US3091509A - Method for preparing polyvinyl alcohol fibers employing wet spinning techniques - Google Patents

Method for preparing polyvinyl alcohol fibers employing wet spinning techniques Download PDF

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US3091509A
US3091509A US19479A US1947960A US3091509A US 3091509 A US3091509 A US 3091509A US 19479 A US19479 A US 19479A US 1947960 A US1947960 A US 1947960A US 3091509 A US3091509 A US 3091509A
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polyvinyl alcohol
solution
fibers
fiber
spinning
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Suda Teruo
Miyazaki Sadamaru
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Kurashiki Rayon Co Ltd
Airco Inc
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Kurashiki Rayon Co Ltd
Airco Inc
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    • DTEXTILES; PAPER
    • D01NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • DTEXTILES; PAPER
    • D01NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

Description

United States Patent METHOD FOR PREPARING PULYVINYL ALCO- HOL FIBERS EMPLOYING WET SPINNING TECHNIQUES Teruo Suda and Sadamaru Miyazaki, Kurashiki City,

Japan, assignors of one-fourth to Air Reduction Company incorporated, New York, N.Y., a corporation of New York, and three-fourths to Kurashiki Rayon Co., 5111., Okayama Prefecture, Japan, a corporation of apan No Drawing. Filed Apr. 4, 1960, Ser. No. 19,479

Claims priority, application Japan Apr. 7, 1959 11 Claims. (Cl. 18-54) This invention relates to an improved process for the production of polyvinyl alcohol fibers or filaments. More particularly, the invention relates to an improved wetspinning process for the production of polyvinyl alcohol fibers involving extruding a solution of polyvinyl alcohol in the formof fine streams into a coagulating liquid to form filaments.

Wet-spinning techniques for the production of polyvinyl aloohol fibers are known in the art. Generally, fibers produced by such prior wet spinning processes have a kidney-shaped cross-section which is composed of distinct skin and core regions. The prior wet spun polyvinyl alcohol fibers tend to be somewhat opaque and diffieult to dye.

It is an object of invention to provide an improved wet spinning process for the production of polyvinyl alcohol fibers.

It is a further object to provide for the production by wet spinning of polyvinyl alcohol fibers having improved properties, -inoluding improved dyea-bility.

Other objects will be apparent from the following detailed description of the invention.

In accordance with this invention, it has now been found that improved polyvinyl alcohol fibers can be wet spun by incorporating sodium carboxymethyl cellulose, sodium alginate or gum arabie in the polymeric spin ning solution and forming fibers from the additive-containing polymer solution by conventional wet spinning techniques. As a result of the incorporation of the abovementioned additives in the polymer spinning solution, wet spun fibers or filaments are obtained which have a more homogeneous cross-sectional configuration and which have greatly improved dyeing properties. Fibers produced by the invention tend to be rounder in cross-section and more transparent.

The following tests are illustrative of the invention and show the advantages obtainable through practice of the instant invention:

Polyvinyl alcohol having an average degree of polym erization of 1700 was dissolved in water to form a solution containing 13% by weight of polymer. A portion of this solution was taken as blank sample 1, and sodium carboxymethyl cellulose (hereinafter referred to as CMC) was added in different amounts to additional quantities of the polymer solution to forms samples 2, 3 and 4, viz. sample 2, 5% CMC; sample 3, CMC; and sample 4, 20%, all percentages being by weight and based on the weight of polyvinyl alcohol in the sample.

The resulting spinning solutions were extruded through a multi-hole spinneret of conventional type into a saturated aqueous coagulating solution of sodium sulfate at 45 C. to form fibers or filaments. coagulating bath immersion length was 1.5 meters, and the fibers were withdrawn from the coagnilating bath at a speed of 10 meters/minute. The fibers were roller stretched 400%. After air drying at 180 C. in a hot-air bath, the filaments were heat-treated in a hot-air bath at 225 C.

