WO2019244830A1 - Fibre de carbone et son procédé de production - Google Patents

Fibre de carbone et son procédé de production Download PDF

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Publication number
WO2019244830A1
WO2019244830A1 PCT/JP2019/023851 JP2019023851W WO2019244830A1 WO 2019244830 A1 WO2019244830 A1 WO 2019244830A1 JP 2019023851 W JP2019023851 W JP 2019023851W WO 2019244830 A1 WO2019244830 A1 WO 2019244830A1
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Prior art keywords
carbon fiber
fiber
elastic modulus
fiber bundle
gpa
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PCT/JP2019/023851
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English (en)
Japanese (ja)
Inventor
奥田治己
渡邉潤
松本直浩
田中文彦
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN201980039521.9A priority Critical patent/CN112368432B/zh
Priority to MX2020013140A priority patent/MX2020013140A/es
Priority to US16/972,068 priority patent/US20210115597A1/en
Priority to JP2019538462A priority patent/JP6702511B1/ja
Priority to KR1020207037337A priority patent/KR20210019029A/ko
Priority to EP19822232.5A priority patent/EP3808880A4/fr
Publication of WO2019244830A1 publication Critical patent/WO2019244830A1/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
    • 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
    • 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
    • D01F9/225—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 from stabilised polyacrylonitriles
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • Patent Documents 4 to 7 propose a technique for improving the processability in a carbonization step by adding entanglement to a carbon fiber precursor fiber bundle, and Patent Documents 8 and 9 by adding twist.
  • Patent Document 10 discloses that the carbon fiber and the matrix are formed by increasing the strand elastic modulus of the obtained carbon fiber by controlling the test length dependence of the pre-carbonized fiber bundle by entanglement or twisting and carbonizing with high tension. There has been proposed a technique for suppressing a decrease in the adhesiveness with the adhesive.
  • Patent Document 12 proposes a carbon fiber in which a decrease in mechanical properties is suppressed even when the diameter of a single fiber is large.
  • the conventional technology has the following problems.
  • Patent Documents 1 and 2 the molecular weight of the polyacrylonitrile copolymer is controlled.
  • the effect of increasing the critical stretching tension in the carbonization step is small, and a large improvement in strand elastic modulus cannot be expected.
  • Patent Document 3 although the stretching ratio up to the preliminary carbonization step is set to be high, the stretching ratio in the carbonization step that easily improves the strand elastic modulus of the carbon fiber is low, and a large improvement in strand elasticity cannot be expected.
  • the stretching ratio up to the preliminary carbonization step is set to be high, the stretching ratio in the carbonization step that easily improves the strand elastic modulus of the carbon fiber is low, and a large improvement in strand elasticity cannot be expected.
  • Patent Documents 4 to 9 no attention was paid to increasing the draw ratio in the carbonization step, and there was no idea to pay attention to them.
  • Patent Document 10 shows that the strand elastic modulus, the adhesiveness to the matrix, and the strand strength can be compatible at a high level, and that the passability in the carbonization step is also good.
  • no attention has been paid to the formability at the time of obtaining a carbon fiber reinforced composite material, or fiber breakage when used as a discontinuous fiber, and there is no idea to pay attention to them.
  • Patent Documents 11 and 12 do not pay special attention to the draw ratio in the carbonization step.
  • the strand elastic modulus is increased to 343 GPa at maximum by increasing the carbonization temperature.
  • conventional approaches to increasing the carbonization temperature tend to result in poor moldability in obtaining carbon fiber reinforced composites, as with commercially available high modulus grade carbon fibers.
  • a first aspect of the carbon fiber of the present invention is a carbon fiber having a strand elastic modulus of 360 GPa or more, a strand strength of 3.5 GPa or more, and a single fiber diameter of 6.0 ⁇ m or more. And a carbon fiber satisfying the following requirements (A) or (B).
  • A) or B When one end is a fixed end and the other end is a free end rotatable with respect to the axis of the fiber bundle, the number of twists remaining is 2 turns / m or more.
