Title of Invention	"A DYE MIXTURE"
Abstract	A dye mixture comprises, as component (A), a reactive dye of the formula (A) wherein each of Y1 and Y2, independently, is a vinyl group or a group of the formula - CH2CH2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and, as component (B), at least one additional reactive dye selected from a monopyrazole dye of the formula (I), a mono or disazo dye of the formula (II), a monoazopyridone dye of the formula (III), a monoazonaphthyl dye of the formula (IV), a disazoaminonaphthyl dye of the formula (V), a formazan dye of the formula (VI), an azoacetoacetanalide dye of the formula (VII), a disazo dye of the formula (VIII), a naphthylamide or a naphthalenetriazole dye of the formula (IX), a metal phthalocyanine dye of the formula (X) or a triphendloxazine dye of the formula (XI). as defined herein.

Title of Invention

"A DYE MIXTURE"

Abstract

A dye mixture comprises, as component (A), a reactive dye of the formula (A) wherein each of Y1 and Y2, independently, is a vinyl group or a group of the formula - CH2CH2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and, as component (B), at least one additional reactive dye selected from a monopyrazole dye of the formula (I), a mono or disazo dye of the formula (II), a monoazopyridone dye of the formula (III), a monoazonaphthyl dye of the formula (IV), a disazoaminonaphthyl dye of the formula (V), a formazan dye of the formula (VI), an azoacetoacetanalide dye of the formula (VII), a disazo dye of the formula (VIII), a naphthylamide or a naphthalenetriazole dye of the formula (IX), a metal phthalocyanine dye of the formula (X) or a triphendloxazine dye of the formula (XI). as defined herein.

