WO2003006723A1 - Compositions de resine pour fibres composites - Google Patents

Compositions de resine pour fibres composites Download PDF

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Publication number
WO2003006723A1
WO2003006723A1 PCT/JP2002/006996 JP0206996W WO03006723A1 WO 2003006723 A1 WO2003006723 A1 WO 2003006723A1 JP 0206996 W JP0206996 W JP 0206996W WO 03006723 A1 WO03006723 A1 WO 03006723A1
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WO
WIPO (PCT)
Prior art keywords
fiber
resin
carbon fiber
ultrafine
fibers
Prior art date
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PCT/JP2002/006996
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English (en)
Japanese (ja)
Inventor
Hiroshi Yasuda
Motoyoshi Ito
Masao Irisawa
Asao Oya
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Calp Corporation
Gun Ei Chemical Industry Co., Ltd.
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Application filed by Calp Corporation, Gun Ei Chemical Industry Co., Ltd. filed Critical Calp Corporation
Publication of WO2003006723A1 publication Critical patent/WO2003006723A1/fr

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Classifications

    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a resin composition for a composite fiber, a composite fiber comprising the resin composition, an ultrafine carbon fiber obtained by carbonizing the composite fiber, an ultrafine activated carbon fiber obtained by activating the carbon fiber, and It relates to a shaped article of fiber.
  • Funinol-based carbon fibers obtained by carbonizing FUNOOL resin fibers and activated carbon fibers obtained by activating them have excellent heat resistance, chemical resistance, conductivity, etc. Insulation materials, sealing materials, canisters for automobiles, flue gas desulfurization adsorbents, dioxin adsorbents. Charge double layer capacitors, lithium batteries, charge double layer capacitors, fuel cell electrode materials, separators, etc. It is used in a wide range of fields, and further use is expected.
  • One of the methods for further improving the performance of such carbon fibers is to make the fibers extremely fine.
  • electrode materials as an application development of ultrafine carbon fibers
  • by further activating ultrafine carbon fibers with a large surface area per unit weight (specific surface area) to obtain ultrafine activated carbon fibers higher performance can be achieved. It can be expected as a material with high quality.
  • ultrafine carbon fiber as a filler for composite materials, not only can a high-rigidity composite material be obtained, but also as a high-rigidity material that can be used for thin-walled molded products. And high conductive paths are formed. A conductive material can be obtained.
  • phenol resin which is a raw material of phenol resin fibers
  • phenol resin fibers is an amorphous resin and has a low degree of polymerization, so that spinning is difficult.
  • the obtained fininol resin fiber had problems that strength and elongation were insufficient and that it was extremely brittle. For this reason, there is a problem that productivity is extremely reduced in a method of increasing the spinning speed by using a small-diameter spinneret.
  • the discharged phenol resin is cooled and solidified at a position very close to the spinneret, the drawing effect during spinning can hardly be expected, and the fiber diameter was limited to about 12 m.
  • a method for obtaining a phenolic ultrafine carbon fiber is disclosed in Japanese Unexamined Patent Publication No. Although it is proposed in Japanese Patent Publication No. 226, etc., when simply combining a phenolic resin and a polyethylene resin, the ultrafine carbon fiber finally obtained shrinks or the fibers are fused together. There is a problem of doing so. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and provides a resin composition for obtaining a conjugate fiber suitable as a precursor of an ultrafine carbon fiber, and an ultrafine carbon fiber obtained by carbonizing the conjugate fiber. It is an object of the present invention to provide an ultrafine activated carbon fiber obtained by activating this carbon fiber, and a shaped article obtained by shaping these fibers.
  • a resin resin composition in which a phenolic resin and a specific polypropylene or a specific polyethylene are mixed at a specific ratio is a resin set for a composite fiber.
  • the composite fiber obtained by spinning the resin composition is suitable as a precursor of the ultrafine carbon fiber, and the average fiber diameter is obtained by carbonizing the composite fiber. It was found that ultrafine carbon fibers having an average particle diameter of 0.5 or less were obtained, and by activating this ultrafine carbon fiber, an ultrafine activated carbon fiber was obtained.
  • the present invention has been completed based on such findings.
