US2987371A - Manufacture of rayon - Google Patents

Manufacture of rayon Download PDF

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Publication number
US2987371A
US2987371A US705368A US70536857A US2987371A US 2987371 A US2987371 A US 2987371A US 705368 A US705368 A US 705368A US 70536857 A US70536857 A US 70536857A US 2987371 A US2987371 A US 2987371A
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Prior art keywords
viscose
yarn
percent
denier
elongation
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US705368A
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Charles L Henry
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Akzona Inc
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American Enka Corp
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Priority to NL233933D priority Critical patent/NL233933A/xx
Priority to NL100295D priority patent/NL100295C/xx
Priority to DENDAT1071277D priority patent/DE1071277B/de
Application filed by American Enka Corp filed Critical American Enka Corp
Priority to US705368A priority patent/US2987371A/en
Priority to BE573565A priority patent/BE573565A/nl
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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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath

Definitions

  • This invention relates to the manufacture of regenerated cellulose fibers, filamentary yarns and the like from viscose and particularly to the manufacture of viscose rayon especially characterized by low elongation, high tenacity and high modulus properties.
  • viscose rayon fabrics have superior characteristics to other types of fabrics, such as luster, softness and design, they lack adequate dimensional stability unless subjected to very expensive finishing treatments.
  • the dimensional stability of cotton fabrics is due to the combined effect of several basic fiber properties, the most important of these properties being strength, elongation and modulus.
  • Viscose rayon filamentary yarns and fibers now produced by conventional processes show elongation at the breaking point in the conditioned state higher than cotton fibers by about 50-100% and more. In the wet state, the elongation at the breaking point of these rayon yarns and fibers exceed that of cotton by about l-200% and more.
  • conventional rayons both regular tenacity and high tenacity types, show conditioned and wet tension moduli markedly lower than the corresponding moduli of cotton fibers. While the higher elongation of normal viscose rayon yarns and fibers is a desirable property in certain end uses, it is a definite disadvantage in many other uses.
  • An object of the present invention is to provide a process for the manufacture of flexible, high tenacity viscose rayon filamentary yarns and fibers which have substantially lower elongations at the breaking point and markedly higher wet and dry tension moduli than normal rayon filaments with the process being substantially as economically attractive as conventional viscose manufacturing processes.
  • Another object of the present invention is to provide 2,987,371 Patented June 6, 1961 low elongation, high tenacity viscose rayon filamentary yarns and fibers having a high modulus while retaining their flexible or resilient character, and which, when used in blends with cotton and other fibers or used alone, canrbe made into fabrics having improved, novel,
  • the filaments so produced are Withdrawn from the primary bath, they are highly stretched, preferably in 'a hot acidic secondary bath, and after-treated by the usual processes.
  • selection of a combination of a low viscose alkali and a high zinc sulfate concentration within their specified limits would allow the use of an acid concentration as low as about 1.5-2.0% according to Equations 1 and 2, however, for best results, it is preferred to select a viscose alkali and zinc sulfate relationship which requires an acid concentration of about 3% or higher.
  • Other spinning variables are correlative with the above described zinc sulfate, viscose alkali, and sulfuric acid relationship.
  • the source of cellulose may be wood pulp, cotton linters, a mixture of the two or even some other source; high alpha wood pulps are preferred.
  • the cellulose content of the viscose may range from about 50-85% with the preferred range being 6.08.0%.
  • the amount of CS may be from 25-50% (based on oven-dry recoverable cellulose); however, the conventional quantities of 32-40% are quite satisfactory.
  • the viscose is ripened to approximately the same level of maturity before spinning as in case of normal viscose used in the industry.
  • the Hottenroth maturity index of 7.3- 6.8 (percent cellulose-percent total alkali) viscose may vary at spinning from about 8-13; however, the preferred range is 9-11. Similarly, the more satisfactory range for a 7.4-5.6 viscose is about 7-9.
  • the primary spinbaths contain sulfuric acid, sodium sulfate and zinc sulfate; for special purposes, the use of magnesium sulfate or ferrous sulfate may be desirable.
  • suitable acid concentrations are determined by the choice of viscose alkali and spinbath zinc sulfate concentrations.
  • An outstanding characteristic of this process is that its acid concentrations generally are below the acid concentrations which will produce filaments with marked crimp developing properties.
  • the filaments Upon increasing the acid in the spinbath to about the maximum allowed by Equation 2 and then above, the filaments will progressively acquire a nonuniform, cross-sectional skin area, and Will, as a result, crimp upon immersion in a relaxed state in hot water. Further increases in acid concentration will finally cause the crimping phenomenon to disappear; at this point the acid concentration is in the lower part of the acid range conventionally used for manufacture of viscose-yarns.
  • zinc sulfate In the primary spinbath, zinc sulfate must be present to the extent of at least 0.1% unless replaced inwhole or in part by other divalent salts, such as ferrous sulfate or magnesium sulfate.
