TREA

Reactive dyes containing a halobenzene nucleus

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Information

  • Patent Grant
  • 6399751
  • Patent Number
    6,399,751
  • Date Filed
    Monday, July 24, 2000
    23 years ago
  • Date Issued
    Tuesday, June 4, 2002
    22 years ago
Information
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




This invention relates to 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 halobenzene nucleus forms part of the chromophoric chain (see for example GB-A-882001). Dyes of this type which contain two such halobenzene nuclei are disclosed in CA64,14316d (1966), which is an English language abstract of an article by Matsui 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 CA59,12949g (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 U.S. Pat. No. 3,301,847 and CA61,16193f (1964) which is an English language abstract of an article by Matsui et al in Kogyo Kagaku Zasshi, (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




at least one chromophore D;




at least a first, halobenzene, reactive group Z


1


, of the formula (I)











in which:




n is 1 or 2




X, or each X independently, is an electron withdrawing group; and




Y is a halogen atom;




at least a second 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)











wherein




m 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 C


1-4


alkoxy, C


1-4


thioalkoxy or N(R


1


)(R


2


), in which each of R


1


and R


2


independently is hydrogen, optionally substituted C


1-4


alkyl or optionally substituted aryl;




(3) a group of the formula (III)











wherein:




x is 1, 2 or 3; y is zero, 1 or 2; and




x+y≦3;




Y


2


, or each Y


2


independently, is a halogen atom or an optionally substituted pyridinium group; and




U or each U independently, is C


1-4


alkyl or C


1-4


alkylsulphonyl;




(4) a group of the formula (IV)






—SO


2


CH


2


CH


2


X


1


  (IV)






wherein X


1


is an eliminatable group;




(5) a group of the formula (V)






—SO


2


(CH


2


)


z


CH═CH


2


  (V)






wherein z is zero or 1; and




(6) a group of formula (VI)






—W—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


11


)C(═O)— in which R


11


is hydrogen or C


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


presents 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 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


2


is selected from the said groups (I)-(III), at least a second linking group L


2


linking the second reactive group Z


2


to one of (i) the or a chromophore D and (ii) the said first reactive group Z


1


, which said linking group L


2


is selected from




(1) a linking group L


1


, but selected independently thereof; or




(2) an amide linkage; and




(3) a sulphonamide linkage; and




optionally at least 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 L


1


has the formula (VII)


1








N(R)  (VII)


1








wherein R is hydrogen or optionally substituted C


1-4


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 formula (VII)


2














wherein each R, 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(R)BN(R)—  (VII)


3








wherein B is a hydrocarbon bridging group as defined above, each R, independently, is 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, optionally substituted, C


2-6


alkylene group optionally interrupted by at least one hetero atom, for example, O, S or N. Optional substituents 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 SO


3


H and salts thereof, C


1-4


alkyl, C


1-4


alkoxy and chloro. The bridging group B is especially preferably an optionally substituted aryl group.




An especially preferred dye embodying the invention has the formula (VIII)






Z


1


—L


1


—D—(L


2


)


a


—Z


2


  (VIII)






wherein:




D is a chromophore;




each of L


1


and L


2


is an amine or piperazine linkage of the formula






—N(R)— (VII)


1


;














wherein:




R, or each R independently, is hydrogen or C


1-4


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 chromophore;




a is zero or 1; and




b is from 2 to 6 inclusive;




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




when a is 1, Z


2


is:




a group of the formula (I), given and defined above but selected independently thereof; or




a group of the formula (II)











wherein:




m 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 C


1-4


alkoxy, thioalkoxy or N(R


1


)(R


2


) in which R


1


is hydrogen, optionally substituted C


1-4


alkyl or optionally substituted aryl and




R


2


is hydrogen or optionally substituted C


1-4


alkyl; or




a group of the formula (III)











wherein:




x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;




Y


2


, or each Y


2


independently, is a halogen atom; and




U, or each U independently, is C


1-4


alkyl or C


1-4


alkylsulphonyl; and




when a is zero, Z


2


is:






—SO


2


CH


2


CH


2


X


1


  (IV)






in which X


1


is an eliminatable group; or






—SO


2


(CH


2


)


z


CH—CH


2


  (V)






wherein




z is zero or 1; or




a group of formula (VI)






—W—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


11


)C(═O)— 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 R in the linking group L


1


of formulae (1)-(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


2


, independently, is preferably a group of the above mentioned formula (I). Moreover, it is even more preferred that each of Z


1


and Z


2


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


2


a group of the formula






—SO


2


CH


2


CH


2


X


1


  (IV)






in which X


1


is an eliminatable group such as OSO


3


H, OPO


3


H


2


and salts of any of these, and Cl, a preferred group (IV) being






—SO


2


CH


2


CH


2


OSO


3


H






(or a salt thereof)






or








—SO


2


(CH


2


)


z


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 (I) above and Z


2


is 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 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 C


1-4


alkoxy, C


1-4


thioalkoxy or N(R


1


)(R


2


) in which R


1


is hydrogen, optionally substituted C


1-4


alkyl or optionally substituted aryl; and




R


2


is hydrogen or optionally substituted C


1-4


alkyl.




In the above formula (II), Y


1


is preferably fluorine, chlorine or optionally substituted pyridinium which may be derived from, for example, nicotinic or isonicotinic acid or their carboxamides.




Each of R


1


and R


2


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


1-4


alkyl or aryl group is substituted, a preferred substituent is hydroxyl, amino, halo, carboxy or sulpho.




In yet another alternative dye in accordance with the invention, Z


1


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


2


, or each Y


2


independently, is halogen atom; and




U, or each U independently, is C


1-4


alkyl or C


1-4


alkylsulphonyl.




In the above formula (III) Y


2


is preferably fluorine or chlorine.




A preferred range of dyes embodying the invention has the formula (XXX)






Z


1


—L


1


—D[L


3


]


q


—[Z


3


—L


4




r


[J


1


]


s


[L


2


]


a


Z


2


[L


5


—J


2


]


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, is an optionally substituted aryl group or a chromophore;




L


3


is a linking group linking Z


3


and D;




L


4


is a linking group linking Z


3


and J


1


;




L


5


is a linking group linking Z


3


and J


2


;




each of q, r, s and t independently, is zero or 1;




each of Z


1


, Z


2


, 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 1, s 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.




In a dye of the formula (XXX), each of L


3


and L


4


, independently, is preferably selected from one of the groups of the formulae (VII)


1


, (VII)


2


and (VII)


3


, 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), q is 1, r is zero, s is 1, a is zero and t is zero and in such a range L


3


is preferably a group of the formula (VII)


3








—N(R)BN(R)—  (VII)


3








wherein B is a triazine group substituted by a non reactive group.




In a dye of the formula (XXX), the chromophore D is preferably an azo chromophore derived from 1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic acid group.




Yet another range of dyes embodying the invention has the formula






Z


1


—L


1


—D


1


[L


3


—Z


3


(L


4


—Z


4


)


l


L


5


—D


2


]


k


[L


2


]


a


Z


2








wherein:




D


1


is a first chromophore;




D


2


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 in claim 1;




Z


4


, when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 1;




L


3


is a linking group linking Z


3


to D


1


;




L


4


is a linking group linking Z


3


to Z


4


;




L


5


is a linking group linking D


2


to one of Z


3


and Z


4


;




each of k and l, independently, is zero or 1; and




each of Z


1


, Z


2


, L


1


, L


2


and a is as defined in claim 1.




