WO2023042597A1 - Faisceau de fibres de carbone et procédé de production s'y rapportant - Google Patents

Faisceau de fibres de carbone et procédé de production s'y rapportant Download PDF

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Publication number
WO2023042597A1
WO2023042597A1 PCT/JP2022/031179 JP2022031179W WO2023042597A1 WO 2023042597 A1 WO2023042597 A1 WO 2023042597A1 JP 2022031179 W JP2022031179 W JP 2022031179W WO 2023042597 A1 WO2023042597 A1 WO 2023042597A1
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Prior art keywords
fiber bundle
carbon fiber
flameproofing
ratio
elongation
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PCT/JP2022/031179
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English (en)
Japanese (ja)
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須賀勇貴
田中文彦
渡邉潤
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東レ株式会社
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Publication of WO2023042597A1 publication Critical patent/WO2023042597A1/fr

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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
    • 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
    • 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 a carbon fiber bundle that is suitable for fabrics that has excellent shapeability while having high properties for enhancing the energy absorption performance of carbon fiber composite materials, and a method for producing the same.
  • CFRP carbon fiber reinforced plastics
  • impact resistance high impact energy absorption performance
  • the carbon fiber fabric uses carbon fiber bundles in which carbon fiber single fibers are bundled, the cross section of the carbon fiber bundles is elliptical in the woven state.
  • the plain weave structure in which one warp and weft alternately rise and fall has the advantage that the number of interlacing yarns is large and the shape is easy to stabilize, but there is a problem that large crimps occur at the intersecting parts where the warp and weft yarn intersect. there is a point In particular, in fabrics using carbon fiber bundles having a large total fineness, this tendency becomes greater because carbon fiber bundles having a large thickness intersect.
  • woven fabrics using carbon fiber bundles include unidirectional woven fabrics and multidirectional woven fabrics, and attempts have been made to reduce or avoid crimping by using a woven structure such as a twill weave structure, but none of these are available.
  • strand strength the excellent resin-impregnated strand strength of carbon fiber bundles
  • crimping of the current woven structure is unavoidable.
  • improving carbon fiber bundles is more effective than improving them, the impact resistance of the entire CFRP was not satisfactory because of the low elongation of the carbon fiber bundles used in the fabric.
  • Patent Document 1 uses a carbon fiber bundle having a thickness of 0.09 mm or less and a basis weight of 85 g/m 2 or less to obtain a thin, wide and flat carbon fiber bundle. reduces the crimp of the carbon fiber bundle, and obtains a high reinforcing effect in thin CFRP.
  • Patent Document 2 As an attempt to increase the strand strength and elongation of the carbon fiber bundle itself, in Patent Document 2, by increasing the fracture toughness value, the maximum strand strength is 8.4 GPa, and the resin-impregnated strand elastic modulus (hereinafter abbreviated as strand elastic modulus ) and achieved 325 GPa (Example 3). Similarly, in Patent Document 3, a maximum strand strength of 7.9 GPa and a maximum strand elastic modulus of 350 GPa are obtained by increasing the fracture toughness of carbon fibers (Example 7). In terms of the cross-sectional shape of the carbon fiber bundle, Patent Document 4 attempts a method of twisting the carbon fiber bundle in the flameproofing step, and obtains a carbon fiber bundle having a flat cross section.
  • strand elastic modulus resin-impregnated strand elastic modulus
  • Patent Document 5 the strand strength of the carbon fiber bundle is increased to a certain level by increasing the distortion of the ratio of the major axis to the minor axis of the carbon fiber single fiber by the method of mixing carbon fibers with different cross-sectional shapes and twisting the carbon fiber bundle. We have succeeded in flattening the cross section of the carbon fiber bundle while keeping it level.
  • Patent Document 1 a high reinforcing effect of the fabric is obtained by thinning the carbon fiber bundles.
  • the elongation and openability of the carbon fiber bundle were not satisfactory values.
  • Patent Documents 2 and 3 an attempt is made to improve the strand strength by improving the toughness, but since twisting is not performed at the stage of the flameproofing treatment, the single fiber cross-sectional shape is not controlled, and the carbon fiber There was a problem that the bundle was thick and thick. Even if the carbon fiber bundle were torn in half and used as a thin bundle, the single fiber cross-sectional shape was not sufficient to reduce the thickness of the bundle.
  • Patent Document 4 although the flatness of the cross section of the carbon fiber bundle is increased by twisting in the flameproofing process, it does not pay attention to the elongation due to the strand strength or strand elastic modulus, so even at the maximum, the examples The strand strength was unsatisfactory at 5.6 GPa, and the elongation was also unsatisfactory.
  • Patent Document 5 attempts to mix and twist carbon fibers with different cross-sectional shapes to increase the degree of distortion of the single fiber cross-sectional shape and increase the flatness of the cross-sectional shape of the carbon fiber bundle, but does not focus on the elongation.
  • the maximum strand strength was 4.8 GPa (Example 7) and the strand elastic modulus was 317 GPa, so the elongation was not satisfactory.
  • attempts to improve the strand strength and elongation of carbon fiber bundles and attempts to improve the flatness of carbon fiber bundles have been made separately until now, but the effects are completely different.
  • the operation performed to improve the flatness reduces the strand strength, it is not easy to combine them, and the combination of the two has not been studied so far.
  • the carbon fiber bundles are more suitable for textiles.
  • Strand strength is high, elongation is high for impact resistance, total fineness is small for crimp reduction, and flatness of carbon fiber bundles is large.
  • An object of the present invention is to provide a carbon fiber bundle having a large degree of distortion.
