Title of Invention

"PROCESS FOR THE MANUFACTURE OF A COLOURED SYNTHETIC MATERIAL OR FIBRE BLEND THEREOF"

Abstract

A process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) -. Formula (1) wherein: A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one -SO2F group or carries a substituent to which at least one -S02F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted l-phenyl-pyrazol-4-yl-5-one or or that one of A or D does not carry an -NCH2CH(OH) CH2C1, -NCOCH2C1 or -NCH2CH2S02F substituent. The presence of one or more -S02F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet fastness and light fastness properties.

Full Text

The present invention relates to a process for the manufacture of a coloured synthetic textile material by application thereto of a dispersion, in an aqueous medium of an azo dye compound. GB-A-856, 348.. relates to water insoluble monoazo dyestuffs and discloses one specific dye containing a 4— fluorosulphonylnaphth—l-yl group which is excluded from the present claims. GB—A—819, 664 relates to water insoluble monoazo dyestuffs and discloses two specific dyes both of which are excluded from the present claims. IJS-A-2,576,037 relates to the coloration of cellulose acetate with certain -SO2F containing azo dyes. Such dyes, particularly those which also contain —NC2H4OH groups or derivatives thereof are dye bath unstable and as such are unsuitable for coloration of polyester textile materials. According to the present invention there is provided a process for the manufacture of a coloured synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a dispersion comprising an aqueous medium and, dispersed therein, from 0.001% to 4% of a dye compound or mixture thereof, which is free from water solubilising groups, under process conditions selected from the following: i) exhaust dyeing at a pH of from 4 to 6.5 at a temperature of from 1250C to 1400C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, in which process a seguestrant may be optionally added; ii) continuous dyeing at a pH of frofn 4 to 6.5, at a temperature of from 1900C to 2250C for from 15 seconds to 5 minutes, in ~Thich a migration inhibitor may optionally be added; iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 160CC to 1850C for 4 to 15 minutes for high temperature steaming, or at a temperature of from 1900C to 2250C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 1200C to 1400C and 1 to2 bar for 10 to 45 minutes for pressure steaming, in which process wetting agents and thickeners of from 5 to 100% by weight of the dye may be optionally be added; iv) discharge printing (by padding the dye onto the textile material, drying and overprinting) at a pH of from 4 to 6.5, in which process migration inhibitors and thickeners may optionally be added; v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 950C to 1000C using a carrier, in which process sequestrants may optionally be added; and vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 850C for acetate or at a temperature of 900C for triacetate and nylon for from 15 to 90 minutes, in which process sequestrants may optionally be added; which dye compound has the formula A-N=N-D (1) wherein A and D each independently is an optionally substituted heterocylic or carboxylic group in which at least one of A and D carries directly at least one —SO2F group or carries a substituent to which at least one —SO2F group is attached and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and p carries directly at least one este r group or carries a substituent to which at least one ester group is attached; and (b) (i) the synthetic textile material is a polyester or fibre blend thereof; (ii) each of A and D independently is an optionally substituted phenyl group; and (iii) one of A and D carries a 4-SO2F group; except for (iv) 4—(4—fluorosulphonylphenylazo) --N,Ndimethylaniline; provided that (v) one of A and D does not carry an -NCH2CH (OH) CH2Cl, —NCOCH2Cl or -NCH2CH2SO2F substituent; and (c) (i) the synthetic textile material is a polyamide or aromatic polyester or fibre blend thereof; and (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae wherein: 1 2 R and R each independently is H or optionally substituted C16—alkyl or optionally substituted aryl; 3 4 5 6 R , R , R and R each independently is H, F, Cl, Br, I, —SO2F