BACKGROUND

[0001] Color has been applied to textiles over the ages. Natural colorants derived from plants and earthen surroundings were used before a dyestuff industry came into being. Issues with dye fixation, durability, light fastness, colorfastness, and depth of color are challenges.

[0002] Attempts to create "ring dyed" yarns have resulted in lengthy processing and poor performance. The most common and prevalent technique is that of indigo dyeing to produce denim. By multiple steps of dipping and oxidizing the dye onto yarn, the dye penetrates only partially into the yarn bundle. The resultant "ring dyeing" creates light and dark highlights on abrasion points once a garment is sewn and processed using chemical and physical abrasive means before and during a laundering process.

[0003] Ring dyeing has been further attempted with the application of pigment dyes mixed with binders. This approach has resulted in fabric with stiff handle and marginal rub- fastness performance. Even with advances to improve performance, color choice and depth of shade versus rub fastness performance remain challenging.

SUMMARY

[0004] The following presents a simplified summary of one or more embodiments of the invention in order to provide a basic understanding of such embodiments. This summary is not an extensive overview of all contemplated embodiments, and is intended to neither identify key or critical elements of all embodiments, nor delineate the scope of any or all embodiments. Its sole purpose is to present some concepts of one or more embodiments in a simplified form as a prelude to the more detailed description that is presented later.

[0005] In a first embodiment, a ring dyed yarn is provided, where the ring dyed yarn includes at least one fiber and a polymer-dye matrix positioned adjacent to a surface portion of the at least one fiber, the polymer-dye matrix comprising a polymer layer and a reactive dye positioned between the polymer layer and the surface portion of the at least one fiber.

[0006] In a first aspect of the first embodiment, the reactive dye is fixed to at least a portion of the surface portion of the at least one fiber. [0007] In a second aspect, alone or in combination with the first aspect of the first embodiment, the polymer layer comprises at least one of a urethane based polymer and an acrylic polymer

[0008] In a third aspect, alone or in combination with any of the previous aspects of the first embodiment, the urethane based polymer has a glass transition temperature (Tg) of -65 °C to 70 °C.

[0009] In a fourth aspect, alone or in combination with any of the previous aspects of the first embodiment, the reactive dye comprises at least one of triazine derivatives, pyridimine derivatives, quinoxaline derivatives, and activated vinyl compounds.

[0010] In a fifth aspect, alone or in combination with any of the previous aspects of the first embodiment, the yarn comprises at least one material selected from the group consisting of cotton, cellulose acetate, polyamide, para-aramid, wool, and polyester.

[0011] In a sixth aspect, alone or in combination with any of the previous aspects of the first embodiment, wherein an inner portion of the yarn is substantially free of the reactive dye.

[0012] In a second embodiment, a fabric is provided, where the fabric includes fibers and a polymer-dye matrix positioned adjacent to a surface portion of the fibers, the polymer-dye matrix comprising a polymer layer and a reactive dye positioned between the polymer layer and the surface portion of the fibers.

[0013] In a first aspect of the second embodiment, the fabric comprises denim.

[0014] In a second aspect of the second embodiment, alone or in combination with the first aspect of the second embodiment, the fibers comprise at least one of cotton fibers and synthetic fibers.

[0015] In a third aspect, alone or in combination with any of the previous aspects of the second embodiment, the fabric includes a flame retardant agent.

[0016] In a fourth aspect, alone or in combination with any of the previous aspects of the second embodiment, the polymer layer comprises a urethane based polymer having a glass transition temperature (Tg) from about -50 °C to about -20 °C.

[0017] In a fifth aspect, alone or in combination with any of the previous aspects of the second embodiment, the percent solids on fabric ratio of polymer to reactive dye is at least 1.3: 1. [0018] In a sixth aspect, alone or in combination with any of the previous aspects of the second embodiment, the fabric has a dry crocking of at least 5.0 and a wet crocking of at least 5.0 in accordance with AATCC Test Method 8.

[0019] In a seventh aspect, alone or in combination with any of the previous aspects of the second embodiment, the fabric has a lightfastness of at least 4.5 at 20 hours and a

lightfastness of at least 4.5 at 40 hours in accordance with AATCC Test Method 16A.

[0020] In a third embodiment, a garment is provided, where the garment includes fabric comprising fibers and a polymer-dye matrix positioned adjacent to a surface portion of the fibers, the polymer-dye matrix comprising a polymer layer and a reactive dye positioned between the polymer layer and the surface portion of the fibers.

[0021] In a fourth embodiment, a method of producing a ring dyed substrate is provided, the method comprising providing fibers; depositing a polymer-dye composition on at least a portion of the fibers, the polymer-dye composition comprising an aqueous mixture of a polymer and a reactive dye; heating the treated fibers such that the polymer-dye composition moves to the surface of the fibers; depositing an alkaline salt mixture to the fibers; and fixing the reactive fiber to the surface of the fibers in response to the alkaline salt mixture deposition.

[0022] In a first aspect of the fourth embodiment, the substrate comprises yarn.

[0023] In a second aspect, alone or in combination with the first aspect of the fourth embodiment, the method further includes forming a fabric from the yarn.

[0024] In a third aspect, alone or in combination with any of the previous aspects of the fourth embodiment, the substrate comprises at least one of a fabric or garment.

[0025] In a fourth aspect, alone or in combination with any of the previous aspects of the fourth embodiment, the heated fibers reach at least 240° F.

[0026] In a fifth aspect, alone or in combination with any of the previous aspects of the fourth embodiment, abrading at least a portion of the surface of the garment to remove at least some of the dye such that the garment has first areas comprising fibers that comprise the dye and second areas comprising fibers that do not include the dye.