  • the concentration of Na SO may range from about 12% to about 26%, although 14-25% is preferable.
  • the temperature of the primary bath should be between 30-70 C. with better operating efliciency and yarn properties resulting between 40-60 C.
  • the freshly formed filaments are led through the bath liquid for a distance of about 6 to about 200 inches; generally 8-20 inches are suflicient for fine denier yarns while 20-100 inches are usually adequate for heavy denier yarns and tows.
  • the filaments are led from the bath to a feed wheel and thereafter stretched from about 50-100% and more. Stretching is preferably done in a secondary bath at a temperature of about 80-100 C.
  • the secondary bath must contain sulfuric acid, preferably 13%.
  • the secondary bath may be made by diluting one part of the primary spinbath with two parts or more of water with sufiicient acid being added, if necessary, to bring the acid concentration within the aforesaid prescribed limits.
  • the filaments are collected at about 60-120 or more meters per minute in a rotating pot, or on a spool or bobbin, and aftertreated in a conventional manner.
  • the filaments may be aftertreated in a continuous manner and then collected.
  • Equations 1 and 2 In commercial practice when using the lower sulfuric acid concentrations and higher zinc sulfate concentrations permitted by Equations 1 and 2, the formation of ag glomerates and hard deposits of ZnS (contaminated with sulfur) and the like in the primary spinbath and on the walls of its container may occur. To prevent this, small quantities of suitable cation-active agents may be incorporated in the viscose and/or primary spinbath.
  • the yarns and fibers produced by the present process have a collection of unique physical properties heretofore not associated with rayon and which are comparable to cotton in most respects.
  • the filaments are a high Quantities of ZnSO greater than 2.0% are undesirable as unfeasibly low acid concentratenacity type having a conditioned tenacity of about 3 g./ .1
  • this product is flexible and resilient and, accordingly, may be satisfactorily processed and converted into fabrics having improved serviceability. Staple fiber so produced is satisfactorily compatible with cotton for the manufacture of spun yarn. Fabrics produced from this spun yarn have strength and dimensional stability comparable to an allcotton fabric, and in addition, have a significantly improved appearance and hand. Furthermore, fabrics derived from 100% staple fibers only require the same resin treatment as do 100% cotton fabrics to impart substantially the same degree of dimensional stability and crease recovery.
  • tension modulus refers to the force required in grams per denier to elongate a single filament, fiber-or yarn by 5% Thus, the higher the value for the tension modulus the more resistant is the filament 0r fiber to being stretched or distorted.
  • the term flexible and resilient is used to describe a. filament that resists breakage or fracture when subjected to abrasive and/ or distortive forces; and its meaning is synonomous with the meaning of non-brittle.
  • FIGURE 1 represents moduli measurements made in a Wet state on these filaments with points p defining their respective tension modulus.
  • the curves for the filaments show a tension moduli comparable to or higher than that for cotton and markedly higher than the modulus for normally produced yarn.
  • Alkali cellulose was prepared in the conventional manner from wood pulp and aged to obtain a degree of polymerization that would yield a viscose solution viscosity of 40-60 seconds by the ball fall method.
  • the aged alkali cellulose was xanthated at about 27 C. for two hours using 36% CS (based on oven-dry recoverable cellulose).
  • the resulting xanthate crumbs were dissolved in a solution of sodium hydroxide of a predetermined alkali concentration to produce a 7.36.82.25 (percent cellulose total alkali expressed as percent 'NaOH-percent 'total sulfur) viscose solution.
  • the freshly prepared viscose solution was deaerated, filtered, and ripened to a Hottenroth maturity index of about 10.5.
  • the viscose solution was spun into four filamentary yarns; that is, yarns of (a) 100 denier-lOOfilaments, (b) 100 denier-60 filaments, (c) 150 denier-40 filaments and (d) 200 denier-40 filaments.
  • the equipment and operating procedure for the spinning of these yarns were essenaqueous primary spinbath containing 5.0% H 18% Na SO and 1.0% ZnSO (maintained at a temperature of 50 C.); the first yarn listed above was manufactured by extruding the viscose through a spinneret with orifices .of 50 microns diameter, the second yarn was prepared using a spinneret with orifices of 60 microns diameter and the third and fourth yarns Were prepared using a spinneret with orifices of 75 microns diameter.
  • the yarn was then withdrawn therefrom and led to the first feed wheel, thence through a secondary bath maintained at a temperature of C., then to a second feed wheel, and finally collected in a rapidly rotating pot.
  • the secondary bath was diluted primary spinbath.
  • the peripheral speeds of the first and second feed wheels were 38 and 80 meters per minute, respectively. Due to the difference in the peripheral speeds of the wheels, the yarn was stretched The collected yarn was washed free of acid and salts. After a finish was applied, the yarn was dried.
  • the yarn was tested for breaking tenacity, breaking elongation and tension modulus (at 5% elongation) in both conditioned and wet states. The conditioned state was obtained by storing the yarn in a room at 75 F. and 60% relative humidity for 24 hours.
  • Denier/fiber 1. 5 1. 5 2. 1. Yarn produced according Tenacity, Ereaklng:
  • Example I Conditioned, g [d 2. 9 3. 2 2.9 2. 5 100 denier-100 file- 1 Wet, g./d- 1.8 2.0 3.1 1.5
  • EXAMPLE II A 7 .4-5.6-2.20 (percent cellulose-percent total alkalipercent total sulfur) viscose was prepared in a manner similar to that described in Example I. At a Hottenroth maturity index of about 8.0, the viscose was spun into 1100 denier, 720-filament yarn by extruding it into a 3.5% H SO 21% Na SO 1.0% ZnSO primary spinbath maintained at 40 C. Using an operating procedure similar to the one used in Example I, a stretch was imparted to the freshly spun yarn sufficient to cause a tension of 650 grams 0n the yarn just before the second feed wheel.
