AU2013318234A1 - Processes to dye and treat BCF yarn - Google Patents

Abstract

Disclosed are processes for applying dyes, stain blocker and anti-soil compositions on BCF yarns during cable or air twisting processes, or heat setting processes, prior to weaving, knitting or tufting. Further discloses are process for applying dyes, stain blocker and anti-soil compositions on BCF yarns prior to heat setting. The processes forego the need to dye and otherwise treat carpets and other textiles made from the BCF yarn using current methods. Also disclosed are systems, BCF yarns, and carpets made from the BCF yarn treated by the disclosed process.

Description

WO 2014/047138 PCT/US2013/060345 PROCESSES TO DYE AND TREAT BCF YARN FIELD OF THE INVENTION [0001] The invention relates to treatment processes for bulk continuous filament (BCF) carpet and related textile fabrics, and specifically, to processes for applying dyes and topical treatment compositions on BCF yarns during twisting processes (cable or air) or heatsetting process prior to weaving, knitting or tufting. The process foregoes the need to dye and otherwise treat carpets and other textiles made from the BCF yarn using current methods. The need for an anti stain treatment is also avoided by the inclusion of an inherently stain resistant fiber, such as cationic dyeable polyamide or polyester. Thus, low inventory overhead is achieved and costly and environmentally unfavorable dyeing and low pH chemical treatment processes are eliminated. Also disclosed herein are systems used to apply the dye and performance enhancement formulations to the BCF yarn, and soil repellent yarns, and carpets with improved anti-soil properties made from the BCF yarn of the disclosed process. BACKGROUND OF THE TECHNOLOGY [0002] Carpets and other fabrics made from synthetic yarns are currently colored using two well-established processes. The first process involves converting colorless white yarns into carpet, and dyeing the carpet in a dye bath. This process is referred to as the "acid dye process." The acid dye process can be either a batch or a continuous dyeing operation. Each dyeing operation requires a large volume of water, steam to set the dyes, and heat to dry the carpet. In addition, collection and disposal of excess dye and acidified performance enhancing solutions add manufacturing cost and place additional burden on waste management and water treatment facilities. The second process adds color pigments into the polymer during the melt spinning process. This process is referred to as the "solution dye process." The solution dye process is a low cost operation, but in comparison to the acid dye process it imposes undesirable inventory allocation measures on the fiber producer and the carpet mill. In order to meet consumer demand, then, the fiber producer and carpet mill may need to keep a costly inventory of colored yarns produced by the solution dye process. Variable production demands and large inventory costs can affect inventory flexibility with the result being the color availability of solution dyed carpets is undesirably limited. 1 WO 2014/047138 PCT/US2013/060345 [0003] Topical chemistries are used to treat carpets and other fabrics for improved stain resistance and/or soil resistance. For nylon carpets, both stain blocker (e.g. acid dye blocker) and anti-soil with fluorochemicals are traditionally used. For polyester carpets, such as such as polyethylene terephthalate (2GT) and polytrimethylene terephthalate (3GT) carpets, and polypropylene carpets, anti-soil chemistry may be applied topically to the tufted carpet as part of the carpet finishing process. Polyester and polypropylene carpets typically do not require a stain blocker treatment because of inherent stain resistance to acid dyes and stains owing to their lack of amine end groups that function as acid dye sites. [0004] Topical application at the carpet mill can be in the form of exhaust application and spray application. Exhaust application (i.e. flex-nip process at high (300 - 400 wt.%) wet pick up), is known to provide an improvement in efficacy over spray-on applications at 10-20 wt.% wet pick-up of anti-soil. Exhaust applications typically use greater amounts of water and energy to dry and cure the carpet than do spray applications. Spray-on fluorochemical products are designed to use less water and energy than exhaust applications, but do not impart satisfactory anti-soil properties. [0005] While various processes are in use in the carpet industry for the dyeing and finishing of carpets, some large scale and some small, most of the carpet made today is dyed and finished on a continuous dye range. This is done mainly in one of two ways: In one case, a two stage process is employed, where the carpet is steamed and dyed first, steamed, rinsed, and excess water extracted; then stain blocker (SB) is applied, the carpet is again steamed and washed, and then anti-soil fluorochemical (FC) is applied in the form of a foam or liquid spray and the carpet is finally dried. (See e.g. U.S. Patent Nos. 5,853,814; 5,948,480 and W02000/000691). In the second, somewhat improved case, called the co-application process, the carpet is also steamed and dyed first, steamed again, rinsed and extracted; and then a blend of SB and FC is applied together at high wet pick up, after which the carpet and chemicals are exposed once again to steam to fix the treatment, followed by drying. (See e.g. U.S. Patent Nos. 6,197,378 and 5,520,962). In both cases, low pH solutions, excess water, and energy are required for the SB and FC to penetrate the carpet and achieve uniform coverage. In sum, the typical prior art process is as follows: BCF yarn ->Twist -> heat set -> tufting -> carpet -+ dye -* stain block / anti-soil. 2 WO 2014/047138 PCT/US2013/060345 SUMMARY OF THE INVENTION [0006] There is a desire to reduce the overall usage of dyeing solutions and stain blocker formulations for environmental and cost reasons. Further, there is also a desire to reduce the amount of water and low pH chemicals used to apply the dyeing and anti-stain formulations. Thus, processes which provide for low inventory needs while applying such beneficial compositions using less water, nominal pH chemicals, and less energy are in demand. [0007] While the development of a process that eliminates the current carpet treatment systems for applying anti-stain and anti-soil compositions is desirable, current processes do exist for good reasons. First, because the appearance of carpet has historically depended on the ability to dye wool or nylon or even polyester tufted carpets to the desired shade, it would not be permissible to