Fiber-reactive dyes

Abstract

The invention relates to fiber-reactive dyes or fiber-reactive azo dyes, dye mixtures comprising one or more of said fiber-reactive dyes, and aqueous textile dye formulations and aqueous printing inks containing at least one of said fiber-reactive dyes.

Description

[0001] FIBER-REACTIVE DYES

[0002] The invention relates to fiber-reactive dyes or fiber-reactive azo dyes, dye mixtures comprising one or more of these fiber-reactive dyes, as well as aqueous textile dyeing formulations and aqueous printing inks containing at least one of these fiber-reactive dyes.

[0003] As is well known, azo dyes are synthetic dyes that contain one or more azo groups in their chemical constitution. Dyes in this class often exhibit high extinction coefficients and are suitable for a wide range of shades. Such components are used, among other things, in the industrial coloring of synthetic and natural textile fibers. So-called fiber-reactive dyes are useful in this area, as they react with the corresponding fibers to form a covalent bond. Such fiber-reactive dyes can be chemically fixed to fibers during the dyeing process and are therefore particularly well suited for dyeing fiber materials such as cellulose, wool, and polyamide.

[0004] In the textile industry, there is a particularly high demand for brilliant, red reactive dyes that exhibit color-stable and lightfast properties and also enable strong colors. Such dyes must also be suitable for use in blends with other dyes for dyeing or printing on different substrates or materials. In particular, the requirements for the fastness of dyed textiles have increased in recent years. For example, many users of the textiles produced now demand good colorfastness, even after multiple washes, in accordance with ISO 105-C09. Dyes with good wash permanence and simultaneously high calibration fastness increase the longevity of textiles.On the other hand, with regard to such dyes, the actual dyeing process must be as efficient and error-free as possible, such as high fixation yields but at the same time easy washout of non-chemically fixed parts.

[0005] Fiber-reactive azo dyes are known, for example, from WO 2012 / 136428 A1, WO 2005 / 090484 A1, or WO 97 / 25377. Dye mixtures comprising multiple fiber-reactive azo dyes have also been disclosed in the past. EP 1 508 596 B1, for example, specifies dye mixtures containing at least two different fiber-reactive azo dyes. Specifically, EP 1 508 596 B1 discloses dye mixtures comprising at least one disazo dye and at least one monoazo dye.

[0006] While these dye mixtures can largely meet the requirements of the textile industry, both the production of these dye mixtures and their use in dyeing are complex. There is still a need for new, red, fiber-reactive dyes that meet the requirements of corresponding dyeing processes and dyed products, while also being as simple as possible to produce and use.

[0007] The object of the present invention was therefore to provide fiber-reactive dyes in the red to ruby-red color spectrum, which have a good color build-up and high fastness properties, provide high fixation yields but also good washability of unfixed portions, and which are at the same time easy to prepare and use.

[0008] This problem is solved by fiber-reactive dyes according to the claims.

[0009] The invention thus relates to fiber-reactive dyes or a fiber-reactive dye according to the general formula (1) defined below

[0010] where n is 1, 2 or 3,

[0011] Ql represents a group of the formula -SO3M (sulfo), -COOM (carboxy) or -PO3M2 (phosphono),

[0012] Q2 represents hydrogen, methyl, ethyl or carboxymethyl (-CH2COOM), R represents hydrogen, methyl or carboxymethyl (-CH2COOM),

[0013] X is carboxypyridino or a halogen,

[0014] Y represents a group of the formula -CH=CH2 or -CH2CH2-Z, where Z is a group which can be split off under alkaline conditions, and where M represents hydrogen or an alkali metal.

[0015] Surprisingly, the inventors discovered that the fiber-reactive dyes according to the general formula (1) defined above do not need to be mixed with mono-azo components to achieve good fastness properties, such as very good light and wet fastness properties, in deep red shades. Therefore, a fiber-reactive dye according to formula (1) can be used per se or on its own to dye fiber materials. Depending on requirements, for example, depending on the desired color, the fiber-reactive dyes can of course also be mixed with other dyes, i.e., dye mixtures containing at least one dye according to formula (1). However, the reactive azo dyes according to the above formula (1) meet the requirements for color buildup, brilliance, degree of fixation, washability of unfixed components, and fastness properties to a high degree, and are easy to prepare and apply.In addition, these dyes are very well suited to achieving well-reproducible dyeing results.

