MXPA01005973A - Dyeing process and dye composition - Google Patents

Abstract

A process for dyeing fibrous substrates which comprises the steps of providing a fibrous substrate;providing at least one optionally (pre)reduced sulphur dye;providing at least one reduction stable direct dye;and optionally providing at least one vat dye;and applying said reduction stable direct dye and said optionally (pre)reduced sulphur dye and optionally said vat dye to said fibrous substrate in the presence of a suitable reducing agent and then reoxidising.

Description

DYEING AND COMPOSITION PROCESS FOR TENIDO Description of the Invention The present invention is directed to a process for dyeing fibrous textile substrates, which comprises the steps of: providing a fibrous textile substrate; provide at least one dye to the sulfur; provide at least one direct dye stable to the reduction; and applying the stable direct dye to the reduction to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent. As has been known for many years, sulfur dyes are advantageously used in the dyeing and / or printing of cellulose fiber materials and / or textile fibers mixed with cellulosic material. In traditional dyeing processes, sulfur dyes are applied in the form (pre) educida soluble in alkali, i.e. "leuco state" (white state), and contacted with the cellulosic fibers in a variety of methods, and subsequently oxidized to obtain color development and / or impart a degree of firmness of the colorant to the dyed cellulosic textile substrate.

Reduction agents traditionally used for the application of sulfur dyes are in particular: sodium bisulphide, sodium sulphide and sodium polysulfides. Other known chemical reduction agents that do not contain Ref: 129900 sulfide ions (ie "sulfur-free" reducing agents) that are useful for the reduction of pigments to sulfur include: sodium borohydride, formamidinsulfinic acid, glyceraldehyde, hydroxyacetone, sodium aldehyde sulfoxylate, sodium hydrosulfite, thioglycolic acid , and various reducing sugars, and mixtures thereof with hydroxylamine sulfate, lignin sulphonates. The prior art only indicates the procedure of dyes to sulfur in a reduction medium. It has been believed that the use of direct dyes in such conditions will result in the destruction of the chromophore. The direct dyes could have been used to darken the sulfur dyes, without being applied in combination with sulfur dyes for simultaneous dyeing in a reduction medium. Patent US 3415808 discloses the dyeing of cellulosic substrates with certain azo dyes for tub treated with lower tub treated rate, there are mentioned in particular the azo dyes containing a benzazolylphenylazo group (in which azolyl ring contains an additional heteroatom and it could be oxaxolyl, thiazolyl, imidazolyl, or triazolyl) under alkaline conditions, in the presence of an excess of a strong reducing agent, there are mentioned reduction agents containing a sulfino or sulphite group; moreover, this patent also mentions the addition of a vat dye or another quinoid compound for tubing to catalyze the vat treatment with the azo dye. It has now surprisingly been found that by dyeing fibrous textile substrates with a sulfur dye in leuco form and a direct dye stable to reduction under reducing conditions and then reoxidating, dyes of remarkable quality (especially colorful and of firm quality) could be obtained while a low proportion of reducing agent - even a moderately sulfur-free reducing agent, such as a reducing sugar, is employed. The invention thus provides a process for dyeing fibrous textile substrates, which comprises the steps of: providing a fibrous textile substrate; providing at least one dye to the optionally (pre) reduced sulfur; provide at least one direct dye stable to the reduction; applying the stable direct dye