Fibre-active isomer yellow dye mixtures, their preparation and their use

Abstract

An isomer mixture of at least one dye of formula (I): wherein-X1 and X2 are independently halogen atoms,-A1, A2 are independently hydrogen atoms or C1-C4 alkyl groups,-R1, R2 are independently-H,-SO3M, C1-C4 alkyl groups, C1-C4 alkoxy groups,-COOH, halogen atoms,-X1 and X2 are independently halogen atoms,-A1, A2 are independently hydrogen atoms or C1-C4 alkyl groups,-R1, R2 are independently-H,-SO3M, C1-C4 alkyl groups, C1-C4 alkoxy groups,-COOH,-CH3,-CH3,-CH3,-CH3,- -Z1 and Z2 are independently fiber active groups of the following 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-CH = CH2, or-NHCO-(CH2) 3-SO2-(CH2) 2-Y, where Y is a group that can be removed under alkaline conditions, and Y is a group that can be removed under alkaline conditions. -M is a salt or a mixture of salts of hydrogen or an organic or inorganic cation # imgabs0 #

Description

Field of the Invention

[0001] The present invention relates to novel isomer mixtures of yellow reactive dyes, to mixtures containing said dyes, to ink compositions comprising said dyes and dye mixtures, to processes for their preparation and to their use in dyeing or printing textile fiber materials. The novel isomer mixtures of reactive dyes according to the invention are suitable for dyeing or printing nitrogen- or hydroxyl-containing fiber materials and produce on such materials a dyeing or printing having good build-up behavior, high fixation rate, excellent elution properties of unfixed dyes and good fastness properties. Background Art

[0002] In the past few years, many countries have committed to improving environmental quality by conserving natural resources and reducing emissions of climate-harmful substances. Governments provide funding to support industries in achieving these goals. Consumers continuously demand environmentally friendly textile products produced according to the highest ecological standards. Brands and retailers are translating these requirements into actual demands, and textile manufacturers are continuously improving their production advantages by investing in modern equipment and selecting environmentally friendly chemicals.

[0003] Accordingly, there is a great demand for such novel reactive dye mixtures which are suitable for the reproducible dyeing and printing of fiber materials which meet the highest ecological and economic requirements and at the same time still provide a dyeing of the desired shade having improved fastness properties such as wash and water fastness and perspiration fastness.

[0004] Furthermore, they should have sufficient substantivity and at the same time good ease of eluting unfixed dyes. They should also exhibit good coloring yields and high reactivity in order to provide in particular a dyeing having good build-up properties and high fixation degrees.

[0005] Reactive dyes which can be used for dyeing and printing hydroxyl- or nitrogen-containing fiber materials are known and are described, for example, in EP0567036. However, these dyes do not provide a high fixation degree when used alone.

[0006] Accordingly, the present invention is based on the problem of providing novel mixtures of reactive dyes which are particularly suitable for the reproducible dyeing and printing of fiber materials in the desired shade and which meet the above requirements to the greatest possible extent. The dye mixtures should also produce a dyeing having good build-up properties, high fixation rate, good elution properties of unfixed dyes and good overall fastness properties such as fastness to chlorine and peroxides. The reactive dyes according to the invention also show satisfactory stability with respect to different dyeing parameters.

[0007] The term "consisting essentially of" followed by one or more features means that in the method or material of the present invention, in addition to the explicitly listed components or steps, components or steps that do not substantially affect the nature and characteristics of the present invention may be included.

[0008] Unless otherwise explicitly stated, the expression "between X and Y" includes the boundaries. This expression means that the target range includes the X and Y values, as well as all values from X to Y.

[0009] Throughout the specification and claims of this application document, the terms "comprising" and "containing" and variants of these terms such as "comprising" and "comprises" mean "including but not limited to", and do not exclude other structural parts, additives, components, integers or steps. In addition, unless the context requires otherwise, the singular encompasses the plural: in particular, in the case of using an indefinite article, unless the context requires otherwise, this application document is understood to contemplate both the plural and the singular.

[0010] In the case of citing upper and lower limits for a property (such as component concentration), a range of values defined by any combination of any upper limit and any lower limit may also be implied. Summary of the Invention

[0011] The present invention relates to an isomer mixture of at least one dye of formula (I):

[0012]

[0013] wherein

[0014] - X1 and X2 are independently a halogen atom,

[0015] - A1, A2 are independently a hydrogen atom or a C1-C4 alkyl group,

[0016] - R1, R2 are independently -H, -SO3M, a C1-C4 alkyl group, a C1-C4 alkoxy group, -COOH, a halogen atom,

[0017] -Z1 and Z2 are independently fiber-reactive () groups 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, where Y is a group removable under alkaline conditions,

[0018] -M is hydrogen or a salt or mixture of salts of an organic or inorganic cation.

[0019] According to a preferred embodiment of the isomer mixture, Z1 and Z2 are independently groups of the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y.

[0020] According to a preferred embodiment of the isomer mixture, Z1 and Z2 are -SO2-CH2-CH2-OSO3M.

[0021] According to a preferred embodiment of the isomer mixture, Z1 and Z2 are in the para position to the azo group, and R1 and R2 are in the ortho position to the azo group.

[0022] According to a preferred embodiment, the isomer mixture corresponds to formula (IA):

[0023]

[0024] where

[0025] X1 and X2 are independently -Cl or -F,

[0026] Y1 and Y2 are independently -CH=CH2 (vinyl) or the group -CH2-CH2-Y, and Y is a group removable under alkaline conditions.

[0027] According to a preferred embodiment, the isomer mixture corresponds to formula (101-a) or formula (101-b) or a salt thereof, or a mixture thereof:

[0028]

[0029] The present invention further relates to a mixture of isomeric dye mixtures, which comprises:

[0030] ·At least one isomer mixture as disclosed above and detailed below, and ·At least one isomer mixture comprising at least one dye of formula (II):

[0031]

[0032] wherein

[0033] -X3 is a halogen atom,

[0034] -A3 is a hydrogen atom or a C1-C4 alkyl group,

[0035] -R3, R4 are independently -H, -SO3M’, C1-C4 alkyl, C1-C4 alkoxy, -COOH, a halogen atom,

[0036] -Z3 is a group of the following 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’, where Y’ is a group removable under basic conditions;

[0037] -M’ is hydrogen, or a salt of an organic or inorganic cation, or a mixture of salts.

[0038] According to a preferred embodiment of the mixture of isomeric dyes, at least one mixture of dyes of formula (II) is the following mixture of dyes: formula (201-a) or formula (201-b) or a salt thereof, or a mixture thereof:

[0039]

[0040]

[0041] The present invention also relates to a mixture of dyes, which at least comprises:

[0042] (A) An isomeric dye mixture selected from:

[0043] (A1) An isomeric mixture of at least one dye of formula (I) as defined above and detailed below, and

[0044] (A2) A mixture of isomeric dye mixtures as defined above and detailed below, and

[0045] (B) At least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II).

[0046] According to a preferred embodiment, the dye mixture comprises at least:

[0047] (A) 20 - 60% by weight, preferably 25 - 55% by weight, especially 30 - 50% by weight of:

[0048] (A1) An isomer mixture of at least one dye of formula (I), or

[0049] (A2) A mixture of an isomer dye mixture of at least one dye of formula (I) and at least one dye of formula (II),

[0050] and

[0051] (B) 40 - 80% by weight, preferably 45 - 75% by weight, especially 50 - 70% by weight of at least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II), each percentage being based on the total of all dyes.

[0052] The present invention further relates to an aqueous ink which comprises at least an isomer mixture of at least one dye of formula (I) as defined above and detailed below, or a mixture of dyes as defined above and detailed below.

[0053] The present invention also relates to the use of at least one reactive dye of formula (I) as defined above and detailed below, or a mixture of dyes as defined above and detailed below, or an ink as defined above and detailed below, for the dyeing or printing of textile materials such as hydroxyl - containing or nitrogen - containing fiber materials, especially cellulose fiber materials.

[0054] The present invention further relates to a textile which is dyed or printed with at least one reactive dye of formula (I) as defined above and detailed below, or a mixture of dyes as defined above and detailed below, or an ink as defined above and detailed below.

[0055] The present invention also relates to a method for dyeing or printing hydroxyl - containing or nitrogen - containing fiber materials, which method comprises using at least one reactive dye of formula (I) as defined above and detailed below, or a mixture of dyes as defined above and detailed below, or an ink as defined above and detailed below.

