US3084021A - Process for producing regenerated cellulose filaments - Google Patents

Process for producing regenerated cellulose filaments Download PDF

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US3084021A
US3084021A US102082A US10208261A US3084021A US 3084021 A US3084021 A US 3084021A US 102082 A US102082 A US 102082A US 10208261 A US10208261 A US 10208261A US 3084021 A US3084021 A US 3084021A
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bath
yarn
viscose
temperature
sulfuric acid
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Morimoto Saichi
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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
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins

Definitions

  • Another object of this invention is to provide a novel and improved process for producing cotton like viscose regenerated cellulose fibres of high tenacity and lower water swelling or high wet modulus.
  • the drawing is a schematic representation of an embodiment of the invention.
  • Viscose regenerated cellulose fibres have heretofore come to be improved in their properties due to repeated studies and efforts made in the art.
  • the so-called high tenacity rayon has come to be produced, with an outstanding commercial success, by the development of stretch spinning process with two spinning baths.
  • the high tenacity rayon has further been improved so remarkably as to be called super high tenacity rayon.
  • the inner structure of viscose regenerated cellulose fibres has come to be disclosed.
  • the properties, particularly mechanical properties of the viscose regenerated cellulose fibre depend upon the degree of orientation and degree of crystallinity of the cellulose molecules forming the fibre, and that these orientation and crystallinity degrees of cellulose molecules largely depend upon or are greatly influenced by the particular mechanical stretch imparted to the viscose gel yarn during its passage through coagulating and regenerating baths.
  • any insoluble ammonium salt is formed in the purification.
  • the decomposed product is filtered to separate the regenerated cellulose, which is washed and dried, then weighed (this weight is represented by S in gram).
  • the filtrate is made alkaline with sodium hydroxide in a round-bottomed flask, which is connected with a condenser to subject the solution to distillation.
  • Ammonia gas distilled out thereby is introduced into a N sulfuric acid (A cc.). After confirming that the distillation of ammonia has been completed, the sulfuric acid solution is titrated with N sodium hydroxide.
  • the values RX as given in this specification and examples have been determined by the particular procedure just mentioned above, but it would be understood by those skilled in the art that the procedure can be modified without departing from the principle, and therefore the residual xanthate ratio referred to in this invention generally means a ratio (percent) of the number of xanthate groups in a viscose gel yarn with respect to the unit of glucose constituting the cellulose in said yarn and its method of measurement is not limited to the above indicated particular one, although this is believed to be most convenient and reliable at the present.
  • the above principle is applicable to a spinning process wherein a viscose of an ordinary viscosity less than about 150 poises (usually 100-50 poises) is spun into a Mueller-type spinning bath to produce yarns with a skin formed by the coagulating action of sulfates in the bath, as well as to a spinning process wherein a viscose of a high viscosity (more than about 150 poises) is spun into a bath having a poor regeneration and coagulation power to form yarns having substantially no skin.
  • Viscose which may be used in this invention may be prepared according to the conventional methods by dissolving wood pulp or cotton linter pulp.
  • the present invention requires a highly xanthated or substantially unripened (at least 50% in xanthate ratio or more than 50 in gamma number) at extrusion, and therefore an alkali cellulose prepared from a cellulose substance should be xanthated with carbon disulfide in an amount more than 40% based upon the weight of the cellulose, and the viscose after the preparation should be kept at a lower temperature (e.g. below 15 C.) so as to prevent the progress of the ripening as much as possible.
  • the aging degree of the alkali cellulose may be suitably selected depending upon the desired degree of polymerization of the cellulose.
  • the substantially unripened or highly xanthated viscose thus prepared is spun in accordance with the principle of this invention mentioned before.
  • This may conveniently be carried out with a four aqueous bath system, as shown in the drawing, consisting of a primary bath, 3, which may be referred to as fibre or yarn forming bath, a secondary bath, 6, which may be referred to as residual xanthate ratio controlling bath, a third bath, 10, which may be referred to as stretching bath and a fourth bath, 17, which may be referred to as regenerating and setting bath.
  • the primary bath or yarn forming bath, 3, is the bath for forming a gel yarn, 4, from a viscose extruded therein through a spinneret or spinning nozzle 12, connected to a source line, 1.
