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

Definitions

• the present invention relates to the manufacture of rayon yarns, filaments, films and the like and more particularly to the production of high tenacity viscose rayon yarn, that is characterized by its high tenacity which makes it especially suitable for use in reinforcing rubber articles such as cord tires and the like.
• Patent 2,696,423 that the combination of the polyethylene oxide compounds having a molecular weight of from about 300 to 1000, among other ether-type modifiers, may be admixed with certain dithiocarbamate modifiers to increase the modification thereof. It is to be understood that the use of polyalkylene oxide compounds as spinning assistants or as per se a viscose modifier forms no part of the present invention.
• the Ethoquad viscose modifier disclosed in said copending application has the following general formula:
• R and R represent preferably an alkyl radical but may include an a-ryl or alicyclic radical with R preferably being an alkyl radical containing six or more carbon atoms and R being an alkyl radical containing one to three carbon atoms;
• Z represents an anion having substantially no surface activity such as hydroxide, halide, sulfate, acetate, etc.;
• x and y are whole numbers of at least one with the preferred combined value of x and y being 2 to 50 or more;
• n is a whole number, possibly one but preferably two and no more than four.
• the aforesaid objects are accomplished by spinning viscose that contains a synergistic combination of additives con sisting of certain polyethylene oxide compounds and cer tain ethoxylated cation-active quaternary ammonium. compounds in amounts to bring about a modification of the cellulose that results in the production of viscose rayon filaments having improved properties as compared to filaments produced under the influence of either type of additive when employed singularly.
• the viscose containing the combination of additive is spun according to the viscose process into filaments in an aqueous acidic coagulating oath containing a Zinc salt. Thereafter, the filaments are given a high degree of stretch before complete regeneration thereof.
• the degree of polymerization of the polyethylene oxide additives may vary depending upon the spinning conditions and the other additives employed. However, the improvement of the present invention is attained only when the molecular weight of the polymerized ethylene oxide lies in the range of about 1500-4500. Below the lower limit the modifying power diminishes; above the upper limit the additive may not dissolve in the viscose to a required minimum quantity. It has been found that the polyethylene oxide compounds induce the desired modifying effect when added to the viscose in amounts of O.55.0% by weight based on the cellulose content in the viscose, hereinafter referred to in short as (C.I.V.).
• the quaternary ammonium compounds contemplated to be incorporated in the viscose with the polyethylene oxide compounds are the socalled Ethoquads as described above in detail. More particularly, the viscose modifier for this purpose has the following general formula:
• the amount of the just described additive should be used in the range of 0.55.0% (C.I.V.) in order to obtain the desired optimum modifying effect.
• the combination of the polyethylene oxide compounds and the ethoxylated cation-active quaternary ammonium compounds be employed in a minimum total concentration of at least 2.0% (C.I.V.), otherwise, the enhanced modification will not be attained.
• the viscose containing the aforesaid combination may have other materials, such as delustrants, incorporated therein and may be prepared in part or in whole from wood pulp, with the degree of maturity. and the percentages of cellulose and alkali of the viscose not being especially. critical. But better results are obtainable when the viscose containsfrom 5.5 to 8.0% cellulose and from 4.0 to' 6.0% alkali and has a maturity in the range of l'18 NH Cl number. Generally these variables are correlative with each other, but not strictly so in order. to obtain the improved yarn properties of the present invention, depending upon the other spinning constants.
• the modifiers may be incorporated in the spinning system in a variety of ways, such as by adding the additives during the dissolving operation or by injecting the additives into a stream of viscose being pumped to. the spinneret.
• the coagulating bath into which this viscose is extruded through a spinneret immersed therein should cont-ain a soluble zinc salt, such as zinc sulfate in the amount of not less than 2%, preferably 3.5% and more.
• the sulfuric acid concentration of the bath may and for better results should be lower than concentrations ordinarily usedin viscose rayon production.
• the amount of acid should be less than 7% with the maintenance of a minimum concentration suificient to coagulate and partially regenerate the cellulose.
