Isomer mixture of reactive dyes and their use for dyeing or printing textile fibre materials

Abstract

The present invention relates to the field of isomer mixtures of reactive dyes suitable for dyeing or printing nitrogen-containing or hydroxyl-containing fibre materials, the dyeings or prints produced thereon having good build-up properties, high fixation, good wash-off of unfixed dye and good all-round fastnesses, as well as good stability to various dyeing parameters, such as good bath stability. Furthermore, the present invention relates to a process for dyeing or printing nitrogen-containing or hydroxyl-containing fibre materials, wherein an isomer mixture of reactive dyes according to the present invention is used. The isomer mixtures according to the invention comprise at least an isomer of formula (la) and an isomer of formula (lb).

Description

Invention Field

[0001] This invention relates to the field of isomer mixtures of reactive dyes suitable for dyeing or printing on nitrogen- or hydroxyl-containing fiber materials, on which dyeing or printing produces good accumulation properties, high fixation rates, good elution properties of unfixed dyes and good omnidirectional fastness, as well as good stability to various dyeing parameters, such as good bath stability.

[0002] Furthermore, the present invention relates to a method for dyeing or printing nitrogen- or hydroxyl-containing fiber materials, wherein a mixture of isomers of reactive dyes according to the invention is used. Background of the Invention

[0004] Over the past few years, many countries have committed to improving environmental quality by conserving natural resources and reducing emissions of climate-damaging substances. Governments are providing funding to support industries in achieving these goals, and consumers are demanding environmentally friendly textiles produced to the highest ecological standards. Brands and retailers are translating these demands into tangible results, and textile manufacturers are continuously improving the quality of their production by investing in modern equipment and selecting environmentally friendly chemicals.

[0005] Therefore, there is a huge demand for novel reactive dye blends suitable for reusable dyeing and printing on fibrous materials that meet the highest ecological and economic requirements while still providing the desired hue and exhibiting greater stability across a variety of dyeing parameters, such as improved bath stability.

[0006] Suitable reactive dyes should also provide good fastness properties, such as wash fastness, water fastness, and perspiration fastness.

[0007] In addition, they should have sufficient direct dyeing properties while easily eluting unfixed dyes. They should also exhibit good coloring rate and high reactivity, with the aim of providing dyeing with good build-up properties and high fixation.

[0008] Reactive dyes that can be used for dyeing and printing hydroxyl- or nitrogen-containing fiber materials are known and have been described, for example, in EP0567036. However, these dyes cannot simultaneously possess both high fixation and good stability to various dyeing parameters, especially good bath stability.

[0009] Therefore, this invention addresses the problem of providing novel reactive dye mixtures, which are particularly suitable for the reproducible dyeing and printing of fibrous materials to desired hues, while satisfying the requirements described above to the greatest extent possible. The dye mixtures should also produce good build-up properties, high fixation rates, good rinsing properties of unfixed dyes, and good overall fastness, such as light and wet fastness, as well as greater stability to various dyeing parameters, such as higher bath stability.

[0010] The term "consisting essentially of" is followed by one or more features, meaning that the method or material of the invention may include, in addition to the expressly listed components or steps, components or steps that do not substantially affect the nature and features of the invention.

[0011] Unless otherwise expressly stated, the expression "includes X to Y" includes the boundary, meaning that the target range includes the values ​​of X and Y, as well as all values ​​from X to Y.

[0012] In the specification and claims of this application, the terms "comprise" and "contain," and variations thereof, such as "comprising" and "comprises," mean "including but not limited to," and do not exclude other parts, additives, ingredients, wholes, or steps. Furthermore, unless the context otherwise requires, the singular includes the plural: in particular, when the indefinite article is used, unless the context otherwise requires, the application documents should be understood to consider both the plural and the singular.

[0013] If an upper and lower limit is described for a property, such as the concentration of a component, it may also mean the range of values ​​defined by any combination of the upper and lower limits. Invention Overview

[0015] This invention relates to a mixture of isomers of at least one reactive dye having formula (I):

[0016]

[0017] in,

[0018] R1 is hydrogen or a C1-C4 alkyl group.

[0019] R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, sulfonyl, carboxyl, or halogen.

[0020] Z is a variable with the formulas -SO2-CH=CH2 and -SO2-(CH2)2-Y.

[0021] The fiber reactive groups are -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, where Y is a group that can be removed under alkaline conditions.

[0022] X is a halogen, and

[0023] M is hydrogen, an organic salt, an alkali metal, or an equivalent of an alkaline earth metal.

[0024] In a preferred embodiment, the isomer mixture according to the invention comprises at least one isomer of formula (Ia):

[0025]

[0026] Isomers of the compound (Ib):

[0027]

[0028] R1, R2, Z, X, and M are defined as above.

[0029] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 1:4 to 4:1.

[0030] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:1.

[0031] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 3:7 to 2:3.

[0032] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:1.

[0033] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 7:3 to 3:2.

[0034] In a preferred embodiment, the isomer mixture according to the invention comprises:

[0035] - At least isomers of formula (Ia), including reactive dyes of formulas (Ia1) and (Ia2):

[0036]

[0037] and,

[0038] - At least an isomer of formula (Ib), which includes a mixture of isomers of formulas (IIa1) and (IIa2):

[0039]

[0040] in,

[0041] R1, R2, Z, X, and M are defined above.

[0042] In a preferred embodiment, the isomer mixture according to the invention comprises an isomer of reactive dye of formula (Ia) containing formula (Ia1) and (Ia2), and an isomer of reactive dye of formula (Ib) containing formula (Ib1) and (Ib2), wherein the weight ratio of reactive dyes (Ia1) and (Ib1) to reactive dyes (Ia2) and (Ib2) is 6:4 to 99:1, preferably 7:3 to 95:5, and more preferably 8:2 to 95:5.

[0043] In a preferred embodiment, R1 is hydrogen, methyl, ethyl, n-propyl, or n-butyl.

[0044] In a preferred embodiment, R2 is hydrogen, methyl, ethyl, sulfonyl, carboxyl, or halogen.

[0045] The present invention also relates to a method for preparing isomer mixtures according to the present invention, comprising:

[0046] (a) Diazotization of the following compound

[0047]

[0048] R2 and Z are as defined above;

[0049] And the resulting diazonium salt reacts with the coupling component of the following formula.

