US2922692A - Color fast synthetic textile fibers from vinyl lactam polymer-containing acrylonitrile polymers - Google Patents

Color fast synthetic textile fibers from vinyl lactam polymer-containing acrylonitrile polymers Download PDF

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US2922692A
US2922692A US631255A US63125556A US2922692A US 2922692 A US2922692 A US 2922692A US 631255 A US631255 A US 631255A US 63125556 A US63125556 A US 63125556A US 2922692 A US2922692 A US 2922692A
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Albert S Messer
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Dow Chemical Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70Material containing nitrile groups
    • D06P3/704Material containing nitrile groups using metallisable or mordant dyes or dyeing by cupro-ionic method

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  • This invention relates to the provision of color fast vinyl lactam polymer-containing acrylonitrile polymer synthetic textile fibers and the like that have been dyed with certain types of dyestuffs and rendered stable to the deleterious efiects of light while in a colored'condition.
  • Certain vinyl lactam polymers are exceptionally well adapted for employment as dye-assisting adjuvants in shaped acrylonitrile polymer articles, particularly polyacrylonitrile fibers and the like, including filaments, yarns, films and related structures.
  • shaped acrylonitrile polymer articles particularly polyacrylonitrile fibers and the like, including filaments, yarns, films and related structures.
  • the various shaped articles that may be fabricated from synthetic, linear, fiber-forming acrylonitrile polymers will hereinafter be illustrated with fibers that are manufactured with such compositions.
  • a great general improvement in dyeability with almost all of the available dyestuffs and coloring agents may be secured when vinyl lactam polymers, particularly polyvinylpyrrolidone, are incorporated in acrylonitrile polymer synthetic textile fibers.
  • certain difficulties may also attend such practice when it is desired to impart coloration to the fibers by means of many direct, acid (including acidpremetaIliZed) and chrome types of dyestuffs.
  • Vinyl lactam polymer-containing acrylic fibers that have been dyed with a dyestuff selected from the group consisting of Patent M 2,922,692 Patented Jan. 26, 1960 direct, acid and chrome dyestuffs may be rendered stable to light and resistant to fading from the initially obtained coloration by a treatment which comprises subjecting them after they have been dyed to an aqueous solution of cuprous ions, preferably obtained from cupricions (as from copper sulfate) that have been converted to cuprous ions by the action of hydroxyl amine sulfate or an equivalent reducing agent for cupric ions. Bene, ficially, the treatment is conducted immediately subse quent to the dyeing operation.
  • the aqueous solution of copper ions that is employed for the treatment contains a quantity of the ions that is equivalent to that which is obtained in an aqueous solution of copper sulfatecoritaining from about 0.5 to 8 percent by weight, based on the weight of the fibers, of dissolved salt, and, more advantageously, from. about 0.5 to 5 percent on the weight of the fibers of the dissolved salt in treating baths wherein the weight ratio of bath-.tofiber may respectively range from about 5:1 to about 100:1.
  • the treating solution advantageously may be made up by the additionof from about 0.005 to 1.6 and, more advantageously, from about 0.005 to 1.0 gram of copper sulfate to each 100 grams of treating solution being prepared.
  • vinyl lactam polymer-containing acrylonitrile; polymer synthetic textile fibers that have been, imbued. with light shades of coloration from direct, acid or chrome .dyes'tutfs may be suitably stabilized against light fading when: the concentration of reagents in the treating solution is at ortowards the lower extremity of the indicated ranges. Darkerzh-nesmay' often be better stabilized with more concentrated'treating solutions.
  • the treatment may beconducted for periods of at least one-half. hour atv temperatures fromna'bout. 70 C. to the boil.
  • a dyed vinyl lactam polymer-containingacrylonitrile polymer synthetic textile fiber thatis st'abilized against fading upon exposure to light by treatment in accordance withv the. present. invention is schematically represented, in an exaggerated perspective, in the accompanying-drawing.