  • the total fineness which is the product of the fiber fineness (g / km) and the number of filaments (lines), is 740 g / km or more.
  • the carbon fiber of the present invention is a carbon fiber that has both excellent tensile modulus and processability into a composite material, and easily maintains the fiber length even when used as a discontinuous fiber.
  • the carbon fiber of the present invention is effective for reducing the required amount of carbon fiber and improving the productivity and mechanical properties of the composite material.
  • a single fiber of carbon fibers and an aggregate thereof are simply referred to as carbon fibers.
  • the aggregate of single fibers of carbon fibers in the present invention includes various forms such as a bundle form, a web form, and a composite form thereof. The method for producing the carbon fiber of the present invention will be described later.
  • the strand elastic modulus of the carbon fiber is preferably as high as possible.
  • the strand elastic modulus can be evaluated according to the tensile test of the resin-impregnated strand described in JIS R7608: 2004. The details of the method for evaluating the strand elastic modulus will be described later.
  • the strand elastic modulus can be controlled by various known methods, in the present invention, it is preferable to control the strand elasticity by the tension in the carbonization treatment.
  • the method for evaluating the diameter of the single fiber will be described later, but it may be calculated from the specific gravity, the basis weight, and the number of filaments of the fiber bundle, or may be evaluated by observation with a scanning electron microscope. As long as the evaluation device used is correctly calibrated, an equivalent result can be obtained by any method.
  • a circle equivalent diameter refers to the diameter of a perfect circle having a cross-sectional area equal to the measured cross-sectional area of a single fiber.
  • the single fiber diameter can be controlled by the discharge amount from the die during spinning of the carbon fiber precursor fiber bundle, the draw ratio in each step, and the like.
  • a first aspect of the carbon fiber of the present invention is a carbon fiber that satisfies one or more of the following requirements in addition to the requirements regarding the above-described strand elastic modulus, strand strength, and single fiber diameter.
  • B When one end is a fixed end and the other end is a free end rotatable with respect to the axis of the fiber bundle, the number of twists remaining is 2 turns / m or more.
  • Strand elastic modulus is satisfied by satisfying either or both of these requirements (a) and (b). Is high, the decrease in molding processability can be effectively suppressed, and the industrial value is great.
  • the number of remaining twists is preferably 2 turns / m or more, more preferably 5 turns / m or more, and further preferably 10 turns / m or more. It is more preferably at least 16 turns / m, more preferably at least 20 turns / m, even more preferably at least 30 turns / m, even more preferably at least 46 turns / m.
  • the fixed end is an arbitrary portion on the fiber bundle that is fixed so as not to rotate around the longitudinal direction of the fiber bundle, and restricts the rotation of the fiber bundle using an adhesive tape or the like.
  • the free end refers to an end that appears when a continuous fiber bundle is cut in a cross section perpendicular to the longitudinal direction, is not fixed to anything, and has an axis in the longitudinal direction of the fiber bundle. It is an end that can be rotated.
  • the remaining number of twists refers to the number of twists per meter of permanent twists of a fiber bundle of carbon fibers.
  • a second aspect of the carbon fiber of the present invention is a carbon fiber in which the single fiber elastic modulus Es (GPa) and the loop breaking load A (N) satisfy the relationship of the formula (1).
  • a ⁇ ⁇ 0.0017 ⁇ Es + 1.02 Formula (1) The constant term in the formula (1) is preferably 1.04, more preferably 1.06, further preferably 1.08, and particularly preferably 1.10.
  • the loop breaking load corresponds to a load at which a break occurs when a single fiber is bent in a loop shape, and is evaluated by a method described later.
  • the single fiber elastic modulus is a tensile elastic modulus of carbon fiber as a single fiber, and has a certain correlation with the strand elastic modulus.
  • the single fiber elastic modulus is described in detail later, but a single fiber tensile test is performed with a plurality of test lengths, the slope of the stress-strain curve at each test length is calculated, and the test length dependency is considered. By doing so, it can be obtained by removing the influence of the compliance of the device system.