3,091,509 Patented May 28, 1963 "ice for 30 seconds. Subsequently, the fibers were formalized in an aqueous bath containing, by weight, 5% formaldehyde, 15% sulfuric acid, and 15 sodium sulfate for 1 hour at 70 C.

The fibers were then tested to determine strength, elongation shrinkage in boiling water, dye absorption when dyed for 2 hours at C. in a bath containing, by weight, 2% Nippon fast violet BB and 10% of sodium sulfate, the weight ratio of dye bath to fibers being 50:1. Similarly, there was also determined the dyeing concentration or saturation value K/S after dyeing to the extent of 10 mg./g. in a bath containing varying concentrations of Congo red and 10% of sodium sulfate for 2 hours at 80 C., the ratio of bath to fibers being 50:1.

The dyeing concentration value K/S equals R being the reflection coeflicient at a wave-length of 520. The following table shows the results obtained:

TABLE I Sample i PPS" cow:

The above results show that, as the amount of CMC is increased up to around 20%, the dye concentration improved markedly and the dye-absorption similarly improved. An addition of over 30% was found impracticable, because the spinning fluid was then diffieult to filter. On the other hand, referring to the effects of CMC concentration on the strength and elongation of the fiber, it will be seenthat the strength dropped somewhat as the amount of CMC increased, whereas the elongation did not substantially change. When the cross-section of these fibers were examined under the microscope, sample (1) had the usual flat shape, with a transparent exterior layer and an interior layer of granular structure, but in the case of samples (3) and (4), this uneven structure was not observed, and the fibers were found to be entirely homogeneous and had a circular crosssection. Sample (2) exhibited an interior granular structure to a slight degree but was essentially circular in cross-section. In addition, the fibers obtained from spinning solutions containing CMC had a soft and smooth feel, and had a tendency to give a tactile impression resembling that of an oil-treated fiber. When sodium sulfate was added along with the CMC, an unevenness was created around the periphery of the cross-section, and the coeflicient of utilization of spinnability was highly advanced in this case.

When these tests were repeated with spinning solutions containing like quantities of sodium alginate instead of CMC the same results were realized.

In order to demonstrate the activity of gum arabic as a spinning solution additive, polyvinyl alcohol having an average degree of polymerization of 1700 was dissolved in water to form a solution containing 15% by weight polymer. Commercial gum arabic was added in varying amounts as indicated in the table below to samples of the polymer solution, one sample being used as a control and containing no gum arabic.

The resulting spinning solution samples were extruded through a multi-hole spinneret into a saturated aqueous coagulating solution of sodium sulfate at 45 C. to form Sample No erized with the polyvinyl alcohol. alcohol with other materials such as amino-acetalized fibers. The coagulating bath immersion length was 1.5 meters, and the fibers left the coagulating bath at a speed of meters/minute. The fibers were roller stretched by-300%. After air dryingat 180 C., the fiberswere heated in air at 225 C. for 30 seconds. The fibers were then formalized in an aqueous bath containing, by weight,'5% formaldehyde, sulfuric acid,-and 15% sodium sulfate at 70 C. for l.hour.

The fibers were then tested for strength,- elongation, shrinkage in boiling water, and dye absorption when dyed for 1 hour at 80 C. in a dye bath containing, by weight, 2% Congo red and 10% sodium sulfate, the weight ratio of dye bath to fibers being 50:1. The dyeing concentration value K/S was also determined after dyeing to the extent of 10 mg./g. in a bath containing varying concentrations of Congo red and 10% sodium. sulfate for 2 hours at 80 C., the ratio of bath to' fibers. being 50:1.

The following table shows the results obtained:

TABLE II ocean None A marked advancement in the concentration of dye was noted with the use of up to of gum arabic whereas at concentrations of 30% the effect tended to diminish. On the other hand, the effect of the gum arabic on strength and elongation was negligible up to 30%. When examined under the microscope, the cross-,- section of the fibers of sample (1a) had a fiat and trans parent external layer and an internal layer having a conventional granular structure. In the case of samples (3a), (4a), and (5a), however, this uneven structure was not found but, instead, a transparent and uniform structure was noted. In samples (2a) and (6a) an insignificant internal granular structure was observed. Such change in the structure and cross-section of the fibers coincided with the improvement in dye concentration. The shape of the fibers approached a true circle in the order of samples from (1a) to (6a), and the fullness of the fibers also showed a similar advancing tendency.