[0016] The fiber-reactive dyes according to the general formula (1) defined above also proved to be extremely stable to wet-chemical processes with higher pH values ​​and to washing processes, even at higher temperatures. Fibers dyed with these dyes exhibit good fastness properties in washing processes, even over a wide pH range, as will be demonstrated below using examples. At the same time, the dyes appear to exhibit a reduction in substantivity upon interaction with the substrate, and the dyes according to formula (1) also exhibit very good washout behavior of the unfixed portions.

[0017] Furthermore, the fiber-reactive dyes according to the general formula (1) defined above have proven highly suitable for dyeing a wide range of fiber materials, such as fiber materials containing hydroxyl groups and / or carbonamide groups. As has been shown, the fiber-reactive dyes exhibit the above-mentioned good properties with respect to a wide range of different fiber materials. The fiber-reactive dyes according to formula (1) can generally be used for dyeing in the form of aqueous solutions or aqueous suspensions. The fiber-reactive dyes according to the general formula (1) defined above can be prepared using conventional synthesis methods. Some synthesis examples are given below.

[0018] The group X in the above formula (1) represents carboxypyridine or a halogen. The group X can preferably be a halogen, especially fluorine or chlorine. The group X can particularly preferably be chlorine. n in the above formula (1), i.e., the number of methylene groups, can be 1, 2, or 3. Preferably, n in the general formula (1) can be 2, i.e., two methylene groups can be provided.

[0019] The group Q1 in the general formula (1) represents a group of the formula -SO3M (sulfo), -COOM (carboxy), or -PO3M2 (phosphono). The groups SO3M (sulfo), -COOM (carboxy), or -PO3M2 (phosphono) include both their acid form and their salt form; the groups can therefore be protonated as acids or as alkali metal salts. Accordingly, M in these groups, as already specified above in connection with formula (1), can represent hydrogen (acid form) or an alkali metal (salt form or alkali metal salts), such as lithium, sodium, or potassium. Preferably, Q1 in the general formula (1) defined above represents a group of the formula -SO3M (sulfo).

[0020] In the general formula (1) specified above, the group Q2 represents hydrogen, methyl, ethyl, or carboxymethyl (-CH2COOM). Preferably, the group Q2 represents hydrogen.

[0021] The group R in the above general formula (1) represents hydrogen, methyl, or carboxymethyl (-CH2COOM). R can preferably represent hydrogen.

[0022] Y in the above general formula (1) stands for a group of the formula -CH=CH2 or -CH2CH2-Z, where Z is a group that can be split off under alkaline conditions. If Y in formula (1) is a group of the formula -CH2CH2-Z, the alkali-splittable or eliminable groups Z are in the ß-position to the adjacent sulfonyl group in formula (1). Z can, for example, stand for halogen or ester groups of organic carboxylic or sulfonic acids. Furthermore, Z can stand for ester groups of inorganic acids, such as phosphoric acid (phosphate group), sulfuric acid (sulfato group), or thiosulfuric acid (thiosulfato group). Preferably, Y in the above general formula (1) can stand for a group of the formula -CH2CH2-Z, where Z is preferably sulfato (-OSO3M).

[0023] If Y in formula (1) is a group of the formula -CH2CH2-Z and Z is formed by a sulfato, thiosulfato, or phosphato group that can be split off under alkaline conditions, these sulfato, thiosulfato, or phosphato groups include both their acid form and their salt form; thus, the groups can again be protonated as acids or as alkali metal salts. In the case that Z is sulfato (-OSO3M), M can again represent hydrogen (acid form) or an alkali metal (salt form or alkali metal salt), such as lithium, sodium, or potassium, as already specified above in connection with formula (1).

[0024] In general, in all cases related to the above-defined formula (1) and the associated group specifications, M can be hydrogen or an alkali metal or alkali. If M is an alkali metal, a corresponding fiber-reactive dye can, of course, be formed by an alkali metal salt, or the corresponding groups can be alkali metal salt groups. If M is hydrogen, the corresponding groups are each protonated, i.e., in acid form. Preferably, in the above-defined general formula (1), M can be an alkali metal salt, in particular sodium.

[0025] The fiber-reactive dyes according to formula (1) above exhibit colorations in the red to ruby-red range of the spectrum. The fiber-reactive azo dyes of formula (1) are generally solids and, when dried, are obtained as powders. For the purpose of dyeing, particularly textiles, the fiber-reactive dyes can, as is customary, be in the form of aqueous preparations, particularly as aqueous solutions or suspensions. A fiber-reactive dye according to the general formula (1) above can essentially be the sole dye in corresponding dye preparations. However, a fiber-reactive dye according to formula 1 can, of course, also be one of several dyes in a dye preparation.

