Fibre-reactive isomeric yellow dye mixtures, their preparation and their use

Abstract

An isomeric mixture of at least one dye of the formula (I): wherein • - X 1 and X2 are independently a halogen atom, • - A1, A2 are independently a hydrogen atom or a C1-C4 alkyl, • - R1, R2 are independently -H, -SO 3M, a C1-C4 alkyl, a C1-C4 alkoxy, • -COOH, a halogen atom, • - Z1, Z2, are independently a fiber reactive radical of formula -SO 2-CH = CH 2, - SO 2-(CH 2) 2-Y, -NH-(CH 2) 2-O-(CH 2) 2-SO 2-CH = CH 2, -NH-(CH 2) 2-O-(CH 2) 2-SO 2-(CH 2) 2-Y, -NH-(CH 2) 2-O-(CH 2) 3- SO 2-CH = CH 2, -NH-(CH 2) 2-O-(CH 2) 3-SO 2-(CH 2) 2-Y, -NHCO-(CH 2) 3-SO 2-CH=CH 2 or -NHCO-(CH 2) 3-SO 2-(CH 2) 2-Y wherein Y is a group removable under alkaline conditions, • - M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

Description

[0001] FIBRE-REACTIVE ISOMERIC YELLOW DYE MIXTURES, THEIR PREPARATION AND THEIR USE

[0002] FIELD OF INVENTION

[0003] The present invention relates to novel isomeric mixtures of reactive dyes of yellow colour, to mixtures containing said dyes, to ink compositions comprising said dyes and dye mixtures, to processes for the preparation thereof and to the use thereof in dyeing or printing textile fibre materials. The novel isomeric mixtures of reactive dyes according to the invention are suitable for the dyeing or printing of nitrogen-containing or hydroxy-group-containing fibre materials and yield on such materials dyeings or prints having a good build-up behaviour, a high fixation rate, excellent washing off properties of the unfixed dyes and good fastness properties.

[0004] BACKGROUND OF THE INVENTION

[0005] Over the past years, many countries have committed to improve the quality of the environment by saving natural resources and reducing the emission of substances which are harmful to the climate. Funds are provided by the governments to support the industry in achieving these goals. The consumer is asking for environmentally friendly textile products which are produced in accordance with highest ecological standards. Brands and retailers are conveying these demands into real requirements and textile manufacturers are continuously improving their production excellence by investing in modern equipment and selecting environmentally friendly chemical substances.

[0006] As a result, there is a huge demand for novel reactive dye mixtures that are suitable for the reproducible dyeing and printing of fibre materials which fulfill highest ecological and economical requirements while still providing dyeings of the desired colour shades with improved fastness properties, such as wash and water fastness and perspiration fastness.

[0007] Furthermore, they should have sufficient substantivity and at the same time have good ease of washing-off of unfixed dye. They should also exhibit a good tinctorial yield and high reactivity, the objective being to provide especially dyeing having good build-up properties and high degrees of fixing. Reactive dyes which can be used for the dyeing and printing of hydroxyl-group- containing or nitrogen-containing fibre materials are known and described, for example, in EP 0 567 036. However, these dyes, when used alone, do not provide high degrees of fixing.

[0008] The present invention is therefore based on the problem of providing new mixtures of reactive dyes that are suitable especially for the reproducible dyeing and printing of fibre materials in the desired colour shades and fulfil the above indicated requirements to the highest possible extent. The dye mixtures should also yield dyeing having good build-up properties, high fixation rates, good washing off properties of the unfixed dyes, and good all-round fastness properties, for example fastness to chlorine and to peroxide. The reactive dyes according to the invention also show satisfactory stability to various dyeing parameters.

[0009] The term "consists essentially of" followed by one or more characteristics, means that may be included in the process or the material of the invention, besides explicitly listed components or steps, components or steps that do not materially affect the properties and characteristics of the invention.

[0010] The expression “comprised between X and Y” includes boundaries, unless explicitly stated otherwise. This expression means that the target range includes the X and Y values, and all values from X to Y.

[0011] Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and do not exclude other moieties, additives, components, integers or steps. Moreover, the singular encompasses the plural unless the context otherwise requires: in particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0012] Where upper and lower limits are quoted for a property, for example for the concentration of a component, then a range of values defined by a combination of any of the upper limits with any of the lower limits may also be implied.

[0013] SUMMARY OF THE INVENTION The invention relates to an isomeric mixture of at least one dye of the formula

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

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

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

[0017] - Z1, Z2, are independently a fiber reactive radical of formula -SC>2-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-

[0018] (CH2)2-Y, -NHCO-(CH2)3-SO2-CH=CH2or -NHCO-(CH2)3-SO2-(CH2)2-Y wherein Y is a group removable under alkaline conditions,

[0019] M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

[0020] According to a favorite embodiment of the isomeric mixture, Z1, Z2 are independently a group of the formula -SC>2-CH=CH2 or -SC>2-(CH2)2-Y.

[0021] According to a favorite embodiment of the isomeric mixture, Z1, Z2 are -SO2- CH2-CH2-OSO3M.

[0022] According to a favorite embodiment of the isomeric mixture, Z1 , Z2 are located in para-position to the azo group and R1, R2 are located in ortho-position to the azo group.

[0023] According to a favorite embodiment, the isomeric mixture responds to formula wherein

[0024] Xi and X2 are independently -Cl or -F,

[0025] Y1, Y2 are independently -CH=CH2 (vinyl) or a radical -CH2-CH2-Y and Y is a group removable under alkaline conditions.

[0026] According to a favorite embodiment, the isomeric mixture responds to formula (101 -a) or formula (101-b) or a salt thereof, or a mixture thereof:

[0027]

[0028] The invention further relates to a mixture of isomeric dye mixtures comprising:

[0029] • at least one isomeric mixture as disclosed above and in details here-under, and

[0030] • at least one isomeric mixture comprising at least one dye of formula (II): wherein

[0031] - X3 is a halogen atom,

[0032] - A3 is a hydrogen atom or a C1-C4 alkyl,

[0033] - R3, R4 are, independently -H, -SO3M’, a C1-C4 alkyl, a C1-C4 alkoxy,

[0034] -COOH, a halogen atom,

[0035] - Z3is a radical of formula

[0036] SO2-CH=CH2, -NH-(CH2)2-O

[0037] CH=CH2, -NH-(CH2)2-O-(CH2)3 NHCO-(CH2)3-SO2-(CH2)2-Y’ wherein Y’ is a group removable under alkaline conditions; - M’ is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

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

[0039] The invention also relates to a dye mixture comprising at least:

[0040] (A) an isomeric dye mixture selected from:

[0041] (A1) an isomeric mixture of at least one dye of the formula (I) as defined above and in detail here-under, and

[0042] (A2) a mixture of isomeric dye mixtures as defined above and in detail hereunder, and

[0043] (B) at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II). According to a favorite embodiment, the dye mixture comprises at least:

[0044] (A) 20 to 60 % by weight, preferably 25 to 55 % by weight, in particular 30 to 50 % by weight, of:

[0045] (A1) an isomeric mixture of at least one dye of the formula (I), or

[0046] (A2) a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), and

[0047] (B) 40 to 80 % by weight, preferably 45 to 75 % by weight, in particular 50 to 70 % by weight, of at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II), each percentage being based on the sum total of all dyes.

[0048] The invention further relates to an aqueous inks comprising at least an isomeric mixture of at least one dye of the formula (I) as defined above and in details hereunder, or a mixture of dyes as defined above and in details here-under.

[0049] The invention also relates to the use of at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes as defined above and in details here-under, or an ink as defined above and in details here-under, in the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogencontaining fibre material, especially cellulosic fibre material.