Full Text	1 REACTIVE DYE MIXTURES This invention relates to a dye mixture. This invention relates to mixtures of reactive dyes, in particular to mixtures of reactive dyes containing, as one component, a disazo dye derived from K-acid. As is well known, reactive dyes contain at least one substituent capable of taking part in a reaction with a group present on a fabric to be dyed during the dyeing operation. EP-A-0149170 discloses a range of dyes of the formula in which one X is hydrogen and the other sulpho, each of Y1 and Y2 independently is a group -CH=CK2, -CK2CK2OSO3H, -CK2CH2SSO3H, -CK2CH2C1 or -CH2CH2OR, and R is a low molecular weight alkanoyl, benzoyl or benzenesulphonyl group, optionally substituted by a C1-4 alkyl, C1-4 alkoxy, nalogen, carboxy or sulpho group. 2 A typical dye has the formula EP-A-0149170 refers only to individual dyes, not mixtures thereof. On the other hand, each of EP-A-0224224, EP-A-0679697, EP-A-0531968, EP-A-0668328 and EP-A-0600322 discloses respective mixtures of dyes, one of which components as a disazo dye derived from H-acid. One particular example of such a dye has the formula This dye is available commercially as C.I.Reactive Black 5 and is added to other dyes as a dulling agent where appropriate. We find surprisingly that the fastness of a dye mixture can be improved if the dye mixture contains, as a component 3 thereof, a dye of the formula (A) wherein each of Y1 and Y2, independently/ is a vinyl group or a group of the formula -CH2CK2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group. The dye mixture may contain, in addition to component (A) , any of a wide range of dyes. More particularly, the present invention provides a dye mixture comprising a reactive dye of the formula (A) , given and defined above; and at least one reactive dye (B) selected from (I) a monoazopyrazole dye of the formula 4 wherein R1 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; R2 is a phenyl or naphthyl group, optionally having at least one substituent thereon, the substituent, cr each substituent, independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a chlorine- atom, a vinyl sulphonyl group, a group SO2CH2CK2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl -sulphonyl group, a group Het and a group L5-Ket, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain and L5 is as defined below; and R6 is a methyl group, an amide group or a carboxyl group or a salt thereof; 5 each of R40 and R41, independently, is an aryl group selected from phenyl and naphthyl groups, each of which, independently, is optionally substituted by a vinylsulphonyl group, a group So2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinylsulphonyl group; or the group Het, where Het is as defined above; at least one of R1, R2, R40 and R41 being, or having thereon at least one substituent which is, reactive; each of L1, L2 and L5 independently is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(=0); C(=O)-O; S(=0)2; S(=O)-NH; C(=O)-NH; and NHC(=O)NH; and each of x, y and z, independently, is zero or i; and, when the group R1 is substituted by a hydroxy group ortho to the azo group, a metallized derivative thereof; (II) a monoazo or disazo dye of the formula 6 wherein: Ket is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain; R3 or each R3, independently, is a chlorine atom, a methyl group, a methoxy group, a sulphonic acid group cr a salt thereof, or is an amino group of the formula in which each of R18 and R19, independently, is hydrogen, chloro, methyl, (C1-4 alkyl) carbonyl, aminocarbcnyl, vinylsulphonyl or a group SO2CH2CH2Q1, in which Q1 is as defined above; R4, or each R4 independently, is hydrogen , a sulphonic acid group or a salt thereof, a C1-8 alkyl (preferably a C1-4 alkyl) group, a C1-4 alkoxy group, a vinyl sulphonyl group or a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, which C1-4 alkyl group or C1-4 alkyl moiety of the C1-4 alkoxy group is optionally interrupted by an oxygen atom to provide an ether group and is optionally substituted by a vinyl sulphonyl group or a group SO2CH2CH2Q2, in which Q2 is as defined above; or R4 (or when q is 2, each R4 independently) is a phenyi group optionally substituted by at least one sulphonic acid group 7 or a salt thereof or at least one group Het, where Ket is as defined above; or R4 is a group Het, where Het is as defined above R5 is an aryl group selected from phenyl and naphthyl groups each optionally substituted by at least one sulphonic acid group or, a salt thereof or at least one group Het, as defined above; R20 is a. hydrogen atom or a C1-4, alkyl group; R21 is a hydrogen atom, a C1-4 alkyl group, a sulphonic acid-C1-4 alkyl group, a chloroalkylsulphonyl-C1-4 alkyl group or a group Het, where Het is as defined above; m is 1 or 2; p is zero, 1 or 2; q is zero, 1 or 2; each of w1 and w2 is zero or 1; and w3 is 1, 2 -or 3; and when p is zero, q is zero; at least one of R4, R5, R18, R19, R21 and Her being, or having thereon at least one substituent which is, reactive; (III) a monoazopyridone dye of the formula 8 wherein: each of R40, R41, L1 and L2 is as defined, above; R7 is optionally present and is a cyano group or the group - CH2SO3H or the group -C(=O)NH2; each of R24 and R25, independently, is a hydrogen atom, a C1-4 alkyl group, a sulpho-C1-4 alkyl group, or a carboxyl group; n is 1 or 2; , r is zero or 1; and each of S1 and s2 is zero or 1; and when R40 is a phenyl or naphthyl group s2 is 1; at least one of R40 and R41 being, or having thereon at least one substituent which is, reactive; (IV) a monoazonaphthyl dye of the formula wherein: each of R1, R40, R41, L1, L2, x, y and z is as defined above; R9 is CH3(C=O)-, Het (as defined above) or an aryl group selected from phenyl and naphthyl, which Ket or aryl group is optionally substituted by at least one substituent, the or each substituent, independently, being 9 selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above; R35 is a C1-4 alkyl or C2_4 alkenyl group, which C1-4 alkyl or C2_4 alkenyl group is optionally substituted by at least one halogen atom, a sulphonic acid group or salt thereof, a chloroalkylsulphonyl group, a vinylsulphonyl group or -SO2CH2CH2Q1, where Ql is as defined above and which C1-4 alkyl or C2_4 alkenyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof; the group Het (as defined above) ; or an aryl group selected from phenyl and naphthyl, which Het or aryl group is optionally substituted by at least one substituent, the substituent or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen atom, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinylsulphonyl group, a vinyisulphonyloxyethyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above; R50 is a vinylsulphonyl group or a group SO2CH2CH2Ql (in which Q1 is as defined above); at least one of R1, R5, R35, R40, R41 and R50 is, or 10 has thereon at leas:: one substituent which is, reactive; L3 is a linking group selected from N(R20}, in which R20 is as defined above; CO; COO; NHCO; NHCONE; SO2NH and SO2; L4 is a linking group selected from N(R21), in which R21 is as defined above, CO, COO, NHCO, NHCONH, SO2NH and SO2;. z is hydroxy, amino or methylamino; a is zero or 1-4; b is zero or 1-3; c is zero or 1; d is zero, 1 or 2; e is zero or 1; and when each of R1 and Z provides a hydroxyl group ortho to the azo group, a metallized derivative thereof; (V) a disazoaminonaphthyl dye of the formula wherein: eacn of R1, R40, R41, L1, L2, x, y and z is as defined above; 11 each of V and W, independently, is NH2 or OH; R14 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each subsrituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; each of R51 and R52 independently is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het3, where Ket3 is an optionally substituted aromatic heterocyclic reactive group cr a reactive group having an aliphatic chain; each of L3 and L4, independently, is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(-0); C(=O)-O; S(=0)2; S(=O)-NH; C(=O)-NH; and NHC(=O)NH; each of f, g and h, independently is zero or 1; and at least one of R14, R40, R41, R51 and R52 is, or has thereon at least one substituent which is, reactive; 12 (VI) a formazan dye of the formula n wherein: each of R16 and R17 independently of one another, each R16 independently of one another and each R17 independently of one another, is a sulphonic acid group or a salt thereof, a vinyl sulphonyl group or a group SO2CHzCH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; each of Het1 and Het2, independently, is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain; and each of R60 and R61, independently, is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above; 13 X1 is a sulphonic acid group or a salt thereof cr halogen; each of i, J and v, independently, is zero, 1 or 2; and each of k, 1, t and u, independently, is zero or 1; and at least one of R16, R17, R50, R51, Het1 and Het2 is, or has thereon at least one substituent which is, reactive; (VII) a dye of the formula wherein: each of R1, R2, R3, R4, R20, R21, R40, L1, Het, x, p, q, w1, w2 and w3 is as defined above; and at least one of R1, R2, R3, R4, R21, R40 and Het is, or has thereon at least one substituent which is, reactive; (VIII) a disazo dye of the formula 14 wherein R55 is an aryl group selected from phenyl and naphthyl groups; R56 is a sulphonic acid group or a salt thereof or a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Ql is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; R57 is an amino group or a group NHRA in which RA is a C1-4 alkyl group; R58 is a sulphonic acid group or a salt thereof; R59 is a sulphonic acid group or a salt thereof, a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or the group R59 is a group Het or a group L10-Ket, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group; R65 is a ureido group or a group HNC(=0)R3 in which R3 is a C1-4 alkyl group; L10 is a linking group selected from N(R20) , in which R20 is hydrogen or CH alkyl; C(=0); C(=0)-0; S(=O)2; S(=O}-NH; C(=0)-NH; and NHC(=0)NH; y1 is zero, 1, 2 or 3; y2 is zero, 1 or 2; y3 is zero or 1; and y4 is zero or 1; and at least one of R56 and R59 is a reactive group. 15 wherein: MPc is a metallophthalocyanine chromophore; each of R70 and R71, independently, is hydrogen or C1-4 alkyl; B is a hydrocarbon bridging group; 16 Het is a reactive heterocyclic group; each of xl, x2 and x3 is a respective average value; x1 + x2 + x3 = 4; X1 is at least 1 x2 is zero or 1; and x3 is at least 1; and (XI) a triphenodioxazine dye of the formula (XI) (or a salt thereof) wherein: each of B1 and B2, independently, is a hydrocarbon bridging group; U1 is H or SO3H; and each of T1 and T2, independently, is halo, C1-4 alkyl, or C1-4 alkoxy; each of R80 and R81 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof; each of Het1 and Het2 is as defined above; and 17 at least one of Het1 and Het2 is a reactive group. Referring to the dye of the formula (A) , preferably at least one of Y1 and Y2 is the group -CH2CH2Q and Q is selected from chlorine, bromine, C1-4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, OP(O)(OH)2, C1-4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl) carbonyloxy, (C1-4 dialkyl) amino or a radical of the formula where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4 alkyl or benzyl and Ane is in each case one equivalent of an anion. More preferably, each of Y1 and Y2 is the group HO3SOCH2CH2. Referring now to the reactive dye (B), dyes in one preferred range thereof contain a group Het, where Het is an optionally substituted aromatic heterocyclic reactive group derived from a halogen-substituted heterocyclic compound selected from 1,3,5-triazine, qumoxaline, phthalazine, pyrimidine, pyridazine and 2-(C1-4 alkylsulphonyl) benzothiazole. More preferably, the aromatic heterocyclic reactive group is substituted and at 18 least one substituent is a halogen atom. An alternative preferred range of reactive dyes (B) contains a group Het, where Het is a reactive group having an aliphatic chain and selected from acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tri- bromoacryloyl, -CO-CC1=CH-COOH, -CO-CH=CC1-COOH, 2-chloropropionyl, 1, 2-dichloroproplonyl, 1, 2-dibromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl, 2-chloro-2, 3, 3-trifluorocyclo- butylcarbonyl, 2, 2, 3, 3-tetrafluorocyclobutylcarbonyl, 2,2,3,3-tetrafluorocyclobutylsulfonyl, 2-(2,2,3,3- tetrafluorocyclobutyl) acryloyi, 1- or 2-alkyl- or 1- or 2-arylsulfonylacryloyl, or a radical of the formula SO2-Y3, SO2NH-Y, CONH-L6-SO2-Y3 or NHCONH-L5-SO2-Y3 where L6 is C1-C4-alkylene or phenylene and Y3 is a vinyl group or a group of the formula CH2CH2Q3 in which Q3 is a leaving group removable under alkaline conditions to provide a vinyl group. It is also preferred that, the reactive dye (B) has at least one of the groups Q1 and Q2 therein and the or each of groups Q1 and Q2 independently is selected from chlorine, bromine, C1-4-alkylsulfonyl, phenylsulfonyi, OSO3H, SSO3H, OP(O) (OH)2, C1_4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl) carboxyloxy, (C1-4 dialkyl) amino or a radical of the formula 19 where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4-alkyl or benzyl and An is in each case one equivalent of an anion. In a dye mixture wherein the reactive dye (B) is a monoazopyrazole dye of the formula (I), given and defined above, it is preferred that at least one of the group [(R41-L2)(R40-L1)y]xR1 and the group R2 has at least one sulphonic acid group substituted thereon and at least the other of the group [(R41-L2) z(R40-L1)y)xR- and the group R2 has a group -S02CH2SO2Q2 substituted thereon, Q2 being as defined above. In respective preferred ranges of the reactive dye (B) of the formula (I) (i) x is zero and the group R1 is substituted by at least one of a sulphonic acid group and the group -So2CH2SO2Q1, wherein Q1 is as defined above; (ii) each of x, y and z is 1, each of L1 and L2 is NH, R40 is the group Het, where Het is a triazine ring subetitutec by a halogen atom and R41 is an optionally substituted phenyl group. (iii) each of x and z is 1, y is zero, L2 is NH and R41 is the group Het, where Het is a difluorochloropyrimidmyl 20 group; and (iv) each of x and z is 1, y is zero, L2 is CONE (in which the nitrogen atom is attached to the group R1 and the carbon to the group R41) and R41 is the group Het, where Het is a 2,3-dichloroqumoxaline group. In a reactive dye (B) of the formula (I), R2 is preferably a phenyl or naphthyl group substituted by (i) at least one of a sulphonic acid group and the group -SO2CH2SO2Q2, where Q2 is as defined in claim 1; or (ii) at least by the group NH-Het, where Het is a triazine ring substituted by ¦ a halogen atom and optionally substituted by the group In a reactive dye (B) of the formula (I), the