[0026] Accordingly, the invention also relates to dye mixtures comprising a fiber-reactive dye according to the general formula (1) specified above. For example, corresponding dye mixtures or a corresponding dye mixture can comprise a fiber-reactive dye according to the above-specified formula (1) and a further fiber-reactive dye, wherein such dye mixtures, based on 100% by weight of dyes in the dye mixture, can comprise 10% by weight to 90% by weight of the fiber-reactive dye according to the above formula (1) and 10% by weight to 90% by weight of the further fiber-reactive dye. Such dye mixtures enable color tuning during dyeing. In particular, a dye outside the red region of the spectrum can be used as the further fiber-reactive dye in order to be able to dye a substrate with a desired color.For example, a fiber-reactive dye according to the general formula (1) can be mixed with another blue dye to color a substrate violet. As is well known, the desired color nuance can be influenced by the amounts of dyes used.

[0027] A further embodiment of dye mixtures can, for example, comprise a first fiber-reactive dye having a first chemical structural formula according to the general formula (1) specified above, and a second fiber-reactive dye having a second chemical structural formula according to the general formula (1) specified above. The first chemical structural formula of the first fiber-reactive dye can differ from the second chemical structural formula of the second fiber-reactive dye, and these dye mixtures can comprise, based on 100% by weight of dyes in the dye mixtures, 10% by weight to 90% by weight of the first fiber-reactive dye and 10% by weight to 90% by weight of the second fiber-reactive dye.

[0028] Such color mixtures also enable color tuning, especially in the red region of the spectrum. Such color mixtures can, for example, produce light red or dark red to brownish shades. At the same time, dyeings with very good fastness properties can be achieved, since the fiber-reactive dyes according to the general formula (1) specified above exhibit very good properties in this regard, as already mentioned.

[0029] In particular, corresponding dye mixtures can preferably comprise a first fiber-reactive dye according to the above-specified general formula (1) and a second fiber-reactive dye according to the above-specified general formula (1), wherein the group Y in the first chemical structural formula of the first fiber-reactive dye is formed by a group of the formula -CH2CH2-Z and Z stands for sulfato (-OSO3M), and wherein the group Y in the second chemical structural formula of the second fiber-reactive dye is formed by a group of the formula -CH=CH2.

[0030] It has been proven that the use of such a dye mixture can further improve the fastness of dyeings.

[0031] Such dye mixtures can preferably be prepared by mechanically mixing the respective dyes in dry, powdered form.

[0032] The fiber-reactive dyes according to the above general formula (1) and the dye mixtures described above can, in principle, be present as preparations in solid form or in aqueous solution or suspension (liquid preparations). The total dye content in aqueous preparations can, for example, be up to about 50 wt.%, such as 0.05 wt.% to 50 wt.%, whereby the electrolyte content in such aqueous preparations can typically be below 10 wt.%. Such aqueous preparations can have a low to high viscosity, depending on the total dye content and the content of other substances, and can also contain thickeners commonly used for printing pastes, for example. Preparations in solid form can contain the electrolyte salts generally found in water-soluble azo dyes, such as sodium chloride, potassium chloride, and sodium sulfate.

[0033] Furthermore, preparations containing the fiber-reactive azo dyes or dye mixtures described above may contain other common auxiliaries, such as buffer substances capable of adjusting a pH value between 3 and 7 in aqueous solution. Examples of buffer substances that can be used include sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium citrate, disodium hydrogen phosphate, or sodium tripolyphosphate. Furthermore, the preparations may contain small amounts of siccatives. Particularly when the azo dyes are present in a liquid, aqueous solution, they may contain other substances that ensure the durability of these preparations, such as anti-mold and / or freezing-point depressants.

[0034] In general, preparations containing the above-described fiber-reactive dyes according to general formula (1) or the dye mixtures likewise described above can be prepared in a conventional and conventional manner, and such preparations can contain the likewise known and conventional additives. The average person skilled in the art can prepare appropriate preparations depending on the particular requirements of a dyeing or printing process based on their general knowledge.

[0035] The invention also relates to such aqueous textile dyeing formulations containing 3 wt.% to 50 wt.% of at least one fiber-reactive dye according to the above general formula (1), or a dye mixture as described above, with a total dye content of 5 wt.% to 50 wt.%, based in each case on 100 wt.% of the aqueous textile dyeing formulation.