[0050] The invention further relates to a textile dyed or printed with at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes according as defined above and in details here-under, or an ink as defined above and in details here-under.

[0051] The invention also relates to a process for dyeing or printing of hydroxy-g roupcontaining or nitrogen-containing fibre materials, which process comprises using at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes as defined above and in details here-under, or an ink as defined above and in details here-under.

[0052] Another object of the invention is a process for the preparation of a mixture of isomeric dyes of at least one dye of the formula (I) as defined above and in details here-under, which comprises: (a) diazotising a compound of the formula (1) wherein R represents R1, R2 or R3, Z represents Z1, Z2 or Z3; and reacting the diazonium salt so obtained with a coupling component of formula (2) whereby an azo compound of formula (3) is obtained

[0053] (3),

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

[0055] (4), wherein X represent X1 , X2 or X3,

[0056] So as to obtain a compound of the formula (5)

[0057] (c) condensing the compound of the formula (5) prepared in step (b) with the compound of formula (6)

[0058] (6).

[0059] Another object of the invention is a process for the preparation of a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II) as defined above and in details here-under, which comprises:

[0060] (a) diazotising a compound of the formula (1) wherein R represents R1, R2 or R3, Z represents Z1, Z2 or Z3; and reacting the diazonium salt so obtained with a coupling component of formula (2)

[0061] (2) whereby an azo compound of formula (3) is obtained

[0062] (3), (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula (4)

[0063] (4), wherein X represent X1 , X2 or X3, and a compound of the formula (5) is obtained,

[0064] (5)

[0065] (c) condensing the compound of the formula (5) prepared in step (b) with the mixture of compounds of formula (6) and (7)

[0066] DETAILED DESCRIPTION

[0067] Dye of formula (I)

[0068] The present invention accordingly relates to a new isomeric mixture of at least one dye of the formula (I): Wherein

[0069] - Xi and X2 are independently a halogen atom,

[0070] - A1, A2 are independently a hydrogen atom or a C1-C4 alkyl,

[0071] R1 , R2 are independently -H, -SO3M, a C1-C4 alkyl, a C1-C4 alkoxy, -COOH, a halogen atom,

[0072] - Z1 , Z2, are independently a fiber reactive radical of formula -SC>2-CH=CH2,

[0073] -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-

[0074] (CH2)2-Y, -NHCO-(CH2)3-SO2-CH=CH2or -NHCO-(CH2)3-SO2-(CH2)2-Y wherein Y is a group removable under alkaline conditions,

[0075] M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

[0076] The isomeric mixture of at least one reactive dye of formula (I) according to the invention provides very good build-up properties, high fixation rates, good washing off properties of the unfixed dyes, and good all-round fastness properties.

[0077] Surprisingly, it was found that the COOH moiety substituted to the central phenyl cycle of the dye according to the formula (I) advantageously greatly increases the solubility of the dye in polar solvents, whilst the colouring properties of the dye remain the same, in comparison to the same dye without substitution with a COOH moiety. The same comparison shows that the dye of formula (I), where the COOH moiety is substituted to the central phenyl cycle, shows a greater affinity to fibre, allowing for a more effective dye.

[0078] "Isomers" and "isomeric mixtures" as used herein include dyes with the same chemical formula but a different arrangement of atoms. According to the invention, the isomeric mixture of reactive dyes of formula (I) comprises reactive dyes with the same chemical formula and thus the same carbon number, but with (substituted)phenyldiazo- moiety and / or Z1, Z2, R1 , R2 groups attached at different positions on the phenyl ring.

[0079] The term "isomeric mixture" as used herein, means a composition comprising more than one isomer of a reactive dye.

[0080] The "isomeric mixture of at least one reactive dye" optionally contains isomers of more than one reactive dye of formula (I). As such, the isomeric mixture contains more than one (i.e., two or more) isomers of a reactive dye of formula (I) and also can contain more than one (i.e., two or more) isomers of a different reactive dye of formula (I). Different reactive dyes of formula (I) have different chemical formulae comprised in formula (I) and thus may have a different carbon number. For example, an isomeric mixture of at least one reactive dye of formula (I) includes a p- vinylsulfonyl reactive dye of formula (I) and its isomers and a p-sulfatoethylsulfonyl reactive dye of formula (I) and its isomers (the isomers having the sulfonic substituent and / or diazo substituents attached at different positions on the phenyl ring).

[0081] These isomeric mixtures as disclosed herein are distinguished from single reactive dyes of formula (I).

[0082] The dyes of formula (I), of which is composed the isomeric mixture, contain at least 2, preferably from 2 to 4 and especially 4, sulfo groups, which are each present either in free acid form or, preferably, in salt form. Suitable salts, represented by M, are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts, a mono-, di- or tri-ethanolamine salt or mixed Na / Li or Na / Li / NF salts.

[0083] By “C1-C4 alkyl” is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms. Preferably, the hydrocarbon- containing chain is linear. Preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl. More preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, n-butyl. Advantageously, the C1-C4 alkyl group is methyl or ethyl.

[0084] By “C1-C4 alkoxy” is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms and substituted by an oxygen atom.

[0085] Preferably, the hydrocarbon-containing chain is linear. Preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, i- propoxy, n-butoxy, s-butoxy, i-butoxy or t-butoxy. More preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, n-butoxy. Advantageously, the C1-C4 alkoxy group is methoxy or ethoxy. As used herein, the term “halogen” refers to a fluorine atom, a chlorine atom or a bromine atom, preferably a fluorine atom or a chlorine atom.

[0086] As halogen, represented by the independent variables Xi, X2 and also as a possible choice for the independent variables R1 , R2, there come into consideration, for example, fluorine or chlorine, preferably chlorine.

[0087] A group Y removable under alkaline conditions may be selected from the group consisting of -Cl, -Br, -F, -OSO3M, -SSO3M, -OCO-CH3, -OPO3M2, -OCO-CeHs, - OSC>2-(Ci-C4alkyl) or -OSC>2-N(Ci-C4alkyl)2. Preferably, Y is selected from the group consisting of -Cl, -OSO3M, -SSO3M, -OCO-CH3, -OCO-CeHs or -OPO3M2, more preferably -Cl or -OSO3M, wherein M has the meanings given above.

[0088] Preferably, Z1, Z2 are independently a fiber reactive radical of formula -SO2- CH=CH2, or -SO2-(CH2)2-Y, even more preferably Z1 , Z2 are independently a group of the formula -SO2-(CH2)2-Y.

[0089] According to a favorite embodiment (Z1, R1) and (Z2, R2) are independently (- SO2-Y; -SO3M), wherein Y and M are as defined above and here-under.

[0090] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein the fibre-reactive groups Z1, Z2 are located in para-position to the azo group.

[0091] Z1 , Z2 are preferably -SO2-CH2-CH2-OSO3M.

[0092] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein R1 , R2 are located in ortho-position to the azo group.

[0093] R1 , R2 are preferably -SO3M.

[0094] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein the diazo groups are located in ortho - position and / or in para-position on the phenyl cycles, with regards to the central chain. A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein R1 and / or R2 are located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.

[0095] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein Z1 and / or Z2 are located in para - position on the terminal phenyl cycles, with regards to the diazo groups.

[0096] A preferred embodiment of the present invention relates to an isomeric mixture of reactive dyes of formula (I), wherein Ai, A2 are H.

[0097] In a more preferred embodiment, the isomeric mixture of at least one reactive dye of formula (I) wherein:

[0098] A1, A2 are H,

[0099] R1 , R2 are -SO3M,

[0100] Z1, Z2 are a fibre-reactive radical of formula -SC>2-CH=CH2 or -SC>2-(CH2)2-Y wherein Y is a group removable under alkaline conditions,

[0101] X is a fluorine atom, and

[0102] M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.

