US3388117A - Filaments of regenerated cellulose - Google Patents

Filaments of regenerated cellulose Download PDF

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Publication number
US3388117A
US3388117A US354975A US35497564A US3388117A US 3388117 A US3388117 A US 3388117A US 354975 A US354975 A US 354975A US 35497564 A US35497564 A US 35497564A US 3388117 A US3388117 A US 3388117A
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cellulose
filaments
viscose
fibers
wet
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US354975A
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English (en)
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Roberts Ronald
Robert T Martin
William C Richardson
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Courtaulds North America Inc
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Courtaulds North America Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • 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

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  • This invention relates to a new and improved class of regenerated cellulose filaments and to a method for making such filaments.
  • Patent 2,937,- 070 reference is made to dry tenacities as high as 8 g./ denier. Fibers having dry tenacities as high as 8 g./ denier have not, however, been generally available, and in point of fact, even Coxs patent does not specifically describe such fibers. In ⁇ any case, such tenacities are not as high as those currently available in nylon which range up to about 9 g./ denier.
  • the remarkable tensile properties of the fibers according to the present invention are clearly not associated with a high degree of crystallinity, because while the degree of orientation, is, as indicated above, higher than that of any known regenerated cellulose fiber, the crystallinity of the novel fibers is relatively low, being of the order of 45% on a scale in which conventional textile grade rayon is 42% and Fortisan, a fiber made by the saponification of cellulose acetate, is 51%.
  • fibers according to the invention are characterized by an exceedingly high tenacity, a high degree of orientation as indicated ⁇ by their birefringence and a high degree of inaccessibility.
  • the physical structure defined by these objectively determined parameters is, of course, not necessarily subject to description in familiar terms and we do not wish to be bound by any particular structural theory in explanation of the extraordinary physical properties of our new fibers. ⁇ On the other hand, it is sometimes useful to the understanding of a new polymer structure to picture it in cornmonplace terms. Bearing in mind the limitations of such models, one may think of the cellulose molecules as chains having a longitudinal axis and different surface characteristics around their circumference and along their length.
  • the picture of the novel fibers which then emerges is one in which the cellulose molecules are laid substantially parallel to, though not necessarily matched along their length with, adjacent molecules and aligned with the liber axis; and in which the molecules are very closely associated laterally.
  • This close lateral association can be inferred not only from the low accessibility of the fibers, but also from the lack of a diffuse background in X-ray photographs.
  • the very Ihigh moduli in both the wet and the dry states also indicate the close alignment of the molecules in the direction of the fiber axis.
  • the drawing is a graph comparing the effect of caustic soda on fibers according to the invention with the effect on prior art fibers.
  • viscose having a gamma value of more than 80, a viscosity of at least 120 poise and a NaOH/cellulose ratio of at least 1, is spun into a coagulating bath having a temperature of at most 30 C. and containing from about 3% to about 8% sulfuric acid, from zero to say 12% Na2SO4 and between about 0.3 and about 1.5% formaldehyde, to form filaments.
  • the filaments are then stretched by at least 500%, the stretching being commenced when the filaments have a gamma value of at least 60, and at least a part of the stretching taking place when the laments are in contact with water at a temperature greater than 80 C.
  • the cellulose used in the present process may have a high degree of polymerization (say 800-1500) but this is not critical and high performance fibers have been obtained with conventional pulps, having lower D.PS.
