REACTIVE DYES CONTAINING A HALOBENZENE NUCLEUS

Abstract: This application relates to reactive dyes having at least one halobenzene nucleus linked to a chromophoric group via an amino linkage and additionally containing a second reactive group.

Description: REACTIVE DYES CONTAINING A HALOBENZENE NUCLEUS This invention relates r.o reactive dyes containing a halobenzene nucleus and, in particular, reactive dyes of this type containing two or more reactive components. Dyes are known which contain a halobenzene nucleus linked via an azo group to another aromatic nucleus such that the haloberisene nucleus forms part of the chromophoric chain (see for example GΩ-A-S82001) . Dyes of this type which contain two such halobenzene nuclei are disclosed in CAS4,14316d (1966), which is an English language abstract of an article by atsui et al, Yuki Gosei Kagaku Kyokai Shi (1966), 24(2), 132-136. Dyes are also known in which the halobenzene nucleus is attached to a chromophoric group by a sulphonamide or amide linkage; see, for example, GB-A- 978162 and CA59,l2949g (1963), which is an English Language abstract of an article by Matsui et al in Yuki Gosei Kagaku Kyokai Shi (1962), 20,1100-1112. Again dyes of this type may contain two such halobenzene nuclei; see GB-A-978162. In other known dyes, the halobenzene nucleus is linked to a chromophoric group by an amine linkage,- see US-A-3301847 and CASl,iC133f (1964) which is an English language abstract of an article by Matsui et al in Kogyo Kagaku 2asβhi, (1964), 67(1) ,94-97. However, such dyes contain only one reactive group. We have now found surprisingly that dyes having at least one halobenzene nucleus linked to a chromophoric group via an amino linkage and additionally containing a second reactive group have particularly high build up, especially in warm dyeing applications. According to the invention there is provided a dye containing a t least one chromophore Dj at least a first, halobenzene, reactive group Z 1 , of the formula (I) in which: n is 1 or 2 χ ; or each X independently, is an electron withdrawing group; and Y is a halogen atom; t least a socond reactive group Z 2 selected from (1) a group of the formula (I) , given and defined above, but selected independently thereof; (2) a group of the formula (II) (II) (T) wherein m is 1 or 2; p is 0 or 1; when is l, p is 1; and when m is 2, p is 0; Y 1 , or each Y L independently, is a halogen atom or an optionally substituted pyridir.iuin group,- and T is C alloxy, C.,thioalkoxy or NCR 1 ) (R 2 ) , in which each of R 1 and R 2 independently is hydrogen, optionally substituted or optionally substituted aryl; (3) a group of the formula (III) wherein: κ is 1, 2 or 3 ; y is zero, 1 or 2; and κ + y ≤ 3; Y*, or each Y 2 independently, is a halogen atom or an optionally substituted pyridinium group; and U or each U independently, is d^alkyl or Ci. 4 alkylsulphonyl ; (4) a group of the formula (IV) -S0 2 CH a CHjX l (IV) wherein X 1 is an eliminatable group; (5) a group of the formula (V) wherein z is aero or 1 ; and (6) a group of formula (VI) -W-C(R 10 )-CH a (VI) wherein: R iJ is hydrogen, c 1-4 alkyl or halogen; and w ie -0C(=O)- or - N (R 11 ) C (=0) - in which R 11 ie hydrogen or 1>4 alkyl; at least a first linking group L 1 , linking the said first, halobenzene, reactive group Z 1 to one of components (i) the or a chromophore D and (ii) the second reactive group Z 2 , which said first linking group L 1 resents an amino nitrogen to the reactive group Z 1 and to the component (i) or (ii) or, when component (i) contains a heterocyclic nitrogen atom, is linked directly to the nitrogen atom and which said first linking group 1 optionally includes a hydrocarbon bridging group, which hydrocarbon bridging group B has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore; and when Z' is selected from the said groups (I)- (III), at least a second linking group L ! linking the second reactive group Z s to one of (i) the or a chromophore D and (ii) the said first reactive group ZS which said linking group L 2 is selected from (1) a linking group L l , but selected independently thereof? or (2) an amide linkage,- and (3) a sulphonamide linkage,- and optionally a leas one aromatic group Ar which, when Z 2 is selected from the said groups (IV)- (VI), may carry the said reactive group Z 2 . Preferably, the linking group 1 has the formula (VII) 1 N(R) (VII) 1 wherein R is hydrogen or optionally substituted C^alkyl, such that the same amino group presents itself to each of the reactive group Z 1 and the component (i) or (ii) , as defined above; or is a piperazinoalkylamino group of the Io ula (VII)' R wherein each , independently, is as defined above, such that respective amino nitrogens, one of the piperazine group and the other of the alkylamino group, present themselves respectively, to the reactive group Z 1 and to the component (i) or (ii), as defined above; or has the formula (VII) 3 -N (Kl dJN (KJ - ( Vl i ) 3 wherein B is 8 hyrirnπarhon bridging group as defined above, each R, independently , ia as defined above and B is optionally linked additionally to at least one additional group -N(R) . The hydrocarbon bridging group B may be a straight or branched, υpLionally substituted, C 2 . 6 alkylene group optionally interrupted by at least one hetero atom, for example, 0,S or N. Optional substituentε are OH alkoxy, carboxy, carboxylic ester or carboxamide. Alternatively the bonding group B may be an optionally substituted arylene especially phenylene group. Optional substituents are S0 3 H and salts thereof, C x . 4 aikyl, ^alko y and chloro. The bridging group E s especially preferably an optionally oubstituted aryl grou . An especially preferred dye embodying the invention has the formula (VIII) Z ι. L i- D -( J) Λ . Z . (Vlll) wherein: D is a chromophore? each of 1 and L 2 is an amine or piperazine linkage of the formula -N(R)- (VII) 1 ; -» ( R) BM (R) - (VI I ) 1 wherein ; R, or each R independently, is hydrogen or d. 4 alkyl ; B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero aton- and is op t ionally a chromophore; a is zero or 1; and b is from 2 to 6 inclusive; 74 is a group in which? n is 1 or 2? X, or each X independently, is an electron withdrawing group; and Y is a halogen atom? and when a is 1, z 2 is: a group of the formula (I), given and defined above hut selected independently thereof; or a group of the formula (Ii; (II) wherein; m ie 1 or 2 ; p is 0 or 1; when m is 1, p is l; and when m is 2, p is 0; Y\ or each Y 1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is (- L4 alkoxy, thioalkoxy or N(R > ) (R 2 ) in which R 1 is hydrogen, optionally substituted Cn alkyl or optionally substituted aryl and R a s hydrogen or optionally substituted C A- „ alkyl; or a group of the formula (III) (U)y wherein: x is 1, 2 or 3 ; y is zero, 1 or 2; and x+y ≤3? Y 2 , or each Y 3 independently, is a halogen atom; and U, or each U independently, is c H alfcyl or C j i..* alkylsulphonyl; and when a is zero, Z 2 iss -S0 2 CH 2 CH 2 χι (IV) in which X 1 is an eliminatable group; or -SO, (CH 2 ) B CH-CH 2 (V) wherein z is zero or 1; or a group of formula (VI) - -C(R 10 )=C;H 2 (VI) wherein: R 15 is hydrogen, C alkyl or halogen; and W is -0C(=0)- or - N(R n )C(=0)- in which R 11 is hydrogen or C 1-4 alkyl . In the halobenzene nucleus of the formula (I) , X or each X independently, may be selected from nitro, cyano, alkylsulphonyl, dialkylaminosulphonyl and sulphonic acid groups and salts thereof. Preferably, x or each X independently, is selected from nitro and cyano. The halogen atom in the halobenzene nucleus of formula (I) is preferably fluorine or chlorine. The group in the linking group L 1 of formulae (l)-(3) may be any of hydrogen, methyl, ethyl, n- or i- propyl or n-, s~ or t-butyl, but is preferably hydrogen. In the dye of formula (VII) , each of Z 1 and Z independently, is preferably a group of the above mentioned formula (I) . Moreover, it is even more preferred that each of Z 1 and Z ! is the same group as the other. However, alternatively, Z 1 may be a halobenzene nucleus of the formula (I) , A may be zero and Z' a group of the formula -SO j CHaCHjX 1 < IV) in which X 1 is an eliminatable group such as 0S0 3 H, OP0 3 H s and salts of any of these, and Cl, a preferred group (IV) being S0 2 CH 2 CH 2 OS0 3 H (or a salt thereof) or -S0 2 (CH 2 ) s CH=CH 2 (V) wherein z is zero or 1. In an other alternative range of dyes, z 1 is a halobenzene nucleus of the formula (D abov* and Z 2 ia a halotriazine nucleus of the formula (II ) wherein m is 1 or 2, p is 0 or 1, when m is 1, p is 1 and when tn is 2, p is 0; Y 1 , or each Y l independently, is a halogen atom or an optionally substituted pyridinium group; and T is C 1-4 alkoxy, C 1 . 