WO2014063028A1

WO2014063028A1 - Process for coloring textile materials

Info

Publication number: WO2014063028A1
Application number: PCT/US2013/065644
Authority: WO
Inventors: Harrie Schoots; Greg MOAKES; William Jun
Original assignee: Celanese International Corporation
Priority date: 2012-10-19
Filing date: 2013-10-18
Publication date: 2014-04-24
Also published as: CN104736762A; WO2014063037A1; US20150299949A1

Abstract

A process for applying color to a textile material comprises contacting the textile material with an aqueous coloring medium comprising at least one dye and/or pigment and an aqueous dispersion of a copolymer binder produced from a monomer composition comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylontrile. The contacting deposits a coating of the coloring medium at least on part of the surface of the textile material so that, after drying, the dye or pigment is bonded to the material surface to produce a colored textile material exhibiting improved depth of shade, crockfastness and lightfastness.

Description

PROCESS FOR COLORING TEXTILE MATERIALS

FIELD

[0001] This application relates to a process for coloring textile materials.

BACKGROUND

[0002] Coloring textile materials with dyes and pigments frequently involves chemically treating the materials before or after application of the dye or pigment so as to increase retention of the colorant.

[0003] For example, it is known from the article by Shen at al. entitled "Application of cationic emulsion adhesive to pigment pad dyeing", Chinese Journal of Printing and Dyeing, 2009, Issue 5, that cationic polymer emulsions formed from n-butyl acrylate and styrene can be applied to the surface of a fabric to improve the rubbing fastness of subsequently applied pigment pad dyes.

[0004] In addition, U.S. Patent No. 5,464,452 discloses a process for fixing a dye to a dyed fine-dimensional yarn fabric made from the group consisting of a polyamide-containing substrate, segmented polyester-polyurethane substrate, and combinations thereof. The process comprises contacting the fabric with an aqueous solution of a dye-fixative composition substantially free of phenol and formaldehyde residues such that the dye-fixative composition is absorbed by the fabric. The dye-fixative composition is selected from the group consisting of (a) polymethacrylic acid, and (b) a copolymer of methacrylic acid and an ethylenically unsaturated comonomer selected from the group consisting of 2-acrylamido-2-methyl-propanesulfonic acid, sodium vinyl sulfonate, sodium styrene sulfonate, lower alkyl acrylates, and combinations thereof.

[0005] However, since these chemical treatments are conducted separately from the application of the dye or pigment to the fabric, they necessarily add cost, time and complexity to the overall dyeing process.

[0006] It is also well-known to apply colorant to a textile fabric by application of a printing paste comprising a binder and a pigment or dye normally together with an additional reactive compound which, after printing, cross-links the binder at a relatively high temperature so as to fix the print and impart the required water resistance to the printed image. In the past, melamine/formaldehyde condensates were most commonly used as the cross-linking agents for the binders used in textile printing pastes. However, the cross-linking reactions using these condensates require temperatures above 120 °C and, since cross-linking is catalyzed by acids via N-methylol groups in the binder, formaldehyde is given off during the cross-linking reaction and also subsequently when the printed textiles are in use. Since formaldehyde is known to have carcinogenic properties, there is a continuing interest in developing formaldehyde-free pigment binder systems.

[0007] For example US Patent No. 5,556,935 discloses a textile printing paste comprising a pigment, a binder, and a cross-linking agent, wherein the cross-linking agent consists essentially of a polyisocyanate mixture prepared by reaction at an NCO:OH equivalent ratio of at least 2: 1 of (A) a polyisocyanate component having an (average) NCO functionality of 2.1 to 4.4 in which at least one polyisocyanate of said polyisocyanate component contains only (cyclo)aliphatically bound isocyanate groups with (B) a polyalkylene oxide polyether alcohol containing a statistical average of 5 to 70 ethylene oxide units. Suitable binders include polymers based on natural or synthetic rubber, styrene/butadiene copolymers, polymers of 2-chlorobutadiene, styrene/acrylonitrile copolymers, polyethylene, chloro sulfonated or chlorinated polyethylene, butadiene/acrylonitrile copolymers, butadiene/methacrylate copolymers, polyacrylates, PVC or optionally partly saponified ethylene/vinyl acetate copolymers, or polyaddition compounds, such as those based on polyurethanes, Using the specified hydrophilicized isocyanates, cross-linking of the binder is said to be effective using curing conditions of 80 to 100 °C. for 1 to 10 minutes.