[0056] Another object of the present invention is a method for preparing an isomer dye mixture of at least one dye of formula (I) as defined above and detailed below, which comprises:

[0057] (a) Diazotizing a compound of formula (1)

[0058]

[0059] wherein R represents R1, R2 or R3, and Z represents Z1, Z2 or Z3;

[0060] and reacting the diazonium salt thus obtained with a coupling component of formula (2)

[0061]

[0062] to thereby obtain an azo compound of formula (3)

[0063]

[0064] (b) Condensing the azo compound of formula (3) prepared in step (a) with a compound of the following formula

[0065]

[0066] wherein X represents X1, X2 or X3,

[0067] to obtain a compound of formula (5)

[0068]

[0069] (c) Condensing the compound of formula (5) prepared in step (b) with a compound of formula (6)

[0070]

[0071] Another object of the present invention is a process for preparing a mixture of at least one dye of formula (I) and at least one isomeric dye mixture of dyes of formula (II) as defined above and detailed below, which comprises:

[0072] (a) Diazotizing a compound of formula (1)

[0073]

[0074] wherein R represents R1, R2 or R3, and Z represents Z1, Z2 or Z3;

[0075] and reacting the diazonium salt thus obtained with a coupling component of formula (2)

[0076]

[0077] to thereby obtain an azo compound of formula (3)

[0078]

[0079] (b) Condense the azo compound of formula (3) prepared in step (a) with the compound of formula (4).

[0080] wherein X represents X1, X2 or X3,

[0081] and obtain the compound of formula (5),

[0082]

[0083] (c) Condense the compound of formula (5) prepared in step (b) with a mixture of the compounds of formula (6) and (7).

[0084] Detailed Description of the Invention

[0085] Dyes of formula (I)

[0086] The present invention thus relates to a new isomer mixture of at least one dye of formula (I):

[0087]

[0088] wherein

[0089] - X1 and X2 are independently a halogen atom,

[0090] - A1, A2 are independently a hydrogen atom or a C1 - C4 alkyl group,

[0091] - R1, R2 are independently -H, -SO3M, C1 - C4 alkyl, C1 - C4 alkoxy, -COOH, a halogen atom,

[0092] - Z1, Z2 are independently a fiber reactive group of the following 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, where Y is a group removable under alkaline conditions,

[0093] - M is hydrogen or a salt or mixture of salts of an organic or inorganic cation.

[0094] The isomer mixture of at least one reactive dye of formula (I) according to the invention provides very good stacking properties, a high fixation rate, good elution properties of unfixed dyes and good overall fastness properties.

[0095] Surprisingly, it has been found that, compared to the same dye not substituted with a COOH moiety, the COOH moiety substituted onto the central phenyl ring of the dye of formula (I) advantageously greatly increases the solubility of the dye in polar solvents, while the coloring properties of the dye remain the same. The same comparison shows that the dye of formula (I) in which the COOH moiety is substituted onto the central phenyl ring shows a greater affinity for the fiber, thus allowing for more efficient dyeing.

[0096] As used herein, "isomers" and "isomer mixture" include dyes having the same chemical formula but different atomic arrangements. According to the invention, the isomer mixture of the reactive dye of formula (I) comprises such reactive dyes which have the same chemical formula and thus the same number of carbons, but have (substituted) phenyl diazo moieties and / or Z1, Z2, R1, R2 groups attached at different positions on the phenyl ring.

[0097] As used herein, the term "isomer mixture" means a composition comprising more than one isomer of a reactive dye.

[0098] The "isomer mixture of at least one reactive dye" optionally contains more than one isomer of the reactive dye of formula (I). Thus, the isomer mixture contains more than one (i.e., two or more) isomers of the reactive dye of formula (I), and may also contain more than one (i.e., two or more) isomers of different reactive dyes of formula (I). Different reactive dyes of formula (I) have different chemical formulas included in formula (I) and thus may have different numbers of carbons. For example, the isomer mixture of at least one reactive dye of formula (I) includes the β-vinylsulfonyl reactive dye of formula (I) and its isomers and the β-ethoxysulfonylsulfate reactive dye of formula (I) and its isomers (the isomers having sulfonic acid substituents and / or diazo substituents attached at different positions on the phenyl ring).

[0099] The isomer mixtures disclosed herein are different from the single reactive dyes of formula (I).

[0100] The dyes of formula (I) which form an isomer mixture contain at least 2, preferably 2 - 4 and especially 4 sulfo groups, each of which is present in free acid form or preferably in salt form. Suitable salts denoted by M are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of organic amines, or mixtures thereof. Examples which may be mentioned are sodium, lithium, potassium or ammonium salts, mono-, di- or triethanolamine salts or mixed Na / Li or Na / Li / NH4 salts.

[0101] “C1 - C4 alkyl” denotes a saturated, straight-chain or branched hydrocarbon-containing chain having 1 - 4 carbon atoms. Preferably the hydrocarbon-containing chain is straight-chain. Preferably the C1 - C4 alkyl is selected from 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 and n-butyl. Advantageously, the C1 - C4 alkyl is methyl or ethyl.

[0102] “C1 - C4 alkoxy” denotes a saturated, straight-chain or branched hydrocarbon-containing chain having 1 - 4 carbon atoms and which is substituted by an oxygen atom.

[0103] Preferably the hydrocarbon-containing chain is straight-chain. Preferably the C1 - C4 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy. More preferably the C1 - C4 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy and n-butoxy. Advantageously, the C1 - C4 alkoxy is methoxy or ethoxy.

[0104] As used herein, the term “halogen” means a fluorine atom, a chlorine atom or a bromine atom, preferably a fluorine atom or a chlorine atom.

[0105] As possible choices for the halogen represented by the independent variables X1, X2 and also as possible choices for the independent variables R1, R2 there are considered, for example, fluorine or chlorine, preferably chlorine.

[0106] The group Y which is removable under alkaline conditions is selected from -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 -Cl, -OSO3M, -SSO3M, -OCO-CH3, -OCO-C6H5 or -OPO3M2, more preferably -Cl or -OSO3M, where M has the meaning given above.

[0107] Preferably Z1, Z2 are independently fiber-reactive groups of the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y, even more preferably Z1, Z2 are independently groups of the formula -SO2-(CH2)2-Y.

[0108] According to a preferred embodiment, (Z1, R1) and (Z2, R2) are independently (–SO2–Y; –SO3M), where Y and M are as defined above and below.

[0109] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein the fiber-reactive groups Z1, Z2 are in the para-position to the azo group.

[0110] Z1, Z2 are preferably -SO2-CH2-CH2-OSO3M.

[0111] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein R1, R2 are in the ortho-position to the azo group.

[0112] R1, R2 are preferably –SO3M.

[0113] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein the diazo group is in the ortho- and / or para-position on the phenyl ring, relative to the central chain.

[0114] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein R1 and / or R2 are in the ortho-position on the terminal phenyl ring, relative to the diazo group.

[0115] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein Z1 and / or Z2 are in the para-position on the terminal phenyl ring, relative to the diazo group.

[0116] A preferred embodiment of the present invention relates to an isomer mixture of a reactive dye of formula (I), wherein A1, A2 are H.

[0117] In a more preferred embodiment, an isomer mixture of at least one reactive dye of formula (I), wherein:

[0118] A1, A2 are H,

[0119] R1, R2 are -SO3M,

[0120] Z1, Z2 are fiber-reactive groups of the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y, where Y is a group removable under alkaline conditions,

[0121] X is a fluorine atom, and

[0122] M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.

[0123] Particularly preferred is an isomer mixture of a dye of formula (IA)

[0124]

[0125] wherein

[0126] X1 and X2 are independently -Cl or -F,

[0127] Y1, Y2 are independently -CH=CH2 (vinyl) or the group -CH2-CH2-Y, and Y is a group removable under basic conditions,

[0128] The preferred embodiments of the variables of formula (I) also apply to the variables of formula (IA).

[0129] The preferred isomer mixtures of the dyes of formula (I) are the isomer mixtures of the dyes of formula (101-a) or (101-b) or their salts:

[0130]

[0131]

[0132] The preferred embodiments of the present invention relate to isomer mixtures of reactive dyes of formula (101-a) or (101-b), wherein the diazo group is in the ortho and para positions on the phenyl ring, relative to the central chain.

[0133] The final product can also optionally be subjected to a conversion reaction. Such a conversion reaction is, for example, by treatment with dilute sodium hydroxide solution to convert the vinylatable reactive groups -SO2-Y, -SO2-Y1 and -SO2-Y2 into their vinyl form, for example, converting β-chloroethylsulfonyl or β-sulfoethylsulfonyl into vinylsulfonyl. Such reactions are known per se. Those conversion reactions are generally affected in a neutral to basic medium, at a temperature of, for example, 20 - 70 °C, at a pH of, for example, 6 - 14.

