Dye mixtures and their use for the dyeing or printing of fabrics

Abstract

The present invention relates to a dye mixture comprising dyes of at least three different formulae, optionally dyes of at least four different formulae, the use of said dye mixture as a dyeing agent and / or printing agent, a method for dyeing a fabric with said dye mixture, and the dyed fabric obtainable with said method.

Description

[0001] MEISSN

[0002] WidenmayerstraBe 47, 80538 Munich

[0003] Archroma (Switzerland) GmbH M / ARCH-014-PC

[0004] DYE MIXTURES AND THEIR USE FOR THE DYEING OR PRINTING OF FABRICS

[0005] Description

[0006] The present invention relates to a dye mixture, the use thereof as a dyeing agent and / or printing agent, a method for dyeing a fabric with said dye mixture, and the dyed fabric obtainable with said method.

[0007] 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.

[0008] As a result, there is a huge demand for novel reactive dyes and 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 good fastness properties, such as wash and water fastness and perspiration fastness. Suitable reactive dyes should provide a unique combinability and a low sensitivity to various dyeing parameters. 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 dyeings having good build-up properties and high degrees of fixing. In many cases, the build-up behaviour of reactive dyes is insufficient to meet the demands being made, especially when dyeing very deep shades. Meissner Bolte M / ARCH-014-PC

[0009] - 2 -

[0010] The present invention provides new mixtures of reactive dyes that are suitable especially for the reproducible dyeing and printing of fibre materials in the desired colour shades, especially shades of red, and fulfill the above indicated requirements to the highest possible extent. The dye mixtures should also yield dyeings having good build-up properties, high fixation rates and good washing off properties of the unfixed dyes, and good all-round fastness properties, for example fastness to light and to wetting.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] The present invention accordingly relates to a dye mixture comprising: at least one dye with formula (1), at least one dye of formula (2), Meissner Bolte M / ARCH-014-PC at least one dye of formula (5), and optionally at least one dye of formula (6) wherein

[0015] Ri and R3 are each independently of the other hydrogen or Ci-C4alkyl,

[0016] R2 and R4are each independently of the other hydrogen or Ci-C4alkyl, Ci-C4alkoxy or sulfo,

[0017] Qi and Q2are each independently of the other and are a fibre-reactive radical of formula

[0018] -(CH2)2-3-SO2-Y2 (3a) or

[0019] -(CH2)2-3_O-(CH2)2-3_SO2-Y3 (3b), Meissner Bolte M / ARCH-014-PC

[0020] - 4 -

[0021] Q3and Q4are independently of each other selected from a group consisting of Hydrogen, Ci-C4alkyl anda fibre-reactive radical of formula

[0022] -(CH2)2-3-SO2-Y5(4a) or

[0023] -(CH2)2-3-O-(CH2)2-3-SO2-Y6(4b), wherein at least one of Q3and Q4is a fibre-reactive radical of formula (4a) or (4b),

[0024] Xi, X2, X3and X4are each independently of the other halogen, 3-carboxypyridin-l-yl or 3- ca rba m oy I py ri d i n- 1 -y I ,

[0025] Yi, Y2, Y3, Y4, Y5and Y6are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions,

[0026] Zi, Z2, Z3, and Z4are each independently of the other -SO2-Y, wherein Y is vinyl or a radical - CH2-CH2-U and U is a group removable under alkaline conditions, M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, k, n, p and r are each independently of the other the number 0, 1 or 2, l, q, t and u are each independently of the other the number 0 or 1, m and v are each independently of the other the number 0 or 1, wherein the diazo component of the dye of formula (1), the diazo component of the dye of formula (2), the diazo component of the dye of formula (5) and the diazo component of the dye of formula (6) each independently of the other are a benzene radical or a naphthyl radical, and wherein the dyes of formula (1) and formula (5) are different from each other, and wherein the dyes of formula (2) and formula (6) are different from each other, if a dye of formula (6) is present.

[0027] Preferably, the dyes of formulae (1), (2), (5) and / or (6) are fiber reactive, i.e. the dyes of formulae (1), (2), (5) and / or (6) contain at least one fibre-reactive substituent.

[0028] More preferably, the dyes of formulae (1), (2), (5) and (6) are fiber reactive, i.e. the dyes of formulae (1), (2), (5) and (6) contain at least one fibre-reactive substituent. Meissner Bolte M / ARCH-014-PC

[0029] - 5 -

[0030] Alternatively, the dyes of formulae (1), (2), and (5) may be fiber reactive, i.e. the dyes of formulae (1), (2), and (5) may contain at least one fibre-reactive substituent, if no dye of formula (6) is present in the dye mixture.

[0031] In a preferred embodiment, the diazo component of the dye of formula (1) and / or the diazo component of the dye of formula (2) each are a naphthyl radical.

[0032] In a more preferred embodiment, the diazo component of the dye of formula (1) and the diazo component of the dye of formula (2) each are a naphthyl radical.

[0033] In a preferred embodiment, the diazo component of the dye of formula (5) and / or the diazo component of the dye of formula (6) each are a benzene radical.

[0034] In a more preferred embodiment, the diazo component of the dye of formula (5) and the diazo component of the dye of formula (6) each are a benzene radical.

[0035] In an even more preferred embodiment, the diazo component of the dye of formula (1) and the diazo component of the dye of formula (2) each are a naphthyl radical, and the diazo component of the dye of formula (5) and the diazo component of the dye of formula (6) each are a benzene radical.

[0036] The diazo component is defined as the terminal aromatic group, such as a naphtyl or benzene radical, which is bound to a diazo group.

[0037] Ri and R3 are each independently of the other hydrogen or Ci-C4alkyl.

[0038] R2 and R4are each independently of the other hydrogen or Ci-C4alkyl, Ci-C4alkoxy or sulfo.