to the reduction and the sulfur dye optionally in (pre) reduced form to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent and then reoxidizing. Furthermore, it has been surprising to find that the direct colorants stable to reduction can be processed with optionally (pre) reduced sulfur dyes and also tub dyes. The result is a process for dyeing fibrous textile substrates, which comprises the steps of: providing a fibrous textile substrate; providing at least one dye to the optionally (pre) reduced sulfur and at least one vat dye; providing at least one direct dye stable to the reduction and a suitable reducing agent; and applying the stable direct dye to the reduction, and the vat dye and the sulfur dye optionally in (pre) reduced form to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent and then reoxidizing. In general, conventional dyes known under this concept and which are defined as "Sulfur Dyes" and "Dyes for Sulfur Bath" in VENKATARAMAN "The Chemistry of Synthetic Dyes" Vol. II (Chapters XXXV) are generally considered as sulfur dyes. and XXXVI) (1952) and Vol. VII (1974) or as defined e.g. in the "Color Index" as "Sulfur Dyes" and also as "Dyes for Sulfur Bath", with the additional indication of "sulfur" and / or with a structure number and a synthetic method involving sulfuration, e.g. as indicated in VENKATARAMAN, as dyes for sulfuric vats. Essentially they are dyes containing aromatically linked oligosulfide bridges, which are reducible to thiol groups and could optionally be of oligomeric to polymeric structure. They are obtained mainly by thionation of the respective intermediates at high temperature, e.g. above 100 ° C, in particular in the temperature range of 110-300 ° C (e.g., drying or melting or in the presence of water and / or an inert organic solvent). In general, as dyes for vat, conventional colorants known under this concept and which are defined as "Dyes for Tina" e.g. are taken into consideration. in the "Color Index" and that do not contain any oligosulfide bridge. Essentially they are dyes containing a conjugated pair of carbonyl groups which in the tub treatment are reversibly reduced to the corresponding ethylene hydroxy groups, such as e.g. a quinonic grouping that is reversibly reduced to the corresponding hydroquinone grouping. Among the sulfur dyes for tubs are indicated in particular those with character of typical sulfur dye, i.e. containing oligosulfide bridges and preferably not containing conjugated pairs of carbonyl groups. A preferred type of sulfur tub dye is represented by the indophenol series containing the carbazole group. The fibrous substrate is selected from the group of: cellulosic fibrous material, fiber materials blended with cellulosic material, and blends of cellulosic fibers with non-cellulosic synthetic fibers. By "cellulosic fibrous material" is meant a substrate containing cellulose fibers, and which could also contain non-cellulosic fibers, which could be mixed with the cellulosic fibers, and be in the form of textile material. The non-cellulosic fibers contemplated include semi-synthetic and fully synthetic polymeric fibrous material which includes, but is not limited to, cellulose acetates, polyamides (alkyl and aromatics), polyesters, polyolefin, polyacrylonitrile, as well as others known in the art which are useful in the formation of mixtures of fiber mixed with cellulose fibers. In addition, the fibers could be in any conventional form, including, but not limited to, raw materials, yarns, yarns, or in the form of a semi-finished product, ie, in the form of rolled skeins or skeins of yarns or fibers, embroidered yarns, woven or woven fabric such as fabrics, as well as in the final form of the product, such as garments. Sulfur dyes (S) that could be used according to the process of the invention