  • CuSO copper sulfate
  • acrylonitrile polymer fiber that may be dyed with direct, acid or chrome dyestuffs and aftertreated for light fastness according to the present invention is derived from a fibervinyl caprolactam.
  • vinyl lactam copolymers When vinyl lactam copolymers are utilized, it is frequently desirable to employ those that contain at least about 60 or even 80 percent by weight of the vinyl lactam monomer polymerized inthe copolymer molecule.
  • a vinyl lactam polymercontaining acrylonitrile polymer synthetic textile fiber to contain up to 20 percent by weight of a dye-receptive vinyl lactam polymer in intimate physical incorporation in the acrylonitrile polymer. It may frequently be of greatest advantage when between about 6 and 12 percent by weight of the vinyl lactam polymer, particularly polyvinylpyrrolidone, is incorporated in the acrylonitrile polymer, particularly polyacrylonitrile, based on the dry weight of the associated polymers.
  • vinyl lactam polymep containing acrylonitrile polymer synthetic textile fibers of the indicated variety may be literally referred to as acrylic fibers for purposes of broad generic classification, it is generally preferred, when brevity is a requirement, to characterize them as being nitrile alloy fibers in order to clearly distinguish them from the conventional prototype acrylic fibers that are known to the art.
  • the vinyl lactam polymer may be uniformly incorporated in the desired quantity in a fiber-forming acrylonitrile polymer composition prior to spinning it into fibers in order to prepare the desired dye-receptive synthetic fiber product.
  • the vinyl lactam polymercontaining acrylonitrile polymer fiber may be a wet spun product in which the vinyl lactam polymer is intimately incorporated by impregnation of the dye-assisting adiuvant from an aqueous solution thereof while the acrylonitrile polymer in the fiber is in a swollen or gel condition.
  • a fiber-forming polymer of acrylonitrile such as polyacrylonitrile may be prepared as a spinning solu tion by dissolving it in asuitable solvent, such as an aqueous 60 percent by weight zinc chloride solution, and extruded in solution into a coagulating bath therefor to initially form an aquagel filamentary structure in which the vinyl lactam polymer may conveniently be incorporated by subjecting the aquagel structure to treatment with an impregnatingrsolution ofthe dye-assisting adjuvant.
  • Such an impregnatingtreatment may often be suitably performed by passing the aquage'lthrough an aqueous treatingbath of dissolved vinyl lactam polymer prior to drying the aquagel to a dehydrated condition.
  • Example I About 5 grams of scoured polyvinylpyrrolidone-containing polyacrylonitrile fiber was given a 2 percent dyeinitially setting the dyebath at 50 C., immersing the fiber in the dyebath, bringing the dyebath to the boil over a minute period, adding 30 percent, on the weight of the fiber, of sodium chloride to the dyebath over a 15 minute period, and continuing the dyeing at the boil for a 2 hour period. The resulting fiber, which was deep and level dyed, was then given a cold rinse with water before being immersed in about 150 milliliters of a treating bath consisting ofJS percent of copper sulfate and 2.5 percent of I hydroxyl amine sulfate, both based on the weight of the fiber.
  • the temperature was rapidly raised to about 95 C. and the dyebath was synthermally maintained for a 30 minute period.
  • the dyed and treated fiber was then removed from the treating solution, rinsed thoroughly with cold water and dried. It had excellent light stability and was extremely color-fast upon exposure to light. For example, when the dyed and treated fiber was tested under exposure to ultra violet light in a standard Atlas Fadeometer, a noticeable color fade did not occur until after expiration of a 20 hour period. In comparison, a similarly dyed but untreated fiber of the same type faded after 'only 5 hours of exposure in the Fadeometer.”
  • Example II w v I Example III
  • the color fastness of a number of dyed vinyl lactam polymer-containing acrylonitrile polymer synthetictextile fiber samples was enhanced to a degree commensurate with that illustrated in the preceding examples.