• Other salts, such as sodium sulfate and spinning assistants are also contained in the spinbath.
• the spinbath should have a temperature of about 40 to 70 C. The length of.
• thread immersion depends upon the spinning speed as well as the particular spinbath employed. Since regeneration is retarded under the spinning conditions described herein, it is preferred to conduct the thread through a spinning tube, of the type described in U.S. Patent No. 2,908,937. As shown therein, the thread is passedthrough the tube during at least part of its travel in the spinbath.
• the freshly spun viscose thread is stretched in the excess of 50%, preferably by 80100% or higher.
• the stretch is applied in a weakly acidic second bath at a temperature, preferably above 80 C., and best at 95 C.
• the thread is then takenup in package form and aftertreated, or aftertreated in a continuous. fashion and then taken up in package form.
• the thread produced in accordance with the present invention is particularly characterized by its very low loss in tenacity when twisted into cord.
• the thread has lower secondary swelling, increased resistance to flex fatigue and other improvements which make it especially suitable for use as reinforcing cords in tires, conveyor belts, etc.
• the thread has the socalled skin structure and non-crenulated surfaces associated with thread produced under the influence of a viscose modifier.
• the viscose containing the just mentioned combination of additives was permitted to age to a maturity value of 1416 NH CI number.
• the viscose was formed into a thread of 1650 denier, 720 filament viscose rayon yarn by extrusion of the viscose through a spinneret into an aqueous coagulating bath having a temperature of 65 C. and containing 4.8% H 50 12% Na SO and 3.5% ZnSO
• the thread was withdrawn therefrom by means of a first godet. Then the thread was guided into and through a second hot weakly acidic bath at a temperature of 94 C. and withdrawn therefrom by means of a second godet.
• the thread was stretched 98% therebetween.
• the yarndraw off speed was 55 meters per minute.
• the aftertreatrnentv ofthe thread was carried out according to the usual processes which includes drying of the thread. Then the thread was given a slashing stretch of about 12% and thereafter dried under tension. The slashed thread was twisted and plied into the tire cord construction of 11.4 x 10.6.
• threads were produced under the same conditions mentioned above in this example except that the sole additive employed was the polyethylene oxide compound of the present example in the amount of 2.0% (C.I.V.). Moreover, threads were also produced under these conditions but while using only the quaternary amine additive of the present example in the amount of 2.5% (C.I.V.).
• EXAMPLE H A viscose having a composition of 7.5% cellulose and 5.5% total alkalinity was prepared in the manner described in Example I. To this viscose the ethoxylated quaternary amine and the polyethylene oxide additives used in Example I were added in the amounts of 2.0% (C.I.V.) and 1.0% (C.I.V.), respectively. After aging, filtering and deaerating, the viscose was formed into a thread of 1650 denier, 720 filament viscose rayon yarn by extrusion through a spinneret into an aqueous acidic coagulating bath having a temperature of 51 C. and containing 5.2% H 80 12% Na SO and 5.0% 2.1180
• the thread After being passed through the coagulating bath, the thread was withdrawn therefrom by means of a first godet. Then, the thread was guided into and through a second hot weakly acidic bath at a temperature of 94 C. and withdrawn therefrom by means of a second godet. Due to a predetermined diiferential in the peripheral speeds of said godets, the thread was stretched 100% therebetween. The yarn draw-off speed was 65 meters per minute.
• the aftertreating of the thread was carried out according to the usual processes. Then the thread was given a slashing stretch of about 12% and thereafter dried under tension. The slashed thread was plied into the tire cord construction of 12.0 x 12.0.
• threads were produced under the same conditions mentioned above in this example except that the sole additive employed was the polyethylene oxide compound of the present example in the amount of 2.0% (C.I.V.). Moreover, threads were also produced under these conditions while using only the quaternary amine additive of the present example in the amount of 2.7% (C.I.V.).
• Example II Quaternary Polyethyl- Strength, g./100 den. amine+ Quaternary ene oxide
• a viscose having a composition of 7.5 cellulose and 5.7% total alkalinity was prepared in the manner described in Example I.
• the viscose after being properly filtered, deaerated and aged was pumped to a spinneret through a conduit.
