EP3760768A1 - Faserherstellungsverfahren und kohlenstofffaserherstellungsverfahren - Google Patents

Faserherstellungsverfahren und kohlenstofffaserherstellungsverfahren Download PDF

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Publication number
EP3760768A1
EP3760768A1 EP18908160.7A EP18908160A EP3760768A1 EP 3760768 A1 EP3760768 A1 EP 3760768A1 EP 18908160 A EP18908160 A EP 18908160A EP 3760768 A1 EP3760768 A1 EP 3760768A1
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EP
European Patent Office
Prior art keywords
spinneret
fiber
gas
producing
solvent
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Pending
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EP18908160.7A
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English (en)
French (fr)
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EP3760768A4 (de
Inventor
Takuya NAGASAKA
Keiichi ISHIO
Naoyuki FURUKAWA
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Toray Industries Inc
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Toray Industries Inc
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Publication of EP3760768A1 publication Critical patent/EP3760768A1/de
Publication of EP3760768A4 publication Critical patent/EP3760768A4/de
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles

Definitions

  • the present invention relates to a method of producing a fiber, which method enables production of a fiber by the dry-jet wet spinning method without causing dew condensation or generation of water droplets on the spinneret surface, and with remarkable stability of running of fibers.
  • the dry-jet wet spinning method is a method in which a spinning dope solution containing a fiber-forming polymer dissolved in a solvent is discharged from a spinneret, and then once allowed to run in air, immediately followed by being guided into a coagulation bath liquid to allow coagulation.
  • this method has less draft restriction in a gas, where the bath-liquid resistance is absent. Therefore, high-speed or high-draft spinning is possible, and the method is used for production of fibers for clothing and industrial uses.
  • the dry-jet wet spinning method enables higher densification of fibers
  • the method has recently been utilized for production of precursor fibers for high strength/high modulus carbon fibers, and the productivity in the dry-jet wet spinning method has been enhanced by performing high-speed spinning or increasing the holes in the spinneret.
  • the droplets generated by the dew condensation cause clogging of the discharge hole of the spinneret, fiber adhesion, uneven fineness, and single-fiber break, and further, spinneret immersion due to contact of the droplets with the coagulation liquid surface, leading to winding on rollers in the subsequent process and fuzzing or yarn break in the stretching process.
  • the operability and the appearance are significantly deteriorated.
  • Such problems become more serious especially when high-speed spinning is carried out, or when the number of holes in the spinneret is increased, in order to increase the productivity.
  • Patent Document 1 a method for preventing dew condensation in dry-jet wet spinning, wherein a gas is allowed to flow, from one direction, in the gas-phase portion of the spinneret surface and the coagulation bath.
  • Patent Document 2 a method for preventing accumulation of the solvent vapor, wherein the gas in the gas-phase portion formed between the discharge surface of the spinneret and the coagulation bath is sucked alternately from two directions sandwiching the discharge surface, has been studied (Patent Document 2).
  • Patent Document 3 a method for controlling the temperature and the humidity in the vicinity of the spinneret to suppress dew condensation on the spinneret surface, wherein the inside of the coagulation chamber is surrounded, and wherein air with a controlled temperature and humidity is circulated therein, has also been studied (Patent Document 3).
  • the technique proposed in Patent Document 1 may be able to effectively suppress dew condensation in some cases.
  • the number of holes is not less than 2,000, where the hole density is increased, or where the gas-phase portion in dry-jet wet spinning has a height of less than 20 mm in the vertically downward direction from the discharge surface of the spinneret to the coagulation bath liquid surface, that is, under conditions where the solvent vapor easily accumulates in the gas-phase portion, deflection of the air flow occurs even by application of the technique proposed in Patent Document 1, causing accumulation of the vapor in some cases. This has been problematic since the dew condensation cannot be prevented.
  • Patent Document 2 there are problems in that, when the hole density is high, insufficiency of suction in the gas-phase portion causes aggregation of the solvent vapor, and that the aggregation proceeds on surfaces not subjected to the exhaustion, causing dew condensation.
  • An object of the present invention is to provide a method of producing a fiber, which method suppresses occurrence of dew condensation on the spinneret, and reduces deterioration of the appearance caused by winding on rollers in the subsequent process or by fuzzing or yarn break in the stretching process, to enable significant improvement of the productivity and the appearance as a whole even under conditions where, for example, not less than 2,000 holes are present and the hole density is high, or where the gas-phase portion formed in the vertically downward direction from the discharge surface of the spinneret to the coagulation bath liquid surface in dry-jet wet spinning has a height of less than 20 mm.