  • the following tabulation lists and identifies some of the dyestuffsemployed for the color stabilized acrylic fibers that were prepared. It also includes the nature of the, dyeing with each dye and the Weight concentrations,
  • acid dyestuffs is meant to comprehend and to include within its generic purview the types of acid dyestuffs that are sometimes referred to and characterized as being acid-premetallized dyes.
  • a dyed synthetic textile fiber that is comprised of (a) a fiber of an intimate alloy composition of (1) a fiber-forming acrylonitrile polymer that contains in the polymer molecule about 85 Weight percent of acrylonitrile and (2) a minor proportion of up to about 20 Weight percent, based on the weight of the dry fiber, of a vinyl lactam polymer, said fiber being colored with (b) a dyestutf attached thereto selected from the group of dyestuffs consisting of direct, acid and chrome types of dyes, which process comprises treating said dyed fiber, for at least about half an hour at a temperature of from about 70 C.
  • said treating solution containing (A) an amount of cupric copper ion equivalent to that which is obtained with between about 0.5 and 8 percent by weight, based on the weight of the fiber, of copper sulfate (CuSO and (B) an amount of a reducing agent for cupric copper ions that is equivalent in activity to an aqueous solution of from 0.5 to 8 percent by weight, based on the weight of the fiber, of hydroxyl amine sulfate to render fast-to-light the color in said dyed fiber.
  • CuSO copper sulfate
  • B an amount of a reducing agent for cupric copper ions that is equivalent in activity to an aqueous solution of from 0.5 to 8 percent by weight, based on the weight of the fiber, of hydroxyl amine sulfate to render fast-to-light the color in said dyed fiber.
  • a color-fast synthetic textile fiber that is comprised of an intimate alloy composition of (1) a fiber-forming acrylonitrile polymer that contains in the polymer molecule at least about 85 weight percent of acrylonitrile and (2) a minor proportion of up to about 20 weight percent, based on the weight of the dry fiber, of a vinyl lactam polymer, which process comprises first dyeing said synthetic textile fiber with a dyestuff selected from the group consisting of direct, acid and chrome types of dyes and subsequently treating said dyed fiber, for at least about half an hour at a temperature be tween about C.
  • a dyestuff selected from the group consisting of direct, acid and chrome types of dyes
  • aqueous treating solution at a bath-to-fiber weight ratio between about 5:1 and 100:1, respectively, said treating solution containing (A) between about 0.5 and 8 percent by weight of copper sulfate (CuSO and (B) between about 0.5 and 8 percent by weight of hydroxyl amine sulfate, both based on the weight of the fiber, to render fast-to-lightthe color in said dyed fiber.
  • CuSO copper sulfate
  • B between about 0.5 and 8 percent by weight of hydroxyl amine sulfate
  • said synthetic textile fiber is comprised of polyacrylonitrile in which there is intimately incorporated an amount between about 6 and 12 percent by weight, based on the weight of dry fiber, of polyvinylpyrrolidone as a dye-assisting adjuvant.

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Description

Jan. 26, 1960 A. s. MESSER I 2,922,692
COLOR FAST SYNTHETIC TEXTILE FIBERS FROM VINYL LACTAM POLYMER-CONTAINING ACRYLONITRILE POLYMERS Filed Dec. 28, 1956 IN VEN TOR.
fl/ber/ I5, Messer BY HTTORNEKS United COLOR FAST SYNTHETIC TEXTILE FIBERS FROM VINYL LACTAM POLYMER-CONTAINING AC- RYLONITRILE POLYMERS Application December 28, 1956, Serial No. 631,255
8 Claims. (Cl. 8-74) This invention relates to the provision of color fast vinyl lactam polymer-containing acrylonitrile polymer synthetic textile fibers and the like that have been dyed with certain types of dyestuffs and rendered stable to the deleterious efiects of light while in a colored'condition.
