The present invention relates to mixtures of reactive dyes, especially black-dyeing or navy- blue-dyeing mixtures, that are suitable for dyeing or printing nitrogen-containing or hydroxy- group-containing fibre materials and yield dyeings or prints having good all-round fastness properties.

The practice of dyeing with reactive dyes has recently led to increased requirements regarding the quality of the dyeings and the profitability of the dyeing process.

Consequently, there continues to be a demand for novel reactive dye mixtures which have improved properties, in particular in respect of application.

Dyeing of natural or synthetic polyamide fibres with reactive dyes according to conventional methods usually requires alkaline after-treatment to remove non-fixed dye.

In the case of wool the alkaline after-treatment causes a partial damage of the fibres and thus a considerable loss of material, apart from the undesired additional consumption of water and chemicals.

Reactive dye mixtures which have a high degree of exhaustion and a high degree of fixing, and which do not require alkaline after-treatment to remove non-fixed dye, are therefore required for dyeing. They should furthermore have a good dyeing yield, high reactivity and good levelness in combination. These requirements are not met in all properties by the known dye mixtures.

The present invention is therefore based on the object of discovering improved reactive dye mixtures for dyeing and printing fibre materials, which have the qualities characterized above to a high degree. In particular, the novel dye mixtures should be distinguished by high degrees of exhaustion, high fixing yields and high fibre-dye bond stabilities. They should furthermore produce dyeings with good allround properties, for example light and wet fastness properties.

It has been found that the object described is largely achieved with the reactive dye mixtures defined below. The dyeings and printings obtained are distinguished especially by uniform colour build-up and, at the same time, constancy of shade at different concentrations, and by good combinability, and exhibit good fibre levelness and no dichroism. The invention relates to a dye mixture, comprising

(A) a dye of the formula

wherein

D is the radical of a carbocyclic or heterocyclic aromatic diazo component,

Ri and R ₂ are each independently of the other hydrogen, CrC ₆ alkyl, CrC ₆ alkoxy, hydroxy-C ₂ -C ₆ alkoxy, C ₂ -C ₆ alkanoylamino, CrC ₆ alkylsulfonyl, carbamoyl, sulfamoyi, or a fibre-reactive group of the formula

-S0 ₂ -Y (2a),

-CONH-(CH ₂ )p-S0 ₂ -Y (2b),

-NHCO-(CH ₂ )p-S0 ₂ -Y (2c),

-NH-CO-CH(Hal)-CH ₂ -Hal (2d),

- -CO-C(Hal)=CH ₂ (2e),

wherein Χ-ι is halogen,

T-i independently has the definition of Xi, is a non-fibre-reactive substituent selected from amino, methylamino, ethylamino, β-hydroxyethylamino, N-methyl-N-p-hydroxyethylamino, N- ethyl-N-p-hydroxyethylamino, N,N-di-p-hydroxyethylamino, β-ethylamino, cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4- methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, 2,5-disulfophenylamino, 2-, 3- or 4- carboxyphenylamino, 1 - or 2-naphthylamino, 1 -sulfo-2-naphthylamino, 4,8-disulfo-2- naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxyl,

or is a fibre the formula (3a),

NH-(CH ₂ ) _2- 3-S0 ₂ -Y (3b) or NH-(CH ₂ ) _2-3 -0-(CH ₂ ) ₂ . (3c),

R ₃ and R ₄ are each independently of the other hydrogen, CrC ₆ alkyl that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano, carboxy, CrC ₆ alkoxy or phenyl,

C ₂ -C ₆ alkano l, phenyl, sulfomethyl or a group of the formula

R ₅ is hydrogen or d-C ₆ alkyl that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano, carboxy, CrC ₆ alkoxy or phenyl,

(R ₆ )o- ₂ denotes from 0 to 2 identical or different substituents from the group hydroxyl, C C ₆ alkyl, C C ₆ alkoxy and -S0 ₃ M,