  • the present invention provides a carbon fiber bundle having a plurality of single fibers, which has a strand elastic modulus of 260 to 350 GPa, a strength of 6.0 to 8.5 GPa, and an elongation of 1.8%.
  • the number of filaments is 1,000 to 9,000, the total fineness is 0.15 to 0.35 g/m, and the average value of the ratio of the major axis to the minor axis of the cross section of the single fiber is 1.01 to 1.08.
  • the carbon fiber bundle has a coefficient of variation of 1 to 4% and a degree of skew of 0.3 to 1.2.
  • the carbon fiber bundle of the present invention has high strand strength and high elongation, and since the total fineness of the carbon fiber bundle is small and the strain of the carbon fiber single fiber is large, the cross section of the carbon fiber bundle can be made thin. As a result, the CFRP made from the woven fabric of this carbon fiber bundle has excellent energy absorption performance.
  • the average value of the ratio of the major axis to the minor axis of the single fiber cross section is 1.01 to 1.08, preferably 1.01 to 1.05, more preferably 1.01 to 1.03. is.
  • the ratio of major diameter to minor diameter refers to the ratio obtained by dividing the major diameter by the minor diameter in the cross section of a single fiber.
  • the cross section of a single fiber refers to the cross section of a single fiber perpendicular to the fiber axis.
  • the major diameter refers to the maximum value of the Feret diameter, which is the length of the longer side of a rectangle drawn so as to circumscribe the cross section of a single fiber.
  • the major axis is the major axis, and the minor axis of the ellipse having the same cross-sectional area as the cross section of the single fiber.
  • the average value is a simple average without weighting, and it means that the closer the average value of the ratio of major diameter to minor diameter is to 1.00, the more single fibers have a circular cross section. Since the elongation of the carbon fiber bundle tends to decrease as the average value of the ratio of major to minor diameters increases, the average value of the ratio of major to minor diameters should be 1.01 or more, and the average value of the ratio to major to minor diameters is 1.08. If it is below, the elongation of the carbon fiber bundle can be maintained without being greatly reduced.
  • a commonly known method for controlling the average ratio of the major axis to the minor axis of the single fiber cross section within the above range is to change the conditions of the coagulation bath.
  • the ratio of the number of single fibers having a ratio of major axis to minor axis of 1.00 to 1.03 is preferably 30 to 90%, more preferably 40 to 85%, and even more preferably 50 to 80%.
  • the greater the ratio of major to minor diameters the easier the spreadability becomes, but if the ratio of the number of single fibers having a ratio of major to minor diameters of 1.00 to 1.03 exceeds 90%, the strand strength may decrease.
  • the ratio of the number of single fibers having a ratio of major axis to minor axis of 1.00 to 1.03 is 30% or more, it is easy to achieve both of these properties at a high level.
  • a monofilament having a ratio of the major axis to the minor axis of 1.00 to 1.03 can be obtained by adjusting the coagulation conditions or by adjusting the force for crushing the monofilament in the direction perpendicular to the fiber axis.
  • the ratio of the number of single fibers having a ratio of major axis to minor axis of 1.04 to 1.10 is preferably 10 to 40%, more preferably 15 to 25%.
  • 10% or more of the single fibers having a ratio of major axis to minor axis of 1.04 to 1.10 are contained, it is easy to achieve both of these properties at a high level.
  • a monofilament having a major/minor diameter ratio of 1.04 to 1.10 can be obtained by adjusting the coagulation conditions or by adjusting the force for crushing the monofilament in the direction orthogonal to the fiber axis.
  • the coefficient of variation of the ratio of major diameter to minor diameter of the number of single fibers is 1 to 4%, preferably 1 to 3%, more preferably 1 to 2%.
  • the coefficient of variation is calculated by dividing the standard deviation by the average value and multiplying by 100, as generally defined.
  • a large coefficient of variation of the ratio of the major diameter to the minor diameter means that the ratio of the major diameter to the minor diameter is widely distributed.
  • the coefficient of variation is 1% or more, the carbon fiber bundle is excellent in opening property, and when it is 4% or less, the elongation of the carbon fiber bundle is not significantly impaired.
  • a method for controlling the coefficient of variation of the ratio of the major axis to the minor axis of the single fiber cross section within the above range will be described later.
  • the distortion of the ratio of the major axis to the minor axis of the single fiber is 0.3 to 1.2, preferably 0.3 to 1.1, more preferably 0.4 to 1.0. , more preferably 0.6 to 1.0.
  • Skewness is a parameter that represents the asymmetry of distribution and is defined by the following equation (1).
  • Skewness n/((n ⁇ 1) ⁇ (n ⁇ 2)) ⁇ (xi ⁇ x>)/s ⁇ 3 (1)
  • n is the number of single fibers (number)
  • xi is the ratio of the major axis to the minor axis of the i-th single fiber (-)
  • ⁇ x> is the average value of the ratio of the major axis to the minor axis (-)
  • s is the ratio of the major axis to the minor axis.
  • ⁇ means that the sum is taken for the number n of single fibers.
  • a skewness value of 0 indicates that the distribution is bilaterally symmetrical
  • a negative value indicates that the tail is on the small side
  • a positive value indicates that the tail is on the large side.
  • a state in which the ratio of the major axis to the minor axis is highly skewed means a state in which there is a certain amount of single fibers with a large ratio of the major axis to the minor axis, but the average value of the ratio of the major axis to the minor axis remains low.
  • the flame resistant fiber is twisted to apply tension to generate a pressing force between the single fibers. Control by transforming. By observing the cross section of the obtained carbon fiber single fiber and making fine adjustments, the carbon fiber bundle of the present invention satisfies the numerical range.
