The practice of dyeing has recently led to higher demands being made on the quality of the dyeings and the profitability of the dyeing process. As a result, there continues to be a need for novel, readily obtainable dyeing compositions having good properties, especially in respect of their application.

Dyeing today requires reactive dyes that, for example, have sufficient substantivity and at the same time exhibit good ease of washing-off of unfixed dye. In addition, they should exhibit a good colour yield and a high reactivity, the objective being especially to obtain dyeings having high degrees of fixing. In many cases, the build-up behaviour of reactive dyes is not sufficient to meet the demands, especially in the dyeing of very deep shades.

The problem underlying the present invention is therefore to provide new mixtures of reactive dyes, which mixtures are especially suitable for dyeing and printing fibre materials and which possess the above-described qualities to a high degree. They should also yield dyeings having good all-round fastness properties, for example fastness to light and to wetting.

The present invention accordingly relates to dye mixtures comprising at least one dye of formula together with at least one dye from the group of formulae

wherein Ri and R2 are each independently of the other hydrogen or unsubstituted or substituted C1-C8alkyl, R3 and R4 are each independently of the other hydrogen or unsubstituted or substituted C1-C4alkyl, (R5) 0-3 denotes from 0 to 3 identical or differing substituents from the group halogen, C1-C4alkyl, C1-C4alkoxy, carboxy, nitro and sulfo, A is unsubstituted or substituted phenylen, unsubstituted or substituted naphthylene, or C2- C8alkylene which may be interrupted by oxygen, D1 and D2 are each independently of the other the radical of a diazo component of the benzene or naphthalene series, q and r are each independently of the other the number 0 or 1, Xi is halogen or a non-fibre-reactive substituent, and Y1 and Y2 are each independently of the other a radical of formula -SO2-Z (3a), - NH-CO- (CH2) m-SO2-Z (3b), - CONH- (CH2) n~SO2~Z (3c), -NH-CO-CH(Hal)-CH2-Hal (3d), -NH-CO-C(Hal)=CH2 (3e) or

wherein X2 is halogen, T1 independently has the definition of X2, is a non-fibre-reactive substituent or is a fibre-reactive radical of formula wherein Z is vinyl or a radical-CH2-CH2-U and U is a group that is removable under alkaline conditions, Q is a group-CH (Hal)-CH2-Hal or-C (Hal) =CH2, m and n are each independently of the other the number 2,3 or 4, Hal is halogen, Y3 is a radical of the above-mentioned formula (3a), or is a radical of formula

wherein s is the number 0 or 1, and X3 is halogen or C1-C4akylsulfonyl, X4 iS halogen or C1-C4alkyl and T2 is hydrogen, cyano or halogen, and V is C2-C4alkanoyl, benzoyl which is unsubstituted or is substituted by a radical of formula (3g), or is a radical of formula

wherein X5 is halogen, and T3 is a non-fibre-reactive substituent.

The diazo components in the dyes of formulae (2a) and (2b) are a phenyl radical or a naphthyl radical.

In the radical of formula (4c), Me is the methyl radical and Et is the ethyl radical. The mentioned radicals come into consideration, besides hydrogen, as substituents at the nitrogen atom.

As C1-C8alkyl there comes into consideration for Ri and R2 each independently of the other e. g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, n- heptyl or n-octyl. A C1-C4alkyl radical is of interest. The mentioned alkyl radicals may be unsubstituted or may be substituted e. g. by hydroxy, sulfo, sulfato, cyano, carboxy, C1-C4alkoxy or phenyl, preferably hydroxy, sulfato, Ci-C4a ! koxy or phenyl. Preference is given to the corresponding unsubstituted radicals.

As C1-C4alkyl there comes into consideration for R3 and R4 each independently of the other e. g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, ter-butyl or isobutyl, preferably methyl or ethyl and especially methyl. The mentioned alkyl radicals may be unsubstituted or may be substituted e. g. by hydroxy, sulfo, sulfato, cyano or carboxyl. Preference is given to the corresponding unsubstituted radicals.

Preferably, one of the radicals R1 and R2 is hydrogen and the other is one of the previously mentioned, unsubstituted or substituted d-Cgatkyt radicals.

Preferably, R4 is hydrogen and R3 is hydrogen or one of the previously mentioned, unsubstituted or substituted C1-C4alkyl radicals.