  • the yarn after washing, finishing and drying had conditioned and wet breaking tenacities of 3.5 g./ denier and 2.1 g./ denier, respectively, and corresponding elongations of 9% and 10%.
  • Conditioned tension modulus (at 5% elongation) was 2.3 g./ denier and the wet modulus was 0.80 g./ denier; the modulus determinations were made on single filaments extracted from the yarn.
  • the first tow was cut into staple fiber of 1.25 inch lengths and is hereafter designated Sample A.
  • the second tow was also cut into staple fiber of 1.25 inch lengths and is hereafter designated Sample B.
  • Spun Yarn A 30/1 yarn was spun from carded Middling cotton.
  • Spun Yarn B 30/1 yarn was spun from a blend of /a staple fiber (Sample A) and /3 carded Middling cotton.
  • Spun Yarn C 30/1 yarn was spun from a blend of /3 conventional rayon staple fiber and /3 carded Middling cotton.
  • the staple fiber is markedly more compatible with cotton than is conventional rayon staple fiber; the higher modulus of the former is probably the principal causative factor of the improved compatibility.
  • Fabric A Woven from spun yarn of 100% carded Middling cotton.
  • Fabric B Woven from spun yarn of 100% staple fiber of this example.
  • Fabric C Woven from spun yarn of 100% conventional rayon staple fiber.
  • fabric derived from staple fiber of this example compares favorably with the shrinkage of an all-cotton fabric, and is 25 vastly superior in all shrinkage characteristics to fabric derived from conventional rayon staple fiber.
  • Cuts ocf Fabric A and Fabric B were padded through a 15% dimethylol ethylene urea resin bath, dried on a tenter frame, cured, scoured, dried relaxed, and steam 3 framed. After the properties of these two fabrics Were measured, the fabrics were washed repeatedly and their dimensional stability measured. Results of these meas urements are shown in Table VI.
  • Ravel Strip Test- Warp strength dry, lbs 36 57 Filling strength, dry, lbs 43 Warp strength, wet, lbs 39 Filling strength. wet, lbs 22 28 Warp elongation, dry, percent 8.9 13. 1 Filling elongation, dry, percen 18.0 24. 9 45 Warp elongation, wet, percent 101 14. 3 Filling elongation, wet, percent..- 20. 7 23. 8 2. Trapezoidal Tear Test Warp strength. dry, lbs 1. 9 5. 7 Filling strength, dry, lbs 1. 6 4. 7 8. Monsanto Crease Recovery- Warp, percent 63 64 Filling, percent 72 62 Washed Fabrics:
  • the yarn collection speed was 75 meters per minute with the yarn being collected in a rapidly rotating pot. After normal aftertreatment, the yarn had a conditioned tenacity of 3.4 g./ denier, a conditioned elongation of 13%, a wet tenacity of 1.9 g./denier and a wet elongation of 16.5%. Conditioned and wet moduli (at 5% elongation) were 1.8 g./ denier and 0.45 g./denier, respectively.
  • EXAMPLE VI A viscose of the same composition and maturity as used in Example I was extruded into 100 denier, 60-filament yarn in three primary spinbaths having different Na SO concentrations.
  • the first primary spinbath contained 5.5% H 14% Na SO and 1.0% ZnSO
  • the second contained 5.5% H SO 18% Na SO and 1.0% ZnSO
  • the third contained 5.5% H SO 22% Na SO and 1.0% ZnSO
  • Table VIII Properties of these yarns are listed in Table VIII.
  • EXAMPLE VII A viscose containing 7.3% cellulose, 6.8% total alkali, and 2.25% total sulfur was ripened to a Hottenroth maturity index of about 10.5 and spun into denier, 60- filament yarn in a manner similar to that described in Example I except that the primary spinbath was composed of 4.5% H SO 18% Na SO and 1% ZnSO The yarn collection speed was 115 meters per minute.
  • the conditioned yarn had a tenacity of 3.7 g./denier and an elongation of 7.8%; the wet yarn had a tenacity of 2.2 g./ denier and an elongation of 7.6%.
  • Yarn modulus (5% elongation) was 2.9 g./ denier for the conditioned state and 1.3 g./denier for the wet state.
  • EXAMPLE IX Alkali cellulose was aged so as to give a viscose solution viscosity of about 40 seconds by the ball fall method.
  • the alkali cellulose was xanthated at 25 C. for two hours with 36% CS (based on oven-dry recoverable cellulose).
  • the resulting cellulose xanthate crumbs were dissolved at 20 C. in a sodium hydroxide solution to produce a viscose having a composition of 6.0% cellulose, 6.0% total alkali, and 1.8% total sulfur.
  • the viscose was ripened to a Hottenroth maturity index of about 11.0 and then spun into 100 denier, 60-filament yarn.
  • the primary spinbath was composed of 4.0% H SO 18% Na SO and 1.0% ZnS the other operating conditions were similar to those of Example I.
  • the finished yarn had a conditioned tenacity of 3.9 g./ denier, a wet tenacity of 2.5 g./denier, a conditioned elongation of 8.0% and a wet elongation of 8.2%.
  • Conditioned modulus elongation) of the yarn was 2.8 g./denier and the wet modulus was 1.3 g./ denier.
  • a process for producing high strength, low elongation, viscose rayon yarn and fiber which comprises extruding a viscose solution having an alkali content between 4.8-7.5 by weight, into filaments in an aqueous acid bath containing Na SO 0.1-2.0% by weight of ZnSO and H 50 in a concentration which, for any given viscose alkali and ZnSO, combination within their respective ranges, is expressed by the following equations:
  • a process for producing high strength, low elongation, viscose rayon yarn and fiber which comprises extruding viscose having an alkali content between 4.8- 7.5% by weight and a cellulose content of about 5.0- 8.5% by weight, into filaments in an aqueous acid bath containing Na SO 0.1-2.0% by weight of ZnSO and H 80, in a concentration which, for any given viscose alkali and ZnSO, combination within their respective ranges, is expressed by the following equations:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
US705368A 1957-12-26 1957-12-26 Manufacture of rayon Expired - Lifetime US2987371A (en)