[0027] In a fifth embodiment, a chemical composition for a ring dyed material is provided, where, the composition includes a urethane based polymer and a reactive dye preferentially attracted to the urethane. [0028] Other aspects and features, as recited by the claims, will become apparent to those skilled in the art upon review of the following non-limited detailed description of the invention in conjunction with the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Having thus described embodiments of the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:

[0030] FIG. 1 is a diagram illustrating a process for preparing a ring dyed substrate, in accordance with an embodiment of the disclosure;

[0031] FIG. 2A is a cross-sectional view of the fiber in FIG. 1 at one stage of the process in accordance with the various embodiments;

[0032] FIG. 2B is a cross-sectional view of the fiber in FIG. 1 at one stage of the process in accordance with the various embodiments;

[0033] FIG. 2C is a cross-sectional view of the fiber in FIG. 1 at one stage of the process in accordance with the various embodiments;

[0034] FIG. 3 is a front elevation view of a fabric and enlarged view of a portion of the fabric in accordance with the various embodiments;

[0035] FIG. 4 is a front elevation view of a fabric and enlarged view of a portion of the fabric in accordance with the various embodiments; and

[0036] FIG. 5 is a block diagram illustrate a process of producing a ring dyed substrate in accordance with the various embodiments;

DETAILED DESCRIPTION

[0037] Embodiments of the present invention will now be described more fully with reference to the accompanying examples and drawings, in which some, but not all, embodiments of the invention are shown. Indeed, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these

embodiments are provided so that this disclosure may satisfy applicable legal requirements. Like numbers refer to like elements throughout. [0038] Where possible, any terms expressed in the singular form herein are meant to also include the plural form and vice versa, unless explicitly stated otherwise. Also, as used herein, the term "a" and/or "an" shall mean "one or more," even though the phrase "one or more" is also used herein. It should also be understood that while some embodiments describe the methods or products as comprising one or more elements, the methods or elements may also consist of or consist essentially of the elements disclosed herein.

[0039] Some dye systems generally incorporate pigments with acrylic polymers to create colored materials. As the depth of color increases, a greater amount of acrylic polymer is needed to secure the color to the substrate being colored. In many cases, this adversely affects the fabric handle and generates colorfastness performance issues of crocking (color transfer when the article is rubbed), and washfastness when the fabric is laundered. When attempting to apply pigment color to individual yarns with acrylic binders, the moisture regain and resultant tacky characteristic of the system make this approach difficult to commercialize. The embodiments presented herein overcome these difficulties.

[0040] The embodiments are directed to ring dyed textiles, polymer-dye compositions, and methods of producing the same. A polymer-dye composition comprising at least one polymer is provided. In some embodiments, the polymer-dye composition comprises at least one urethane polymer. The urethane polymer can be an emulsion polymer and have a low glass transition temperature (Tg) in the range of, for example, about -65 °C to about 70 °C. Low Tg urethanes provide good flexibility and aesthetic fabric handle. In some embodiments, the Tg of the urethane polymer ranges from about -50 °C to about -20 °C. In particular embodiments, the Tg of the urethane polymer is -42 °C.

[0041] In some embodiments, the polymer-dye composition comprises a urethane based polymer with a molecular weight ranging from 1,000 to 400,000 g/mole. In an embodiment, the urethane based polymer has a molecular weight ranging from 2,000 to 200,000 g/mole. The urethane based polymer is designed to attract and hold selective dyes. The urethane based polymer, in some embodiments, comprises a polyurethane dispersion. The term "polyurethane dispersion" as used herein describes stable mixtures of polyurethane polymers in water.

Polyurethane polymers are generally characterized by their monomer content and most commonly involve the reaction of a diisocyanate with a polyol and chain extender. The polyurethane dispersion can be a stable aqueous mixture of any known polyurethane. Typically, the polyurethanes suitable for use in the aqueous polyurethane dispersions are the reaction products (a) an isocyanate compound having at least two isocyanate (~NCO) functionalities per molecule; and (b) a polyol having at least two hydroxy functionalities per molecule and a molecular weight ranging from 250 to 10,000 g/mole.

[0042] Exemplary polyol include hydroxy-containing or terminated polyethers, polyesters, polycarbonates, polycaprolactones, polythioethers, polyetheresters, polyolefms, and polydienes. Suitable polyether polyols for the preparation of polyether polyurethanes and their dispersions include the polymerization products of cyclic oxides such as ethylene oxide, propylene oxide, tetrahydrofuran, or mixtures thereof. Polyether polyols commonly found include polyoxyethylene (PEO) polyols, polyoxypropylene (PPO) polyols,

polyoxytetramethylene (PTMO) polyols, and polyols derived from the mixture of cyclic oxides such as poly(oxyethylene-co-polypropylene) polyols. Typical molecular weight of polyether polyols can range from 250 to 10,000 g/mole.

[0043] Suitable polyester polyols for the preparation of polyester polyurethanes and their aqueous dispersions include hydroxy-terminated or containing reaction products of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1-4, butanediol, furan dimethanol, polyether diols, or mixtures thereof, with dicarboxylic acids or their ester-forming derivatives. Modified polyether polyurethanes such as polyetherester polyurethanes and polyethercarbonate polyurethanes may also be suitable polyurethanes for the preparation of aqueous polyurethane dispersions. These modified polyether polyurethanes can be derived by incorporating additional polyester polyols or polycarbonate polyols into polyether polyols during the polyurethane manufacturing. The polyurethane dispersion as component in the compositions of the dye binding composition is selected from polyether polyurethanes, polyester polyurethanes, polycarbonate polyurethanes, polyetherester polyurethanes, polyethercarbonate polyurethanes, polycaprolactone polyurethanes, hydrocarbon polyurethanes, aliphatic polyurethanes, aromatic polyurethanes, and combinations thereof.

[0044] Polyurethane dispersion as used herein encompasses both conventional emulsions of polyurethane polymers, for example where a preformed polyurethane polymer is emulsified into an aqueous medium with the addition of surfactants and application of shear, and also includes stable mixtures of self-dispersing polyurethane polymers. These polyurethane dispersions are generally free of external surfactants because chemical moieties having surfactant like characteristics have been incorporated into the polyurethane polymer and therefore are "self emulsifying" or "self dispersing." Representative examples of internal emulsifier moieties that can be incorporated into the polyurethane dispersions useful in the present invention include ionic groups such as sulfonates, carboxylates, and quaternary amines, as well as nonionic emulsifier groups such as polyethers.