More especially, R1 and R2 are hydrogen.

More especially, R4 is hydrogen and R3 is hydrogen, methyl or ethyl.

Preferably, (R5) 0-3 denotes from 0 to 3 identical or differing substituents from the group halogen, C1-C4alkyl, C1-C4alkoxy and sulfo.

When the diazo component in the dye of formula (2a) is a naphthyl radical, there come into consideration for (R5) o-3 from 1 to 3, and especially 1 or 2, sulfo groups. The naphthyl radical is bonded to the azo group preferably in the 2-position.

When the diazo component in the dye of formula (2a) is a phenyl radical, there come into consideration for (R5) o-3 from 0 to 3, preferably from 0 to 2, identical or differing substituents from the group chlorine, methyl, methoxy and sulfo. q is preferably the number 0.

The radicals D1 and D in the dye mixtures according to the invention may contain the substituents that are customary for azo dyes.

From the range of substituents there may be mentioned by way of example : alkyl groups having from 1 to 12 carbon atoms, especially from 1 to 4 carbon atoms, such as methyl, ethyl, n-or iso-propyl, or n-, iso-, sec-or tert-butyl ; alkoxy groups having from 1 to 8 carbon atoms, especially from 1 to 4 carbon atoms, such as methoxy, ethoxy, n-or iso-propoxy, or n-, iso-, sec-or tert-butoxy; C1-C4alkoxy substituted in the alkyl moiety, for example by hydroxy, C1-C4alkoxy or sulfato, e. g. 2-hydroxyethoxy, 3-hydroxypropoxy, 2-sulfatoethoxy, 2- methoxyethoxy or 2-ethoxyethoxy; alkanoylamino groups having from 2 to 8 carbon atoms, especially C2-C4alkanoylamino groups, such as acetylamino or propionylamino ; benzoyl- amino or C2-C4alkoxycarbonylamino groups, such as methoxycarbonylamino or ethoxy- carbonylamino ; amino; N-mono-or N, N-di-C1-C4alkylamino which is unsubstituted or is substituted in the alkyl moiety, for example by hydroxy, sulfo, sulfato or C1-C4alkoxy, e. g. methylamino, ethylamino, N, N-dimethyl-or N, N-diethylamino, sulfomethylamino, ß-hydroxy- ethylamino, N, N-di (ß-hydroxyethylamino), N-ß-sulfatoethylamino ; phenylamino which is unsubstituted or is substituted in the phenyl moiety by methyl, methoxy, halogen or sulfo ; N- C1-C4alkyl-N-phenylamino which is unsubstituted or is substituted in the alkyl moiety by hydroxy, sulfo or sulfato or in the phenyl moiety by methyl, methoxy, halogen or sulfo, e. g. N- methyl-N-phenylamino, N-ethyl-N-phenylamino, N-p-hydroxyethyl-N-phenylamino or N-ß- sulfoethyl-N-phenylamino ; naphthylamino which is unsubstituted or is substituted by sulfo ; alkanol groups having from 2 to 8 carbon atoms, especially from 2 to 4 carbon atoms, for example acetyl or propionyl ; benzoyl ; alkoxycarbonyl having from 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl ; alkylsulfonyl having from 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl ; phenyl-or naphthyl-sulfonyl ; trifluor- methyl, nitro, cyano, hydroxy, halogen, such as fluorine, chlorine or bromine; carbamoyl, N- C1-C4alkylcarbamoyl, such as N-methylcarbamoyl or N-ethylcarbamoyl ; sulfamoyl, N-Cl-C4- alkylsulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropyl- sulfamoyl or N-butylsulfamoyl ; N-(ß-hydroxyethyl)-sulfamoyl, N, N-di (P-hydroxyethyl) sulfam- oyl, N-phenylsulfamoyl, ureido, carboxy, sulfomethyl, sulfo or sulfato as well as fibre-reactive radicals. The alkyl radicals may, in addition, be interrupted by oxygen (-O-) or by an amino group (-NH-,-N (C1-C4alkyl)-).

In one embodiment of the present invention that is of interest, at least one of the radicals D and D2 carries at least one fibre-reactive group.

In another embodiment of the present invention that is of interest, each of the radicals D1 and D2 carries at least one fibre-reactive group.

