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WO2024122529A1 - Fibres de carbone et leur procédé de production - Google Patents

Fibres de carbone et leur procédé de production Download PDF

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Publication number
WO2024122529A1
WO2024122529A1 PCT/JP2023/043416 JP2023043416W WO2024122529A1 WO 2024122529 A1 WO2024122529 A1 WO 2024122529A1 JP 2023043416 W JP2023043416 W JP 2023043416W WO 2024122529 A1 WO2024122529 A1 WO 2024122529A1
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Prior art keywords
fiber
carbon fiber
carbon
furnace
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Japanese (ja)
Inventor
秀和 吉川
圭 立花
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Teijin Ltd
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Teijin Ltd
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    • 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
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

Definitions

  • the present invention relates to carbon fibers and their manufacturing methods.
  • Carbon fiber has excellent specific strength and specific modulus of elasticity, and is lightweight, so it is used as a reinforcing fiber for thermosetting and thermoplastic resins in a wide range of applications, including aircraft, sports and leisure, and general industry. As its applications expand, even higher performance is required of carbon fiber reinforced composite materials (hereafter also referred to as composites).
  • precursor fibers (resin fibers) with oil applied are heated in air to make them flame-resistant, then heated in a first heating furnace (C1 furnace) at a temperature of 300°C to 700°C in an inert atmosphere (particularly a nitrogen atmosphere), and further heated in a second heating furnace (C2 furnace) at a temperature of 800°C to 1500°C in an inert atmosphere (particularly a nitrogen atmosphere) to carbonize.
  • C1 furnace first heating furnace
  • C2 furnace second heating furnace
  • the fibers are transported (from upstream to downstream) from the C1 furnace to the C2 furnace while being stretched at a specific stretch ratio. It is also possible to obtain carbon fibers with a high elastic modulus by processing at even higher temperatures, if necessary.
  • the pressure vessel has, for example, an inner frame (liner) made of metal or resin, and an outer layer of a carbon fiber-reinforced composite material containing carbon fiber as reinforcing fibers and resin.
  • Patent Document 1 discloses a tow prepreg containing a specific epoxy resin composition and reinforcing fibers. This document describes the use of tow prepregs to produce fiber-reinforced composite materials, and claims that these fiber-reinforced composite materials can be suitably used in high-pressure vessels filled with hydrogen gas, such as those used in fuel cells.
  • Patent Document 2 discloses an epoxy resin composition suitable for use in fiber-reinforced composite materials such as tow prepregs, and aims to provide a method for curing the epoxy resin composition for fiber-reinforced composite materials suitable for use in the filament winding method.
  • Improvements to manufacturing methods are being made to improve the performance of carbon fiber.
  • Patent Document 3 proposes suppressing the moisture content of the carbon fiber precursor acrylic fiber bundle when applying a silicone oil agent before the flame-resistant process, which is said to suppress the diffusion of the oil agent in the flame-resistant furnace and reduce adhesion to the fiber bundle.
  • Patent Document 4 also describes a carbon fiber bundle in which, when a single fiber tensile test is carried out with a test length of 10 mm, the probability of the presence of defects of 50 nm or more on the recovered fracture surface is 35% or less, and the scatterer length lf obtained by small-angle scattering of a microbeam is 46 nm or more.
  • This document claims that by controlling the defects that are the starting points of fracture within a certain range and further lengthening the scatterer obtained by SAXS, a carbon fiber bundle that exhibits high tensile strength can be obtained.
  • Patent Document 5 discloses carbon fibers for filament winding (FW) molding that have specific physical properties and a constant rate of variation in thread width when unwound. This document claims to provide carbon fibers suitable for FW molding applications and a manufacturing method thereof.
  • Patent document 6 describes a carbon fiber for pressure vessels that has a specific strand modulus and tensile elongation, and claims that by using this carbon fiber as a reinforcing fiber, a pressure vessel with good properties can be obtained.
  • Conventional carbon fibers sometimes fail to provide the desired physical properties (especially strength).
  • pressure vessels manufactured using fiber-reinforced resin composite materials containing conventional carbon fibers sometimes fail to provide the desired pressure resistance.
  • the carbon fiber described in Patent Document 6 above has a high elastic modulus and is expected to be expensive, so it may not be suitable for general-purpose use.
  • the present invention aims to provide a carbon fiber with improved physical properties (especially strength) and a method for producing carbon fiber that can be used for general purposes.
  • the object of the present invention can be achieved by the following aspects of the present invention.
  • XPS method X-ray photoelectron spectroscopy
  • the ratio (M/P) of the tensile modulus M (GPa) to the normalized scattering integrated intensity P measured by small angle X-ray scattering measurement (SAXS) is 230 or more. 3.
  • TEM transmission electron microscope
  • the precursor fiber having the silicone-based oil agent attached thereto After subjecting the precursor fiber having the silicone-based oil agent attached thereto to a flame retardant treatment, the precursor fiber is subjected to a first heat treatment in a first heating furnace under an inert atmosphere at a treatment temperature of 300° C. to 700° C.; and A method for producing carbon fibers, comprising subjecting the fibers subjected to the first heat treatment to a second heat treatment at a treatment temperature of 1000° C. or more in an inert atmosphere in a second heating furnace, In the second heating furnace, the atmosphere inside the furnace is circulated from the outlet side to the inlet side. How carbon fiber is manufactured.
  • XPS X-ray photoelectron spectroscopy
  • ⁇ Aspect 9> A method for producing a fiber according to claim 7 or 8, wherein the silicone-based oil agent adhered to the precursor fiber before the flame retardant treatment is in an amount of 0.01% by weight to 0.8% by weight with respect to the precursor fiber before the silicone-based oil agent is adhered thereto.
  • ⁇ Aspect 11> 11 The method of any one of aspects 7 to 10, wherein the treatment temperature in the second heating furnace is greater than 1200° C.
  • the present invention provides carbon fibers with improved physical properties (especially strength) and a method for producing carbon fibers that can be used for general purposes.
  • FIG. 1 is a cross-sectional photograph of the carbon fiber according to Example 1 observed by a transmission electron microscope (TEM).