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Application Number Priority Date Filing Date Title
NL233933D NL233933A (nl) 1957-12-26
NL100295D NL100295C (nl) 1957-12-26
DENDAT1071277D DE1071277B (nl) 1957-12-26
US705368A US2987371A (en) 1957-12-26 1957-12-26 Manufacture of rayon
BE573565A BE573565A (nl) 1957-12-26 1958-12-03 Werkwijze voor het vervaardigen van draden en stapelvezels uit viscose, alsmede de aldus ver-vaardigde draden en stapelvezels.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083075A (en) * 1962-07-09 1963-03-26 William R Saxton Process of manufacturing regenerated cellulose fiber
US3163185A (en) * 1962-09-28 1964-12-29 Kendall & Co Dimensionally stable, directionally stiff woven fabric
US3341645A (en) * 1963-03-07 1967-09-12 Teijin Ltd Method of producing viscose rayon staple and a spinning apparatus for use in the method
EP2707526B1 (de) 2011-05-12 2015-11-25 Glanzstoff Bohemia s.r.o. Verfahren zur herstellung von celluloseregeneratfasern
EP2664697B1 (de) 2012-05-14 2016-03-02 Glanzstoff Bohemia s.r.o. Flammhemmende Celluloseregeneratfasern und Verfahren zu deren Herstellung