  • the single fiber elastic modulus is increased, the loop breaking load tends to decrease.
  • the loop breaking load is low, the carbon fiber is easily broken by the force in the bending direction during the forming process as the discontinuous fiber, and the effect of improving the rigidity of the carbon fiber reinforced composite material is reduced by shortening the fiber length.
  • the single fiber diameter increases. Even when the thickness is 6.0 ⁇ m or more, both can be compatible at a high level. Also, the larger the single fiber diameter, the more the carbon fiber reinforced composite material, the more the fuzzing due to the friction between the carbon fibers when unwinding from the bobbin and the friction with the guide member such as a roller can be further suppressed, and the forming process Can be enhanced.
  • the sizing agent may be removed by a known method, such as a method of removing the sizing agent with a solvent in which the sizing agent is soluble.
  • a known method such as a method of removing the sizing agent with a solvent in which the sizing agent is soluble.
  • the number of twists is 5 to 80 turns / m. If the number of twists is within the above range, the alignment of the fiber bundles can be controlled with less fluff, and as a result, the stress transmission between the fiber bundles becomes smooth, and the knot strength tends to increase. From the viewpoint of improving the handleability during molding, the number of twists in the third embodiment is preferably from 20 to 80 turns / m.
  • the ⁇ 0.5 power of the crystallite size Lc is an index indicating a certain strength of a material. It can be interpreted that the larger Lc- 0.5 is, the stronger the material is, and the smaller Lc- 0.5 is, the more brittle the material is. Therefore, satisfying the expression (4) means that the product of the strand elastic modulus and the toughness of the material is equal to or more than a certain value, and the strand elastic modulus and the toughness of the material are compatible at a high level. It is thought to mean that.
  • the carbon fiber satisfying the formula (4) can be obtained by increasing the drawing tension in the carbonization step.
  • the surface oxygen concentration O / C is preferably 0.05 to 0.50.
  • the surface oxygen concentration is an index indicating the amount of a functional group containing an oxygen atom introduced into the surface of the carbon fiber, and can be evaluated by photoelectron spectroscopy described later. The higher the surface oxygen concentration, the better the adhesion between the carbon fiber and the matrix, and the easier it is to improve the mechanical properties of the carbon fiber reinforced composite material.
  • the surface oxygen concentration O / C is more preferably 0.07 to 0.30. When the surface oxygen concentration O / C is 0.05 or more, the adhesion to the matrix is at a sufficient level. When the surface oxygen concentration is 0.50 or less, peeling of the carbon fiber surface due to excessive oxidation is suppressed. The mechanical properties of are improved. A method for keeping the surface oxygen concentration O / C within the above range will be described later.
  • the carbon fiber precursor fiber bundle which is the basis of the carbon fiber of the present invention can be obtained by spinning a spinning solution of a polyacrylonitrile copolymer.
  • the above-mentioned polyacrylonitrile copolymer is dissolved in a solvent in which the polyacrylonitrile copolymer is soluble, such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, nitric acid, an aqueous solution of zinc chloride, and an aqueous solution of rhoda soda, to obtain a spinning solution.
  • a solvent in which the polyacrylonitrile copolymer is soluble, such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, nitric acid, an aqueous solution of zinc chloride, and an aqueous solution of rhoda soda, to obtain a spinning solution.
  • a solvent in which the polyacrylonitrile copolymer such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, nitric acid, an aqueous solution of zinc chloride, and an aqueous solution of rhoda soda.
  • the single fiber fineness of the carbon fiber precursor fiber bundle can be controlled by a known method such as a discharge amount of a spinning solution from a die and a draw ratio.
  • the obtained carbon fiber precursor fiber bundle is usually in the form of continuous fiber. Further, the number of filaments per yarn is preferably 1,000 to 80,000. In the present invention, the carbon fiber precursor fiber bundle may be twisted as necessary to adjust the number of filaments per filament of the obtained carbon fiber.
  • the oxidizing treatment of the carbon fiber precursor fiber bundle is preferably performed in an air atmosphere at a temperature in the range of 200 to 300 ° C.