treat the carpet with compositions such as anti-stain or anti-soil chemistries beforehand that might interfere with the process of uniform dyeing. Further, the dyeing process would tend to remove the topical treatment chemistries, rendering them ineffective. [0008] Second, as mentioned above, treatment of yarn or fabric with performance enhancement formulations for stain and soil resistance typically involves fixing with steam, and low pH may also be required especially for acid dyed fabrics. Therefore, it was deemed most practical to process carpets in the order described above, where carpet is formed, then steamed and dyed, steamed again, rinsed and extracted; and then SB and FC is applied, again involving steaming and/or rinsing in the various processes of the prior art. [0009] Carpets have also long been constructed of dyed or pigmented yarns, which constructions are treated in numerous possible ways, including the options of further dyeing, and the application of stain and/or soil resistant compositions with the concomitant use of steam and rinse water, as in the processes described above. [0010] The invention disclosed herein provides a process to make textile fabrics, especially tufted articles, without the requirements for dyeing and subsequent stain and soil resistant chemistry application, thus avoiding the costs associated with maintaining large inventories as well as waste generated by steam fixation and rinsing attendant with such large-scale fabric applications. As disclosed herein, the process involves application of dyes and topical chemistries to undyed yarns immediately after twisting or cabling one or more such yarns together. The chemistries are then heat-set onto the twisted yarn under dry conditions, and the twisted yarn subsequently weaved or tufted into a finished fabric or carpet. Novel systems that 3 WO 2014/047138 PCT/US2013/060345 enable the efficient application of dye solutions and topical chemistries to yarn subsequent to twisting and prior to winding and heat-setting are also disclosed. [0011] Specifically, the disclosed process uses a dye solution or topical chemistry composition applicator positioned within a mechanical twisting process downstream of the twisted yarn take-up reel and upstream of the yarn winder. In sum, the disclosed process moves the back end, large scale and wasteful stain blocker application step up front during or after yarn twisting. Thus, the carpet manufacturing process now becomes: BCF yarn -- twist -- dye -+ optional SB/FC -- > heat set (optionally dry heat set) -+ tufting -+ carpet. Surprisingly, the disclosed process is as effective, or even more effective, than processes of the prior art in terms of fabric soil resistance. Additionally, neutral pH dye solutions (4-7.5 pH) can be used instead of the prior art low pH dye solutions (1-3 pH). This reduces the environmental impact of prior art processes. Moreover, the need for a stain blocker application is not necessary due to the inclusion of a cationic dyeable polyamide or polyester. In other words, the stain blocker application can be consciously excluded while not sacrificing stain resistant properties. [0012] As described above, the process of the disclosed invention is counterintuitive since treating the carpet yarn prior to heat setting and tufting is known to affect the quality of the finished carpet, particularly during dyeing. Further, the inventive process is also counter intuitive because soil resistant compositions tend to be very difficult to apply uniformly to twisted yarn bundles at the usual line speed without substantial waste [30 to 80 yards-per-minute (ypm)]. Moreover, the disclosed process is counter intuitive because the prior art yarn twisting apparatuses have not previously accepted topical chemistry applications to twisted yarn prior to winding. However, as shown below, nylon and polyester carpets manufactured with the treated BCF yarn show one or more of the following desirable characteristics: * At least equivalent dyeing characteristics vs. the current state of the art processes. * At least equivalent stain and soil repellant performance vs. the current state of the art processes. * Desirable aesthetic attributes otherwise not generated by the current state of the art processes. [0013] In one aspect, a process for treating twisted BCF yarn with one or more dye compositions is disclosed. The process comprises: (a) providing twisted BCF yarn; (b) winding 4 WO 2014/047138 PCT/US2013/060345 said BCF yarn on a take-up reel; and (c) contacting said BCF yarn with said dye composition while said BCF yarn is in motion and prior to said BCF yarn contacting and winding up on said take-up reel. The dye composition can be comprised of an acid dye composition or a disperse dye composition. [0014] In another aspect, a process for treating twisted BCF yarn with one or more dye compositions is disclosed. The process comprises: (a) providing twisted BCF yarn; (b) contacting said BCF yarn with said dye composition while said BCF yarn is in motion; and (c) heat setting said BCF yarn after contacting said BCF yarn with said dye composition. The dye composition can be comprised of an acid dye composition or a disperse dye composition. [0015] In a further aspect, a process for treating twisted BCF yarn with one or more dye compositions and performance enhancing compositions is disclosed. The process comprises: (a) providing twisted BCF yarn; (b) winding said BCF yarn on a take-up reel; (c) contacting said BCF yarn with said dye composition; (d) optionally contacting said BCF yarn with a first performance enhancing composition comprising a stain blocking composition; and (e) contacting said BCF yarn with a second performance enhancing composition comprising an anti-soil composition and prior to said BCF yarn contacting and winding up on said take-up reel, wherein said BCF yarn is in motion while contacted with said dye, said optional first performance enhancing composition, and said second performance enhancing composition. The dye composition can be comprised of an acid dye composition or a disperse dye composition. The stain blocking composition can be comprised of species having acidic moieties that associate with polymer amine end groups and protect them from staining by acidic dye stains. The general category of chemicals suitable to the process of the instant invention can comprise any chemical that blocks positively charged dye sites. The anti-soil composition can be comprised of a high specific surface energy chemical or other material, for example a fluorochemical that imparts high specific surface energy properties such as high contact angles for water and