ISOMERIC MIXTURES OF REACTIVE DYES AND THEIR USE FOR DYEING OR PRINTING TEXTILE FIBRE MATERIALS - Patent application

Abstract

The present invention relates to the field of isomeric mixtures of reactive dyes which are suitable for dyeing or printing nitrogen-containing or hydroxyl-group-containing fibre materials and to the production of materials such as dyed or printed products having good build-up behaviour, high fixation rates, good wash-off of unfixed dyes and good all-round fastness properties as well as good stability towards various dyeing parameters such as good bath stability.Furthermore, the present invention relates to a process for dyeing or printing nitrogen-containing or hydroxyl-group-containing fibre materials, using the isomeric mixtures of reactive dyes according to the invention.The isomeric mixtures of the present invention comprise at least the isomers of formula (Ia) and the isomers of formula (Ib). [Formula 1] JPEG2025505046000053.jpg104124

Description

[Technical field]

[0001] The present invention relates to isomer mixtures of reactive dyes which are suitable for dyeing or printing nitrogen-containing or hydroxy-group-containing fibre materials and to the field of the production of materials such as dyed or printed products which have good build-up behaviour, high fixation rates, good wash-off of unfixed dye and good all-round fastness properties as well as good stability towards various dyeing parameters, such as good bath stability.

[0002] The present invention further relates to a process for dyeing or printing nitrogen-containing or hydroxyl-group-containing fibre materials, in which the isomer mixtures of reactive dyes according to the invention are used. [Background technology]

[0003] In recent years, many countries have committed themselves to improving the quality of the environment by conserving natural resources and reducing emissions of substances that are harmful to the climate. Governments provide funds to support the industry towards achieving these goals. Consumers are demanding eco-friendly textile products that are produced according to the highest environmental standards. Brands and retailers are translating these demands into practical requirements, and textile manufacturers are constantly improving their production excellence by investing in the latest equipment and choosing eco-friendly chemicals.

[0004] As a result, there is a great demand for new reactive dye mixtures which are suitable for reproducibly dyeing and printing textile materials, which meet the highest environmental and economic requirements while also providing dyeings of the desired shades together with improved stability towards various dyeing parameters, such as improved bath stability.

[0005] Suitable reactive dyes should also provide good fastness properties, such as wash fastness and water fastness as well as sweat fastness.

[0006] Furthermore, they should have sufficient dyeing properties and at the same time good wash-off of unfixed dyes. They should also exhibit good color yields and high reactivity, the aim being in particular to provide dyeings with good build-up properties and high fixation rates.

[0007] Reactive dyes which can be used for dyeing and printing hydroxyl- or nitrogen-containing fibre materials are known and are described, for example, in EP-A-0 567 036. However, these dyes do not offer a high fixation rate in combination with good stability towards the various dyeing parameters, in particular good bath stability. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent Application Publication No. 0567036 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention is therefore based on the problem of providing new reactive dye mixtures which are particularly suitable for reproducibly dyeing and printing textile materials in the desired shades and which meet the requirements set out above to the greatest possible extent. Said dye mixtures should also result in dyeings which have good build-up, high fixation rates, good wash-off of unfixed dyes and good all-round fastness properties, such as fastness to light and humidity, as well as improved stability to various dyeing parameters, such as improved bath stability.

[0010] The term "consisting essentially of," followed by one or more features, means that the methods or materials of the invention may include components or steps in addition to those components or steps explicitly recited that do not significantly affect the properties and characteristics of the invention.

[0011] The phrase "included between X and Y" is inclusive unless expressly stated otherwise. This phrase means that the targeted range includes values ​​X and Y, as well as all values ​​from X to Y.

[0012] Throughout the description and claims, the words "comprising" and "containing," as well as variations of these words, such as "comprising" and "comprises," mean "including but not limited to" and do not exclude other moieties, additives, ingredients, integers or steps. Furthermore, the singular encompasses the plural unless the context otherwise requires: in particular where the indefinite article is used, the specification is to be understood as contemplating the plural as well as the singular unless the context otherwise requires.

[0013] When upper and lower limits are recited for a property, e.g., concentration of a component, broad ranges of values ​​defined by a combination of any of the upper limits with any of the lower limits can also be implied. [Means for solving the problem]

[0014] The present invention relates to at least one compound of formula (I):

[0015] [ka] [In the formula, R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, sulfo, carboxy or halogen; Z is a fibre-reactive radical of the formula -SO2-CH=CH2, -SO2-(CH2)2-Y, -NH-(CH2)2-O-(CH2)2-SO2-CH=CH2, -NH-(CH2)2-O-(CH2)2-SO2-(CH2)2-Y, -NH-(CH2)2-O-(CH2)3-SO2-CH=CH2, -NH-(CH2)2-O-(CH2)3-SO2-(CH2)2-Y, -NHCO-(CH2)3-SO2-CH=CH2 or -NHCO-(CH2)3-SO2-(CH2)2-Y, Y is a group removable under alkaline conditions; X is a halogen; M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.

[0016] In a preferred embodiment, the isomeric mixture according to the invention comprises at least one isomer of formula (Ia):

[0017] [ka] and isomers of formula (Ib):

[0018] [ka] where R1, R2, Z, X and M are defined above.

[0019] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 1:4 to 4:1.

[0020] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:1.

[0021] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 3:7 to 2:3.

[0022] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:1.

[0023] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 7:3 to 3:2.

[0024] In one preferred embodiment, the isomer mixture according to the invention comprises at least of the formulae (Ia1) and (Ia2):

[0025] [ka] and isomers of formula (Ia) containing reactive dyes of the formula at least of the formulae (IIa1) and (IIa2):

[0026] [ka] and an isomer of formula (Ib) including a mixture of isomers of R1, R2, Z, X and M are defined above.

[0027] In a preferred embodiment, the isomer mixture according to the present invention comprises isomers of formula (Ia) comprising reactive dyes of formulae (Ia1) and (Ia2) and isomers of formula (Ib) comprising reactive dyes of formulae (Ib1) and (Ib2), wherein the weight ratio of said reactive dyes (Ia1) and (Ib1) to said reactive dyes (Ia2) and (Ib2) is in the range of 6:4 to 99:1, preferably 7:3 to 95:5, more preferably 8:2 to 95:5.

[0028] In a preferred embodiment, R1 is hydrogen, methyl, ethyl, n-propyl or n-butyl.

[0029] In a preferred embodiment, R2 is hydrogen, methyl, ethyl, sulfo, carboxy or halogen.