  • a viscose is about poises or less
  • an ordinary Mueller-type bath solution containing sulfuric acid, sodium sulfate and zinc sulfate and heated above normal temperature is required to be used in the primary bath, while when the viscose is of a viscosity higher than about 150 poises a bath solution containing a smaller amount of sulfuric acid and sodium sulfate and a very small amount of zinc sulfate and being kept at a temperature around or below normal temperature is required to be used.
  • the secondary bath, 6, or residual xanthate ratio controlling bath is the bath for adjusting the residual xanthate ratio of the filament yarn formed in the primary bath so as to be within 20-40%. It is necessary that the re generating power of the secondary bath be smaller than that of the primary bath and it is preferable that the acidity of the secondary bath is kept about or less than /2 that of the primary bath.
  • the gel filament yarn should have applied thereto to it as little stretch as possible or no stretch at all so as to substantially avoid any elongation of the yarn at these stages.
  • the third bath, -10, or stretching bath is the bath for imposing a first and positive stretch on the gel filament yarn during its passage therethrough.
  • the third bath may be of the same composition and temperature as the secondary bath. Generally it is preferable, however, to use a bath with regenerating power a little stronger than that of the secondary 'ba-th so as to decompose 4060%, at most 70%, of the residual xanthate groups (in the gel yarn just before entering this bath) during the stretching process in this bath.
  • the fourth bath, 17, or regenerating and setting bath is the bath for imposing a second stretch on the gel filament yarn and for substantially decomposing the remaining xanthate groups to set the internal structure of the regenerated cellulose yarn.
  • the primary bath or viscose filament yarn forming bath according to this invention may generally be classified into two types depending upon the viscosity of a viscose employed.
  • a series of the baths following to the primary bath also vary in their compositions and other conditions depending upon the primary bath. More particularly, the primary bath and hence the subsequently associated bath vary in their conditions depending upon whether (A) the viscosity of the spinning viscose solution is less than about 150 poises or (B) it is higher than about 150 poises.
  • filament guide rolls 5, 7, 8, 11, 12, 15 and 16 are employed.
  • godet rollers 9, 13 and 14 are placed respectively after the second, third and fourth baths.
  • the degree of polymerization of cellulose in a viscose to be employed in the case of (A) may be ordinary one (eg about 250-400) or may be high (cg. more than about 500). However it is necessary to make its viscosity below about 150 poises, preferably within about 50-100 poises, by controlling the cellulose content depending upon the polymerization degree. It is generally preferable to use a viscose containing 3-11% cellulose and 3-13% total alkali and whose combined carbon disulfide amount is at least 50%, preferably 75-90%, as expressed by xanthate ratio (or gamma number).
  • a Mueller-type bath is used as the primary or filament forming bath, and the subsequent spinning conditions are selected in accordance with the, principle of this invention mentioned hereinbefore. It has been found that the use of the following baths with conditions indicated give satisfactory results.
  • Zinc sulfate .g./l 40-80.
  • Secondary Bath General Preferable range range Sulfuric acid g./l-. 5-30 -25 Sodium sulfateg./l 30-120 80-100 Zine sulfate g./l 0-100 10-30 Temperature 0.- 5-30 10-20 RX of yarn just before entering the thlrd bath percent- -40 -35 Str (as little als possible)
  • Third Bath General Preferable range range Sulfuric acid g./l 10-50 25-35 Sodium sulfate ./1 -120 50- ⁇ 30 71nc sulfate /1 0-100 10-30 Temperature.
  • the subsequent spinning conditions may be same as those of (A) indicated before, but it is preferable that the residual xanthate ratio (RX) of the filament just before entering the third bath is controlled to be 30'- 40%.
  • Crimp development may be effected by, any suitable conventional manner. For example the crimp formation can be carried out by relaxing the regenerated filament yarn (cut into staple or not), under non-tensioned condition, into a cellulose swelling liquid such as water, warm Water, a dilute aqueous solution of sodium hydroxide and the like.