[0134] The preferred isomer mixture of the reactive dye of formula (101-a) is the isomer mixture of the dyes of formula (101-a1) and (101-a2) or their salts:

[0135]

[0136]

[0137] The preferred isomer mixture of the reactive dye of formula (101-b) is the isomer mixture of the dyes of formula (101-b1) and (101-b2) or their salts, wherein (101-b1) corresponds to the mono- or divinyl form of (101-a1), and wherein (101-b2) corresponds to the mono- or divinyl form of (101-a2).

[0138] The isomer mixture of the dyes according to the invention dyes the carrier to which they are applied in a golden-yellow shade, which shade has a high degree of fixation and good overall fastness properties, in particular wash fastness, chlorine and oxygen fastness.

[0139] Dye mixtures

[0140] The isomer mixture of the dyes of formula (I) exhibits high compatibility with other reactive dyes and can therefore be applied in combination with other dyes to adjust specific shades, or applied as a two-color or three-color mixture to provide various shades.

[0141] · Mixtures of dyes having formula (II)

[0142] According to a first embodiment of this variant, the invention further relates to a dye mixture comprising:

[0143] · at least one isomer mixture of a dye of formula (I), and

[0144] · at least one isomer mixture comprising at least one dye of formula (II):

[0145]

[0146] wherein

[0147] - X3 is a halogen atom,

[0148] - A3 is a hydrogen atom or a C1-C4 alkyl group,

[0149] - R3, R4 are independently -H, -SO3M', C1-C4 alkyl, C1-C4 alkoxy, -COOH, halogen atom,

[0150] - Z3 is a group 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', where Y' is a group removable under alkaline conditions;

[0151] - M' is hydrogen or a salt or mixture of salts of an organic or inorganic cation.

[0152] As used herein, "isomers" and "mixtures of isomers" include dyes having the same chemical formula but different atomic arrangements. According to the present invention, a mixture of isomers of the reactive dye of formula (II) comprises such reactive dyes which have the same chemical formula and thus the same carbon number, but have (substituted) phenyl diazo structural moieties and / or Z3, R3, R4, COOH groups attached at different positions on the phenyl ring.

[0153] As used herein, the term "mixture of isomers" denotes a composition comprising more than one isomer of a reactive dye.

[0154] A "mixture of isomers of at least one reactive dye" optionally contains more than one isomer of a reactive dye of formula (II). Thus, the mixture of isomers contains more than one (i.e., two or more) isomers of a reactive dye of formula (II) and may also contain more than one (i.e., two or more) isomers of different reactive dyes of formula (II). Different reactive dyes of formula (II) have different chemical formulas comprised in formula (II) and may thus have different carbon numbers. For example, a mixture of isomers of at least one reactive dye of formula (II) includes a β-vinylsulfonyl reactive dye of formula (II) and its isomers and a β-sulfoethylsulfonyl reactive dye of formula (II) and its isomers (the isomers having sulfonic acid substituents and / or diazo substituents attached at different positions on the phenyl ring).

[0155] These mixtures of isomers as disclosed herein are different from a single reactive dye of formula (II).

[0156] The dyes of formula (II) contain at least 2, preferably 2 - 3 and in particular 3 sulfonic groups, each present in free acid form or preferably in salt form. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of organic amines, or mixtures thereof. Examples which may be mentioned are sodium, lithium, potassium or ammonium salts, mono-, di- or triethanolamine salts or mixed Na / Li or Na / Li / NH4 salts.

[0157] The term "C1 - C4 alkyl" denotes a saturated, straight-chain or branched hydrocarbon-containing chain having 1 - 4 carbon atoms. Preferably, the hydrocarbon-containing 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. Advantageously, the C1 - C4 alkyl is methyl or ethyl.

[0158] The term "C1 - C4 alkoxy" denotes a saturated, straight-chain or branched hydrocarbon-containing chain having 1 - 4 carbon atoms and substituted by an oxygen atom.

[0159] 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. More 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.

[0160] As halogen represented by the variable X3 and also as a possible selection for the variable R3, for example, fluorine or chlorine is considered, and chlorine is preferred.

[0161] The group Y' removable under basic conditions may be selected from -Cl, -Br, -F, -OSO3M', -SSO3M', -OCO-CH3, -OPO3M'2, -OCO-C6H5, -OSO2-(C1-C4 alkyl), or -OSO2-N(C1-C4 alkyl)2. Preferably, Y' is selected from -Cl, -OSO3M', -SSO3M', -OCO-CH3, -OCO-C6H5, or -OPO3M'2, and more preferably -Cl or -OSO3M', where M' has the meaning given above.

[0162] Preferably, Z3 is a fiber-reactive group of the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y', and even more preferably Z3 is a group of the formula -SO2-(CH2)2-Y'.

[0163] According to a preferred embodiment, (Z3, R3) is (–SO2–Y'; –SO3M'), where Y' and M' are as defined above and below.

[0164] In a preferred embodiment of the present invention, in the reactive dye of formula (II), the fiber-reactive group Z3 is located at the para-position of the azo group.

[0165] Z3 is preferably -SO2-CH2-CH2-OSO3M'.

[0166] A preferred embodiment of the present invention relates to a mixture in which, in the reactive dye of formula (II), R3 is located at the ortho-position of the azo group.

[0167] R3 is preferably –SO3M'.

[0168] A preferred embodiment of the present invention relates to an isomer mixture of the reactive dye of formula (II), in which the diazo group is located at the ortho-position and / or para-position on the phenyl ring, relative to the central chain.

[0169] A preferred embodiment of the present invention relates to an isomer mixture of the reactive dye of formula (II), in which R3 is located at the ortho-position on the terminal phenyl ring, relative to the diazo group.

[0170] Preferred embodiments of the present invention relate to isomer mixtures of reactive dyes of formula (II), wherein Z3 is in the ortho position on the terminal phenyl ring, relative to the diazo group.

[0171] Preferred embodiments of the present invention relate to isomer mixtures of reactive dyes of formula (II), wherein the COOH group is in the ortho position on the phenyl ring, relative to the central chain.

[0172] Preferred embodiments of the present invention relate to isomer mixtures of reactive dyes of formula (II), wherein R4 is in the meta position on the phenyl ring, relative to the central chain.

[0173] Preferred embodiments of the present invention relate to mixtures of reactive dyes, wherein in the dye of formula (II), A3 is H.

[0174] Among the dyes of formula (II), the dyes of formula (IIA) are particularly preferred

[0175]

[0176] wherein

[0177] X3 is -Cl or -F,

[0178] Y3 is -CH=CH2 (vinyl) or the group -CH2-CH2-Y', and Y' is a group removable under basic conditions,

[0179] The preferred embodiments of the variables X3, Y3, Y', M' of formula (II) also apply to the variables of formula (IIA).

[0180] Preferred isomer mixtures of the dyes of formula (II) are isomer mixtures of the following dyes: of formula (201-a) or (201-b) or their salts:

[0181]

[0182] Preferred embodiments of the present invention relate to isomer mixtures of reactive dyes of formula (201-a) or (201-b), wherein the diazo group is in the ortho and para positions on the phenyl ring, relative to the central chain.

[0183] The final product can also optionally be subjected to a conversion reaction. Such a conversion reaction is, for example, by treatment with dilute sodium hydroxide solution to convert the vinylatable reactive group -SO2-Y3 into its vinyl form, for example, converting β-chloroethylsulfonyl or β-sulfoethylsulfonyl into vinylsulfonyl. Such reactions are known per se. Those conversion reactions are generally affected in a neutral to basic medium, at a temperature of, for example, 20-70 °C, at a pH of, for example, 6-14.

[0184] The preferred isomer mixture of the reactive dye of formula (201-a) is an isomer mixture of dyes of formula (201-a1) and (201-a2) or their salts:

[0185]

[0186] The preferred isomer mixture of the reactive dye of formula (201-b) is an isomer mixture of dyes of formula (201-b1) and (201-b2) or their salts, where (201-b1) corresponds to the vinyl form of (201-a1), and where (201-b2) corresponds to the vinyl form of (201-a2).

[0187] According to a preferred embodiment, the present invention relates to a mixture of isomer dye mixtures comprising an isomer dye mixture of formula (I) and an isomer dye mixture of formula (II), wherein the compounds of formula (I) and formula (II) are present in a ratio of (I):(II) of 9:1 to 1:9, preferably 3:1 to 1:9, more preferably 1:1 to 1:8, and even more preferably 1:1 to 1:6, where the ratio is expressed as a molar equivalent value.