4 thioalkoxy or N(R l ) (R-<) in which R 1 is hydrogen, optionally substituted C 1-4 alkyl or optionally substituted aryl; and R a i3 hydrogen or optionally ssubscituted C h lky1. In the above formula (II) , Y l is preferably fluorine, chlorine or optionally substituted pyridinium which may be derived from, for example, nicotinic or isonicotinic acid or their carboκa ides . Each of R 1 and R J is preferably hydrogen, but at least one of R 1 and R 2 may be a C 1<4 alkyl group and indeed R 1 may additionally be an optionally substituted aryl, preferably phenyl, group. When such a C.. 4 alkyl or aryl group is substituted, a preterred substituent is hydroxyl, amino, halo, carboxy or sulpho. In yet another alternative dye i accordance with the invention, Z l is a halobenzene nucleus of the formula ( I) and Z 2 is a halopyrimidine nucleus of the formula wherein x is 1, 2 or 3; y is 0, 1 or 2; and x+y ≤ 3; Y a , or each Y ! independently, is halogen atom; and U, or each U independently, is C 1-4 alkyl or Ci. 4 alkylsulphonyl . In the above formula (III) Y 5 is preferably fluorine or chlorine. A preferred range of dyas embodying the invention has the formula (XXX) Z l -L l -D [ 3 ] q - [Z 3 -L 4 r [J 1 ] , [L 2 ] a Z z [L 5 -^] t (XXX) wherein: Z 3 is a third reactive group selected from the groups of the formulae (I) - (III) , given and defined above; each of J 1 and J 2 , independently, ie an optionally substituted aryl group or a chromophore; r J is a linking group linking Z J and D; 4 is a linking group linking z 5 and J 1 ; 5 is a linking group linking z a and J 2 ,- each of q, r, s and t independently, is aero or 1; each of Z l , Z*, L 1 , L 2 and a is as defined above,- and when at least one of a and t is 1, Z 2 is selected from the groups of the formulae (I) -(III), given and defined above. In one such range of dyes, q is 1, r is l, e is 1, each of a and t is zero and Z 2 is selected from the groups of the formulae (IV) -(VI), given and defined above. In another such range, q is 1, r is 1, s is zero, a is zero and t is 1. n a dye of the formula (XXX) , each of 3 and L*, independently, is preferably selected from OΠΘ of the S groups of the formulae (VII) i , (VII) » and (VII ) ', given and defined above; each of L 3 and L 4 is preferably a group of the formulae (VII) 1 , given and defined above. In one preferred range of dyes of the formula (XXX) , σ 0 is 1, r i θ zero, s is 1, a is zero and t is zero and in such a range 3 is preferably a group of the formula (VII) 3 -N(R)BN(R)- (VII)' wherein B is a triazine group substituted by a non l b reactive yroup. in a dye of the formula (XXX) , the chromophore D is preferably an azo chromophore derived from l-hydroxy-8- aminonaphthalene substituted by at least one sulphonic acid group. 20 Yet another range of dyes embodying the invention has the formula Z i - l -D l [L 3 -Z 5 (L«-Z 4 ) jtf-D 1 ] * ft 2 ] & wherein ? D 1 is a first chromophore; D 3 is a second chromophore; Z 3 , when present, is a third reactive group selected from the groups of the formulae (I) -(III), given and defined m claim 1? IS , when present, is a fourth reactive group selected from the groups of the formulae (I) -(ill), given and defined in claim 1; IS is a linking group linking S 3 to D 1 - lS is a linking group linking Z to Z*; IS is a linking group linking D s to one of Z 3 and Z 4 each of k and 1, independently, is zero or 1; and each of Z 1 , Z 2 , : , U and a is as defined in claim 1. In one range of such dye of formula (XXXI), a iε 1, Z ! is a group of the formula (I) , given and defined above, k is zero and D 1 is a tetrakisazo chromophore containing two residues of H-acid linked together by a group forming part of the chromophore. In another such range, a ia 1, each of Z 1 and Z 2 is a group of the formula (I) , given and defined above, each o£ k and I ie 1; each of ϋ 1 aπ D 2 is a disazo chromophore containing a respective residue of H-acid, each cf Z 3 and Z 4 iε a group of the formula (II), given and defined above, and L* is a linking group of the formula (VII) s or (VII) 3 , given and defined above. In still further such ranges (i) a is 1, Z 2 ie a group of the formula (I) , given and defined above, k is 1 and 2 is 1; or (li) a iB 1, T? is a group of the formula (I) , given and defined above, k is I and 2 is sere Yet another preferred range of dyes embodying the invention has the formula (XXXII) Z ι _ L ι_ Z 3 - 3 -D-Z 2 (XXXII) wherein: Z 3 is a third reactive group selected from the groups (I) -(III), given and defined above and - is a third linking group selected from the groups (VII) 1 , (VII) 2 and (VII) 3 , given and defined above; Z 2 is a second reactive group selected from the groups (IV) -(VI), given and defined above; and each of z 1 and L 1 is as defined above. In ouch dyαα o£ the formula (XXXII) , L 1 ic preferably a linking group of the formula (VII) 2 or (VII) 3 , given and defined above and Z 3 is preferably a group of the formula (ID , given and defined above. Another range of dyes embodying the invention has the formula (XXXIII) l β D-L^Z'-I -Z 1 (XXXIII ) wherein: Z z is selected from groups of the formulae I- (III), given and defined above; and each of D, Z\ 1 and 1 is as defined above. In such dyes ol the formula (XXXIII) , Z 2 io preferably a group of the formula (II) , given and defined above and U iα preferably a linking group selected from the groups (viϊ) VII) 2 and (VII) 3 , given and defined above, more preferably a group of the formula (VII) 2 or (VII) 3 , given and defined above; and L 1 is a group of the formula (VII) 3 , given and defined above, in which 3 is an optionally substituted aryl group, or is alternatively a chromophoric bridging grou . In the range of dyes of formulae (XXXII) , a preferred chromophore D is a disazo dye containing a residue derived from H-acid and having azo yroups at the 2- and 7- positions. Another preferred chromophore TM ia a group of the formula Other ranges of dyes embodying the invention are of the respective formulae D a -L a -Z ϊ - 3 -D 1 -L l -Z 1 (XXXIV) wherein: each of D 1 and D a , independently, ia a chromophore ; L 3 iε> a linking group selec ed from groups f the formula (I) -(III), given and defined above; and each of Z\ Z 2 , L l and 2 is ae defined above; and (XXXV) wherein: each of D : and D s , independently, is a chromophore; L 3 is a linking group selected from the groups of the formulae (I) -(III), given and defined above; and eaαh of z 1 , Z s , L 5 and L 2 is as defined above; and (XXXVI) wherein ; one of Z 3 and Z 4 ie a reactive group S 2 ; each of z 3 nd 7 , independently, is a reactive group selected from the formulae (IV) -(VI), given and defined above; each of t and u, independently, is zero or i and at least one of t and u is 1 ,- D is chromophore; Ar is an optionally substituted aryl group; Ii 1 is a group of the formula wherein each R, independently, is as defined in claim; and Z 1 is as defined above. In such dyes of formulae (XXXVI) , D is preferably a disazo dye containing a residue derived from K-acid. In a dye embodying the invention, the or a chromophore D may contain a heterocyclic nitrogen atom, in which case the linking group may have the formula or — ®BN(R) (VI!)" wherein each of B,R and b is es defined above and the 10 bond Φ is linked ho the heterocyclic nitroqen atom of the chromophore. Such dyes, may have the formula 15 Z L I D N _f L* -fc 2* - LAAr] t wherein: D N is a chromophore containing a heterocyclic group including a nitrogen atom; 20 L 1 is a group of the formula (VII) 4 ox (VII)\ given and defined above, directly attached via the bond Φ, to the nitrogen atom of the said chromophore D**; Ar is an optionally substituted aryl group; 7.5 and each of Z 1 , Z s , L 2 , 5 , a and t is as defined above. A typical chromophore D containing a heterocyclic 30 nitrogen atom has the formula In the above formulae, wherever lAL 5 , J 1 , J 2 or B is or has an optionally substituted phenyl group, optional substituents are S0 3 H or a salt thereof, C h alky!, especially methyl and chloro, especially S0 3 H. Again, in all of the above formulae, where the groups Z 2 is any of the groups of the formulae (I) -(III), it is most preferably of the formula (II) , Likewise in all such formulae, where Z 2 is any of the groups (IV) -(VI), it is most preferably of the formula (IV) or (V) , wherein Z is zero. In a dye according to the invention, in general, the or each chromophoric group independently preferably comprises an azo (which may be a monoazo, polyazo or metal complex azo) , anthraquinon , hydrazone, phthalocyanine, triphenodioxazine or for azan group. Examples of chromophoric groups which may be present are those given as types (a) - (g) of the group π D 1 " in formula (I) of US-A-54B4899, which is incorporated herein by reference . Preferred azo groups are monoazo and disazo groups. Preferred monoazo groups have the formula -Ar 1 -N=N-Ar 2 - wherein Ar : ie an aryl or heteroaryl group and Ar* is an aryl group. It is preferred that each aryl group independently is a mono- or di -cyclic aryl group. Preferred aryl yroups are optionally outaotiuuted phenyl and optionally aubαtit-utθd naphthyl. Preferred heteroaryl groups are pyridonyl and pyrazolonyl. A first preferred monoazo group is of the Formula (IX) (or salt thereof) . • whereinc Ar 1 is an aryl group, preferably «t benzene or naphthalene nucleus; R 3 , or each R 3 independently, is Cj,.« alkyl, nitro, halo or sulphonic acid or a salt thereof; c ia zero or 1 to 4; R*. or each R* independently, is a sulphonic acid or a salt thereof; and d is 1 or 2; and is more preferably of the formula: wherein each of Ar 1 , R 3 and a are as defined above, R* is sulpho and c is zero or 1. Λr l is preferably optionally subs ituted phenyl or naphthy , especially a phenyl or naphthyl group having at least one sulpho substituent. Further optional substituents which may be present on Ar include a halogen atom, especially chlorine; an alkyl radical, especially C^ alkyl, more especially methyl; an acylamido radical, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy radical, especially C_._ alkoxy, more especially methoxy. As examples of phenyl groups having at least one sulpho substituent there may be mentioned 2-, 2- or 4- sulphσ henyl ,- 2-sulpho-4-nitrophenyl; 2-sulpho-S- nitrophenyl ; 4-σulpho-2-methylphenyl j 5-sulpho-2- mβthylphenyl ; 2-sulpho-4-meth.ylpr.enyl ; S-sulpho-2- methoxyphenyl; 2-eulpho-4-methoxyphenyl; 4-sulpho-2- chlorophenyl; 5-acetamido-2 -sulphophenyl; 5-sulpho-2- carboxyphenyl ; 2 , 4-disulphophenyl ; 2 , 5-disulphophenyl ; and 3 , 5 -disulphophenyl . As examples of naphthyl groups having at least one sulpho substituent there may be mentioned l-sulphonaphth-2-yl; l,5-disulphonaphth-2-yl; 1,5, "?