[0039] Preferably, Ri, R2, R3 and R4are each independently of the other hydrogen or Ci-C4alkyl.

[0040] More preferably, Ri, R2 and R4are each hydrogen.

[0041] More preferably, R3 is Ci-C4alkyl. Meissner Bolte M / ARCH-014-PC

[0042] - 6 -

[0043] Even more preferably, Ri, R2and R4are each hydrogen and Rs is Ci-C4alkyl.

[0044] Ci-C4alkyl may refer to methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl, and more preferably ethyl.

[0045] Ci-C4alkoxy may refer to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy, and more preferably methoxy.

[0046] Xi, X2, X3and X4are each independently of the other halogen, 3-carboxypyridin-l-yl or 3- carbamoylpyridin-l-yl, preferably halogen.

[0047] Commonly used halogens are fluorine, chlorine and bromine, preferably fluorine and chlorine, more preferably chlorine.

[0048] Preferably, Xi, X2, X3and X4are each chlorine.

[0049] Qi and Q2are each independently of the other and are a fibre-reactive radical of formula

[0050] -(CH2)2.3-SO2-Y2(3a) or

[0051] -(CH2)2-3-O-(CH2)2-3-SO2-Y3(3b).

[0052] Preferably, Qi and Q2are each -(CH2)2.3-SO2-Y2(3a).

[0053] Q3and Q4are independently of each other selected from a group consisting of hydrogen, Ci-C4alkyl and a a fibre-reactive radical of formula

[0054] -(CH2)2-3-SO2-Y5(4a) or

[0055] -(CH2)2-3-O-(CH2)2-3-SO2-Y6(4b).

[0056] Preferably Q3is hydrogen.

[0057] Alternatively, Q3is a fibre-reactive radical of formula (4a) or (4b).

[0058] Preferably, Q4is a fibre-reactive radical of formula -(CH2)2-3-SO2-Y5(4a) or

[0059] -(CH2)2-3-O-(CH2)2-3-SO2-Y6(4b). Meissner Bolte M / ARCH-014-PC

[0060] - 7 -

[0061] More preferably, Q4is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a).

[0062] More preferably, Qi and Q2are each -(CH2)2-3-SO2-Y2(3a),

[0063] Q3is hydrogen, and / or Q4is a fibre-reactive radical of formula -(CH2)2-3-SO2-Y5(4a).

[0064] Alternatively, Qi and Q2are each -(CH2)2.3-SO2-Y2(3a),

[0065] Q3is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a), and / or Q4is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a).

[0066] Even more preferably, Qi and Q2are each -(CH2)2.3-SO2-Y2(3a),

[0067] Q3is hydrogen, and Q4is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a).

[0068] Alternatively, Qi and Q2are each -(CH2)2.3-SO2-Y2(3a),

[0069] Q3is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a), and Q4is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a).

[0070] Yi, Y2, Y3, Y4, Y5and Y6are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions. Groups removable under alkaline conditions U include -Cl, -Br, -F, -OSO3M, -SSO3M, -OCO-CH3, -OPO3M2, -OCO-C6H5, -OSO2- Ci-C4alkyl or -OSO2-N(Ci-C4alkyl)2.

[0071] U is preferably a group of the formula -Cl, -OSO3M, -SSO3M, -OCO-CH3, -OCO-C6H5or - OPO3M2, especially -Cl or -OSO3M.

[0072] Sulfo groups -SO3M are present either in free acid form, wherein M is hydrogen, or in salt form. Preferably, sulfo groups -SO3M are present in their free acid form, wherein M is hydrogen.

[0073] M may be an alkali metal, alkaline earth metal or hydrogen. M may also be ammonium, an organic amine, or mixtures thereof. Examples for M may each independently of the other be Meissner Bolte M / ARCH-014-PC

[0074] - 8 - hydrogen, sodium, lithium, potassium or ammonium, a mono-, di- or tri -ethanolamine, preferably hydrogen.

[0075] Preferably, Yi, Y2, Y3, Y4, Y5and Y6are each independently of the other vinyl or a radical - CH2-CH2-U and U is -Cl or -OSO3M, wherein M is an alkali metal, alkaline earth metal or hydrogen, preferably hydrogen.

[0076] Preferbly m and / or v are the number 0. More preferably, m and v are the number 0.

[0077] Preferably, I and q are the number 0. Preferably, t and u are the number 1.

[0078] More preferably, I and q are the number 0, and t and u are the number 1.

[0079] Preferably, p and r are the number 0. Preferably, k and n are the number 2.

[0080] More preferably, p and r are the number 0, and k and n are the number 2.

[0081] Even more preferably, I and q are the number 0, t and u are the number 1, p and r are the number 0, and k and n are the number 2.

[0082] In a preferred embodiment, the at least one dye of formula (1) is at least one dye of formula wherein

[0083] Xi is a halogen, preferably chlorine,

[0084] Yi is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0085] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen. Meissner Bolte M / ARCH-014-PC

[0086] - 9 -

[0087] In a preferred embodiment, the at least one dye of formula (2) is at least one dye of formula (2a), wherein

[0088] X2is a halogen, preferably chlorine,

[0089] Y2is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0090] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0091] In a preferred embodiment, the at least one dye of formula (5) is at least one dye of formula (5a), wherein

[0092] Rs is hydrogen or Ci-C4alkyl, preferably hydrogen or ethyl,

[0093] X3is a halogen, preferably chlorine,

[0094] Y and Y4are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0095] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen. Meissner Bolte M / ARCH-014-PC

[0096] - 10 -

[0097] In a preferred embodiment, the at least one dye of formula (6) is at least one dye of formula wherein

[0098] X4is a halogen, preferably chlorine,

[0099] Y and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0100] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0101] In an alternative embodiment, the at least one dye of formula (6) is at least one dye of formula (6b), wherein

