Reactive dyes containing a halobenzene nucleus

Abstract

The invention relates to reactive dyes containing a halobenzene nucleus and, in particular, reactive dyes containing a halobenzene nucleus and two or more reactive components.

Description

[0001] This invention relates to reactive dyes containing a halobenzene nucleus and, in particular, reactive dyes of this type containing two or more reactive components.

[0002] 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.

[0003] 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.

[0004] 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.

[0005] 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.

[0006] According to the invention there is provided a dye containing

[0007] at least one chromophore D;

[0008] at least a first, halobenzene, reactive group Z1, of the formula (I) 1

[0009] in which:

[0010] n is 1 or 2

[0011] X, or each X independently, is an electron withdrawing group; and

[0012] Y is a halogen atom;

[0013] at least a second reactive group Z2 selected from

[0014] (1) a group of the formula (I), given and defined above, but selected independently thereof;

[0015] (2) a group of the formula (II) 2

[0016] wherein

[0017] 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;

[0018] Y1 or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and

[0019] T is C1-4alkoxy, C1-4thioalkoxy or N(R1) (R2), in which each of R1 and R2 independently is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl;

[0020] (3) a group of the formula (III) 3

[0021] wherein:

[0022] x is 1, 2 or 3; y is zero, 1 or 2; and

[0023] x+y≦3;

[0024] Y2, or each Y2 independently, is a halogen atom or an optionally substituted pyridinium group; and

[0025] U or each U independently, is C1-4alkyl or C1-4alkylsulphonyl;

[0026] (4) a group of the formula (IV)

—SO2CH2CH2X1  (IV)

[0027] wherein

[0028] X1 is an eliminatable group;

[0029] (5) a group of the formula (V)

—SO2(CH2)zCH═CH2  (V)

[0030] wherein

[0031] z is zero or 1; and

[0032] (6) a group of formula (VI)

—W—C (R10)═CH2  (VI)

[0033] wherein:

[0034] R10 is hydrogen, C1-4alkyl or halogen; and

[0035] W is —OC(═O)— or —N(R11)C(═O)— in which R11 is hydrogen or C1-4 alkyl;

[0036] at least a first linking group L1, linking the said first, halobenzene, reactive group Z1 to one of components (i) the or a chromophore D and (ii) the second reactive group Z2, which said first linking group L1 presents an amino nitrogen to the reactive group Z1 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 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

[0037] when Z2 is selected from the said groups (I)-(III), at least a second linking group L2 linking the second reactive group Z2 to one of (i) the or a chromophore D and (ii) the said first reactive group Z1, which said linking group L2 is selected from

[0038] (1) a linking group L1, but selected independently thereof; or

[0039] (2) an amide linkage; and

[0040] (3) a sulphonamide linkage; and

[0041] optionally at least one aromatic group Ar which, when Z2 is selected from the said groups (IV)-(VI), may carry the said reactive group Z2.

[0042] Preferably, the linking group L1 has the formula (VII)1

N(R)  (VII)1

[0043] wherein R is hydrogen or optionally substituted C1-4alkyl, such that the same amino group presents itself to each of the reactive group Z1 and the component (i) or (ii), as defined above; or

[0044] is a piperazinoalkylamino group of the formula (VII)24

[0045] 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 Z1 and to the component (i) or (ii), as defined above; or

[0046] has the formula (VII)3

—N(R)BN(R)—  (VII)3

[0047] 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).

[0048] The hydrocarbon bridging group B may be a straight or branched, optionally substituted, C2-6alkylene 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 SO3H and salts thereof, C1-4alkyl, C1-4alkoxy and chloro. The bridging group B is is especially preferably an optionally substituted aryl group.

[0049] An especially preferred dye embodying the invention has the formula (VIII)

Z1-L1-D-(L2)aZ2  (VIII)

[0050] wherein:

[0051] D is a chromophore;

[0052] each of L1 and L2 is an amine or piperazine linkage of the formula

—N(R)—  (VII)1;

[0053] 5

—N(R)BN(R)—  (VII)3

[0054] wherein:

[0055] R, or each R independently, is hydrogen or C1-4 alkyl;

[0056] 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;

[0057] a is zero or 1; and

[0058] b is from 2 to 6 inclusive;

[0059] Z1 is a group 6

[0060] in which:

[0061] n is 1 or 2;

[0062] X, or each X independently, is an electron withdrawing group; and

[0063] Y is a halogen atom; and

[0064] when a is 1, Z2 is:

[0065] a group of the formula (1), given and defined above but selected independently thereof; or

[0066] a group of the formula (II) 7

[0067] wherein:

[0068] 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;

[0069] Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and

[0070] 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

[0071] R2 is hydrogen or optionally substituted C1-4 alkyl; or

[0072] a group of the formula (III) 8

[0073] wherein:

[0074] x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;

[0075] Y2, or each Y2 independently, is a halogen atom; and

[0076] U, or each U independently, is C1-4 alkyl or C1-4 alkylsulphonyl; and

[0077] when a is zero, Z2 is:

—SO2CH2CH2X1  (IV)

[0078] in which X1 is an eliminatable group; or

—SO2(CH2)zCH═CH2  (V)

[0079] wherein z is zero or 1; or

[0080] a group of formula (VI)

—W—C(R10)═CH2  (VI)

[0081] wherein:

[0082] R10 is hydrogen, C1-4alkyl or halogen; and

[0083] W is —OC(═O)— or —N(R11)C(═O)— in which R11 is hydrogen or C1-4 alkyl.

[0084] 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.

[0085] The halogen atom in the halobenzene nucleus of formula (I) is preferably fluorine or chlorine.

[0086] The group R in the linking group L1 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.

[0087] In the dye of formula (VII), each of Z1 and Z2, independently, is preferably a group of the above mentioned formula (I). Moreover, it is even more preferred that each of Z1 and Z2 is the same group as the other.

[0088] However, alternatively, Z1 may be a halobenzene nucleus of the formula (I), A may be zero and Z2 a group of the formula

—SO2CH2CH2X1  (IV)

[0089] in which X1 is an eliminatable group such as OSO3H, OPO3H2 and salts of any of these, and Cl, a preferred group (IV) being

—SO2CH2CH2OSO3H (or a salt thereof)

[0090] or

—SO2(CH2)zCH═CH2  (V)

[0091] wherein z is zero or 1.