[0008] According to the present invention, it has now been found that, by combining an aqueous dispersion of an acrylate/acrylonitrile copolymer with a conventional dye or pigment, it is possible to produce a water-based coloring medium which can be applied directly to an untreated textile material by, for example exhaustion or spraying, to produce a colored textile material. Even with a low level of dye or pigment in the coloring medium and without repeated applications of the coloring medium, the process produces a colored textile material exhibiting improved depth of shade, crockfastness and lightfastness. Moreover, the process does not require a high temperature curing step or employ time-consuming post treatment or extensive final washing steps. As a result the time required to produce a marketable colored product is significantly reduced over most existing pigment dyeing processes. SUMMARY

[0009] In one aspect, the invention resides in a process for applying color to a textile material, the process comprising:

(a) providing an aqueous coloring medium comprising at least one dye and/or pigment and an aqueous dispersion of a copolymer binder produced from a monomer mixture comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylonitrile; and

(b) contacting the textile material with said aqueous coloring medium to deposit the coloring medium at least on part of the surface of the textile material and produce a colored textile material.

[0010] In one embodiment, the aqueous coloring medium is deposited on the colored textile material by spraying.

[0011] In a further aspect, the invention resides in a process for applying color to a textile material, the process comprising:

(a) contacting the textile material with an aqueous composition comprising a dye or pigment to deposit the dye and/or pigment at least on part of the surface of the textile material;

(b) adding an aqueous dispersion of a copolymer binder produced from a monomer mixture comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylonitrile to the aqueous composition to produce an aqueous coloring medium; and

(c) contacting the textile material with said aqueous coloring medium to further deposit the coloring medium at least on part of the surface of the textile material and produce a colored textile material

[0012] In one embodiment, the contacting steps (a) to (c) are conducted by exhaustion in the same dye bath.

[0013] In one embodiment, the copolymer is binder produced from a monomer composition comprising one or more alkyl acrylate and/or alkyl methacrylate monomers selected from butyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof. For example, the monomer mixture may comprise at least 70 wt% of said one or more alkyl acrylate or methacrylate monomers and up to 20 % by weight, such as from 0.1 to 20% by weight, such as 5 to 15 % by weight, for example from 6 to 12 %, by weight of acrylonitrile based on the total weight of monomers in said monomer composition. The monomer mixture may also comprise from 0.1 wt to about 10 wt , based on total monomers in the monomer composition, of one or more ethylenically unsaturated cross-linking co-monomers.

[0014] In one embodiment, the textile material comprises at least 50 wt cotton and the dye or pigment is selected from an indigo dye, a sulfur dye and a disperse dye.

[0015] In yet a further aspect, the invention resides in a textile material colored with a non- white dye or pigment bound to the textile material by a copolymer binder produced from a monomer mixture comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylonitrile, wherein the colored textile material has a dry crockfastness of at least 4 when measured by AATCC Test Method 8 and shade loss of less than 20% when measured by AATCC Test Method 2A.

DETAILED DESCRIPTION

[0016] A process for applying color to a textile material comprises contacting the textile material with an aqueous coloring medium comprising at least one dye and/or pigment and an aqueous dispersion of a copolymer binder produced from a monomer composition comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylontrile. The contacting deposits a coating of the coloring medium at least on part of the surface of the textile material so that, after drying, the dye or pigment is bonded to the material surface to produce a colored textile material exhibiting improved depth of shade, crockfastness and lightfastness.