All commercial forms of CMC, sodium alginate and gum arabic are suitably used in accordance with this invention.

Similarly commercial forms of polyvinyl alcohol are suitable for use but the polyvinyl alcohol preferably consists of at least about 98% vinyl alcohol units. Minor amounts of other monomers can, however, be copolym- Blends of polyvinyl polyvinyl alcohol as described in Osugi et al. US. Patent 2,906,594 can also-be employed.

In carrying out the invention the additive, viz. CMC, sodium alginate, or gum arabic is added to-the spinning solution in an amount sufficient to improve the dyeing properties of filaments prepared therefrom. Generally it is preferred to use at least about 2% of additive based on the'weight of polyvinyl alcohol polymer, although at least about 5% of additive is particularly preferred in the case of CMC and sodium alginate. Excessive amounts of CMC, sodium alginate or gum arabic which cause spinning difiiculties or which undesirably alfect other filament properties to a significant degree should be avoided. Generally, it is preferred to use about 2-30% based on the weight of polyvinyl alcohol although amounts outside this range can be used.

The amount of polyvinyl alcohol and other polymers,

4 when used, is selected in accordance with conventional procedures. Generally, concentrations of about 15% by weight, e.g. 13-15%, are employed, but higher or lower concentrations in accordance with known spinning techniques are fully applicable. 1 In'this connection, reference is made to Cline et al. US. Patent 2,610,360.

The spinning solution containing polyvinyl alcohol and the above-specified additives can be spun to form filaments or fibers by known wet spinning methods, as described for example inthe above-mentioned Cline et al. patent and the above-mentioned Osugi et al. patent. A n especially preferred spinning technique is described 1r copending application Serial No. 336,166 of Tomonari el al. filed February 10, 1953, now US Patent No 2,988,802, dated June 20, 1961. Other wet spinning methods can, however, be used.

After formation of the fibers by wet spinning the fila ments can be further treated by stretching, heat treating acetalization, and the like to produce fibers with desir able and outstanding properties, using known technique: as described in said patents.

The present invention thus provides. a. simple, conven ient and inexpensive method for producing polyvinyl'al cohol fibers having improved dyeing properties by. we spinning techniques. The process of the invention over comes dyeing diificultiespeculiar to previous'wet spin ning techniques used in theproduction of polyvinyl al cohol fibers.

' It has 'been found that commercial'soluble"starch. a described in coperiding application Tan'a'be'et al.,ES .N 814,368, filed May 20, 1959, now Patent No.'3;044,974 dated July 17, 1962, may-be used'in" combination wit] the above-mentionedadditives, particularly with CMC to provide further improved dye concentrationiatleast in equal amount of such starch being used and *pr'eferabl about 2 /2 times the-quantity of CMC' or otheradditiv of this invention.

The invention will be further understood from the' fol lowing specific examples of practicalapplication. Ho t ever, it will be understood that 'these examples' are nc to be construed as limiting the scope of the'presentir vention in any'manner. In these examples;all-parts at by weight.

Example 1 section was homogeneous and circular in shape, and

exhibited substantially better dyeing characteristics the the fiber used as control which was spun from a solutic containing no CMC.

Example 2 Wet-spinning was effected with a water solution e01 taining 12% -of polyvinyl alcohol having an averag degree of polymerization 2000 and CMC '(10%'bas on the polyvinyl alcohol) in a saturated water soluti'c of sodium sulfate at 45 C. The fiber was subjected roller-stretching by 400%, continuously dried in a he air bath at C., and then heat-treated-in super-heat steam under 1 atmosphere pressure at 210 C. for minutes. The fiber was then benzalized in a water s'ol tion containing benzaldehyde (1%), sodium dibuty naphthalene-sulfonate (0.3%), sulfuric acid (2%) 60 C. for one hour. The fiber was homogenous, ax round in cross-sectional, shape whereas the control h: an uneven structure. When tested with cellitone fa blue FFR, the former fiber dyed to a far deeper shat than the latter control fiber.