oil, or even a non-fluorochemical particulate material having similar properties. The anti-soil composition can further comprise an anti-stain component. [0016] In even another aspect, a process for treating twisted BCF yarn with one or more dye compositions and performance enhancing compositions is disclosed. The process comprises: (a) providing twisted BCF yarn; (b) contacting said BCF yarn with said dye composition; (c) optionally contacting said BCF yarn with a first performance enhancing composition comprising a stain blocking composition; (d) contacting said BCF yarn with a second performance 5 WO 2014/047138 PCT/US2013/060345 enhancing composition comprising an anti-soil composition, wherein said BCF yarn is in motion while contacted with said dye, said optional first performance enhancing composition, and said second performance enhancing composition and; (e) heat setting said BCF yarn after contacting said BCF yarn with said dye composition, said optional first performance enhancing composition, and said second performance enhancing composition. The dye compositions and performance enhancing compositions are disclosed above. [0017] In a further aspect, an untufted, twisted BCF yarn comprising a dye component is disclosed, wherein said dye component is present on said twisted BCF yarn prior to tufting the BCF yarn. The dye component is selected from acid and disperse dye ingredients. The yarn can comprise polyamide fiber and/or have polymer components selected from polyester. The yarn can be tufted and manufactured into carpet or fabrics. [0018] In yet another aspect, an untufted, twisted BCF yarn comprising a dye component, an anti-soil component, and an optional anti-stain component is disclosed, wherein said dyeing component, anti-soil component and optional anti-stain component are present on said twisted BCF yarn prior to tufting the BCF yarn. The dye component is selected from acid and disperse dye ingredients. The anti-soil component and optional anti-stain component can be selected from the compositions disclosed above. The stain blocking component is optionally present at an amount on weight of fiber of about 0.5 to about 40 ppm elemental sulfur content. The anti soil component is present at an amount on weight of fiber from about 100 ppm to about 1000 ppm elemental fluorine content. The yarn can comprise polyamide fiber and/or have polymer components selected from polyester. The yarn can be tufted and manufactured into carpet or fabrics. [0019] In yet a further aspect, a process for manufacturing carpet is disclosed comprising providing an untufted, twisted BCF yarn comprising a dye component, an optional stain blocker component, and an anti-soil component, tufting said BCF yarn, and weaving into said carpet. Because of the dye and performance enhancing components present on the BCF yarn prior to tufting and weaving, there is no need to process the finished carpet by dyeing or treating with an acidified stain blocker composition and an anti-soil composition under the current state of the art processes. [0020] In yet even another aspect, a system for applying a dye composition to twisted BCF fiber is disclosed. The system comprises: (a) a first yarn take-up device that transmits a single 6 WO 2014/047138 PCT/US2013/060345 yarn member made from at least two individual yarn members; (b) a dye composition applicator disposed downstream of said yarn take-up device that applies said dye composition to said single yarn member; and (c) a second yarn take-up device that receives a dyed single yarn member. The dyeing composition can be comprised of acid dye or disperse dye ingredients. [0021] In yet even a further aspect, a system for applying a dye composition and at least one performance enhancing composition to twisted BCF fiber is disclosed. The system comprises: (a) a first yarn take-up device that transmits a single yarn member made from at least two individual yarn members; (b) a dye composition applicator disposed downstream of said yarn take-up device that applies said dye composition to said single yarn member; (c) an optional anti-stain component applicator disposed downstream of said dye composition applicator that applies anti-stain composition to said single yarn member; (d) an anti-soil applicator disposed downstream of said dye composition applicator that applies anti-soil composition to said single yarn member; and (d) a second yarn take-up device that receives a dyed single yarn member. The dyeing composition can be comprised of acid dye or disperse dye ingredients. The anti stain composition can be comprised of species having acidic moieties which associate with polymer amine end groups and protect them from staining by acidic dye stains. The anti-soil composition can be comprised of a high specific surface energy chemical or other material, for example a fluorochemical that imparts high specific surface energy properties such as high contact angles for water and oil, or even a non-fluorochemical particulate material having similar properties. The anti-soil composition can further comprise an anti-stain component. DEFINITIONS [0022] While mostly familiar to those versed in the art, the following definitions are provided in the interest of clarity. [0023] OWF (On weight of fiber): The amount of chemistry that was applied as a % of weight of fiber. [0024] WPU (Wet pick-up): The amount of water and solvent that was applied on carpet before drying off the carpet, expressed as a % of weight of fiber. DETAILED DESCRIPTION OF THE INVENTION [0025] A process for treating twisted BCF yarn is disclosed comprising contacting the BCF yarn with a dye composition while said yarn is in motion and prior to contacting and winding the 7 WO 2014/047138 PCT/US2013/060345 yarn onto a take-up reel or winder to create a yarn package or cake. The process can also include contacting the BCF yarn with one or more performance enhancing compositions comprising stain blockers and anti-soil compositions. The dye composition comprises a dye component and is adapted to be continuously applied onto twisted BCF yarn at 10 to 100 ypm, preferably, 30 to 80 ypm. The stain blocker composition comprises an anti-stain component and is adapted to be continuously applied onto twisted BCF yarn at a wet pick-up of 10 to 50%, preferably 15 to 30%. The anti-soil composition comprises an anti-soil component and is adapted to be continuously applied onto twisted BCF yarn at a wet pick-up of between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%. The twisted BCF yarn can be optionally heat set after contacting the yarn with the dye composition and the one or more performance enhancing