[0045] In an embodiment, an isocyanate-terminated polyurethane prepolymer is made from isocyanates, polyols, optional chain extender, and at least one monomer containing a hydrophilic group to render the prepolymer water dispersible. The polyurethane dispersion can then be prepared by dispersing the isocyanate-terminated polyurethane prepolymer in water with other polyisocyanates. Further chain extension can be affected by the addition of chain extenders to the aqueous dispersion. Depending on the choice of the hydrophilic group used to render the polyurethane polymer water dispersible, an additional reaction step may be needed to convert the hydrophilic group to an ionic species, for example converting a carboxyl group to an ionic salt or an amine to an amine salt or cationic quaternary group.

[0046] In other embodiments, the polymer-dye composition comprises one or more acrylic polymers. Although acrylic co- and ter- polymer systems, without careful engineering, may exhibit poorer migration properties and hand aesthetic characteristics than urethane materials, acrylic polymers have yielded promising results in the entrapment of reactive dyes.

[0047] In particular embodiments, the polymer-dye composition includes a reactive dye.

Exemplary reactive dyes include triazine derivatives, pyridimine derivatives, quinoxaline derivatives, and activated vinyl compounds.

[0048] Reactive dyes can include three components: a chromophore that dictates the color, solubilizing groups that aid in the dye dissolving in an aqueous environment, and one or more reactive moieties. The reactive moieties are responsible for enabling the dye to form covalent bonds between the dye chromophore and hydroxyl groups on cellulosic fibers. There are a number of reactive moieties that are available to enable bonding to occur including: vinyl sulphone, monochlorotriazine, monfluorotriazine, difluorocholorpyrimidine, dechlorotriazine, dichloroquinoxaline, trichloropyrimidine, and vinyl amide. In many cases, several of these reactive moieties are engineered into a dye structure to maximize the probability that a dye will form a permanent bond with the fiber. As described herein, dyes containing bis vinyl sulphones, bis fluorotriazines, vinyl sulphones, and/or monochlorotrazine/vinyl sulphones moieties have been all shown to have excellent lightfastness, colorfastness and color retention characteristics.

[0049] A multitude of fiber and fiber blends that can be treated include cellulosic and plant based fibers such as cotton, linen, flax, hemp, rayon, flame resistant rayon, and their derivatives; natural fibers such as silk and wool; synthetic fibers such as polyethylene (e.g., DYNEEMA®, a super high density polyethylene), polypropylene, aliphatic polyamides, para- and meta- aramids (e.g., KEVLAR® and NOMEX®), modacrylics, and/or blends of these materials and fibers. In some embodiments, the yarn contains fiber comprised of 100% cotton. In other embodiments, the yarns comprise cotton fibers blended with non-cotton fibers. The blend of fibers, in some embodiments, is at least 50% cotton fibers.

[0050] Referring now to the figures, Fig. 1 illustrates a process 100 for producing a ring dyed yarn. Although a yarn is illustrated, it will be understood that the process 100 can also be applied to fabrics and garments. A first stage yarn 110A treated with the polymer-dye composition is provided. Fig. 2A illustrates a cross-sectional view of the first stage yarn 110A. The area 200 comprises the fibers of the yarn, which is saturated with the polymer-dye mixture.

[0051 ] Returning to Fig. 1 , the first stage yarn 11 OA undergoes a drying step in which the yarn 11 OA is subjected to heat.

[0052] As shown in Fig. 1, the application of heat results in second stage yarn HOB. In an aqueous mixture of urethane polymer and a reactive dye, the dye is attracted to the urethane. As heat is applied to the surface of the substrate, the reactive dye and urethane polymer migrate together to the surface portion leaving little or no dye and/or polymer in the center of the yarn structure. The heat causes the water to evaporate from the treated material and the

polymer/dyestuff matrix of the polymer to cure. The polymer/dye matrix on the surface portion of the substrate results in a ring-dyed yarn, fabric, or garment.

[0053] Fig. 2B shows the cross-sectional view of the second stage yarn HOB. A polymer-dye matrix area 210 forms as the composition migrates toward the surface or outer portion of the yarn HOB leaving substantially no polymer-dye composition in an inner core area 212 of the yarn HOB. In the illustrated embodiment, the core area 212 comprises only the yarn fibers and not the polymer-dye composition.

[0054] Referring again to Fig. 1, the second stage yarn 11 OB is then subjected to a fixation step. To fix or otherwise attach the reactive dye to the surface, the second stage yarn 11 OB is treated with a salt brine/ alkali mixture that causes the reactive dye to become insolubilized or attached to bonding sites within the urethane matrix to produce a third stage yarn 1 IOC. One possible outcome of this treatment is that the reactive dye becomes insolubilized and is not easily removed from the polymer matrix. The urethane polymer or polymer system can be engineered to contain hydroxyl groups either in the urethane system or through the addition of other polymeric materials to which the dyes can form covalent bonds. It will be understood, however, that the hydroxyl groups are not required for fixation to occur.

[0055] Fig. 2C illustrates a cross-section view of the third stage yarn 1 IOC. On the outside of the yarn 1 IOC is a polymer portion 216. A fixed dye portion 214 is positioned adjacent to the surface or outer portion of the yarn and surrounds at least a portion of the core area 212. The fixed dye portion 214 is positioned between the polymer portion 216 and the outer portion of the yarn.

[0056] Treated yarn or fabric can be constructed into knitted, woven, or non- woven substrates and converted into garments. Fig. 3 illustrates a fabric 300 that includes a ring dyed yarn 320 (e.g., a yarn produced by the process 100 described above) in the warp direction and untreated filling yarns 310. In the illustrated embodiment, the fabric 300 is a 3x1 Left Hand Twill woven denim fabric. The ring dyed yarn 320 includes an outer dyed portion 322 and an inner non-dyed portion 324.

[0057] Fig. 4 illustrates a fabric 400 comprising a 3x1 Left Hand Twill woven denim fabric after a laundering process with pumice stones. Abrasion of the fabric or garment surface from sanding, stone washing, or other means, removes the polymer/dye coating such that the fiber color underneath is exposed. The fabric 400 includes ring dyed yarns 420 in the warp direction that have been abraided and untreated filler yarns 410. The ring dyed yarns 420 include an outer dyed portion 422 that has been abraided and an inner non-dyed portion 424. [0058] Experiments have revealed that without the alkali/salt brine treatment, the initial durability of the reactive dye is poor with more than 50% of the color removed when the substrate is laundered at low temperatures.