[0103] Particularly preferred are isomeric mixtures of dyes of formula (IA) wherein

[0104] Xi and X2 are independently -Cl or -F, Yi, Y2 are independently -CH=CH2 (vinyl) or a radical -CH2-CH2-Y and Y is a group removable under alkaline conditions,

[0105] Favorite embodiments of variables of formula (I) also apply to variables of formula (IA).

[0106] A favorite isomeric mixture of dyes of formula (I) is an isomeric mixture of dyes of formula (101 -a) or (101-b) or salts thereof: A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (101 -a) or (101-b), wherein the diazo groups are located in ortho-position and in para-position on the phenyl cycles, with regards to the central chain.

[0107] The end product can optionally also be subjected to a transformation reaction. Such a transformation reaction is, for example, the conversion of a vinylatable reactive group -SO2-Y, -SO2-Y1 and -SO2-Y2 into its vinyl form by treatment with dilute sodium hydroxide solution, such as, for example, the conversion of the p- chloroethylsulfonyl radical or -sulfatoethylsulfonyl radical into the vinylsulfonyl radical. Such reactions are known per se. Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.

[0108] A favorite isomeric mixture of reactive dyes of formula (101 -a) is an isomeric mixture of dyes of formula (101-a1) and (101-a2) or a salt thereof:

[0109] (101-a1)

[0110] (101-a2)

[0111] A favorite isomeric mixture of reactive dyes of formula (101-b) is an isomeric mixture of dyes of formula (101-b1) and (101-b2) or a salt thereof, wherein (101-b1) corresponds to the mono- or di-vinyl form of (101-a1) and wherein (101-b2) corresponds to the mono- or di-vinyl form of (101-a2).

[0112] The isomeric mixtures of dyes according to the invention dye the support to which they are applied in a golden-yellow shade having a high degree of fixation and good all-round fastness properties, in particular washing-fastness, chlorine and oxygen fastness.

[0113] Dye mixtures

[0114] The isomeric mixture of dyes of formula (I) exhibits a high compatibility with other reactive dyes and can therefore be applied in combination with other dyes in order to adjust a specific shade or in dichromatic or trichromatic mixtures to provide a variety of chromatic tones.

[0115] • Mixtures with a dye of formula (II)

[0116] According to a first embodiment of this variant, the invention further relates to a dye mixture comprising:

[0117] • at least one isomeric mixture of dyes of formula (I), and

[0118] • at least one isomeric mixture comprising at least one dye of formula (II): wherein

[0119] - X3 is a halogen atom,

[0120] - A3 is a hydrogen atom or a C1-C4 alkyl,

[0121] - R3, R4 are, independently -H, -SO3M’, a C1-C4 alkyl, a C1-C4 alkoxy,

[0122] -COOH, a halogen atom,

[0123] - Z3is a radical of formula

[0124] SO2-CH=CH2, -NH-(CH2)2-O

[0125] CH=CH2, -NH-(CH2)2-O-(CH2)3 NHCO-(CH2)3-SO2-(CH2)2-Y’ wherein Y’ is a group removable under alkaline conditions;

[0126] - M’ is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

[0127] "Isomers" and "isomeric mixtures" as used herein include dyes with the same chemical formula but a different arrangement of atoms. According to the invention, the isomeric mixture of reactive dyes of formula (II) comprises reactive dyes with the same chemical formula and thus the same carbon number, but with (substituted)phenyldiazo- moiety and / or Z3, R3, R4, COOH groups attached at different positions on the phenyl ring.

[0128] The term "isomeric mixture" as used herein, means a composition comprising more than one isomer of a reactive dye.

[0129] The "isomeric mixture of at least one reactive dye" optionally contains isomers of more than one reactive dye of formula (II). As such, the isomeric mixture contains more than one (i.e., two or more) isomers of a reactive dye of formula (II) and also can contain more than one (i.e., two or more) isomers of a different reactive dye of formula (II). Different reactive dyes of formula (II) have different chemical formulae comprised in formula (II) and thus may have a different carbon number. For example, an isomeric mixture of at least one reactive dye of formula (II) includes a - vinylsulfonyl reactive dye of formula (II) and its isomers and a p-sulfatoethylsulfonyl reactive dye of formula (II) and its isomers (the isomers having the sulfonic substituent and / or diazo substituents attached at different positions on the phenyl ring).

[0130] These isomeric mixtures as disclosed herein are distinguished from single reactive dyes of formula (II).

[0131] The dyes of formula (II) contain at least 2, preferably from 2 to 3 and especially 3, sulfo groups, which are each present either in free acid form or, preferably, in salt form. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts, a mono-, di- or tri-ethanolamine salt or mixed Na / Li or Na / Li / NH4 salts.

[0132] By “C1-C4 alkyl” is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms. Preferably, the hydrocarbon- containing chain is linear. Preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl. More preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, n-butyl. Advantageously, the C1-C4 alkyl group is methyl or ethyl.

[0133] By “C1-C4 alkoxy” is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms and substituted by an oxygen atom.

[0134] Preferably, the hydrocarbon-containing chain is linear. Preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, i- propoxy, n-butoxy, s-butoxy, i-butoxy or t-butoxy. More preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, n-butoxy. Advantageously, the C1-C4 alkoxy group is methoxy or ethoxy.

[0135] As halogen, represented by the variable X3 and also as a possible choice for the variable R3, there come into consideration, for example, fluorine or chlorine, preferably chlorine.

[0136] A group Y’ removable under alkaline conditions may be selected from the group consisting of -Cl, -Br, -F, -OSO3M’, -SSO3M’, -OCO-CH3, -OPO3M’2, -OCO-CeHs, - OSC>2-(Ci-C4alkyl) or -OSC>2-N(Ci-C4alkyl)2. Preferably, Y’ is selected from the group consisting of -Cl, -OSO3M’, -SSO3M’, -OCO-CH3, -OCO-CeHs or -OPO3M’2, more preferably -Cl or -OSO3M’, wherein M’ has the meanings given above.

[0137] Preferably, Z3 is a fiber reactive radical of formula -SC>2-CH=CH2, or -SO2- (CH2)2-Y’, even more preferably Z3 is a group of the formula -SC>2-(CH2)2-Y’.

[0138] According to a favorite embodiment (Z3, R3) is (-SO2-Y’ ; -SO3M’), wherein Y’ and M’ are as defined above and here-under.

[0139] In a preferred embodiment of the present invention, in the reactive dye of formula (II), the fibre-reactive group Z3 is located in para-position to the azo group.

[0140] Z3 is preferably -SO2-CH2-CH2-OSO3M’.

[0141] A preferred embodiment of the present invention is directed to a mixture wherein, in the reactive dye of formula (II), R3 is located in ortho-position to the azo group.

[0142] R3 is preferably -SO3M’.

[0143] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein the diazo group is located in orthoposition and / or in para-position on the phenyl cycles, with regards to the central chain.

[0144] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein R3 is located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.

[0145] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein Z3 is located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.

[0146] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein the COOH group is located in orthoposition on the phenyl cycles, with regards to the central chain. A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein R4 is located in meta-position on the phenyl cycles, with regards to the central chain.

[0147] A preferred embodiment of the present invention relates to a mixture of reactive dyes, wherein in the dye of formula (II), A3 is H.

[0148] Among the dyes of formula (II), particularly preferred are dyes of formula (HA)

[0149] X3 is -Cl or -F,

[0150] Y3 is -CH=CH2 (vinyl) or a radical -CH2-CH2-Y’ and Y’ is a group removable under alkaline conditions,

[0151] Favorite embodiments of variables X3, Y3, Y’, M’ of formula (II) also apply to variables of formula (HA).