[0092] In an other alternative range of dyes, Z1 is a halobenzene nucleus of the formula (I) above and Z2 is a halotriazine nucleus of the formula (II) 9

[0093] wherein m is 1 or 2, p is 0 or 1,

[0094] when m is 1, p is 1 and

[0095] when m is 2, p is 0;

[0096] Y11 or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and

[0097] T is C1-4 alkoxy, C1-4thioalkoxy or N(R1) (R2) in which R1 is hydrogen, optionally substituted C1-4 alkyl or optionally substituted aryl; and

[0098] R2 is hydrogen or optionally substituted C1-4alkyl.

[0099] In the above formula (II), Y1 is preferably fluorine, chlorine or optionally substituted pyridinium which may be derived from, for example, nicotinic or isonicotinic acid or their carboxamides.

[0100] Each of R1 and R2 is preferably hydrogen, but at least one of R1 and R2 may be a C1-4 alkyl group and indeed R1 may additionally be an optionally substituted aryl, preferably phenyl, group.

[0101] When such a C1-4 alkyl or aryl group is substituted, a preferred substituent is hydroxyl, amino, halo, carboxy or sulpho.

[0102] In yet another alternative dye in accordance with the invention, Z1 is a halobenzene nucleus of the formula (I) and Z2 is a halopyrimidine nucleus of the formula 10

[0103] wherein

[0104] x is 1, 2 or 3; y is 0, 1 or 2; and x+y≦3;

[0105] Y21 or each Y2 independently, is halogen atom; and

[0106] U, or each U independently, is C1-4alkyl or C1-4alkylsulphonyl.

[0107] In the above formula (III) Y2 is preferably fluorine or chlorine.

[0108] A preferred range of dyes embodying the invention has the formula (XXX)

Z1-L1-D[L3]q-[Z3-L4r[J1]s[L2]aZ2[L5-J2]t  (XXX)

[0109] wherein:

[0110] Z3 is a third reactive group selected from the groups of the formulae (I)-(III), given and defined above;

[0111] each of J1 and J2, independently, is an optionally substituted aryl group or a chromophore;

[0112] L3 is a linking group linking Z3 and D;

[0113] L4 is a linking group linking Z3 and J1;

[0114] L1 is a linking group linking Z2 and J2;

[0115] each of q, r, s and t independently, is zero or 1;

[0116] each of Z1, Z2, L1, L2 and a is as defined above; and

[0117] when at least one of a and t is 1, Z2 is selected from the groups of the formulae (I)-(III), given and defined above.

[0118] In one such range of dyes, q is 1, r is 1, s is 1, each of a and t is zero and Z2 is selected from the groups of the formulae (IV)-(VI), given and defined above.

[0119] In another such range, q is 1, r is 1, s is zero, a is zero and t is 1.

[0120] In a dye of the formula (XXX), each of L3 and L41 independently, is preferably selected from one of the groups of the formulae (VII)1, (VII)2 and (VII)3, given and defined above;

[0121] each of L3 and L4 is preferably a group of the formulae (VII)1, given and defined above.

[0122] 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 L3 is preferably a group of the formula (VII)3

—N(R)BN(R)—  (VII)3

[0123] wherein B is a triazine group substituted by a non-reactive group.

[0124] 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.

[0125] Yet another range of dyes embodying the invention has the formula

Z1-L1-D1[L3-Z3(L4-Z4)lL5-D2]k[L2]aZ2

[0126] wherein:

[0127] D1 is a first chromophore;

[0128] D2 is a second chromophore;

[0129] Z3, when present, is a third reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 1;

[0130] Z4, when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 1;

[0131] L3 is a linking group linking Z3 to D1;

[0132] L4 is a linking group linking Z3 to Z4;

[0133] L1 is a linking group linking D2 to one of Z3 and Z4;

[0134] each of k and l, independently, is zero or 1; and

[0135] each of Z1, Z2, L1, L2 and a is as defined in claim 1.

[0136] In one range of such dye of formula (XXXI), a is 1, Z2 is a group of the formula (I), given and defined above, k is zero and D1 is a tetrakisazo chromophore containing two residues of H-acid linked together by a group forming part of the chromophore.

[0137] In another such range, a is 1, each of Z1 and Z2 is a group of the formula (I), given and defined above, each of k and l is 1;

[0138] each of D1 and D1 is a disazo chromophore containing a respective residue of H-acid,

[0139] each of Z3 and Z4 is a group of the formula (II), given and defined above, and

[0140] L4 is a linking group of the formula (VII)2 or (VII)3, given and defined above.

[0141] In still further such ranges

[0142] (i) a is 1, Z2 is a group of the formula (I), given and defined above, k is 1 and l is 1; or

[0143] (ii) a is 1, Z2 is a group of the formula (I), given and defined above, k is 1 and l is zero.

[0144] Yet another preferred range of dyes embodying the invention has the formula (XXXII)

Z1-L1-Z3-L3-D-Z2  (XXXII)

[0145] wherein:

[0146] Z3 is a third reactive group selected from the groups (I)-(III), given and defined above; and

[0147] L3 is a third linking group selected from the groups (VII)1, (VII)2 and (VII),3 given and defined above;

[0148] Z2 is a second reactive group selected from the groups (IV)-(VI), given and defined above; and

[0149] each of Z1 and L1 is as defined above.

[0150] In such dyes of the formula (XXXII), L1 is preferably a linking group of the formula (VII)2 or (VII)3, given and defined above and Z3 is preferably a group of the formula (II), given and defined above.

[0151] Another range of dyes embodying the invention has the formula (XXXIII)

D-L2-Z2-L1-Z1  (XXXIII)

[0152] wherein:

[0153] Z2 is selected from groups of the formulae I-(III), given and defined above; and

[0154] each of D, Z1, L1 and L1 is as defined above.

[0155] In such dyes of the formula (XXXIII), Z2 is preferably a group of the formula (II), given and defined above and L2 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

[0156] L1 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.