  • the MI (melt index) measured under the conditions of 10 to 50% by mass of the phenolic resin and a temperature of 230 ° (: a load of 21.18 N) is 10 to 1%. 0 0 g 1 0 minute polypropylene 9 0-5 0 consist mass% conjugate fiber resin composition, 1 0-5 0 mass% phenol resin and density 0. 9 4 0 g / cm 3 or more, the temperature MI (mel index) measured under the condition of 190 ° C and load of 2.
  • Resin composition for composite fiber consisting of 90 to 50% by mass of polyethylene of 30 g / 10 minutes, having an average fiber diameter of 5 to 100 m obtained by spinning these resin compositions.
  • a conjugate fiber an ultrafine carbon fiber having an average fiber diameter of 0.5 ⁇ m or less obtained by carbonizing the conjugate fiber, and an ultrafine activated carbon fiber obtained by activating this ultrafine carbon fiber. Is what you do.
  • the present invention also provides a shaped article obtained by shaping these fibers.
  • Fig. 1 shows the aggregate of the fuynol-based ultrafine carbon fibers in Example 1.
  • Fig. 1 shows the aggregate of the fuynol-based ultrafine carbon fibers in Example 1.
  • Figure 3 shows the phenolic carbon fiber aggregate in Comparative Example 1.
  • Figure 4 shows the aggregate of phenolic carbon fibers in Comparative Example 1.
  • Figure 5 shows the aggregate of the phenolic microfine carbon fibers in Comparative Example 2.
  • Figure 6 shows the aggregate of the fininol-based ultrafine carbon fibers in Comparative Example 2.
  • the funinol resin used in the present invention is obtained by subjecting a funinol and an aldehyde to a condensation polymerization reaction in the presence of a reaction catalyst.
  • a reaction catalyst for example, Phenol, o_cresol, m-cresol, p-cresol, bisphenol A, 2,3—xylenol, 3,5—xylenol, p—tertiary butylphenol, resorcinol And the like.
  • aldehydes include formaldehyde, paraformaldehyde, hexamethylene tetramine, furfural, benzaldehyde, and salicylaldehyde.
  • the molar ratio between the aldehydes and the phenols is not particularly limited, but is preferably 0.6: 1 to 0.886: 1.
  • the reaction catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as oxalic acid and p-toluenesulfonic acid, oxycarboxylic acids such as citric acid and tartaric acid, and zinc compounds such as zinc chloride and zinc acetate. Is mentioned.
  • the phenol resin used in the present invention is not limited to a linear molecule but may be a partially branched molecule.
  • the composition may be a single phenol resin or a mixture of two or more components at an arbitrary ratio.
  • the molecular weight of the phenol resin is also not particularly limited, but in order to be fusible in a temperature range appropriate for melt spinning and to have a viscosity range appropriate for melt spinning, the average molecular weight is from 500 to 50, It is preferably in the range of 0 0 0.
  • the softening point of the phenol resin is not particularly limited, but is preferably 90 ° C. or more, and particularly preferably 120 to 130 ° C. In the present invention, a novolac type phenol resin having a softening point of 90 ° C. or more is preferable.
  • Examples of the polypropylene used in the present invention include homopolypropylene, block polypropylene and random polypropylene.
  • the homopolypropylene is a resin obtained by polymerizing propylene alone, and the block polypropylene and the random polypropylene are It is a copolymer of propylene and another comonomer.
  • the other comonomer use ethylene or C4 to C6 olefin (1-butene, 1-pentene, 1-hexene, etc.) Can be.
  • polyethylene examples include high-pressure low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and other homopolymers of ethylene or copolymers of ethylene and ⁇ -olefin; 'Copolymers of ethylene with other vinyl monomers, such as vinyl acetate copolymers, and the like.
  • Examples of the ⁇ -olefin copolymerized with ethylene include propylene, 1-butene, 4-methyl-11-pentene, 11-hexene, and 1-octene.
  • Other vinyl monomers include, for example, butyl esters such as butyl acetate; (meth) acrylic acid, (methyl) methyl acrylate, (meth) ethyl acrylate, Examples include (meth) acrylic acid such as ⁇ -butyl (meth) acrylate and its alkyl ester.
  • the ⁇ I (mel to index) measured under the condition of a temperature of 230 ° (: load 21.18 ⁇ ) is 10 to 100 g / 10 min.