[0050]

[0051] This yields the following azo compound.

[0052]

[0053] R2 and Z are as defined above;

[0054] (b) Condensate the azo compound of formula (3) prepared in step (a) with the compound of the following formula.

[0055]

[0056] Where X represents the same halogen as defined above.

[0057] This provides compounds of the following formula.

[0058]

[0059] R2, Z, and X are as defined above;

[0060] (c) Condensate the compound of formula (5) prepared in step (b) with a mixture of isomers of the following formula.

[0061]

[0062] R1 and M are defined above.

[0063] Thus, a mixture of reactive dye isomers according to formula (1) of the present invention is obtained.

[0064] In a preferred embodiment, the isomer mixture of formula (6) comprises two isomers, one of which has a sulfonyl group at the meta position of aniline and the other has a sulfonyl group at the para position of aniline.

[0065] The present invention also relates to aqueous inks containing a mixture of isomers of at least one reactive dye according to formula (1) of the present invention.

[0066] The present invention also relates to the use of at least one isomer mixture of reactive dyes according to formula (I) or inks according to the present invention in the dyeing or printing of textile materials such as hydroxyl- or nitrogen-containing fiber materials, especially cellulose fiber materials.

[0067] The present invention also relates to a method for dyeing or printing textile materials, such as hydroxyl- or nitrogen-containing fiber materials, the method comprising using a mixture of isomers of at least one reactive dye according to formula (I) of the present invention or an aqueous ink according to the present invention.

[0068] The present invention also relates to textiles dyed or printed using a mixture of isomers of at least one reactive dye according to formula (I) or an aqueous ink according to the present invention.

[0069] Detailed description

[0070] A mixture of isomers of reactive dyes having formula (I)

[0071] This invention relates to a mixture of isomers of at least one reactive dye having formula (I):

[0072]

[0073] in,

[0074] R1 is hydrogen or a C1-C4 alkyl group.

[0075] R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, sulfonyl, carboxyl, or halogen.

[0076] Z is a fiber-reactive group with 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, wherein Y is a group that can be removed under alkaline conditions.

[0077] X is a halogen, and

[0078] M is hydrogen, an organic salt, an alkali metal, or an equivalent of an alkaline earth metal.

[0079] According to the present invention, at least one reactive dye isomer mixture provides very good aggregation properties, high fixation rate, good rinsing properties of unfixed dyes, good all-around fastness properties and improved stability for various dyeing parameters, especially improved bath stability.

[0080] The terms "isomers" and "mixtures of isomers" as used herein include dyes having the same chemical formula but different atomic arrangements. According to the invention, a mixture of isomers of the reactive dye of formula (I) comprises reactive dyes having the same chemical formula and thus the same number of carbon atoms, but with the -SO3M portion attached to different positions on the benzene ring.

[0081] The term "isomer mixture" as used in this article refers to a composition containing one or more reactive dye isomers.

[0082] A “mixture of at least one reactive dye isomer” may optionally include isomers of one or more reactive dyes of formula (I). Therefore, the mixture of isomers contains one or more (i.e., two or more) isomers of the reactive dye of formula (I), and may also contain one or more (i.e., two or more) isomers of different reactive dyes of formula (I). Different reactive dyes of formula (I) have different chemical formulas included within the scope of formula (I), and therefore have different carbon numbers. For example, a mixture of at least one reactive dye isomers of formula (I) includes a β-vinylsulfonyl reactive dye of formula (I) and its isomers, as well as a β-sulfoethylsulfonyl reactive dye of formula (I) and its isomers (isomers with sulfonic acid substituents attached to different positions on the benzene ring).

[0083] The isomer mixtures disclosed herein are distinct from the single reactive dye of formula (I).

[0084] “C i -C j "Alkyl" refers to a saturated, straight-chain or branched hydrocarbon chain containing i to j carbon atoms.

[0085] "C1-C4 alkyl" refers to a saturated, straight-chain or branched hydrocarbon chain containing 1 to 4 carbon atoms. Preferably, the hydrocarbon chain is straight-chain. Preferably, the C1-C4 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, more preferably, the C1-C4 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, and advantageously, the C1-C4 alkyl is methyl or ethyl.

[0086] "C1-C4 alkoxy" refers to a saturated, straight-chain or branched hydrocarbon chain containing 1 to 4 carbon atoms that are replaced by oxygen atoms.

[0087] Preferably, the hydrocarbon chain is straight-chain. Preferably, the C1-C4 alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, or tert-butoxy. Preferably, the C1-C4 alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, and n-butoxy. Advantageously, the C1-C4 alkoxy group is methoxy or ethoxy.

[0088] The term "halogen" as used in this article refers to a fluorine atom, a chlorine atom, or a bromine atom, preferably a fluorine atom or a chlorine atom.

[0089] As used herein, the term "sulfonyl" refers to the -SO3M group. The sulfonyl-SO3M exists as a free acid (M is hydrogen) or, preferably, as a salt. Suitable salts are, for example, alkali metal or alkaline earth metal salts. Other salts considered are organic amine salts, ammonium salts, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium, or ammonium salts, mono-, di-, or triethanolamine salts, or mixed sodium / lithium or sodium / lithium / NH4 salts.

[0090] As used herein, the term "Y" refers to a group that is removable under basic conditions, selected from the group consisting of -Cl, -Br, -F, -OSO3M, -SSO3M, -OCO-CH3, -OPO3M2, -OCO-C6H5, -OSO2-C1-C4 alkyl, or -OSO2-N(C1-C4 alkyl)2. Preferably, Y is selected from the group consisting of -Cl, -OSO3M, -SSO3M, -OCO-CH3, -OCO-C6H5, or -OPO3M2, more preferably -Cl or -OSO3M, wherein M has the meaning given above.

[0091] 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.

[0092] In a preferred embodiment, R2 is hydrogen, methyl, ethyl, sulfonyl, carboxyl, or halogen. More preferably, R2 is hydrogen, sulfonyl, or halogen. Advantageously, R2 is sulfonyl.

[0093] In a more preferred embodiment, a mixture of isomers of at least one reactive dye of formula (I), wherein:

[0094] R1 is an ethyl group.

[0095] R2 is sulfonyl.

[0096] Z is a fiber-reactive group with the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y, where Y is a group that can be removed under alkaline conditions.