  • the number of permanent crimps to be formed somewhat depends upon the fineness of filaments spun. Generally, the coarser the filament is, the crimp number is less. However, in accordance with this invention, even when each filament is 10 deniers or above it is possible to form about 30 or more crimps per inch. In case of fineness of 1-3 deniers, the number of crimps per inch would come up to 50-70.
  • the crimped filaments or staple fibres obtained in the case of (A) are useful as wool-like fibres. Particularly, those having more than 50 inherent crimps per inch obtainable according to this process are entirely novel and unprecedented in the art. These crimps are not lost by usual handling or mechanical stretching.
  • the crirnped fibres of this invention even with such increased number of crimps show about 70-100% when measured by the crimp recovery from stretch test (this may be referred to as a wet meth- (*B) SPINNING A VISCOS'E OF MORE THAN ABOUT 150 POISES
  • the high viscosity (higher than about 150 poises) of viscoses may be obtained by increasing the content of the viscose cellulose or the cellulose polymerization degree in a conventional manner well known in the art.
  • the primary or filament forming bath is conditioned so as to be poor in the coagulating and regenerating power, and the subsequent spinning conditions are selected in accordance with the principle of this invention mentioned hereinbefore. It has been found that the use of the following baths with the conditions indicated give satisfactory results.
  • Secondary Bath General range Preferable range Less than 30 20S0 0-30 Sulfuric acid g./l Sodium sulfate--. g./1.- Temperature RX of yarn just before entering the third bath percent Stretch 20-40 25- (as little as possible)
  • Third Bath General range Preferable range Sulfuric acid g./l Less than 30 Sodium sulfate- .g./l.. 20-80 Temperature.
  • Sulfuric acid Sodium sulfate ponds cooperate with the zinc sulfate and serve to reduce the degree of primary gel swelling of the gel filaments, and therefore the use of such modifiers is particularly useful in cases of the above mentioned (A) and (A') or where a Mueller-type bath is used as the primary or filament forming bath for a viscose having a viscosity less than about 150 poises.
  • R is a member selected from the group consisting of alkyl, aryl and cycloalkyl, R is a member selected from the group consisting of hydrogen and alkyl groups containing 1-4 carbon atoms, and n is an integer at least equal to 1.
  • Examples of the compounds expressed by the above formula are diethyleneglycolbutylmercaptan, decaethylencglycolpropylmercaptan, pentadecaethyleneglycolphenylmercaptan, decaethyleneglycolbutylmercaptan, etc.
  • Aliphatic and alicyclic amines are also useful as the coagulation modifiers, among which are, for example, triethanolamine, triethylamine, cyclohexylamine, benzylaminc, etc.
  • the salts of N-substituted dithiocarbamic acid are also useful, among which are, for example, amyl dithiocarbamate, cyclohexyl dithiocarbamatc, N-methylcyclohexyl dithiocarbamate, methyl dithiocarbamate, etc.
  • each of R and R is a member selected from the group consisting of hydrogen, alkyl and aryl, n is an integer equal to at least 1.
  • compounds expressed by the above formula are, for instance, polyethyleneglycol, phenoxycthanol, ethoxyethoxyethanol, butoxylethoxyethanol, etc.
  • mercaptoamines and N-substituted mercap todithiocarbamatcs such as B-mercaptoethylamine, 'y-mcrcaptopropylamine, orthoaminothiophenol, N-substituted- B-mercaptoethylcarbamate, etc.
  • the amount of these modifiers to be present in the viscose may vary depending upon the particular viscose, spinning speed and bath conditions. Generally, good results are obtained if the modifier(s) is used in an amount from 0.1 to 1.0 millimolc per grams of the viscose. A larger amount of the modifiers over the range recited above may be used, but the effect of the modifier is not progressively enhanced by such an excess amount of use.
  • incorporation or addition of such modifier to a viscose may be carried out at any stage in the process of preparation of the viscose.
  • predissolve or predisperse the modifier in a dilute aqueous solution of sodium hydroxide may be used later for dissolving a cellulose xanthate.
  • it may be added directly to the viscose.
  • a two-bath stretch spinning system is known to produce the so-called high tenacity rayon or super high tenacity rayon.
  • the conventional two-bath stretch spinning process is characterized by forming a gel filament yarn in the primary bath and then immediately stretching the so formed gel yarn in the secondary bath to effect orientation of the cellulose molecules.