Fibre-reactive radicals are to be understood as being those that are capable of reacting with the hydroxy groups of cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk, or with the amino and possibly the carboxy groups of synthetic polyamides to form covalent chemical bonds. The fibre-reactive radicals are generally bonded to the dye radical directly or via a bridging member. Suitable fibre-reactive radicals are, for example, those having at least one removable substituent on an aliphatic, aromatic or heterocyclic radical, or those wherein the mentioned radicals contain a radical suitable for reaction with the fibre material, such as, for example, a vinyl radical.

Such fibre-reactive radicals are known perse and a large number of them have been described, for example in Venkataraman"The Chemistry of Synthetic Dyes"Volume 6, pages 1-209, Academic Press, New York, London 1972 or in US-A-5 684 138.

Preferably, D1 and D2 are each independently of the other a radical of formula wherein (R6) 0. 3 denotes from 0 to 3 identical or differing substituents from the group halogen, Ci-C4- alkyl, C1-C4alkoxy, carboxy, nitro and sulfo, especially halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, and Y4 is a radical of the above-mentioned formula (3a), (3b), (3c), (3d), (3e) or (3f).

As halogen there comes into consideration for R5 and R6 e. g. fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and especially chlorine.

As C1-C4alkyl there comes into consideration for R5 and R6 e. g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl or ethyl and especially methyl.

As C1-C4alkoxy there comes into consideration for R5 and R6 e. g. methoxy, ethoxy, n-prop- oxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, preferably methoxy or ethoxy and especially methoxy.

T1 is preferably a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e).

When T1 is a non-fibre-reactive substituent, it may be, for example, hydroxy; C1-C4alkoxy ; C1-C4alkylthio which is unsubstituted or is substituted e. g. by hydroxy, carboxy or sulfo ; amino; amino mono-or di-substituted by C1-C8alkyl, wherein the alkyl is unsubstituted or is further substituted e. g. by sulfo, sulfato, hydroxy, carboxy or phenyl, especially by sulfo or hydroxy, and may be interrupted one or more times by the radical-O-; cyclohexylamino ; morpholin ; N-C1-C4alkyl-N-phenylamino or phenylamino or naphthylamino, wherein phenyl or naphthyl is unsubstituted or is substituted e. g. by C1-C4alkyl, C1-C4alkoxy, carboxy, sulfo or halogen.

Examples of suitable non-fibre-reactive substituents T1 are amino, methylamino, ethylamino, ß-hydroxyethylamino, N-methyl-N-3-hydroxyethylamino, N-ethyl-N-p-hydroxyethylamino, N, N-di-p-hydroxyethylamino, (3-sulfoethylamino, cyclohexylamino, morpholino, 2-, 3-or 4- chlorophenylamino, 2-, 3-or 4-methylphenylamino, 2-, 3-or 4-methoxyphenylamino, 2-, 3-or 4-sulfophenylamino, disulfophenylamino, 2-, 3-or 4-carboxyphenylamino, 1-or 2-naphthyl- amino, 1-sulfo-2-naphthylamino, 4, 8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N- methyl-N-phenylamino, methoxy, ethoxy, n-or iso-propoxy and hydroxy.

As a non-fibre-reactive radical, T1 is preferably defined as being C1-C4alkoxy, C1-C4alkylthio which is unsubstituted or is substituted by hydroxy, carboxy or sulfo, hydroxy, amino, N- mono-or N, N-di-C1-C4alkylamino which is unsubstituted or is substituted in the alkyl moiety by hydroxy, sulfato or sulfo, morpholino, phenylamino which is unsubstituted or is substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or methoxy, or N-Ci-C4- alkyl-N-phenylamino which is unsubstituted or is substituted in the same manner, wherein

the alkyl is unsubstituted or is substituted by hydroxy, sulfo or sulfato, or naphthylamino which is unsubstituted or is substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T1 are amino, N-methylamino, N-ethylamino, <BR> <BR> <BR> N-p-hydroxyethylamino, N-methyl-N-p-hydroxyethylamino, N-ethyl-N-p-hydroxyethylamino, N, N-di-p-hydroxyethylamino, 3-sulfoethylamino, morpholino, 2-, 3-or 4-carboxyphenylamino, 2-, 3-or 4-sulfophenylamino or N-C1-C4alkyl-N-phenylamino.