  • the method of producing a fiber of the present invention has the following constitution. That is, a method of producing a fiber, the method comprising discharge, from a spinneret, a spinning dope solution containing a fiber-forming polymer dissolved in a solvent, once allowing the solution to run in air, and then guiding the solution into a coagulation bath liquid to allow coagulation, wherein a gas-phase portion formed in a vertically downward direction from an discharge surface of the spinneret to a coagulation bath liquid surface has an air flow rate per unit time (Af) which satisfies, in relation to the amount of the solvent in the spinning dope solution per unit time (As) in the gas-phase-portion volume (Vh), the relational expression 0.0008 m 3 ⁇ Af/(As/Vh) ⁇ 0.0015 m 3 , and the hourly average of the absolute humidity at each of four points in an outer periphery of the spinneret in the gas-phase portion is not more
  • Af air
  • the method of producing a carbon fiber of the present invention also has the following constitution. That is, a method of producing a carbon fiber, comprising producing a fiber by the above method of producing a fiber, performing oxidation treatment in an oxidizing gas at 200 to 300°C, and then heating the fiber in an inert gas at not less than 1,000°C.
  • the relative standard deviation of the wind velocities at four points in the outer periphery of the spinneret in the gas-phase portion is preferably not more than 40%.
  • the number of holes in the spinneret is preferably not less than 2,000 and not more than 50,000.
  • the fiber-forming polymer is preferably an acrylonitrile copolymer.
  • occurrence of dew condensation on a spinneret can be suppressed, and deterioration of the appearance caused by winding on rollers in the subsequent process or by fuzzing or yarn break in the stretching process can be reduced, thereby enabling significant improvement of the productivity and the appearance as a whole even under conditions of dry-jet wet spinning where, for example, not less than 2,000 holes are present and the hole density is high, or where the distance between the spinneret and the coagulation bath liquid is less than 20 mm.
  • the present invention is especially suitable for production of acrylonitrile precursor fibers for carbon fibers.
  • Fig. 1 shows schematic top and front views of a spinning region in a case where an air supply nozzle or an exhaust nozzle is arranged in the present invention.
  • the method of the present invention can be used for production of acrylonitrile fibers for clothing, acrylonitrile fibers for production of carbon fibers, aromatic polyamide fibers, and the like.
  • the method shows the most remarkable effect in cases of production of acrylonitrile fibers for production of carbon fibers.
  • a spinning dope solution containing a fiber-forming polymer dissolved in a solvent is used.
  • the fiber-forming polymer examples include acrylonitrile copolymers and aromatic polyamides.
  • a polymerization method for obtaining the polymer solution polymerization, emulsion/suspension polymerization, bulk polymerization, or the like is used. Either a batch method or a continuous method may be used.
  • examples of the solvent in which the polymer is dissolved include dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), aqueous zinc chloride solutions (ZnCl 2 aq), and aqueous sodium thiocyanate solutions (NaSCN aq).
  • DMSO dimethylsulfoxide
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • ZnCl 2 aq aqueous zinc chloride solutions
  • NaSCN aq aqueous sodium thiocyanate solutions
  • the spinning dope solution is discharged from a discharge surface of a spinneret arranged above a coagulation bath through a gas-phase portion, and then the solution is allowed to coagulate in a coagulation bath, to form a fiber.
  • the temperature of the spinning dope solution and the temperature of the coagulation bath their conditions are preferably set such that the difference that emerges between the atmospheric temperature and the dew point (atmospheric temperature - dew point) of the gas-phase portion formed in the vertically downward direction from the discharge surface of the spinneret to the coagulation bath liquid surface is as large as possible.
  • a low temperature is preferred from the viewpoint of reducing the amount of evaporation of the solvent as long as the temperature is not less than the freezing point of the solvent used for the spinning dope solution.
  • the temperature is preferably not less than the freezing point and not more than the freezing point +20°C, further, not less than the freezing point +5°C, and not more than the freezing point +15°C.
  • the spinning dope solution maintains an appropriate viscosity, so that a favorable spinnability and an excellent operability can be achieved.
  • As the coagulation bath an aqueous solution of the same solvent as the solvent used for the spinning dope solution is usually used.