[0102] X4is a halogen, preferably chlorine,

[0103] Y and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0104] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen. Meissner Bolte M / ARCH-014-PC

[0105] - 11 -

[0106] In a more preferred embodiment, the at least one dye of formula (1) is at least one dye of formula (la), (la), the at least one dye of formula (2) is at least one dye of formula (2a), the at least one dye of formula (5) is at least one dye of formula (5a), the at least one dye of formula (6) is at least one dye of formula (6a), (6a), wherein Meissner Bolte M / ARCH-014-PC

[0107] - 12 -

[0108] R3 is hydrogen or Ci-C4alkyl, preferably hydrogen or ethyl,

[0109] Xi, X2, X3and X4are each independently of the other halogen, preferably chlorine,

[0110] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0111] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0112] In a preferred alternative embodiment, the at least one dye of formula (1) is at least one dye of formula (la), the at least one dye of formula (2) is at least one dye of formula (2a), (2a), the at least one dye of formula (5) is at least one dye of formula (5a), the at least one dye of formula (6) is at least one dye of formula (6b), (6b), Meissner Bolte M / ARCH-014-PC

[0113] - 13 - wherein

[0114] R3 is hydrogen or Ci-C4alkyl, preferably hydrogen or ethyl,

[0115] Xi, X2, X3and X4are each independently of the other halogen, preferably chlorine,

[0116] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0117] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0118] In an even more preferred embodiment, the at least one dye of formula (1) is at least one dye of formula (la), (la), the at least one dye of formula (2) is at least one dye of formula (2a), the at least one dye of formula (5) is at least one dye of formula (5a), Meissner Bolte M / ARCH-014-PC

[0119] - 14 - (5a), and the at least one dye of formula (6) is at least one dye of formula (6a), wherein

[0120] Rs is hydrogen or Ci-C4alkyl, preferably hydrogen or ethyl,

[0121] Xi, X2, X3and X4are each independently of the other halogen, preferably chlorine,

[0122] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0123] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0124] In a more preferred alternative embodiment, the at least one dye of formula (1) is at least one dye of formula (la), the at least one dye of formula (2) is at least one dye of formula (2a), Meissner Bolte M / ARCH-014-PC

[0125] - 15 - the at least one dye of formula (5) is at least one dye of formula (5a), the at least one dye of formula (6) is at least one dye of formula (6b),

[0126] (6b), wherein

[0127] R3 is hydrogen or Ci-C4alkyl, preferably hydrogen or ethyl,

[0128] Xi, X2, X3and X4are each independently of the other halogen, preferably chlorine,

[0129] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0130] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0131] Preferably, a dye of formula (6), (6a) or (6b) is only present in the dye mixture, if R3 in formula (5) or (5a) is hydrogen Meissner Bolte M / ARCH-014-PC

[0132] - 16 -

[0133] In a preferred embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), (laa), wherein

[0134] Yi is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0135] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0136] In a preferred embodiment, the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), (2aa). wherein

[0137] Y2is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0138] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0139] In a preferred embodiment, the at least one dye of formula (5) or (5a) is at least one dye of formula (5aa) or formula (5ab), Meissner Bolte M / ARCH-014-PC

[0140] - 17 - , wherein

[0141] Y and Y4are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0142] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0143] In a preferred embodiment, the at least one dye of formula (6) or (6a) is at least one dye of formula (6aa), wherein

[0144] Y and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0145] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen. Meissner Bolte M / ARCH-014-PC

[0146] - 18 -

[0147] In an alternative embodiment, the at least one dye of formula (6) or (6b) is at least one dye of formula (6ba),

[0148] (6ba) wherein

[0149] Y and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0150] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0151] In a more preferred embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), (laa), the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), Meissner Bolte M / ARCH-014-PC

[0152] - 19 - the at least one dye of formula (5) or (5a) is at least one dye of formula (5aa) or (5ab), , and / or the at least one dye of formula (6) or (6a) is at least one dye of formula (6aa), (6aa), wherein

[0153] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0154] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0155] In an alternative embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), Meissner Bolte M / ARCH-014-PC

[0156] - 20 - (laa), the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), (2aa), the at least one dye of formula (5) or (5a) is at least one dye of formula (5aa) or (5ab), , and / or the at least one dye of formula (6) or (6b) is at least one dye of formula (6ba), Meissner Bolte M / ARCH-014-PC

[0157] - 21 - wherein

[0158] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0159] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0160] In a further preferred embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), (laa), the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), (2aa), the at least one dye of formula (5) or (5a) is at least one dye of formula (5aa), Meissner Bolte M / ARCH-014-PC

[0161] - 22 - (5aa), and the at least one dye of formula (6) or (6a) is at least one dye of formula (6aa), (6aa), wherein

[0162] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0163] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0164] In a preferred alternative embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), (laa), the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), Meissner Bolte M / ARCH-014-PC

[0165] - 23 - (2aa), the at least one dye of formula (5) or (5a) is at least one dye of formula (5aa), (5aa), and the at least one dye of formula (6) or (6b) is at least one dye of formula (6ba), wherein

[0166] Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0167] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0168] In an alternative embodiment, the at least one dye of formula (1) or (la) is at least one dye of formula (laa), Meissner Bolte M / ARCH-014-PC

[0169] - 24 - (laa), the at least one dye of formula (2) or (2a) is at least one dye of formula (2aa), (2aa), and the at least one dye of formula (5) or (5a) is at least one dye of formula (5ab), (5ab), wherein

[0170] Y, Yi, Y2and Y4, are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, and

[0171] M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0172] An example of a dye of formula (1), (la) and (laa) is dye (101) Meissner Bolte M / ARCH-014-PC

[0173] - 25 -

[0174] An example of a dye of formula (2), (2a) and (2aa) is dye (201) (201).

