US2988420A - Process for spinning polyacrylonitrile filament having low degree of crimp and high cimp reversibility - Google Patents

Process for spinning polyacrylonitrile filament having low degree of crimp and high cimp reversibility Download PDF

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US2988420A
US2988420A US793502A US79350259A US2988420A US 2988420 A US2988420 A US 2988420A US 793502 A US793502 A US 793502A US 79350259 A US79350259 A US 79350259A US 2988420 A US2988420 A US 2988420A
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spinning
polymer
crimp
cell
filament
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Jr James Francis Ryan
Tichenor Robert Lauren
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US793502A priority Critical patent/US2988420A/en
Priority to BE587165A priority patent/BE587165A/fr
Priority to FR818013A priority patent/FR1248593A/fr
Priority to DE19601435610 priority patent/DE1435610A1/de
Priority to CH1431362A priority patent/CH419434A/de
Priority to SE1519/60A priority patent/SE300282B/xx
Priority to GB5319/60A priority patent/GB944424A/en
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    • 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
    • D01D5/04—Dry 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/217—Spinnerette forming conjugate, composite or hollow filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section

Definitions

  • Fibers of this type have been prepared by use of special spinning conditions or after-treatments which bring about differential physical properties overthe cross section of singlecomponent filaments, or by spinning together two or more materials to form a composite filament, i.e., one which contains the components in an eccentric relationship over the cross section of the filaments. If the twocomponents of a composite filament possess substantially different shrinkage, a crimp is caused bythe differential shrinkage of the spun and drawn components.
  • Another object of this invention is to provide a process which will reduce the crimp level in a composite filament while retaining a given degree of crimp reversibility.
  • a composite filament is prepared having 10 to 18 helical crimps per inch of extended length and having an equilibrium crimp reversibility of 25 to 50%.
  • the process of the invention requires the simultaneous spinning of two fiber-forming compositions into a composite filament, and its extrusion into a spinning cell under conditions which afford a rapid setting-up of the fiber structure.
  • the composite filament due to the eccentric relationship of its components and their composition will be capable of crimping from the straight state upon shrinkage and will have crimp reversibility.
  • the polymeric components are positioned so that the edge of the composite filament comprising the lower shrinking component faces the center of the spinning cell and 'the edge of the filament comprising the higher shrinking component faces the periphery of the spinning cell.
  • a less concentrated spinning solution is used for the polymer that yields the lower shrinking homofilament than is used for the other polymeric component.
  • the crimp reversibility of the filaments of this invention is determined by the following test.
  • a single filament is separated from the single end or tow of drawn, unrelaxed fibers.
  • a three-inch length of the filament is attached to opposite sides of a rectangular copper wire frame with 30% slack between the ends.
  • the rack and filament is then boiled off for 15 minutes to develop the crimp.
  • the crimped filament is then transferred to a special viewing holder by ta ping or gluing the ends so that about 10% slack is present and the filament length between the clamped ends is approximately 2.5 inches.
  • the filament and viewing holder are then mounted vertically in a stoppered test tube containing desiccant. The tube is stored vertically overnight (18-24 hours) at 70 C. Following this conditioning period to dry the filament the tube is then brought to room temperature (approximately 25 C.).
  • a p i (ECR) (orirnps, dry, per inch of ex tended length)
  • extended length is meant the length of a filament or yarn as measured under sufficient tension to pull out of the crimp and give an essentially straight filament or yarn. All crimp counts are stated in terms of extended length.
  • Another property of the filaments of this invention that is of great importance is their ability to recover from compaction.
  • the following test is used to measure this property.
  • Crimped fibers were cut in 2-inch lengths, hand carded and made into pellets weighing 0.20 gram. The pellets were placed into a cylinder (0.5 inch diameter hole) under a freely sliding piston that exerted 1,000 p.s.i. for two minutes. The height of the pellet under compression was measured. Compressed pellets of the same fiber were removed from the cylinder and: (I) allowed to recover in dry air overnight and then (2) exposed to steam at atmospheric pressure for minutes. The heights of the recovered pellets were measured after treatments '1' and 2 and the recovery from compaction calculated:
  • a closed spinning cell comprising a cylindrical cell surmounted by a spinning head, means for circulating an evaporative medium through the cell which enters through the spinning head around the threadline, means for extruding the solution through the spinneret in the head, and means for withdrawing the yarn through the bottom of the cell.
  • the spinning head used is similar to that shown in US. 2,615,198 issued to G. N. Flannagan.
  • head temperature when hereafter used means the temperature of the gas as it issues from the gas heater and before it enters the spinning cell.
  • cell temperature is meant the inside temperature of the wall of the spinning cell.