  • the carbon fiber bundle of the present invention has 1,000 to 9,000 filaments.
  • the number of filaments is the number of single fibers contained in the carbon fiber bundle. If the number of filaments is 1,000 or more, sufficient elongation can be obtained, and if the number of filaments is 9,000 or less, the total fineness is reduced. It can be kept small to obtain a suitable crimp angle for textiles.
  • the number of filaments can be arbitrarily determined in the process of manufacturing the polyacrylonitrile-based carbon fiber precursor fiber bundle.
  • the carbon fiber bundle of the present invention has a total fineness of 0.15-0.35 g/m, more preferably 0.20-0.30 g/m.
  • the total fineness is the mass per 1m of the carbon fiber bundle, and is related to the single fiber diameter and the number of filaments of the carbon fiber bundle. The smaller the total fineness, the smaller the crimp angle. If the total fineness is 0.15 g/m or more, CFRP with excellent impact resistance can be obtained, and if it is 0.35 g/m or less, a crimp angle suitable for woven fabric can be obtained.
  • the total fineness can be obtained by measuring the length of the carbon fiber bundle and the mass for that length. The total fineness can be controlled by adjusting the number of filaments other than the single fiber diameter. Identical properties tend not to be obtained.
  • the carbon fiber bundle of the present invention has a strand elastic modulus of 260 to 350 GPa, preferably 270 to 320 GPa, more preferably 270 to 300 GPa.
  • the strand elastic modulus is an index that indicates how difficult it is to deform a carbon fiber bundle when a load is applied, in other words, it is an index that indicates the lightness of the material.
  • the strand elastic modulus of the carbon fiber bundle can be evaluated according to the resin-impregnated strand tensile test described in JIS R7608:2004. Although the stress-strain curve of the carbon fiber bundle exhibits downwardly convex nonlinearity, the strain range is set to 0.1 to 0.6%, and the strand elastic modulus within that range is used.
  • the strand elastic modulus is 260 GPa or more, the carbon fiber bundle is lightweight, and if the strand elastic modulus is 350 GPa or less, the elongation can be kept high relative to the strength obtained, so sufficient impact resistance can be obtained. can get.
  • the strand elastic modulus can be controlled by the maximum temperature in the carbonization process, the heat treatment time at the maximum temperature, the heating rate, the stretching ratio, and the like.
  • the carbon fiber bundle of the present invention has a strand strength of 6.0 to 8.5 GPa, preferably 6.5 to 8.0 GPa, more preferably 7.0 to 8.0 GPa.
  • Strand strength is an index showing how difficult it is to break when a load is applied to a carbon fiber bundle.
  • the strand strength of the carbon fiber bundle can be evaluated according to the resin-impregnated strand tensile test described in JIS R7608:2004. If the strand strength is 6.0 GPa or more, sufficient impact resistance can be obtained, and although there is no upper limit for the strand strength, if the strand strength is as high as 8.5 GPa, the impact resistance tends to reach a sufficiently satisfactory level.
  • Strand strength can be enhanced by controlling various conditions such as flameproofing conditions and carbonization conditions, such as defect suppression and fracture toughness improvement.
  • the carbon fiber bundle of the present invention has an elongation of 1.8% or more, preferably 2.0% or more, more preferably 2.2% or more, and still more preferably 2.4% or more. .
  • the elongation of the carbon fiber bundle can be evaluated according to the resin-impregnated strand tensile test described in JIS R7608:2004. It is difficult to measure the elongation of carbon fiber bundles because the stress-strain curve exhibits nonlinearity, but in this tensile test, the elongation is calculated by dividing the above-mentioned strand strength by the above-mentioned strand elastic modulus. .
  • the elongation of the carbon fiber bundle can be adjusted by controlling the balance between the strand strength and the strand elastic modulus.
  • the area ratio obtained by dividing the area of the cross section of the carbon fiber bundle by the area of the rectangle defined later is preferably 0.50 to 0.70. , more preferably 0.60 to 0.70. If the area ratio is 0.78, it means that the cross section is elliptical with respect to the theoretically defined rectangle. This indicates that the single fibers forming the carbon fiber bundle are partially dented. If it is 0.70 or less, the carbon fiber bundle can be made flat because it partially has a single fiber having a depression as an effect of inserting a plurality of fiber bundles into one groove. It is possible to ensure the flatness of the carbon fiber bundle when it is made into a woven fabric.
  • the cross-sectional shape of the carbon fiber bundle is affected by the flameproofing tension and twist angle, but partial depressions in the carbon fiber bundle are mainly caused by inserting multiple fiber bundles into one groove in the flameproofing process and making them contact each other. can be controlled by
  • a polyacrylonitrile-based polymer is preferably used as a raw material for producing a polyacrylonitrile-based carbon fiber precursor fiber bundle (hereinafter sometimes abbreviated as a precursor fiber bundle).
  • the polyacrylonitrile-based polymer preferably accounts for 90 to 100 mol % of at least acrylonitrile polymer.
  • the polyacrylonitrile-based polymer preferably contains a copolymer component from the viewpoint of improving strand strength.
  • a monomer that can be used as a copolymerization component a monomer containing one or more carboxylic acid groups or amide groups is preferably used from the viewpoint of promoting flame resistance.
  • either a dry-wet spinning method or a wet spinning method may be used as the spinning method, but it is preferable to use the dry-wet spinning method, which is advantageous for the strand strength of the resulting carbon fiber bundle.