[0175] An example of a dye of formula (5), (5a) and (5aa) is dye (501) (501).

[0176] An example of a dye of formula (5), (5a) and (5ab) is dye (502) (502).

[0177] An example of a dye of formula (6), (6a) and (6aa) is dye (601) Meissner Bolte M / ARCH-014-PC

[0178] - 26 - (601).

[0179] An example of a dye of formula (6), (6b) and (6ba) is dye (602) (602).

[0180] Other possbile examples include dyes of formulae (101), (201), (501), (502), (601) and (602), wherein at least one vinyl group of each formula may be replaced by a radical -CH2- CH2-U and U is a group removable under alkaline conditions, preferably -Cl or -OSO3M, wherein M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, preferably hydrogen.

[0181] Preferably, other possible examples include dyes of formulae (101), (201), (501), (502), (601) and (602), wherein at least one vinyl group, such as one or two vinyl groups, is replaced by a radical -CH2-CH2-U and U is -Cl or -OSO3M, wherein M is hydrogen.

[0182] Preferably, the molar ratio of at least one dye of formula (2), preferably formula (2a), more preferbly (2aa), to at least one dye of formula (1), preferably formula (la), more preferably (laa), is from 1: 1 to 5: 1, preferably 2: 1 to 4: 1, more preferably 2: 1 to 3: 1. Meissner Bolte M / ARCH-014-PC

[0183] - 27 -

[0184] The molar ratio of at least one dye of formula (2), preferably formula (2a), more preferbly (2aa), to at least one dye of formula (1), preferably formula (la), more preferably (laa), may be 70:30.

[0185] More preferably, the molar ratio of at least one dye of formula (2a), preferbly (2aa), to at least one dye of formula (la), preferably (laa), is from 1:1 to 5:1, preferably 2:1 to 4: 1, more preferably 2:1 to 3: 1.

[0186] The molar ratio of at least one dye of formula (2a), preferbly (2aa), to at least one dye of formula (la), preferably (laa), may be 70:30.

[0187] Preferably, the molar ratio of at least one dye of formula (6), preferably formula (6a) or (6b), to at least one dye of formula (5), preferably formula (5a), is from 1:1 to 9:1, preferably 2:1 to 7:1, more preferably 3: 1 to 5:1, even more preferably 3:2 to 7:3.

[0188] The molar ratio of at least one dye of formula (6), preferably formula (6a) or (6b), to at least one dye of formula (5), preferably formula (5a), may be 6:4, 7:3, or 8:2, preferably 7:3.

[0189] More preferably, the molar ratio of at least one dye of formula (6a), preferably formula (6aa), or formula (6b), preferably formula (6ba), to at least one dye of formula (5a), preferably formula (5aa), is from 1:1 to 9: 1, preferably 2: 1 to 7:1, more preferably 3:1 to 5:1, even more preferably 3:2 to 7:3.

[0190] The molar ratio of at least one dye of formula (6a), preferably formula (6aa), or formula (6b), preferably formula (6ba), to at least one dye of formula (5a), preferably formula (5aa), may be 6:4, 7:3, or 8:2, preferably 7:3.

[0191] Alternatively, no dye of formula (6), (6a) or (6b) is present. Preferably, no dye of formula (6), (6a), (6aa), (6b) or (6ba) is present, if formula (5) or (5a) is formula (5ab).

[0192] Preferably, the weight ratio of the combination of at least one dye of formula (2), preferably formula (2a), and at least one dye of formula (1), preferably formula (la), to the combination of at least one dye of formula (5), preferably formula (5a), and at least one dye Meissner Bolte M / ARCH-014-PC

[0193] - 28 - of formula (6), preferably formula (6a) or (6b), is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:1 to 3:2, if a dye of formula (6) is present.

[0194] More preferably, the weight ratio of the combination of at least one dye of formula (2a), preferably formula (2aa), and at least one dye of formula (la), preferably formula (laa), to the combination of at least one dye of formula (5a), preferably formula (5aa), and at least one dye of formula (6a), preferably formula (6aa), or formula (6b), preferably formula (6ba), is from 1:4 to 4: 1, preferably 1:3 to 3:1, more preferably 1: 1 to 3:2, if a dye of formula (6) is present.

[0195] The weight ratio of the combination of at least one dye of formula (2a), preferably formula (2aa), and at least one dye of formula (la), preferably formula (laa), to the combination of at least one dye of formula (5a), preferably formula (5aa), and at least one dye of formula (6a), preferably formula (6aa), or formula (6b), preferably formula (6ba), may be 55:45, if a dye of formula (6) is present.

[0196] Preferably, the weight ratio of the combination of at least one dye of formula (2), preferably formula (2a), and at least one dye of formula (1), preferably formula (la), to at least one dye of formula (5), preferably formula (5a), is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1: 1 to 3:2, if a dye of formula (6) is not present.

[0197] More preferably, the weight ratio of the combination of at least one dye of formula (2a), preferably formula (2aa), and at least one dye of formula (la), preferably formula (laa), to at least one dye of formula (5a), preferably formula (5ab), is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:1 to 3:2, if a dye of formula (6) is not present.

[0198] The weight ratio of the combination of at least one dye of formula (2), preferably formula (2a), and at least one dye of formula (1), preferably formula (la), to at least one dye of formula (5), preferably formula (5a), may be 55:45, if a dye of formula (6) is not present.