Certain vinyl lactam polymers, particularly polyvinyl pyrrolidone, are exceptionally well adapted for employment as dye-assisting adjuvants in shaped acrylonitrile polymer articles, particularly polyacrylonitrile fibers and the like, including filaments, yarns, films and related structures. For convenience, the various shaped articles that may be fabricated from synthetic, linear, fiber-forming acrylonitrile polymers will hereinafter be illustrated with fibers that are manufactured with such compositions. A great general improvement in dyeability with almost all of the available dyestuffs and coloring agents may be secured when vinyl lactam polymers, particularly polyvinylpyrrolidone, are incorporated in acrylonitrile polymer synthetic textile fibers. Despite this, certain difficulties may also attend such practice when it is desired to impart coloration to the fibers by means of many direct, acid (including acidpremetaIliZed) and chrome types of dyestuffs.
By way of illustration, when vinyl lactam polymercontaining acrylonitrile polymer fibers are dyed with many of the direct, acid and chrome dyestuifs, the colored synthetic fiber product has a tendency to be unstable upon exposure to light so that they may definitely and noticeably fade in a most undesirable manner. This is notwithstanding the fact that good color yields and intense depths of shade may be initially achieved with such dyestuffs on vinyl lactam polymer-containing acrylonitrile polymer fibers and that such varieties of dyestuffs are normally quite color stable on exposure to light when they have been applied to thevarieties of fibers for which they were originally designed and intended to be utilized upon.
This failure to be light fast when colored with direct, acid and chrome dyestuffs, as is apparent, tends to limit the otherwise generally utile characteristics of vinyl lactam polymer-containing acrylonitrile polymer synthetic fibers from employment as textile materials that are intended to be colored by such dyestuffs to avoid the obviously undesirable consequences that might accrue. It would be advantageous to overcome this deficiency in such fibers.
Therefore, it is principally the objective of the present invention to provide light stabilized vinyl lactam polymercontaining acrylic fibers and the like dyed with either direct, acid or chrome dyestulfs that would be substantially free from tendencies to fade upon exposure to light, including ultra violet light, in the course of their useful lives as textile materials. Other objectives and advantages ancillary. to the principal objective that may be realized by practice of the present invention are manifest in the ensuing description and specification.
In accordance with the present invention, Vinyl lactam polymer-containing acrylic fibers that have been dyed with a dyestuff selected from the group consisting of Patent M 2,922,692 Patented Jan. 26, 1960 direct, acid and chrome dyestuffs may be rendered stable to light and resistant to fading from the initially obtained coloration by a treatment which comprises subjecting them after they have been dyed to an aqueous solution of cuprous ions, preferably obtained from cupricions (as from copper sulfate) that have been converted to cuprous ions by the action of hydroxyl amine sulfate or an equivalent reducing agent for cupric ions. Bene, ficially, the treatment is conducted immediately subse quent to the dyeing operation. Advantageously, the aqueous solution of copper ions that is employed for the treatment contains a quantity of the ions that is equivalent to that which is obtained in an aqueous solution of copper sulfatecoritaining from about 0.5 to 8 percent by weight, based on the weight of the fibers, of dissolved salt, and, more advantageously, from. about 0.5 to 5 percent on the weight of the fibers of the dissolved salt in treating baths wherein the weight ratio of bath-.tofiber may respectively range from about 5:1 to about 100:1. Thus, the treating solution advantageously may be made up by the additionof from about 0.005 to 1.6 and, more advantageously, from about 0.005 to 1.0 gram of copper sulfate to each 100 grams of treating solution being prepared. Of course, when other copper ion-providing salts are utilized, their gravimetric proportions will vary from the indicated values for copper sulfate in accordance 'with the copper equivalent weight of the particular copper salt that is employed. The same ranges of weight concentrations in solution may advantageously be employed for a hydroxyl amine sulfate reducing agent and, in a similar manner, when other reducing agents for cupric ions are utilized, proportions of them that are equivalent in reducing activity to such concentrations of hydroxyl amine sulfate are usually advan tageous. In many instances it may be suitable'to employ an approximately equal weight perecnt'age of copper sulfate and hydroxyl amine sulfate in'the treating solution. Frequently, vinyl lactam polymer-containing acrylonitrile; polymer synthetic textile fibers that have been, imbued. with light shades of coloration from direct, acid or chrome .dyes'tutfs may be suitably stabilized against light fading when: the concentration of reagents in the treating solution is at ortowards the lower extremity of the indicated ranges. Darkerzh-nesmay' often be better stabilized with more concentrated'treating solutions.