compositions. Heat setting temperatures can range from about 1250C to about 2000C, including from about 1600C to about 1950C. Heat setting dwell times can range from about 0.5 to about 4 minutes, including from about 0.5 to about 3 minute and from about 0.5 to about 1 minute. [0026] Dye components for use in the disclosed dye compositions are acid dyes or disperse dyes. Acid dye components are well known to those skilled in the art and are water-soluble ionic species containing one or more organic chromophore moieties. Acid dyes are typically provided in powder form and different acid dyes can be used in combinations to arrive at a precisely defined color choice depending on process conditions such as the use rate of each selected dye component, the use rate of the one or more acid auxiliaries employed, and the residence time of the substrate in the dyeing zone. Examples of suitable acid dye compositions are Orange 3G, Red 2B and Blue 4R. Disperse dye components are likewise well known to those skilled in the art and are water-insoluble nonionic species containing one or more organic chromophore moieties. Disperse dyes are either provided in paste form in combination with a dispersing agent or in powder form. Different disperse dyes can be used in combinations to arrive at a precisely defined color choice depending on process conditions such as the use rate of each selected disperse dye component, the specific dispersing agent or agents employed, and the residence time of the substrate in the dyeing zone. Examples of suitable disperse dye compositions are Disperse Red 60, Disperse Yellow 86 and Disperse Violet 33. [0027] Anti-stain components for use in the disclosed stain blocker compositions have a component bearing an acidic moiety which associates with polymer amine end groups and protects them from staining by acidic dye stains. The general category of chemicals suitable to 8 WO 2014/047138 PCT/US2013/060345 the process of the instant invention can comprise any chemical that blocks positively charged dye sites. Stain blockers are available in various forms such as syntans, sulfonated novolacs, sulfonated aromatic aldehyde condensation products (SACs) and/or reaction products of formaldehyde, phenolics, substituted phenolics, thiophenolics, sulfones, substituted sulfones, polymers or copolymers of olefins, branched olefins, cyclic olefins, sulfonated olefins, acrylates, methacrylates, maleic anyhydride, and organosulfonic acids. They are usually made by reacting formaldehyde, phenol, polymethacrylic acid, maleic anyhydride, and sulfonic acid depending on specific chemistry. Further, the stain blocker is typically water soluble and generally penetrates the fiber while the anti-soil, usually a fluorochemical, is a non-water soluble dispersion that coats the surface of fiber. [0028] Examples of stain blockers include, but are not limited to: phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock Hill, N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I. du Pont de Nemours and Company, Wilmington, Del.); polymers of methacrylic acid such as the SCOTCHGARD FX series carpet protectors (from 3M Company, St. Paul Minn.); sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga); and stain resist chemistries from ArrowStar LLC, Dalton and Tri-Tex, Canada. [0029] Anti-soil components for use in the disclosed anti-soil compositions impart high specific surface energy properties such as high contact angles for water and oil (e.g. water and oil "beads up" on surfaces treated by it). The anti-soil component can comprise a fluorochemical dispersion, which dispersion may be predominantly either cationic or anionic, including those selected from the group consisting of fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical guanidines, non telomeric fluorochemicals, and fluorochemicals incorporating C2 to C8 chemistries. Alternatively, the fluorochemical can have one or more monomeric repeat units hearing less than or equal to eight fluorinated carbons, including less than or equal to six fluorinated carbons. Example fluorochemical anti-soil components include: DuPont TLF 10816 and 10894; Daikin TG 2511, and DuPont Capstone® RCP. Non-fluorinated anti-soil components can include: silicones, silsesquioxanes and silane-modified particulates, organosilane-modified particulates and alkylated particulates, anionic non-fluorinated surfactants and anionic hydrotrope non 9 WO 2014/047138 PCT/US2013/060345 fluorinated surfactants, including sulfonates, sulfates, phosphates and carboxylates. (See U.S. Patent No. 6,824,854, herein incorporated by reference). [0030] The dye composition is adapted to contact the twisted BCF yarn while it is in motion and prior to contacting the take-up reel or winder. Further, the dye composition can be at a neutral pH (e.g. 4 to 9, including 5.5 to 7.5) because the yarn can be optionally heat set after application of the composition. The process foregoes the need for harsh low pH chemicals; deionized water is suitable for use in the disclosed process. [0031] The stain blocker composition is adapted to contact the twisted BCF yarn while it is in motion and prior to contacting the take-up reel or winder. Further, the stain blocker composition can be at a neutral pH (e.g. 6 to 8) because the yarn can be optionally heat set after application of the composition. The process foregoes the need for harsh low pH chemicals. [0032] The anti-soil composition is adapted to contact the twisted BCF yarn while it is in motion and prior to contacting the take-up reel or winder. Further, the anti-soil composition can be at a neutral pH (e.g. 6 to 8) because the yarn can be optionally heat set after application of the composition. The process foregoes the need for harsh low pH chemicals. [0033] The contacting can be performed by any suitable device that applies wet ingredients to a dry substrate, including, but not limited to: applicator pad, nip rollers, wet-wick, dip-tank, sprayer, and mister. [0034] Another option is to transport dye solution or other treatment to the yarn using one or more rotating rolls covered with wicks. Here, the yarn may contact one roll or pass between two or more rotating rolls. The wicks on the surface of the rolls may be supplied with the treatment by one or more radially oriented capillaries extending from the inside to the outer surface of the cylindrical roll. The wicks may be located in a portion of of the surface or be distributed evenly throughout the surface. Where treatment to a localized portion of the yarn length is desired, a roll with a portion of wicks will be selected. Where treatment is desired along the entire length of the yarn, a roll with