US3109700A - Method for making rayon filaments - Google Patents

Method for making rayon filaments Download PDF

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Publication number
US3109700A
US3109700A US192322A US19232262A US3109700A US 3109700 A US3109700 A US 3109700A US 192322 A US192322 A US 192322A US 19232262 A US19232262 A US 19232262A US 3109700 A US3109700 A US 3109700A
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US
United States
Prior art keywords
formaldehyde
viscose
filaments
spinning
bath
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US192322A
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English (en)
Inventor
Klein Elias
Donald S Nelson
Basil E M Bingham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Courtaulds North America Inc
Original Assignee
Courtaulds North America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL292282D priority Critical patent/NL292282A/xx
Priority to BE631869D priority patent/BE631869A/xx
Application filed by Courtaulds North America Inc filed Critical Courtaulds North America Inc
Priority to US192322A priority patent/US3109700A/en
Priority to FR933566A priority patent/FR1354723A/fr
Priority to GB17510/63A priority patent/GB1035245A/en
Priority to AT361363A priority patent/AT243972B/de
Priority to DEC29846A priority patent/DE1278686B/de
Application granted granted Critical
Publication of US3109700A publication Critical patent/US3109700A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/27—Process of spinning viscose where viscose has high degree of polymerization

Definitions

  • This invention relates to a method for themanufaoture of rayon filaments by the viscose process andin particular to an improved process by means of which high tenacity filaments can be made more easily than has hitherto been possible.
  • One particularly useful technique is to start with a cellulose having a high degree of polymerization, and prepare and spin the viscose under conditions such that degradation of the celluloseis avoided to the greatest degree possible.
  • these conditions involve xanthating the alkali cellulose without substantial ageing and spinning the viscose, unripened, at a very high gamma value into a spinning bath low in acid and salt (Na SO and containing substantially no zinc.
  • the filaments thus formed are stretched to a very high degree (150350%) while incompletely regenerated, regeneration being completed during or after stretching.
  • Fibers made in accordance with this process have a crystallinity of say 5060%. They have a substantially circular cross section, a smooth, non-crenulated surface and no discernible skin-core structure.
  • Formaldehyde for many purposes is a superior re tardant to others which have been proposed; for example, it avoids the condensed filaments which are obtained using zinc salts.
  • the viscose may be ripened 3,109,700 Patented Nov. 5, 1963 ice carried into the spinning bath and the resulting build-up of the formaldehyde concentration in the bath. Moreover, it was found that when formaldehyde was added to the viscose, it caused a substantial reduction in gamma value, thus upsetting the entire spinning system. This was a particularly serious obstacle in the formation of the highly crystalline high tenacity fibers referred to above, since obtaining these fibers depcn s on the use of substantially unripened, high gamma value 'viscose.
  • the present invention is based upon two discoveries:
  • the invention therefore comprises, in a first aspect, a process for the manufacture of rayon filaments wherein viscose is extruded into an acid spinning bath to form filaments and the filaments are stretched, characterized in that formaldehyde in substantially monomeric form is mixed with the viscose prior to spinning.
  • the invention comprises a process for the manufacture of rayon wherein viscose is extruded into an acid regenerating bath and subsequently stretched, and characterized in that formaldehyde is added to the viscose just prior to spinning.
  • the drawing illustrates an embodiment of the invention wherein the two improvements are used together.
  • the invention is, of course, of general applicability in that it can be employed in any viscose process where a high degree of stretch is to be applied to the newly spun filaments.
  • the viscose in the most general aspect of the invention, may have from 1 to say 10% cellulose, and 2 to 10% NaOH.
  • viscosity at spinning may range from 20 to 450 seconds (ball fall), preferably 30-400. In accordance with the invention, at the time of spinning it will contain between about 0.2 and about 1.5% formaldehyde.