-trisulphαnsphch-2-yl; 3,6, 8-trisuiphonaphth-2-yl; 5, 7-dιsulphcnaphth-2-yl; g-sulphcnaphth-2-yl; 4-,S-,6-, cr 7-suIphonaphth-l-yl; 4, 8-di3uipncnaphth-ι-yli' 3 , 8-disulphonaphth-ι-yl , • 2, 5, 7-trisuiphonaphth-i-yl; and 3 , 5 , 7-triaulphonaphth- 1-yl. preferred op i nal subetitruer. £ -which i-nay be p ftsen on the naphthalene nucleus of Formula (IX) are those mentioned above for Ar 1 . Groups of the Formula (IX) εre preferably linked to a group l or L 2 at the 6-, 7- or δ-position f especially the 6- cr 8 -position. When 1 or 2 i3 to be linked at the 8 -position, it is preferred chat R s is a sulpho group at the 5- or 6- poeicion, Thus a preferred monoazo dye embodying the invention has the formula - XVII ) wherein: each R independently and a is as defined above ; one of Z 3 and Z* is a group Z 1 and the other is a group Z 2 ; the group Z 4 is selected from the groups of the formulae (I) -(III), given and defined above. Ar 1 is a benzene or naphthalene nucleus; R\ or each 2 independently, is d -4 alkyl, nitro, halo or sulphonic acid or salt thereof; z is zero or 1-4? R 4 , or each R 4 independently, is a sulphonic acid or a salt thereof; and d is i or 2. K preferred di.g&zo group is o the Fo mula (XI) (or salt thereof) : Ar l -N=N-M~N=N-E (XI) wherein: M and E are each independently optionally substituted phenylene or naphthalene,- and Ar 1 i- as defined above. It is preferred that E is optionally substituted naphthalene and S optionally substituted phenylene. The optional subs ituents which may be present on M or S are preferably independently selected from hale, especially chloro; alkoxy, especially c * alkoxy; alkyl, especially methyl; sulpho; uarbαxy; hydroxy,- amino; acylamino, especially aeetamido, benzamido and eulphonated benzamido, and pyrimidir.ylamino or triaziriyl amino cellulose-reactive groups. As Examples of groups represented by and E, there nay be mentioned phenylene, 2-methyl-l,4~ phenylene, sulphophenylene, ureidophenylene, 7-sulpho- 1, -naphthalene, 6-sulpho-l,4-naphthalene; 8-sulpho- 1,4 -naphthalene and 6-hydroxy-4-sulpho-1, 5-naphthalene. O 99/27019 25 An especially preferred range of disazσ-dyes has the formula (XVIII) (XVIII) wherein: one of Z s and Z 6 is a group S 1 and the o her is a group Z 2; each of f and g independently is zero or 1; when Z s or Z s is any of the groups of the formulae (I) -(III), given and defined above, f or g respectively is 1 and when Z s or Z* is any of the groups of the formulae (IV) -(VI), given and defined above, f or g respectively is zero; each of c and e, independently, is zero or 1- 4; d is 1 or 2 / each independently is ao defined above/ each of Ar : and Ar 2 independently is an optionally substituted aryl group; and each of R s and R 4 is as defined above. In a dye of the formula (XVIII) , each of Z s and Z* may be the same group ( I ) wherein X, Y and n are as defined above. Alternatively, one of Z s and Z 3 may be a group of the formula (I) , given and defined above, and the other of Z 5 and Z 6 may be selected from groups of the formulae (II) and (III) , given and defined above. In such a dye it is preferred that one of Z 5 and Z 6 is a group of the formula (I) , given and defined above, and the other of Z 5 and Z i is a group of the formula (II) . Another especially preferred range of dieazo dyes has the formula wherein: E ia a hydrocarbon bridging group as defined above, and preferably an optionally substituted aryl group; one of G 1 and G 2 is OH and the other is H 2 ; each of X, Y, Y 1 , Ar 1 , Ar 2 , R a , R\ R s , c, d and e is as defined above. In a dye of the formula (XViii) , one of Z s and 2« may be a group wherein : X , and n are as defined in claim 1 and the other of Z 5 and Z β ia th© group -SO a CH 3 CH,O80 | H or -SO a CH«CH 8 . Typically such a dye has the formula wherein G 5 its C 2 H 4 OS0 3 H or a salt thereof or -CH=CH 2 ; G 1 and G 5 are as def ined above ,- R* and d are ae defined above; and eaπh of h a i, independently, a 2βro, 1 or A more preferred range of such dyes has the formula where each of G 1 G 2 and G 3 is ae defined above . When the chromophore D is an anthraquinone , a preferred anthraquinone group is of the Formula (XII) (or a salt thereof) . o wherein the anthraquinone nucleus optionally σontainc a sulphonic acid group in the R-, fi-, 7-, nr -position and V is a divalent organic linkinq group, preferably of the benzene series . V is a bridging group B, preferably phenylene, diphenylene, or 4,4' -divalent stilbene or azobenzene radicals which are optionally sulphonated. It is preferred that V contains one sulphonic acid group for each benzene ring present therein, A preferred anthraquinone dye of has the formula D Λ -L 3 -Ar-L 2 -Z :! -L. 1 -Z 1 wherein ; D A is an anthraquinone chromophore; I 3 is a linking of the formula (VII) 1 , given and defined above; Ar is ar. optionally substituted aryl group,- and each of Z 1 , Z 2 , L l and JS ie as dsfinad above. More preferably each of L 1 and L 2 independently, is a linking group of the formula (VII) 1 , (VII) 3 or (VII) 3 , given and defined above; and still more preferably, each of 1 and 2 , independently is a group of the formula (VII) 3 , given and defined above, in which B is an optionally substituted aryl group. When the chromophore D is a phth& ocyanine , a preferred phthalocyanme group is of the Formula (XIII) (or a sail Lhereul) . wherein Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine; L is as hereinbefore defined; each independently is a hydroxy or a substituted or unsubstituted amino group, V 1 is a divalent organic linking group, preferably a C 1-4 - alkylene or phenylene linking group; and a and b are each .independently 1, 2 or 3 provided that a + t> is not greater than 4. Preferably such a metal phthalocyanins dye has the formula (30, HA Cu Pc - (SO, NR 21 R" ) y wherein: Cu Pc is a copper phthalocyanine chromophore, • x + y + z - 4.: each of R 2i and R 22 , independently, is hydrogen or optionally substituted c,. 4 alkyl 3 is a hydrocarbon bridging group; and Z'- is as defined above. when che chromophore D is a triphe o ioxazi β a p araxie triphenodiϋxazine iϋ is of the Formula (XIV) (or a salt thereof) . wherein: each Y J independently is a covalent bond, C 2 . 4 -alkylene, phenylene or suiphophenylene; U- is H or S0 : H; and T 1 and T 2 are halo, especially chloro, c - alkyl, or C 1-4 alkoxy. Eacl ϊ 3 is preferably -C 2 H 4 - or -C 3 H S - , U 1 is preferably S0 3 H -mύ T 1 c-nd a are preferably Cl , methyl or ethyl . Preferably such a riphenrl. n , -'S rift yp. has he ormula z -ιy- [z 3 -L 3 ] q -D T - ΓZ I Γ -L 2 -Z 2 wherein: D τ xa a tnphendioxazine chromophore; each of 2 , V and IS , independently, is a linking group of the formula (Vir) 1 , (VII) 2 or (VII) 3 , given and defined above; each of Z 2 , Z : and Z 4 is a reactive group selected from groups of the formulae (I) -(III), given and defined above; each of a_ and is zero or 1,- and each of S 1 and L 1 is as defined above. Iπ siir.h a Λy& , 7? ia preferably a group of the formula (I) , qiven and defined above and each of Z : and Z* is a group of the formula (II) , given and defined above; and.each of IS , IS , IS and 4 is preferably a group of the formula (VII) 3 , given and defined above. When the chromophore D is a formazan. a preferred group is of the Formula (XV) (or a salt thereof) . (XV) wherein: X is H, S0 3 H or Cl ; and each r independently has a value of 0, 1 or 2. provided that the formazan group has at least one, an p eferably at least two, sulpho groups. It is preferred that each r has l e of 1. Preferably such a formazan dye has the formula [Z A ] a -D F -L-Z B -L 1 -Z 1 wherein: D F is a formazan chromophore; one of 2 A and Z* iε a group Z*, given and defined above,- each of L J and * i= a linking group of the formula (VII) 1 , (VII) 2 or (VII) 3 , given and defined above; each of A ' - and IS is as Pe med above; 7, k . s selected from groups of the formulae (IV) - (VI) , gxven and defined above; and 7S is selected from groups of the formulae (I) - (III) , given and defined above. According to one process aspect, the invention provides a process for preparing a dye of the formula (VIII) 1 Z 1 - ' - -O-L 2 ~ Z Z (Vl ; λ wherein: D is a chromophore; each of IS and L 2 independently, is N(R) ; each R, independently, is hydrogen or C^ lkyl; each of Z 1 and Z 2 is a group in which : n is 1 or 2 X, or each X independently, is an electron withdrawing group; and Y is a halogen atom, which process comprises reacting a chromophoric compound .1 the formula (XX) wherein each of D and R is as defined above, with at least two moles, per mole of the chromophoric compound of the formula (XX) , of a dihalσbenzene component comprising at least one dihalobenzene compound of the formula (XXI) wherein each of X, Y and n ia as defined above, to obtain the dye of the formula ( llϊ) 1 . When the dye is of the formula (XVIII) given above, the chromophoric compound of the formula (XX) can be prepared by protecting one amino group of a phenylene diamine sulphonic acid and then diaεσtising this and coupling a first portion of the diazotised phenylene diamine sulphonic acid to the naphthalene nucleus under acid conditions so as to couple on to the benzene ring of the naphthalene nucleus containing an amino group and then taking second portion of the same diazotised and protected phenylene diamine sulphonic acid compound referred to above (or a different such compound) and coupling this under neutral or alkaline conditions to the benzene ring of the naphthalene nucleus containing a hydroxy1 group to obtain a diamine dyestuff having respective protected amino groups . The protective group can then be removed by hydrolysis. According to another process aspect, the invention provides a process for preparing a dye of the formula (VIII) 1 z ι_ L ι_ _ L 2_ Z - (VIII) 2 wherein: D is a chromophore; each of L 1 and L 2 independently, is fR) ; each , independently, is hydrogen or C h al y1 ; Z 1 is a group in which; n is 1 or 2 X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; and Z 2 is selected from the groups (II) and (III) defined above; which process comprises reacting a chromophoric compound of the formula (XX) H( )N-D-N(R)H (XX) wherein each of D and R is as defined above, with one mole, per mole of the chromophoric compound of the formula (XX) , of each of (a) a dihalobenzene compound of the formula (XXI) (XXI) wherein each of Z, X, Y and n is as defined above,- and (b) a compound selected from (T). (xxiii ) (U ) y wherein: m is l or 2; p is 0 or 1; when m is 1, p is 1; and when is 2 , p is 0; Y 1 , or each Y 1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is C^alkoxy, C 1-4 thioalkσχy or N(R X ) (R*) , in which each of R 1 and R 2 independently is hydrogen, optionally substituted C 1-4 alkyl or optionally substituted aryl; x is i, 2 or j; y is zero, l or - ; and -x. +y s 3 ; Y 2 , or each Y 5 ind p≥ndently, ia a halogen atom or an optionally substituted pyridinium group; L τ or each U independently, is c,. 