[0059] Additional experiments that involve applying, drying, and curing only the polymer to the fabric without the dye in the mixture, have also been conducted. When reactive dye is applied and dried to this treated substrate and subsequent dye fixation attempted with an alkali/salt brine solution, color fixation was not observed on the urethane polymer because the polymer did not have any sites available for reaction with the reactive moieties of the reactive dye. In experiments where the polymer was engineered with receptor sites for the dye, color fixation was observed. In other cases where hydroxyl rich material is incorporated with the urethane polymer system without the dye in the mixture, applied to fabric, dried, cured, and then treated with reactive dye and fixed with the alkali/salt brine, the dye reacts with the groups on the surface of the fabric or fiber. However, poor light fastness, crocking, and rubbing are observed in these cases.

Mix preparation with Polymer and Reactive Dye

[0060] In one method for the application of color, the polymer-dye compositions is applied to a substrate in a single bath, the coated substrate is then dried, the polymer-dye composition cured, and then the dye is fixed to the substrate with alkali.

[0061] A water based urethane mixture can be prepared having about 0.5% to about 10% solids depending upon the weight of the fabric or the size of the yarn to which it is being applied. In some embodiments, the urethane mixture has 2.5% to 6.0% urethane solids. A mineral based defoamer can be added should foam generation during processing become a problem. Reactive dye is generally added to the polymer mixture after pre-dilution. In further embodiments, one or more reactive dyes are added to the aqueous urethane mixture in a concentration range from about 0.01 g/1 to 70 g/1. Because the majority of the dye migrates to the fabric surface, concentrations can be 25% to 30% less than the amount typically needed to color cellulose based materials (1 g/1 to 20 g/1). The ratio of urethane solids to reactive dye can affect performance. The dried polymer range on the surface of the substrate, in some embodiments, is equal to or greater than 2.5% solids on fabric. In this way, a satisfactory surface coating of polymer is achieved. This polymer loading can easily support 1.5% to 2.0% dye concentrations without adversely affecting colorfastness performance. As a greater depth of color is desired, additional polymer can be added to the formulation as additional dye is added.

Treatment and drying of the polymer/dye mixture onto yarn, fabric, or garments.

[0062] Fig. 5 illustrates a schematic diagram of a production assembly 500 for producing a ring dyed substrate. Untreated yarn 510 yarn is dipped into a bath 520 of the polymer-dye composition and then squeezed through a squeeze roller set 530 to remove excess liquid. In other embodiments, a previously dyed yarn can be used. Although the illustrated embodiment depicts dipping, other application methods include foaming, kiss coating, or printing. In some embodiments in which the dipping method is employed, wet pickup levels between about 45% and 250%, depending on the fiber blend and absorbency of the yarn, are achieved. Percent wet pickup is calculated as the [(fabric wet weight after padding)-(fabric dry weight before padding)]/(fabric dry weight before padding) * 100. Prior to treatment of fabric, fabric can be prepared through a number of processes including desizing, scouring, bleaching, and/or mercerizing to enhance absorbency and whiteness of the fabric. Should a base color other than white be desired, fabric can be dyed prior to treatment.

[0063] The polymer-dye composition can be applied to a number of materials comprised of fibers including cotton, polyester, acetate, rayon, jute, wool, modacrylic, nylon, super high density polyethylene (SHDPE), polypropylene, para-aramids (KEVLAR®, TWARON®), meta- aramids (NOMEX®, CONEX®), cotton and cellulosic blends containing durable flame resistant polymers including ammonia treated tetrakis hydroxyl methyl phoshonium chloride urea precondensate or dialkylphosphonocarboxylic acid amide, and the like. Any mixture of fibers can be spun into yarns, and the fibers can be treated in yarn, fabric, or garment form.

Flammability performance is not negatively affected by the polymer-dye composition, and fabric can be dyed after the flame retardant treatment. Colorfastness performance is excellent at elevated temperatures while lightfastness performance is dyestuff dependent.

[0064] After the yarn is run through the squeeze roller set 530, hot air is applied to the yarn via driers 540A and 540B positioned above and below the assembly line. The application of hot air allows the polymer-dye composition to migrate to the surface portion of the yarn and the water to evaporate from the yarn. The yarn can be dried by heating the yarn with, for example, infrared heat, hot air, dry cans, microwave, or a combination of these methods. To achieve a ring-dyed appearance, it is necessary to apply enough heat to the surface of the yarn so that the dye -polymer composition migrates to the surface as the water evaporates. In cases where an even coloration is desired, an even application of heat to the treated yarn can be applied because water tends to migrate towards heat. Spotty heat treatment can result in uneven color distribution. After the water has been evaporated, the dye-polymer composition forms a film and the dye becomes trapped within the film matrix.

[0065] The yarn can then be repackaged for further treatment as described below. In the illustrated embodiment, the treated yarn is wound onto a spool 550.

[0066] In other embodiments, the dye -polymer composition is applied by padding and subsequently squeezing the excess from the fabric with a mangle. Application can also be achieved with foam application, kiss roll mixture transfer, or printing techniques.

[0067] In addition, the dye-polymer composition is applied to garments (dyed or white) by spraying to a wet pickup of 70 to 250% of the weight of the garments, drying, fixing the dye with alkali through additional spraying or dipping techniques, and subsequently wet processing the treated garments with abrasive pumice stones to remove the polymer/dye matrix from the surface particularly at seams and sewn areas of the garment. The garments can be enzyme washed to create a smoother, cleaner surface and softeners can be added to enhance the garment handle.

[0068] In particular embodiments, the polymer-dye composition is applied to at least a portion of a fabric using a Kusters pad, which allows control of chemical and dye application across the width of the fabric for shade consistency. Once the polymer/dye amalgam has been applied to the fabric, drying and curing of the polymer film can be achieved on a tenter frame, infrared driers, dry cans, hot flue oven, roller oven, microwave, or a combination of these methods. Fabrics can be dried at temperatures that promote the drying of water. In some embodiments, fabric surface reaches at least 240°F. This temperatures range ensures that the polymer film is completely cured. Fabric temperatures above 350°F are not detrimental to the polymer, but may cause yellowing of the fabric or poor stretch and growth performance of the fabric after treatment if spandex is in incorporated into the fabric.