  • the cellulose Will preferably be of high DP (say 350 to 1200) and the viscose will have a viscosity of say 30 to 250 seconds (ball fall).
  • the viscose will contain, just prior to spinning, between about /2 and about 1% formaldehyde.
  • the concentration of the formaldehyde solution added to the viscose should be between about 1 and about 20% by weight, preferably between about 2' and about 6% by weight. Under these conditions between about 99 and about 70, preferably between about 99 and about 90% of the formaldehyde will be in mono-.
  • the formaldehyde may be added to the viscose batchwise in a suitable mixing device and agitated vigorously, or in order to cut down the residence time of the formaldehyde in the viscose, the techniques used for injecting pigment solutions into viscose may be employed.
  • the residence time of the formaldehyde in the viscose should be kept as short as possible. The minimum time will depend on spinning conditions.
  • the purpose of using formaldehyde is to retard regeneration, i.e. to prevent a decrease in gamma number, in the spinning bath. If, however, the residence time for the formaldehyde in the viscose is such as to cause a decrease in gamma number before spinning, which is equal or greater than the retarding effect obtained in the spinning bath, the advantage of the formaldehyde is lost. This ultimate limit is usually reached with a residence time on the order of two hours. However, it is preferred to spin with a residence time of not more than 90 min., say 10 to 60 minutes.
  • the invention envisions spinning viscose containing monomeric formaldehyde into any of the acid spinning baths hitherto employed in the art.
  • the bath may contain from say 3 to 10% H 80 from 6 to 23% Na SO and from to 6% ZnS0
  • Other components such as MgSO and the organic coagulation modifiers such as polyethylene glycol, may also be present in the bath, and the latter may be present in the viscose.
  • the bath may have a temperature between say 15 C. and 50 C.
  • the viscose may be spun at an extrusion ratio of say 0.2 to 1.5, with a bath travel of say 3 to 25 inches.
  • the invention will be used in the production of high tenacity filaments as indicated above.
  • the viscose is spun into a bath containing 3 to 7% H 80 6 to 18% Na S0 and less than 0.1% ZnSO
  • the bath may have a temperature from say 15 to 30 C.
  • the viscose is spun at an extrusion ratio of from about 0.3 to about 0.6.- A bath travel of say 3 to 10 inches is used.
  • the filaments are stretched. This may be carried out in the spinning bath itself, in a secondary acid bath, in a water bath, in stream or in air.
  • the degree of stretch applied will, of course, vary with the nature of the process, but will in general be between about 40% and about 350%.
  • the filaments will be removed from the spinning bath before they are more 4 than regenerated and stretched, preferably in hot water or steam (see the copending applications of Klein, Serial No. 184,510, filed April 2, 1962, and Richardson, Serial No. 191,004, filed April 30, 1962, both assigned to the assignee of the present application), by between about 150% and about 350%.
  • the regeneration of filaments can be completed, if it has not already been completed during stretching.
  • the filaments can be washed and desulfurized in the conventional way and can be cut up into staple either before or after these treatments.
  • Example I To illustrate the effect of formaldehyde on the ripeness of viscose, a viscose containing 5.91% cellulose and 5.98% NaOH, having a ball-fall viscosity of 364 seconds, a salt figure of 20.4 and a gamma value of 63.1 was mixed with an equal weight of 1.8% aqueous formaldehyde (98% monomer), under reduced (25 mm. Hg)vpressure. At intervals after mixing had begun the salt (NaCl) figure was determined. Theresults were as follows:
  • the average filament dry tenacity was 4.99 g./den.
  • Example III Example IV Samples of a viscose containing 3% cellulose, 3.8% NaOH and 1% HCHO, of which about 93% was in monomeric form, were spun at different times after the addition of the formaldehyde into a bath containing 5% H 80 8% Na SO and no zinc. The filaments were stretched to the maximum degree, washed and dried. The tenacity of the several samples was then measured. The results are tabulated below:
  • Viscose having a gamma number between and 95 and containing between about 0.5 and about 1% formaldehyde, at least of said formaldehyde being monomeric.