  • the cellulose is converted to alkali cellulose in conventional manner. Normally between about 2000 and about 3000 parts of a caustic soda liquor having a concentration of say 18 to 21% NaOH is used per 100 parts of cellulose. Steeping is carried out at say 16 to 25 C. for 20 to 60 minutes.
  • the press weight ratio is conventionally 2.2 to 2.8.
  • a sequestering agent capable, under alkaline (pHlO) conditions, of chelating polyvalent cations such as calcium, magnesium and iron, present as trace impurities in the pulp or liquor.
  • HlO alkaline
  • a particularly useful group includes the alkali metal and especially the sodium salts of amino carboxylic acids such as imino diacetic acid (IDA), nitrilotriacetic acid (NTA) and ethylenediamine tetraacetic acid (EDTA).
  • IDA imino diacetic acid
  • NTA nitrilotriacetic acid
  • EDTA ethylenediamine tetraacetic acid
  • the sequestering agent is normally used in a proportion of 0.02 to 2 parts by weight per 100 parts of tat-cellulose. As will appear below, a portion of this may be added to the dissolving soda.
  • the resulting alkali cellulose is shredded at say 16 to 24 C. for say .5 to 1.5 hours and is charged with or without aging (say to 30 hours) to a Xanthating vessel.
  • Xanthation is preferably conducted at constant temperature, or as close to constant temperature as possible, in the range of say 18-32" C. under conditions which avoid localized heating ⁇ This can be achieved by thorough mixing of the alkali crumbs with the carbon disulde, but inadequate mixing can be compensated for by adding the carbon disulfide in two or more increments and allowing sufcient time between each addition for the mixture to react. .In this way, the amount of free liquid carbon disulfide in the reaction vessel at any time is restricted.
  • the gamma number of the viscose at spinning is above 80. Preferably it is above 100, say 100 to 115.
  • the amount of CS2 added will be say 1.33 to 1.05 times the equivalent amount.
  • the Xanthate crumbs are dissolved and the resulting viscose is preferably kept cool, for example below C., from the time it is iirst made until it is spun. This may be accomplished by adding the Xanthate to dilute, (1.5 to 4% NaOH) caustic at -5 to 5 C. and maintaining some refrigeration during the mixing process so that the temperature does not rise above about 10 C.
  • the dissolving liquor may contain a sequestering agent of the type indicated above, the total amount of combined agent used in both the steep liquor and the dissolving liquor, being in the range 0.02 to 2 parts/100 parts of nt-cellulose. Additional carbon disulfide, say 2 to 10% on cellulose may be added to the dissolver or subsequently, if desired.
  • the properties of the viscose are not impaired by storage before or after deaeration so long as the gamma number does not decay to below at the time the viscose is spun.
  • the viscose must have a gamma number above S0 at spinning, and preferably above 100. Normally, the gamma number will range from say to 105.
  • the viscosity at spinning will be at least poiscs, preferably between about and about 600 poises.
  • the viscose will preferably contain between 3.5 and 6% cellulose, with an NaOH/cellulose ratio of at least 1 and usually between about 1.1 and about 1.6. We have found that fibres having tenacities of 10 g.p.d. and higher are made more consistently when the viscosity of the viscose is high and within the range 150 to 600 poises.
  • the viscose is spun at a spinning speed of say 25 to 70 metres/minute into a coagulating bath relatively low in regenerative power, containing by weight, between about 3% and about 8%, preferably between about 4 and about 6% H2804 and between about 0 and about 12%, preferably not more than 5%, Na2SO4. It will be understood that there will always be some Na2SO4 in the bath from neutralization of the viscose caustic soda ⁇
  • the spin bath also contains between about 0.3 and about 1.5% formaldehyde.
  • the lilaments When the lilaments have been in the spin bath long enough to acquire sufiicient strength, they are stretched by at least 500%, and preferably by between about 550% and about 850%. At this stage the gamma number must be not less than 60 and is preferably 615 to 90.
  • filaments may be stretched in the coagulating bath or in air, but are preferably stretched in a secondary bath of hot (80 C.100 C.) water.
  • This bath may contain up to say 4% H280., but is preferably substantially neutral, containing less than 0.1% H2502. See Klein Patent 3,109,698.
  • Regeneration will normally be accomplished during stretching. However, if necessary, the .laments can be contacted with a final bath of hot water or hot dilute acid to complete the regeneration.