group R1 may be substituted by a hydroxy group ortho to the azo group and the reactive dye (B) may then be in the form of a copper complex. Reference is now made to a dye mixture wherein the reactive dye (B) is monoazo or disazo dye of the formula (II), given 21 and defined above. In such a mixture it is preferred that in the reactive dye (B) of the formula (II), when m is 1 and R4 is alkyl, R4 is C1-4 alkyl. It is also preferred that the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by at least one sulphqnic acid group or a salt thereof or by a group Het, wherein Het is a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above. In an especially preferred reactive dye (B) of the formula (II), m is 1, so that the dye is a monoazo dye. In preferred ranges of monoazo dyes (B) of the formula (II) in a mixture in accordance with the invention, (i) each of wl, w2, p and q is zero, w3 is at least 2, at least one of the groups R3 is a sulphonic acid group and the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q, where Ql is as defined above. (ii) each of w1 and w2 is zero, each of p and q is 1, R21 is hydrogen and R4 is selected from a triazine ring substituted by at least one halogen atom and optionally additionally substituted by an amino croup; and a pyrimidine group substituted by at lease one halogen atom and optionally additionally substituted by a methyl group; (in) each of w1, w2, p and q is 1, R20 is hydrogen, Het 22 is a triazine ring substituted by a halogen atom, R21 is hydrogen and R4 is selected from a phenyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above, and a straight or branched C2_4 alkylene chain substituted by a substituent selected from a hydroxyl group; a sulphonic acid group or salt thereof; a vinylsulphonyl group, a group -SO2CH2CH2Q2, where Q2 is as defined above; and a pyrimidinylamino group in which the pyrimidinyl group is substituted by at least one halogen atom and optionally additionally by a methyl group; and which straight or branched C2-4 alkylene group optionally contains a hetero atom selected from 0, S and N (H) ; (iv) each of w1 and w2 is zero, each of p and q is 1 and each of R21 and R4 is the group OSO3H; and (v) w1 is zero, w2 is 1, p is 1, q is 1, R21 is hydrogen, R4 is a pyrimidmyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and Het is a non-reactive heterocyclic group of the formula _23 An especially preferred dye mixture contains a dye of the formula (44) as the reactive dye (B) of formula (II) Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazopyridone dye of the formula (III), given and defined above. In respective preferred ranges of the reactive dye (B) of the formula (III) , (1) each of r, s1 and s2 is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is selected from a phenyl group substituted by at least one of a chlorine atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above; and a straight or branched chain C2-4 alkylene group optionally containing at least one oxygen atom and substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above; (ii) each of r and s1 is 1, s2 is zero, L2 is NH, R41 is 24 a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a metnyl group and R40 is a naphtho- (1, 2-d) -1, 2, 3-triazole substituted by at least one sulphonic acid group or salt thereof; and (iii) each of r1, S1 and s2 is 1, L1 is CONH (in which the carbon atom is attached to the group R40), L2 is NK, R40 is an optionally substituted phenyl group and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group. Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazonaphthyl dye of the formula (IV), given and defined above. In one preferred range of such dyes, (i) x is zero, d xs 1 and a or b is 1. More preferably e is zero. In other preferred respective ranges, (ii) x is 1, y is zero, z is 1, L2 is NK and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group; (iii) x is 1, y is zero, z is 1, L2 is CONH (with the 25 carbon atom attached to the group R1 and the nitrogen atom to the group R41) and R41 is a phenyl group substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above; and (iv) each of x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is an aromatic group selected from phenyl and naphthyl groups each substituted by at least one of a sulphonic acid group or a salt thereof, a vinylsulphonyl group and the group -SO2CH2CH2Q1, where Q1 is as defined above. In such ranges (ii) - (iv) of dyes (B) of the formula (IV), more preferably, e is zero. In other preferred ranges of the reactive dye (B) of the formula (IV), (v) e is 1, c is zero, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a methyl group; (vi) e is 1, c is zero, L3 is CONH {where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a phenyl group optionally substituted by at least one substituent, the or each substituent being selected from methoxy, carboxyethyl, sulphoethyl, carboxyethenyl, 1,2-dibromoalkyl, chloroethylsulphonyl, vinylsulphonyl, a 26 group of the formula -SO2CH2CH2Q1, where Q1 is as defined above and a 2, 3-dichloroquinoxalme group. (vii) e is 1, c is 1, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9) , R9 is a phenyl group substituted at least by the group L4-R35, where L4 is NH and R35 is a vinyl group optionally substituted by a halogen atom or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group; and (viii) e is I, c is zero, L3 is N(R20), where R20 is as defined above (and is more preferably a hydrogen atom or a methyl group) and R9 is a vinylsulphonyl group, a group -SO2CH2CH2Q1 wherein Q1 is as defined in claim 1, or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group. In yet another preferred range (iX) e is 1, c is zero, L3 is N(R20), where R20 is as defined above and R9 is a triazine ring substituted by at least one halogen atom. In this range the triazine ring is preferably substituted by two halogen atoms or by one halogen atom and a morpholmyl group. In another preferred range, (x) e is 1, c is 1, L3 is N(R20), where R20 is as 27 defined above, L4 is the group R21, where R21 is as defined above, and R35 is selected from a phenyl group optionally substituted by a sulphonic acid group or salt thereof, a halogen atom, a vinylsulphonyloxyalkyl group, a vinylsulphonyl group or the group -SO2CH2CH2Q1, where Q1 is as defined above; and a C1-4 alkyl group optionally substituted by a vinysulphonyl group, the group -SO2CH2CH2Q1, where Q1 is as defined above, a sulphonic acid group or a salt thereof or a chlcroalkylsulphonyl group, which C1-4 alkyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof. In dye mixtures containing a reactive dye (B) of the formula (IV) within the above ranges x is preferably zero. In the reactive dye (B) of the formula (IV) , each of the groups R1 and the naphthalene nucleus may be substituted by a respective hydroxyl group ortho to the azo group and the reactive dye (B) may then be in the form of a copper-complex thereof. An especially preferred dye mixture contains a dye of the formula (53) as the reactive dye (B) 28 Reference is now made to a dye mixture wherein, the reactive dye (B) is a disazo dye of the formula (V) , given and defined above. In such dyes, the respective sulphonic acid groups on the naphthalene nucleus are preferably in the 3-and 6- positions (i.e. such dyes are preferably derived from H-acid). In one preferred range of dyes of the formula (i) V is amino, W is hydroxy, each of R1 and R14 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinyl sulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above and R14 is optionally additionally substituted by at least one methoxy group. It is also preferred, especially for one sub-range within the range {i}, that each of x and h is zero. Such a range of dyes includes those of the formula (A) and a mixture in accordance with the invention may indeed contain only dyes of the formula (A) , one such dye of the mixture being regarded as a dye of the formula (A) and at least one other such dye of the mixture being regarded as a dye of the formula (V). In an alternative preferred range of dyes of the formula (V), especially for another sub-rarge within the-range (i) , at least one of x and h is 1 and more preferably each of x and h is 1. In a preferred sub-range (ii) of dyes (3) of the formula (V) , within the range (i) , x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent. independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above. In the preferred ranges (i) and (ii) above, more preferably, each of f, g and h is 1, each of L3 and L4 is NH, R51 is a triazine ring substituted by a halogen atom and R52 is a phenyl group substituted by at least one substituent,- the or each substituent independently being selected from a halogen atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above. In a preferred range (iii) of reactive dyes (3) of the formula {V}, v is amino, W is hydroxy, h is zero and R14 is a naphthalene group substituted by at lease one sulphonic acid group. More preferably, in this range (m), each of x, y and z is 1, R1 is a phenyl group optionally substituted by a sulphonic acid group or a salt thereof, each of L1 and 30 L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above. In a preferred range (IV) of the reactive dyes (B) of the formula (V), V is amino, w is hydroxy, h is 1, f is zero, g is 1, L4 is NH and R52 is the group Het3, where Het3 is a substituted aromatic heterocyclic group. In this range (iv) , more preferably the group Het3 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and still more preferably x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above. In a preferred range (v) of the reactive dyes (3) of the formula (V) , V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NHCO {where either the nitrogen or carbon atom thereof is attached to the group R14) and R52 is the group Het3, where Het3 is a reactive group having an aliphatic chain. More preferably, m this range (v) , the group Het3 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and still more preferably x is zero and Rl is a phenyl group substituted by a vinylsulphonyl group or 31 SO2CH2CH2Q1, where Q1 is as defined above. One especially preferred dye mixture contains a dye of the formula (105) as a dye of the formula (V) and more preferably additionally contains a dye of the formula (44) as another dye (B) , of the formula (II) Another especially preferred dye mixture contains at least one and more preferably both of the dyes of the formulae (163) and (167) 32 Reference is now made to a dye mixture wherein the reactive dye (B) is a formazan dye of the formula (VI) , given and defined above. In preferred respective ranges of the reactive dye (3) of the formula (VI) (i) each of u and v is zero, i is 1, R16 is a sulphonic acid group or a salt thereof, j is 2 and one R17 is a sulphonic acid group or a salt thereof and the other R17 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above; and (11} v is zero, 1 is 1, R16 is a sulphonic acid group or a salt thereof, j is 1, R17 is a sulphonic acid group, u is 1 and Het is a triazine ring substituted by a halogen 33 atom. In one preferred sub-range within the range (ii), each of k and 1 is zero, t is 1 and R61 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof, while in another preferred sub-range with the range (ii), each of k, 1 and t is 1, each of R50 and R61 independently is a phenyl group subsicuted by at least one sulphonic acid group or a salt thereof and Het2 is a triazme ring substituted by a halogen atom. In yet another preferred sub-range within the range (ii), each of k and t is zero, 1 is 1 and Het2 is a reactive group having an aliphatic chain. Reference is now made to a dye mixture wherein the reactive dye (B) is a dye of the formula (VII), given and defined above. In one preferred range of such dyes, x is zero and each of p, q, w and W2 is 1. More preferably, in such a. range, R1 is a naphthalene ring substituted by at least one sulphonic acid group. It is also preferred that, in such a range, w3 is 1 and R3 is a methoxy group. Moreover, a preferred group of R20 is hydrogen and preferred groups of R21 are hydrogen, methyl and ethyl. A preferred group R4 is a phenyl group substituted by at least one sulphonic acid group. In another preferred range of such dyes (VII), each of p, q, w1 and w2 is zero. More preferably, m such a range, w3 34 is 3 and at least one of R3 is a sulphonic acid ,group. Other groups of R3 are preferably methyl, methoxy, amino or further sulphonic acid groups. It is also preferred that where, in such dyes, x is 1, R1 is a phenyl or naphthyl group substituted by at least one sulphonic acid group, L1 is NH and R40 is a reactive halopyrimidine group, especially a group containing at least one, more especially at least two fluorine atoms and particularly a difluorochloropyrimidme group, and that where, in such dyes x is zero, R1 is a phenyl group substituted by a vinyl sulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and optionally additionally substituted by at least one methoxy group. Reference is now made to a dye mixture wherein the reactive dye (3) is a disazo dye of the formula (VIII), given and defined above. In one preferred range of such dyes, R55 is a naphthyl group; R56 is a sulphonic acid group or a salt thereof; R59 is a group L10-Het, where L10 is the group N(H)- and Het is a reactive heterocyclic group substituted by at least one halogen atom; Y1 is 1, 2 or 3; and each of y2, y3 and y4 is zero. 35 A particularly preferred such disazo dye of the formula (VIII) in a dye mixture embodying the invention has the formula In another preferred range of such dyes of the formula (VIII) R55 is a phenyl group; the group R56 or each group R56 independently is a sulphonic acid group or a salt thereof or is a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above; y1 is 1 or 2; and at least one group R56 is a said reactive group or the group R53 is or includes a reactive group. More preferably, at least one group R56 or the group R59 rs a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above; or at least one group R56 is a sulphonic acid group or a salt thereof and R59 is the group L10-Het, where L10 is the group N(H)- and Het is a reactive triazine group substituted by a 36 halogen atom and additionally by the group NHCH2CH2SO3H. Especially preferred dyes have the formulae Reference is now made to a dye mixture wherein the reactive dye (B) is a phthalocyanine dye of the formula (X) , given and defined above. Preferably, in the reactive dye (B) of the formula (X) , respective average values of x1, x2 and x3 are x1 is 3, x2 is zero and x3 is 1, three of the four isomdole rings of the phthalocyanine have a respective sulphonic acid substituent (or a salt thereof) thereon and the other isomdole ring has a group SO2NH-B-NH-Het substituted