4 alkyl or C 1-4 alkylsulphonyl ; and Y is as defined above; the said reactions of the compound of the formula (XX) with each of the respective compounds of the formulae (XII) and (XIII) being carried out simultaneously or one before the other, in either order, to obtain a dye of the formula (VTIi} 5 . According co yet another process aspect, tne invention provides s procest Zvz. re a g a dy Of the formula (VIII} 3 Z 1 -L l -D-Z ; (VTTTA wherein : D is a chromophore L 1 iε N (R) , in which R iε hydrogen or C 1-4 alkyl ,- Z 1 is a group in which n is 1 or 2; X, or ach X independently, is an electron withdrawing group; and Y is a hydrogen atom and Z 2 is a group of the formula (IV) -SOjCHjCHjX 1 (IV) wherein X 1 is an eliminatable group; a group of the formula (V) -SO J CH J ), CH«CH 2 (V) wherein z is zero or 1; and a group of formula (VI) - -C(R 10 )=CH 2 (VI) wherein: R 10 is hydrogen, C h lky! or halogen; and is -0C(~0)- or -N(R n )C(=0) - in which R 11 is hydrogen or C 1-4 alkyl; which process comprises reacting a chromophoric compound of the formula (XXIV) H(R)N-D-Z i (XXIV) wherein D and Z z are as defined above, with a dihalobenzene compound of the formula (XXI) (XXI) wherein each of x, Y and n is as defined above, to obtain the dye of the formula (VIII) 3 . Although dye formulae have been shown in the form of their free acid in this specification, the invention also includes dyes and processes using dyes in the salt form, particularly their salts with «_lk.dii metals such as tne potassium, sodium, lithium or mixed sod . nm/iithium salt and th ir salts with tetraalkylammonium ions. The dyes may be used for dyeing, printing or ink-jet printing, for example, of textile materials and paper. The process for colouration is preferably performed at a pH of 7.1 to 13, more preferably 10 to 12. pH levels above 7 can be achieved by performing the process for colouration in the presence of an acid-binding agent. The substrate may be any of a textile material, leather, paper, hair or film, hut is preferably a natural or artificial textile .material containing amino or hydroκyl groups, for example textile material such as wool, silk, poiyaiaides and modified polyacrylonitrile fibres, and more preferably a cellulosic material, especially cotton, viscose and regenerated cellulose, for example, that commercially available as Tencel. For this purpose the dyes can be applied to the textile materials at a pH above 7 by, £ut example, exhaust dyeing, padding or printing, including 1 nfc-jet printing. Textile materials are coloured bright shades and possess good fastness to light and wet treatments such as washing. The new dyes are particularly valuable for colouring cellulosic textile materials . For this purpose, the dyes are preferably applied to the cellulosic textile material at a pH above 7 in conjunction with a treatment with an acid binding agent. PitsftϋjcttU acid-binding agents include alkali metal carbonates, bicarhonarps, hydroxides, mαtasilicates and mixtures thereof, for example sodium bicarbonate, sodium carbonate, sodium metasilicate, sodium hydroxide and the corresponding potassium salts. The dyes benefit from the excellent build-up and high fixation. Ar least for cellulosic materials, exhaust dyeing can be carried out at a relatively low temperature of about 50-70°C, especially about 6<J*c. The new dyes can be applied to textile material containing and ne groups, such as wool and polyamide textile materials, from a neutral to mildly alkaline dyebath. The dyeing process can be carried out at a constant or substantially constant pii, that is to say that tuts pπ of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process. The dyes may be in α liquid form, or solid form, for sxamplo .-i granular or powdered form. We find surprisingly that such dyes give a much higher build up, as compared with known dyestulls, particularly n warm dyeing applications at about fiO'C. in addition, « wide selection of dye backbones is possible, giving the potential to provide h gh fastness dyes. Dyes embodying the invention are especially uββful lux application to substrat p * by ink-jet technologies. Substrates which are particularly useful are cellulosic textiles and paper. The dye used in the ink is preferably puiiliβd by removal of substantially all the inorganic salts and byproducts which are generally present in a commercial dye at the end of its synthesis. Such purification assists in the preparation of a low viscosity aqueous solution suitable for use in an ink jet printer. To assist in the achievement of heavy depths of shades the dye should preferably have a water-solubility of at least 5%, and more preferably from 5% to 25%, by weight . Solubility of the dye can be enhanced by converting the sodium salt, in which form it is normally synthesised, either partially or wholly, into the lithium or ammonium salt. Purification and ion exchange can conveniently be effected by use of membrane separation processes which permit the separation of unwanted inorganic materials and by-products directly from an aqueous solution or dispersion of the dye followed by partial or complete exchange of the counter-ion. The ink preferably contains up to 20% by weight of dye and more preferably from 2% to 10%, especially from 3% to 8%. The ink may also contain a humectant, which may also function as a water iscible solvent, which preferably comprises a glycol or dihydroxyglycolether, or mixture thereof, in which one or both hydroxy groups are secondary hydroxy groups, such as propane-1,2- diol,butane-l,3-diol and 3- (3-hydroxy-prop-2-oxy)propan- 2-ol. Where the humectant has a primary hydroxy group this is prefereably attached to a carbon atom adjacent to a carbon atom carrying a secondary or tertiary hydroxy group. The humectant may comprise up to a total of 10% by weight of a polyol, especially a glycol cr dihydroxyglycolether, having two or more primary hydroxy groups, such as ethyleneglycol, ρroρane-1, 3-diol,butane- 1, 4 -diol, 2- (2-hydroxyethoxy) ethanol and 2-(2-[2- hydroxyethoxy) ethanol and/or an alcohol with a primary hydroxy group, such as ethanol, n-propanol and n-butanol. However, it preferably contains not more than 5% by weight, and is more preferably free from, such compounds. In the context of the humectant, the term "alcohol" means a compound having only one hydroxy group attached to an aliphatic carbon atom. The ink preferably contains from 5% to 25%, by weight, more especially from 10% to 20%, of humectant . If desired, the ink may be buffered to a pH from 5 to 8, especially to a pH from 6 to 7, with a buffer such as the sodium salt of mβtanilic acid or an alkali metal phosphate, or di- or triethanolamine. The ink preferably also contains one or more preservatives to inhibit the growth of fungi, bacteria and/or algae because these can block the jet of the ink jet printing equipment. Where the ink jet printing technique involves the charging and electrically controlled deflection of drops the solution preferably contains a conducting material such as an ionised salt to enhance the accumulation of charge on the drop. Suitable salts for this purpose are alkali metal salts of mineral acids. The remainder of the ink is preferably water, especially de-ionised water to avoid the introduction of impurities into the ink. Especially preferred embodiments of the invention will now be described in more detail with reference to the following Examples in which all parts and percentages are by weight unless otherwise stated. Although preparation and dyeing with any single dye is exemplified, particular advantage could be seen when eyeing with mixtures of dyes. Pr p ative Eacampias Exampl 1 2-amino-4- (N-acetyl) aminobenzer.e-1-sulphonic acid (0.5 , 182g! was dissolved in water (feUOml) at H 7 and 2M sodium nitrite solution added (0.526 , 263ml). This solution was Added dropwise to a mixture of hydrochloric acid 35% (1.13M, 100ml, SG - 1.18) and ice (lKg) , maintaining a temperature of 0-5 3 C. The mixture was stirred for O.bnrs with excess nitrous acid at 0-S°C. A solution of sulphamic acid (10%) was added to remove excess nitrous acid to obtain a suspension of a diazotized diamine for coupling. H-ftcid (0.475M, lθ3g) was dissolved in water ! 