Hal is halogen,

Y is vinyl or a -CH ₂ -CH ₂ -U radical and U is a group that is removable under alkaline conditions,

p is the number 2, 3 or 4,

M is hydrogen, Li, Na, K, Mg, Ca or ammonium that is unsubstituted or mono-, di-, tri- or tetrasubstituted by CrC ₆ alkyl, C ₂ -C ₆ -hydroxyalkyl or mixtures thereof; and

(B) at least one dye of the formula

wherein

Qi and Q ₂ are each independently of the other hydrogen, CrC ₆ alkyl that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano, carboxy, CrC ₆ alkoxy or phenyl,

C ₂ -C ₆ alkanoyl, phenyl, sulfomethyl or a group of the formula (3d) as defined above,

D-i is the radical of a diazo component, which is itself a mono- or bis-azo dye or contains such a dye,

D ₂ has the same definition as D-i or is a radical of formula

wherein

(Q ₃ )o-3 denotes from 0 to 3 identical or different substituents selected from the group halogen, hydroxyl, CrC ₆ alkyl, CrC ₆ alkoxy, carboxy and sulfo,

Z ₃ is a radical of formula (2a) - (2h) as defined above and

M is hydrogen, Li, Na, K, Mg, Ca or ammonium that is unsubstituted or mono-, di-, tri- or tetrasubstituted by CrC ₆ alkyl, C ₂ -C ₆ -hydroxyalkyl or mixtures thereof.

Preferably the dye mixtures according to the invention contain as component (A) a dye of formula

wherein

Ri is CrC ₆ alkoxy, -S0 ₃ M or C2-C ₆ alkanoylamino,

R ₂ is hydrogen, CrC ₆ alkyl, CrC ₆ alkoxy, hydroxy-C ₂ -C ₆ alkoxy, C ₂ -C ₆ alkanoylamino, CrC ₆ alkylsulfonyl, carbamoyl, sulfamoyl, -S0 ₃ M or a fibre-reactive group of the formula (2a) - (2h) as defined in claim 1 , and

D, M, R ₃ and R ₄ are as defined in claim 1 .

In a further preferred embodiment the dye mixtures according to the invention contain as component (A) a dye of formula (1 ), wherein D corresponds to a radical of formula

wherein

R ₇ , R ₈ and R ₉ represent each independently of the other hydrogen, hydroxy, amino, Ci-C ₆ alkylamino, di-Ci-C ₆ alkylamino, C ₆ -Ci ₄ arylamino, di-C ₆ -Ci ₄ arylamino,

C ₇ -Ci ₅ aralkylamino, di-C ₇ -Ci ₅ aralkylamino, Ci-C ₆ alkyl-C ₇ -Ci ₅ aralkylamino, CrC ₆ alkyl, d- C ₆ alkoxy, hydroxy-C ₂ -C ₆ alkoxy, C ₂ -C ₆ alkanoylamino, Ci-C ₆ alkylsulfonyl, carbamoyl, sulfamoyl or -S0 ₃ M,

Z and Z ₂ represent each independently of the other hydrogen or a fibre-reactive group of the formula (2a) - (2h) as defined in claim 1 or a fibre-reactive group of the formula

wherein R ₅ and Y are as defined above.

Dyes of formula (1 ), wherein D corresponds to a radical of formula

wherein Y denotes vinyl or 2-sulfatoethylsulfonyl,

are particularly preferred.

Further preferred dyes of formula (1 ) are those wherein R ₂ is a fibre-reactive group of the formula (2c) or (2d), wherein p is the number 3 and Y denotes vinyl or 2-chloroethyl.

Moreover, dyes of formula (1 ) are preferred, wherein R ₃ is hydrogen and R ₄ is hydrogen, methyl, ethyl, acetyl, phenyl or 4-(2-sulfatoethylsulfonyl)phenyl.

