which is preferred.
  • the matrix is glass, it is preferable to premix the glass powder and the inorganic primary composite element in the same manner.
  • the melting point of the coated inorganic material which is the matrix of the inorganic primary composite element, is higher and more preferable than the melting point or softening point of the metal or glass matrix.
  • an inorganic primary composite element can be added to an aqueous dispersion of a ceramic raw material, followed by stirring and mixing.
  • the matrix melting point of the inorganic primary composite element is lower because the affinity with ceramics is improved.
  • the ceramic composite of the present invention is basically used for ceramics and the like. It can be manufactured by a standard method of manufacturing ceramics.
  • the primary composite element used in the polymer or rubber composition of the present invention for the secondary matrix composite contains one or more carbon nanotubes or inorganic composite elements in an amount of 0.1% by weight or more, preferably 0.5% by weight or more. And more preferably at least 1.0% by weight, even more preferably at least 2% by weight.
  • the primary composite element of the present invention is granular or fibrous.
  • the granular primary composite element can be produced by, for example, uniformly dispersing the carbon nanotube or the dielectric inorganic composite element in a monomer or a solvent in advance during radical polymerization such as emulsion polymerization or suspension polymerization.
  • Examples of methods for uniformly dispersing carbon nanotubes or dielectric inorganic composite elements in monomers such as emulsion polymerization, suspension polymerization and polycondensation beforehand include a method using a papermaking dispersing device such as pulper, a sand mill and a roller mill. There is a method using a crusher.
  • the primary composite fiber of the present invention can be produced by dissolving a granular primary composite element in a solvent, by wet spinning or dry spinning, or by a method such as melt spinning of a condensation polymer and a method of kneading with a polymer.
  • the multi-walled carbon nanotube has a diameter of several tens of nanometers, for example, specifically, a hollow inner diameter of 10 nm and an outer diameter of 8 to 50 nm. It is possible to use both carbon nanotubes such as a single-walled carbon nanotube of 114 nm. In particular, when high compressive modulus is required as in the present invention, it is not necessary to consider interlayer slippage, so that the C1-C covalent bond density in the fiber direction per unit fiber area of the multi-walled carbon nanotube is larger than that of the single-walled carbon nanotube. preferable. Multi-walled carbon nanotubes are easy to manufacture and are economically less expensive than single-walled carbon nanotubes.
  • a surface treatment or a chemical modification of carbon nanotubes or the like may be previously performed as a pretreatment.
  • the surface treatment method include, for example, a method of coating with a surfactant.
  • the chemical modification method include, for example, a graft polymerization method.
  • carbon dioxide gas is preferably used. Although performed in a supercritical or subcritical state, this new mixing method was effective in lowering the viscosity of the matrix polymer and simultaneously improving the affinity.
  • the matrix polymer used for the primary composite element is, for example, polyolefin (polyethylene such as low-density polyethylene (LDPE) or high-density polyethylene (HDPE), polypropylene, polybutylene, polyisoprene, and copolymers thereof), and polystyrene.
  • polyolefin polyethylene such as low-density polyethylene (LDPE) or high-density polyethylene (HDPE)
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • polypropylene polybutylene
  • polyisoprene polystyrene
  • polyester polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polylactic acid, polyethylene adipate terephthalate, and copolymers thereof), polyamide (polypropylene prolatatam, polyhexamethylene adipate, etc.)
  • Polycarbonate polyethylenebenzimide, polybenzimidazole, polyparadiaminobenzterephthalamide, etc., polyethylene naphthalate (PEN), polyether ether Ketone (PEEK), polyether (polymethylene oxide, polyethylene oxide), polyether sulfone (PES), polysulfone (PSF), cellulose (cellulose acetate, cellulose nitrate, etc.), polyacrylonitrile and copolymers, polyvier alcohol And two-dimensional polymers such as copolymers and phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, triaryl cyanur
  • a friction material such as a brake material or a wear-resistant material such as a coating
  • a three-dimensional thermosetting resin or the above thermoplastic polymer three-dimensionally cross-linked by copolymerization is preferred because of its excellent heat resistance during friction.