[0188] According to a more preferred embodiment, the present invention relates to a mixture of isomer dye mixtures comprising an isomer dye mixture of formula (IA) and an isomer dye mixture of formula (IIA), wherein the compounds of formula (IA) and formula (IIA) are present in a ratio of (IA):(IIA) of 9:1 to 1:9, preferably 3:1 to 1:9, more preferably 1:1 to 1:8, and even more preferably 1:1 to 1:6, where the ratio is expressed as a molar equivalent value.

[0189] The dye of formula (II) and its preparation method have been disclosed in EP0567036.

[0190] · Monochromatic and polychromatic mixtures

[0191] According to a second embodiment of this variant, the present invention further relates to a dye mixture comprising:

[0192] (A) A mixture of dyes selected from:

[0193] (A1) At least one isomer mixture of a dye of formula (I) as defined above, or

[0194] (A2) A mixture of at least one dye of formula (I) and an isomer dye mixture of at least one dye of formula (II),

[0195] And further comprising:

[0196] (B) At least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II).

[0197] According to a preferred embodiment, the present invention further relates to a dye mixture comprising:

[0198] (A) 20 - 60% by weight, preferably 25 - 55% by weight, especially 30 - 50% by weight of:

[0199] (A1) An isomer mixture of at least one dye of formula (I) as defined above, or

[0200] (A2) A mixture of at least one dye of formula (I) and an isomer dye mixture of at least one dye of formula (II),

[0201] and

[0202] (B) 40 - 80% by weight, preferably 45 - 75% by weight, especially 50 - 70% by weight of at least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II), each percentage being based on the total sum of all dyes.

[0203] The preferred embodiments of the dye of formula (I), the dye of formula (II), and the dye mixture of at least one dye of formula (I) and at least one dye of formula (II) (which have been described in detail above) also apply to the composition comprising (A) and (B).

[0204] Examples of dyes suitable as component (B) in the mixture according to the present invention are:

[0205] Lemon yellow: C.I.R YE25, C.I.R YE37, C.I.R YE95, C.I.R YE105, C.I.R YE135, C.I.R YE143, C.I.R YE160, C.I.R YE161, C.I.R YE167, C.I.R YE175, C.I.R YE186, C.I.R YE204, C.I.R YE207;

[0206] Normal yellow: C.I.R YE15, C.I.R YE17, C.I.R YE27, C.I.R YE67, C.I.R YE111, C.I.R YE125, C.I.R YE165, C.I.R YE168, C.I.R YE208, C.I.R YE209, C.I.R YE211;

[0207] Golden Yellow: C.I.R YE84, C.I.R YE107, C.I.R YE138, C.I.R YE145, C.I.R YE162, C.I.R YE74, C.I.R YE176, C.I.R YE181, C.I.R YE186, C.I.R YE201, C.I.R YE205, C.I.R YE206, C.I.R YE210, C.I.R YE214, C.I.R YE217, C.I.R YE218, C.I.R YE219, C.I.R YE222

[0208] Orange: C.I.R OR7, C.I.R OR11, C.I.R OR12, C.I.R OR13, C.I.R OR16, C.I.R OR20, C.I.R OR35, C.I.R OR64, C.I.R OR69, C.I.R OR72, C.I.R OR82, C.I.R OR84, C.I.R OR95, C.I.OR116, C.I.R OR117, C.I.R OR122, C.I.R OR129, C.I.R OR131, C.I.R OR132, C.I.R OR133, C.I.R OR134, C.I.R OR135, C.I.R OR136, C.I.R OR140, C.I.OR143

[0209] Brown: C.I.R BR7, C.I.R BR11, C.I.R BR19, C.I.R BR37, C.I.R BR46, C.I.R BR48, C.I.R BR49, C.I.R BR51;

[0210] Red: C.I.R RE3, C.I.R RE23, C.I.R RE24, C.I.R RE49, C.I.R RE56, C.I.R RE58, C.I.R RE114, C.I.R RE120, C.I.R RE123, C.I.R RE124, C.I.R RE141, C.I.R RE158, C.I.R RE159, C.I.R RE171, C.I.R RE174, C.I.R RE180, C.I.R RE183, C.I.R RE184, C.I.R RE194, C.I.R RE195, C.I.R RE198, C.I.R RE218, C.I.R RE221, C.I.R RE222, C.I.R RE227, C.I.R RE228, C.I.R RE237, C.I.R RE238, C.I.R RE239, C.I.R RE242, C.I.R RE243, C.I.R RE245, C.I.R RE250, C.I.R RE264, C.I.R RE265, C.I.R RE266, C.I.R RE267, C.I.R RE268, C.I.R RE269, C.I.R RE270, C.I.R RE271, C.I.R RE273, C.I.R RE277, C.I.R RE278, C.I.R RE279, C.I.R RE280, C.I.R RE281, R RE286, C.I.R RE287, C.I.R RE288, C.I.R RE289

[0211] Blue: C.I.R BL13, C.I.R BL19, C.I.R BL52, C.I.R BL72, C.I.R BL114, C.I.R BL160, C.I.R BL182, C.I.R BL204, C.I.R BL209, C.I.R BL220, C.I.R BL221, C.I.R BL221A, C.I.R BL235A, C.I.R BL235, C.I.R BL260, C.I.R BL263, C.I.R BL276, C.I.R BL282, C.I.R BL285 Royal: C.I.R BL29, C.I.R BL49, C.I.R BL105, C.I.R BL181, C.I.R BL187, C.I.R BL198, C.I.R BL224, C.I.R BL261, C.I.R BL268, C.I.R BL269, C.I.R BL279;

[0212] Dark blue: C.I.R BL79, C.I.R BL120, C.I.R BL171, C.I.R BL184, C.I.R BL193, C.I.R BL194, C.I.R BL203, C.I.R BL214, C.I.R BL222, C.I.R BL225, C.I.R BL230, C.I.R BL238, C.I.R BL250, C.I.R BL257, C.I.R BL264, C.I.R BL265, C.I.R BL271, C.I.R BL276, C.I.R BL271A, R BL284

[0213] Olive: C.I.R GR19, C.I.R GR21, C.I.R GR25, C.I.R GR29, C.I.R GR34;

[0214] Black: C.I.R BK5B, C.I.R BK5A, C.I.R BK5, C.I.R BK8, C.I.R BK13, C.I.R BK31, C.I.R BK39, C.I.R BK49.

[0215] The dye mixture according to the invention preferably comprises one or more dyes selected from the following as component (B): C.I.R BL220, C.I.R BL235, C.I.R.Bl285, C.I.R BL19, C.I.R BL279, C.I.R RE286, C.I.R RE287, C.I.R RE289 and R YE222.

[0216] Process for preparing reactive dyes of formula (I)

[0217] The present invention further relates to a method for preparing a mixture of reactive dyes of formula (I), which comprises:

[0218] (a) diazotizing a compound of formula (1)

[0219]

[0220] wherein R represents R1, R2 or R3 as defined above, and Z represents Z1, Z2 or Z3 as defined above;

[0221] and reacting the diazonium salt thus obtained with a coupling component of formula (2)

[0222]

[0223] to obtain an azo compound of formula (3)

[0224]

[0225] wherein R represents R1, R2 or R3 as defined above, and Z represents Z1, Z2 or Z3 as defined above;

[0226] (b) Condensing the azo compound of formula (3) prepared in step (a) with the compound of formula (4)

[0227]

[0228] wherein X represents X1, X2 or X3 as defined above,

[0229] Thereby providing a compound of formula (5)

[0230]

[0231] wherein R, Z and X are as defined above;

[0232] (c) Condensing the compound of formula (5) prepared in step (b) with the compound of formula (6)

[0233]

[0234] wherein R, Z and X are as defined above,

[0235] Thus, in the case where A1 = A2 = H, an isomer mixture of the reactive dye of formula (I) according to the present invention is provided. When A1 and / or A2 is different from H, derivatives of molecule (6) having suitable substituents on the NH2 group should be used.

[0236] The present invention also relates to a method for preparing a mixture of an isomeric dye mixture of at least one dye of formula (I) and at least one dye of formula (II), wherein the method comprises the same steps a) and b) as described above, and further comprises a step (c), and step (c) consists of condensing the compound of formula (5) prepared in step (b) with a mixture of the compounds of formula (6) and formula (7)

[0237]

[0238]

[0239] wherein R, Z and X are as defined above.