the wicks evenly distributed throughout the surface will be selected. [0035] To control the amount of dye solution or other treatment that contacts the yarn is metered by the use of a pump. This permits precise application of the dye or chemical treatment to the desired amount. The amount may be varied over the length of the yarn. 10 WO 2014/047138 PCT/US2013/060345 [0036] Further, multiple rolls can be used in series. For example, one roll can apply a first color onto one side of the moving yarn and another roll to apply a second color onto the other side of the yarn to create a unique two color yarn. Further, two sets of nip rolls can be used. The first set can apply the primary color and the second set can apply a second color or performance enhancing chemical onto the yarn. Any combination of the above options can be used to make yarn with multiple colors, color depth and with various performance chemicals. [0037] The wet pick-up of the anti-soil composition is between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%. The resulting twisted BCF yarn, if a fluorine based anti soil component is used, can have an on weight of fiber from about 100 ppm to about 1000 ppm elemental fluorine, including from about 100 to about 500 ppm elemental fluorine, from about 200 to about 400 ppm, and from about 100 ppm to about 300 ppm elemental fluorine. [0038] The wet pick-up of the stain blocker composition is present on weight of fiber from about 500 ppm to about 4%, including from about 1000 ppm to about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1%. Common stain blockers use sulfonated moieties as part of the chemistry, which results in the presence of sulfur on the treated fiber. The sulfur content can range from about 50 ppm with 5% stain blocker to about 1 ppm with 0.1% stain blocker on weight of fiber. Thus, based on the above stain blocker concentrations, the sulfur content on weight of fiber will range from about 0.5 ppm to about 40 ppm, including from about 1 ppm to about 30 ppm, from about 5 ppm to about 20 ppm, and from about 5 ppm to about 10 ppm. Sulfur content can be determined by x-ray diffraction or other methods. [0039] The performance enhancing compositions can further comprise one or more components selected from the group consisting of: odor control agents, anti-microbial agents, anti-fungal agents, fragrance agents, bleach resist agents, softeners, and UV stabilizers. [0040] The twisted BCF yarn can be made from polyamide fibers, such as those made from nylon 6,6, nylon 6, nylon 4,6, nylon 6,10, nylon 10,10, nylon 12, its copolymers, and blends thereof. Further, the twisted BCF yarn can also have additional polymer components, such as polyester. The additional polymer components can be incorporated with the polyamide (by melt-blend or co-polymerization) prior to making a polyamide fiber (e.g. a polyamide/polyester fiber), or can be stand-alone fibers that are twisted with the polyamide fibers to make the twisted 11 WO 2014/047138 PCT/US2013/060345 BCF yarn. However, cationic dyeable nylon, polyester, and acrylic fiber may also be used either together or exclusively. [0041] When only cationic dyeable nylon and/or polyester is present in the BCF yarn of the present invention, the use of a stain blocker is unnecessary. In other words, a stain blocker is excluded from the process, further streamlining and reducing costs and environmental exposure of these chemicals. A suitable cationic dyeable nylon may be any of the nylon compositions mentioned above, such as nylon 6 or nylon 66, that has been modified with sulfoisophthalic acid, sodium salt as a co-monomer, such as 5-sulfoisophthalic acid. [0042] As stated above, the BCF yarn can be manufactured with polyamide and / or polyester polymer components. An unexpected benefit of the disclosed process has been discovered in that, whereas a small amount of anti-soil composition is applied compared to known exhaust processes, a high anti-soil component content, such as fluorine, is achieved on the surface of the yarn. Further, the anti-soil composition applied in the process of the disclosed invention can be either fluorochemical or non-fluorochemical based, or a mixture of fluorochemical or fluoropolymer material with non-fluorinated soil resistant materials. [0043] The disclosed process may be used with yarns that do not require subsequent dyeing or performance enhancing chemical treatments, having been dyed and optionally treated with one or more performance enhancing compositions prior to twisting. The yarns can be made by acid dyed as well as disperse dyed fibers. Yarns suitable for use in the process may further comprise inherent stain resistance, whether by base composition as in the case of polyester, or by the inclusion of strong acid functionality in the polymer composition of the yarn, as in the case of nylon. Use of a dye applicator with the disclosed process eliminates the need for subsequent dyeing and enables the creation of colored carpets that improve inventory flexibility, improve color options, are stain resistant, and are soil resistant without the need for dyeing and performance enhancing chemical applications as practiced under the current state of the art. [0044] The twisted BCF yarn made with the various aspects of the disclosed process, by itself or blended with non-treated fibers and yarns, can be tufted and manufactured into carpets or fabrics. [0045] The disclosed process can also be advantageously applied in certain processes where a styling advantage might be derived from differential dyeing and finishing after carpet formation. For example, a soil resistant or stain resistant twisted yarn of the disclosed invention 12 WO 2014/047138 PCT/US2013/060345 could optionally be tufted into a carpet among untreated yarns prior to dyeing, thus creating an aesthetic alternative. [0046] Alternatively, the disclosed process can be modified to include dye application, optional anti-stain application and/or anti-soil application after the twisted BCF yarn is wound and prior to heat setting. For example, the twisted BCF yarn is unwound from a core or package, contacts the dye applicator, contacts the optional anti-stain applicator, and contacts the anti-soil applicator, then goes through a heat setting process to lock in the yarn twist, dye, anti-soil, and optional anti-stain. [0047] Further disclosed is a system for applying a dye composition and one or more performance enhancing compositions to the twisted BCF yarn. The system includes: (a) a first yarn take-up device that transmits a single yarn member made from at least two individual yarn members; (b) a dye composition applicator disposed downstream