| Title of Invention | GLUCOKINASE ACTIVATORS |
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| Abstract | The present invention relates to a compound comprising an amide of the formula 1; wherein the * indicates an asymmetric carbon atom; R 1 and R 2 are independently hydrogen, halo, amino, hydroxyamino, nitro, cyano, sulfonamido, lower alkyl, -OR5, -C(O)OR5, perfluoro-iower alkyl, lower alkyl thio, perfluoro-iower alkyl thio, lower alkyl sulfonyl, perfluoro-iower alkyl sulfonyl or lower alkyl sulfinyl; R3 is cycloalkyl having from 3 to 7 carbon atoms; R4 is -C(O)NHR4O; or an unsubstituted or mono-substituted five or six-membered heteroaromatic ring connected by a ring carbon atom to the amine group shown, which five or six-membered heteroaromatic ring contains from 1 to 3 heteroatoms selected from ~ sulfur, oxygen or nitrogen, with one heteroatom being nitrogen which is adjacent to the connecting ring carbon atom; said mono-substituted heteroaromatic being monosubstituted at a position on a ring carbon atom other than adjacent to said connecting carbon atom with a substituent selected from the group consisting of lower alkyl, halo, nitro, cycano, -(CH2)n-OR6, (CHVn-C(O)OR 7, -(CHVn,-C(O)NHR6,-C(O)- C(O)OR8, -(CHVn-NHR6; R4O is hydrogen, lower alkyl, lower alkenyl, hydroxy lower alkyl, halo lower alkyl, - (CH2)n-C(O)OR5 or -C(O)-(CH2)n-C(O)OR6; R5 is hydrogen, lower alkyl or perfluoro-iower alkyl; I R6, R 7 and R8 are independently hydrogen or lower alkyl; and n is 0, 1, 2, 3 or 4; "lower alkyl" and "lower alkoxy" indicate groups with 1 to 7 carbon atoms; and "lower alkenyl" indicates groups with 2 to 6 carbon atoms; or a pharmaceutically acceptable salt thereof. |
| Full Text | Black-dyeing inks and their use The present invention relates to black-dyeing inks based on navy blue copper complex azo or copper complex formazan dyes, black-dyeing mixtures based on such dyes and novel dyes. The inks on which the present invention is based are particularly suitable for printing paper, preferably by the ink-jet printing process, and for dyeing or printing fibre materials which contain nitrogen or hydroxyl groups, and give dyeings or prints which are distinguished by a high fastness to light. The present invention therefore relates to black-dyeing aqueous inks comprising 20 to 95% by weight of at least one dye (A), together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the ink, and 1 to 40% by weight of a water-miscible organic solvent, based on the total weight of the ink, the dye (A) containing, as the colouring part of the molecule, one or more radicals of the formula(l), (II), {lll}or(lV) formula (V), (Vt), (Vll) or (Vlll) and one or more radicals of the abovementioned formula (I), (II), (III) or {IV), in which {G)o-2 is 0 to 2 identical or different substituents from the group consisting of substituted or unsubstituted amino, hydroxyl and nitro, L is substituted or unsubstituted amino, R is halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, nitro or cyano, (V)o-2 is 0 to 2 identical or different substituents from the group consisting of halogen, C ,- C4alkyl, C,-C4alkoxy, p-sulfatoethylsulfonyl and sulfo, (W)o.i is an N-acyi radical, if any, n is the number 0,1,2 or 3, m is the number 1,2 or 3 and r and q are the number 0 or 1. CrC4alkyl R and V is, for example, methyl, ethyl, propyl, isopropyl. butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and in particular methyl. C1-Ctalkoxy R and V is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, preferably methoxy or ethoxy, and in particular methoxy. Halogen R and V is, for example, fluorine, chlorine or bromine, preferably chlorine or bromine, and in particular chlorine. Ca-C4alkanoylamino R is, for example, acetylamino or propionylamino, in particular acetylamino. R is preferably C1-C4alkyl, C,-C4aikoxy, hydroxyl, carboxyl, nitro or cyano, in particular C,-Calkyl, C1-C4alkoxy, hydroxyl or carboxyl, and especially carboxyl. V is preferably halogen, p-sulfatoethylsulfonyl or sulfo, in particular sulfo. Substituted or unsubstituted amino G and L is, for example, amino, N-mono- or N,N-di- C,-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy, hydioxyl, suHato or sulfo, or phenylamino or N"C,-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by C,-C4alkyi, Ct-Caalkoxy, C2-C4atkanoyiamino, suifo, carboxyl or halogen, in particular amino or phenylamino. An N-acy! radical W is, for example, C2-C4alkanoylamino, for example acetylamino or propionylamino, benzoylamirw which is unsubstituted or substituted in the phenyl ring by C,- which Ti and Ta independently of one another are fluorine or chlorine, C1-C4alkylthro which is unsubstituted or substituted in the alkyl moiety by hydroxy), sulfate, sulfo or carboxyl, hydroxy!, amino, N-mono- or N,N-di-C,-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl, C1-C4alkoxy, sulfato or sulfo, morpholino, phenylamino or N-CrC4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, mtft;;/ .:r methoxy and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups. q is preferably the number 1. m is preferably the number 2 or 3, in particular 2. It R is carboxyl, the sum of m + n is preferably 3 or 4, and in particular 3. Inks according to the invention which are preferred are those which contain a radical of the formula (IV) in which q is the number 1, n is the number 0 and m is the number 2 or 3. The sulfa groups of the dyes (A), (B) and (C) in the inks according to the invention are either in the form of the free sulfonic acid or, preferably, in the salt form thereof, for example as the sodium, lithium, potassium or ammonium salt or as the salt of an organic amine, for example as the triethanolammonium sait. The dyes (A), (B) and (C) in the inks according to the invention contain no further colouring molecular moieties in addition to the colouring molecular moieties mentioned. The dye (A) in the inks according to the invention preferably contains, as the colouring molecular moiety (chromophore), one or two radicals of the formula (1), (II), (III) or (IV). If the dye (A) contains a radical of the formula (I), (II), (ill) or (IV), a non-chromophoric radical is bonded to this radical via the free valency drawn in the formulae (I), (II), (III) and (IV). Examples of a non-chromophoric radical are the following: C2-C6alkanoylamino which is unsubstituted or substituted in the alkyl moiety by hydroxy!, sulfo, carboxyl or C1-Calkoxy, which can in its turn be substituted in the alkyl moiety by carboxyl, for example acetylamino, hydroxyacetylamino, methoxyacetylamino, carboxymethylenoxyacetylamino, propionylamino or p-carboxypropionylamino; N-C1-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo, carboxyl or C-Calkoxy, for example 3-su!fopropylamino or 4-sulfobutylamino; benzoylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, sulfo, halogen, C,-C4alkyl or C,-C4alkoxy; Ca-Cealkoxycarbonylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, C1-C4alkyl or C,-C4alkoxy; phenoxycarbonylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, C,-C4alkyl or CrC4alkoxy; phenylsuifonylamino which is unsubstituted or substituted in the phenyl moiety by C1-C4alkyl or C2-C4aikanoylamino, or C1-C4alkylsulfonylamino, for example methyl- or independently of one another are a substituent which is not fibre-reacted, for example C,-C4alkoxy, C1-C4alkylthio which is unsubstituted or substituted in the aikyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C,-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl, C,-C4alkoxy, sulfato or sulfo, morpholino, phenylamino or N-C|-C4alky!-N-phenylamino, which are unsubstituted or substituted in the phenyl ring by sulfo. carboxyl, acetylamino, chlorine, methyl or methoxy, and in which the alkyl is unsubstituted or substituted by hydroxy!, sulfo or sulfate, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups. Non-chromophoric radicals which are bonded via the free valency in the formuia (|), (it), (iH) or (IV) are also fibre-reactive radicals. Fibre-reactive radicals are, for example, an alkanoyl or alkylsulfonyl radical substituted by an atom which can be split off or a group which can be split off, an all The fibre-reactive radical and the chromophore of the formula (1), (II), (III) or (IV) can be bonded to one another by a bridge member. Bridge members are, in addition to the direct bond or, for example, an amino group, the most diverse radicals. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; the bridge member can furthermore also be composed of different such radicals. The bridge member as a njle contains at least one functional group, for example the carbonyl, sulfonyl, carbonylamino, sulfonylamino or the amino group, it being possible for the amino group to be further substituted by C ,-C4alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano. C1-Calkoxy, C1-Caalkoxycarbonyl, carboxyl, suifamoyi, sulfo orsulfalo. An aliphatic radical is, for example, an alkylene radical having 1 to 7 carbon atoms or branched isomers thereof. The carbon chain of the alkylene radical can be interrupted by a heteroatom, for example an oxygen atom. An aromatic radical is, for example, a phenylene radical, which can be substituted by C-Calkyl, for example methyl or ethyl, C,-C4alkoxy, for example methoxy or ethoxy, halogen, for example fluorine, bromine or, in particular, chlorine, carboxyl or sulfo, and a heterocyclic radical is, for example, a piperazine or a triazine radical, it being possible for the triazine radical to contain a substituent whicli can be split off, tor example fluorine or chlorine. Such fibre-reactive radicals are known per se and a large number are 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 dyes (A) which comprise a chromophore of the formula (1), (II), (III) or (IV) are known or can be prepared analogously to known dyes. Suitable dyes (A) which comprise a chromophore of the formula (IV) are, for example, C.I. Reactive Blue 52,70.83, 84, 104,157.160, 182.202.209, 212, 218,220,221, 226, 228 and 232 and the dyes of the formulae (IV.1), (IV.2), (IV.3), (IV.4), (IV.5). {IV.6), (IV.7) and preferably C.I. Reactive Blue 52 and 182 and the dyes of the formulae (IV.1), (IV.2), {IV.3), (IV.4), (IV.5), {1V.6), {IV.7) and (IV.8), and in particular the dyes of the formulae {IV.1), (IV.2), (IV.3), (IV.4), (1V.5), (1V.6), (tV.7) and (1V.8). Suitable dyes which comprise a chromophore of the formula (IV) and contain a fibre-reactive radical are furthermore described, for example, in GB-A-2 148 921, US-A-4 994 562, US-A-5 021 557. US-A-5 023 274, US-A-5 076 811, US-A-5 112 958 and US-A-5 371 200. If the dye (A) contains two radicals of the formula (I), (II), (III) or (IV), these radicals are bonded to one another by a bridge member, in each case via the free valency in the formulae (I), (II), (111) and (IV). Bridge members are the most diverse radicals. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; the bridge member can furthermore also be composed of different such radicals. The bridge member as a rule contains at least two functional groups, for example the carbonyl, sulfonyl, carbonylamino, sulfonylamino or the amino group, it being possible for the amino group to be further substituted by CrC4alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano, CrC4alkoxy, d-Cialkoxycarbonyl, carboxyl, sulfamoyi, sulfo or sulfato. An aliphatic radical is, for example, an alkylene radical having 1 to 10 carbon atoms or branched isomers thereof. The carbon chain of the alkylene radical can be interaipted by a heteroatom, for example an oxygen atom. The term aliphatic radical also Includes cycloaliphatic radicals. An aromatic radical is, for example, a naphthylene radical, the radical of a diphenyl or stilbene, or, in particular, a phenylene radical, which can be substituted by C1-Calkyl, for example methyl or ethyl, C1-Cialkoxy, for example methoxy or ethoxy, halogen, for example fluorine, bromine or, in particular, chlorine, carboxyl or sulfo, and a heterocyclic radical is, for example, a triazine radical. The dyes (A) which comprise two chromophore radicals of the formula (1), (11), (111) or (IV) bonded to one another via a bridge member are known or can be prepared analogously to known dyes. A suitable dye is, for exan:iple, the dye of the formula {IV.9) Suitable dyes (A) which comporise two chromophore radicals of the formula (IV) borwled to one another via a bridge member are furthermore described, for example, in GB-A-1 389 053, GB-A-2 148 921, US-A-5 232 462, US-A-5,410,041 and US-A-5,684,138. The chromophore of the formula (I), (II) or (III) contained in the dye (A) is preferably one or two radicals of the formula (1.1), (1.2), (1.3). (1.4), (1.5), (11.1). (11.2), (11.3) or (IH.1) The chromophore contained in the dye (C) is preferably a mono- or disazo radical containing sulfo groups or a radical of the formula {V), {VI), (VII) or (VIII) and a radical of the formula (I), (11), (111) or (IV). The mono- or disazo radicals and the radicals of the formulae (V), (Vi), (VII) and (VIII) on which the dyes (B) and (C) of the inks according to the invention are based are, for example, yellow-, orange-, red- or claret- to violet-colouring dye radicals. Suitable dye radicals of the formula (V), (VI), (VII) and (VIM) are, for example, those of the formulae (V.l), (V.2), (V.3). (V.4), (V.5), {V.6), (V.7), (VI.1), (VII.1), (VIII.1), (VIII.2) and (VIII.3) Examples of substituents in the mono- or disazo radical are the following: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfate; alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfate; phenyl which is unsubstituted or substituted by C,-C4atky], C1-C4alkoxy, halogen, carboxyl or sulfo; acylamino groups having 1 to 8 carbon atoms, in particular such alkanoylamino groups, for example acetylamino or propionylamino; benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo; phenylamino which is unsubstituted or substituted in the phenyl ring by C1-C6alkyl, CrC4alkoxy, halogen or sulfo; N,N-dt-B-hydroxyethylamino; N,N-di-B-sulfatoethylamino; sulfobenzylamino; N,N-disulfobenzylamino; alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl; alkylsulfonyl having 1 to 4 cartaon atoms, such as methylsulfonyl or ethylsu(fonyi; triftuoromethyl; nitro; amino; cyano; halogen, such as fluorine, chlorine or bromine; carbamoyl; N-alkylcarbamoyI having 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono- or N,N-dialkylsulfamoyl having in each case 1 to 4 carbon atoms, such as N-methylsulfamoyI, N-ethylsulfamoyI, N-propylsulfamoyI, N-isopropylsulfamoyl or N-butylsulfamoyI, it being possible for the alkyl radicals to be further substituted, for example by hydroxy! or sulfo; N-(B-hydroxyethyl)-sulfamoyl; N,N-di-(B-hydroxyethyl)-sulfamoyl; N-phenylsulfamoyI which is unsubstituted or substituted by Cr C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo; ureido; hydroxyl; carboxyl; sulfomethyl or sulfo, and the fibre-reactive radicals described above. The mono- or disazo radicals containing sulfo groups in the dyes (B) and (C) of the inks according to the invention are preferably those of the formula (2) or (3) -D-N=N-(M-N=NVK (3), in which D is the radical of a diazo component of the benzene or naphthalene series, M is the radical of a middle component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series and u is the number 0 or 1, where D, M and K can carry substituents customafy in azo dyes, for example d-Caalkyl or CrCalkoscy which are unsubstituted or further substituted by hydroxyl, sulfo or sulfate, halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyi, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, Ca-C4alkanoylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4all A radical of the formula (2) or (3) in the dye (B) has bonded to it, via the free valency drawn in the formula (2) or (3), a non-chromophoric substituent, for example one of the substituents mentioned above for mono- or disazo radicals, or a radical of the formula is not fib re-reactive, for example C-Cialkoxy, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl, C,-C4aikoxy, sulfato or sulfo, morpholino, phenylamino or N-Cr C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy, and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups. The radicals mentioned can also satisfy the free valency of the dye (B) which comprises a chromophore radical of the formula (V), (VI), (Vll) or (VIII). The dyes (B) which comprise a chromophore of the formula (2), {3), (V), {VI), (VH) or (VIIl) are known or can be prepared analogously to known dyes. Suitable dyes (B) which comprise a chromophore of the formula (2) are, for example, the dyes of the formulae (2.1). (2.2), (2,3) and (2.4) Two radicals of the formula (2), (3), (V), (VI). (VII) or (VIM), contained in the dye (B) are bonded to one another by a bridge member, in each case via the free valency. Bridge members are, for example, those radicals which have already been described above in connection with the dye (A) containing two radicals of the formula (I), (II), (III) or (IV). The dyes {B) which comprise two chromophore radicals of the formula (2), (3), (V), (Vl), (VII) or (VIII) bonded to one another via a bridge member are known or can be prepared analogously to known dyes. Suitable dyes (B) which comprise two chromophore radicals of the foimula (2) bonded to one another via a bridge member are, for example, the dyes of the formulae (2.5), (2.6) and (2.7) The dye radicals in the dye (C) are bonded to one another via a bridge member, in each case via the free valency in the formula (1), (11), (III) or (IV) and the formula (2). (3), (V), (VI), (VII) or (VIII). Bridge members are, for example, those radicals which have already been described above in connection with the dye (A) containing two radicals of the formula (I), (II), (III) or (IV). The dyes (C) on which the inks according to the invention are based are known in some cases or can be prepared analogously to known dyes. The present invention also relates to the novel dyes (C) on which the inks according to the invention are based. Suitable dyes (C) and dyes (B) which comprise two chromophore radicals bonded to one another via a bridge member are furthermore described, for example, in US-A-5 232 462, US-A-5 243 033, US-A-5,410,041 and US-A-5,684,138. The radicals of the formulae (2) and (3) each contain at least one sulfo group, preferably 1 to 4 sulfo groups, in particular 1 to 3 sulfo groups, and especially 2 sulfo groups. The dye (C) preferably contains, as the chromophore, a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (1.1). (1.2), (1.3), (1.4), (1.5), (11.1), (11.2), (11.3), (III.1), (IVb) or (IVc). The radicals of the formulae (2) and (3) are preferably radicals of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), {4i), (4j), (4k). (41), (4m). (4n). (4o), (4p), (4q) or (4r) in which {R2)(M is 0 to 4 identical or different substituents from the group consisting of halogen, nitre, cyano, trifluoromethyl, sulfamoyi, carbamoyl, C1-CialkyI, C1-C4aikoxy which is unsubstituted or substituted by hydroxy] or C1-C4alkoxy, amino, C2-C4all r (Ri)o-3. (R2)o-3. (R4)o-3 and Z are each as defined above and (Ri")o-3 is 0 to 3 identical or different substituents from the group consisting of Ct-C4all C,-C4alkoxy R,, R,", Rj, R4, RB and Rg independently of one another are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, preferably methoxy or ethoxy, and in particular methoxy. Ct-Calkoxy R2 is unsubstituted or substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy, for example radicals of the formula -O-CHjCHa-OH or -O-CHaCHa-OCHg. Halogen Ri, R,", Rj, R4, Rg and Rg independently of one another are, for example, fluorine, chlorine or bromine, preferably chlorine or bromine, and in particular chlorine. Ca-Calkanoylamino R, and R2 independently of one another are, for example, acetylamino or propionylamino, In particular acetylamino. C2-C4-alkanoyl R3 is, for example, acetyl, propionyl or butyryl, preferably acetyl or propionyl, and in particular acetyl. C-Cialkylsulfonylamino Rg is, for example, methylsulfonylamino or ethylsulfonylamino, in particular methylsulfonylamino. The leaving group U is, for example, -CI, -Br, -F, -OSOaH, -SSO3H, -OCO-CH3, -OPOaHs, -OCO-CfiHs, -OS02-CrC4alkyl or -OSOz-N(C1-C4alkyl)2. Preferably, U is a group of the formula -CI, -OSO3H, -SSO3H, -OCO-CH3, -OCO-CgHs or -OPOaHa, in particular -CI or -OSO3H, and particularly preferably -OSO3H. The radicals of the formulae {4a) to (4r) are preferably radicals which contain no fibre-reactive group. Radicals which are of particular interest are those of the formulae (4a), (4d), (4e), (41), (4k), (4n), (4o), (4p), (4q) and (4r), in particular the radicals of the formulae (4a), (4d), (4e), (40), (4p), (4q) and (4r). The radicals of the formulae (4e), (4o), (4p) and (4q) are of special interest. Preferred inks are those in which the dye (A) has the formula (5) Bi is an aliphatic or aromatic bridge member, F, and F2 independently of one another are a radical of the formula (I), (II), (III) or (IV), and Xi and Xa independently of one another are halogen, hydroxyl, C,-C4alkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, CrC*alkylthio which is unsubstituted or substituted in the alt Ba and B3 independently of one another are an aliphatic or aromatic bridge member, Ai, Aa and Aa independently of one another are a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (VI) or (Vlt), F3 is a radical of the formula (I), (II), (111) or (IV) and X3, X4, X5 and Xe independently of one another are halogen, hydroxy!, GrGialkoxy which is unsubSitSKisd or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, C1-C4alkyithio which is unsubstituted or substituted in the allyl moiety, phenyithio which is unsubstituted or substituted in the phenyl ring, amino, N-mono-or N.N-di-C1-Cealkylamino whidi are unsubstituted or substituted in the alkyl moiety, Cj-Cr cycloalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C1-C4alkyl-N-phenyl- or N-C,-C4alky)-N-naphthylamino which are unsubstituted or substituted in the aryi moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino or piperidin-1-yl. branched. The alkyl radicals can be further substituted, for example by hydroxyl, sulfo, sulfate, cyano or carboxyl. Examples are the following radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicals substituted by hydroxyl, sulfo, sulfate, cyano or carboxyl. Preferred substituents are hydroxyl, sulfo, sulfate or carboxyl, in particular hydroxyl or sulfate, and preferably hydroxyl. Aliphatic bridge members Bi, 82 and 83 are, for example, a Ca-Ciaalkylene radical, in particular a Ca-Cealkylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of -NH-, -N(CH3}- or, in particular, -O- and is unsubstituted or substituted by hydroxyl, sulfo, sulfate, cyano or carboxyl. Preferred substituents of the alkylene radicals mentioned for B,, B2 and B3 are hydroxy!, sulfo or sulfate, in particular hydroxyl. Aliphatic bridge members B,, 83 and 83 are furthermore, for example, Cs-Cg-cycioalkylene radicals, such as, in particular, cydohexylene radicals. The cycloalkylene radicals mentioned can be unsubstituted or substituted by Cj-CjalkyI, Cj-Cjalkoxy, C2-C.,alkanoylamino, sulfo, halogen or carboxyl, in particular by CrCAalkyl. Aliphatic bridge members Bi, 82 and B3 are furthermore methylene-cyclohexylene, ethylene-cyclohexylene or methylene-cyclohexylene-methylene radicals which are unsubstituted or substituted in the cydohexylene ring by CT Calkyl, in particular methyl. Aromatic bridge members Bi, 82 and 83 are C1-Cgalkylenephenylene, such as methylenephenylene, Cj-C4alkylenephenylene-C,-C4alkylene, for example methyienephenylenemethylene, or phenylene which are unsubstituted or substituted by C,-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, or a radical of the formula in which the benzene rings I and II are unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy, Ca-Cnalkanoylamino, sulfo, halogen or carboxyl and L is the direct bond or a C2-Cioalkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula -CH=CH-, -N=N-, -NH-, -CO-, -NH-CO-, -NH-SO2- -NH-CO-NH-, -0-, -S- or -SO3-. Aromatic bridge members Bi, 83 and B3 are preferably phenyiene, which can be substituted as mentioned above. Preferably, the aromatic bridge members Bi, Bg and B3 are unsubstitutsd or substituted by sulto. Bi, Ba and B3 are preferably a C2-Ci2a(kylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of -NH-, -N(CH3)- or -O- and is unsubstituted or substituted by hydroxyl, sulfo, sulfate, cyano or carboxyl; or a Cs-Cgcycloalkylene radical, d-Cealkylenephenylene radical or phenyiene radical which are unsubstituted or substituted by CrC4alkyt, CrC4alkoxy, C2-C4alkanoyiamino, sulfo, halogen or carboxyl; or Bi, 82 and 83 are a radical of the formula (8), in which the benzene rings I and It are unsubstituted or substituted by CrCaikyl, C,-C4alkoxy, CrC4alkanoylamino, suifo, halogen or carboxyl and L is the direct bond or a C2-C,oalkylene radical, which can be interrupted by 1,2 or 3 oxygen atoms, or L is a bridge member of the formula -CH=CH-, -N=N", -NH-, -CO-, -NH-CO-, -NH- Bi, Ba and B3 are particularly preferably a Cg-Ctaalkylene radical, which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxyl, sulfo, suitato, cyano or carboxyl, or a phenyiene radical which is unsubstituted or substituted by C|-C4alkyl, C1-C4ail Bridge members Bi, B? and 83 of particular interest are Cj-Cgalkylene radicals, in particular those of the formula -GH2-GH(Ra2)- or -(RsEJ-CH-CHa-, in which R22 is C1-C4alkyl, in particular methyl. Halogen Xi, X, X3, X4, X5 and Xg independently of one another are, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and in particular chlorine. C1-C4alkoxy Xi, X2, X3, X4, X5 and Xg independently of one another are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, in particular methoxy or ethoxy. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C1-C4alkoxy, for example methoxy or ethoxy, hydroxyi, sulfo or carboxyi. C1-C4alkylthio Xi, X2, X3, X4, X5 and Xa independently of one another are, for example, methylthio, ethyllhio, propylthio, isopropylthio or butylthio. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C1-C4alkoxy, for example methoxy or ethoxy; hydroxyi; sulfo or carboxyi. The radicals substituted in the alkyl moiety by one or two radicals from the group consisting of hydroxyi, sulfo and carboxyi are preferred. N-mono- or N.N-di-C1-Cealkylamino, preferably N-mono- or N,N-di-C1-C4alkylamino, Xi, X2, X3, X4, X5 and Xg independently of one another are, for example, N-methylamino, N-ethylamino, N-propylamino, N-butylamino, N-hexyiamino, N,N-dimethylamino or N,N-di-ethylamino. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C2-C4alkanoyiamino, for example acetylamino or propionylamino; C1-C4alkoxy, for example methoxy or ethoxy; hydroxyi; sulfo; sulfate; carboxyi; carbamoyl; sulfamoyl or P-sulfatoethylsulfonyl. The radicals mentioned are uninterrupted or interrupted in the alkyl moiety by oxygen. Examples of radicals which are substituted in the alkyl moiety and which are interrupted in the alkyl moiety by oxygen are N-p-hydroxyethylamino, N,N-di-[3-hydroxyethylamino, N-2-{p-hydroxyethoxy)-ethylamino, N-2-{2-(p-hydroxyethoxy)ethoxy]ethylamino, N-p-sulfatoethylamino, N-p-sulfoethylamino, N-carboxymethylamino, N-p-carboxyethylamino, N-a,p-dicarboxyethylamino, N-a,v-dicarboxypropylamino, N-ethyl-N-p-hydroxyethylamino and N-methyl-N-p-hydroxyethylamino. The radicals which are substituted in the alkyl moiety by hydroxy!; sulfo; sulfate; carboxyi or carbamoyl are preferred. Cs-C7cycloalkylamino Xi, X2, X3, X4, X5 and Xg independently of one another can include both the unsubstituted radicals and the radicals which are substituted in the cycloalkyi ring. for example by C,-C4alky[, for example methyl or ethyl, in particular methyl, or carboxyl. Preferred such radicals are the corresponding cyclohexyl radicals. Phenylamino or N-C,-C4a!kyl-N-phenylamino, preferably phenylamino, X,, X2, X3, X4, Xg and Xg independently of one another can include both the unsubstituted radicals and the radicals which are substituted in the phenyl ring, for example by C1-C4alkyl, for example methyl or ethyl, which is unsubstituted or further substituted, for example by carboxyl; C1-Calkoxy, for example methoxy or ethoxy; carboxyl; carbamoyl; N-C-C4alkylcarbamoyl, which Is unsubstituted or further substituted in the alkyl moiety, for example by carboxyl, for example N-carboxymethylcarbamoyI; sulfo or halogen, for example chlorine or bromine. The substituted radicals, preferably the radicals substituted by carboxyl, carboxymethyl, N-carboxymethylcarbamoyl or sulfo, in particular sulfo, are preferred. Naphthylamino or N-C1-C4alkyl-N-naphthylamino, preferably naphthylamino, Xi, Xz, Xa, X4. X5 and Xfi independentiy of one another can include both the unsubstituted radicals and the. radicals substituted in the naphthyl ring, for example by sulfo. The radicals substituted by 1 to 3, in particular 2 to 3, sulfo groups are preferred. Benzylamino X,, X2, X3, X4, X5 and Xs which are unsubstituted or substituted in the phenyl moiety independently of one another can include both the unsubstituted radicals and the radicals substituted in the phenyl ring, for example by C1-C4alkyl, for example methyl or ethyl; C1-C4alkoxy, for example methoxy or ethoxy; carboxyl; sulfo or halogen, for example chlorine or bromine. The radicals substituted in the phenyl ring by carboxyl are preferred. Xi, X2, Xa, X4, Xs and Xe are preferably halogen, C1-C4alkoxy, oralkylthio which are unsubstituted or substituted in the alkyl moiety by C1-Cialkoxy, hydroxy!, sulfo or carboxyl. N-mono, or N,N-di-C1-C4alky[amino which are unsubstituted or substituted in the alkyf moiety by C3-C4alkanoylamino, CrC4alkoxy, hydroxyl, sulfo, sulfato, carboxyl, carbamoyl or suifamoyl, Cs-Cj-cycloalkylamino which is unsubstituted or substituted by CrC4alkyl or carboxyl, phenylamino or N-C,-C4alkyI-N-phenylamino which are unsubstituted or substituted in the phenyl moiety by C,-C4alkyl, which is unsubstituted or further substituted by carboxyl, C1-C4alkoxy, carboxyl, carbamoyl, N-CrC4alkylcarbamoyl, which is unsubstituted or further substituted in the alkyl moiety by carboxyl. sulfo or halogen, naphthylamino which is substituted in the aryl moiety by sulfo, or benzyiamino which is unsubstituted or substituted in the phenyl moiety by C,-C4all Ru. R12, RIS. R16. Ri9 and R20 are preferably hydrogen or CrCialkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato or carboxyl, preferably hydrogen or C|-C4alkyl, and in particular hydrogen. The radicals F, and F2 in the dye of the formula (5) can be different or identical. Preferably, the radicals Fi and Fj are identical. The radicals A, and A2 in the dye of the formula (6) can be different or identical. Preferably, the radicals Ai and Aa are identical. The radicals X, and X2 in the dye of the formula (5) can be different or identical. Preferably, the radicals X, and X2 are identical. The radicals X3 and X* in the dye of the formula (6) can be different or identical. Preferably, the radicals X3 and X4 are identical. The radicals X5 and Xe in the dye of the formula (7) can be different or identical. Preferably, the radicals X5 and Xe are identical. Preferred inks are those in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which Rio. Rni Ri2i Ri3i Ri"ii RiSi Ri6r Ri7i Ri8. R19. 20. Rzi. Bi, B2, B3, Fi, Fj, F3, Ai, A2, A3, Xi, X2, X3, X4, Xs and Xe are as defined and preferred above under formulae (5), (6) and (7). Particularly preferred inks are those in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which R10. R11. R12, Ri3, Rt4, Ri5. R16. Ri7, R,8. Ri9. R20 and R21 are hydrogen, Bi, Bz and B3 independently of one another are a radical of the formula -CH2-CH{R22)- or -(Rz2)-CH-CH2-, in which R22 is C1-C4alkyl, in particular methyl, Fi, Fa and F3 independently of one another are a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (1.1), (1.2), (1.3), (1.4), (1.5), (ll.l), (IL2), (11.3), (III.1), (IVb) or (IVc), Ai, A2 and Aa independently of one another are a radical of the fomiula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (41), (4]), (4k), (41), (4m), (4n). (4o). (4p). (4q). (4r). (V), (VI) or (VII). preferably (4a), (4d), (4e), (4o), (4p), (4q), (4r). (V), (VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V), (VI) or (VII), which contain no fibre-reactive substituents, and Xi, X2, X3, X4, Xs and Xe independently of one another are halogen, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo or carboxyl, in particular sulfa or carboxyl, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by C2-C4alkanoylamino, CrC4alkoxy, hydroxy!, sulfo, sulfato, carboxyl or carbamoyl, in particular hydroxyl, sulfo or carboxyl, or morpholino. A particularly preferred embodiment of the present invention comprises inks which comprise at least one dye (A) of the formula (5) together with at least one dye (C) of the formula (7), in which Rio, Rn.Ris, R13. R18. R19. R20. R2i,B,,B3, Fi, Fa, F3, A3, X,,X2,Xs and Xe are as defined and