The treatment may beconducted for periods of at least one-half. hour atv temperatures fromna'bout. 70 C. to the boil.
may be-realized in comparison with untreated fibers 'of the sametype that have been dyed with the same varieties of dyestuffs. A dyed vinyl lactam polymer-containingacrylonitrile polymer synthetic textile fiber thatis st'abilized against fading upon exposure to light by treatment in accordance withv the. present. invention is schematically represented, in an exaggerated perspective, in the accompanying-drawing. Y
Although copper sulfate" (CuSO;,)- is," as has been i n dicated, a preferred source of'copper ions, other copper salts may also be utilized for'such purpose including cop per acetate, copper chlorideandthelike. Likewise, such reducing agentsizas sodium sulfoxylate formaldehyde, me-
O ftentimes, however, ebullient tempera-- tures, or temperatures of at least. about C. are better 3 tallic elemental copper, mixtures of sodium bisulfite with glyoxal and the like may also be employed in the practice of the invention, despite the great desirability of hydroxyl amine sulfate for such application. No special dyeing technique or procedure for the direct, acid or chrome dyestuffs is necessary when it is intended to stabilize the colored vinyl lactam polymer-containing acrylonitrile polymer fiber by practice of the invention. The usual and conventional techniques that are commonly employed in the art may be used on the fibers prior to the stabilizing treatment.
Advantageously, the vinyl lactam polymer containing V mg of Benzo Azurme GA (Cl. 502), a direct dye, by
acrylonitrile polymer fiber that may be dyed with direct, acid or chrome dyestuffs and aftertreated for light fastness according to the present invention is derived from a fibervinyl caprolactam. When vinyl lactam copolymers are utilized, it is frequently desirable to employ those that contain at least about 60 or even 80 percent by weight of the vinyl lactam monomer polymerized inthe copolymer molecule.
Generally, it is beneficial for a vinyl lactam polymercontaining acrylonitrile polymer synthetic textile fiber to contain up to 20 percent by weight of a dye-receptive vinyl lactam polymer in intimate physical incorporation in the acrylonitrile polymer. It may frequently be of greatest advantage when between about 6 and 12 percent by weight of the vinyl lactam polymer, particularly polyvinylpyrrolidone, is incorporated in the acrylonitrile polymer, particularly polyacrylonitrile, based on the dry weight of the associated polymers. While vinyl lactam polymep containing acrylonitrile polymer synthetic textile fibers of the indicated variety may be literally referred to as acrylic fibers for purposes of broad generic classification, it is generally preferred, when brevity is a requirement, to characterize them as being nitrile alloy fibers in order to clearly distinguish them from the conventional prototype acrylic fibers that are known to the art.
. Various techniques and procedures may be invoked for providing a vinyl lactam polymer-containing acrylonitrile polymer fiber of the indicated variety. For example, the vinyl lactam polymer may be uniformly incorporated in the desired quantity in a fiber-forming acrylonitrile polymer composition prior to spinning it into fibers in order to prepare the desired dye-receptive synthetic fiber product. Advanta'geously, however, the vinyl lactam polymercontaining acrylonitrile polymer fiber may be a wet spun product in which the vinyl lactam polymer is intimately incorporated by impregnation of the dye-assisting adiuvant from an aqueous solution thereof while the acrylonitrile polymer in the fiber is in a swollen or gel condition. Thus, a fiber-forming polymer of acrylonitrile such as polyacrylonitrile may be prepared as a spinning solu tion by dissolving it in asuitable solvent, such as an aqueous 60 percent by weight zinc chloride solution, and extruded in solution into a coagulating bath therefor to initially form an aquagel filamentary structure in which the vinyl lactam polymer may conveniently be incorporated by subjecting the aquagel structure to treatment with an impregnatingrsolution ofthe dye-assisting adjuvant. Such an impregnatingtreatment may often be suitably performed by passing the aquage'lthrough an aqueous treatingbath of dissolved vinyl lactam polymer prior to drying the aquagel to a dehydrated condition.