Fixation of the dye [0069] Once the dye/polymer mixture has been applied to the yarn, the dye can be fixed to the yarn and the yarn can be incorporated into the warp, filling, or knit depending on how the yarn is processed. In other cases, the yarn can be first converted into a fabric before fixation to enhance efficiency. The dye can be fixed to the substrate by padding the yarn or fabric with a salt brine mixture containing alkali. Salt brine salt levels in the form of sodium chloride can range from 80g/l to 150 g/1. In some embodiments, the sodium chloride level is in the range of about lOOg/1 to 120 g/1 based upon a 220% wet pickup. Alkalinity can be achieved using a multitude of bases. In some cases, sodium hydroxide and sodium carbonate are used to minimize cost. The alkalinity levels selected are proportional to the concentration of reactive dye. Under alkaline conditions, reactive dyes are activated and either react with available hydroxyl groups to form covalent bonds or the activated dyes react with water to become hydro lyzed. When the salt/alkali mixture is introduced to the urethane polymer/dye matrix, the reactive dye becomes fixed within the polymeric matrix resulting in excellent fastness properties.

[0070] The polymer and reactive dyestuff are selected based on their attraction to one another. For ring dyeing to result, the polymer is engineered to migrate preferentially with the water to the surface rather than to be attracted to the fiber and hindered from migration. Radiant heat can be applied to the surface of the fabric to encourage migration of water and the polymer- dye composition to the heated surface because of the motive force created from the surface evaporation of water. Subsequent fixation results from the hydrolysis of the dye, which changes the solubility characteristics of the dye within the matrix. Because the majority of the polymer- dye matrix is on or near the fabric surface, the amount of dye required to dye the yarn or fabric is reduced by between 50% and 75% to achieve comparable colors to normal reactive dyeings.

[0071] Yarn can be treated to achieve near indigo colors, woven, and then treated with alkali/salt brine solutions to achieve indigo-like denim for which only abrasion is necessary to achieve denim-like appearing garments. This technology extends the color range from indigo to a broad color range including yellows, oranges, reds, greens, violets, blue, and colors resulting from the combination of a broad range of dye combinations.

[0072] The typical environmental issues associated with the processing of indigo garments includes the initial alkali treatment and washing of the raw yarn to improve yarn absorbency and removal of size after the weaving process. The sizing material represents up to 6% of the weight of the fabric being produced and leads to large amounts of waste. The embodiments described herein eliminate the alkali pretreatment and the need for the application and subsequent removal of sizing material. Once the dye/polymer mixture is applied and cured on the surface, very little is removed during and after fixation, so very little dye waste is observed during processing. In addition, the concentration of dye needed to achieve medium to dark shades is reduced by 50% to 75%.

[0073] Color removal during wet processing is achieved through the abrasion of the polymer from fabric surface using multiple abrasion techniques.

[0074] When only reactive dyes are used to dye cellulosic materials, penetrative dyeing in which the entire yarn bundle is dyed typically results and ring dyeing is not readily achievable. In cases where a cotton fabric is treated and cured with polymeric material alone; and reactive dyes subsequently applied and fixed with alkali/salt, the reactive dye has no substantivity for the polymer unless specific hydroxyl rich material (poly vinyl alcohol for example) has been introduced to the polymeric matrix prior to curing. The reactive dyes evenly dye the cotton fiber underneath the polymer and no color difference is observed between polymer treated cotton and untreated cotton fabric.

[0075] In the present embodiments, reactive dyes can be quarantined or preferentially attracted to a polymeric material prior to curing and fixed to the substrate surface or outer portion of the substrate with heat leaving little to no dye inside of the cotton yarn bundle. Furthermore, if the reactive dyes are not fixed with alkali, a substantial portion of the dye can be easily removed with washing. The additional fixation step locks the dye beneath the surface of the polymer and creates exceptional color fastness properties on a broad range and saturation of color. The polymer matrix is very effective at holding the majority or all of the dye in place to allow fixation to occur.

[0076] For fabrics for which bleaching is desired, it has been found that the fabric can be bleached with hydrogen peroxide through a cold pad process without adversely affecting color or polymer integrity. Hydrogen peroxide bleaching can also be done on the dyed garment with negligible removal of the color of the dyed yarn. Most color change can result from abrasion of the polymer/dye matrix rather than actual removal of the dye through the use of surfactants or alkalinity. Materials that generally degrade reactive dyes such as hypochlorite bleaches, reducing agents such as sodium hydrosulfite (sodium dithionite), and strongly oxidative agents such as potassium permanganate are still effective in destroying these dyes even when the dyes are trapped in the polymeric matrix.

[0077] The embodiments described herein result in very little fugitive dye that otherwise might be available to redeposit on uncolored yarns. This has been demonstrated after stone washing and/or enzyme treatment of yarn or fabric that have been treated with the polymer-dye composition. Washfastness test results on treated fabrics also confirm a negligible amount of color loss and color redeposition on most fiber types including acetate, cotton, nylon-6,6, polyester, orlon, or wool with typical results across a broad range of dyes of 4.0 - 5.0 on a grey scale when tested in accordance with AATCC 61 3 A at 160° F. In addition, lightfastness (AATCC 16 - Option 1) after 40 exposure hours had ratings of 3.5 or greater on the majority of the selected dyes. (The grading scale ranges from 1.0 to 5.0 with a 1.0 rating poor and 5.0 rating excellent). Ozone and Burnt Gas Fading when tested in accordance to AATCC 109 and AATCC 23 respectively had performance values of 4.0 or above on all dyes tested.

[0078] This technology can be applied to a multitude of fibers and fiber blends. Even fibers that typically do not readily accept dyes have been found to accept color applied through the formation of a dye/polymer matrix on the surface of the substrate. Examples have been provided below. These examples are designed to illustrate the flexibility of the process and resulting ring-dyed products, but does not limit the scope of applications.