For the radical T3, the definitions and preferred meanings mentioned for T1 when it is a non- fibre-reactive radical apply. T3 is especially morpholino or 2-, 3-or 4-sulfophenylamino.

In the case of fibre-reactive radicals T1 of formulae (4a) and (4b), Z is preferably ß-chloro- ethyl. In the case of fibre-reactive radicals T1 of formulae (4c) and (4d), Z is preferably vinyl or ß-sulfatoethyl.

When T1 is a fibre-reactive radical, T1 is preferably a radical of formula (4c) or (4d) and especially of formula (4c).

Hal in the fibre-reactive radicals of formulae (3d), (3e) and (4e) is preferably chlorine or bromine, especially bromine.

When Xi in the dye of formula (2a) is halogen, there comes into consideration, for example, fluorine, chlorine or bromine.

When Xi in the dye of formula (2a) is a non-fibre-reactive substituent, there comes into consideration, for example, the definition given above for T1 when it is a non-fibre-reactive substituent, the preferred meaning given for T1 applying.

Preferably, Xi is halogen, especially fluorine or chlorine and more especially chlorine.

X2 in the fibre-reactive radical of formula (3f) is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine and especially chlorine.

T2, X3 and X4 as halogen are, for example, fluorine, chlorine or bromine, especially chlorine or fluorine.

X3 as C1-C4alkylsulfonyl is, for example, ethylsulfonyl or methylsulfonyl and especially methylsulfonyl.

X4 as C1-C4alkyl is, for example, methyl, ethyl, n-or iso-propyl, n-, iso-or tert-butyl and especially methyl.

X3 and X4 are preferably each independently of the other chlorine or fluorine.

T2 is preferably hydrogen, cyano or chlorine.

X5 in the fibre-reactive radical of formula (3h) is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine and especially chlorine.

Preferably, V is benzoyl which is unsubstituted or is substituted in the phenyl ring by a radical of the above-mentioned formula (3g), or is a radical of the above-mentioned formula (3h) wherein for X3, X4, X5, T2, T3 and s the above-mentioned definitions and preferred meanings apply.

As the leaving group U there comes into consideration, for example,-Cl,-Br,-F,-OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-C6H5, -OSO2-C1-C4alkyl or -OSO2-N(C1-C4alkyl)2.

Preferably, U is a group of formula -Cl, -OSO3H, -SSO3H, -OCO-CH3, -OCO-C6H5 or -OPO3H2, especially -Cl or -OSO3H and most preferably-OS03H.

Examples of suitable radicals Z are accordingly vinyl, ß-bromo- or ß-chloro-ethyl, ß-acetoxyethyl, p-benzoytoxyethyi, ß-phosphatoethyl, ß-sulfatoethyl and ß-thiosulfatoethyl. Z is preferably vinyl, ß-chloroethyl or ß-sulfatoethyl.

Preferably, D1 and D2 are each independently of the other a radical of formula

preferably of formula (5a), (5b) or (5e), wherein (R6a) 0-2 denotes from 0 to 2 identical or differing substituents from the group halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, especially methyl, methoxy and sulfo, Y4a is a, p-dibromopropionylamino or a-bromoacryloylamino, m is the number 2 or 3, especially 3, n is the number 2 or 3, especially 2, and Zi, Z2, Z3 and Z4 are each independently of the others vinyl, ß-chloroethyl or ß-sulfatoethyl.

Z1 and Z2 are preferably each independently of the other vinyl or ß-sulfatoethyl.

Z3 is preferably ß-chloroethyl or ß-sulfatoethyl, especially ß-chloroethyl.

Z4 is preferabty p-chioroethyi or ß-sulfatoethyl, especially ß-sulfatoethyl.

When A in the dyes of formula (2a) is an unsubstituted or substituted phenylen radical or naphthylene radical, there come into consideration as substituents, for example, identical or differing radicals from the group halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, preferably C1-C4alkyl, C1-C4alkoxy and sulfo and especially methyl, methoxy and sulfo. In that case, the fibre-reactive radical Y1 is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f), preferably of formula (3a) or (3c) and especially of formula (3a).

