WO2022203046A1 - Faisceau de fibres de carbone - Google Patents

Faisceau de fibres de carbone Download PDF

Info

Publication number
WO2022203046A1
WO2022203046A1 PCT/JP2022/014411 JP2022014411W WO2022203046A1 WO 2022203046 A1 WO2022203046 A1 WO 2022203046A1 JP 2022014411 W JP2022014411 W JP 2022014411W WO 2022203046 A1 WO2022203046 A1 WO 2022203046A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber bundle
carbon fiber
carbonized
width
parallel
Prior art date
Application number
PCT/JP2022/014411
Other languages
English (en)
Japanese (ja)
Inventor
祐太郎 中村
究 太田
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to CN202280023345.1A priority Critical patent/CN117120676A/zh
Priority to EP22775827.3A priority patent/EP4317552A1/fr
Priority to MX2023011242A priority patent/MX2023011242A/es
Priority to JP2023509330A priority patent/JPWO2022203046A1/ja
Publication of WO2022203046A1 publication Critical patent/WO2022203046A1/fr
Priority to US18/471,852 priority patent/US20240018695A1/en

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D11/00—Other features of manufacture
    • D01D11/04—Fixed guides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H57/00—Guides for filamentary materials; Supports therefor
    • B65H57/02—Stationary rods or plates
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/18—Separating or spreading
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H2701/00—Handled material; Storage means
    • B65H2701/30—Handled filamentary material
    • B65H2701/31—Textiles threads or artificial strands of filaments
    • B65H2701/314—Carbon fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch

Definitions

  • the present invention relates to a carbon fiber bundle that can be easily handled during advanced processing even if the carbon fiber bundle has a large total fineness, and that yields a molded product in which the carbon fibers are uniformly distributed.
  • Carbon fiber has excellent specific strength and specific modulus, so it is widely used from sports and leisure goods to aerospace applications.
  • sports applications such as golf club shafts and fishing rods and aircraft applications, it has been developed into so-called general industrial applications such as windmill components for power generation, automobile components, CNG tanks, seismic reinforcement of buildings, and ship components.
  • a carbon fiber bundle having a large mass per unit (total fineness) is required.
  • One of the causes is thought to be thickness unevenness in the width direction of carbon fiber bundles having a large total fineness.
  • the firing process, the process of applying a sizing agent, etc. the adjacent process fiber bundles are prevented from contacting, entangling or sticking together. Therefore, it is necessary to restrict the width using a width restriction guide or the like.
  • the width restriction guide When passing through the width regulating guide, the fiber bundle is pushed from both sides, and unevenness in thickness tends to occur.
  • unevenness in thickness tends to occur because the width is narrowed by the concavely curved guide.
  • Patent Document 1 when winding 60,000 carbon fiber bundles, the fiber bundles are twisted 90 degrees at the traversing location, twisted back, and wound with a concavely curved guide, so that the carbon fibers at the time of unwinding A method for producing a wide carbon fiber bundle with a uniform yarn width and a large total fineness is disclosed.
  • Patent Document 2 discloses a method of reducing variations in yarn width by using a guide that stabilizes the yarn path when winding 36,000 carbon fiber bundles.
  • Patent Document 3 24,000 fiber bundles are baked, impregnated with a sizing agent, and brought into contact with a heat roller having a surface temperature of 120 to 140° C. for 15 to 30 seconds, thereby reducing the flatness of the cross section of the fiber bundle (carbon fiber bundle (ratio of width to thickness) of 40-90 and a drape value (softness of the carbon fiber bundle) of 50-100 mm.
  • Patent Document 1 As shown in the comparative example of the present application, the variation rate of thickness is large.
  • Patent Literatures 2 and 3 do not describe the variation rate of the thickness of the carbon fiber bundles, and are not controlled.
  • the fabric passes through the comb guide, dries with a large variation in thickness, and is wound up, so the variation in thickness remains large.
  • the present invention solves the conventional problems, and even if the carbon fiber bundle has a large total fineness, it can be easily handled during advanced processing, and the carbon fiber is uniformly distributed and a molded product with a uniform fiber content can be obtained.
  • An object of the present invention is to provide a carbon fiber bundle that can be
  • the carbon fiber bundle of the present invention has the following features.
  • [1] A carbon fiber bundle having a total fineness of 2 g/m or more and a thickness variation rate of 30% or less in the width direction of the fiber bundle.
  • [2] The carbon fiber bundle according to [1], wherein the number of single fibers is 20000 or more.
  • [3] The carbon fiber bundle according to [1] or [2], wherein the fiber bundle has an average thickness of 0.18 to 0.28 mm.
  • the carbonized fiber bundle is twisted by 90° in the plane direction of the carbon fiber bundle in contact with the roller immediately before the parallel rod.
  • the maximum width of the carbonized fiber bundle in contact with the parallel bars is relative to the width of the carbonized fiber bundle in contact with the roller immediately before the parallel bars.
  • the roller is located upstream from the parallel rod in the running direction of the carbonized fiber bundle, and the length direction of the roller is substantially perpendicular to the length direction of the parallel rod. , [13] or [14].
  • the distance from the center of the roller to the center of the parallel bar is preferably 200 to 1500 mm at the shortest position, more preferably 500 to 1000 mm, [13] to [15] ]
  • the carbonized fiber bundle is flat, and one surface A of the carbonized fiber bundle is brought into contact with the parallel rod positioned upstream in the traveling direction of the carbonized fiber bundle.
  • the other surface B of the carbonized fiber bundle is brought into contact with the parallel rod located downstream in the running direction of the carbonized fiber bundle, and the carbonized fiber bundle is passed through the averaging member.
  • the method for producing a carbon fiber bundle according to any one of [11] to [16]. [18] Any one of [11] to [17], including changing the orientation of the surface of the carbonized fiber bundle about the length direction of the carbonized fiber bundle before the passing. A method for producing the described carbon fiber bundle.
  • Changing the direction of the surface includes a roller positioned upstream of the two or more parallel rods in the running direction of the carbonized fiber bundle, and a roller positioned most upstream of the two or more parallel rods in the running direction of the carbonized fiber bundle.
  • the carbon fiber bundle of the present invention also has the following features. [1a] contacting one surface A of the carbonized fiber bundle with a first rod; and contacting the other surface B of the carbonized fiber bundle with a second rod. Production method. [2a] The manufacturing method according to [1a], including changing the orientation of the surface of the carbonized fiber bundle with the longitudinal direction of the carbonized fiber bundle as an axis.
  • the manufacturing method according to [2a] wherein it is particularly preferable to incline at approximately 90° in the direction.
  • [4a] The manufacturing method according to [2a] or [3a], wherein changing the orientation of the surface; contacting the first rod; and contacting the second rod are performed in this order. .
  • [5a] Changing the direction of the surface; contacting the first rod; and contacting the second rod in this order, so that the carbon fiber bundle before performing these steps
  • the manufacturing method according to any one of [2a] to [4a] wherein the width of the carbon fiber bundle after these steps is widened to be within the range of 105 to 120% with respect to the width of 100%.
  • [6a] The manufacturing method according to any one of [1a] to [5a], which is a method for manufacturing the carbon fiber bundle according to any one of [1] to [10].