[0240] Thus, in the case where A1 = A2 = A3 = H, an isomer mixture of the reactive dye of formula (I) and the reactive dye of formula (II) according to the present invention is provided. When A1 and / or A2 and / or A3 is different from H, derivatives of molecule (6) and / or (7) having suitable substituents on the NH2 group should be used.

[0241] In the process for preparing the isomeric dye mixtures (I) and (I), the preferred embodiments of the variables A, R, Z and X correspond respectively to the preferred choices of A1, A2, A3, R1, R2, R3, Z1, Z2, Z3 and X1, X2, X as defined above in the description of these compounds.

[0242] Compositions and uses

[0243] The fiber-reactive dyes according to the invention and dye mixtures comprising them are suitable for dyeing and printing, in particular for printing a wide variety of materials, especially hydroxyl- or nitrogen-containing fiber materials. Examples include paper, silk, leather, wool, polyamide fibers and polyurethanes, and especially all types of cellulosic fiber materials. Such fiber materials are, for example, natural cellulosic fibers such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing hydroxyl-containing fibers present in blended fabrics, such as blends of cotton and polyester fibers or polyamide fibers.

[0244] The invention also relates to aqueous inks comprising the dyes of formula (I) according to the invention or dye mixtures comprising them, and to the use of such inks for printing a plurality of substrates (especially textile fiber materials) in an inkjet printing process, the above definitions and preferences applying to the dyes and dye mixtures, the inks and the substrates.

[0245] The dyes of formula (I) according to the invention and dye mixtures comprising them exhibit very good stacking behavior, high final stacking and high fixation colorities (especially in printing applications on cellulosic fiber materials) and improved stability with respect to different printing parameters.

[0246] The dyes of formula (I) according to the invention and dye mixtures comprising them are also suitable as colorants for use in recording systems. Such recording systems are, for example, commercially available inkjet printers for paper or textile printing, or writing instruments such as fountain pens or ballpoint pens, and especially inkjet printers. For this purpose, the dyes according to the invention are first made into a form suitable for use in the recording system. A suitable form is, for example, an aqueous ink which comprises the dyes of formula (I) according to the invention or dye mixtures comprising them as colorants. The ink can be prepared in a conventional manner by mixing the individual components together in the desired amounts of water.

[0247] As substrates, the above-mentioned hydroxyl- or nitrogen-containing fiber materials are considered, especially cellulosic fiber materials. The fiber material is preferably a textile fiber material.

[0248] Substrates which can also be considered are paper and plastic films.

[0249] As examples of paper, mention may be made of commercially available inkjet papers, photo papers, glossy papers, plastic-coated papers such as Epson inkjet paper, Epson photo paper, Epson glossy paper, Epson glossy film, HP special inkjet paper, Encad photo glossy paper and Ilford photo paper. The plastic film is for example transparent or cloudy / opaque. A suitable plastic film is for example 3M transparent film.

[0250] Depending on the properties of the use, such as textile printing or paper printing, it may be necessary to adjust, for example, the viscosity or other physical properties of the ink, in particular the properties which influence the affinity for the substrate under discussion.

[0251] The dyes of formula (I) according to the invention or dye mixtures comprising them for use in the aqueous ink should preferably have a low salt content, that is to say they should have a total salt content of less than 0.5% by weight, based on the weight of the dye. Dyes which have a relatively high salt content due to their preparation and / or due to subsequent addition of diluents can be desalted, for example, by membrane separation processes such as ultrafiltration, reverse osmosis or dialysis.

[0252] Based on the total weight of the ink, the ink preferably has a total content of the dyes or dye mixtures according to the invention of from 1 to 35% by weight, in particular from 1 to 30% by weight and preferably from 1 to 20% by weight. In this case, preferred lower limits are limits of 1.5% by weight, preferably 2% by weight and in particular 3% by weight.

[0253] The ink may comprise 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 di alkane; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone, polyalkylene glycols such as polyethylene glycol or polypropylene glycol; C2-C6 alkylene glycols and thiodiols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol; other polyols such as glycerol or 1,2,6-hexanetriol; and C1-C4 alkyl ethers of polyols 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 in particular 1,2-propanediol, in an amount generally of from 2 to 30% by weight, in particular from 5 to 30% by weight and preferably from 10 to 25% by weight, based on the total weight of the ink.

[0254] In addition, the ink may further contain a solubilizer, such as β-caprolactam.

[0255] The ink may contain a thickener of natural or synthetic origin, especially for the purpose of adjusting the viscosity.

[0256] Examples of thickeners that may be mentioned include commercially available alginate / ester thickeners, starch ethers or locust bean gum ethers, especially sodium alginate itself or mixtures with modified celluloses (such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose or hydroxypropylmethylcellulose), especially mixtures with preferably 20-25% by weight of carboxymethylcellulose. Also mentionable synthetic thickeners are those based on poly(meth)acrylic acid or poly(meth)acrylamide and polyalkylene glycols (with a molecular weight of, for example, 2000-20000), such as polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of ethylene oxide and propylene oxide.

[0257] The ink contains such a thickener, for example, in an amount of 0.01-2% by weight, especially 0.01-1% by weight and preferably 0.01-0.5% by weight based on the total weight of the ink.

[0258] The ink may further contain a buffering substance, such as borax, borate / ester, phosphate / ester, polyphosphate / ester or citrate / ester. 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 an amount of especially 0.1-3% by weight, preferably 0.1-1% by weight based on the total weight of the ink in order to establish a pH value of, for example, 4-9, especially 5-8.5.

[0259] As a further additive, the ink may contain a surfactant or a wetting agent.

[0260] Suitable surfactants include commercially available anionic or non-ionic 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%-60% aqueous solution) with glycerol and / or propylene glycol is considered, and the amount thereof is preferably 0.1-30% by weight, especially 2-30% by weight.

[0261] Preferably, the ink has a viscosity of 1-40 mPa·s, especially 1-20 mPa·s and more especially 1-10 mPa·s.

[0262] In addition, the ink may further comprise conventional additives, such as defoamers or, in particular, preservatives that inhibit fungal and / or bacterial growth. Such additives are generally used in an amount of 0.01-1% by weight, based on the total weight of the ink.

[0263] As preservatives, formaldehyde-generating reagents are considered, such as paraformaldehyde and tri oxane, in particular an aqueous formaldehyde solution of approximately 30-40% by weight, 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. Suitable preservatives are, for example, a 20% by weight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol ( GXL).

[0264] The ink may further comprise additional additives, such as fluorinated polymers or telomers, such as polyethoxy perfluoroalcohols ( or products), in an amount of, for example, 0.01-1% by weight, based on the total weight of the ink.

[0265] In the case of an inkjet printing method, individual ink droplets are ejected from a nozzle in a controlled manner onto a substrate. It is mainly the continuous inkjet method and the drop-on-demand method for this purpose. In the case of the continuous inkjet method, the droplets are generated continuously, and the droplets not required for the printing operation are discharged into a container and recycled. On the other hand, in the case of the drop-on-demand method, droplets are generated as needed and used for printing; that is, droplets are generated only when the printing operation requires them. The generation of droplets can be achieved, for example, by a piezoelectric inkjet head or by thermal energy (bubble jet). Preferably, printing is carried out by a piezoelectric inkjet head and by the continuous inkjet method.

[0266] The present invention also relates to the use of at least one reactive dye of formula (I) according to the invention or a mixture comprising such a dye or an ink according to the invention for dyeing or printing textile materials, such as hydroxyl- or nitrogen-containing fiber materials, in particular cellulose fiber materials, or, in other words, to a method for dyeing or printing textile materials, such as hydroxyl- or nitrogen-containing fiber materials, in particular cellulose fiber materials, wherein at least one reactive dye of formula (I) according to the invention or a mixture comprising such a dye or an ink according to the invention is used.

[0267] The reactive dyes of formula (I) according to the invention, or mixtures comprising such dyes, or the inks according to the invention are suitable for conventional dyeing and printing processes and can be applied to and fixed on the fiber material in various ways, in particular in the form of an aqueous dye solution or a printing paste.

[0268] The processes according to the invention for dyeing and printing hydroxyl- or nitrogen-containing fiber materials can be carried out according to conventional dyeing and printing processes, for example according to the so-called cold pad-batch dyeing process, in which the dyes or dye mixtures or inks according to the invention are applied together with an alkali on a padder and then fixed by storage at about room temperature (for example 25 - 35 °C) for a number of hours. Alternatively, the dyeing and printing processes according to the invention can be carried out according to the exhaustion process, in which the article is impregnated with an optionally salt-containing aqueous solution comprising the dyes or dye mixtures according to the invention, and the dyes or dye mixtures are fixed after or in the presence of an alkali treatment, optionally with the action of heat.