300ml) at pH 7.5. This solution was added dropwise to the above diazn suspension with good agitation over lhr at 0-2°C. The mixture was then stirred at 0-2°C for a further 2hrs at pH 2-3, and allowed to warm to room temperature over 18hrs. The viscous suspension was adjusted to pH 6 using sodium hydroxide solution (46/48%) and a solution of a monoazo dye was thereby obtained. The above monoazo dye solution s cooled to 0-5°C an a batch of the diazotized diamine prepared as above was added. The mixture was stirred at 0-5°C and pH 6-7 for 2hrs and subsequently over 19hrs at room temperature while maintaining the pH at 6-7 using 2M sodium caibonate solution, thereby obtaining a diβaao dye solution. Hydrolysis was then carried out by adding sodium hydroxide solution (46/48%, 800g) to the above disazo dye solution (vol = 5L) and heating at 70-75 β C for l.bhrs. The reaction mixture was cooled to 20°C and neutralised by controlled addition c 35% hydrochloric acid. After screening to remove a small amount of impurity sodium chloride was added (15% w/v) and stirring continued to allow precipitatior. of the resultant diαminodisazo product. This was collected by filtration and dried at 40°C (285g; 0.242M; strength - 68.3%). The above diaminodisazo dye (0.01M, 11.78g) was dissolved in water/acetone (100ml, 1:1) o 50°C. A solution of 1, 5-difluoro-9 , 4-dinitrobenzene (0.023M, 4.7g taken as 100% strength) in acetone (20ml) was added over 0.25hr and the mixture heated at 55°C for 3hrs. The pH was maintained at 7 throughout the reaction by the addition of 2N sodium carbonate solution. The reaction mixture was cooled to 20°C and acetone (150ml) added to precipitate the dye. The product was collected by filtration and washed with acetone (50ml) and dried a 40C lυ give a greenish-navy dye (11.12ςj; 0.0075M; strengfh = 74.8%) (X M9y =» 6C7nm; ε Mβx - 57,036). Example 2 The method of Example 1 was followed except that the diaminydisβzo was reacted with 1, 5-dichloro-2, 4- dini .robenzene in place of 1, 5-difluoro-2, - dinitrobenzene to give a greenish-navy dye [ ^ K = 607nm; ε^ - 48,212) . Example 3 The method of Example 1 was followed except that the diaminodisazo was reacted with 1, 5-difluoro-2-cyan- - nitrobenzene in place of 1,5-difluoro 2, -dinitrober Ane Lυ give e greenish-navy dye (λ t κ * 607nm; ε Muc = 56,416). Example 4 The method of Example I was followed except that the diaminodisazo was reacted wi h 1, 5-dif Uθro-2- nitrobAnzene in place of 1, 5-difluoro-2, 4-dinitrobenzene to give a greenish-navy dye^,, - 6Q8nm; ε Ml)C = 54,660). Examples 5 4-Ammo benzene sulphatoethylsulp one (0.1 , 30g) was stirred in ice/water (400 ml) and hydrochloric acid 35% (0.58M, 52ml, SG-1.18) and the temperature maintained at below G"C. 2M Sodium nitrite solution (0-104M, 52ml) wa. added dropwise at below 5°C and the mixture stirred for a further 2 hours. A solution of sulphamic acid was added (10%) to remove excess nitrous acid and provide a diazo suspension for coupling, H-Λcid (0.103M f ΛD . ήg) was dissolved in water (300ml) at pH 6 and the solution cooled to 5°C. This solution was added dropwise to the above diazo suspension with good agitation, while maintaining the temperature below 5"C. The mixture was then stirrnH for 18 hours, allowing the temperature to rise to 20 β C. Sodium chloride (10% w/v) was added and the mixture stirred for 1 hour. The precipitated monoazo dye was collected Joy filtration and resiurnyd in ethanol (SOOml) for 1 hour at 2-0 ύ c. The product was collected by filtration and dried at 40°C. (70g; 0.0825M strength = 72%). 3-Amino-5 ' -fluoro-2 ' , 4 ' -dinitrodiphenylamine-4- sulphonic acid (U.0068M, 3.2g) was Uxisolved in water (100 ml) at 50-60°C and th* solution cooled to 20*C. 2M Sodium nitrite solution (0.008M, 4ml) was added and the mixture cooled to 0-2°C and added dropwise to ice (50g) and hydrochloric acid 35% (0.09M, 8ml), while maintaining the temperatuiw at 0-2°C. The resulting yellow suspension was stirred at 0-2°C for ..0.5 hour and a solution of sulphamic acid (10%) added to remove excess nitrous acid and provide a diazo suspension for coupling. The diazo suspension was then added dropwise to a solution of the above mono«7o dye (0.006M, 5.1g) in water (150ml) at pH 5 and 0-2°C. The pH of the coupling mixture was maintained at pH 5 by the addition of 2M sodium carbonate solution and stirred this pil for IS hours, allowing the temperature to rise to 20°C. Sodium chloride was added (20% w/v) and the product collected by filtration. The solid was reslurried in ethanol (100ml) for 1 hour at 20°C, collected by filtration and. dried at 40 3 C to obtain a greenish-navy dye (4.4g 0.003M; strength = 67%) (λ^ - 603n ; ε Kkx - 54,279) of the structure given below: Examples 6-61 Other disa∑o naphthalene structures embodying the invention are shown as Examples 6 to 61 in Table 1. They can be prepared by methods analogous to those outlined in Examples 1 tc 5. Examples 62-67 Still further diaazo naphthalene dyes embodying the invention, in which the chromophore has been doubled up via a linking group, are shown in Examples 62 to 67 in Table 2. Example 68 This Example describes how a dye may be synthesised where the fibre-reactive halobenzene group is attached via a linking diamine to a second fibre-reactive group, and thereby Lo a chromophore. The W-dichlorotriasinyl dβcivativft of the- 20 dye resulting from azo-ccupling 7-aminonaphthalena-l, 3, 6-trisulphonic acid with m-ureidoanilme was prepared by conventional means. A solution of this dye (35 mmol in 430ιπl) was added at room temperature with stirring to W-(4- aminophβr.yDp.perazine (7.5q, 42 mmol) dissolved in 50/50 acetone/water (400 ml) maintained at pH 6-6.5 by addition of sodium carbonate solution. After completion of the reaction the solution was conceniiated, and the product was precipitated by addition of methylated spirit. To a solution of this intermediate (8.4 mmol) in 50/50 acetone/water (200 ml) was added a solution of 1,5- ifluoro-2, -άinitrob«nzene (9.5 mmol) m acetone (20ml), maintaining the pH at 8.5 by addition of sodium carbonate solution. Cn completion of the reaction, the pH was adjusted to 6.5 and the solution was concentrated tc ca 100 ml. Methylated sμϋii: was added, and the product: dye WΛ* filtered, washed with eths and dried. A^ at ) =• 3 9nm, S na* = 33000 1 mol "1 cm" 1 , half band width >150nm. This material dyed cotton a bright golden yellow shade with very good fastness properties. Examples 69-77 By following the principles described in Example 68, dyes ot a similar nature may be prepared as furrher exemplified by dyes 1.9-77 listed in Table 3. Examples 79-97 Oisazo naphthalene riyft.q containing two reactive groups attached to the chromophore as descrioed in Example 68 are exemplified by Examples 78 to 97 listed in Table 4. pxamultcb 38-127 Further yellow dyes may be prepared by the methods described in Examples 1-6 and 68, and are listed in Tables 5 to 9. Examples 126-160 Monoazo naphthalene dyes embodyiny the invention are list<?ri in Tables 10 tc 12. Examples .-.W A variety of dyes embodying the invention, containing blue and green chromophores, are listed in Tables 13 to 16. ADDlicaLiuα Examples Examples 190 - 192 Each of the dyes (U.2 parts) of respective Exam les 1, 3 and 5 was dissolved in respective ..mounts of water (50 parts) at 25°C and pH 9. Cotton fabric (5 parts) and Glaubers salt (2.5 parts) were added. The dyes were fixed to the cotton by raising the temperature to between 50*c- feϋ'Ci basifying Lu pH 11.0 and maintaining this for lhr. The cotton was removed and washed in soapy water to give a dark greenish-navy cotton having high general fastness properties. Examples 103 and 194 Each of the dyes (0.2 parts) cf respective Examples 2 and 4 was dissolved in water (50 parts) at 25°C and pH 9. Cotton fabrxc (5 pa ts) and salt (4 parts) were added. h dy«s were f 5 xft to cotton by raisinq the temperature to 80- 1C0°C and maintaining this for lhr. The cotton was removed and washed in soapy water to give a deep greenish-navy cotton having good fastness properties. Examples 195-198 Methodology for applying dyes embodying the present invention to cotLυπ may be further exemplified by mean* of the following pad-batch dyeinq protocol. Example 195 - 19H Example 195. -Dye from Example 5 (0.5 parts) was dissolved in water (30 parts) at 25°C and the following agents were added: Pri asol NF (1 part of 2U% solution) and sodium silicate Q70 (9.5 parts of 50% solution), sodium hydroxide (5.1 parts of 10% solution). The solution was made up to 50 parts by addition of water, and then padded onto woven cotton fabric ( " 70% pick-up). The cloth was wrapped in cling film and batched at room temperature for 24 hours. The cling film was removed and the dyed cloth was rinsed successively with cold water and hot water, then washed b with a soap solution, rinsed with water, and ried to give cotton coloured a dull qreenish blue shade. Example 196.- If the amount of dye used in Example χy3 is doubled and the procedure repeate , a greemoh-navy shade is obtained. 0 Example 197.- If the amount of dye used in Example 193 is trebled and the procedure repeated, a dark navy shade is obtained. Example 193.- If six times the amount of dye in Example 193 is used and the procedure repeated, an simost black shade 5 is obtained. Other dyes from the above Examples, particularly those containing the 2,4-dinitrofluorobenzene unit and/or a vinyl sulphone group or its sulphate half-esLtr precursor, can be cψplied to cotton by the same method. 