  • the filaments may be given the usual desulfurization, souring, washing and drying treatments conventional in the art. They may be cut up to form staple either immediately after regeneration or subsequently, if it is desired to produce staple fiber.
  • the steep liquor contained 0.01% Sequestrene NA-4 (EDTA).
  • the press-weight ratio was 2.70i0-05.
  • the alkali cellulose was shredded for 1 hour at 18 C. in a Blaschke pfleiderer and, without aging, was Xanthated. Xanthation was carried out in two stages, or in a single stage, as specified in Table I below. 1n carrying out two stage Xanthation the pressure in the xanthation churn was measured.
  • Example l1 a commercially available polynosique fiber for the behavior in caustic soda. Specifically, samples of each ber were let stand in caustic soda of varying concentrations at room temperature and immediately drawn while still wet, in an Instron tester to break.
  • Viscosity Gamma Viscose temp., Stretch, (poises) Number Age, Hrs.
  • C Percent Percent Percent Temp., percent HzSOi NazSOi HCHO C.
  • the dry tenacity and elongation are measured at 65% from to 60 grams/denier/100% extension.
  • Example 9 The general procedure of Examples 1-8 was carried out to make an additional sample. In this specific instance a two stage xanthation was employed with 35% CS2 based on cellulose, added in each stage. The xanthation temperature was 22 C. and the time 4 hours 10 minutes. Approximately 4% CS2 was added to the dissolver which was kept rat 8 C. The viscose contained 4.86% cellulose, and 6.78% soda. lt was spun after four hours at a gamma number of 113.4, a temperature of 7 C. and a viscosity of 426 poises. The spinning bath contained 4.53% H2504, 1.47% HCHO and around 1% Na2SO4. Its temperature was 22 C. The laments were stretched 841% in hot water, washed and dried. They had a conditioned tenacity of 10.60 g./denier.
  • Example 10 Another sample was prepared using the general technique of Examples 1-8. Specifically a viscose containing 4.48% cellulose and 6.75% NaOH was spun at a gamma number of 99.3 and a viscosity of 388 poises into a bath containing 5.20% H2504, 0.77% formaldehyde and about 1% Na2SO4 and having a temperature of about 28 C. The iilarnents were stretched 578% in water at 95 C.,
  • Regenerated cellulose filaments having a conditioned tenacity above about 9.5 g./ denier, a Wet tenacity at least 0.75 times the conditioned tenacity and a conditioned birefringence of at least 0.053.
  • Cellulose filaments characterized by a conditioned tenacity of at least 9.5/ denier, a conditioned birefringence of at least 0.053 and a D20 inaccessibility of at least 65%.
  • Regenerated cellulose filaments having a conditioned tenacity of at least g./denier, a wet tenacity of at least 8 g./denier and a. conditioned biretringence of at least 0.053.
  • Regenerated cellulose filaments having a conditioned tenacity of at least 9.5 g./denier, a conditioned bircringence of at least 0.053 and whose wet work product is substantially unatlected when impregnated with aqueous solutions containing from 0 to 20% NaOH at 25 C.
  • a method for making high tenacity regenerated cellulose tlamentary material which comprises extruding viscose having a ,gamma number greater than 80, viscosity of at least 120 poises and a NaOH/cellulose ratio of at least 1 into a coagulating bath having a temperature not greater than C. and containing between about 3% and about 8% H2804, between 0 and about 12% Na2SO4 and from 0.3 to 1.5% HCI-IO to form filaments, stretching the filaments by at least 500%, and then completing the regeneration of said filaments.
  • a method for making high tenacity regenerated cellulose filamcntary material which comprises reacting cellulose with sodium hydroxide to form alkali cellulose, Xanthating the alkali cellulose to form sodium cellulose Xanthate dissolving the cellulose Xanthate to form viscose having a NaOH/cellulose ratio of at least .1, a viscosity of at least poises and a gamma number greater than 80, spinning said viscose into a coagulating bath low in regenerative power and containing formaldehyde to form filaments, removing the filaments from the coagulating bath While their gamma number' is not less than 60, and
  • the viscose contains 0.02 to 2% based on cellulose of a sequestering agent capable of chelating polyvalent cations in alkaline solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
US354975A 1963-03-28 1964-03-26 Filaments of regenerated cellulose Expired - Lifetime US3388117A (en)

