![United States Patent [19] [11] Patent Number: 4,588,409 Sercus [45] Date of Patent: May 13, 1986](http://data.docslib.org/img/274b37bfd24442c9cbe668519f933523-1.webp)
81-18? SF 55/151686
United States Patent [19] [11] Patent Number: 4,588,409 Sercus [45] Date of Patent: May 13, 1986
‘[54] COLOR-CHANGING DYED PRODUCT AND 4,314,812 2/1982 E6655 61111...... 8/457 PROCESS ‘ FOREIGN PATENT DOCUMENTS [76] Inventor: Owen H. Sercus, 125 W. 12th St., 55 30450 3/1980 Ja - pan ...... 8/638 New York, N-Y- 10011 1060556 3/1967 United Kingdom ...... 8/642 [21] APPI- NO-1 564325 OTHER PUBLICATIONS [22] Flledl Dec- 2,2’ 1983 Mayston, R. S. Amer. Dyestuff Reporter 2/ 17/64, pp. [51] Int. c1.4 ...... D06P 5/13; DO6P 5/02; 142-147 1306111 5/00 Trotman, E. R. Dyeing Chemical Technology of [52] US. Cl...... 8/403; 8/441; Textile Fibers» Chas- Griffen & Co- Ltd» London, 1975, 8/485; 8/543; 8/638; 8/102; 8/107; 8/918; pp: 514550. 8/642; 8/924; 8/922; 8/927; 8/928 Falrchild’s Dictionary of Textiles, p. 185. [58] Field Of Search ...... 8/403, 441, 457, 485, Primm Exam,-,,e,_Pau1 Lieberman 8/638' 642’ 102 Assistant Examiner-—-John F. McNally [56] References Cited [57] ABSTRACT US. PATENT DOCUMENTS Textile products comprising a cellulosic substrate are 638,819 12/1889 Stimpson . colored with two or more dyes which differ in their 1,615,205 I/ 1926 Muelberger . respective resistance to chlorine bleaches. The initial 1,810,662 6/1931 Kritschevsky . color of the textile is determined by the combined effect 2,022,413 ll/ 1935 Ellis et a1...... 8/5 of the dyes. Thereafter, textile products whichv may be 3,030,227 4/1962 Clifford et al. . 8/478 in the form of garments, bed linens, draperies, or yard 3,125,403 3/1964 Senger ...... 8/65 goods, are treated with an aqueous solution of bleach to 3,220,793 11/1965 Parsons et a]. .. .. 8/14 3,447,888 6/1969 Wcisz et al. .. 8/69 decolorize, to a pre-determined degree, one or more of 3,619,103 11/1971 Williams ...... 8/14 the dyes, to thereby change the color of the textiles. 3,934,971 l/l976 Blanchard et a1. 8/485 4,314,811 2/1982 Feess et al...... 8/457 9 Claims, No Drawings 4,588,409 1 2 can be changed in color, or even returned to white, for COLOR-CHANGING DYED PRODUCI‘ AND printing or redyeing. PROCESS Another object of the invention is to provide textiles with the inherent capability of predetermined color SUMMARY OF THE INVENTION change in order to permit garment manufacturers to This invention relates to a new textile product and obtain the bene?t of large volume purchases from mills speci?cally to a colored cellulosic textile product which and thereafter vary the colors of portions of the textile can be treated employing methods which are adaptable to meet their seasonal inventory requirements. for use either by textile mills or in home laundries to DETAILED DESCRIPTION OF THE change the textile from its original color to a completely 10 INVENTION different color. _ - In about 1956 a new series of dyes termed reactive BACKGROUND dyes began to appear on the market. These dyes, the As will be readily apparent to those in the fashion ?rst of which were based on a mono- or di-halo triazine industry, the ability to change easily and predictably the nucleus, color of textiles in the form of garments, bed linens and other home furnishings, would be of great commercial signi?cance. The ability to change the color of a favor ite garment in one’s own home would extend the range and life of the owner’s wardrobe without signi?cant 20 cost. The ability to effect color changes would also be of signi?cant commercial and economic importance to textile mills and manufacturers. For example, knowing that the color of a given run of textiles produced for a 25 where X1 is halogen, X2 may be halogen or some innoc particular season can be changed to colors for a follow uous substituent, and R is a radical including a chromo ing season would permit mills to establish large invento phore group, are capable of reacting with a cellulosic ries for a longer selling season. As presently structured, substrate, thus actually binding the color to the sub the mills must dispose of their inventories of textiles in strate. Such dyes and variants thereof are now well fashion colors by means of “close outs”, which