of said yarn take-up device that applies said dye composition to said single yarn member; (c) an optional anti-stain blocker applicator disposed downstream of said dye composition applicator that applies anti-stain composition to said single yarn member; (d) an anti-soil applicator disposed downstream of said dye composition applicator that applies anti-soil composition to said single yarn member; and (e) a second yarn take-up device that receives a dyed single yarn member. The first yarn take up device can be a take-up roll or reel that can twist the at least two individual yarn members into a single yarn member. Alternatively, the first yarn take-up device can receive BCF yarn that has been air twisted. The individual yarn members can be single filaments or fibers, or yarns made from a plurality of filaments or fibers. Each applicator can be any suitable device that applies wet ingredients to a dry substrate, including, but not limited to: applicator pad, nip rollers, wet-wick, dip-tank, sprayer, and mister. The wet pick-up of composition is between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%. The resulting twisted BCF yarn, if a stain blocker is used, is present on weight of fiber from about 500 ppm to about 4%, including from about 1000 ppm to about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1%. The resulting twisted BCF yarn, if a fluorine based anti-soil component is used, can have an on weight of fiber from about 100 ppm to about 1000 ppm elemental fluorine, including from about 100 to about 500 ppm elemental fluorine, from about 200 to about 400 ppm, and from about 100 ppm to about 300 ppm elemental fluorine. The second yarn take-up device can be a winder. 13 WO 2014/047138 PCT/US2013/060345 [0048] In a cable twisting process, a creel yarn and a bucket yarn, which is fed at a spindle speed of 7000 rpm, pass through an anti-balloon device and onto a take-up roll. From here, the twisted yarn is wound up on a winder. [0049] In one aspect of the disclosed process, a creel yarn and bucket yarn, which is fed at a spindle speed of 7000 rpm, pass through anti-balloon device and onto a take-up roll. A dye applicator is disposed downstream of take-up roll, which applies a dye component or other treatment to the twisted yarn. From here, the twisted and dyed yarn is wound up on a winder. [0050] Another aspect of the disclosed process includes two or more treatments such as both a dye applicator and anti-stain / anti-soil applicator. In this aspect, a creel yarn and bucket yarn, which is fed at a spindle speed of 7000 rpm, pass through an anti-balloon device and onto a take-up roll. A dye applicator is disposed downstream of take-up roll, which applies a first treatment, namely a dye component to the twisted yarn. An anti-soil I anti-stain applicator is disposed downstream of the dye applicator, which applies an anti-soil / anti-stain component to the dyed, twisted yarn. From here, the twisted and treated yarn is wound up on a winder. [0051] In a suitable heat setting process, cable twisted BCF yarn enters a false twisting unit, followed by a coiler or stuffer box, prebulker, and finally a heatset chamber to produce a heatset yarn. [0052] In an aspect of the disclosed process, where the cable twisted BCF yarn is dyed prior to heat setting, the cable twisted BCF yarn enters the dye applicator (or other treatment applicator), followed by a false twisting unit, a coiler or stuffer box, prebulker, and finally a heatset chamber to produce a dyed, heatset yarn. [0053] The disclosed process is counterintuitive and surprisingly results in yarn that contains acceptable dyed and performance enhancement properties when manufactured into a carpet or fabric. One would expect that rearranging the process as described above would fowl up down stream carpet manufacturing processes and lead to poor quality carpet. Thus, the results reported below are surprising and unexpected. EXAMPLES [0054] The following are examples of carpets made from BCF fibers that have been treated according to various aspects of the process disclosed above, and similar fibers with no 14 WO 2014/047138 PCT/US2013/060345 treatment. Selection of alternative dyeing and performance enhancing components, fibers and textiles having different surface chemistries will necessitate minor adjustments to the variables herein described. Test Methods Acid Dye Stain Test. [0055] Acid dye stain resistance is evaluated using a procedure modified from the American Association of Textile Chemists and Colorists (AATCC) Method 175-2003, "Stain Resistance: Pile Floor Coverings." 9 wt % of aqueous staining solution is prepared, according to the manufacturer's directions, by mixing cherry-flavored KOOL-AID* powder (Kraft/General Foods, White Plains, N.Y., a powdered drink mix containing, inter alia, FD&C Red No. 40). A carpet sample (4x6-inch) is placed on a flat non-absorbent surface. A hollow plastic 2-inch (5.1cm) diameter cup is placed tightly over the carpet sample. Twenty ml of the KOOL-AID@ staining solution is poured into the cup and the solution is allowed to absorb completely into the carpet sample. The cup is removed and the stained carpet sample is allowed to sit undisturbed for 24 hours. Following incubation, the stained sample is rinsed thoroughly under cold tap water, excess water is removed by centrifugation, and the sample is dried in air. The carpet sample was visually inspected and rated for staining according to the FD&C Red No. 40 Stain Scale described in AATCC Method 175-2003. Stain resistance is measured using a 1-10 scale. An undetectable test staining is accorded a value of 10. Example 1 (Comparative) [0056] Two 920 denier white acid dyeable Nylon 66 BCF made from acid dyeable polymer were cable twisted on Volkman at 7000 rpm to form a 6.25 tpi two ply yarn. The winding speed was about 50 ypm. The cable twisted yarn as subsequently heatset on Superba with 129 0 C saturated steam. The holdup time in the channel was about 36 seconds. The heat treated yarn was converted into a 35 oz per square yard, 1/8 gauge, 22/32" pile height cut pile carpet and dyed on a continuous dyer to medium beige color. The finished carpet was tested for repellence and acid stain resistance. It was rated to have 1 (failed) on 24 hour stain test and 0 for both oil and water repellence. 