In one range of such dye of formula (XXXI), a is 1, Z


2


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 is 1, each of Z


1


and Z


2


is a group of the formula (I), given and defined above, each of k and l is 1;




each of D


1


and D


2


is a disazo chromophore containing a respective residue of H-acid,




each of Z


1


and Z


4


is a group of the formula (II), given and defined above, and




L


4


is a linking group of the formula (VII)


2






or (VII)


3


, given and defined above.




In still further such ranges




(i) a is 1, Z


2


is a group of the formula (I), given and defined above, k is 1 and l is 1; or




(ii) a is 1, Z


3


is a group of the formula (I), given and defined above, k is 1 and l is zero.




Yet another preferred range of dyes embodying the invention has the formula (XXXII)






Z


1


—L


1


—Z


3


—L


3


—D—Z


2


  (XXXII)






wherein:




Z


3


is a third reactive group selected from the groups (I)-(III), given and defined above; and




L


3


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 such dyes of the formula (XXXII), L


1


is 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 (II), given and defined above.




Another range of dyes embodying the invention has the formula (XXXIII)




Other ranges of dyes embodying the invention are of the respective formulae






D


2


—L


2


—Z


2


—L


3


—D


1


—L


1


—Z


1


  (XXXIV)






wherein:




each of D


1


and D


2


, independently, is a chromophore;




L


3


is a linking group selected from groups of the formula (I)-(III), given and defined above; and




each of Z


1


, Z


2


, L


1


and L


2


is as defined above; and











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 above; and




each of Z


1


, Z


2


, L


1


and L


2


is as defined above; and











wherein:




one of Z


3


and Z


4


is a reactive group Z


2


;






D—L


2


—Z


2


—L


1


—Z


1


  (XXXIII)






wherein:




Z


2


is selected from groups of the formulae I-(III), given and defined above; and




each of D, Z


1


, L


1


and L


2


is as defined above.




In such dyes of the formula (XXXIII), Z


2


is preferably a group of the formula (II), given and defined above and L


2


is preferably a linking group selected from the groups (VII)


1


, (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 B is an optionally substituted aryl group, or is alternatively a chromophoric bridging group.




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 groups at the 2- and 7-positions.




Another preferred chromophore D is a group of the formula











each of Z


3


and Z


4


, independently, is a reactive group selected from the formulae (IV)-(VI), given and defined above;




each of t and u, independently, is zero or 1 and at least one of t and u is 1;




D is a chromophore;




Ar is an optionally substituted aryl group;




L


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 H-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











wherein each of B, R and b is as defined above and the bond {circle around (1)} is linked to the heterocyclic nitrogen atom of the chromophore.




Such dyes, may have the formula






Z


1


—L


1


—D


N


&Brketopenst;L


2


&Brketclosest;


a


Z


2


&Brketopenst;L


5


—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 above, directly attached via the bond {circle around (1)}, to the nitrogen atom of the said chromophore D


N


;




Ar is an optionally substituted aryl group;




and each of Z


1


, Z


2


, L


2


, L


5


, a and t is as defined above.




A typical chromophore D containing a heterocyclic nitrogen atom has the formula











In the above formulae, wherever L


1


-L


5


, J


1


, J


2


or B is or has an optionally substituted phenyl group, optional substituents are SO


3


H or a salt thereof, C


1-4


alkyl, especially methyl and chloro, especially SO


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), anthraquinone, hydrazone, phthalocyanine, triphenodioxazine or formazan group. Examples of chromophoric groups which may be present are those given as types (a)-(g) of the group “D


1


” in formula (I) of U.S. Pat. No. 5,484,899, 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


1


is an aryl or heteroaryl group and Ar


2


is an aryl group.




It is preferred that each aryl group independently is a mono- or di-cyclic aryl group. Preferred aryl groups are optionally substituted phenyl and optionally substituted naphthyl. Preferred heteroaryl groups are pyridonyl and pyrazolonyl.




A first preferred monoazo group is of the Formula (IX) (or salt thereof):











wherein:




Ar


1


is an aryl group, preferably a benzene or naphthalene nucleus;




R


3


, or each R


3


independently, is C


1-4


alkyl, nitro, halo or sulphonic acid or a salt thereof;




c is zero or 1 to 4;




R


4


, or each R


4


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


4


is sulpho and c is zero or 1.




Ar


1


is preferably optionally substituted phenyl or naphthyl, 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


1-4


alkyl, more especially methyl; an acylamido radical, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy radical, especially C


1-4


alkoxy, more especially methoxy.




As examples of phenyl groups having at least one sulpho substituent there may be mentioned 2-, 3- or 4-sulphophenyl; 2-sulpho-4-nitrophenyl; 2-sulpho-5-nitrophenyl; 4-sulpho-2-methylphenyl; 5-sulpho-2-methylphenyl; 2-sulpho-4-methylphenyl; 5-sulpho-2-methoxyphenyl; 2-sulpho-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 1-sulphonaphth-2-yl; 1,5-disulphonaphth-2-yl; 1,5,7-trisulphonaphth-2-yl; 3,6,8-trisulphonaphth-2-yl; 5,7-disulphonaphth-2-yl; 6-sulphonaphth-2-yl; 4-,5-,6-, or 7-sulphonaphth-1-yl; 4,8-disulphonaphth-1-yl; 3,8-disulphonaphth-1-yl; 2,5,7-trisulphonaphth-1-yl; and 3,5,7-trisulphonaphth-1-yl.




Preferred optional substituents which may be present on the naphthalene nucleus of Formula (IX) are those mentioned above for Ar


1


.




Groups of the Formula (IX) are preferably linked to a group L


1


or L


2


at the 6-, 7- or 8-position, especially the 6- or 8-position. When L


1


or L


2


is to be linked at the 8-position, it is preferred that R


5


is a sulpho group at the 5- or 6-position.




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


4


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


3


, or each R


3


independently, is C


1-4


alkyl, nitro, halo or sulphonic acid or salt thereof;




c is zero or 1-4;




R


4


, or each R


4


independently, is a sulphonic acid or a salt thereof; and




d is 1 or 2.




A preferred disazo group is of the Formula (XI) (or salt thereof):






Ar


1


—N═N—M—N═N—E  (XI)






wherein:




M and E are each independently optionally substituted phenylene or naphthalene; and




Ar


1


is as defined above.




It is preferred that E is optionally substituted naphthalene and M is optionally substituted phenylene. The optional substituents which may be present on M or E are preferably independently selected from halo, especially chloro; alkoxy, especially C


1-4


alkoxy; alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino, especially acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups.




As Examples of groups represented by M and E, there may be mentioned phenylene, 2-methyl-1,4-phenylene, sulphophenylene, ureidophenylene, 7-sulpho-1,4-naphthalene, 6-sulpho-1,4-naphthalene; 8-sulpho-1,4-naphthalene and 6-hydroxy-4-sulpho-1,5-naphthalene.