  • the MI of the polypropylene is less than 10 g / 10 minutes, the phenolic resin islands in the sea-island structure will not be formed well when producing a conjugate fiber described later, and the spinnability and the like will be significantly reduced.
  • the MI exceeds 100 g / 10 minutes, the sea-island structure with the phenol resin becomes non-uniform, so that the spinnability is remarkably reduced and stable fiber formation cannot be performed.
  • polyethylene if the density is less than 0.940 g / cm, the carbon fibers are shrunk in the step of carbonizing the composite fibers. Density polyethylene, the preferred properly a 0. 9 4 0 ⁇ 0. 9 6 8 g / cm 3.
  • the fiber will be cut when spinning the conjugate fiber, making it difficult to perform good spinning. If the MI of the polyethylene exceeds 30 g / 10 minutes, phase separation occurs between the phenol resin and the polyethylene, so that the fibers are cut and it becomes difficult to perform good spinning.
  • the mixing ratio of the phenol resin to the polypropylene or the polyethylene is 10 to 50% by mass of the phenol resin and 90 to 50% by mass of the propylene resin or the polyethylene.
  • resin 1 0-3 0 weight 0/0, polypropylene or port Ryechiren is 9 0-7 0% by weight. If the phenolic resin content is less than 10% by mass, sufficient fininol-based ultrafine carbon fibers cannot be obtained, and if the phenolic resin content exceeds 50% by mass, a good sea-island structure cannot be obtained. Deterioration or the structure of carbon fiber obtained by carbonization becomes uneven.
  • additives may be added to the resin composition for composite fibers of the present invention as needed.
  • the additive include an antioxidant, an ultraviolet absorber, a pigment, and a dye.
  • the resin composition for a conjugate fiber of the present invention can be obtained by mixing and kneading a fu ⁇ ol resin with polypropylene or polyethylene by a known method.
  • a known kneading apparatus can be used, and examples thereof include an extruder-type kneading machine, a mixing roll, a Banbury mixer, and a high-speed twin-screw continuous mixer.
  • H The kneading time of the phenolic resin and polypropylene or polyethylene is appropriately selected depending on the amount of the resin, the mixing ratio of the phenolic resin and the polypropylene or polyethylene, and the desired fiber diameter of the phenolic resin as an island component.
  • the kneading temperature of the phenol resin and the polypropylene or polyethylene is not particularly limited, but is preferably in the range of 180 to 280 ° C, more preferably in the range of 200 to 260 ° C. It is.
  • the resin composition thus obtained is extruded in a molten state from a spinneret and melt-spun to form a sea-island composite in which the sea component is a polyolefin resin and the island component is a fuyunol resin.
  • Fiber can be obtained. Further, by subjecting the island component phenol resin to a curing treatment, a cured composite fiber can be obtained. Next, the cured composite fiber is carbonized under an inert atmosphere to obtain a fluorinated ultrafine carbon fiber. By activating this ultrafine carbon fiber, an ultrafine activated carbon fiber can be obtained.
  • the finol-based ultrafine carbon fiber can be obtained by simply carbonizing the conjugate fiber, so that the working environment is remarkably improved and the finol-based ultrafine carbon fiber can be easily manufactured.
  • the temperature during melt spinning is not particularly limited, but is preferably in the range of 150 to 300 ° C, more preferably in the range of 160 to 250 ° C.
  • the pore diameter of the spinneret is appropriately selected depending on the fiber diameter of the intended conjugate fiber, and is not particularly limited, but is preferably from 0.1 to 5.0 mm, more preferably from 0.2 to 4.0 mm.
  • the melting method a known method can be used, and examples thereof include an extruder method and a melter method.
  • the heating method any of an electric heating method, a steam heating method, and a heating medium heating method can be used.
  • Spinning speed is not particularly limited However, it is preferably from 50 to 6,000 m / min, more preferably from 200 to 4,000 m / min.
  • a phenol resin and polyethylene may be melted and kneaded, and this may be directly spun in a molten state, or the phenol resin and polyethylene may be kneaded, pelletized once, and then melted. It may be spun.
  • the curing treatment of the phenolic resin is performed by a known method, for example, a method of curing the phenolic resin with an aldehyde in the presence of a bridge catalyst.