[0157] 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.

[0158] Another preferred chromophore D is a group of the formula 11

[0159] Other ranges of dyes embodying the invention are of the respective formulae

D2-L2-Z2-L3-D1-L1-Z1  (XXXIV)

[0160] wherein:

[0161] each of D1 and D2, independently, is a chromophore;

[0162] L3 is a linking group selected from groups of the formula (I)-(III), given and defined above; and

[0163] each of Z1, Z21 L1 and L2 is as defined above; and 12

[0164] wherein:

[0165] each of D1 and D21 independently, is a chromophore;

[0166] L3 is a linking group selected from the groups of the formulae (I)-(III), given and defined above; and

[0167] each of Z1, Z2, L1 and L2 is as defined above; and 13

[0168] wherein:

[0169] one of Z3 and Z4 is a reactive group Z2;

[0170] each of Z3 and Z4, independently, is a reactive group selected from the formulae (IV)-(VI), given and defined above;

[0171] each of t and u, independently, is zero or 1 and at least one of t and u is 1;

[0172] D is a chromophore;

[0173] Ar is an optionally substituted aryl group;

[0174] L1 is a group of the formula 14

[0175] wherein each R, independently, is as defined in claim; and

[0176] Z1 is as defined above.

[0177] In such dyes of formulae (XXXVI), D is preferably a disazo dye containing a residue derived from H-acid.

[0178] 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 15

[0179] wherein each of B,R and b is as defined above and the bond {circle over (1)} is linked to the heterocyclic nitrogen atom of the chromophore.

[0180] Such dyes, may have the formula

Z1-L1-DN&Brketopenst;L2&Brketclosest;a Z2 &Brketopenst;L5—Ar]t

[0181] wherein:

[0182] DN is a chromophore containing a heterocyclic group including a nitrogen atom;

[0183] L1 is a group of the formula (VII)4 or (VII)5, given and defined above, directly attached via the bond {circle over (1)}, to the nitrogen atom of the said chromophore DN;

[0184] Ar is an optionally substituted aryl group;

[0185] and each of Z1, Z2, L2, L5, a and t is as defined above.

[0186] A typical chromophore D containing a heterocyclic nitrogen atom has the formula 16

[0187] In the above formulae, wherever L1-L5, J1, J2 or B is or has an optionally substituted phenyl group, optional substituents are SO3H or a salt thereof, C1-4alkyl, especially methyl and chloro, especially SO3H.

[0188] Again, in all of the above formulae, where the groups Z2 is any of the groups of the formulae (I)-(III), it is most preferably of the formula (II).

[0189] Likewise in all such formulae, where Z2 i s any of the groups (IV)(VI), it is most preferably of the formula (IV) or (V), wherein Z is zero.

[0190] 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 “D1” in formula (I) of U.S. Pat. No. 5,484,899, which is incorporated herein by reference.

[0191] Preferred azo groups are monoazo and disazo groups. Preferred monoazo groups have the formula

—Ar1—N═N—Ar2—

[0192] wherein Ar1 is an aryl or heteroaryl group and Ar2 is an aryl group.

[0193] 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.

[0194] A first preferred monoazo group is of the Formula (IX) (or salt thereof): 17

[0195] wherein:

[0196] Ar1 is an aryl group, preferably a benzene or naphthalene nucleus;

[0197] R3, or each R3 independently, is C1-4 alkyl, nitro, halo or sulphonic acid or a salt thereof;

[0198] c is zero or 1 to 4;

[0199] R4, or each R4 independently, is a sulphonic acid or a salt thereof; and

[0200] d is 1 or 2;

[0201] and is more preferably of the formula: 18

[0202] wherein each of Ar1R3 and a are as defined above, R4 is sulpho and c is zero or 1.

[0203] Ar1 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 C1-4 alkyl, more especially methyl; an acylamido radical, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy radical, especially C1-4 alkoxy, more especially methoxy.

[0204] 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.

[0205] 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.

[0206] Preferred optional substituents which may be present on the naphthalene nucleus of Formula (IX) are those mentioned above for Ar1.

[0207] Groups of the Formula (IX) are preferably linked to a group L1 or L2 at the 6-, 7- or 8-position, especially the 6- or 8-position. When L1 or L2 is to be linked at the 8-position, it is preferred that R5 is a sulpho group at the 5- or 6- position.

[0208] Thus a preferred monoazo dye embodying the invention has the formula (XVII) 19

[0209] wherein:

[0210] each R independently and a is as defined above;

[0211] one of Z3 and Z4 is a group Z1 and the other is a group Z2;

[0212] the group Z4 is selected from the groups of the formulae (I)-(III), given and defined above.

[0213] Ar1 is a benzene or naphthalene nucleus;

[0214] R3, or each R3 independently, is C1-4 alkyl, nitro, halo or sulphonic acid or salt thereof;

[0215] c is zero or 1-4;

[0216] R4, or each R4 independently, is a sulphonic acid or a salt thereof; and

[0217] d is 1 or 2.

[0218] A preferred disazo group is of the Formula (XI) (or salt thereof):

Ar1—N═N—M—N═N—E  (XI)

[0219] wherein:

[0220] M and E are each independently optionally substituted phenylene or naphthalene; and

[0221] Ar1 is as defined above.

[0222] 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 C1-4 alkoxy; alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino, especially acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups.

[0223] 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.

[0224] An especially preferred range of disazo-dyes has the formula (XVIII) 20

[0225] wherein:

[0226] one of Z5 and Z6 is a group Z1 and the other is a group Z2;

[0227] each of f and g independently is zero or 1;

[0228] when Z5 or Z6 is any of the groups of the formulae (I)-(III), given and defined above, f or g respectively is 1 and when Z5 or Z6 is any of the groups of the formulae (IV)-(VI), given and defined above, f or g respectively is zero;

[0229] each of c and e, independently, is zero or 1-4;

[0230] d is 1 or 2;

[0231] each R independently is as defined above;

[0232] each of Ar1 and Ar2 independently is an optionally substituted aryl group; and

[0233] each of R3 and R4 is as defined above.