  • FIGURE 1 is a central cross-sectional elevation of a spineret assembly which can be used to make the composite filaments of this invention
  • FIGURE 2 is a transverse cross-sectional plan view of the apparatus of FIGURE 1 taken at 2-2 thereof and showing details of the top of the back plate;
  • FIGURE 3 is a transverse cross-sectional plan view taken at 33 of FIGURE 1 showing details of the bottom of the back plate;
  • FIGURE 1A is an enlarged portion taken from FIG- URE 1 to show details of the spinneret at the spinning orifice;
  • FIGURE 4 is a central cross-section elevation of a spinneret assembly which can be used to extrude 3 concentric circles of composite filaments.
  • FIGURES 5, 6, and 7 show greatly magnified cross sections, i.e., sections perpendicular to the filament axis, of typical filaments of this invention produced by dry spinning.
  • one components is shade to show the separation between components.
  • the bottom spinneret plate 2 which-contains a circle of orifices 3. is held in place against back plate 1 by retaining rings 12 and 14 and by bolt 13.
  • a fine-mesh screen 4 e.g., 200 mesh per inch, is pressed into position between, and serves as a spacer between, spinneret plate 2 and back plate 1.
  • Back plate 1 contains two annular chambers 8 and 9 whichare connected to suitable piping and filtration apparatus (not shown) to receive different spinning compositions. Lead holes 11 go from annular chamber 9 to annular space 7. Lead holes 10 lead from annular chamber 8 to annular space 6.
  • Annular spaces 6 and 7 are separated by wall 5 which is disposed above orifices 3 and spaced from spinneret plate 2 by screen 4 to permit free and contiguous passage of the spinning fluids from annular spaces 6 and 7 through orifices 3, the mesh of screen 4 being fine enough to permit spinning fiuid passage through orifices 3, as shown in detail in FIGURE 1A.
  • FIGURE 2 are shown four lead holes 10 and four lead holes 11 equally'spaced within the concentric chambers 8 and 9, respectively.
  • FIGURE 3 are shown the concentric inner and outer annular spaces 6 and 7 and the fine-mesh screen 4 partially in section.
  • intrinsic viscosity with the symbol (n) as used herein signifies the value of ln (n) at the ordinate axis intercept (i.e., when c equals 0) in a graph of as ordinate with 0 values (grams per ml. of solution) as abscissas.
  • (n) is a symbol for relative viscosity, which is the ratio of the flow times in a viscosimeter of a polymer solution and the solvent.
  • ln is the logarithm to the base e. All measurements on polymers containing acrylonitrile combined in the polymer molecule were made with DMF solutions at 25 C.
  • polymer A 20% solution in DMF of polyacrylonitrile of (n) 1.95 and containing 27 milliequivalents of acid groups per kilogram of polymer (as determined by titration in a DMF solution) (hereinafter designated polymer A) was FIGURE 1 and thence to annular space 7 and out into the spinning cell (9 inches in diameter by 14 feet long) as part of a composite filament so that it faces the center of the spinning cell.
  • Example I The product of Example I was dyed with a basic dye by immersion in a dye bath at 50 C., heating to the boiling point in a period of minutes and then holding at the boiling point for 30 minutes.
  • the dye bath comprised an aqueous solution containing the following:
  • the above prepared staple develops 16 helical crimps per inch of extended length when boiled free of restraint in water.
  • the helically crimped fibers thus prepared have an ECR of 40% and a A c.p.i. of 6.4 crimps per inch. Substantially 'all of the mechanical crimp is removed.
  • the staple has a tenacity of 2.2 grams per denier (g.p.d.) and an elongation at the break of 40% and a denier per filament of 3.0 (0.34 Tex) after boiling and drying.
  • EXAMPLE II The properties of the product of thisinvention as made in Example I are compared with the properties .of other composite fibers in Table I below. It will be noted that the fiber of Example I meets the requirements of the present invention since it has a high crimp reversibility (ECR of or larger) coupled with a low crimp intensity (10 to 18 crimps per inch of extended length). Data listed in Table I for other fibers not made by this process show that a reduction in crimp is accompanied by a reduction in crimp reversibility.
  • the ratio of bath to fiber was maintained at 50:1.
  • Staple fibers corresponding to items 1-5 in Table I were spun into similar yarns (60 Tex, 8.5Z, woolen system) and fabrics knitted.
  • EXAMPLE III the cell respectively in the composite filaments. Temspectively.
  • peratures of 110, 330, and 180 were used for the solution, head, and cell temperature respectively.
  • the gas was conducted through the cell at a rate of 80 lbs. per
  • Example I The yarn (8.8 d.p.f. 1.0 Tex, as-spun) was Wound up at 375 y.p.m. and 350 combined tows then drawn 4.5 as in Example I.
  • the two products obtained from part III A and part III B had 24.9 and 32.0 crimps per inch after boiling in water, and ECRs of 24% and 21% respectively.
  • the as-spun yarn of III A and IH B contained 30.5 and 29.5% of DMF respectively.
  • polymer B has the greater shrinkage (e.g., 24% vs. 22% for polymer A).
  • a 21.5% solution in DMF of polymer A was fed to annular space 15 (157 grams/minute) (FIGURE 4) so that the polymer solution was extruded as the component facing the cell center in the outermost and the innermost circle of filaments while a 28.5% solution in DMFof v.polymer B was fed to annular space 16 (157 grams/ minute) so that'this polymer formed the component of a composite fiber facing the wall of the spinning cell on the outer and inner circles of filaments while facing the center of the cell on the middle circle of filaments.