An especially preferred range of disazo-dyes has the formula (XVIII)











wherein:




one of Z


5


and Z


6


is a group Z


1


and the other is a group Z


2


;




each of f and g independently is zero or 1;




when Z


5


or Z


6


is any of the groups of the formulae (I)-(III), given and defined above, f or g respectively is 1 and when Z


5


or Z


6


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 R independently is as defined above;




each of Ar


1


and Ar


2


independently is an optionally substituted aryl group; and




each of R


3


and R


4


is as defined above.




In a dye of the formula (XVIII), each of Z


5


and Z


6


may be the same group











wherein X, Y and n are as defined above.




Alternatively, one of Z


5


and Z


6


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


6


is a group of the formula (II).




Another especially preferred range of disazo dyes has the formula











wherein:




B is 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 NH


2


;




each of X, Y, Y


1


, Ar


1


, Ar


2


, R


3


, R


4


, R


5


, c, d and e is as defined above.




In a dye of the formula (XVIII), one of Z


5


and Z


6


may be a group











wherein:




X, Y and n are as defined in claim 1 and the other of Z


5


and Z


6


is the group —SO


2


CH


2


CH


2


OSO


3


H or —SO


2


CH═CH


2


.




Typically such a dye has the formula











wherein




G


3


is C


2


H


4


OSO


3


H or a salt thereof or —CH═CH


2


;




G


1


and G


2


are as defined above;




R


4


and d are as defined above; and




each of h and i, independently, is zero, 1 or 2.




A more preferred range of such dyes has the formula











where each of G


1


G


2


and G


3


is as defined above.




When the chromophore D is an anthraquinone, a preferred anthraquinone group is of the Formula (XII) (or a salt thereof).











wherein the anthraquinone nucleus optionally contains a sulphonic acid group in the 5-, 6-, 7-, or 8-position and V is a divalent organic linking 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


A


—L


3


—Ar—L


2


—Z


2


—L


1


—Z


1








wherein:




D


A


is an anthraquinone chromophore;




L


3


is a linking of the formula (VII)


1


, given and defined above;




Ar is an optionally substituted aryl group; and




each of Z


1


, Z


2


, L


1


and L


2


is as defined above.




More preferably each of L


1


and L


2


independently, is a linking group of the formula (VII)


1


, (VII)


2


or (VII)


3


, given and defined above; and still more preferably, each of L


1


and L


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 phthalocyanine, a preferred phthalocyanine group is of the Formula (XIII) (or a salt thereof).











wherein Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine; L is as hereinbefore defined; each W 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+b is not greater than 4.




Preferably such a metal phthalocyanine dye has the formula











wherein:




Cu Pc is a copper phthalccyanine chromophore;






x+y+z≦


4;




each of R


21


and R


23


, independently is hydrogen or optionally substituted C


1-4


alkyl;




B is a hydrocarbon bridging group; and




Z


1


Is as defined above.




When the chromophore D is a triphenodioxazine a preferred triphenodioxazine group is of the Formula (XIV) (or a salt thereof).











wherein:




each Y


1


independently is a covalent bond, C


2-4


-alkylene phenylene or sulphophenylene;




U


1


is H or SO


3


H; and




T


1


and T


2


are halo, especially chloro, C


1-4


-alkyl, or alkoxy.




Each Y


3


is preferably —C


2


H


4


— or —C


3


H


6


—, U


1


is preferably SO


3


H and T


1


and T


3


are preferably Cl, methyl or ethyl.




Preferably such a triphendioxazine dye has the formula






Z


1


—L


1


—[Z


3


—L


3


]


q


—D


T


—[Z


4


]


r


—L


2


—Z


2








wherein:




D


T


is a triphendioxazine chromophore; each of L


2


, L


3


and L


4


, independently, is a linking group of the formula (VII)


1


, (VII)


2


or (VII)


3


, given and defined above;




each of Z


2


, Z


3


and Z


4


is a reactive group selected from groups of the formulae (I)-(III), given and defined above;




each of q and z is zero or 1; and




each of Z


1


and L


1


is as defined above.




In such a dye, Z


2


is preferably a group of the formula (I), given and defined above and each of Z


3


and Z


4


is a group of the formula (II), given and defined above; and each of L


1


, L


2


, L


3


and L


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).











wherein:




X


1


is H, SO


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, and preferably at least two, sulpho groups.




It is preferred that each r has a value 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 Z


A


and Z


B


is a group Z


2


, given and defined above;




each of L


3


and L


4


is a linking group of the formula (VII)


1


, (VII)


2


or (VII)


3


, given and defined above;




each of Z


1


and L


1


is as defined above;




α is zero or 1;




Z


A


is selected from groups of the formulae (IV)-(VI), given and defined above; and




Z


B


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






Z


2


—L


1


—D—L


2


—Z


2


  (VIII)


1








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;




each of Z


1


and Z


2


is a group











in which:




n is 1 or 2




X


n


or each X independently, is an electron withdrawing group; and




Y 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


.




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 diazotising this and coupling a first portion of the diazotised phenylene diamine sulphonic acid to the naphthalene nucleus under acid conditions so as to couple or, to the benzene ring of the naphthalene nucleus containing an amino group and then taking a 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 hydroxyl 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


1


—L


1


—D—L


2


—Z


2


  (VIII)


2








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




Z


2


is selected from the groups (II) and (III) defined above;




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 one mole, per mole of the chromophoric compound of the formula (XX), of each of




(a) a dihalobenzene compound of the formula (XXI)











wherein each of Z, X, Y and n is as defined above; and




(b) a compound selected from



















wherein:




m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, D is 0;




Y


2


, or each Y


1


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


1


)(R


2


), in which each of R


1


and R


2


independently is hydrogen, optionally substituted C


1-4


alkyl or optionally substituted aryl;




x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;




Y


2


, or each Y


1


independently, is a halogen atom or an optionally substituted pyridinium group;




U or each U independently, is C


1-4


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 of the formula (VIII)


2


.




According to yet another process aspect, the invention provides a process for preparing a dye of the formula (VIII)


3








Z


1


—L


1


—D—Z


2


  (III)


3








wherein:




D is a chromophore




L


1


is N(R), in which R 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 hydrogen atom; and Z


2


is a group of the formula (IV)






—SO


2


CH


2


CH


2


X


1


  (IV)






wherein X


1


is an eliminatable group;






a group of the formula  (V)








—SO


2


(CH


2


)


2 CH═CH




2


(V)






wherein z is zero or 1; and






a group of formula  (VI)








—W—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


11


)C(═O)— 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


2


  (XXIV)






wherein D and Z


2


are as defined above, with a 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)


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 alkali metals such as the potassium, sodium, lithium or mixed sodium/lithium salt and their 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, hot is preferably a natural or artificial textile material containing amino or hydroxyl groups, for example textile material such as wool, silk, polyamides 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, for example, exhaust dyeing, padding or printing, including ink-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.




Preferred acid-binding agents include alkali metal carbonates, bicarbonates, hydroxides, metasilicates 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.




At least for cellulosic materials, exhaust dyeing can be carried out at a relatively low temperature about 50-70° C., especially about 60° C.