Further preferred dyes of formula (1 ) are those wherein R-i is-S0 ₃ M, R ₂ represents a fibre- reactive group of the formula (2c), wherein p is the number 3, Y denotes vinyl or

2-chloroethyl and R ₄ is hydrogen, methyl, acetyl, phenyl or 4-(2-sulfatoethylsulfonyl)phenyl or R ₂ represents a fibre-reactive group of the formula (2d), wherein Hal denotes bromo.

Preferably the dye mixtures according to the invention contain as component (B) at least one dye of the formula (4) wherein D-i corresponds to a radical of formula (7)

wherein

(Rio)o-3 denotes from 0 to 3 identical or different substituents selected from the group halogen, hydroxyl, CrC ₆ alkyl, CrC ₆ alkoxy, C ₂ -C ₆ alkanoylamino, carboxy and sulfo,

Z ₄ is a fibre-reactive radical of formula -S0 ₂ -Y, wherein Y is vinyl or β-sulfatoethyl,

K-i is the radical of formula wherein

R-io is hydrogen, sulfo, or CrC ₆ alkoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato, and

Rii and Ri ₂ are each independently of the other hydrogen, sulfo, nitro, CrC ₆ alkyl,

CrC ₆ alkoxy, C ₂ -C ₆ alkanoylamino, -SO2NR ₃ R4, wherein R ₃ and R ₄ are as defined above, ureido, or a radical of formula (2f) as defined above.

Further preferred dyes of formula (4) are those wherein wherein D ₂ corresponds to a radical of formula

wherein Y is vinyl or 2-sulfatoethyl.

The combination of components (A) and (B) as described above provides dyeings of navy- blue to black colour. In order to adjust the desired shade and to improve the brilliance of the dyeings, it is appropriate to add at least one further yellow, orange or red dyestuff to the dye mixtures.

Accordingly, a further object of the invention is a dye mixture as described above additionally comprising a dye of formula

R 1.3

(10),

wherein

D ₃ is a radical of the formula

Ri ₃ is hydrogen or d-C ₆ alkyl that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano, carboxy, CrC ₆ alkoxy or phenyl,

Ri4 is hydrogen, CrC ₈ alkyl, CrC ₆ alkoxy, C ₂ -C ₆ alkanoylamino, ureido, halogen or sulfo, Q ₄ rep

wherein X ₂ denotes chlorine or fluorine,

V-i is a radical of the formula (3a), (3b) or (3c) as defined in claim 1 or radical of the formula (3e) or (3f)

(SO.H),

3e),

D ₄ , D ₅ and D ₆ are each independently of the others a radical of formula

wherein

(Q ₃ )o denotes from 0 to 3 identical or different substituents selected from the group halogen, CrC ₆ alkyl, CrC ₆ alkoxy, carboxy and sulfo,

Z ₅ is a radical of formula

-CONH-(CH ₂ ) _p -S0 ₂ -Y (2b),

Y is vinyl or a radical -CH ₂ -CH ₂ -U and U is a leaving group removable under alkaline conditions,

X is the radical -CHXrCH ₂ -Xi or -CX ₁ =CH ₂ , wherein X-, is halogen, p is the number 2, 3 or 4,

q is 0 or 1 ,

A is a phenylene radical which is unsubstituted or substituted by sulfo, CrC ₆ alkyl, Ci-C ₆ - alkoxy, halogen, C2-C ₆ alkanoylamino, ureido or a radical of formula

or a naphthylene radical which is unsubstituted or substituted by sulfo or hydroxy,

T ₂ is halogen or 1 -pyridinyl which is unsubstituted of substituted by carbamoyl or carboxy, V ₂ , V ₃ and V ₄ are each independently of the other -NR ₁₅ R ₁₆ , wherein R ₁₅ and Ri ₆

independently of the other denote hydrogen; CrC ₆ alkyl which is unsubstituted or substituted by sulfo, sulfato, hydroxy, carboxy or phenyl; cyclohexyl; phenyl which is unsubstituted or substituted by CrC ₆ alkyl, CrC ₆ alkoxy, amino, C ₂ -C ₆ alkanoylamino, carboxy, sulfo or halogen; naphthyl which is unsubstituted or substituted by CrC ₆ alkyl, CrC ₆ alkoxy, amino, C2-C ₆ alkanoylamino, carboxy, sulfo or halogen; or morpholino.