  • the cross-linking catalyst include acidic catalysts such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, and p-toluenesulfonic acid, ammonia, hydroxylic acid sodium, sodium hydroxide, potassium hydroxide, and barium hydroxide.
  • Basic catalysts such as sodium carbonate are exemplified.
  • the aldehydes include formaldehyde, paraformaldehyde, and benzaldehyde furfural.
  • reaction conditions during the curing treatment are appropriately selected according to the type, amount used, reaction method, etc. of the crosslinking catalyst and aldehydes.
  • hydrochloric acid is used as the crosslinking catalyst
  • formaldehyde is used as the aldehydes
  • the mixture is treated with an aqueous solution of 5 to 20% by mass of hydrochloric acid and 5 to 20% by mass of formaldehyde at 60 to 110 ° C for 3 to 30 hours.
  • a composite fiber having an average fiber diameter of 5 to 100 m can be obtained.
  • an ultrafine carbon fiber having an average fiber diameter of 0.5 Hm or less can be obtained.
  • the carbonization of the composite fiber is performed by a known method.
  • the inert gas used for carbonization include nitrogen, argon, and the like.
  • the carbonization temperature is preferably in the range of 600 to 1200 ° C, more preferably in the range of 800 to 1000 ° C.
  • the activation of microfine carbon fibers can be performed by subjecting the microfine carbon fibers to a gasification reaction with steam. it can.
  • Examples of the shaped article of the conjugate fiber, the ultrafine carbon fiber, and the ultrafine activated carbon fiber of the present invention include chopped strands, nonwoven fabrics, cloths, felts, papers, and long fibers. Can be manufactured.
  • the method for measuring the physical properties of each fiber in this example is as follows.
  • Photographing was performed using a scanning electron microscope JSM-T22OA manufactured by JEOL Ltd., and the fiber diameter was measured based on the electron micrograph.
  • a phenol resin powder obtained by repeating the same operation three times was mixed with polypropylene (MID measured at 230 ° C and a load of 21.18 N) having a MI of 60 g / 10 min (Idemitsu Petrochemical Co., Ltd.).
  • Y-605 GM was mixed so that the mass ratio was 30:70.
  • 20000 g of this mixed resin was kneaded at 230 ° C. using a kneading PCM 30 co-directional twin screw extruder manufactured by Ikegai Iron Works to obtain a composite resin bellet.
  • the obtained composite resin was melt-spun at a nozzle temperature of 170 ° C.
  • An island-shaped uncured conjugate fiber was obtained.
  • the obtained uncured conjugate fiber was immersed in an aqueous solution of hydrochloric acid-formaldehyde (18% by mass of hydrochloric acid and 10% by mass of formaldehyde) at 96 ° C. for 24 hours to obtain a cured fiber.
  • the cured fiber was carbonized in a nitrogen stream at 600 ° C. for 10 minutes to remove propylene, a sea component, to obtain a phenolic ultrafine carbon fiber.
  • the obtained phenolic ultrafine carbon fiber is
  • Activation treatment was performed at 900 ° C. for 5 minutes to obtain ultrafine activated carbon fibers.
  • the fiber diameter and specific surface area of these ultrafine carbon fibers and ultrafine activated carbon fibers were measured by the above-described methods. Table 1 shows the results.
  • FIG. 1 is an electron micrograph at a magnification of 1000 ⁇
  • FIG. 2 is an electron micrograph at a magnification of 500 ⁇ . From the electron micrographs, it was found that the polypropylene (sea portion) disappeared due to the heat, and a number of ultrafine carbon fibers (average fiber diameter 0.2 urn) extending long in the fiber axis were formed independently. It was confirmed that. By activating the ultrafine carbon fiber, an ultrafine activated carbon fiber having a specific surface area of 220 m 2 / g could be obtained.
  • Example 1 polypropylene having an MI of 60 g / 10 minutes and a polypropylene having an MI of 20 g / 10 minutes measured at 230 ° C. under a load of 2.1.18 N (Idemitsu Petrochemical Co., Ltd.)
  • Y-2000 GV Y-2000 GV
  • the ultra-fine carbon fiber (average fiber diameter 0.2 m) It was confirmed that they were formed individually and independently. Further, by performing the activation treatment of the ultrafine carbon fibers, it was possible to obtain the ultrafine activated carbon fibers having a specific surface area of 250 m 2 / g.