  • the carbon fiber precursor fiber bundle is subjected to a flame-resistant treatment, and becomes a flame-resistant fiber bundle.
  • the carbonization of the oxidized fiber bundle is performed subsequent to the oxidization.
  • the oxidized fiber bundle obtained by the oxidization treatment is heat-treated in an inert atmosphere at a maximum temperature of 500 to 1000 ° C. until the density becomes 1.5 to 1.8 g / cm 3. Is preferred.
  • the oxidized fiber bundle is subjected to a pre-carbonization treatment to form a pre-carbonized fiber bundle.
  • the pre-carbonized fiber bundle is carbonized.
  • the preliminary carbonized fiber bundle obtained by the preliminary carbonization treatment is subjected to a carbonization treatment in an inert atmosphere.
  • the maximum temperature of the carbonization treatment is preferably 1500 ° C. or higher, more preferably 2300 ° C. or higher.
  • the highest temperature in the carbonization step is preferably higher from the viewpoint of increasing the strand elastic modulus and single fiber elastic modulus of the obtained carbon fiber, and if it is 1500 ° C or higher, the strand elastic modulus, single fiber elastic modulus and knot strength, and the loop A carbon fiber having a high level of breaking load can be obtained.
  • the tension in the carbonization step is 5 mN / dtex or more, preferably 5 to 18 mN / dtex, more preferably 7 to 18 mN / dtex, and more preferably 9 to 18 mN / dtex. Is particularly preferred.
  • the tension in the carbonization step is the tension (mN) measured on the exit side of the carbonization furnace, and the total fineness (dtex) which is the product of the single fiber fineness (dtex) of the used carbon fiber precursor fiber bundle and the number of filaments. Shall be removed.
  • the tension is preferably higher, but if too high, the permeability of the carbonization step and the quality of the obtained carbon fiber may be reduced, It is good to set in consideration of both.
  • a method for producing a carbon fiber that further satisfies the following requirement (c) or (ii) is more preferable. It is more preferable that both (c) and (d) are satisfied.
  • C) The number of twists of the fiber bundle to be subjected to the carbonization treatment is 2 turns / m or more.
  • the number of twists of the fiber bundle during the carbonization treatment is 2 turns / m or more.
  • the number of twists is preferably 5 turns / m or more, more preferably 10 turns / m or more, further preferably 16 turns / m or more, and still more preferably 30 turns / m or more.
  • 46 turns / m or more Although the upper limit of the number of twists is not particularly limited, it is effective to reduce the number of twists to approximately 60 turns / m or less in order to increase the productivity and the stretching limit in the carbonization step.
  • the number of twists of the fiber bundle during the carbonization treatment is the number of twists of the fiber bundle that has been carbonized. If the tension in the carbonization step is increased without imparting twist, single fiber breakage occurs, and the fluff increases, thereby reducing the passability of the carbonization step or causing the entire fiber bundle to break, In some cases, the tension cannot be maintained.
  • the number of twists is such that the carbon fiber precursor fiber bundle or the oxidized fiber bundle, the pre-carbonized fiber bundle is once wound on a bobbin, and then, when the fiber bundle is unwound, the surface orthogonal to the unwinding direction of the bobbin.
  • the number of filaments of the fiber bundle during the carbonization treatment is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more. If the number of twists of the fiber bundle during the carbonization treatment is the same, the larger the number of filaments, the greater the distance between the center axis of the twist and the outer periphery of the fiber bundle. The single fiber elastic modulus of the obtained carbon fiber can be effectively increased.
  • the upper limit of the number of filaments is not particularly limited, and may be set according to the intended use.
  • the inert gas used in the inert atmosphere for example, nitrogen, argon, xenon and the like are preferably exemplified, and nitrogen is preferably used from an economic viewpoint.
  • the carbon fiber bundle obtained by the above manufacturing method may be subjected to additional graphitization treatment in an inert atmosphere up to 3000 ° C., and the elastic modulus of the single fiber may be appropriately adjusted according to the application.