or C>6—alkyl, C16—alkoxy, C14alkanoylamino, -NHSWalkyl or —Ophenyl, each of which may be optionally subs t it u ted; R, R8 and R9 each independently is H, C16-alkyl, N02, -COOC1 —CN, formyl, protected formyl or -S02.F provided that at least one of R' to R9 is —SO2F or carries a substituent to which at least one —SO2F' group is attached and provided that R7 and R9 are not both —SO2F; and wherein R' and R2 each independently is H or optionally substituted C16—alkyl; R3 is optionally substituted C16—alkyl or C16—alkoxy; R4 is optionally substituted C16—alkyl or C16-alkoxy; R10 is optionally substituted C1~-alkyl, NO2 or Cl; 15 18 R to R each in dependently is H, C1 alkoxy, F, Cl, Br, I, -SO2F, NO2, CN or -NR R 12 R is NO2 or —SO2F; R" is H; and R'3 and R14 each in dependently is -H or —Cl; provided that (iii) one of the nuclei A and D does not carry an -NCH2CH (OH) CH2Cl, —NCOCH2Cl or -NCH2CH2SO2F substituent; and (d) (i) the synthetic textile material in an aromatic polyester or fibre blend thereof; and (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from corripounds of the formulae wherein: 1 2 P and R each independently is H or optionally substituted C16—alkyl or optionally substituted aryl; 3 4 5 6 R , R , R and R each independently is H, F, Cl, Br, I, -SO2F or C16—alkyl, C16-alkoxy, C14alkanoylamino, -NHSO2alkyl or —Ophenyl, each of which may be optionally substituted; R7, P8 and R9 each independently is H, C16—alkyl, NO2, —C00C16—alkyl, —OCOalkyl, Cl, F, Br, I, —C0C16-alkyl, -CN formyl, protected formyl or —SO2F provided that at least one of P' to R9 is —SO2F or carries a substituent to which at least one —SO2F group is attached and provided that R7 and P9 are not both -1-SO2F; (4) wherein: P1 and P2 each independently is H or optionally substituted C16—alkyl or optionally substituted aryl; 3 4 5 6 d R10, P11, P'3 and R14 each independently is H, alkoxy, alkyl, NO2, —SO2F, F, Cl, Br, I or —CN; except for 4- (4-fluorosulphonylphenylazo) -N,Ndimethylaniline; in which 1 2 P and R each independently is optionally substituted C16—alkyl; P4 is alkyl or a group of Formula -N(R'9)—Y-X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, 20 alkyleneOalkylene, alkyleneNHalkylene, —N(R )—Z-, -COOZor -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneaalkylene, alkyleneNHalkylene or a direct link and P20 is H, alkyl, aryl or alkylaryl, W is 21 21 21 -CO2R , —OCOR or -OH in which P is alkyl., aryl, alkylaryl, alkylOalkyl or alkylOH, and P19 is H or alkyl; P5 is H, C16-alkoxy or -Ophenyl; P'0 is NO2 or Cl; and P13 and P'4 each independently is H or Cl; and wherein: P' and P2 each independently is H or optionally substituted C16—alkyl; P3 is optionally substituted C16—alkyl or C16—alkoxy; P4 is optionally substituted C16—alkyl or C,6-alkoxy; 10 optionally or P is substituted C>6-alkyl, NO2 Cl; 15 18 P to P each independently is H, Cj 12 P is NO2 or- -SO2 F; 11 P is H; and 13 14 P and P each independently is H or Cl; provided that one of the nuclei A and D does not carry an -NCH2CH2SO2F substituent; and (e) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae CH3 F02 (278) whereby a coloured synthetic textile material is obtained. Different compounds of Formula (1) may be mixed or the compounds of Formula (1) may be mixed with dyes which do not contain an —SO2F group. The mixtures may be simple physical mixtures or may be mixed crystals formed for example by co-crystallisation. Such mixtures generally show improvement in dyeing properties. Crystalline modifications of compounds of Formula (1) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment. The presence of one or more -SO2F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet-fastness and light-fastness properties. According to a first embodiment of the present invention there is provided a process for manufacturing a coloured synthetic textile material or fibre blend thereof which comprises apply to the synthetic textile material, under the conditions set out above, an aqueous dispersion of an azo dye compound or mixture thereof, which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A or D carries directly at least one —SO2F group or carries a substituent to which at least one -SO2F group is attached and at least one of A or D carries directly at least one ester group or carries a substituent to which at least one ester group is attached, in accordance with requirement (a) above. Azo dyes containing both an —SO2F and an ester group have improved performances in wash fastness properties over azo dyes carrying only an —SO2F group. The synthetic textile material may be selected from secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile and aromatic polyester. The synthetic textile material is preferably polyamide or aromatic polyester, more preferably aromatic polyester such as polyhexamethylene adiparnide or pdlyethylene terephthalate and especially polyethlene terephthalate. Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are those of polyester celllulose such as polyester—cotton. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn, woven or knitted fibres. According to a second embodiment of the present invention there i~s provided a process for manufacturing a coloured polyester textile material or fibre blend thereof which comprises applying to the polyester textile material, in accordance with requirement (b) above, an aqueous dispersion of an azo dye compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D each independently is an optionally substituted phenyl group and one of A and D carries a 4—SO2F group, except for 4—(4— fluorosulphonylphenylaZO) —N,N—dimethylaniline, provided that one of A and D does not carry an -NHCH2CH(OH)CH&l, -NCOCH~Cl or -NCH2CH2SO2F substituent. According to a third embodiment of the present invention, there is provided a process for manufacturing a coloured polyamide or aromatic polyester textile material or fibre blend thereof, which comprises applying to the textile material, in accordance with requirement (c) above, an aqueous dispersion of an azo dye compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are such as to provide a dye compound selected from compounds of the formulae (3) and (5), as defined above in relation to requirement (c) In particular, it will be noted that the respective definitions of Formulae (3) and (5) include the proviso that one of the nuclei A and D does not carry an NCH2CH(OH)CH2Cl, -NCOCH2Cl or -NCH2CH2SO2F substituent. According to a fourth embodiment of the present invention, •there is provided a process for manufacturing a coloured polyester textile material or fibre blend thereof, which comprises applying to the textile material, in accordance with requirement (d) above, an aqueous dispersion of an azo dye compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are such as to provide a dye compound selected from compounds of the formulae (3), (4), (5) and (7), as defined above in relation to requirement (ci) In particular, it will be noted that these respective definitions of the Formulae (3), (4), (5) and (7) include the proviso that one of the nuclei A and D does not carry an —NCH2CH2SO2F group. Moreover, in the definition of Formula (4) in relation to requirement (d) above, ~l2 ~ SO2F R'0 P~1, R'~ and R'4 each independently is H, alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or —CN, and the compound 4—(4— fluorosulphonylphenylazo) -N, N-dimethylaniline is excluded. According to a fifth embodiment of the present invention, there is provided a process for manufacturing a coloured synthetic textile material or fibre blend thereof, which comprises applying to the textile material, in accordance with requirement (e) above, an aqueous dispersion of an azo dye dompound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are such as to provide a dye compound selected from compounds of the formulae (267), (268), (269), (273), (275), (276), (277) and •(278), as defined above in relation to requirem~nt'(e) above. The dye compounds of Formula (1). preferably have low solubility in water, typically less than 1% preferably less than 0.5% and especially less than 0.2% solubility in water. The dyes of Formula (1) are thus free from water solubilising groups such as —SO3H, -CO2H, —PO3H and quaternary amino. The dye compounds of Formula (1), optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends thereof by methods which are conventionally employed in dyeing disperse dyes to such materials and fibre blends. The process conditions may be selected from the following i) exhaust dyeing at a pH of from 4 to 6.5, at a temperature of from 1250C to 1400C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar; a