  • the spinning process includes a spinning process in which a spinning solution is discharged from a spinneret into a coagulating bath by a dry-wet spinning method for spinning, a washing process in which the fiber bundle obtained in the spinning process is drawn while being washed in a water bath, and the It preferably comprises a dry heat treatment step of dry heat-treating the fiber bundle obtained in the water washing step, and optionally includes a steam drawing step of steam-drawing the fiber bundle obtained in the dry heat treatment step. In addition, it is also possible to change the order of each step as appropriate.
  • the spinning solution is obtained by dissolving the polyacrylonitrile-based polymer described above in a solvent in which polyacrylonitrile is soluble, such as dimethylsulfoxide, dimethylformamide and dimethylacetamide.
  • the coagulation bath preferably contains a solvent such as dimethylsulfoxide, dimethylformamide and dimethylacetamide used as a solvent for the spinning solution, and a so-called coagulation promoting component.
  • a solvent such as dimethylsulfoxide, dimethylformamide and dimethylacetamide used as a solvent for the spinning solution
  • a so-called coagulation promoting component a component that does not dissolve the polyacrylonitrile-based polymer and is compatible with the solvent used for the spinning solution can be used.
  • water As the coagulation promoting component.
  • the cross-sectional shape changes depending on the coagulation conditions, and the cross-section becomes circular when the concentration of the solvent in the coagulation bath is low (40% by mass or less) and when it is high (near 80% by mass). It becomes a ⁇ -shaped cross section when it is concentrated.
  • the fibers are preferably provided with an oil such as silicone.
  • silicone oils preferably contain amino-modified silicones.
  • a known method for the dry heat treatment process can be used for the dry heat treatment process.
  • the drying temperature is 100-200°C.
  • a precursor fiber bundle suitable for obtaining the carbon fiber bundle of the present invention can be obtained by performing steam drawing as necessary. Steam drawing is preferably performed at a draw ratio of 2 to 6 times in pressurized steam.
  • a carbon fiber bundle is obtained by subjecting a precursor fiber bundle to a flameproofing step, a preliminary carbonization step, and a carbonization step.
  • the resulting flameproofed fiber bundle has a 1,370 cm -1 peak intensity in the infrared spectrum.
  • the ratio of the peak intensity at 453 cm -1 is in the range of 0.70 to 0.75, and the ratio of the peak intensity at 1,254 cm -1 to the peak intensity at 1,370 cm -1 in the infrared spectrum is 0.50 to 0
  • it is controlled to be in the 0.65 range.
  • the peak at 1,453 cm ⁇ 1 in the infrared spectrum is derived from alkene, and decreases as flame resistance progresses.
  • a peak at 1,370 cm ⁇ 1 and a peak at 1,254 cm ⁇ 1 are peaks derived from the flameproof structure, and increase as the flameproofing progresses.
  • the ratio of the peak intensity at 1,453 cm -1 to the peak intensity at 1,370 cm -1 is preferably about 0.63 to 0.69. .
  • the peak intensity ratio decreases as the flameproofing progresses, and the decrease is particularly large in the initial stage.
  • the amount of the copolymer component contained in the polyacrylonitrile-based polymer constituting the precursor fiber bundle is small, and the precursor fiber
  • the conditions may be set mainly by paying attention to a high degree of crystal orientation of the bundle, a small single fiber fineness of the precursor fiber bundle, and a high flameproofing temperature in the latter half.
  • the polyacrylonitrile-based carbon fiber precursor fiber bundle was heated until the ratio of the peak intensity at 1,453 cm -1 to the peak intensity at 1,370 cm -1 in the infrared spectrum was in the range of 0.98 to 1.10. Minute flameproofing (first flameproofing step), followed by a higher temperature than the first flameproofing step, where the ratio of the peak intensity at 1,453 cm to the peak intensity at 1,370 cm in the infrared spectrum is 0. .70 to 0.75 and for 5 to 20 minutes until the ratio of the 1,254 cm -1 peak intensity to the 1,370 cm -1 peak intensity in the infrared spectrum is in the range of 0.50 to 0.65. Flameproofing (second flameproofing step) is preferred.
  • the flameproofing temperature should be adjusted to a high value, but an appropriate flameproofing temperature depends on the properties of the precursor fiber bundle.
  • a flameproofing temperature of preferably 260-290° C. is preferred to control the range of the infrared spectrum described above.
  • the flameproofing temperature need not be constant, and may be set in multiple stages.
  • the flameproofing temperature is high and the flameproofing time is short.
  • the flameproofing time is preferably 10 to 25 minutes, and the flameproofing is preferably performed at a flameproofing temperature within the above range.
  • the flameproofing time mentioned here means the time during which the fibers stay in the flameproofing furnace
  • the flameproof fiber bundle means the fiber bundle after the flameproofing process and before the preliminary carbonization process.
  • the peak intensity described here refers to the absorbance at each wavelength after baseline correction of the spectrum obtained by measuring the infrared spectrum of a small amount of the flameproof fiber bundle sampled, especially the peak splitting. not performed.
  • the concentration of the sample is diluted with KBr so as to be 0.67% by mass and measured. In this way, the infrared spectrum should be measured every time the setting of the flameproofing conditions is changed, and the conditions should be examined.
  • the strand strength of the obtained carbon fiber bundle can be controlled.
  • the flameproofing step means heat-treating the precursor fiber bundle at 200 to 300°C in an oxygen-containing atmosphere.
  • the total processing time of the flameproofing step can be appropriately selected, preferably within the range of 15 to 40 minutes.
  • the flameproofing treatment time is set so that the specific gravity of the obtained flameproofed fiber is preferably 1.28 to 1.32.