  • the carbon fiber bundle of the present invention has a large total fineness, it is easy to handle during advanced processing, and a molded product in which the carbon fibers are uniformly distributed can be obtained.
  • FIG. 4 is a diagram showing a method of calculating a variation rate of thickness of a carbon fiber bundle;
  • FIG. 4 is a diagram showing an example of an apparatus used for measuring the dynamic friction coefficient between fibers and the dynamic friction coefficient between fibers and metals of carbon fiber bundles.
  • FIG. 4 is a diagram showing an example of an averaging member used for producing the carbon fiber bundles of the present invention; 1 is a perspective view showing an example of a state in which carbonized fiber bundles of the present invention pass through parallel bars.
  • FIG. FIG. 4 is a top view showing an example of a state in which the carbonized fiber bundle of the present invention passes through parallel bars; It is a figure which shows an example of the arrangement place of the averaging member of this invention. It is a figure which shows an example of the winder of this invention.
  • the carbon fiber bundle of the present invention is a carbon fiber bundle having a total fineness of 2 g/m or more and a thickness variation rate of 30% or less in the width direction of the fiber bundle.
  • the carbon fiber bundle of the present invention is a carbon fiber bundle having a total fineness of 2.0 g/m or more. Since the productivity of carbon fiber bundles depends on the total fineness of the carbon fiber bundles, carbon fiber bundles having a large mass per unit length can be produced efficiently. More preferably, the total fineness is 2.5 g/m or more, and most preferably 3 g/m or more. When the total fineness of 2.0 g/m is expressed in dtex, it is 20000 dtex.
  • the variation rate of the thickness of the carbon fiber bundle in the width direction of the fiber bundle of the present invention (hereinafter, "the variation rate of the thickness of the carbon fiber bundle in the width direction of the fiber bundle” is simply referred to as the “thickness variation rate”. ) can be measured by the method described later.
  • the carbon fiber bundle of the present invention preferably has a variation rate of thickness of the carbon fiber bundle of 30% or less. By setting the variation rate of the thickness of the carbon fiber bundle to 30% or less, it is possible to produce a compact in which the carbon fibers are uniformly distributed.
  • the variation rate of the thickness of the carbon fiber bundle is more preferably 20% or less, more preferably 15% or less.
  • the carbon fiber bundle of the present invention preferably has 20,000 or more single fibers. As the number of single fibers increases, the productivity increases, which is preferable. In addition, the greater the number of single fibers, the greater the variation in thickness, so the carbon fiber bundle manufacturing method of the present invention can be easily applied. From these points of view, the number of single fibers is more preferably 30,000 or more, and even more preferably 40,000 or more.
  • the carbon fiber bundle of the present invention preferably has an average thickness of 0.18 to 0.28 mm. If the average thickness of the fiber bundle is 0.18 mm or more, the width of the carbon fiber bundle having a large total fineness does not become too large, and the handleability tends to be good. can be made smaller. From these points of view, the average thickness of the fiber bundle is more preferably 0.20 to 0.27 mm, still more preferably 0.21 to 0.25 mm.
  • the carbon fiber bundle of the present invention preferably has a width variation rate of 13% or less in the length direction of the fiber bundle.
  • the fluctuation rate of the width of the fiber bundle is 13% or less, it becomes easy to produce a molded body in which the carbon fibers are uniformly distributed.
  • the variation rate of the thickness of the carbon fiber bundle is more preferably 12% or less, and even more preferably 11% or less.
  • the fluctuation rate of the width of the carbon fiber bundle in the length direction of the fiber bundle of the present invention can be measured by the method described later.
  • a two-dimensional line laser displacement meter is installed on the point, and displacement data are simultaneously acquired in a row at equal intervals of 0.1 mm in the width direction of the carbon fiber bundle.
  • the average value and standard deviation of the width of the 300 fiber bundles obtained at the same time are calculated, and the ratio of the two is defined as the "variation rate of the width in the length direction of the carbon fiber bundle" of the carbon fiber bundle to be measured, Let the average value of the width of the fiber bundle be the width of the carbon fiber.
  • the carbon fiber bundle of the present invention preferably has a width of 13 to 18 mm. If the width of the carbon fiber is 13 mm or more, the thickness does not become too large, and the variation rate of the thickness can be easily reduced. From these points of view, the width of the carbon fiber bundle is more preferably 13.5 to 16.5 mm, even more preferably 14 to 17 mm.
  • the flatness (width/average thickness) of the carbon fiber bundle of the present invention is preferably 60-70. If the flatness of the carbon fiber bundle is 60 or more, the thickness of the carbon fiber bundle will not be too large, and if it is 70 or less, the width will not be too wide and the handleability will be good. From these points of view, the flatness is more preferably 61-69, more preferably 62-68.
  • the carbon fiber bundle of the present invention preferably has a cantilever value of 210 to 250 mm. If the cantilever value is 210 mm or more, the bundling property of the carbon fiber bundle running on the yarn path can be ensured during high-order processing, and resin impregnation is performed from the creel housing the carbon fiber bundle when the carbon fiber bundle is impregnated with resin. It is possible to prevent the occurrence of fluff on the yarn path leading to the process. If the cantilever value is 250 mm or less, it is possible to ensure good openability between the carbon fiber filaments during advanced processing. More preferably, the cantilever value is 220 mm or more and 240 mm or less. The cantilever value of the carbon fiber bundle can be measured by the method described later.
  • Method for measuring cantilever value of carbon fiber bundle The measurement is performed under an environment of room temperature of 25° C. and humidity of 50%. About 1 m of carbon fiber bundle is unwound from the carbon fiber bundle package without tension and cut out. In order to eliminate the influence of the curl of the cut carbon fiber bundle, one end of the carbon fiber bundle was fixed, the other end was attached with a weight of 13 mg / tex, and held in a vertically suspended state for 30 minutes. , and cut out 30 cm so as not to include the end, and use it as a carbon fiber bundle for testing.