  • the upper limit of the temperature of the coagulation bath is preferably not more than 20°C, more preferably not more than 10°C, still more preferably not more than 7°C. In cases where the upper limit of the temperature of the coagulation bath is within this preferred range, occurrence of dew condensation can be effectively suppressed.
  • the lower limit of the temperature of the coagulation bath is preferably not less than 0°C, more preferably not less than 1°C. In cases where the lower limit of the temperature of the coagulation bath is within this preferred range, a favorable spinnability and an excellent operability can be achieved.
  • the number of holes in the spinneret is preferably 2,000 to 50,000, more preferably 4,000 to 20,000. In cases where the number of holes is within this preferred range, a good productivity can be achieved. Moreover, the mass of the spinneret does not increase excessively, and workability can be easily secured, and the increase in the equipment cost can be suppressed.
  • the spinneret area occupied by each hole is preferably 5 mm 2 to 10 mm 2 . In cases where the spinneret area occupied by each hole is within this preferred range, a good productivity can be achieved. Moreover, even when a sufficient space is not secured in the gas-phase portion between the spinneret and the coagulation bath in dry-jet wet spinning, occurrence of dew condensation can be effectively suppressed.
  • a gas-phase portion formed between a discharge surface of the spinneret and a coagulation bath liquid surface has an air flow rate per unit time (Af) which satisfies, in relation to the amount of the solvent in the spinning dope solution per unit time (As) in the gas-phase-portion volume (Vh), the relational expression 0.0008 m 3 ⁇ Af/(As/Vh) ⁇ 0.0015 m 3 , and the hourly average of the absolute humidity at each of four points (measurement points A to D) in an outer periphery of the spinneret in the gas-phase portion is not more than 20 g/m 3 .
  • Examples of methods therefor include a method in which a dehumidified air blower is arranged at a position distant from the spinneret, and the air is blown into the gas-phase portion at a certain air flow rate, and a method in which an air supply nozzle or an air exhaust nozzle is arranged in the outer periphery of the spinneret, and the air is supplied and exhausted at the same time or the direction of the air supply/exhaust is changed over time.
  • Af/(As/Vh) is 0.0008 m 3 to 0.0015 m 3 , preferably 0.0009 m 3 to 0.0014 m 3 , more preferably 0.0010 m 3 to 0.0013 m 3 .
  • the coagulation bath liquid surface fluctuates, leading to instability of the spinning performance, so that the effect may be insufficient.
  • the hourly average of the absolute humidity at each of the four points in the outer periphery of the spinneret is preferably not more than 20 g/m 3 , more preferably not more than 15 g/m 3 , still more preferably not more than 10 g/m 3 .
  • the relative standard deviation of the wind velocities at the four points in the outer periphery of the spinneret is preferably not more than 40%, more preferably not more than 20%, still more preferably not more than 10%.
  • the relative standard deviation of the wind velocities at the four points in the outer periphery of the spinneret is within this preferred range, occurrence of dew condensation on the discharge surface of the spinneret can be suppressed irrespective of the shape of the spinneret, that is, irrespective of whether it is circular, rectangular, or the like.
  • the air flow rate per unit time (Af) is calculated from, among the wind velocities measured at the four measurement points in the outer periphery of the spinneret, the wind velocity at one point positioned in the upstream side of the air flow, and the cross-sectional area as determined by seeing the spinneret from the upstream side of the air flow.
  • the gas-phase-portion volume (Vh) is calculated from the discharge area calculated from the outermost discharge holes of the spinneret, and the height of the gas-phase portion formed in the vertically downward direction from the discharge surface to the coagulation bath liquid surface.
  • the amount of the solvent in the discharged dope solution (As) is the amount of the solvent contained in the dope solution discharged from the spinneret per unit time.
  • the wind velocities and the absolute humidities at the four points in the outer periphery of the spinneret are measured at positions arranged such that the outer periphery of the spinneret is equally divided into four portions, and such that each position is at the middle point of the height from the liquid surface to the spinneret surface, and 30 mm distant from the outermost discharge holes of the spinneret, irrespective of the shape of the spinneret.
  • the four points in the outer periphery of the spinneret in cases where the spinneret has a circular shape, arbitrary four points on the circumference may be selected such that the outer circumference is equally divided into four portions.
  • the spinneret has a rectangular shape
  • the four midpoints of the segments constituting the outer periphery may be selected.
  • the wind velocity, the temperature, and the relative humidity can be measured using Climomaster MODEL 6501 (Kanomax Japan Inc.).