15 WO 2014/047138 PCT/US2013/060345 Example 2 (inventive) [0057] Two 997 denier white Nylon 66 BCF made from cationic dyeable polymer were cable twisted on Volkman at 7000 rpm to form a 6.25 tpi two ply yarn using the process described above. The winding speed was about 50 ypm. A dye applicator was inserted between the take up roll and the winder. A 1/2 inch wide, 1.5" thick cotton wick (Wet Wick by Perperell MA) was used to apply premet dyes (Yellow 2BRLSM by Greenville Colorants 24 grams/liter, Red B by huntsman 0.860 grams/liter, Blue 3GL by huntsman 9.1 grams/liter, wetting agent DOSS by Star technologies 15 grams/liter, pH 7.1) onto the cable twisted yarn. The cable twisted yarn went through the wet. wick about 50 ypm. The cable twisted yarn was subsequently heatset on Suessen with 200*C dry air. The holdup time in the channel was about 60 seconds. The heatset yarn was converted into 35 oz/yd, 22/32" pile height on a 1/8 gauge tufting machine. Latex and secondary backing were added to the tufted carpet to secure tufts. The finished carpet had a light beige color (Minota L 63.34, a 3.26, b 12.56). The finished carpet was tested for repellence and stain resistance using (AATCC) Method 175-2003. It was rated to have 10 for both 24 hour stain and WAQE, but 0 for water and oil repellence. Example 3 (inventive) [0058] Two 997 denier white Nylon 66 BCF made from cationic dyeable polymer were cable twisted on Volkman at 7000 rpm to form a 6.25 tpi two ply yarn. The winding speed was about 50 ypm. The cable twisted yarn was heatset on Suessen with 200*C dry air. Two color wicking stations arranged in series were inserted between the creel and the false twisting unit. A %" wide, 1.5" thick cotton wick was used in each wicking station to apply premet dyes (Huntsman Yellow 3RL 5.31 g/l, Red B 1.14 g/l, Blue 3GL 1.53 g/l, wetting agent Doss 15 g/l, pH 8.5) onto the cable twisted yarn. The processing speed was about 350 ypm. The holdup time inside the heatset channel was about 60 seconds. The heatset yarn was converted into 35 oz, 22/32" pile height cut pile carpet on a 1/8 gauge tufting machine. The finished carpet had light beige color (Minota L 70.76, a 2.78, b 10.66) and was tested for repellence and stain resistance using (AATCC) Method 175-2003. It was rated to have 9 for both 24 hour stain and WAQE, but 1 for water and 0 for oil repellence. Example 4 (inventive) [0059] Two 997 denier white Nylon 66 BCF made from cationic dyeable polymer were cable twisted on Volkman at 7000 rpm to form a 6.25 tpi two ply yarn using the process described above. The winding speed was about 50 ypm. A dye applicator was inserted between the take up roll and the winder. A 0.5" inch wide, 1.5" thick cotton wick (Wet Wick by Perperell MA) was 16 WO 2014/047138 PCT/US2013/060345 used to apply premet dyes (Yellow 3RL 5.31 g/Il, Red B 1.14 g/l, Blue 3GL 1.51 g/Il, wetting agent Doss 15 g/l, pH 8.5) onto the cable twisted yarn. The cable twisted yarn went through the wet wick about 50 ypm. The cable twisted yarn was subsequently heatset on Suessen with 2000C dry air. A wicking unit was inserted between the creel and the false twisting unit. Fluoro-chemical (50% A-201 anti-soil chemical) was applied to the cable twisted yarn through the wick. The holdup time in the channel was about 60 seconds. The heatset yarn was analyzed to have 390 ppm Fluorine. The heatset yarn was converted into 35 oz/yd, 22/32" pile height on a 1/8 gauge tufting machine. Latex and secondary backing were added to the tufted carpet to secure tufts. The finished carpet had a light beige color and was tested for repellency and stain resistance using (AATCC) Method 175-2003. It was rated to have 9 for both 24 hour and WAQE stain resistance and 3 for water, 4 for oil repellence. Example 5 (inventive) [0060] Two 997 denier white Nylon 66 BCF made from cationic dyeable polymer were cable twisted on Volkman at 7000 rpm to form a 6.25 tpi two ply yarn using the process described above. Two wicking stations arranged in series were inserted between the take up roll and the winder. A %" wide, 1.5" thick cotton wick was used in the first wicking station to apply premet dyes (Yellow 3RL 5.31 g/l, Red B 1.14 g/l, Blue 3GL 1.53 g/Il, wetting agent Doss 15 g/l, pH 8.5) onto the cable twisted yarn. A %" wide, 1.5" thick cotton wick was used in the second station to apply Fluoro chemical (50% A-201) onto the cable twisted yarn. The processing speed was about 50 ypm. The cable twisted yarn was heatset on Suessen at 200*C. The holdup time inside the heatset channel was about 60 seconds. The heatset yarn was analyzed to have 170 ppm Fluorine. It was converted into 35 oz, 22/32" pile height cut pile carpet on a 1/8 gauge tufting machine. The finished carpet had light beige color (Minota L 70.46, a 3.42, b 10.39) and was tested for water/oil repellence and stain resistance using (AATCC) Method 175 2003. It was rated to have 9 for 24 hour and WAQE stain resistance, 4 for water and 5 for oil repellence. 17 WO 2014/047138 PCT/US2013/060345 Example 6 (inventive) [0061] A 1245 denier, 64 filament nylon BCF made from cationic dyeable polymer (Type 294AT) was processed on a rewinding machine. Two wicking stations with /" wide, 1" thick were inserted between the creel and winder. Pre-metalized dyes (Isolan yellow NW 2.52 gIl, red S-RL 2.54 gIl, blue 3GL 27.57 g/Il, pH 5) were used to dye the BCF yarn to medium blue color. The winding speed was about 300 yards per minute. The test yarn was knitted into sock, treated with steam for two minutes. The treated sock had a medium blue color (L51.47, a -2.18, b -2.71) Example 7 (inventive) [0062] This example was similar to example 6, except new dye formulation (Dystar Isolan yellow NW 23.0 g/l, red S-RL 6.03 g/l, black 2S-CP 2.359 g/l, pH 5) was used to dye 1245 294AT yarn. The dyed yarn was converted into a 1/8" pile height, 12 oz/yd loop pile carpet on a 5/64 gauge machine. The tufted carpet was treated with steam for 2 minutes to set the dye. It had a medium gold color (L 45.30, a 14.26, b 26.59) Example 8 (inventive) [0063] Two 1100 denier 6 dpf white dyeable polyester BCF (item WS-1) were cable twisted on Volkman cable twisting machine at 6900 rpm to form 5.75tpi two ply yarn using the process described in above. The winding speed was about 50 rpm. The cable twisted yarn was heatset on Suessen with 185"C dry air. Two color wicking stations arranged in series were inserted between the creel and the false twisting unit. A %2" wide, 1.5" thick cotton wick was used in each wicking station to apply disperse dyes (Dianix yellow E-3GE 23.73 g/l, red E-FB 13.74 g/l, blue ER-AM 6.16 g/I by Dystar, Techwet Spmia 5 g/I by Dyetech Inc. pH 5.0) onto the moving cable twisted yarn. The processing speed was about 350 ypm. The holdup time inside the heatset channel was about 60 seconds. The heatset yarn was converted into 45 oz, 22/32" pile height cut pile carpet on a 1/8 gauge tufting machine. The finished carpet had a medium brown color (Minota L 44.83, a 7.68, b 17.11). 18