Examples

Example #1A - Treatment and ring dyeing of 100% cotton bull denim - (Urethane + Dye) no alkali fixation

[0079] A 12 oz/yd2 100% cotton 3x1 right hand twill fabric with 74 ends and 42 picks comprised of 8.5/1 Ansler Ringspun warp yarn and 6.0/1 Open end filling yarn was desized, scoured, bleached, and mercerized prior to treatment. A Urethane/Dye mixture was prepared to engineer a 3% urethane solids add on and a 0.72 percent reactive dye concentration by weight based upon a chemical mixture wet pickup of 72%>. In one case, low molecular weight polyvinyl alcohol (PVA) was added to ensure that the reactive dye had hydroxyl groups to which covalent bonds could be formed. In the control case, no PVA was added. The reactive dye selected was NOVACRON® Blue CR (Reactive Blue 235). Mix #1, comprised of urethane and Blue CR was padded onto bull denim and excess chemical removed with a mangle. The fabric was dried in a

Warner Mathis oven for 90 seconds at 360° F. Formulations for Mix #1 and Mix#2 are provided in Table 1 A below.

Table 1A

Note: Chemical Wet Pickup = 72%

[0080] The fabric was washed in four liters of 160°F water for 25 seconds; 25 seconds with two liters of 160° F water and 1 g/1 sulfonated castor oil; and finally rinsed with four liters of clean 160° F water and 2.5 g/1 of 20% acetic acid. Excess water was extracted from the fabric before drying on a hot head press. Approximately 50% of the dye was removed from the sample.

Example #1B - Treatment and ring dyeing of 100% cotton bull denim - (Urethane + Dye) alkali fixation

[0081] The fabric was processed as in Example #1A. Before the washing step, a mixture of 11.25 g/liter caustic soda, 15g/liter soda ash, and 1.08 g/liter salt bring as provided in Table IB below was applied to the fabric and processed through a Werner Mathis steamer at 118° C with a dwell time of 50 seconds. Table IB

Note: Chemical wet pickup = 220%

[0082] The fabric was washed as outlined in Example #1A, extracted and dried. Almost no color was removed in the washing process. Experiments were repeated with the addition of 0.4% polyvinyl alcohol solids in the urethane mixture with no appreciable washfastness performance differences.

Example #1C - Finishing of dyed 100% cotton bull denim fabric

[0083] Fabric from Example #1 A and Example #1B were finished by processing the fabric through a pad containing 50 g/1 of PHOTOBEX® JVA (an emulsified wax, 20% solids). Excess mix was removed by a mangle and the fabric vacuum extracted to a wet pickup of 45%. The fabric was dried at 340°F for 70 seconds and then tested for colorfastness properties.

Washfastness performance was evaluated using AATCC 61 2A (120°F) and 3A (160°F) protocols. Results have been depicted in Table 1C. Results were best for the fabrics that had been treated with the alkali/salt brine solution with negligible shade change or color transfer after laundering at 160°F.

Table 1C

Example #1D - Wet processing of finished 100% cotton bull denim pant legs

[0084] Fabric from Example #1C was crafted into mock pant legs with a felied seam to mimic seams found in denim pant garments. Pant legs were laundered in a 65 lb Washex machine with a 2: 1 pumice stone to fabric ratio, 10: 1 water to fabric ratio, and a fabric load level of 10 pounds. The pant legs were wet processed at 100°F for 60 minutes and then separated from the pumice stone. The pant legs were then rinsed with water at 120°F to remove pumice sand, extracted, and tumble dried at 160°F until dry. There was abrasion at the felied seam where the polymer/dye matrix had been removed leaving untreated, undyed white highlights. There was no redeposition of the color onto the abraded white areas typical of indigo and pigment dyes. Colorfastness properties were measured again and found to be nearly identical to properties of the fabric before wet processing. Example #2A - Ring Dyeing of 100% Cotton bottom weight fabric with multiple reactive dye colors - Application and Processing

[0085] An 8.7 oz/yd ² 3x1 Right Hand Twill 100% combed cotton fabric with 117 ends and 56 picks comprised of a 30/2 ply warp and 26/2 ply filling was desized, scoured, bleached, and mercerized prior to treatment. A series of 12 reactive dyes were selected and mixtures of each prepared and processed as follows:

1) 1.0 gram of Defoamer CH2 (a mineral based defoamer available from the Apollo Chemical Company) was added to 200 ml of water and vigorously stirred.

2) 69.0 grams of TST-U60 (60% active urethane) (available from Texstream

Technologies) was added to the water and defoamer and diluted to 500 ml.

3) In a separate container, 10.0 grams of powdered reactive dye (available from

Huntsman Corporation) was added to 250 ml of 140 F water and stirred until all of the dye had dissolved. The dye solution was adjusted to a pH of 4.8 to 5.6 with acetic acid.

4) While stirring the urethane mixture, the dye solution was added. Additional water was added to produce 1.00 liter of solution.

5) A 12 inch wide fabric sample was processed through the mixture and excess mix removed with a mangle set at 20 psi. A wet pickup of between 72% and 75% was measured resulting in a urethane solids add on of approximately 3.0% and a dye concentration of 0.72% to 0.75%.

6) Fabric was dried and cured at 360°F for 90 seconds in a Werner Mathis oven.

7) Fabric was processed through a mixture of alkali/salt brine consisting of 11.25 g/1 caustic soda, 15 g/1 soda ash, and 108 g/1 salt brine (NaCl). A wet pickup of between 225%) and 250%) resulted when processing fabric through a pad with no squeezing. Fabric was steamed at 118°C for 50 seconds.

8) Fabric was rinsed in 4 liters of 160°F water for 30 seconds. Little to no dye was rinsed from the fabric. Additional washing was achieved by stirring the fabric in 2 liters of water at 160°F with 2 grams of sulfonated castol oil for 30 seconds to remove any soluble dye. A final rinsing in 4 liters of water at 160°F for 30 seconds completed the washing cycle. The fabric was extracted and dried on a hot head press. 9) Fabric was finished as described above in Example #1C.

Testing was completed on each of the 12 dyes selected and the results depicted in Tables 2 A and 2B1-2B2 below.