  • This conventional process has inherent defects, that is an improvement of one respect of the fibre properties, such as tenacity has inevitably accompanied sacrifice in other valuable properties.
  • the gel yarn formed in the primary bath is not immediately stretched but is controlled so as to obtain a particular regeneration state with a stretch as little as possible, and thereafter it is progressively regenerated while being subjected to suitable successive stretching during its passage through the subsequent successive baths in which the regenerating power increases progressively.
  • any suitable apparatus may be used so far as it is adapted to fulfill the spinning conditions as specified above.
  • the four baths are arranged in series at suitable intervals, each being provided with suitable guides.
  • a viscose is extruded through a spinneret into the primary bath.
  • the filaments formed in the bath are guided upwardly out of the bath to a guide roller located between and above the primary bath and sec ondary bath. Since the filaments must be controlled so as to have a residual xanthate ratio from 25-35% when entering the third bath, the travel or immersion length of the filaments within the primary bath should be selected so that the filaments leaving the primary bath do not become below about 20% in the residual Xanthate ratio.
  • the filaments While passing through the fourth bath the filaments are stretched due to a differential in speed between the second and third godet rollers. From the third godet roller the filaments may be passed to a conventional purification apparatus such as for washing with water followed or not followed by refining, bleaching, etc. It will be understood that if the secondary bath and the third bath are identical in the composition and temperature, a single bath may be used therefor but the second godet roller is arranged above the bath at a suitable position. a
  • the spinning speed (final wind-up speed) is 20-80 m./min. for the process of (A) and (A'), and is -30 m./min. for the process of (B).
  • regenerated cellulose fibres produced by the novel multi-bath spinning process of this invention as described above and products such as fabrics made of such fibres have outstanding properties and are very useful as such. However, sometimes, it may be desired that these fibres and their products have more excellent compressive resiliency, crimp recovery from stretch in dry state and other properties. It has been found that these desirable additional properties are obtained if these regenerated fibres or their products are subjected to the particular resin treatment which will be fully described hereinlater.
  • an excellentresin treatment can be effected by impregnating fibres or articles made thereof with an aqueous solution of a salt of melamine with an oxy acid containing hydroxyl group(s) in the molecule, such as lactic acid, glycolic acid, thioglycolic acid, gluconic acid, etc., and then allowing formaldehyde gas (vapor) to at thereon in the presence of a small amount of water.
  • a salt of melamine with an oxy acid containing hydroxyl group(s) in the molecule, such as lactic acid, glycolic acid, thioglycolic acid, gluconic acid, etc.
  • an oxy acid is'reacted with melamine in the proportions of 0.3-3.0 moles of the oxy acid per mole of melamine.
  • an aqueous solution containing 0.5 to 4% of the melamine 'salt at a temperature from normal temperature to.
  • the impregnated article is squeezed or centrifuged to remove an excess liquid and dried at a temperature ranging from 60 to C. Thereafter formaldehyde vapor is allowed to act on the fibres or article.
  • the temperature of the formalde hyde vapor may be from normal temperature to 100 C., but preferably 30 C. to 50 C. If the temperature at the formaldehyde treatment exceeds 100' C. there is a danger that the formaldehyde is connected in a polymerized form to melamine with a result .to cause enbrittlement of the fibres.
  • a 30-40% aqueous formalin may be employed.
  • formaldehyde gas produced by heating at a temperature below 100 C. para-formaldehyde may be used. It is preferable that the amount of formaldehyde to be employed is about 2 to 5 moles per mole of melamine as contained in the fibres.
  • Examples 1-4 are to illustrate the multi-bath spinning process of (A)
  • Examples 5-7 relate to the process of (A')
  • Examples 8-10 are to illustrate the spinning process of (B).
  • Examples 11-14 are to illustrate the resin treatment of (C).