include those that are provided in either the non-reduced (Si) form, for subsequent reduction by the coloring agent (s) to the appropriate sulfur in the application of the bath, or could be provided to the bath as pre-reduced sulfur dyes (S2), in particular as concentrated liquid compositions, which are frequently aqueous alkaline solutions containing the thiolate of the dye to alkali-soluble leuco sulfur, or as dry compositions. As pre-reduced sulfur dyes (S2), more specifically pre-reduced sulfur colorants are used which are in a partially reduced form which is sufficient to be readily soluble in alkaline solutions, and which could, if desired, be more reduced for the application, and more or completely reduced sulfur dyes that are easily soluble in alkaline solutions, and can be used directly for the application. Both are covered by the term leuco sulfur dyes. Solubilized sulfur dyes (Bunte salts) (S3) could also be used according to the invention. Examples of sulfur dyes (S) that could be used according to the process of the invention include, but are not necessarily limited to the following ("I.C." is set to "Color Index"): I.C. of Yellow Sulfur 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 20 and 23, I.C. of Yellow Sulfur Leuco 2, 4, 7, 9, 12, 15, 17, 18, 21, 22 and 23, and I.C. of Yellow Sulfur solubilized 2, 4, 5, 19, 20 and 23; I.C. of Orange Sulfur 1, 2, 3, 4, 5, 6, 7 and 8, I.C. of Orange Sulfur Leuco 1, 3, 5 and 9, and I. C. of Orange Sulfur solubilized 1, 3, 5, 6, 7 and 8; I.C. of Sulfur Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 and 13, I.C. of Red Sulfur Leuco 1, 4, 5, 6, 11 and 14, and I.C. of Solubilized Sulfur Red 3, 6, 7, 11 and 13; I.C. of Violet Sulfur 1, 2, 3, 4 and 5, I.C. of Violet Sulfur Leuco 1 and 3, and I. C. of Violet Sulfur Solubilized 1; I.C. of Blue Sulfur 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and 19, I.C. of Blue Sulfur Leuco 1, 2, 3, 5, 7, 8, 9, 11, 13, 15 and 20, I.C. of Solubilized Blue Sulfur 1, 2, 4, 5, 6, 7, 10, 11, 13 and 15, and I.C. from Blue 43 to Tina (sulfur); I.C. of Sulfur Green 1, 2, 3, 4, 5, 6, 7, 8: 1, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 , 24, 25, 26, 27, 28, 29, 31, 32 and 33, IC of Sulfur Green Leuco 1, 2, 3, 4, 7, 11, 16, 30, 34, 35, 36 and 37, and I.C. of Sulfur Green Solubilized 1, 2, 3, 6, 7, 9, 19, 26 and 27; I.C. of Coffee Sulfur 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 12, 13, 14, 14: 1, 15, 15: 1, 16, 17, 18, 19, 20, 21, 22, 23 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 53: 1, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 68, 69, 70, 71, 72, 73, 74, 76, 77, 78, 79, 84, 85, 87, 88 89, 90, 91, 93 and 94, IC of Café Azufre Leuco 1, 3, 4, 5, 8 10, 11, 12, 14, 15, 21, 23, 26, 31, 37, 43, 44, 81, 82, 86 87, 90, 91, 92, 93, 94, 95 and 96, and IC of Solubilized Sulfur Coffee 1, 4, 5, 8, 10, 11, 12, 14, 15, 16, 21, 26, 28, 31, 51, 52, 56, 60, 75, 80 and 83; I.C. of Black Sulfur 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17, I.C. of Black Sulfur Leuco 1, 2, 6, 9, 10, 11 and 18, I.C. of Solubilized Black Sulfur 1, 2, 5, 7 and 11. A more complete and particularized listing of the pigments mentioned above could be found in the Color Index, 3a. Ed., Published by the Society of Dyers and Colourists (London, GB), as well as in the supplementary volumes published therein. Sulfur dyes (S) could be used in a commercially available form; the reduced or pre-reduced soluble, i.e. leuco sulfur dyes (S2), could be used in particular in a commercially available form, and which could contain some residual excess of the reducing agent from its production, and, especially in the liquid form, could contain if required or desired , some reducing agent added to stabilize the reduced form against an oxidation influence of the surrounding air.

