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US3622264A - Fiber blends of polyolefin with polyvinylpyridines of quinolines with and without a polyethylene oxide and acid and disperse dye variegated dyeing thereof - Google Patents

Fiber blends of polyolefin with polyvinylpyridines of quinolines with and without a polyethylene oxide and acid and disperse dye variegated dyeing thereof Download PDF

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US3622264A
US3622264A US736555A US3622264DA US3622264A US 3622264 A US3622264 A US 3622264A US 736555 A US736555 A US 736555A US 3622264D A US3622264D A US 3622264DA US 3622264 A US3622264 A US 3622264A
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vinylpyridine
anionic
filamentary
filamentary assembly
dyeing
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Charles N Brown
Andor Schwarcz
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UNIROYAL HOLDING Inc WORLD HEADQUARTERS MIDDLEBURY CONNECTICUT 06749 A CORP OF NEW JERSEY
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/021—Material containing basic nitrogen using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/024—Material containing basic nitrogen using dispersed dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/929—Carpet dyeing

Definitions

  • Beck ABSTRACT This invention relates to a process for dyeing fabrics and textile articles made from polyolefin fibers or twocolor or multicolor patterns using a mixture of different classes of dyes in a single dyebath, which may optionally contain an anionic and nonionic surfactant.
  • Synthetic fibers other than the polyolefins such as those made from polyamides or polyacrylonitriles, can be modified to pennit the achievement of multicolor efi'ects in a single dyeing procedure.
  • Polyolefin fibers which some respects offer better than the aforementioned fibers, are not available in forms which can be dyed to a multicolor effect using a single dyeing step.
  • a further object of this invention is that such dyeing to a multicolor pattern of such fabrics be accomplished in a single dyeing step with a mixture of anionic dyes and disperse dyes.
  • a fabric or textile article such as a carpet pile
  • two or more classes of yarns all of which have been formed from a polyolefin.
  • Two of the classes of fibers are comprised of a major portion of a poly(alpha-olefin), their properties differing only in their dyeing behavior, which is the basis for the classification described in this specification.
  • One class is essentially undyeable with anionic dyes in the process of this invention, while the other one is highly dyeable with anionic dyes, and both classes are susceptible to dyeing with disperse dyes.
  • the dyeable polyolefin fibers used in this invention comprise the following two classes:
  • This fiber is referred to herein as two-component fiber.
  • the total amount of the B plus C components in said composition is greater than 3 percent by weight.
  • Such fibers are dyeable with anionic and propert es 1 other and graft copolymers of alpha-olefins with polymers of other alpha-olefins.
  • the class includes polyethylene, polypropylene, poly( 3-methyl- 1 -butene), poly( 4-methyll pentene), copolymers of propylene and 4-methyl-l-pentene,
  • the preferred material is polypropylene, by which we mean any polymer of propylene and any copolymer containing predominantly polymerized propylene together with any other comonomer copolymerized therewith.
  • the dye receptor compounds suitable for admixing with said alpha-monoolefin polymers are thermoplastic homopolymers of pyridine-type monocyclic and polycyclic compounds, including quinolines, and their copolymers with each other.
  • One of the classes of pyridine-type compounds useful for this purpose in this invention are the polymers of vinylpyridines such as: 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3-methyl-6-vinylpyridine, 2-ethyl-5-vinylpyridine, 2- methyl-S-vinylpyridine, 2-ethyl-6-vinylpyridine, 2- isopropenylpyridine, etc.
  • Preferred materials of this class for use in this invention are polymers of at least one vinylpyridine compound, by which is meant homopolymers of vinylpyridine compounds such as poly(Z-vinylpyridine), poly(4-vinylpyridine), poly(2-methyl-5-vinylpyridine), poly(2- isopropenylpyr'idine), etc., copolymers of various vinyl-substituted pyridine compounds with each other, such as copolymers of 3-vinylpyridine and 2-methyl-5-vinylpyridine in any desired proportions, copolymers of 2-vinylpyridine with 2- isopropenylpyridine in any desired proportions, copolymers of 4-vinylpyridine with 2-vinylquinoline in any desired proportions, as well as copolymers of three, four, or more of these polymerizable materials. Copolymers of vinylpyridines with other monoethylenically unsaturated monomers, such as styrene, ethylene or propylene are also operative in the
  • the (C) component of the 3component fiber (anionic dyeable) used in this invention is selected from the following groups of compounds:
  • Polyethylene glycol also referred to herein as PEG having a degree of polymerization of at least 4;
  • Copolymers of ethylene oxide with other alkylene oxides having a degree of polymerization of the ethylene oxide units of at least 4 and containing a minimum of 60 percent by weight ethylene oxide.
  • These compounds are exemplified by the series of block copolymers produced by condensing ethylene oxide with a product formed by the condensation of propylene oxide with propylene glycol (formula of such copolymers: HO-(Ql-LO) (C l-I 0) (C H O) H and sold under the trademark Pluronic).
  • Other useful copolymers are derived from the polymerization of ethylene oxide and propylene oxide;
  • polyethylene glycol such as its ethers and esters having a degree of polymerization of ethylene oxide of at least 4 and an ethylene oxide content of at least 60 percent by weight.
  • examples of such derivatives are: (a) polyethylene glycol alkyl ethers; (b) alkylaryl polyethoxyalcohols sold under the trademark lriton (the octylphenylpolyethoxy ethanol series); (c) polyoxyethylene derivatives of long-chain fatty-acid esters of hexitol anhydrides including sorbitans, sorbides, mannitans and mannides, such as polyethylene glycol hexitol carboxylates, polyoxyethylene sorbitan monolaurate sold under the trademark Tween 20" and polyoxyethylene sorbitan monostearate; and polyethylene glycol carboxylate esters such as polyethylene glycol monostearate and polyethylene glycol distearate.
  • Additional colors can be obtained in the present invention by varying the composition of the two-component" or three-component” fibers.
  • Such variation may include: (1) varying the type and/or amount of polyolefin; (2) varying the chemical structure and/or amount of the dye receptor polymer; (3) varying the chemical structure and/or amount of the hydrophilic compound used in the three-component" fiber.
  • a textile article such as a fabric or carpet pile is assembled, whether by weaving, tufting, knitting, felting, hool ing or other means, from the two classes of yarns described, which may optionally include uncolored nondye receptorcontaining or pigmented polyolefin fibers, and dyed with a mixture of an anionic dye and a disperse dye in the present of a nonionic surfactant or in mixture of a nonionic and an anionic surfactant, only those portions of the fabric made of the three-component fibers will be dyed by anionic dyes. These same three-component fibers will also be dyed by disperse dyes.
  • the portion of the fabric composed of two-component fibers will remain essentially undyed by the anionic dyes, and therefore will only be dyed by disperse dyes, lf included in the textile article, the nondye receptor containing yarns will remain undyed.
  • anionic dyes of certain colors and disperse dyes of difi'erent colors the fabrics containing combinations of the abovedescribed two-component" and three-component" yarns can be conveniently dyed to a two-color or multicolor pattern, in a single dyeing step, in which the fabric is exposed to the above mixture of anionic and disperse dyes.
  • the two-component fiber is essentially undycable with anionic dyes by conventional dyeing procedures using a nonionic surfactant in the dyebath, some staining (i.e., a slight takeup of dye on the surface of the fiber) will occur with anionic dyes. This may be undesirable in cases where staining decreases a desired contrast in the color of the two classes of yarns dyed with a mixture of anionic and disperse dyes.
  • a further feature of the present invention is the discovery of certain surfactant compositions used in the dyeing of articles composed of the above-described polyolefin yarns which are dyeable with anionic and/or disperse dyes. These compositions facilitate the production of multicolor patterns by increasing the color contrasts obtainable with the two classes of fibers previously described.
  • These surfactant compositions are mixtures of anionic and nonionic surfactants which are applied to the yarn in an acidic dyebath.
  • anionic surfactants used in the dyebath greatly enhance the uptake of anionic dyes of both two-component fibers" and three-component fibers.
  • Nonionic surfactants have little effect on the dye uptake of the three-component fiber and virtually no effect on the dye uptake of the two-component fiber.
  • the nature of the surfactant has in general little, if any effect on the dye uptake of disperse dyes.
  • a mixture of anionic and nonionic surfactants increases the dye uptake of the three-component fiber while having little or no effect on the dye uptake of the twocomponent fiber, when both fibers are dyed simultaneously in the same dyebath.
  • the color contrast obtained in dyeing with this mixture of surfactants is greater than that obtainable with either anionic or nonionic surfactants alone. This is a very important factor in the styling of multicolor pattern fabrics or yarns.