' aeaaeez The invention will be further illustrated in and by the following examples wherein,-unless otherwise indicated, all parts and percentages are to be taken by weight, In each of the examples the vinyl lactam polymer-containing acrylic fiber consisted ofS-run polyacrylonitrile yarn in which there was intimately incorporated about percent by weight, on the dry weight of the fiber, of polyvinylpyrrolidone as a dye-assisting adjuvant.
Example I About 5 grams of scoured polyvinylpyrrolidone-containing polyacrylonitrile fiber was given a 2 percent dyeinitially setting the dyebath at 50 C., immersing the fiber in the dyebath, bringing the dyebath to the boil over a minute period, adding 30 percent, on the weight of the fiber, of sodium chloride to the dyebath over a 15 minute period, and continuing the dyeing at the boil for a 2 hour period. The resulting fiber, which was deep and level dyed, was then given a cold rinse with water before being immersed in about 150 milliliters of a treating bath consisting ofJS percent of copper sulfate and 2.5 percent of I hydroxyl amine sulfate, both based on the weight of the fiber. After placing the dyed fiber in the treating solution, the temperature was rapidly raised to about 95 C. and the dyebath was synthermally maintained for a 30 minute period. The dyed and treated fiber was then removed from the treating solution, rinsed thoroughly with cold water and dried. It had excellent light stability and was extremely color-fast upon exposure to light. For example, when the dyed and treated fiber was tested under exposure to ultra violet light in a standard Atlas Fadeometer, a noticeable color fade did not occur until after expiration of a 20 hour period. In comparison, a similarly dyed but untreated fiber of the same type faded after 'only 5 hours of exposure in the Fadeometer."
I Example II w v I Example III In substantially identical repetitions of the procedures of Example I with different dyestufis and slight variations in the concentrations of the reagents in the stabilizing treatment solutions, the color fastness of a number of dyed vinyl lactam polymer-containing acrylonitrile polymer synthetictextile fiber samples was enhanced to a degree commensurate with that illustrated in the preceding examples. The following tabulation lists and identifies some of the dyestuffsemployed for the color stabilized acrylic fibers that were prepared. It also includes the nature of the, dyeing with each dye and the Weight concentrations,
- all based on the weight of the fiber, of the copper sulfate CS) and hydroxyl amine sulfate (HAS) reagents that were m the particular treatnig solutions employed for stabrlizmg the dyed fibers.
Acid dyestuffs:
Direct dyes:
2 percent Cuprofix Rubine BL-Pr. 491; 4 percent CS+4 percent HAS 2 percent Diazo Fast Blue 2RWC.I. 317; 4 percent CS+4 percent HAS 1 percent Direct Brilliant Sky Blue 63 ex. cone.-
C.I. 518; 4 percent CS+4 percent HAS 5 percent Direct Black E ex. conc.C;I. 581; 5 percent CS+5 percent HAS 2 percent Diamine Brown MBA-C.I. 420; 4 percent CS+4 percent HAS Chrome dyestuffs:
1.4 percent Anthranol Chrome Red GL conc.Pr.