Textile Material

[0017] The term "textile fibers" is used herein to individual staple fibers or filaments (continuous fibers), yarns, fabrics, and articles (e.g., garments). Yarns may include, for instance, multiple staple fibers that are twisted together ("spun yarn"), filaments laid together without twist ("zero-twist yarn"), filaments laid together with a degree of twist, and a single filament with or without twist ("monofilament"). The yarn may or may not be texturized. Suitable fabrics may likewise include, for instance, woven fabrics, knit fabrics, and non- woven fabrics. Garments may be apparel and industrial garments. The terms "fabrics" and "textiles" also include home goods such as linens, drapery, and upholstery (automotive, boating, airline included) made of the cotton fibrous materials described herein. The present process is, however, particularly applicable to the dyeing of finished garments so that the garments are substantially uniformly covered with a single color, rather than printing one or more on certain parts of the garments.

[0018] The textile material can be formed of natural fibers, such as cotton, silk, linen, wool, angora and mohair, or of synthetic fibers, such as polyester fibers, aramid fibers, polyamide (nylon) fibers, acrylic (acrylonitrile) fibers, spandexes, rayons, Tencel and cellulose acetate fibers. Combinations of natural and synthetic fibers can also be used. Materials containing significant amounts of cotton (at least 25 wt , such as at least 50 wt , even up to 100 wt%) are particularly suitable for use in the present process.

Dye or Pigment

[0019] Any dye or pigment conventionally used to color textile materials can be used in the present process and can be applied by both batch and continuous processes. In this respect, the term "dye" is used in its commonly accepted sense to mean a colorant which either is itself liquid or is soluble in its vehicle (resulting in a solution), while the term "pigment" refers to colorants which are insoluble in the vehicle (resulting in a suspension). In addition, dyed goods have a wide variety of dye classes that each use different dye-fiber fixation methods; such as Van der Waal forces, covalent bonding, ionic bonds, physical entrapment; whereas in a pigment dyed garment attachment of the pigment to the garment is by physical entrapment.

[0020] Any pigment colorant known in the art that will provide the color desired to a textile material can be used in the present process. Examples of such pigment colorants, with specific pigments and/or colors specified in parenthesis, include, but are not limited to, arsenic pigments (Paris green); carbon pigments (carbon black, ivory black, vine black lamp black); cadmium pigments (cadmium green, cadmium red, cadmium yellow, cadmium orange); iron oxide pigments (caput mortuum, oxide red, red ochre, sanguine, Venetian red, mars black; Prussian blue pigments; chromium pigments (chrome green, chrome yellow); cobalt pigments (cobalt blue, cerulean blue, cobalt violet, aureolin); lead pigments (lead white, Naples yellow, cremnitz white, red lead); copper pigments (Paris green, verdigris, viridian, Egyptian blue, han purple); titanium pigments (titanium white, titanium beige, titanium yellow, titanium black); ultramarine pigments (ultramarine, ultramarine green shade, French ultramarine); mercury pigments (vermilion); zinc pigments (zinc white); clay earth (iron oxide) pigments (raw sienna, burnt sienna, raw umber, burnt yellow, yellow ochre); organic pigments (pigment red 170, phthalo green, phthalo blue, quinacridone magenta); and lapis lazuli. In one embodiment, the pigments may be selected from organic pigments. In such embodiments, the pigments may be selected from carbon pigments. In other embodiments, the pigments may be selected from inorganic pigments. In one or more of these embodiments, the pigments may be selected from iron oxide pigments. In one or more other embodiments, the pigments may be selected from chromium pigments. In still other embodiments, the pigments may be selected from copper pigments.

[0021] Any known dye material can be used in the present process, although generally preference is given to indigo dyes, sulfur dyes and disperse dyes and especially to disperse dyes.

[0022] Indigo has been used to dye fabric with "indigo blue" since before recorded history. Indigotin (C^H^r^C^) is the true coloring matter of indigo. When pure, indigotin forms a dark, rich blue powder or bronzy blue-colored needle crystals. The most important reaction of indigotin is its reaction with reducing agents. When subjected to a reducing agent in the presence of alkali, indigotin combines with two atoms of hydrogen and is reduced to a colorless body, known as indigo- white or the leuco form, which is insoluble in water, but dissolves in alkali, with a yellow color. The lueco form of the indigo dye deposited onto cotton yarn is generally subjected to a "skying" process wherein the lueco form of the dye is oxidized with air to a blue indigo color.