[0030] The present invention also relates to a process for preparing an isomer mixture according to the invention, comprising the steps of: (a) Below formula

[0031] [ka] wherein R2 and Z are defined above. Diazotizing the compound; The diazonium salt thus obtained is represented by the following formula:

[0032] [ka] whereby a coupling component of the formula

[0033] [ka] wherein R2 and Z are defined above. obtaining an azo compound of formula (I); (b) reacting the azo compound of formula (3) prepared in step (a) with the azo compound of formula (3)

[0034] [ka] wherein X represents a halogen as defined above. whereby a compound of the formula

[0035] [ka] wherein R2, Z and X are defined above. providing a compound of (c) reacting the compound of formula (5) prepared in step (b) with a compound of formula

[0036] [ka] wherein R1 and M are defined above. to prepare an isomeric mixture of reactive dyes of formula (1) according to the present invention. The present invention relates to a method comprising the steps of:

[0037] In a preferred embodiment, the isomeric mixture of the compound of formula (6) comprises two isomers, one having a sulfo group at the meta position of the aniline and the other having a sulfo group at the para position of the aniline.

[0038] The present invention also relates to an aqueous ink comprising the isomeric mixture of at least one reactive dye of formula (1) according to the present invention.

[0039] The present invention also relates to the use of at least one isomer mixture of reactive dyes of formula (I) according to the invention or of an ink according to the invention in the dyeing or printing of textile materials, such as hydroxyl-group-containing or nitrogen-containing fibre materials, in particular cellulosic fibre materials.

[0040] The present invention also relates to a process for dyeing or printing textile materials, such as hydroxyl-group-containing or nitrogen-containing fibre materials, in particular cellulosic fibre materials, which comprises using an isomer mixture of at least one reactive dye of formula (I) according to the present invention or an aqueous ink according to the present invention.

[0041] The present invention also relates to a textile dyed or printed with an isomer mixture of at least one reactive dye of formula (I) according to the present invention or with an aqueous ink according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] Isomer mixtures of reactive dyes of formula (I) The present invention relates to at least one compound of formula (I):

[0043] [ka] [In the formula, R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, sulfo, carboxy or halogen; Z is a fibre-reactive radical of the formula -SO2-CH=CH2, -SO2-(CH2)2-Y, -NH-(CH2)2-O-(CH2)2-SO2-CH=CH2, -NH-(CH2)2-O-(CH2)2-SO2-(CH2)2-Y, -NH-(CH2)2-O-(CH2)3-SO2-CH=CH2, -NH-(CH2)2-O-(CH2)3-SO2-(CH2)2-Y, -NHCO-(CH2)3-SO2-CH=CH2 or -NHCO-(CH2)3-SO2-(CH2)2-Y, Y is a group removable under alkaline conditions; X is a halogen; M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.

[0044] The isomer mixture of at least one reactive dye of formula (I) according to the present invention provides very good build-up, high fixation rates, good wash-off of unfixed dye and good all-round fastness properties as well as improved stability towards various dyeing parameters, in particular improved bath stability.

[0045] "Isomers" and "isomeric mixtures" as used herein include dyes that have the same chemical formula but different arrangements of atoms. According to the present invention, an isomeric mixture of reactive dyes of formula (I) includes reactive dyes that have the same chemical formula and therefore the same number of carbon atoms, but in which the -SO3M moiety is attached at different positions on the phenyl ring.

[0046] The term "isomer mixture" as used herein means a composition containing more than one isomer of a reactive dye.

[0047] An "isomeric mixture of at least one reactive dye" optionally contains more than one isomer of the reactive dye of formula (I). Thus, an isomeric mixture contains more than one (i.e., two or more) isomer of the reactive dye of formula (I), and may also contain more than one (i.e., two or more) isomer of different reactive dyes of formula (I). Different reactive dyes of formula (I) have different chemical formulas contained in formula (I), and therefore have different carbon numbers. For example, an isomeric mixture of at least one reactive dye of formula (I) includes β-vinylsulfonyl reactive dye of formula (I) and its isomers, and β-sulfatoethylsulfonyl reactive dye of formula (I) and its isomers (these isomers have sulfone substituents attached to different positions on the phenyl ring).

[0048] These isomeric mixtures as disclosed herein are distinct from single reactive dyes of formula (I).

[0049] "Ci-Cj alkyl" means a saturated, straight or branched hydrocarbon-containing chain containing i to j carbon atoms.

[0050] "C1-C4 alkyl" means a saturated, linear or branched hydrocarbon-containing chain containing 1 to 4 carbon atoms. Preferably, the hydrocarbon-containing chain is linear. Preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl. More preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, n-butyl. Advantageously, the C1-C4 alkyl group is methyl or ethyl.

[0051] "C1-C4 alkoxy" means a saturated, straight or branched hydrocarbon-containing chain containing 1 to 4 carbon atoms and substituted with an oxygen atom.

[0052] Preferably, the hydrocarbon-containing chain is linear. Preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy or t-butoxy. More preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, n-butoxy. Advantageously, the C1-C4 alkoxy group is methoxy or ethoxy.

[0053] As used herein, the term "halogen" refers to a fluorine, chlorine or bromine atom, preferably a fluorine or chlorine atom.

[0054] As used herein, the term "sulfo" refers to the -SO3M group. The sulfo group -SO3M exists in the form of free acid (M is hydrogen) or, preferably, in the form of a salt. Suitable salts are, for example, alkali metal or alkaline earth metal salts. Further salts that come into consideration are organic amine salts, ammonium salts, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts, mono-, di- or tri-ethanolamine salts or mixed Na / Li or Na / Li / NH4 salts.

[0055] As used herein, the term "Y" refers to a group removable under alkaline conditions selected from the group consisting of -Cl, -Br, -F, -OSOM, -SSOOM, -OCO-CH3, -OPOOM2, -OCO-CH5, -OSO2-C1-C4 alkyl or -OSO2-N(C1-C4 alkyl). Preferably, Y is selected from the group consisting of -Cl, -OSOM, -SSOOM, -OCO-CH3, -OCO-CH5 or -OPOOM2, more preferably -Cl or -OSOM, where M has the meaning given above.

[0056] In a preferred embodiment, R1 is hydrogen, methyl, ethyl, n-propyl or n-butyl. More preferably, R1 is hydrogen, methyl or ethyl. Advantageously, R1 is ethyl.