• a solution containing the combination of additives used in Example I was injected and later intimately mixed in the amounts of 1.5% (C.I.V.) ethoxylated quaternary amine and 1.0% (C.I.V.) poly- .cthylene oxide into the viscose in the manner described in copending application Serial No. 655,004, filed April 25, 1957, and having common ownership herewith.
• the viscose containing the additives was formed into a thread of 1650 denier, 1100 filament viscose rayon yarn 6 in an aqueous acidic coagulating bath having a temperature of 55 C. and containing 4.7% H 12% Na SO and 4.4% ZnSO
• the freshly spun thread was stretched 93%, aftertreated and slash stretched as described in Example 11.
• the thread was then plied into the tire cord construction of 11.4 x 10.6.
• threads were produced under the same conditions mentioned above in this example except that the sole additive employed was the polyethylene oxide compound of the present example in the amount of 2.0% (C.I.V.). Moreover, threads were also produced under these conditions while using only the quaternary amine additive of the present example in the amount of 2.0% (C.I.V.).
• EXAMPLE IV A viscose having a composition of 7.5 cellulose and 5.6% total alkalinity was prepared in the manner described in Example I. To this viscose the ethoxylated quaternary amine and the polyethylene oxide additives used in Example I were added in the amounts of 1.5% (C.I.V.) and 0.5% (C.I.V.), respectively. After aging, filtering and deaerating, the viscose was formed into a thread of 1100 denier, 720 filament in an aqueous acidic coagulating bath having a temperature of 55 C. and containing 4.6% H 50 12% Na SO and 4.4% ZnSO The freshly spun thread was stretched 98%, aftertreated and slash stretched as described in Example II. The
• Polymerized ethylene oxide having an average molecular weight of 2000 in the amount of 1.5% (C.I.V.) and the ethoxylated quaternary amine used in Example I in the amount of 0.5% (C.I.V.) were added to a portion of the viscose.
• To another portion of the viscose polymerized ethylene oxide having an average molecular weight of 1000 in the amount of 1.0% ('ClV.) and the ethoxylated quaternary amine used in Example I in the amount of 1.0% (C.I.V.) were added.
• To a third portion of the viscose polymerized ethylene oxide having an average molecular weight of 1000 in the amount of 2.5% C.I.V.) was added.
• conditioned 463 470 458 Slashed singles, conditioned 504 486 485 Slashed singles, wet- 347' 338 331 Cords, conditioned.” 415 395 395 Cords, oven dry 494 484 471 where R is an alkyl radical with at least 6 carbon atoms; x+y 250 and Z is an innocuous anion, in the amount of 0.5 to 5.0% by weight based on the cellulose content 7 and polyethylene oxide having a molecular weight in the range of 1500-4500 in the amount of 0.5 to 5.0% by weight based on the cellulose.
• the totaljminimum amount of said compound and polyethylene oxide being at least 2.0% by Weight based on the cellulose content, into an aqueous spinbath containing less than 7 sulfuric acid and at least 2% zinc sulfate and stretching the freshly spun thread.
• a method of producing viscose rayon filaments having improved strength comprising adding to a viscose the methyl chloride quaternary derivative of an ethoxylated quaternary ammonium compound, having the general formula:
• R is a saturated, straight chain, hydrocarbon radical containing 8-18 carbon atoms in the amount of about 1-2% by Weight based on the cellulose content and polyethylene oxide having a molecular Weight in the range of 15004500 in the amount of about 0.5-1.0% by Weight based on the cellulose content, the total minimum amount of said compound and polyethylene oxide being at least 2.0% by weight based on the cellulose content, spinning the resulting viscose into a thread in an aqueous coagulating bath containing less than 7% sulfuric acid and at least 2% zinc sulfate, and passing the freshly spun thread into a second weakly acidic bath at a temperature above C. while stretching the thread to the extent of at least 80%.
• a viscose spinning composition containing an ethoxylated quaternary ammonium compound, having the general formula:
• R is a saturated, straight chain, hydrocarbon radical containing 8-18 carbon atoms in the amount of about 12% by weight based on the cellulose contentand polyethylene oxide having a molecular weight in the range of 15004500 in the amount of about 0.51.0% by weight based on the cellulose content, the total minimum amount of said compound and polyethylene oxide being at least 2.0% by Weight based on the cellulose content.

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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)

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Cited By (1)

Citations (10)

• 0
  • BE BE572234D patent/BE572234A/xx unknown
• 1957
  • 1957-11-29 US US699516A patent/US3026170A/en not_active Expired - Lifetime
• 1958
  • 1958-10-27 GB GB34356/58A patent/GB836762A/en not_active Expired

Patent Citations (10)

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