  • FIG. 2 is a cross-sectional photograph of the carbon fiber according to Example 5 observed by a TEM.
  • FIG. 3 is a cross-sectional photograph of the carbon fiber according to Example 8 observed by a TEM.
  • TEM transmission electron microscope
  • the carbon fiber according to the present invention is The atomic ratio of silicon atoms to carbon atoms (Si/C) on the fiber surface as measured by X-ray photoelectron spectroscopy (XPS) is 0.001 to 0.020.
  • silicone-based oils are used for purposes such as suppressing adhesion between fibers (yarn adhesion). Silicone-based oils that adhere to the fiber surface can change during high-temperature treatment in the carbon fiber manufacturing process and remain on the surface of the carbon fiber as impurities. Such residues can reduce the physical properties of the carbon fiber.
  • the carbon fiber according to the present invention has an atomic ratio of silicon atoms to carbon atoms (Si/C) on the fiber surface when measured by X-ray photoelectron spectroscopy (XPS method) of 0.001 to 0.020.
  • XPS method X-ray photoelectron spectroscopy
  • the method for obtaining carbon fibers with a reduced Si/C atomic ratio on the fiber surface is not particularly limited, but in particular, when producing carbon fibers from precursor fibers to which a silicone-based oil agent has been added, the atmosphere pressure inside the C2 furnace on the outlet side is made higher than the atmosphere pressure inside the C2 furnace on the inlet side, and thus the atmosphere inside the furnace is circulated from the outlet side to the inlet side in the second heating furnace.
  • gas resulting from silicone oil is generated in large amounts in a relatively low temperature range (e.g., 600-800°C).
  • a relatively low temperature range e.g. 600-800°C.
  • the carbon fiber is not particularly limited, and may be any carbon fiber such as pitch-based, rayon-based, polyacrylonitrile (PAN)-based, etc., but acrylonitrile-based carbon fiber is preferred in terms of operability, processability, mechanical strength, etc.
  • PAN polyacrylonitrile
  • the fineness, strength, and other properties of the carbon fiber are also not particularly limited, and any known carbon fiber can be used without limitation.
  • the form of the carbon fiber is not particularly limited, but may be in the form of a carbon fiber bundle composed of multiple single threads (filaments). From the viewpoint of productivity, the number of filaments constituting the carbon fiber bundle is preferably 1,000 to 80,000, and more preferably in the range of 2,000 to 50,000.
  • the single thread diameter of the carbon fiber may be 4 ⁇ m to 20 ⁇ m, and is preferably 5 ⁇ m to 10 ⁇ m.
  • the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface as measured by X-ray photoelectron spectroscopy (XPS) is 0.001 to 0.020 (also may be expressed as 0.1% to 2.0%).
  • This atomic ratio may be 0.002 or more, 0.003 or more, 0.004 or more, 0.005 or more, 0.006 or more, 0.007 or more, 0.008 or more, 0.009 or more, 0.010 or more, or 0.011 or more, and/or 0.019 or less, 0.018 or less, 0.017 or less, 0.016 or less, or 0.015 or less.
  • This atomic ratio is preferably 0.002 to 0.018, more preferably 0.004 to 0.016, and even more preferably 0.006 to 0.015.
  • carbon fibers exhibiting particularly good strength and composite properties can be obtained.
  • the ratio (Si/C) of silicon atoms (Si) to carbon atoms (C) on the surface of carbon fibers can be determined by X-ray photoelectron spectroscopy (XPS) using an X-ray photoelectron spectrometer.
  • X-ray photoelectron spectroscopy is also called ESCA (Electron Spectroscopy for Chemical Analysis).
  • the fibers are cut and spread out on a stainless steel sample support, and then the photoelectron escape angle is set to 90 degrees, MgK ⁇ is used as the X-ray source, and the sample chamber is maintained at a vacuum of 1 ⁇ 10 ⁇ 6 [Pa].
  • the binding energy value B.E. of the main peak of C1s is first adjusted to 284.6 [eV].
  • the Si2p peak area is obtained by drawing a straight baseline in the range of 96 to 108 [eV]
  • the C1s peak area is obtained by drawing a straight baseline in the range of 281 to 297 [eV].
  • the abundance ratio of Si2p to the C1s peak on the carbon fiber surface is calculated by the ratio of the Si2p peak area to the C1s peak area, and this can be regarded as the abundance ratio (Si/C) of silicon atoms (Si) and carbon atoms (C) on the fiber surface of the carbon fiber.
  • the Si/C ratio can be measured before applying a sizing agent to the carbon fiber, or after removing the sizing agent attached to the carbon fiber by immersing the carbon fiber in an appropriate solvent, for example.
  • the carbon fibers preferably have an agglutination number of 10 or less, and preferably have no gloss when observed on the surface of the carbon fibers.
  • the number of carbon fiber agglutinations is preferably 8 or less, 6 or less, 4 or less, 2 or less, or 1 or less, and most preferably zero.
  • the number of adhered fibers can be determined by cutting 3,000 filaments of carbon fiber into 5 mm lengths, dispersing them in 10 mL of acetone, subjecting them to ultrasonic treatment, and then observing them under an optical microscope at 100x magnification to count the number of adhered (adhered) threads.
  • the carbon fibers preferably have a tensile modulus greater than 240 GPa and less than 330 GPa.
  • the tensile modulus of the carbon fiber may be 250 GPa or more, 260 GPa or more, or 270 GPa or more, and/or 320 GPa or less, 310 GPa or less, 300 GPa or less, 290 GPa or less, or 280 GPa or less.
  • the tensile modulus of the carbon fiber is more preferably 250 GPa to 300 GPa, and even more preferably 260 GPa to 290 GPa.
  • the tensile modulus of carbon fiber can be measured using the method specified in JIS R 7608.
  • the normalized scattering integrated intensity measured by small angle X-ray scattering measurement may be 1.00 to 1.40.