  • the carbon nanotube or dielectric inorganic composite element and in the secondary matrix composite the dispersion and orientation of the primary composite element can be measured by image analysis of scanning electron micrographs and X-ray diffraction. it can.
  • a method of molding the primary composite element into a secondary matrix composite molded article includes, for example, an abrasive material, a clutch paper, a pressing method, an injection molding method, an extrusion molding method, or an electrostatic coating method. Friction or wear-resistant materials such as brake materials, tires, Materials are manufactured, but the present invention is not limited to only these methods.
  • a high-hardness filler may be blended as a filler in the abrasive, the friction material, the tire and the wear-resistant material.
  • Fillers such as diamond, alumina, silica, and silicon carbide with high hardness, zinc oxide, clay, tanolek, barium sulfate, aluminum sulfate, cash dust, dalaphite, calcium carbonate, bentonite, organically modified bentonite, fine particle silica, carbohydrate
  • xymethylcellulose, sodium bicarbonate, mica, silicon oxide and the like It does not preclude the incorporation of these fillers in addition to the primary composite element of the present invention into the secondary matrix composite molded article of the present invention. Similarly, it does not prevent the mixing of fibers such as aramide pulp, pulp, and cotton as the material holding the filler.
  • the primary composite element of the present invention can vary its size to sub-micron power several cm as needed.
  • the primary composite element is a fiber
  • its diameter can be from submicron to several mm
  • the fiber length can be several millimeters and several centimeters by applying conventional spinning technology, making it easy to handle and carcinogenic. Sexual concerns disappear.
  • the method for producing the carbon nanotube highly elastic primary composite fiber can be produced by a general wet method, dry method, melt spinning, or the like.
  • the simplest production method is solvent-based wet or dry spinning, in which carbon nanotubes can be dispersed and used in a solvent in advance.
  • Matrices suitable for wet and dry spinning include polyvinyl alcohol, acrylonitrile, cellulose acetate, and the like.
  • Suitable matrices for melt spinning include polyamides, polyesters, polyurethanes, polycarbonates, and the like.
  • the fiber matrix is not limited to those exemplified above.
  • low-melting polyethylene may be used as the fiber for tires, when importance is attached to the force matrix in which nylon, polyester, viscose, aramide, etc., which are generally excellent in heat resistance, are used.
  • the high elasticity fiber is a form in which the high elasticity of the carbon nanotube can be used most efficiently.
  • carbon nanotubes are too fine to handle by themselves, and it is necessary to consider the working environment.However, by using a composite element with a high elasticity fiber primary composite, handling operability is improved. Improved and general handling is possible.
  • an antistatic agent, a sizing agent, and the like may be used during fiber production as long as the performance of the rubber product is not impaired.
  • the production of the primary composite fiber of the present invention is easier in wet spinning or dry spinning than in melt spinning.
  • Wet spinning or dry spinning can also be performed at the monomer stage prior to polymerization.A small amount of polymer is dissolved in a solvent, and a carbon solution or a dielectric inorganic composite element is added to a slightly viscous polymer solution. After pre-dispersion, secondary aggregates are pulverized by a sand mill, and the filtered additive is quantitatively added to the polymer solution as appropriate, followed by wet or dry spinning to obtain primary composite fibers.
  • a multi-layer structure is obtained by using a split-type composite spinneret as a spinneret and spinning a polymer having a different composition in a composite manner, and by using a static mixer and spinning another polymer having a different composition in the fiber direction.
  • the present invention is not limited to these examples, and the composite of the fibers may be a sea-island type.
  • melt spinning as in wet spinning, carbon nanotubes or dielectric inorganic composite elements are mashed at the monomer stage before polymerization, pre-dispersed with a homomixer, and then pulverized into secondary aggregates with a sand mill or the like. Then, after filtration, polymerization is performed, and a primary composite fiber can be produced by general melt spinning.