[0057] In a preferred embodiment, R2 is hydrogen, methyl, ethyl, sulfo, carboxy or halogen. More preferably, R2 is hydrogen, sulfo or halogen. Advantageously, R2 is sulfo.

[0058] In a more preferred embodiment, R1 is ethyl; R2 is sulfo; Z is a fiber-reactive radical of formula -SO2-CH=CH2 or -SO2-(CH2)2-Y, Y being a group removable under alkaline conditions; X is a fluorine atom, M is hydrogen, an organic salt, an alkali metal, or one equivalent of an alkaline earth metal; An isomeric mixture of at least one reactive dye of formula (I).

[0059] In a preferred embodiment, the isomeric mixture according to the invention comprises at least one isomer of formula (Ia):

[0060] [ka] and isomers of formula (Ib):

[0061] [ka] wherein R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0062] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 1:4 to 4:1.

[0063] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:1.

[0064] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 3:7 to 2:3.

[0065] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:1.

[0066] In one embodiment, the isomer mixture according to the present invention comprises the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 7:3 to 3:2.

[0067] Advantageously, the mixture of isomers of formulae (Ia) and (Ib) in said ratio provides the isomer mixture according to the invention with improved stability with respect to various dyeing parameters, in particular improved bath stability, compared to the stability of the isomers used alone. Notably, the mixture of isomers of formulae (Ia) and (Ib) in said ratio according to the invention has a synergistic effect with respect to the bath stability of said mixture, when compared to the bath stability of the isomers used alone.

[0068] In another preferred embodiment, the isomer mixture according to the invention comprises at least one isomer of formula (Ia1) and (Ia2):

[0069] [ka] and an isomer of formula (Ia) containing a reactive dye of at least of the formulae (IIa1) and (IIa2):

[0070] [ka] and an isomer of formula (Ib) including a mixture of isomers of R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0071] In a preferred embodiment, the isomer mixture according to the present invention comprises isomers of formula (Ia) which comprise reactive dyes of formulae (Ia1) and (Ia2) and isomers of formula (Ib) which comprise reactive dyes of formulae (Ib1) and (Ib2), wherein the weight ratio of reactive dyes (Ia1) and (Ib1) to reactive dyes (Ia2) and (Ib2) is in the range of 6:4 to 99:1, preferably 7:3 to 95:5, more preferably 8:2 to 95:5.

[0072] In a preferred embodiment, the isomer mixture according to the invention comprises at least: - Formula (IIa):

[0073] [ka] and isomers of - Formula (IIb):

[0074] [ka] wherein R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0075] In said preferred embodiment, the isomer mixture according to the invention advantageously comprises at least: - Formula (IIIa):

[0076] [ka] Isomers of - Formula (IIIb):

[0077] [ka] Isomers of - Formula (IIIc):

[0078] [ka] isomers of, and - Formula (IIId):

[0079] [ka] wherein R1, R2, X and M each have the meanings and preferred meanings given above.

[0080] The isomer mixture of reactive dyes of formula (1) according to the present invention is present in the form of free acid or, preferably, in the form of its salt.Salts that come into consideration are, for example, alkali metal, alkaline earth metal and ammonium salts or the salts of organic amines.Sodium, lithium, potassium and ammonium salts as well as the salts of mono-, di- and tri-ethanolamines can be mentioned as examples.

[0081] In a preferred embodiment, the isomer mixture according to the invention may comprise further additives, for example sodium chloride or dextrin.

[0082] If desired, the isomer mixture according to the invention may contain further auxiliaries, for example buffers, dispersants or anti-dusts, which improve handling or increase storage stability. Such auxiliaries are known to those skilled in the art.

[0083] In one embodiment, the isomer mixtures according to the invention are suitable for dyeing or printing textiles, in particular nitrogen-containing or hydroxyl-group-containing fibre materials.

[0084] As used herein, the terms "textile", "textile material" and "fibrous material" should be interpreted broadly and may be in a very wide variety of manifestations, for example in the form of fibers, yarns, fabrics, garments, knits, wovens and nonwovens. The copolymers according to the invention are suitable for treating a wide variety of textile materials. The textiles according to the invention are hydroxyl- or nitrogen-containing fibrous materials, in particular cellulosic fibrous materials. The textiles according to the invention may be natural or synthetic textiles, such as cotton, silk, wool, linen, polyamide, polyurethane, polyacrylic, polyester, polyolefin, polylactide and hemp, or may also be blends of natural textile materials and synthetic textile materials (i.e. polyamide, polyurethane, polyacrylic, polyester, polyolefin or polylactide), such as blends of cotton with polyester or polyamide fibers.

[0085] Process for preparing the isomer mixture according to the invention The present invention also relates to a process for preparing an isomeric mixture of at least one reactive dye of formula (I), comprising the steps of: (a) Below formula

[0086] [ka] wherein R2 and Z have the meanings as defined above. Diazotizing the compound; The diazonium salt thus obtained is represented by the following formula:

[0087] [ka] whereby a coupling component of the formula

[0088] [ka] wherein R2 and Z are as defined above. obtaining an azo compound of formula (I); (b) reacting the azo compound of formula (3) prepared in step (a) with the azo compound of formula (3)

[0089] [ka] wherein X represents a halogen as defined above. whereby a compound of the formula

[0090] [ka] wherein R2, Z and X are as defined above. providing a compound of (c) reacting the compound of formula (5) prepared in step (b) with a compound of formula

[0091] [ka] [wherein R1 and M are as defined above] to prepare an isomeric mixture of reactive dyes of formula (1) according to the present invention. The present invention relates to a method comprising the steps of:

[0092] The isomeric mixture of reactive dyes of formula (1) obtained in step (c) can optionally be subjected to a conversion reaction, for example the conversion of the vinylizable reactive group -SO2-Y into its vinyl form by treatment with dilute sodium hydroxide solution, for example the conversion of β-chloroethylsulfonyl radicals or β-sulfatoethylsulfonyl radicals into vinylsulfonyl radicals. Such reactions are known per se. They are generally carried out in neutral to alkaline media, at temperatures of, for example, 20-70° C. and at a pH of, for example, 6-14.

[0093] Suitable compounds of formula (1) are, for example, 2-hydroxy-4-β-sulfatoethyl-1-aminobenzene, 2-methoxy-4-β-sulfatoethyl-1-aminobenzene, and 2-sulfo-4-β-sulfatoethyl-1-aminobenzene, which are commercially available.