As CrC ₆ alkyl or there come into consideration for R- _\ - R ₁₇ and Qi , Q ₂ and Q ₃ , each independently of the others, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl, preferably methyl and ethyl and especially methyl.

As CrC ₆ alkoxy there come into consideration for R-i - R ₁₈ and Qi - Q ₃ , each independently of the others, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy and especially methoxy.

If any substituent is C2-C ₆ alkanoylamino, there come into consideration, for example, acetylamino, propionylamino and butyrylamino, preferably acetylamino and propionylamino and especially acetylamino.

If any substituent is halogen, there come into consideration, for example, fluorine, chlorine and bromine, preferably chlorine and bromine and especially chlorine. As the leaving group U there come into consideration, for example, -CI, -Br, -F, - OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OP0 ₃ H ₂ , -OCO-C ₆ H ₅ , -OS0 ₂ -CrC6alkyl and -OS0 ₂ -N(C C6alkyl) ₂ . Preferably, U is a group of formula -CI, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OP0 ₃ H ₂ , especially -CI or -OSO ₃ H and more especially -OSO ₃ H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- or β-chloroethyl,

β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl.

Preferably, Y is vinyl, β-chloroethyl or β-sulfatoethyl, especially vinyl or β-sulfatoethyl.

The radicals D, D-i and D ₂ in the dyes of formulae (1 ) and (4) 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 6 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 6 carbon atoms, especially from 1 to 4 carbon atoms, such as methoxy, ethoxy, n- or iso-propoxy, or n-, iso-, sec- or tert-butoxy; CrC ₆ alkoxy substituted in the alkyl moiety, for example by hydroxy, CrC ₆ alkoxy 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 C ₂ -C ₆ alkanoylamino groups, such as acetylamino or propionylamino; benzoyl- amino or C ₂ -C ₆ alkoxycarbonylamino groups, such as methoxycarbonylamino or ethoxy- carbonylamino; amino; N-mono- or N,N-di-Ci-C ₆ alkylamino which is unsubstituted or is substituted in the alkyl moiety, for example by hydroxy, sulfo, sulfato or CrC ₆ alkoxy, e.g. methylamino, ethylamino, Ν,Ν-dimethyl- or Ν,Ν-diethylamino, sulfomethylamino, β-hydroxy- ethylamino, N,N-di^-hydroxyethylamino), Ν-β-sulfatoethylamino; phenylamino which is unsubstituted or is substituted in the phenyl moiety by methyl, methoxy, halogen or sulfo; N- Ci-C ₆ alkyl-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, Ν-β-hydroxyethyl-N-phenylamino or Ν-β- sulfoethyl-N-phenylamino; naphthylamino which is unsubstituted or is substituted by sulfo; alkanoyl 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; trifluoro- methyl, nitro, cyano, hydroxy, halogen, such as fluorine, chlorine or bromine; carbamoyl, N- Ci-C6alkylcarbamoyl, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl, N-C ₁ -C6- alkylsulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropyl- sulfamoyl or N-butylsulfamoyl; N-(p-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 (-0-) or by an amino group (-NH-, -N(C C6alkyl)-).

In one embodiment of the present invention that is of interest, at least one of the radicals D-i and D ₂ in formula (4) carries at least one fibre-reactive group.