[0036] Furthermore, the invention also relates to printing inks containing 0.05 wt.% to 40 wt.% of at least one fiber-reactive dye according to the above general formula (1), or a dye mixture as described above, with a total content of dyes of 0.1 wt.% to 40 wt.%, based in each case on 100 wt.% of the printing ink.

[0037] Accordingly, the invention also relates to the use of fiber-reactive dyes according to the general formula (1) specified above, or of the dye mixtures described above for dyeing substrates.

[0038] In principle, all known and conventional dyeing processes for fiber-reactive dyes can be used, including both conventional textile dyeing processes and printing processes, including digital inkjet processes. The implementation of such dyeing and printing processes using the fiber-reactive dyes according to the formula (1) specified above or the dye mixtures described above is also within the skill of the average person skilled in the art, and this average person skilled in the art can select a specific process according to the specific requirements of the dyeing or printing process.Some examples of such known dyeing or printing processes and the results achievable in this context by using the fiber-reactive dyes according to the above-specified formula (1) or the above-described dye mixtures are described below. The fiber-reactive dyes according to the above-described formula (1) can be used not only in the described processes, but also in dyeing methods not explicitly addressed below. For example, the fiber-reactive dyes according to the above-specified general formula (1) or the above-described dye mixtures can be used in the so-called exhaust process for dyeing substrates comprising cellulose fibers.Dyes with very good color yields can be achieved from both short and long liquors using a wide variety of acid-binding agents and, if necessary, neutral salts such as sodium chloride or sodium sulfate. The liquor ratio can be chosen within a wide range and can, for example, be between 1:3 and 1:100, or between 1:5 and 1:30.

[0039] Water-soluble, basic salts of alkali metals and / or alkaline earth metals of inorganic or organic acids, or compounds that release alkali when heated, can be used as acid-binding agents and to assist in the fixation of azo dyes to the cellulose fibers. For example, alkali metal hydroxides and / or alkali metal salts of weak to medium-strength inorganic or organic acids, such as sodium and potassium compounds, can be used. Specific examples of acid-binding agents include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, disodium hydrogen phosphate, trisodium phosphate, or water glass.

[0040] Dyeing can be carried out in aqueous baths at temperatures between 40°C and 105°C, for example at 60°C, but also at temperatures up to 130°C under pressure. Conventional dyeing auxiliaries can also be used if necessary. Any unfixed dye can be removed in a post-treatment.

[0041] Such post-treatment can be carried out, for example, at a pH value of 7 to 9 and at temperatures of 60°C to 100°C. During the dyeing process, the substrate or material to be dyed can be placed in a warm bath, which can then be gradually heated to the desired temperature to complete the dyeing process. The neutral salts mentioned above, e.g., sodium chloride or sodium sulfate, can support or accelerate the extraction of the dyes and can, if necessary, be added to the bath only after the actual dyeing temperature has been reached.

[0042] Another example of a dyeing process in which the fiber-reactive dyes according to the general formula (1) specified above or the dye mixtures described above can be used, among others, is the so-called padding process. Excellent color yields and a very good color build-up are also achieved on cellulose fibers using the padding process, and fixation can be achieved by holding the dye at room temperature or at elevated temperatures, for example, up to 60°C, by steaming, or with dry heat in the usual way.

[0043] As already mentioned, the fiber-reactive dyes according to the general formula (1) specified above or the dye mixtures described above can also be used for printing substrates. Conventional printing processes for cellulose fibers, which can be carried out in one or two phases, produce vibrant prints with good contour definition and a clear white background. The print quality is only slightly dependent on fluctuating fixing conditions. In single-phase printing processes for cellulose fibers, printing can be carried out, for example, with a printing paste containing sodium bicarbonate or another acid-binding agent, followed by steaming at 100°C to 130°C. Two-phase printing can be carried out, for example, by printing with neutral or weakly acidic printing inks and subsequent fixing.This can be achieved, for example, by passing the material through a hot, electrolyte-containing alkaline bath or by padding with an alkaline, electrolyte-containing padding liquor, followed by a soaking or steaming process, or even by a subsequent dry heat treatment of the alkaline-padded material. For dry heat fixing, for example, hot air at a temperature of 120°C to 200°C can be used in accordance with the usual heat-fixing processes. Steaming can be done using superheated steam and pressurized steam at temperatures of up to 160°C, in addition to the usual steam at 101°C to 103°C.