[0097] X is a fluorine atom, and

[0098] M is hydrogen, an organic salt, an alkali metal, or an equivalent of an alkaline earth metal.

[0099] In a preferred embodiment, the isomer mixture according to the invention comprises at least one isomer of formula (Ia):

[0100]

[0101] Isomers of the compound (Ib):

[0102]

[0103] Among them, R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0104] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 1:4 to 4:1.

[0105] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:1.

[0106] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 3:7 to 2:3.

[0107] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:1.

[0108] In one embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 7:3 to 3:2.

[0109] Advantageously, compared to the isomers used individually, the mixture of isomers of formula (Ia) and (Ib) in the stated proportions provides improved stability of the isomer mixture according to the invention for various staining parameters, particularly improved bath stability. It is noteworthy that the mixture of isomers of formula (Ia) and (Ib) in the stated proportions according to the invention exhibits a synergistic effect in bath stability compared to the bath stability of the isomers used individually.

[0110] In another preferred embodiment, the isomer mixture according to the invention comprises at least one isomer of formula (Ia) of the reactive dye containing formulas (Ia1) and (Ia2):

[0111]

[0112] and,

[0113] - At least an isomer of formula (Ib), which includes a mixture of isomers of formulas (IIa1) and (IIa2):

[0114]

[0115] Among them, R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0116] In a preferred embodiment, the isomer mixture according to the invention comprises an isomer of formula (Ia) of reactive dye containing formulas (Ia1) and (Ia2) and an isomer of formula (Ib) of reactive dye containing formulas (Ib1) and (Ib2), 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, and more preferably from 8:2 to 95:5.

[0117] In a preferred embodiment, the isomer mixture according to the invention comprises at least:

[0118] -Isomers of formula (Ⅱa):

[0119] and,

[0120] -Isomers of formula (Ⅱb):

[0121]

[0122] Among them, R1, R2, Z, X and M each have the meanings and preferred meanings given above.

[0123] In the preferred embodiment, the isomer mixture according to the invention advantageously comprises at least:

[0124] -Isomers of formula (Ⅲa):

[0125]

[0126] -Isomers of formula (Ⅲb):

[0127]

[0128] -Isomers of formula (Ⅲc):

[0129] and

[0130] -Isomers of formula (Ⅲd):

[0131]

[0132] in

[0133] R1, R2, X, and M each have the meanings and preferred meanings given above.

[0134] The isomer mixture of reactive dyes according to formula (1) of the present invention exists in the form of a free acid, or preferably in the form of its salt, such as, for example, salts of alkali metals, alkaline earth metals, and ammonium salts or organic amines. Sodium salts, lithium salts, potassium salts, and ammonium salts, as well as monoethanolamine salts, diethanolamine salts, and triethanolamine salts, can be mentioned as examples.

[0135] In a preferred embodiment, the isomer mixture according to the invention may contain additional additives, such as sodium chloride or dextrin.

[0136] If necessary, the isomer mixtures according to the invention may contain additional adjuvants, such as adjuvants that can improve handling or storage stability, such as buffers, dispersants or dust suppressants, which are known to those skilled in the art.

[0137] In embodiments, the isomer mixtures according to the invention are suitable for dyeing or printing textiles, particularly nitrogen- or hydroxyl-containing fiber materials.

[0138] The terms “textile,” “textile material,” and “fiber material” as used herein must be interpreted broadly and can have very wide forms of representation, for example, in the form of fibers, yarns, fabrics, clothing, knitwear, woven fabrics, and nonwoven fabrics. The copolymers according to the invention are suitable for processing a variety of textile materials. The textiles according to the invention are hydroxyl- or nitrogen-containing fiber materials, particularly cellulose fiber materials. The textiles according to the invention can be natural or synthetic textiles, such as cotton, silk, wool, linen, polyamide, polyurethane, polyacrylic acid, polyester, polyolefin, polylactic acid, and hemp, or blends of natural textile materials with synthetic textile materials (i.e., polyamide, polyurethane, polyacrylic acid, polyester, polyolefin, or polylactic acid), such as blends of cotton with polyester or polyamide fibers.

[0139] Preparation method of isomer mixture according to the present invention

[0140] The present invention also relates to a method for preparing a mixture of isomers of at least one reactive dye of formula (I), comprising:

[0141] (a) Diazotization of the following compound

[0142]

[0143] R2 and Z have the meanings defined above;

[0144] And the resulting diazonium salt reacts with the coupling component of the following formula.

[0145]

[0146] This yields the following azo compound.

[0147]

[0148] R2 and Z are as defined above;

[0149] (b) Condensate the azo compound of formula (3) prepared in step (a) with the compound of the following formula.

[0150]

[0151] Where X represents the same halogen as defined above.

[0152] This provides compounds of the following formula.

[0153]

[0154] R2, Z, and X are as defined above;

[0155] (c) Condensate the compound of formula (5) prepared in step (b) with a mixture of isomers of the following formula.

[0156]

[0157] R1 and M are defined above.

[0158] Thus, a mixture of reactive dye isomers according to formula (1) of the present invention is obtained.

[0159] The mixture of isomers of the reactive dye of formula (1) obtained in step (c) may optionally undergo a conversion reaction. Such a conversion reaction is, for example, the conversion of the vinylizable reactive group -SO2-Y to its vinyl form using a dilute sodium hydroxide solution, for example, the conversion of a β-chloroethylsulfonyl group or a β-ethyl sulfate sulfonyl group to a vinylsulfonyl group; these reactions are known per se. These conversion reactions are typically carried out in a neutral to alkaline medium at temperatures, for example, from 20 to 70 °C, and at a pH, for example, from 6 to 14.

[0160] 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, and are commercially available.

[0161] In step (a), the amine of formula (1) is typically diazotized in an aqueous solution of an inorganic acid at low temperatures, such as 0°C to 40°C, by the action of nitrous acid, and the reaction with the coupling component of formula (2) is carried out at a weakly acidic, neutral, or weakly alkaline pH.

[0162] The compounds of formula (3) can be prepared by methods known per se, such as by conventional diazotization and coupling reactions, as described in, for example, US-A-4341699, GB-A-1576237, US-A-4754023, EP-A-94055 and US-A-5298607.