preferred above. Hsj is as defined and preferred for Rio, Ria, RH, R17, Ria and R21, RE* and Rs independently of one another are as defined and preferred for Ru R,a, R,5, R,e, R,9 and R20, B4 is as defined and preferred for B,, B2 and 83, A4 is a radical of the formula (VIII), F4 is as defined and preferred for Fi, Fj and Fg and X7 is as defined and preferred for Xi, X2, Xa, X4, X5 and Xe- The inks according to the invention preferably comprise 30 to 95% by weight of at least one dye (A) together with 5 to 70% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of dyes (A), (B) and (C) in the ink. If the ink according to the invention comprises at least one dye (A) together with at least one dye (B). the dye (A) is present, for example, in an amount of 60 to 95% by weight, preferably 70 to 95% by weight, in particular 75 to 90% by weight, and the dye (B) is present, foe -example, in an amount of 5 to 40% by weight, preferably 5 to 30% by weight, and in particular 10 to 25% by weight, based on the total weight of the dyes (A) and (B) in the ink. If the ink according to the invention comprises at least one dye (A) together with at least one dye (C), the dye (A) is present, for example, in an amount of 25 lo 90% by weight, preferably 30 to 80% by weight, and in particular 30 to 70% by weight, and the dye (C) is present, for example, in an amount of 10 to 75% by weight, preferably 20 to 70% by weight, and in particular 30 to 70% by weight, based on the total weight of the dyes (A) and (C) in the ink. The inks according to the invention can comprise further dyes for shading, in addition to the abovementioned dyes. Preferably, the inks comprise no substantial amounts of a further dye which does not fall under the definition according to the claims of the dyes in the inks according to the invention. "Substantial amounts" in this connection is to be understood as meaning, for example, amounts of more than 5% by weight, based on the total weight of the dyes (A), {8} and (C) in the ink. The dyes used In the inks according to the invention should preferably have a low salt content, i.e. comprise a total content of salts of less than 0.5% by weight, based on the weight of the dyes. Dyes which have relatively high salt content due to their preparation and/or the subsequent addition of diluents can be desalinated, for example, by membrane separation processes, such as ultrafiltration, reverse osmosis or dialysis. The inks preferably comprise a total content of dyes of 1 to 35% by weight, in particular 1 to 30% by weight, and preferably 1 to 20% by weight, based on the total weight of ink. A limit of 2.5% by weight, in particular 5% by weight, and preferably 7.5% by weight, is preferred here as the lower limit. Those inks which have a viscosity of 1 to 40 mPas (millipascal-seconds) are preferred. The inks comprise water-miscible solvents in an amount of 1 to 40% by weight, for example C,-C4 alcohols, for example methanol, elhanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or isobutanol; amides, for example dimethylformamide or dimethylacetamide, ketones or ketone alcohols, for example acetone or diacetone alcohol; ethers, for example tetrahydrofuran or dioxane; nitrogen-containing heterocvclic compounds, for example N-methyi-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, polyalkylene glycols, for example polyethylene glycol or polypropylene glycol; C-Cgalkylene glycols and thioglycols, for example ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodlglycol, hexylene glycol and diethylene glycol; further polyols, for example glycerol or 1,2,6-hexanetriol; and Ct-CAalkyl ethers of polyhydric alcohols, for example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-{2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxylethanol or 2-12-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or, in particular, 1,2-propylene glycol, preferably in an amount of 2 to 30% by weight, in particular 5 to 30% by weight, and especially TO to 25% by weight, based on the total weight of the ink. The inks can furthermore also comprise solubilizing agents,for example e-caprolactam. The inks can comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity. Examples of thickeners are commercially available alginate thickeners, starch ethers or carob bean flower ethers, in particular sodium alginate, by itself or as a mixture With modified cellulose, for example methyl-, ethyl-, carboxymethyl-, hydroxyethyl-, methylhydroxyethyl-. hydroxypropy!- or hydroxypropylrnethyfcellulose, in particular with preferably 20 to 25% by weight of carboxymethylcellulose. Synthetic thickeners are furthermore, for example, those based on po!y(meth)acrylic acids or poly(meth)acrylamides. The inks comprise such thickeners, for example, in an amount of 0.01 to 2% by weight. In particular 0.01 to 1 % by weight, 3nd preferably 0.01 to 0.5% by weight, based on the total weight of the ink. The inks can furthermore comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate. Examples are borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium tripolyphosphate, sodium pentaphosphate and sodium citrate. They are used, in particular, in amounts of 0.1 to 3% by weight, preferably 0.1 to 1%by weight, based on the total weight of the ink, in order to establish a pH of, for example, 4 to 10, preferably 5 to 8. The inks can comprise surfactants or humectants as further additives. Surfactants are the commercially available anionic or nonionic surfactants. Humectants are, for example, urea, glycerol, propylene glycol 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 0.1 to 30% by weight, in particular 2 to 30% by weight, in the inks according to the invention. If desired, the inks can also comprise acid donors, such as butyrolactone or sodium hydrogen phosphate, preservatives, substances which inhibit fungal and/or bacterial growth, foam suppressants, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or de-aerating agents. Presen/atives are, in particular, formaldehyde-releasing agents, for example paraformaldehyde and trioxane, in particular aqueous, approximately 30 to 40% by weight formaldehyde solutions, sequestering agents are, for example, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, and in particular sodium polymetaphosphate, especially sodium hexametaphosphate, emulsifiers are, in particular, adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oieyl alcohol and ethylene oxide, water-insoluble solvents are high-boiling saturated hydrocarbons, in particular paraffins with a boiling range from about 160 to 210""C {so-called white spirits) oxidizing agents are, for example, an aromatic nitro compound, in particular an aromatic mono- or dinitrocarboxylic acid or -sulfonic acid, which may be present as an aikylene oxide adduct, in particular a nitrobenzenesulfonic acid, and de-aerating agents are, for example, high-boiling solvents, in particular terpentine oils, higher alcohols, preferably Ca to C,o alcohols, terpene alcohols or de-aerating agents based on mineral and/or silicone oils, in particular commercial formulations of about 15 to 25% by weight of a mixture of mineral oil and silicone oil and about 75 to 85% by weight of a Ca alcohol, for example 2-ethyl-n-hexanol. These are usually used in amounts of 0.01 to 5% by weight based on the total weight of the ink. The inks can be prepared in the customary manner by mixing the individual constituents into the desired amount of water. If necessary, the inks are clarified by filtration through an extra-fine filter. The inks according to the invention are suitable, for example, for printing. Examples of appropriate printing processes are conventional printing, screen printing and ink-jet printing processes. The inks according to the invention are particularly suitable for use in recording systems of a type in which an ink is pressed out of a small opening in the form of droplets directed against a substrate on which an image is formed. Suitable substrates are, for example, textile fibre materials, paper or films of plastic. Suitable recording systems are, for example, commercially available ink-jet printers for use in printing of paper or textiles, or writing implements, such as fountain pens or ball-point pens, and in particular ink-jet printers. It may be necessary, for example, to adjust the viscosity or other physical properties of the ink, in particular those which have an influence on the affinity for the particular substrate, according to the method of use. The inks according to the invention which comprise dyes with fibre-reactive radicals are thus suitable for use in the printing of paper or textiles. Inks which comprise dyes without fibre-reactive radicals are particularly suitable for recording on paper, and especially for use in the printing of paper. Textile fibre materials are, in particular, fibre materials containing nitrogen or containing hydroxy! groups, tor example textile fibre materials of cellulose, silk, wool or synttietic polyamides. Examples of paper which can be printed witti the inks according to the invention are commercially available ink-jet paper, photographic paper, glazed paper and paper coated with plastic, for example Epson Ink-Jet Paper, Epson Photo Paper. Epson Glossy Film, HP Special Ink-Jet Paper, Encad Photo Gloss Paper and llford Photo Paper. Films of plastic which can be printed with the inks according to the invention are, for example, transparent or milky/opaque. Suitable films of plastic are, for example, 3M Transparency-Film. The present invention thus also relates to a process for printing paper, films of plastic or textile fibre materials, in particular by the ink-jet printing process, which comprises using an aqueous ink which comprises 20 to 95% by weight of at least one dye (A) together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the ink, and 1 to 40% by weight of a water-miscible organic solvent, based on the total weight of the ink, wherein the dyes (A), (B) and (C) are as defined and preferred above. In the case of the ink-jet printing process, individual drops of the ink are sprayed out of a jet in a controlled manner onto a substrate. The continuous ink-jet method and the drop-on-demand method are chiefly used for this. In the case of the continuous ink-jet method, the drops are produced continuously, drops which are not required for printing being diverted into a collecting container and recycled. In the case of the drop-on-demand method, on the other hand, drops are produced and printed as required, i.e. drops are only produced if this is necessary for printing. The drops can be produced, for example, by means of a piezo ink-jet head or by means of thermal energy (bubble jet). Printing by means of a piezo ink-jet head is preferred for the process according to the invention. Printing by the continuous ink-jet method is furthermore preferred for the process according to the invention. The records produced, such as, for example, prints, are distinguished by good biaclt shades without a change in shade