  • EXAMPLE 1 A cotton linters cellulose pulp was steeped for 2 hours in an aqueous solution containing 230 g./l. of sodium hydroxide and the alkali cellulose was pressed until to be 2.6 times the weight of the original pulp used. After shredding the alkali cellulose in a conventional manner, carbon disulfide in the amount of 50% based upon the weight of a-cellulose was added thereto, and the xanthation reaction was then allowed to proceed for 3.5 hours while elevating the temperature from 20 to 28 C. After the reaction the cellulose xanthate was dissolved by adding thereto predetermined amounts of sodium hydroxide and water to give a viscose containing 7.0% cellulose and 6.0% total sodium hydroxide. After ripening at 5 C. for hours, its viscosity was 91 poises and the xanthate ratio was 70%.
  • the viscose in the substantially unripened state was spun through a spinneret having 720 holes of 0.06 mm. diameter into a primary bath under the following condition to form viscose gel yarn:
  • EXAMPLE 2 A dissolving wood pulp was steeped for 2 hours in an aqueous solution containing 230 g./l. of sodium hydroxide and the alkali cellulose was pressed until to be 2.7 times the weight of the original pulp. Then the alkali cellulose was shredded at 30 C. for 15 hours. Immediately there after or without being aged, to the alkali cellulose was added 45% carbon disulfide (based on the weight of a-cellulose), and the xanthation reaction was then allowed to proceed for 3 hours while elevating the temperature from 20 C. to 28 C.
  • the cellulose xanthate was dissolved in a sodium hydroxide solution in which decaethylene glycol tertiary butyl mercaptan had been dissolved in such an amount as to be 0.3 millimole/ grams of viscose. Thereby a viscose having a cellulose content of 6% and a total sodium hydroxide content of 6% was obtained.
  • This viscose was deaerated while being ripened at 5 C. for 20 hours, and was, under the conditions of a viscosity of 78 poises and a xanthate ratio of 65%, extruded through a spinneret of 720 holes 13 of 0.06 mm. diameter into a primary bath of the following conditions:
  • the formed viscose gel yarn was then immediately and, Without imposing a tension as possible, passed into and through the following secondary bath:
  • EXAMPLE 3 An alkali cellulose prepared by the same operation as in Example 1 from a cotton cellulose pulp was shredded at 15 C. for 2 hours. After the addition of 50% (based upon the weight of a-cellulose) carbon disulfide, xanthation reaction was allowed to proceed for 3 hours while elevating the temperature from 20 C. to 25 C. The highly xanthated cellulose thus obtained was dissolved in a dilute aqueous solution of sodium hydroxide in which cyclohexyl amine had been dissolved in such an amount as to be 2 millimoles/ grams of viscose.
  • the yarn was successively washed with water, oiled and dried, and was then wound up on a bobbin (about 50 m./min.).
  • the yarn was twisted into a two-ply twisted cord under the same conditions as in Example 1.
  • the properties of this cord are as follows:
  • EXAMPLE 5 A viscose prepared by the same operation as in Example 2 except that beta-mercapto-ethyl amine was. added to the viscose in the amount of 3 millimoles/lOO grams of viscose, was filtered and deaerated. The viscose hav- The primary bath was as follows:
  • the third bath was as follows:
  • the fourth bath was as follows:
  • the primary bath was as follows:
  • the primary bath was as follows:
  • the third bath was as follows: Sulfuric acid g./l 10 Sodium sulfate g./l 100 Temperature C 25 In this third bath, the gel yarn was stretched by 60%.
  • the fourth bath was as follows:
  • the first bath was as follows: Sulfuric acid; g./1 29 o ium. ul at 0 Zing: sulfate g,/1 0.120 Temperature C
  • Sulfuric acid g./1 29 o ium. ul at 0 Zing: sulfate g,/1 0.120 Temperature C
  • the gel .viscose yarn after leaving this bath was immediately passed .through. the following secondaryibathz Sulfuric acid 1 1.0 51
  • the average cllirlo'sepolynierization degree of the viscose was 480 This viscose at a"visc'o sit y of. 300 poises. and "a xapthate ratio of 73% was spun withwth e same spinning apparatusas in Example 8.
  • The. primary bathw was'a's follows: K
  • Abrasion resistance .Measured with Universal Weartester (unit, number of times).