0 Eampe,, 1?? Dyes embodying the present Invention may be applied to textile substrates, especially cotton, by conventional printing technology, as the following exemplifies. A dye from Example 5 (30 parts) was dissolved in a solution b containiny Manutex F 700 (500 parts of a 10% solution) and Vitexo. D (20 parts) . The solution was made up to 1000 parts by the addition of water and printed by means of a Zimmer screen printer. The printed cloth was dried aud padded through a solution containing sodium, silicate RdegBe, 700 parts) made up tc 1000 parts by the addition of water (80% pickup) . Immediately after padding, the printed cotton wa3 steamed in a Roaches Flasn-ager steam chamber at 120 deg C for 45 seconds . The printed cloth was rinsed in cold water, washed with a soap solution at the boii, rinsed again in cold water and dried to give a dull greenish navy prir.t on the cotton. Sy««,pla ?.QQ Dyes embodying the present invention may be used in the preparation of inka specially formulated for application by ink-jet technology. As an Example, the dye from Example 5 (6 parts) was dissolved in a solution of propylene glycol (15 parts) and water (79 pa ts) ■ When this solution was applied to cotton which had previously been prβtrβatcd (for t-Λώiuple , with a prβ reat βnt agønt described in E?-A-0534660; by means of commercial ink-jet printing equipment, deep navy shades were obtained. Other dyes from ths above examples as wel 1 as others describeri by the Invention may be used to prepare inks suitable for ink-jet printing. Reactive dyes, including those of Examples 1-189, are usually isolated as their sodium baits, and are contaminated with inorganic impurities resulting from the method of preparation. Dyes free of impurities suitable for ink jet printing, and/or with increased solubility, may be prepared by conventional ion exchange techniques, where for example sodium is replaced by lithium and inorganic impurities ar* simultaneously removed. Dye from Example 1 (10 parts) was dissolved in water (100 pacts) and treated on a reverse osm sis rig nntiL the permeate conductivity was 10 micro reciprocal ohms. A solution of lithium chloride was added to the dye solution and treatment on the r.o. rig was continued until the permeate conductivity had ecreased to 1 micro reciprocal ohm. The sample was concentrated to a volume of about ΘO parts, after which the solution was buffered and other formulating agents were added. The dye solution was then diluted to 90 parts by addition of water, al which sta e it was suitable for storage. Dye solution prepared in this way could be diluted and applied to cotton by the methods described in any of the Examples 190, 195-158, or formulated into an ink by addition of suitable humectants and/or cosolvecilfi, and applied by ink-jet methodology to cotton, for example by the method described in Example 200. In all these cases, dull blue, greenish navy or black shades were imparted to the substrate, depending on the amount of dye applied. Example 202 Dye from Example 1 was ion exchanged to che lithium IUJM as in Example 201, and formulated into an .ink with the composition: dye {5 parts), propylene glycol (12 parts), diethanolamine (sufficient to buffer the final pH to 7 - 8.5), and water (to bring the total to 100 parts). The ink was aαded to the ink iwsβrvoir of an ink jet printer (e.g. HP Desk Jet 500) and printed onto-paper (Logic 300), to give a black print of generally good fastness properties. Table 1 Example ( ij nm) Colour on cotton Table 1 - Table 1 Table 1 J> 4*. σ> -t- ro Table 1 - dark bluish- green - dark bluish- green dark blulsh- rjrβen dark blulsh- grββπ - Table 1 dark Dfuish- green dark bluish- green h- Table 2 Example (w,/ϊ nrn) Cύlϋui uπ cotton Table 3 Example X m ^nm w 1Λ nm Colour on cotton 69 Golden yeilow Ma = \ 70 -N-- 307 H 140 Golden yellow 71 Golden yellow -M N- Golden 72 419 200 -N- yellow H Golden yellow lden 74 NHC J NH 410 170 Go yellow Golden yellow Golden yellow Coidcn yellow Table 4 Example B Y Colour on cotton NH OH Greenish navy NH 2 OH Greenish navy Table 4 NH OH Greenish nav> OH NH 2 Greenish navy NH 2 OH Greenish navy CD o D Table 4 94 OH NH Greenish navy OH NH 2 Greenish navy Table 5 tlxample Structure λn t x nm ι/2 nm Colum on cotton 98 Dye-SCjH«OH 407 148 Golden yellow 85 Dye-N(CH 3 )Ph 403 133 Golden yellow 100 Uye-NHC 2 H 4 50 2 H 407 129 Golden yellow 101 Dye-NHC 2 H 4 0C 2 H θH 412 134 Golden yellow 102 Dye-NHC 6 H 3 .m-S0 3 H 409 143 Golden yellow 103 Dve-NHC 2 H.NH-Dye Golden yellow 104 Dye— N 412 130 Golden yellow -NH-Dye Table s Example structure λ fl ^ nm Wv 2 nm Colour on cotton 105 Dye-SCjH 4 OH 437 151 Mid yellow 106 430 135 Mid yellow 107 Dye-NHCjH 4 OC H4θH 436 141 Mid yellow 108 435 132 Mid yellow 109 439 143 Mid yellow 110 438 14Q Mid yellow 111 437 131 Mid yellow 112 Dye-NHC 2 H<NH-Dye Mid yellow 113 Dye-NHC3H 6 NH-Dye Mid yellow Table 7 max rπ -Example Structure (Via nm) Colour on cotton Table 8 Example Ol er substituents Colour on 1 7 4- 1.3-(Sθ3H)j 3-SO ? C ? H 4 0SO 2 H Yellow H β 3- 1.4-(S0 3 H, 2 12° 4- 1.1" (Sθ3H) ? 3'- Yellow 121 " • - 1.1'.4-(S0 3 H)3 3- I Z X 2 O I z O ϋ o o X X 0 o I T o o ffl Q. £ IN in CN CN c 3 o £ S e 10 *8 '35 J2 09 .3 V m co Table 10 133 134 S0 3 H H Blueish red υ c O T3 a Ό \— t Ct 3 cr c O O X rt I o n O O CΛ α ε to 9 "3 « Ό ■ α fl) cr c « n ■ o r : <■> 4 Ό cr cr cr X X o w C o rt O o CΛ o C <o r— cn Table 12 Example B Colour on cotton H H Reddish yellow H S0 3 H Reddish yellow M H Reddish yellow 0 ) 0. iC C∑ l CJ) u O) π c e o f CO c m c c o cα s O O X X O 0 X t 2 X s xn xn Φ h- 03 >n o Table 13 Example Colour on cotton h Table 14 Sam le R R - R" x y z Co ' 01 on- cotton .. 2 Q 2 Green H 1.5 0.5 2 Green 167 C 2 H 4 H H 2 0 2 Bluish- green 168 C 3 H β CH 3 CH 3 1.7 0.3 2 Bluish green 160 H C 2 H 4 ϋyo 3 H 2.5 0.5 1 Green H 170 -yyy H H 1.5 1.5 1 Green H 1 SO.H H C 2 H«S0 3 H 2.5 0 1.5 Green H H 3 o 1 ereen o c α 4) υ c o 01 as 3 •— 55 C O o - u o J UJ X o u o Q. S K CO CD LU I*- Table 15 C! c ' Greenish blue Table 16 HN ' Colour on Example cotton 132 183 184 Tabie 16 h

Claims: 1. A dye containing al least one chromophore D; at leas s fi.rat, halobenzene, reactive group Z 1 , of the formula (I) (I) in which: n is I or 2 X, cr each X independently, is an electron withdrawing group; and Y is a halogen atom; at Iβaat a second reactive group Z 2 eβlectftd from (l) s group of the formula (I) , given and defined above, but selected independently thereof ; (2) a group of the formula (II) wherein TΠ is 1 or 2; p is 0 or 1; when m is l, p is 1; and when m is 2, p is 0; Y 1 , or each Y l independently, is a halogen atom or an optionally substituted pyridinium yroup, and T is Curtlkυλy, C l<4 thioaIkoxy or X(R l ) (R 2 ) , in which ea of R l and ft 2 independently is hydrogen, optionally oubetitutβd C,.,alkyl or optionally α bβticutαd aryl ; (3) a group of the formula (III) (U) y wherein : x is 1 , 2 or 3 ; y is zero , l or 2 ; and x + y ≤ ό ; Y 1 , or each Y 1 independently, iσ a halogen atom o an optionally aubotitutβd pyridinium gτoup; and U or oach U independently, ie C h al y1 or C^alkylsulphnnyl ; (4) a group of the formula (IV) -SOjCHjCHj 1 (XV) wherein X 1 is an elitπinatable group; (5) a group of the formula (V) ■ S0 2 ( CH 2 ) z CH=CH 2 (V) wherein z is zero or l; and (6) a group uf formula (VI) -W-C(R 10 )«CH, (VT) whe-rβtn: R 10 is hydrogen, C 1 . 4 alkyl or halogen; and W is -0C(=Ol- or - N(R u )C(«0)- in which R u is hydrogen or C 1- alkyl; at least a first linking group \ linking the said first, halobenzene, reactive group Z 1 to one of components (i) the or a chromophore D and (ii) the second reactive group 2 s , which said first linking group L 1 presents an amino nitrogen to the reauLive group Z 1 ana to the component (i) ur (ii) or, when component (i) cυuLains a heterocyclic nitrogen atom, is linked directly to the nitrogen atom and wh. rh said first Uniting group L 1 optionally includes a hydrocarbon bridging group, which hydrocarbon bridging group B has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore; and when Z* is selected from the said groups (I) -(III), at least a second linking group 2 linking the second reactive group Z : to one of (i) the or a chromophore D and (ii) the said first reactive group Z 1 , which said linking group L* is selected, from (1) a linking group L 1 , buc selected independently thereof; υr (2) <m a ide linkage / and (3) oulphona ide 1. n age ; and optionally at least one aromatic group Ar which, when Z* is selected from the said groups (IV) - (VI), may carry the said reactive group Z 2 . 2. A dye according to claim l, wherein the linking group L l has the formula (VII) 1 N(R) (VII) 1 wherein R is hydrogen or optionally subsLituted Cι. t alJcyl. such that the same aπiπυ group prcoentβ itself to each ot the reactive group S 1 and the component ti) or tii) , as defined in claim 1. 3. A dye according to claim 1, wherein the linking group 1 is a piperazinoalkylaitd.no group of the formula (VII)' R wherein each R, independently, is aa defined in claim 2, such that respective amir.o nitrogens, one of che piperazine group and the other of the alkylamino group, present themselves respectively, to the reactive group Z 1 and to the component (i) or (ii) , a3 defined in αlaim 1. «. A dye according to claim 1, wherein the linking group r, 1 has the formula (VII) 1 -M(R)BN(R)- (VII) 3 wherein B is a hydrocarbon bridging group as defined in claim l, each R, independently , is as defined in claim 1 and B is optionally linked additionally to at least one additional group -N(R) . 5. A dye according no claim 4, wherein the hydrocarbon bridging group B is an optionally substituted aryl group. 6. A dye acαording to any preceding frlaim, of the formula (VIII) Z i - l -D- ( 'J.