  • the anionic component of the mixture of surfactants has the general formula (R-A) wherein R represents a hydrophobic group which is either a substituted or nonsubstituted alkyl, aryl or alkylaryl group having 6 or more carbon atoms (preferably between 9 and 40 carbon atoms) per A group; and A is an anionic group exemplified by one or more of the fol- Commercial Name Chemical Description Sodium laurylsulfate C H SO Na Sodium tetradecylsulfate C H SO Na Sodium cetylsulfate C H SQNB Aerosol TR Bis(tridecyl)ester of sodium aulfosuccinic acid Aerosol OT Dioctyl ester of sodium sulfosuccinic acid Aerosol A!
  • operative nonionic surfactants in the present invention are copolymers of ethylene oxide with other alkylene oxides, polyoxyalkylene glycol esters, fatty amide condensates, alkanolamides, etc. Some of these nonionic surfactants, such as some of the ester types, may hydrolyze in an acidic dyebath, yielding the free acid, which may behave as an anionic surfactant. Such materials are not recommended for use in the process of this invention as nonionic components of the surfactant mixture. Examples of nonionic surfactants suitable for use in this invention are:
  • the ratio (A/N) of the weight of anionic surfactant (A) to that of the weight of the nonionic surfactant (N) has an effect 5 on the contrast of shades obtainable with the two classes of fibers.
  • This ratio of the weight of A to N depends upon the structure of both anionic and nonionic surfactants, the numerical value of said ratio varying between about 0.1 and 5.
  • a ratio close to 1:1 is often satisfactory in the process of this invention.
  • the total amount of anionic and nonionic surfactant required in the dyebath is between 0.5 and percent owg (on the weight of the goods), preferably between 1 and 6 percent owg.
  • EXAMPLE 1 Three parts of a 1:1 copolymer (by weight) of 2-vinylpyridine and Zmethyl-S-vinylpyridine (prepared by suspension polymerization using azo-bis-isobutyronitrile as initiator, and having intrinsic viscosity 0.9 measured in pyridine at 30 C.) were blended in an extruder at 500 F. with 100 parts of isotactic polypropylene (melt index 5 6 and the resultant blend was chopped into pellets and dried. The pellets were then melt extruded at 530 F. into a 156-filament yarn using a conventional melt-spinning apparatus. The resultant yarn was drawn 4:1 at 275 F.
  • the dyes suitable for use in this invention fall into two denier/filament.
  • the tenacity ofthe yam was 3.1 grams/denier categories.
  • One category is the broad group of anionic dyes, a d "8 ga i n at r ak was 35 percent-
  • This yam is which includes the so-called strong acid dyes, direct dyes, and referred to in the examples herein as the two-component the premetallized dyes. They dye only the above-described fiber.”
  • the other category is the disperse Another yarn, made from a blend of three parts of the 1:1 dyes which dye both the three-component fibers" and twocopolymer of 2-vinylpyridine and 2-methyl-5-vinylpyridine, component fibers.” Two parts of polyethylene glycol of 600,000 molecular weight Some of the strong acid dyes useful in the present invention and one hundred (100) parts of isotactic polypropylene was are typified by the following: prepared by the same process as described above. This yarn is Acid Yellow 23 1 4 25 referred to in the examples herein as three-component Acid Orange 7 (CI. No. 15510) fiber.”
  • Acid Red 73 27290 Alternate rows of two-" and three-component fiber Acid Blue 45 63010) yarns were tufted into a jute fabric carpet backing in a level Acid Blue 78 (CI. No. 62105) pile design
  • Other useful anionic dyes are the acid metallized dyes, Six samples of the tufted carpet were then dyed with various yp y combinations of anionic and disperse dyes using the following Acid Yellow 54 NO. 19010) procedure;
  • Acid Orange 72 18740 The samples of tufted carpet were first prescoured with an Acid Red 186 (Cl 18810) aqueous solution containing 1 percent owg (on the weight of AidB1ue158(Cl-N0- 14380) the goods) Triton X-100 (an octylphenol condensate with Still other anionic y are the neutral metallized y 9-10 moles of ethylene oxide) and 1 percent owg sodium car- YP y the following: bonate for 20 minutes at 180 F using a 30:1 bath to fiber Acid Yellow 121 (C1 18690) ratio. The samples were then dyed for 45 minutes in an aque- Acid Orange 60 (The half-Chr QOmPIeX 0f 'p y ous dyebath at 200 F. containing 3 percent owg acetic acid, 1
  • Direct Blue 67 (Cl. No. 27925)
  • Other categories of anionic dyes which are applicable to out invention are the reactive dyes, typified by Reactive Orange 1, and the mordant acid dyes, typified by Mordant Red 3 (Cl. No. 58005).
  • Latyl Orange 3R Color Index Disperse Orange 21 Cibacete Brilliant Pink FG (Color Index Disperse Red lnterchem Blue RLF 40 (Cl. No. 61 1 15)
  • 75 EXAMPLE 3 Five samples of tufted carpet made according to the procedure described in example 1 were dyed by the procedure described in example 2, using mixtures of difierent types of anionic and nonionic surfactants in the dyebath and only an anionic dye, as listed in table Il. The resultant dyed carpet samples had rows of three-component fiber" yarns which were deeply colored, whereas the rows of two-component fiber yarns showed little or no uptake of dye.
  • a filamentary assembly suitable for dyeing to a mu]- ticolor pattern through exposure to a mixture of anionic and disperse dyes said filamentary assembly containing a plurality of synthetic fibers, at least one of said fibers having been formed from a mixture comprising (A) an alpha-monoolefin polymer, and (B) between about i and 5 percent by weight on TABLE II Amount Amount (percent (percent Sample Dye (3% owg) Anionic surfactant owg) N anionic surfactant owg) 7 Anthraquinone Blue SKY Aerosol 0T 1 C 3H27O(CHzCHzO)9H 6 do Fatty alcohol phosphate 1 CrgHmO(CHzCHz-O)9H 3 -do C12H250-(CHz-OHO)7CH2COONa 1 Plurom'e L-122 3 1 Copracyl Orange R Sodium dodecylsulfate 1 Triton X305
  • a two-component yarn, containing three parts of poly(2- vinylpyridine) and 100 parts of isotactic polypropylene was prepared similarly.
  • Skeins of the two types of yarns were dyed as in example 1 in a single dyebath containing 1.5 percent owg Capracyl Orange R and 3 percent owg lnterchem Blue RLF 40
  • the two-component yarn dyed to a medium blue and the three-component yarn dyed to a bluish-brown shade.
  • a filamentary assembly as defined in claim 1 which is a yarn.
  • a filamentary assembly as defined in claim 1 which is a f bric. l r h l A...
  • the filamentary assembly defined in claim 1 in which the alpha-monoolefin polymers in the twoand three-component fibers are selected from the group consisting of: polyethylene, polypropylene, poly(3-methyl-l-butene) or poly(4-methyi-lpentene).
  • the pyridine-type polymer in the two-component fiber is selected from the group consisting of homopolymers of (a) vinylpyridines, (b) alkylvinylpyridines, (c) vinylquinolines, (d) alkylvinylquinolines, (e) copolymers of vinylpyridine monomers with alkylvinylpyridine monomers, (f) copolymers of vinylpyridine monomers with a monoethylenically unsaturated monomer; and the pyridine-type polymer in the three-component fiber is selected from the group consisting of homopolymers of(a), (b), (c), (d) and copolymers of(e).
  • the filamentary assembly defined in claim 7 which also contains an uncolored nondye receptor containing alphamonoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
  • the filamentary assembly defined in claim 7 which also contains a pigmented alpha-monoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
  • the filamentary assembly defined in claim 7 in which the pyridine-type dye receptor polymers are selected from the group consisting of a. poly( 2-vinylpyridine) b. poly(2-methyl-5-vinylpyridine) c. poly(4-vinylpyridine) d. poly(2-vinylquinoline) e. the copolymer of 2-vinylpyridine and 2-methyl-5-vinylpyridine f. the copolymer of 2-vinylpyridine and styrene in the case of the two-component fibers g. the copolymer of 2-methyl-5-vinylpyridine and styrene in the case of two-component fibers 11.
  • the pyridine-type dye receptor polymer is the copolymer of 2-methyl-5-vinylpyridine and 2-vinylpyridine, and
  • the polyethylene glycol homopolymer has a molecular weight between 100,000 and 7,000,000.
  • the pyridine-type dye receptor polymer in the two component fiber is a copolymer of styrene and 2-vinylpyridine
  • the pyridine-type dye receptor polymer in the three-component fiber is a copolymer of 2-methyl-5- vinylpyridine and 2-vinylpyridine
  • the polyethylene glycol homopolymer has molecular weight between about 100,000 and 7,000,000.
  • the anionic surfactant has the general formula R-A wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having at least six carbon atoms and A represents an anionic group selected from (a) sulfonate, (b) sulfate, (c) phosphate, (:1) polyphosphate or (e) carboxylate, said group being in free acid or salt form.
  • nonionic surfactant has the general formula R-O-X-l-l wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having six or more carbon atoms,
  • X represents homopolymers of ethylene oxide, or propylene oxide or copolymers of said oxides with each other, all of said polymers having a degree of polymerization of alkylene oxide units between 1 and 100.
  • H represents hydrogen
  • nonionic surfactant is a copolymer of ethylene oxide and propylene oxide.
  • a process for dyeing the filamentary assembly defined in claim 1 to a multicolor pattern of high-color contrast comprising exposing said filamentary assembly to a mixture of anionic and nonionic surfactants under acidic conditions in the presence of a mixture of anionic and disperse dyes.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