[0094] In step (a), an amine of formula (1) is generally diazotized by the action of nitrous acid in an aqueous mineral acid solution at low temperature, for example between 0° C. and 40° C., and the reaction with a coupling component of formula (2) is carried out at a weakly acidic, neutral or weakly alkaline pH.

[0095] Compounds of formula (3) can be prepared according to processes known per se, such as by conventional diazotisation and coupling reactions as described in US-A-4341699, GB-A-1576237, US-A-4754023, EP-A-94055 and US-A-5298607.

[0096] Suitable compounds of formula (4), for example cyanuric fluoride or cyanuric chloride, are commercially available.

[0097] In step (b), an azo compound of formula (3) is condensed with a compound of formula (4) in aqueous solution at low temperature, for example 0° C. to 40° C., at a weakly acidic, neutral or weakly alkaline pH.

[0098] In step (c), the intermediate of formula (5) is condensed with a mixture of isomers of a compound of formula (6) at low temperature, for example, 0° C. to 40° C., in an aqueous mineral acid solution at weakly acidic, neutral or weakly alkaline pH.

[0099] In a preferred embodiment, the isomeric mixture of the compound of formula (6) comprises two isomers, one having a sulfo group at the meta position of the aniline and the other having a sulfo group at the para position of the aniline.

[0100] A suitable isomeric mixture of a compound of formula (6) is for example a mixture of N-ethyl-3-sulfoaniline and N-ethyl-4-sulfoaniline, said isomers being commercially available.

[0101] The isomeric mixture can be synthesized by sulfonation of N-ethylaniline or can be obtained by physically mixing the two isomers.

[0102] In a preferred embodiment, the isomeric mixture of the compound of formula (6) has a weight ratio of the isomer containing a sulfo group at the meta position of aniline (N-ethyl-3-sulfoaniline) to the isomer containing a sulfo group at the para position of aniline (N-ethyl-4-sulfoaniline) of 1:4 to 4:1, preferably 1:4 to 1:1, more preferably 3:7 to 2:3.

[0103] In a preferred embodiment, the isomeric mixture of the compound of formula (6) has a weight ratio of the isomer containing a sulfo group at the meta position of aniline (N-ethyl-3-sulfoaniline) to the isomer containing a sulfo group at the para position of aniline (N-ethyl-4-sulfoaniline) of 1:4 to 4:1, preferably 4:1 to 1:1, more preferably 7:3 to 3:2.

[0104] Advantageously, the mixture of compounds of formula (6) in said ratio leads to obtaining an isomeric mixture of reactive dyes of formula (1) according to the invention in the same ratio, which makes it possible to obtain an improved stability with respect to various dyeing parameters, in particular an improved bath stability, when compared to the stability of the isomers used alone. Notably, the mixture of isomeric reactive dyes of formula (1) according to the invention in said ratio has a synergistic effect with respect to the bath stability of said mixture, when compared to the bath stability of the isomers used alone.

[0105] The individual process steps mentioned above can also be carried out in different sequences, so that, if appropriate, in some cases simultaneously, different process variants are possible. The reaction is generally carried out stepwise in succession, with the simple reaction sequence between the individual reaction components, which is known per se, being determined by the specific conditions.

[0106] Compositions and Uses The present invention also relates to an aqueous ink comprising the isomeric mixture of at least one reactive dye of formula (1) according to the present invention, and to the use of such an ink in an inkjet printing method for printing various substrates, in particular textile fiber materials, wherein the definitions and preferences given above apply for said dyes, said inks and said substrates.

[0107] The isomer mixture of at least one reactive dye according to the present invention exhibits very good build-up behavior, high final build-up and high fixation rates, especially in printing applications on cellulosic fibre materials, as well as improved stability towards various printing parameters.

[0108] The isomer mixture of reactive dyes of formula (1) according to the invention is also suitable as colorants for use in recording systems. Such recording systems are, for example, commercial inkjet printers for paper or textile printing, or writing instruments such as fountain pens or ballpoint pens, in particular inkjet printers. For this purpose, the dyes according to the invention are first brought into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink comprising the isomer mixture according to the invention as colorant. The ink can be prepared in a conventional manner by mixing the individual components together in the desired amount of water.

[0109] As substrates there come into consideration the above-mentioned hydroxyl- or nitrogen-containing fibre materials, in particular cellulosic fibre materials. The fibre materials are preferably textile fibre materials.

[0110] Substrates also contemplated are paper and plastic films.

[0111] Examples of paper include commercially available inkjet paper, photo paper, glossy paper, plastic coated paper, such as Epson Ink-jet Paper, Epson Photo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper and Ilford Photo Paper. Plastic films are, for example, transparent or opaque / semi-transparent. A suitable plastic film is, for example, 3M Transparency Film.

[0112] Depending on the nature of the use, e.g. textile printing or paper printing, it may be necessary, for example, to adapt the viscosity or other physical properties of the ink accordingly, in particular properties which have an influence on the affinity for the substrate in question.

[0113] The isomer mixtures according to the invention used in aqueous inks should preferably have a low salt content, i.e. they should have a total salt content of less than 0.5% by weight, relative to the weight of the dye. Dyes which have a relatively high salt content as a result of their preparation and / or as a result of the subsequent addition of a diluent can be desalted, for example, by membrane separation procedures such as ultrafiltration, reverse osmosis or dialysis.

[0114] The ink preferably has a total content of isomer mixtures according to the invention of 1 to 35% by weight, in particular 1 to 30% by weight, preferably 1 to 20% by weight, relative to the total weight of the ink, the preferred lower limit in this case being a limit of 1.5% by weight, preferably 2% by weight, in particular 3% by weight.

[0115] The ink may be made of a water-miscible organic solvent, such as a C1-C4 alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or isobutanol; an amide, such as dimethylformamide or dimethylacetamide; a ketone or a ketone alcohol, such as acetone or diacetone alcohol; an ether, such as tetrahydrofuran or dioxane; a nitrogen-containing heterocyclic compound, such as N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, a poly-alkylene glycol, such as polyethylene glycol or polypropylene glycol; a C2 C6 alkylene glycols and thioglycols, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thio-diglycol, hexylene glycol and diethylene glycol; other polyols, such as glycerol or 1,2,6-hexane-triol; and C1-C4 alkyl ethers of polyhydric alcohols, such as 2-methoxy-ethanol, 2-(2-methoxy-ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxy-ethoxy)ethoxy]ethanol or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of 2 to 30% by weight, in particular 5 to 30% by weight, preferably 10 to 25% by weight, based on the total weight of the ink.