are often 30 known in the textile industry and are available from at a loss. With the ability to predictably and selectively , various manufacturers. M ‘ change the colors of unsold inventory to other readily Reactive dyes differ one from another in their resis salable colors, or even to white, for printing, or redye tance to bleaching, and in particular, in their resistance ing, “close out” sales would become unnecessary. to chlorine based bleaches such as those normally used The availability of textiles whose colors can be 35 in home laundries. Thus, for example, some typical quickly and inexpensively changed would also permit reactive dyes have the following resistance to bleach, smaller manufacturers to purchase two or more colors measured on a scale of l to 5 (with 5 indicating full at the relatively large minimum yardage for single runs imposed by the large mills. stability to bleach under normal conditions). US. Pat. No. 3,030,227 describes a process in which a fabric is dyed with a dyestuff which is acid resistant BLEACH and with a resin-bonded pigment susceptible to decom REACTIVE DYE RESISTANCE position upon treatment with acid. In combination, the Color Index Reactive Yellow 22 1 two coloring materials impart a certain color to the Color Index Reactive Orange 86 4-5 fabric. If it is desired to change the color, the fabric is 45 Color Index Reactive Yellow 86 2 treated with acid to decompose the resin-bonded pig Color Index Reactive Orange 14 1 Color Index Reactive Blue (conc.) 163 1 ment, leaving the fabric colored only by the acid resis Color Index Reactive Blue 4 3-4 tant dyestuff. Color Index Reactive Blue 10 3 The procedure of US. Pat. No. 3,030,227 is useful, Color Index Reactive Red 31 4 but has a number of drawbacks. In the ?rst place, the 50 Color Index Reactive 'Red 2 1 Color Index Reactive Orange 4 4 number of suitable dyestuffs or pigments available is Color Index Reactive Brown 10 4 rather limited so that a full range of colors is dif?cult to achieve. More importantly, the acids required for ef fecting the color change are not normally available to Bleach resistance ratings are normally available from the consumer for use in home laundries. Finally the 55 dye manufacturers. For example, the ratings for the treatment leaves the textile with an offensive odor. above dyes which are “Procion” @ dyes sold by Impe It is an object of the present invention to provide a rial Chemical Industries (ICI), are published by ICI. method of changing the color of textiles, either in the In accordance with the present invention a cellulosic form of garments and other ?nished products, or as substrate is dyed with a combination of dyes, preferably piece goods, that can be practised quickly and easily reactive dyes, of different colors, at least one dye hav using materials which are readily available to consum ing high stability toward bleach (e.g., 4-5 on the above ers. scale) and at least one being susceptible to decoloriza It is a further object of~ the invention to provide a tion upon treatment with bleach (e. g., 1-2 on the above method of changing the color of textiles and garments scale). The dyed material is stable toward all treatments which can be safely and simply practised by the con 65 normally applied to colored fabrics; for example, it is sumer in the home laundry or local laundromat. stable to laundering using hot water and conventional It is also an object of this invention to provide textile soaps or synthetic detergents. However, when treated - mills with a method of producing colored textiles which with conventional home bleach, for example, conven 4,588,409 3 4 tional aqueous hypochlorite solutions, the unstable dye a concentration which will produce the desired inten is decolorized, leaving the stable dye to determine the sity of color. Thereafter, the substrate is washed in an color of the substrate. Thus, a complete shift in color acidi?ed oxidizing solution to convert the dye back to can be accomplished using readily available materials the form of a water insoluble pigment and to develop which can normally be put to use by the consumer in the ?nal color. the home laundry. Alternatively, the vat dye may be obtained from the ~ Certain vat dyes are also known to be