  • Example 1 polypropylene having a MI of 60 g / 10 minutes was used.
  • Example 1 was repeated except that the MI measured at 230 ° C and a load of 21.18 N was changed to polypropylene (Y-900 GV, manufactured by Idemitsu Petrochemical Co., Ltd.) with a weight of 10 g / 10 minutes. Similarly, a cured composite fiber having an average fiber diameter of 30 m was obtained. In the same manner as in Example 1, the obtained composite fiber was carbonized to obtain a carbon fiber, and the carbon fiber was activated to obtain an activated carbon fiber. Table 1 shows the measurement results.
  • Electron micrographs confirmed that the ultrafine carbon fibers (average fiber diameter: 0.2 m) were formed independently of each other. In addition, by performing the activation treatment of the ultrafine carbon fiber, an ultrafine activated carbon fiber having a specific surface area of 197 m 2 / g was obtained.
  • Example 1 the MI was measured at a density of 0.963 g / cm 3 at 190 ° C. and a load of 21.18 N with a MI of 14 g.
  • the average fiber diameter was changed in the same manner as in Example 1 except that the polyethylene fiber was changed to 1/10 min.
  • Example 2 30 m of cured bicomponent fibers were obtained.
  • the obtained conjugate fiber was carbonized to obtain a carbon fiber, and the carbon fiber was activated to obtain an activated carbon fiber.
  • Table 1 shows the measurement results. Electron micrographs confirmed that the ultrafine carbon fibers (average fiber diameter 0.2 m) were formed individually and independently. In addition, by performing the activation treatment of the ultrafine carbon fiber, the specific surface area is 230 An ultra-fine activated carbon fiber of m 2 / g was obtained.
  • Example 1 the polypropylene having MI of 60 g / 10 min was measured at a density of 0.964 g / cm 3 at 190 ° C. and a load of 21. Cured bicomponent fibers having an average fiber diameter of 30 ⁇ were obtained in the same manner as in Example 1 except that the polyethylene fiber was changed to polyethylene (120 YK, manufactured by Idemitsu Petrochemical Co., Ltd.) for 10 minutes. In the same manner as in Example 1, the obtained conjugate fiber was carbonized to obtain a carbon fiber, and the carbon fiber was activated to obtain an activated carbon fiber. Table 1 shows the measurement results.
  • Electron micrographs confirmed that the ultrafine carbon fibers (average fiber diameter 0.2 m) were formed individually and independently. By activating the ultrafine carbon fibers, ultrafine activated carbon fibers having a specific surface area of 199 m 2 / g could be obtained.
  • Example 1 the polypropylene having MI of 60 g / 10 min was measured at a density of 0.940 g / cm 3 , 190 ° C., and a load of 21.18 N to have a MI of 20 g / 10 N.
  • Cured bicomponent fibers having an average fiber diameter of 30 m were obtained in the same manner as in Example 1 except that the polyethylene was changed to 10-minute polyethylene (074 G, manufactured by Idemitsu Petrochemical Co., Ltd.).
  • the obtained composite fiber was carbonized to obtain a carbon fiber, and the carbon fiber was activated to obtain an activated carbon fiber. Table 1 shows the measurement results.
  • Electron micrographs confirmed that the ultrafine carbon fibers (average fiber diameter 0.2 m) were formed individually and independently. Further, by performing the activation treatment of the ultrafine carbon fiber, an ultrafine activated carbon fiber having a specific surface area of 270 m 2 / g could be obtained. table 1
  • the phenol resin synthesized in Example 1 was melt-spun at a nozzle temperature of 150 ° C. to obtain a raw phenol fiber. Further, the obtained raw fibers were immersed in an aqueous solution of hydrochloric acid-formaldehyde (18% by mass of hydrochloric acid, 10% by mass of formaldehyde) at 96 ° C. for 24 hours to obtain hardened fibers. Next, the cured fiber was carbonized in a nitrogen stream at 900 ° C. for 30 minutes to obtain a phenolic carbon fiber. The obtained fuynol-based carbon fiber is activated using steam at 900 ° C. for 5 minutes to obtain activated carbon. Fiber was obtained.