[0269] The amount of the dyes or dye mixtures or inks according to the invention used for dyeing or for printing can vary within wide limits, depending on the desired depth of shade; generally, amounts of from 0.01 to 15% by weight, in particular from 0.1 to 10% by weight, based on the article to be dyed or printed, have proven advantageous.

[0270] The invention also relates to textiles which are dyed or printed with at least one reactive dye of formula (I) according to the invention, or a dye mixture according to the invention, or an aqueous ink according to the invention.

[0271] The dyed and printed materials produced using the dyes or dye mixtures or inks according to the invention have high coloring strength and high fiber-dye binding stability in both the acidic and basic ranges, are remarkable by their non-photochromic properties, and also have good light and chlorine fastness, good elution behavior, and excellent handling properties (repeatability, fixing time, etc.).

[0272] 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, and percentages relate to weight percentages, and ratios are expressed as molar equivalent values. Parts by weight are related to parts by volume and are given in the ratio of kilograms per liter.

[0273] Experimental part:

[0274] The following examples serve to illustrate the present invention. Unless otherwise indicated, temperatures are given in degrees Celsius, masses are expressed as g / g (100% active ingredient), parts are parts by weight, and percentages relate to weight percentages, and ratios are expressed as molar equivalent values. Parts by weight are related to parts by volume and are given at a ratio of kilograms per liter.

[0275] Example

[0276] Experimental part I (Synthesis)

[0277] - To maintain the pH at an appropriate value, a 32% hydrochloric acid solution, a 20% sodium carbonate solution, or a 30% sodium hydroxide solution was used.

[0278] - Water and ice were used for the cooling step.

[0279] - The reaction was monitored using an HPLC analysis method, which indicated the end of the reaction.

[0280] - All products used for the synthesis were commercially available.

[0281] Example 1

[0282] Example 1-a

[0283] This example illustrates the synthesis of the compound of formula (I).

[0284] (a) 109.0 g of 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl)benzenesulfonic acid was finely dispersed in 200 parts of water and diazotized according to the following procedure:

[0285] (a1) 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl)benzenesulfonic acid and a 32% hydrochloric acid solution were mixed in water, where the stoichiometry (HCl 32%: 2-amino-5-((2-(sulfatooxy)ethyl)sulfonyl)benzenesulfonic acid) was 2.0 - 3.0:1.0.

[0286] (a2) The mixture obtained in step (a1) was diazotized at 0 - 30 °C with a 4N sodium nitrite solution in a slightly molar excess of 1.05 - 1.1:1.0 (sodium nitrite: the mixture obtained in step (a1)) to ensure complete diazotization.

[0287] (a3) The reaction mixture obtained in step (a2) was stirred for 1 hour and the excess nitrite was neutralized by adding a 10% sulfamic acid solution, thus providing the desired diazonium salt.

[0288] Then, 46.0 g of 3-aminophenylurea pre-dispersed in water was cooled with ice and coupled as follows: the diazonium salt mixture obtained in step (a3) was added, maintained at 0 - 30 °C by adding ice, and maintained at pH 4.5 - 6.0 by adding 20% sodium carbonate solution. After the coupling was completed, the reaction mass was heated to 25 - 40 °C and treated with 32% HCl solution at pH 1.0 - 1.5 for 1 - 3 hours to remove the triazene. Then, the obtained mixture was cooled to 20 - 25 °C and dissolved using 20% sodium carbonate solution at pH 6.5 - 7.0.

[0289] (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 at 0 - 5 °C and the mixture was stirred for 10 minutes using a dispersion device under vigorous stirring.

[0290] The mixture obtained in step (a) was cooled with ice at 0 - 5 °C and pH 6.0 - 8.0, and 55.5 g of cyanuric chloride was added rapidly (less than 1 minute) to the mixture. The pH of the mixture was adjusted by adding 20% sodium carbonate solution and maintained at 5.0 - 6.0 at 15 - 25 °C for 1 hour. After the reaction was completed, the suspension was at a temperature of 15 - 25 °C and a pH of 5.0 - 6.0.

[0291] (c) 23.0 g of 3,5-diaminobenzoic acid was added to water at a temperature of 20 - 25 °C, and the pH of this solution was adjusted and maintained at 9.0 - 9.5 by adding 30% sodium hydroxide solution while heating and stirring the solution at 60 - 65 °C for 1 hour.

[0292] The 3,5-diaminobenzoic acid solution was added to the mixture obtained in step (b) heated at 55 - 65 °C within 5 min. The subsequent mixture was heated to 55 - 65 °C while maintaining the pH at 4.0 - 4.5 by adding 20% sodium carbonate solution, and the mixture was stirred at 55 - 65 °C until the reaction was completed.

[0293] After the reaction was completed, the reaction mass was cooled to a temperature of 35 - 40 °C, and unreacted 3,5-diaminobenzoic acid was quenched with a few drops of acetic anhydride. Then the pH of the reaction mass was set at 5.5 - 6.0 using 20% sodium carbonate solution, and the reaction mass was heated to 30 - 50 °C, subjected to a reverse osmosis process and dried, resulting in a crude reactive dye, the main component of which (in the form of the free acid) corresponds to formula (101-a):

[0294]

[0295] Example 1-b

[0296] Compound (101-b) can be obtained from compound (101-a) using conditions known from the literature.

[0297] For example, the conversion of the vinylatable active group -SO2-CH2-CH2-OSO3H into its vinyl form is achieved by treatment with dilute sodium hydroxide solution, for example the conversion of β-sulphatoethylsulphonyl into vinylsulphonyl. Such reactions are known per se. Those conversion reactions are generally effected in a neutral to alkaline medium, at a temperature of for example 20-70 °C, at a pH of for example 6-14.

[0298]

[0299] Example 2

[0300] Example 2-a

[0301] This example illustrates the synthesis of the compound of formula (II).

[0302] (a) 109.0 g of 2-amino-5-((2-(sulphatooxy)ethyl)sulphonyl)benzenesulphonic acid was finely dispersed in 200 parts of water and diazotized according to the following procedure:

[0303] (a1) 2-Amino-5-((2-(sulphatooxy)ethyl)sulphonyl)benzenesulphonic acid and 32% hydrochloric acid solution were mixed in water, where the stoichiometric ratio (32% HCl:2-amino-5-((2-(sulphatooxy)ethyl)sulphonyl)benzenesulphonic acid) was 2.0-3.0:1.0,

[0304] (a2) The mixture obtained in step (a1) was diazotized at 0-30 °C with 4N sodium nitrite solution in a slight molar excess of 1.05-1.1:1.0 (sodium nitrite:mixture obtained in step (a1)) to ensure complete diazotization,

[0305] (a3) The reaction mixture obtained in step (a2) was stirred for 1 hour and the excess nitrite was neutralized by addition of 10% aminosulphonic acid solution, thus providing the desired diazonium salt.

[0306] Then, 46.0 g of 3-aminophenylurea, which had been previously dispersed in water, was cooled with ice and coupled as follows: The diazonium salt mixture obtained in step (a3) was added, and the temperature was maintained at 0 - 30 °C by adding ice and at pH 4.5 - 6.0 by adding 20% sodium carbonate solution. After the coupling was completed, the reaction mass was heated to 25 - 40 °C and treated with 32% HCl solution at pH 1.0 - 1.5 for 1 - 3 hours to remove the triazene. Then, the obtained mixture was cooled to 20 - 25 °C and dissolved using 20% sodium carbonate solution at pH 6.5 - 7.0.

[0307] (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 at 0 - 5 °C, and the mixture was stirred for 10 minutes using a dispersing device under vigorous stirring.

[0308] The mixture obtained in step (a) was cooled with ice at 0 - 5 °C and pH 6.0 - 8.0, and 55.5 g of cyanuric chloride was added rapidly (less than 1 minute) to the mixture. The pH of the mixture was adjusted by adding 20% sodium carbonate solution, and it was maintained at 5.0 - 6.0 at 15 - 25 °C for 1 hour. After the reaction was completed, the suspension was at a temperature of 15 - 25 °C and a pH of 5.0 - 6.0.

[0309] (c) 66.0 g of 2-amino-4-sulfobenzoic acid was dissolved in water at a temperature of 20 - 25 °C, and the pH of this solution was adjusted and maintained at 5.5 by adding 20% sodium carbonate solution.