  • a melt-blowing method can be used in addition to a spinning method such as a general spin draw.
  • a more preferred form of the melt spinning method of the present invention is P ⁇ Y (Preoriented Yam) which is a semi-drawn state in which a matrix polymer is oriented, although a microcrystalline net structure is not formed by drawing.
  • the fiber melt-spun at the first roller take-off speed of less than 1,000 m / min is an undrawn yarn.
  • Semi-drawn yarn is manufactured at a take-up speed of up to about 3, OOOmZ.
  • Stretching as a matrix polymer is such that microcrystals are not completely formed, but during the process of stretching the matrix polymer in the molten state, the uniformly dispersed force-bon nanotubes are oriented in the fiber axis direction.
  • the degree of extension of the matrix polymer in the molten state is large, in other words, the take-up speed of the spinning first roller is large because the orientation of the carbon nanotubes is large.
  • the development of the microcrystalline net structure of the matrix polymer by post-stretching causes stress concentration in the microcrystalline portion, and the carbon The stress is not distributed to the carbon nanotubes or inorganic composite elements, and a sufficient reinforcing effect cannot be realized.
  • the object of the present invention is to exhibit the effects of polishing, friction and abrasion resistance in a compression elastic region where deformation is extremely small, it is economically disadvantageous because the number of steps is increased. There is no significant difference in the desired effects of the present invention.
  • the critical condition is generally about 30 ° C and 7MPa is generally considered as an absolute condition.
  • many compounds such as nitrogen gas, oxygen gas, methanol, ethanol, and acetone are known in addition to carbon dioxide gas, and can be used in the present invention. Among these, carbon dioxide and nitrogen gas are easy to handle because they do not oxidize the matrix and do not explode and are not flammable.
  • a dispersion mixer used for the above mixing and dispersion for example, a general single-screw or twin-screw extruder can be used. These may be used in combination. It is preferable that a carbon dioxide gas injection part is attached to the melt part of the extruder. Dispersibility can be improved by installing an appropriate number of Lamond super mixers or static mixers of 20 or more stages manufactured by Environmental Science Co., Ltd. between the filter and the die of the extruder.
  • the pressure at which the matrix polymer or oligomer is mixed with the carbon nanotube or the inorganic composite element is preferably IMPa or higher when the supercritical fluid is carbon dioxide. More preferably, it is 2 MPa, more preferably 3 MPa or more.
  • oligomers or monomers having a small molecular weight are used in the matrix polymer. It is preferable that the addition is carried out in a small amount and the polycondensation proceeds again, because the mixing efficiency is further improved.
  • the matrix polymer is a condensation polymer such as polyester, polyamide or polyurethane
  • the molecular weight reduced during dispersion mixing can be recovered by vacuum heating polymerization, solid phase polymerization or the like.
  • the temperature at the time of mixing varies depending on the matrix polymer, but a high temperature is preferred, and it is particularly preferable that the temperature is at least 10 ° C higher than the melting point. Also in the case of addition polymers, it is preferable to add an appropriate amount of a low-molecular-weight compound in order to improve the mixing efficiency in order to improve the thermoplasticity.
  • the injection amount of carbon dioxide gas needs to be appropriately selected depending on the type of the matrix polymer.
  • the matrix polymer is a polycondensation polymer
  • the compound is mixed with a compound having a bifunctional group such as carbon dioxide, water, a monomer, oxycarboxylic acid, diol, dicarboxylic acid, amino acid, and diamine, so that the above-described supercritical or subcritical polymer is obtained.
  • the amount of carbon dioxide gas may be very small because the molecular weight and viscosity decrease during dispersion mixing in a critical field. Preferably it is 0.01% by weight or more.
  • the standard of the amount of the compound having a bifunctional group such as a monomer is preferably about 10% to 3% by weight of the weight of the carbon nanotube.