When A in the dyes of formula (2a) is a C2-C8alkylene radical which may be interrupted by oxygen, there comes into consideration, for example, ethylene, propylene, isopropylene, butylen, isobutylene,-(CH2) 2-O-(CH2) 2-,-(CH2) 3-O-(CH2) 2-or-(CH2) 3-O-(CH2) 3-. In that case, the fibre-reactive radical Y1 is preferably a radical of formula (3a). A preferred C2-C8-alkylene which may be interrupted by oxygen, such as, for example, a radical of formula - (CH2) 2-4-0- (CH2) 2-4-, is a C2-C6alkylene radical which may be interrupted by oxygen, such as, for example, -(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)2- or -(CH2)3-O-(CH2) 3-, and especially a C2-C4alkylene radical which may be interrupted by oxygen, such as, for example, -(CH2) 2-O-(CH2) 2-.

In a preferred embodiment of the dye mixtures according to the invention, the radical-A-Y1 is a radical of the above-mentioned formula (5a), (5b), (5c), (5d) or (5e) or a radical of formula - (CH2) 2-4-0- (CH2) 2-4-S02-Zs (5f), wherein Z5 is vinyl, ß-chloroethyl or ß-sulfatoethyl, especially vinyl or ß-chloroethyl.

In an especially preferred embodiment of the dye mixtures according to the invention, the radical-A-Y1 in the dye of formula (2a) is a radical of formula (5a), (5b) or (5c), preferably of formula (5a) or (5b) and especially of formula (5a).

Preference is given to the dyes of formula (1) wherein D1 and D2 are each independently of the other a radical of formula (5a), (5b), (5c), (5d) or (5e), preferably of formula (5a), (5b) or (5e), and especially of formula (5a), and

Ri and R2 are hydrogen.

The radicals D1 and D2 in the dyes of formula (1) are identical or non-identical, preferably non-identical.

Special preference is given to the dyes of formula (1) wherein Ri and R2 are hydrogen, D1 is a radical of formula D2 is a radical of formula wherein R6a and R6b are each independently of the other methyl or methoxy, and Zia and Z1b are each independently of the other vinyl, ß-chloroethyl or P-sulfatoethyl.

As a dye of formula (1) there also comes into consideration a dye mixture that comprises at least one compound of formulae (1a) and (1b)

together with at least one compound of formulae (1 c) and (1 d)

wherein D1 and D2 are non-identical, and Pi, R2, D1 and D2 have the definitions and preferred meanings given above.

Preferably, the dye of formula (2a) in the dye mixtures according to the invention is a dye of formula

R3 is hydrogen, methyl or ethyl, and Z1 is vinyl, ß-chloroethyl or (3-sulfatoethyl.

As a dye of formula (2b) there come into consideration, for example, the dyes of formulae

In one embodiment of interest, the dye mixtures according to the invention comprise at least one dye of formula (1) together with at least one dye of formula (2a).

The reactive dyes of formulae (1), (2a) and (2b) in the dye mixtures according to the invention comprise sulfo groups each of which is either in the form of the free sulfonic acid or, preferably, in the form of a salt thereof, for example in the form of the sodium, lithium, potassium or ammonium salt, or in the form of a salt of an organic amine, for example in the form of the triethanolammonium salt.

The reactive dyes of formulae (1), (2a) and (2b) and hence also the dye mixtures may comprise further additives, for example sodium chloride or dextrin.

In the dye mixture according to the invention, the dyes of formula (1) are in a weight ratio to the dyes of formula (2a) and/or (2b) of, for example, from 1: 99 to 99: 1, preferably from 5: 95 to 95: 5 and especially from 10: 90 to 90: 10.

The dyes of formulae (1), (2a) and (2b) are known or may be prepared by methods known per se. Dyes of formula (1) are disclosed, for example, in WO-A-00/06652. Dyes of formula (2a) are described, for example, in Kokai JP 50-000178.

The dye mixtures according to the invention may be prepared, for example, by mixing the individual dyes. That mixing process is carried out, for example, in suitable mills, for example ball mills or pin mills, and also in kneaders or mixers.

The dye mixtures according to the invention may, where appropriate, comprise other auxiliaries that, for example, improve handling or increase storage stability, such as, for example, buffers, dispersants or humectants. Such auxiliaries are known to the person skilled in the art.