stable to bleach manufacturer in the form of the leuco compound, and and it is therefore possible to substitute a vat dye for the the vatting step can be omitted. In this case, the dye is bleach stable reactive dye, in some circumstances. Pref applied to the cellulosic substrate in aqueous solution, erably however both the dyes are reactive dyes. for example, by padding, followed by treatment to acid The invention therefore comprises, in a ?rst aspect, a ify and oxidize the compound in order to fix the pig ‘colored textile material comprising a cellulosic sub ment on the fabric and develop the desired color. strate dyed with at least two dyes of different colors, Where the dyes used are of the same type, the bleach one of said dyes being stable to bleach and the other stable dye or dyes and the decolorizable dye or dyes are being subject to decolorization by bleach. 15 applied together. On the other hand when different In another aspect, the invention comprises a method types of dyes are used, e.g., vat dyes and reactive dyes, of providing a textile product capable of having its the dyes are applied sequentially. It is of course also color changed by domestic treatment which comprises possible to apply two dyes of the same type sequen dyeing a cellulosic substrate with two dyes, the ?rst of tially. which is stable to household bleach, while the other, The amount of each dye deposited is open to wide having a different color from the ?rst, is not. variation and is dictated by the colors desired for the Textile products which can be treated according to textile after coloring and after the decolorizing treat the invention range from yarns and threads to woven, ment. nonwoven and knitted fabrics, as well as garments and In order to determine the bleach stability of a particu other structures made from such products, provided 25 lar dyestu?‘ the following test procedure can be used: that a portion of said yarns, threads or fabrics, is cellu A. A swatch of white cotton fabric, such as 100% cot losic. Such products are referred to herein as cellulosic ton twill, or the like, is batch dyed in accordance with substrates. The cellose component in the cellulosic sub the instructions provided by the manufacturer of the strate may be natural, such as cotton, linen, ramie, dyestuff. hemp, sisal or the like, or it may be synthetic, i.e., rayon B. The dyed fabric is dried. made by the viscose, cuprammonium or other conven C. A solution of bleach containing 0.1% available chlo tional process. The cellulose component may include rine is prepared. A piece of the dyed textile, weighing cellulose esters such as cellulose acetate provided suf? approximately 5 grams is placed in a container into cient hydroxyl sites remain available for reaction with which 100 ml. of aqueous bleach solution is added. the reactive dye. In addition to the cellose component, The textile is immersed and allowed to stand for the substrate may include various other textile compo thirty minutes at 20° C. Thereafter the textile sample nents such as polyarnide, polyester, acrylic or even is removed, thoroughly rinsed and dried. polyole?n yarns or threads. Such materials may or may D. By visual inspection the treated piece is compared not be receptive to the reactive dyes and may them with a sample of the dyed fabric. If there is no percep selves be colored in a union dyeing or cross dyeing 40 tible difference, the dye is graded 5. If the fabric is procedure with some other species of dyestuff. white, or near white, the dye is graded 1. The substrate is originally dyed with the reactive dye In practicing the invention, when it is desired to or vat dye by any conventional method, following the change the color of a substrate dyed in accordance with instructions furnished by the dye manufacturer. For the invention, the substrate is simply exposed to a con example, the dye may be applied by various continuous 45 ventional home bleach solution. Conveniently, this may or batch dyeing operations, or by printing. Most reac be done by placing the substrate in a home washing tive dyes are applied in the presence of an alkaline me machine of any available type, adding household bleach dium and after application are subjected to a steaming in the amount