This invention relates to a process for dyeing fabrics and textile articles made from polyolefin fibers or two-color or multicolor patterns using a mixture of different classes of dyes in a single dyebath, which may optionally contain an anionic and nonionic surfactant.

Description

ilg i ted States atem Charles N. Brown ('olumhla, S.(..; Andor Schwurcz, lompton Lakes. NJ.
lnvcnlurn App] Nu. 7.16.555
Filed June 13, I968 Putentcd Nov. 23. I971 Asnignce Uniroyal, Inc.
New York, N.Y.
u.s.c1 s/21.s 31, s/100, 8/180, 8/168, 8/41, 8/42, 8/39, 8/25, 8/26, 57/140,57/13 Y, 161/62, 161/169. 161/179, 8/115.7.8/1l5.5,8/DIG.9
1m.Cl D06p3/82 [50] Field of Search 8/21 D,
115.7,DIG. 9;57/14O BY; 161/62, 169, 179
1 5 6 References Cited UNITED STATES PATENTS 3,150,917 9/1964 Gagliardi 8/21 D 3,315,014 4/1967 Coover et a1. 260/895 3,316,328 4/1967 Press 8/168 3,329,557 7/1967 Magat et a1. 161/172 3,361,843 1/1968 Miller 8/180 UX 3,5 30,201 9/1970 Schwarcz 260/857 Primary Examiner-Donald Levy Attorney-Thomas A. Beck ABSTRACT: This invention relates to a process for dyeing fabrics and textile articles made from polyolefin fibers or twocolor or multicolor patterns using a mixture of different classes of dyes in a single dyebath, which may optionally contain an anionic and nonionic surfactant.
FIBER BLENDS OF POLYOLEFIN WITH POLYVINYLlYftEINES OF QUKNOLINES WETH AND WHTHOUT A POLYETHYLENE OWE AND ACE AND msraasr. DYE VARIEGAT ED EYE'LJG TEEREOF The advantages of obtaining a multicolor effect in a single dyeing procedure, as compared to predyeing the individual color components in a number of dyeing steps are obvious. The use of a single dyeing step offers cost advantages as well as flexibility in eliminating the necessity for warehousing the variety of colors needed to assembly the final textile article from predyecl components. Synthetic fibers other than the polyolefins, such as those made from polyamides or polyacrylonitriles, can be modified to pennit the achievement of multicolor efi'ects in a single dyeing procedure. Polyolefin fibers, however, which some respects offer better than the aforementioned fibers, are not available in forms which can be dyed to a multicolor effect using a single dyeing step.
It is an object of this invention to provide a fabric of yarns composed predominantly of a polyolefin capable of being piece-dyed to a multicolor pattern. A further object of this invention is that such dyeing to a multicolor pattern of such fabrics be accomplished in a single dyeing step with a mixture of anionic dyes and disperse dyes. Other objects of our invention will be apparent to one skilled in the art from a consideration of this specification.
These objects can be achieved by assembling a fabric or textile article, such as a carpet pile, from two or more classes of yarns, all of which have been formed from a polyolefin. Two of the classes of fibers are comprised of a major portion of a poly(alpha-olefin), their properties differing only in their dyeing behavior, which is the basis for the classification described in this specification. One class is essentially undyeable with anionic dyes in the process of this invention, while the other one is highly dyeable with anionic dyes, and both classes are susceptible to dyeing with disperse dyes. Exposure of a fabric containing these two or more classes of yarns to a mixture of anionic and disperse dyes will result in the yarns which are essentially undyeable with anionic dyes being dyed substantially only by the disperse dyes. Thus, the fabric achieves a twocolor pattern predetermined by the arrangement of the classes of yarns in the fabric. Since anionic and disperse dyes are generally compatible in the dyebath, these fabrics can be dyed to their two-color pattern in a single dyeing step by such a mixture of dyes. Inclusion of pigmented or uncolored poly(alphaolefin) fiber yarns allows the introduction of still other colors to form said multicolor pattern.
US. Pat. No. 3,315,014, discloses the use of blends of polypropylene with 1 to 25 percent vinylpyridine polymers to produce fibers which are dyeable with disperse and anionic dyes. We have found however, that when such fibers (referred to below as two-component" fibers), contain lower levels of vinylpyridine polymer and are used according to the present invention, they are dyeable only with disperse dyes. This fiber is combined with another polyolefin fiber which is highly dyeable with both anionic and disperse dyes, as described below, to yield the present invention.
The dyeable polyolefin fibers used in this invention comprise the following two classes:
1. A fiber formed from a blend of (A) an alpha-monoolefin polymer and (B) between about 1 and percent by weight of a pyridine-type polymer dye receptor, said fiber being dyeable with disperse dyes and essentially undyeable with anionic dyes in the process used in this invention. This fiber is referred to herein as two-component fiber.
2. A fiber formed from a blend of (A) less than 97 percent by weight of an alpha-monoolefin polymer; (B) between about 0.5 and 5 percent by weight of a pyridine-type polymer dye receptor and (C) between about 0.5 and 5 percent by weight of a hydrophilic compound which is a homopolymer or derivative thereof, or copolymer containing ethylene oxide units CH 20), in prescribed amounts. The total amount of the B plus C components in said composition is greater than 3 percent by weight. Such fibers are dyeable with anionic and propert es 1 other and graft copolymers of alpha-olefins with polymers of other alpha-olefins. The class includes polyethylene, polypropylene, poly( 3-methyl- 1 -butene), poly( 4-methyll pentene), copolymers of propylene and 4-methyl-l-pentene,
5 and copolymers of any of the foregoing monomers with each other and/or with other copolymerizable monomers. The preferred material is polypropylene, by which we mean any polymer of propylene and any copolymer containing predominantly polymerized propylene together with any other comonomer copolymerized therewith.
The dye receptor compounds, suitable for admixing with said alpha-monoolefin polymers are thermoplastic homopolymers of pyridine-type monocyclic and polycyclic compounds, including quinolines, and their copolymers with each other.
One of the classes of pyridine-type compounds useful for this purpose in this invention are the polymers of vinylpyridines such as: 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3-methyl-6-vinylpyridine, 2-ethyl-5-vinylpyridine, 2- methyl-S-vinylpyridine, 2-ethyl-6-vinylpyridine, 2- isopropenylpyridine, etc. Preferred materials of this class for use in this invention are polymers of at least one vinylpyridine compound, by which is meant homopolymers of vinylpyridine compounds such as poly(Z-vinylpyridine), poly(4-vinylpyridine), poly(2-methyl-5-vinylpyridine), poly(2- isopropenylpyr'idine), etc., copolymers of various vinyl-substituted pyridine compounds with each other, such as copolymers of 3-vinylpyridine and 2-methyl-5-vinylpyridine in any desired proportions, copolymers of 2-vinylpyridine with 2- isopropenylpyridine in any desired proportions, copolymers of 4-vinylpyridine with 2-vinylquinoline in any desired proportions, as well as copolymers of three, four, or more of these polymerizable materials. Copolymers of vinylpyridines with other monoethylenically unsaturated monomers, such as styrene, ethylene or propylene are also operative in the case of the Z-component fibers."
The (C) component of the 3component fiber (anionic dyeable) used in this invention is selected from the following groups of compounds:
1. Polyethylene glycol (also referred to herein as PEG) having a degree of polymerization of at least 4;