[0152] A favorite isomeric mixture of dyes of formula (II) is an isomeric mixture of dyes of formula (201 -a) or (201 -b) or a salt thereof:

[0153] A preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (201 -a) or (201 -b), wherein the diazo group is located in ortho-position and in para-position on the phenyl cycles, with regards to the central chain.

[0154] The end product can optionally also be subjected to a transformation reaction. Such a transformation reaction is, for example, the conversion of a vinylatable reactive group -SO2-Y3 into its vinyl form by treatment with dilute sodium hydroxide solution, such as, for example, the conversion of the p-chloroethylsulfonyl radical or p -sulfatoethylsulfonyl radical into the vinylsulfonyl radical. Such reactions are known per se. Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.

[0155] A favorite isomeric mixture of reactive dyes of formula (201 -a) is an isomeric mixture of dyes of formula (201-a1) and (201-a2) or a salt thereof:

[0156] (201-a1)

[0157] (201 -a2)

[0158] A favorite isomeric mixture of reactive dyes of formula (201 -b) is an isomeric mixture of dyes of formula (201 -b1) and (201 -b2) or a salt thereof, wherein (201 -b1) corresponds to the vinyl form of (201-a1) and wherein (201-b2) corresponds to the vinyl form of (201 -a2).

[0159] According to a favorite embodiment, the invention relates to a mixture of isomeric dye mixtures comprising isomeric dye mixtures of formula (I) and isomeric dye mixtures of formula (II) wherein the compounds of formula (I) and the compounds of formula (II) are present in ratio (I) : (II) from 9:1 to 1:9, preferably 3:1 to 1 :9, more preferably 1 :1 to 1 :8, further preferably 1:1 to 1:6, wherein the ratios are expressed as molar equivalent value.

[0160] According to a more favorite embodiment, the invention relates to a mixture of isomeric dye mixtures comprising isomeric dye mixtures of formula (IA) and isomeric dye mixtures of formula (IIA) wherein the compounds of formula (IA) and the compounds of formula (IIA) are present in ratio (IA) : (IIA) from 9:1 to 1:9, preferably 3:1 to 1:9, more preferably 1 :1 to 1 :8, further preferably 1:1 to 1 :6, wherein the ratios are expressed as molar equivalent value.

[0161] Dyes of formula (II) and methods for their preparation have been disclosed in EP0567036. • Mono and Polychromic mixtures

[0162] According to a second embodiment of this variant, the invention further relates to a dye mixture comprising:

[0163] (A) a mixture of dyes selected from:

[0164] (A1) an isomeric mixture of at least one dye of the formula (I) as above defined, or

[0165] (A2) a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), and further comprising:

[0166] (B) at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II).

[0167] According to a favorite embodiment, the invention further relates to a dye mixture comprising:

[0168] (A) 20 to 60 % by weight, preferably 25 to 55 % by weight, in particular 30 to 50 % by weight, of:

[0169] (A1) an isomeric mixture of at least one dye of the formula (I) as above defined, or

[0170] (A2) a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), and

[0171] (B) 40 to 80 % by weight, preferably 45 to 75 % by weight, in particular 50 to 70 % by weight, of at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II), each percentage being based on the sum total of all dyes.

[0172] Favorite embodiments of dyes of the formula (I), of dyes of the formula (II), and of dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), which have been expressed in detail above, also apply to the compositions comprising (A) and (B).

[0173] Examples for dyes suitable as component (B) in the mixtures according to the invention are

[0174] Lemon Yellow: C.l. R YE 25, C.l. R YE 37, C.l. R YE 95, C.l. R YE 105, C.l. R

[0175] YE 135, C.l. R YE 143, C.l. R YE 160, C.l. R YE 161 , C.l. R YE 167, C.l. R YE 175,

[0176] C.l. R YE 186, C.l. R YE 204, C.l. R YE 207;

[0177] Normal Yellow: C.l. R YE 15, C.l. R YE 17, C.l. R YE 27, C.l. R YE 67, C.l. R

[0178] YE 111 , C.l. R YE 125, C.l. R YE 165, C.l. R YE 168, C.l. R YE 208, C.l. R YE 209,

[0179] C.l. R YE 211; Golden Yellow: C.l. R YE 84, C.l. R YE 107, C.l. R YE 138, C.l. R YE 145, C.l. R YE 162, C.l. R YE 74, C.l. R YE 176, C.l. R YE 181 , C.l. R YE 186, C.l. R YE 201, C.l. R YE 205, C.l. R YE 206, C.l. R YE 210, C.l. R YE 214, C.l. R YE 217, C.l. R YE 218, C.l. R YE 219, C.l. R YE222

[0180] Orange: C.l. R OR 7, C.l. R OR 11 , C.l. R OR 12, C.l. R OR 13, C.l. R OR 16, C.l. R OR 20, C.l. R OR 35, C.l. R OR 64, C.l. R OR 69, C.l. R OR 72, C.l. R OR 82, C.l. R OR 84, C.l. R OR 95, C.l. OR 116, C.l. R OR 117, C.l. R OR 122, C.l. R OR 129, C.l. R OR 131, C.l. R OR 132, C.l. R OR 133, C.l. R OR 134, C.l. R OR 135, C.l. R OR 136, C.l. R OR 140, C.l. OR 143

[0181] Brown: C.l. R BR 7, C.l. R BR 11 , C.l. R BR 19, C.l. R BR 37, C.l. R BR 46, C.l. R BR 48, C.l. R BR 49, C.l. R BR 51;

[0182] Red: C.l. R RE 3, C.l. R RE 23, C.l. R RE 24, C.l. R RE 49, C.l. R RE 56, C.l. R RE 58, C.l. R RE 114, C.l. R RE 120, C.l. R RE 123, C.l. R RE 124, C.l. R RE 141 , C.l. R RE 158, C.l. R RE 159, C.l. R RE 171, C.l. R RE 174, C.l. R RE 180, C.l. R RE 183, C.l. R RE 184, C.l. R RE 194, C.l. R RE 195, C.l. R RE 198, C.l. R RE 218, C.l. R RE 221 , C.l. R RE 222, C.l. R RE 227, C.l. R RE 228, C.l. R RE 237, C.l. R RE 238, C.l. R RE 239, C.l. R RE 242, C.l. R RE 243, C.l. R RE 245, C.l. R RE 250, C.l. R RE 264, C.l. R RE 265, C.l. R RE 266, C.l. R RE 267, C.l. R RE 268, C.l. R RE 269, C.l. R RE 270, C.l. R RE 271 , C.l. R RE 273, C.l. R RE 277, C.l. R RE 278, C.l. R RE 279, C.l. R RE 280, C.l. R RE 281 , R RE 286, C.l. R RE 287, C.l. R RE 288, C.l. R RE 289

[0183] Blue: C.l. R BL 13, C.l. R BL 19, C.l. R BL 52, C.l. R BL 72, C.l. R BL 114, C.l. R BL160, C.l. R BL182, C.l. R BL 204, C.l. R BL 209, C.l. R BL 220, C.l. R BL 221 , C.l. R BL 221A, C.l. R BL 235A, C.l. R BL 235, C.l. R BL 260, C.l. R BL 263, C.l. R BL 276, C.l. R BL 282, C.l. R BL 285Royal: C.l. R BL 29, C.l. R BL 49, C.l. R BL 105, C.l. R BL 181 , C.l. R BL 187, C.l. R BL 198, C.l. R BL 224, C.l. R BL 261 , C.l. R BL 268, C.l. R BL 269, C.l. R BL 279;

[0184] Navy: C.l. R BL 79, C.l. R BL 120, C.l. R BL 171 , C.l. R BL 184, C.l. R BL 193, C.l. R BL 194, C.l. R BL 203, C.l. R BL 214, C.l. R BL 222, C.l. R BL 225, C.l. R BL 230, C.l. R BL 238, C.l. R BL 250, C.l. R BL 257, C.l. R BL 264, C.l. R BL 265, C.l. R BL 271, C.l. R BL 276, C.l. R BL 271A, R BL 284

[0185] Olive: C.l. R GR 19, C.l. R GR 21 , C.l. R GR 25, C.l. R GR 29, C.l. R GR 34;

[0186] Black: C.l. R BK 5B, C.l. R BK 5A, C.l. R BK 5, C.l. R BK 8, C.l. R BK 13, C.l. R BK 31 , C.l. R BK 39, C.l. R BK 49.