  • This "normalized scattering integrated intensity" of the carbon fiber is expressed as a ratio to the measured value of a carbon fiber Tenax (registered trademark) filament (product name: HTA40, manufactured by Teijin Limited) as a standard sample. For example, if the scattering integrated intensity value of the carbon fiber Tenax (registered trademark) filament (product name: HTA40) as a standard sample is A and the scattering integrated intensity value of the target carbon fiber is B, the normalized scattering integrated intensity of the target carbon fiber is expressed as B/A.
  • This normalized scattering integral intensity of the carbon fibers may be 1.00 or more, greater than 1.00, 1.05 or more, or 1.10 or more, and/or 1.30 or less, 1.25 or less, 1.20 or less, 1.18 or less, or 1.15 or less.
  • the normalized scattering integral intensity of the carbon fiber is preferably 1.00 to 1.20, more preferably 1.05 to 1.18, and even more preferably 1.05 to 1.15.
  • the scattering integrated intensity (a.u.) of carbon fiber can be measured by small angle X-ray scattering (SAXS) using a small angle X-ray scattering measuring device.
  • SAXS small angle X-ray scattering
  • the data from three shifted areas with an exposure time of 10 min is merged to obtain a two-dimensional SAXS image.
  • a one-dimensional scattering profile for the scattering spectrum q is obtained from the two-dimensional SAXS image, and the peak area when this is plotted using Kratky can be regarded as the scattering integrated intensity.
  • the scattering integrated intensity of the standard sample, carbon fiber Tenax (registered trademark) filament (product name: HTA40, manufactured by Teijin Limited), and the scattering integrated intensity of the target carbon fiber are measured, and the ratio (B/A) of the scattering integrated intensity value B of the target carbon fiber to the scattering integrated intensity value A of the standard sample is calculated, thereby obtaining the "normalized scattering integrated intensity" of the target carbon fiber.
  • the ratio (M/P) of the tensile modulus M (GPa) to the normalized scattering integrated intensity P measured by small angle X-ray scattering (SAXS) may be 200 or more.
  • the M/P ratio of the carbon fibers may be 210 or more, 220 or more, 230 or more, 240 or more, or greater than 240, and/or 280 or less, 270 or less, 260 or less, or 255 or less.
  • the carbon fibers have a ratio of tensile modulus M to normalized scattering integrated intensity P (M/P) of 230 or more, which provides particularly improved physical properties (tensile strength and composite properties).
  • M/P ratio of the carbon fibers is particularly preferably 230 to 260, or even more than 240 and not more than 255.
  • the normalized scattering integral intensity P reflects minute defects in the fiber.
  • the tensile modulus is relatively high while the number of defective sites in the carbon fiber is reduced, the value of M/P becomes relatively high, and it is believed that carbon fiber with particularly good physical properties can be obtained.
  • the method for obtaining such carbon fibers is not particularly limited, but for example, they can be produced by relatively increasing the carbonization temperature (treatment temperature in the C2 furnace) and suppressing the stretch ratio in the C1 furnace.
  • the carbonization temperature (treatment temperature in the C2 furnace) and the stretch ratio in the C1 furnace please refer to the following description of the production method according to the present invention.
  • the carbon fibres may have a tensile strength of 5000 MPa or greater.
  • the tensile strength of the carbon fibers may be 5100 MPa or more, 5200 MPa or more, 5300 MPa or more, 5400 MPa or more, or 5500 MPa or more, and/or 6500 MPa or less, 6400 MPa or less, 6300 MPa or less, 6200 MPa or less, 6100 MPa or less, or 6000 MPa or less.
  • the carbon fiber has a tensile strength of more than 5100 MPa.
  • the tensile strength of the carbon fiber is more preferably 5200 MPa to 6500 MPa, and even more preferably 5500 MPa to 6300 MPa.
  • carbon fibers with relatively high tensile strength there are no particular limitations on the method for obtaining carbon fibers with relatively high tensile strength, but for example, carbon fibers can be obtained by producing them from precursor fibers produced by a dry-wet spinning method.
  • the tensile strength of carbon fibers can be measured in accordance with JIS R 7608.
  • the number of voids located within a depth of 200 nm from the surface of the carbon fiber may be 50 voids/ 40,000 nm2 or less, 40 voids/40,000 nm2 or less, or 30 voids/40,000 nm2 or less.
  • the number of voids is preferably 5/40,000 nm2 or less, more preferably 4/40,000 nm2 or less, 3/40,000 nm2 or less, 2/40,000 nm2 or less, or 1/40,000 nm2 or less, and most preferably zero/ 40,000 nm2 .
  • a carbon fiber having particularly improved physical properties tensile strength and composite properties
  • the measurement evaluation of the number of voids in carbon fiber by TEM can be carried out by the following procedure. That is, the fiber to be measured is dehydrated with ethanol, replaced with a general embedding epoxy resin, and heat cured at 120 ° C for 40 minutes to obtain a measurement sample. This sample is sliced to a thickness of about 90 nm with an ultramicrotome, and a zero-loss image (cross-sectional view) is observed and photographed with an accelerating voltage of 120 KV using a transmission electron microscope.
  • the number of voids present in an area range of 40,000 nm2 within a depth range of 200 nm from the surface of the carbon fiber is measured.
  • an area of 200 nm square as close as possible to the fiber surface can be set, and the number of voids present in this area can be measured.
  • depth from the surface means the length in the direction from the surface of the fiber toward the center of the fiber in the fiber cross section perpendicular to the fiber axis direction of the carbon fiber.
  • three or more fibers are arbitrarily selected, observed under a TEM, and the average of the measured values (for three or more fibers) is taken as the number of voids.
  • the method for producing the carbon fiber according to the present disclosure is not particularly limited.
  • the carbon fiber according to the present disclosure can be produced in particular by the following production method according to the present disclosure.
  • the method for producing carbon fibers according to the present disclosure includes: After subjecting the precursor fiber having the silicone-based oil agent attached thereto to a flame retardant treatment, the precursor fiber is subjected to a first heat treatment in a first heating furnace (C1 furnace) at a treatment temperature of 300° C. to 700° C. in an inert atmosphere; and The fiber subjected to the first heat treatment is subjected to a second heat treatment in a second heating furnace (C2 furnace) at a treatment temperature of 1000° C. or more under an inert atmosphere; In the second heating furnace, the atmosphere inside the furnace is circulated from the outlet side to the inlet side.