  • the gas was conducted through the cell at a rate of 81.6 lbs. per hour and temperatures of 110, 345, and 195 C. were used on the solution, head, and cell respectively.
  • the yarn (7.8 d.p.f.) was wound up at 350 y.p.m., drawn 4X, cut and dried as in Example I to give 3 d.p.f. staple.
  • the staple from the spin with the lower polymer concentration had 14.5 crimps per inch upon boil-off While the staple from the higher polymer concentration had 17.4 crimps per inch after boil-off.
  • the change to lower concentrationin the spinning soluticn of the polymer yielding the lower shrinking homofilament is preferably accompanied by an increase in the (n) of the polymer to maintain the viscosity of the spin ning solution at the desired level.
  • EXAMPLE VI Using the equipment of Example V, a 23.5% solution in DMF of polymer A was extruded (147 grams/minute) so as to face the cell wall in the outer edge of filaments and a 28.5% solution in DMF of polymer B was extruded (147 grams/minute) so as to face the center of the cell in the outer ring of filaments. The gas was conducted through the cell at a rate of 81.6 lbs. per hour. Temperatures used were 110, 280, and 182 C. for the solution, head, and cell respectively. The yarn was wound up at 350 y.p.m., drawn 4.0x, cut and dried and relaxed as in Example I to give a 3 d.p.f. staple with 22.6 crimps per inch after boiling in water.
  • EXAMPLE VII This example illustrates the critical elfect of the rate of fiow of the evaporative medium in the spinning cell.
  • Example VI The two polymer solutions of Example VI were extruded in the same manner as in Example VI with temperatures of 110, 345, and 182 C. for the solution, head, and cell temperatures respectively and the yarn wound up at 350 y.p.m.
  • the gas was conducted through the spinning cell at a rate of 64.5 lbs. per hour while in the second instance the gas was conducted through the cell at a rate of 81.6 lbs. per hour.
  • a 3 d.p.f. staple with 19.7 crimps per inch was obtained from the first spin while the second staple (3 d.p.f.) spun at the higher aspiration rate contained only 17.4 crimps per inch.
  • the use of the higher flow rate of gas reduced the DMF content of the as-spun yarn from 29.6% to 25 EXAMPLE VIII This example illustrates the critical selection of the cell 0 temperature.
  • Example V Using the solutions, apparatus and conditions of Example V (i.e., 21.5% solution of polymer A and 28.5% solution of polymer B at 157 and 157 grams/minute respectively) and the same spinning conditions with the exception that the cell temperature was C. composite filaments were obtained after drawing 4x and relaxing having 21.0 crimps per inch. The use of a higher cell temperature of C. with all other conditions being the same reduced the crimp intensity of the composite filament to 14.5 crimps per inch. Residual solvent content of the two as-spun yarns (7.8 d.p.f.) were 29 (est.) and 24 (est.) percent respectively for 170 and 195 C. WhenExaInple I is repeated with all conditions the same assume 9 except for raising the cell temperature to 210 C. filaments having 10 helical crimps per inch and ECR of 35% are obtained. The as-spun yarn contains 14% DMF.
  • Example IX The procedure of Example I was followed with the replacement of the acrylonitrile homopolymer with a 94/6 mixture of the acrylonitrile homopolymer and a copolymer of acrylonitrile and styrenesulfonic acid (96/4%) to give a total acidity in the blended polymer of 45 meq. of acid groups per kilogram of polymer.
  • the differential ionic content between the blended polymer and the copolymer was 195 meq./kg.
  • the final staple fiber had a denier per filament of 2.9, a tenacity of 2.1 g.p.d. and an elongation of 31% and had 15 helical crimps per inch of extended length after bo'iling ofi.
  • the ECR was 34%.
  • the fibers were scoured in a 2% solution of a non-ionic surfactant (the condensation product of polypropylene glycol and ethylene oxide) at the boil for 15 minutes, rinsed, centrifuged, dried, and carded for visual comparisons of dye quality.
  • a non-ionic surfactant the condensation product of polypropylene glycol and ethylene oxide
  • the fibers of this example show greater dye penetration across the polymer-polymer interface and a greater tendency to ring dye. At equal lengths of dyeing time, the fiber of this example gives a brighter black than did the fiber of Example I.
  • Example I fibers The dyeings were repeated using dyes equivalent to 7.3, 11.0, and 14.6% dye based on the fiber weight.
  • the highest level of dye was needed in order to get bright dark acceptable blacks with this dye procedure.
  • the fibers of this example gave bright black shades at levels of 7.3, and 11% dye that were equivalent to the 14.6% dye level on the other fiber.
  • Single component filaments made of the polymer blend (45 meg/kg. total acidity) are only dyed to light shades by the above procedures.
  • a convenient and economical way to produce the fibers of this example consists of blending the acrylonitrile homopolymer with or more of its weight of waste stock of the composite filaments obtained in spin- 10 ning the fibers of this example and then spinning a solution of this blend with a solution of the acidic copolymer as indicated above.
  • Suitable polymers for use in this invention can be found in all classes of linear fiber-forming polymers that have a solubility such that they can be dry spun. The two polymers selected must have the required difference in shrinkage and in swellability so that the composite filament crimps and a reversible crimp results. Suitable polymers, methods for selecting them, and crimping methods are described in coassigned and copending Taylor application, Serial No. 640,722 filed February 18, 1957. The following is a brief description of such subjeot matter:
  • Either component of the composite, crimp reversible filaments of this invention can be found in many groups of synthetic addition polymer materials.
  • the necessary differential reversible length change between the components is readily obtained by altering the content of ionizable groups in the two polymers.
  • Such ionizable groups are readily obtained by copolymerizing acrylonitrile, for example, with monomers containing acid groups such as .carboxylic, sulfonic or phosphonic in either the salt or free-acid form.
  • sudfonated polymerizabl-e monomers and their salts are eminently suited for use in this invention: p-styrenesulfonic Iacid, methallylsulfonic acid, allylsulfonic acid and ethylenesulfonic acid.
  • the required ionizable groups can be incorporated into a polymeric component by the blending of 2 or more polymers.
  • the polymers should preferably be compatible Vinyl polymers other than acrylonitrile polymers can be used in this invention which, although not having the required reversible length change per se, can be modified by acidic or basic modifiers as suggested above, so that the copolymers do have the required reversible length change.
  • methyl acrylate methyl methacrylate, methyl vinyl ketone, acrylamide, N-tertiarybutylacrylamide, vinyl methoxyethyl ether, methoxyethyl acrylate and vinyl acetate.
  • the composite filaments of this invention are charaoterized in that at least one of the components contains at least 50 milliequivalents of an ionizable group per kilogram of polymer. It is preferred that one component, in addition to containing at least 50 milliequivalents, contains a substantial excess of ionizable groups over the other component where both components contain such groups. It is desired to point out, however, that the non ionic disperse dye enhancing monomers disclosed herein increase the effect of the ionizable groups in said component in proportion to the concentration of the nonionic modifier. It is therefore desired, in order to obtain the substantial effects of this invention, to make allowance, where necessary, for the non-ionic modifier content.
  • polyacrylonitrile the homopolymer of (n) 1.5 to 2.5 and a copolymer containing at least acrylonitrile from 1 to 5% of an acidic modified monomer (95 to 350 milliequivalents of acidity per kilogram of polymer) of (n) 1.0 to 2.5 is preferred. Even more preferred is the use of polyacrylonitrile and a copolymer of acrylonitrile containing sulfonic acid groups as discussed in the above cited copending application in the amount of 200 to 300 milliequivalents of acidity per kilogram of polymer.
  • This preferred combination affords, under the processing conditions of this invention, a medium level of crimp intensity to 18 crimps per inch of extended length) that affords a pleasing handle in fabrics, a high level of crimp reversibility (25 to 50 EUR percent) which gives good recovery from compaction (300 to 400% from steaming), high bulk when incorporated into such articles as sweaters, and good dyeabil-ity with basic dyes.
  • the filaments of this invention can be used in the preparation of normally spun yarns, however, for some applications, e.g., yarns intended for the knitting of sweaters, displaying little or no pilling, it has been found desirable to use a high degree of twist in spinning the yarns.
  • a twist multiplier of 2.0 to 4.0 is conveniently used in such applications as is consistent with the desired aesthetics.
  • the twist multiplier is related to the twist (turns per inch, t.p.i.) by the following relationship:
  • t.p.i. Twist multiplier X /cotton count from to the extent that the residual solvent content in the as-spun fiber is less than the amount indicated by curve 1 of FIGURE 8 of the drawings for filaments of that as-spun denier, the polymer in one of said spinning solutions being substantially polyacrylonitrile and the polymer of another spinning solution being a copolymer of acrylonitrile and from about 1 to 5% of an acid-groupcontaining monomer, said copolymer containing at least milliequivalents of an ionizable group per kilogram of copolymer.
  • a process for preparing a composite filament having from about 10 to 18 helical crimps per inch and an equilibrium crimp reversibility of from about 25 to 50% comprising simultaneously spinning at least two solutions of fiber-forming polymers into a spinning cell in the form of a composite filament and evaporating solvent therefrom to the extent that the residual solvent content in the as-spun fibers is less than the amount indicated by curve 1 of FIGURE 8 of the drawings for filaments of that as-spun denier, the polymer of one of said spinning solutions being substantially polyacrylonitrile and the polymer of another of said spinning solutions being a copolymer of acrylonitrile and from about 1 to 5% of styrenesulfonic acid said copolymer containing at least 50 milliequivalents of ionizable groups per kilogram of copolymer.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
US793502A 1959-02-16 1959-02-16 Process for spinning polyacrylonitrile filament having low degree of crimp and high cimp reversibility Expired - Lifetime US2988420A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US793502A US2988420A (en) 1959-02-16 1959-02-16 Process for spinning polyacrylonitrile filament having low degree of crimp and high cimp reversibility
BE587165A BE587165A (fr) 1959-02-16 1960-02-01 Filaments composites frisés et leur préparation
FR818013A FR1248593A (fr) 1959-02-16 1960-02-09 Filaments composites frisés et leur préparation
DE19601435610 DE1435610A1 (de) 1959-02-16 1960-02-09 Kunstfaden und Herstellung desselben
CH1431362A CH419434A (de) 1959-02-16 1960-02-09 Kunstfaden und Verfahren zur Herstellung desselben
SE1519/60A SE300282B (de) 1959-02-16 1960-02-15
GB5319/60A GB944424A (en) 1959-02-16 1960-02-15 Improvements relating to crimped composite filaments of synthetic polymers

