US2696423A - Viscose modifiers - Google Patents

Viscose modifiers Download PDF

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Publication number
US2696423A
US2696423A US228975A US22897551A US2696423A US 2696423 A US2696423 A US 2696423A US 228975 A US228975 A US 228975A US 22897551 A US22897551 A US 22897551A US 2696423 A US2696423 A US 2696423A
Authority
US
United States
Prior art keywords
viscose
bath
yarn
sodium
dithiocarbamate
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
US228975A
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English (en)
Inventor
Dietrich Melvin Adam
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 BE523478D priority Critical patent/BE523478A/xx
Priority to NL94986D priority patent/NL94986C/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US228975A priority patent/US2696423A/en
Priority to GB11991/52A priority patent/GB741727A/en
Priority to DEP7722A priority patent/DE1108849B/de
Priority to FR1116102D priority patent/FR1116102A/fr
Priority to CH308243D priority patent/CH308243A/de
Application granted granted Critical
Publication of US2696423A publication Critical patent/US2696423A/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
    • 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

Definitions

  • ers should have no rad'ical'hving more than 1 8 carbon atoms; thosev containing 5a.y having nmorev are Vtoo insoluble.
  • the yarn produced by this and other examples has a number of properties which distinguishes it sharply from other regenerated cellulose yarn.
  • the most readily apparent modifications are the unsual cross-section and surface features.
  • the skin area is much greater, the boundary between the skin and core is very diffuse and the yarn has no appreciable crenulations so that the yarn has a relatively smooth surface.
  • Such yarns are described also in the Cox patents, U. S. 2,536,014, 2,535,044 and 2,535,045, issued on December 26, 1950, on applications filed December 14, 1946, April 26, 1947, and April 26, 1947, respectively.
  • filaments of the invention have smooth surface and considerably lower secondary swelling (water take-up by dried yarns) results in more resistance to fibrillating, laundering, and fatiguing than exhibited by normal crenulated viscose yarns.
  • Example II A 5-6.5 viscose (5% cotton linters cellulose- 6.5% total sodium hydroxide) modified with 0.25% sodium amyl dithiocarbamate is prepared and spun in the manner described in Example I, using a 10.5% sulfuric acid, 17.0% sodium sulfate, Zinc sulfate coagulating and regenerating bath. The yarns are washed, slashed, and some of the yarn was plied to a cord of 1100/2 construction. Yarn and cord properties are given in Table Il, along with those for a regular Viscose control.
  • Example IV A 5-6.5 viscose (5% cotton linters cellulose- 6.5% total sodium hydroxide) modified with 0.06% sodium hexamethylene bis (dithiocarbamate) is prepared and spun in the manner described in Example I, using a 9.5% sulfuric acid, 17.0% sodium sulfate, 10.0% zinc sulfate ccagulating and regenerating bath. The yarns are washed, slashed, and part of slashed yarn was plied to a cord of 1100/2 construction.
  • Yarn and cord properties are given in Table IV, along with those for a regular viscose control. It will be noted that the yarn from the modified, unripened viscose shows large improvements in cord strength and fatigue resistance of the cord over yarn produced from unripened unmodified viscose spun under similar conditions, even though the dry yarn tenacity of the modified item is actually lower than that of the control. This may be attributed, in part, to the greatly improved elongatlons.
  • Example V A 5-6.5 viscose (5% cotton linters cellulose-6.5% total sodium hydroxide) modified with 0.3% potassium pentamethylene dithiocarbamate is prepared and spun in the manner described in Example I, using an 8.5% sulfuric acid, 17.0% sodium sulfate, 10.0% zinc sulfate coagulating and regenerating bath. The yarns are washed, slashed, and part of the yarn plied to a cord of 1100/2 construction. Yarn and cord properties are given in Table V, along with those for a regular viscose control.