  • a first heating furnace C1 furnace
  • C2 furnace second heating furnace
  • the atmosphere inside the second heating furnace is circulated from the exit side to the entry side.
  • a countercurrent atmosphere is formed inside the furnace against the direction of fiber travel, and it is believed that the silicone-based oil that vaporizes and changes in quality due to heating is efficiently removed from the fiber surface.
  • the "entrance side” is the side where the fiber enters the furnace
  • the "exit side” is the side where the fiber leaves the furnace.
  • gas resulting from silicone oil is thought to be generated in large amounts in a relatively low temperature range (e.g., 600-800°C).
  • the fibers are exposed to a countercurrent flow of the atmosphere inside the furnace near the C2 furnace entrance, which is close to this temperature range, and this is thought to be particularly effective in reducing reattachment of gas to the fiber surface and adhesion of silicon-containing impurities that accompanies subsequent high-temperature treatment.
  • the precursor fiber having the silicone-based oil agent adhered thereto is subjected to a flame retardant treatment, and then a first heat treatment is performed in a first heating furnace (C1 furnace) at a treatment temperature of 300°C to 700°C in an inert atmosphere.
  • a first heating furnace C1 furnace
  • silicone oils such as amino-modified silicone and epoxy-modified silicone, but are not particularly limited.
  • the amount of silicone-based oil (OPU) attached to the precursor fiber before the flame retardant treatment is preferably 0.01% to 0.8% by weight of the precursor fiber before the silicone-based oil is attached.
  • This proportion of silicone oil may be 0.1% by weight or more, 0.15% by weight or more, or 0.2% by weight or more, and/or 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or less, or 0.4% by weight or less, based on the precursor fiber before the silicone oil is applied.
  • This proportion of silicone oil is more preferably 0.1 to 0.6% by weight, and even more preferably 0.2 to 0.4% by weight, based on the precursor fiber before the silicone-based oil is applied.
  • the method for applying the silicone oil to the precursor fiber is not particularly limited, and any known method can be used.
  • the carbon fiber precursor fiber (abbreviated as "precursor fiber") used in the method according to the present disclosure is not particularly limited, but preferably includes acrylic precursor fiber.
  • the acrylic precursor fiber is preferably produced by spinning a spinning solution containing 90% by mass or more, preferably 95% by mass to 99.9% by mass of acrylonitrile, and 10% by mass or less of other monomers, which is obtained by homopolymerization or copolymerization.
  • the other monomers include monomers copolymerizable with acrylonitrile, such as acids and salts thereof, such as acrylic acid and itaconic acid, esters such as methyl acrylate, ethyl acrylate, and methyl methacrylate, and amides such as acrylamide. These can be used alone or in combination of two or more types depending on the desired fiber properties.
  • Acrylic precursor fibers can be produced, for example, by preparing a spinning dope containing a polyacrylonitrile polymer, coagulating this spinning dope by dry spinning, wet spinning, or dry-wet spinning to obtain coagulated fibers, and then washing the obtained coagulated fibers with water, stretching, oiling, drying, and steam stretching.
  • Polyacrylonitrile polymers can be polymerized, for example, by solution polymerization or suspension polymerization. In steam stretching, the total stretch ratio can be set to 5 to 15 times.
  • organic solvents, inorganic solvents, and inorganic salt solvents can be used as the solvent for spinning.
  • the spinning method is not particularly limited, but when precursor fibers produced by a dry-wet spinning method are used, carbon fibers with relatively high physical properties (especially relatively high tensile strength) can be obtained.
  • the precursor fiber may be in the form of a fiber bundle composed of multiple single threads (filaments).
  • the number of filaments in the precursor fiber is preferably 1,000 filaments or more, and more preferably 2,000 filaments or more. There is no particular upper limit to the number of filaments, but it may be, for example, 30,000 filaments or less, 20,000 filaments or less, 10,000 filaments or less, or 5,000 filaments or less.
  • the fiber fineness of the precursor fiber may be 0.5 to 2.0 dtex.
  • the specific gravity of the precursor fiber may be 1.10 to 1.25 (g/cm 3 ), and in particular 1.15 to 1.20 (g/cm 3 ).
  • the precursor fiber having the silicone oil attached thereto is heated in an oxidizing atmosphere.
  • the flame-retardant treatment can be carried out, for example, using a heating furnace, and can be particularly carried out in air.
  • the precursor fiber is heated in heated air for 10 to 120 minutes, preferably 30 to 90 minutes.
  • the temperature of the heat treatment may be 200°C to 280°C, or 230°C to 260°C.
  • the flame retardant treatment can be performed at a draw ratio of 0.85 to 1.20, preferably 0.90 to 1.15.
  • the specific gravity of the flame-retardant treated precursor fiber may be 1.30 to 1.45 (g/cm 3 ), and in particular 1.32 to 1.40 (g/cm 3 ).
  • the flame-retardant treated precursor fiber is heat-treated at 300° C. to 700° C. in an inert atmosphere in a first heating furnace (C1 furnace).
  • the heating temperature in the first heating treatment may be 350°C or more, 400°C or more, 450°C or more, or 500°C or more, and/or 650°C or less, 600°C or less, or 550°C or less.
  • the inert atmosphere may be an inert gas atmosphere, for example, a nitrogen gas atmosphere.
  • the first heating furnace is not particularly limited, and a known carbonization furnace (particularly the first carbonization furnace) can be used.
  • the fibers are usually transported from the first heating furnace to the second heating furnace by a suitable means such as a roller. Along the traveling direction of the fibers, the first heating furnace is disposed on the upstream side, and the second heating furnace is disposed on the downstream side.
  • the draw ratio of the fiber in the first heating furnace is less than 0.9 times the maximum draw ratio.
  • the draw ratio of the fiber in the first heating furnace may be 0.8 times or less, less than 0.8 times, 0.7 times or less, or less than 0.7 times the maximum draw ratio, and/or 0.4 times or more, more than 0.4 times, 0.5 times or more, or more than 0.5 times.