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GB12261/63A GB1074131A (en) 1963-03-28 1963-03-28 Filaments of renegerated cellulose

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CH (1) CH428084A (en))
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ES (1) ES298070A1 (en))
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3494996A (en) * 1965-07-20 1970-02-10 Itt Rayonier Inc Method for producing high tenacity rayon
US3539679A (en) * 1965-08-03 1970-11-10 Mitsubishi Rayon Co Process for producing polynosic fibers
US3632468A (en) * 1968-04-09 1972-01-04 Rayonier Inc High-crimp, high-strength rayon filaments and staple fibers and process for making same
WO2014118082A1 (de) 2013-01-29 2014-08-07 Continental Reifen Deutschland Gmbh Verstärkungslage für gegenstände aus elastomerem material, vorzugsweise für fahrzeugluftreifen und fahrzeugluftreifen
WO2014118083A1 (de) 2013-01-29 2014-08-07 Cordenka Gmbh & Co. Kg Hochfestes viskose-multifilamentgarn mit niedrigem garntiter
EP2781633A1 (de) 2013-03-18 2014-09-24 Continental Reifen Deutschland GmbH Hybridkord aus wenigstens zwei miteinander verdrehten Multifilamentgarnen

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663704A (en) * 1950-04-19 1953-12-22 American Viscose Corp Process and composition for producing improved viscose
US2847272A (en) * 1953-06-25 1958-08-12 Courtaulds Ltd Production of artificial filaments, threads and the like
CA590660A (en) * 1960-01-12 Heuer Kurt Metal-organic salt addition in viscose spinning
US2933475A (en) * 1955-09-20 1960-04-19 Du Pont Chelates and methods of making the same
US3038780A (en) * 1959-10-23 1962-06-12 Eastman Kodak Co Spinning solution containing an aluminum complex
US3079213A (en) * 1958-06-02 1963-02-26 Yardney International Corp Antimicrobial treatment of organic materials and composition therefor
US3107970A (en) * 1960-10-04 1963-10-22 Toho Rayon Kk Process for the manufacture of high tenacity viscose rayon
US3226461A (en) * 1962-02-27 1965-12-28 Courtaulds North America Inc Manufacture of regenerated cellulose fibers from viscose
US3337671A (en) * 1958-07-31 1967-08-22 Chimiotes S A Method of making regenerated cellulose filaments

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA590660A (en) * 1960-01-12 Heuer Kurt Metal-organic salt addition in viscose spinning
US2663704A (en) * 1950-04-19 1953-12-22 American Viscose Corp Process and composition for producing improved viscose
US2847272A (en) * 1953-06-25 1958-08-12 Courtaulds Ltd Production of artificial filaments, threads and the like
US2933475A (en) * 1955-09-20 1960-04-19 Du Pont Chelates and methods of making the same
US3079213A (en) * 1958-06-02 1963-02-26 Yardney International Corp Antimicrobial treatment of organic materials and composition therefor
US3337671A (en) * 1958-07-31 1967-08-22 Chimiotes S A Method of making regenerated cellulose filaments
US3038780A (en) * 1959-10-23 1962-06-12 Eastman Kodak Co Spinning solution containing an aluminum complex
US3107970A (en) * 1960-10-04 1963-10-22 Toho Rayon Kk Process for the manufacture of high tenacity viscose rayon
US3226461A (en) * 1962-02-27 1965-12-28 Courtaulds North America Inc Manufacture of regenerated cellulose fibers from viscose

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3494996A (en) * 1965-07-20 1970-02-10 Itt Rayonier Inc Method for producing high tenacity rayon
US3539679A (en) * 1965-08-03 1970-11-10 Mitsubishi Rayon Co Process for producing polynosic fibers
US3632468A (en) * 1968-04-09 1972-01-04 Rayonier Inc High-crimp, high-strength rayon filaments and staple fibers and process for making same
WO2014118082A1 (de) 2013-01-29 2014-08-07 Continental Reifen Deutschland Gmbh Verstärkungslage für gegenstände aus elastomerem material, vorzugsweise für fahrzeugluftreifen und fahrzeugluftreifen
WO2014118083A1 (de) 2013-01-29 2014-08-07 Cordenka Gmbh & Co. Kg Hochfestes viskose-multifilamentgarn mit niedrigem garntiter
CN104968847A (zh) * 2013-01-29 2015-10-07 大陆轮胎德国有限公司 用于由弹性材料制成的物品的、优选用于车辆充气轮胎的加强层以及车辆充气轮胎
EP2781633A1 (de) 2013-03-18 2014-09-24 Continental Reifen Deutschland GmbH Hybridkord aus wenigstens zwei miteinander verdrehten Multifilamentgarnen
WO2014146869A1 (de) * 2013-03-18 2014-09-25 Continental Reifen Deutschland Gmbh Hybridkord aus wenigstens zwei miteinander verdrehten multifilamentgarnen
US9677198B2 (en) 2013-03-18 2017-06-13 Continental Reifen Deutschland Gmbh Hybrid cord consisting of at least two multifilament yarns twisted together

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NL6403353A (en)) 1964-09-29
DE1494559A1 (de) 1969-06-04
LU45764A1 (en)) 1964-05-27
BE645841A (en)) 1964-07-16
ES298070A1 (es) 1964-10-16
AT259129B (de) 1967-12-27
GB1074131A (en) 1967-06-28
CH428084A (de) 1967-01-15

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