  • Example III A 5-6.5 viscose (5% cotton linters cellulose- 6.5% total sodium hydroxide) modified with 0.16% sodium butyl monoethanol dithiocarbamate is prepared and spun in the manner described in Example I, using an 8.5% sulfuric acid, 17.0% sodium sulfate, 10% zinc sulfate coagulating and regenerating bath. The yarns are washed, slashed, and a part of the slashed yarn plied to a cord of 1100/2 construction. Yarn and cord properties are given in Table III, along with those for a regular viscose control. lt will be noted that the yarn from the modified, unripened viscose shows large improvements in cord strength and fatigue resistance of the cord over yarn produced from unripened unmodified viscose spun under similar conditions.
  • Example VI tents cant-:be usedinfthewviscose l' when l the dithiocarbamatesfi described 1 herein-i vare"added andthere appears tobean vadvantage 'ins'tret'chfaljility land level ofyarnl'propertiesfif salt 4.indices hifgherithan While the majoritybfnthe .fc-item mdiers; haVe.b.een .45 5 are used.
  • the modifier may be added tothe '-causticuse'dzin: con- 75 m'tcrting the fxan'thatefcrumbs iitolviscose for ⁇ .to ⁇ already .pceparedrviscose ".It:. is.'obvious"from this thatthe controlled vweights of modicrfcould..alsoi'beadded -tofthe cellulosic components being converted into viscose such as the celluloseala-lkali;cellulose..onxanthatecrumbs.
  • the dithiocarbamate m'diiers may'be us'ed alone or in admixture wvit-hcentain'f'ther: compounds which augment ⁇ the modification action and which in themselves .smay'bemodiers Such compounds include .al'number of carbon ldisulde -to obtainsalt indices bf ⁇ 5 -or-'over .'in unrip'ened viscoses.
  • the spinning baths suitable 'forusein 'theiln” entin “contain 'sulfuric'.acidi and-zinc sulfate.
  • Zinc slf'ate an essential componenti 'of 'thel spinning Abathl since, inlits absence, lthe dithiocarbamate compounds havefno'- effect on spinningl and'- yarn properties.
  • Sodium"v slfate is us- ⁇ uallypres'ent1but is not essential.
  • flf desiredfadditional salts fdivalent-m'etals knownlto reinforce'lor supplement the'action of 'zinc sulfate-may be'uSQd, Suchasferrus sulfate, manganese sulfate, onn'i'ckel sulfate, particularly .the ⁇ rst-nam-edfsalt. .Theuse'cf Vthese 4divalentmetal salts makes it "possible to use. smaller "amounts" of ,zinc sulfate than are necessary in their absence.
  • the .spinning bath contains -from 4% to 12% of su'lfuric acid, from 13% to 25% of sodium sulfate, and from' 1% to 15% of Zinc sulfate, optionally with 1% to about 5% ,ferrous sulfate.
  • the temperature range of best spinnability is from 40 C. to 75 C.
  • the bath acidity as low as is practical for a given spinning speed in order to get optimum filament structure and yarn properties.
  • concentrations should be adjusted to each other and to the composition of the viscose. lt is desirable to use as high a total solids content as possible in the coagulating bath to give the highest degree of gel shrinkage and improved stretchability.
  • the filaments may be given a long travel of 130 to 250 inches in the primary bath by means of a multiple roller setup which gradually applies tension to the traveling filaments and thereby Orients them while they are still plastic.
  • the preferred method is to apply a part or all of the stretch beyond the primary bath in a secondary bath or to use a combination of air and hot bath stretch.
  • the secondary bath may consist simply of water or of dilute (1% to 3%) sulfuric acid, or it may have the same composition as the coagulating bath but at a greater dilution, e. g., one-fourth of the concentration of the coagulating bath.
  • the thread can be given a travel of to 50 inches in the secondary bath of hot water or dilute bath.
  • the temperature of the secondary bath is preferably between 50 C.
  • Stretches of 80% to 100% are preferred for producing high tenacity yarn and to 30% for textile type yarns.
  • the preferred procedure is to draw off the freshly coagulated gel yarn with a feed wheel speed equal to or less than the jet velocity and to apply all of the stretch between positivly driven rollers traveling at different speeds. The amount of stretch applied depends on the properties desired for the yarn.
  • the bobbin process has been used in the example, but it is immaterial whether spinning is by bobbin, bucket, or continuous processes.
  • the yarn cake is washed free of acid and salt and then dried under tension. lf preferred, it may be twisteror Slasher-dried to enable the dry elongation of the finished product to be controlled.