The dye mixtures according to the invention are suitable for dyeing and printing an extremely wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples are paper, silk, leather, wool, polyamide fibres and polyurethanes and also especially cellulosic fibre materials of all kinds. Such fibre materials are, for example, the natural cellulosic fibres, such as cotton, linen and hemp, and also cellulose and regener- ated cellulose. The dye mixtures according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, e. g. mixtures of cotton with polyester fibres or polyamide fibres.

The present invention accordingly relates also to the use of the dye mixtures according to the invention in the dyeing or printing of hydroxyl-group-containing or nitrogen-containing, especially cellulosic, fibre materials.

The dye mixtures according to the invention can be applied to the fibre material and fixed to the fibre in a variety of ways, especially in the form of aqueous dye solutions and dye print pastes. They are suitable both for the exhaust process and for dyeing in accordance with the pad-dyeing process; they can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The build-up behaviour is very good, the degrees of fixing are high and unfixed dye can be washed off easily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very low. The dye mixtures according to the invention are also suitable for printing, especially on cotton, and also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics that contain wool.

The dyeings and prints produced using the dye mixtures according to the invention can be reproduced very well, have a high tinctorial strength and a high fibre-to-dye binding stability in both the acidic and the alkaline range, and furthermore have good fastness to light and very good wet-fastness properties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration. Fibre-level and surface-level dyeings are obtained.

The dye mixtures 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 instruments, such as fountain pens and

ballpoint pens and especially inkjet printers. For that purpose the dye mixture according to the invention is first brought into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink that comprises the dye mixture according to the invention as colorant. The inks can be prepared in customary manner by mixing together the individual constituents in the desired amount of water.

Substrates that come into consideration include the above-mentioned hydroxyl-group- containing or nitrogen-containing fibre materials, especially cellulosic fibre materials.

The dyes 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.

The inks preferably have a total content of dyes of 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.

The inks may comprise water-miscible organic solvents, for example C1-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, diacetone alcohol ; ethers, e. g. tetrahydrofuran or dioxane; nitrogen-containing heterocyclic compounds, e. g. N-methyl-2-pyrrolidone or 1, 3-dimethyl-2-imidazolidone, poly- alkylen glycols, e. g. polyethylene glycol, or polypropylene glycol ; C2-C6alkylene glycols and thioglycols, e. g. ethylene glycol, propylene glycol, butylen 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-methoxyethanol, 2- (2-methoxy- ethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) 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, especi- ally from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink.

In addition, the inks may also comprise solubilisers, e. g £-caprolactam.

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

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. methylcellulose, ethylcellulose, carboxymethyl- cellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropyl methylcellulose, especially with preferably from 20 to 25 % by weight carboxy- methylcellulose. Synthetic thickeners that may 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 e. g. from 2000 to 20 000, for example polyethylene glycol or poly- propylene glycol or the mixed polyalkylene glycols of ethylene oxide and propylene oxide.

The inks comprise 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.

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.

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

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.

Preference is given to inks having a viscosity of from 1 to 40 mPa-s, especially from 1 to 20 mPa-s and preferably from 1 to 10 mPa-s.

The inks may also comprise customary additives, such as antifoam agents or especially preservatives that inhibit the growth of fungi and/or bacteria. Such additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink.

Preservatives that come into consideration include formaldehyde-yielding agents, e. g. paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40 % by weight formaldehyde solutions, imidazole compounds, e. g. 2- (4-thiazolyl) benzimidazole, thiazole compounds, e. g. 1, 2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one, iodine com- pounds, nitriles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1,2- benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one. A suitable preservative is e. g. a 20 % by weight solution of 1, 2-benzisothiazolin-3-one in dipropylene glycol (Proxel@ GXL).

The inks may also comprise further additives, such as fluorinated polymers or telomers, e. g. polyethoxyperfluoroalcohols (Forafaco or Zonylo products) in an amount of e. g. from 0.01 to 1 % by weight, based on the total weight of the ink.

In inkjet printing, individual droplets of the ink are sprayed onto a substrate in a controlled manner from a nozzle. For this purpose, predominantly the continuous inkjet method and the drop-on-demand method are used. In the continuous inkjet method, the droplets are produced continuously and any droplets not required for the printing are conveyed to a collecting vessel and recycled, whereas in the drop-on-demand method droplets are produced and printed as required; that is to say droplets are produced only when required for the printing. The production of the droplets can be effected, for example, by means of a piezo-inkjet head or by means of thermal energy (bubble jet). Printing by means of a piezo- inkjet head and printing in accordance with the continuous inkjet method are preferred.