  • the carbon fiber bundle obtained as described above is preferably subjected to a surface treatment after the carbonization treatment to introduce a functional group containing an oxygen atom in order to improve the adhesive strength between the carbon fiber and the matrix.
  • a surface treatment method gas phase oxidation, liquid phase oxidation, and liquid phase electrolytic oxidation are used, but liquid phase electrolytic oxidation is preferably used from the viewpoint of high productivity and uniform treatment.
  • the method of liquid phase electrolytic oxidation is not particularly limited, and may be a known method.
  • the amount of current at the time of electrolytic surface treatment for performing liquid phase electrolytic oxidation is preferably 2 to 100 c / g, and more preferably 2 to 80 c / g.
  • the amount of current at the time of electrolytic surface treatment is 2 c / g or more, a sufficient oxygen-containing functional group is introduced into the carbon fiber surface, adhesion to resin is easily obtained, and a decrease in the elastic modulus of the composite material can be suppressed. If it is not more than g, the formation of defects on the carbon fiber surface due to the electrolytic surface treatment can be suppressed, and the decrease in loop breaking load can be suppressed.
  • a functional group containing an oxygen atom can be introduced into the carbon fiber bundle, and the surface oxygen concentration O / C of the carbon fiber bundle can be adjusted.
  • the current amount and the treatment time in the surface treatment may be adjusted by a known method.
  • a sizing agent can be attached to the carbon fiber bundle so as to further improve the handleability and high-order workability, or to increase the adhesive strength between the carbon fiber and the matrix.
  • the sizing agent can be appropriately selected according to the type of matrix used for the carbon fiber reinforced composite material.
  • the amount of adhesion and the like may be finely adjusted from the viewpoint of handleability and higher workability.
  • the adhesive strength between the carbon fiber and the matrix may be reduced due to the thermal decomposition product of the sizing agent, such as when using a matrix with a high molding temperature, the sizing adhesion amount should be reduced as much as possible, and the sizing treatment should be performed. Need not be performed.
  • the strand strength and the strand elastic modulus of the carbon fiber are determined according to the following procedure in accordance with the resin impregnated strand test method of JIS R7608: 2004. However, in the case where the fiber bundle of carbon fibers has a twist, it is evaluated after untwisting by giving the same number of twists in reverse rotation as the number of twists.
  • the curing conditions normal pressure, a temperature of 125 ° C. and a time of 30 minutes are used. Ten strands of the carbon fiber bundle are measured, and the average value is defined as the strand strength and the strand elastic modulus. Note that the strain range for calculating the strand elastic modulus is 0.1 to 0.6%.
  • a guide bar is installed at a height of 60 cm from the horizontal plane, and an arbitrary position of the carbon fiber bundle is fixed to the guide bar with a tape, and then the carbon fiber bundle is separated at a position 50 cm away from the fixed end. Cut to form free ends.
  • the free end is sealed so as to be sandwiched between tapes, and processed so as not to unravel into single fiber units.
  • the number of turns n (turn) is recorded.
  • the number of remaining twists is calculated by the following equation. The average of the above three measurements is taken as the number of remaining twists in the present invention.
  • Apparent single fiber elastic modulus (GPa) Slope in the range of 0.3 to 0.7% strain (MPa /%) / 10
  • E app (GPa) the average value of the apparent single fiber elastic modulus was calculated, and the reciprocal 1 / E app (GPa ⁇ 1 ) was plotted on the vertical axis (Y axis).
  • the reciprocal 1 / L 0 (mm ⁇ 1 ) of the gauge length L 0 (mm) is plotted on the horizontal axis (X axis).
  • the Y intercept in such a plot is read, and the reciprocal of the Y intercept is the single fiber elastic modulus after compliance correction, and this value is used as the single fiber elastic modulus in the present invention.