The direct dye stable to reduction has proven to be a surprising element in this process. Sulfur dyes - as mentioned before - are defined as one of a group of dyes produced by heating several organic compounds with sulfur. The characteristic groupings in the chromophore in the oxidized form are = C- (S) nC = where the two carbons are ring members of two different aromatic rings, and n is a figure that indicates the oligomeric degree of the oligosulfide bridge, mainly a in the range of 2 to 4; I.C. numbers in the range of 53000 to 54999. Like tub dyes, sulfur dyes are reduced to a water-soluble form, "leuco", from the application - in particular to the corresponding thiolate form - and then reoxidized to its original state colored by fixation. However, it has been discovered that these direct dyes, which are not classified as sulfur dyes or vat dyes, can be processed as sulfur dyes and the color produced is not affected or improved after the application of reduction and reoxidation. A first example of this is the I.C. of Direct Blue 86, 189 or 199. These colors are all classified as direct dyes, and still surprisingly the chromophore is not destroyed by the reduction process and by the improved color resistance in the current art of applying these colors as direct dyes. In addition, it was found that increased properties of firmness to washing were obtained. The I.C. of Direct Yellow 148: 1 and I.C. of Direct Yellow 29 also behave this way. For purposes of this invention stable to the reduction does not mean inert or unaffected by the reduction. Stable to the reduction as used in this specification and in the claims means: a compound whose chromophore is not destroyed undergoing reduction. While the original color of the compound could be altered by the reduction, it still produces a commercially acceptable color, especially in reoxidation. Surprisingly, many of these direct dyes exhibit enhanced dye strength or improved wash fastness or both, when processed in a reduction medium. When these direct dyes which are stable to reduction are processed together with sulfur dyes or combinations of sulfur dyes and vat dyes, increased dyeing strength or improved wash resistance has been observed, or both wash fastness and dye resistance in some cases when it is processed in a reduction medium. In many cases these increases are more than an additive effect that suggests an unexpected synergy between these components. Suitable reducing agents include sodium bisulfide, sodium sulfide and sodium polysulfides. Other chemical reduction agents that do not contain sulfur ions (ie known "sulfur-free" reducing agents) that are useful for the reduction of pigments to sulfur include: sodium borohydride, formamidinsulfinic acid, sodium formaldehyde sulfoxylate, sodium hydrosulfite, acid thioglycolic, and sulfur-free reducing agents, preferably glyceraldehyde, hydroxyacetone and various reducing sugars, eg glucose or dextrose, and mixtures of one or more thereof with hydroxylamine sulfate or lignin sulphonates. The sulfur-free reduction agent (s) (R) is preferred for environmental reasons. These reducing agents without sulfur (R) can be used in the dyeing bath; they could be used to reduce a dye to sulfur (Si) or (S3) or a pre-reduced dye present in the dyeing bath, or to maintain the reduced condition (leuco form) of pre-reduced dyes (S2). The dyeing is carried out adequately under alkaline conditions, preferably at a pH > 10, usually with Na 2 CO 3 or NaOH. The liquor ratio for effects could be in any suitable interval for the particular method of dyeing and machine used. The concentration of (R) could be selected depending on the amount and concentration of the dye and in the nature of (R), and could vary further depending on the type of substrate and particular dyeing method. The reducing agent (R) is suitably added in any amount that is found to adequately reduce a dye to the sulfur, in particular (Si) and also (S3) to its reduced form under the dyeing operation conditions, and / or to maintain the reduced condition of pre-reduced sulfur dyes, in particular (S2). The dyeing temperature could also vary depending on the method and dyeing apparatus, and is advantageously in the range of 35 ° to 130 ° C. The dyeing can then be completed by reoxidation, which could be carried out by aeration or by addition of a conventional oxidation agent, preferably a peroxide, a persulfate or a catalyzed bromate. The direct dyes stable to reduction can also be prepared as pourable aqueous liquid suspensions capable of reduction. The pourable aqueous liquid suspensions capable of reduction, consisting essentially of: a direct dye stable to reduction; and an agent that stabilizes the suspension in an effective amount to maintain a uniform distribution of the direct dye stable to the reduction in suspension over a period of at least 24 hours. The agent that stabilizes the suspension is one or more water-soluble compounds that are present in an amount of less than 10% by weight of the suspension. This agent that stabilizes the suspension is preferably selected from the group of carboxymethyl cellulose; xanthan gum; gum