thereon. More preferably B is a straight or branched C2-4 alkylene group 37 and Het is a triazire ring substituted by at least one halogen aton and optionally additionally substituted by a methoxy group. Reference is now made to a dye mixture wherein the reactive dye (B) is a triphendioxazine dye of the formula (XI), given and defined above, or a salt thereof. Preferably, in such a reactive dye (B) of the formula (XI), each of T1 and T2 is a halogen atom, each U1 is a sulphonic acid group or a salt thereof, each of B1 and B2 independenrly is a straight or branched C2-4 alkylene group, each of Ket and Het2 independently is a triazine ring substituted by a halogen atom and each of R80 and R81 independently is a phenyl group substituted by at least one sulphonic acid group or a salt thereof. The dyes of the formula (A) can be prepared by diazotising each of the amines (XX) and (XXI) wherein each of Y1 and Y2 is as defined above and firstly coupling the diazotised amine (XXI) under strongly acid conditions (pH 1-2) to H-acid to provide an azo group ortho to the amine group and thereafter coupling the diazotised 38 amine (XX) under slightly acidic, neutral or alkaline conditions (pK 6-7) to the H-acid to provide an azo group ortho to the hydroxy group. The diazotisation reactions may each be carried out by adjusting the pH of the amine with a buffer to about 5.3 -6, adding an aqueous solution of hydrochloric acid and ice to cool to 0-5°C and then adding a sodium nitrite solution. The coupling reactions may each be carried out by adjusting the pH as described above and allowing reaction to take place at a temperature of from 4 to 8°C for at least 3 hours. These and other methods of preparing the dyes of the formula (A) are described in EP-A-0149170. Likewise iiisazo dyes (B) of the formula (V) maybe prepared in an analogous manner. Methods of preparation of such dyes are also disclosed in DE-A-3375658 and DE-A-3622080. Dyes (B) of the formula (I) may be prepared by the methods disclosed m DE-A-3717667. Dyes (B) of the formula (II) may be prepared by the method disclosed in DE-A-3927790, DE-A-3515651 and EP-A-0761768. Dyes (B) of the formula (III) may be prepared by the methods disclosed m US-A-4618671, DE-A-3717814 and DE-A- 39 3829595. Dyes (B) of the formula (IV) may be prepared by the method disclosed m US-A-484I031, EP-A-0343262 and EP-3-0776947. Dyes (B) of the formula (VI) may be prepared by the methods disclosed in DE-A-3737536, DE-A-3743236 and DE-A-3840653. Dyes (B) of the formula (X) may be prepared by the methods disclosed in WO-A-98/49240. Dyes (B) of the formula (XI) may be prepared by the methods disclosed in DE-A-3423581 and EP-A-0773264. Examples of dyes (B) of the formula (VII) are CI Reactive Yellow 57, CI Reactive Yellow 106, CI Reactive Yellow 160 -and CI Reactive Yellow 167, all commercially available. A preferred dye mixture in accordance with the invention comprises, by weight of the total weight of the dyes, from 10 - 99.5% by weight, inclusive of component (A), given and defined above, and from 0.5 to 90% by weight inclusive of component (B), given and defined above. Respective progressively more preferred ranges are as follows: 10 - 99% by weight, inclusive of component (A) and from 1 to 90% by weight, inclusive of component (B) ; 40 from 10 - 98.5% by weight, inclusive, of component (A) and from 1.5 - 90% by weight, inclusive, of component (B) ; from 10 - 97% by weight, inclusive, of component: (A) and from 3 - 90% by weight, inclusive, of component (B) ; from 10 - 95% by weight, inclusive, of component (A) and from 5 - 90% by weight, inclusive, of component (B) ; from 10 - 90% by weight, inclusive, of component (A) and from 10 - 90% by weight, inclusive, of component (3) ; from 15 - 90% by weight, inclusive, of component (A) and from 10 - 85% by weight, inclusive, of component (B) ; from 20 - 90% by weight, inclusive, of component (A) and from 10 - 80% by weight, inclusive, of component (B) ; from 30 - 90% by weight, inclusive, of component (A) and from 10 - 70% by weight, inclusive, of component (B) ; and In an especially preferred mixture, component (B) is a mixture of dyes (B) . Mixtures embodying the invention can be prepared by merely mixing the individual dyes or, m some cases, by synthesis using a mixture of diazotising components. This method is especially suitable when component (B) is at least one dye of the formula (V) . The dye mixture may be isolated, for 41 example, by spray drying or salting out. The mixtures can be used to dye or print on substrates containing a hydroxyl group or nitrogen atom, for example, silk, leather, wool, polyamides, polyurethanes and cellulosic materials, especially cotton. The mixtures provide excellent properties including resistance to modern peroxide based detergents, fastness to repeat washing, good light fastness, excellent wash-off, good build-up, good compatibility of the dyes with one another and a robustness to process variables. The reactive dye (A) alone gives a navy shade on cotton and may be mixed with at least one yellow, orange, red or blue reactive dye (B) to give a forest green, navy, brown or black shade. The mixtures have outstanding properties in comparison with known mixtures, for example CI Reactive Black 5, referred to above, which is often used in a mixture with other dyes as a dulling agent. Preferred embodiments of the invention will now be described in more detail with reference to the following Examples, in which the numbers assigned to the dyes are -those given in Table 2 and all parts are by weight unless otherwise stated. In the Examples, dye A has the formula 42 Example 1: 75 parts of dye (A)1, 20 parts of dye (167) and 5 parts of dye (163) were mixed. The mixture was used to dye cotton, by application of cold pad batch and warm exhaust (40, 50 or 60°C) techniques as described below, xn a navy shade resulting in good light fastness and fastness to repeated washing. Exhaust application: l00g of cotton fabric were dyed in a dyebath that contained 1000 mi water, 12g of the mixture of Example 1, 2. 5g sodium carbonate, 1g 32 weight% sodium hydroxide solution and 60g sodium sulphate decahydrate. The dyeing was started at 30°C, the temperature was raised to 50°C over a period of 30 minutes and the dyeing was continued for a further 60 minutes at this temperature. After cooling to room temperature the dyeing was rinsed and boiled with detergent, and dried. Cold pad-batch application: 43 At room temperature woven cotton fabric was scaked in a padder with dye liquor that contained per l000g dye liquor 60g of dye mixture of Example 1, 50g sodium silicate (38° B'e) and 30g 32 weight% sodium hydroxide solution. After 70% pick-up the paddings are rolled and covered with cling film. After storing for 8h at room temperature the paddings are removed from the cling film, rinsed in cold water, hot rinsed with detergent, and dried. Example 2: 60 parts of dye (A)"-, 24 parts cf dye (44) and 16 parts of dye (105) were mixed mechanically. The dye mixture was applied to cotton using the application and fixing methods of Example' 1, resulting in a black shade providing outstanding fastness properties. Example 3: Dye (A)1 and dye (53) were synthesised separately according to known procedures. 65 parts of reaction solution of dye (A)1 and 35 parts of reaction solution of dye (53) were mixed and the dye mixture was isolated by spray drying. The dye mixture was applied to cotton using the application and fixing methods of Example 1, resulting in a black shade providing outstanding fastness properties. Further examples were made achieving the same outstanding fastness properties and these are given in Table 1: 44 Table 1 Example Parts Yellow Parts Red Dye Parts dye (A) Dye No. Yellow Dye No. Red dye 4 60 10 20 126 20 5 58 14 25 127 17 6 65 23 14 121 21 7 55 44 25 129 20 8 70 49 15 91 15 9 65 15 10 105 25 Example Parts Orange Parts dye (A) Dye No. Orange dye 10 67 55 33 11 62 61 38 12 60 69 . 40 45 Example 13: l00g of cotton fabric was dyed according to the procedures described for Example 1 using 3g of a dye mixture containing 1.5g dye (A)1, 0.6g dye (1), 0.3g dye (2) and 0.57g dye (94) resulting in a brown shade providing outstanding fastness properties. Example 14: lOOg of cotton fabric was dyed in a dyebath that contained 1000ml water, 3g of a mixture containing 1.4g dye (A)1; 0.13g dye (150), O.54g dye (15), 0.30g dye (69), 0.28g dye (90) and 0.35g dye (101), 15g sodium carbonate and 60g sodium chloride. Dyeing was started at 40°C, the temperature was raised to 60\|C over a period of 20 minutes and dyeing was continued for a further 60 minutes- at this temperature. After cooling to room temperature the dyeing was rinsed and boiled with detergent resulting in a brown shade providing outstanding fastness properties. For each of the dyes shown in Table 2 below, dye mixtures may be applied according to any of the procedures described in Examples 1 and 14 or by similar application methods to achieve outstanding fastness properties. 46 Still further (binary mixture) examples were made and when applied via the cold pad-batch application method of Example 1 achieved the same outstanding fastness properties, as shown in Table 2. Table 2 Example Parts dye (A) Yellow/Orange Parts Dye No. Yellow/Orange dye 15 17 10 4 16 34 10 7 17 17 49 3 18 34 49 6 19 17 44 3 20 34 44 6 21 17 23 7 22 34 23 14 23 17 "61 3 24 34 61 6 25 17 53 2.4 26 34-53 6 27 17 67 3 28 34 67 6 29 17 85A 2 30 34 85A 4 31 17 85B 3 32 34 85B 6 54 55 56 5" 58 71 WE CLAIM: 1. A dye mixture comprising, components A and 8, wherein component (A) is a reactive dye of the formula (A) Wherein each of Y1 and Y2, Independently, is a vinyl group or a group of the formula-ChhCfyQ in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and component (B) Is at least one reactive dye of the formula (V) 72 Wherein: R1 is phenyl group optionally having at least one substttuent thereon, the substituents, or each substttuent Independently, being selected from a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or is a naphthyl group optionally having at least one substttuent thereon, the substttuents, or each substttuent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; R14 is phenyl group optionally having at least one substttuent thereon, the substttuents, or each substttuent independently, being selected from a C1-4 alkyl group, a CM alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or is a naphthyl group optionally having at least one substttuent thereon, the substituents, or each substttuent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; each of R40 and R41 independently is an aryl group selected from phenyl and naphthyl groups, each of which independently, Is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-re active group having an aliphatic chain; 73 each of R51 and R52 independently is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het3, where Het3 is an optionally substituted aromatic heterocyclic reactive group or a reactive group having an aliphatic chain; each of L1,L2,L3 and L4, independently, is a linking group selected from the group consisting of N (R20); C(=O); C(=O)-O; S(=O)2; S(=O)-NH; C(-O)-NH; and NHC(=O)NH; in which R20 is C1-4 alkyl or hydrogen; each of V and W, Independently, is NH2 or OH; each of x,y,z,f,g and h, independently is zero or 1; and at least one of R14, R40, R41, R51 and R52 is, or has thereon at least one substituent which is reactive. 2. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), V is amino, W is hydroxy, each of R1 and R14 is a phenyl group substituted by at least one substituent, the or each substituent Independently being, a vinylsulphonyl group or a group SO2CH2CH2Q1 and R14 iS optionally additionally substituted by at feast one methoxy group. 3. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), each of x and h is zero. 4. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), at least one of x and h is 1. 5. The dye mixture as claimed in claim 1, wherein, each of x and h is 1. 6. The dye mixture as claimed in claim 2, wherein each of x,y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being a sulphonic acid group of salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1. 74 7. The dye mixture as claimed in claim 6, wherein each off, g and h is 1, each of L3 and L4 is NH, R51 is a triazine ring substituted by a halogen atom and R52 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a halogen atom, a sulphonic acid group or a salt thereof, a vinylsuiphonyl group and a group SO2CH2CH2Q1. 8. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), V is amino, W is hydroxy, h is zero and R14 is a naphthalene group substituted by at least one sulphonic acid group. 9. The dye mixture as claimed in claim 8, wherein each of x,y and z is 1, R1 is a phenyl group, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1. 10. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NH and R52 is the group Het3, where Het3 is a substituted aromatic heterocyclic group. 11.The dye mixture as claimed in claim 10, wherein the group Het3 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by methyl group. 12. The dye mixture as claimed in claim 11, wherein x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group of SO2CH2CH2Q1. 13.The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NHCO, wherein either the nitrogen or carbon atom thereof is attached to the group R14, and R52 is the group Het3, where Het3 is a reactive group having an aliphatic chain. 14.The dye mixture as claimed in claim 13, wherein, the group Het3 is a vinylsulphonyl group or SO2CH2CH2Q1. 75 15.The dye mixture as claimed in claim 14, wherein x is zero and R1 Is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1. 16. The dye mixture as claimed in claim 1, which contains a dye of the formula (105) 17.The dye mixture as claimed in claim 16, which additionally contains a dye of the formula (44) 76 18. The dye mixture as claimed in claim 1, which contains a dye of the formula (167) A dye mixture comprises, as component (A), a reactive dye of the formula (A) wherein each of Y1 and Y2, independently, is a vinyl group or a group of the formula - CH2CH2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and, as component (B), at least one additional reactive dye selected from a monopyrazole dye of the formula (I), a mono or disazo dye of the formula (II), a monoazopyridone dye of the formula (III), a monoazonaphthyl dye of the formula (IV), a disazoaminonaphthyl dye of the formula (V), a formazan dye of the formula (VI), an azoacetoacetanalide dye of the formula (VII), a disazo dye of the formula (VIII), a naphthylamide or a naphthalenetriazole dye of the formula (IX), a metal phthalocyanine dye of the formula (X) or a triphendloxazine dye of the formula (XI). as defined herein.