  • the hourly average of the absolute humidity at four points in the outer periphery of the spinneret is obtained by measuring the wind velocity, the temperature, and the relative humidity as described above 12 times at 5-minute intervals, calculating the absolute humidities using the above calculation equation, and then calculating their average for each measurement point.
  • the direction of the nozzle is preferably set such that the nozzle outlet is arranged in the spinneret direction, and in parallel to the coagulation bath liquid surface as shown in Fig. 1 . More specifically, the nozzle is arranged such that it is inclined at an angle of preferably 60° to 120°, more preferably 80° to 100° from the vertically downward direction (defined as 0°) toward the spinneret direction, and still more preferably at an angle of 90°.
  • Fig. 1 shows a case where each nozzle is arranged at an angle of 90°.
  • the nozzle In cases where the nozzle is arranged such that it is inclined at an angle (nozzle angle) of 90°, vapor generated from the solvent can be efficiently scavenged, and adhesion of dewdrops on the spinneret surface can be highly effectively suppressed.
  • the air flow In cases where the nozzle is inclined at an angle within this preferred range, in cases of the air supply nozzle, the air flow is less likely to hit the spinneret surface and cause a turbulent flow, so that the accumulation does not happen and occurrence of dew condensation can be effectively prevented; in cases of the air exhaust nozzle, although the vapor generated from the solvent is easily sucked while it is in contact with the spinneret surface, the growth of droplets can be effectively prevented.
  • Either the air supply nozzle or the exhaust nozzle is less likely to cause fluctuation of the coagulation bath liquid surface.
  • phenomena which affect negatively the appearance and the process stability including spinneret immersion due to contact of the liquid surface with the spinneret, adhesion between single fibers and the like, can be effectively prevented.
  • the present invention is especially effective for production of an acrylonitrile fiber, especially an acrylonitrile fiber as a carbon fiber precursor, using an acrylonitrile copolymer.
  • the spinning dope solution used for the dry-jet wet spinning is a solution containing: an acrylonitrile copolymer containing acrylonitrile at not less than 90% by mass; and a vinyl monomer copolymerizable therewith; dissolved in the solution.
  • an acrylonitrile copolymer containing acrylonitrile at not less than 90% by mass and a vinyl monomer copolymerizable therewith; dissolved in the solution.
  • the concentration of the polymer in the spinning dope solution is within this preferred range, the content of the solvent is appropriate and the amount of the solvent vapor is not too large in the gas-phase portion between the spinneret and the coagulation bath liquid in dry-jet wet spinning, so that dew condensation is less likely to occur. Further, an increase in the viscosity and gelation during polymerization of the acrylonitrile copolymer can be suppressed, and in dry-jet wet spinning, the discharge hole of the spinneret is less likely to be clogged, so that fiber adhesion, uneven fineness, and single-fiber break can be effectively prevented. Moreover, winding on rollers in the subsequent process, and fuzzing or yarn break in the stretching process can be also effectively prevented. Thus, excellent operability is achieved and the deterioration of the appearance of products can be effectively prevented.
  • the present invention can be preferably applied to cases where each fiber having a filament number of usually within the range of 2,000 to 50,000, and a single fiber fineness of usually within the range of 0.5 dtex to 3 dtex, are obtained.
  • the fibers after fiber formation in the coagulation bath may be stretched directly in a stretching bath, or stretching in a bath may be carried out after removal of the solvent by washing with water.
  • the following is a description of a method of producing a carbon fiber from a fiber obtained by the method of producing a fiber wherein the fiber-forming polymer is an acrylonitrile copolymer.
  • An acrylonitrile fiber produced by the method of producing an acrylonitrile fiber is subjected to oxidation treatment in an oxidizing gas such as air at 200 to 300°C.
  • the processing temperature is preferably increased from a low temperature to a high temperature in a plurality of steps.
  • the fiber is preferably stretched at a high stretch ratio as long as fuzzing does not occur.
  • the resulting oxidized fiber is heated at not less than 1,000°C in an inert gas such as nitrogen, to produce a carbon fiber.
  • the present invention is described below more concretely by way of Examples.
  • the wind velocities and the absolute humidities at the four points in the outer periphery of the spinneret used in the present Examples were measured at positions arranged such that the outer periphery of the spinneret having a rectangular shape was equally divided into four portions, wherein each point was positioned at the middle point of the height from the liquid surface to the spinneret surface, and 30 mm distant from the outermost discharge holes of the spinneret.