  • Spinning may be carried out with the aid of spinning tubes such as described in Millhiser U. S. Patent 2,440,057 or Drisch et al. U. S. Patent 2,511,699.
  • These tubes of relatively small diameter and of substantial length confine the bath and filaments in their critical stage of formation so that no substantial tension is imposed on the filaments because the speed of concurrent bath ow is y maintained only slightly below the speed of the filament bundle passing through the tube. It is thus possible to materially increase the rate of spinning over methods earlier described without substantially sacrificing the desirable properties set forth above.
  • novel and improved yarns obtainable through the process of this invention can, in general, be used instead of regular regenerated cellulose fibers for any purpose where the latter are finding applications, more particularly in the textile and tire cord industries.
  • the production of yarns having smooth (non-crenulated) surfaces is highly advantageous, for such yarns have very high strength and improved soil and abrasion resistance.
  • the combination of high tenacity and high fatigue resistance represents a material advance and a new type of regenerated cellulose article.
  • a process for the production of regenerated cellulose articles which comprises adding to viscose a soluble salt of an N-substituted dithiocarbamic acid and extruding the resultant viscose into an acid coagulating bath containing about 1% to about 15 sinc sulfate.
  • dithiocarbamate is sodium hexamethylene bis (dithiocarbamate).
  • a process for the production of regenerated cellulose articles which comprises adding to viscose a soluble salt of an N-substituted dithiocarbamic acid containing no radical containing more than 18 carbon atoms and extruding the resultant viscose'into an acid coagulating bath containing about 1% to about 15% zinc sulfate.
  • a process for the production of regenerated cellulose articles which comprises adding to viscose up to about 0.5% of a soluble salt of an N-substituted dithiocarbamic acid and extruding the resultant viscose into an acid coagulating bath containing about 1% to about 15% Zinc sulfate.
  • a process for the production of regenerated cellulose articles which comprises adding to viscose up to about 0.5% of a soluble salt of an N-substituted dithiocarbamic acid and regenerating the resultant viscose by extruding it into an acid bath containing about 1% to about 15% Zinc sulfate, thereby reducing the gel swelling ratio of the resultant gel structure to less than 1.0.
  • a process for the production of regenerated cellulose structures which comprises extruding into an acid coagulating bath viscose containing a measured amount of a salt of an N-substituted dithiocarbamic acid which salt is soluble in 6% aqueous sodium hydroxide to the extent of at least about 0.05%, said bath containing about 1% to about 15% zinc sulfate.
  • a process for the production of regenerated cellulose articles wliich comprises adding to viscose an alkalimetal salt of an N-substituted dithiocarbamic acid and extruding the resultant viscose into an acid coagulating bath containing about 1% to about 15% zinc sulfate.
  • a process for the production of regenerated cellulose articles which comprises adding to viscose about 0.05% to about 0.5% of a soluble salt of an N-substituted dithiocarbamic acid; extruding the resultant viscose into an acid coagulating bath containing about 1% to about 15% Zinc sulfate; and stretching the resultant formed article about 20% to about 100% during spinning.
  • a process for the production of regenerated cellulose articles which comprises adding to viscose about 0.05% to about 0.5% of a soluble salt of an N-substituted dithiocarbamic acid and extruding ⁇ the resultant viscose into an acid coagulating bath maintained at 40 C. to C; which contains about 4% to about 12% sulfuric acid, about 13% to about 25% sodium sulfate and about 3% to about 10% zinc sulfate.
  • N-substituted dithiocarbamic acid contains a cyclohexyl group attached to said nitrogen (Ng) atom.
  • N-substituted dithiocarbamic acid is a mono-N- substituted dithiocarbamic acid.
  • N-substituted dithiocarbamic acid is' a di-N-substituted dithiocarbamic acid.