  • the draw ratio of the fiber in the first heating furnace is more preferably 0.6 times to 0.8 times, and even more preferably 0.7 times to 0.8 times.
  • the maximum draw ratio D in the first heat treatment can be calculated from the following formula by guiding the fiber into the first heating furnace, fixing the inlet roller speed A, gradually increasing the outlet roller speed b, and setting the point at which the fiber becomes frayed or broken as the maximum draw speed B.
  • Maximum stretch ratio D B/A
  • the draw ratio in the first heating furnace By setting the draw ratio in the first heating furnace to the above range, it is possible to obtain carbon fiber with relatively few fiber defects (particularly voids). Furthermore, by setting the draw ratio in the first heating furnace to the above range and setting the processing temperature in the second heating furnace to a relatively high temperature (e.g., greater than 1200°C, 1300°C or higher, 1350°C or higher, or 1400°C or higher), it is possible to improve the tensile strength of the carbon fiber while suppressing fiber defects (particularly voids).
  • a relatively high temperature e.g., greater than 1200°C, 1300°C or higher, 1350°C or higher, or 1400°C or higher
  • the fiber subjected to the first heat treatment is subjected to a second heat treatment in a second heating furnace (C2 furnace) under an inert atmosphere at a treatment temperature of 1000° C. or more.
  • C2 furnace second heating furnace
  • the fiber subjected to the first heat treatment is also referred to as an "intermediate carbon fiber.”
  • the second heating furnace is not particularly limited, and a known carbonization furnace (particularly a second carbonization furnace) can be used.
  • the second heating furnace is disposed downstream of the first heating furnace along the traveling direction of the fibers.
  • the inert atmosphere may be an inert gas atmosphere, for example, a nitrogen gas atmosphere.
  • the pressure in the outlet side of the C2 furnace can be made higher than the pressure in the inlet side of the C2 furnace.
  • the "inlet side” is the side where the fibers enter the furnace, and the “outlet side” is the side where the fibers leave the furnace.
  • the difference (P2-P1) between the furnace pressure (inlet pressure) P1 measured at the inlet side of the C2 furnace and the furnace pressure (outlet pressure) P2 measured at the outlet side of the C2 furnace is 0.01 Pa or more.
  • This difference (P2-P1) is more preferably 0.02 Pa or more, 0.03 Pa or more, 0.04 Pa or more, 0.05 Pa or more, or 0.1 Pa or more.
  • the "furnace pressure on the inlet side” and the “furnace pressure on the outlet side” can each be measured using a micromanometer.
  • the C2 furnace may have an exhaust port for discharging the gas in the furnace to the outside of the furnace.
  • the exhaust port is preferably installed on the inlet side of the C2 furnace. In this case, in combination with the flow of the atmosphere in the furnace from the outlet side to the inlet side formed according to the present method, the discharge of the gas components derived from the silicone-based oil to the outside of the furnace is particularly well promoted.
  • the exhaust port near the entrance of the C2 furnace, that is, in a part of the C2 furnace that is closest to the C1 furnace. It is believed that gases resulting from silicone oil are generated in large amounts in a relatively low temperature range (e.g., 600-800°C). When the exhaust port is installed near the entrance of the C2 furnace, which is close to this temperature range, the gas components derived from the silicone-based oil are exhausted outside the furnace, which is believed to effectively reduce the accumulation of silicon-containing impurities that accompany subsequent high-temperature processing.
  • a relatively low temperature range e.g. 600-800°C
  • the heating temperature (treatment temperature) in the second heat treatment may be 1050°C or more, 1100°C or more, or 1200°C or more, and/or 2000°C or less, 1800°C or less, 1600°C or less, or 1400°C or less.
  • the treatment temperature in the second heating furnace is greater than 1200°C, and even greater than 1300°C.
  • the heating temperature in the second heating treatment relatively high, carbon fibers having relatively high tensile strength can be obtained.
  • the ratio (T/P) of the treatment temperature T (° C.) in the second heating furnace to the normalized scattering integrated intensity P measured by small angle X-ray scattering measurement (SAXS) for the produced carbon fiber may be a value of 1000 to 1400.
  • SAXS small angle X-ray scattering measurement
  • the treatment temperature T (° C.) in the second heating furnace is particularly the maximum value (highest temperature) of the treatment temperature in the second heating furnace.
  • the T/P value may be 1100 or more, 1150 or more, or 1200 or more, and/or 1350 or less, 1300 or less, or 1290 or less.
  • This T/P value is preferably 1200 or more, more preferably 1200 to 1300, and even more preferably 1200 to 1290. In this case, carbon fibers with particularly improved physical properties (tensile strength and composite properties) are obtained.
  • the normalized scattering integrated intensity P of the produced carbon fibers measured by small angle X-ray scattering measurement (SAXS) can be measured according to the method described above for carbon fibers.
  • the Si/C value on the fiber surface is reduced to 1/5 or less (20% or less) of the value before the second heat treatment.
  • the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface when the fiber (intermediate carbon fiber) immediately after being subjected to the first heat treatment is measured by X-ray photoelectron spectroscopy (XPS method) relative to the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface when the fiber (carbon fiber) immediately after being subjected to the second heat treatment is measured by X-ray photoelectron spectroscopy (XPS method) (i.e., the atomic ratio (Si/C) immediately after being subjected to the second heat treatment/the atomic ratio (Si/C) immediately after being subjected to the first heat treatment) is preferably 1/5 or less, more preferably 1/6 or less, 1/7 or less, 1/8 or less, 1/9 or less, 1/10 or less, 1/11 or less, 1/12 or less, 1/13 or less, 1/14 or less, or even 1/15
  • the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface when the fiber (carbon fiber) immediately after being subjected to the second heat treatment is measured by X-ray photoelectron spectroscopy (XPS method) is preferably 20% or less, 18% or less, 16% or less, 14% or less, 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or even 1% or less, relative to the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface when the fiber (intermediate carbon fiber) immediately after being subjected to the first heat treatment is measured by X-ray photoelectron spectroscopy (XPS method).