The new dyes can be applied to textile material containing amine groups, such as wool and polyamide textile materials, from a neutral to mildly alkaline dyebath. The dyeing process ran be carried out at a 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 a liquid form, or solid form, for example in granular or powdered form.




We find surprisingly that such dyes give a much higher build up, as compared with known dyestuffs, particularly in warm dyeing applications at about 60° C.




In addition, a wide selection of dye backbones is possible, giving the potential to provide high fastness dyes.




Dyes embodying the invention are especially useful for application to substrates by ink-jet technologies. Substrates which are particularly useful are cellulosic textiles and paper.




The dye used in the ink is preferably purified by removal of substantially all the inorganic salts and by-products 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 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 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 miscible solvent, which preferably campfires 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-1,3-diol and 3-(3-hydroxy-prop-2-oxy)propan-2-ol.




Where the humectant has a primary hydroxy group this is preferably 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 or dihydroxyglycolether, having two or more primary hydroxy groups, such as ethyleneglycol, propane-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-proponol 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 metanilic 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 crop. 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 dyeing with mixtures of dyes.











PREPARATIVE EXAMPLES




Example 1




2-amino-4-(N-acetyl)aminobenzene-1-sulphonic acid (0.5M, 182 g) was dissolved in water (600 ml) at pH 7 and 2M sodium nitrite solution added (0.526M, 263 ml). This solution was added dropwise to a mixture of hydrochloric acid 35% (1.13M, 100 ml, SG=1.18) and ice (1 Kg), maintaining a temperature of 0-5° C. The mixture was stirred for 0.5 hrs with excess nitrous acid at 0-5° 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-Acid (0.475M, 183 g) was dissolved in water (600 ml) at PH 7.5. This solution was added dropwise to the above diazo suspension with good agitation over 1 hr at 0-2° C. The mixture was then stirred at 0-2° C. for a further 2 hrs at pH 2-3, and allowed to warm to room temperature over 18 hrs.




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 was cooled to 0-5° C. and a batch of the diazotized diamine prepared as above was added. The mixture was stirred at 0-5° C. and PH 6-7 for 2 hrs and subsequently over 18 hrs at room temperature while maintaining the pH at 6-7 using 2M sodium carbonate solution, thereby obtaining a diazo dye solution.




Hydrolysis was then carried out by adding sodium hydroxide solution (46/48%, 800 g) to the above diazo dye solution (vol=5L) and heating at 70-75° C. for 1.5 hrs.




The reaction mixture was Cooled to 20% and neutralised by controlled addition of 35% hydrochloric acid. After screening to remove a mull amount of impurity sodium chloride was added (15% w/v) and stirring continued to allow precipitation of the resultant diaminodisazo product. This was collected by filtration and dried at 40° C. (285 g; 0.242M; strength=69.3%).




The above diaminodisazo dye (0-01M, 11.18 g) was dissolved in water/acetone (100 ml, 1:1) at 50° C. A solution of 1,5-difluoro-2,4-dinitrobenzene (0.023M, 4.7 g taken as 100% strength) in acetone (20 ml) was added over 0.25 hr and the mixture heated at 55° C. for 3 hrs. 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 (150 ml) added to precipitate the dye, The product was collected by filtration and washed with acetone (50 ml) and dried at 40° C. to give a greenish-navy dye(11.12 g; 0.0075M; strength=74.8%) (λ


Max


=607 nm; ε


Max


=57,036).




Example 2




The method of Example 1 was followed except that the diaminodisazo was reacted with 1,5-dichloro-2,4-dinitrobenzene in place of 1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy dye (λ


Max=


607 nm; ε


Max


=48,212).




Example 3




The method of Example 1 was followed except that the diaminodisazo was reacted with 1,5-difluoro-2-cyan-4-nitrobenzene in place of 1,5-difluoro 2,4-dinitrobenzene to give a greenish-navy dye (λ


Max


=607 nm; ε


Max


=56,416).




Example 4




The method of Example 1 was followed except that the diaminodisazo was reacted with 1,5-difluoro-2-nitrobenzene in place of 1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy dye (λ


Max


=608 nm; ε


Max


=54,660).




Example 5




4-Amino benzene sulphatoethylsulphone (0.1 m, 30 g) was stirred in ice/water (400 ml) and hydrochloric acid 35% (0.58M, 52 ml, SG=1.18) and the temperature maintained at below 5° C. 2M sodium nitrite solution (0.104M, 52 ml) was 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-Acid (0.103M, 42.6 g) was dissolved in water (300 ml) 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 stirred for 18 hours, allowing the temperature to rise to 20° C. Sodium chloride (10% w/v) was added and the mixture stirred for 1 hour. The precipitated monoazo dye was collected by filtration and reslurred in ethanol (600 ml) for 1 hour at 20° C. The product was collected by filtration and dried at 40° C. (70 g; 0.0825M; strength=72%).




3-Amino-5′-fluoro-2′,4′-dinitrodiphenylamine-4-sulphuric acid (0.0068M, 3.2 g) was dissolved in water (100 ml) at 50-60° C. and the solution cooled to 20° C. 2M Sodium nitrite solution (0.008M, 4 ml) was added and the mixture cooled to 0-2° C. and added dropwise to ice (50 g) and hydrochloric acid 35% (0.09M, 8 ml), while maintaining the temperature at 0-2° C. the resulting yellow suspension was stirred at 0-20° 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 monoazo dye (0.006M, 5.1 g) in water (150 ml) 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 at this pH for 18 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 (100 ml) for 1 hour at 20° C. collected by filtration and dried at 40° C. to obtain a greenish-navy dye (4.4 g: 0.003M; strength=67%; (λ


Max


=608 nm; ε


Max=


54,279) of the structure given below:











Examples 6-61




Other diazo 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 to 5.




Examples 62-67




Still further diazo 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 to a chromophore.











The N-diachlorotriazinyl derivative of the azo dye resulting from azo-coupling 7-aminonaphthalena-1,3,6-trisulphonic acid with m-ureidoaniline was prepared by conventional means. A solution of this dye (35 mmol in 450 ml) was added at room temperature with stirring to N-(4-aminophenyl)piperazine (7.5 g, 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 concentrated, and the product was precipitated by addition of methylated spirit. To a solution of this intermediate (8.4 of mmol) in 50/50 acetone/water (200 ml) was added a solution of 1,5-difluoro-2,4-dinitrobenzene (8.5 mmol) in acetone (20 ml), maintaining the pH at 8.5 by of sodium carbonate solution. On completion of the reaction, the pH was adjusted to 6.5 and the solution was concentrates ca 100 ml. Methylated spirit was added, and the product dye was filtrated, washed with meths and dried. λ


max


(water)=379 nm, ε


max


=33000 l mol


−1


cm


−1


, half band width >150 nm. 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 of a similar nature may be prepared as further exemplified by dyes 69-77 listed in Table 3.




Examples 78-97




Disazo naphthalene dyes containing two reactive groups attached to the chromophore as described in Example 68 are exemplified by Examples 76 to 97 listed in Table 4.




Examples 98-127




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 128-160




Monoazo naphthalene dyes embodying the invention are listed in Tables 10 to 12.




Examples 161-189




A variety of dyes embodying the invention, containing blue and green chromophores, are listed in Tables 13 to 16.