prescribed by the bleach manufacturer, a process to ?x the dyes. The precise conditions will vary normal amount of any home detergent to serve as a with the speci?c dyes and are readily ascertainable from wetting agent, and operating the machine in the usual the manufacturer’s literature furnished with the dye manner. While it is believed that the above is suf?cient stuff. By way of example, Procion ® type reactive dyes to permit the average consumer to practice the inven are normally applied in an aqueous medium (which may tion, the various parameters of the treatment may be be a printing paste) having a pH of between about 8.5 described more precisely as follows: and about 11. Adjuvants such as thickening agents, The substrate, such as a garment, is placed into migration control agents, mineral salts, for example contact with between about 5 kg. and about 10 kg. of sodium sulfate, and surfactants may also be in the dye water per kg of substrate. The water contains a conven mixture. The dye may be applied at a temperature of tional chlorine bleaching agent in an amount equivalent between about 20° C. and about 400° C. After a time to a concentration of sodium hypochlorite of between which can range from as little as 10 seconds up to 120 60 about 0.2% and about 0.3% by weight. The precise minutes, the material can be steamed at 100° C. to 130° agent used is not critical. Such readily available com C. for from 30 seconds to about 10 minutes, washed mercial products as Purex ®, Clorox® and Javelle with synthetic detergent and dried. Water are entirely acceptable. A small amount of a Vat dyes can be applied to the cellulosic substrate detergent, say from about 0.5 to 1.0 ounces is also using established procedures on non-continuous ma 65 added. The purpose of the detergent is to wet the cellu chines or by padding methods. The vat dye pigments losic ?bers to accelerate the action of the hypochlorite can be solublized in an aqueous medium by chemical to remove the chlorine-sensitive dye. The nature of the reduction and then applied to the cellulosic substrate at detergent, again, is not critical. It may be anionic, for 4,588,409 ' 5 6. example, an alkyl benzene sulphonate; non-ionic, such as described in Example I. The results are set out in as ethylene oxide condensate; or blends of anionic and Table II: non-anionic detergents. TABLE II The color changing treatment is carried out at the temperature normally prescribed for the commercial 5 Sam- Concen- Orig ple tration Bleach inal Treated bleaching agent. This will usually be between about 20° No. Dyes (oz/gal) Ratings Color Color and about 30° C. The time of the treatment is again not H Procion Yellow 0.23 2 Navy Purple critical, and may range from 10 to 60 minutes. After the MX-8G treatment, the water remaining in the washing machine, Cl Reactive Red 11 0.672 4 or other container, with the substrate will normally Procion Blue MX-G 3.17 l appear colored. It should be noted that under the condi I Procion Yellow 0.42 4-5 Navy Slate MX-3SA Blue tions of the normal home laundry, the color from the CI Reactive Red 2 0.60 l wash water, so far as it is due to reactive dye residues, Procion Blue MX-G 2.64 1 will not affect other cellulosic materials which may be Cone. in the machine with the colored materials to be treated. J Cl Reactive Red 11 0.364 4 Navy Light The load may be drained, rinsed with clean water and CI Reactive Blue 4.48 Purple 109(s) dried. The colored garments or textile substrates will K Procion Yellow 0.665 2 Dark Light then be found to have assumed the color of the bleach MX-8G stable dye (or combination of bleach stable dyes) with Procion Blue MX-G 0.60 Green Mint which they were treated when originally colored. L CI Reactive Red 2 0.03 1 Navy Dusty CI Reactive Blue 4 0.49 3-4 Blue The invention will be further described with refer Procion Blue 4.88 l ence to the following speci?c examples which are in MX-G Con. tended as illustrative only. M Procion Yellow 1.87 4-5 Brown Gold MX-3RA EXAMPLE I Procion Scarlet 0.56 l 25 MX-BRA A series of samples of cotton fabric 12" X 5" were pad Procion Blue MX-G 0.322 1 dyed with aqueous solutions of various reactive dyes in Cone. . the concentrations noted in Table I below to give a variety of