Example 3 A water solution containing 14% of polyvinyl alcohol of an average degree of polymerization of 1700 and CMC (8% based on the polyvinyl alcohol) and soluble starch (20% based on the polyvinyl alcohol) was subjected to wet-spinning in a saturated water solution of sodium sulfate at 50 C., then roller-stretched by 400%, and continuously dried. The fiber was then heat-treated in a hot air bath of 225 C. for 30 sec., and was formalized in a water solution containing formaldehyde sodium sulfate (15%) and sulfuric acid (15%) at 60 C. for one hour. The fiber was transparent and homogeneous, and its cross-section was circular, having a soft and smooth feel. The dyeing characteristics were substantially better than in the control to which CMC and soluble starch were not added.

Example 4 Wet-spinning was effected with a water solution containing 13% of polyvinyl alcohol of an average degree of polymerization of 1500 and CMC (5% based on the polyvinyl alcohol) and sodium sulfate (15% based on the polyvinyl alcohol) in a saturated water solution of sodium sulfate at 45 C. Spinning was followed by roller-stretching by 400% and continuous drying by heating. The fiber was then heat-treated in a saturated water solution of sodium sulfate at 120 C., and formalized with a water solution of formaldehyde (5% sodium sulfate (15%) and sulfuric acid (15%). The fiber has a cross-section with high degree of fullness and with only slight unevenness along the periphery of the cross section. Compared with the control which involved no addition of CMC and sodium sulfate, it showed a much better dyeing action.

Example 5 A water solution of 13% of polyvinyl alcohol of a degree of polymerization grade of 1600 and sodium alginate based on the polyvinyl alcohol) was subjected to wet-spinning in a saturated water solution of sodium sulfate at 50 C., and heat-treating in a saturated water solution of sodium sulfate at 125 C. for 2 hours. The fiber was then acetalized in a water solution containing formaldehyde (5%), fl-cyclohexylamino butylaldehyde (2%), sulfuric acid (15%), and sodium sulfate (10%), at 60 C. for 2 hours. This fiber had a homogeneous and circular cross section, and the dye concentration was significantly higher when compared with fiber from a control to which no sodium alignate was added in tests with an acid dye (acid brilliant scarlet 3R) (2%), and sulfuric acid (1%), with dye bath ratio of 50:1, at 80 C., for one hour.

Example 6 A water solution was prepared by adding to water a polyvinyl alcohol of a degree polymerization of 1600 and an amino-acetalized polyvinyl alcohol which was acetalized by means of B-cyclohexylaminobutyl aldehyde. The quantities of the polyvinyl alcohol and amino-acetalized polyvinyl alcohol were selected to provide a solution of an average percentage of aminoacetalation of 1% and a total concentration of polyvinyl alcohol component of 15%. To this solution was added CMC in the amount of 10% based on the polyvinyl alcohol component present. This water solution was wet-spun in a saturated aqueous solution of sodium sulfate at C., and after roller-stretching by 200%, it was dried by means of hot-air.

This fiber was stretched by 200% in hot air at 225 C., and was then heat-treated at 230 C. at constant yarn length. Benzalization was effected in a water solution of benzaldehyde (2%), methanol (40%), and sulfuric acid (10%) at C. for one hour. The fiber was homogeneous and had a round cross-section. Compared with the control to which no CMC was added, it attained a transparent skin layer.

6 substantially greater concentration of dye when tested with acid brilliant scarlet 3R (2%), acetic acid (1%), with a dye bath ratio of 50:1, at C. for one hour. Both fibers absorbed the dye in the dyeing bath completely.