  • ⁇ Loop breaking load> Place a single fiber about 10cm long on a glass slide, drop 1-2 drops of glycerin at the center and twist both ends of the single fiber lightly in the circumferential direction to form a loop at the center of the single fiber. Put the cover glass on. This is set on the stage of a microscope, and a moving image is shot under the conditions that the total magnification is 100 times and the frame rate is 15 frames / second. While adjusting the stage each time so that the loop does not deviate from the field of view, the both ends of the looped fiber are pulled at a constant speed in the opposite direction while being pressed with a finger toward the slide glass, whereby strain is applied until the single fiber breaks.
  • ⁇ Knotting strength of carbon fiber bundle> For measurement of knot strength, a carbon fiber bundle having a weight loss rate of 0.15% or less when heated at 450 ° C. was used. When evaluating the carbon fiber bundle to which the sizing has been applied, the sizing agent is removed by washing in acetone, and the dried carbon fiber bundle is used. After drying, the weight loss rate of the carbon fiber bundle when heated at 450 ° C. is evaluated, and the carbon fiber bundle is repeatedly washed until it becomes 0.15% or less.
  • ⁇ Crystallite size Lc and degree of crystal orientation ⁇ 002 of carbon fiber bundle> A carbon fiber bundle to be subjected to measurement is aligned and solidified using a collodion-alcohol solution to prepare a square pillar measurement sample having a length of 4 cm and a side of 1 mm. The prepared measurement sample is measured using a wide-angle X-ray diffractometer under the following conditions.
  • Crystallite size (nm) K ⁇ / ⁇ 0 cos ⁇ B
  • K 1.0, ⁇ : 0.15418 nm (wavelength of X-ray)
  • ⁇ 0 ( ⁇ E 2 ⁇ 1 2 ) 1/2
  • ⁇ E apparent half width (measured value) rad
  • ⁇ 1 1.046 ⁇ 10 ⁇ 2 rad
  • B Bragg diffraction angle.
  • XRD-6100 manufactured by Shimadzu Corporation was used as the wide-angle X-ray diffractometer.
  • Single fibers are randomly extracted from the carbon fiber bundle, and wide-angle X-ray diffraction measurement is performed using an apparatus capable of using an X-ray ⁇ -beam.
  • the measurement is carried out using a microbeam having a wavelength of 0.1305 nm arranged in a shape of 3 ⁇ m in the fiber axis direction and 1 ⁇ m in the fiber diameter direction while scanning the single fiber in steps of 1 ⁇ m in the fiber diameter direction.
  • the irradiation time for each step is 2 seconds.
  • the camera length which is the distance between the detector and the sample, is set to fall within the range of 40 to 200 mm.
  • ⁇ 002 (s) (%) (180 ⁇ FWHM ⁇ ) / 180 ⁇ 100 (%).
  • the surface oxygen concentration O / C of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, the carbon fiber from which dirt attached to the surface has been removed using a solvent is cut into about 20 mm and spread on a copper sample support. Next, the sample support is set in the sample chamber, and the inside of the sample chamber is maintained at 1 ⁇ 10 ⁇ 8 Torr. Subsequently, using AlK 1, 2 as an X-ray source and measures the photoelectron escape angle as 90 °.
  • Example 10 A carbon fiber bundle was obtained in the same manner as in Example 9 except that the number of twists was changed to 5 turns / m. The carbonization process passability was good, and the quality of the obtained carbon fiber bundle was also good. The formability grade was AA, a very high level. Table 1 shows the evaluation results of the obtained carbon fibers.
  • Example 6 A carbon fiber bundle was prepared in the same manner as in Example 2 except that a carbon fiber precursor fiber bundle having a single fiber fineness of 0.8 dtex was used, the tension during the carbonization treatment was 10.3 mN / dtex, and the maximum temperature was 1900 ° C. Got. The carbonization process passability was good, and the quality of the obtained carbon fiber bundle was also good. Since the number of remaining twists is out of the range of the present invention, the grade of the formability is B and lower than that of Example 2. Table 2 shows the results of the evaluation of the obtained carbon fiber bundle.