  • the matrix polymer is a polymer having a conjugate bond such as polyolefin
  • the molecular weight cannot be recovered by post-polymerization as in the case of a polycondensate, so that a large decrease in the molecular weight cannot be expected. Therefore, it is preferable to increase the amount of gaseous carbon dioxide as a carrier in order to improve supercritical or subcritical fluidity.
  • the standard of the amount of the low molecular weight substance to be added is preferably about 10% to 3% by weight of the weight of the carbon nanotube or the inorganic composite element.
  • the matrix polymer is, for example, a two-component glycidyl monomer and a hardening agent such as a thermosetting epoxy resin
  • the carbon nanotubes or the inorganic composite element are previously dispersed in the handling, ease, and monomer. Thereafter, the two components are mixed and polymerized, and then put into a mold and molded, whereby the primary composite element of the present invention can be produced. Further, when the viscosity increases during the curing, it can be formed into a fibrous shape by extrusion.
  • thermosetting phenolic resin carbon nanotubes or phenol, cresol, xylenol, etc.
  • the inorganic composite element By dispersing the inorganic composite element in advance, it is polymerized by a standard method such as direct oxidation method, sulfate method, chlorobenzene method, Raschig method, cumene method, etc., extruded into a fibrous form, cured, and cured.
  • the primary composite element of the invention can be manufactured.
  • the thermosetting resin literally develops a three-dimensional cross-linked structure by heating, and has excellent heat resistance and dimensional stability. Also, it is the main matrix polymer of the molded article of the present invention, and the more similar the polymer of the primary composite element and the molded article, the better the affinity with the molded article. .
  • thermosetting unsaturated polyester disperses carbon nanotubes or inorganic composite elements at the time of polycondensation, dissolves with a cross-linking monomer, mixes with a filler, puts it in a mold, and cures by heating radio-canole cross-linking.
  • the next composite element can be manufactured in the same manner as the above-mentioned phenol resin.
  • the amounts and combinations of polymerization catalysts, polymerization accelerators, and stabilizers used for radical crosslinking vary widely, but should be appropriately selected.
  • a premix or prepredder containing a primary composite element must be manufactured before molding of the final molded article, and then molded and cured to produce the final molded article of the present invention. You can also.
  • the inorganic composite element of the present invention When the surface of the inorganic composite element of the present invention is covered with a dielectric inorganic substance and at least both ends of the carbon nanotube are covered, the inorganic composite element exhibits dielectric properties and is charged with static electricity.
  • the charged particles are oriented perpendicular to the surface to be coated by applying an electric field to the surface to be coated.
  • the coating of the present invention in which the carbon nanotubes are oriented perpendicular to the coating film can be performed by forming the coating film with the binder while keeping the charged particles oriented vertically to the coating surface. Even if a single coating is less than 1 ⁇ m, the thickness of the coating can be increased by stacking the coatings. It is particularly suitable as a base coat for improving the durability of the coating film.
  • the reinforcing element used in the rubber composition composite of the present invention has high elasticity, it is not necessary to have a high fiber breaking strength. Therefore, multi-walled carbon nanotubes are less expensive than single-walled carbon nanotubes, and are economically economical. preferable. Since carbon nanotubes are expensive, the smaller the blending amount contained in the above-mentioned highly elastic primary composite element, the more economically preferable.
  • the amount of the carbon nanotubes contained in the high elastic fiber primary composite element varies depending on the application, but is at least 0.1% by weight, preferably at least 0.5% by weight, and more preferably. It is preferably at least 1.0% by weight. If the amount is less than 0.1% by weight, a sufficient effect cannot be obtained.
  • aramide fiber is famous as a high elasticity fiber.
  • the aramide fiber has a large tensile modulus, but has a large compressive modulus, and is weak to bending.