[0199] In a preferred embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1: 1 to 5:1, preferably 2: 1 to 4:1, more preferably 2:1 to 3: 1, Meissner Bolte M / ARCH-014-PC

[0200] - 29 - the molar ratio of at least one dye of formula (601), to at least one dye of formula (501), is from 1:1 to 9:1, preferably 2:1 to 7: 1, more preferably 3:1 to 5:1, even more preferably 3:2 to 7:3, and / or the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (601), is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:1 to 3:2, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (601), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0201] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1:1 to 5:1, preferably 2: 1 to 4:1, more preferably 2:1 to 3:1, the molar ratio of at least one dye of formula (602), to at least one dye of formula (501), is from 1:1 to 9:1, preferably 2:1 to 7: 1, more preferably 3:1 to 5:1, even more preferably 3:2 to 7:3, and / or the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (602), is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:1 to 3:2, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (602), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0202] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1:1 to 5:1, preferably 2: 1 to 4:1, more preferably 2:1 to 3:1, and / or the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to at least one dye of formula (502) is from 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:1 to 3:2, if a dye of formula (6) is not present, Meissner Bolte M / ARCH-014-PC

[0203] - 30 - wherein at least one vinyl group in formulae (101), (201) and (502), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0204] In a preferred embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1: 1 to 5: 1, preferably 2: 1 to 4: 1, more preferably 2: 1 to 3: 1, the molar ratio of at least one dye of formula (601), to at least one dye of formula (501), is from 1: 1 to 9: 1, preferably 2: 1 to 7: 1, more preferably 3: 1 to 5: 1, even more preferably 3:2 to 7:3, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (601), is from 1:4 to 4: 1, preferably 1:3 to 3: 1, more preferably 1: 1 to 3:2, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (601), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0205] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1: 1 to 5: 1, preferably 2: 1 to 4: 1, more preferably 2: 1 to 3: 1, the molar ratio of at least one dye of formula (602), to at least one dye of formula (501), is from 1: 1 to 9: 1, preferably 2: 1 to 7: 1, more preferably 3: 1 to 5: 1, even more preferably 3:2 to 7:3, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (602), is from 1:4 to 4: 1, preferably 1:3 to 3: 1, more preferably 1: 1 to 3:2, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (602), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen. Meissner Bolte M / ARCH-014-PC

[0206] - 31 -

[0207] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is from 1: 1 to 5: 1, preferably 2: 1 to 4: 1, more preferably 2: 1 to 3: 1, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to at least one dye of formula (502) is from 1:4 to 4: 1, preferably 1:3 to 3: 1, more preferably 1: 1 to 3:2, if a dye of formula (6) is not present, wherein at least one vinyl group in formulae (101), (201) and (502), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0208] In a preferred embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is 70:30, the molar ratio of at least one dye of formula (601), to at least one dye of formula (501), is from 1: 1 to 9: 1, preferably 2: 1 to 7: 1, more preferably 3: 1 to 5: 1, even more preferably 3:2 to 7:3, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (601), is 55:45, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (601), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0209] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is 70:30, the molar ratio of at least one dye of formula (602), to at least one dye of formula (501), is from 1: 1 to 9: 1, preferably 2: 1 to 7: 1, more preferably 3: 1 to 5: 1, even more preferably 3:2 to 7:3, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to the combination of at least one dye of formula (501) and at least one dye of formula (602), is 55:45, if a dye of formula (6) is present, wherein at least one vinyl group in formulae (101), (201), (501) and (602), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen. Meissner Bolte M / ARCH-014-PC

[0210] - 32 -

[0211] In an alternative embodiment, the molar ratio of at least one dye of formula (201), to at least one dye of formula (101), is 70:30, and the weight ratio of the combination of at least one dye of formula (201) and at least one dye of formula (101), to at least one dye of formula (502) is 55:45, if a dye of formula (6) is not present, wherein at least one vinyl group in formulae (101), (201) and (502), such as one or two vinyl groups, may be replaced by a radical -CH2-CH2-U, wherein U is -Cl or -OSO3M, wherein M is hydrogen.

[0212] The dyes of formulae (1), (2), (5) and (6) are known in some cases, or they can be prepared in accordance with processes known per se, such as by customary diazotization, coupling and condensation reactions as described, for example, in EP 0141367 Al, US-A-4341699, GB-A-1576237, US-A-4754023, EP-A-94055, US-A-5298607 and WO 2002085986 Al.

[0213] A variant of the processes known per se comprises first condensing one of (i) the amino substituted azo compound and (ii) the amine carrying the reactive group with (iii) cyanuric halide, for example, cyanuric chloride or cyanuric fluoride, and reacting the resulting reaction product with the other of the (i) amino substituted azo dye and (ii) the amine carrying the reactive group, which has been condensed beforehand with cyanuric halide. Alternatively, the precursor of (i) the amino azo dye is condensed with the primary condensation product of (ii) the amine carrying the reactive group and (iii) cyanuric halide, and the resulting secondary condensation product is subsequently diazotated and coupled (analogously to the process described in Example 3 of US-A-5298607).

[0214] The condensation reactions between (i) the amino substituted azo compound, the precursor of (i), (ii) the amine carrying the reactive group and cyanuric halide are generally carried out analogously to known processes, usually in aqueous solution at temperatures of, for example, from 0 to 70°C and a pH of, for example, from 3 to 10.

[0215] 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- Meissner Bolte M / ARCH-014-PC

[0216] - 33 -

[0217] Y, -SO2-Y1, -SO2-Y2, -SO2-Y4 and / or -SO2-Y5 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.

[0218] 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.

[0219] The dye mixture according to the invention can be prepared, for example, by mixing the individual dyes together. The mixing procedure is affected, for example, in suitable mills, e.g. ball mills or pin mills, as well as in kneaders or mixers. The dye mixtures according to the invention can also be prepared, for example, by dissolving the reactive dyes of formulae (1), (2) and (5), or formulae (1), (2), (5) and (6) directly in the dyebath or the printing medium.

[0220] The invention further relates to the use of the dye mixture as a dyeing agent and / or as a printing agent.

[0221] The reactive dye mixtures according to the invention may comprise further additives, for example sodium chloride or dextrin.