2. Copolymers of ethylene oxide with other alkylene oxides, having a degree of polymerization of the ethylene oxide units of at least 4 and containing a minimum of 60 percent by weight ethylene oxide. These compounds are exemplified by the series of block copolymers produced by condensing ethylene oxide with a product formed by the condensation of propylene oxide with propylene glycol (formula of such copolymers: HO-(Ql-LO) (C l-I 0) (C H O) H and sold under the trademark Pluronic). Other useful copolymers are derived from the polymerization of ethylene oxide and propylene oxide;
3. Derivatives of polyethylene glycol, such as its ethers and esters having a degree of polymerization of ethylene oxide of at least 4 and an ethylene oxide content of at least 60 percent by weight. Examples of such derivatives are: (a) polyethylene glycol alkyl ethers; (b) alkylaryl polyethoxyalcohols sold under the trademark lriton (the octylphenylpolyethoxy ethanol series); (c) polyoxyethylene derivatives of long-chain fatty-acid esters of hexitol anhydrides including sorbitans, sorbides, mannitans and mannides, such as polyethylene glycol hexitol carboxylates, polyoxyethylene sorbitan monolaurate sold under the trademark Tween 20" and polyoxyethylene sorbitan monostearate; and polyethylene glycol carboxylate esters such as polyethylene glycol monostearate and polyethylene glycol distearate.
Additional colors can be obtained in the present invention by varying the composition of the two-component" or three-component" fibers. Such variation may include: (1) varying the type and/or amount of polyolefin; (2) varying the chemical structure and/or amount of the dye receptor polymer; (3) varying the chemical structure and/or amount of the hydrophilic compound used in the three-component" fiber. In order to describe the present invention most conveniently, only the achievement of a two-color combination is exemplified herein, but this in no way should be inferred as a limitation of the scope of the present invention.
When a textile article such as a fabric or carpet pile is assembled, whether by weaving, tufting, knitting, felting, hool ing or other means, from the two classes of yarns described, which may optionally include uncolored nondye receptorcontaining or pigmented polyolefin fibers, and dyed with a mixture of an anionic dye and a disperse dye in the present of a nonionic surfactant or in mixture of a nonionic and an anionic surfactant, only those portions of the fabric made of the three-component fibers will be dyed by anionic dyes. These same three-component fibers will also be dyed by disperse dyes. On the other hand, the portion of the fabric composed of two-component fibers will remain essentially undyed by the anionic dyes, and therefore will only be dyed by disperse dyes, lf included in the textile article, the nondye receptor containing yarns will remain undyed. By choosing anionic dyes of certain colors and disperse dyes of difi'erent colors, the fabrics containing combinations of the abovedescribed two-component" and three-component" yarns can be conveniently dyed to a two-color or multicolor pattern, in a single dyeing step, in which the fabric is exposed to the above mixture of anionic and disperse dyes.
Although the two-component fiber" is essentially undycable with anionic dyes by conventional dyeing procedures using a nonionic surfactant in the dyebath, some staining (i.e., a slight takeup of dye on the surface of the fiber) will occur with anionic dyes. This may be undesirable in cases where staining decreases a desired contrast in the color of the two classes of yarns dyed with a mixture of anionic and disperse dyes.
A further feature of the present invention is the discovery of certain surfactant compositions used in the dyeing of articles composed of the above-described polyolefin yarns which are dyeable with anionic and/or disperse dyes. These compositions facilitate the production of multicolor patterns by increasing the color contrasts obtainable with the two classes of fibers previously described. These surfactant compositions are mixtures of anionic and nonionic surfactants which are applied to the yarn in an acidic dyebath.
According to copending Pat. application Ser. No. 705,303, anionic surfactants used in the dyebath greatly enhance the uptake of anionic dyes of both two-component fibers" and three-component fibers. Nonionic surfactants have little effect on the dye uptake of the three-component fiber and virtually no effect on the dye uptake of the two-component fiber. Likewise, the nature of the surfactant has in general little, if any effect on the dye uptake of disperse dyes.
Surprisingly, a mixture of anionic and nonionic surfactants increases the dye uptake of the three-component fiber while having little or no effect on the dye uptake of the twocomponent fiber, when both fibers are dyed simultaneously in the same dyebath. The color contrast obtained in dyeing with this mixture of surfactants is greater than that obtainable with either anionic or nonionic surfactants alone. This is a very important factor in the styling of multicolor pattern fabrics or yarns.
The anionic component of the mixture of surfactants has the general formula (R-A) wherein R represents a hydrophobic group which is either a substituted or nonsubstituted alkyl, aryl or alkylaryl group having 6 or more carbon atoms (preferably between 9 and 40 carbon atoms) per A group; and A is an anionic group exemplified by one or more of the fol- Commercial Name Chemical Description Sodium laurylsulfate C H SO Na Sodium tetradecylsulfate C H SO Na Sodium cetylsulfate C H SQNB Aerosol TR Bis(tridecyl)ester of sodium aulfosuccinic acid Aerosol OT Dioctyl ester of sodium sulfosuccinic acid Aerosol A! Diamyl ester of sodium sulfowccinic acid Victawet 35B (Z-ethylhexyl ),Na,( P 0 Barisol Super BRM Aliphatic phosphated ester Alkapent CC Aliphatic phosphated ester, acid form Alkapent M60 Aromatic phosphated ester, acid form Chemsol 700-5 Modified organic phosphated ester Chcmsol 935-N Phosphated ester of long chain fatty alcohol Estranol CP Alkyl phosphate Alkapent A Aliphatic phosphated ester, free acid Gafac IRS-610 Phosphated ester Gafac LO-529 Sodium salt of a phosphated ester Zelek UN Fatty alcohol phosphate Diethanolamirre salt of a l:l mixture of monoand di-fatty alcohol phosphates (made from the fatty alcohols and P,O,)
Solar 25 Coconut oil fatty acid amine Laureltcx 802 condensate Potassium salt of a phosphate alcohol Rozak BD-IOO Phosphated ethoxylated oleyl-alcohol Fosterge LF Acid Organo-phospho-acid Seycopen BB Phosphated polyalcohol Crestol Phosphated complex alcohol Warcosol NF/3 Complex of sulfonated polyester and phosphated alcohol Surfactant 08-44 Detergent 9294 Phosphated ester, free acid Anionic phosphate ester Seyco Phosphonic Acid Aromatic phosphsted ester, free acid The nonionic surfactants are the conventional ones represented by the general formula R-O-X-H wherein R represents a hydrophobic group which is either a substituted or unsubstituted alkyl, aryl or alkylaryl group having 6 or more carbon atoms (preferably between 9 and 40 carbon atoms); X represents a nonionic hydrophilic group such as homopolymers of ethylene oxide or propylene oxide or copolymers of these materials with each other, with a degree of polymerization of alkylene oxide units between 1 and 100, preferably between 3 and 50; O and H are oxygen and hydrogen respectively. In addition to the compounds listed above, operative nonionic surfactants in the present invention are copolymers of ethylene oxide with other alkylene oxides, polyoxyalkylene glycol esters, fatty amide condensates, alkanolamides, etc. Some of these nonionic surfactants, such as some of the ester types, may hydrolyze in an acidic dyebath, yielding the free acid, which may behave as an anionic surfactant. Such materials are not recommended for use in the process of this invention as nonionic components of the surfactant mixture. Examples of nonionic surfactants suitable for use in this invention are:
Commercial Name Chemical Description Triton X45 Octylphenol-(CH,CH,O), Triton X- Octylphcnol-(CH CH,O) li Triton X-305 Octylphenol-(CH,CH,0), H
Tergitol 15-S-9 Pluronics The ratio (A/N) of the weight of anionic surfactant (A) to that of the weight of the nonionic surfactant (N) has an effect 5 on the contrast of shades obtainable with the two classes of fibers. This ratio of the weight of A to N depends upon the structure of both anionic and nonionic surfactants, the numerical value of said ratio varying between about 0.1 and 5. A ratio close to 1:1 is often satisfactory in the process of this invention. The total amount of anionic and nonionic surfactant required in the dyebath is between 0.5 and percent owg (on the weight of the goods), preferably between 1 and 6 percent owg.
the basic teachings of said examples may be varied by one skilled in the art.
EXAMPLE 1 Three parts of a 1:1 copolymer (by weight) of 2-vinylpyridine and Zmethyl-S-vinylpyridine (prepared by suspension polymerization using azo-bis-isobutyronitrile as initiator, and having intrinsic viscosity 0.9 measured in pyridine at 30 C.) were blended in an extruder at 500 F. with 100 parts of isotactic polypropylene (melt index 5 6 and the resultant blend was chopped into pellets and dried. The pellets were then melt extruded at 530 F. into a 156-filament yarn using a conventional melt-spinning apparatus. The resultant yarn was drawn 4:1 at 275 F. and texturized to yield a final yarn of 22 The dyes suitable for use in this invention fall into two denier/filament. The tenacity ofthe yam was 3.1 grams/denier categories. One category is the broad group of anionic dyes, a d "8 ga i n at r ak was 35 percent- This yam is which includes the so-called strong acid dyes, direct dyes, and referred to in the examples herein as the two-component the premetallized dyes. They dye only the above-described fiber."
three-component fibers." The other category is the disperse Another yarn, made from a blend of three parts of the 1:1 dyes which dye both the three-component fibers" and twocopolymer of 2-vinylpyridine and 2-methyl-5-vinylpyridine, component fibers." two parts of polyethylene glycol of 600,000 molecular weight Some of the strong acid dyes useful in the present invention and one hundred (100) parts of isotactic polypropylene was are typified by the following: prepared by the same process as described above. This yarn is Acid Yellow 23 1 4 25 referred to in the examples herein as three-component Acid Orange 7 (CI. No. 15510) fiber."
Acid Red 73 27290) Alternate rows of two-" and three-component fiber Acid Blue 45 63010) yarns were tufted into a jute fabric carpet backing in a level Acid Blue 78 (CI. No. 62105) pile design Other useful anionic dyes are the acid metallized dyes, Six samples of the tufted carpet were then dyed with various yp y combinations of anionic and disperse dyes using the following Acid Yellow 54 NO. 19010) procedure;
Acid Orange 72 18740) The samples of tufted carpet were first prescoured with an Acid Red 186 (Cl 18810) aqueous solution containing 1 percent owg (on the weight of AidB1ue158(Cl-N0- 14380) the goods) Triton X-100 (an octylphenol condensate with Still other anionic y are the neutral metallized y 9-10 moles of ethylene oxide) and 1 percent owg sodium car- YP y the following: bonate for 20 minutes at 180 F using a 30:1 bath to fiber Acid Yellow 121 (C1 18690) ratio. The samples were then dyed for 45 minutes in an aque- Acid Orange 60 (The half-Chr QOmPIeX 0f 'p y ous dyebath at 200 F. containing 3 percent owg acetic acid, 1
methyl4'(zhydmxyssulfamoyl PhenylaZ)5' 40 percent owg of a nonionic surfactant having the formula P c n mcn cn o n and various combinations of f Red 209 anionic and disperse dyes as listed in table I. The bath to fabric Acid Blue 168 ratio was 30:1. After dyeing, the samples were postscoured for Examples 5 33? the direct dyes useful m the present 15 minutes at 160 F. with an aqueous solution of 0.5 percent mveimon are e o owmg: ow Triton X-100. D ed c ets having alternate rows of two Dlrect Yellow 44 (CL 29000) difiirent colors result d as il e cribed in table 1. g
TABLE I Color of the dyed fibers Percent Percent Sample Anionic dye owg Disperse dye owg 2-component 3-comp0nent 1 --{6lili;f' 3:2 fiilil orofifilitfiiiiii '1 331 l Brown- 2 Carbolan Blue 2G8 1.0 Calcosperse Yellow 4RD 0.7 Yellow Green. 3.... 0.76 Foron Blue R 0.75 Blue-.- Brown. 4... 0. 7 Calcosyn Blue RP 1.0 Blue..- Brown. 5.. 1.0 Calcosyn Sapphire Blue R 1.5 Blue-.- Brown. 6. 0. 7 Polydye Yellow GSF 1.0 Yellow Green.
Direct Blue 67 (Cl. No. 27925) Other categories of anionic dyes which are applicable to out invention are the reactive dyes, typified by Reactive Orange 1, and the mordant acid dyes, typified by Mordant Red 3 (Cl. No. 58005).
The following are examples of some of the disperse dyes which are useful in this invention:
Latyl Yellow 4R1. (C.l. No. 26070) Latyl Orange 3R (Color Index Disperse Orange 21 Cibacete Brilliant Pink FG (Color Index Disperse Red lnterchem Blue RLF 40 (Cl. No. 61 1 15) To illustrate the novel textile articles and their methods of preparation, the following examples are given. It should be understood that these examples are merely illustrative and are not to be regarded as limitations to the appended claims. since 75 EXAMPLE 3 Five samples of tufted carpet made according to the procedure described in example 1 were dyed by the procedure described in example 2, using mixtures of difierent types of anionic and nonionic surfactants in the dyebath and only an anionic dye, as listed in table Il. The resultant dyed carpet samples had rows of three-component fiber" yarns which were deeply colored, whereas the rows of two-component fiber yarns showed little or no uptake of dye.
When these dyeings were repeated on other samples of tufted carpet using either the anionic surfactant or the nonionic surfactant alone (not both), the contrast in color between adjacent rows of two-component yarns and threecomponent yarns was not as pronounced as the color contrast obtained in said rows with the use of both the anionic and the nonionic surfactant. When only an anionic surfactant was used, a reduced contrast was observed, which was caused by increased pickup of anionic dye by the two-component yarn." Reduced contrast was also observed with use of the nonionic surfactant alone, due to reduced dye uptake by the "three-component yarn in comparison to the uptake with the mixed surfactant system.
Having thus described our invention, what we claim and desire to protect by Letters Patent is:
l. A filamentary assembly suitable for dyeing to a mu]- ticolor pattern through exposure to a mixture of anionic and disperse dyes, said filamentary assembly containing a plurality of synthetic fibers, at least one of said fibers having been formed from a mixture comprising (A) an alpha-monoolefin polymer, and (B) between about i and 5 percent by weight on TABLE II Amount Amount (percent (percent Sample Dye (3% owg) Anionic surfactant owg) N anionic surfactant owg) 7 Anthraquinone Blue SKY Aerosol 0T 1 C 3H27O(CHzCHzO)9H 6 do Fatty alcohol phosphate 1 CrgHmO(CHzCHz-O)9H 3 -do C12H250-(CHz-OHO)7CH2COONa 1 Plurom'e L-122 3 1 Copracyl Orange R Sodium dodecylsulfate 1 Triton X305 4 l 4 dO e C12H25O-(CHzCHzO)1-CH2COONB 2 Triton X-100s 2 1 Dioctyl ester of sodium sullosuccinlc acid.
2 Diothanolamino salt of con nt.
4 Octylphenol condensate with moles of ethylene oxide. lgctylphenol eondonsnte wifiljlgnples ot cthyloneoxide.
EXAMPLE 4 Three parts of poly(2-vinylpyn'dine) (prepared by suspension polymerization as described in example I) were milled at 320 F. with two parts of the following hydrophilic compounds:
a. monomethyl ether of poly(ethylene glycol) (PEG), 550