[0023] Sulfur dyes are sulfur-containing, complex synthetic organic dyes and are the most commonly used dyes manufactured for cotton in terms of volume. They are primarily used for dark colors such as blacks, browns, and dark blues. They are cheap, generally have good wash- fastness and are easy to apply. Sulfur dyes are water insoluble and have to be treated with a reducing agent and an alkali at a temperature sufficient to break up the dye into small particles. The dye then becomes water soluble and hence can be absorbed by a textile material. The dyes are absorbed from a bath containing sodium sulfide or sodium hydrosulfite and are made insoluble within the textile by oxidation. During this process these dyes form complex larger molecules which is the basis of their good wash-fastness.

[0024] Disperse dyes were originally developed for the dyeing of cellulose acetate and are water-insoluble. They are generally finely ground in the presence of a dispersing agent (surfactant) and are sold as a paste or spray-dried and sold as a powder. Suitable disperse dyes for use in the dyeing method herein are those described under "Disperse Dyes" in the Colour Index, 3rd edition (3rd revision 1987 inclusive of Additions and Amendments up to No. 85). Such dyes include, for example, carboxylic acid group-free and/or sulfonic acid group-free nitro, amino, aminoketone, ketoninime, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine and coumarin dyes and especially anthraquinone and azo dyes, such as mono- or di-azo dyes. Such disperse dyes are also those described in detail in U.S. Patent Publication No. 2006/0048308. That '308 patent document, and especially its disclosure of the several structural formulas for disperse dye materials disclosed therein, is incorporated herein by reference.

[0025] Examples of commercially available primary red color disperse dyes include Disperse Red 60 (Intrasil Brilliant Red 2B 200%), Disperse Red 50 (Intrasil Scarlet 2GH), Disperse Red 146 (Intrasil Red BSF), Disperse Red 127 (Dianix Red BSE), Dianix Red ACE, Disperse Red 65 (Intrasil Red MG), Disperse Red 86 (Terasil Pink 2 GLA), Disperse Red 191 (Intrasil Pink SRL), Disperse Red 338 (Intrasil Red 4BY), Disperse Red 302 (Tetrasil Pink 3G), Disperse Red 13 (Intrasperse Bordeaux BA), Disperse Red 167 (Foron Rubine S-2GFL), and Disperse Violet 26 (Intrasil Violet FRL). Examples of commercially available primary blue color disperse dyes include Disperse Blue 60 (Terasil Blue BGE 200%), Disperse Blue 291 (Intrasil Blue MGS), Disperse Blue 118 (Terasil Blue GBT), Terasil Blue HLB, Dianix Blue ACE, Disperse Blue 87 (Intrasil Blue FGB), Disperse Blue 148 (Palnnil Dark blue 3RT), Disperse Blue 56 (Intrasil Blue FBL), and Disperse Blue 332 (Bafixan Turquoise 2 BL liq.). Examples of commercially available primary yellow color dyes include Disperse Yellow 64 (Disperite Yellow 3G 200%), Disperse Yellow 23 (Intrasil Yellow 5R), Palanil Yellow HM, Disperse Brown 19 (Dispersol Yellow D-7G), Disperse Orange 30 (Foron Yellow Brown S-2RFL), Disperse Orange 41 (Intrasil Orange 4RL), Disperse Orange 37 (Intrasil Dark Orange 3GH), Disperse Yellow 3, Disperse Orange 30, Disperse Yellow 42, Disperse Orange 89, Disperse Yellow 235, Disperse Orange 3, Disperse Yellow 54, Disperse Yellow 233 (Foron Yellow S-6GL),

[0026] The preferred types of disperse dye materials useful herein include the quinoline dyes, the anthraquinone dyes and the azo dyes. The dyeing method herein is equally useful with disperse dyes whether they are classified as high energy dyes, medium energy dyes or low energy dyes. Useful disperse dyes which can be used herein also include dyes which are especially formulated for to serve as automotive dyes, lightfast dyes or fluorescent dyes.