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  • Inorganic Fibers (AREA)

Abstract

La présente invention vise à fournir une fibre de carbone destinée à un matériau composite renforcé par des fibres de carbone qui n'est pas facilement endommagé pendant un procédé de moulage et qui affiche un excellent module d'élasticité. La fibre de carbone possède un module d'élasticité de brin d'au moins 360 GPa, une résistance de brin d'au moins 3,5 GPa et un diamètre de fibre unique d'au moins 6,0 µm, et satisfait une ou plusieurs des exigences ci-dessous. (A) Lorsque l'une des extrémités est une extrémité fixe et que l'autre extrémité est une extrémité libre qui peut tourner autour de l'axe d'un faisceau de fibres, le nombre de torsion restant est d'au moins 2 tours/m. (B) La finesse totale, qui est le produit de la finesse de fibre unique (g/km) en tant que fibre de carbone et du nombre de filaments (compte), est d'au moins 740 g/km. De plus, le module d'élasticité de fibre unique Es (Gpa) et la charge de rupture de boucle A (N) de la fibre de carbone satisfont la relation d'expression (1). (1) : A ≥ -0,0017 × Es + 1,02. En outre, le diamètre de fibre unique de la fibre de carbone est d'au moins 6,0 µm, la relation entre le module d'élasticité de brin E (GPa) de la fibre de carbone et la résistance de nœud B (MPa) de la fibre de carbone telle qu'évaluée à un taux de perte de chauffage de 0,15 % ou moins à 450 °C satisfait l'expression (2), et le nombre de torsions de la fibre de carbone est de 20 à 80 tours/m. (2) : B ≥ 6,7 × 109 × E-2,85
PCT/JP2019/023851 2018-06-18 2019-06-17 Fibre de carbone et son procédé de production WO2019244830A1 (fr)

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CN201980039521.9A CN112368432B (zh) 2018-06-18 2019-06-17 碳纤维及其制造方法
MX2020013140A MX2020013140A (es) 2018-06-18 2019-06-17 Fibra de carbono y metodo para producir la misma.
US16/972,068 US20210115597A1 (en) 2018-06-18 2019-06-17 Carbon fiber and method of producing same
JP2019538462A JP6702511B1 (ja) 2018-06-18 2019-06-17 炭素繊維およびその製造方法
KR1020207037337A KR20210019029A (ko) 2018-06-18 2019-06-17 탄소 섬유 및 그의 제조 방법
EP19822232.5A EP3808880A4 (fr) 2018-06-18 2019-06-17 Fibre de carbone et son procédé de production

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JP2018115113 2018-06-18
JP2018115112 2018-06-18
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JP2018161056 2018-08-30
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KR (1) KR20210019029A (fr)
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MX (1) MX2020013140A (fr)
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JP2019218677A (ja) * 2018-06-18 2019-12-26 東レ株式会社 炭素繊維束の製造方法
WO2021044935A1 (fr) * 2019-09-04 2021-03-11 東レ株式会社 Composition de résine et article moulé

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TWI767796B (zh) * 2021-07-22 2022-06-11 臺灣塑膠工業股份有限公司 碳纖維的製造方法和碳纖維複合瓶
CN113737316A (zh) * 2021-10-14 2021-12-03 西安康本材料有限公司 一种单槽多丝碳纤维生产工艺

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JPH10195718A (ja) 1996-12-27 1998-07-28 Toray Ind Inc 炭素繊維およびその製造方法
JPH11269727A (ja) * 1998-03-18 1999-10-05 Toray Ind Inc ポリアクリロニトリル系黒鉛化繊維束およびその製造方法
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
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JP7358793B2 (ja) 2018-06-18 2023-10-11 東レ株式会社 炭素繊維束の製造方法
WO2021044935A1 (fr) * 2019-09-04 2021-03-11 東レ株式会社 Composition de résine et article moulé

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CN112368432A (zh) 2021-02-12
KR20210019029A (ko) 2021-02-19
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CN112368432B (zh) 2023-07-28
EP3808880A4 (fr) 2022-11-02
TW202006201A (zh) 2020-02-01
MX2020013140A (es) 2021-01-29
US20210115597A1 (en) 2021-04-22
JP6702511B1 (ja) 2020-06-03

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