molecular weight (M .W.
b. octylphenol ether of PEG, 1,320 M.W.;
c. polyoxyethylene sorbitan monostearate of 1,350 M.W.;
d. ethylene oxide propylene oxide alternating copolymer of 2,600 MW. and 75 percent (by weight) ethylene oxide content;
e. PEG 400 M.W.
Five parts of each of the milled samples were then milled at 360 F. into separate batches of isotactic polypropylene contruded at 500 F. into 8-filament yarns, and drawn 4:1 at 275 F to yield 15 denier/filament three-component yarns."
A two-component yarn, containing three parts of poly(2- vinylpyridine) and 100 parts of isotactic polypropylene was prepared similarly.
Skeins of the two types of yarns were dyed as in example 1 in a single dyebath containing 1.5 percent owg Capracyl Orange R and 3 percent owg lnterchem Blue RLF 40 The two-component yarn" dyed to a medium blue and the three-component yarn dyed to a bluish-brown shade.
EXAMPLE 5 three-component yarn" resultant colors obtained were brighter and the contrast between the two-component yarn and the three-component yarn" was more pronounced than the corresponding a 1:1 mixture of monoand dHatty alcohol phosphates (made from the fatty alcohols plus P). :A poly(ethylene glycoD-poly (propylene glycol) block copolymer having a molecular weight or 4,900 and 20% (by weight) poly(ethylene glycol) o weight of the fiber of a vinyl pyridine or vinyl quinoline dye receptor polymer, and at least one other fiber having been formed from a mixture comprising (A) less than 97 percent by weight of an alpha-monoolefin polymer, (B) between about 0.5 and 5 percent by weight of a vinyl pyridine or vinyl quinoline dye receptor polymer and (C) between about 0.5 and 5 percent by weight of a hydrophilic compound which is a homopolymer of ethylene oxide, or an alkyl ether or allcyl ester derivative thereof, or copolymer of ethylene oxide with an alkylene oxide other than ethylene oxide, said hydrophilic compound having a degree of polymerization not less than 4 and an ethylene oxide content not less than 60 percent by weight, and wherein the total amount of the (B) and (C) components in said fiber is greater than 3 percent by weight, with the result that said fiber containing (A) and (B) only in said filamentary assembly is dyeable with disperse dyes and said fiber containing (A), (B) and (C) in said filamentary assembly is dyeable with both the anionic and disperse dyes, thereby giving said assembly when dyed with anionic and disperse dyes in a single dye bath a variegated color effect.
2. A filamentary assembly as defined in claim 1 which is a yarn.
3. A filamentary assembly as defined in claim 1 which is a f bric. l r h l A...
4. A carpet which contains the filamentary assembly as defined in claim 1.
5. The filamentary assembly defined in claim 1 in which the alpha-monoolefin polymers in the twoand three-component fibers are selected from the group consisting of: polyethylene, polypropylene, poly(3-methyl-l-butene) or poly(4-methyi-lpentene).
6. The filamentary assembly defined in claim 5 in which the pyridine-type polymer in the two-component fiber is selected from the group consisting of homopolymers of (a) vinylpyridines, (b) alkylvinylpyridines, (c) vinylquinolines, (d) alkylvinylquinolines, (e) copolymers of vinylpyridine monomers with alkylvinylpyridine monomers, (f) copolymers of vinylpyridine monomers with a monoethylenically unsaturated monomer; and the pyridine-type polymer in the three-component fiber is selected from the group consisting of homopolymers of(a), (b), (c), (d) and copolymers of(e).
7. The filamentary assembly defined in claim 6 in which the derivatives of polyethylene glycol are selected from the group consisting of (a) polyethylene glycol alkyl ethers (b) alkylaryl polyethoxy alcohols, (c) polyethylene glycol hexitol carboxylates and (d) polyethylene glycol carboxylates.
8. The filamentary assembly defined in claim 7 which also contains an uncolored nondye receptor containing alphamonoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
Q. The filamentary assembly defined in claim 7 which also contains a pigmented alpha-monoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
10. The filamentary assembly defined in claim 7 in which the pyridine-type dye receptor polymers are selected from the group consisting of a. poly( 2-vinylpyridine) b. poly(2-methyl-5-vinylpyridine) c. poly(4-vinylpyridine) d. poly(2-vinylquinoline) e. the copolymer of 2-vinylpyridine and 2-methyl-5-vinylpyridine f. the copolymer of 2-vinylpyridine and styrene in the case of the two-component fibers g. the copolymer of 2-methyl-5-vinylpyridine and styrene in the case of two-component fibers 11. The filamentary assembly defined in claim 10 in which the homopolymer of ethylene glycol has a molecular weight between 100,000 and 7,000,000.
12. The filamentary assembly defined in claim 1 in which a. the alpha-monoolefin polymer is polypropylene,
b. the pyridine-type dye receptor polymer is the copolymer of 2-methyl-5-vinylpyridine and 2-vinylpyridine, and
c. the polyethylene glycol homopolymer has a molecular weight between 100,000 and 7,000,000.
13. The filamentary assembly defined in claim 1 in which a. the alpha-monoolefin polymer is polypropylene,
b. the pyridine-type dye receptor polymer in the two component fiber is a copolymer of styrene and 2-vinylpyridine, and the pyridine-type dye receptor polymer in the three-component fiber is a copolymer of 2-methyl-5- vinylpyridine and 2-vinylpyridine, and
c. the polyethylene glycol homopolymer has molecular weight between about 100,000 and 7,000,000.
14. The filamentary assembly defined in claim 1 which has been contacted with a mixture of anionic and nonionic surfactants under acidic conditions in the mixture of anionic and disperse dyes, to enhance the uptake of anionic dyes by the three-component fiber thus increasing the color contrast between said dyed two-component and three-component fibers thus dyed.
15. The filamentary assembly defined in claim 14 in which the weight ratio of anionic surfactant to nonionic surfactant in the dyebath is between about 0.1 and 5.
16. The filamentary assembly defined in claim 14 in which the total amount of anionic and nonionic surfactants in the dyebath is between about 0.5 and 10 percent on the weight of the goods (owg).
ll The filamentary assembly defined in claim 14 in which the anionic surfactant has the general formula R-A wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having at least six carbon atoms and A represents an anionic group selected from (a) sulfonate, (b) sulfate, (c) phosphate, (:1) polyphosphate or (e) carboxylate, said group being in free acid or salt form.
118. The filamentary assembly defined in claim 17 in which the nonionic surfactant has the general formula R-O-X-l-l wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having six or more carbon atoms,
0 represents oxygen,
X represents homopolymers of ethylene oxide, or propylene oxide or copolymers of said oxides with each other, all of said polymers having a degree of polymerization of alkylene oxide units between 1 and 100.
H represents hydrogen.
19. The filamentary assembly defined in claim 17 in which the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide.
20. A process for dyeing the filamentary assembly defined in claim 1 to a multicolor pattern of high-color contrast comprising exposing said filamentary assembly to a mixture of anionic and nonionic surfactants under acidic conditions in the presence of a mixture of anionic and disperse dyes.
21. A process for dyeing as defined in claim 20 in which the filamentary assembly is a yarn.
22. A process for dyeing as defined in claim 20 in which the filamentary assembly is a fabric.
23. A process for dyeing as defined in claim 20 in which the filamentary assembly is contained in a carpet.