  • a metal pressing plate is placed on the test carbon fiber bundle, and the edge (linear) of the pressing plate is aligned with the boundary line.
  • the holding plate is moved in the horizontal direction toward the slope at a speed of 0.5 cm/sec, and the movement of the holding plate is stopped when the end of the test carbon fiber bundle comes into contact with the slope. Measure the shortest distance between the point where the end of the bundle touches the slope and the boundary line. The measurement is performed once for each of the five test carbon fiber bundles, and the simple average value of the obtained numerical values is taken as the cantilever value of the carbon fiber bundle.
  • the carbon fiber bundle of the present invention preferably has stickiness of 0.18 m or less. If the sticking property is 0.18 m or less, the bundling property of the carbon fiber bundle running on the yarn path can be ensured during high-order processing, and the carbon fiber bundle is accommodated when impregnating the carbon fiber bundle with the matrix resin. It is possible to prevent the occurrence of fluff on the yarn path from the creel to the resin impregnation step.
  • the sticking property is more preferably 0.16 m or less. The sticking property of the carbon fiber bundle can be measured by the method described later.
  • the measurement is performed at room temperature of 25° C., humidity of 50%, and windless environment.
  • a spool with a diameter of 20 to 25 cm on which the carbon fiber bundle is wound is kept so that its axial direction is horizontal, and the carbon fiber bundle is unwound without applying tension, and the height of the center of the shaft of the spool is 10 cm. Cut the carbon fiber bundle at the bottom position.
  • the direction in which the carbon fiber bundle is wound obliquely around the spool advances upward, and the spool is vertically wound. Stand upright and hold without vibration.
  • the carbon fiber bundle is cut off at a position 10 cm from the contact start point with the spool, and the length of the carbon fiber bundle peeled off from the spool is measured. The measurement is performed three times, and the simple average value of the obtained numerical values is used as the measured sticking property of the carbon fiber bundle.
  • the carbon fiber bundle of the present invention preferably has a sizing agent adhesion amount of 0 to 20% by mass. If the amount of the sizing agent adhered is 20% by mass or less, the fiber bundles are less likely to stick to each other, and the variation rate of the thickness can be easily reduced. From this viewpoint, the adhesion amount of the sizing agent is more preferably 15% by mass or less, further preferably 10% by mass or less, and most preferably 5% by mass or less.
  • the lower limit value is preferably 0% by mass from the viewpoint of thickness unevenness, but is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint that the carbon fiber bundles are gathered together to improve handleability.
  • the carbon fiber bundle of the present invention preferably has a dynamic friction coefficient between fibers of 0.2 or less. If the coefficient of dynamic friction between fibers is 0.2 or less, the frictional force between single yarns is reduced, so the occurrence of fluff due to friction between carbon fiber filaments is suppressed, and the fluff, called ringer, surrounds the bobbin to produce carbon fiber. It is possible to prevent the phenomenon that the bundle cannot be unwound. 0.17 or less is more preferable.
  • the dynamic friction coefficient between fibers can be measured by the method described later.
  • FIG. 1 An example of a measuring device is shown in FIG.
  • a carbon fiber bundle 1 to be measured is tightly wound and fixed on a drive roller 1 having a diameter of 30 mm having a heating device, with a winding angle in the range of 0.1 to 0.5 mm so that the thickness is uniform.
  • the surface temperature of the driving roller 1 is set at 30°C.
  • the carbon fiber bundle of the present invention preferably has a fiber-to-metal dynamic friction coefficient of 0.18 or less. If the fiber-to-metal dynamic friction coefficient is 0.18 or less, the frictional force between the metal guide and the carbon fiber filament is reduced, so the abrasion resistance is improved.
  • the coefficient of dynamic friction between fibers and metals is more preferably 0.16 or less. The coefficient of dynamic friction between fibers and metals can be measured by the method described later.
  • the carbon fiber bundle 2 to be measured is simply placed on the drive roller 1 and the carbon fiber bundle 1 is not wound.
  • the driving roller 1 is a metal roller (material: S45C-H, mesh 400 with satin finish), and the surface temperature is 30°C.
  • the drive roller 1 is rotated at a rotation speed of 60 rpm, and the central value T4 (g) of the indicated values of the spring balance after 5 minutes is read.
  • the measurement is performed twice, and the fiber-to-metal dynamic friction coefficient is calculated from the obtained average value of T4.
  • Fiber-to-metal dynamic friction coefficient ⁇ -1 ln ((average value of T4) / (T3 x total fineness))
  • the method for producing the carbon fiber bundle of the present invention is not particularly limited, and for example, it can be produced by a method including the following steps (a) to (i).
  • FIGS. 6 and 7 show a general process diagram of the process transition for applying the sizing agent to the carbonized fiber bundles, and the averaging member in the present invention is arranged in the broken line portion indicated by A in FIG.
  • the raw spinning solution is spun and coagulated to obtain a coagulated yarn.
  • the spinning dope used in step (a) is not particularly limited.
  • An organic solvent solution of an acrylonitrile copolymer is preferable from the viewpoint of developing mechanical properties such as strength of carbon fibers.
  • the acrylonitrile copolymer is a polymer having 90% by mass or more of repeating units derived from acrylonitrile, preferably a copolymer having 95% by mass or more of repeating units derived from acrylonitrile.
  • repeating units derived from other than acrylonitrile include, for example, acrylic acid, methacrylic acid, itaconic acid, acrylic acid derivatives such as methyl acrylate, methacrylic acid Methacrylic acid derivatives such as methyl, acrylamide derivatives such as acrylamide, methacrylamide, N-methylolacrylamide and N,N-dimethylacrylamide, and vinyl monomers such as vinyl acetate can be mentioned.
  • the copolymerization component may be one kind, or two or more kinds. A vinyl monomer having one or more carboxyl groups is preferred as the copolymer component.
  • the polymerization method for producing the acrylonitrile copolymer is not particularly limited, and examples thereof include solution polymerization in an organic solvent that dissolves the acrylonitrile copolymer and precipitation polymerization in water.