Table 2 A

MFT = Monoflourotriazine

MCT = Monochlorotriazine

VS = Vinylsulphone Table 2B1

Table 2B2

After wash swatch is darker than the original swatch with no color loss

[0086] For nearly all dyes, the crocking, lightfastness, ozone resistance, burnt gas fading, and 120°F and 160°F washfastness results were outstanding. Results were significantly better than those achieved with reactive dyeing of cotton at comparable color levels on a continuous dye range. Table 2C below details the differences in performance for different types of dyed fabrics and the polymer-dye matrix substrates described herein. Table 2C

Example 2B - Ring Dyeing - Verification of Ring Dyed effect

[0087] Fabric from Example 2A was folded over the edge of a table and the folded area lightly sanded with 100 grit sand paper to remove the surface coating of the polymer/dye film on the surface of the fabric. In all cases, white yarn was detected in areas where the fabric was sanded demonstrating that the fabric was ring dyed.

Example 3A - Treatment of 9.5/1 Ansler Ring Spun 100% cotton yarn to create denim- like ring dyed fabric (Sample ID 198-10 and 198-11)

[0088] A mixture was prepared by mixing 75.0 grams of TST U-60 (60%> active urethane) (Texstream Technologies), 1.0 gram of Defoamer CH2 (Apollo Chemical Company), 15.0 grams of NOVACRON® Navy CBN (available from Huntsman Corporation), and 0.75 grams of NOVACRON® Red SB (available from Huntsman Corporation). The mixture was diluted to one liter with 110°F water. A single end 9.5/1 Ansler Ring Spun 100% cotton yarn was dipped in this mixture and excess mix removed with a rubber over metal squeeze roller achieving a wet pickup of 130%. The yarn was dried by blowing hot air (86°C) onto the yarn for a period of 105 seconds. The processed yarn was woven as the filling yarn across 32 ends/inch of 4.5/1 open end 100% cotton yarn. A reverse oxford weave inserting 56 picks per inch of the 8.5/1 treated yarn produced a canvas-like fabric with yarns in one direction that were dyed. [0089] An additional Red/Orange color was produced from the same yarn by using 10.0 g/1 of NOVACRON® Red SB and 2.0 g/1 of NOVACRON® Orange C-3R (available from Huntsman Corporation) using the same formulation and process described above.

[0090] The fabric was cut into 12 inch strips and processed through a continuous oven at

340°F for 70 seconds to ensure that the coating was totally cured. The dye was immobilized by the application of alkali and salt brine followed by steaming as described in Example #1B.

Example 3B - Treatment of 80/15/5 PROTEX® C/Pima Cotton/KEVLAR® Flame Resistant yarn to create lightweight denim-like Flame Resistant ring dyed twill fabric

[0091] A mixture was prepared by mixing 75 grams of TST U-60 (60% active urethane),

1.0 gram of defoamer CH2, 15.0 grams of NOVACRON® Navy CBN, and 0.75 grams of NOVACRON® Red SB in one liter of 110°F water. A single end of 80/15/5 PROTEX® C (modacrylic fiber)/Pima Cotton/KEVLAR® (para-amid) flame resistant yarn was dipped through this mixture and excess mix removed with a rubber over metal squeeze roller to achieve a wet pickup of 130%. The yarn was dried by blowing hot air (86°C) onto the yarn for a period of 105 seconds. The processed yarn was woven as the filling yarn across 96 ends/inch of 36/1 Ring Spun yarn comprised of 65/25/10 FR Rayon/KEVLAR®/Nylon (polyamide) fiber mixture. A 2x1 Left Hand twill fabric was produced by inserting 58 picks per inch of the dyed/treated yarn.

[0092] An additional Red/Orange color was produced from the same yarn by using 10 g/1 of NOVACRON® Red SB and 2.0 g/1 of NOVACRON® Orange C-3R using the same formulation and process described above.

[0093] The fabric was cut into 12 inch strips and processed through a continuous oven at

340°F for 70 seconds to ensure that the coating was totally cured. The dye was immobilized by the application of alkali and salt brine followed by steaming as described in Example #1B.

Example 3C - Treatment of 15.1/1 50/50 cotton/polyester core-spun polyester yarn to create lightweight denim-like ring dyed twill fabric (Sample ID 198-9)

[0094] A navy mixture was prepared as described in Example 1C. A single end of 15.1/1

50/50 cotton/polyester core-spun yarn with a polyester core was dipped through this mixture and excess mix removed with a rubber over metal squeeze roller achieving a wet pickup of 130%. The yarn was dried by blowing hot air (86°C) onto the yarn for a period of 105 seconds. The processed yarn was woven as the filling yarn across 84 ends/inch of 60/40 cotton/polyester warp yarn. A 2x1 Left Hand twill fabric was produced by inserting 58 picks per inch of the dyed/treated yarn.

[0095] The fabric was cut into 12 inch strips and processed through a continuous oven at

340°F for 70 seconds to ensure that the coating was totally cured. The dye was immobilized by the application of alkali and salt brine followed by steaming as described in Example #1B.

Example 3D - Removal of size and finishing of the treated and dyed yarn

[0096] Before finishing, sizing from the warp yarns was removed and the fabrics from

Examples 3 A, 3B, and 3C scoured and bleached. The desize/bleach formulation consisted of hydrogen peroxide, an organic stabilizer, sodium hydroxide, a non-ionic surfactant, and a chelating agent. This mixture was padded onto the fabric at 120°F with a wet pickup of 150%, rolled on a tube, wrapped in plastic, and placed in a warm 105°F oven for 12 hours. Fabric was washed and dried. Little to no dye was removed in the desize/bleaching process. The fabric was finished with PHOTOBEX® JVA as described in Example #1C, made into pant legs, and laundered as described in Example #1D. Pant legs of Example #3 A (Denim) were laundered for 90 minutes instead of 60 minutes before rinsing. The pant legs clearly demonstrated that the dyed yarn was ring dyed and that the portions that were abraded had the white bleached color of the yarn showing through. All fabrics were tested after finishing assessing colorfastness performance. Results are provided in Tables 3A-3B below.

Table 3A

Table 3B

[0097] In all cases, colorfastness performance for all fabrics was good. The

measurement of rub fastness for the depth of colors being evaluated was exceptional with little to no color transferred in either dry or wet form. Minimal staining of untreated yarns was observed in any woven fabrics nor staining on multi-fiber swatches even at elevated 160°F wash temperatures.

[0098] For the flame resistant fabric produced from Example #3B, vertical flammability testing when tested in accordance to ASTM D 6413 initially and after 100 washing and drying cycles had char lengths under 4 inches and after flame less than 2 seconds. The polymer/dye coating was found to have no effect on the flammability performance.