[0187] Preferably, the dye mixture according to the invention comprises one or more dyes selected from C.l. R BL 220, C.l. R BL 235, C.l. R.BI 285, C.l. R BL 19 ,C.I. R BL 279, C.l. R RE 286, C.l. R RE 287, C.l. R RE 289 and R YE 222 as component (B).

[0188] Process for the preparation of the reactive dye of formula (I)

[0189] The present invention further relates to a process for the preparation of the mixture of reactive dye of formula (I), which comprises:

[0190] (a) diazotising a compound of the formula (1) wherein R represents R1, R2 or R3 as defined above, Z represents Z1 , Z2 or Z3 as defined above; and reacting the diazonium salt so obtained with a coupling component of whereby an azo compound of formula (3)

[0191] (3), is obtained, wherein R represents R1, R2 or R3 as defined above, Z represents Z1 , Z2 or Z3 as defined above; (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula (4) (4), wherein X represent X1 , X2 or X3 as defined above, thereby providing a compound of formula (5) wherein R, Z and X are defined above;

[0192] (c) condensing the compound of the formula (5) prepared in step (b) with the compound of formula (6) wherein R, Z and X are defined above, thus providing the isomeric mixture of reactive dye of formula (I) according to the invention in the case when A1 = A2 = H. When A1 and / or A2 are different from H, then a derivative of the molecule (6) bearing appropriate substituents on NH2 groups should be used.

[0193] The invention also relates to a method for preparing a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), wherein said method comprises the same steps a) and b) as recited above and further comprises one step (c) consisting in condensing the compound of the formula (5) prepared in step (b) with the mixture of compounds of formula (6) and formula (7)

[0194] (6) (7) wherein R, Z and X are defined above, thus providing the isomeric mixture of reactive dye of formula (I) and reactive dye of the formula (II), according to the invention in the case when A1 = A2 = A3 = H. When A1 and / or A2 and / or A3 are different from H, then a derivative of the molecule (6) and / or (7) bearing appropriate substituents on NH2 groups should be used.

[0195] The favourite embodiments of variables A, R, Z and X in the method for preparing isomeric dye mixtures (I) and (I) correspond to favourite choices of, respectively, A1 , A2, A3, R1 , R2, R3, Z1 , Z2, Z3 and X1, X2, X3 as above defined in the description of these compounds.

[0196] Compositions and Uses

[0197] The fibre-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-group-containing or nitrogen-containing fibre materials. Examples include paper, silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.

[0198] The present invention also concerns an aqueous ink comprising the dyes of formula (I) according to the invention, or dye mixtures comprising them, and to the use of such inks in an ink-jet printing method for printing a variety of substrates, especially textile fibre materials, the definitions and preferences indicated above applying to the dyes and dyes mixtures, the inks and the substrates.

[0199] The dyes of formula (I) according to the invention, and dye mixtures comprising them, show very good build-up behaviour, a high end build-up and a high degree of fixation, especially in printing applications on cellulosic fibre materials, as well as an improved stability towards varying printing parameters.

[0200] 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 ink-jet printers for paper or textile printing, or writing instruments, such as fountain pens or ballpoint pens, and especially ink-jet printers. For that purpose, the dyes according to the invention are first brought into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink, which comprises the dyes of formula (I) according to the invention, or the dye mixtures comprising them, as colorants. The inks can be prepared in customary manner by mixing together the individual components in the desired amount of water. As substrates there come into consideration the above-mentioned hydroxyl- group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials. The fibre materials are preferably textile fibre materials.

[0201] Substrates that also come into consideration are paper and plastics films.

[0202] As examples of paper there may be mentioned commercially available ink-jet paper, photo paper, glossy paper, plastics-coated paper, e.g. Epson Ink-jet Paper, Epson Photo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper and Ilford Photo Paper. Plastics films are, for example, transparent or cloudy / opaque. Suitable plastics films are, for example, 3M Transparency Film.

[0203] Depending on the nature of the use, for example textile printing or paper printing, it may be necessary, for example, for the viscosity or other physical properties of the ink, especially properties that have an influence on the affinity for the substrate in question, to be adapted accordingly.

[0204] The dyes of formula (I) according to the invention, or the dye mixtures comprising them, used in the aqueous inks should preferably have a low salt content, that is to say they should have a total content of salts of less than 0.5 % by weight, based on the weight of the dyes. Dyes that have relatively high salt contents as a result of their preparation and / or as a result of the subsequent addition of diluents can be desalted, for example by membrane separation procedures, such as ultrafiltration, reverse osmosis or dialysis.

[0205] The inks preferably have a total content of dye or dye mixture according to the invention from 1 to 35 % by weight, especially from 1 to 30 % by weight and preferably from 1 to 20 % by weight, based on the total weight of the ink. The preferred lower limit in this case is a limit of 1.5 % by weight, preferably 2 % by weight and especially 3 % by weight.

[0206] The inks may comprise water-miscible organic solvents, for example 01- C4alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso-butanol; amides, e.g. dimethylformamide or dimethylacetamide; ketones or ketone alcohols, e.g. acetone or diacetone alcohol; ethers, e.g. tetra hydrofuran or dioxane; nitrogen-containing heterocyclic compounds, e.g. N- methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, poly-alkylene glycols, e.g. polyethylene glycol or polypropylene glycol; C2 C6alkylene glycols and thio-glycols, e.g. ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thio-diglycol, hexylene glycol and diethylene glycol; other polyols, e.g. glycerol or 1,2,6-hexane- triol; and C1-C4alkyl ethers of polyhydric alcohols, e.g. 2-methoxy-ethanol, 2-(2- methoxy-ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxy- ethoxy)ethoxy]ethanol or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2- pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to 30 % by weight, especially from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink.

[0207] In addition, the inks may also comprise solubilisers, e.g. p-caprolactam.

[0208] The inks may comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.

[0209] Examples of thickeners that may be mentioned include commercially available alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellulose, e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, especially with preferably from 20 to 25 % by weight carboxymethyl cellulose. Synthetic thickeners that may also be mentioned are, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides and also polyalkylene glycols having a molecular weight of, for example, from 2000 to 20 000, such as, for example, polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of ethylene oxide and propylene oxide.

[0210] The inks contain such thickeners, for example, in an amount of from 0.01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0.01 to 0.5 % by weight, based on the total weight of the ink.

[0211] The inks may also comprise buffer substances, e.g. borax, borates, phosphates, poly-phosphates or citrates. Examples that may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used especially in amounts of from 0.1 to 3 % by weight, preferably from 0.1 to 1 % by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5.

[0212] As further additives, the inks may comprise surfactants or humectants.