[0310] The 2-amino-4-sulfobenzoic acid solution was added to the mixture obtained in step (b) within 5 min, and the mixture was heated to 45 - 50 °C. While maintaining the pH at 4.0 - 4.5 by adding 20% sodium carbonate solution, the mixture was stirred at 45 - 50 °C until the reaction was completed.

[0311] After the reaction was completed, the reaction mass was cooled to a temperature of 20 - 25 °C, and the unreacted 2-amino-4-sulfobenzoic acid was quenched with a few drops of acetic anhydride. Then the pH of the reaction mass was set at 5.0 - 5.5 using 20% sodium carbonate solution, and the reaction mass was heated to 30 - 50 °C, subjected to a reverse osmosis process and dried, which gave a crude reactive dye whose main component (in the form of the free acid) corresponded to formula (201-a):

[0312]

[0313] (201-a)

[0314] Example 2-b

[0315] Compound (201)-b can be obtained from compound (201-a) using conditions known from the literature.

[0316] For example, the conversion of the vinylatable active group -SO2-CH2-CH2-OSO3H into its vinyl form is achieved by treatment with dilute sodium hydroxide solution, for example, the conversion of β-sulfoethylsulfonyl into vinylsulfonyl. Such reactions are known per se. Those conversion reactions are generally affected in a neutral to alkaline medium, at a temperature of, for example, 20 - 70 °C and at a pH of, for example, 6 - 14.

[0317]

[0318] Examples 3-7

[0319] This example illustrates different mixtures of compound (101) with one or more compounds (201) and / or other dyes from the above list.

[0320] Example 3-a

[0321] This example illustrates a mixture of compounds (101-a) and (201-a) having a molar ratio of 20:80 of mixture (101-a:201-a).

[0322] 47.0 g of the molecule of formula (101-a) and 113.3 g of the molecule of formula (201-a) are dissolved in water at a temperature of 20 - 25 °C, and the pH of this solution is adjusted and maintained at 6.0 - 6.5 by adding 20% sodium carbonate solution. Once the solution is obtained, the reaction mass is dried to give Example 3, which is in the free acid form, corresponding to formula (101-a):(201-a), as a mixture with a molar ratio of 20:80.

[0323] Example 3-b

[0324] This example illustrates a mixture of compounds (101-b) and (201-b) having a molar ratio of 20:80 of mixture (101-b:201-b). It is achieved in a manner similar to that described in Example 3-a.

[0325] Example 4-a

[0326] In a manner similar to that described in Example 3, a mixing ratio of (101-a):(201-a) of 33:66 is obtained by mixing 106.7 g of the molecule of formula (101-a) and 130.4 g of the molecule of formula (201-a).

[0327] Example 4-b

[0328] This example illustrates a mixture of compounds (101-b) and (201-b), where the molar ratio of the mixture (101-b:201-b) is 33:66. It is achieved in the same manner as described in Example 4-a.

[0329] Example 5

[0330] This example illustrates a 30:70 weight ratio mixture by separately mixing the corresponding weights of the following substances:

[0331] - Dye (101-a) from Example 1-a, and

[0332] - R.YE.222

[0333] It is achieved in the same manner as described in Example 4-a.

[0334] Example 6

[0335] This example illustrates a 50:50 weight ratio mixture by separately mixing the corresponding weights of the following substances:

[0336] - Dye (101-a) from Example 1-a, and

[0337] - R.YE.222

[0338] It is achieved in the same manner as described in Example 4-a.

[0339] Example 7

[0340] This example illustrates a 30:70 weight ratio mixture by separately mixing the corresponding weights of the following substances:

[0341] - Dye mixture from Example 4-a, and

[0342] - R.YE.222

[0343] It is achieved in the same manner as described in Example 3-a.

[0344] Example 8

[0345] This example illustrates a 50:50 weight ratio mixture by separately mixing the corresponding weights of the following substances:

[0346] - Dye mixture from Example 4-a, and

[0347] - R.YE.222

[0348] It is implemented in the same manner as described in Example 3-a.

[0349] Example 9

[0350] This example illustrates a 30:70 weight ratio mixture by separately mixing the following substances in the corresponding weights:

[0351] - the dye mixture from Example 4-b, and

[0352] - R.YE.222

[0353] It is implemented in the same manner as described in Example 3-a.

[0354] Example 10

[0355] This example illustrates a 30:70 weight ratio mixture by separately mixing the following substances in the corresponding weights:

[0356] - the dye mixture from Example 1-b, and

[0357] - R.YE.222

[0358] It is implemented in the same manner as described in Example 3-a.

[0359] Experimental part II (Application)

[0360] The following examples are used to illustrate the present invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are by weight, and percentages relate to weight percentages. Volume parts are related to the ratio of weight parts (kg) and volume (L).

[0361] Application Example A: Dyeing-padding

[0362] The cotton warp knitted fabric is introduced into an aqueous dye bath at a bath ratio of 1:10 at 60 °C, which contains the dye baths AE 1 to AE 4 of the present invention and the reference dye baths AE 5 and AE 6, and each dye bath is tested at six different concentrations.

[0363] Each composition of the dye baths AE 1 to AE 6 is prepared at the 6 concentrations C1 to C6 described in Table 1 below, which contains sodium chloride and a certain amount of the following substances:

[0364] - the single dye of Dye Example 1-a, which provides Application Example 1 (AE1)

[0365] - the dye mixture from Dye Example 4-a, which provides Application Example 2 (AE2),

[0366] - The dye mixture from Dye Example 5, which provides Application Example 3 (AE3),

[0367] - The dye mixture from Dye Example 6, which provides Application Example (AE4),

[0368] - The dye mixture from Dye Example 7, which provides Application Example 5 (AE5),

[0369] - The dye mixture from Dye Example 8, which provides Application Example 6 (AE6),

[0370] - The dye mixture from Dye Example 3a, which provides Application Example 7 (AE7),

[0371] - The dye mixture from Dye Example 1b, which provides Application Example 8 (AE8),

[0372] - The dye mixture from Dye Example 4b, which provides Application Example 9 (AE9)

[0373] - The dye mixture from Dye Example 9, which provides Application Example 10 (AE10),

[0374] - The dye mixture from Dye Example 10, which provides Application Example 11 (AE11),

[0375] - The single dye of formula R.YE205 (AE X) as a reference, or

[0376] - The single dye of formula R.YE222 (AE Y),

[0377] Table 1 : Dye bath composition

[0378]

[0379]

[0380] * The percentage of the dye mixture or dye is based on the weight of the cotton fabric.

[0381] [g / l] means grams of salt per liter of solution

[0382] After 45 minutes at 60 °C, calcined sodium carbonate is added in the amounts given in Table 1. The dyeing is continued for 45 minutes. Then the dyed article is rinsed with water, soaped and rinsed again, and then dried.

[0383] The dyeing color strength obtained with Dyeing Liquids 1 - 6 was measured spectrophotometrically.

[0384] Table 2 shows the stacking properties of application examples AE1 to AE11 according to the present invention and of the single dyes of formula R.YE 205 (AE5) and R.YE.222 (AE6) as a reference. Compared to the single dye components, the dye mixtures according to the present invention show very good stacking properties. The staining color strength is given in units of RD (= "reference depth"), which is a quantity obtained by an in-house test method that defines the color depth and is related to the standard depth SD according to ISO 105-A-1984 (E), page 4.

[0385] Table 2: Stacking: Dependence on dye concentration and reference depth (RD) of the application examples

[0386] Dye % (*) 0 0.5 1.0 2.0 4.0 6.0 RD ex.AE1 0 0.77 1.21 1.96 2.21 2.22 RD ex.AE2 0 0.41 0.80 1.47 2.29 2.48 RD ex.AE3 0 0.52 0.97 1.75 2.48 2.50 RD ex.AE4 0 0.40 1.04 1.72 2.36 2.41 RD ex.AE5 0 0.42 0.76 1.45 2.39 2.61 RD ex.AE6 0 0.41 0.84 1.52 2.43 2.68 RD ex.AE7 0 0.22 0.4 0.81 1.44 2.11 RD ex.AE8 0 0.45 0.88 1.39 1.78 1.82 RD ex.AE9 0 0.40 0.74 1.41 1.98 2.30 RD ex.AE10 0 0.42 0.80 1.48 2.32 2.50 RD ex.AE11 0 0.42 0.8 1.43 2.07 2.27 RD R.YE205 (AE X) 0 0.42 0.84 1.58 2.36 2.42 RD R.YE222 (AE Y) 0 0.50 0.79 1.48 2.36 2.58

[0387] * The % of the dye mixture or dye is based on the weight of the cotton fabric.