135; 3 percent CS+3 percent HAS 2 percent Omega Chrome Red BC.I. 652; 3 percent CS+3 percent HAS 2 percent Chrome Fast Orange 3 RL A CFPr. 247;
3 percent CS+3 percent HAS 2 percent Chrome Blue 2R-Pr. 7; 2 percent CS+2 percent HAS 2 percent Alizarine Light Grey ZBLW-Pr. 206; 2
percent CS+2 percent HAS Those skilled in the art will readily recognize and appreciate that the treatment of the present invention difiers in both substance and essence from certain diverse copper ion treatments that are known in connection with other of the conventional prototype acrylic and other synthetic fibers to either directly assist in chemically attaching a dyestutf that otherwise would not become associated with the polymer in the fiber or for causing a metallizing efiect of an already attached dyestufi in the fiber. As has been indicated and as it is intended to be construed herein and in the hereto-appended claims, the term acid dyestuffs is meant to comprehend and to include within its generic purview the types of acid dyestuffs that are sometimes referred to and characterized as being acid-premetallized dyes.
What is claimed is:
1. Process of rendering color-fast a dyed synthetic textile fiber that is comprised of (a) a fiber of an intimate alloy composition of (1) a fiber-forming acrylonitrile polymer that contains in the polymer molecule about 85 Weight percent of acrylonitrile and (2) a minor proportion of up to about 20 Weight percent, based on the weight of the dry fiber, of a vinyl lactam polymer, said fiber being colored with (b) a dyestutf attached thereto selected from the group of dyestuffs consisting of direct, acid and chrome types of dyes, which process comprises treating said dyed fiber, for at least about half an hour at a temperature of from about 70 C. to the boil with an aqueous treating solution at a bath-to-fiber weight ratio between about 5:1 and 100:1, respectively, said treating solution containing (A) an amount of cupric copper ion equivalent to that which is obtained with between about 0.5 and 8 percent by weight, based on the weight of the fiber, of copper sulfate (CuSO and (B) an amount of a reducing agent for cupric copper ions that is equivalent in activity to an aqueous solution of from 0.5 to 8 percent by weight, based on the weight of the fiber, of hydroxyl amine sulfate to render fast-to-light the color in said dyed fiber.
2. As an article of manufacture, a colored and color fast-to-light synthetic textile fiber obtained as the product of the process of claim 1.
3. Process of manufacturing a color-fast synthetic textile fiber that is comprised of an intimate alloy composition of (1) a fiber-forming acrylonitrile polymer that contains in the polymer molecule at least about 85 weight percent of acrylonitrile and (2) a minor proportion of up to about 20 weight percent, based on the weight of the dry fiber, of a vinyl lactam polymer, which process comprises first dyeing said synthetic textile fiber with a dyestuff selected from the group consisting of direct, acid and chrome types of dyes and subsequently treating said dyed fiber, for at least about half an hour at a temperature be tween about C. and the boil, with an aqueous treating solution at a bath-to-fiber weight ratio between about 5:1 and 100:1, respectively, said treating solution containing (A) between about 0.5 and 8 percent by weight of copper sulfate (CuSO and (B) between about 0.5 and 8 percent by weight of hydroxyl amine sulfate, both based on the weight of the fiber, to render fast-to-lightthe color in said dyed fiber.
4. The process of claim 3, the after-dyeing treatment being conducted at a temperature between about C. and the boil.
5. The process of claim 3, wherein the after-dyeing treatment is conducted in an aqueous treating solution containing separate amounts of between about 0.5 and 5 percent by weight ofthe copper sulfate and the hydroxyl amine sulfate, both based on the Weight of the fiber.
6. The process of claim 3, wherein about equal weights of copper sulfate and hydroxyl amine sulfate are contained in the aqueous treating solution employed after said dyeing.
7. The process of claim 3, wherein the treating bath-tofiber weight ratio that is utilized in the after-dyeing treatment is in the neighborhood of 30: 1.
8. The process of claim 3, wherein said synthetic textile fiber is comprised of polyacrylonitrile in which there is intimately incorporated an amount between about 6 and 12 percent by weight, based on the weight of dry fiber, of polyvinylpyrrolidone as a dye-assisting adjuvant.
References Cited in the file of this patent UNITED STATES PATENTS 2,643,990 Han June 30, 1953 2,790,783 Coover Apr. 30, 1957 FOREIGN PATENTS 678,106 Great Britain Aug. 27, 1952 696,984 Great Britain Sept. 9, 1953 OTHER REFERENCES Am. Dyestutf Reporter for May 9, 1955, p. P323, art. by W. H. Hindle.