The present invention accordingly relates also to aqueous inks comprising the dye mixtures according to the invention and to the use of such inks in an inkjet printing method for the

printing of various substrates, especially textile fibre materials, the definitions and preferred meanings mentioned above applying to the dye mixtures, the inks and the substrates.

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

Example 1: 100 parts of a cotton fabric are introduced at a temperature of 60°C into a dyebath comprising 3.0 parts of the dye of formula

3.0 parts of the dye of formula

and 60 parts of sodium chloride in 1000 parts of water. After 45 minutes at 60°C, 20 parts of calcined soda are added. The temperature of the dyebath is maintained at 60°C for a further 45 minutes. The dyed fabric is then rinsed and dried in the customary manner. A deep-red dyeing having good fastness properties is obtained.

Example 2: Following the procedure given in Example 1 but using instead of 3.0 parts of the dye of formula (101) 0.6 part of the dye of formula (101) and instead of 3.0 parts of the dye of formula (102) 5.4 parts of the dye of formula (102) a deep-red dyeing having good fastness properties is likewise obtained. Example 3: Following the procedure given in Example 1 but using instead of 3.0 parts of the dye of formula (101) 3.0 parts of the dye of formula

and instead of 3.0 parts of the dye of formula (102) 3.0 parts of the dye of formula a deep-red dyeing having good fastness properties is likewise obtained.

Examples 4 to 60: Following the procedure given in Example 1 but using instead of 3.0 parts of the dye of formula (101) 3.0 parts of the dye of general formula wherein Dl,, y and D2, y each correspond to the radical given in Table 1 and those radicals are as defined in Table 2, deep-red dyeings having good fastness properties are likewise obtained.

Table 1: Ex. D1xy D2xy colour shade 4 D11 D11 deep-red 5 D12 D12 deep-red 6 D13 D13 deep-red 7 D14 D14 deep-red 8 D15 D15 deep-red 9 D16 D16 deep-red 10 D17 D17 deep-red 11 D18 D18 deep-red 12 D19 D19 deep-red 13 D20 D20 deep-red 14 D21 D21 deep-red 15 D22 D22 deep-red 16 D23 D23 deep-red 17 D24 D24 deep-red 18 D25 D25 deep-red 19 D26 D26 deep-red 20 D10 D12 deep-red 21 D12 D10 deep-red 22 D10 D13 deep-red 23 D13 D10 deep-red 24 D10 D20 deep-red <BR> <BR> <BR> 25 D21 D13 deep-red<BR> 26 D10 D14 deep-red 27 D10 D15 deep-red 28 D10 D16 deep-red 29 D10 D17 deep-red 30 D10 D18 deep-red 31 D10 D19 deep-red <BR> <BR> 32 D10 D21 deep-red<BR> 33 D10 D22 deep-red

34 D10 D23 deep-red 35 D10 D24 deep-red 36 D10 D25 deep-red 37 D10 D26 deep-red 38 D13 D20 deep-red 39 D14 D11 deep-red 40 D29 D32 deep-red <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> 41 D29 D30 deep-red<BR> 42 D29 D10 deep-red 43 D29 D31 deep-red 44 D33 D33 deep-red 45 D28 D28 deep-red 46 D28 D27 deep-red <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> 47 D10 D29 deep-red<BR> 48 D10 D31 deep-red 49 D11 D31 deep-red 50 D31 D11 deep-red 51 D33 D11 deep-red 52 D34 D34 deep-red 53 D21 D34 deep-red 54 D34 D21 deep-red 55 D34 D10 deep-red 56 D10 D34 deep-red 57 D31 D31 deep-red 58 D10 D33 deep-red 59 D13 D32 deep-red 60 D19 D21 deep-red Table 2 :

Examples 61 to 70: Following the procedure given in Example 1 but using instead of 3.0 parts of the dye of formula (102) 3.0 parts of the dye of formula

or 3.0 parts of the dye of the above-mentioned formula 65 (2ba), 66 (2bb), 67 (2bc), 68 (2bd), 69 (2be) or 70 (2bf) deep-red dyeings having good fastness properties are likewise obtained.