[0213] Suitable surfactants include commercially available anionic or non-ionic surfactants. As humectants in the inks according to the invention there come into consideration, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 % to 60 % aqueous solution) and glycerol and / or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight.

[0214] Preference is given to inks having a viscosity of from 1 to 40 mPa.s, especially from 1 to 20 mPa.s and more especially from 1 to 10 mPa.s.

[0215] Furthermore, the inks may in addition comprise customary additives, e.g. antifoams or especially preservatives that inhibit fungal and / or bacterial growth. Such additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink.

[0216] As preservatives there come into consideration formaldehyde-yielding agents, for example paraformaldehyde and trioxane, especially aqueous, approximately from 30 to 40 % by weight formaldehyde solutions, imidazole compounds, for example 2- (4-thiazolyl)-benzimidazole, thiazole compounds, for example 1,2-benzisothiazolin-3- one or 2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1 ,2-benzisothiazolin-3-one or 2-n-octyl- isothiazolin-3-one. A suitable preservative is, for example, a 20 % by weight solution of 1 ,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL).

[0217] The inks may in addition comprise further additives, such as fluorinated polymers or telomers, for example polyethoxyperfluoroalcohols (Forafac® or Zonyl® products) in an amount of, for example, from 0.01 to 1 % by weight, based on the total weight of the ink.

[0218] In the case of the ink-jet printing method, individual droplets of ink are sprayed onto a substrate from a nozzle in a controlled manner. It is mainly the continuous inkjet method and the drop-on-demand method that are used for that purpose. In the case of the continuous ink-jet method, the droplets are produced continuously, droplets not required for the printing operation being discharged into a receptacle and recycled. In the case of the drop-on-demand method, on the other hand, droplets are generated as desired and used for printing; that is to say, droplets are generated only when required for the printing operation. The production of the droplets can be effected, for example, by means of a piezo ink-jet head or by thermal energy (bubble jet). Preference is given to printing by means of a piezo ink-jet head and to printing according to the continuous ink-jet method.

[0219] The present invention also concerns the use of at least one reactive dye of formula (I) according to the invention, or a mixture comprising such a dye, or the ink according to the invention, in the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogen-containing fibre material, especially cellulosic fibre material, or in other words, a process for the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogen-containing fibre material, especially cellulosic fibre material, 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.

[0220] The reactive dye of formula (I) according to the invention, or a mixture comprising such a dye, or the ink according to the invention are suitable for customary dyeing and printing methods and can be applied to the fibre material and fixed thereto in a wide variety of ways, especially in the form of aqueous dye solutions or print pastes.

[0221] The process for dyeing and printing of hydroxy-group-containing or nitrogencontaining fibre materials according to the invention can be carried out in accordance with customary dyeing and printing methods, for example, according to the so-called cold pad-batch process, in which the dye according to the invention, or the dye mixture, or the ink is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35°C. Alternatively, the process for dyeing and printing according to the invention can be carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing, solution comprising the dye or dye mixture according to the invention, and the dye or the dye mixture is fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat. The amounts in which the dye or the dye mixture according to the invention or the ink according to the invention is used for dyeing or for printing can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or printed, have proved advantageous.

[0222] The present invention also concerns a textile 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 the aqueous ink according to the invention.

[0223] The dyeings and prints produced using the dye or the dye mixture or the ink according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both the acidic and the alkaline range, are remarkable through their non photochromic character, and also have good light and chlorine fastnesses, good wash-off behaviour, excellent operational excellence (reproductibility, fixing time, etc.)

[0224] 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 percent by weight, ratio are expressed as molar equivalent value. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

[0225] Experimental part:

[0226] 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 percent by weight, ratio are expressed as molar equivalent value. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

[0227] EXAMPLES

[0228] EXPERIMENTAL PART I (Synthesis)

[0229] - For maintaining pH to appropriated values, either hydrochloric acid 32% solution, sodium carbonate 20% solution or sodium hydroxide 30% solution is used,

[0230] - Water and ice are used for cooling steps,

[0231] - Reactions are monitored using HPLC analysis method, this latter indicating the end of reaction,

[0232] - All products used for synthesis are commercially available. Example 1 :

[0233] Example 1-a

[0234] This example illustrates the synthesis of a compound of formula (I).

[0235] (a) 109.0 g of 2-Amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic finely dispersed in 200 parts of water, are diazotized according to the following procedure :

[0236] (a1) mixing 2-Amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid and hydrochloric acid 32% solution in water with the stoichiometry (HCI 32% : 2-Amino-5- ((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid) of 2.0 - 3.0 : 1.0,

[0237] (a2) diazotization of the mixture obtained in step (a1) with a 4N solution of sodium nitrite in slight molar excess (sodium nitrite: mixture obtained in step (a1)) of 1.05-1.1 : 1.0 to ensure complete diazotization, at 0-30°C

[0238] (a3) the reaction mixture obtained in step (a2) is stirred for one hour and excess of nitrite is neutralized by addition of sulfamic acid 10% solution, thus providing the required diazonium salt.

[0239] Then, 46.0 g of 3-Aminophenylurea previously dispersed in water, is cooled down with ice and coupled by adding the diazonium salt mixture obtained at the step (a3) at 0-30°C being kept by ice addition and, at pH 4.5 - 6.0 being kept by addition of sodium carbonate 20% solution. After coupling completion, the reaction mass is warmed to 25-40°C and treated with HCI 32% solution for triazene removal at pH 1.0- 1.5 for 1 to 3 hours. Then, the mixture obtained is cooled down to 20-25°C and dissolved at pH 6.5-7.0 using sodium carbonate 20% solution.

[0240] (b) 55.5 g of cyanuric chloride are suspended in water with 1 g of buffer (hydrogen disodium phosphate) and ice. The temperature of said suspension is set up at 0-5°C and the mix is stirred for 10 min under vigorous stirring with the use of a dispersing apparatus.

[0241] The mixture obtained at step (a) is cooled with ice at 0-5°C and at pH 6.0-8.0, and 55.5 g of cyanuric chloride is rapidly (less than 1 min) added to said mixture. The pH of said mixture is adjusted and maintained at 5.0-6.0 for one hour at 15-25°C by addition of sodium carbonate 20% solution. After reaction completion, the suspension is at a temperature of 15-25°C and at a pH of 5.0-6.0.

[0242] (c) 23.0 g of 3,5-diaminobenzoic acid are loaded in water at a temperature of 20-25°C and the pH of this solution is adjusted and maintained at 9.0 - 9.5 by addition of sodium hydroxide 30% solution while the solution is heated and stirred for 1 hour at 60-65°C.

[0243] 3,5-diaminobenzoic acid solution is added over 5 min to the mixture obtained in step (b) heated at 55 - 65°C. The subsequent mixture is heated 55 - 65°C, while the pH is maintained at 4.0 - 4.5 by addition of sodium carbonate 20% solution, the mixture is stirred at 55 - 65°C until reaction completion.

[0244] After reaction completion, the reaction mass is cooled to a temperature of 35 - 40°C and unreacted 3,5-diaminobenzoic acid is quenched with drops of acetic anhydride. The pH of said reaction mass is then set up at 5.5-6.0 with sodium carbonate 20% solution and the reaction mass is heated up to 30-50°C, submitted to reverse osmosis process and dried leading to the crude reactive dye which main component, in the form of the free acid, corresponds to the formula (101-a):

[0245] Example 1-b

[0246] Compound (101-b) can be obtained using literature known conditions from compound (101-a)

[0247] For example, the conversion of a vinylatable reactive group -SO2-CH2-CH2- OSO3H into its vinyl form is implemented by treatment with dilute sodium hydroxide solution, such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical. Such reactions are known per se. Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.