[0163] Suitable compounds for formula (4) are, for example, cyanuric fluoride or cyanuric chloride, and are commercially available.

[0164] In step (b), the azo compound of formula (3) and the compound of formula (4) are condensed in an aqueous solution at low temperatures, such as 0°C to 40°C, at a weakly acidic, neutral, or weakly alkaline pH.

[0165] In step (c), the intermediate of formula (5) and the isomer of formula (6) are condensed in an aqueous solution of an inorganic acid at a low temperature, for example, from 0°C to 40°C, at a weakly acidic, neutral or weakly alkaline pH.

[0166] In a preferred embodiment, the isomer mixture of formula (6) comprises two isomers, one of which has a sulfonyl group at the meta position of aniline and the other has a sulfonyl group at the para position of aniline.

[0167] Suitable mixtures of isomers of formula (6) are, for example, mixtures of N-ethyl-3-sulfonaniline and N-ethyl-4-sulfonaniline, which are commercially available.

[0168] This mixture of isomers can be synthesized by sulfonation of N-ethylaniline or by physically mixing the two isomers.

[0169] In a preferred embodiment, the isomers of the mixture of isomers of formula (6) have a weight ratio of 1:4 to 4:1, preferably 1:4 to 1:1, and more preferably 3:7 to 2:3, between the meta-isomer of sulfonyl in aniline (N-ethyl-3-sulfonylaniline) and the para-isomer of sulfonyl in aniline (N-ethyl-4-sulfonylaniline).

[0170] In a preferred embodiment, the isomers of the mixture of isomers of formula (6) have a weight ratio of 1:4 to 4:1, preferably 4:1 to 1:1, and more preferably 7:3 to 3:2, between the meta-isomer of aniline (N-ethyl-3-sulfoaniline) and the para-isomer of aniline (N-ethyl-4-sulfoaniline).

[0171] Advantageously, the mixture of compounds of formula (6) in the stated proportion results in a mixture of isomers of the reactive dye according to formula (1) in the same proportion as the isomers used alone, which leads to improved stability for various dyeing parameters, particularly improved bath stability. It is noteworthy that the mixture of isomers of the reactive dye according to formula (1) in the stated proportion exhibits a synergistic effect in bath stability compared to the bath stability of the isomers used alone.

[0172] Since the various process steps mentioned above may be carried out in different orders, and under certain appropriate conditions, it is possible to carry out different process variations simultaneously, the reactions are generally carried out stepwise between individual reactant components determined by specific conditions, in a simple, known order of reactions.

[0173] Compositions and Applications

[0174] The present invention also relates to aqueous inks comprising a mixture of isomers of at least one reactive dye according to formula (1) of the present invention, and the use of such inks in inkjet printing methods for printing on various substrates, particularly textile fiber materials, the definitions and preferences indicated above being applicable to dyes, inks and substrates.

[0175] The isomer mixture of at least one reactive dye of the present invention exhibits excellent aggregation properties, high end aggregation and high fixation, especially in printing applications on cellulose fiber materials, and improved stability for different printing parameters.

[0176] The isomer mixture of reactive dyes according to formula (1) is also suitable for use as colorants in recording systems. Such recording systems are, for example, commercially available inkjet printers for printing on paper or textiles, or writing instruments such as pens or ballpoint pens, and especially inkjet printers. For this purpose, the dyes according to the invention are first formulated in a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink containing the isomer mixture of the invention as a colorant. The ink can be prepared in a conventional manner by mixing the individual components together in a desired amount of water.

[0177] As a base material, hydroxyl-containing or nitrogen-containing fiber materials, especially cellulose fiber materials, can be considered. Textile fiber materials are preferred.

[0178] Other substrates to consider are paper and plastic film.

[0179] Examples of commercially available paper include inkjet paper, photographic paper, glossy paper, and plastic-coated paper, such as Epson inkjet paper, Epson photographic paper, Epson glossy paper, Epson glossy film, HP inkjet paper, Encad photo glossy paper, and Ilford photographic paper. Plastic films, for example, can be transparent or opaque / cloudy. A suitable plastic film is, for example, 3M transparent film.

[0180] Depending on the nature of the application, such as textile printing or paper printing, it may be necessary to adjust the viscosity or other physical properties of the ink, especially those that affect the affinity of the substrate.

[0181] The isomer mixtures according to the invention used in water-based inks should preferably have a low salt content, that is, their total salt content should be less than 0.5% by weight based on the weight of the dye. Dyes with relatively high salt content due to their preparation and / or subsequent addition of diluents can be desalted, for example by membrane separation procedures such as ultrafiltration, reverse osmosis or dialysis.

[0182] Based on the total weight of the ink, the ink preferably contains a total content of 1 to 35% by weight of the isomer mixture according to the invention, particularly 1 to 30% by weight, and more preferably 1 to 20% by weight. In this case, the preferred lower limit is 1.5% by weight, more preferably 2% by weight, and particularly 3% by weight.

[0183] The ink may contain water-miscible organic solvents, such as C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, or isobutanol; amides, such as dimethylformamide or dimethylacetamide; ketones or ketols, such as acetone or diacetone alcohol; ethers, such as tetrahydrofuran or dioxane; nitrogen-containing heterocyclic compounds, such as N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolinone; polyalkylene glycols, such as polyethylene glycol or polypropylene glycol; C2-C6 alkylene glycols and thiodiols, such as ethylene glycol, propylene glycol, butanediol, triethylene glycol, thiodiglycol, hexanediol, and diethylene glycol; and other multi-components. Alcohols, such as glycerol or 1,2,6-hexanetriol; and C1-C4 alkyl ethers of polyols, such as 2-methoxyethanol, 2-(2-methoxy-ethoxy)ethanol, 2-(2-ethoxy-ethoxy)ethanol, 2-[2-(2-methoxy-ethoxy)ethoxy]ethanol or 2-[2-(2-ethoxy-ethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propanediol, typically in a content of 2% to 30% by weight, particularly 5% to 30% by weight, and preferably 10% to 25% by weight, based on the total weight of the ink.

[0184] In addition, inks may contain solubilizers, such as β-caprolactam.

[0185] Inks may contain thickeners of natural or synthetic origin, especially for the purpose of adjusting viscosity.