Full Text

1
REACTIVE DYE MIXTURES This invention relates to a dye mixture.
This invention relates to mixtures of reactive dyes, in particular to mixtures of reactive dyes containing, as one component, a disazo dye derived from K-acid.
As is well known, reactive dyes contain at least one substituent capable of taking part in a reaction with a group present on a fabric to be dyed during the dyeing operation.
EP-A-0149170 discloses a range of dyes of the formula

in which one X is hydrogen and the other sulpho, each of Y1 and Y2 independently is a group -CH=CK2, -CK2CK2OSO3H, -CK2CH2SSO3H, -CK2CH2C1 or -CH2CH2OR, and R is a low molecular weight alkanoyl, benzoyl or benzenesulphonyl group, optionally substituted by a C1-4 alkyl, C1-4 alkoxy, nalogen, carboxy or sulpho group.

2
A typical dye has the formula

EP-A-0149170 refers only to individual dyes, not mixtures
thereof.
On the other hand, each of EP-A-0224224, EP-A-0679697, EP-A-0531968, EP-A-0668328 and EP-A-0600322 discloses respective mixtures of dyes, one of which components as a disazo dye derived from H-acid. One particular example of such a dye has the formula

This dye is available commercially as C.I.Reactive Black 5 and is added to other dyes as a dulling agent where appropriate.
We find surprisingly that the fastness of a dye mixture can be improved if the dye mixture contains, as a component

3
thereof, a dye of the formula (A)

wherein each of Y1 and Y2, independently/ is a vinyl group or a group of the formula -CH2CK2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group.
The dye mixture may contain, in addition to component (A) , any of a wide range of dyes.
More particularly, the present invention provides a dye mixture comprising a reactive dye of the formula (A) , given and defined above; and
at least one reactive dye (B) selected from (I) a monoazopyrazole dye of the formula

4
wherein R1 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
R2 is a phenyl or naphthyl group, optionally having at least one substituent thereon, the substituent, cr each substituent, independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a chlorine- atom, a vinyl sulphonyl group, a group SO2CH2CK2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl -sulphonyl group, a group Het and a group L5-Ket, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain and L5 is as defined below; and
R6 is a methyl group, an amide group or a carboxyl group or a salt thereof;

5
each of R40 and R41, independently, is an aryl group selected from phenyl and naphthyl groups, each of which, independently, is optionally substituted by a vinylsulphonyl group, a group So2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinylsulphonyl group; or the group Het, where Het is as defined above;
at least one of R1, R2, R40 and R41 being, or having thereon at least one substituent which is, reactive;
each of L1, L2 and L5 independently is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(=0); C(=O)-O; S(=0)2; S(=O)-NH; C(=O)-NH; and NHC(=O)NH; and
each of x, y and z, independently, is zero or i; and, when the group R1 is substituted by a hydroxy group ortho to the azo group, a metallized derivative thereof;
(II) a monoazo or disazo dye of the formula

6
wherein: Ket is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain;
R3 or each R3, independently, is a chlorine atom, a methyl group, a methoxy group, a sulphonic acid group cr a salt thereof, or is an amino group of the formula

in which each of R18 and R19, independently, is hydrogen, chloro, methyl, (C1-4 alkyl) carbonyl, aminocarbcnyl, vinylsulphonyl or a group SO2CH2CH2Q1, in which Q1 is as defined above;
R4, or each R4 independently, is hydrogen , a sulphonic acid group or a salt thereof, a C1-8 alkyl (preferably a C1-4 alkyl) group, a C1-4 alkoxy group, a vinyl sulphonyl group or a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, which C1-4 alkyl group or C1-4 alkyl moiety of the C1-4 alkoxy group is optionally interrupted by an oxygen atom to provide an ether group and is optionally substituted by a vinyl sulphonyl group or a group SO2CH2CH2Q2, in which Q2 is as defined above; or R4 (or when q is 2, each R4 independently) is a phenyi group optionally substituted by at least one sulphonic acid group

7
or a salt thereof or at least one group Het, where Ket is as defined above; or R4 is a group Het, where Het is as defined above
R5 is an aryl group selected from phenyl and naphthyl groups each optionally substituted by at least one sulphonic acid group or, a salt thereof or at least one group Het, as defined above;
R20 is a. hydrogen atom or a C1-4, alkyl group;
R21 is a hydrogen atom, a C1-4 alkyl group, a sulphonic acid-C1-4 alkyl group, a chloroalkylsulphonyl-C1-4 alkyl group or a group Het, where Het is as defined above;
m is 1 or 2;
p is zero, 1 or 2;
q is zero, 1 or 2;
each of w1 and w2 is zero or 1; and
w3 is 1, 2 -or 3; and
when p is zero, q is zero;
at least one of R4, R5, R18, R19, R21 and Her being, or having thereon at least one substituent which is, reactive;
(III) a monoazopyridone dye of the formula

8 wherein: each of R40, R41, L1 and L2 is as defined, above;
R7 is optionally present and is a cyano group or the group - CH2SO3H or the group -C(=O)NH2;
each of R24 and R25, independently, is a hydrogen atom, a C1-4 alkyl group, a sulpho-C1-4 alkyl group, or a carboxyl group;
n is 1 or 2; ,
r is zero or 1; and
each of S1 and s2 is zero or 1; and when R40 is a phenyl or naphthyl group s2 is 1;
at least one of R40 and R41 being, or having thereon at least one substituent which is, reactive;
(IV) a monoazonaphthyl dye of the formula

wherein: each of R1, R40, R41, L1, L2, x, y and z is as defined above;
R9 is CH3(C=O)-, Het (as defined above) or an aryl
group selected from phenyl and naphthyl, which Ket or aryl group is optionally substituted by at least one substituent, the or each substituent, independently, being

9
selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above;
R35 is a C1-4 alkyl or C2_4 alkenyl group, which C1-4 alkyl or C2_4 alkenyl group is optionally substituted by at least one halogen atom, a sulphonic acid group or salt thereof, a chloroalkylsulphonyl group, a vinylsulphonyl group or -SO2CH2CH2Q1, where Ql is as defined above and which C1-4 alkyl or C2_4 alkenyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof; the group Het (as defined above) ; or an aryl group selected from phenyl and naphthyl, which Het or aryl group is optionally substituted by at least one substituent, the substituent or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen atom, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinylsulphonyl group, a vinyisulphonyloxyethyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above;
R50 is a vinylsulphonyl group or a group SO2CH2CH2Ql (in which Q1 is as defined above);
at least one of R1, R5, R35, R40, R41 and R50 is, or

10 has thereon at leas:: one substituent which is, reactive;
L3 is a linking group selected from N(R20}, in which R20 is as defined above; CO; COO; NHCO; NHCONE; SO2NH and SO2;
L4 is a linking group selected from N(R21), in which R21 is as defined above, CO, COO, NHCO, NHCONH, SO2NH and SO2;.
z is hydroxy, amino or methylamino;
a is zero or 1-4;
b is zero or 1-3;
c is zero or 1;
d is zero, 1 or 2;
e is zero or 1; and
when each of R1 and Z provides a hydroxyl group ortho to the azo group, a metallized derivative thereof;
(V) a disazoaminonaphthyl dye of the formula

wherein: eacn of R1, R40, R41, L1, L2, x, y and z is as defined above;

11
each of V and W, independently, is NH2 or OH;
R14 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each subsrituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
each of R51 and R52 independently is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het3, where Ket3 is an optionally substituted aromatic heterocyclic reactive group cr a reactive group having an aliphatic chain;
each of L3 and L4, independently, is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(-0); C(=O)-O; S(=0)2; S(=O)-NH; C(=O)-NH; and NHC(=O)NH;
each of f, g and h, independently is zero or 1; and
at least one of R14, R40, R41, R51 and R52 is, or has thereon at least one substituent which is, reactive;

12 (VI) a formazan dye of the formula
n

wherein: each of R16 and R17 independently of one another, each R16 independently of one another and each R17 independently of one another, is a sulphonic acid group or a salt thereof, a vinyl sulphonyl group or a group SO2CHzCH2Ql in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
each of Het1 and Het2, independently, is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain; and
each of R60 and R61, independently, is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above;

13
X1 is a sulphonic acid group or a salt thereof cr halogen; each of i, J and v, independently, is zero, 1 or 2; and each of k, 1, t and u, independently, is zero or 1; and
at least one of R16, R17, R50, R51, Het1 and Het2 is, or has thereon at least one substituent which is, reactive;
(VII) a dye of the formula

wherein: each of R1, R2, R3, R4, R20, R21, R40, L1, Het, x, p, q, w1, w2 and w3 is as defined above; and
at least one of R1, R2, R3, R4, R21, R40 and Het is, or
has thereon at least one substituent which is, reactive;
(VIII) a disazo dye of the formula

14
wherein R55 is an aryl group selected from phenyl and naphthyl groups;
R56 is a sulphonic acid group or a salt thereof or a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Ql is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
R57 is an amino group or a group NHRA in which RA is a C1-4 alkyl group;
R58 is a sulphonic acid group or a salt thereof;
R59 is a sulphonic acid group or a salt thereof, a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or the group R59 is a group Het or a group L10-Ket, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group;
R65 is a ureido group or a group HNC(=0)R3 in which R3 is a C1-4 alkyl group;
L10 is a linking group selected from N(R20) , in which R20 is hydrogen or CH alkyl; C(=0); C(=0)-0; S(=O)2; S(=O}-NH; C(=0)-NH; and NHC(=0)NH;
y1 is zero, 1, 2 or 3;
y2 is zero, 1 or 2;
y3 is zero or 1; and
y4 is zero or 1; and at least one of R56 and R59 is a reactive group.