in artificial light (metamerism) with an outstanding fastness to light. Records which are produced with inks comprising a dye (A) together with a dye (C) show no "orange bieeding" of the black shade. The present invention also relates to black-dyeing dye mixtures which comprise 20 to 95% by weight of at least one dye (A) together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the dye mixture, where the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which the radicals Rio, Rn, R12. R13, R14, Ris, Rie, R17, R18. Ri9. Reo. Rat, B,, Bz, Bg, F,, Fa, F3, A,, Aa, Aa, X,, Xj, X3, X4, X5 and Xe are as defined and preferred above under the formulae (5), (6) and (7). The dye mixtures according to the invention can be orepared, for example, by mixing the individual dyes. This mixing process is carried out, for example, in suitable mills, for example ball or pinned disc mills, and in kneaders or mixers. The dye mixtures according to the invention in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7) and the radicals R,o, Ri3 and Bzu Rn, R12, Ris, R16. Rigand R20; Ri4- R!7and R,8; Bi, 82 and 83; Fi, FaandFa; Ai, Aaand A3 and Xi, X2, X3, X4, X5 and Xe in each case have identical meanings, can be prepared by reacting the compounds of the formulae (10a) and (10b) halogen, for example fluorine or chlorine, with one another in any sequence and, in the case where dye intermediates are used, the resulting intermediate products are converted into the desired dyes, and, if appropriate, a further reaction with a compound of the formula (13) H-X, (13) in which Xi is as defined under the formula (5), with the exception of halogen, follows. The preparation of the end dyes from the intermediates is, in particular, coupling reactions which lead to azo dyes. Since the individual process steps described above can be carried out in a different sequence, and in some cases also at the same time, if appropriate, various process variants are possible. In general, the reaction is carried out stepwise In succession, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions. One process variant comprises reacting the compounds of the formulae (10a) and (10b) independently of one another with in each case an approximately equivalent amount of a halogenotriazine compound of the formula (11) to give the compounds of the formulae (14a) and (14b) and then subjecting a mixture of approximately two molar equivalents of the compounds of the formulae (14a) and (14b) to a condensation reaction with approximately one molar equivalent of a diamine of the formula (12) and, if appropriate, following this condensation step with a further reaction with a compound of the formula (13). The ratio of the dyes of the formulae (5), (6) and (7) In the mixture can vary in the range statedanddependshereon the ratio ofthe compounds of the formulae (14a) and (14b) in the reaction mixture. The individual condensation reactions are carried out, for example, by processes which are known per se, as a rule in aqueous solution at a temperature of, for example, 0 to SCC and a pH of, for example, 4 to 10. The present invention relates to a process for the preparation of the dye mixtures according to the Invention which do not comprise substantial amounts of a compound of the formula (6), which comprises (i) reacting the compounds of the fonnulae (10a) and (10b) independently of one another with in each case a halogenotriazine compound of the formula (11) to give the compounds of the formulae (14a) and (14b), (ii) reacting the compound of the formula (14b) with an excess of a diamine of the formula (12) such that a mixture of the compounds of the formulae (12) and (15) (iii) subjecting this mixture to a condensation reaction with a compound of the formula (14a) in an equimolar amount which corresponds to the number of amino groups which have not been acylated by the compound of the formula (14b), to give a mixture of the compounds of the formulae (Sa) and (7a) (iv) if appropriate reacting the radicals X with a compound of the formula (13), in which Ai, F,, R,o, Fill, Ri2 and Ru are as defined and preferred under the formulae (5) and (6), X is halogen, for example fluorine or chlorine, and Xi is as defined and preferred under the formula (5), and Is not halogen. The ratio of the dyes of the formulae (5a) and (7a) in the mixture can vary in the range stated and depends here on the ratio of the compounds of the formulae (12) and (14b) according to process step (ii), the molar ratio of the compounds of the formulae (12) and (14b) being greater than 1 and, for example, 1.5 to 10, and preferably 2 to 6- Process step (ii) is advantageously carried out at a pH of 5 to 7. The compounds of the formulae {10a), (10b), (12) and (13) are known or can be obtained analogously to known compounds. The present invention furthermore relates to dyes of the formula (9) B4 is as defined and preferred for B,, B2 and B3, A4 is a radical of the formula (VIII), F4 is as defined and preferred for Fi, Fa and F3 and X7 is as defined and preferred for X,, Xj, X3, X4, X5 and Xg. Dyes of the formula (9) can be prepared by an addition reaction of a compound of the formula (16) in which Ifie radicals R23, R20, Bzs. B, F* and W are as defined and preferred above and X is halogen, for example fluorine or chlorine, in the presence of a base, for example an alkali metal hydroxide, in particular sodium hydroxide, at a pH of, for example, 7 to 12, preferably 8 to 10. If appropriate, the radical X7 can be introduced by first reacting the compound of the formula (16) or the resulting addition product of the compounds of the formulae (16) and (17) with a compound of the formula H-X?, In which X7 is as defined and preferred, with the exception of halogen, by processes known per se. The compounds of the formula (16) and (17) are known or can be prepared by processes known per se. Bs is an aromatic bridge member and Fs is a radical of the formula (I), (II), (111), (IVa), (IVb) or (IVc), in particular (1.1), (1.2), (1.3), (1.4), (1.5). (11.1), (11.2), (11.3), (III.1), (IVb) or (IVc), A4 is a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (41). (4j). (4k). (41), (4m), (4n). (40), (4p), (4q), (4r), (V), (VI) or (VII), preferably (4a), (4d), (4e), (4o), (4p), (4q), (4r), (V), (VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V), (VI) or (VII), and Xa and Xg are as defined and preferred above for X], X2, X3, X4, Xs and Xg. Rse and R29 are as defined and preferred above for Rio, Ria, RM, RI7> R18 and Rat. R27and Rjaare as defined and preferred above for R,,, R13, R15, Rie, Rigand Rao. A4 is as defined and preferred above for radicals A,, A3 and A3 of the formulae {4a), (4b), (4c), (4d), (4e), (4f), (4g), {4h), (4i), {4j), (4k), (41), (4m). (4n). (4o), {4p), (4q). (4r), (V), (VI) and (VII). B5 is as defined and preferred above for aromatic bridge members B,, B2 and 83. Fs is as defined and preferred above for radicals Fi, F2 and F3 of the fomulae (1), (11), (1!!), (IVa). (IVb) and (IVc). The present invention also relates to dyes (C) of the formula (18) in which Rz6. R27. Raa and R29 are as defined and preferred above, Bs is an aliphatic bridge member, Fg is as defined and preferred above, A4 is a radical of the formula (4o) (Ri)o.3is 0 to 3 identical or different substituents from the group consisting of C,-C4alkyl, C,-C4aikoxy, C2-C4alkanoylamino, halogen, carboxyl and sulfo, in particular a sulfo group, (Ri")o.3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo, In particular a sulfo group, {R2)o-3 is 0 to 3 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyi, carbamoyl, C,-C4alkyl, CrC4alkoxy which is unsubstituted or substituted by hydroxyl or CrC4alkoxy, amino, C2-C4alkanQylamino, ureido, hydroxyl, carboxyl, sulfomethyl, CrC4alkylsulfonyianino and sulfo, in particular halogen, d-Calkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, Cz-C4aikanoylamino. ureido, C1-Calkylsulfonylamino and sulfo, and 2 is vinyl or a radical -CH2-CH2-U and U is a leaving group, and Xa and Xg are as defined and preferred above. The radical A4 preferably contains no fibre-reactive group of the formula -SO2-Z. B5 is as defined and preferred above for aliphatic bridge members Bi, B2 and 83. The dyes of tfie formula (18) according to the invention can be prepared by processes known per se, such as are described, for example, in US-A-5,684,138. The invention also relates to a process for dyeing or printing fibre materials containing hydroxy! groups or containing nitrogen w/ith the dyes or dye mixtures according to the invention. Fibre materials are, for example, the natural cellulosic fibres, such as cotton, linen, jute or hemp, and modified cellulosic fibres, such as cellulose or regenerated cellulose. The dyes and dye.mixtures according to the invention are also suitable for dyeing or printing natural polyamide fibre materials, for example silk or wool, synthetic polyamide fibre materials, for example polyamide 6 or polyamide 6.6, or wool and synthetic polyamide blend fabrics. The dyes and dye mixtures according to the invention are particularly suitable for dyeing or printing natural polyamide fibre materials, and here in particular wool or chlorinated woo! or wool with a washing machine-resistant finish. The textile fibre materials mentioned can be in the most diverse forms of processing here, for example as fibre, yarn, fluff, woven fabric or knitted fabric. The dyes and dye mixtures according to the invention are suitable for customary dyeing and printing processes and can be applied and fixed to the fibre material in the most diverse ways, in particular in the form of aqueous dye solutions or printing pastes. They are suitable both for the exhaust method and for pad dyeing, in which the goods are impregnated with aqueous dye solutions, which may contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, with the action of heat if appropriate. The dyes and dye mixtures according to the invention are also suitable for the so-called cold pad-batch process, in which the dye is applied on the padder together with the alkali and is then fixed by storage at room temperature for several hours. » Dyeing of natural and synthetic polyamide fibre materials, in particular wool, is preferably carried out by the exhaust method at a pH of about 3 to 7, in particular 4 to 6, and at temperatures of, for example, 70 to 120°C, and in particular 90 to 105°C. In addition to water and the dyes or dye mixtures according to the invention, the dye liquors or printing pastes can comprise further additives, for example shading dyes, salts, buffer substances, wetting agents, antifoams, levelling agents or agents which influence the properties of the textile material, for example softening agents, additives for a flame-retardant finish or soil-, water- and oil-repellent agents, as well as water-softening agents and natural or synthetic thicl The dye mixtures according to the invention In which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7) and the dyes according to the invention has the formula (9) and (18) are furthermore distinguished by a good solubility. In the following examples parts are parts by weight. The temperatures are degrees Celsius. Parts by weight and parts by volume bear the same relationship as the gram and cubic centimetre. Example 1 a) 9.22 parts of cyanuric chloride are suspended in 150 parts of ice-water. The pfH is brought to 5 with 1 N sodium hydroxide solution and the temperature is kept at 0 to 2°C. A neutral solution of 29.80 parts of the copper complex of 5-amino-3-[3-phenyl-5-{2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonic acid in 250 parts of water is added to this suspension at 0 to 3""C. During the addition the pH is kept at 5 with a 2 N sodium hydroxide solution. After the addition, the mixture is stirred at 0 to 3°C and pH 5 for about a further 2 hours. A solution of 5-[4,6-dichloro-1,3,5-triazin-2-ylamino]-3-E3-phenyl-5-(2-carboxy-5-sulfophenyl)-1 -formazano]-4-hydroxybenzenesulfonic acid is obtained. b) 3.56 parts of cyanuric chloride are suspended in 50 parts of ice-water. The pH is brought to 5.5 with 1 N sodium hydroxide solution and the temperature is kept at 0 to 2°C. A neutral solution of 10.02 parts of 4-(2-ureido-4-aminophenylazo)-azobenzene-3,4"-disulfonic acid in 120 parts of water is added to this suspension at 0 to 3""C. During the addition the pH is kept at 5.5 with 1 N sodium hydroxide sciution. After the addition the mixture is stirred at 0 to 5°C and pH 5.5 for about a further 3 hours. A suspension of 4-[2-ureido-4-{4,6-dichloro-1,3,5-triazin-2-ylamino)phenylazo]-azobenzene-3,4"-disulfonic acid is obtained. c) The suspension obtained according to b) Is added dropwise to a solution of 2.31 parts of 1,2-diaminopropane in 50 parts of ice-water, which has been brought to pH 5,5 to 6 with 16% hydrochloric acid, the pH being kept at 6 with 1 N sodium hydroxide solution. During the dropwise addition the temperature is allowed to rise to about 20°C. To bring the reaction to completion the temperature is increased to 50°C in the course of several hours and the pH is increased to 6.5 to 7. d) The solution obtained according to a) is allowed to run slowly into the solution obtained according to c), the pH being kept at 6.5 by addition of a 1N sodium hydroxide solution and the temperature being kept at 15 to 20""C. To bring the reaction to completion the temperature is increased to 50""C and the pH is increased to 8.5 to 9. A few drops of 1,2-diaminopropane are added to the reaction mixture at a temperature of 35 to 40°C in order to eliminate an excess of the compound according to process step a) in the reaction mixture. The pH is increased to 10 by addition of a 2 N sodium hydroxide solution. The reaction mixture is then allowed to cool to room temperature and the pH is brought to 8 with 2 N hydrochloric acid. The reaction mixture is clarified by filtration, and freed from the salt by dialysis and the resulting solution is freeze-dried. 54.6 parts of a dye mixture which comprises about 46% by weight of a dye which, in the form of the free acid, has the formula {101) Example 2 a) 9.65 parts of cyanuric fluoride are added to a neutral solution of 35.80 parts of the copper complex of 5-aminQ-3-[3-pheny(-5-(2-carbQxy-5-sulfophenyl)-1-formazanQ]-4-hydroxybenzenesulfonic acid in 350 parts of water at 0 to 2°C in the course of 10 minutes. During the addition the pH is kept at 5.8 to 6 with a 15% sodium hydroxide solution. After the addition the mixture is stirred for about 15 minutes, the pH is brought to 3.5 to 3.8 with 32% hydrochloric acid and the mixture is stirred again for about 15 minutes. The pH is then brought to about 5.8 to 6 with a 15% sodium hydroxide solution. A solution of 5-[4,6-difluoro-l,3,5-tria2in-2-ylamino]-3-[3-phenyl-5-(2-carbaxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonic acid is obtained. b) 3.38 parts of cyanuric fluoride are slowly added to a neutral solution of 10.02 parts of 4-(2-ureido-4-aminophenylazo)-azobenzene-3,4"-disuifonic acid in 120 parts of water at 0 to 2°C. During the addition the pH is kept at 7.3 to 7.5 with a 15% sodium hydroxide solution. After the addition the mixture is stirred at 0 to 2""C for about 10 minutes and the pH is kept at 7.3 to 7.5. The pH is then brought to 3.5 with 32% hydrochloric acid and the mixture is stirred again at 0°C for about 10 minutes. A solution of 4-[2-ureido-4-(4,6-difluoro-1,3,5-triazin-2-ylamino)phenylazo]-azobenzene-3,4"-disulfonic acid is obtained. c) The cold solution (0°C) obtained according to b) is slowly added dropwise to a solution of 2.31 parts of 1,2-diaminopropane in 50 parts of water at 200 and a pH of 6 to 6.5. The pH is kept at 6 to 6.5 here with 1 N sodium hydroxide solution and the temperature is kept at 20 to 25°C. To bring the reaction to completion the mixture is stirred under these conditions for a few hours. d) The suspension obtained according to c) is cooled to 0 to 5°C and the pH is brought to 8.5 with a 15% sodium hydroxide solution. The solution obtained according to a) is then metered in, the pH being kept at 8.5 with 15% sodium hydroxide solution. The temperature is slowly increased to 20 to 25°C and the pH to 9. To bring the reaction to completion the mixture is stirred under these conditions for some hours. The resulting solution is then rendered neutral, clarified by filtration, freed from the salt by dialysis and freeze-dried. 42.8 parts of a dye mixture which comprises about 46% by weight of a dye which, in the form of the free acid, has the formula (105) Ixample 3 0.7 parts of the dye mixture obtained according to Example 2d), comprising the dyes of the srmulae (105) and (106), are dissolved in 200 parts of water, and 1.92 parts of morpholine re added at 20°C and a pH of 8. The reaction mixture is heated to 50 to 55°C and the pH is roughtto 10 by addition of 15% sodium hydroxide solution. The mixture is stirred at this jmperature for about a further 1 hour. The reaction mixture is then allowed to cool to room 5mperature and the pH is brought to 7 to 7.5 with 16% hydrochloric acid. The resulting olutlon is freed from the salt by dialysis and freeze-dried. 11.1 parts of a dye mixture which omprises about 46% by weight of a dye which, in the form of the free acid, has the formula 107) The dye mixture gives prints on paper and dyeings and prints on cotton and wool in blacit colour shades of high lastness to light. Examples 4 to 30 The procedure described in Example 1 is repeated, using an equimolar amount of a disazo dye AI-NHE, in which A| is a radical of the formula n place of 10.02 parts of 4-(2-ureido-4-aminophenylazo)-azoben2ene-3,4"-disulfonic acid. A Tiixture of dyes which, in the form of the free acid, have the formulae (101) and (102), in The dye mixtures give prints on paper and dyeings and prints on cotton and wool in blacl Examples 31 to 57 The procedure described in Example 2 is repeated, using an equimolar amount of a disazo dye Ai-NHa, in which A, is a radical of the formula {104a) and Ri, Ri", R2 and Rg" are each as defined in Table 1, in place of 10.02 parts of 4-(2-ureido-4-aminophenylazo)-azobenzene-3,4-"-disulfonic acid. A mixture of dyes which, in the fomi of the free acid, have the formulae (105) and (106), in The dye mixtures give prints on paper and dyeings and prints on cotton and wool in black colour shades of high fastness to light. Examples 58 to 63 The procedure described in Example 1 is repeated, using an equimolar amount of a formazan dye F1-NH2, in which F, is in each case as defined in Table 2, in place of 29.80 parts of the copper complex of 5-amino-3-[3-phenyl-5-{2-carboxy-5-sulfophenyl)-l- formazanol-4-hydroxybenzenesulfonic acid. A mixture of dyes which, in the form of the free acid, have the formulae (101) and (102), in which F, is in each case as defined in Table 2, The procedure described in Example 1 is repeated, except that an equimolar amount of a copper complex azo dye FrNHz, in which Fi is in each case as defined In Table 4, is used in place of the 29.80 parts of the copper complex of 5-amino-3-[3-phenyl-5-(2-carboxy-5-suifophenyl)-1-formazano]-4-hydroxybenzenesulfonic acid. A mixture of dyes which, in the form of the free acid, have the formulae (101) and (102), in which Fi is in each case as defined in Table 4, Ai is a radical of the formula (104) defined in Table 5, is used in place of the 2.83 parts of 1,2-diaminopropane. A mixture of dyes which, in the form of the free add, have the formulae (109) and (110) The dye mixtures give prints on paper and dyeings and prints on cotton and wool in black colour shades of high fastness to light. Examples 111 to 141 The procedure described in-Excnple 3 is repeated, except that an equimolar amount of a compound of the formula H-X, in which the radical X is in each case as defined in Table 6, is used in place of the 1.92 parts of morpholine. A mixture of dyes which, in the form of the free acid, have the formulae (111) and (112) Example 142 a) 14 parts of cyanuric fluoride are added dropwise to a neutral solution of 52 parts of 4-(2- ureido-4-aminophenylazo)-azobenzene-3,4"-disulfon[c acid and 5 parts of disodtum hydrogen phosphate in 500 parts of water at a temperature below 2°C. the pH being l diaminopropane in 54 parts of water are added dropwise such that the temperature does not exceed SC and the pH remains at a value of 6. The pH is then kept at a value of 6. A solution of 4-{2-ureido-4-[4-(2-aminopropylamino)-6-fluoro-1,3,5-triazin-2- ylamino]phenylazo}-azobenzene-3,4"-disulfonic acid is obtained. b) 14 parts of cyanuric fluoride are added dropwise to a neutral solution of 60 parts of the copper complex of 5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4- hydroxy-benzenesuifonic acid and 5 parts of disodium hydrogen phosphate in 500 parts of water at a temperature below 2°C, the pH being kept constant by addition of sodium hydroxide solution. A solution of 5-[4,6-difluorQ-1,3,5-triazin-2-ylaminol-3-{3-phertyl-5-(2- carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonic acid is obtained. c) The solution according to b) is added to ttie solution according to a), the pH being increased to and kept at a value of 8.5. The mixture is allowed to warm to room temperature, the solution is freed from the salt by dialysis and the dye is concentrated by evaporation. A dye which, in the form of tine free acid, is the compound of the formula (113) is obtained. The dye dyes cotton and wool in olive colour shades of high fastness to light. Example 143 19 parts of morpholine are added at 20""C and a pH of 8.5 to a solution obtained according to Example 142 c), which comprises the dye of the formula (113). The reaction mixture is heated to 50 to 55°C and the pH is brought to 10 by addition of sodium hydroxide solution. The mixture is stirred at this temperature for about a further one hour. The reaction mixture is then allowed to cool to room temperature, and the pH is brought to 7 to 7.5 with aqueous hydrochloric acid. The resulting solution is freed from the salt by dialysis and evaporated. A dye which, in the form of the