[0186] Examples of thickeners that may be mentioned include commercially available alginate thickeners, starch ethers, or locust bean starch ethers, particularly sodium alginate alone or in mixtures with modified cellulose such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose, or hydroxypropylmethylcellulose, particularly with a preferred amount of 20 to 25% by weight of carboxymethylcellulose. Synthetic thickeners that may also be mentioned are, for example, thickeners based on poly(meth)acrylic acid or poly(meth)acrylamide and polyalkylene glycols with molecular weights, for example, from 2000 to 20000, such as polyethylene glycol or polypropylene glycol or a mixture of ethylene oxide and propylene oxide.

[0187] The ink may contain these thickeners, for example, in a content of 0.01 to 2% by weight, particularly 0.01 to 1% by weight, and preferably 0.01 to 0.5% by weight, based on the total weight of the ink.

[0188] The ink may also contain buffering substances such as borax, borates, phosphates, polyphosphates, or citrates. Examples include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate, and sodium citrate. Based on the total weight of the ink, these substances are used, particularly in amounts from 0.1% to 3% by weight, preferably from 0.1% to 1% by weight, to establish a pH value, for example, from 4 to 9, and especially from 5 to 8.5.

[0189] As for other additives, inks may contain surfactants or wetting agents.

[0190] Suitable surfactants include commercially available anionic or nonionic surfactants. As a wetting agent in the ink according to the invention, a mixture of, for example, urea or sodium lactate (advantageously in the form of a 50% to 60% aqueous solution) with glycerol and / or propylene glycol can be considered, preferably in a content of 0.1% to 30% by weight, particularly 2% to 30% by weight.

[0191] Inks with a viscosity range of 1 to 40 mPa·s are preferred, especially those with a viscosity range of 1 to 20 mPa·s, and even more so those with a viscosity range of 1 to 10 mPa·s.

[0192] In addition, the ink may contain conventional additives, such as antifoaming agents or, in particular, preservatives that inhibit the growth of fungi and / or bacteria. The amount of these additives is typically from 0.01% to 1% by weight, based on the total weight of the ink.

[0193] As preservatives, formaldehyde-producing agents are considered, such as paraformaldehyde and triformaldehyde, especially aqueous formaldehyde solutions containing approximately 30 to 40% by weight; imidazole compounds, such as 2-(4-thiazolyl)-benzimidazole; thiazole compounds, such as 1,2-benzisothiazolin-3-one or 2-n-octylisothiazolin-3-one; iodine compounds; nitriles; phenols; haloalkyl sulfides; or pyridine derivatives, especially 1,2-benzisothiazolin-3-one or 2-n-octylisothiazolin-3-one. A suitable preservative is, for example, a 20% by weight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol. GXL).

[0194] The ink may contain additional additives, such as fluoropolymers or telomers, such as polyethoxylated perfluoroalcohols (PEPs). or The content of the product is based on the total weight of the ink, for example, from 0.01% to 1% by weight.

[0195] In inkjet printing methods, individual ink droplets are ejected from a nozzle onto a substrate in a controlled manner. This is primarily achieved using continuous inkjet printing and on-demand inkjet printing. In continuous inkjet printing, droplets are generated continuously, and droplets not needed for the printing operation are discharged into a container and recycled. On the other hand, in on-demand inkjet printing, droplets are generated only as needed for printing; that is, droplets are only generated when required for the printing operation. For example, droplet generation can be achieved using a piezoelectric inkjet head or thermal energy (bubble inkjet). Printing using a piezoelectric inkjet head and printing according to a continuous inkjet printing method are preferred.

[0196] The present invention also relates to the use of a mixture of isomers of at least one reactive dye according to formula (I) or an ink according to the present invention in the dyeing or printing of textile materials, such as hydroxyl- or nitrogen-containing fiber materials, particularly cellulose fiber materials; or in other words, to a method of dyeing or printing textile materials, such as hydroxyl- or nitrogen-containing fiber materials, particularly cellulose fiber materials, wherein a mixture of isomers of at least one reactive dye according to formula (I) or an ink according to the present invention is used.

[0197] The isomer mixtures according to the invention or the inks according to the invention are suitable for conventional dyeing and printing methods and can be applied to and fixed to fibrous materials in a variety of ways, particularly in the form of aqueous dye solutions or print pastes.

[0198] The dyeing and printing process for hydroxyl- or nitrogen-containing fiber materials according to the invention can be carried out according to conventional dyeing and printing methods, for example, according to the so-called cold pad-batch process, wherein the isomer mixture according to the invention is applied together with an alkali onto a padding machine and then fixed by storing at about room temperature, for example, from 25 to 35°C for several hours. Alternatively, the dyeing and printing process according to the invention can be carried out by an immersion dyeing method, wherein the goods are immersed in an aqueous solution of an optional salt-containing isomer mixture according to the invention, the isomer mixture being fixed after alkali treatment or optionally under heat in the presence of an alkali.

[0199] The amount of the isomer mixture according to the invention or the ink according to the invention used for dyeing or printing can vary in a wide range depending on the desired depth of shade. Generally, an amount from 0.01 to 15% by weight, particularly from 0.1 to 10% by weight, has proven advantageous, depending on the goods being dyed or printed.

[0200] The present invention also relates to textiles dyed or printed using a mixture of isomers of at least one reactive dye according to formula (I) or an aqueous ink according to the present invention.

[0201] Dyeing and printing produced using the isomer mixtures according to the invention exhibit high color strength and high fiber-dye binding stability in both acidic and alkaline ranges, significant non-photochromic properties, and good light and chlorine fastness, good elution performance, good bath stability, and excellent operability (reproducibility, fixation time, etc.).

[0202] The following examples are used to illustrate the present invention. Unless otherwise stated, temperatures are expressed in degrees Celsius, mass is expressed in g / g (100% active ingredient), parts are parts by weight, percentages are percentages by weight, and ratios are expressed in molar equivalents. Parts by weight relative to parts by volume are expressed in kilograms to liters. Example

[0203] - To maintain the pH value at an appropriate level, use a 32% hydrochloric acid solution, a 20% sodium carbonate solution, or a 30% sodium hydroxide solution.

[0204] Water and ice are used for the cooling process.

[0205] The reaction was monitored using high-performance liquid chromatography (HPLC), which indicated the end of the reaction.

[0206] - All products used in the synthesis are commercially available.