[0116] In addition, the ink may include a solubilizer, such as β-caprolactam.

[0117] The ink may contain thickeners of natural or synthetic origin, notably to adjust the viscosity.

[0118] Examples of thickeners that may be mentioned include commercially available alginic acid thickeners, starch ethers or locust bean flour ethers, especially sodium alginate as such or with modified celluloses, such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose or hydroxypropylmethylcellulose, particularly preferably in a mixture with 20 to 25% by weight of carboxymethylcellulose.Synthetic thickeners that may also be mentioned are, for example, those based on poly(meth)acrylic acid or poly(meth)acrylamide, and also, for example, polyalkylene glycols with a molecular weight of 2000 to 20000, such as polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of ethylene oxide and propylene oxide.

[0119] The ink contains such a thickener in an amount of, for example, 0.01 to 2 wt %, particularly 0.01 to 1 wt %, and preferably 0.01 to 0.5 wt %, relative to the total weight of the ink.

[0120] The inks may contain buffer substances, such as borax, borates, phosphates, poly-phosphates or citrates. Examples that may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used in particular in amounts of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, relative to the total weight of the ink, to establish, for example, a pH value of 4 to 9, in particular 5 to 8.5.

[0121] As further additives, the ink may contain surfactants or humectants.

[0122] Suitable surfactants include commercially available anionic or nonionic surfactants. As humectants in the inks according to the invention, for example, mixtures of urea or sodium lactate (advantageously in the form of a 50% to 60% aqueous solution) with glycerol and / or propylene glycol, preferably in an amount of 0.1 to 30% by weight, in particular 2 to 30% by weight, are considered.

[0123] Preference is given to inks having a viscosity of 1 to 40 mPa·s, in particular 1 to 20 mPa·s and more particularly 1 to 10 mPa·s.

[0124] Furthermore, the ink may additionally contain customary additives, such as antifoaming agents or preservatives, in particular those which inhibit fungal and / or bacterial growth. Such additives are usually used in an amount of 0.01 to 1% by weight, relative to the total weight of the ink.

[0125] As preservatives, formaldehyde-yielding agents such as paraformaldehyde and trioxane, in particular an approximately 30-40% by weight aqueous solution of formaldehyde, imidazole compounds such as 2-(4-thiazolyl)-benzimidazole, thiazole compounds such as 1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols, haloalkylthio compounds or pyridine derivatives, in particular 1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one, come into consideration. A suitable preservative is, for example, a 20% by weight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL).

[0126] The ink may additionally contain further additives such as fluorinated polymers or telomers, e.g., polyethoxyperfluoroalcohols (Forafac® or Zonyl® products), e.g., in an amount of 0.01 to 1% by weight, based on the total weight of the ink.

[0127] In the case of inkjet printing, individual droplets of ink are sprayed from a nozzle in a controlled manner onto a substrate. This is mainly the case of the continuous inkjet and drop-on-demand methods used for that purpose. In the case of the continuous inkjet, the droplets are generated continuously and those not needed for the printing job are removed to a receptacle and recycled. On the other hand, in the case of the drop-on-demand method, the droplets are generated as desired and used for printing; that is, they are generated only when they are needed for the printing job. The generation of the droplets can be carried out, for example, by a piezo inkjet head or by thermal energy (bubble jet). Preference is given to printing with piezo inkjet heads and by the continuous inkjet method.

[0128] The present invention also relates to the use of at least one isomer mixture of reactive dyes of formula (I) according to the present invention or to an ink according to the present invention in the dyeing or printing of textile materials, such as hydroxyl-group-containing or nitrogen-containing fibre materials, in particular cellulosic fibre materials, or in other words to a process for dyeing or printing hydroxyl-group-containing or nitrogen-containing textile materials, in particular cellulosic fibre materials, using an isomer mixture of at least one reactive dye of formula (I) according to the present invention or an ink according to the present invention.

[0129] The isomer mixtures according to the invention or the inks according to the invention are suitable for customary dyeing and printing processes and can be applied to and fixed on the fibre material in a wide variety of ways, in particular in the form of aqueous dye solutions or printing pastes.

[0130] The process for dyeing and printing the hydroxy-group-containing or nitrogen-containing fibre materials according to the invention can be carried out according to customary dyeing and printing methods, for example by the so-called cold pad-batch process, in which the isomer mixture according to the invention is applied to a padder together with alkali and then fixed by storage for several hours at about room temperature, for example at 25-35° C. Alternatively, the process for dyeing and printing according to the invention can be carried out by the exhaust dyeing process, in which the article is impregnated with an aqueous solution of the isomer mixture according to the invention, optionally containing salts, and said isomer mixture is fixed after alkali treatment or in the presence of alkali, optionally under the action of heat.

[0131] The amount of isomer mixtures according to the invention or inks according to the invention used for dyeing or for printing can vary within wide limits, depending on the desired dyeing strength; in general, amounts of 0.01 to 15% by weight, in particular 0.1 to 10% by weight, relative to the article to be dyed or printed, have proven advantageous.

[0132] The present invention also relates to a textile dyed or printed with an isomer mixture of at least one reactive dye of formula (I) according to the present invention or with an aqueous ink according to the present invention.

[0133] Dyeings and prints produced using the isomer mixtures according to the invention have high tinctorial strength and high fibre-dye bond stability in both the acidic and alkaline ranges, are notable for their non-photochromic properties, and also have good light- and chlorine-fastness, good wash-off behaviour, good bath stability, excellent operational excellence (reproducibility, fixing times, etc.).

[0134] The following examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, masses are expressed as g / g (100% active ingredient), parts are parts by weight, percentages refer to weight percent, and ratios are expressed as molar equivalent values. Parts by weight refer to parts by volume in the ratio of kilograms to liters. EXAMPLES

[0135] - Use a 32% solution of hydrochloric acid, a 20% solution of sodium carbonate or a 30% solution of sodium hydroxide to maintain the pH at the optimum value; - Water and ice are used for the cooling step, - the reaction was monitored using an HPLC analytical method, the latter indicating the end of the reaction; - All products used for the synthesis are commercially available.