[0248] Example 2

[0249] Example 2-a

[0250] This example illustrates the synthesis of a compound of formula (II).

[0251] (a) 109.0 g of 2-Amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic finely dispersed in 200 parts of water, are diazotized according to the following procedure :

[0252] (a1) mixing 2-Amino-5-((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid and hydrochloric acid 32% solution in water with the stoichiometry (HCI 32% : 2-Amino-5- ((2-(sulfatooxy)ethyl)sulfonyl-benzenesulfonic acid) of 2.0 - 3.0 : 1.0,

[0253] (a2) diazotization of the mixture obtained in step (a1) with a 4N solution of sodium nitrite in slight molar excess (sodium nitrite: mixture obtained in step (a1)) of 1.05-1.1 : 1.0 to ensure complete diazotization, at 0-30°C

[0254] (a3) the reaction mixture obtained in step (a2) is stirred for one hour and excess of nitrite is neutralized by addition of sulfamic acid 10% solution, thus providing the required diazonium salt.

[0255] Then, 46.0 g of 3-Aminophenylurea previously dispersed in water, is cooled down with ice and coupled by adding the diazonium salt mixture obtained at the step (a3) at 0-30°C being kept by ice addition and, at pH 4.5 - 6.0 being kept by addition of sodium carbonate 20% solution. After coupling completion, the reaction mass is warmed to 25-40°C and treated with HCI 32% solution for triazene removal at pH 1.0- 1.5 for 1 to 3 hours. Then, the mixture obtained is cooled down to 20-25°C and dissolved at pH 6.5-7.0 using sodium carbonate 20% solution.

[0256] (b) 55.5 g of cyanuric chloride are suspended in water with 1 g of buffer (hydrogen disodium phosphate) and ice. The temperature of said suspension is set up at 0-5°C and the mix is stirred for 10 min under vigorous stirring with the use of a dispersing apparatus.

[0257] The mixture obtained at step (a) is cooled with ice at 0-5°C and at pH 6.0-8.0, and 55.5 g of cyanuric chloride is rapidly (less than 1 min) added to said mixture. The pH of said mixture is adjusted and maintained at 5.0-6.0 for one hour at 15-25°C by addition of sodium carbonate 20% solution. After reaction completion, the suspension is at a temperature of 15-25°C and at a pH of 5.0-6.0.

[0258] (c) 66.0 g of 2-amino-4-sulfobenzoic acid are dissolved in water at a temperature of 20-25°C and the pH of this solution is adjusted and maintained at 5.5 by addition of sodium carbonate 20% solution.

[0259] 2-amino-4-sulfobenzoic acid solution is added over 5 min to the mixture obtained in step (b) and the mixture is heated to 45-50°C. While the pH is maintained at 4.0 - 4.5 by addition of sodium carbonate 20% solution, the mixture is stirred at 45 - 50°C until reaction completion.

[0260] After reaction completion, the reaction mass is cooled to a temperature of 20- 25°C and unreacted 2-amino-4-sulfobenzoic acid is quenched with drops of acetic anhydride. The pH of said reaction mass is then set up at 5.0-5.5 with sodium carbonate 20% solution and the reaction mass is heated up to 30-50°C, submitted to reverse osmosis process and dried leading to the crude reactive dye which main component, in the form of the free acid, corresponds to the formula (201-a):

[0261] Example 2-b

[0262] Compound (201)-b can be obtained using literature known conditions from compound (201-a) For example, the conversion of a vinylatable reactive group -SO2-CH2-CH2- OSO3H into its vinyl form is implemented by treatment with dilute sodium hydroxide solution, such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical. Such reactions are known per se. Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.

[0263] Examples 3-7:

[0264] This example illustrates different mixes of the compounds (101) with one or more compounds (201) and / or other dyes from the list recited above.

[0265] Example 3-a:

[0266] This example illustrates a mixture of compounds (101 -a) and (201 -a) with a mix (101 -a : 201 -a) of 20:80 molar ratio value.

[0267] 47.0 g of molecule of formula (101-a) and 113.3 g of 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 addition of sodium carbonate 20% solution. Once solution is obtained, reaction mass is dried to provide the example 3, in the form of the free acid, corresponding to the formulas (101-a) : (201-a) as a mix in the molar ratio 20 : 80

[0268] Example 3-b:

[0269] This example illustrates a mixture of compounds (101-b) and (201-b) with a mix (101-b : 201-b) of 20 : 80 molar ratio value. It is achieved in a similar manner as described in the example 3-a

[0270] Example 4-a: In a similar manner as described in example 3, a mix Ratio of (101-a) : (201-a) as 33 : 66 molar ratio is obtained by mixing 106.7 g of molecule of formula (101-a) and 130.4 g of molecule of formula (201-a).

[0271] Example 4-b:

[0272] This example illustrates a mixture of compounds (101-b) and (201 -b) with a mix (101-b : 201 -b) of 33 : 66 molar ratio value. It is achieved according to a same manner as described in the example 4-a.

[0273] Example 5

[0274] This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :

[0275] Dye (101-a) from example 1 -a

[0276] - and R. YE. 222

[0277] It is achieved according to a same manner as described in the example 4-a

[0278] Example 6

[0279] This example illustrates a mixture as 50 : 50 weight ratio value by mixing respectively the corresponding weight of :

[0280] Dye (101-a) from example 1 -a

[0281] - and R. YE. 222

[0282] It is achieved according to a same manner as described in the example 4-a

[0283] Example 7:

[0284] This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :

[0285] - a dye mix from example 4-a

[0286] - and R. YE. 222

[0287] It is achieved according to a same manner as described in the example 3-a

[0288] Example 8

[0289] This example illustrates a mixture as 50 : 50 weight ratio value by mixing respectively the corresponding weight of :

[0290] - a dye mix from example 4-a

[0291] - and R. YE. 222

[0292] It is achieved according to a same manner as described in the example 3-a Example 9

[0293] This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :

[0294] - a dye mix from example 4-b

[0295] - and R. YE. 222

[0296] It is achieved according to a same manner as described in the example 3-a

[0297] Example 10:

[0298] This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :

[0299] - a dye mix from example1-b

[0300] - and R. YE. 222

[0301] It is achieved according to a same manner as described in the example 3-a

[0302] EXPERIMENTAL PART (applications)

[0303] The following Examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, Parts are by weight. Percentages relate to percent by weight. Parts by volume relate to a ratio of weight part (kilogram) to volume (liter)

[0304] Application Example A: Exhaust Dyeing - Build-Up:

[0305] A cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1:10 which contains the inventive dyebaths AE 1 to AE 4 and reference dyebaths AE5 and AE6, each dyebath being tested at six different concentrations.

[0306] Each composition of dyebaths AE 1 to AE 6 is prepared in 6 concentrations C1 to C6 described in table 1 below, containing sodium chloride nd amount of either

[0307] - a single dye of dyestuff example 1-a providing application example 1 (AE 1)

[0308] - a dyestuff mixture from dyestuff example 4-a providing application example 2 (AE 2),

[0309] - a dyestuff mixture from dyestuff example 5 providing application example 3 (AE 3),- a dyestuff mixture from dyestuff example 6 providing application example (AE 4),

[0310] - a dyestuff mixture from dyestuff example 7 providing application example 5 (AE 5), - a dyestuff mixture from dyestuff example 8 providing application example 6 (AE 6),

[0311] - a dyestuff mixture from dyestuff example 3a providing application example 7 (AE 7),

[0312] - a dyestuff mixture from dyestuff example 1b providing application example 8 (AE 8),

[0313] - a dyestuff mixture from dyestuff example 4b providing application example 9 (AE 9),

[0314] - a dyestuff mixture from dyestuff example 9 providing application example 10 (AE 10),

[0315] - a dyestuff mixture from dyestuff example 10 providing application example 11 (AE 11),

[0316] - as benchmark the single dyestuff of formula R. YE 205 (AE X),

[0317] - or the single dyestuff of formula R.YE 222 (AE Y),

[0318] Table 1: dye bath composition

[0319] % of dyestuff mixture or dyestuff is with respect to the weight of the cotton fabric

[0320] [g / l] refers to grams of salt per litter of solution

[0321] After 45 minutes at 60°C calcined sodium carbonate is added in the amount given in Table 1. Dyeing is continued for 45 minutes. The dyed goods are then rinsed with water, soaped and rinsed again and then dried.