  • organic solvents used in the spinning dope include polar organic solvents such as dimethylacetamide, dimethylsulfoxide, and dimethylformamide. Since the spinning stock solution obtained using these polar organic solvents does not contain metal elements, the content of metal elements in the resulting carbon fiber bundle can be reduced.
  • the solid content concentration of the spinning dope is preferably 20% by mass or more.
  • the spinning method may be either wet spinning or dry-wet spinning.
  • wet spinning a filament is spun into a temperature-controlled coagulating liquid from a spinneret having a large number of discharge holes and coagulated, and a large number of formed filaments are collectively collected as a coagulated yarn.
  • a known one such as a mixed solution of a polar organic solvent used for the spinning dope and water can be used.
  • step (b) the coagulated yarn obtained in step (a) is washed and drawn to obtain a precursor process yarn. Any known washing method may be used as long as the solvent can be removed from the coagulated yarn.
  • a denser fibril structure can also be formed by drawing the fibers in the air or in an aqueous solvent solution having a lower solvent concentration and a higher temperature than the coagulated liquid before washing the coagulated yarn. After washing the coagulated yarn, the fibers are drawn in hot water to further enhance the orientation of the acrylonitrile copolymer in the fibers.
  • an oil agent is applied to the precursor process yarn obtained in the step (b), dried and densified to obtain a precursor fiber bundle.
  • the oil agent a known one can be used, and examples thereof include an oil agent composed of a silicone compound such as silicone oil.
  • the method of drying and densification is not particularly limited, as long as the precursor process thread to which the oil agent is adhered is dried by a known drying method to be densified.
  • the fibers after drying and densification are drawn by 1.8 to 6 times in pressurized steam at 130 to 200 ° C., between heating rollers or on a heating plate, as necessary, to improve the orientation of the precursor fiber bundle. Further refinement and densification may be performed.
  • step (d) the precursor fiber bundle obtained in step (c) is subjected to a flameproof treatment to obtain a flameproof fiber bundle.
  • a flameproof treatment for example, a method of passing through a hot blast oven set so that the temperature rises stepwise from 220 to 260° C. for 30 to 100 minutes can be mentioned.
  • the fibers may be stretched during the flameproofing treatment. Moderate elongation in the flameproofing treatment can maintain or improve the orientation of the fibril structure forming the fibers, making it easier to obtain carbon fiber bundles with excellent mechanical properties. It is preferable that the density of the single fibers constituting the flameproof fiber bundle is 1.33 to 1.40 g/cm 3 .
  • step (e) the flameproof fiber bundle obtained in step (d) is carbonized to obtain a carbonized fiber bundle.
  • a carbonization treatment for example, a first carbonization treatment in which the maximum temperature is set to 600° C. to 800° C. in an inert atmosphere such as nitrogen, and a maximum temperature of 1200° C. to 2000° C. in an inert atmosphere such as nitrogen.
  • a treatment including a second carbonization treatment in which heat treatment is performed as ° C. can be mentioned.
  • the treatment time for the first carbonization treatment is preferably 1 to 3 minutes.
  • the treatment time in the second carbonization treatment is preferably 1.3 to 5 minutes.
  • the strength and elastic modulus of the carbon fiber bundle can be controlled by the temperature and treatment time in the second carbonization treatment.
  • a large shrinkage occurs in the fibers, so the elongation rate is preferably -5% to -2%.
  • a third carbonization treatment may be additionally performed as necessary.
  • step (f) the carbonized fiber bundle obtained in step (e) is subjected to surface oxidation treatment.
  • a known method can be employed for the surface oxidation treatment, and examples thereof include electrolytic oxidation, chemical oxidation, and air oxidation. Among them, electrolytic oxidation is preferred.
  • a sizing agent is applied to the carbonized fiber bundle obtained in step (f).
  • the sizing agent can be applied to the carbonized fiber bundle by applying a solution in which the sizing agent is dissolved in an organic solvent, or an emulsion in which the sizing agent is dispersed in water using an emulsifier or the like, to the carbonized fiber bundle and then drying. Before and after applying the sizing agent, it is preferable to separate adjacent carbonized fiber bundles with a comb guide or the like so that they do not stick together.
  • a sizing agent is selected that has a dynamic friction coefficient between fibers of 0.20 or less and a dynamic friction coefficient between fibers of 0.18 or less, measured by the method described in the specification. There is no particular limitation as long as the sizing agent has a coefficient of dynamic friction between fibers of 0.20 or less and a coefficient of dynamic friction between fibers and metals of 0.18 or less.
  • the amount of sizing agent attached to the carbon fiber bundle can be adjusted by adjusting the concentration of the sizing agent in the solution or emulsion, or by adjusting the amount of squeezing after application of the solution or emulsion.
  • the amount of the sizing agent attached to the carbon fiber bundle is preferably 0.4 to 2.0% with respect to the total mass of the carbon fiber bundle to which the sizing agent is attached.
  • the method of drying after application of the solution or emulsion is not particularly limited, and can be carried out using, for example, hot air, a hot plate, a heating roller, an infrared heater, or the like.
  • the carbonized fiber bundle is widened using a carbonized fiber bundle averaging member, and the fiber bundle is Uniform thickness. It is preferable that the averaging member applies an external force to the fiber bundle to widen the width of the fiber bundle, thereby loosening the single fibers so that the single fibers can be easily moved. Friction between the fiber and the metal member, air flow, vibration, or the like is used as a means for applying an external force to the single fiber. When producing a large number of carbon fiber bundles, it is preferable to spread in a direction to avoid contact with adjacent fiber bundles. The averaging member constantly applies a physical external force to the single fibers that make up the running fiber bundle, and the single fibers change their positions within the fiber bundle, resulting in a carbon fiber bundle with a good cantilever value and sticking properties. is obtained.