[0234] In a dye of the formula (XVIII), each of Z5 and Z6 may be the same group 21

[0235] wherein X, Y and n are as defined above.

[0236] Alternatively, one of Z5 and Z6 may be a group of the formula (I), given and defined above, and the other of Z5 and Z6 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 Z5 and Z6 is a group of the formula (I), given and defined above, and the other of Z5 and Z6 is a group of the formula (II).

[0237] Another especially preferred range of disazo dyes has the formula 22

[0238] wherein:

[0239] B is a hydrocarbon bridging group as defined above, and preferably an optionally substituted aryl group;

[0240] one of G1 and G2 is OH and the other is NH2;

[0241] each of X, Y, Y1, Ar1Ar2, R3, R4, R5, c, d and e is as defined above.

[0242] In a dye of the formula (XVIII), one of Z5 and Z6 may be a group 23

[0243] wherein: X, Y and n are as defined in claim 1 and the other of Z5 and Z6 is the group —SO2CH2CH2OSO3H or —SO2CH═CH2.

[0244] Typically such a dye has the formula 24

[0245] wherein

[0246] G3 is C2H4OSO3H or a salt thereof or —CH═CH2;

[0247] G1 and G2 are as defined above;

[0248] R4 and d are as defined above; and

[0249] each of h and i, independently, is zero, 1 or 2.

[0250] A more preferred range of such dyes has the formula 25

[0251] where each of G1 G2 and G3 is as defined above.

[0252] When the chromophore D is an anthraquinone, a preferred anthraquinone group is of the Formula (XII) (or a salt thereof). 26

[0253] 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.

[0254] 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.

[0255] A preferred anthraquinone dye of has the formula

DA-L3-Ar- L2-Z2- L1-Z1

[0256] wherein:

[0257] DA is an anthraquinone chromophore;

[0258] L3 is a linking of the formula (VII)1, given and defined above;

[0259] Ar is an optionally substituted aryl group;

[0260] and

[0261] each of Z1, Z2, L1 and L2 is as defined above.

[0262] More preferably each of L1 and L2, 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 L1 and L21 independently is a group of the formula (VII)3, given and defined above, in which B is an optionally substituted aryl group.

[0263] When the chromophore D is a phthalocyanine, a preferred phthalocyanine group is of the Formula (XIII) (or a salt thereof). 27

[0264] 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, V1 is a divalent organic linking group, preferably a C1-4-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.

[0265] Preferably such a metal phthalocyanine dye has the formula 28

[0266] wherein:

[0267] Cu Pc is a copper phthalocyanine chromophore;

[0268] X+Y+Z≦4;

[0269] each of R21 and R22, independently, is hydrogen or optionally substituted C1-4alkyl;

[0270] B is a hydrocarbon bridging group; and

[0271] Z1 is as defined above.

[0272] When the chromophore D is a triphenodioxazine a preferred triphenodioxazine group is of the Formula (XIV) (or a salt thereof). 29

[0273] wherein:

[0274] each Y3 independently is a covalent bond, C2-4-alkylene, phenylene or sulphophenylene;

[0275] U1 is H or SO3H; and

[0276] T1 and T2 are halo, especially chloro, C1-4-alkyl, or C1-4 alkoxy.

[0277] Each Y3 is preferably —CH2H4— or —C3H6—, U1 is preferably SO3H and T1 and T2 are preferably Cl, methyl or ethyl.

[0278] Preferably such a triphendioxazine dye has the formula

Z1-L1-[Z3-L3]q-DT-[Z4]r-L2-Z2

[0279] wherein:

[0280] DT is a triphendioxazine chromophore;

[0281] each of L2, L3 and L4, independently, is a linking group of the formula (VII)11 (VII)2 or (VII)3 given and defined above;

[0282] each of Z2, Z3 and Z4 is a reactive group selected from groups of the formulae (I)-(III), given and defined above;

[0283] each of q and r is zero or 1; and

[0284] each of Z1 and L1 is as defined above.

[0285] In such a dye, Z2 is preferably a group of the formula (I), given and defined above and each of Z3 and Z4 is a group of the formula (II), given and defined above; and each of L1, L2, L3 and L4 is preferably a group of the formula (VII)3, given and defined above.

[0286] When the chromophore D is a formazan, a preferred group is of the Formula (XV) (or a salt thereof). 30

[0287] wherein:

[0288] X1 is H, SO3H or Cl; and

[0289] each r independently has a value of 0, 1 or 2.

[0290] provided that the formazan group has at least one, and preferably at least two, sulpho groups.

[0291] It is preferred that each r has a value of 1.

[0292] Preferably such a formazan dye has the formula

[ZA]a-DF-L-ZB-L1-Z1

[0293] wherein:

[0294] DF is a formazan chromophore;

[0295] one of ZA and ZB is a group Z2, given and defined above;

[0296] each of L3 and L4 is a linking group of the formula (VII)1, (VII)2 or (VII)3, given and defined above;

[0297] each of Z1 and L1 is as defined above;

[0298] a is zero or 1;

[0299] ZA is selected from groups of the formulae (IV)-(VI), given and defined above; and

[0300] Z8 is selected from groups of the formulae (I)-(III),given and defined above.

[0301] According to one process aspect, the invention provides a process for preparing a dye of the formula (VIII)1

Z1 -L1-D-L2-Z2  (VIII)1

[0302] wherein:

[0303] D is a chromophore;

[0304] each of L1 and L2 independently, is N(R);

[0305] each R, independently, is hydrogen or C1-4-alkyl;

[0306] each of Z1 and Z2 is a group 31

[0307] in which:

[0308] n is 1 or 2

[0309] X, or each X independently, is an electron withdrawing group; and

[0310] Y is a halogen atom,

[0311] which process comprises reacting a chromophoric compound of the formula (XX)

H(R)N-D-N(R)H  (XX)

[0312] 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) 32

[0313] wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII)1.

[0314] 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 on 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.