  • carbon nanotubes exhibit a large elastic modulus even under compression
  • the highly elastic primary composite elements used in the present invention also exhibit high elasticity under compression, and are more preferable than aramide fibers, which fulfill the purpose of the present invention. .
  • the thickness of the high-elasticity fiber primary composite element is a single fiber having a thickness of 0.1 ldTex or more, which is preferable in terms of productivity and economy, alone or bundled, and formed into a rod shape having a thickness of several mm. You can also. As the fiber thickness becomes thinner, the surface area increases, and it has a good affinity with the matrix, making it difficult to fall off. In addition, the number of fibers per unit area increases, and the ability to capture road surfaces and the like improves. On the other hand, as the fiber thickness decreases, the apparent elastic modulus decreases, and the ability to catch road surfaces and the like decreases. The fiber thickness should be selected appropriately in consideration of the characteristics of the road surface to be supplemented and the required braking function.
  • the content of the above-mentioned highly elastic fiber primary composite element used in a rubber composition such as a tire is a force related to the fiber thickness.
  • the content is 1% by weight or more, more preferably 5% by weight or more. In applications where functions are required, the content is 10% by weight or more.
  • the primary composite element of the high elastic fiber is partially concentrated as in the rubber composition stud of the present invention, it may be used in an amount of 15% by weight or more.
  • the knitting efficiency should be taken into consideration, such as increasing the fiber thickness as the fiber content increases.
  • the fiber length of the primary composite element is often lmm to several cm, which is easily mixed with the rubber composition matrix.
  • kneading can be performed using a general kneader, Banbury mixer, or roll-type kneader.
  • the rubber of the rubber composition matrix is generally used, for example, natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, styrene-isoprene-styrene block.
  • copolymers butyl rubber, atari rubber, acrylonitrile butadiene rubber, ethylene-propylene rubber, polysulfide rubber and the like, and one or more kinds may be used.
  • the rubber composition is used after vulcanization.
  • non-elemental vulcanizing agents such as iodide, tetramethylthiuram disulphide, tetraethylthiuram disulphide, bismorpholine disulfide, disulfide Vulcanizing agents such as pentamethylenethiuram tetrasulfide, organic peroxides, quinone dioxime, phenol formaldehyde resins, nitroso compounds and diisocyanates, zinc oxide, magnesium oxide, zinc peroxide, triethylenetetramine, methylenedianiline,
  • Uses vulcanization accelerators, vulcanization aids such as diphenyldanidine, hexamethylene diamine carbamate, ethylenediamine power rubamate, bis-p-aminocyclohexylmethane power rubamate, stearic acid, oleic acid, etc. can do.
  • a foaming agent may be added to the rubber composition.
  • the foaming agent include dinitrosopentamethylenetetramine, azodicarbonamide, and P, P'_oxybisbenzenesulfonylhydrazide.
  • Auxiliaries include urea.
  • the rubber composition may contain other additives such as a softening agent, an antioxidant, a pigment, etc. which are generally added and blended, and further, if necessary, a vulcanization retarder, a tackifier and the like. May be.
  • a filler other than the primary composite element examples include carbon black, silica, zinc oxide, and calcium carbonate.
  • the rubber product of the present invention can be used as a stud tire by preparing a rubber or polymer molded product in advance as a stud molded product containing a high elastic fiber primary composite element at a high content. Unlike steel studs, they are made of rubber or polymer, which can significantly reduce the environmental impact of dust without significantly damaging the road surface.
  • the rubber or polymer studs of the present invention can be molded by injection molding or extrusion, and then can be molded by cutting. During injection or extrusion, the highly elastic fiber primary composite element can be oriented, and braking can be performed. Performance can be improved efficiently.
  • Examples of the vulcanized rubber composition obtained by vulcanizing a part or all of the rubber composition of the present invention include, for example, rubber parts for automobiles such as natural rubber tires, synthetic rubber tires, bladders and liners, cables, Examples include rubber products such as belts, hoses, sheets, and packings that require braking or durability performance, and are particularly preferably applied to tires.