[0136] Examples 1a and 1b: (a) 109.0 g of 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid, finely dispersed in 200 parts of water, are diazotized according to the following procedure: (a1) 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid and a 32% solution of hydrochloric acid in water were mixed at a stoichiometry of 2.0-3.0:1.0 (HCl 32%:2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid); (a2) diazotizing the mixture obtained in step (a1) with a 4N solution of sodium nitrite at 0-30° C. with a slight molar excess of 1.05-1.1:1.0 (sodium nitrite:mixture obtained in step (a1)) to ensure complete diazotization; (a3) The reaction mixture obtained in step (a2) is stirred for 1 hour and excess nitrite is neutralized by adding 10% sulfamic acid solution to obtain the required diazonium salt.

[0137] 46.0 g of 3-aminophenylurea predispersed in water is then cooled with ice and coupled by adding the diazonium salt mixture obtained in step (a3) ​​at 0-30°C maintained by addition of ice and at pH 4.5-6.0 maintained by addition of sodium carbonate 20% solution. After completion of coupling, the reaction mass is warmed to 25-40°C and treated with HCl 32% solution at pH 1.0-1.5 for 1-3 hours for triazene removal. The resulting mixture is then cooled to 20-25°C and dissolved at pH 6.5-7.0 using sodium carbonate 20% solution.

[0138] (b) The mixture obtained in step (a) is cooled with ice at 0-5° C. and pH 6.0-8.0, and 53.0 g of cyanuric fluoride is added to the mixture within 5-20 minutes. The pH of the mixture is maintained at this value by addition of a 30% solution of sodium hydroxide, and the temperature is maintained within 0-5° C. by addition of ice. After completion of the addition, the mixture obtained is stirred within the above conditions for 5-10 minutes. Then, a 32% solution of hydrochloric acid is added to the mixture obtained to adjust the pH to 3.0-4.0, while the temperature is maintained at the above value by addition of ice. (c) A mixture of N-ethyl-3-sulfoaniline and N-ethyl-4-sulfoaniline was dissolved in water to obtain (N-ethyl-3-sulfoaniline:N-ethyl-4-sulfoaniline). (c-1) in the example (1a) of formula (101a) in a molar ratio of 3:2, or (c-2) In Example (1b) of formula (101b), Prepared by physical mixing.

[0139] The mixture obtained in step (b) having a pH of 3.0-4.0 is cooled to a temperature of 0-5° C., and 57.0 g of the mixture (N-ethyl-3-sulfoaniline:N-ethyl-4-sulfoaniline) obtained in (c) as (c-1) or (c-2) is added to the mixture over a period of 5-10 minutes. During the addition, the pH is adjusted and maintained at 6.0-7.0 using 30% sodium hydroxide solution, and the temperature is maintained below 10° C. After the addition is complete, the reaction is stirred under the same conditions as above for 20-30 minutes, then heated to 20-30° C. while maintaining the pH at 6.0-7.0, and stirred under these conditions for 2-4 hours.

[0140] After completion of the reaction, the reactants are heated to 30-50°C, subjected to a reverse osmosis process, and dried to obtain a crude isomeric mixture of reactive dyes, the major components of which are in the form of free acids and have the formula (101a) or (101b), respectively:

[0141] [ka] Corresponds to.

[0142] Examples 2a and 2b and Comparative Examples 3-5: The following dyes can be prepared in a manner similar to that described in Example 1. Examples 2a and 2b:

[0143] [ka]

[0144] Comparative Example 3:

[0145] [ka]

[0146] Comparative Example 4:

[0147] [ka]

[0148] Comparative Example 5:

[0149] [ka]

[0150] Comparative Example 6:

[0151] [ka]

[0152] Comparative Example 7: (a) 109.0 g of 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid, finely dispersed in 200 parts of water, are diazotized according to the following procedure: (a1) 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid and a 32% solution of hydrochloric acid in water were mixed at a stoichiometry of 2.0-3.0:1.0 (HCl 32%:2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid); (a2) diazotizing the mixture obtained in step (a1) with a 4N solution of sodium nitrite at 0-30° C. with a slight molar excess of 1.05-1.1:1.0 (sodium nitrite:mixture obtained in step (a1)) to ensure complete diazotization; (a3) The reaction mixture obtained in step (a2) is stirred for 1 hour and excess nitrite is neutralized by adding 10% sulfamic acid solution to obtain the required diazonium salt.

[0153] 46.0 g of 3-aminophenylurea predispersed in water is then cooled with ice and coupled by adding the diazonium salt mixture obtained in step (a3) ​​at 0-30°C maintained by addition of ice and at pH 4.5-6.0 maintained by addition of sodium carbonate 20% solution. After completion of coupling, the reaction mass is warmed to 25-40°C and treated with HCl 32% solution at pH 1.0-1.5 for 1-3 hours for triazene removal. The resulting mixture is then cooled to 20-25°C and dissolved at pH 6.5-7.0 using sodium carbonate 20% solution.

[0154] (b) 55.5 g of cyanuric chloride is suspended in water with 1 g of buffer (di-sodium hydrogen phosphate) and ice. The temperature of the suspension is adjusted to 0-5° C. and the mixture is stirred under vigorous stirring using a dispersing device for 10 minutes.

[0155] The mixture obtained in step (a) is cooled with ice at 0-5° C. and at a pH of 6.0-8.0, and 55.5 g of cyanuric chloride are added rapidly (less than 1 min) to the mixture. The pH of the mixture is adjusted and maintained at 5.0-6.0 at 15-25° C. over 1 hour by adding a 20% solution of sodium carbonate. After completion of the reaction, the suspension has a pH of 5.0-6.0 at a temperature of 15-25° C.

[0156] (c) 58.0 g of 2-sulfoaniline is dissolved in water at a temperature of 20-25°C and the pH of the solution is adjusted and maintained at 6.0-7.0 by the addition of 30% sodium hydroxide solution.

[0157] The 2-sulfoaniline solution is added to the mixture obtained in step (b) over a period of 5 minutes and the mixture is heated to 60-70° C. The mixture is stirred at 60-70° C. until completion of the reaction while the pH is maintained at 5.0-5.5 by addition of 20% sodium carbonate solution.

[0158] After the reaction is completed, the reaction mass is cooled to a temperature of 20-25°C, and the unreacted 2-sulfoaniline is quenched with a few drops of acetic anhydride. Then, the pH of the reaction mass is adjusted to 5.5-6.0 with 32% hydrochloric acid solution, and the reaction mass is heated to 30-50°C, subjected to reverse osmosis process, and dried to obtain a crude reactive dye, the main component of which is in the form of free acid and has the following formula:

[0159] [ka] Corresponds to.

[0160] Comparative Examples 8 and 9: The following dyes can be prepared in a manner similar to that described in Comparative Example 6.