different shades. The dyed fabrics were then placed in a Whirlpool ® brand top loading home wash 30 ing machine (about 16 gallons maximum water capac EXAMPLE III p‘ » ity) with suf?cient white cotton garments to give a full A series of eleven samples consisting variously of load, and washed using approximately one cup of cotton twill, broadcloth, poplin and denim fabric mea Tide® brand detergent and one cup of bleach (Clo suring approximately 6” X36" were dyed with various rox ®). The machine was set on “hot”. During the 35 reactive dyes and treated as described in Example I. The approximately 8 minute wash cycle, the water became fabrics ranged in weight from about 2 oz./sq. yard for the dark colored. The machine continued through the fol poplins and broadcloth, up to about 10 oz./sq. yard for lowing cycles following washing: spin-2 minutes; rinse the twill and denim fabrics. The results are set out in 4 minutes; spin-2 minutes; rinse~4 minutes; and spin Table III: dry-6 minutes. After removal from the washing ma chine and drying the following changes were noted: TABLE III Sam- Concen- Orig TABLE I ple tration Bleach inal Treated Sam- Concen- Orig No. Dyes (oz/gal) Ratings Color Color ple tration Bleach inal Treated No. Dyes (oz/gal) Ratings Color Color 45 N CI Reactive Blue 4 0.66 3-4 Med. Light Dark Blue A CI Reactive 6.02 1 Orange Rose Procion Blue 4X-G 0.10 1 Blue Yellow 22 Gone. CI Reactive Red 11 0.60 4 0 CI Reactive Red 11 0.378 4 Purple Pink B Procion Yellow 1.61 4/5 Dark Light Procion Blue MX-G 0.21 1 MX3RA 50 conc Procion Blue MX-G 1.85 1 Green Green P Procion Yellow 2.40 4-5 Brown Gold C CI Reactive 2.60 1 Dark Medium MX-3RA Yellow 22 CI Reactive Red 2 0.60 1 Cl Reactive Blue 4 5.50 '3‘ Green Blue CI Reactive Blue 4 0.30 3-4 CI Reactive Blue 4 3.46 3‘ Dark Slate Q CI Reactive Red 2 0.28 1 Purple Blue CI Reactive Red 2 1.41 1 Purple Blue CI Reactive Blue 4 0.84 3-4 E CI Reactive Red 11 1.68 4 Dark Cran 55 R CI Reactive 0.84 1 Dark Light Procion Blue MX-G 0.93 1 Purple berry Yellow 22 CI Reactive 2.70 1 Dark Blue CI Reactive Blue 4 2.00 3-4 Gray Blue Yellow 22 Gray S Procion Yellow 0.65 4-5 Red Bright CI Reactive Blue 4 2.60 i Green MX-3RA CI Reactive Red 11 0.75 4 CI Reactive Red 2 1.00 1 Yellow G Procion Blue MX-G 1.08 1 Dark Tan T Procion Yellow 0.375 4-5 Dark Medium Procion Orange 1.29 4 Green MX-3RA MX-ZR Procion Orange 0.75 4 Green Brown MX-2R CI Reactive Blue 4 1.25 3-4 U Procion Yellow 0.65 4-5 Dark Light EXAMPLE II 65 MX-3RA CI Reactive Red 11 0.80 4 Red Pink Eight samples of 100% cotton broadcloth, measuring V Procion Yellow 0.36 4-5 Me- Light approximately 6"><36", and weighing about 4 oz./sq. MX-SRA dium yard were dyed with various reactive dyes and treated Procion Blue MX-G 0.17 1 Dark Avocado — 4,588,409 7 8 TABLE III-continued TABLE V-continued Sam- Concen- Orig- Sam- Concen ple tration Bleach inal Treated ple tration Bleach Initial Final No. Dyes (oz/gal) Ratings Color Color No. Dyes (oz/gal) Ratings Color Color Green 5 Cl Reactive Red 2 2 l W Procion Yellow 1.50 4-5 Black Brown AS CI Vat Yellow 2 6 4-5 Orange Yellow MX-3RA Cl Reactive Red 2 0.6 l Procion Orange 4.00 3-4 AT CI Vat Yellow 2 1.7 4-5 Green Yellow MX-ZR Procion Blue MX-G 1.9 l Procion Blue MX-G 6.50 l 10 Cone. conc. AU Cl Vat Red l0 6.7 4-5 Purple Red Procion Blue MX-G .6 1 Cone. AV CI Vat Red 10 6 4-5 Orange Red EXAMPLE IV Cl Reactive 1 Individual swatches of cotton broadcloth, measuring 15 Yellow 22 about 6A X 36" were batch dyed with reactive dyes and treated in accordance with the procedure of Example I. When blends of cotton and polyester are used, the The results are tabulated in Table IV. In Table IV the dyed samples differ in shade from the pure cotton fab concentration is given in terms of dye (solid) actually rics because the polyester ?bers do not accept the vat deposited on the fabric (% by weight of fabric). 