[0044] In principle, the fiber-reactive dyes according to the general formula (1) specified above or the dye mixtures described above, as already mentioned, are generally suitable for dyeing fiber materials or fiber-containing substrates, for example, for dyeing fiber materials containing hydroxyl groups. Such hydroxyl-containing materials can be of both natural and synthetic origin, such as cellulose fiber materials or their regenerated products and polyvinyl alcohols. Materials containing cellulose fibers include, for example, cotton, but also other plant fibers such as linen, hemp, jute, and ramie fiber. Regenerated cellulose fibers include, for example, rayon, modal, and viscose rayon.The materials to be printed or dyed can be, for example, in the form of flat structures such as paper and leather, in the form of films such as polyamide films, or in the form of a mass made of, for example, polyamide or polyurethane. In particular, the materials to be dyed or printed can be in the form of fibers of the aforementioned materials.

[0045] However, fiber materials made of natural polyamides or synthetic polyamides and polyurethanes can also be dyed with the fiber-reactive dyes according to the general formula (1) specified above or the dye mixtures described above. Conventional dyeing and printing processes known from the literature and to the skilled person can be used to dye these materials. Such processes and dyeing methods are described, for example, in H.-K. Rouette, Handbook of Textile Finishing, 2006, Deutscher Fachverlag GmbH, Frankfurt am Main.

[0046] For example, the material to be dyed can be introduced into the bath at a temperature of approximately 40°C, agitated for some time, the dyebath then adjusted to the desired slightly acidic, preferably slightly acetic, pH, and the actual dyeing can be carried out at a temperature between 60°C and 98°C. However, dyeing can also be carried out at boiling temperature or in closed dyeing apparatus at temperatures up to 106°C.

[0047] Since the azo dyes according to formula (1) above are very water-soluble, they can also be used in conventional continuous dyeing processes. In general, the fiber-reactive azo dyes according to formula (1) can be applied and fixed to the above-mentioned materials, in particular to the above-mentioned textile fiber materials, using the application techniques known for water-soluble and fiber-reactive azo dyes.

[0048] Preferably, the use of fiber-reactive dyes according to the general formula (1) specified above, or of the dye mixtures described above, can be provided specifically for dyeing or printing fiber materials containing hydroxyl groups and / or carbonamide groups.

[0049] The preparation or synthesis of the fiber-reactive dyes according to the general formula (1) specified above can be carried out according to known standard synthesis methods for azo dyes, i.e., can generally involve coupling diazotized amines with corresponding coupling components. During this azo coupling reaction, the diazonium salt obtained from the diazotization step is reacted with the coupling component. The components used in such syntheses can be prepared according to likewise known preparation processes for azo dyes in a manner familiar to the average person skilled in the art and in the required proportions.

[0050] Furthermore, the azo dyes prepared chemically according to formula (1) above can also be separated from their synthesis or reaction solutions using equally well-known methods, for example, by precipitation from the reaction media using electrolytes such as sodium chloride or potassium chloride, or by evaporation or spray-drying the reaction solutions. A buffer substance can also be added to the reaction solutions, as is customary. If desired, salts originating from or formed in the reaction can be partially or completely removed by reverse osmosis or nanofiltration before the azo dyes are separated.

[0051] For a better understanding, some examples concerning the preparation or synthesis, application and some results with regard to the fiber-reactive dyes according to the general formula (1) specified above are given below.

[0052] Examples

[0053] Production or synthesis examples

[0054] In the following synthesis examples, the compounds described by formula are presented in the form of their sodium salts. However, the corresponding compounds shown and described as examples can also be prepared, isolated, and used in the form of other salts, such as lithium or potassium salts, or even in protonated form as acids.

[0055] Example 1 Preparation of the fiber-reactive dye according to the following formula (2): In a first reaction vessel, 11 parts of 2-sulfo-4-((2-(sulfoxy)ethyl)sulfonyl)aniline are suspended with 100 parts of water, and 12 parts of hydrochloric acid (35%) are added. At room temperature, 5 parts of a sodium nitrite solution (40%) are added and diazotized at room temperature. The reaction mixture is stirred for 40 minutes at room temperature, after which 1 part of sulfamic acid solution is added and cooled to 0-5°C. A neutral solution (pH 6-6.5) of 5 parts of 6-amino-l-naphthol-3-sulfonic acid in 40 parts of water is then added very quickly, and the reaction mixture is stirred for 30 minutes at 0-5°C and pH 0.8, after which the pH is increased to 6-6.5. In a second reaction vessel, 4 parts of cyanuric chloride are suspended in 50 parts of water at 0-5°C (optionally with the addition of 0.5 part of sodium dioctylsulfosuccinate) and, after stirring for 30 minutes, 5.5 parts of p-phenylenediamine-2,5-disulfonic acid are added and the pH is increased to 4-4.5.After stirring for 2 hours at 0-5°C, 3 parts of 2-aminoethanesulfonic acid are added. The mixture is warmed to room temperature and stirred at pH 7.5-7.8 for 3 hours. The mixture is then cooled to 0-5°C and diazotized by adding 3.5 parts of sodium nitrite and 9 parts of hydrochloric acid (32%). The reaction mixture is stirred for 40 minutes at 0-5°C, after which 1 part of sulfamic acid (99%) is added.