[0161] Comparative Example 8

[0162] [ka] Comparative Example 9

[0163] [ka]

[0164] Application Examples 10a-10b-11a-11b and Comparative Application Examples 12-18: Application Examples 10a-10b-11a-11b and Comparative Application Examples 12-18 are prepared according to the following dyeing instructions: Pad-batch dyeing: on a padder with a squeezing effect of 75% (70%) liquid pick-up, a bleached (mercerized) cotton creton fabric is impregnated with an aqueous dyeing liquor containing X g of the isomer mixture according to the invention or a comparative dye per liter, 1 g of moisturizer (ALBAFLOW® PAD), 2 g of dyebath softener (ALBATEX® DBS), 20 ml of sodium hydroxide 36° Be' and 70 ml of sodium silicate (water glass) 38° Be'. The immersion time is 2 seconds. After padding, the fabric is rolled up and then stored at a temperature of 25° C. for 24 hours. After storage, the dyed cotton material is rinsed in room temperature water (10 min), boiled in water (5 min) and subsequently rinsed in room temperature water (10 min). Dyed fabrics are obtained depending on the concentration (X g / l) of the isomer mixture of reactive dyes. Tables 1 and 2 summarize the concentrations (X g / l) of the isomeric mixtures of reactive dyes, the maximum build-up at the same E25 and the fixation percentages at the same reference depth for Application Examples 10-11 and Comparative Application Examples 12-18.

[0165] Application example 10a is obtained using the isomer mixture (formula (101a)) according to example 1a. Application example 10b is obtained using the isomer mixture (formula (101b)) according to example 1b.

[0166] Application example 11a is obtained using the isomer mixture (formula (102a)) according to example 2a. Application example 11b is obtained using the isomer mixture (formula (102b)) according to example 2b.

[0167] Comparative Application Examples 12 to 18 are obtained using dyes according to Comparative Examples 3 to 9, respectively.

[0168] The tinctorial strength of the dyeings according to Application Examples 10-11 and Comparative Application Examples 12-18 is given in units of RD (= "reference depth"), which is a quantity obtained by an internal test method defining the colour depth and which correlates with the standard depth according to ISO 105-A-1984(E), page 4. The reference depth of the fabrics dyed according to Application Examples 10-11 and Comparative Application Examples 12-18 is measured photospectrometrically.

[0169] Build-up diagrams are prepared and maximum build-up is determined in the usual manner.

[0170] [Table 1]

[0171] The percentage fixation in Application Examples 10a-10b-11a-11b and Comparative Application Examples 12-18 is determined in the usual manner by cutting test pieces of dyed fabric of specified size having RD equal to 1 and dissolving / extracting the unfixed dye in boiling aqueous phosphate buffer solution (pH 7).

[0172] [Table 2]

[0173] Application Examples 19a-19b-20a-20b and Comparative Application Examples 21-27: Application Examples 19a-19b-20a-20b and Comparative Application Examples 21-27 are prepared according to the following pad-batch dyeing instructions which allow the bath stability to be measured:

[0174] Dyeing of fabric T0: On a padder with a squeezing action of 75% (70%) liquid pick-up, a bleached (mercerized) cotton creton fabric is impregnated with an aqueous dyeing liquor containing X g of an isomer mixture according to the invention or a comparative dye per liter, 1 g of moisturizer (ALBAFLOW® PAD), 2 g of dyebath softener (ALBATEX® DBS), X ml of sodium hydroxide 36° Be' and 20 ml of soda ash. The immersion time is 2 seconds. After padding, the fabric is rolled up and then stored at a temperature of 25° C. for 24 hours.

[0175] The aqueous dye liquors are placed back into the thermostatic bath at 25° C. for 10 minutes to prevent them from cooling down between the two pad-batch dyeings and to make it possible to measure the bath stability of the isomeric dye mixtures according to the invention at the dyeing temperature conditions.

[0176] Dyeing of fabric T10: After 10 minutes, the aqueous dye liquor is put back into the padder and the bleached (mercerized) cotton creton fabric is impregnated with the liquor. After padding, the fabric is rolled up and then stored at a temperature of 25° C. for 24 hours.

[0177] The aqueous dye liquor is placed back into the thermostatic bath at 25° C. for 20 minutes.

[0178] Dyeing of fabric T20: After 20 minutes, the aqueous dye liquor is put back into the padder and the bleached (mercerized) cotton creton fabric is impregnated with the liquor. After padding, the fabric is rolled up and then stored at a temperature of 25° C. for 24 hours.

[0179] The aqueous dye liquor is placed back into the thermostatic bath at 25° C. for 30 minutes.

[0180] Dyeing of fabric T30: After 30 minutes, the aqueous dye liquor is put back into the padder and the bleached (mercerized) cotton creton fabric is impregnated with the liquor. After padding, the fabric is rolled up and then stored at a temperature of 25° C. for 24 hours.

[0181] The obtained different dyed cotton fabrics T0, T10, T20 and T30 are stored in a thermostatic bath at 25° C. for 24 hours. The dyed cotton fabrics T0, T10, T20 and T30 are then rinsed in room temperature water (10 min), boiled in water (5 min), followed by rinsing in room temperature water (10 min), spin-drying and ironing.

[0182] The resulting dyed fabrics T0, T10, T20 and T30 are stored overnight in the dark and then their tinting strength is measured colorimetrically using a Datacolor 600 spectrocolorimeter.

[0183] For dyed fabrics T0, the color strength measurement is named "immediate strength measurement". For all dyed fabrics T0, the dye concentration (g / l) is adjusted to reach an RD equivalent of 0.5 and this RD value is set as the reference, which is defined as 100%.

[0184] For dyed fabrics T10, T20 and T30, their tinting strengths are measured respectively and compared with the instantaneous density measurements.

[0185] The determination of the bath stability of the isomer mixtures of reactive dyes according to the invention, and also of the comparative dyes, is the corresponding time to reach a loss of color strength of more than 5% compared to the instantaneous concentration measurement.

[0186] Table 3 summarizes the concentrations (X g / l) and bath stabilities of the isomeric mixtures of reactive dyes.

[0187] Application example 19a is obtained using the isomer mixture (formula (101a)) according to example 1a. Application example 19b is obtained using the isomer mixture (formula (101b)) according to example 1b.

[0188] Application example 20a is obtained using the isomer mixture (formula (102a)) according to example 2a. Application example 20b is obtained using the isomer mixture (formula (102b)) according to example 2b.