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US793502A US2988420A (en) 1959-02-16 1959-02-16 Process for spinning polyacrylonitrile filament having low degree of crimp and high cimp reversibility

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BE (1) BE587165A (de)
CH (1) CH419434A (de)
DE (1) DE1435610A1 (de)
FR (1) FR1248593A (de)
GB (1) GB944424A (de)
SE (1) SE300282B (de)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3245112A (en) * 1963-06-27 1966-04-12 Du Pont Metal to screen seal for spinnerets
US3310456A (en) * 1962-12-05 1967-03-21 American Cyanamid Co Composite acrylonitrile fiber dyeable with both acid and basic dyestuffs and method of manufacture
US3320633A (en) * 1965-08-25 1967-05-23 Du Pont Apparatus for forming two component yarns
US3324215A (en) * 1963-11-20 1967-06-06 Dow Chemical Co Method for preparing crimped acrylonitrile polymer fibers
US3330896A (en) * 1962-07-12 1967-07-11 American Cyanamid Co Method of producing bulky yarn
US3330895A (en) * 1962-07-12 1967-07-11 American Cyanamid Co Method of making acrylic bicomponent yarn or fabric with latent crimp development
US3350741A (en) * 1965-04-22 1967-11-07 Toho Beslon Co Spinneret device for spinning side-by-side type of composite fibers
US3375548A (en) * 1965-09-29 1968-04-02 Mitsubishi Rayon Co Apparatus for producing conjugated filaments
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3425091A (en) * 1966-12-12 1969-02-04 Kanebo Ltd Spinneret and nozzle assembly for the manufacture of composite filaments
US3602014A (en) * 1968-05-31 1971-08-31 Allied Chem Ladies hosiery of improved stretch properties made from bifilament yarns
US3621087A (en) * 1967-07-31 1971-11-16 Toyo Rayon Co Ltd Process for the preparation of acrylic fibers with odd-shaped sections
US4941812A (en) * 1988-05-10 1990-07-17 E. I. Du Pont De Nemours And Company Spinneret for production of a hollow filament within a hollow filament composite fiber having spacing means
US5458968A (en) * 1994-01-26 1995-10-17 Monsanto Company Fiber bundles including reversible crimp filaments having improved dyeability
US6413071B1 (en) 2000-03-27 2002-07-02 Basf Corporation Thin plate spinnerette assembly