Copolymer Binder

[0027] The aqueous coloring medium employed in the present process also comprises at least one binder comprising an aqueous dispersion of a copolymer produced from a monomer composition comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylonitrile. Typically, the monomer composition comprises at least 80 weight %, or even at least 85 weight %, of the alkyl acrylate or alkyl methacrylate monomers and up to 20 % by weight, such as from 0.1 to 20% by weight, for example from 5 to 15 % by weight, preferably from 6 to 12 %, of acrylontrile, both percentages being based on the total weight of the monomer composition. Suitable alkyl acrylates and methacrylates include butyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof.

[0028] The copolymer binder will frequently contain, in addition to the main monomers described above, minor amounts of co-monomers which can provide cross-linking with both cellulose hydroxyl moieties within the cotton fibers and cross-linking within the polymer itself. Such cross-linking co-monomers are unsaturated so as to polymerize into the polymer backbone and will also contain at least one functional group such as nitrogen, oxygen and/or silicon atoms.

[0029] Thus the polymer binder used herein can comprise from about 0.1 wt% to about 10 wt%, such as from about 0.5 wt.% to about 8 wt.%, for example from about 1 wt.% to about 6 wt.%, based on total monomers in the polymer, of one or more ethylenically unsaturated cross- linking co-monomers having, for example, at least one amide, epoxy, or alkoxysilane group. Specific examples of such co-monomers include, for instance, acrylamides, such as N- methylolacrylamide (NMA), N-methylolmethacrylamide, diacetoneacrylamide, etc., as well as esters or ethers thereof, such as isobutoxy ethers or esters of N-methylolacrylamide, of N- methylolmethacrylamide. Also suitable are epoxide-functional co-monomers, such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, etc. Further examples are silicon-functional co-monomers, such as acryloxy-propyltri(alkoxy)silanes and methacryloxy-propyltri(alkoxy)silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, with alkoxy groups which can be present being, for example, methoxy, ethoxy and ethoxypropylene glycol ether radicals. Yet other suitable crosslinking co-monomers have hydroxy and/or carboxyl groups, such as hydroxyalkyl methacrylates and acrylates (e.g., hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate), acetylacetoxyethyl acrylate or methacrylate, dimethylaminoethyl acrylate, etc.

[0030] The polymer binder can also contain, in addition to the main monomers and self cross-linking co-monomers, minor amounts of multifunctional external cross-linking co- monomers. Thus the copolymers used herein can optionally comprise from about 0.1 wt% to about 10 wt%, based on total monomers in the copolymer, of one of more of these multifunctional cross-linking co-monomers. Suitable external crosslinking agents may also include phenol formaldehyde resins, resorcinol formaldehyde resins, melamine formaldehyde resins, hydroxymethylsubstituted imidazolidinones or thioimidazolidinones, hydroxymethyl substituted pyrimidinones or hydroxymethyl substituted triazinones or glycoluriles or their self- condensation products are suitable or mixed condensates from two or more of the compounds mentioned, or a mixture from two or more of the compounds mentioned. When employed, such crosslinking agents are typically combined with the polymer after it is formed.

[0031] The polymer binders used herein can frequently be selected from commercially available aqueous copolymer dispersions. Alternatively, suitable cellulose-reactive copolymers can be prepared in conventional fashion using known emulsion polymerization techniques and raw materials. In general, such emulsion copolymers can be prepared by polymerizing appropriate co-monomers in appropriate amounts in an aqueous reaction mixture using conventional polymerization initiators and catalysts and conventional polymerization conditions. Suitable polymerization processes are described in the Kirk-Othmer Encyclopedia of Chemical Technology, 4^th Ed Vol. 24, pp. 954-963 (Wiley 1996). The copolymer emulsions so prepared can be stabilized with conventional emulsifiers (surfactants) and/or protective colloids. Prior to use as a binder in the coloring medium, the polymeric dispersions are normally diluted with water to a polymeric solids content of less than 20 wt , such as from about 3 wt to about 12 wt , more preferably from about 4 wt to about 6 wt . Generally, the pH of the aqueous polymeric dispersions used in the coloring medium is adjusted to a value from about 3 to about 7, more preferably from about 5 to about 7.