sequestrant may be optionally added; ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 1900C to 2250C for from 15 seconds to 5 minutes; a migration inhibitor may optionally be added; iii). printing direct at a pH of from 4 to 6.5, at a temperature of from 1600C to 1850C for ~4 to 15 minutes for high temperature steaming, or at a temperature of from 1900C to 2250C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 1200C to 1400C and 1 to 2 bar for 10 to 45 minutes for pressure steaming; wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may be optionally be added; iv) discharge printing (by padding the dye onto the textile material, drying and overprinting) at a pH of from 4 to 6.5; migration inhibitors and thIckeners may optionally be added; v) carrier dyeing at a pH of froin 4 to 6.5, at a temperature of from 950C to 1000C using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol; sequestrants may optionally be added; and vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 850C for acetate or at a temperature of 900C for triacetate and nylon for from 15 to 90 minutes; sequestrants may optionally be added. In all of the above processes the dye compound of Formula (1) is applied as a dispersion comprising from 0.001% to 4% of the compound in aqueous medium. The azo dye compounds used in a process cf the invention generally provide coloured textile material which shows good fastness to washing, light and heat. Provided that at least one of the above defined requirements (a) — (e) is satisfied, the heterocvclic group represented by A and D may be selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4— and 1,3,4—thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3—triazolyl and 1,2,4—triazolyl. The carboxylic group represented by A or D may be phenyl or naphthyl. For the avoidance of doubt optionally substituted isoquinolinyl represented by A includes structures of the formula: in which m is from 1 to 4 and m is preferably 3. A and D each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl or quinolinyl, more preferably thien-2—yl, phenyl, naphth-lyl, naphth—2—yl, thiazolyl—2—yl, isothiazol—5—yl, pyrid4—one-5-yi or quinolinyl. A is especially preferably thien-2-yl or phenyl and D is especially preferably phenyl or naphth-l-yl. Examples of suitable substituents for A and D are cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, -trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, —Coalkyl, -COOalkyl, —OCOalkyl, -COaryl, -COCaryl, -OCOaryl, -NHCOalkyl, -NHCOaryl, —NHSO2aikyl, -NHSO2aryl, —Salkyl, —Saryl, -SO2alkyl, —SO2aryl, —SCN or —NP1P2 in 1 2 which R and. P each independently is —H, alkyl, aryl or cycloalkyl. All the alkyl, alkoxy, aryl, aryloxy parts of 1 2 the above substituents for A, D, P. and R may optionally be substituted by —OH, -CN, —F, —Br, -I, -SO2F, alkoxy, alkenyl, phenyl, phenylSO2F, aryloxy, aryloxySO2F, —N(alykl)2, —OCOalkyl, -OCOalkylCl, —COOalkyl, -COOalkylOH, -COOalkylCN, -COOalkylCOalkyl, -CoOalkylphenyl, -OCO phenyl, -COphenylSO2F, -OCOphenylNO2, —OCOphenylalkyl, -OCOphenylalkoxy, -COaphenyl, -OCO(fluorosulphonylphenyl), -OalkylCN, -COOalkylOalkyl, -COOalkylOphenyl, -OCOalkylOphenyl, -COOalkylOalkylOalkyl, —OCOalkylCOOalkyl, -OalkylCOOalkyl, -OalkylCOOalkylOalkyl, -OalkylCOOalkylCOOalkYl, -OalkylOCOalkylOalkyl, -COOalkylOCOalkyl, -COOalkylCOOalkyi, in which L is —H or alkyl. In all of the suitable substituents for A and D each alkyl is preferably C110—alkyl, each alkoxy is preferably C1,c-alkoxy, each alkenyl is preferably C28-alkenyl, each of which may be straight or branched chain, each aryl is preferably phenyl or Paphthyl and each heterocyclic group may be any of the groups described above for A and D and each alkyl, alkoxy, alkenyl, aryl, heterocyclic or phenyl 1 2 group may carry an -SO2F substituent. P and P together with the —N atomto which they are attached may form a 5-or 6— membered ring such as morpholino or piperidino. A further suitable substituent for A and D is a group of Formula -N(R'9)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, optionally substituted alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, 20 alkyleneNHalkylene or -NP -Z- or -O—Z- in which Z is optionally substituted alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and ~2O is -H, optionally substituted alkyl, aryl or alkylaryl, 21 21 21 W is -CO2P , -OCOR , -OH or -CN in which P 15 optionally substituted alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, P~9 is —H or optionally substituted alkyl. 