15

wherein: MPc is a metallophthalocyanine chromophore;
each of R70 and R71, independently, is hydrogen or
C1-4 alkyl;
B is a hydrocarbon bridging group;

16
Het is a reactive heterocyclic group; each of xl, x2 and x3 is a respective average value;
x1 + x2 + x3 = 4;
X1 is at least 1
x2 is zero or 1; and
x3 is at least 1; and
(XI) a triphenodioxazine dye of the formula (XI) (or a
salt thereof)

wherein: each of B1 and B2, independently, is a hydrocarbon bridging group;
U1 is H or SO3H; and
each of T1 and T2, independently, is halo, C1-4 alkyl, or C1-4 alkoxy;
each of R80 and R81 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof;
each of Het1 and Het2 is as defined above; and

17
at least one of Het1 and Het2 is a reactive group.
Referring to the dye of the formula (A) , preferably at least one of Y1 and Y2 is the group -CH2CH2Q and Q is selected from chlorine, bromine, C1-4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, OP(O)(OH)2, C1-4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl) carbonyloxy, (C1-4 dialkyl) amino or a radical of the formula

where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4 alkyl or benzyl and Ane is in each case one equivalent of an anion. More preferably, each of Y1 and Y2 is the group HO3SOCH2CH2.
Referring now to the reactive dye (B), dyes in one preferred range thereof contain a group Het, where Het is an optionally substituted aromatic heterocyclic reactive group derived from a halogen-substituted heterocyclic compound selected from 1,3,5-triazine, qumoxaline, phthalazine, pyrimidine, pyridazine and 2-(C1-4 alkylsulphonyl) benzothiazole. More preferably, the aromatic heterocyclic reactive group is substituted and at

18
least one substituent is a halogen atom.
An alternative preferred range of reactive dyes (B) contains
a group Het, where Het is a reactive group having an aliphatic
chain and selected from acryloyl, mono-, di- or
trichloroacryloyl, mono-, di- or tri- bromoacryloyl,
-CO-CC1=CH-COOH, -CO-CH=CC1-COOH, 2-chloropropionyl,
1, 2-dichloroproplonyl, 1, 2-dibromopropionyl,
3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl,
2-sulfatoethylaminosulfonyl, 2-chloro-2, 3, 3-trifluorocyclo-
butylcarbonyl, 2, 2, 3, 3-tetrafluorocyclobutylcarbonyl,
2,2,3,3-tetrafluorocyclobutylsulfonyl, 2-(2,2,3,3-
tetrafluorocyclobutyl) acryloyi, 1- or 2-alkyl- or 1- or 2-arylsulfonylacryloyl, or a radical of the formula SO2-Y3, SO2NH-Y, CONH-L6-SO2-Y3 or NHCONH-L5-SO2-Y3 where L6 is C1-C4-alkylene or phenylene and Y3 is a vinyl group or a group of the formula CH2CH2Q3 in which Q3 is a leaving group removable under alkaline conditions to provide a vinyl group.
It is also preferred that, the reactive dye (B) has at least
one of the groups Q1 and Q2 therein and the or each of groups
Q1 and Q2 independently is selected from chlorine, bromine,
C1-4-alkylsulfonyl, phenylsulfonyi, OSO3H, SSO3H, OP(O) (OH)2,
C1_4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl)
carboxyloxy, (C1-4 dialkyl) amino or a radical of the formula

19
where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4-alkyl or benzyl and An is in each case one equivalent of an anion.
In a dye mixture wherein the reactive dye (B) is a monoazopyrazole dye of the formula (I), given and defined above, it is preferred that at least one of the group
[(R41-L2)(R40-L1)y]xR1 and the group R2 has at least one sulphonic acid group substituted thereon and at least the other of the group [(R41-L2) z(R40-L1)y)xR- and the group R2 has a group -S02CH2SO2Q2 substituted thereon, Q2 being as defined above.
In respective preferred ranges of the reactive dye (B) of the formula (I)
(i) x is zero and the group R1 is substituted by at least one of a sulphonic acid group and the group -So2CH2SO2Q1, wherein Q1 is as defined above;
(ii) each of x, y and z is 1, each of L1 and L2 is NH, R40 is the group Het, where Het is a triazine ring subetitutec by a halogen atom and R41 is an optionally
substituted phenyl group.
(iii) each of x and z is 1, y is zero, L2 is NH and R41 is the group Het, where Het is a difluorochloropyrimidmyl

20 group; and
(iv) each of x and z is 1, y is zero, L2 is CONE (in which the nitrogen atom is attached to the group R1 and the carbon to the group R41) and R41 is the group Het, where Het is a 2,3-dichloroqumoxaline group.
In a reactive dye (B) of the formula (I), R2 is preferably a phenyl or naphthyl group substituted by
(i) at least one of a sulphonic acid group and the group -SO2CH2SO2Q2, where Q2 is as defined in claim 1; or
(ii) at least by the group NH-Het, where Het is a triazine ring substituted by ¦ a halogen atom and optionally substituted by the group

In a reactive dye (B) of the formula (I), the group R1 may
be substituted by a hydroxy group ortho to the azo group
and the reactive dye (B) may then be in the form of a copper complex.
Reference is now made to a dye mixture wherein the reactive dye (B) is monoazo or disazo dye of the formula (II), given

21 and defined above.
In such a mixture it is preferred that in the reactive dye (B) of the formula (II), when m is 1 and R4 is alkyl, R4 is C1-4 alkyl.
It is also preferred that the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by at least one sulphqnic acid group or a salt thereof or by a group Het, wherein Het is a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above.
In an especially preferred reactive dye (B) of the formula (II), m is 1, so that the dye is a monoazo dye. In preferred ranges of monoazo dyes (B) of the formula (II) in a mixture in accordance with the invention,
(i) each of wl, w2, p and q is zero, w3 is at least 2, at least one of the groups R3 is a sulphonic acid group and the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q, where Ql is as defined above.
(ii) each of w1 and w2 is zero, each of p and q is 1, R21 is hydrogen and R4 is selected from a triazine ring substituted by at least one halogen atom and optionally additionally substituted by an amino croup; and a
pyrimidine group substituted by at lease one halogen atom and optionally additionally substituted by a methyl group;
(in) each of w1, w2, p and q is 1, R20 is hydrogen, Het

22
is a triazine ring substituted by a halogen atom, R21 is hydrogen and R4 is selected from a phenyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above, and a straight or branched C2_4 alkylene chain substituted by a substituent selected from a hydroxyl group; a sulphonic acid group or salt thereof; a vinylsulphonyl group, a group -SO2CH2CH2Q2, where Q2 is as defined above; and a pyrimidinylamino group in which the pyrimidinyl group is substituted by at least one halogen atom and optionally additionally by a methyl group; and which straight or branched C2-4 alkylene group optionally contains a hetero atom selected from 0, S and N (H) ;
(iv) each of w1 and w2 is zero, each of p and q is 1
and each of R21 and R4 is the group OSO3H; and
(v) w1 is zero, w2 is 1, p is 1, q is 1, R21 is

hydrogen, R4 is a pyrimidmyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and Het is a non-reactive heterocyclic group of the formula

_23
An especially preferred dye mixture contains a dye of the formula (44) as the reactive dye (B) of formula (II)

Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazopyridone dye of the formula (III), given and defined above.
In respective preferred ranges of the reactive dye (B) of the formula (III) ,
(1) each of r, s1 and s2 is 1, each of L1 and L2 is NH,

R40 is a triazine ring substituted by a halogen atom and R41 is selected from a phenyl group substituted by at least one of a chlorine atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above; and a straight or branched chain C2-4 alkylene group optionally containing at least one oxygen atom and substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above;
(ii) each of r and s1 is 1, s2 is zero, L2 is NH, R41 is

24
a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a metnyl group and R40 is a naphtho- (1, 2-d) -1, 2, 3-triazole substituted by at least one sulphonic acid group or salt thereof; and
(iii) each of r1, S1 and s2 is 1, L1 is CONH (in which the carbon atom is attached to the group R40), L2 is NK, R40 is an optionally substituted phenyl group and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group.
Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazonaphthyl dye of the formula (IV), given and defined above.
In one preferred range of such dyes,
(i) x is zero, d xs 1 and a or b is 1. More preferably e is zero.
In other preferred respective ranges,
(ii) x is 1, y is zero, z is 1, L2 is NK and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group;
(iii) x is 1, y is zero, z is 1, L2 is CONH (with the

25
carbon atom attached to the group R1 and the nitrogen atom to the group R41) and R41 is a phenyl group substituted by a vinylsulphonyl group or a group -SO2CH2CH2Q1, where Q1 is as defined above; and
(iv) each of x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is an aromatic group selected from phenyl and naphthyl groups each substituted by at least one of a sulphonic acid group or a salt thereof, a vinylsulphonyl group and the group -SO2CH2CH2Q1, where Q1 is as defined above.
In such ranges (ii) - (iv) of dyes (B) of the formula (IV), more preferably, e is zero.
In other preferred ranges of the reactive dye (B) of the formula (IV),
(v) e is 1, c is zero, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a methyl group;
(vi) e is 1, c is zero, L3 is CONH {where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a phenyl group optionally substituted by at least one substituent, the or each substituent being selected from methoxy, carboxyethyl, sulphoethyl, carboxyethenyl, 1,2-dibromoalkyl, chloroethylsulphonyl, vinylsulphonyl, a

26
group of the formula -SO2CH2CH2Q1, where Q1 is as defined above and a 2, 3-dichloroquinoxalme group.
(vii) e is 1, c is 1, L3 is CONH (where either the
nitrogen or carbon atom thereof is attached to the group R9) , R9 is a phenyl group substituted at least by the group L4-R35, where L4 is NH and R35 is a vinyl group optionally substituted by a halogen atom or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group; and
(viii) e is I, c is zero, L3 is N(R20), where R20 is as
defined above (and is more preferably a hydrogen atom or a methyl group) and R9 is a vinylsulphonyl group, a group -SO2CH2CH2Q1 wherein Q1 is as defined in claim 1, or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group. In yet another preferred range
(iX) e is 1, c is zero, L3 is N(R20), where R20 is as
defined above and R9 is a triazine ring substituted by at least one halogen atom. In this range the triazine ring is preferably substituted by two halogen atoms or by one halogen atom and a morpholmyl group.
In another preferred range,
(x) e is 1, c is 1, L3 is N(R20), where R20 is as

27
defined above, L4 is the group R21, where R21 is as defined above, and R35 is selected from a phenyl group optionally substituted by a sulphonic acid group or salt thereof, a halogen atom, a vinylsulphonyloxyalkyl group, a vinylsulphonyl group or the group -SO2CH2CH2Q1, where Q1 is as defined above; and a C1-4 alkyl group optionally substituted by a vinysulphonyl group, the group -SO2CH2CH2Q1, where Q1 is as defined above, a sulphonic acid group or a salt thereof or a chlcroalkylsulphonyl group, which C1-4 alkyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof.
In dye mixtures containing a reactive dye (B) of the formula (IV) within the above ranges x is preferably zero.
In the reactive dye (B) of the formula (IV) , each of the groups R1 and the naphthalene nucleus may be substituted by a respective hydroxyl group ortho to the azo group and the reactive dye (B) may then be in the form of a copper-complex thereof.
An especially preferred dye mixture contains a dye of the formula (53) as the reactive dye (B)

28
Reference is now made to a dye mixture wherein, the reactive dye (B) is a disazo dye of the formula (V) , given and defined above. In such dyes, the respective sulphonic acid groups on the naphthalene nucleus are preferably in the 3-and 6- positions (i.e. such dyes are preferably derived from H-acid).
In one preferred range of dyes of the formula
(i) V is amino, W is hydroxy, each of R1 and R14 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinyl sulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above and R14 is optionally additionally substituted by at least one methoxy group.
It is also preferred, especially for one sub-range within the range {i}, that each of x and h is zero. Such a range of dyes includes those of the formula (A) and a mixture in accordance with the invention may indeed contain only dyes of the formula (A) , one such dye of the mixture being regarded as a dye of the formula (A) and at least one other such dye of the mixture being regarded as a dye of the formula (V).
In an alternative preferred range of dyes of the formula