  • Compressiveresilienc'e Cut fibres are piled up on a flat plate" and are" compressed by a column body "at a speed of 10 cm./min. When the pressure has reached 25.5 g./c'm.'-, the compression is discontinued and the column body is returned'to the original position ata speed of 10 cmL/min'. The same compression as in the above is againapplied. 'Whilelthese procedures the pressure. variation is continuouslymeasured by Instron (tensile tester) to findtthework done. If the. workdonein fthefirst compression stroke is F and the :work done in the second compression stroke is F then the compressive resilience is representedas follows:
  • Crimp recovery from stretch (dry state) g X100 1 mole to lactic acid 0.68 1110a
  • the fabric was dried to be 20 %Zwater content. Then the fabric'was exposed to formaldehyde gas; geperated. by. heating. paraeformaldehydeto 50 C.
  • the same muslin fabric as in the above was soaked in a 6% trimethylol melamine solution containing 0.6%of magnesium chloride as a catalyst. Thereafter the fabric was dried at 85 Cfor 5 minutes, and then heatftreated .at C. for 5 minutes. Then the fabr icwas washed with-hot water and Abrasion resistance (number of times) Crease resistance (degrees) Tear Deposition strength- (a) of resin (percent) Lactic acid melamine- Trimethylol melamine.-.
  • a bulk of crimped staple fibres obtained in Example 6 was immersed in a 3% solution of melamine lactate (melamine to lactic 'acid' in equimolecular proportions) at 70 C. After removing an excess solution by a centrifugal separation, the fibres were dried at 80 C. Then the fibres were exposed to a 38% formalin vapor at 30 C. for hours, and then were subjected to heat treatment at 160 C. for 3 minutes. The fibres thus treated were 78% in compressive resilience and 98% in crimp recovery from stretch (in dry state). The fibres were spun and woven into muslin 9. The properties of this fabric are as follows:
  • said third bath reducing the residual xanthate ratio by at most 70%
  • said fourth bath containing 30-100 gms./l. of sulfuric acid and 0-200 gms./l. of sodium sulfate and being maintained at a temperature of above 50 C., the stretch at said third bath being 30 to and at said fourth bath, 10 to 80%, and
  • each successive bath in the plurality of baths being at least as strong in regenerating power as its preceding bath.
  • the secondary bath contains 10-25 g./l. of sulfuric acid, 80- 100 g./l. of sodium sulfate and 10-30 g./l. of zinc sulfate and maintained at a temperature between 10 C. and 20 C.
  • the third bath contains 25-30 g./l. of sulfuric acid, 50-80 g./l. of sodium sulfate and 10-30 g./l. of zinc sulfate and maintained at a temperature between 25 C. and 35 C.
  • the fourth bath contains 50-70 g./l.
  • the primary bath contains less than 60 g./l. of sulfuric acid, less than 100 g./l. of sodium sulfate and less than 5 g./l. of zinc sulfate and is maintained at a temperature between 0 C. and 30 C.
  • the secondary bath contains less than 30 g./l. of sulfuric acid, 20-80 g./l. of sodium sulfate and is maintained at a temperature between 0 C. and 30 C.
  • the third bath contains less than 30 g./l. of sulfuric acid, 20-80 g./l. of sodium sulfate and is maintained at a temperature between 0 C.
  • the fourth bath contains 30-100- g./l. of sulfuric acid and 50-150 g./l. of sodium sulfate and is maintained at 23 a temperature above 20. C., the stretch at the third bath being 3 0 l5 0% and the stretch at the fourth bathbeing -50%..
  • A,proce ss asclaimed in claim 1 wherein the-primary bathcontains.1545 g./l. of sulfuric acid, -70 g. -/l. of sodiumfsulfa'teand. less than 1 g./1. of zinc sulfate and.is-maintained atatemperature between 5 C. and 20 C., the secondary bathcontains 5-15-g.'/l. of sulfuric acid, 40. .60 g./l. o f so dium sulfate and is maintained a-tlatemperature between. 5 C. and 20 C., the third bath contains-5 15 g./l. of sulfuric acid, g./l.
  • the fourth bath contains 40 70..g. l. of sulfuric acid'and g./l. of sodium sulfate andfismaintained at, a temperature between :30 C. and 70 C., the stretch at the third bath being 60- and the-stretch at the fourth bath being 10-30%, and theresidual xanthate ratio just'before entering the thirdbathbeing,25 35%.