free acid, has the formula {114) is obtained. The dye dyes cotton and wool in olive colour shades of high fastness to light. The procedure described in Example 142 is repeated, except that an equimolar amount of a disazo dye A1-NH2, in which Ai is a radical of the formula (2-ureido-4-aminophenylazo)-azobenzene-3,4"-disulfonic acid. Valuable dyes which dye cotton and wool in olive colour shades of high fastness to light are likewise obtained. The procedure described in Example 142 is repeated, except that an equimolar amount of a formazan dye shown in Table 2 or of a copper complex azo dye shown in Table 4 is used in place of the 60 parts of the copper complex of 5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-l-forma2ano]-4-hydroxybenzenesulfonic acid. Valuable dyes which dye cotton and wool in olive colour shades of high fastness to light are likewise obtained. The procedure described in Example 142 is repeated, except that an equimolar amount ot a diamine according to Table 5 is used in place of the 7.4 parts of 1,2-diaminopropane. Valuable dyes which dye cotton and wool in olive colour shades of high fastness to light are likewise obtained. The procedure described in Example 143 is repeated, except that an equimolar amount of a compound X-H, in which X is in each case as defined in Table 6, is used in place of the 19 parts of morpholine. Valuable dyes which dye cotton and wool in olive colour shades of high fastness to light are likewise obtained. Example 144 a) 9.22 parts of cyanuric chloride are suspended in 150 parts of ice-water. The pH is brought to 5 with 1 N sodium hydroxide solution and the temperature is kept at 0 to 2°C. A neutral solution of 29.80 parts of the copper complex of 5-amlno-3-[3-phenyl-5-(2-carboxy-5- sulfophenyl)-1 -formazano]-4-hydroxybenzenesulfonic acid in 250 parts of water is added to this suspension at 0 to 3°C. During the addition the pH is kept at 5 with a 2 N sodium hydroxide solution. After the addition the mixture is stirred at 0 to 3°C and pH 5 for about a further 2 hours. A solution of 5-[4,6-dichloro-l ,3,5-trian-2-ylamino|-3-[3-phenyl-5-(2- carboxy-5-suifophenyl)-1-formazano]-4-hydroxybenzenesulfonic acid is obtained. b) The solution obtained according to a) is added dropwise to a solution, brought to pH 6 to 6.5 with 32% hydrochloric acid, of 37.1 parts of 1,2-diaminopropane in 50 parts of ice-water, the pH being kept at 6.5 by addition of a 15% sodium hydroxide solution. During the dropwise addition the temperature Is allowed to rise to about 20°C. To bring the reaction to completion the mixture is stirred at SCC for 2 days. The crystalline product is then filtered off, washed with water and taken up in 700 parts of water. Complete solution occurs by increasing the pH to 9.5 with 15% sodium hydroxide solution. The dye is precipitated again by addition of 90 parts of sodium chloride, filtered off and washed with 15% sodium chloride solution. After drying at 50°C in vacuo 54.8 parts of a compound which, in the form of the free acid, has the formula c) 10.96 parts of the compound according to b) are dissolved in 75 parts of water under neutral conditions and the pH is then brought to 8.8 with 1 N sodium hydroxide solution. A neutral solution of 4.58 parts of a compound of the formula (obtained by vinylation of C.I. Reactive Red 23 in an alkaline medium) in 50 parts of water is added dropwise to this solution at 50 to 55°C, the pH being kept at 8.8 by addition of a 1N sodium hydroxide solution. To bring the reaction to completion the mixture is further stirred for some hours. The solution is clarified by filtration, freed from the salt by dialysis and freeze-dried. 11.3 parts of a compound which, in the form of the free acid, has the formula (115) Application example 1 10.0 parts of the dye mixture according to Exampie 1 are dissolved in 90.0 parts of distilled water and 10 parts of 1.2-propylene glycol and the solution is filtered. The ink thus obtained is printed onto a commercially available ink-jet paper or photographic paper or a glossy film (for example Epson Glossy Film) by means of a drop-on-demand inlt-jet printer. The resulting print in a black shade has a very good fastness to light. The procedure described in application example 1 is repeated, except that one of the dye mixtures according to Examples 2 to 141 is used in place of the dye mixture according to Example 1. Black prints of very good fastness to light are likewise obtained. are dissolved in 40 parts of distilled water and 5.0 parts of 1,2-propy!ene glycol and the solution is filtered. The ink thus obtained is printed onto a commercially available ink-jet paper, photographic paper or a glossy film (for example Epson Glossy Film) or onto cotton I according to application example 5 by means of a drop-on-demand ink-jet printer. The resulting print in a black shade has a very good fastness to light. Application example 3 3.78 parts of a dye of the formula (1V.8) and 1.20 parts of a dye of the formula (116), in which Ai is a radical of the formula (104), are dissolved in a mixture of 35 parts of distilled water, 5 parts of 1,2-propylene glycol and 5.0 parts of glycerol and the solution is filtered. The ink thus obtained is printed onto a commercially available ink-jet paper or photographic paper or a glossy film (for example Epson Glossy Film) by means of a drop-on-demand ink-jet printer. The resulting print in a black shade has a very good fastness to light. Application example 4 The following inks (a) to (m) are prepared by dissolving the compounds stated in distilled water and the stated solvents. The inks are filtered and printed onto a commercially available ink-jet paper or photographic paper or a glossy film {for example Epson Glossy Film) by means of a drop-on-demand ink-jet printer. The prints in a black shade obtained with the inks (a) to (m) have a very good fastness to light. (a) 8.1 parts of a dye of the formula (IV.7); I.Bpartsof a dye of the formula (2.4); 10.0 parts of 1,2-propylene glycol; 10.0 parts of glycerol and 70.1 parts of water. (b) 9.2 parts of a dye of the formula (IV.2); 2.1 parts of a dye of the fomiula (2.7); 20.0 parts of 1,2-propylene glycol and 68.7 parts of water. (c) 7.5 parts of a dye of the formula (IV.3); 2.3 parts of a dye of the formula (2.1); 20.0 parts of glycerol and 70.2 parts of water. (d) 8.2 parts of a dye of the formula (IV.4); 1.9 parts of a dye of the formula (2.2); 0.2 parts of C.I. Reactive Red 23; 10.0 parts of 1,2-propylene glycol; 5.0 parts of e-caprolactam and 74.7 parts of water. (e) 7.7 parts of a dye of the formula (1V.5); 2.5 parts of a dye of the fomiula (2.3); 0.1 part of C.I. Reactive Red 130; 10.0 parts of 1,2-propylene glycol; 10.0 parts of glycerol; 5.0 parts of N-methylpyrrolidone and 64.7 parts of water. (f) 8.6 parts of a dye of the formula (IV.6); 2.7 parts of a dye of the formula (2.6); 20.0 parts of 1,2-propylene glycol and 68.7 parts of water. (g) 9.0 parts of a dye of the formula (IV.9); 1.7partsof a dye of the fomiula (2.5); 0.1 part of C.I. Reactive Red 23; 10.0 parts of 1,2-propylene glycol; 10.0 parts of glycerol and 69.2 parts of water. (h) 10.0 parts of the dye mixture according to Example 1; 0.1 part of C.l. Reactive Red 23; 10.0 parts of 1,2-propylene glycol; 5.0 parts of glycerol; 5.0 parts of e-caprotactam and 69.9 parts of water. (i) 9.2 parts of a dye of the formula (IV.3); 1.8 parts of a dye of the formula (2.6); 20.0 parts of 1,2-propylene glycol and 69.0 parts of water. (j) 9.0 parts of the dye mixture according to Example 1; 1.0 part of the dye according to Example 144; 20.0 parts of 1,2-propylene glycot; 5.0 parts of e-capro(actam and 65.0 parts of water. Application example 5 a) Mercerized cotton-satin is added with a liquor comprising 30 g/l of sodium carbonate (liquor pick-up 70%) and dried. b) An aqueous ink with a viscosity of 2 mPa.s, comprising -15% by weight of the dye mixture according to Example 1, -15% by weight of 1,2-propylene glycol, - 0.5% by weight of borax and - 69.5% by weight of water, is printed with a drop-on-demand ink-jef head (bubble jet) onto the cotton-satin pretreafed according to step a). The print is dried completely, fixed in saturated steam for 4 minutes at 102°C, rinsed in the cold, washed out at the boil, rinsed again and dried. A black print with very good fastness to light is obtained. The procedure described in application example 5 is repeated, except that one of the dye mixtures according to Examples 2 to 141 is used in place of the dye mixture according to Example 1. Black prints of very good fastness to light are likewise obtained. Dyeing instructions 2 parts of the dye obtained according to Example 142 are dissolved in 400 parts of water; 1500 parts of a solution which comprises 53 g of sodium chloride per litre are added to this. 100 parts of cotton fabric are introduced into this dyebath at 40""C. After 45 minutes 100 parts of a solution which comprises 16 g of sodium hydroxide and 20 g of calcined sodium carbonate per litre are added. The temperature of the dyebath Is kept at 40°C for a further 45 minutes. Thereafter, the dyed goods are rinsed, soaked at the boil with a nonionic detergent for a quarter of an hour, rinsed again and dried. Printing instructions 3 parts of the dye obtained according to Example 142 are sprinkled, with rapid stirring, into 100 parts of a stock thickener comprising 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 bicarbonate. A cotton fabric is printed with the printing paste thus obtained and dried and the resulting printed materia! is steamed in saturated steam for 2 minutes at 102""C. The printed fabric is then rinsed, soaked at the boil, if appropriate, and rinsed again, and then dried. WHAT IS CLAIMED IS: 1. A black-dyeing aqueous ink comprising 20 to 95% by weight of at least one dye (A), together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the totai weight of the dyes (A), (B) and (C) in the ink, and 1 to 40% by weight of a water-miscible organic solvent, based on the total weight of the ink, the dye (A) containing, as the colouring part of the molecule, one or more radicals of the formula (I), (11), (III) or (IV) to. the dye (B) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the formula (V), (VI), (VII) or (VIII) and the dye (C) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the abovementioned formula (V), (VI), (VII) or (VIII) and one or more radicals of the abovementioned formula (I), (II), (III) or {IV), in which (G)o.3 is 0 to 2 identical or different substituents from the group consisting of substituted or unsubstituted amino, hydroxyl and nitro, L is substituted or unsubstituted amino, R is halogen, C-C4alkyl, C1-C4a[koxy, C2-C4alkanoylamino, hydroxyl, carboxyi, nitro or cyano, (V)o.2 is 0 to 2 identical or different substituents from the group consisting of halogen, C1-Calkyl, C1-C4alkoxy, p-suifatoethylsul(onyl and sulfo, (W)Q.t is an N-acy! radical, if any, n is the number 0,1, 2 or 3, m is the number 1, 2 or 3 and r and q are the number 0 or 1. 