  • a more preferable treatment time for the flameproofing step depends on the flameproofing temperature. Unless the specific gravity of the flameproof fiber bundle is 1.28 or more, the strand strength of the carbon fiber bundle may decrease. If the specific gravity of the flameproof fiber bundle is 1.32 or less, the strand strength can be increased.
  • the specific gravity of the flameproofing fiber bundle is controlled by the treatment time of the flameproofing step and the flameproofing temperature.
  • the timing of switching from the first flameproofing step to the second flameproofing step is such that the specific gravity of the fiber bundle is preferably in the range of 1.21 to 1.23. Also in this case, the conditions of the flameproofing step are controlled with priority given to satisfying the range of the infrared spectrum intensity ratio. Preferred ranges of the treatment time for flameproofing and the flameproofing temperature vary depending on the properties of the precursor fiber bundle and the copolymer composition of the polyacrylonitrile polymer.
  • twisting treatment for adjusting the degree of distortion is performed in this second flameproofing step, and the twist angle of the fiber bundle during the flameproofing treatment is preferably 0.2° or more.
  • the method of twisting the fibers during the flameproofing treatment can be selected from known methods. Specifically, there is a method in which the precursor fiber bundle is once wound on a bobbin and then, when the fiber bundle is unwound, the bobbin is rotated in a plane orthogonal to the unwinding direction, or a method in which the fiber bundle is running without being wound on the bobbin.
  • the twist can be controlled by a method of bringing a rotating roller or belt into contact with the fiber bundle to impart a twist. The larger the twist angle, the more the effect of improving the flatness of the carbon fiber bundle can be obtained.
  • the tension of the fiber bundle during the flameproofing treatment is preferably 0.7 to 1.5 mN/dtex.
  • the tension in the flameproofing step was obtained by dividing the tension (mN) measured at the inlet side of the flameproofing furnace by the total fineness (dtex), which is the product of the single fiber fineness (dtex) of the precursor fiber bundle used and the number of filaments. shall be By controlling the tension within the above numerical range, it becomes easier to give the carbon fiber monofilament a dent.
  • the second flameproofing step a plurality of fiber bundles are put into one groove of the roller for flameproofing.
  • This keeps the tension on the individual flameproofed fiber bundles low while increasing the overall tension of the multiple fiber bundles per groove, so that on the roller some single fibers have A directional stress is applied, and the ratio of the major axis to the minor axis of the cross section of the single fiber tends to increase.
  • the cross-sectional shape of some single fibers can be controlled while maintaining the overall cross-sectional shape.
  • the plural is preferably 2 to 6, more preferably 3 to 5.
  • the fiber bundles obtained in the first and second flameproofing steps are treated in an inert atmosphere at a maximum temperature of 500 to 1,200 ° C. to a specific gravity of preferably 1.5. Heat treat to ⁇ 1.8.
  • the draw ratio in the preliminary carbonization step is preferably 1.00 to 1.20. If the draw ratio in the preliminary carbonization step is 1.00 or more, the strand elastic modulus tends to increase, and the strand strength tends to increase. When the draw ratio in the preliminary carbonization step is 1.20 or less, the strand elastic modulus is easily suppressed to 350 GPa or less.
  • the pre-carbonized fiber bundle is carbonized in an inert atmosphere, preferably at a maximum temperature of 1,000-1,500°C, more preferably at a maximum temperature of 1,000-1,200°C.
  • the maximum temperature of this carbonization step is preferably low from the viewpoint of increasing the elongation of the obtained carbon fiber bundle, and if it is too low, the strand strength may decrease, so it is preferable to set it in consideration of both. .
  • the maximum temperature treatment time in the carbonization step is preferably 20 to 60 seconds.
  • the temperature elevation rate in the carbonization step is preferably 0.40-1.10°C/sec, more preferably 0.40-0.60°C/sec.
  • the rate of temperature rise in the carbonization step affects the desorption rate of cracked gas, and therefore affects the strand strength.
  • the heating rate is defined as the average rate at which the fiber passes through the temperature range of 1,000 to 1,100°C per second.
  • the temperature is often controlled by the set temperature of the heater, so the temperature rise rate is calculated from the temperature at the center of the installation position of each heater and the fiber passage timing. If the heating rate is 0.40° C./second or more, a stable strand elastic modulus can be easily obtained, and if it is 1.10° C./second or less, a decrease in strand strength can be easily suppressed.
  • the carbon fiber bundles obtained as described above are preferably subjected to oxidation treatment to introduce oxygen-containing functional groups.
  • the carbon fiber bundle is obtained by subjecting the fiber bundle obtained in the carbonization step to electrolytic surface treatment.
  • electrolytic surface treatment 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 liquid-phase electrolytic oxidation method is not particularly limited, and a known method may be used.
  • a sizing treatment can be applied to impart bundling properties to the obtained carbon fiber bundles.
  • a sizing agent having good compatibility with the matrix resin can be appropriately selected according to the type of the matrix resin used in CFRP.
  • the carbon fiber bundle of the present invention is preferably used mainly as yarn for crimped fabrics.
  • a unidirectional woven fabric or a multidirectional woven fabric can be used. It is effective to use it for bidirectional fabrics.
  • a plain weave structure in which one warp and one weft are alternately floating and interlaced is preferable because the number of crossing points of weaving yarns is large and the shape is easily stabilized.
  • the reinforcing fabric can be manufactured by the following method.
  • the flat and substantially untwisted carbon fiber bundles as described above are used as warp and/or weft yarns, and are transversely unwound so that the flatness of the carbon fiber bundles does not deteriorate and untwisting is not applied.