Example 7 A 20% water solution of polyvinyl alcohol of an average degree of polymerization grade of 1000, containing gum arabic (9% based on the polyvinyl alcohol), was subjected to wet-spinning at 50 C. in an aqueous solution containing sodium sulfate (410 g./l.), and the fiber obtained was dried. After heat-treatment in hot air at 220 C. for one minute, the fiber was formalized in a water solution containing formaldehyde (4%) and sulfuric acid (15%) at 60 C. for 2 hours. This fiber had good resistance to boiling water, its cross section was more homogeneous and transparent than that from con trol (with no addition of gum arabic) which was opaque, and in which a granular structure was noted inside a When tested with Nippon fast violet BB the former fiber exhibited a much higher concentration of dye than the control fiber.

Example 8 A water solution containing 15% of polyvinyl alcohol of an average degree of polymerization of 1700 and gum arabic (10% based on the polyvinyl alcohol) was wetspun in a saturated sodium sulfate water solution at 45 C., was subjected to roller-stretching by 400%, and was continuously dried in hot air at 180 C.

This fiber was heat-treated in super-heated steam at 1 atmosphere pressure at 210 C. for 2 min, and was benzalized in a water solution containing benzaldehyde (1%), sodium dibutylnaphthalenesulfonate (0.3%), and sulfuric acid (2%) at 60 C. for one hour. The fiber had a transparent and uniform cross-section. On the other hand, the control fiber formed from a solution to which no gum arabic was added was opaque anduneven in its crosssection. When tested with cellitone fast blue FFR, the former fiber was dyed to a far deeper color than the latter.

Example 9 A 14% water solution of polyvinyl alcohol with an average degree of polymerization grade of 1600, and gum arabic (13% against polyvinyl alcohol) was wet-spun in an aqueous solution saturated with sodium sulfate at 50 C., and the fiber was air dried. This fiber was hot- =stretched by 700% in hot air at 230 C., and shrunk by 15% in air at a temperature of 235 C. Acetalization of the fiber was then effected by means of an aqueous solu tion containing formaldehyde (0.5% fl-cyclohexylaminobutylaldehyde (2% sulfuric acid (15%) and sodium sulfate (10%) at 60 C. for 2 hours. Compared with the control fiber, which involved no addition of gum arabic, a much higher color concentration was achieved when the fiber was dyed with acid scarlet 3R (acid dye) (2% sulfuric acid (1% with a dye bath ratio 50:1, at 80 C. for one hour.

Example 10 A water solution was prepared by adding to water a polyvinyl alcohol of an average degree of polymerization grade of 1700 and the aminoacetalized polyvinyl alco hol which had been 30% acetalized by means of fl-cyclohexylaminobutylaldehyde. The quantities of the two polyvinyl alcohols were selected to provide in the solution an average percentage acetalization of 1%, and a total polyvinyl alcohol component concentration of 15 To this solution gum arabic (9% of polyvinyl alcohol component) was added. The solution was then subjected to wet-spinning in a saturated aqueous solution of sodium sulfate at 45 C. and the fiber was rollerstretched by 200% and then dried in hot air. The fiber was further stretched in hot air of 225 C- by 200%,

' known techniques.

and heat-treated at 230'fC. =at constant yarn length.

Benzalization was then iafiect'ed by means of a water solution of benzaldehyde (2%), methanol (40%),and sulfuric acid at 60l C; for-one hour. As compared with the control fiber which involved no gurm arabic,

spun in a saturated aqueous solution of-sodium sulfate at 50- C. The fiber was wet-heat-treated in a saturated sodium sulfate bath at 120 C. for 2 hours, and formalized in usual manner. This fiber showcd'much bctter-dyeing characteristics than the control fiber'which was formed without use of gum arabic and had a transparent appear- Example 12 A water solution containing 13% of polyvinyl alcohol with an averagedegree of polymerization of 2000 and.

gum arabic (15% based on polyvinyl alcoholiwaswetspun in a saturated aqueous solution "of sodium" sulfate a-t75 C. The fiber was heat-treated -in at 230 C. with constant yarn length audit was then formalized in an aqueous solution of formaldehyde 5% ),s'1ilfu'n'c acid and sodium sulfate (5%) at 65 C; forione" hour.