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2515834A (en) * 1942-11-13 1950-07-18 Du Pont Cellulose filaments and method of producing same
US2581835A (en) * 1946-03-22 1952-01-08 Du Pont Method of spinning viscose
US2594496A (en) * 1949-04-12 1952-04-29 American Viscose Corp Method of making artificial fibers or threads from viscose
US2607955A (en) * 1949-08-25 1952-08-26 Textile & Chem Res Co Ltd Spinning of viscose
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers
US2674025A (en) * 1949-08-15 1954-04-06 Texiclon Corp Polymeric filaments
US2732279A (en) * 1951-12-07 1956-01-24 Shozo tachikawa
US2775505A (en) * 1952-06-05 1956-12-25 American Viscose Corp Spinning regenerated cellulose filaments
US2781275A (en) * 1951-05-12 1957-02-12 American Enka Corp Viscose solution and method of spinning

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2515834A (en) * 1942-11-13 1950-07-18 Du Pont Cellulose filaments and method of producing same
US2581835A (en) * 1946-03-22 1952-01-08 Du Pont Method of spinning viscose
US2594496A (en) * 1949-04-12 1952-04-29 American Viscose Corp Method of making artificial fibers or threads from viscose
US2674025A (en) * 1949-08-15 1954-04-06 Texiclon Corp Polymeric filaments
US2607955A (en) * 1949-08-25 1952-08-26 Textile & Chem Res Co Ltd Spinning of viscose
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers
US2781275A (en) * 1951-05-12 1957-02-12 American Enka Corp Viscose solution and method of spinning
US2732279A (en) * 1951-12-07 1956-01-24 Shozo tachikawa
US2775505A (en) * 1952-06-05 1956-12-25 American Viscose Corp Spinning regenerated cellulose filaments

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083075A (en) * 1962-07-09 1963-03-26 William R Saxton Process of manufacturing regenerated cellulose fiber
US3163185A (en) * 1962-09-28 1964-12-29 Kendall & Co Dimensionally stable, directionally stiff woven fabric
US3341645A (en) * 1963-03-07 1967-09-12 Teijin Ltd Method of producing viscose rayon staple and a spinning apparatus for use in the method
EP2707526B1 (de) 2011-05-12 2015-11-25 Glanzstoff Bohemia s.r.o. Verfahren zur herstellung von celluloseregeneratfasern
US9828697B2 (en) 2011-05-12 2017-11-28 Glanzstoff Bohemia S.R.O. Flame-retardant regenerated cellulose filament fibers and process for production thereof
EP2664697B1 (de) 2012-05-14 2016-03-02 Glanzstoff Bohemia s.r.o. Flammhemmende Celluloseregeneratfasern und Verfahren zu deren Herstellung

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DE1071277B (nl) 1959-12-17
NL233933A (nl)
BE573565A (nl) 1959-04-01
NL100295C (nl)

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