APPLICATION EXAMPLES




Examples 190-192




Each of the dyes (0.2 parts) of respective Examples 1, 3 and 5 was dissolved in respective amounts 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.-60° C., basifying to pH 11.0 and maintaining this for 1 hr. The cotton was removed and washed in soapy water to give a dark greenish-navy cotton having high general fastness properties.




Examples 193 and 194




Each of the dyes (0.2 parts) of respective Examples 2 and 4 was dissolved in water (50 parts) at 25° C. and pH 9. Cotton fabric (5 parts) and salt (4 parts) were added. The dyes were fixed to cotton by raising the temperature to 80-100° C. and maintaining this for 1 hr. The cotton was removed and washed in soapy water to give a deep greenish-navy cotton having good tastness properties.




Examples 195-198




Methodology for applying dyes embodying the present invention to cotton may be further exemplified by means of the following pad-batch dyeing protocol.




Example 195-198




Example 195. Dye from Example 5 (0.5 parts) was dissolved in water (30 parts) at 25° C. and the following agents were added: Primasol NF (1 part of 20% solution) and sodium silicate Q70 (9.5 part 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 to 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 with a soap solution, rinsed with water, and dried to give cotton coloured a dull greenish blue shade.




Example 196. If the amount of dye used in Example 193 is doubled and the procedure repeated, a greenish-navy shade is obtained.




Example 197. If the amount of dye used in Example 193 is trebled and the procedure repeated, a dark navy shade is obtained.




Example 198. If six times the amount of dye in Example 193 is used and the procedure repeated, an almost black shade 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-ester precursor, can be applied to cotton by the same method.




Example 199




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 containing Manutex F 700 (500 parts of a 10% solution) and Vitexol 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 and padded through a solution containing sodium silicate (48edge, 700 parts) made up to 1000 parts by the addition of water (80% pickup). Immediately after padding, the printed cotton was steamed in a Roaches Flash-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 boil, rinsed again in cold water and dried to give a dull greenish navy print on the cotton.




Example 200




Dyes embodying the present invention may be used in the preparation of inks specially formulate 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 parts). When this solution was applied to cotton which had previously been pretreated (for example, with a pretreatment agent described in E2-A-0534660) by means of commercial ink-jet printing equipment, deep navy shades were obtained.




Other dyes from the above examples as well as others described by the Invention may be used to prepare inks suitable for ink-jet printing.




Example 201




Reactive dyes, including those of Examples 1-189, are usually isolated as their sodium salts, and are contaminated with inorganic impurities resulting from the method of preparation. Dyes free of impurities suitable for ink let 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 are simultaneously removed.




Dye from Example 1 (10 parts) was dissolved in water (100 parts) and treated on a reverse osmosis rig until 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 to decreased to 1 micro reciprocal ohm, The sample was concentrated to a volume of about 80 parts, after which the solution was buffered and other formulating agents were added. The dye solution was then diluted to 90 parts by addition or water, at which stage 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, 195-198, or formulated into an ink by addition of suitable humectants and/or cosolvents, 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 of black, shades were imparted to the substrate, depending on the amount of dye applied.




Example 202




Dye from Example 1 was ion exchange to the lithium form 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 added to the ink reservoir 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











































λ


max


nm









(w


1/2


nm)









Colour on






Example




A




B




cotton

















6




























606 (121) greenish-navy













7




























607 (105) greenish-navy













8




























623 (121) dark bluish-green













9




























616 (121) greenish-navy













10




























603 (105) greenish-navy













11




























618 (130) greenish-navy













12




























614 (110) dark bluish-green













13




























594 (112) greenish-navy













14




























595 (108) greenish-navy













15




























604 (110) dark bluish-green













16




























645 (137) very dull dark green













17




























604 (119) greenish-navy













18




























603 (127) greenish-navy













19




























600 (134) greenish-navy













20




























596 120) greenish-navy













21




























609 (111) greenish-navy













22




























604 (120) greenish-navy













23




























625 (104) greenish-navy













24




























620 (112) drak bluish-green













25




























632 (114) dark bluish-green













26




























609 (141) dark bluish-green













27




























602 (125) greenish-navy













28




























605 (143) dark blusish-green













29




























596 (129) greenish-navy













30




























607 (109) greenish-navy













31




























595 (107) greenish-navy













32




























622 (123) greenish-navy













33




























619 (114) dark bluish-green













34




























606 (114) dark bluish-green













35




























618 (113) dark bluish-green













36




























616 (110) dark bluish-green













37




























616 (106) greenish-navy













38




























616 (111) dark bluish-green













39




























608 (111) greenish-navy













40




























608 (110) greenish-navy













41




























608 (116) greenish-navy













42




























616 (111) dark bluish-green













43




























615 (120) dark blusish-green













44




























615 (118) dark bluish-green













45




























greenish-navy













46




























dark bluish-green













47




























greenish-navy













48




























dark bluish-green













49




























greenish-navy













50




























dark bluish-green













51




























greenish-navy













52




























dark bluish-green













53




























dark bluish-green













54




























greenish-navy













55




























dark bluish-green













56




























dark bluish-green













57




























greenish-navy













58




























greenish-navy













59




























dark bluish-green













60




























dark bluish-green













61




























greenish-navy






















TABLE 2











































λ


max


nm









(w


1/2


nm)









Colour on






Example




A




B




cotton









62




























609 (118) dull dark green













63




























608 (112) dull dark green













64




























630 (130) dull dark green













65




























Greenish-navy













66




























Greenish-navy













67




























Greenish-navy






















TABLE 3













































Colour on






Example




L




λ


max


nm




w


1/2


nm




cotton









69
















415




139




Golden yellow













70
















307




140




Golden yellow













71
















403




200




Golden yellow













72
















419




200




Golden yellow













73
















366




119




Golden yellow













74




NHC


2


H


4


NH




410




170




Golden










yellow






75
















378




155




Golden yellow













76
















389




150




Golden yellow













77
















360




160




Golden yellow






















TABLE 4










































Example




A




B




X




Y




Colour on cotton









78




























NH


2






OH




Greenish navy













79




























OH




NH


2






Greenish navy













80




























NH


2






OH




Greenish navy













81




























OH




NH


2






Greenish navy













82




























NH


2






OH




Greenish navy













83




























OH




NH


2






Greenish navy













84




























NH


2






OH




Greenish navy













85




























OH




NH


2






Greenish navy













86




























NH


2






OH




Greenish navy













87




























OH




NH


2






Greenish navy













88




























NH


2






OH




Greenish navy













89




























OH




NH


2






Navy













90




























NH


2






OH




Navy













91




























OH




NH


2






Greenish navy













92




























NH


2






OH




Greenish navy













93




























OH




NH


2






Greenish navy













94




























OH




NH


2






Greenish navy













95




























NH


2






OH




Greenish navy













96




























OH




NH


2






Greenish navy













97




























OH




NH


2






Greenish navy






















TABLE 5









































Example




Structure




λ


max


nm




w


½


nm




Colour on cotton


















98




Dye-SC


2


H


4


OH




407




148




Golden yellow






99




Dye-N(CH


3


)Ph




403




138




Golden yellow






100




Dye-NHC


2


H


4


SO


3


H




407




129




Golden yellow






101




Dye-NHC


2


H


4


OC


2


H


4


OH




412




134




Golden yellow






102




Dye-NHC


6


H


3


-m-SO


3


H




409




143




Golden yellow






103




Dye-NHC


2


H


4


NH-Dye






Golden yellow













104
















412




130




Golden yellow






















TABLE 6













































Colour on






Example




Structure




λ


max


nm




w


½


nm




cotton









105




Dye-SC


2


H


4


OH




437




151




Mid yellow













106
















430




135




Mid yellow













107




Dye-NHC


2


H


4


OC


2


H


4


OH




436




141




Mid yellow













108
















435




132




Mid yellow













109
















439




143




Mid yellow













110
















438




149




Mid yellow













111
















437




131




Mid yellow













112




Dye-NHC


2


H


4


NH-Dye






Mid yellow






113




Dye-NHC


3


H


6


NH-Dye






Mid yellow
























TABLE 7











λ


max


nm






Ex-





(w


1/2


nm)