Claims (22)

  1. 2. A filamentary assembly as defined in claim 1 which is a yarn.
  2. 3. A filamentary assembly as defined in claim 1 which is a fabric.
  3. 4. A carpet which contains the filamentary assembly as defined in claim 1.
  4. 5. The filamentary assembly defined in claim 1 in which the alpha-monoolefin polymers in the two- and three-component fibers are selected from the group consisting of: polyethylene, polypropylene, poly(3-methyl-1-butene) or poly(4-methyl-1-pentene).
  5. 6. The filamentary assembly defined in claim 5 in which the pyridine-type polymer in the two-component fiber is selected from the group consisting of homopolymers of (a) vinylpyridines, (b) alkylvinylpyridines, (c) vinylquinolines, (d) alkylvinylquinolines, (e) copolymers of vinylpyridine monomers with alkylvinylpyridine monomers, (f) copolymers of vinylpyridine monomers with a monoethylenically unsaturated moNomer; and the pyridine-type polymer in the three-component fiber is selected from the group consisting of homopolymers of (a), (b), (c), (d) and copolymers of (e).
  6. 7. The filamentary assembly defined in claim 6 in which the derivatives of polyethylene glycol are selected from the group consisting of (a) polyethylene glycol alkyl ethers (b) alkylaryl polyethoxy alcohols, (c) polyethylene glycol hexitol carboxylates and (d) polyethylene glycol carboxylates.
  7. 8. The filamentary assembly defined in claim 7 which also contains an uncolored nondye receptor containing alpha-monoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
  8. 9. The filamentary assembly defined in claim 7 which also contains a pigmented alpha-monoolefin fiber which is not susceptible to dyeing by said anionic and disperse dyes.
  9. 10. The filamentary assembly defined in claim 7 in which the pyridine-type dye receptor polymers are selected from the group consisting of a. poly(2-vinylpyridine) b. poly(2-methyl-5-vinylpyridine) c. poly(4-vinylpyridine) d. poly(2-vinylquinoline) e. the copolymer of 2-vinylpyridine and 2-methyl-5-vinylpyridine f. the copolymer of 2-vinylpyridine and styrene in the case of the two-component fibers g. the copolymer of 2-methyl-5-vinylpyridine and styrene in the case of two-component fibers
  10. 11. The filamentary assembly defined in claim 10 in which the homopolymer of ethylene glycol has a molecular weight between 100,000 and 7,000,000.
  11. 12. The filamentary assembly defined in claim 1 in which a. the alpha-monoolefin polymer is polypropylene, b. the pyridine-type dye receptor polymer is the copolymer of 2-methyl-5-vinylpyridine and 2-vinylpyridine, and c. the polyethylene glycol homopolymer has a molecular weight between 100,000 and 7,000,000.
  12. 13. The filamentary assembly defined in claim 1 in which a. the alpha-monoolefin polymer is polypropylene, b. the pyridine-type dye receptor polymer in the two-component fiber is a copolymer of styrene and 2-vinylpyridine, and the pyridine-type dye receptor polymer in the three-component fiber is a copolymer of 2-methyl-5-vinylpyridine and 2-vinylpyridine, and c. the polyethylene glycol homopolymer has molecular weight between about 100,000 and 7,000,000.
  13. 14. The filamentary assembly defined in claim 1 which has been contacted with a mixture of anionic and nonionic surfactants under acidic conditions in the mixture of anionic and disperse dyes, to enhance the uptake of anionic dyes by the three-component fiber thus increasing the color contrast between said dyed two-component and three-component fibers thus dyed.
  14. 15. The filamentary assembly defined in claim 14 in which the weight ratio of anionic surfactant to nonionic surfactant in the dyebath is between about 0.1 and 5.
  15. 16. The filamentary assembly defined in claim 14 in which the total amount of anionic and nonionic surfactants in the dyebath is between about 0.5 and 10 percent on the weight of the goods (owg).
  16. 17. The filamentary assembly defined in claim 14 in which the anionic surfactant has the general formula R-A wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having at least six carbon atoms and A represents an anionic group selected from (a) sulfonate, (b) sulfate, (c) phosphate, (d) polyphosphate or (e) carboxylate, said group being in free acid or salt form.
  17. 18. The filamentary assembly defined in claim 17 in which the nonionic surfactant has the general formula R-O-X-H wherein R represents a substituted or unsubstituted alkyl, aryl, or alkylaryl group having six or more carbon atoms, O represents oxygen, X represents homopolymers of ethylene oxide, or propylene oxide or copolymers of said oxideS with each other, all of said polymers having a degree of polymerization of alkylene oxide units between 1 and 100. H represents hydrogen.
  18. 19. The filamentary assembly defined in claim 17 in which the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide.
  19. 20. A process for dyeing the filamentary assembly defined in claim 1 to a multicolor pattern of high-color contrast comprising exposing said filamentary assembly to a mixture of anionic and nonionic surfactants under acidic conditions in the presence of a mixture of anionic and disperse dyes.
  20. 21. A process for dyeing as defined in claim 20 in which the filamentary assembly is a yarn.
  21. 22. A process for dyeing as defined in claim 20 in which the filamentary assembly is a fabric.
  22. 23. A process for dyeing as defined in claim 20 in which the filamentary assembly is contained in a carpet.
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US3957425A (en) * 1974-04-19 1976-05-18 E. I. Du Pont De Nemours And Company Concentrated acid red 151 dye-surfactant solution of 15 to 25%
US4059949A (en) * 1974-02-15 1977-11-29 E. I. Du Pont De Nemours And Company Sheath-core cospun heather yarns
US4131422A (en) * 1977-02-22 1978-12-26 Milliken Research Corporation Polymer-printed fabric and method for producing same
US4167847A (en) * 1977-02-23 1979-09-18 Toray Industries, Inc. Bulky yarn and method for producing the same
US20050153133A1 (en) * 2002-10-08 2005-07-14 Negola Edward J. Dyed olefin yarn and textile fabrics using such yarns
US20050217037A1 (en) * 2002-10-08 2005-10-06 Negola Edward J Dyed polyolefin yarn and textile fabrics using such yarns
US20100122486A1 (en) * 2008-11-17 2010-05-20 Osada Fishing Net Co., Ltd. Method for producing fishing net and fishing net produced by the method
US8759430B1 (en) 2010-06-02 2014-06-24 Aquadye Fibers, Inc. Acid dyed polyester (PET) or olefin yarns and textile fabrics using such yarns
JP2021112236A (en) * 2020-01-16 2021-08-05 孝和 松木 Men's etiquette sheet