arabic; polyacrylamide; and combinations thereof. These pourable aqueous suspensions may optionally further contain a preservative, especially a biocide or a fungicide or combinations thereof, to control or inhibit the growth of unwanted microorganisms. This becomes important in cases where the suspension could be stored before use. Usually these additives are added in a range of 0.01 to 0.5% by weight of the liquid phase of the suspension. An example of a biocide would be a glutaraldehyde biocide AMA-4750. An example of a fungicide is Givgard DXN The condom as used herein may mean a biocide, fungicide or any other substance, known in the art, which prolongs the useful life of the suspension. Mixtures of dye containing both sulfur and direct dyes can be prepared as a pourable aqueous liquid suspension capable of reduction. This pourable aqueous liquid suspension capable of reduction consists essentially of: a dye to sulfur; a direct dye stable to reduction; and an agent that stabilizes the suspension in an amount effective to maintain a uniform distribution of the dye to the sulfur in the suspension for a period of at least 24 hours. The agent that stabilizes the suspension is preferably present in an amount of less than 10% by weight of the suspension. The present preferred sulfur dye has a content of inorganic sulphides and inorganic polysulfides, such that upon acidification to pH 3 in phosphoric acid at 22 ° C it will not generate more hydrogen sulfide which can react with aqueous sodium hydroxide to form 1000 ppm sulfur ion, based on the weight of the dye to sulfur. The agent that stabilizes the suspension is preferably selected from the group of: carboxymethyl cellulose; xanthan gum; gum arabic; polyacrylamide; and combinations thereof. The aforementioned sulfur dye is selected from the group of: non-reduced sulfur dyes (Si); pre-reduced sulfur dyes (S2); and solubilized sulfur dyes (Bunte salts) (S3). The mixture of dye to sulfur / direct dye can be stabilized or further concentrated by the addition of an agent that stabilizes the suspension. In the mixture of sulfur dye / direct dye, the additives can be added to prolong the life of the mixture. The additive is preferably selected from the group of preservatives, such as biocides, fungicides and combinations thereof. An additional dye mixture containing at least one direct dye, at least one vat dye and at least one optionally (pre) reduced sulfur dye can be prepared as a pourable aqueous liquid capable of reduction, comprising: at least one dye of tub, at least one optionally (pre) reduced sulfur dye and at least one direct dye stable to reduction. While many colorants can be used for tub, I.C. of Blue for Tina 1, I.C. of Blue for Tina 2, I.C. of Blue for Tina 3, I.C. from Azul to Tina 4. I.C, they are all of interest. The I.C. Blue for Tina 1, or indigo, has shown a particular synergistic effect when combined with certain direct dyes stable to reduction and with sulfur dyes. The sulfur dye is selected from the group of: non-reduced sulfur dyes (Si); solubilized sulfur dyes (Bunte salts) (S3); and combinations thereof, sulfur dyes could alternatively be used (pre) reduced (S2). The resulting mixture of vat dye / sulfur / direct can be further modified with suspending agents, and additive for protection against microorganisms. Multiple colorants for tub or sulfur or direct or combinations thereof can be prepared to obtain colors that have not been obtained with only sulfur or tub dyes at present. In the use of dyes, in many cases, a dispersing agent will be added to the sulfur. The dispersing agent is preferably anionic and is more preferably selected from the group of: lignin sulphonates; condensates of naphthalenesulfonic acid formaldehyde. Suspension agents and preservatives, i.e. additives to protect against microorganisms already discussed, can be used in conjunction with dispersing agents. Any combination of dispersing agents, suspending agents and additives may be used with either the sulfur dye / direct dye mixture or the dye / dye mixture to the sulfur / direct dye. The invention thus also provides a process for dyeing fibrous textile substrates, which comprises the steps of: providing a fibrous textile substrate; providing at least one dye to the optionally (pre) reduced sulfur; providing at least one vat dye, providing at least one direct dye stable to the reduction; and applying the stable direct dye to the reduction, the vat dye and the sulfur dye optionally (pre) reduced to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent and then reoxidizing. The fibrous substrate is selected from the group of: cellulose fibrous material, fiber materials blended with cellulosic material, and blends of cellulosic fibers with non-cellulosic synthetic fibers. Suitable reducing agents are selected from the group of: sodium bisulfide; Sodium sulfide; sodium polysulfides; sodium borohydride; formamidinsulfinic acid; glyceraldehyde; hydroxyacetone; Sodium formaldehyde sulfoxylate; sodium hydrosulfite; thioglycolic acid; and various reducing sugars, and combinations of one or more thereof with hydroxylamine sulfate or lignin sulfonates.