1920 21 Where X, Z, P , P or P 15 or contains alkyl it is preferably C18—alkyl, more preferably C16-alkyl, each of which may be straight or branched chain or cyclic alkyl. Where X or Z is alkenyl it is preferable C28-alkenyl which may be straight or branched chain or cyclic 20 21 alkenyl. Where X, Z, R or P is aryl it is preferably phenyl or naphthyl, more preferably phenyl. Where X or Z is heterocyclic it may be selected from any of the heterocyclic groups defined above for A. Where X, Z or P is alkylOalkyl it is preferably C16—alkylOC1~6—alkyl, each alkyl of which may be straight or branched chain and the alkylOalkyl group may be cyclic ether. Where X or Z is alkylNHalkyl it is preferably C,6—alkylNHC1~6—alkyl in which each alkyl may be straight or branched chain and P21 is alkylaryl it is preferably C,6—alkylaryl, more preferably C16—alkylphenyl and especially benzyl or ethylphenyl. Where ~2l is alkylOH it is preferably C16-alkylOH. The optional substituents for any of the groups represented by x, z, ~l9, ~20 or may be selected from any of the optional substituents listed for A, D, P' or 2 P. Preferred substituents for A and D are cyano, nitro, chloro, bromo, fluorosulphonyl, C~6—alkyl, C,~-alkoxy, —C0C16—alkyl, —NHCOC16—al kyl, -OCOC,6—alkyl, -COOC,6-alkyl, phenoxy, 4-SO2Fphenoxy., P'9NYXW in which 19 12 R , Y, X and W are as herein before defined and -NP P in which P3 and ~2 each independently is -H, C16—alkyl, C,6-alkyl substituted by -OH, -CN, -Cl, phenyl, —OCOC1~6—alkyl, -COOC,6—alkyl, -COOC1~-aIkYi -COOC1~-aIkYi —C,4—alkyl (4—fluorosulphonylphenyl), -OCO (3-fluorosulphonylphenyl), ~OCO(4-fluorosulphony1phenyl), -C24—alkenyl, ~COOC16—alkylOC1~6-alkyl, -0C16-alkylCN, ~ -COOalkylOCOalkyl and -COOalkylCOOalkyl or where R' and ~2 together with the —N atom to which they are attached form a morpholino or piperidino ring. The compounds of Formula (1) preferably carry a total of from one to three —SO2F groups, more preferably one or two —SO2F groups and especially one -SO2F group. The compounds of Formula (1) more preferably carry one —SO2F group and one ester group. A number of compounds of Formula (1) used in the above coloration process are novel. In particular, compounds of the formula (1), which satisfy the above requirement (a) are novel compounds. In these compounds, each of A and D independently is an optionally substituted heterocyclic or carbocyclic group, at least one of A and D carries directly at least one —SO2F group or carries a substituent to which at least one, -SO2F group is attached and at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached. In an azo dye compound, used in a process according to a first embodiment of the invention, A and D each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl or pyridonyl, more preferably thienyl, phenyl, thiazolyl, isothiazolyl, or pyridonyl and especially thien-2-yl, phenyl, thiazol-2-yl, isothiazol-5—yl or pyrid-4-one-5-yl. B' is preferably phenyl. Preferred compounds of Formula (1) in which, in accordance with the first embodiment of the invention requirement (a) is satisfied, are those in which A is phenyl and D is phenyl; A is thien-2-yl and D is phenyl; and A is phenyl and D is naphth—l-yl. The optional substituents for A and D are any of those defined for A and D above. Other preferred groups of novel compounds within Formula (1) for use in processes embodying the invention are those of Formulae (3), (4), (7) and (5), defined successively below. In particular, for processes according to the first, third and fourth embodiments of the invention, an azo dye compound of Formula (3) may be employed, provided that respective requirements (a), (c) and (d), defined above, are satisfied. Formula (3) wherein: P and R each is optionally 1 2 independently —H or substituted C,6—alkyl or optionally substituted aryl; P3, P4, P5 and P6 each independently is -H, —F, -Cl, —Br, -I, -SO2F or C16-alkyl, C16-alkoxy, C14alkanoylaminO, -NHSO2alkyl or Ophenyl, each of which may be optionally substituted; R7, P8 and P9 each independently is —H, C] -NO2, -COOC,6-alkyl, -OCOalkyl, —Cl, -F, -Br, -I, -COC,~6-alkyl, -CN, formyl, protected