20 dye or the reactive dye and therefore undergo no dis TABLE IV cernible color change. This fact can be employed to create additional ornamental effects and color changes Concen Sam- tration in such cotton blends. ple % weight Bleach Initial Final What is claimed is: No. Dyes of fabric Ratings Color Color 25 1. A colored textile product capable of changing AJ Procion Blue MX-‘G 4.00 1 Black Red color upon treatment with bleach, comprising a woven, CI Reactive 1.50 l _ non-woven, or knitted cellulosic fabric, uniformly dyed Orange 14 CI Reactive Red ll 2.00 4 throughout its cross-section in every plane perpendicu AK CI Reactive Blue 4 4.00 3-4 Black Blue lar to the fabric surface with at least two dyes of differ Cl Reactive 1.50 l 30 ent colors, one of said dyes being a reactive dye or a vat Orange l4 dye stable to bleach and the other being a reactive dye CI Reactive Red 2 2.00 1 AL Procion Blue MX-G 4.00 1 Black Yellow which is subject to decolorization-by bleach. ‘ Procion Yellow 1.50 4-5 2. The product claimed in claim 1 wherein the dyes MX-SRA include one reactive dye stable to bleach and one reac CI Reactive Red 2 2.00 1 35 tive dye subject to decolorization by bleach. AM Procion Blue MX-G 4.00 1 Black Orange Procion Yellow 1.50 4-5 3. A method of providing a colored textile product MX-3RA capable of having its color changed by treatment with CI Reactive Red 11 2.00 4 bleach, which consists essentially of dyeing a woven, AN CI Reactive Blue 4 4.00 3-4 Black Green non-woven, or knitted cellulosic fabric throughout its Procion Yellow 1.50 4-5 40 MX-BRA cross-section in every plane perpendicular to the fabric CI Reactive Red 2 2.00 1 surface, with two dyes, one of which is a reactive dye or A0 C1 Reactive Blue 4 4.00 3-4 Black Purple a vat dye which is stable to household bleach, and the CI Reactive 1.50 1 Orange 14 other of which, having a different color from the ?rst CI Reactive Red 11 2.00 4 45 dye, is a reactive dye subject to decolorization by bleach. 4. The method claimed in claim 3 wherein both the EXAMPLE V dyes are reactive dyes. 5. A method of providing color variability in a textive Swatches of 100% cotton twill (l0 oz./sq. yard) fab product which consists essentially of dyeing a cellulosic ric measuring 6'' X 36" were dyed with vat dyes. The 50 substrate uniformly throughout its cross-section with a vat dispersions were applied using the “pad-dry-chemi ?rst dye which is a vat dye or a reative dye stable to cal pad-steam-wash” process. Thereafter, the vat-dyed household bleach and with a second dye different in cellulosic substrates were further dyed with Procion color from said ?rst dye, and which is a reactive dye reactive dyes using the procedure described in the man subject to decolorization by bleach and subsequently ufacturer’s instructions. The treated swatches were then 55 treating the dyed substrate with an aqueous solution of cut in two, and one part of each was treated with bleach bleach. in accordance with the procedure described in Example 6. The method claimed in claim 5 wherein the bleach I. Results are tabulated in Table V. is chlorine bleach. TABLE V 7. A method of providing a colored textile product Sam- Concen- 60 capable of having its color changed by treatment with ple tration Bleach Initial Final bleach which consists essentially of dyeing a cellulosic No. Dyes (oz/gal) Ratings Color Color substrate uniformly throughout its cross-section with AP CI Vat Blue 6 5 4-5 Green Blue two dyes, one of which is a vat dye which is stable to CI Reactive 2 1 household bleach and the other of which, having a Yellow 22 65 different color from the ?rst dye, is a reactive dye sub AQ CI Vat Blue 6 5 4-5 Purple Blue Procion Scarlet 2 l ject to decolorization by bleach. MX-3RA 8. A method of providing a colored textile product AR CI Vat Blue 6 5 4-5 Garnet Blue capable of having its color changed by treatment with 4,588,409 10 bleach, which consists essentially of dyeing a woven, color upon treatment with bleach, comprising a woven, non-woven, or knitted cellulosic fabric throughout its non-woven, or knitted cellulosic fabric, uniformly dyed cross-section with two dyes, one of which is a vat dye throughout its cross-section with at least two dyes of which is stable to household bleach and the other of different colors, one of said dyes being a vat dye stable which, having a color different from the vat dye, is a 5 to bleach, and the other being a reactive dye which is reactive dye subject to decolorization by bleach. subject to decolorization by bleach. 9. A colored textile product capable of changing ‘R ‘I i t ‘I
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