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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)
US228975A 1951-05-29 1951-05-29 Viscose modifiers Expired - Lifetime US2696423A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE523478D BE523478A (en(2012)) 1951-05-29
NL94986D NL94986C (en(2012)) 1951-05-29
US228975A US2696423A (en) 1951-05-29 1951-05-29 Viscose modifiers
GB11991/52A GB741727A (en) 1951-05-29 1952-05-12 Manufacture of regenerated cellulose structures from viscose
DEP7722A DE1108849B (de) 1951-05-29 1952-05-28 Verfahren zur Herstellung von Gebilden aus regenerierter Cellulose
FR1116102D FR1116102A (fr) 1951-05-29 1952-05-28 Procédé perfectionné de production d'articles en cellulose régénérée
CH308243D CH308243A (de) 1951-05-29 1952-05-28 Verfahren zur Herstellung von geformten Gebilden aus regenerierter Cellulose.

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Application Number Priority Date Filing Date Title
US228975A US2696423A (en) 1951-05-29 1951-05-29 Viscose modifiers

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US2696423A true US2696423A (en) 1954-12-07

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US228975A Expired - Lifetime US2696423A (en) 1951-05-29 1951-05-29 Viscose modifiers

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BE (1) BE523478A (en(2012))
CH (1) CH308243A (en(2012))
DE (1) DE1108849B (en(2012))
FR (1) FR1116102A (en(2012))
GB (1) GB741727A (en(2012))
NL (1) NL94986C (en(2012))

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852333A (en) * 1954-05-21 1958-09-16 Du Pont Viscose spinning process
US2860480A (en) * 1956-04-18 1958-11-18 Du Pont Regenerated cellulose structures and process for producing them
US2879170A (en) * 1957-10-02 1959-03-24 Du Pont Chemical composition and process
US2891836A (en) * 1955-04-26 1959-06-23 Du Pont Viscose process
US2942931A (en) * 1959-05-05 1960-06-28 Rayonier Inc Viscose process
US2954270A (en) * 1955-12-14 1960-09-27 Chimiotex Sa Process of producing a shrinkable cellulose textile filament
US2958569A (en) * 1954-10-20 1960-11-01 American Enka Corp Production of threads and other shaped objects from viscose
US2966391A (en) * 1955-10-12 1960-12-27 Spinnfaser Ag Manufacture of regenerated cellulose fibers
US2970883A (en) * 1956-01-16 1961-02-07 American Enka Corp Manufacture of viscose rayon
DE1100871B (de) * 1956-08-29 1961-03-02 Glanzstoff Ag Verfahren zur Herstellung hochfester Faeden durch Verspinnen von Viskose
US2974005A (en) * 1956-09-14 1961-03-07 American Enka Corp Manufacture of rayon
US2978292A (en) * 1955-03-18 1961-04-04 American Enka Corp Manufacture of rayon
US2983572A (en) * 1958-06-06 1961-05-09 American Enka Corp Manufacture of viscose rayon
US3026170A (en) * 1957-11-29 1962-03-20 American Enka Corp Manufacture of viscose rayon
US3113828A (en) * 1960-03-15 1963-12-10 Chimiotex Process for the manufacture of regenerated cellulosic material
US3116352A (en) * 1957-05-02 1963-12-31 Beaunit Corp Viscose spinning
US3116354A (en) * 1957-05-02 1963-12-31 Beaunit Corp Viscose spinning process
US3116353A (en) * 1957-05-02 1963-12-31 Beaunit Corp Spinning viscose
US3126435A (en) * 1956-07-25 1964-03-24 Production of regenerated cellulose
US3151194A (en) * 1961-09-01 1964-09-29 American Enka Corp Process for the manufacture of shaped bodies from viscose, and the products thus obtained
US3182107A (en) * 1956-12-18 1965-05-04 Fmc Corp Method of producing all-skin viscose rayon
US3418405A (en) * 1962-09-10 1968-12-24 Kurashiki Rayon Co Method of manufacturing flat viscose fibers
US3529052A (en) * 1963-02-26 1970-09-15 Fmc Corp Method of manufacturing rayon fiber