  • the wind velocity, the temperature, and the relative humidity were measured using Climomaster MODEL 6501 (Kanomax Japan Inc.).
  • the absolute humidity (AH) [g/m 3 ] was calculated from the temperature (T) [°C] and the relative humidity (RH) [%] measured with the Climomaster, using the following calculation equation (e: saturated vapor pressure [hPa]).
  • e 6.11 ⁇ 10 7.5 T / T + 237.3
  • AH 217 ⁇ e / t + 273.15 ⁇ RH / 100
  • the hourly average of the absolute humidity at each of the four points in the outer periphery of the spinneret was obtained by measuring the wind velocity, the temperature, and the relative humidity as described above 12 times at 5-minute intervals, calculating the absolute humidities using the above calculation equation, and then calculating their average for each measurement point.
  • the air flow rate per unit time (Af) was calculated from, among the wind velocities measured at the four measurement points, the wind velocity at one point positioned in the upstream side of the air flow, and the cross-sectional area as determined by seeing the spinneret from the upstream side of the air flow.
  • the gas-phase-portion volume (Vh) was calculated from the discharge area calculated from the outermost discharge holes of the spinneret, and the height of the gas-phase portion formed in the vertically downward direction from the discharge surface to the coagulation bath liquid surface.
  • the amount of the solvent in the discharged dope solution (As) is the amount of the solvent contained in the dope solution discharged from the spinneret per unit time.
  • the sizes and the number of dewdrops on the spinneret surface were measured after one week of continuous spinning, and scored according to the following standard.
  • Dewdrop diameter less than 2 mm: 1 point/dewdrop Dewdrop diameter, not less than 2 mm and less than 5 mm: 5 points/dewdrop Dewdrop diameter, not less than 5 mm: 10 points/dewdrop
  • the fuzz number in the acrylonitrile fibers was counted for a length of 1000 m to evaluate the appearance on a scale of 1 to 5.
  • the evaluation standard was as follows.
  • Evaluation was carried out on a scale of 1 to 5 and based on the yarn break frequency during production of 10 t of acrylonitrile fibers.
  • the evaluation standard was as follows.
  • a solution of an acrylonitrile copolymer composed of 99% by mass acrylonitrile and 1% by mass itaconic acid in DMSO was prepared by solution polymerization.
  • the resulting acrylonitrile copolymer solution was discharged once into air from the discharge surface of the spinneret to allow the solution to pass through the gas-phase portion, and then discharged into a coagulation bath liquid composed of 35% by mass DMSO/65% by mass water, to obtain a coagulated fiber.
  • the resulting coagulated fiber was then washed with water, and an oil agent was applied thereto while performing stretching in a bath stretching process, followed by performing drying and a stretching process.
  • an oil agent was applied thereto while performing stretching in a bath stretching process, followed by performing drying and a stretching process.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that the degree of dehumidification was increased.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that a 9,000-hole spinneret was used.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that a 2,000-hole spinneret was used.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that the air supply/exhaust nozzles were not operated.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that the degree of dehumidification was decreased.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that the degree of dehumidification was further decreased.
  • An acrylonitrile precursor fiber was obtained in the same manner as in Examples 1 to 4 except that Af/(As/Vh) was changed as shown in Table 1, and that the supplied air was not dehumidified.
  • Table 1 also shows the degree of dew condensation on the discharge surface, the appearance of the acrylonitrile fibers, and the process stability in each of the Examples and the Comparative Examples.
  • the present invention can be practically used not only for suppressing occurrence of dew condensation on the spinneret surface in production of precursor fibers for carbon fibers, but also as means for improving productivity by suppression of dew condensation in any dry-jet wet spinning.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Fibers (AREA)
EP18908160.7A 2018-02-27 2018-11-02 Faserherstellungsverfahren und kohlenstofffaserherstellungsverfahren Pending EP3760768A4 (de)

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JP2018032781 2018-02-27
PCT/JP2018/040807 WO2019167344A1 (ja) 2018-02-27 2018-11-02 繊維の製造方法および炭素繊維の製造方法

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EP3760768A1 true EP3760768A1 (de) 2021-01-06
EP3760768A4 EP3760768A4 (de) 2021-11-17

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US (1) US20200407885A1 (de)
EP (1) EP3760768A4 (de)
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CN111684114A (zh) 2020-09-18
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WO2019167344A1 (ja) 2019-09-06
JPWO2019167344A1 (ja) 2020-12-17
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EP3760768A4 (de) 2021-11-17
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