  • each weaving yarn may be opened or widened during or after weaving.
  • the reinforcing fabric as described above is used for forming preforms, prepregs, and CFRP, and exhibits excellent properties as a reinforcing base material. At least one sheet of any one of the reinforcing fabrics can be used for the preform.
  • the reinforcing fabric thus obtained is preferably used for members requiring high mechanical properties. It is preferable to form this reinforcing fabric into CFRP as a fabric prepreg or vacuum forming using a fabric substrate.
  • the carbon fiber bundle of the present invention satisfies all of the strand elastic modulus, strand strength, elongation, total fineness, the average value of the ratio of the major diameter to the minor diameter, the coefficient of variation, and the degree of distortion to enhance the impact resistance of CFRP. point is important.
  • the methods for measuring various physical property values used in the present invention are as follows.
  • Total fineness> A 10 m length sample of the carbon fiber bundle to be measured is dried at 120° C. for 2 hours, and the measured mass is divided by 10 to obtain the total fineness, which is the mass per 1 m.
  • the carbon fiber bundle to be measured is dried at 120° C. for 2 hours before use.
  • a dry automatic density meter is used, nitrogen is used as a measurement medium, a 10 cc type sample container is used, and the volume of the sample is adjusted to 3 to 6 cc. Measurement is performed 3 times and the average value is used.
  • an Accupic 1330 type dry automatic density meter manufactured by Shimadzu Corporation was used.
  • the strand strength, strand elastic modulus and elongation of the carbon fiber bundle are obtained according to the resin-impregnated strand test method of JIS R7608:2004, according to the following procedure.
  • normal pressure, temperature of 125° C., and time of 30 minutes are used. Seven carbon fiber strands are measured, and the average values are taken as the strand strength, strand elastic modulus and elongation.
  • the strain range for calculating the strand elastic modulus is 0.1 to 0.6%.
  • twist angle in flameproof treatment is calculated by the following formula using the basis weight y (g/m), density d (g/cm 3 ), and twist number T (turn/m) of the precursor fiber bundle used. .
  • Twist angle (°) arctan ⁇ (0.01 x y/( ⁇ x d)) 0.5 x 10 -6 x ⁇ x T ⁇ .
  • the method for evaluating the ratio of the major axis to the minor axis, the coefficient of variation, and the degree of skewness is not particularly limited as long as the evaluation is performed according to the above definitions, but the evaluation can be performed, for example, as follows. First, the carbon fiber bundles are aligned and put together with a carbon tape so as to wrap them in a cylindrical shape. In this state, scissors are applied perpendicular to the fiber axis to cut, thereby exposing the cross section of the single fiber. Such single fiber cross-sections are observed using a scanning electron microscope and saved as images.
  • the saved images are read into the open source image analysis software "ImageJ” (Version 1.53h) and the single fiber cross-section contours are traced using the “Polygon selections” tool. At this time, one contour is traced with 20 to 100 points. The contour trace is then converted to a smooth curve using the "Fit spline” tool. After conversion, the points are moved and fine-tuned to better match the profile of the monofilament cross-section and the traced curve. Subsequently, the “AR (aspect ratio)” is calculated using the “Analyze particles” tool. In addition, the aspect ratio refers to the ratio of major axis to minor axis in the present invention.
  • the number of single fibers may be any number, but the number of single fibers is selected so that no statistical deviation appears. For example, the same operation is performed on 50 single fibers. At this time, single fibers are evenly selected from different portions of the carbon fiber bundle.
  • the ratio of the number of single fibers having a specific ratio of major axis to minor axis is a value (%) obtained by dividing the number of single fibers having a specific ratio of major axis to minor axis by the total number of evaluated single fibers and multiplying by 100.
  • the average value (-), coefficient of variation (%), and skewness (-) are calculated from all evaluated single fiber counts.
  • the skewness of the ratio of major diameter to minor diameter is calculated according to the following formula (1).
  • Skewness n/((n ⁇ 1) ⁇ (n ⁇ 2)) ⁇ (x i ⁇ x>)/s ⁇ 3 (1)
  • n is the number of single fibers (pieces)
  • x i is the ratio of the major diameter to the minor diameter of the i-th single fiber (-)
  • ⁇ x> is the average value of the ratio of the major diameter to the minor diameter (-)
  • s is the major diameter to the minor diameter.
  • ⁇ means that the sum is taken for the number n of single fibers.
  • SEM scanning electron microscope
  • S-4800 manufactured by Hitachi High-Technologies Corporation was used as a scanning electron microscope, and observation was carried out at an accelerating voltage of 5 keV.
  • Openability is evaluated in a state in which no sizing agent is adhered to the carbon fiber bundle. If the sizing agent is adhered, it is removed by burning off the sizing agent in an oven or by washing in a solvent before evaluation. A carbon fiber bundle of 2 cm is sampled, and is assumed to be untwisted. A carbon fiber bundle is placed on a 10 cm square glass plate, and a slide glass is placed on it. The carbon fiber bundle is moved 10 times alternately by 3 mm in the axial direction and the vertical direction. The yarn width change was measured before and after this operation, and the average value obtained by repeating this operation 10 times was used as an index of the openability. The greater the ratio of the yarn width expansion, the better the openability.
  • the openability is judged from A to C by how many times the yarn width of the carbon fiber bundle is larger than the yarn width before measurement.
  • the cross-sectional shape of the carbon fiber bundle is measured as follows.
  • the carbon fiber bundle is allowed to hang under its own weight in a state where it is substantially untwisted and with almost no tension applied, and the entire carbon fiber bundle is fixed by applying an adhesive or the like. Cut so as not to destroy the shape of A cross section of the cut carbon fiber bundle is observed with a polarizing microscope to acquire an image.