[0207] Examples 1a and 1b:

[0208] (a) 109.0 g of 2-amino-5-((2-(sulfoxy)ethyl)sulfonyl-benzenesulfonic acid was finely dispersed in 200 parts of water and diazotized according to the following procedure:

[0209] (a1) Mix 2-amino-5-((2-(sulfooxy)ethyl)sulfonyl-benzenesulfonic acid with a 32% aqueous solution of hydrochloric acid, with a stoichiometric ratio (HCl 32% : 2-amino-5-((2-(sulfooxy)ethyl)sulfonyl-benzenesulfonic acid) of 2.0-3.0 : 1.0.

[0210] (a2) Under conditions of 0-30℃, the mixture obtained in step (a1) is diazotized with a slightly molar excess of 4N sodium nitrite solution at a ratio of 1.05-1.1:1.0 (sodium nitrite: mixture obtained in step (a1)) to ensure complete diazotization.

[0211] (a3) Stir the reaction mixture obtained in step (a2) for 1 hour, add 10% aminosulfonic acid solution to neutralize the excess nitrite, thereby obtaining the desired diazonium salt.

[0212] Then, 46.0 g of 3-aminophenylurea, pre-dispersed in water, was cooled with ice, and the diazonium salt mixture obtained in step (a3) ​​was added for coupling at 0-30°C maintained by ice and at pH 4.5-6.0 maintained by the addition of 20% sodium carbonate solution. After coupling, the reactants were heated to 25-40°C and treated with 32% hydrochloric acid solution at pH 1.0-1.5 for 1-3 hours to remove triazine. The resulting mixture was then cooled to 20-25°C and dissolved with 20% sodium carbonate solution at pH 6.5-7.0.

[0213] (b) Cool the mixture obtained in step (a) with ice at 0-5°C and pH 6.0-8.0, and add 53.0 g of cyanuric fluoride to the mixture over 5-20 minutes. Maintain the pH of the mixture at this value by adding 30% sodium hydroxide solution, and maintain the temperature at 0-5°C by adding ice. Stir the resulting mixture under the above conditions for 5-10 minutes after the addition is complete. Then, add 32% hydrochloric acid solution to the resulting mixture to set the pH at 3.0-4.0, while maintaining the temperature at this value by adding ice.

[0214] (c) A mixture of N-ethyl-3-sulfoaniline and N-ethyl-4-sulfoaniline was prepared by physical mixing (N-ethyl-3-sulfoaniline:N-ethyl-4-sulfoaniline).

[0215] (c-1) The mixing molar ratio is 3:2, formula (101a) of Example (1a), or

[0216] (c-2) The mixing molar ratio is 2:3, and the formula (101b) of Example (1b) is used.

[0217] The mixture with a pH of 3.0-4.0 obtained in step (b) is cooled at 0-5°C, and 57.0 g of the mixture (N-ethyl-3-sulfonaniline:N-ethyl-4-sulfonaniline) given in (c-1) or (c-2) in (c) is added to the mixture over a period of 5-10 minutes. During the addition, the pH is set and maintained at 6.0-7.0 using a 30% sodium hydroxide solution, and the temperature is kept below 10°C. After the addition is complete, the reaction mixture is stirred for 20-30 minutes under the same conditions as above, then heated to 20-30°C while maintaining the pH at 6.0-7.0, and stirred under these conditions for 2-4 hours.

[0218] After the reaction is complete, the reactants are heated to 30-50℃, subjected to reverse osmosis treatment, and dried to obtain a crude mixture of reactive dye isomers, the main components of which correspond to formula (101a) or (101b) in the form of free acids:

[0219]

[0220] Examples 2a, 2b and Comparative Examples 3-5:

[0221] The following dyes can be prepared in a manner similar to that described in Example 1.

[0222] Examples 2a and 2b:

[0223]

[0224] Comparative Example 3:

[0225]

[0226] Comparative Example 4:

[0227]

[0228] Comparative Example 5:

[0229]

[0230] Comparative Example 6:

[0231]

[0232] Comparative Example 7:

[0233] (a) 109.0 g of 2-amino-5-((2-(sulfoxy)ethyl)sulfonyl-benzenesulfonic acid was finely dispersed in 200 parts of water and diazotized according to the following procedure:

[0234] (a1) Mix 2-amino-5-((2-(sulfooxy)ethyl)sulfonyl-benzenesulfonic acid with a 32% aqueous solution of hydrochloric acid, with a stoichiometric ratio (HCl 32% : 2-amino-5-((2-(sulfooxy)ethyl)sulfonyl-benzenesulfonic acid) of 2.0-3.0 : 1.0.

[0235] (a2) Under conditions of 0-30℃, the mixture obtained in step (a1) is diazotized with a slightly molar excess of 4N sodium nitrite solution at a ratio of 1.05-1.1:1.0 (sodium nitrite: mixture obtained in step (a1)) to ensure complete diazotization.

[0236] (a3) Stir the reaction mixture obtained in step (a2) for 1 hour, add 10% aminosulfonic acid solution to neutralize the excess nitrite, thereby obtaining the desired diazonium salt.

[0237] Then, 46.0 g of 3-aminophenylurea, pre-dispersed in water, was cooled with ice, and the diazonium salt mixture obtained in step (a3) ​​was added for coupling at 0-30°C maintained by ice and at pH 4.5-6.0 maintained by the addition of 20% sodium carbonate solution. After coupling, the reactants were heated to 25-40°C and treated with 32% hydrochloric acid solution at pH 1.0-1.5 for 1-3 hours to remove triazine. The resulting mixture was then cooled to 20-25°C and dissolved with 20% sodium carbonate solution at pH 6.5-7.0.

[0238] (b) 55.5 g of cyanuric chloride was suspended in water with 1 g of buffer (disodium hydrogen phosphate) and ice. The temperature of the suspension was set to 0-5 °C, and the mixture was stirred vigorously for 10 minutes using a dispersing device.

[0239] Cool the mixture obtained in step (a) with ice at 0-5°C and, at pH 6.0-8.0, rapidly (in less than 1 minute) add 55.5 g of cyanuric chloride to the mixture. Adjust and maintain the pH of the mixture at 5.0-6.0 for 1 hour by adding 20% ​​sodium carbonate solution at 15-25°C. After the reaction is complete, the suspension temperature is 15-25°C and the pH is 5.0-6.0.