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2893820A (en) * 1956-07-16 1959-07-07 Du Pont Process for the production of regenerated cellulose filaments
DE1232699B (de) * 1958-10-01 1967-01-19 Benckiser Gmbh Joh A Verfahren zur Herstellung von kuenstlichem Fasermaterial

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2535044A (en) * 1947-04-26 1950-12-26 Du Pont Spinning of viscose

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE539320C (de) * 1928-06-01 1931-11-24 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von kuenstlichen Textilprodukten von mattem Glanz
FR831554A (fr) * 1937-01-05 1938-09-08 Ig Farbenindustrie Ag Procédé de fabrication de produits de réaction insolubles contenant de l'azote etdu soufre

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2535044A (en) * 1947-04-26 1950-12-26 Du Pont Spinning of viscose

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852333A (en) * 1954-05-21 1958-09-16 Du Pont Viscose spinning process
US2958569A (en) * 1954-10-20 1960-11-01 American Enka Corp Production of threads and other shaped objects from viscose
US2978292A (en) * 1955-03-18 1961-04-04 American Enka Corp Manufacture of rayon
US2891836A (en) * 1955-04-26 1959-06-23 Du Pont Viscose process
US2966391A (en) * 1955-10-12 1960-12-27 Spinnfaser Ag Manufacture of regenerated cellulose fibers
US2954270A (en) * 1955-12-14 1960-09-27 Chimiotex Sa Process of producing a shrinkable cellulose textile filament
US2970883A (en) * 1956-01-16 1961-02-07 American Enka Corp Manufacture of viscose rayon
US2860480A (en) * 1956-04-18 1958-11-18 Du Pont Regenerated cellulose structures and process for producing them
US3126435A (en) * 1956-07-25 1964-03-24 Production of regenerated cellulose
DE1100871B (de) * 1956-08-29 1961-03-02 Glanzstoff Ag Verfahren zur Herstellung hochfester Faeden durch Verspinnen von Viskose
US2974005A (en) * 1956-09-14 1961-03-07 American Enka Corp Manufacture of rayon
US3182107A (en) * 1956-12-18 1965-05-04 Fmc Corp Method of producing all-skin viscose rayon
US3116352A (en) * 1957-05-02 1963-12-31 Beaunit Corp Viscose spinning
US3116354A (en) * 1957-05-02 1963-12-31 Beaunit Corp Viscose spinning process
US3116353A (en) * 1957-05-02 1963-12-31 Beaunit Corp Spinning viscose
US2879170A (en) * 1957-10-02 1959-03-24 Du Pont Chemical composition and process
US3026170A (en) * 1957-11-29 1962-03-20 American Enka Corp Manufacture of viscose rayon
US2983572A (en) * 1958-06-06 1961-05-09 American Enka Corp Manufacture of viscose rayon
US2942931A (en) * 1959-05-05 1960-06-28 Rayonier Inc Viscose process
US3113828A (en) * 1960-03-15 1963-12-10 Chimiotex Process for the manufacture of regenerated cellulosic material
US3151194A (en) * 1961-09-01 1964-09-29 American Enka Corp Process for the manufacture of shaped bodies from viscose, and the products thus obtained
US3418405A (en) * 1962-09-10 1968-12-24 Kurashiki Rayon Co Method of manufacturing flat viscose fibers
US3529052A (en) * 1963-02-26 1970-09-15 Fmc Corp Method of manufacturing rayon fiber

Also Published As

Publication number Publication date
GB741727A (en) 1955-12-14
DE1108849B (de) 1961-06-15
FR1116102A (fr) 1956-05-04
NL94986C (en(2012))
BE523478A (en(2012))
CH308243A (de) 1955-07-15

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