As compared with the control fiber which was produced without use of gum ar'abic, the former fiber had a much rounder cross-section, being substantially a circular'form.

Ithad a transparent appearance and alhi'gh dye concentration when dyed.

'Example 13 Wet-spinning was etfected with a water solution con- .taining 13% of polyvinyl alcohol havingan average degree of polymerization grade of 1700 and-gum arabic (10% based on the polyvinyl alchol) and a bluepigment (1% based on the polyvinyl alcohol) in a saturated aqueous-solution of sodium sulfate at 45 C., and the fiber produced was heat-treated in hot air at 220 C.

The fiber was then formalized in an aqueous solution containing formaldehyde (5%), sulfuric acid (15% and sodium sulfate (15%) at 70 C. for one hour. The fiber could be dyed to a remarkably high concentration of dye, and had much brighter hue as compared with .the-

control fiber formed without gum arabic.

It will be understood that, unless otherwise indicated, conventional wet-spinning operations are employed in -producing the fiber-s and subsequent heat treatment,

stretching and relaxation are effected iii-accordance with Similarly, conventionalapparatus is employed in carrying out the process of this invention including conventional mixing and emulsifying units, spinning devices and fiber treating apparatus. ditions and the relative relationships set forth in the examples are those preferred in carrying out the process of the invention but it will be understood that other conditions and relationships :may be used within'the scope of the invention, 'Similarly, conventional dyeing tech- The conniques and apparatusizare suitably employed upon the .fibers produced by the .process of this invention.

It will also be under-'st'ciod that various changes and modifications in' addition to those indicated above may be made in the embodiments herein described without departing from the scope ofthe invention as defined in the appended claims. 'It' is intendedftherefore, that all matter contained in the foregoing description shall be interpreted as illustrative-only and not as limit-ative of the invention.

We claim:

1. The method of preparing polyvinyl alcoholfibers which comprises-forming an aqueous polyvinyl alcohol spinning solution containing polyvinyl alcohol in an amount suitable for wet spinning offibers and containing an additive selected from the group consisting of sodium carboxymethyl cellulose, sodium alginate and gum arabic in the amount of 2 to 30%' by=wei-ght based on the weight of the polyvinyl alcohol in said solution and sufiicient to improve the dyeing properties of fibers formed fromsaid solution, and wet-spinning said solutioninto. a coagulating liquid efiecti ve-to coagulate :said polyvinyl-alcohol in said solution to form fibers.

2. The method-of.- claim I, wherein .saidv additive is sodium carboxymethyl. cellulose.

3. The method of claim .1, wherein. .said additiveis sodium: alginate.

4. The-method-ofuclaim1, wherein saidadditive is gum arabic. q

- 5.-The method 'of. claim 1,;wherein said. coagulating .liquid is an=aqueous sodium sulfate solution.

- 6. The method of claim 1,-wherein said polyvinyl alco- -hol is present in said aqueous solution in an amount up to about 20% by weight.

7. The method of preparing polyvinyl alcohol fibers having improved dyeabilityiir'liich comprises forming an aqueous polyvinyl: aleoholspinning solution= containing about 15% byweight of polyviny-l alcohol' and containing 2 to 30% by weightbased-on the weight'oft-saidpolyvinyl alcohol in said solution of an additive selected-from the group consistingof sodium 'carboxymethylr-wcellulose, sodium alginate randz, anabic, said -a.mount\-ofsaid additive: beingsuflicient toimprove the dyeingproperties offibersformed fronrsaid solution, "and wet spinning said solution to form fibers.

'8JThe method of claim- 7, whereinsaid'additive is sodium carboxymethyl cellulose.

' 9. The method of claim 7,-wherein said additive is -'-sodium alginate.