[0388] The data in Table 2 show that the fabrics dyed with the dyes of the present invention exhibit excellent stacking properties at the same level as the reference dyes.

[0389] Application Example B: Dyeing-fastness

[0390] Examples B1-B4 and reference

[0391] At 60 °C, the bleached cotton warp knitted fabric was introduced into an aqueous dye bath with a bath ratio of 1:6, which contained 55 g / l sodium chloride and:

[0392] - a single dye from Dye Example 1-a

[0393] - a dye mixture from Dye Example 4-a

[0394] - a dye mixture from Dye Example 5,

[0395] - a dye mixture from Dye Example 7,

[0396] - a single dye of formula R.YE222,

[0397] The composition of dye baths B1 - B5 is described in Table 3 below.

[0398] Table 3 : Dye bath composition

[0399]

[0400] * The % of the dye mixture or dye is based on the weight of the cotton fabric.

[0401] After 45 minutes at 60 °C, 16.0 g / l of calcined sodium carbonate was added to the dye bath. Dyeing was continued for 45 minutes. The dyed fabric was removed from the dye liquor and washed by rinsing the fabric in a water bath at 60 °C with a liquor ratio of 6:1 for 10 minutes. This washing process was repeated two more times. A yellow-toned fabric with a reference depth (RD) of 1.0 was obtained, corresponding to a color depth of 1 / 1 SD (standard depth according to ISO 105-A-1984(E)).

[0402] The washed fabric was subjected to the following color fastness tests:

[0403] (a) Wash C1S at 60 °C according to ISO 105-C06,

[0404] (b) Water severity according to ISO 105-E01,

[0405] (c) Perspiration alkaline according to ISO 105-E04,

[0406] (d) Perspiration acid according to ISO 105-E04.

[0407] The change in color was determined according to the Blue Scale. A higher grade indicates excellent color fastness properties. The data in Tables 4, 5, 6, and 7 show that the fabrics dyed with the dye mixtures of the present invention exhibit good fastness properties compared to the reference dyes from Table 8.

[0408] Table 4 : Fastness properties of the single dye of Dye Compound Example 1-a

[0409]

[0410] Table 5 : Fastness properties of Dye Mixture Example 4-a

[0411]

[0412] Table 6 : Fastness properties of Dye Mixture Example 5

[0413]

[0414] Table 7 : Fastness properties of Dye Mixture Example 7

[0415]

[0416] Table 8 :Fastness properties of the single dyes of the formula R.YE222

[0417]

[0418] Application Example C

[0419] The washed fabrics obtained in Application Example A were subjected to the following measurements and fastness tests:

[0420] (a) Measurement of the dye concentration at 1RD

[0421] (b) Degree of fixation at 1RD

[0422] (c) Light fastness according to ISO 105 - B02

[0423] (d) Chlorine fastness at 40 mg / L according to ISO 105 - E03

[0424] (e) Oxidative bleaching damage at 50 °C according to M&S C10A

[0425] The change in color was determined according to the Grey Scale, except for the light fastness test using the Blue Scale. A higher grade indicates excellent fastness properties. The data in Tables 9 and 10 show that the fabrics dyed with the dyes / dye mixtures of the present invention exhibit good fastness properties compared to the reference dyes in Tables 9 and 10.

[0426] Table 9 :General properties of the dyes / dye mixtures of the present invention relative to the reference dyes

[0427]

[0428]

[0429] Table 10 :General properties of the dye compounds / dye mixtures of the present invention relative to the reference dyes

[0430]

Claims

1. An isomer mixture of at least one dye of formula (I): wherein - X1 and X2 are independently a halogen atom, - A1, A2 are independently a hydrogen atom or a C1-C4 alkyl group, - R1, R2 are independently -H, -SO3M, C1-C4 alkyl, C1-C4 alkoxy, -COOH, a halogen atom, - Z1, Z2 are independently a fiber-reactive group 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, where Y is a group removable under alkaline conditions, - M is hydrogen, or a salt of an organic or inorganic cation, or a mixture of salts.

2. The isomer mixture according to claim 1, wherein Z1, Z2 are independently a group of the formula -SO2-CH=CH2 or -SO2-(CH2)2-Y.

3. The isomer mixture according to claim 1 or claim 2, wherein Z1, Z2 are -SO2-CH2-CH2-OSO3M.

4. The isomer mixture according to any one of claims 1-3, wherein Z1, Z2 are in the para position to the azo group, and R1, R2 are in the ortho position to the azo group.

5. The isomer mixture according to any one of claims 1-4, wherein it corresponds to formula (IA): wherein X1 and X2 are independently -Cl or -F, Y1, Y2 are independently -CH=CH2 (vinyl) or the group -CH2-CH2-Y, and Y is a group removable under alkaline conditions.

6. The isomer mixture according to any one of claims 1-5, wherein it corresponds to formula (101-a) or formula (101-b) or a salt thereof, or a mixture thereof:

7. A mixture of isomeric dye mixtures, comprising: · at least one isomer mixture according to any one of claims 1-6, and · at least one isomer mixture comprising at least one dye of formula (II): wherein - X3 is a halogen atom, - A3 is a hydrogen atom or a C1-C4 alkyl group, - R3, R4 are independently -H, -SO3M', C1-C4 alkyl, C1-C4 alkoxy, -COOH, a halogen atom, -Z3 is a group 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’, where Y’ is a group removable under basic conditions; -M’ is hydrogen, or a salt of an organic or inorganic cation, or a mixture of salts.

8. The mixture of isomeric dye mixtures according to claim 7, wherein at least one dye mixture of formula (II) is a dye mixture as follows: of formula (201-a) or formula (201-b) or a salt thereof, or a mixture thereof:

9. A dye mixture, which at least comprises: (A) An isomeric dye mixture selected from: (A1) A mixture of isomers of at least one dye of formula (I) according to any one of claims 1-6, and (A2) A mixture of isomeric dye mixtures as defined in claim 7 or 8, and (B) At least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II).

10. The dye mixture according to claim 9, which at least comprises: (A) 20-60% by weight, preferably 25-55% by weight, especially 30-50% by weight of: (A1) A mixture of isomers of at least one dye of formula (I), or (A2) A mixture of at least one dye of formula (I) and a mixture of isomeric dye mixtures of at least one dye of formula (II), and (B) 40-80% by weight, preferably 45-75% by weight, especially 50-70% by weight of at least one reactive dye different from the dye mixture of formula (I) and the dye mixture of formula (II), each percentage being based on the total of all dyes.

11. An aqueous ink, which at least comprises a mixture of isomers of at least one dye of formula (I) according to any one of claims 1-6, or a mixture of dyes according to any one of claims 7-10.

12. Use of at least one reactive dye of formula (I) according to any one of claims 1-6, or a mixture of dyes according to any one of claims 7-10, or an ink according to claim 11, for dyeing or printing textile materials, such as hydroxy- or nitrogen-containing fiber materials, especially cellulose fiber materials.

13. A textile dyed or printed with at least one reactive dye of formula (I) according to any one of claims 1-6, or a mixture of dyes according to any one of claims 7-10, or an ink according to claim 11.

14. A process for dyeing or printing hydroxyl- or nitrogen-containing fiber materials, which process comprises using at least one reactive dye of formula (I) according to any one of claims 1 - 6, or a mixture of dyes according to any one of claims 7 - 10, or an ink according to claim 11.

15. A process for preparing an isomeric dye mixture of at least one dye of formula (I) as defined in any one of claims 1 - 6, which process comprises: (a) diazotizing a compound of formula (1) wherein R represents R1, R2 or R3, and Z represents Z1, Z2 or Z3; and reacting the diazonium salt thus obtained with a coupling component of formula (2) to obtain an azo compound of formula (3) (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of the following formula wherein X represents X1, X2 or X3, to obtain a compound of formula (5) (c) condensing the compound of formula (5) prepared in step (b) with a compound of formula (6) 16. A process for preparing a mixture of an isomeric dye mixture of at least one dye of formula (I) as defined in any one of claims 7 - 10 and at least one dye of formula (II), which process comprises: (a) diazotizing a compound of formula (1) wherein R represents R1, R2 or R3, and Z represents Z1, Z2 or Z3; and reacting the diazonium salt thus obtained with a coupling component of formula (2) to obtain an azo compound of formula (3) (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula (4) wherein X represents X1, X2 or X3, and obtaining a compound of formula (5), (c) condensing the compound of formula (5) prepared in step (b) with a mixture of compounds of formula (6) and (7)

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