  • the braking performance was measured on a 0 ° C ice surface using a portable 'skid' resistance 'tester made in the UK. The measured value was calculated and displayed as the converted value of the test piece, with the sample not containing the high modulus fiber primary composite element as the blank, and the measured value as 100. The larger this value, the better the braking performance.
  • the multi-walled carbon nanotubes were dispersed in water at 0.5% by weight, the secondary aggregation was broken and crushed by a sand mill, and the maximum length of the carbon nanotubes was adjusted so as not to exceed 1 ⁇ .
  • Silicic acid concentration 2% by weight silicate aqueous sol by ion exchange method is gradually added with stirring, heated to 70 ° C, and silica gel is deposited on the surface of multi-walled carbon nanotubes to a thickness of about 20 nm by sol-gel reaction and filtered. After drying with a hot air drier at 100 ° C, baking at 500 ° C in an inert gas atmosphere with an electric furnace was performed to produce the dielectric inorganic composite element of the present invention. Was confirmed by transmission electron microscope observation and electron beam diffraction. The calculated values obtained from the silica thickness and the carbon nanotube surface area obtained by microscopic observation and the amount of silica deposited on the carbon nanotubes were shown to be almost quantitative.
  • Lead solder is heated and melted in a platinum crucible, 10 parts by weight of the above inorganic composite element is added, well stirred and dispersed with a glass rod, and rolled into a 1 mm thick plate to produce the lead solder matrix composite of the present invention. did.
  • a test piece was cut out according to the JIS bending test and compared with the additive-free material. As a result, the flexural modulus improved 2.3 times.
  • the sample was placed in a mold and sintered, and the flexural modulus of the glass specimen increased 3.8 times.
  • Example 1 Inorganic composite element manufactured in Example 1 coated on an iron plate by an electrodeposition coating apparatus
  • the hardness of the phenolic resin coating film of the present invention after curing containing 1% by weight was higher than the hardness of general dusts such as quartz and feldspar, which were superior to iron.
  • Observation of the coating cross section with a scanning electron microscope confirmed that the inorganic composite elements in the coating were oriented perpendicular to the coating surface.
  • a phenol resin containing 1% by weight of inorganic primary composite element is melted, melt-blown and spun to produce a fiber with a single fiber thickness of about 0.5 / i, cured, cut into 1mm lengths, and then immersed in water.
  • the time required to use the primary composite element abrasive of the present invention as a primary composite element abrasive and blow it from a nozzle onto an aluminum plate as an object to be polished at high pressure to polish holes of the same depth was compared with that of an artificial diamond abrasive having almost the same particle size.
  • the polishing time S was reduced by more than 50%.
  • a suspension polymerized polyacrylonitrile 10% by weight rodin salt aqueous solution and a rodan salt aqueous solution obtained by dispersing and mixing 1% by weight of carbon nanotubes and 0.5% by weight of polyatarilononitrile with a homomixer and a sand mixer are mixed at 5: 1. After wet spinning, drawing by 8 times, washing with water, drying and cutting to 10 mm, polyacrylonitrile staples containing 1% by weight of carbon nanotubes as primary composite elements and having a single fiber thickness of lDtex were produced.
  • the molded product of the present invention was 60% more durable than the comparative molded product.
  • the polyacrylonitrile staple which is the primary composite element used in the present invention, is less expensive than aramide pulp, so that the molded product of the present invention is more economically advantageous than the comparative molded product.
  • the multi-walled carbon nanotubes and the bisphenol A type polycarbonate (250 ° C., load 2.12 kg, falling weight for 10 minutes, unit g: 25) were dry blended so that the carbon nanotubes became 1% by weight.
  • an extruder with a 40 mm diameter vent consisting of a supply section, carbon dioxide supply section, shear kneading compression reaction section, decompression section, vacuum pump suction vent section, kneading compression section, a part of the filter, and a 20-stage static mixer
  • the mixture was taken out in a cord shape, cooled with water, and cut to produce polymer composition pellets.