  • the acquired images are loaded into the open-source image analysis software "ImageJ" (Version 1.53h) and the single fiber cross-section contours are traced using the "Polygon selections" tool. At this time, one contour is traced with 20 to 100 points on the contour.
  • the contour trace is then converted to a smooth curve using the "Fit spline” tool.
  • the "Analyze particles” tool is used to obtain the length and position information of the Feret diameter and the area within the contour.
  • the length of the line segment that intersects perpendicularly with the line segment that is the Feret diameter and has the longest distance to the contour is obtained.
  • the cross-sectional shape of the carbon fiber bundle is determined by the area within the contour, the Feret diameter, and the length of the line segment perpendicular to the Feret diameter, and calculated according to the following formula (2).
  • A is the Feret diameter
  • B is the length of the aforementioned line segment perpendicular to the Feret diameter
  • C is the area within the contour, which correspond to the letters in FIG.
  • the cross-sectional shape is determined by determining the area ratio of the carbon fiber bundle cross-section from the rectangle (A ⁇ 2B) defined by two sides and the area (C) within the contour.
  • Example 1 A polyacrylonitrile-based polymer was polymerized by a solution polymerization method using dimethylsulfoxide as a solvent to obtain a spinning solution.
  • the resulting spinning solution was once discharged into the air from a spinneret and introduced into a coagulation bath consisting of an aqueous solution of 35% by mass of dimethyl sulfoxide maintained at 0°C to obtain a coagulated filament by a dry-wet spinning method.
  • the coagulated yarn was washed with water by a conventional method, it was stretched 3.5 times in two hot water baths. Subsequently, an amino-modified silicone-based silicone oil agent was applied to the fiber bundle after the water-bath drawing, and a drying and densification treatment was performed using a heating roller at 160°C.
  • the fiber was drawn 3.7 times in pressurized steam to make the total draw ratio 13 times, and then entangled to obtain a precursor fiber bundle having 6,000 single fibers.
  • the single fiber fineness of the precursor fiber bundle was 0.7 dtex.
  • the conditions for the first flameproofing step are a flameproofing temperature of 250°C and a flameproofing time of 11 minutes
  • the second flameproofing step is carried out under the conditions of a flameproofing temperature of 280°C and a flameproofing time of 6 minutes (conditions 1) While maintaining a tension of 0.8 mN/dtex in an oven in an air atmosphere, two precursor fiber bundles are put into each groove of the rollers before and after the flameproofing furnace for flameproofing treatment, and the flameproof fiber bundles are got At this time, the flameproofing step was performed while twisting the precursor fiber bundle at 15 turns per meter.
  • the obtained flame-resistant fiber bundle was subjected to a preliminary carbonization treatment at a draw ratio of 1.20 in a nitrogen atmosphere at a maximum temperature of 800°C to obtain a preliminary carbonized fiber bundle.
  • the obtained pre-carbonized fiber bundle was carbonized in a nitrogen atmosphere at a maximum temperature of 1,400° C. and a draw ratio of 0.950.
  • the rate of temperature increase in the carbonization step was 0.45° C./second, and the residence time at the maximum temperature was 60 seconds.
  • Tables 1 and 2 show the physical properties of the final carbon fiber bundle obtained by subjecting the obtained carbon fiber bundle to surface treatment and coating treatment with a sizing agent.
  • Example 2 By changing the draw ratio at the time of flameproofing, the tension at the time of flameproofing was set to 1.0 mN / dtex, and the carbon fiber precursor fiber bundle was twisted at 15 rotations per 1 m, and each groove of the roller before and after the flameproofing furnace A carbon fiber bundle was obtained in the same manner as in Example 1, except that three carbon fiber precursor fiber bundles were added to the . Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 3 A carbon fiber bundle was obtained in the same manner as in Example 2, except that the tension during flameproofing was changed to 1.2 mN/dtex by changing the draw ratio during flameproofing. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 4 A carbon fiber bundle was obtained in the same manner as in Example 2, except that the tension during flameproofing was changed to 1.5 mN/dtex by changing the draw ratio during flameproofing. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 5 A carbon fiber bundle was obtained in the same manner as in Example 2, except that two precursor fiber bundles were put into each groove of the rollers before and after the flameproofing furnace. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • the first flameproofing step was performed under the conditions of a flameproofing temperature of 250°C and a flameproofing time of 11 minutes, and the second flameproofing step was carried out under the conditions of a flameproofing temperature of 288°C and a flameproofing time of 5 minutes (Condition 2).
  • the tension at the time of flameproofing was set to 1.0 mN/dtex, and the precursor fiber bundle was twisted at 7 turns per 1 m, and 4 twists per groove of the rollers before and after the flameproofing furnace.
  • a carbon fiber bundle was obtained in the same manner as in Example 1, except that one precursor fiber bundle was added. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 7 The conditions for the first flameproofing step were a flameproofing temperature of 250°C and a flameproofing time of 11 minutes, and the conditions of the second flameproofing step were a flameproofing temperature of 283°C and a flameproofing time of 5 minutes (Condition 3). obtained a carbon fiber bundle in the same manner as in Example 6. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 8 The conditions for the first flameproofing step were a flameproofing temperature of 250°C and a flameproofing time of 11 minutes, and the conditions of the second flameproofing step were a flameproofing temperature of 281°C and a flameproofing time of 7 minutes (Condition 4). obtained a carbon fiber bundle in the same manner as in Example 6. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 9 A carbon fiber bundle was obtained in the same manner as in Example 8, except that the number of filaments in the precursor fiber bundle was 8,000. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Example 10 The single fiber fineness of the precursor fiber bundle is 0.5 dtex, the first flameproofing step is performed at a flameproofing temperature of 250 ° C., and the flameproofing time is 11 minutes.