2. An ink according to claim 1, wherein the dye (A) contains, as the colouring part of the molecule, one or two radicals of the formula (I), (II), (III) or (IV), the dye (B) contains, as the colouring part of the molecule, one or two mono- or disazo radicals containing sulfo groups or one or two radicals of the formula (V), (VI), (VlI) or (Vlll), and the dye (C) contains, as the colouring part of the molecule, a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (Vl), (VII) or (VII)) and a radical of the formula (I), (II), (111) or (IV). 3. An ink according to claim 1 or 2, wherein the dye (A) has the formula (5) B) is an aliphatic or aromatic bridge member, Fi and Fz independently of one another are a radical of the formula (I), (II), (III) or (IV), and Xi and Xa independently of one another are halogen, hydroxyl, C1-C4alkoxy which is unsubstituled or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring. C1-Calkylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono-or N.N-di-CrCgalkylamino which are unsubstituted or substituted in the alkyl moiety, Cs-Cycycloalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C1-C4alkyl-N-phenyl- or N-C,-C4alkyl-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino or piperidin-1-yl. B2 and B3 independently of one another are an aliphatic or aromatic bridge member, Ai, Aa and A3 independently of one another are a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (VI) or (Vll), F3 is a radical of the formula (I), (11), (111) or (IV) and X3, X4. X5 and Xe independently of one another are halogen, hydroxyl, C1-Calkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, C1-C4aikylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono-or N.N-di-C-Csalkylamino which are unsubstituted or substituted in the alkyl moiety, C5-C7cycioalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C,-C4alkyl-N-phenyl- or N-CTC4alkyl-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino orpjperidin-l-yl. 5. An ink according to any one of claims 1 to 4, wherein the radical of tfie formula (IV) in tfie dye (A) or (C) is a radical of the formula (IVa), (IVb) or (IVc) 6. An ink according to any one of claims 1, 2 and 4, wherein the mono- or disazo radicals containing suifo groups in the dye (B) or (C) have the formula (4a), (4b), (4c), (4d), (4e), (4f), in which (ROo-s is 0 to 3 identical or different substituents from the group consisting of C i-Cjalkyl, Cj-Cjaikoxy, C2-C4alkanoylamino, halogen, carboxyl and sulfo and Z is vinyl or a radical -CHa-CHa-U and U is a leaving group, in which (R£)(M is 0 to 4 identical or different substituents trom the group consisting o1 halogen, nitro, cyano, trifluoromethyl, sulfamoyi, carbamoyl, C,-C4alkyl, C,-C4aikoxy which is unsubstituted or substituted by hydroxy! or Ct-C4alkoxy, amino, Ca-Calkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyi, C1-C4a!Kylsu)fonylamino and sullo and Z is as defined above, (Ri)o-3. (R2)o-3, (R4)o-3 and Z are each as defined above and (Ri")o-3 is 0 to 3 identical or different substituents from the group consisting ofCrCialkyl, CrCnalkoxy, halogen, carboxyl and sulfo. 7. A process for printing paper, films of plastic or textile fibre materials by the ink-jet printing process, which comprises using an aqueous inl 8. A black-dyeing dye mixture comprising 20 to 95% by weight of at least one dye (A), together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the dye mixture, in which the dye {A) has the formula (5) n which 10, Rii, Ri2. Ri3. Ri4, Ris, Ris, Ri7, Ria. Ri9. 20 and Rji independently of one another are lydrogen or substituted or unsubstituted C1-C4alkyl, 3,, B2 and B3 independently of one another are an aliphatic or aromatic bridge member, \\, A2 and A3 independently of one another are a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (VI) or (VII), r,, F2 and F3 independently of one another are a radical of the formula (I), (II), (III) or (IV) and Xi, X2, X3, X4, Xs and Xs independently of one another are halogen, hydroxyl, CrCialkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, CrCaikylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono- or N,N-di-C,-Cealkylamino which are unsubstituted or substituted in the alkyl moiety, C5-C7- cycloalkylamino which is unsubstituted or substituted in the cycloalkyi ring, phenyl- or naphthylamino or N-CrC4a(ky(-N-pheny(- or N-C1-C4a(kyl-N-naphfhyfamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino or pipe rid in-1-yl. 9. A dye mixture according to claim 8, which includes at least one dye (A) of the formula (5) together with at least one dye (C) of the formula (7). 10. A process for the preparation of a dye mixture according to any one of claims 8 and 9, which comprises (i) reacting the compounds of the formulae (10a) and (10b) FrN(R,o)H (10a) and ArN(R,4)H (10b) in each case independently of one another with a haiogenotriazine compound of the formula (11) (ifi) subjecting this mixture to a condensation reaction with a compound of the formula (14a) in an equimolar amount which corresponds to the number of amino groups which have not been acylated by the compound of the lormula (14b), to give a mixture of the compounds of the formulae (5a) and (7a) (iv) if appropriate reacting the halogen atoms X with a compound of the formula (13) H-Xi (13) in which Ai, Fi, Rio, Rn, R12 and Ru are as defined in claim 8, X is fluorine or chlorine and Xi is as defined in claim 8, with the exception of halogen. Rja. 24 and R25 independently of one another are hydrogen or substituted or unsubstituted C-Caikyl, B4 is an aliphatic or aromatic bridge member, A4 is a radical of tiie formula (VIII) in which (W)o.i is an N-acyl radical, if any, F4 is a radical of the formula (I), (II), (III) or (IV) in which (G)o.2 is 0 to 2 identical or different substituents from the group consisting of substituted or unsubslituted amino, hydroxyl and nitro, L is substituted or unsubslituted amino, R is halogen, C1-C4alkyl, C1-Calkoxy, C2-C4alkanoy!amino, hydroxyl, carboxyl, nitro or cyano, n is the number 0,1, 2 or 3, m is the number 1, 2 or 3 and q is the number 0 or 1, and X7 is halogen, hydroxy!, Crdaikoxy which Is unsubslituted or substituted in the alky! moiety, phenoxy which is unsubslituted or substituted in the phenyl ring, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety, pfienylthio which is unsubslituted or substituted In ihe phenyl ring, amino, N-mono- or N,N-di-C1-Cealkylamlno which are unsubstituted or substituted in the alkyi moiety. Cs-Crcycloalkyiamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-CrC4alkyl-N-phenyl- or N-C1-Calkyl-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in Ihe phenyl moiety, morpholino or piperidin-1-yl. 12. A dye of the formula (18) in which le. R27, R28 and R29 independently of one another are hydrogen or substituted or unsubstituted CrC4alkyl, Bs is an aromatic bridge member, A4 is a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (41), (4j), (4k), (41), (4m), (4n), (4o), {4p), (4q), (4r), (V), (VI) or (Vll) —y in which (R2)o-4 is 0 to 4 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyi, carbamoyl, C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl orC,-C4alkoxy, amino, C2-C4alkanoylamino, ureido, hydroxy carboxyl, sulfomethyl, C,-C4alkylsul{onylamino and sulfo and Z is as defined above, in which (Rg)o.z is 0 to 2 identical or different substituents from the group consisting of C ,-CialkyI, C,-Caa!koxy, halogen, carboxyl and suite; and Z is as defined above, unsubstituted amino, hydroxyl and nitro, (V)o.2 is 0 to 2 identical or different substituents from the group consisting of halogen, C i- Calkyl, CTC4alkoxy, p-sulfatoethylsulfonyl and sutfo and (W)o.i is an N-acyl radical, if any, Fs is a radical of the formula (I), (11), {111}, (IVa), (IVb) or (IVc) Xa and Xg independently of one another are halogen, hydroxyl, C1-C4alkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, CrCialkylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono-or N.N-di-C1-Cgalkylamino which are unsubstituted or substituted in the alkyl moiety, Cs-CTcycloalkylamino which is unsubstituted or substituted in the cycloalkyi ring, phenyl- or naphthylamino or N-C1-C4alkyl-N-phenyl- or N-C1-C4alkyi-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino or piperidin-1-yi, with the proviso that A4 is not a radical of the formula (4k) if Bs is a sulfo-substituted phenylene radical. (Ri)o-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, Cr C4alkoxy, C2-C4alkanoylamino, halogen, carboxyl and sulfo, (R,")o.3 is 0 to 3 identical or different substituents from the group consisting of C i-C4alkyl, C1-Calkoxy, halogen, carboxyl and sulfo, (82)0-3 is 0 to 3 identical or different substituenls from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyi, carbamoyl, C1-C4a)kyl, C,-C4a(koxy whicfi is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, GrG4alkartoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, CrC4alkylsulfonylamino and sulfo and Z Is vinyl or a radical -CHa-CHj-U and U is a leaving group, Fg is a radical of the formula (1), (11), (til), (IVa), (IVb) or (IVc) (G}o-2 is 0 to 2 identical or different substituents from the group consisting of substituted or unsubstituted amino, hydroxy! and nitro and L is substituted or unsubstituted amino, and Xa and Xg independently of one another are halogen, hydroxyl, C1-C4alkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, C(-C4alkyIthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono-or N.N-di-C1-Cealkylamino which are unsubstituted or substituted in the alkyl moiety, Cs-C?-cycloalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C1-C4a!l nitrogen, which comprises using a dye mixture according to claim 8 or 9, a dye of the formula (9) according to claim 11 or a dye of the formula (18) according to claim 12 or 13. 15. A black-dyeing aqueous ink substantially as herein described and exemplified. 16. A process for the preparation of a dye mixture substantially as herein described and exemplified. |
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| Patent Number | 206966 | ||||||||||||||||||||||||||||||
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| Indian Patent Application Number | IN/PCT/2001/1308/CHE | ||||||||||||||||||||||||||||||
| PG Journal Number | 26/2007 | ||||||||||||||||||||||||||||||
| Publication Date | 29-Jun-2007 | ||||||||||||||||||||||||||||||
| Grant Date | 16-May-2007 | ||||||||||||||||||||||||||||||
| Date of Filing | 20-Sep-2001 | ||||||||||||||||||||||||||||||
| Name of Patentee | M/S. F. HOFFMANN-LA ROCHE AG | ||||||||||||||||||||||||||||||
| Applicant Address | Grenzacherstrasse 124 CH-4070 Basle | ||||||||||||||||||||||||||||||
Inventors:
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| PCT International Classification Number | A61 K 31/421 | ||||||||||||||||||||||||||||||
| PCT International Application Number | PCT/EP2000/002450 | ||||||||||||||||||||||||||||||
| PCT International Filing date | 2000-03-20 | ||||||||||||||||||||||||||||||
PCT Conventions:
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