The process for dyeing with a mixture of vat dyes, optionally (pre) reduced sulfur dyes and direct dyes stable to reduction comprises the steps of: providing the dyes, applying the dyes to the fibrous textile substrate with a dyebath, in presence of an appropriate reducing agent and then reoxidizing. The sulfur dye is selected from the group of: non-reduced sulfur dyes (Si); solubilized sulfur dyes (Bunte salts) (S3); and combinations thereof and sulfur (pre) reduced dyes (S2). The fibrous substrate is selected from the group of: cellulose fibrous material, fiber materials mixed with cellulosic material and mixtures of cellulosic fibers with non-cellulosic synthetic fiber. Suitable reducing agents are selected from the group of: sodium bisulfide; Sodium sulfide; sodium polysulfides; sodium borohydride; formamidinsulfinic acid; glyceraldehyde; hydroxyacetone; Sodium formaldehyde sulfoxylate; sodium hydrosulfite; thioglycolic acid; and various reducing sugars, and combinations of one or more thereof with hydroxylamine sulfate or lignin sulfonates.

In the following Examples the percentages are by weight and the temperatures are indicated in degrees Centigrade.

EXAMPLE 1 A dyeing of a textile substrate was performed in a laboratory dyeing apparatus as follows: 10 g of 100% cotton interlaced fabric is placed in a 150 ml stainless steel dye box containing 100 ml of water bath. had. The dyeing bath is an aqueous solution consisting of 1 g / L of Sandopure® SD, 20 g / L of sodium sulfate, 6 g / L of soda, 4 g / L of caustic soda in 50% liquid, 9 g / L Sandozol® Reducer RDT-L liquid, l.lg of I.C. of Blue Sulfur 15, and 0.4 g of I.C. of Direct Blue 199. The dye box is then placed in a Zeltex Polycolor laboratory dyeing machine preheated to 50 ° C. The dyeing machine is then heated at 93 ° C to 3 ° C / minute. The dyeing machine is kept at this temperature for 30 minutes and then cooled to 60 ° C at 3 ° C / minute. The dye box is removed after the dyeing machine and the fabric is rinsed under the tap water jet until it is cleaned. The dyed fabric is then oxidized in 100 ml of solution containing 1 g / L of soda and 2 g / L of Clariant® Oxidiser A powder at 60 ° C for 15 minutes. The fabric is then rinsed with cold water and dried. A dark glossy greenish blue was obtained which had good washing firmness.

EXAMPLE 2 A dyeing of a textile substrate was performed in a continuous laboratory dyeing apparatus as follows, a 100% cotton cross-cloth is cushioned at 68-74% by moisture taken up with a dyebath solution. The dyeing bath is an aqueous solution consisting of 75 g / L of caustic soda in 50% liquid, 75 g / L of Sandozol® Reducer RDT-L liquid, 15 g / L of sodium hydrosulfite, 122.5 g / L of IC of Black Sulfur 1 and 75 g / L of I.C. of Direct Blue 199. The dyeing bath is then heated to 50 ° C and maintained for 5 minutes at this temperature. Then the solution of the dyeing bath is added to the tundish of dye pads. The fabric is then cushioned by the dyebath solution and subjected to steam for 1 minute at 100-103 ° C. The dyed fabric is then washed under the water jet of the wrench until cleaned. The dyed fabric is then oxidized in an aqueous solution containing 7.5 g / L of acetic acid (glacial) and 7.5 g / L of Clariant® Oxidiser B liquid at 60 ° C for 30 seconds. The fabric is then rinsed with cold water and dried. A dark glossy bluish black was obtained that was unobtainable with sulfur dyes, which has good wash fastness.

Example 3 A dyeing of a textile substrate was performed in a continuous laboratory dyeing apparatus as follows, a non-mercerized 100% cotton denim fabric is cushioned at 68-74% by the moisture captured with a solution of the dyeing bath . The dyeing bath is an aqueous solution consisting of 7.5 g / L of Penetrant® EH, 22.5 g / L of Sulfalox® 100, 45 g / L of caustic soda in 50% liquid, 75 g / L of Sandozol® Reducer Liquid RDT-L, 150 g / L of IC of Black Sulfur Leuco 1, and 75 g / L of I.C. of Direct Blue 199. The dyeing bath is then heated to 70 ° C. Then the solution of the dyeing bath is added to the tundish of dye pads. The fabric is then cushioned by the solution of the dyeing bath and subjected to steam for 1 minute at 100-103 ° C. The dyed fabric is then washed under the water jet of the wrench until cleaned. The dyed fabric is then oxidized in an aqueous solution containing 7.5 g / L of acetic acid (glacial) and 7.5 g / L of liquid Clariant® Oxidiser B at 60 ° C for 30 seconds. The fabric is then rinsed with cold water and dried. A unique glossy bluish black was obtained not obtainable with sulfur dyes, which have good wash fastness.

EXAMPLE 4 (Comparative Example) A dyeing of a textile substrate was performed in a continuous laboratory dyeing apparatus as follows, a 100% cotton cross-cloth is cushioned at 68-74% by the moisture collected with a solution of the water bath. had. The dyeing bath is an aqueous solution consisting of 7.5 g / L of Penetrant® EH, 10 g / L of sodium chloride, and 75 g / L of I.C. of Direct Blue 199. The dyeing bath is then heated to 38 ° C. Then the solution of the dyeing bath is added to the tundish of dye pads. The fabric is then cushioned by the solution of the dyeing bath and is subjected to steam for 1 minute at 100-103 ° C. The dyed fabric is then washed under the water jet of the wrench until cleaned. The dyed fabric is then oxidized in an aqueous solution containing 7.5 g / L acetic acid (glacial) and 7.5 g / L liquid Clariant® Oxidiser B at 60 ° C for 30 seconds. The fabric is then rinsed with cold water and dried. A dark brilliant turquoise blue was obtained. The fabric exhibited poor firmness when washed.