[0056] The solution in the first reaction vessel is then added to the suspension containing the diazotized component from the second reaction vessel, the pH is adjusted to 6-6.5 by adding sodium carbonate, and the mixture is stirred for 3 h at 0-5°C. The fiber-reactive dye or the bis-azo component according to formula (2) above is then obtained as a dark red powder by spray or tray drying of the reaction solution or the combined reaction media from the first and second reaction vessels.

[0057] Example 2

[0058] Preparation of the fiber-reactive dye according to the following formula (3):

[0059]

[0060] The preparation of the fiber-reactive azo dye according to formula (3) can be carried out in the same way or with analogous synthesis steps as the preparation of the azo dye according to

[0061] Formula (2) in Example 1 can be used, except that a corresponding amount of aminoethanoic acid is used instead of 2-aminoethanesulfonic acid. The fiber-reactive dye according to formula (3) is obtained as a dark red dye powder.

[0062] Example 3 Preparation of the fiber-reactive dye according to the following formula (4): The preparation of the fiber-reactive azo dye according to formula (4) can again be carried out in the same manner or with analogous synthesis steps as the preparation of the azo dye according to formula (2) in Example 1, except that an appropriate amount of α-(phosphonomethyl)glycine is used instead of 2-aminoethanesulfonic acid. The fiber-reactive dye according to formula (4) is obtained as a dark red dye powder. Example 4

[0063] Preparation of the fiber-reactive dye according to the following formula (5):

[0064] The fiber-reactive azo dye according to formula (5) can be prepared in the same manner or with analogous synthesis steps as the preparation of the azo dye according to formula (2) in Example 1. However, at the end of the synthesis and before drying, the temperature is adjusted to 12-13°C and the pH is increased to 11 by adding a solution of 33% sodium hydroxide in water dropwise. These conditions are maintained for 30 minutes, and then the pH is adjusted to 6.0 by adding 32% hydrochloric acid. The fiber-reactive dye according to formula (5) is obtained as a dark red dye powder. Example 5

[0065] Preparation of the fiber-reactive dye according to the following formula (6):

[0066] The fiber-reactive azo dye according to formula (6) can be prepared in the same manner or with analogous synthesis steps as the preparation of the azo dye according to formula (2) in Example 1, except that an appropriate amount of N-methyl-6-amino-l-naphthol-3-sulfonic acid is used instead of 6-amino-l-naphthol-3-sulfonic acid. The fiber-reactive dye according to formula (6) is obtained as a dark red dye powder. Application examples

[0067] The following are examples of dyeing processes for substrates using dye preparations comprising one of the above-described azo dyes of formulas (2), (3), (4), (5), and (6). In other words, one of the above-described azo dyes according to formulas (2), (3), (4), (5), and (6) is used to prepare a dye solution, and the respective dye solution comprising one of the azo dyes according to formulas (2), (3), (4), (5), and (6) is then used to dye a respective substrate.

[0068] Example 6

[0069] To prepare dye solutions or dye baths, 2 parts of the corresponding azo dye (formula (2), (3), (4), (5), or (6)) and 50 parts of sodium chloride are dissolved in 1000 parts of water, and 5 parts of sodium carbonate, 0.7 part of sodium hydroxide, and 1 part of a wetting agent are added. 100 g of a cotton fabric (substrate) are added to this dye bath. The temperature of the respective dye bath is initially maintained at 25°C for 10 minutes, then increased to the final temperature (60°C) within 30 minutes, and this temperature is maintained for a further 60 minutes. The dyed fabric or cotton fabric is then rinsed with water. The dyed substrate or cotton fabric is neutralized at 40°C for 10 minutes in 1000 parts of an aqueous solution containing 1 part of acetic acid (50%). Rinse with water at 70°C and then soap with boiling detergent for 15 minutes, rinse again and dry.In each case, a red color with very good fastness properties is obtained.