[0222] If desired, the reactive dye mixtures according to the invention may comprise further auxiliaries which, for example, improve handling or increase storage stability, such as buffers, dispersants or anti-dusts. Such auxiliaries are known to the person skilled in the art.

[0223] All definitions and preferred embodiments, as set forth above, apply analogously, to the use of the dye mixture.

[0224] The dye mixture is suitable for the dyeing and I or printing of an extremely wide variety of materials, especially hydroxy-group-containing or nitrogen-containing fibre materials. Examples thereof are paper, silk, leather, wool, polyamide fibres and polyurethanes as well as, especially, cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dye mixture according to the invention invention are also suitable for the dyeing or printing of hydroxy-group-containing fibres that are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres. Meissner Bolte M / ARCH-014-PC

[0225] - 34 -

[0226] The said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of fibres, yarn, woven fabric or knitted fabric.

[0227] Accordingly, the present invention also relates to a method for the dyeing or printing of hydroxy-group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials, which method comprises using at least one dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (1), together with at least one dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (2), together with at least one dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (5) and and / or at least one dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (6) wherein Ri, R2, R3, R4, Qi, Qz, Q3, Q4, XI, X2, X3, X4, Yi, Y2, Y3, Y4, Y5, Y6, ZI, Z2, Z3, Z4, U, M, k, n, p, r, I, q, t, u, m and v each have the meanings and preferred meanings defined above.

[0228] The dye mixture according to the invention is 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.

[0229] Preferably, the dye mixture is used for dyeing or printing a fabric. Preferably, the fabric contains cellulose acetate, cotton, polyamide, polyester, polyacrylonitril and / or wool. In another embodiment, the fabric consists of cellulose acetate, cotton, polyamide, polyester, polyacrylonitril and / or wool.

[0230] The invention further relates to a method for dyeing a fabric with a dye mixture, comprising the following steps: i) dyeing a fabric, preferably a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitril and / or wool, with the dye mixture, and ii) drying the dyed fabric of i), preferably with dry heat or steam.

[0231] All definitions and preferred embodiments, as set forth above, apply analogously, to the method for dyeing a fabric with the dye mixture. Meissner Bolte M / ARCH-014-PC

[0232] - 35 -

[0233] The method for dyeing a fabric with a dye mixture according to the invention can be carried out in accordance with customary dyeing methods, for example, according to the so-called cold pad-batch process, in which the dye mixture 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. Preferably, the method for dyeing according to the invention is carried out according to the exhaust-dyeing method, in which the goods, preferably materials or fabrics, more preferably hydroxy-containing or nitrogen-containing fibre, are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.

[0234] The dye solution, also called dye liquor, in addition to containing water and the dyes, may also comprise further additives, for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellants, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.

[0235] The amounts in which the dye mixtures or the individual dyes are used in the dye solution 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 on the print paste, have proved advantageous.

[0236] The inventive dye mixtures used in accordance with the method of the present invention are distinguished by high and uniform colour build-up, good exhaustion and fixing behaviour, good constancy of shade even in different concentrations, a low sensitivity to various dyeing parameters and, in particular, very good combinability. Dyeing times can be reduced. Furthermore, they have sufficient substantivity and at the same time have a very good ease of washing off of unfixed dye and can advantageously be applied at short liquor ratios, for example, at a liquor ratio of from 1:4 to 1:6, preferably 1:6. The dyeings produced in accordance with the method of the invention exhibit brilliant shades of very good fastness properties, such as fastness to washing, to water, to sea water, to cross-dyeing and to Meissner Bolte M / ARCH-014-PC

[0237] - 36 - perspiration, as well as good fastness to chlorine, to pleating, to hot-pressing and to rubbing, and good reproducibility.

[0238] The invention further relates to a dyed fabric obtainable by the method of dyeing a fabric with a dye mixture.

[0239] All definitions and preferred embodiments, as set forth above, apply analogously, to the dyed fabric.

[0240] The dye mixtures and dyes according to the invention 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 implements, such as fountain pens or ballpoint pens, and especially ink-jet printers. For that purpose, the dye mixture according to the invention are first converted into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink comprising at least one dye of the dye mixture according to the invention as colorant. The inks can be prepared in customary manner by mixing together the individual constituents customary in ink-jet printing in the desired amount of water. Conveniently, individual inks, comprising at least one dye of formula (1), at least one dye of formula (2), at least one dye of formula (5) and / or one dye of formula (6) are used in a multi color ink-jet printer and mixing is affected on the substrate by digital printing.

[0241] Examples of substrates that come into consideration for ink-jet printing, in addition to paper or plastics films, include the above-mentioned hydroxy-group-containing or nitrogen containing fibre materials, especially cellulosic fibre materials. The substrates are preferably textile fibre materials.

[0242] The following Examples serve to illustrate the invention. Unless otherwise indicated therein, parts are parts by weight and percentages are percentages by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

[0243] Temperatures are given in degrees Celsius. Meissner Bolte M / ARCH-014-PC

[0244] - 37 -

[0245] Examples

[0246] The washing fastness, fixation properties, and exhaustion and build-up properties of Red 1 or Red 3 have been compared to the mixtures as outlined in Table 1. The results of these comparisons have been summarized in Tables 2 to 6. The dyes, dye mixtures and scientific parameters are defined as follows:

[0247] Red 1 is a mixture of the dyes with formula (201) and formula (101) with a molar ratio of 70:30 (formula (201) : formula (101))

[0248] (201) (101).

[0249] Red 2 VS is a mixture of the dyes with formula (601) and formula (501) with a molar ratio of

[0250] 70:30 (formula (601) : formula (501))

[0251] (601) (501).