EXAMPLE 5 A dyeing of a textile substrate was performed in a laboratory dyeing apparatus as follows: 10 g of 100% cotton interlaced fabric is placed in a 150 ml stainless steel dye box containing 100 ml of bath had. The dyeing bath is an aqueous solution consisting of 1 g / L of Sandopure® SD, 20 g / L of sodium sulfate, 6 g / L of soda, 4 g / L of caustic soda in 50% liquid, 9 g / L of Sandozol® Reducer RDT-L liquid, 1.05 g of IC of Blue Sulfur 15, 0.096 g of I.C. of Yellow Direct 29n. , and 0.026 g of I.C. of Direct Blue 199. The dye box is then placed in a Zeltex Polycolor laboratory dyeing machine preheated to 50 ° C. The dyeing machine is then heated at 93 ° C to 3 ° C / minute. The dyeing machine is kept at this temperature for 30 minutes and then cooled to 60 ° C at 3 ° C / minute. The dye box is removed after the dyeing machine and the fabric is rinsed under the tap water jet until cleaned. The dyed fabric is then oxidized in 100 ml of solution containing 1 g / L of soda and 2 g / L of Clariant® Oxidiser A powder at 60 ° C for 15 minutes. The fabric is then rinsed with cold water and dried. A dark glossy blue-green was obtained which has good firmness properties at full humidity.

EXAMPLE 6 A dyeing of a textile substrate was performed in a laboratory dyeing apparatus as follows: 10 g of 100% cotton interlaced fabric was placed in a 150 ml stainless steel dye box containing 100 ml of bath arrested. The dyeing bath is an aqueous solution consisting of 20 g / L of sodium sulfate, 6 g / L of soda, 4 g / L of caustic soda in 50% liquid, 9 g / L of an aqueous solution of glucose to 53%, 1.1 g of IC of Blue Sulfur 15, and 0.4 g of I.C. of Direct Blue 199. The dye box is then placed in a Zeltex Polycolor laboratory dyeing machine preheated to 50 ° C. The dyeing machine is then heated at 93 ° C to 3 ° C / minute. The dyeing machine is kept at this temperature for 30 minutes and then cooled to 60 ° C at 3 ° C / minute. The dye box is removed after the dyeing machine and the fabric is rinsed under the tap water jet until cleaned. The dyed fabric is then oxidized in 100 ml of solution containing 1 g / L of soda and 1 g / L of sodium persulfate at 60 ° C for 15 minutes. The fabric is then rinsed with cold water and dried. A dark glossy greenish blue was obtained which has good firmness when washed.

Example 7 A dyeing of a textile substrate was performed in a continuous laboratory dyeing apparatus as follows, a 100% cotton cross-cloth is cushioned at 68-74% by the moisture taken up with a dyebath solution. The dyeing bath is an aqueous solution consisting of 75 g / L of caustic soda in 50% liquid, 75 g / L of an aqueous solution of glucose at 53%, 15 g / L of sodium hydrosulfite, 122.5 g / L of IC of Black Sulfur 1 and 75 g / L of I.C. of Direct Blue 199. The dyeing bath is then heated to 50 ° C and maintained for 5 minutes at this temperature. Then the solution of the dyeing bath is added to the dye pad trough. The fabric is then cushioned by the solution of the dyeing bath and subjected to steam for 1 minute at 100-103 ° C. The dyed fabric is then washed under the water jet of the wrench until cleaned. The dyed fabric is then oxidized in an aqueous solution containing 7.5 g / L of acetic acid (glacial) and 7.5 g / L of an aqueous solution of 13% sodium bromate catalyzed at 60 ° C for 30 seconds. The fabric is then rinsed with cold water and dried. A dark glossy bluish black was obtained, not obtainable with sulfur dyes, which have a good wash fastness.

EXAMPLE 8 A dyeing of a textile substrate was performed in a continuous laboratory dyeing apparatus as follows, a 100% cotton mercerized denim fabric is cushioned at 68-74% by moisture taken up with a solution from the dyeing bath. The dyeing bath is an aqueous solution consisting of 22.5 g / L of thioureotroxide, 45 g / L of caustic soda in 50% liquid, 75 g / L of an aqueous solution of glucose, 150 g / L of I.C. of Black Sulfur Leuco 1, and 75 g / L of I.C. of Direct Blue 199. The dyeing bath is then heated to 70 ° C. Then the dyebath solution was added to the dye pad tundish. The fabric is then cushioned by the solution of the dyeing bath and subjected to steam for 1 minute at 100-103 ° C. The dyed fabric is then washed under the water jet of the wrench until cleaned. The dyed fabric is then oxidized in an aqueous solution containing 7.5 g / L acetic acid (glacial) and 7.5 g / L an aqueous solution of 13% sodium bromate catalyzed at 60 ° C for 30 seconds. The fabric is then rinsed with cold water and dried. A unique glossy bluish black was obtained not obtainable with sulfur dyes, which has good fastness to washing.