-Z 3 (VIII) wherein: D is a chromophore; each of L l and L 2 is an amine or piperazine linkage of the formula -N(R)- (VII) 1 ; - (VII) 2- or -N(R)BN(R)- (VII) 3 wherein: R, or each R independently, is hydrogen or d. « alkyl; B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromopho ; a is zero or l; and b is trom 2 co 6 inclusive; Δ l is a yxuup in which: n ia 1 or 2; X, or each X independently, iβ an electron withdrawing group; and is a halogen atom; and when a is 1, Z 2 is J a group of the Cormuia ) , given and defined above but selected independently thexeof, - or a group of the formula (II) (T) D wherein: is 1 or 2; p is 0 or 1; when, m is 1, p is 1; and when m is 2, p is 0; Y 1 , or each Y 1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is n alkoxy, thioalkoxy or N(R ; ) (R 2 ) in which R λ is hydrogen, optionally substituted C_. t alkyl or optionally substituted aryl and R J is hydrogen or optionally substituted C l-4 alkyl; or a grυuy of the formula (III) (U) y wherein: x is 1, 2 or 3; y is zero, 1 or 2; and x+y ≤2 ; Y*, or each Y* independently, is a halogen atom; and U, or each U independently, is C 1-4 alkyl or C^ alkylsulphonyl ; and when a ia zero, Z 2 is: - SO J CH J CH J 1 (IV) in which X 1 is an eliminatable group ; or -S0 2 (CH 2 ) Z CH-CH, (V) wherein z is zero or 1; or a group of formula (VI) - -C(R 10 )-CH 2 (VI) wherein: R 10 is hydrogen, C 1 . 4 alkyl or halogen; and W is -OC(-O)- or - N(R u )C(=0)- in which R is hydrogen or C^ alkyl. 7. A dye according to any preceding claim , wherein, in formula (I) , X, or each X independently, is selected from nitro, cyano, alkylsulphonyl, dialkylaminosulphonyl and sulphonic acid or a salt thereof. 8. A dye according to any preceding claim, wherein a group of the formula (II) is present, in which Y 1 , or each Y independently, ie fluorine, chlorine or optionally substituted pyridinium. 9. A dye according to any one of claims 2 to 8, wherein R, or each R independently, is hydrogen. 10. A dye according to any preceding claim, wherein each of Z 1 and 74 , independently, is a group: wherein each of X, n and Y is as defined in claim 1. 11. A dye according to claim 10, wherein each of Z l and Z 2 s the sa e as the other. 12. A dye according to any one of claims l to 9, wherein a is 1 and Z 3 is (T)p wherein Y 1 , m. T and p are as defined in claim 1. 13. A dye according to any one of claims 1 to 9, wherein a is 1 and Z 2 is (U)y where Y 1 , X, U n y are as defined in. claim 1. 14. A dye according tc *ny one of claims 1 to 9, wherein a is zero and Z 1 is -SO-CH^X 1 (IV) where X 1 is as defined in claim 1; or -SO,(CHa),CH»CHa (V) wherein z is as defined in claim l. 15. A dye according to any preσediny claim, wherein D ie an azo chromophore. 16. A dye according to claim i , wherein D 13 a monoazo chromophore . 17. A dye according to claim IS, which has the formula (XVII) wherein: each R independently and a ia aα e ine in claim 1 ; one υ£ Z 1 and Z* is α group Z 1 and the other ia is a group Z Λ ; the group Z 4 ia selected from the groups of the formulae (I) -(III), given and defined in claim l; Ar is a benzene or naphthalene nucleus; R s , or each κ s independently, ie c^ alkyl, nitro, halo o aulphυπic duid <jχ- salt L ereof / c is zero or 1-4 / R 4 , or each K. independently, ic a culphonio aσid or a salt thereof; and d ie 1 or 2. 18. A dye according to claim 15, wherein D is a disazo chromophore . 19. A dye according to claim 18, which has the formula (XVIII) (XVTTT) wherein; one of z 5 and z* is a group t and the other is a group Z J ' each of f and g independently is zero or 1; when Z 5 or Z' ie any of the groups of the formulae (I) -(III), given and defined in claim 1, f or g respectively is 1 and when Z 5 or Z β is any of the groups of the formulae (IV) -(VI), given and defined in claim 1, f or g respectively is zero; each of c and e, independently, is zero or 1-4; d ia 1 or 2; each independently is as defined in claim 1; each of Ar 1 and AI* is an optionally substituted aryl group; and aaoh of Α 1 and R* io ao defined in claim 17. 20. A dye according to claim 19, wherein each of Z ! and Z* is the same group wherein X, Y and n are as defined in claim 1. 21. A dye according to claim 19, wherein one of Z* and Z* is a group of the formula (I), given and defined in claim i, and the oLhei: of Z* and *- is selected from groups of the formulae (II) and (III), given and defined in alaim 1. 22. A dye according to claim 18. which dye has the formula wherein : B is a hydrocarbon bridging group as defined in claim 1 ; one of G l and G 2 is OH and the other is NH,,- each of X, Y, Y l and n is as defined in claim 1; each of AT 1 , Ar 2 , R3, *, C and d is as defined in claim 19; and each of I. 5 and c iσ ac defined in claim 1 . 23. A dye according to claim 22, wherein B is an optionally substituted aryl group. 24. A dye according to claim 19, wherein one of Z* and Z* is a group wherein : X, Y and n are as defined, in claim i and the other Of Z s and 2* is the group -S0 2 CII 2 CII a OS0 3 H or 25 . A dy« according to claim 24 , which has the formula wherein G 3 is C s H 4 OSO,H or a salt thereof or -CH-CHj / G 1 and G* are as defined in claim 22; R* and d are eta defined in claim 17; and each of h and i, independently, ig zero, 1 or- 7 26. A dye arrfir ing to claim 25. which has the formula where each of G 1 and G ! is as defined in claim 22 and & is as defined in claim 25. 21. A. dye according to claim 1, of the formula Z i -I^-D [L 3 ] q - [Z>-L\ [ J 1 ] 4 [ »] α J [L 5 - J 2 ] e wherein-. 7, 1 .a a chird reactive group selected from the groups of the formulae (I) -(III), given and defined in claim 1; each of J 1 and J 2 , independently, is an optionally substituted aryl group or a chromophore,- L 1 is a linking group linking Z 3 and D; L* is a linking group linking Z 3 and J 1 ; L* is a linking group linking Z 2 and J J ; each of q, r, s and t independently, is zero or 1; each of z 1 , Δ '* , ι4 , i? and a is as defined in claim i , ■ and when at least one of a and t is 1, Z : is aalcctcd from the groups of che formulae (I) - (III) , given and defined "in claim 1. 28. A dye according to claim 27, wherein q is 1, r is l, s is 1, each of a and t is zero and Z a is selected from the groups of the formulae (IV) - (VI) , given and defined in claim 1. 29. A dye according to claim 27, wherein q is 1, r is 1, s is zero, a is zero and t is 1. 30. A dye according to =uιy one of claims 27 to 29, wherein eac of L 1 and \ independently, iβ selected from one of the groups of the formulae (VTT) 1 , (VII) S and (VII) 3 , given and de ine in claim 6. 31. A dye according to claim 30, wherein each of 3 and * is a group of the formulae (VII) 1 , given and defined in claim 6. 32. A dye according to claim 27, wherein q is 1, r is zero, a is 1, a is zero and t is zero. 33. A dye according to claim 32, wherein 5 is a group of the formula (VII} 1 -N(R)BN(R)- (VII)' wherein D io a triazine group subs .i.tur.ftd by a non- reactive group. 34. A dye according to any one of claims 27 to 33, wherein the chromophore D is an azo chromophore derived from 1-hydroxy-θ-aminonaphthalenβ substituted by at least one sulphonic acid group. 35. A dye according to claim 1 of the formula Z x -L l -D l [ 3 -Z J (L*-Z*) j '-D*] „ L *] ,Z* wherein: D 1 is a first chromophore; D 3 is a second chromophore,- Z J , when present, is a thixu reactive group selected from the yxυups of the formulae (I) - (ill) , given and defined in claim 1; z 4 , when present, is a ffmrth reactive group oelectβd from t-.hft groups of the formulae (I) - (III) , given and defined in claim 1; L 1 is a linking group linking Z* to D\- * is a linking group linking Z J to Z*,- s is a linking group linking D 2 to one of Z 3 and Z*; each of k and I, independently, is zero or 1; and each of Z 1 , Z 2 , L 1 , L 5 and a is as defined in claim l. 36. A dye according to claim 33 whtuβin « is 1, Z 2 ia α group of the fcitu la (I) , given and defined in claim 1, k ia ^e o and D 1 ia α tctrakieaao chromophore πr tainmg two rcaidueβ of H-acid linked together by a group forming part of the chromophore. 37. A dye according to claim 35, wherein a is 1, each of Z l and Z 2 is a group of the formula (I) , given and defined in claim 1, each of and 1 is 1,- each of D 1 and D 2 is a disazo chromophore containing a respective residue of H-acid, each of Z J and Z* is a group of the formula (II), given and defined in claim 1, and 1 is - linking group of the formula (VII) 2 or (VII) 1 , given and dcfinαd m claim 6. 39. A dye according to claim 35. wherein a is 1, Z 2 is Λ group of the formula (I) , given and defined m claim 1, k is 1 and 1 is l. 3S. A dye according to claim 35, wherein a is 1, Z 2 is a group of the formula (I) , given and defined in claim 1, k is 1 and 1 ia zero. 40. A dye according to claim 1, of the formula wherein: '? is a third reactive group selected from the groups (I) -(III), given and defined in claim 1/ and L* io a third linking group selβπtftd from the groups (VII) 1 , (VII)' and (vττ)», given and defined in claim fi Z a ia a second reactive group selected from the groups (IV)-(VT), given and defined in claim 1; and each of Z 1 and L l is as defined in claim 1. 41. A dye according to claim 40, wherein L 1 is a linking group of the formula (VII) 2 or (VII) 3 , given and defined in claim S . 42. A dye according to claim 40 or claim 41, wherein 2 s is a group of the form la (lϊ) , given and defined in claim 1. 43. A dye according to claim 1, of the formula D-L*-Z*-L l -Z l wherein: Z is selected from groups of the formulae I- (III), given and defined in claim 1; and each of D, Z 1 , L and L 1 is as defined in claim l . 44. A dye according to claim 43, wherein z 1 is a group of the formula (II), given and defined in vlniirt 1. 45. A dye according to claim 43 or claim 44, wherein J is a. linking group (selected from th-. groups (VXD 1 , (VII) 2 5»nd (vτt) J , given and defined in claim 6. 