  • the averaging member used to produce the carbon fiber bundles of the present invention may be any means as long as it constantly applies a physical external force to single fibers. It is sufficient if the positions of the single fibers constituting the carbonized fiber bundle can be shifted with respect to each other by a physical external force while avoiding contact between them, so that the distribution can be made uniform.
  • the shape of the averaging member that applies an external force to the single fibers by the friction between the fibers and the metal member is not particularly limited.
  • a parallel-bar guide, a comb guide, or the like can be used, but a parallel-bar guide capable of efficiently applying an external force to single fibers and capable of adjusting the applied external force is preferable.
  • An example of a parallel bar guide is shown in FIG.
  • the parallel bar guide is preferably two straight bars with smooth surfaces held in parallel.
  • the surface of the carbonized fiber bundle is A and a surface B opposite said surface A are each brought into contact with said bar one or more times. By doing so, the fiber bundle spreads in the width direction, and the sticking of the single fibers is easily loosened. It is sufficient for the rod to have parallel surfaces with which the carbonized fiber bundles come into contact.
  • the shape of the rod is not particularly limited, such as a round shape or a square shape. is preferred. Since the fiber bundle is loosened when the surface A and the surface B come into contact with the bar once, respectively, the variation rate of the thickness can be easily reduced. From the point of view of loosening the fiber bundle, the first rod contacts the surface A and the second rod contacts the surface B, so that the surface A, the surface B, the surface A, and the surface B are alternately contacted in this order. is preferred.
  • the distance between adjacent parallel bars is 15 to 50 mm. If the distance between the parallel bars adjacent to each other is 15 mm or more, the carbonized fiber bundle can be easily passed through, and if the distance is 50 mm or less, the effect of widening the width is likely to be obtained. From these points of view, the distance between adjacent parallel bars is more preferably 17 to 45 mm, more preferably 19 to 40 mm.
  • the carbonized fiber bundle is twisted by 90° in the plane direction of the carbon fiber bundle in contact with the roller immediately before the parallel rod. It is preferable to let it pass through in contact with .
  • an external force is applied to the carbonized fiber bundle, and the width of the carbonized fiber bundle tends to widen.
  • the adjacent carbonized fiber bundles do not come into contact with each other, which saves space.
  • the maximum width of the carbonized fiber bundle in contact with the parallel bars is the width of the carbonized fiber bundle in contact with the roller immediately before the parallel bars. 5-20% wider is preferred.
  • the rod is preferably fixed, but the resistance of the rod is such that the surface speed of the rod becomes slower than the speed of the fiber bundles so that frictional force is generated between the carbon fiber bundles and the fiber bundles and an external force is applied. , the rod may rotate.
  • the carbon fiber bundle is wound on the winding core while being traversed to obtain a spool of the carbon fiber bundle.
  • the method of winding the carbon fiber bundle may be any method as long as it can wind the carbon fiber bundle onto the spool without twisting or the like.
  • it instead of winding it on a spool, it may be transferred to a packing box or the like.
  • Examples 1 to 10 Manufacture of carbon fiber bundles
  • a precursor fiber bundle with a single fiber fineness of 1.33 dtex and a single fiber number of 50,000 is heated in air at 240°C to 260°C in a hot air circulation type flameproofing furnace at an elongation rate of -3.9% for 66 minutes.
  • pre-carbonization treatment is performed for about 1.5 minutes at an elongation rate of 1.5% in a heat treatment furnace with a maximum temperature of 700 ° C. in a nitrogen atmosphere.
  • carbonization treatment was carried out for about 1.5 minutes in a heat treatment furnace with a maximum temperature of 1350° C. in a nitrogen atmosphere at an elongation rate of ⁇ 4.5% to obtain a carbonized fiber bundle.
  • the carbonized fiber bundle is run in a 5% by mass aqueous solution of ammonium bicarbonate, and the carbonized fiber bundle is used as an anode, and an electric current is applied between the opposite electrode so that the amount of electricity is 30 coulombs per 1 g of the carbonized fiber bundle. After that, it was washed with hot water at 90°C and dried. Then, it was immersed in an aqueous dispersion containing 6.0% of a sizing agent containing bisphenol A type epoxy resin as a main component. Next, after passing through a nip roller, the carbonized fiber bundle was dried by contacting with a roller heated to 150° C. for 30 seconds to obtain a carbonized fiber bundle with a sizing agent of 1.6 wt % attached to the carbon fiber bundle. rice field.
  • the process of averaging the carbonized fiber bundles with the sizing agent attached was run.
  • the averaging member parallel bars were used in which two cylinders with a diameter of 5 mm were arranged in parallel with a center-to-center distance of 30 mm, and the parallel bars were arranged perpendicular to the plane having the width direction of the fiber bundle.
  • the installation angle of the parallel bars was adjusted so that the gap between the cylinders was 0 mm when viewed from the running direction of the carbonized fiber bundle.
  • the carbonized fiber bundle is twisted 90° in the axial direction by the parallel rods, the width direction of the fiber bundle is set as the vertical direction, and the carbonized fiber bundle is passed in contact with the parallel rods, and then twisted back by 90° with the horizontal roller. , the carbon fiber bundle was wound onto 10 spools.
  • the carbon fiber bundles obtained in these examples have a small variation in the thickness of the fiber bundle in the width direction of the fiber bundle, a fixed amount of resin is applied to a unit amount of carbon fiber by a touch roll method. Therefore, the fiber content in the molded product becomes uniform.
  • Example 1 A carbon fiber bundle was obtained in the same manner as in Example 1, except that the carbon fiber bundle was wound on four spools at the winding unit without running the step of homogenizing the carbon fiber bundle after the sizing step. rice field. Various evaluation results are shown in Table 1. The resulting carbon fiber bundle was poor in that the thickness variation rate of the carbon fiber bundle was greater than 35%.
  • the carbon fiber bundle of the present invention has a large total fineness, it is easy to handle during advanced processing, and a molded product in which the carbon fibers are uniformly distributed can be obtained.