  • the supply of carbon dioxide was 0.1% by weight
  • the dispersion mixing temperature in the shear kneading compression reaction section was 260 ° C
  • the pressure was 3 MPa
  • the residence time was 1 minute under the subcritical state of carbon dioxide.
  • a primary filament multifilament of 32 dTex and 32 filaments is produced at a spinning temperature of 250 ° C. and a first mouth pulling speed of 800 m / min. , And cut to 10 mm to produce a polycarbonate composite table as a primary composite element.
  • X-ray diffraction results showed that the orientation of the matrix polymer was not perfect, but it was in an undrawn state, but it was confirmed that the carbon nanotubes were oriented in the fiber axis direction.
  • This multifilament had a smooth surface with no breaks and a tensile modulus of 8.9 GPa, which was superior to the comparative 2.5 Gpa containing no carbon nanotubes.
  • an extruder with a 40 mm diameter vent consisting of a supply section, carbon dioxide supply section, shear kneading compression reaction section, decompression section, vacuum pump suction vent section, kneading compression section, filter part, and 20-stage static mixer Then, it was taken out in a cord form, cooled with water, and cut to produce a polymer composition pellet.
  • the supply of carbon dioxide was 1% by weight
  • the dispersion in the shear kneading and compression reaction section was 180 ° C
  • the pressure was 3 MPa
  • the residence time was 1 minute under the subcritical state of carbon dioxide.
  • Carbon nanotubes for acrylic solids The above dope and the dispersion are mixed so that the content of the solution is 5% by weight, and the mixture is spun into a 50% water / dimethylformamide coagulation bath, stretched 5 times, dried and densified, cut into 5 mm lengths, and lOdTex acrylic High modulus fiber primary composite elements were produced.
  • Example 9 In the same manner as in Example 9, only the carbon nanotubes were changed so as to contain 0.5% by weight based on the acrylic solid content, and an acrylic high elasticity fiber primary composite element of lOdTex was produced.
  • a secondary matrix composite of the present invention was prepared in the same manner as in Comparative Example 2 except that the carbon black in Comparative Example 2 was changed to 30 parts by weight, and 5 parts by weight of the polyethylene composite fiber primary composite element of Example 8 was added. A rubber composition was produced, and a test piece for a braking test was produced. In this case, the high modulus fiber primary composite element was randomly dispersed in the test piece.
  • Example 11 The rubber composition produced in Example 11 was extrusion-molded, and a high elastic fiber primary composite element oriented in the extrusion direction at the time of molding was cut and cut so as to be perpendicular to the friction surface of the test piece, and a test piece for a braking test was obtained. Manufactured.
  • a rubber composition as a secondary matrix composite of the present invention was produced in the same manner as in Comparative Example 2, except that 10 parts by weight of the acrylic high elastic fiber primary composite element of Example 9 was added instead of the carbon black of Comparative Example 2. Then, a test piece for a braking test was manufactured. In this case, the high modulus primary composite elements were randomly dispersed in the test pieces.
  • a rubber composition as a secondary matrix composite of the present invention was produced in the same manner as in Comparative Example 2 except that 15 parts by weight of the acrylic high elastic fiber primary composite element of Example 9 was added instead of the carbon black of Comparative Example 2.
  • Extrusion molding cutting so as to occupy 30 Q / o of the friction area of the specimen, so that the highly elastic fiber primary composite element oriented in the extrusion direction at the time of molding is perpendicular to the friction surface of the specimen.
  • a stud-type test specimen for a braking test was manufactured by mounting the rubber composition of Comparative Example 2 on the other part of the mold.
  • a rubber composition as a secondary matrix composite of the present invention was produced in the same manner as in Comparative Example 2 except that 15 parts by weight of the acrylic high elastic fiber primary composite element of Example 9 was added instead of the carbon black of Comparative Example 2. Then, a test piece for a braking test was manufactured. In this case, the high modulus primary composite elements were randomly dispersed in the test pieces.