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL284970A (de) * 1961-11-02
US3166788A (en) * 1962-10-24 1965-01-26 Monsanto Co Spinning for conjugate spinning

Citations (5)

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US1867298A (en) * 1928-05-05 1932-07-12 American Bemberg Corp Artificial yarn, particularly artificial silk yarn
GB514638A (en) * 1937-05-11 1939-11-14 Ig Farbenindustrie Ag Improvements in the manufacture of artificial silk
US2439814A (en) * 1943-05-13 1948-04-20 American Viscose Corp Crimped artificial filament
US2443711A (en) * 1943-05-13 1948-06-22 American Viscose Corp Method of manufacturing artificial filaments
US2517946A (en) * 1946-10-03 1950-08-08 Kohorn Henry Von Method of producing yarn

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1867298A (en) * 1928-05-05 1932-07-12 American Bemberg Corp Artificial yarn, particularly artificial silk yarn
GB514638A (en) * 1937-05-11 1939-11-14 Ig Farbenindustrie Ag Improvements in the manufacture of artificial silk
US2439814A (en) * 1943-05-13 1948-04-20 American Viscose Corp Crimped artificial filament
US2443711A (en) * 1943-05-13 1948-06-22 American Viscose Corp Method of manufacturing artificial filaments
US2517946A (en) * 1946-10-03 1950-08-08 Kohorn Henry Von Method of producing yarn

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330896A (en) * 1962-07-12 1967-07-11 American Cyanamid Co Method of producing bulky yarn
US3330895A (en) * 1962-07-12 1967-07-11 American Cyanamid Co Method of making acrylic bicomponent yarn or fabric with latent crimp development
US3310456A (en) * 1962-12-05 1967-03-21 American Cyanamid Co Composite acrylonitrile fiber dyeable with both acid and basic dyestuffs and method of manufacture
US3245112A (en) * 1963-06-27 1966-04-12 Du Pont Metal to screen seal for spinnerets
US3324215A (en) * 1963-11-20 1967-06-06 Dow Chemical Co Method for preparing crimped acrylonitrile polymer fibers
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3350741A (en) * 1965-04-22 1967-11-07 Toho Beslon Co Spinneret device for spinning side-by-side type of composite fibers
US3320633A (en) * 1965-08-25 1967-05-23 Du Pont Apparatus for forming two component yarns
US3375548A (en) * 1965-09-29 1968-04-02 Mitsubishi Rayon Co Apparatus for producing conjugated filaments
US3425091A (en) * 1966-12-12 1969-02-04 Kanebo Ltd Spinneret and nozzle assembly for the manufacture of composite filaments
US3621087A (en) * 1967-07-31 1971-11-16 Toyo Rayon Co Ltd Process for the preparation of acrylic fibers with odd-shaped sections
US3602014A (en) * 1968-05-31 1971-08-31 Allied Chem Ladies hosiery of improved stretch properties made from bifilament yarns
US4941812A (en) * 1988-05-10 1990-07-17 E. I. Du Pont De Nemours And Company Spinneret for production of a hollow filament within a hollow filament composite fiber having spacing means
US5458968A (en) * 1994-01-26 1995-10-17 Monsanto Company Fiber bundles including reversible crimp filaments having improved dyeability
US6413071B1 (en) 2000-03-27 2002-07-02 Basf Corporation Thin plate spinnerette assembly

Also Published As

Publication number Publication date
FR1248593A (fr) 1961-03-09
CH419434A (de) 1966-08-31
SE300282B (de) 1968-04-22
GB944424A (en) 1963-12-11
DE1435610A1 (de) 1969-02-13
BE587165A (fr) 1960-08-01

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