  • XPS method X-ray photoelectron spectroscopy
  • the atomic ratio (Si/C) of silicon atoms to carbon atoms on the fiber surface when measured by X-ray photoelectron spectroscopy (XPS) for the fiber (intermediate carbon fiber) immediately after being subjected to the first heat treatment may be in the range of 0.190 to 0.210, or may be 0.192 to 0.205, or 0.194 to 0.200.
  • the fibers that have been subjected to the second carbonization step can be further subjected to a graphitization treatment at a high temperature of 2000° C. to 3000° C., if desired.
  • the graphitization treatment further advances graphitization (high crystallization of carbon), resulting in a carbon fiber with a higher elastic modulus.
  • the carbon fiber obtained above is preferably subjected to a surface oxidation treatment in order to improve wettability with a sizing agent and/or a matrix resin.
  • the surface oxidation treatment can be performed by any conventionally known method, but electrolytic oxidation is generally used industrially because the apparatus is simple and the process is easy to control.
  • the amount of electricity used in the surface oxidation treatment is preferably in the range of 10 to 150 coulombs per gram of carbon fiber. By adjusting the amount of electricity within this range, it is possible to obtain carbon fiber that has excellent mechanical properties as a fiber and improved adhesion to resin.
  • electrolyte examples include nitric acid, sulfuric acid, ammonium sulfate, and sodium bicarbonate.
  • the electrolyte concentration of the electrolyte is preferably 0.1N or more, and more preferably 0.1 to 1N.
  • the surface-oxidized carbon fiber can be subjected to a sizing treatment as necessary.
  • the sizing treatment can be performed by a known method.
  • a known sizing agent can be appropriately used depending on the application. It is preferable to uniformly attach the sizing agent to the carbon fiber and then dry it.
  • the carbon fiber according to the present invention is a carbon fiber for a pressure vessel.
  • the carbon fiber according to the present invention can be used as a reinforcing fiber for a pressure vessel including a fiber-reinforced composite material.
  • a pressure vessel formed using the carbon fiber according to the present disclosure has particularly good pressure resistance.
  • a pressure vessel is a vessel designed to store gas or liquid at a specific pressure different from atmospheric pressure. In recent years, with the spread of fuel cell vehicles, pressure vessels having sufficient performance for purposes such as in-vehicle use and hydrogen stations have been developed.
  • the present disclosure includes a pressure vessel containing the carbon fiber according to the present disclosure.
  • the pressure vessel can be manufactured according to a known method, for example, by manufacturing an intermediate body by winding a tow prepreg containing carbon fiber around an inner frame (liner) made of metal or resin, and subjecting the intermediate body to a heat curing treatment.
  • a pressure vessel containing the carbon fiber disclosed herein can have a tank breaking strength of 140 to 160 MPa when measured using the method described in the examples.
  • the maximum draw ratio in the first heating treatment was calculated by guiding the fibers into the first heating furnace (C1 furnace), fixing the entry speed A, gradually increasing the exit roller speed b, and setting the maximum draw speed B at the point where the fibers were fuzzed or cut, and calculating the maximum draw ratio D from the following formula.
  • Each drawing condition was determined by multiplying the obtained maximum draw ratio by 0.Y (0.9, 0.8, or 0.7).
  • Maximum stretch ratio D B/A
  • Each stretching ratio (B/A) x 0. Y
  • the maximum stretch ratio for the second heat treatment was also determined in the same manner as above.
  • CF strength The tensile strength of carbon fiber (CF strength) was measured by the method specified in JIS R 7608.
  • the number of adhered carbon fibers was measured as follows: 3,000 filaments of carbon fiber cut into 5 mm lengths were dispersed in 10 ml of acetone and subjected to ultrasonic treatment, after which the number of adhered (adhered) threads was counted using a 100x optical microscope.
  • the pressure state inside the furnace was checked by measuring the values of the micromanometers on the inlet and outlet sides.
  • the carbonization furnace often has a labyrinth structure at the part where the fiber is introduced into the furnace to prevent the intrusion of external air and to maintain an inert atmosphere inside the furnace body.
  • the value of the micromanometer on the inlet side indicates the pressure difference between the inside of this inlet labyrinth and the atmospheric pressure outside the furnace.
  • the value of the micromanometer on the outlet side indicates the pressure difference between the inside of the outlet labyrinth and the atmospheric pressure outside the furnace.
  • the outlet side is higher than the inlet side, for example, 1.0 Pa on the inlet side and 1.1 Pa on the outlet side, it was determined that the inlet side is lower than the outlet side.
  • the void number measurement evaluation using a TEM was carried out according to the following procedure.
  • the fiber to be measured was dehydrated with ethanol, replaced with a general embedding epoxy resin, and heat-cured at 120°C for 40 minutes to obtain a measurement sample.
  • the sample was sliced to a thickness of about 90 nm using a Leica ultramicrotome UC-6, and a zero-loss image (cross-sectional view) was observed and photographed using a transmission electron microscope TECNAI G2 manufactured by FEI at an acceleration voltage of 120 KV.
  • the number of voids present in an area of 200 nm square was counted as close to the surface of the carbon fiber as possible, and the number of voids (pieces/40,000 nm 2 ) was obtained.
  • Three fibers were randomly selected for measurement, TEM observation was performed, and the average of the measured values (three fibers) was taken as the number of voids.
  • Si2p peak area was determined by drawing a straight baseline in the range of 96 to 108 [eV]
  • C1s peak area was determined by drawing a straight baseline in the range of 281 to 297 [eV].
  • the abundance ratio (Si/C) of Si2p to C1s peak on the carbon fiber surface was calculated from the ratio of the Si2p peak area to the C1s peak area.
  • the ratio (Si/C) of silicon atoms (Si) to carbon atoms (C) on the fiber surface of the carbon fibers was measured for the carbon fibers after the first heat treatment and the carbon fibers after the second heat treatment.
  • SAXS small angle X-ray scattering
  • a one-dimensional scattering profile for the scattering spectrum q was obtained from the two-dimensional SAXS image, and the peak area when this was plotted using Kratky was defined as the scattering integral intensity.