[0252] Red 2 SAS is a mixture of the dyes with formula (501), wherein the-CH2-CH2-OSO3M or -CH2- CH2-CI groups are cleavable under alkaline conditions, and formula (601), wherein the -CH2- CH2-OSO3M groups are cleavable under alkaline conditions, with a molar ratio of 70:30 (formula (601) : formula (501). Meissner Bolte M / ARCH-014-PC

[0253] - 38 -

[0254] (601) with cleavable group, (501) with cleavable group.

[0255] Red 3 is a dye of formula (502), wherein the -CH2-CH2-OSO3M groups are cleavable under alkaline conditions

[0256] (502) with cleavable group.

[0257] All dyes have been treated alike and according to the following protocols in order to obtained the comparative data.

[0258] Table 1 : Examples of dyes mixes in weight% ratio Meissner Bolte M / ARCH-014-PC

[0259] - 39 -

[0260] E25

[0261] All dyes have been synthesized in a standard lab using the state-of-the-art knowledge and are not further formulated. The dyes were dialyzed (salt removal), dried, adjusted to same color strength E25=0.6 before being tested in exhaustion conditions.

[0262] RD@ 8%, Cone, % @ 1 RD

[0263] Bezugstiefe (BZT) or Reference Depth (RD) is a unit to determine / classify a depth of a color / shade.

[0264] It is determined how much dyestuff is needed to reach a specific depth, which is in the present case 1 RD. Similar strength comparisons could also be done with the Hilfstypen-Richttyptiefen / Standard Depth (SD). Measurements are done with a Datacolor spectrophotometer. a* / b*CIELAB values

[0265] Color values in the CIELAB color space (also referred to as L*a*b*) are determined with a standard spectrophotometer. Values are reported in Table 2

[0266] Table 2: Exhaustion: CIELAB values at same strength E25

[0267] Wash 60°C

[0268] Wash 60°C is a test for color fastness to domestic and commercial laundering. Meissner Bolte M / ARCH-014-PC

[0269] - 40 -

[0270] The following Examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

[0271] Example 1: Exhaust Dyeing - Build-Up:

[0272] A cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1: 10 which contains the amount of dyes mix examples as reported in Table 1 and sodium chloride as indicated in Table 3.

[0273] Table 3: Composition of dyebaths 1 to 6 containing dyes mix examples as reported in Table 1

[0274] * % of dyestuff mixture or dyestuff is with respect to the weight of the cotton fabric

[0275] After 30 minutes at 60°C, calcined sodium carbonate is added in the amount given in Table 1 over 30 minutes time. Dyeing is continued for 40 to 80 minutes. The dyed goods are then rinsed with water, soaped and rinsed again and then dried.

[0276] The tinctorial strengths of the red dyeings obtained with the dyeing liquors 1 to 6 of Table 3 are measured photospectrometrically. Table 4 shows the build-up properties of the dyes and dyes mix examples as reported in Table 1. 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. Meissner Bolte M / ARCH-014-PC

[0277] - 41 -

[0278] T able 4: Build-up: dependance of reference depth (RD) from dye concentration

[0279] Example 2: Exhaust Dyeing - Fastness:

[0280] A bleached cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 10: 1 which contains 40 g / l of sodium chloride, and appropriate dye % of each dye or dye mix according to table 1.

[0281] After 30 minutes at 60°C, 5.0 g / l of calcined sodium carbonate are added to the dyebath over 30 minutes time. Dyeing is continued for 60 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 10: 1 at 60°C.

[0282] This washing treatment is repeated another one time. Further washing treatments are then successively repeated one time at 95°C, at 70°C and at 60°C. Red 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.

[0283] Washing off: The measurements and therefore evaluation of the washing off profile and performance are done on a MATHIS COLORSTAR® System using the SMART LIQUOR® software, both being commercially available and very well known in the dyeing field.

[0284] The Software calculates values out of washed fabric after dyeing by considering the extracted amount of dye after each subsequent washing step (W1 to W5). Changes in colour are determined according to the wash off calculation.

[0285] As example, if the entire unfixed dye were removed during the first wash, the parameter would be 100. Meissner Bolte M / ARCH-014-PC

[0286] - 42 -

[0287] Table 5: Exhaustion: Washing off values for reference and new mix products

[0288] The lower the calculated values are, the better the fixation and the washing off properties are and therefore the superior fastness properties are. The data of Tables 4, 5 and 6 demonstrate that the fabric dyed with the inventive dyestuff mixture exhibit good fastness and overall properties.

[0289] Table 6: Exhaustion: fixation values for reference and new mix products

[0290] Printing Procedure I

[0291] 3 parts of a mixture Mix Red 1 1 Red 2 SAS are sprinkled, with rapid stirring, into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. The print paste so obtained is used to print a cotton fabric, and the resulting printed material is dried and steamed in saturated steam for 2 minutes at 102°C. The printed fabric is then rinsed, if desired soaped at the boil and rinsed again, and subsequently dried. Meissner Bolte M / ARCH-014-PC

[0292] - 43 -

[0293] Printing Procedure II

[0294] (a) Mercerised cotton-satin is padded using a liquor containing 30 g / l of sodium carbonate and 50 g / l of urea (liquor uptake 70%) and dried.

[0295] (b) The cotton-satin pre-treated according to Step (a) is printed using an aqueous ink containing

[0296] - 15 % of a mixture Mix Red 1 1 Red 2 SAS,

[0297] - 15 % of 1,2-propylene glycol and

[0298] - 70 % of water using a drop-on-demand inkjet head (bubble jet). The print is dried completely and fixed in saturated steam at 102°C for 8 minutes, cold-rinsed, washed off at the boil, rinsed again and dried.