Blaker: Am. Dyest. Rep., January 21, 1952, pp. 39-43.
Br. Rayon and Silk Jour., August 1953, p. 54.

Claims (1)

1. PROCESS OF RENDERING COLOR-FAST A DYED SYNTHETIC TEXTILE FIBER THAT IS COMPRISED OF (A) A FIBER OF AN INTIMATE ALLOY COMPOSITION OF (1) A FIBER-FORMING ACRYLONITRILE POLYMER THAT CONTAINS IN THE POLYMER MOLECULE ABOUT 85 WEIGHT PERCENT OF ACRYLONITRILE AND (2) A MINOR PROPORTION OF UP TO ABOUT 20 WEIGHT PERCENT, BASED ON THE WEIGHT OF THE DRY FIBER, OF A VINYL LACTAM POLYMER, SAID FIBER BEING COLORED WITH (B) A DYESTUFF ATTACHED THERETO SELECTED FROM THE GROUP OF DYESTUFFS CONSISTING OF DIRECT, ACID AND CHROME TYPES OF DYES, WHICH PROCESS COMPRISES TREATING SAID DYED FIBER, FOR AT LEAST ABOUT HALF AN HOUR AT A TEMPERATURE OF FROM ABOUT 70*C. TO THE BOIL WITH AN AQUEOUS TREATING SOLUTION AT A BATH-TO-FIBER WEIGHT RATIO BETWEEN ABOUT 5:1 AND 100:1, RESPECTIVELY, SAID TREATING SOLUTION CONTAINING (A) AN AMOUNT OF CUPRIC COPPER ION EQUIVALENT TO THAT WHICH IS OBTAINED WITH BETWEEN ABOUT 0.5 AND 8 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE FIBER, OF COPPER SULFATE (CUSO4), AND (B) AN AMOUNT OF A REDUCING AGENT FOR CUPRIC COPPER IONS THAT IS EQUIVALENT IN ACTIVITY TO AN AQUEOUS SOLUTION OF FROM 0.5 TO 8 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE FIBER, OF HYDROXYL AMINE SULFATE TO RENDER FAST-TO-LIGHT THE COLOR IN SAID DYED FIBER.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3099517A (en) * 1960-12-16 1963-07-30 Dow Chemical Co Process of treating wet-spun acrylonitrile polymer fibers
US3226178A (en) * 1962-10-31 1965-12-28 Du Pont Process for dyeing and aftertreating polyethylene oxide modified nylon fibers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB678106A (en) * 1950-01-20 1952-08-27 Ici Ltd Process for dyeing polyamide textile materials
US2643990A (en) * 1951-01-31 1953-06-30 Chemstrand Corp Method of preparing polymers
GB696984A (en) * 1950-07-05 1953-09-09 Union Carbide & Carbon Corp Process of dyeing artificial textile fibres
US2790783A (en) * 1956-07-18 1957-04-30 Eastman Kodak Co Mixtures comprising acrylonitrile polymers with polyvinylpyrrolidone and fibers thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB678106A (en) * 1950-01-20 1952-08-27 Ici Ltd Process for dyeing polyamide textile materials
GB696984A (en) * 1950-07-05 1953-09-09 Union Carbide & Carbon Corp Process of dyeing artificial textile fibres
US2643990A (en) * 1951-01-31 1953-06-30 Chemstrand Corp Method of preparing polymers
US2790783A (en) * 1956-07-18 1957-04-30 Eastman Kodak Co Mixtures comprising acrylonitrile polymers with polyvinylpyrrolidone and fibers thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3099517A (en) * 1960-12-16 1963-07-30 Dow Chemical Co Process of treating wet-spun acrylonitrile polymer fibers
US3226178A (en) * 1962-10-31 1965-12-28 Du Pont Process for dyeing and aftertreating polyethylene oxide modified nylon fibers

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