formyl or -SO2F provided that at least one of P1 to P9 is —SO2F or carries a substituent to which at least one -SO2F group is attached and provided that P7 and P9 are not both -SO2F. Where P', R8 and P9 is or contains alkyl the alkyl may be optionally substituted. Protected formyl groups include for example oxazolidone, imidazoline, thiazolidine, i~isulphite, cyanohydrin, hydrazone and oxime. The compounds of Formula (3) are novel. The optional substituents for groups represented by P' to P9 may be selected from any of the substituents described above for A and D. The optional substituents for P1 to P9 are preferably —CN, —OH, -0C0C16—alkyl, -COOC,6-al kyl, phenyl, -OCOphenyl, -OCOphenyl SO2F, phenylSO2F, -OphenylSO2F, -CO2phenylSO2F -COOC1-6— alkylOCOC,-6—alkyl and ~COOC16-alkylCOOC1~6—alkyl. Preferred compounds of Formula (3) are those in which P' and ~2 each independently is -CH3, -C2H5, -C2H4CN, —C2H4OH, —CH (CH3) CH2CH3, —C4H9, -CH2 (4-fluorosulphonylphenyl), -C2H4 (4-fluorosulphonylphenyl), ~C3H7(4-fluorosulphonylphenyl), P3. R4, P5 and P6 each independently is -H, —Cl, -CH3, -OCH3, -NHCOCH3, —NHCOC2H5, -NHSO2CH3 or -SO2F and R7, r~i and R9 each independently is -H, -NO2, -CN, -COCH3, -COOC2H5, -SO2F or -CH3 provided that both R7 and P9 are not -SO2F. Especially preferred compounds of Formula (3) are those in which 1 2 P and P each independently is -C2H4CN, -C2H5 or (4-fluorosulphonylphenyl) C16-alkyl; P3 is —H, —OCH3, —CH3 or -SO2F; P4 and P5 each independently is -H, —Cl or —SO2F; P6 is -H, —NHCOCH3, —NHCOC2H5, —CH3 or -SO2F; R~ is -NO2, -COCH3, —COOC2H5 or -SO2F; 8 R is -H, -SO2F or -Cl; and R9 is —NO2, -SO2F or —CHO. For processes according to second and fourth embodiments of the invention, an azo dye compound of Formula (4) may be employed, provided that respective requirements (b) and (d), defined above, are satisfied. R11 R'0 R4 Ri2 N=N N R1 R13 Ri4 ~6 wherein: 1 2 P and P each independently is H or optionally substituted C,6—alkyl or optionally substituted aryl; 3 4 5 6 R , P , P and P each independently is H, F, Cl, Br, I, —SO2F or C16—alkyl, C16-alkoxy, C,4—alkanoylamino, -NHSO2alkyl or -Ophenyl each of which may be optionally substituted; 12 R is -SO2F; and 10 11 13 14 R , P , P and P each independently is H, alkoxy, alkyl, NO2, —SO2F, F, Cl, Br, I or -CM. For a process according •to a first embodiment of the invention, an azo dye compound of Formula (4) ' may be employed, provided that requirement (a), defined above, is satisfied, i.e. provided that the compound contains an ester group. Formula (4) wherein: 1 P and R2 each independently is 1-I or optionally substituted C16-alkyl or optionally substituted aryl; P3, P4, P5 and P6 each independently is H, F, Cl, Br, I, —SO2F, or C,6—alkyl, C,~—alkoxy, C,4alkanylamino, NHSO2alkyl or -Ophenyl, each of which is optionally substituted; and P'0 to P'4 each in dependently is —H, alkoxy, alkyl, —NO2, -SO2F, —F, -Cl, —Br, —I or —CM; 10 12 11 13 provided that when P is SO2F, P is not —NO2 and P , P 14 and P are not all -H. In formulae (4) and (4) ' as appropriate, where a group represented by p10 to ~lLi is a ikyl it is preferably C,10-alkyl, more preferably C16-alkyl. Where a group represented by R'0 to P'4 is a lkoxy it is preferably C110-alkoxy, more preferably C16—alkoxy. Compounds of Formulae (4) and (4) are preferably those in which P and P each is —C2H5, -C3H7, 1 2 independently -C4H9, -C5H11, -C6H13, -CH (CH3) CH2CH3, —CH2phenyl, —C2H4phenyi,. -C3H6phenyl, —C2H4CN, -C2H4OH, -C2H4OCH,, -C2H4COOCH3, -C4H8COCH3, -C2H4COCH3, -C2H4OCOCH3, -C3H6OCOCH3, —C4H8OCOCH3, -C2H4OCOphenyl, -C2H4OCOphenyl (SO2F), -C2H4COOC2H4OCH3, -C2H4OC2H4COOC2H4OCH3, allyl, -C2H4Ophenyl, -C2H40 (fluorosulphonylphenyl), -CH2CH (CN) (0C2H4), C,~-alkylph -COOC,6-alkylOCOC,6-alkyl or -COOC,6-alkylCOOC1~6—alkyl; P3 is —H, —OCH3 or -Cl; P4 is -H, —CH3, -NHCOCH3, -NHCOC2H5, TNHCOCH(CH3)2, -NHCOC3H6Cl, -NHCOC (CH3) ~ -OCH3, -0C4H9, —F, —Cl, —Br, -I or -NHSO2C16alkyl; P5 is -H, —OCH3, -0C2H5 or -Cl; P6 is —H, —CH3, -OCH3, -F, —Cl, Br, -I or —NHSO2C,.