Claims (27)

1. A process for treating twisted bulked continuous filament (BCF) yarn with a dye composition comprising: a. providing twisted BCF yarn; b. winding said BCF yarn on a take-up reel; and c. contacting said BCF yarn with said dye composition while said BCF yarn is in motion and prior to said BCF yarn contacting and winding up on said take-up reel wherein said BCF yarn is selected from the group consisting of cationic dyeable nylon and polyester.

2. The process of claim 1, further comprising heat setting said BCF yarn after contacting said BCF yarn with said dye composition.

3. The process of claim 1, wherein said dye composition comprises one or more acid dye components.

4. The process of claim 1, wherein said dye composition comprises one or more disperse dye components.

5. The process of claim 1, wherein said dye composition comprises at least one performance enhancing composition.

6. A process for treating twisted BCF yarn with a dye composition and at least one performance enhancing composition comprising: a. providing twisted BCF yarn; b. winding said BCF yarn on a take-up reel; c. contacting said BCF yarn with said dye composition; and d. contacting said BCF yarn with a performance enhancing composition prior to said BCF yarn contacting and winding up on said take-up reel, wherein said BCF yarn 19 WO 2014/047138 PCT/US2013/060345 is in motion while contacted with said dye composition and said first performance enhancing composition.

7. The process of claim 6, wherein said performance enhancing composition excludes an anti-soil component.

8. The process of claim 6, wherein said first performance enhancing composition comprises an anti-stain component.

9. The process of claim 6, wherein said first performance enhancing composition comprises both an anti-stain component and an anti-soil component.

10. The process of claim 6 further comprising contacting said BCF yarn with a second performance enhancing composition after contacting with said first performance enhancing composition and prior to said BCF yarn contacting and winding up on said take-up reel.

11. The process of claim 10, wherein said first performance enhancing composition comprises an anti-stain component and said second performance enhancing composition comprises an anti-soil component.

12. The process of one of claims 6-9 further comprising heat setting said BCF yarn after contacting said BCF yarn with said first performance enhancing composition.

13. The process of claim 10 or 11 further comprising heat setting said BCF yarn after contacting said BCF yarn with said second performance enhancing composition.

14. The process of one of claims 8, 9, and 11, wherein said anti-stain component is one or more selected from the group consisting of: syntans, sulfonated novolacs, sulfonated aromatic aldehyde condensation products (SACs) and/or reaction products of formaldehyde, phenolics, substituted phenolics, thiophenolics, sulfones, substituted sulfones, polymers or copolymers of olefins, branched olefins, cyclic olefins, sulfonated olefins, acrylates, methacrylates, maleic anyhydride, and organosulfonic acids.

15. The process of one of claims 7, 9, and 11, wherein said anti-soil component is selected from the group consisting of fluorochemicals, , silicones, silsesquioxanes, silane modified particulates, organosilane-modified particulates, alkylated particulates, anionic non fluorinated surfactants, and anionic hydrotrope non-fluorinated surfactants. 20 WO 2014/047138 PCT/US2013/060345

16. The process of claim 15, wherein said fluorochemical is selected from the group consisting of: fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical guanidines, and fluorochemicals incorporating C2 to C8 chemistries.

17. The process of claim 15, wherein said fluorochemical has one or more monomeric repeat units bearing less than or equal to six perfluorinated carbons.

18. The process of claim 15, wherein said fluorochemical is a fluorochemical urethane.

19. The process of one of claims 8, 9, or 11, wherein said anti-stain component is present at an on weight of fiber from about 500 ppm to about 4%.

20. The process of one of claims 1-11, wherein said dye composition has a pH from about 4 to about 9.0.

21. The process of claim 6, wherein said first performance enhancing composition comprises a component selected from the group consisting of: odor control agents, anti microbial agents, anti-fungal agents, fragrance agents, bleach resist agents, softeners, and UV stabilizers.

22. The process of claim 6, wherein said first performance enhancing composition comprises a component selected from the group consisting of: dye auxiliaries, sequestrants, pH control agents, and surfactants.

23. The process of one of claims 7, 9, or 11, wherein said anti-soil component is present at an on weight of fiber from about 100 ppm elemental fluorine to about 1000 ppm elemental fluorine.

24. The process of claim 2, wherein said heat setting is performed at a temperature from about 1250C to about 200*C.

28. The process of claim 27, wherein said polyester fiber is selected from the group consisting of poly(ethylene terephthalate), poly(propylene terephthalate), poly(butylene terephthalate), copolymers, and blends thereof.

29. The process of claim 1 or 6, wherein said BCF yarn comprises a polyamide component and a polyester component. 21 WO 2014/047138 PCT/US2013/060345

30. The process of any of the preceding claims, wherein said contacting is performed by a device selected from the group consisting of: applicator pad, wet-wick, dip-tank, sprayer, and mister. 22