(V), especially for another sub-rarge within the-range (i) , at least one of x and h is 1 and more preferably each of x and h is 1.
In a preferred sub-range (ii) of dyes (3) of the formula (V) , within the range (i) , x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent. independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In the preferred ranges (i) and (ii) above, more preferably, each of f, g and h is 1, each of L3 and L4 is NH, R51 is a triazine ring substituted by a halogen atom and R52 is a phenyl group substituted by at least one substituent,- the or each substituent independently being selected from a halogen atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (iii) of reactive dyes (3) of the formula {V}, v is amino, W is hydroxy, h is zero and R14 is a naphthalene group substituted by at lease one sulphonic acid group. More preferably, in this range (m), each of x, y and z is 1, R1 is a phenyl group optionally substituted by a sulphonic acid group or a salt thereof, each of L1 and

30
L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (IV) of the reactive dyes (B) of the formula (V), V is amino, w is hydroxy, h is 1, f is zero, g is 1, L4 is NH and R52 is the group Het3, where Het3 is a substituted aromatic heterocyclic group. In this range (iv) , more preferably the group Het3 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and still more preferably x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (v) of the reactive dyes (3) of the formula (V) , V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NHCO {where either the nitrogen or carbon atom thereof is attached to the group R14) and R52 is the group Het3, where Het3 is a reactive group having an aliphatic chain. More preferably, m this range (v) , the group Het3 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and still more preferably x is zero and Rl is a phenyl group substituted by a vinylsulphonyl group or

31 SO2CH2CH2Q1, where Q1 is as defined above.
One especially preferred dye mixture contains a dye of the formula (105) as a dye of the formula (V)

and more preferably additionally contains a dye of the formula (44) as another dye (B) , of the formula (II)

Another especially preferred dye mixture contains at least one and more preferably both of the dyes of the formulae (163) and (167)

32

Reference is now made to a dye mixture wherein the reactive dye (B) is a formazan dye of the formula (VI) , given and defined above.
In preferred respective ranges of the reactive dye (3) of the formula (VI)
(i) each of u and v is zero, i is 1, R16 is a sulphonic acid group or a salt thereof, j is 2 and one R17 is a sulphonic acid group or a salt thereof and the other R17 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as
defined above; and
(11} v is zero, 1 is 1, R16 is a sulphonic acid group or a salt thereof, j is 1, R17 is a sulphonic acid group, u is 1 and Het is a triazine ring substituted by a halogen

33
atom. In one preferred sub-range within the range (ii), each of k and 1 is zero, t is 1 and R61 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof, while in another preferred sub-range with the range (ii), each of k, 1 and t is 1, each of R50 and R61 independently is a phenyl group subsicuted by at least one sulphonic acid group or a salt thereof and Het2 is a triazme ring substituted by a halogen atom. In yet another preferred sub-range within the range (ii), each of k and t is zero, 1 is 1 and Het2 is a reactive group having an aliphatic chain.
Reference is now made to a dye mixture wherein the reactive dye (B) is a dye of the formula (VII), given and defined above.
In one preferred range of such dyes, x is zero and each of p, q, w and W2 is 1. More preferably, in such a. range, R1 is a naphthalene ring substituted by at least one sulphonic acid group. It is also preferred that, in such a range, w3 is 1 and R3 is a methoxy group. Moreover, a preferred group of R20 is hydrogen and preferred groups of R21 are hydrogen, methyl and ethyl. A preferred group R4 is a phenyl group substituted by at least one sulphonic acid group.
In another preferred range of such dyes (VII), each of p, q, w1 and w2 is zero. More preferably, m such a range, w3

34
is 3 and at least one of R3 is a sulphonic acid ,group. Other groups of R3 are preferably methyl, methoxy, amino or further sulphonic acid groups. It is also preferred that where, in such dyes, x is 1, R1 is a phenyl or naphthyl group substituted by at least one sulphonic acid group, L1 is NH and R40 is a reactive halopyrimidine group, especially a group containing at least one, more especially at least two fluorine atoms and particularly a
difluorochloropyrimidme group, and that where, in such dyes x is zero, R1 is a phenyl group substituted by a vinyl sulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and optionally additionally substituted by at least one methoxy group.
Reference is now made to a dye mixture wherein the reactive dye (3) is a disazo dye of the formula (VIII), given and defined above.
In one preferred range of such dyes,
R55 is a naphthyl group;
R56 is a sulphonic acid group or a salt thereof;
R59 is a group L10-Het, where L10 is the group N(H)- and Het is a reactive heterocyclic group substituted by at least one halogen atom;
Y1 is 1, 2 or 3; and
each of y2, y3 and y4 is zero.

35
A particularly preferred such disazo dye of the formula (VIII) in a dye mixture embodying the invention has the formula

In another preferred range of such dyes of the formula (VIII)
R55 is a phenyl group;
the group R56 or each group R56 independently is a sulphonic acid group or a salt thereof or is a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above;
y1 is 1 or 2; and
at least one group R56 is a said reactive group or the group R53 is or includes a reactive group.
More preferably, at least one group R56 or the group R59 rs a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above; or at least one group R56 is a sulphonic acid group or a salt thereof and R59 is the group L10-Het, where L10 is the group N(H)- and Het is a reactive triazine group substituted by a

36 halogen atom and additionally by the group NHCH2CH2SO3H.
Especially preferred dyes have the formulae

Reference is now made to a dye mixture wherein the reactive dye (B) is a phthalocyanine dye of the formula (X) , given and defined above.
Preferably, in the reactive dye (B) of the formula (X) , respective average values of x1, x2 and x3 are x1 is 3, x2 is zero and x3 is 1, three of the four isomdole rings of the phthalocyanine have a respective sulphonic acid substituent (or a salt thereof) thereon and the other isomdole ring has a group SO2NH-B-NH-Het substituted thereon. More preferably B is a straight or branched C2-4 alkylene group

37
and Het is a triazire ring substituted by at least one halogen aton and optionally additionally substituted by a methoxy group.
Reference is now made to a dye mixture wherein the reactive dye (B) is a triphendioxazine dye of the formula (XI), given and defined above, or a salt thereof.
Preferably, in such a reactive dye (B) of the formula (XI), each of T1 and T2 is a halogen atom, each U1 is a sulphonic acid group or a salt thereof, each of B1 and B2 independenrly is a straight or branched C2-4 alkylene group, each of Ket and Het2 independently is a triazine ring substituted by a halogen atom and each of R80 and R81 independently is a phenyl group substituted by at least one sulphonic acid group or a salt thereof.

The dyes of the formula (A) can be prepared by diazotising
each of the amines (XX) and (XXI)

wherein each of Y1 and Y2 is as defined above and firstly coupling the diazotised amine (XXI) under strongly acid conditions (pH 1-2) to H-acid to provide an azo group ortho to the amine group and thereafter coupling the diazotised

38
amine (XX) under slightly acidic, neutral or alkaline conditions (pK 6-7) to the H-acid to provide an azo group ortho to the hydroxy group.
The diazotisation reactions may each be carried out by adjusting the pH of the amine with a buffer to about 5.3 -6, adding an aqueous solution of hydrochloric acid and ice to cool to 0-5°C and then adding a sodium nitrite solution.
The coupling reactions may each be carried out by adjusting the pH as described above and allowing reaction to take place at a temperature of from 4 to 8°C for at least 3
hours.
These and other methods of preparing the dyes of the formula (A) are described in EP-A-0149170.
Likewise iiisazo dyes (B) of the formula (V) maybe prepared in an analogous manner. Methods of preparation of such dyes are also disclosed in DE-A-3375658 and DE-A-3622080.
Dyes (B) of the formula (I) may be prepared by the methods disclosed m DE-A-3717667.
Dyes (B) of the formula (II) may be prepared by the method disclosed in DE-A-3927790, DE-A-3515651 and EP-A-0761768.
Dyes (B) of the formula (III) may be prepared by the methods disclosed m US-A-4618671, DE-A-3717814 and DE-A-

39 3829595.
Dyes (B) of the formula (IV) may be prepared by the method disclosed m US-A-484I031, EP-A-0343262 and EP-3-0776947.
Dyes (B) of the formula (VI) may be prepared by the methods disclosed in DE-A-3737536, DE-A-3743236 and DE-A-3840653.
Dyes (B) of the formula (X) may be prepared by the methods disclosed in WO-A-98/49240.
Dyes (B) of the formula (XI) may be prepared by the methods disclosed in DE-A-3423581 and EP-A-0773264.
Examples of dyes (B) of the formula (VII) are CI Reactive Yellow 57, CI Reactive Yellow 106, CI Reactive Yellow 160 -and CI Reactive Yellow 167, all commercially available.
A preferred dye mixture in accordance with the invention comprises, by weight of the total weight of the dyes, from 10 - 99.5% by weight, inclusive of component (A), given and defined above, and from 0.5 to 90% by weight inclusive of component (B), given and defined above. Respective progressively more preferred ranges are as follows:
10 - 99% by weight, inclusive of component (A) and from 1 to 90% by weight, inclusive of component (B) ;

40
from 10 - 98.5% by weight, inclusive, of component (A) and from 1.5 - 90% by weight, inclusive, of component (B) ;
from 10 - 97% by weight, inclusive, of component: (A) and from 3 - 90% by weight, inclusive, of component (B) ;
from 10 - 95% by weight, inclusive, of component (A) and from 5 - 90% by weight, inclusive, of component (B) ;
from 10 - 90% by weight, inclusive, of component (A) and
from 10 - 90% by weight, inclusive, of component (3) ;
from 15 - 90% by weight, inclusive, of component (A) and from 10 - 85% by weight, inclusive, of component (B) ;
from 20 - 90% by weight, inclusive, of component (A) and from 10 - 80% by weight, inclusive, of component (B) ;
from 30 - 90% by weight, inclusive, of component (A) and from 10 - 70% by weight, inclusive, of component (B) ; and
In an especially preferred mixture, component (B) is a mixture of dyes (B) .
Mixtures embodying the invention can be prepared by merely mixing the individual dyes or, m some cases, by synthesis using a mixture of diazotising components. This method is especially suitable when component (B) is at least one dye of the formula (V) . The dye mixture may be isolated, for