[0315] According to another process aspect, the invention provides a process for preparing a dye of the formula (VIII)1

Z1-L1-D-L2-Z2  (VIII)2

[0316] wherein:

[0317] D is a chromophore;

[0318] each of L1 and L2 independently, is N(R);

[0319] each R, independently, is hydrogen or C1-4alkyl;

[0320] Z1 is a group 33

[0321] in which:

[0322] n is 1 or 2

[0323] X, or each X independently, is an electron withdrawing group; and

[0324] Y is a halogen atom; and

[0325] Z2 is selected from the groups (II) and (III) defined above;

[0326] which process comprises reacting a chromophoric compound of the formula (XX)

H(R)N-D-N(R)H  (XX)

[0327] 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

[0328] (a) a dihalobenzene compound of the formula (XXI) 34

[0329] wherein each of Z, X, Y and n is as defined above; and

[0330] (b) a compound selected from 35

[0331] wherein:

[0332] 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;

[0333] Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and

[0334] T is C1-4alkoxy, C1-4thioalkoxy or N(R1) (R2), in which each of R1and R2 independently is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl;

[0335] x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;

[0336] Y2, or each Y2 independently, is a halogen atom or an optionally substituted pyridinium group;

[0337] U or each U independently, is C1-4alkyl or C1-4alkylsulphonyl; and

[0338] Y is as defined above;

[0339] 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 (VIII)2.

[0340] According to yet another process aspect, the invention provides a process for preparing a dye of the formula (VIII)3

Z1-L1-D-Z2  (VIII)3

[0341] wherein:

[0342] D is a chromophore

[0343] L1 is N(R), in which R is hydrogen or C1-4alkyl;

[0344] Z1 is a group 36

[0345] in which n 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)

—SO2 CH2 CH2 X1  (IV)

[0346] wherein

[0347] X1 is an eliminatable group;

[0348] a group of the formula (V)

—SO2(CH2)2CH═CH2  (V)

[0349] wherein

[0350] z is zero or 1; and

[0351] a group of formula (VI)

—W—C(R10)═CH2  (VI)

[0352] wherein:

[0353] R10 is hydrogen, C1-4alkyl or halogen; and

[0354] W is —OC(═O)— or —N(R11)C(═O)—

[0355] in which R11 is hydrogen or C1-4alkyl;

[0356] which process comprises reacting a chromophoric compound of the formula (XXIV)

H(R)N-D-Z2  (XXIV)

[0357] wherein D and Z2 are as defined above, with a dihalobenzene compound of the formula (XXI) 37

[0358] wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII)3.

[0359] 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.

[0360] The dyes may be used for dyeing, printing or ink-jet printing, for example, of textile materials and paper.

[0361] 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.

[0362] The substrate may be any of a textile material, leather, paper, hair or film, but 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.

[0363] 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.

[0364] 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.

[0365] At least for cellulosic materials, exhaust dyeing can be carried out at a relatively low temperature of about 50-70° C., especially about 60° C.

[0366] 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 can be carried out at a constant or substantially constant pH, that is to say that the pH 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.

[0367] The dyes may be in a liquid form, or solid form, for example in granular or powdered form.

[0368] 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.

[0369] In addition, a wide selection of dye backbones is possible, giving the potential to provide high fastness dyes.

[0370] 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.

[0371] 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.

[0372] 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%.

[0373] The ink may also contain a humectant, which may also function as a water miscible 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-1,3-diol and 3-(3-hydroxy-prop-2-oxy)propan-2-ol.

[0374] 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 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-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.

[0375] 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.

[0376] 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.

[0377] 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

[0378] 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.

[0379] H-Acid (0.475M, 183 g) was dissolved in water (800 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.

[0380] The viscous suspension was adjusted to pH 6 using sodium hydroxide solution (46/48%) and a solution of a monoazo dye was thereby obtained.

[0381] 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 disazo dye solution.

[0382] Hydrolysis was then carried out by adding sodium hydroxide solution (46/48%, 800 g) to the above disazo dye solution (vol=5 L) and heating at 70-75° C. for 1.5 hrs.

[0383] The reaction mixture was cooled to 20° C. and neutralised by controlled addition of 35% hydrochloric acid. After screening to remove a small 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=68.3%).

[0384] The above diaminodisazo dye (0.01M, 11.78 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.

[0385] 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%) (λMax=607 nm; εMax=57,036).

Example 2

[0386] 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(λMax=607 nm; εMax=48,212).

Example 3

[0387] 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(λMax=607 nm; εMax=56,416).

Example 4

[0388] 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(λMax=608 nm; εMax=54,660).

Example 5

[0389] 4-Amino benzene sulphatoethylsulphone (0.1M, 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.

[0390] 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 reslurried 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%).

[0391] 3-Amino-5′-fluoro-2′,4′-dinitrodiphenylamine-4-sulphonic 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 0-2° 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.

[0392] 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%) (λMax=603 nm; εMax=54,279) of the structure given below: 38

Examples 6-61

[0393] Other disazo 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

[0394] Still further disazo 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

[0395] 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. 39

[0396] The N-dichlorotriazinyl derivative of the azo dye resulting from azo-coupling 7-aminonaphthalene-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 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 addition of sodium carbonate solution. On completion of the reaction, the pH was adjusted to 6.5 and the solution was concentrated to ca 100 ml. Methylated spirit was added, and the product dye was filtered, washed with meths and dried. λMax(water)=379 nm, εMax=33000 1 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

[0397] 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

[0398] Disazo naphthalene dyes containing two reactive groups attached to the chromophore as described in Example 68 are exemplified by Examples 78 to 97 listed in Table 4.

Examples 98-127

[0399] 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

[0400] Monoazo naphthalene dyes embodying the invention are listed in Tables 10 to 12.

Examples 161-189

[0401] A variety of dyes embodying the invention, containing blue and green chromophores, are listed in Tables 13 to 16.

Application Examples

Examples 190-192

[0402] 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

[0403] 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 fastness properties.

Examples 195-198

[0404] 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

[0405] 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 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 with a soap solution, rinsed with water, and dried to give cotton coloured a dull greenish blue shade.

Example 196

[0406] If the amount of dye used in Example 193 is doubled and the procedure repeated, a greenish-navy shade is obtained.

Example 197

[0407] If the amount of dye used in Example 193 is trebled and the procedure repeated, a dark navy shade is obtained.