Coloring Medium

[0032] The coloring medium employed in the present process is produced by mixing the aqueous copolymer dispersion described above with the desired dye or pigment to produce an aqueous mixture containing from about 1% to about 10%, more preferably from about 2 wt% to about 7 wt%, of copolymer solids and from about 0.1 wt% to about 15 wt%, more preferably from about 8 wt% to about 12 wt%, of the dye or pigment, with the remainder being water. In one embodiment, the coloring medium includes up to 12 wt% of an auxiliary binding agent typically used in pigment dyeing, such as Trichromatic AC50. [0033] In addition to the dye or pigment and the copolymer binder, the aqueous coloring medium can optionally contain various fiber and fabric treating adjuvants. Such adjuvants can include, for example, optical brighteners, fabric softeners, antistatic agents, antibacterial agents, anti-wrinkling agents, ironing aids, flame-retardants, enzymes, UV stabilizers, anti-foaming agents, perfumes, and the like.

Dyeing Process

[0034] The coloring medium can be applied to the textile material by any known method of applying liquids, such as dyes, to textiles. For example, the coloring medium can be applied by exhaustion processing; that is, batchwise, with the textile material being immersed in a dilute aqueous treatment bath containing the coloring medium. In another embodiment, the textile material can be treated on a continuous apparatus for immersion treating textiles, as is disclosed, for example, in U.S. Patent No. 4,920,621, the disclosure of which is incorporated herein by reference. An alternative application method, particularly suitable for woven and knit textile fabrics, is continuous padding. It is also possible to apply the coloring medium to a textile yarn for example in a continuous slasher type machine to allow, for example, the production of a crockfast denim fabric with the warp yarn, but not the weft yarn, having dye or pigment applied thereto. Another suitable application method is printing, particularly where it is desired to apply the coloring medium to selected parts, rather than the entire textile material. One method of applying the coloring medium is by spraying since this decreases application time and reduces the amount of dye or pigment required.

[0035] In an alternative embodiment, the textile material is initially subjected to a first contacting step with an aqueous composition comprising a dye or pigment, but without the copolymer binder, under conditions to deposit the dye and/or pigment at least on part of the surface of the textile material. For example, the first contacting step may be conducted at a temperature of 10 to 60 °C for a period of 10 to 30 minutes using at a liquor ratio of 1: 1 to 30: 1, preferably 5: 1 to 30: 1, more preferably 10: 1 to 30: 1. At the end of the first contacting step, an aqueous dispersion of the copolymer binder is added to the aqueous composition to produce an aqueous coloring medium. The textile material is then subjected to a second contacting step with the aqueous coloring medium to further deposit the coloring medium at least on part of the surface of the textile material and produce a colored textile material. For example, the first contacting step may be conducted at a temperature of 10 to 60 °C for a period of 10 to 30 minutes using at a liquor ratio of 1: 1 to 30: 1, preferably 5: 1 to 30: 1, more preferably 10: 1 to 30: 1. The first and second contacting steps may be conducted by exhaustion in the same dye bath without intermediate rinsing of the textile material.

[0036] After application of the coloring medium, the textile material may be rinsed with water to remove any excess coloring medium, although extensive washing is not required and in some cases even the water rinsing step way be omitted.. The textile material is then heated to remove water from the coloring medium deposited on the material. Generally, the heating is conducted at a temperature of about 80 to about 150 °C, such as about 80 to about 110 °C, for example about 85 to about 100 °C. While such a heating step may be insufficient to effect substantial curing or cross-linking of the polymeric material, it is believed that, where present, the cross-linking co-monomer results in the molecular weight of the polymer deposit increasing during the drying step. In one embodiment, the dried textile material comprises from about 1 % by weight to about 6 % by weight of the combination of the dye or pigment and binder material.

[0037] In some cases, it may be desirable to chemically or physically treat the textile material prior to application of the coloring medium to enhance bonding of the dye or pigment to the material. Examples of such pre-treatments include enzyme treatement and or treatment with a cationizing agent. Similarly, a color retention agent and/or a softening agent can be applied to the textile material after application of the coloring medium. In one embodiment, such a post- treatment includes contacting the colored textile material with a mixture of a softening agent and the copolymer dispersion described above, preferably in the same dye bath used to apply the coloring medium to the textile material and preferably without an intermediate rinsing step.