[0070] Example 7

[0071] An aqueous solution containing 25 g / l of dye according to formula (2), additionally containing the additives customary in this process, such as a wetting agent, a migration inhibitor, and a weak oxidizing agent such as sodium m-benzenesulfonate, is padded onto a cotton fabric at room temperature with a liquor pickup of typically 60-80% and then dried. In a second process, the colored cotton substrate is padded through a liquor containing 250 g / l of table salt, 20 g / l of sodium carbonate, and 10 ml / l of sodium hydroxide solution (38°Be) and then steamed under saturated steam (102°C) for 60 seconds. The unfixed portions are then washed out in a continuous washing machine, yielding a dark red-dyed substrate with a very good level of fastness.

[0072] In order to check the suitability or potential of the azo dyes according to the general formula (1) specified above, substrates dyed using these azo dyes were also subjected to some standard tests.

[0073] For example, stability to washing processes at elevated temperatures was tested. Various standards have been defined in the textile industry for this, such as a household wash at 60°C according to ISO 105-C06 / C2S.

[0074] Table 1 summarizes the results of such a wash, carried out according to ISO 105-C06 / C2S. Cotton fabrics dyed with the azo dyes according to formulas (2), (3), (4), (5), and (6) described above were subjected to a wash according to ISO 105-C06 / C2S and subsequently tested for fastness. Table 1 specifically shows the behavior of the azo dyes with respect to the staining of accompanying fabrics or fibers. The accompanying fibers, as defined according to ISO 105-C06 / C2S, are abbreviated in Table 1 as follows:

[0075] CO: Cotton

[0076] CV: Viscose

[0077] PES: Polyester

[0078] PA: polyamide

[0079] In addition, the color change of the original dyeing was evaluated (column CC in Table 1). The standardized evaluation of fastness is based on a rating from 1 to 5, with 5 being the best rating and indicating that no dyeing of the accompanying fibers is detectable.

[0080] Table 1.

[0081] As can be seen from Table 1, the substrates or cotton fabrics dyed with the fiber-reactive dyes according to the above general formula (1) show very good wash fastness properties, in particular no visible staining of accompanying fabric of any kind. Furthermore, no color change of their own (CC in Table 1) can be seen.

[0082] In contrast, known azo dyes of the same type hardly exhibit their own color changes and also hardly stain polyester (PES) and polyamide (PA) during the standard washing process. However, especially in the case of intense, dark red tones on fabrics, especially cotton, such known azo dyes often clearly stain the accompanying cellulosic fabric. Typical ratings for known azo dyes are 3-4 for CO and CV in Table 1. It can therefore be stated that when substrates dyed with known azo dyes are washed, the accompanying cellulosic fabrics are clearly stained red.

[0083] To test the durability of dyed textiles, the textile industry often subjects them to a multiple wash fastness test, as defined in standard ISO 105-C09, for example. This standard simulates the effect of multiple household washes at elevated temperatures and with a higher proportion of bleaching agents and detergents. The requirement for the dyes is, on the one hand, that their bond to the fibers is maintained during this test, and, on the other hand, that the color body is stable against the oxidizing and bleaching effects of the chemicals used. This requirement can also be met to a high degree by substrates or textiles dyed with fiber-reactive azo dyes according to the general formula (1) specified above.

[0084] In addition, the fiber-reactive azo dyes according to the above general formula (1) also exhibit good lightfastness, as demonstrated, for example, by tests according to ISO 105-B02. Non-fixed portions can also be easily washed out during post-treatment of dyed substrates. The excellent performance of the fiber-reactive azo dyes according to the above general formula (1) and the substrates dyed with them in the standardized tests customary in the textile industry demonstrates the high suitability of the corresponding azo dyes for dyeing, particularly fiber-based substrates. It has been shown that the fiber-reactive azo dyes are very well suited on their own to achieve intense red dyeings, but that the azo dyes can also be used as combination components in dye mixtures with, for example, yellow and blue fiber-reactive dyes, for the production of high-quality textiles.The industrial dyeing processes can be designed in such a way that time-, energy- and water-saving washout processes are possible.

[0085] The embodiments show possible embodiments, whereby it should be noted at this point that the invention is not limited to the specifically illustrated embodiments thereof, but rather various combinations of the individual embodiments with each other are also possible and this possibility of variation lies within the skill of the person skilled in the art in this technical field due to the teaching of technical action by means of the objective invention.