46. A dye according to claim 43, wherein 2 is a linking group of the formula (VII) 2 or (Vii) 3 , given and defined in claim 6. 47. A dye according to any one of claimβ 43 to 46, wherein L 1 is a group of the formula (VII 3 ) , given and defined in claim 6, in which B is an optionally substituted aryl group. 48. A dye according to any onw of claimβ 43 to 46, wherein 1 is a group of the luAmula (VI D , given and defined in claim 6 , in which B is a chromophoric bridging yroup . 49. A. Hye according to any one of claims 40 to 48 , wherein the chromophore D is a disazo dye containing a residue derived from H-acid and having azo groups at the 2 - and 7- positions . 50 . A dye according to any one of claims 43 to 48 , wherein D is a group of the formula 51 . A dye according to claim l , of the formula D 2 -L , -Z 2 -L 1 -D 1 -L 1 -Z x wherein: each of D 1 and D 2 , independently, is a chromophore ; L 1 13 t linking group selected from groups of the formula (I) -(III), given and defined in claim 1; and each of Z % , 14 and * is as defined in claim 1. bϋ . A dye according to claim 1 , of the ormula wherein: each of D 1 and D 2 , independently, is a chromophore , ■ L 3 is a linking group selected from the groups of the formulae (I) -(III), given and defined in claim 1; and each of Z\ Z ! , L 1 and L 2 is as defined in claim 1. 53. A dytt according to claim 1, of the formula. wherein: one of Z 3 and Z* is a reactive group Z 2 ; each of Z l and Z\ independently, is a reactive group selected from the formulae (IV) -(VI), given and de ined in claim 1 ; each of t and u, independently, is zero or 1 and at least one of t and u is 1; D is a chromophore; 105 Ar is an optionally substituted aryl group; 1 is a group of the formula (R)N-B-N(R —N(R) wherein each R, independently, is as defined in claim; and Z l is as defined in claim 1. 54. A dye according to claim 53, wherein D is a disazo dye containing a residue derived from H-acid. 55. A dye according to claim l, wherein the or a chromophore D contains a heterocyclic nitrogen atom and the linking group has the formula (VII)* or — Θ BN(R)— wherein each of B , R and b is as defined in claim 6 and the bond Φ ia linked to the heterocyclic nitrogen atom of the chromophore . 56. A dye a coxdiag to claim 55 , of the formula Z i -U-D N -f L 2 -fc- Z 2 - - I Ar] t wherein: D N is a chromophore containing a heterocyclic-: group including a nitrogen atom; L 1 is a group of the formula (VII) 4 or (VII) 5 , given and defined in claim 55, directly attached via the bond Φ, to the nitrogen atom of the said chromophore D"; Ar is an optionally substituted aryl group,- and each of Z l , Z i , L\ 3 , a and t is as defined in claim 27. 57. A dye according to claim 56, wherein the chromophore D has the formula 58. A dye according to any one of claims 27 to 56, which is an azo dye having at least two azo groups therein. 59. A dyy accGzdiuy Lu claim 15, wherein D is a Crisazc or tefcrakisazo chromophore. SO. A dye according to claim . , wherein the chro ophor* D is an anthraquinone. 61. A dye according to claim SO, which is of the formula D^- -Ar-L'-Z'-I^-Z 1 wherein: D* is an anthraquinone chromophore; 3 is a linking of the formula (VII) 1 , given and defined in claim 6; Ar is an optionally substituted aryl group; and each of Z 1 , Z 2 , L 1 and 2 is as defined in claim 1. 62. A dye according to claim 61, wherein each of L 1 and * ' independently, is a linking group of the formula (VII) 1 , (VTT) i nr (VTT , g-i.ven and defined -π c.s.m β. 63. A dye according to claim 62, wherein each of L 1 and L 2 , independently is a group of the formula (vil) ', given and defined in claim 6, in which B is an optionally substituted aryl group. 64. A dye according to claim l , wherein the chromophore D is a metal phthalocyanine . 65. A dye accorαing to claim 64, of the formula Cu Pc - (S0 2 NR" R" ) γ I (SO, NH-B-NH-2 1 ), wherein: Cu Pc is a copper phthalocyanine chromophor ; X + Y + Z ≤ 4; each of R J1 and R 22 , independently, is hydrogen or optionally substituted C 1 . 4 al yl; B is a hydrocarbon bridging group; and Z 1 is as defined in claim 1. 66. A dye according to claim 1, wherein the chromophore D is a triphendioxazine chromophore. 67. A dye according to claim 66, which is of the formula Z^-L Z'- 3 ]., -D τ -[Z « ] r -L 2 -Z 2 wherein: D τ is a triphendioxazine chromophore; each of L*, V and \ independently, is a linking group of the formula (VII) 1 , (VII) 2 or (VII) 3 , given and defined in claim 6; each of Z J , Z* and Z* is a reactive group selected from groups of the formulae (I) -(III), given and defined in claim l; each of g and r is <_e.cu x 1; and each of Z 1 and 1 ia as defined in claim 1. 68. A dye according to claim 57, wherein Z 2 is a group of the formula (I) , given and defined in claim 1 and each of Z 3 and Z* is a group of the formula (II) , given and defined in claim 1. 69. A dye according to claim 67 or claim 68, wherein each of L 1 , 2 , L 2 and L* is a group of the formula (VII) 3 , given and defined in claim 6. vo. A dye according to claim l, wherein the li otuophore D is a formazan. cjhiuiiiuμliu.te. 71. A dye according to claim 70, of the formula fZ A U -D^-L-Z^L^Z 1 wherein: D 7 is a formazan chromophore; one of Z A and Z* is a group Z 2 , given and defined in claim 1; Li is a linking group of the formula (VII) 1 , (VII) * or (VII) J , given and defined in αlaim 6 f each of Z 1 and L l is as defined in claim 1; 110 a is zero or 1; Z A is selected from groupβ of che formulae (IV) -(VI) , given and defined in r.lΛ-im . ; and Z B is selected from groups of the formulae (I) - (III) , iven and defined in claim 1. 72. A dye of the formula 73. A dye of the ormula 74. A dye of the formula CN A dye of the formula 7fi. A d ft cf the formula 77 . A dye of the formula 78 . A process for preparing a dye of the formula (VIII) 1 Z l - 1 -D- 2 -Z 2 (VIII) 1 wherei i D is a chromophore; each of L 1 and L 2 independently, is N(R) ; each R, independently, is hydrogen or C 1-4 al yl; each of Z 1 and Z 2 is a group in which: n is 1 or 2 X, or each X independently, ia an eleσtron withdrawing grou ■ and is a halogen atom, which process comprises reacting a chromophoric compound of the formula (XX) H (R) N-D-N (R) H (XX) wherein each of D and R is as defined above, with at least two moles, per mole of the chromophoric compound of the formula (XX) , of a dihalobenzene component comprising at least one dihalobenzene compound of the formula (XXI) wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII) 1 . 79. A process for preparing a dye of the formula (VIII) 1 Zi-LX.D_I.J_ZJ (VIII) a wherein: D is a chromophore; each of L 1 and L 2 independently, is N(R) ; each R, independently, is hydrogen or C 1-4 alkyl; Z 1 is a group in which: n is 1 or 2 X, or each X independently, is an electron withdrawing group; and Y is a halogen atom,- and , 2 is selected from the groups (li) and (III) given and defined in claim 1; which proceαa comprises reacting a chromophoric compound of th« formula (XX) H(R)N-D-N(R)H (XX) wherein each of D and R ΪB as defined above, with one mole, per mole of the chromophoric compound of the formula (XX) , of each of (a) a dihalobenzene compound of the formula (XXI) (XXI) wherein each of Z, X, Y and n ie aβ defined above,- and (b) a compound selected from (xxiii) (UL wherein: m is 1 or 2; p is 0 or l; when m is 1, p is l; and when m is 2, p is 0; Y\ or each Y λ independently, is a halogen atom or an optionally substituted pyridinium group; and T is Cj..«alkoxy, C 1 . 4 chioalkoxy or N(R X ) (R 2 ) , in which esrh of R 1 and R* independently is hydrogen, optionally substituted C^ lk l or optionally substituted aryl; x ie 1, 2 or 3 ; y iβ zero, l or 2; and x +y _ 3 } Y a , or each Y J independently, is a halogen atom or an optionally substituted pyridinium group; U or each U independently, is C^alkyl or Ci.«alkylsulphonyl ; and _ iβ as defined above; the said reacli-uia of the compound of the formula. (XX) with each of the respective compounds of the formulae (XII) and (XIII) being carried out simultaneously or one before the other, in either order, to obtain a dye of the fo mula (VIII) > . 80 . A process for preparing a dye of the formula (Vlll) 3 Z 1 - 1 -D-Z' (VIII) J wherein : D is a chromophore l is N (R) , in which R is hydrogen or C^alkyl ; Z 1 is a group Y (X)n (i) in which n is 1 or 2; X, or each X independently, is an electron withdrawing group; and Y is a hydrogen atom,- and Z 2 is a group of the formula (IV) -SO, CHjCHaX 1 (IV) wherein X 1 is an eliminatable group; a group of the formula (V) wherein z is zero cr 1 ; and a group of formula (VI ) -W-C (R 10 ) »CHi (VI) 5 wherein: 10 is hydrogen, C^alkyl or halogen; and w is -0C (=0) - or -N ^ C t-O) - in which R 11 is hydrogen or C^alkyl ; which process comprises reacting a chromophoric 10 compound of the formula (XXIV) H (R) N-D-Z 2 (XXIV) wherein D and Z 1 are as defined above , with a dihalobenzene compound of the formula (XXI ) 20 wherein each of X, Y and n is as defined above, to H obtain the dye of the formula (VIII)'' . 81. A process for the colouration of a substrate, which process comprises applying to the substrate a dye 25 according to any one of claimβ 1 to 77. 82. A process according to claim 81, wherein the dye is applied to the substrate by exhaust dyeing, padding or printing. 30 83. A process according to claim B2 , wherein the dye is applied by ink jet printing.

Inventors: RABJOHNS MICHAEL ALAN, TAYLOR JOHN ANTHONY, RABJOHNS, MICHAEL, ALAN, TAYLOR, JOHN, ANTHONY
Applicants: BASF AG, RABJOHNS MICHAEL ALAN, TAYLOR JOHN ANTHONY, BASF AKTIENGESELLSCHAFT, RABJOHNS, MICHAEL, ALAN, TAYLOR, JOHN, ANTHONY
Application year: 1998
Main classification: C09B
IPC codes: B41J2, B41M5, C09B62, C09D11, D06P5