  • FIG. 3 is a 1000 ⁇ magnification electron micrograph
  • FIG. 4 is a 500 ⁇ magnification electron micrograph.
  • the obtained fuynol-based carbon fiber has an average fiber diameter of 10 m
  • the activated carbon fiber has a specific surface area of 500 m 2 / g.
  • Example 1 a polypropylene having an MI of 60 g / 10 minutes and a MI of 34 g / 10 minutes measured at 230 ° C. under a load of 21.18 N (Idemitsu Petrochemical Co., Ltd.) In the same manner as in Example 1 except that the cured composite fiber had an average fiber diameter of 30 m. In the same manner as in Example 1, the obtained conjugate fiber was carbonized to obtain a fine carbon fiber, and this carbon fiber was activated to obtain an activated carbon fiber. Table 2 shows the measurement results.
  • FIGS. 5 and 6 show electron micrographs of the obtained ultrafine carbon fiber.
  • FIG. 5 is a photomicrograph of ⁇ 100 magnification and
  • FIG. 6 is a photomicrograph of ⁇ 500 magnification. From the electron micrographs, it was confirmed that the ultrafine carbon fibers (average fiber diameter: 0.2 ⁇ m) were formed individually, but were fused and shrunk. By activating the ultrafine carbon fibers, ultrafine activated carbon fibers having a specific surface area of 2000 m 2 / g could be obtained.
  • Example 1 MI was measured at 60 g / 10 min with a polypropylene at 190 ° C. under a load of 2.18 N. Chemical company, 210 JZ) In the same manner as in Example 1, a composite resin bellet was obtained.
  • the obtained composite resin was melt-spun at a nozzle temperature of 150 ° C.
  • stable extrusion could not be performed, and good spinning could not be performed due to fiber breakage, but sea-island uncured conjugate fibers with an average fiber diameter of 100 m could be obtained.
  • the obtained conjugate fiber was cured and carbonized to obtain a carbon fiber, and the carbon fiber was activated to obtain an activated carbon fiber. Table 2 shows the measurement results.
  • the ultrafine carbon fibers (average fiber diameter: 0.3 m) were formed individually and independently. Further, by performing the activation treatment of the ultrafine carbon fiber, an ultrafine activated carbon fiber having a specific surface area of 198 m 2 / g could be obtained.
  • Example 1 a polypropylene having an MI of 4.0 g / 10 min measured at 230 ° C. under a load of 21.'18 N was prepared from polypropylene having an MI of 60 g / 10 min.
  • a composite resin velvet was obtained in the same manner as in Example 1 except that Y-400 GP manufactured by Chemical Co., Ltd. was used.
  • the obtained composite resin was melt-spun at a nozzle temperature of 170 ° C.
  • stable extrusion could not be performed, and good spinning could not be performed because the fibers were cut.However, it was not possible to obtain sea-island type uncured composite fibers having an average fiber diameter of 100 ⁇ m.
  • the obtained composite fiber was cured and carbonized to obtain carbon fiber in the same manner as in Example 1, and the carbon fiber was activated to obtain an activated carbon fiber. Table 2 shows the measurement results.
  • an ultrafine carbon fiber having an average fiber diameter of 0.5 Um or less can be easily produced.

Abstract

L'invention concerne une composition de résine pour fibres composites qui comprend de 10 à 50 % en poids de résine phénolique et de 90 à 50 % en poids de polypropylène, et présente un indice de fluidité (MI) de 10 à 100 g/10 min à 230 °C sous une charge de 21,18 N, ou une composition de résine pour fibres composites qui comprend de 10 à 50 % en poids de résine phénolique et de 90 à 50 % en poids de polyéthylène, et présente une densité égale ou supérieure à 0,940 g/cm3 et un MI de 10 à 30 g/10 min. Ces compositions de résine permettent d'obtenir des fibres composites qui peuvent être utilisées comme précurseurs pour la production de fibres de carbone ultrafines. La carbonisation des fibres composites obtenues permet de produire des fibres de carbone ultrafines présentant un diamètre moyen égal ou inférieur à 0,5 νm.
PCT/JP2002/006996 2001-07-10 2002-07-10 Compositions de resine pour fibres composites WO2003006723A1 (fr)

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