In another embodiment of the present invention that is of interest, each of the radicals D-i and D ₂ 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 per se 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. The dye of formula (1 ) is, for example, a dye of the formula

(104),

^max ⁼ 575 nm ^max ⁼ 591 nm

(112),

ίτΐθχ = 585 nm ίτΐθχ = 605 nm

^ _max = 608 nm

ίτΐθχ = 565 nm ίτΐθχ = 566 nm

Γτΐθχ = 580 nm _max = 564 nm The dye of formula (4) is, for example, a dye of the formula

(404),

so ₂

H0 ₃ so

(406),

(408),

(410),

595 nm

= 531 nm

The dye of formula (10) is, for example, a dye of the formula

The dye of formula (11 ) is, for example, a dye of the formula

(1103) or

The dye of formula (12) is, for example, a dye of the formula (1201),

(1104) or

f ^S ° ² (1105).

The dyes of formulae (1 ), (4), (10), (11) and (12) are known in some cases or they can be prepared in accordance with processes known perse. Dyes of the formula (1) are disclosed, for example, in EP-A 647683. Dyes of the formula (4) are known from, for example, WO 2005/090484. Dyes of the formula (10) are disclosed, for example, in EP-A 775 731 . Dyes of the formula (1 1 ) are known from, for example, EP-A 785 237 683. Finally, dyes of the formula (12) are disclosed, for example, in EP-A 1 035 171 .

The dyes of the formula (1 b)

wherein

Ri ₇ is hydrogen, CrC ₆ alkyl, CrC ₆ alkoxy, hydroxy-C ₂ -C ₆ alkoxy, C ₂ -C ₆ alkanoylamino, CrC ₆ alkylsulfonyl, carbamoyl, sulfamoyl, -S0 ₃ M or a fibre-reactive group of the formula

-NHCO-(CH ₂ ) ₃ -S0 ₂ -Y (2c1 ),

Ri ₈ is CrC ₆ alkoxy, -S0 ₃ M or C ₂ -C ₆ alkanoylamino,

and R ₃ , D, M and Y are as defined in claim,

are novel and constitute a further object of the invention.

In order to suppress metameric effects that may occur on application of some of the dye mixtures according to the invention, it may be appropriate to add a small amount of a turquois dyestuff, for example a metal complex dye of formula

to the dye mixtures. The dye mixtures according to the invention can be prepared, for example, by mixing the individual dyes together. The mixing procedure is effected, 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 directly in the dyebath or the printing medium. The amount of the individual reactive dyes is governed by the shade to be obtained.

The dye of formula (1 ) usually is present in an amount of 1 .0 - 50.0 % by weight, preferably 2.0 - 40.0 % by weight, in particular 3.0 - 25.0 % by weight, based on the total amount of dyes.

The dye of formula (4) appropriately is present in an amount of 20.0 - 90.0 % by weight, preferably from 30.0 - 80.0 % by weight, in particular from 35.0 - 65.0 % by weight, based on the total amount of dyes.

The dyes of formulae (10), (1 1 ) and (12) are advantageously present in amounts of 3.0 - 50.0 % by weight, preferably from 5.0 - 45.0 % by weight, in particular from 10.0 - 40.0 % by weight, based on the total amount of dyes.

The reactive dyes of formulae (1 ), (4) and (10) - (12) and accordingly also the dye mixtures according to the invention may comprise further additives, for example, sodium chloride or dextrin.

If desired, the reactive dyes of formulae (1 ), (4) and (10) - (12) and accordingly also the 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.

The dye mixtures according to the invention are suitable for the dyeing and printing of an extremely wide variety of materials, especially nitrogen-containing fibre materials. Examples thereof are silk, leather and in particular wool. The dye mixtures according to the invention and the reactive dyes according to the invention are also suitable for the dyeing or printing of nitrogen-group-containing fibres that are contained in blend fabrics, for example mixtures of wool with polyester fibres or polyamide fibres. The said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of loose stock, fibres, yarn, woven fabric or knitted fabric.

Wool can advantageously be dyed in various forms, for example as tippy wool, as fabric or as fur.