[0240] (c) At a temperature of 20-25°C, 58.0 g of 2-sulfoaniline was dissolved in water, and the pH of the solution was adjusted and maintained at 6.0-7.0 by adding 30% sodium hydroxide solution.

[0241] Add a 2-sulfoaniline solution to the mixture obtained in step (b) within 5 minutes, and heat the mixture to 60-70°C. Maintain the pH at 5.0-5.5 by adding 20% ​​sodium carbonate solution, and stir the mixture at 60-70°C until the reaction is complete.

[0242] After the reaction is complete, the reactants are cooled to 20-25°C, and the unreacted 2-sulfoaniline is quenched by dropping acetic anhydride. Then, the pH of the reactants is adjusted to 5.5-6.0 with a 32% hydrochloric acid solution, and the reactants are heated to 30-50°C for reverse osmosis treatment and dried to obtain a crude reactive dye. Its main component, in the form of free acid, corresponds to the following formula:

[0243]

[0244] Comparative Examples 8 and 9:

[0245] The following dyes can be prepared in a manner similar to that described in Comparative Example 6.

[0246] Comparative Example 8

[0247]

[0248] Comparative Example 9

[0249]

[0250] Application examples 10a-10b-11a-11b and comparison examples 12-18:

[0251] Application Examples 10a-10b-11a-11b and Comparative Application Examples 12-18 were prepared according to the following staining instructions:

[0252] Pad-batch dyeing: Bleached (mercerized) printed cotton fabrics are dyed on a pad with a squeezing effect having a dye absorption rate of 75% (70%) by immersing them in an aqueous dyeing solution containing X g of the isomer mixture or contrast dye according to the invention and 1 g of wetting agent per liter. PAD), 2g dye bath softener ( DBS), 20 ml of 36°Bé sodium hydroxide and 70 ml of 38°Bé sodium silicate (water glass). Immersion time was 2 seconds. After padding, the fabric was rolled up and stored at 25°C for 24 hours. After storage, the dyed cotton was cold washed with water (10 minutes), boiled in water (5 minutes), and then cold washed with water (10 minutes). Various dyed fabrics were obtained according to the concentration (X g / L) of the reactive dye isomer mixture. Tables 1 and 2 summarize the concentration (X g / L) of the reactive dye isomer mixture of Application Examples 10-11 and Comparative Application Examples 12-18, the maximum accumulation performance at the same E25, and the fixation at the same reference depth.

[0253] Application Example 10a was obtained from a mixture of isomers according to Example 1a (Formula (101a)). Application Example 10b was obtained from a mixture of isomers according to Example 1b (Formula (101b)).

[0254] Application Example 11a was obtained from a mixture of isomers according to Example 2a (Formula (102a)). Application Example 11b was obtained from a mixture of isomers according to Example 2b (Formula (102b)).

[0255] Comparative Application Examples 12-18 were obtained from dyes based on Comparative Examples 3-9, respectively.

[0256] The dyeing intensity of the dyed fabrics 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 testing method that specifies the color depth and is associated with the standard depth SD according to ISO 105-A-1984(E), page 4. The reference depth of the dyed fabrics according to Application Examples 10-11 and Comparative Application Examples 12-18 is measured by photometry.

[0257] Create an accumulation plot and determine the maximum accumulation degree in the usual way.

[0258]

[0259] Table 1. Maximum accumulation performance measurements of application examples 10a-10b-11a-11b and comparative application examples 12-18.

[0260] The fixation degree of Application Examples 10a-10b-11a-11b and Comparative Application Examples 12-18 was determined in a conventional manner by cutting dyed fabric samples of specified size with RD equal to 1 and dissolving / extracting the unfixed dye with a phosphate buffered aqueous solution (pH 7) during boiling.

[0261]

[0262]

[0263] Table 2. Fixation measurements of Application Examples 10-11 and Comparative Application Examples 12-18

[0264] Application examples 19a-19b-20a-20b and comparison examples 21-27:

[0265] Application Examples 19a-19b-20a-20b and Comparative Application Examples 21-27 were prepared according to the following pad-batch dyeing instructions for measuring bath stability.

[0266] Dyed fabric T0: Bleached (mercerized) printed cotton fabric is dyed on a roller with a squeezing effect having a dye absorption rate of 75% (70%) by immersion in an aqueous dyeing solution containing X g of the isomer mixture or contrast dye according to the invention and 1 g of wetting agent per liter. PAD), 2g dye bath softener ( (DBS), X ml 36°Bé sodium hydroxide and 20 ml soda ash. Immersion time is 2 seconds. After padding, roll up the fabric and store at 25°C for 24 hours. Return the aqueous dyeing solution to the constant temperature bath at 25°C for 10 minutes, allowing it to remain uncooled between two pad-batch dyeing cycles, so that the bath stability of the isomer dye mixture according to the invention can be measured under the dyeing temperature conditions.

[0267] For dyed fabric T10: After 10 minutes, the aqueous dyeing solution is returned to the padding machine, and the bleached (mercerized) printed cotton fabric is then impregnated with the dyeing solution. After impregnation, the fabric is rolled up and stored at 25°C for 24 hours.

[0268] Return the staining solution to a 25°C constant temperature bath for 20 minutes.

[0269] For dyed fabric T20: After 20 minutes, the aqueous dyeing solution is returned to the padding machine, and the bleached (mercerized) printed cotton fabric is then impregnated with the dyeing solution. After impregnation, the fabric is rolled up and stored at 25°C for 24 hours.

[0270] Return the staining solution to a 25°C constant temperature bath for 30 minutes.

[0271] For dyed fabric T30: After 30 minutes, the aqueous dyeing solution is returned to the padding machine, and the bleached (mercerized) printed cotton fabric is then impregnated with the dyeing solution. After impregnation, the fabric is rolled up and stored at 25°C for 24 hours.

[0272] The different dyed cotton fabrics T0, T10, T20 and T30 were stored in a constant temperature bath at 25°C for 24 hours. Then the dyed cotton fabrics T0, T10, T20 and T30 were cold washed with water (10 minutes), boiled in water (5 minutes), then cold washed with water (10 minutes), spun dry and ironed.