[0086] The scope of protection is determined by the claims. However, the description must be used to interpret the claims. Individual features or combinations of features from the various embodiments described may represent independent inventive solutions. The problem underlying the independent inventive solutions can be derived from the description.

[0087] All information on value ranges in this description is to be understood as including any and all sub-ranges thereof, e.g. the information 1 to 10 is to be understood as including all sub-ranges starting from the lower limit of 1 and the upper limit of 10, ie all sub-ranges begin with a lower limit of 1 or greater and end with an upper limit of 10 or less, e.g. 1 to 1.7, or 3.2 to 8.1, or 5.5 to 10.

Claims

Patent claims 1. Fiber-reactive dyes according to the general formula defined below (1) where n is 1, 2 or 3, Ql represents a group of the formula -SO3M (sulfo), -COOM (carboxy) or -PO3M2 (phosphono), Q2 is hydrogen, methyl, ethyl or carboxymethyl (-CH2COOM), R is hydrogen, methyl or carboxymethyl (-CH2COOM), X is carboxypyridino or a halogen, Y represents a group of the formula -CH=CH2 or -CH2CH2-Z, where Z is a group which can be split off under alkaline conditions, and wherein M is hydrogen or an alkali metal.

2. Fiber-reactive dyes according to claim 1, characterized in that X in the general formula (1) is a halogen.

3. Fiber-reactive dyes according to claim 2, characterized in that X in the general formula (1) is chlorine.

4. Fiber-reactive dyes according to one of the preceding claims, characterized in that n in the general formula (1) is 2.

5. Fiber-reactive dyes according to one of the preceding claims, characterized in that Ql in the general formula (1) represents a group of the formula -SO3M (sulfo).

6. Fiber-reactive dyes according to one of the preceding claims, characterized in that Q2 in the general formula (1) is hydrogen.

7. Fiber-reactive dyes according to one of the preceding claims, characterized in that R in the general formula (1) is hydrogen.

8. Fiber-reactive dyes according to one of the preceding claims, characterized in that Y in the general formula (1) represents a group of the formula -CH2CH2-Z, and that Z is sulfato (-OSO3M).

9. Fiber-reactive dyes according to one of the preceding claims, characterized in that M is sodium.

10. Dye mixtures comprising a fiber-reactive dye according to one of claims 1 to 9 and a further fiber-reactive dye, wherein the dye mixtures, based on 100% by weight of dyes in the dye mixtures, comprise 10% by weight to 90% by weight of the fiber-reactive dye according to one of claims 1 to 9 and 10% by weight to 90% by weight of the further fiber-reactive dye.

11. Dye mixtures comprising a first fiber-reactive dye according to one of claims 1 to 9 having a first chemical structural formula according to the general formula (1), and a second fiber-reactive dye according to one of claims 1 to 9 having a second chemical structural formula according to the general formula (1), wherein the first chemical structural formula of the first fiber-reactive dye differs from the second chemical structural formula of the second fiber-reactive dye, and wherein the dye mixtures comprise, based on 100% by weight of dyes in the dye mixtures, 10% by weight to 90% by weight of the first fiber-reactive dye and 10% by weight to 90% by weight of the second fiber-reactive dye.

12. Dye mixtures according to claim 11, characterized in that the group Y in the first chemical structural formula of the first fiber-reactive dye is formed by a group of the formula -CH2CH2-Z and Z stands for sulfato (-OSO3M), and in that the group Y in the second chemical structural formula of the second fiber-reactive dye is formed by a group of the formula -CH=CH2.

13. Process for the preparation of a dye mixture according to one of the claims 10 to 12, characterized in that the respective dyes are mechanically mixed together in dry, powdered form.

14. Aqueous textile dyeing formulations containing 3% by weight to 50% by weight of at least one fiber-reactive dye according to one of claims 1 to 9 or a dye mixture according to one of claims 10 to 12, with a total dye content of 5% by weight to 50% by weight, based in each case on 100% by weight of the aqueous textile dyeing formulation.

15. Printing inks containing 0.05 wt.% to 40 wt.% of at least one fiber-reactive dye according to one of claims 1 to 9 or of a dye mixture according to one of claims 10 to 12, with a total dye content of 0.1 wt.% to 40 wt.%, based in each case on 100 wt.% of the printing ink.

16. Use of fiber-reactive dyes according to one of claims 1 to 9 or of dye mixtures according to one of claims 10 to 12 for dyeing or printing fiber materials containing hydroxyl groups and / or carbonamide groups.

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