am-





Colour on






ple




Structure




cotton











114
















435 (172) mid yellow













115
















422 (148) golden yellow













116
















406 (124) golden yellow






















TABLE 8








































Example
















Other Substituents




Colour on cotton









117




4-




1,3-(SO


3


H)


2


3-SO


2


C


2


H


4


OSO


2


H




Yellow






118




3-




1,4-(SO


3


H)


2


2′-SO


2


C


2


H


4


OSO


3


H




Yellow













119




4-




1,1′-(SO


3


H)


2






Yellow





























120




4-




1,1′-(SO


3


H)


2






Yellow





























121




4′-




1,1′,4-(SO


3


H)


3






Yellow






































TABLE 9















































Colour on






Example




A




B




X




Y




cotton









122




























H




H




Greenish- yellow













123




























H




CN




Greenish- yellow













124




























H




CONH


2






Greenish- yellow













125




























C


2


H


4


OH




H




Greenish- yellow













126




























C


2


H


4


OH




CONH


2






Greenish- yellow













127




























H




H




Greenish- yellow






















TABLE 10















































Colour on






Example




A




B




X




Y




cotton









128




























SO


3


H




H




Bluish red













129




























SO


3


H




H




Bluish red













130




























H




SO


3


H




Bluish red













131




























SO


3


H




H




Bluish red













132




























SO


3


H




H




Bluish red













133




























H




SO


3


H




Bluish red













134




























SO


3


H




H




Bluish red













135




























SO


3


H




H




Bluish red













136




























SO


3


H




H




Bluish red













137




























H




SO


3


H




Bluish red













138




























SO


3


H




H




Bluish red






















TABLE 11













































Colour on






Example




A




B




X




cotton


















139




























H




Red













140




























SO


3


H




Red













141




























H




Red













142




























SO


3


H




Red













143




























H




Red













144




























SO


3


H




Red













145




























SO


3


H




Red













146




























SO


3


H




Red













147




























H




Red













148




























H




Red













149




























SO


3


H




Red






















TABLE 12















































Colour on






Example




A




B




X




Y




cotton









150




























H




H




Reddish yellow













151




























H




SO


3


H




Reddish yellow













152




























Me




H




Reddish yellow













153




























H




H




Reddish yellow













154




























H




H




Orange













155




























H




SO


3


H




Orange













156




























Me




H




Orange













157




























H




H




Orange













158




























H




H




Orange













159




























H




SO


3


H




Orange













160




























Me




H




Orange






















TABLE 13









































Colour on






Example




A




cotton









161
















Greenish blue













162
















Greenish blue













163
















Greenish blue













164
















Greenish blue






















TABLE 14



















































Colour on






Example




R




R′




R″




x




y




z




cotton





















165
















H




H




2




0




2




Green













166
















H




H




1.5




0.5




2




Green













167




C


2


H


4






H




H




2




0




2




Bluish-













green






168




C


3


H


6






CH


3






CH


3






1.7




0.3




2




Bluish-













green













180
















H




C


2


H


4


OSO


3


H




2.5




0.5




1




Green













170
















H




H




1.5




1.5




1




Green













171
















H




C


2


H


4


SO


3


H




2.5




0




1.5




Green













172
















H




H




3




0




1




Green






















TABLE 15










































Example




A




B




X




Y




Colour on cotton









173




























Cl




Cl




Blue













174




























Cl




Cl




Blue













175




























Cl




Et




Blue













176




























Cl




Cl




Greenish blue













177




























Cl




Et




Greenish blue













178




























Cl




Cl




Greenish blue













179




H
















Cl




Cl




Greenish blue













180




























Cl




Me




Blue













181




























Cl




Cl




Greenish blue






















TABLE 16











































Colour on






Example




A




X




cotton









182
















H




Dull greenish blue













183
















H




Dull greenish blue













184
















H




Dull greenish blue













185
















H




Dull greenish blue













186
















H




Dull blue













187
















H




Dull greenish blue













188
















3-SO


3


H




Dull greenish blue













189
















4-SO


2


C


4


H


6


OSO


3


H




Dull greenish blue













Claims