[0273] The resulting dyed fabrics T0, T10, T20 and T30 were stored overnight in the dark, and their color intensity was then measured using a Datacolor 600 spectrochromiste.

[0274] For dyed fabric T0, the determination of its color intensity is called "instantaneous intensity determination". For all dyed fabrics T0, the dye concentration (g / l) is set to achieve a reference depth value equivalent to 0.5, and this RD value is set as a reference value defined as 100%.

[0275] The coloring intensity of dyed fabrics T10, T20, and T30 was measured and compared with the instantaneous intensity measurement.

[0276] The determination of bath stability of the reactive dye isomer mixture and the contrast dye according to the present invention refers to the time when the loss of coloring strength reaches more than 5% compared with the instantaneous strength determination.

[0277] Table 3 summarizes the concentration (X g / l) and bath stability of the isomer mixtures of reactive dyes.

[0278] Application Example 19a was obtained from a mixture of isomers according to Example 1a (Formula (101a)). Application Example 19b was obtained from a mixture of isomers according to Example 1b (Formula (101b)).

[0279] Application Example 20a was obtained from a mixture of isomers according to Example 2a (Formula (102a)). Application Example 20b was obtained from a mixture of isomers according to Example 2b (Formula (102b)).

[0280] Comparative Application Examples 21-27 were obtained from dyes based on Comparative Examples 3-9.

[0281]

[0282] Table 3 Bath stability measurements for Application Examples 19-20 and Comparative Application Examples 12-18

[0283] The results summarized in Tables 1, 2 and 3 show that the isomer mixtures (101a or 101b) and (102a or 102b) according to the invention are superior to the comparative dyes.

[0284] In particular, textiles dyed using the isomer mixtures (101a or 101b) and (102a or 102b) according to the invention simultaneously exhibit very good aggregation properties, i.e., a maximum RD value greater than 2.00, very good fixation, i.e., fixation greater than or equal to 90%, and improved bath stability when the isomer mixtures (101a or 101b)-(102a or 102b) are present in the dye bath. In particular, compared with the contrast dyes, the isomer mixtures (101a or 101b) and (102a or 102b) according to the invention show a color strength loss of more than 5% after 30 minutes, while the contrast dyes achieve a color strength loss of up to 5% after 20 minutes.

[0285] Furthermore, the results in Table 3 show the synergistic effect of the isomer mixture (101a or 101b) on bath stability when compared individually with the individual isomers (104) and (105) constituting the isomer mixture of the present invention.

[0286] Therefore, compared with isomers used alone or with prior art dyes, the isomer mixtures according to the present invention exhibit very good aggregation properties and very high fixation, while also demonstrating superior bath stability.

Claims

1. A mixture of isomers of at least one reactive dye having formula (I): (I) The isomer mixture comprises at least one isomer of formula (Ia): (him) Isomers of the compound (Ib): (One) in, R1 is hydrogen or a C1-C4 alkyl group. R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, sulfonyl, carboxyl, or halogen. Z is a fiber-reactive group with 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, wherein Y is a group that can be removed under alkaline conditions. X is a halogen, and M is hydrogen, an organic salt, an alkali metal, or an equivalent of an alkaline earth metal. The mixture contains isomers of formula (Ia) and (Ib) in a weight ratio ranging from 1:4 to 4:

1.

2. The isomer mixture according to claim 1, wherein the mixture comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 1:4 to 1:

1.

3. The isomer mixture according to claim 1, wherein the mixture comprises an isomer of formula (Ia) and an isomer of formula (Ib) in a weight ratio ranging from 4:1 to 1:

1.

4. The isomer mixture of claim 1, wherein the mixture comprises: - At least isomers of formula (Ia), including reactive dyes of formulas (Ia1) and (Ia2): (Ia1) and (Ia2) and, - At least an isomer of formula (Ib), which includes a mixture of isomers of formula (Ib1) and (Ib2): (Ib1) and (Ib2) in, R1, R2, Z, X, and M are as defined in claim 1.

5. The isomer mixture according to claim 4, wherein the weight ratio of reactive dyes (Ia1) and (Ib1) to reactive dyes (Ia2) and (Ib2) ranges from 6:4 to 99:

1.

6. The isomer mixture according to claim 1, wherein R1 is hydrogen, methyl, ethyl, n-propyl or n-butyl.

7. The isomer mixture according to claim 1, wherein R2 is hydrogen, methyl, ethyl, sulfonyl, carboxyl, or halogen.

8. A method for preparing a mixture of isomers according to any one of claims 1 to 7, the method comprising: (a) Diazotization of the following compound (1) Wherein R2 and Z are as defined in any one of claims 1 to 7; And the resulting diazonium salt reacts with the coupling component of the following formula. (2) This yields the following azo compound. (3)， Wherein R2 and Z are as defined in any one of claims 1 to 7; (b) Condensate the azo compound of formula (3) prepared in step (a) with the compound of the following formula. (4)， Wherein X represents the same halogen, and as defined in any one of claims 1 to 7, This provides compounds of the following formula. (5) Wherein R2, Z and X are as defined in any one of claims 1 to 7; (c) Condensate the compound of formula (5) prepared in step (b) with a mixture of isomers of the following compound. (6) Wherein R1 and M are as defined in any one of claims 1 to 7 The isomer mixture of the compound of formula (6) contains two isomers, one of which has a sulfonyl group at the meta position of aniline, and the other of which has a sulfonyl group at the para position of aniline. Thus, a mixture of isomers of the reactive dye of formula (1) according to any one of claims 1 to 7 is obtained.

9. An aqueous ink comprising a mixture of isomers of at least one reactive dye of formula (1) according to any one of claims 1 to 7.

10. The use of at least one isomer mixture of reactive dyes of formula (I) according to any one of claims 1 to 7 or the use of water-based inks according to claim 9 in the dyeing or printing of textile materials.

11. The application according to claim 10, wherein the textile material is a hydroxyl-containing or nitrogen-containing fiber material.

12. Textiles dyed or printed using a mixture of isomers of at least one reactive dye of formula (I) according to any one of claims 1 to 7 or an aqueous ink according to claim 9.

13. A method for dyeing or printing hydroxyl- or nitrogen-containing fibrous materials, the method comprising using an isomer mixture of at least one reactive dye of formula (I) according to any one of claims 1 to 7 or an aqueous ink according to claim 9.

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