Example 4 - Impact of urethane/dye ratio on color, durability, colorfastness performance of 100% Cotton

[0099] An 8.7 oz/yd2 3x1 right hand twill constructed from 30.25/2 combed ring spun

100% cotton warp yarn and 25.25/2 combed ring spun 100 cotton filling yarn with 117 ends per inch and 56 picks per inch was treated with a mixture of 10.0 g/1 of NOVACRON® Navy CBN and 69 g/1, 46 g/1, and 23 g/1 of TST-U60 urethane. Wet pickup of the urethane/dye mixtures was 72%. All urethane and dye migrated to the yarn surface upon drying and curing at 340°F for 105 seconds. Dye/urethane solids ratios were varied from roughly 1.3: 1 to 4: 1 and colorfastness performance was evaluated after fixation of the dye with alkali/salt as outlined in Example #1B. Higher urethane to dye ratios yielded better colorfastness performance. Testing results are detailed in Table 4. Table 4

Table 4 Continued

Example 5 - Two tone dyeing of 100% cotton fabric and yarn - Ring dyeing process followed by piece dyeing process

[00100] A 12.1 oz/yd2 100% cotton canvas constructed from 4/1 open end warp yarns and

8/2 open end filling yarns was desized, scoured, and bleached in preparation for treatment.

[00101] Step 1 - A mixture containing 4.1% urethane solids and 1.0 % NOVACRON®

Blue CR was padded onto the fabric and excess solution removed with squeeze rolls to achieve a pickup of 72%). Fabric was dried, and the polymer cured by processing the fabric through an oven set to 340°F. The dye was fixed by processing through a salt brine/alkaline solution followed by steaming for 50 seconds at 218°F. No appreciable dye was removed in the washing process and a medium blue color resulted.

[00102] Step 2 - a reactive dye mixture comprised of 4.0% alginate antimigrant, 4.7% salt brine solution, 0.1% barasol wetting agent, and 0.5% NOVACRON® Yellow CROl was padded onto the fabric, excess solution removed with a squeeze roll to a wet pickup of 75%, the fabric dried with a combination of electric predryers and steam cans. The reactive dye was fixed by processing through salt brine/alkaline solution as described in Example 1C, washed, neutralized with acetic acid, and dried.

[00103] The blue shade was greener in cast than before treatment. The surface of the fabric was sanded revealing the dyed yellow fiber beneath the blue-green polymer matrix.

Example 5A - Two tone dyeing of 100% cotton fabric and yarn - Piece dyeing process followed by Ring Dyeing process

[00104] The same fabric from Example 5 was selected. Step 2 from Example 5 was followed to dye the ground color. The dyed fabric was treated with the process described in Example 5, step 1 in which the fabric was ring dyed with a Blue color. Compared to the fabric color from Example 5, step 1 prior to step 2, the fabric color was greener. When the surfaced was sanded, the yellow base color was readily apparent with almost so staining from the blue in the yellow ground color. When wet processed with pumice stones, tonal effects were created ranging from dark blue-green to light yellow green coloration.

Example 5B - Treatment of 100% polypropylene

[00105] A 4.0 oz/yd2 100% polypropylene fabric constructed from 625 denier polypropylene woven with 24 ends and picks into a plain weave was processed as described in Example 5 , step 1 except the polymer was cured by placing in a dispatch oven at 235°F for 10 minutes. The fabric after the initial dyeing process was blue; however, after processing as described in Example 5, step 2 with the yellow reactive dye, the cast of the fabric did not appreciably change and remained blue. When sanded removing the surface polymeric/dye matrix, the white polypropylene was readily apparent. None of the yellow reactive dye was fixed to the polypropylene.

Example 6 - Treatment of 88/12 Cotton/Nylon Flame resistant fabric

[00106] A 5.5 oz/yd2 woven fabric consisting of a 18/1 75/25 cotton/nylon 66 warp and a

16/1 100% cotton filling with a construction of 108 x 50 in a 3x1 left hand twill weave was desized, scoured, and bleached. The fabric was treated with a urea precondensate of tetra-kis hydroxy methyl phosphonium chloride and cured with gaseous ammonia to produce a flame resistant fabric with 2.4% phosphorus content. The treated substrate was padded through a mixture containing 69 g/1 TST U-60 (4.14% urethane solids) (Texstream Technologies), 0.1% Defoamer CH2 (Apollo Chemical Company), 15 g/1 NOVACRON® Navy CBN (Huntsman Corporation - Reactive Black 5). A wet pickup of 72% yielded a urethane concentration of 3.0%) solids and dye solids add on of 1.34%. Fabric was processed through predryers to reduce the water content to about 60% and completely dried on steam cans. Curing was completed by heating to 340°F for a period of 65 seconds. The dye was fixed by padding and steaming an alkali/salt mixture as described in Example 1C.

[00107] Fabric was washed, dried, and tested for crocking, lightfastness, and washfastness at 160°F. Vertical flammability was tested on treated undyed fabric, treated unwashed dyed fabric, and dyed fabric after a one hour stonewash procedure. (Stonewashing was done in a 65 lb Washex with liquor to fabric ratio of 12: 1 and a pumice stone to fabric ratio of 2: 1 at a temperature of 130°F). Colorfastness results were excellent and vertical flammability testing passed with char lengths less than 4.0 inches when tested in accordance with NFPA 701 protocol. Lightfastness results were a function of dye selected. Three other reactive dyes were evaluated and results have been depicted in Table 5.

Table 5

Table 5 Continued

[00108] There are numerous variations of this process that can result in unique fabrics and garments with enhanced performance characteristic and/or design interests. Some have been outlined in the Examples.

[00109] While certain exemplary embodiments have been described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative of and not restrictive on the broad invention, and that this invention not be limited to the specific constructions and arrangements shown and described, since various other updates, combinations, omissions, modifications and substitutions, in addition to those set forth in the above paragraphs, are possible.

[00110] Those skilled in the art may appreciate that various adaptations and modifications of the just described embodiments can be configured without departing from the scope and spirit of the invention. Therefore, it is to be understood that, within the scope of the appended claims, the invention may be practiced other than as specifically described herein.