Landscapes

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

Abstract

L'invention concerne un faisceau de fibres de carbone ayant une finesse totale supérieure ou égale à 2 g/m. Le taux de variation de l'épaisseur du faisceau de fibres dans le sens de la largeur du faisceau de fibres est inférieur ou égal à 30 %. L'invention concerne un procédé de production de faisceaux de fibres de carbone, consistant à : appliquer un agent d'encollage sur un faisceau de fibres carbonisées ; sécher celui-ci ; amener ensuite une surface et la surface opposée des surfaces dans le sens de la largeur du faisceau de fibres carbonisées en alternance en contact avec deux barres parallèles ou plus et faire passer le faisceau de fibres carbonisées à travers les barres ; et enrouler le faisceau de fibres carbonisées autour d'une bobine.
PCT/JP2022/014411 2021-03-26 2022-03-25 Faisceau de fibres de carbone WO2022203046A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202280023345.1A CN117120676A (zh) 2021-03-26 2022-03-25 碳纤维束
EP22775827.3A EP4317552A1 (fr) 2021-03-26 2022-03-25 Faisceau de fibres de carbone
MX2023011242A MX2023011242A (es) 2021-03-26 2022-03-25 Haz de fibra de carbono.
JP2023509330A JPWO2022203046A1 (fr) 2021-03-26 2022-03-25
US18/471,852 US20240018695A1 (en) 2021-03-26 2023-09-21 Carbon fiber bundle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-052932 2021-03-26
JP2021052932 2021-03-26

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/471,852 Continuation US20240018695A1 (en) 2021-03-26 2023-09-21 Carbon fiber bundle

Publications (1)

Publication Number Publication Date
WO2022203046A1 true WO2022203046A1 (fr) 2022-09-29

Family

ID=83397483

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/014411 WO2022203046A1 (fr) 2021-03-26 2022-03-25 Faisceau de fibres de carbone

Country Status (6)

Country Link
US (1) US20240018695A1 (fr)
EP (1) EP4317552A1 (fr)
JP (1) JPWO2022203046A1 (fr)
CN (1) CN117120676A (fr)
MX (1) MX2023011242A (fr)
WO (1) WO2022203046A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01282362A (ja) * 1988-05-09 1989-11-14 Nippon Oil Co Ltd 炭素繊維束の開繊方法
JP2006305854A (ja) * 2005-04-28 2006-11-09 Toray Ind Inc 炭素繊維束への樹脂含浸方法
JP2011011830A (ja) 2009-06-30 2011-01-20 Mitsubishi Rayon Co Ltd ガイド装置、連続繊維束の巻取機、連続繊維束の製造方法、および炭素繊維束
JP2011252264A (ja) 2011-08-01 2011-12-15 Toho Tenax Co Ltd フィラメントワインディング用炭素繊維束の製造方法
JP2012154000A (ja) 2011-01-27 2012-08-16 Toray Ind Inc フィラメントワインディング成形用炭素繊維およびその製造方法
WO2018212016A1 (fr) * 2017-05-17 2018-11-22 株式会社新菱 Procédés de production de faisceaux de fibres de carbone régénérées, fibres de carbone régénérées et fibres de carbone broyées régénérées, appareil de production de faisceaux de fibres de carbone régénérées, procédé de production de résine renforcée par fibres de carbone, et faisceaux de fibres de carbone régénérées
WO2019146484A1 (fr) * 2018-01-26 2019-08-01 東レ株式会社 Mat de fibres de renforcement, et matériau de moulage de résine renforcé par des fibres et procédé de production associé
CN112048854A (zh) * 2020-09-11 2020-12-08 江苏恒神股份有限公司 缠绕成型用碳纤维束及其制备方法和应用
JP2021052932A (ja) 2019-09-27 2021-04-08 有限会社平山造園 抱き枕