  • the scattering integral intensity value B of the target carbon fiber was measured, and the ratio (B/A) to the scattering integral intensity value A measured in the same manner for a standard sample, carbon fiber Tenax (registered trademark) filament (product name: HTA40, manufactured by Teijin Ltd.), was calculated to obtain the "normalized scattering integral intensity" of the target carbon fiber.
  • a carbon fiber bundle was impregnated with a resin having the following resin composition around a cylinder-shaped aluminum liner having a length of 450 mm, an outer diameter of 126 mm, and a thickness of 2 mm, and filament winding was performed with a back tension of 20 N/bundle. After winding one hoop layer, three helical layers were laminated. Another hoop layer, five helical layers, and then one hoop layer were wound, and the resulting mixture was cured in a curing oven at 120°C for five hours to obtain a pressure vessel for evaluating tank breaking strength.
  • Resin composition 100 parts by weight of bisphenol A type epoxy resin 80 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride
  • the bisphenol A epoxy resin used was EPON 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.
  • the 4-methylcyclohexane-1,2-dicarboxylic anhydride used was Lindride 52 (trade name) manufactured by LINDAU CHEMICAL INC.
  • This pressure vessel for tank burst strength evaluation was subjected to water pressure of 5 MPa/min using a burst test device, held at 10 MPa for 1 minute, and then pressure was increased by 5 MPa/min and applied again, and this process was repeated to measure the burst strength (pressure). This measurement was performed twice for each example and comparative example, and the average value was calculated for each.
  • Examples 1 to 5 Comparative Examples 1 to 2>>
  • carbon fibers were produced under various conditions shown in Tables 1-1 and 1-2, and the physical properties of the produced carbon fibers and the strength of pressure tanks produced from the carbon fibers were evaluated.
  • Example 1 The precursor fiber was an acrylic precursor fiber. According to a conventional method, the precursor fiber was spun by a dry-wet spinning method using an organic solvent as a spinning solvent, and then washed with water, dried, and stretched to produce the precursor fiber described in Table 1-1 below. After applying a silicone oil to the precursor fiber, the precursor fiber was flame-retarded at 250°C, subjected to a first heat treatment in a temperature range of 300 to 600°C in a C1 furnace, and then further subjected to a second heat treatment at a maximum temperature of 1400°C in a C2 furnace to produce a carbon fiber. Subsequently, a surface treatment was performed by a conventional method, and then a sizing agent was applied to obtain the carbon fiber according to Example 1. The precursor fiber had 0.3% by weight of a silicone oil attached thereto.
  • Example 1 the stretch ratio in the C1 furnace was set to 0.8 times the maximum stretch ratio.
  • the pressure state of the atmosphere in the C2 furnace was adjusted so that the pressure on the outlet side of the C2 furnace was higher than the pressure on the inlet side of the C2 furnace (inlet side ⁇ outlet side).
  • the pressure difference between the inlet side pressure of the C2 furnace (Pa) and the outlet side pressure of the C2 furnace (Pa) was 0.3 Pa.
  • the obtained carbon fiber according to Example 1 was used to fabricate a pressure vessel (tank) using the filament winding method as described above, and the tank's breaking strength (pressure) was measured.
  • Example 1 The evaluation results for Example 1 are shown in Tables 1-1 and 1-2 below.
  • OPU in Table 1-1 is the ratio (by weight) of the silicone-based oil adhering to the precursor fiber before the flame retardant treatment to the precursor fiber before the silicone-based oil was attached (the same applies to Tables 2-1 and 3-1).
  • the "draw ratio” in Table 1-2 is shown as a ratio relative to the maximum draw ratio, and the "carbonization temperature” in the table is the maximum temperature in the second heat treatment (the same applies to Tables 2-2 and 3-2).
  • Example 2 to 5 carbon fibers were produced in the same manner as in Example 1, except that the draw ratio in the first heat treatment and/or the maximum temperature in the second heat treatment were changed as shown in Table 1-2 below, and the physical properties of the carbon fibers and the strength of pressure vessels produced from the carbon fibers were evaluated. The production conditions and evaluation results are shown in Tables 1-1 and 1-2 below.
  • Comparative Examples 1 and 2 carbon fibers were produced in the same manner as in Example 1, except that the draw ratio in the C1 furnace was set to 0.8 or 0.7 times the maximum draw ratio, and the pressure state of the atmosphere in the C2 furnace was adjusted so that the pressure on the outlet side of the C2 furnace was the same as or lower than the pressure on the inlet side of the C2 furnace (inlet side ⁇ outlet side).
  • the production conditions and evaluation results are shown in Tables 1-1 and 1-2 below.
  • the carbon fibers of Examples 1 to 5 have higher tensile strength than Comparative Examples 1 and 2, and pressure vessels made from composites produced using these carbon fibers exhibited relatively high tank breaking strength.
  • the carbon fibers of Examples 1 to 5 had a lower Si/C ratio measured by XPS, ranging from 0.009 to 0.014. Without intending to be limited by theory, it is believed that in Examples 1 to 5, the amount of impurities (particularly impurities resulting from silicone-based oils applied in advance to the fiber surface during the carbon fiber manufacturing process) accumulated on the carbon fiber surface was reduced, resulting in relatively high tensile strength.
  • the adhesion and gloss shown in Table 1 are both believed to reflect the adhesion of impurities to the carbon fiber surface. All of Examples 1 to 5 had relatively low adhesion values and no gloss was observed.
  • Example 5 the Si/C ratio measured by XPS was relatively low at 0.012, while the ratio M/P of the tensile modulus M to the normalized scattering integral intensity P was relatively low at 224.5.
  • the number of voids observed by TEM was also relatively large. Although there is no intention to be limited by theory, it is believed that in Example 5, the draw ratio in the C1 furnace was higher than in Examples 1 to 4, being 0.9 times the maximum draw ratio, and therefore the carbon fiber had many defects (especially voids), and as a result, it showed relatively lower tensile strength and composite properties than Examples 1 to 4.
  • the results of TEM observation of the cross section of the carbon fiber of Example 5 are shown in Figure 2. As can be seen in Figure 2, voids were observed in the carbon fiber of Example 5 (areas surrounded by dotted lines in the figure).