  • a rubber composition was produced in the same manner as in Comparative Example 2 except that 10 parts by weight of the carbon black of Comparative Example 2 was added instead of 10 parts by weight of the acrylic fiber of Comparative Example 3, and a test piece for a braking test was produced. did. In this case, the fibers were randomly dispersed in the test specimen.
  • Table 1 shows the braking test results of Comparative Examples 2 and 4, and Examples 11 to 16.

Abstract

L'invention concerne un élément composite primaire inorganique, qui comprend: un nanotube de carbone comme noyau; un élément composite primaire diélectrique contenant un polymère matriciel dans lequel au moins un nanotube de carbone ou l'élément composite primaire inorganique est dispersé de façon uniforme selon une quantité d'au moins 0,1 % en poids relativement au poids total; et un composite matriciel secondaire contenant ledit élément composite primaire diélectrique selon une quantité d'au moins 0,5 % en poids relativement au poids total. De préférence, l'élément composite primaire se présente sous la forme d'une particule ou d'une fibre. Plus particulièrement, par exemple, un article façonné à partir du composite matriciel secondaire est un composite matriciel de métal, de céramique ou de verre, et est réalisé avec un matériau abrasif, de friction ou de revêtement; ou alors il est un article façonné à partir d'un mélange caoutchouté, tel qu'un pneu.
PCT/JP2005/000331 2004-01-21 2005-01-14 Composite matriciel secondaire contenant un nanotube de carbone WO2005070825A1 (fr)

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JP2007297463A (ja) * 2006-04-28 2007-11-15 Teijin Ltd 強化樹脂組成物およびその製造法
JP2009519136A (ja) * 2005-12-20 2009-05-14 インテル コーポレイション 高特性相互接続用カーボンナノチューブはんだ複合材料
JP2012087041A (ja) * 2010-09-22 2012-05-10 Yamagata Prefecture 多層カーボンナノチューブ分散配合水性ゲル及びその製造方法並びにその用途
CN113038684A (zh) * 2021-03-04 2021-06-25 中科超睿(青岛)技术有限公司 一种碳纳米管修饰高密度吸氢中子靶及其制备方法

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JP2003523603A (ja) * 2000-02-16 2003-08-05 フラーレン インターナショナル コーポレイション 効率的な電子電界放出のためのダイヤモンド／カーボンナノチューブ構造体
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JPH08325195A (ja) * 1995-05-31 1996-12-10 Nec Corp 金属被覆カーボンナノチューブおよびその製造方法
JP2002544356A (ja) * 1999-05-18 2002-12-24 アトフイナ・リサーチ・ソシエテ・アノニム 強化された高分子
JP2003523603A (ja) * 2000-02-16 2003-08-05 フラーレン インターナショナル コーポレイション 効率的な電子電界放出のためのダイヤモンド／カーボンナノチューブ構造体
JP2004002621A (ja) * 2002-03-26 2004-01-08 Toray Ind Inc カーボンナノチューブ含有ペースト、カーボンナノチューブ分散コンポジットおよびカーボンナノチューブ分散コンポジットの製造方法

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Publication number Priority date Publication date Assignee Title
JP2009519136A (ja) * 2005-12-20 2009-05-14 インテル コーポレイション 高特性相互接続用カーボンナノチューブはんだ複合材料
JP2007297463A (ja) * 2006-04-28 2007-11-15 Teijin Ltd 強化樹脂組成物およびその製造法
JP2012087041A (ja) * 2010-09-22 2012-05-10 Yamagata Prefecture 多層カーボンナノチューブ分散配合水性ゲル及びその製造方法並びにその用途
CN113038684A (zh) * 2021-03-04 2021-06-25 中科超睿(青岛)技术有限公司 一种碳纳米管修饰高密度吸氢中子靶及其制备方法

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