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01282362A (ja) * 1988-05-09 1989-11-14 Nippon Oil Co Ltd 炭素繊維束の開繊方法
JP2006305854A (ja) * 2005-04-28 2006-11-09 Toray Ind Inc 炭素繊維束への樹脂含浸方法
JP2011011830A (ja) 2009-06-30 2011-01-20 Mitsubishi Rayon Co Ltd ガイド装置、連続繊維束の巻取機、連続繊維束の製造方法、および炭素繊維束
JP2012154000A (ja) 2011-01-27 2012-08-16 Toray Ind Inc フィラメントワインディング成形用炭素繊維およびその製造方法
JP2011252264A (ja) 2011-08-01 2011-12-15 Toho Tenax Co Ltd フィラメントワインディング用炭素繊維束の製造方法
WO2018212016A1 (fr) * 2017-05-17 2018-11-22 株式会社新菱 Procédés de production de faisceaux de fibres de carbone régénérées, fibres de carbone régénérées et fibres de carbone broyées régénérées, appareil de production de faisceaux de fibres de carbone régénérées, procédé de production de résine renforcée par fibres de carbone, et faisceaux de fibres de carbone régénérées
WO2019146484A1 (fr) * 2018-01-26 2019-08-01 東レ株式会社 Mat de fibres de renforcement, et matériau de moulage de résine renforcé par des fibres et procédé de production associé
JP2021052932A (ja) 2019-09-27 2021-04-08 有限会社平山造園 抱き枕
CN112048854A (zh) * 2020-09-11 2020-12-08 江苏恒神股份有限公司 缠绕成型用碳纤维束及其制备方法和应用

Also Published As

Publication number Publication date
MX2023011242A (es) 2023-10-03
JPWO2022203046A1 (fr) 2022-09-29
EP4317552A1 (fr) 2024-02-07
CN117120676A (zh) 2023-11-24
US20240018695A1 (en) 2024-01-18

Similar Documents

Publication Publication Date Title
JP5772012B2 (ja) フィラメントワインディング成形用炭素繊維およびその製造方法
US8129017B2 (en) Carbon fiber strand and process for producing the same
JP5161604B2 (ja) 炭素繊維の製造方法
KR100570592B1 (ko) 탄소 섬유용 아크릴로니트릴계 전구체 섬유 및 그 제조 방법
PT2208812E (pt) Fio de fibra de carbono e processo para produzir o mesmo
US6294252B1 (en) Precursor fiber bundle for production of a carbon fiber bundle, a process for producing the precursor fiber bundle, a carbon fiber bundle, and a process for producing the carbon fiber bundle
JP6520767B2 (ja) 炭素繊維用前駆体繊維束とその製造方法および炭素繊維の製造方法
JP2015067910A (ja) 炭素繊維およびその製造方法
JP7342700B2 (ja) 炭素繊維束およびその製造方法
JP5741815B2 (ja) 炭素繊維前駆体アクリル繊維束および炭素繊維束
JP5297644B2 (ja) 炭素繊維束およびその製造方法
TWI769513B (zh) 生產碳纖維的方法以及使用該方法製得的碳纖維
JP2012188781A (ja) 炭素繊維およびその製造方法
WO2022203046A1 (fr) Faisceau de fibres de carbone
JP6024858B1 (ja) 合糸糸条束の製造方法および得られた合糸糸条束を用いる炭素繊維の製造方法
JP5473468B2 (ja) 炭素繊維前駆体繊維束およびその製造方法、ならびに炭素繊維束
JP4979478B2 (ja) アクリロニトリル系炭素繊維前駆体繊維束およびこれを用いた炭素繊維束、ならびにその製造方法
JP2010071410A (ja) 溝付きローラー及びそれを用いた炭素繊維の製造装置と製造方法
JP2023133739A (ja) 炭素繊維束
JP3918285B2 (ja) 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
JP2023134229A (ja) 炭素繊維束、炭素繊維前駆体繊維束およびその製造方法
JPH0364430B2 (fr)
JP2022113763A (ja) 炭素繊維束の製造方法
JPH0335402B2 (fr)
JP2004076208A (ja) 炭素繊維前駆体束の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22775827

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023509330

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2023/011242

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2022775827

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022775827

Country of ref document: EP

Effective date: 20231026