Claims

1. Meissner Bolte M / ARCH-014-PC- 44 -Claims1. A dye mixture comprising: at least one dye with formula (1),at least one dye of formula (2),at least one dye of formula (5),and optionally at least one dye of formula (6)Meissner Bolte M / ARCH-014-PC- 45 -whereinRi and R3 are each independently of the other hydrogen or Ci-C4alkyl,R2 and R4are each independently of the other hydrogen or Ci-C4alkyl, Ci-C4alkoxy or sulfo,Qi and Q2are each independently of the other and are a fibre-reactive radical of formula-(CH2)2-3-SO2_Y2 (3a) or-(CH2)2-3-O-(CH2)2-3-SO2-Y3 (3b),Q3and Q4are independently of each other selected from a group consisting of hydrogen, Ci- C4alkyl and a fibre-reactive radical of formula-(CH2)2-3-SO2-Y5(4a) or-(CH2)2-3-O-(CH2)2-3-SO2-Y6 (4b), wherein at least one of Q3and Q4is formula (4a) or (4b),Xi, X2, X3and X4are each independently of the other halogen, 3-carboxypyridin-l-yl or 3- ca rba m oy I py ri d i n- 1 -y I ,Yi, Y2, Y3, Y4, Y5and Y6are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions,Zi, Z2, Z3, and Z4are each independently of the other -SO2-Y, wherein Y is vinyl or a radical - CH2-CH2-U and U is a group removable under alkaline conditions,Meissner Bolte M / ARCH-014-PC- 46 -M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, k, n, p and r are each independently of the other the number 0, 1 or 2, l, q, t and u are each independently of the other the number 0 or 1, m and v are each independently of the other the number 0 or 1, wherein the diazo component of the dye of formula (1), the diazo component of the dye of formula (2), the diazo component of the dye of formula (5) and the diazo component of the dye of formula (6) each independently of the other are a benzene radical or a naphthyl radical, and wherein the dyes of formula (1) and formula (5) are different from each other, and wherein the dyes of formula (2) and formula (6) are different from each other, if a dye of formula (6) is present.

2. Dye mixture according to claim 1, wherein the diazo component of the dye of formula (1) and / or the diazo component of the dye of formula (2) are a naphtyl radical, and / or the diazo component of the dye of formula (5) and / or the diazo component of the dye of formula (6) are a benzene radical.

3. Dye mixture according to claims lor 2, wherein Ri, R2, R3 and / or R4are hydrogen or Ci-C4alkyl, and / or wherein Xi, X2, X3 and / or X4, are each independently of the other halogen, preferably Chlorine.

4. Dye mixture according to at least one of claims 1 to 3, wherein Qi and / or Q2are a fibre-reactive radical of formula -(CH2)2.3-SO2-Y2(3a), Q3is a fibre-reactive radical of formula -(CH2)2.3-SO2-Y5(4a) or hydrogen, and / or Q4is a fibre- reactive radical of formula -(CH2)2.3-SO2-Y5(4a), and / or wherein m and / or v are the number 0.

5. Dye mixture according at least one of claims 1 to 4,Meissner Bolte M / ARCH-014-PC- 47 - wherein I and q are the number 0, and / or t and u are the number 1.

6. Dye mixture according to at least one of claims 1 to 5, wherein k and / or n are the number 2, and / or p and / or r are the number 0.

7. Dye mixture according to at least one of claims 1 to 6, wherein the at least one dye of formula (1) is at least one dye of formula (la),wherein the at least one dye of formula (2) is at least one dye of formula (2a),wherein the at least one dye of formula (5) is at least one dye of formula (5a), and / orwherein the at least one dye of formula (6) is at least one dye of formula (6a),Meissner Bolte M / ARCH-014-PC- 48 -whereinR3 is hydrogen or Ci-C4alkyl,Xi, X2, X3and X4are each independently of the other halogen, preferably chlorine,Y, Yi, Y2, Y4, and Y5are each independently of the other vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, andM is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

8. Dye mixture according to at least one of claims 1 to 7, wherein the molar ratio of at least one dye of formula (2), preferably formula (2a), to at least one dye of formula (1), preferably formula (la), is from 1: 1 to 5: 1, preferably 2: 1 to 4: 1, more preferably 2: 1 to 3: 1.

9. Dye mixture according to at least one of claims 1 to 8, wherein the molar ratio of at least one dye of formula (6), preferably formula (6a), to at least one dye of formula (5), preferably formula (5a), is from 1: 1 to 9: 1, preferably 2: 1 to 7: 1, more preferably 3: 1 to 5: 1, or wherein no dye of formula (6) is present.

10. Dye mixture according to at least one of claims 1 to 9, wherein the molar ratio of at least one dye of formula (2), preferably formula (2a), and at least one dye of formula (1), preferably formula (la), to at least one dye of formula (5), preferably formula (5a), and at least one dye of formula (6), preferably formula (6a), is from 1:4 to 4: 1, preferably 1:3 to 3: 1, more preferably 1: 1 to 3:2, if a dye of formula (6) is present.Meissner Bolte M / ARCH-014-PC- 49 -11. Dye mixture according to at least one of claims 1 to 9, wherein the molar ratio of at least one dye of formula (2), preferably formula (2a), and at least one dye of formula (1), preferably formula (la), to at least one dye of formula (5), preferably formula (5a), is from 1:4 to 4: 1, preferably 1:3 to 3: 1, more preferably 1: 1 to 3:2, if a dye of formula (6) is not present.

12. Use of a dye mixture according to at least one of claims 1 to 11 as a dyeing agent and / or as a printing agent.

13. Use according to claim 12 for dyeing or printing a fabric, preferably a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitril and / or wool,14. Method for dyeing a fabric with a dye mixture, comprising the following steps: i) dyeing a fabric, preferably a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitril and / or wool, with a dye mixture according to at least one of claims 1 to 11, and ii) drying the dyed fabric of i), preferably with dry heat or steam.

15. A dyed fabric obtainable by the method according to claim 14.

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