Example 198

[0408] If six times the amount of dye in Example 193 is used and the procedure repeated, an almost black shade is obtained.

[0409] 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

[0410] Dyes embodying the present Invention may be applied to textile substrates, especially cotton, by conventional printing technology, as the following exemplifies.

[0411] 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 (48 degBe, 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

[0412] Dyes embodying the present invention may be used in the preparation of inks 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 parts) . When this solution was applied to cotton which had previously been pretreated (for example, with a pretreatment agent described in EP-A-0534660) by means of commercial ink-jet printing equipment, deep navy shades were obtained.

[0413] 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

[0414] 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 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 are simultaneously removed.

[0415] Dye from Example 1 (10 parts) was dissolved in water (100 parts) and treated on a reverse osmosis rig until 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 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 of 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 or black shades were imparted to the substrate, depending on the amount of dye applied.

Example 202

[0416] Dye from Example 1 was ion exchanged 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
40
			λmax nm
			(w1/2 nm)
Example	A	B	Colour on cotton
6	41	42	606 (121) greenish-navy
7	43	44	607 (105) greenish-navy
8	45	46	623 (121) dark bluish-green
9	47	48	618 (121) greenish-navy
10	49	50	603 (105) greenish-navy
11	51	52	618 (130) greenish-navy
12	53	54	614 (110) dark bluish-green
13	55	56	594 (112) greenish-navy
14	57	58	595 (108) greenish-navy
15	59	60	604 (110) dark bluish-green
16	61	62	645 (137) very dull dark green
17	63	64	604 (119) greenish-navy
18	65	66	603 (127) greenish-navy
19	67	68	600 (134) greenish-navy
20	69	70	596  120) greenish-navy
21	71	72	609 (111) greenish-navy
22	73	74	604 (120) greenish-navy
23	75	76	625 (104) greenish-navy
24	77	78	620 (112) dark bluish-green
25	79	80	632 (114) dark bluish-green
26	81	82	609 (141) dark bluish-green
27	83	84	602 (125) greenish-navy
28	85	86	605 (143) dark bluish-green
29	87	88	596 (129) greenish-navy
30	89	90	607 (109) greenish-navy
31	91	92	595 (107) greenish-navy
32	93	94	622 (123) greenish-navy
33	95	96	619 (114) dark bluish-green
34	97	98	606 (114) dark bluish-green
35	99	100	618 (113) dark bluish-green
36	101	102	616 (110) dark bluish-green
37	103	104	616 (106) greenish-navy
38	105	106	616 (111) dark bluish-green
39	107	108	608 (111) greenish-navy
40	109	110	608 (116) greenish-navy
41	111	112	608 (116) greenish-navy
42	113	114	616 (111) dark bluish-green
43	115	116	615 (120) dark bluish-green
44	117	118	615 (118) dark bluish-green
45	119	120	greenish-navy
46	121	122	dark bluish-green
47	123	124	greenish-navy
48	125	126	dark bluish-green
49	127	128	greenish-navy
50	129	130	dark bluish-green
51	131	132	greenish-navy
52	133	134	dark bluish-green
53	135	136	dark bluish-green
54	137	138	greenish-navy
55	139	140	dark bluish-green
56	141	142	dark bluish-green
57	143	144	greenish-navy
58	145	146	greenish-navy
59	147	148	dark bluish-green
60	149	150	dark bluish-green
61	151	152	greenish-navy

[0417]

TABLE 2
153
			λmax nm
			(w1/2 nm)
Example	A	B	Colour on cotton
62	154	155	609 (118) dull dark green
63	156	157	608 (112) dull dark green
64	158	159	630 (130) daull dark green
65	160	161	Greenish-navy
66	162	163	Greenish-navy
67	164	165	Greenish-navy

[0418]

TABLE 3
166
				Colour on
Example	L	λmax nm	w1/2 nm	cotton
69	167	415	139	Golden yellow
70	168	367	140	Golden yellow
71	169	403	200	Golden yellow
72	170	419	200	Golden yellow
73	171	366	119	Golden yellow
74	NHC2H4NH	410	170	Golden
				yellow
75	172	378	155	Golden yellow
76	173	389	150	Golden yellow
77	174	360	160	Golden yellow

[0419]

TABLE 4
175
Exam-					Colour on
ple	A	B	X	Y	cotton
78	176	177	NH2	OH	Greenish navy
79	178	179	OH	NH2	Greenish navy
80	180	181	NH2	OH	Greenish navy
81	182	183	OH	NH2	Greenish navy
82	184	185	NH2	OH	Greenish navy
83	186	187	OH	NH2	Greenish navy
84	188	189	NH2	OH	Greenish navy
85	190	191	OH	NH2	Greenish navy
86	192	193	NH2	OH	Greenish navy
87	194	195	OH	NH2	Greenish navy
88	196	197	NH2	OH	Greenish navy
89	198	199	OH	NH2	Navy
90	200	201	NH2	OH	Navy
91	202	203	OH	NH2	Greenish navy
92	204	205	NH2	OH	Greenish navy
93	206	207	OH	NH2	Greenish navy
94	208	209	OH	NH2	Greenish navy
95	210	211	NH2	OH	Greenish navy
96	212	213	OH	NH2	Greenish navy
97	214	215	OH	NH2	Greenish navy

[0420]

TABLE 5
216
Example	Structure	λmax nm	w1/2 nm	Colour on cotton
98	Dye-SC2H4OH	407	148	Golden yellow
99	Dye-N(CH3)Ph	403	138	Golden yellow
100	Dye-NHC2H4SO3H	407	129	Golden yellow
101	Dye-NHC2H4OC2H4OH	412	134	Golden yellow
102	Dye-NHC6H3-m-SO3H	409	143	Golden yellow
103	Dye-NHC2H4NH-Dye			Golden yellow
104	217	412	130	Golden yellow

[0421]

TABLE 6
218
Example	Structure	λmax nm	w1/2 nm	Colour on cotton
105	Dye-SC2H4OH	437	151	Mid yellow
106	219	430	135	Mid yellow
107	Dye-NHC2H4OC2H4OH	436	141	Mid yellow
108	220	435	132	Mid yellow
109	221	439	143	Mid yellow
110	222	438	149	Mid yellow
111	223	437	131	Mid yellow
112	Dye-NHC2H4NH-Dye			Mid yellow
113	Dye-NHC3H6NH-Dye			Mid yellow