EXAMPLE 9 A dyeing of a textile substrate was performed in a laboratory dyeing apparatus as follows: 10 g of 100% interlaced cotton fabric is placed in a 150 ml stainless steel dye box containing 100 ml of bath had. The dyeing bath is an aqueous solution consisting of 20 g / L of sodium sulfate, 6 g / L of soda, 4 g / L of caustic soda in 50% liquid, 9 g / L of a 53% aqueous solution of glucose, 1.05 g of I.C. of Blue Sulfur 15, 0.096 g of I.C. of Direct Yellow 29 and 0.026 g of I.C. of Direct Blue 199. The dye box is then placed in a Zeltex Polycolor laboratory dyeing machine preheated to 50 ° C. The dyeing machine is then heated at 93 ° C to 3 ° C / minute. The dyeing machine is kept at this temperature for 30 minutes and then cooled to 60 ° C at 3 ° C / minute. The dye box is removed after the dyeing machine and the fabric is rinsed under the tap water jet until cleaned. The dyed fabric is then oxidized in 100 ml of solution containing 1 g / L of soda and 1 g / L of sodium persulfate at 60 ° C for 15 minutes. The fabric is then rinsed with cold water and dried. A dark glossy blue-green was obtained which has good firmness properties to the total wash.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (8)

2. Having described the invention as above, the content of the following claims is claimed as property: 1. A process for dyeing fibrous textile substrates, characterized in that it comprises the steps of: providing a fibrous textile substrate; providing at least one dye to the optionally (pre) reduced sulfur; provide at least one direct dye stable to the reduction; and applying the stable direct dye to the reduction and the sulfur dye optionally in (pre) reduced form to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent and after reoxidation. 2. A process according to claim 1 for dyeing fibrous textile substrates, characterized in that it comprises the steps of: providing a fibrous textile substrate; providing at least one dye to the optionally (pre) reduced sulfur; provide at least one vat dye; provide at least one direct dye stable to the reduction; and applying the stable direct dye to the reduction, the vat dye and the sulfur dye optionally in (pre) reduced form to the fibrous textile substrate with a dyeing bath, in the presence of a suitable reducing agent and after reoxidizing.
3. 3. A process according to claim 1 or 2, characterized in that the direct dye stable to the reduction is selected from the group of: I.C. of Direct Blue 86; I.C. of Azul Directo 189, I.C. of Direct Blue 199; I.C. of Direct Yellow 148: 1; I.C. of Yellow Direct 29; and combinations thereof.
4. 4. A pourable aqueous liquid suspension capable of reduction, characterized in that it comprises: a non-reduced sulfur dye (Si); a direct dye stable to the reduction and an agent that stabilizes the suspension and optionally a vat dye.
5. 5. A pourable aqueous liquid capable of reduction, characterized in that it comprises: a solubilized sulfur dye (S3); and a direct dye stable to the reduction and optionally a vat dye.
6. 6. A pourable aqueous liquid suspension capable of reduction, according to claim 4, characterized in that it comprises: an agent that stabilizes the suspension in an amount effective to maintain a uniform distribution of dye to the sulfur in the suspension for a period of at least 24 hours. hours, the agent that stabilizes the suspension is present in an amount of less than 10% by weight of the suspension.
7. 7. A pourable aqueous liquid or liquid suspension capable of reduction, in accordance with the claim 4 or 5, characterized in that the sulfur dye has a content of inorganic sulphides and inorganic polysulphides in such a way that upon acidification to pH 3 in phosphoric acid at 22 ° C, it will not generate more hydrogen sulfide that can react with the hydroxide of aqueous sodium to form 1000 ppm sulfur ion, based on the weight of the dye to sulfur.
8. 8. A pourable aqueous liquid according to claim 4 or 5, characterized in that it also comprises a condom.