[0038] The present process is particularly applicable to pigment dyeing, such as to impart neon colors to 100% cotton fabric or garments. Using the present process significant time savings can be realized over conventional pigment dyeing processes resulting from a decrease in the time required for the pigment to exhaust to the fabric and omission of the extensive washing steps normally required. It has been found that the resulting dyed fabric/garment has increased washfastness and crockfastness properties, as well as a decreased tendency to shrink and torque in comparison to fabric/garments dyed using commercially available pigment binders. In addition it has been found that fabric/garments dyed using the present process give desirable uneven removal color when exposed to known washing procedures such as stone washing. [0039] The invention will now be more particularly described with reference to the following non-limiting Examples, in which all parts are by weight unless otherwise indicated.

Comparative Example

[0040] A coloring medium is prepared from a commercially available pigment and commercially available binder (such as binder AC50 marketed by Trichromatic in California). When the coloring medium is applied to a fabric, such as 100% cotton or 60%/40% cotton/polyester blend, either by the application method of spraying or traditional exhaustion, a typical (never exceeded) dry crock of 3 and a wet crock of 2 is achievable. In addition, there is approximately 30% shade loss after a washfastness test according to American Association of Textile Chemists and Colorists (AATCC) Test Method 2A.

Example 1

[0041] A coloring medium similar to that used in the Comparative Example is prepared but the AC50 binder is replaced by a commercially available aqueous acrylic dispersion produced by emulsion polymerization of monomer composition consisting of 91.5 parts of ethyl acrylate, 8.5 parts of acrylonitrile and 3 parts of N-methylolacrylamide (NMA). The dispersion is stabilized with 1.8 parts of a non-ionic surfactant and 1.1 parts of an anionic surfactant. The as-supplied dispersion has a solids content of 45-55 % by weight and is diluted with water to a solids content of 1-3 % by weight before being used in this Example.

[0042] When the coloring medium is applied to a fabric, such as 100% cotton or 60%/40% cotton/polyester blend, either by the application method of spraying or traditional exhaustion, a dry crock of 4-4.5 and a wet crock of 3 are obtained. In addition, there is zero shade loss after the AATCC 2A washfastness test.

Example 2

[0043] A cotton fabric is subjected to a conventional enzyme pretreatment (1-2% active enzyme species) in a dye bath for 20 minutes at a liquor ratio of 5: 1, a pH of 5-5.5 and a temperature of 35°C. The pH is then raised to 9 to destroy the enzyme and the fabric is rinsed for 5 minutes with cold water at a liquor ratio of 15: 1.

[0044] After rinsing, the fabric is subjected to a conventional cationic pretreatment at a liquor ratio of 15: 1, initially at room temperature for 20 minutes and then at 55°C for 5 minutes. The cationic pretreatment solution is then dropped and the fabric is rinsed for 5 minutes with cold water at a liquor ratio of 15: 1. [0045] An aqueous mixture containing 5 wt of a commercially available pigment (no binder) is then added to the dye bath and the fabric is treated with the pigment mixture for 15-20 minutes at a liquor ratio of 15: 1 and a temperature of 55°C.

[0046] Without dropping the pigment mixture, the acrylic dispersion employed in Example 2 is then added to the dye bath to yield 4-6 gm of acrylic per liter of the coloring medium. The fabric is the contacted with the coloring medium for 10 minutes at room temperature and 10 minutes at 55°C.

[0047] The pigment/acrylic binder mixture is then dropped from the dye bath but, without rinsing the fabric, an aqueous mixture of a softener and 3g/liter of the acrylic dispersion employed in Example 2 is added to the bath and the fabric is treated with this mixture for 20 minutes at a liquor ratio of 15: 1 and a temperature of 60°C.