[0322] The tinctorial strengths of the dyeings obtained with the dyeing liquors 1 to 6 are measured spectrophotometrically.

[0323] Table 2 shows the build-up properties of the application examples according to the invention AE1 to AE11 and the single dyes of formula R. YE 205 (AE 5) and R. YE. 222 (AE 6) as benchmarks. The dyestuff mixtures according to the present invention shows very good build-up properties in comparison to the single dyestuff components. The tinctorial strengths of the dyeings are given in units of RD (= “Reference Depth”), a quantity obtained by an internal test method that specifies the colour depth and correlates with the standard depth SD according to ISO 105-A-1984 (E), page 4.

[0324] Table 2: Build-up: dependence from dyestuff concentration of Application example and reference depth (RD)

[0325] * % of dyestuff mixture or dyestuff is with respect to the weight of the cotton fabric

[0326] The data of Table 2 demonstrate that the fabrics dyed with the inventive dyestuff exhibit excellent build-up properties, at same level than benchmark dyes.

[0327] Application Example B: Exhaust Dyeing - Fastness:

[0328] Example B1 to B4 and reference :

[0329] A bleached cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :6 which contains 55 g / l of sodium chloride, and

[0330] - a single dye from dyestuff example 1-a

[0331] - a dyestuff mixture from dyestuff example 4-a

[0332] - a dyestuff mixture from dyestuff example 5,

[0333] - a dyestuff mixture from dyestuff example 7,

[0334] - of the single dyestuff of formula R.YE 222, The compositions of dyebaths B 1 to B 5 are described in table 3 below.

[0335] Table 3: dye bath composition

[0336] * % of dyestuff mixture or dyestuff is with respect to the weight of the cotton fabric

[0337] After 45 minutes at 60°C 16.0 g / l of calcined sodium carbonate are added to the dyebath. Dyeing is continued for 45 minutes. The dyed fabric is taken out of the dyeing liquor and submitted to a washing treatment by rinsing the fabric for 10 minutes in a water bath with a liquor ratio of 6:1 at 60°C. This washing treatment is repeated another two times. Yellow shaded fabrics with a reference depth (RD) of 1.0 which corresponds to a colour depth of 1 / 1 SD (standard depth according to ISO 105- A-1984 (E)) are obtained.

[0338] The washed fabrics are subjected to the following colour fastness tests:

[0339] (a) Washing C1S at 60°C according to ISO 105-C06,

[0340] (b) Water severe according to ISO 105-E01,

[0341] (c) Perspiration alkaline according to ISO 105-E04,

[0342] (d) Perspiration acid according to ISO 105-E04.

[0343] Changes in colour are determined according to the Blue Scale. Higher ratings indicate superior fastness properties. The data of Tables 4, 5, 6, 7 demonstrate that the fabric dyed with the inventive dyestuff mixture exhibit good fastness properties when compared to the benchmark dyestuff from table 8.

[0344] Table 4: Fastness properties of single dye of dyestuff compound example 1-a Table 5: Fastness properties of dyestuff mixture example 4-a

[0345] Table 6: Fastness properties of a dyestuff mixture example 5

[0346] Table 7: Fastness properties of dyestuff mixture example 7 Table 8: Fastness properties of single dyestuff of compound of formula R.YE 222 Application Example C

[0347] The washed fabrics obtained in application example A are subjected to the following measurements and fastness tests:

[0348] (a) Measurement of dyestuff concentration at 1 RD (b) Fixation degree at 1 RD

[0349] (c) Light fastness according to ISO 105-B02,

[0350] (d) Chlorine fastness 40 mg / L according to ISO 105-E03,

[0351] (e) Oxidative Bleach damage 50°C according to M&S C10A, Changes in colour are determined according to the Grey Scale except for the light fastness test which uses Blue Scale. Higher ratings indicate superior fastness properties. The data of Tables 9 and 10 demonstrate that the fabric dyed with the inventive dyestuff I dyestuff mixtures exhibit good fastness properties when compared to the benchmark dyestuffs of the tables 9 and 10.

[0352] Table 9: General properties of invention dyestuff I dyestuff mixture vs benchmark dyes

[0353]

[0354] Table 10: General properties of invention dyestuff compounds I dyestuff mixtures vs benchmark dyes

Claims

CLAIMS1 . An isomeric mixture of at least one dye of the formula (I):- Xi and X2 are independently a halogen atom,- A1, A2 are independently a hydrogen atom or a C1-C4 alkyl,R1 , R2 are independently -H, -SO3M, a C1-C4 alkyl, a C1-C4 alkoxy, -COOH, a halogen atom,- Z1, Z2, are independently a fiber reactive radical of formula -SC>2-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=CH2or -NHCO-(CH2)3-SO2-(CH2)2-Y wherein Y is a group removable under alkaline conditions,M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

2. The isomeric mixture of claim 1 , wherein Z1, Z2 are independently a group of the formula -SO2-CH=CH2or -SO2-(CH2)2-Y.

3. The isomeric mixture of claim 1 or claim 2, wherein Z1 , Z2 are -SO2-CH2-CH2- OSO3M.

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

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

6. The isomeric mixture according to any one of claims 1 to 5, wherein it responds 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 isomeric mixture according to any one of claims 1 to 6, and• at least one isomeric 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,- R3, R4 are, independently -H, -SO3M’, a C1-C4 alkyl, a C1-C4 alkoxy,-COOH, a halogen atom,- Z3is a radical of formulaSO2-CH=CH2, -NH-(CH2)2-OCH=CH2, -NH-(CH2)2-O-(CH2)3NHCO-(CH2)3-SO2-(CH2)2-Y’ wherein Y’ is a group removable under alkaline conditions;- M’ is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.

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

9. A dye mixture comprising at least:(A) an isomeric dye mixture selected from:(A1) an isomeric mixture of at least one dye of the formula (I) according to any one of claims 1 to 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 from the dye mixture of formula (II).

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

11. An aqueous inks comprising at least an isomeric mixture of at least one dye of the formula (I) according to any one of claims 1 to 6, or a mixture of dyes according to any of the claims 7 to 10.

12. Use of at least one reactive dye of formula (I) according to any of the claims 1 to 6 or a mixture of dyes according to any of the claims 7 to 10, or an ink according to claim 11 in the dyeing or printing of textile material such as hydroxyl-group- containing or nitrogen-containing fibre material, especially cellulosic fibre material.

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

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

15. A process for the preparation of a mixture of isomeric dyes of at least one dye of the formula (I) as defined in any of the claims 1 to 6, which comprises:(a) diazotising a compound of the formula (1)wherein R represents R1, R2 or R3, Z represents Z1, Z2 or Z3; and reacting the diazonium salt so obtained with a coupling component of formula (2)(2) whereby an azo compound of formula (3) is obtained(3),(b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula(4), wherein X represent X1 , X2 or X3,So as to obtain a compound of the formula (5)(c) condensing the compound of the formula (5) prepared in step (b) with the compound of formula (6)(6).

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

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