10. The. method of claim 7, wherein said-- additive .is gum arabic.

11. The method of claim 7, wherein said wetzspinning is effected by introducing saidsolution into an aqueous sodium sulfate solution.

References fiitedinathe'file of-this patent UNITED-STATES PATENTS 2,092,512 Hermann et a1 Sept. 7, 1937 2,146,295 Hermann et a1. Feb. 7, 1939 2,364,738 Marberg et a1 Dec. 12, 1944 2,524,008 Deney Sept. 26, 1950 2,716,049 Latour Aug. 23, 1955 2,764,568 Hawkins Sept. 25, 1956 2,906,594- Osu'gi et a1. Sept/29, 1959

Claims (2)

1. THE METHOD OF PREPARING POLYVINYL ALCOHOL FIBERS WHICH COMPRISING FORMING AN AQUEOUS POLYVINYL ALCOHOL SPINNING SOLUTION CONTAINING POLYVINYL ALCOHOL IN AN AMOUNT SUITABLE FOR WET SPINNING OF FIBERS AND CONTAINING AN ADDITIVE SELECTED FROM THE GROUP CONSISTING OF SODIUM CARBOXYMETHYL CELLULOSE, SODIUM ALGINATE AND GUM ARABIC IN THE AMOUNT OF 2 TO 30% BY WEIGHT BASED ON THE WEIGHT OF THE POLYVINYL ALCOHOL IN SAID SOLUTION AND SUFFICIENT TO IMPROVE THE DYEING PROPERTIES OF FIBERS FORMED FROM SAID SOLUTION, AND WET SPINNING SAID SOLUTION INTO A COAGULATING LIQUID EFFECTIVE TO COAGULATE SAID POLYVINYL ALCOHOL IN SAID SOLUTION TO FORM FIBERS.
5. THE METHOD OF CLAIM 1, WHEREIN SAID COAGULATING LIQUID IS AN AQUEOUS SODIUM SULFATE SOLUTION.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3298862A (en) * 1962-09-05 1967-01-17 Kelco Co Paper sizing process

Citations (7)

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Publication number Priority date Publication date Assignee Title
US2092512A (en) * 1932-10-18 1937-09-07 Chemische Forschungs Gmbh Reabsorbable threads, bands, tubes, and the like
US2146295A (en) * 1931-03-10 1939-02-07 Chemische Forschungs Gmbh Polymerized vinyl alcohol articles and process of making same
US2364738A (en) * 1941-10-18 1944-12-12 Interchem Corp Textile decorating compositions
US2524008A (en) * 1946-05-03 1950-09-26 Pierce & Stevens Inc Adhesive composition
US2716049A (en) * 1951-11-01 1955-08-23 Du Pont Water-soluble yarn
US2764568A (en) * 1955-04-07 1956-09-25 Hawkins Raymond Landis Water resistant adhesive
US2906594A (en) * 1955-12-21 1959-09-29 Air Reduction Polyvinyl alcohol filaments of improved dye affinity and method of preparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2146295A (en) * 1931-03-10 1939-02-07 Chemische Forschungs Gmbh Polymerized vinyl alcohol articles and process of making same
US2092512A (en) * 1932-10-18 1937-09-07 Chemische Forschungs Gmbh Reabsorbable threads, bands, tubes, and the like
US2364738A (en) * 1941-10-18 1944-12-12 Interchem Corp Textile decorating compositions
US2524008A (en) * 1946-05-03 1950-09-26 Pierce & Stevens Inc Adhesive composition
US2716049A (en) * 1951-11-01 1955-08-23 Du Pont Water-soluble yarn
US2764568A (en) * 1955-04-07 1956-09-25 Hawkins Raymond Landis Water resistant adhesive
US2906594A (en) * 1955-12-21 1959-09-29 Air Reduction Polyvinyl alcohol filaments of improved dye affinity and method of preparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3298862A (en) * 1962-09-05 1967-01-17 Kelco Co Paper sizing process

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