The method according to the invention for dyeing and printing can be carried out in accordance with customary dyeing and printing methods, for example, according to the so- called cold pad-batch process, in which the dye 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 according to the invention for dyeing and printing is carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed without an alkali treatment, optionally under the action of heat.

The dye liquors or print pastes, 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.

The amounts in which the individual dyes are used in the dyebaths or print pastes can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or on the print paste, have proved advantageous.

The dyes of formulae (1 ), (4) and (10) - (12) used in the method according to the invention are distinguished in dyeing or printing by 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 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 and prints produced in accordance with the method of the invention exhibit very good fastness properties, such as wash and water fastness and perspiration fastness, and good

reproducibility.

Special appliances are not required. It is possible to use, for example, the customary dyeing apparatus, e.g. open baths, winch becks, jiggers, or paddle jet or circulation apparatus.

Processing is conveniently carried out in the temperature range from e.g. 70 to 1 10°C and, preferably, from 80 to 105°C, for example, at 100°C. The treatment time may typically be from 20 to 100 minutes and, preferably, from 30 to 60 minutes. The pH of the liquor is usually in the range from 3 to 7 and, preferably, from 4 to 6.

The dyeing or printing method according to the invention allow for considerable savings of resources, such as water and energy. The time required for dyeing or printing is considerably reduced.

The gentle dyeing or printing method using the dichromatic or trichromatic dye mixtures according to the invention ensures a high quality of the dyed wool and reduces the wastage of material.

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 ink-jet 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 or the dyes 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 mixture according to the invention or the dyes 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 formulae (1 ), (4) and (10) - (12) are used in a multi color ink-jet printer and mixing is effected on the substrate by digital printing. For example, one ink comprises a dye of formula (1 ). Another ink comprises a dye of formula (4) and still another ink comprises a dye of formula (10). 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.

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.

I. Preparation Examples

Example 1.1

(A) Preparation of 2-amino-4-[4-(2-chloroethylsulfonyl)butyrylamino]benzenesulf onic acid 76.04 g (0.40 mol) 2,4-diaminobenzenesulfonic acid are dissolved in 400 ml deionised water and 39.7 ml NaOH (30 %). The pH value is increased to 7.3 by addition of 44 g NaHC0 ₃ . Subsequently, the solution is cooled down by addition of 600 g ice and 1 12 g (0.48 mol) 4-(2-chloroethylsulfonyl)butyryl chloride is added within 30 min under vigorous stirring. After further 15 min of stirring the pH value is lowered to 5.6 by addition of 4.5 g HCI (32 %).

Afterwards, 8 g diatomaceous earth is added and after 10 min of stirring 1434 g solution is filtered off.

(B) Preparation of diazonium salt

87.9 g (0.35 mol) of 4-(2-sulfatoethylsulfonyl)aniline are added to 1000 g ice/water mixture. The pH value is adjusted to 0.5 by addition of 73.6 g HCI (32 %) and 74.5 ml 4N-NaN0 ₂ is added slowly under stirring within 40 min. After 1 h of stirring the excess of of nitrite is destroyed by addition of 7.4 g sulfamic acid (10 %).

(C) Coupling reaction

The suspension of the diazonium salt obtained in step (B) is cooled down to 1 °C and 1075.5 g of the solution prepared in step (A) is added within 25 min, whereupon an orange solution is obtained. The mixture is stirred for further 70 min under cooling with ice.

Afterwards the pH value is adjusted to 3.0 by addition of 183.1 ml Na ₂ C0 ₃ (15 %).

Subsequently, further 50 g of the solution prepared in step (A) is added within 25 min and pH is decreased to 2.94 by addition of 2.3 1 ml Na ₂ C0 ₃ (15 %). While the mixture is still cooled with ice, another 185 g of the solution prepared in step (A) is added within 15 min. Addition of 3.7 ml Na ₂ C0 ₃ (15 %) causes an increase of pH to 3.06. After stirring stirred over night by RT the reaction mixture is filtered. The precipitate is washed with 500 ml water and dried.