[0189] Comparative Application Examples 21 to 27 are obtained using dyes according to Comparative Examples 3 to 9, respectively.

[0190] [Table 3]

[0191] The results, summarized in Tables 1, 2 and 3, demonstrate the superiority of the isomer mixtures (101a or 101b) and (102a or 102b) according to the invention compared to the comparative dyes.

[0192] In particular, textiles dyed with the isomer mixtures according to the invention (101a or 101b) and (102a or 102b), respectively, exhibit at the same time very good build-up properties (i.e. the maximum RD value is greater than 2.00), very good fixation rates (i.e. the fixation rates are 90% or more); moreover, the isomer mixtures (101a or 101b) to (102a or 102b) when present in the dyebath show improved bath stability, in particular a loss of color strength of more than 5% after 30 minutes for the isomer mixtures according to the invention (101a or 101b) and (102a or 102b) compared to the comparative dyes, which reach a maximum loss of color strength of 5% after 20 minutes.

[0193] Furthermore, the results in Table 3 show a synergistic effect with respect to bath stability of the isomer mixture (101a or 101b) when compared individually with each of the isomers (104) and (105) that constitute the isomer mixture according to the invention.

[0194] The isomer mixtures according to the invention therefore exhibit very good build-up properties and very high fixation rates, while at the same time exhibiting excellent bath stability compared to the isomers employed alone or compared to prior art dyes.

Claims

1. At least one of formula (I): 【Chemistry 1】 [In the formula, R １ is hydrogen or C １ ~C ４ is alkyl, R ２ is hydrogen, C １ ~C ４ Alkyl, C １ ~C ４ alkoxy, sulfo, carboxy or halogen; Z is a group of the formula -SO ２ -CH=CH ２ , -SO ２ - (CH ２ ) ２ -Y, -NH-(CH ２ ) ２ -O-(CH ２ ) ２ -SO ２ -CH=CH ２ , -NH-(CH ２ ) ２ -O-(CH ２ ) ２ -SO ２ - (CH ２ ) ２ -Y, -NH-(CH ２ ) ２ -O-(CH ２ ) ３ -SO ２ -CH=CH ２ , -NH-(CH ２ ) ２ -O-(CH ２ ) ３ -SO ２ - (CH ２ ) ２ -Y, -NHCO-(CH ２ ) ３ -SO ２ -CH=CH ２ Or -NHCO-(CH ２ ) ３ -SO ２ - (CH ２ ) ２ is a fiber-reactive radical of -Y, where Y is a group removable under alkaline conditions; X is a halogen; M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.

2. At least one compound represented by formula (Ia): 【Chemistry 2】 and isomers of formula (Ib): 【Chemistry 3】 including the isomers R １ , R ２ , Z, X and M are as defined in claim 1; 2. The isomeric mixture of claim 1.

3. 10. An isomer mixture according to any of the preceding claims, comprising the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio in the range of 1:4 to 4:

1.

4. 10. An isomer mixture according to any of the preceding claims, comprising the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:1, preferably from 3:7 to 2:

3.

5. 10. An isomer mixture according to any of the preceding claims, comprising the isomer of formula (Ia) and the isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:1, preferably from 7:3 to 3:

2.

6. at least of the formulae (Ia1) and (Ia2): 【Chemistry 4】 and an isomer of formula (Ia) containing a reactive dye of at least of the formulae (IIa1) and (IIa2): 【Chemistry 5】 and an isomer of formula (Ib) including a mixture of isomers of R １ , R ２ , Z, X and M are as defined in claim 1; 10. An isomeric mixture according to any of the preceding claims.

7. 7. The isomer mixture according to claim 6, wherein the weight ratio of reactive dyes (Ia1) and (Ib1) to reactive dyes (Ia2) and (Ib2) ranges from 6:4 to 99:1, preferably from 7:3 to 95:5, more preferably from 8:2 to 95:

5.

8. R １ 4. The isomeric mixture according to any of the preceding claims, wherein is hydrogen, methyl, ethyl, n-propyl or n-butyl.

9. R ２ 2. The isomeric mixture according to any of the preceding claims, wherein is hydrogen, methyl, ethyl, sulfo, carboxy or halogen.

10. A process for preparing an isomer mixture according to any one of claims 1 to 9, comprising the steps of: (a) Below formula 【Chemistry 6】 [In the formula, R ２ and Z is defined according to any one of claims 1 to 9. by diazotizing a compound of formula (I); The diazonium salt thus obtained is represented by the following formula: 【Chemistry 7】 whereby a coupling component of the formula 【Chemistry 8】 [In the formula, R ２ and Z is defined according to any one of claims 1 to 9. obtaining an azo compound of formula (I); (b) reacting the azo compound of formula (3) prepared in step (a) with the azo compound of formula (3) 【Chemistry 9】 wherein X represents the same halogen and is defined according to any one of claims 1 to 9. whereby a compound of the formula 【Chemistry 10】 [In the formula, R ２ , Z and X are defined according to any one of claims 1 to 9. providing a compound of (c) reacting the compound of formula (5) prepared in step (b) with the compound of formula 【Chemistry 11】 [In the formula, R １ and M is defined according to any one of claims 1 to 9. with an isomeric mixture of a compound of formula (1) according to any one of claims 1 to 9 to prepare an isomeric mixture of a reactive dye of formula (1) according to any one of claims 1 to 9. The method includes:

11. 11. The method of claim 10, wherein the isomeric mixture of the compound of formula (6) comprises two isomers, one isomer having a sulfo group at the meta position of the aniline and the other isomer having a sulfo group at the para position of the aniline.

12. 10. An aqueous ink comprising an isomeric mixture of at least one reactive dye of formula (1) according to any one of claims 1 to 9.

13. 13. Use of an isomer mixture of at least one reactive dye of formula (I) according to any of claims 1 to 9 or an aqueous ink according to claim 12 in the dyeing or printing of textile materials, such as hydroxyl-group-containing or nitrogen-containing fibre materials, in particular cellulosic fibre materials.

14. 13. A textile dyed or printed with an isomeric mixture of at least one reactive dye of formula (I) according to any one of claims 1 to 9 or with an aqueous ink according to claim 12.

15. 13. A process for dyeing or printing hydroxy-group-containing or nitrogen-containing fibre materials, comprising using an isomer mixture of at least one reactive dye of formula (I) according to any of claims 1 to 9 or an aqueous ink according to claim 12.

Images