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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)
US192322A 1962-05-04 1962-05-04 Method for making rayon filaments Expired - Lifetime US3109700A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL292282D NL292282A (en(2012)) 1962-05-04
BE631869D BE631869A (en(2012)) 1962-05-04
US192322A US3109700A (en) 1962-05-04 1962-05-04 Method for making rayon filaments
FR933566A FR1354723A (fr) 1962-05-04 1963-05-03 Perfectionnements à la fabrication de filaments de rayonne viscose
GB17510/63A GB1035245A (en) 1962-05-04 1963-05-03 Improvements in the manufacture of viscose rayon filaments
AT361363A AT243972B (de) 1962-05-04 1963-05-03 Verfahren zur Herstellung von Reyonfasern
DEC29846A DE1278686B (de) 1962-05-04 1963-05-03 Verfahren zum Herstellen von Faeden aus regenerierter Cellulose nach dem Viskoseverfahren

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US192322A US3109700A (en) 1962-05-04 1962-05-04 Method for making rayon filaments

Publications (1)

Publication Number Publication Date
US3109700A true US3109700A (en) 1963-11-05

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ID=22709171

Family Applications (1)

Application Number Title Priority Date Filing Date
US192322A Expired - Lifetime US3109700A (en) 1962-05-04 1962-05-04 Method for making rayon filaments

Country Status (6)

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US (1) US3109700A (en(2012))
AT (1) AT243972B (en(2012))
BE (1) BE631869A (en(2012))
DE (1) DE1278686B (en(2012))
GB (1) GB1035245A (en(2012))
NL (1) NL292282A (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337671A (en) * 1958-07-31 1967-08-22 Chimiotes S A Method of making regenerated cellulose filaments
US3352957A (en) * 1962-11-06 1967-11-14 Chimiotex Process for spinning cellulosic fibers
US3381075A (en) * 1962-05-28 1968-04-30 Teijin Ltd Process for preparation of viscose regenerated cellulose fibers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2942931A (en) * 1959-05-05 1960-06-28 Rayonier Inc Viscose process
CA626141A (en) * 1961-08-22 F. Walker Bernard Manufacture of rayon
US3018158A (en) * 1959-05-05 1962-01-23 Rayonier Inc Viscose process
US3026169A (en) * 1960-03-23 1962-03-20 American Enka Corp Manufacture of viscose rayon
US3026170A (en) * 1957-11-29 1962-03-20 American Enka Corp Manufacture of viscose rayon

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE419032A (en(2012)) * 1935-12-12
DE752586C (de) * 1941-10-24 1953-05-26 Hirschberg Verfahren zur Herstellung von kuenstlichen Fasern mit verminderter Quellbarkeit und guter Schlingfestigkeit nach dem Viskoseverfahren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA626141A (en) * 1961-08-22 F. Walker Bernard Manufacture of rayon
US3026170A (en) * 1957-11-29 1962-03-20 American Enka Corp Manufacture of viscose rayon
US2942931A (en) * 1959-05-05 1960-06-28 Rayonier Inc Viscose process
US3018158A (en) * 1959-05-05 1962-01-23 Rayonier Inc Viscose process
US3026169A (en) * 1960-03-23 1962-03-20 American Enka Corp Manufacture of viscose rayon

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337671A (en) * 1958-07-31 1967-08-22 Chimiotes S A Method of making regenerated cellulose filaments
US3381075A (en) * 1962-05-28 1968-04-30 Teijin Ltd Process for preparation of viscose regenerated cellulose fibers
US3352957A (en) * 1962-11-06 1967-11-14 Chimiotex Process for spinning cellulosic fibers

Also Published As

Publication number Publication date
NL292282A (en(2012)) 1900-01-01
BE631869A (en(2012)) 1900-01-01
GB1035245A (en) 1966-07-06
AT243972B (de) 1965-12-10
DE1278686B (de) 1968-09-26

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