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DE19623030A1 (en) * 1996-06-08 1997-12-11 Pfeiffer Erich Gmbh & Co Kg Discharge unit for media

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US3150917A (en) * 1962-04-23 1964-09-29 Gagliardi Domenick Donald Treatment of polyolefin articles and resulting products
US3315014A (en) * 1960-02-04 1967-04-18 Uniroyal Inc Dyeable polypropylene fibers containing polymers of vinyl pyridines
US3316328A (en) * 1961-04-04 1967-04-25 Iowa Mfg Company Stereoregular polyolefin compositions
US3329557A (en) * 1955-04-06 1967-07-04 Du Pont Static resistant filament and process therefor
US3361843A (en) * 1964-06-15 1968-01-02 Uniroyal Inc Method of dyeing a blend of a polyolefin and a nitrogen containing polymer by using a dyebath containing lewis acids
US3530201A (en) * 1966-12-06 1970-09-22 Uniroyal Inc Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide

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US3329557A (en) * 1955-04-06 1967-07-04 Du Pont Static resistant filament and process therefor
US3315014A (en) * 1960-02-04 1967-04-18 Uniroyal Inc Dyeable polypropylene fibers containing polymers of vinyl pyridines
US3316328A (en) * 1961-04-04 1967-04-25 Iowa Mfg Company Stereoregular polyolefin compositions
US3150917A (en) * 1962-04-23 1964-09-29 Gagliardi Domenick Donald Treatment of polyolefin articles and resulting products
US3361843A (en) * 1964-06-15 1968-01-02 Uniroyal Inc Method of dyeing a blend of a polyolefin and a nitrogen containing polymer by using a dyebath containing lewis acids
US3530201A (en) * 1966-12-06 1970-09-22 Uniroyal Inc Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059949A (en) * 1974-02-15 1977-11-29 E. I. Du Pont De Nemours And Company Sheath-core cospun heather yarns
US3957425A (en) * 1974-04-19 1976-05-18 E. I. Du Pont De Nemours And Company Concentrated acid red 151 dye-surfactant solution of 15 to 25%
US4063880A (en) * 1974-04-19 1977-12-20 E. I. Du Pont De Nemours And Company Concentrated disazo dye-surfactant solution
US4131422A (en) * 1977-02-22 1978-12-26 Milliken Research Corporation Polymer-printed fabric and method for producing same
US4167847A (en) * 1977-02-23 1979-09-18 Toray Industries, Inc. Bulky yarn and method for producing the same
US20050153133A1 (en) * 2002-10-08 2005-07-14 Negola Edward J. Dyed olefin yarn and textile fabrics using such yarns
US20050217037A1 (en) * 2002-10-08 2005-10-06 Negola Edward J Dyed polyolefin yarn and textile fabrics using such yarns
US7335417B2 (en) 2002-10-08 2008-02-26 Aquadye Fibers, Inc. Dyed olefin yarn and textile fabrics using such yarns
US20100122486A1 (en) * 2008-11-17 2010-05-20 Osada Fishing Net Co., Ltd. Method for producing fishing net and fishing net produced by the method
US9295240B2 (en) * 2008-11-17 2016-03-29 Osada Fishing Net Co., Ltd. Method for producing fishing net and fishing net produced by the method
US8759430B1 (en) 2010-06-02 2014-06-24 Aquadye Fibers, Inc. Acid dyed polyester (PET) or olefin yarns and textile fabrics using such yarns
JP2021112236A (en) * 2020-01-16 2021-08-05 孝和 松木 Men's etiquette sheet

Also Published As

Publication number Publication date
BE730546A (en) 1969-09-29
FR2010797A7 (en) 1970-02-20
NL6908864A (en) 1969-12-16
DE1904137A1 (en) 1970-02-05

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