  • Example 6 In Example 6, except that the flame-resistant temperature was relatively low (240° C.), carbon fibers were produced and evaluated in the same manner as in Example 1. The production conditions and evaluation results are shown in Tables 2-1 and 2-2 below.
  • Example 7 carbon fiber was produced and evaluated in the same manner as in Example 6, except that the draw ratio in the C1 furnace was set to 0.9 times the maximum draw ratio.
  • the production conditions and evaluation results are shown in Tables 2-1 and 2-2 below.
  • Comparative Example 3 carbon fiber was produced and evaluated in the same manner as in Example 6, except that the pressure state of the atmosphere in the C2 furnace was set to "entrance side ⁇ exit side.” The production conditions and evaluation results are shown in Tables 2-1 and 2-2 below.
  • the carbon fiber of Example 7 which had a relatively high stretch ratio in the C1 furnace, had a Si/C ratio of 0.013 measured by XPS, but a relatively low M/P ratio (tensile modulus M/normalized scattering integrated intensity P) of 229.2, and a relatively large number of voids observed by TEM, resulting in lower tensile strength and composite properties than Example 6.
  • M/P ratio tensile modulus M/normalized scattering integrated intensity P
  • Example 8 In Example 8, the precursor fibers shown in Table 3-1 below, which were produced by a wet spinning method, were used, and carbon fibers were produced and evaluated in the same manner as in Example 1, except that the maximum temperature in the second heat treatment was 1300°C.
  • Example 9 carbon fibers were produced and evaluated in the same manner as in Example 8, except that the draw ratio in the C1 furnace was set to a relatively high maximum draw ratio of 0.9 times.
  • Comparative Example 4 carbon fibers were produced and evaluated in the same manner as in Example 8, except that the pressure on the outlet side of the C2 furnace was set to be the same as or lower than the pressure on the inlet side of the C2 furnace (inlet side ⁇ outlet side).
  • FIG. 3 shows the results of TEM observation of the cross section of the carbon fiber of Example 8. As can be seen in Figure 3, voids were observed in the carbon fiber of Example 8 (areas surrounded by dotted lines in the figure), but the number of voids was relatively small (see Table 3-2).
  • the carbon fiber of Example 9 which had a relatively high draw ratio in the C1 furnace, had a relatively low M/P ratio (tensile modulus M/normalized scattering integrated intensity P) of 209.6, and also had a relatively large number of voids observed by TEM, showing physical properties lower than those of Example 8.
  • M/P ratio tensile modulus M/normalized scattering integrated intensity P

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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne : des fibres de carbone qui ont des propriétés physiques améliorées (en particulier, en termes de résistance) ; et un procédé qui permet de produire des fibres de carbone qui peuvent être largement utilisées. La présente invention concerne des fibres de carbone dans lesquelles le rapport atomique (Si/C) d'atomes de silicium sur atomes de carbone dans les surfaces des fibres est de 0,001 à 0,020 tel que mesuré par spectroscopie photoélectronique à rayons X (XPS).
PCT/JP2023/043416 2022-12-07 2023-12-05 Fibres de carbone et leur procédé de production Ceased WO2024122529A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS575923A (en) * 1980-06-11 1982-01-12 Mitsubishi Rayon Co Ltd Preparation of carbon fiber
JPS62250227A (ja) * 1986-04-18 1987-10-31 Mitsubishi Rayon Co Ltd 高性能アクリル系炭素繊維
JP2000160436A (ja) * 1998-11-30 2000-06-13 Toray Ind Inc 炭素繊維、及び炭素繊維用プリカーサーの製造方法
JP2002327374A (ja) * 2001-02-28 2002-11-15 Toray Ind Inc 繊維強化プラスチック用炭素繊維および繊維強化プラスチック
JP2003096625A (ja) * 2001-07-16 2003-04-03 Toray Ind Inc 炭素繊維の製造方法
JP2008038327A (ja) * 2006-07-10 2008-02-21 Toray Ind Inc 炭素繊維前駆体繊維製造用ポリアクリロニトリル系重合体溶液ならびに炭素繊維前駆体繊維、炭素繊維、およびそれらの製造方法
JP2009256833A (ja) * 2008-04-18 2009-11-05 Toray Ind Inc 炭素繊維および補強織物
JP2011241507A (ja) * 2010-05-19 2011-12-01 Toho Tenax Co Ltd 耐炎化繊維束、炭素繊維束およびそれらの製造方法
JP2014194108A (ja) * 2014-06-13 2014-10-09 Toho Tenax Co Ltd ポリアクリロニトリル系炭素繊維ストランド及びその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS575923A (en) * 1980-06-11 1982-01-12 Mitsubishi Rayon Co Ltd Preparation of carbon fiber
JPS62250227A (ja) * 1986-04-18 1987-10-31 Mitsubishi Rayon Co Ltd 高性能アクリル系炭素繊維
JP2000160436A (ja) * 1998-11-30 2000-06-13 Toray Ind Inc 炭素繊維、及び炭素繊維用プリカーサーの製造方法
JP2002327374A (ja) * 2001-02-28 2002-11-15 Toray Ind Inc 繊維強化プラスチック用炭素繊維および繊維強化プラスチック
JP2003096625A (ja) * 2001-07-16 2003-04-03 Toray Ind Inc 炭素繊維の製造方法
JP2008038327A (ja) * 2006-07-10 2008-02-21 Toray Ind Inc 炭素繊維前駆体繊維製造用ポリアクリロニトリル系重合体溶液ならびに炭素繊維前駆体繊維、炭素繊維、およびそれらの製造方法
JP2009256833A (ja) * 2008-04-18 2009-11-05 Toray Ind Inc 炭素繊維および補強織物
JP2011241507A (ja) * 2010-05-19 2011-12-01 Toho Tenax Co Ltd 耐炎化繊維束、炭素繊維束およびそれらの製造方法
JP2014194108A (ja) * 2014-06-13 2014-10-09 Toho Tenax Co Ltd ポリアクリロニトリル系炭素繊維ストランド及びその製造方法

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