[0422]

TABLE 7
		λmax nm
		(w1/2 nm)
Exam-		Colour on
ple	Structure	cotton
114	224	435 (172) mid yellow
115	225	422 (148) golden yellow
116	226	406 (124) golden yellow

[0423]

TABLE 8
227
Example	228		Other substituents	Colour on cotton
117	4-	1,3-(SO3H)2	3′-SO2C2H4OSO3H	Yellow
118	3-	1,4-(SO3H)2	2′-SO2C2H4OSO3H	Yellow
119	4-	1,1′-(SO3H)2	229	Yellow
120	4-	1,1′-(SO3H)2	230	Yellow
121	4′-	1,1′,4-(SO3H)3	231	Yellow

[0424]

TABLE 9
232
Example	A	B	X	Y	Colour on cotton
122	233	234	H	H	Greenish-yellow
123	235	236	H	CN	Greenish-yellow
124	237	238	H	CONH2	Greenish-yellow
125	239	240	C2H4OH	H	Greenish-yellow
126	241	242	C2H4OH	CONH2	Greenish-yellow
127	243	244	H	H	Greenish-yellow

[0425]

TABLE 10
245
Example	A	B	X	Y	Colour on cotton
128	246	247	SO3H	H	Blueish red
129	248	249	SO3H	H	Blueish red
130	250	251	H	SO3H	Blueish red
131	252	253	SO3H	H	Blueish red
132	254	255	SO3H	H	Blueish red
133	256	257	H	SO3H	Blueish red
134	258	259	SO3H	H	Blueish red
135	260	261	SO3H	H	Blueish red
136	262	263	SO3H	H	Blueish red
137	264	265	H	SO3H	Blueish red
138	266	267	SO3H	H	Blueish red

[0426]

TABLE 11
268
				Colour on
Example	A	B	X	cotton
139	269	270	H	Red
140	271	272	SO3H	Red
141	273	274	H	Red
142	275	276	SO3H	Red
143	277	278	H	Red
144	279	280	SO3H	Red
145	281	282	SO3H	Red
146	283	284	SO3H	Red
147	285	286	H	Red
148	287	288	H	Red
149	289	290	SO3H	Red

[0427]

TABLE 12
291
Exam-					Colour on
ple	A	B	X	Y	cotton
150	292	293	H	H	Reddish yellow
151	294	295	H	SO3H	Reddish yellow
152	296	297	Me	H	Reddish yellow
153	298	299	H	H	Reddish yellow
154	300	301	H	H	Orange
155	302	303	H	SO3H	Orange
156	304	305	Me	H	Orange
157	306	307	H	H	Orange
158	308	309	H	H	Orange
159	310	311	H	SO3H	Orange
160	312	313	Me	H	Orange

[0428]

TABLE 13
314
Example	A	Colour on cotton
161	315	Greenish blue
162	316	Greenish blue
163	317	Greenish blue
164	318	Greenish blue

[0429]

TABLE 14
319
							Colour on
Example	R	R′	RΔ	x	y	z	cotton
165	320	H	H	2	0	2	Green
166	321	H	H	1.5	0.5	2	Green
167	C2H4	H	H	2	0	2	Bluish-
							green
168	C3H6	CH3	CH3	1.7	0.3	2	Bluish-
							green
169	322	H	C2H4OSO3H	2.5	0.5	1	Green
170	323	H	H	1.5	1.5	1	Green
171	324	H	C2H4SO3H	2.5	0	1.5	Green
172	325	H	H	3	0	1	Green

[0430]

TABLE 15
326
Example	A
173	327
174	328
175	329
176	330
177	331
178	332
179	H
180	333
181	334
				Colour
				on
Example	B	X	Y	cotton
173	335	Cl	Cl	Blue
174	336	Cl	Cl	Blue
175	337	Cl	Et	Blue
176	338	Cl	Cl	Greenish blue
177	339	Cl	Et	Greenish blue
178	340	Cl	Cl	Greenish blue
179	341	Cl	Cl	Greenish blue
180	342	Cl	Me	Blue
181	343	Cl	Cl	Greenish blue

[0431]

TABLE 16
344
			Colour on
Example	A	X	cotton
182	345	H	Dull greenish blue
183	346	H	Dull greenish blue
184	347	Dull greenish blue
185	348	H	Dull greenish blue
186	349	H	Dull blue
187	350	H	Dull greenish blue
188	351	3-SO3H	Dull greenish blue
189	352	4-SO2C2H4OSO3H	Dull greenish blue

Claims

1. A dye containing at least one chromophore D; at least a first, halobenzene, reactive group Z1, of the formula (I) 353in 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 Z2 selected from (1) a group of the formula (I), given and defined above, but selected independently thereof; (2) a group of the formula (II) 354wherein 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 C1-4alkoxy, C1-4thioalkoxy or N(R1) (R2), in which each of R1 and R2 independently is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl; (3) a group of the formula (III) 355wherein: 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 C1-4alkyl or C1-4alkylsulphonyl; (4) a group of the formula (IV)—SO2CH2CH2X1  (IV)wherein X1 is an eliminatable group; (5) a group of the formula (V)—SO2(CH2)zCH═CH2  (V)wherein z is zero or 1; and (6) a group of formula (VI)—W—C(R10)═CH2  (VI)wherein: R10 is hydrogen, C1-4alkyl or halogen; and W is —OC(═O)— or —N(R11)C(═O)— in which R11 is hydrogen or C1-4 alkyl; at least a first linking group L1, linking the said first, halobenzene, reactive group Z1 to one of components (i) the or a chromophore D and (ii) the second reactive group Z2, which said first linking group L1 presents an amino nitrogen to the reactive group Z1 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 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 when Z2 is selected from the said groups (I)-(III), at least a second linking group L2 linking the second reactive group Z2 to one of (i) the or a chromophore D and (ii) the said first reactive group Z1, which said linking group L2 is selected from (1) a linking group L1, but selected independently thereof; or (2) an amide linkage; and (3) a sulphonamide linkage; and optionally at least one aromatic group Ar which, when Z2 is selected from the said groups (IV)-(VI), may carry the said reactive group Z2.