41 example, by spray drying or salting out.
The mixtures can be used to dye or print on substrates containing a hydroxyl group or nitrogen atom, for example, silk, leather, wool, polyamides, polyurethanes and cellulosic materials, especially cotton.
The mixtures provide excellent properties including resistance to modern peroxide based detergents, fastness to repeat washing, good light fastness, excellent wash-off, good build-up, good compatibility of the dyes with one another and a robustness to process variables.
The reactive dye (A) alone gives a navy shade on cotton and may be mixed with at least one yellow, orange, red or blue reactive dye (B) to give a forest green, navy, brown or black shade.
The mixtures have outstanding properties in comparison with known mixtures, for example CI Reactive Black 5, referred to above, which is often used in a mixture with other dyes as a dulling agent.
Preferred embodiments of the invention will now be described in more detail with reference to the following Examples, in which the numbers assigned to the dyes are -those given in Table 2 and all parts are by weight unless otherwise stated. In the Examples, dye A has the formula

42
Example 1:
75 parts of dye (A)1, 20 parts of dye (167) and 5 parts of dye (163) were mixed. The mixture was used to dye cotton, by application of cold pad batch and warm exhaust (40, 50 or 60°C) techniques as described below, xn a navy shade resulting in good light fastness and fastness to repeated washing.
Exhaust application:
l00g of cotton fabric were dyed in a dyebath that contained 1000 mi water, 12g of the mixture of Example 1, 2. 5g sodium carbonate, 1g 32 weight% sodium hydroxide solution and 60g sodium sulphate decahydrate. The dyeing was started at 30°C, the temperature was raised to 50°C over a period of 30 minutes and the dyeing was continued for a further 60 minutes at this temperature. After cooling to room temperature the dyeing was rinsed and boiled with detergent, and dried.
Cold pad-batch application:

43
At room temperature woven cotton fabric was scaked in a padder with dye liquor that contained per l000g dye liquor 60g of dye mixture of Example 1, 50g sodium silicate (38° B'e) and 30g 32 weight% sodium hydroxide solution. After 70% pick-up the paddings are rolled and covered with cling film. After storing for 8h at room temperature the paddings are removed from the cling film, rinsed in cold water, hot rinsed with detergent, and dried.
Example 2:
60 parts of dye (A)"-, 24 parts cf dye (44) and 16 parts of dye (105) were mixed mechanically. The dye mixture was applied to cotton using the application and fixing methods of Example' 1, resulting in a black shade providing outstanding fastness properties.
Example 3:
Dye (A)1 and dye (53) were synthesised separately according to known procedures. 65 parts of reaction solution of dye (A)1 and 35 parts of reaction solution of dye (53) were mixed and the dye mixture was isolated by spray drying. The dye mixture was applied to cotton using the application and fixing methods of Example 1, resulting in a black shade providing outstanding fastness properties.
Further examples were made achieving the same outstanding fastness properties and these are given in Table 1:

44
Table 1

Example Parts Yellow Parts Red Dye Parts dye (A) Dye No. Yellow Dye No. Red dye
4 60 10 20 126 20 5 58 14 25 127 17 6 65 23 14 121 21 7 55 44 25 129 20 8 70 49 15 91 15 9 65 15 10 105 25

Example Parts Orange Parts dye (A) Dye No. Orange dye
10 67 55 33
11 62 61 38 12 60 69 . 40

45
Example 13:
l00g of cotton fabric was dyed according to the procedures described for Example 1 using 3g of a dye mixture containing 1.5g dye (A)1, 0.6g dye (1), 0.3g dye (2) and 0.57g dye (94) resulting in a brown shade providing outstanding fastness properties.
Example 14:
lOOg of cotton fabric was dyed in a dyebath that contained 1000ml water, 3g of a mixture containing 1.4g dye (A)1; 0.13g dye (150), O.54g dye (15), 0.30g dye (69), 0.28g dye (90) and 0.35g dye (101), 15g sodium carbonate and 60g sodium chloride. Dyeing was started at 40°C, the temperature was raised to 60|C over a period of 20 minutes and dyeing was continued for a further 60 minutes- at this temperature. After cooling to room temperature the dyeing was rinsed and boiled with detergent resulting in a brown shade providing outstanding fastness properties.
For each of the dyes shown in Table 2 below, dye mixtures may be applied according to any of the procedures described in Examples 1 and 14 or by similar application methods to achieve outstanding fastness properties.

46
Still further (binary mixture) examples were made and when applied via the cold pad-batch application method of Example 1 achieved the same outstanding fastness properties, as shown in Table 2.
Table 2

Example Parts dye (A) Yellow/Orange Parts Dye No. Yellow/Orange
dye 15 17 10 4 16 34 10 7 17 17 49 3 18 34 49 6 19 17 44 3 20 34 44 6
21 17 23 7

22 34 23 14 23 17 "61 3 24 34 61 6 25 17 53 2.4 26 34-53 6 27 17 67 3 28 34 67 6 29 17 85A 2 30 34 85A 4 31 17 85B 3 32 34 85B 6

54

55

56

5"

58

71
WE CLAIM:
1. A dye mixture comprising, components A and 8, wherein component (A) is a reactive dye of the formula (A)

Wherein each of Y1 and Y2, Independently, is a vinyl group or a group of the formula-ChhCfyQ in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and component (B) Is at least one reactive dye of the formula (V)

72
Wherein:
R1 is phenyl group optionally having at least one substttuent thereon, the substituents, or each substttuent Independently, being selected from a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
or is a naphthyl group optionally having at least one substttuent thereon, the substttuents, or each substttuent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; R14 is phenyl group optionally having at least one substttuent thereon, the substttuents, or each substttuent independently, being selected from a C1-4 alkyl group, a CM alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or is a naphthyl group optionally having at least one substttuent thereon, the substituents, or each substttuent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
each of R40 and R41 independently is an aryl group selected from phenyl and naphthyl groups, each of which independently, Is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-re active group having an aliphatic chain;

73
each of R51 and R52 independently is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het3, where Het3 is an optionally substituted aromatic heterocyclic reactive group or a reactive group having an aliphatic chain; each of L1,L2,L3 and L4, independently, is a linking group selected from the group consisting of N (R20); C(=O); C(=O)-O; S(=O)2; S(=O)-NH; C(-O)-NH; and NHC(=O)NH; in which R20 is C1-4 alkyl or hydrogen; each of V and W, Independently, is NH2 or OH; each of x,y,z,f,g and h, independently is zero or 1; and at least one of R14, R40, R41, R51 and R52 is, or has thereon at least one substituent which is reactive.
2. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of
the formula (V), V is amino, W is hydroxy, each of R1 and R14 is a phenyl
group substituted by at least one substituent, the or each substituent
Independently being, a vinylsulphonyl group or a group SO2CH2CH2Q1
and R14 iS optionally additionally substituted by at feast one methoxy
group.
3. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of
the formula (V), each of x and h is zero.
4. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of
the formula (V), at least one of x and h is 1.
5. The dye mixture as claimed in claim 1, wherein, each of x and h is 1.
6. The dye mixture as claimed in claim 2, wherein each of x,y and z is 1,
each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen
atom and R41 is a phenyl group substituted by at least one substituent, the
or each substituent independently being a sulphonic acid group of salt
thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1.

74
7. The dye mixture as claimed in claim 6, wherein each off, g and h is 1,
each of L3 and L4 is NH, R51 is a triazine ring substituted by a halogen
atom and R52 is a phenyl group substituted by at least one substituent, the
or each substituent independently being selected from a halogen atom, a
sulphonic acid group or a salt thereof, a vinylsuiphonyl group and a group
SO2CH2CH2Q1.
8. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of
the formula (V), V is amino, W is hydroxy, h is zero and R14 is a
naphthalene group substituted by at least one sulphonic acid group.
9. The dye mixture as claimed in claim 8, wherein each of x,y and z is 1, R1
is a phenyl group, each of L1 and L2 is NH, R40 is a triazine ring substituted
by a halogen atom and R41 is a phenyl group substituted by at least one
substituent, the or each substituent independently being a sulphonic acid
group or a salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1.
10. The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of
the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NH
and R52 is the group Het3, where Het3 is a substituted aromatic
heterocyclic group.
11.The dye mixture as claimed in claim 10, wherein the group Het3 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by methyl group.
12. The dye mixture as claimed in claim 11, wherein x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group of SO2CH2CH2Q1.
13.The dye mixture as claimed in claim 1, wherein, in the reactive dye (B) of the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NHCO, wherein either the nitrogen or carbon atom thereof is attached to the group R14, and R52 is the group Het3, where Het3 is a reactive group having an aliphatic chain.
14.The dye mixture as claimed in claim 13, wherein, the group Het3 is a vinylsulphonyl group or SO2CH2CH2Q1.

75
15.The dye mixture as claimed in claim 14, wherein x is zero and R1 Is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1.
16. The dye mixture as claimed in claim 1, which contains a dye of the formula (105)

17.The dye mixture as claimed in claim 16, which additionally contains a dye of the formula (44)

76
18. The dye mixture as claimed in claim 1, which contains a dye of the formula (167)
A dye mixture comprises, as component (A), a reactive dye of the formula (A) wherein each of Y1 and Y2, independently, is a vinyl group or a group of the formula - CH2CH2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and, as component (B), at least one additional reactive dye selected from a monopyrazole dye of the formula (I), a mono or disazo dye of the formula (II), a monoazopyridone dye of the formula (III), a monoazonaphthyl dye of the formula (IV), a disazoaminonaphthyl dye of the formula (V), a formazan dye of the formula (VI), an azoacetoacetanalide dye of the formula (VII), a disazo dye of the formula (VIII), a naphthylamide or a naphthalenetriazole dye of the formula (IX), a metal phthalocyanine dye of the formula (X) or a triphendloxazine dye of the formula (XI). as defined herein.

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Patent Number

203824

Indian Patent Application Number

IN/PCT/2001/01303/KOL

PG Journal Number

10/2007

Publication Date

09-Mar-2007

Grant Date

09-Mar-2007

Date of Filing

10-Dec-2001

Name of Patentee

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG.

Applicant Address

DEUTSCHLAND K.G., PATENT-UND LIZENZABETEILUNG, INDUSTRIEPARK HOCHST/GEBAUDE D706, D-65926 FRANKFURT, GERMANY.

Inventors:

#	Inventor's Name	Inventor's Address
1	ZAMPONI, ANDREA MARIA	SCHIMPERSTRASSE 37, D-68165 MANNHEIM, GERMANY

PCT International Classification Number

C 09 B 62/00

PCT International Application Number

PCT/IB00/00902

PCT International Filing date

2000-06-21

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9914837.1	1999-06-24	U.K.
2	9929150.2	1999-12-09	U.K.