Thus, 365.1 g crude product containing (according to spectrometric analysis) 42.4 % of monoazo compound are obtained corresponding to 77.2 % yield.

(D) Preparation of diazonium salt

The product prepared in step (C) is dissolved in 2700 ml water under stirring. The solution is cooled to RT and 57 ml 4N-NaN0 ₂ is added within 5 min. After addition of 120 g ice, 80 g HCI (32 %) is added slowly under stirring within 60 min. The suspension is stirred under cooling for further 2 h and the the excess of of nitrite is destroyed by addition of 1 1 g sulfamic acid (10 %).

(E) Second coupling reaction

66.5 g (0.23 mol) 1 -hydroxy-7-methylamino-3-naphthalenesulfonic acid are dissolved in 370 ml water by addition of 22.7 ml NaOH (30 %) at RT.

The suspension of the diazonium salt prepared in step (D) is cooled down to 6 °C and the solution of the coupling component is added under cooling within 10 min. The pH is increased to 3.1 by addition of 150 ml Na ₂ C0 ₃ (15 %). Subsequently, 330 g NaCI are added in portions and the reaction mixture is filtered through a suction filter. The filter cake is washed with 400 g NaCI (10 %) and dried in vacuum at 40 °C giving a green dye of the following structure:

^max = wavelength of the absorption maximum)

The compound of formula (106) dyes wool in a green shade having good allround fastness properties. I. Application Examples

Example 11.1

1 .25 part of the green-dyeing dye of formula (106), 0.12 part of the navy-dyeing dye of formula (412), 0.38 part of the red-dyeing dye of formula (41 1 ) and 0.25 part of the yellow- dyeing dye of formula (1 101 ) are dissolved in 200 parts of water, and 10.0 part of sodium sulfate, 4.0 part of a levelling assistant (based on the condensation product of a higher aliphatic amine and ethylene oxide) and 0.4 part of sodium acetate are added. The pH is then brought to a value of 5.0 with 0.3 ml/l acetic acid (80 %). The dyebath is heated at 40°C for 10 minutes and 10 parts of a woollen fabric (pretreated for at least 30 min at 80 °C with 0.2 g/l Ultravon ^® GPN extra, a commercial wetting agent supplied by Huntsman, liquor ratio 1 : 40, and subsequently spun) are then added. The bath is heated to a temperature of 100°C in the course of about 50 minutes and dyeing is carried out at this temperature for 60 minutes. Thereafter, the bath is allowed to cool to 50°C and the dyed goods are removed. The woollen fabric is washed with hot and cold water and then centrifuged and dried. A black dyeing is obtained which has good light and wet fastness properties and good levelness.

Example II.2

As described in Example 11.1 , a black dyeing having good light and wet fastness properties and good levelness is prepared from 0.40 part of the green-dyeing dye of formula (106), 1.14 part of the navy-dyeing dye of formula (413) and 0.46 part of the yellow-dyeing dye of formula (1203).

Example 11 - 3

As described in Example 11.1 , a black dyeing having good light and wet fastness properties and good levelness is prepared from 0.42 part of the green-dyeing dye of formula (106), 0.95 part of the navy-dyeing dye of formula (413) and 0.63 part of the yellow-dyeing dye of formula (1 102).

Example II.4

As described in Example 11.1 , a black dyeing having good light and wet fastness properties and good levelness is prepared from 0.58 part of the green-dyeing dye of formula (106), 1 .07 part of the navy-dyeing dye of formula (412) and 0.35 part of the yellow-dyeing dye of formula (1 101 ).

Example II.5

As described in Example 11.1 , a black dyeing having good light and wet fastness properties and good levelness is prepared from 0.36 part of the green-dyeing dye of formula (106), 1 .06 part of the navy-dyeing dye of formula (412), 0.28 part of the yellow-dyeing dye of formula (1 101 ) and 0.30 part of the turquois-dyeing dye of formula (1301 ).