  • 1. A dye comprisingat least one chromophore D; at least a first, halobenzene, reactive group Z1, of the formula (I) wherein: n is 1 or 2;X, or each X independently is an electronic withdrawing group; and Y is a halogen atom; at least a second reactive group Z2 selected from the group consisting of: a group of the formula (IV) —SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group; anda group of the formula (V) —SO2(CH2)zCH═CH2  (V) wherein z is zero or 1;at least a first linking group L3, linking said first, halobenzene, reactive group Z1 to one of components (i) a chromophore D and (ii) the second reactive group Z2, which said first linking group L3 presents an amino nitrogen to the reactive group Z1 and to the component (i) or, when component (i) contains a heterocyclic nitrogen atom, is linked directly to the nitrogen atom and which said first linking group L1 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 optionally at least one aromatic group Ar which may carry the said reactive group Z2; which dye is selected from the group consisting of dyes of the formulae (VIII), (XXX), (XXXI), (XXXII), (XXXVI) and (XXXVII), wherein: formula (VIII) is:Z1—L11—D—Z2  (VIII) wherein:D is a chromophore; L11 is a group of L1, which is an amine or piperazine linkage of the formula —N(R)—  (VII)1; wherein: R, or each R independently, is hydrogen or optionally substituted C1-4alkyl;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 chromophore; b is from 2 to 6 inclusive; and each of Z1 and Z2 is as defined above; formula (XXX) is: Z1—L1—D[L3]q—[Z3—L4]r[J1]sZ2  (XXX) wherein: Z3 is a third reactive group selected from the groups of the formulae (I)-(III),wherein: formula (I) is given and defined above;formula (II) is wherein:m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0; Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is C1-4 alkoxy, thioalkoxy or N(R1)(R2) in which R1 is hydrogen, optionally substituted C1-4 alkyl or optionally substituted aryl; and formula (III) is wherein:X is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3; Y2, or each Y2 independently, is a halogen atom or an optionally substituted pyridinium group; and U, or each U independently, is C1-4 alkyl or C1-4 alkylsulphonyl; J1 is an optionally substituted aryl group or a chromophore; L3 is a linking group linking one of Z3 and J1 to D; L4 is a linking group linking Z3 and J1; each of q, r and s independently, is zero or 1; and each of Z1, Z2 and L2 is as defined above; formula (XXXI) is: Z1—L1—D1[L3—Z3(L4—Z4)1L5—D2]kZ2  (XXXI) wherein: D1 is a first chromophore;D2 is a second chromophore; Z3, when present, is a third reactive group selected from the groups of the formulae (I)-(III), given and defined above; Z4, when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined above; L3 3 is a linking group linking Z3 to D1; L4 is a linking group linking Z3 to Z4; L5 is a linking group linking D2 to one of Z3 and Z4; each of k and l, independently, is zero or 1; and each of Z1, Z2 and L1 is as defined above; formula (XXXII) is: Z1—L1—Z3—L3—D—Z2  (XXXII) wherein: Z3 is a third reactive group selected from the groups (I)-(III), given and defined above andL3 is a third linking group selected from the groups (VII)1, (VII)2 and (VII)3, given and defined above; Z2 is a second reactive group selected from the groups (IV)-(V), given and defined above; and each of Z1 and L1 is as defined above; formula (XXXVI) is: wherein: one of Z3 and Z4 is a reactive group Z2 selected from the formulae (IV) and (V) given and defined above;the other of Z3 and Z4, independently, is a reactive group selected from the formulae (IV) and (V), given and defined above, and formula given and defined below; each of t and u, independently, is zero or 1 and at least one of t and u is 1; when Z3 is a reactive group Z2, t is 1 and when Z4 is a reactive group Z2, u is 1; D is a chromophore; Ar is an optionally substituted aryl group; L1 is a group of the formula (XLI) wherein B and each R, independently, is as defined above;Z1 is a group of the formula (I), given and defined above; and wherein: formula (VI) is —W—C(R10)═CH2(VI) wherein: R10 is hydrogen, C1-4alkyl or halogen; andW is —OC(═O)— or —N(R11)C(═O)— in which R11 is hydrogen or C1-4alkyl; and formula (XXXVII) is: Z1—L1—DN—Z2  (XXXVII) wherein: DN is a chromophore containing a heterocyclic group including a nitrogen atom;L1 is a group of the formula (VII)4 or (VII)5, wherein B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero group and is optionally a chromophore, R is hydrogen or C1-4 alkyl and b is from 2 to 6 inclusive;which group of the formula (VII)4 or (VII)5 is directly attached via the bond {circle around (1)}, to the nitrogen atom of the said chromophore DN; and each of Z1 and Z2 is as defined above.
  • 2. A dye according to claim 1, wherein the linking group L1 has the formula (VII)1 N(R)  (VII)1 wherein R is hydrogen or optionally substituted C1-4 alkyl, such that the same amino group presents itself to each of the reactive group Z1 and the component (i), as defined in claim 1.
  • 3. A dye according to claim 1, wherein the linking group L3 is a piperazinoalkylamino group of the formula (VII)2wherein each R, independently, is hydrogen or optionally substituted C1-4 alky, such that the same amino group presents itself to each of the reactive group Z1 and the component (i), as defined in claim 1.
  • 4. A dye according to claim 1, wherein the linking group L1 has the formula (VII)3 —N(R)BN(R)—  (VII)3 wherein B is a hydrocarbon bridging group as defined in claim 1, 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 to claim 4, wherein the hydrocarbon bridging group B is an optionally substituted aryl group.
  • 6. A dye according to claim 1, of the formula (VIII)Z1—L11—D—Z2  (VIII) wherein:D is a chromophore; L11 is a group of L1 which is an amine or piperazine, linkage of the formula wherein; R, or each R independently, is hydrogen or C1-4 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 chromophore; b is from 2 to 6 inclusive; Z1 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 Z2 is: —SO2CH2CH2X1  (IV) in which X1 is an eliminatable group; or—SO2(CH2)zCH═CH2  (V) wherein z is zero or 1.
  • 7. A dye according claim 1, 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 claim 2, wherein R, or each R independently, ie hydrogen.
  • 9. A dye according to claim 1, wherein D is an azo chromophore.
  • 10. A dye according to claim 9, wherein D is a monoazo chromophore.
  • 11. A dye according to claim 10, which has the formula (XVII) wherein: R is halogen, optionally substituted C1-4 alkyl or optionally substituted aryl;Z1 is of the formula (I); wherein formula (I) is wherein: n is 1 or 2;X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; Z2 is of the formula —SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group; or—SO2(CH2)zCH═CH2  (V) wherein Z is zero or 1;Ar is a benzene or naphthalene nucleus; R3, or each R3 independently, is C1-4 alkyl, nitro, halo or sulphonic acid or salt thereof; c is zero or 1-4; R4, or each R4 independently, is a sulphonic acid or a salt thereof; and d is 1 or 2.
  • 12. A dye according to claim 9, wherein D is a disazo chromophore.
  • 13. A dye according to claim 12, which has the formula (XVIII) wherein: one of Z5 and Z6 is a group Z1 and the other is a group Z2;each of f and g independently is zero or 1; when Z5 or Z6 is a group of the formula (I), f or g respectively is 1 and when Z5 or Z6 is any of the groups of the formulae (IV) and (V), f or g respectively is zero; wherein: formula (I) is wherein: n is 1 or 2;X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; wherein: formula (IV) is—SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group; andformula (V) is —SO2(CH2)zCH═CH2  (V) wherein z is zero or 1;each of c and e, independently, is zero or 1-4; d is 1 or 2; each R independently is hydrogen or optionally substituted C1-4 alkyl, such that the same amino group presents itself to each of the reactive group Z1 and the component (i) wherein component (i) is a chromophore D; each of Ar1 and Ar2 is an optionally substituted aryl group; and each of R3 and R4 is C1-4 alkyl, nitro, halo or sulphonic acid or salt thereof.
  • 14. A dye according to claim 13, wherein one of Z5 and Z6 is a group wherein:X is an electron withdrawing group, Y is a halogen atom and n is 1 or 2 and the other of Z5 and Z6 is the group —SO2CH2CH2OSO3H or —SO2CH═CH2.
  • 15. A dye according to claim 14, has the formula (XLIII) wherein: G3 is C2H4OSO3H or a salt thereof or —CH═CH2;G1 and G1 are different and are OH or NH2; R4 is sulphonic acid or a salt thereof and d is 1 or 2; and each of h and i, independently, is zero, 1 or 2.
  • 16. A dye according to claim 15, wherein the dye has the formula (XLIV) where each of G1 and G2 is different and is OH or NH2 and G1 is C2H4OSO3H or a salt thereof or —CH═CH2.