  • a carbon fiber bundle was obtained in the same manner as in Example 8 except that the curing time was 6 minutes (Condition 5). Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Comparative Example 2 A carbon fiber bundle was obtained in the same manner as in Comparative Example 1 except that the tension during flameproofing was changed to 1.6 mN/dtex by changing the draw ratio during flameproofing, and the temperature conditions for flameproofing were changed to Condition 2. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Comparative Example 3 A carbon fiber bundle was obtained in the same manner as in Comparative Example 1, except that the tension during flameproofing was changed to 2.0 mN/dtex by changing the draw ratio during flameproofing, and the flameproofing temperature condition was changed to Condition 6. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Comparative Example 5 A carbon fiber bundle was obtained in the same manner as in Comparative Example 4, except that the tension during flameproofing was changed to 2.5 mN/dtex by changing the draw ratio during flameproofing. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Comparative Example 6 A carbon fiber bundle was obtained in the same manner as in Comparative Example 4, except that the tension during flameproofing was changed to 1.5 mN/dtex by changing the draw ratio during flameproofing. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • Comparative Example 7 A carbon fiber bundle was obtained in the same manner as in Comparative Example 4, except that the tension during flameproofing was changed to 0.6 mN/dtex by changing the draw ratio during flameproofing. Tables 1 and 2 show the evaluation results of the obtained carbon fiber bundles.
  • the carbon fiber bundle of the present invention is a carbon fiber that is suitable for a textile reinforcing material that has both excellent mechanical properties peculiar to carbon fiber and flatness of the cross section of the carbon fiber bundle in a high balance.
  • a high-performance fabric reinforcing material can be obtained with high productivity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne un matériau composite à base de fibres de carbone, qui a une excellente absorption d'énergie et qui est composé de fibres de carbone ayant une résistance élevée et un allongement élevé, qui est produit par un procédé de production permettant d'obtenir une excellente quantité produite. Le faisceau de fibres de carbone selon l'invention ayant une pluralité de monofibres a un module d'élasticité des brins de 260 à 350 GPa, une résistance de 6,5 à 8,5 GPa, un allongement d'au moins 1,8 %, un nombre de filaments de 1 000 à 9 000 et une finesse totale de 0,15 à 0,35 g/m, la valeur moyenne des rapports grand axe/petit axe dans des sections transversales des monofibres étant de 1,01 à 1,08, le coefficient de variation étant de 1 à 4 % et l'asymétrie étant de 0,3 à 1,2.
PCT/JP2022/031179 2021-09-15 2022-08-18 Faisceau de fibres de carbone et procédé de production s'y rapportant WO2023042597A1 (fr)

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JPS58191244A (ja) 1982-04-28 1983-11-08 三菱レイヨン株式会社 炭素繊維からなる薄地織物及びその製造法
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
JP2002069754A (ja) * 2000-08-31 2002-03-08 Toho Tenax Co Ltd 高強度・高伸度炭素繊維及びその成形材料
JP2002294518A (ja) * 2001-03-30 2002-10-09 Mitsubishi Rayon Co Ltd 炭素繊維前駆体アクリロニトリル系糸条及びその製造方法
JP2015067910A (ja) 2013-09-27 2015-04-13 東レ株式会社 炭素繊維およびその製造方法
WO2016068034A1 (fr) 2014-10-29 2016-05-06 東レ株式会社 Faisceau de fibres de carbone et son procédé de fabrication
JP2017128838A (ja) * 2016-01-15 2017-07-27 東レ株式会社 炭素繊維前駆体繊維束および炭素繊維束の製造方法
JP2017137614A (ja) 2016-01-28 2017-08-10 東レ株式会社 炭素繊維束およびその製造方法
JP2021059829A (ja) 2019-10-09 2021-04-15 東レ株式会社 炭素繊維およびその製造方法
WO2021090641A1 (fr) * 2019-11-06 2021-05-14 東レ株式会社 Procédé de fabrication de faisceau de fibres de carbone

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58191244A (ja) 1982-04-28 1983-11-08 三菱レイヨン株式会社 炭素繊維からなる薄地織物及びその製造法
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
JP2002069754A (ja) * 2000-08-31 2002-03-08 Toho Tenax Co Ltd 高強度・高伸度炭素繊維及びその成形材料
JP2002294518A (ja) * 2001-03-30 2002-10-09 Mitsubishi Rayon Co Ltd 炭素繊維前駆体アクリロニトリル系糸条及びその製造方法
JP2015067910A (ja) 2013-09-27 2015-04-13 東レ株式会社 炭素繊維およびその製造方法
WO2016068034A1 (fr) 2014-10-29 2016-05-06 東レ株式会社 Faisceau de fibres de carbone et son procédé de fabrication
JP2017128838A (ja) * 2016-01-15 2017-07-27 東レ株式会社 炭素繊維前駆体繊維束および炭素繊維束の製造方法
JP2017137614A (ja) 2016-01-28 2017-08-10 東レ株式会社 炭素繊維束およびその製造方法
JP2021059829A (ja) 2019-10-09 2021-04-15 東レ株式会社 炭素繊維およびその製造方法
WO2021090641A1 (fr) * 2019-11-06 2021-05-14 東レ株式会社 Procédé de fabrication de faisceau de fibres de carbone

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