2. A dye according to claim 1, wherein the linking group L1 has the formula (VII)1

3. A dye according to claim 1, wherein the linking group L1 is a piperazinoalkylamino group of the formula (VII)2

4. A dye according to claim 1, wherein the linking group L1 has the formula (VII)3

5. A dye according to claim 4, wherein the hydrocarbon bridging group B is an optionally substituted aryl group.

6. A dye according to any preceding claim, of the formula (VIII)

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 Y1, or each Y independently, is 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 Z1 and Z2, independently, is a group:

11. A dye according to claim 10, wherein each of Z1 and Z2 is the same as the other.

12. A dye according to any one of claims 1 to 9, wherein a is 1 and Z2 is

13. A dye according to any one of claims 1 to 9, wherein a is 1 and Z2 is

14. A dye according to any one of claims 1 to 9, wherein a is zero and Z2 is

15. A dye according to any preceding claim, wherein D is an azo chromophore.

16. A dye according to claim 15, wherein D is a monoazo chromophore.

17. A dye according to claim 16, which has the formula (XVII)

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)

20. A dye according to claim 19, wherein each of Z5 and Z6 is the same group

21. A dye according to claim 19, wherein one of Z5 and Z6 is a group of the formula (I), given and defined in claim 1, and the other of Z5 and 6 Z is selected from groups of the formulae (II) and (III), given and defined in claim 1.

22. A dye according to claim 18, which dye has the formula

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 Z5 and Z6 is a group

25. A dye according to claim 24, which has the formula

26. A dye according to claim 25, which has the formula

27. A dye according to claim 1, of the formula

28. A dye according to claim 27, wherein q is 1, r is 1, s is 1, each of a and t is zero and Z2 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 any one of claims 27 to 29, wherein each of L3 and L4, independently, is selected from one of the groups of the formulae (VII)1, (VII)2 and (VII)3, given and defined in claim 6.

31. A dye according to claim 30, wherein each of L3 and L4 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, s is 1, a is zero and t is zero.

33. A dye according to claim 32, wherein L3 is a group of the formula (VII)3

34. A dye according to any one of claims 27 to 33, wherein the chromophore D is an azo chromophore derived from 1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic acid group.

35. A dye according to claim 1 of the formula

36. A dye according to claim 35 wherein a is 1, Z2 is a group of the formula (I), given and defined in claim 1, k is zero and D1 is a tetrakisazo chromophore containing two residues 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 Z1 and Z2 is a group of the formula (I), given and defined in claim 1, each of k and l is 1; each of D1 and D2 is a disazo chromophore containing a respective residue of H-acid, each of Z3 and Z4 is a group of the formula (II), given and defined in claim 1, and L4 is a linking group of the formula (VII)2 or (VII)3, given and defined in claim 6.

38. A dye according to claim 35, wherein a is 1, Z2 is a group of the formula (I), given and defined in claim 1, k is 1 and l is 1.

39. A dye according to claim 35, wherein a is 1, Z2 is a group of the formula (I), given and defined in claim 1, k is 1 and l is zero.

40. A dye according to claim 1, of the formula

41. A dye according to claim 40, wherein L1 is a linking group of the formula (VII)2 or (VII)3, given and defined in claim 6.

42. A dye according to claim 40 or claim 41, wherein Z3 is a group of the formula (II), given and defined in claim 1.

43. A dye according to claim 1, of the formula

44. A dye according to claim 43, wherein Z4 is a group of the formula (II), given and defined in claim 1.

45. A dye according to claim 43 or claim 44, wherein L2 is a linking group selected from the groups (VII)1, (VII) 2 and (VII)31, given and defined in claim 6.

46. A dye according to claim 43, wherein L2 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 claims 43 to 46, wherein L1 is a group of the formula (VII3) , given and defined in claim 6, in which B is an optionally substituted aryl group.

48. A dye according to any one of claims 43 to 46, wherein L1 is a group of the formula (VII3) , given and defined in claim 6, in which B is a chromophoric bridging group.

49. A dye 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 1, of the formula

52. A dye according to claim 1, of the formula

53. A dye according to claim 1, of the formula.

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 1, wherein the or a chromophore D contains a heterocyclic nitrogen atom and the linking group has the formula

56. A dye according to claim 55, of the formula

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 dye according to claim 15, wherein D is a trisazo or tetrakisazo chromophore.

60. A dye according to claim 1, wherein the chromophore D is an anthraquinone.

61. A dye according to claim 60, which is of the formula

62. A dye according to claim 61, wherein each of L1 and L2, independently, is a linking group of the formula (VII)1, (VII)2 or (VII)3, given and defined in claim 6.

63. A dye according to claim 62, wherein each of L1 and L2, independently is a group of the formula (VII)3, given and defined in claim 6, in which B is an optionally substituted aryl group.

64. A dye according to claim 1, wherein the chromophore D is a metal phthalocyanine.

65. A dye according to claim 64, of the formula

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

68. A dye according to claim 67, wherein Z2 is a group of the formula (I), given and defined in claim 1 and each of Z3 and Z4 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 L1, L2, L3 and L4 is a group of the formula (VII)3, given and defined in claim 6.

70. A dye according to claim 1, wherein the chromophore D is a formazan chromophore.

71. A dye according to claim 70, of the formula

72. A dye of the formula

73. A dye of the formula

74. A dye of the formula

75. A dye of the formula

76. A dye of the formula

77. A dye of the formula

78. A process for preparing a dye of the formula (VIII)1

79. A process for preparing a dye of the formula (VIII)1

80. A process for preparing a dye of the formula (VIII)3

81. A process for the colouration of a substrate, which process comprises applying to the substrate a dye according to any one of claims 1 to 77.

82. A process according to claim 81, wherein the dye is applied to the substrate by exhaust dyeing, padding or printing.

83. A process according to claim 82, wherein the dye is applied by ink jet printing.