[0048] The softener/acrylic binder mixture is then dropped from the dye bath and the fabric is dried, without pre-rinsing, at 90°C. The final fabric has the following properties:

• a wet crockfastness as determined according to AATCC Test Method 8 of at least at least 4;

• a dry crockfastness as determined according to AATCC Test Method 8 of 4-5;

• a lightfastness as determined according to AATCC Test Method 16, Option 3 (using a xenon light source for 40 hours) of at least 3; and

• a washfastness as determined according to AATCC Test Method 61 (IIA) of at least 4 after 5 accelerated wash cycles

• a shade loss of less than 20% when measured by AATCC Test Method 2A.

Claims

1. A process for applying color to a textile material, the process comprising:

2. The process of claim 1, wherein the aqueous coloring medium is deposited on the colored textile material by spraying.

3. A process for applying color to a textile material, the process comprising:

(c) contacting the textile material with said aqueous coloring medium to further deposit the coloring medium at least on part of the surface of the textile material and produce a colored textile material.

4. The process of claim 3, wherein the contacting (a) is conducted at a temperature of 10 to 60 °C for a period of 10 to 30 minutes.

5. The process of claim 3 or claim 4, wherein the contacting (a) is conducted at a liquor ratio of 1: 1 to 30: 1, preferably 5: 1 to 30: 1, more preferably 10: 1 to 30: 1.

6. The process of any one of claims 3 to 5, wherein the aqueous dispersion is added to the aqueous composition in amount to provide from 1 to 10 gm of said copolymer per liter of said aqueous coloring medium.

7. The process of any one of claims 3 to 6, wherein the contacting (c) is conducted at a temperature of 10 to 60 °C for a period of 10 to 30 minutes.

8. The process of any one of claims 3 to 7, wherein the contacting (c) is conducted at a liquor ratio of 5: 1 to 30: 1, preferably 10: 1 to 30: 1.

9. The process of any one of claims 3 to 8, wherein the contacting steps (a) to (c) are conducted by exhaustion in the same dye bath.

10. The process of any preceding claim and further comprising treating the textile material with a cationizing agent prior to contacting the textile material with the dye and/or pigment.

11. The process of any preceding claim and further comprising contacting the colored textile material with a mixture of said aqueous copolymer dispersion and a softener.

12. The process of any preceding claim and further comprising drying the colored textile material at a temperature from about 80 to about 150 °C.

13. The process of claim 12, wherein the drying is conducted without subjecting the colored textile material to an intermediate water rinsing step.

14. The process of any preceding claim, wherein the copolymer binder is produced from a monomer mixture comprising one or more alkyl acrylate or methacrylate monomers selected from butyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof.

15. The process of any preceding claim, wherein the copolymer binder is produced from a monomer mixture comprising at least 70 wt% of said one or more alkyl acrylate or methacrylate monomers.

16. The process of claim 15, wherein the monomer mixture further comprises up to 20 % by weight, such as from 0.1 to 20% by weight, for example from 5 to 15 % by weight, preferably from 6 to 12 %, by weight of acrylonitrile based on the total weight of monomers in said monomer composition.

17. The process of claim 15 or claim 16, wherein the monomer mixture further comprises from 0.1 wt% to about 10 wt%, based on total monomers in the monomer composition, of one or more ethylenically unsaturated cross-linking co-monomers.

18. The process of any preceding claim, wherein the aqueous polymeric dispersion is produced by emulsion polymerization.

19. The process of any preceding claim, wherein the aqueous polymeric dispersion comprises an anionic surfactant stabilizer.

20. The process of any preceding claim, wherein the aqueous dispersion has a copolymer solids content of less than 20 wt%.

21. The process of any preceding claim, wherein the dye or pigment is selected from an indigo dye, a sulfur dye and a disperse dye.

22. The process of any preceding claim, wherein the textile material comprises at least 50 wt% cotton.

23. A textile material colored with a non- white dye or pigment bound to the textile material by a copolymer produced from a monomer mixture comprising (i) one or more alkyl acrylate or alkyl methacrylate monomers, wherein the alkyl group has from 1 to 12 carbon atoms, and (ii) acrylonitrile, wherein the colored textile material has a dry crockfastness of at least 4 when measured by AATCC Test Method 8 and a shade loss of less than 20% when measured by AATCC Test Method 2A.