  • 17. A dye according to claim 1, of the formula (XXX)Z1—L1—D[L3]q[Z3—L4]r[J1]sZ2(XXX) wherein: Z3 is a third reactive group selected from the groups of the formulae (I)-(III), wherein: formula (I) is in which: n is 1 or 2;X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; formula (II) is wherein m is 1 or 2;p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0; Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is C1-4 alkoxy, C1-4 thioalkoxy or N(R1)(R2), wherein each of R1 and R2 independently is halogen, optionally substituted C1-4 alkyl or optionally substituted aryl; and formula (III) is wherein: x is 1, 2, or 3;y is zero, 1 or 2; and x+y≦3; Y2, or each Y2 independently, is a halogen atom or an optionally substituted pyridinium group; and U or each U independently, is C1-4 alkyl or C1-4 alkylsulphonyl; J1 is an optionally substituted aryl group or a chromophore; L3 is a linking group linking one of Z3 and J1 to D; L4 is a linking group linking Z3 and J1; each of q, r and s, independently, is zero or 1; and each of Z1, Z2 and L1 is as defined in claim 1.
  • 18. A dye according to claim 17, wherein each of L3 and L4, independently, is selected from one of the groups of the formulae (VII)1, (VII)2 and (VII)3, wherein: R, or each R independently, is hydrogen or C1-4 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 chromophore; and b is from 2 to 6 inclusive.
  • 19. A dye according to claim 18, wherein each of L3 and L4 is a group of the formulae (VII)1,—N(R)—  (VII)1 wherein R, or each R independently, is hydrogen or C1-4 alkyl.
  • 20. A dye according to claim 7, wherein q is 1, r is zero and s is 1.
  • 21. A dye according to claim 20, wherein L3 is a group of the formula (VII)3 —N(R)BN(R)—  (VII)3 wherein D is a triazine group substituted by a non-reactive group.
  • 22. A dye according to claim 17, wherein the chromophore D is an azo chromophore derived from 1-hydroxy-8-aminoaphthalene substituted by at least one sulphamic acid group.
  • 23. A dye according to claim 1 of the formula (XXXI)Z1—L1—D1[L3—Z3(L4—Z4)1L5—D2]kZ2  (XXXI) wherein:D1 is a first chromophore; D2 is a second chromophore; Z3, when present, is a third reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 17; Z4 when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 17; L3 is a linking group linking Z3 to D1; L4 is a linking group linking Z3 to Z4; L5 is a linking group linking D2 to one of Z3 and Z4; each of k and l, independently, is zero or 1; and each of Z1, Z2 and L1 is as defined in claim 1.
  • 24. A dye according to claim 1, of the formula (XXXII)Z1—L1—Z3—L3—D—Z2  (XXXII) wherein: Z3 is a third reactive group selected from the groups (I)-(III), given and defined in claim 17; andL3 is a third linking group selected from the groups (VII)1, (VII)2 and (VII)3, wherein: R, or each R independently, is hydrogen or C1-4 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 chromophore; and b is from 2 to 6 inclusive; Z2 is a second reactive group selected from the groups (IV)-(V), given and defined in claim 1; and each of Z1 and L1 is as defined in claim 1.
  • 25. A dye according to claim 24, wherein L1 is a linking group of the formula (VII)2 or (VII)3, wherein: R, or each R independently, is hydrogen or C1-4 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 chromophore; and b is from 2 to 6 inclusive.
  • 26. A dye according to claim 24, wherein Z3 is a group of the formula (II), whereinm is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0, Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and T is C1-4alkoxy, C1-4thioalkoxy or N(R1)(R2), wherein each of R1 and R2 independently is halogen, optionally substituted C1-4alkyl or optionally substituted aryl.
  • 27. A dye according to claim 24, 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.
  • 28. A dye according to claim 1, wherein D is a group of the formula (XLII)
  • 29. A dye according to claim 1, of the formula (XXXVI) wherein:one of Z3 and Z4 is a reactive group Z2 selected from the formulae (IV) and (V), given and defined below; the other of Z3 and Z4, independently, is a reactive group selected from the formulae (IV)-(VI), given and defined below; each of t and u, independently, is zero or 1 and at least one of t and a is 1; when Z3 is a reactive group Z2, t is 1 and when Z4 is a reactive group Z2, a is 1; D is a chromophore; Ar is an optionally substituted aryl group; L1 is a group of the formula (XLI) wherein each R, independently, is hydrogen or optionally substituted C1-4 alkyl; andZ1 is a group of the formula (I), given and defined below; wherein: formula (I) is wherein: n is 1 or 2;X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; formula (IV) is—SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group;formula (V) is —SO2(CH2)zCH═CH2  (V) wherein z is zero or 1; andformula (VI) is—W—C(R10)═CH2  (VI) wherein: R10 is hydrogen, C1-4 alkyl or halogen; andW is —OC(═O)— or —N(R11)C(═O)— in which R11 is hydrogen or C1-4 alkyl.
  • 30. A dye according to claim 29, wherein D is a disazo dye containing a residue derived from H-acid.
  • 31. A dye according to claim 1, of the formula (XXXVII)Z1—L1—DN—Z2  (XXXVII) wherein: DN is a chromophore containing a heterocyclic group including a nitrogen atom;L1 is a group of the formula (VII)4 or (VII)5, wherein B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero group and is optionally a chromophore, R is hydrogen or C1-4 alkyl and b is from 2 to 6 inclusive;which group of the formula (VII)4 or (VII)5 is directly attached via the bond {circle around (1)}, to the nitrogen atom of the said chromophore DN; and Z1 is a halobenzene of the formula (I) wherein: n is 1 or 2;X, or each X independently, is an electron withdrawing group; and Y is a halogen atom; Z2 is selected from the group consisting of (4) a group of the formula (IV) —SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group; and(5) a group of the formula (V) —SO2(CH2)zCH═CH2  (V) wherein z is zero or 1.
  • 32. A dye according to claim 31, wherein the chromophore D has the formula (XLII)
  • 33. A dye according to claim 10, which is an azo dye having at least two azo groups therein.
  • 34. A dye according to my claim 9, wherein D is a trisazo or tetrakisazo chromophore.
  • 35. A dye of the formula
  • 36. A dye of the formula
  • 37. A process for preparing a dye of the formula (VIII)3 Z1—L1—D—Z2  (VIII)3 wherein:D is a chromophore L1 is N(R), in which R is hydrogen or C1-4 alkyl; Z1 is a group in whichn is 1 or 2; X, or each X independently, is an electron withdrawing group; and Y is a hydrogen atom; and Z2 is a group of the formula (IV) —SO2CH2CH2X1  (IV) wherein X1 is an eliminatable group; ora group of the formula (V) —SO2(CH2)2CH═CH2  (V) wherein z is zero or 1;which process comprises reacting a chromophoric compound of the formula (XXIV)H(R)N—D—Z2  (XXIV) wherein D and Z2 are as defined above, with a 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)3.
  • 38. A process for the colouration of a substrate, which process comprises applying to the substrate a dye according to claim 1.
  • 39. A process according to claim 38, wherein the dye is applied to the substrate by exhaust dyeing, padding or printing.
  • 40. A process according to claim 39, wherein the dye is applied by ink jet printing.
Priority Claims (1)
Number Date Country Kind
9723924 Nov 1997 GB
PCT Information
Filing Document Filing Date Country Kind
PCT/GB98/03406 WO 00
Publishing Document Publishing Date Country Kind
WO99/27019 6/3/1999 WO A
US Referenced Citations (1)
Number Name Date Kind
3301847 Mangani et al. Jan 1967 A
Foreign Referenced Citations (4)
Number Date Country
1321960 Jun 1963 FR
882001 Nov 1961 GB
887870 Jan 1962 GB
978162 Dec 1964 GB