  • reaction of formaldehyde with melamine is effected in the presence 01510 to 30%, based upon the weight of the product, of water;
  • Procession treating fibers which comprises (a) applyingrto said fibers a 0.5 to 4% solution of a'salt-com sistingof'melamine and an oxyacid in the proportions of 0.3 to 3.0 moles of the oxy acid per mole of melamine, r

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  • Mechanical Engineering (AREA)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3204017A (en) * 1962-06-19 1965-08-31 Toho Rayon Kk Process for the manufacture of bulky fibrous wadding materials
US3219740A (en) * 1961-05-23 1965-11-23 Teikoku Jinzo Kenshi Kk High speed tubular spinning of fine viscose rayon yarn
US3324216A (en) * 1962-05-16 1967-06-06 Toyo Spinning Co Ltd Viscose spinning process
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
US20060032003A1 (en) * 2004-08-16 2006-02-16 Kim Mun S Method for manufacturing three-dimensional fabric and three dimensional fabric using the same
US20180127898A1 (en) * 2016-09-28 2018-05-10 Lakehead University Method for production of man-made textile yarns from wood fibers
CN112210846A (zh) * 2020-09-25 2021-01-12 恒天海龙（潍坊）新材料有限责任公司 一种植物性抗菌抗病毒、护肤保健纤维素纤维的制备方法
CN117306018A (zh) * 2023-11-03 2023-12-29 云起(青岛)材料科技有限公司 多功能蛋白复合再生纤维素纤维的制备方法
CN117306018B (zh) * 2023-11-03 2024-05-31 云起(青岛)材料科技有限公司 多功能蛋白复合再生纤维素纤维的制备方法

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CN112692097B (zh) * 2020-12-22 2022-10-18 比尔安达(上海)润滑材料有限公司 一种医用导丝及其制作方法

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US2327516A (en) * 1939-07-22 1943-08-24 Fink Heinrich Manufacture of artificial filaments and fibers from viscose
US2517694A (en) * 1943-09-14 1950-08-08 American Viscose Corp Crimped artificial filament
US2427993A (en) * 1944-07-26 1947-09-23 Ind Rayon Corp Production of rayon
US2479218A (en) * 1944-12-12 1949-08-16 Int Paper Canada Process for making rayon filaments
US2611928A (en) * 1948-11-23 1952-09-30 American Viscose Corp Method for producing high tenacity artificial yarn and cord
US2715763A (en) * 1950-06-27 1955-08-23 American Viscose Corp Synthetic textile fiber
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US3219740A (en) * 1961-05-23 1965-11-23 Teikoku Jinzo Kenshi Kk High speed tubular spinning of fine viscose rayon yarn
US3324216A (en) * 1962-05-16 1967-06-06 Toyo Spinning Co Ltd Viscose spinning process
US3204017A (en) * 1962-06-19 1965-08-31 Toho Rayon Kk Process for the manufacture of bulky fibrous wadding materials
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
US20060032003A1 (en) * 2004-08-16 2006-02-16 Kim Mun S Method for manufacturing three-dimensional fabric and three dimensional fabric using the same
US20180127898A1 (en) * 2016-09-28 2018-05-10 Lakehead University Method for production of man-made textile yarns from wood fibers
US10501871B2 (en) * 2016-09-28 2019-12-10 Lakehead University Method for production of man-made textile yarns from wood fibers
CN112210846A (zh) * 2020-09-25 2021-01-12 恒天海龙（潍坊）新材料有限责任公司 一种植物性抗菌抗病毒、护肤保健纤维素纤维的制备方法
CN117306018A (zh) * 2023-11-03 2023-12-29 云起(青岛)材料科技有限公司 多功能蛋白复合再生纤维素纤维的制备方法
CN117306018B (zh) * 2023-11-03 2024-05-31 云起(青岛)材料科技有限公司 多功能蛋白复合再生纤维素纤维的制备方法

Also Published As

Publication number Publication date
FR1286962A (fr) 1962-03-09
BE600664A (fr) 1961-06-16
GB915356A (en) 1963-01-09
DE1258544B (de) 1968-01-11
CH443555A (de) 1967-09-15

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