~6—al kyl; P'0 is -H, -OCH3, -NO2, Cl, -Br or -CN; P'1 is —H; 12 P is —SO2F or -NO2; P'3 is —H, -OCH3, —SO2F, —Cl, —Br or -NO2F; and P'4 is —H, -OCH3, —Cl, -Br or —CN, provided that at least one of P3 or P5 is —H and that at least one of P4 or P6 is -H. More preferably compounds of Formula (4) are those in which 1 2 R and R each independently is -C2H5, -C4H9, -CH (CM3) CH2CH3, —C2H4OCOCH3, -C4H8OCOCH3, -C2H4OCOphenyl, -CH2phenyl, C16—alkylphenylSO2F, C,6-alkylOphenylSO2F, -COOC1~-aIkYi -C00C16-alkYi -COOC,6-alkylOCOC1~~6alkyi or ~COOC16-alkylCOOCi~o-alkyl P4 is —H, -CH, or -NHCOCH-,; P¾ K p~ and Pa' are -H; plC and p13 each independently is —H, —Cl, —Br or —NO2; P'2 is —SO2F; and R'4 is -H, —Cl or -Br. An especially preferred compound of Formula (4) is that in which P' is -C2H5; P' is —C,H4OCCphenyl; P4 is —CH3; 10 3 5 6 11 P and p13 are both —Cl; P12 is —SO2F; and P , P , P , P and R"~ are all —H. For processes according to the first, second, third and fourth embodiments of the invention, an azo dye compound of Formula (7) may be employed, provided that respective requirements (a), (b), (c) and (d) are satisfied and provided that when used in a process according to a first aspect of the invention, then in Formula (7), when ~ is a group of Formula —N(P'9 )—Y—X—W, 21 W is othe in which P and P each is optionally 1 2 independently substituted C,6—alkyl; P4 is aikyl or a group of Formula —N(R'9)—Y-X—W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, 20 alkyleneOalkylene, alkylene-NH—alkylene, —NR -Z—, —COOZ or -O—Z in which Z is alkvlene, alkenylene, arylene, heterocyclic, alkyleneoalkylene, alk~lene-MH—alkylene or a direct link and p~0 is —H, alkyl, aryl or alkylaryl, W 21 21 is —CO2P , —OCOR or —OH in which R~ is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and P' ~ is -H or alkyl; • P5 is -H, C,6—alkoxy or -Ophenyl; P'0 is —NO2 or -Cl; and P'3 and P'4 each independently is -H or -Cl. In the dyes of Formula (7) P' and P2 each independently is preferably C16-alkyl or Ca6-alkyl substituted by phenyl or -COOCP6—alkyl, and more preferably is ethyl, propyl, butyl, 1-methyipropyl, hexyl, benzyl, ethyiphenyl or propylphenyl. P4 is preferably a group of Formula -N(P'9)-Y-X-W in which R'9 is preferably —H or C,6—alkyl, more preferably -H; Y is preferably a direct link or C 0, more preferably C 0; X is preferably a direct link, C,8—alkylene, C28-alkenylene, any of the carbocyclic or heterocyclic groups defined above for A, C,6-alkylOC,.6-alkyl, -MP20-Z—, -COOZ or -O—Z— in which~ P20 is preferably -H, C,6—alkyl, phenyl or benzyl; and Z is preferably a direct link or C16—alkylene, C28— alkenylene, phenyl, benzyl or any of the heterocyclic groups defined above for A. X is more preferably a direct link, CH2, C2H4, 20 CH2C(CH3)2, cyclohexyl, CH CH, phenyl, -MR -Z, —COOZ or -O-Z- in which 20preferably direct P is preferably -H, Z is a link, C16alkyl or benzyl. 21 ~1 W is —CO2P , —OCOP~ or —OH in which P" is C,~—alkyi, phenyl, chlorobenzyl, C,6—alkoxybenzyl, benzyl, C1~— alkylOC,~6-alkyl or C,6—alkylOH more preferably ethyl. methyl, butyl or 1,3—dimethylbutyl. Dyes in which both A and D are phenyl and in which one of A and D carries a 4—SO2F group are gen~rally more stable and build up better on polyester textile material than do the corresponding 2-SO2F dyes. For processes according to first, third and fourth embodiments of the invention, an azo compound of Formula (5) may be employed, provided that respective requirements (a), (c) and (d) are satisfied. Formula (5) wherein: 1 2 P and P each independently is H or optionally substituted C,6alkyl; P3 is optionally substituted C16alkyl or C,6alkoxy; P4 is optionally substituted C,6alkyl or C,~alkoxy; P'0 is optionally substituted C,8alkyl, NO2 or Cl; and P to P each is -H, -F, -Cl, -Br, 15 18 independently -I, -SO2F, —NO2, -CM, —NP,P2, OH or optionally substituted —C,6-alkyl or C16—alkoxy; 12 P is NO2 or -SO2F; P" is H; and R~ and P'4 each independently is H or Cl. The optional substituents for any of the groups represented by P'5 to P'8 may be selected from any of optional substituents described above for A, D, P1 and P~. Compositions comprising dispersions of the compounds of Formula (1) in aqueous media are used in a process of the present invention. The compositions typically comprise from 1% to 30% of a compound of Formulae (1) in an aqueous medium. The compositions are preferably buffered at pH 2 to 7 more preferably at pH 4 to 6. For use, they may be diluted to provide a dye concentration therein of from 0.001% to 4%. These dispersions may further comprise ingredients conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl ethoxylates which may be sulphonated or phosphated, inorganic salts, de—foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the compound of Formulae (1) . Wetting agents may be used at from 0% to 20% on the weight of the compound (1) . The dispersions may •be prepared by bead milling the compound of Formula (1) with glass beads or sand in an aqueous medium. The compounds of Formula (1) may be obtained by usual methods for the preparation of azo compounds such as by diazotisation of an amine of Formula A—NH2 and coupling onto a component D-X in which A and D are as hereinbefore defined and X is a group displaceable by a diazotised amine. Typically the amine, A-NH2 may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from —100C to 100C. Coupling onto the component D—X may be achieved by adding the diazotised amine to a mixture of D-X in an alkanol such as methanol at a temperature from 0CC to 100C. After coupling the compound of Formula (1) may be recovered from the reaction mixture by any convenient means such as by filtration. Fluorosulphonyl groups.may be introduced into the compounds of Formula (1) or into the A and D components prior to coupling by methods generally available in the literature. For example reaction of the compound of Formula (1), A-NH2, the NH2 being protectedas necessary, or D-X, in which A, and D are as hereinbefore defined, with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 300C to 1400C gives the chlorosulphonyl derivative. The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative. Alternatively the compound of Formula (1), A-NH2 or D—X may be sulphonated with sulphuric acid or oleum to give the suiphonic acid derivative which may be converted to the chlorosuiphonyl derivative by reaction, either of the free acid or an inorganic salt thereof, with thionylchloride optionally in the presence of a chlorophosphorus compound such as phosphorus oxychioride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 200C to 1100C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphcnyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above. The compounds of Formulae (1) are useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which have excellent wet and light fastness properties. Therefore, the present invention provides for a process for the manufacture of a coloured synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a dispersion comprising an aqueous medium and, dispersed therein, from 0.001% to 4% of a dye compound or mixture thereof, which is free from water solubilising groups, comprising: exhaust dyeing at a pH of from 4 to 6.5 at a temperature of from 1250C to 1400C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, in which process a sequestrant of the kind such as herein described may be optionally added; which dye compound has the formula A-N=N-D (1) wherein A and D each independently is an optionally substituted heterocyclic or carboxylic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached; and (b) (i) the synthetic textile material is a polyester or fibre blend thereof; (ii) each of A and D independently is an optionally substituted phenyl group; and (iii)one of A and D carries a 4-SO2F group; except for (iv) 4- (4-f luorosulphonylphenylazo) -N,Ndimethylaniline; provided that (vii) one of A and D does not carry an -NCH2CH (OH) CH2Cl, -NCOCH2Cl OR -NCH2CH2SO2F substituent; and (c) (i) the synthetic textile material is a polyamide or aromatic polyester or fibre blend thereof and; R6 (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae: wherein R' and R2 each independently is H or optionally substituted C, ~alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I,-SO2F or C16alkyl, C,~alkoxy, C, 4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; 7 8 R , R and R9 each independently is H, C16alkyl, NO2,-COOC~6alkyl, -OCOlakyl, Cl, F, Br, I,-COC,~ 6alkyl, -CN, formyl, protected formyl or SO2F provided that at least one of R' to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F; and R12 (5) wherein R' and R2 each independently is H or optionally substituted C,~alkyl; R' is optionally substituted C,~alkyl or C1~ ~alkoxy; —32- R6 R4 is optionally substituted C,~6alkyl or C, 6alkoxy; R10 is optionally substituted C,~alkyl, NO2 or Cl; R'5 to R'8 each independently is H, C1~6alkyl, C~ 6alkoxy, F, Cl, Br, I, -SO2F, NO2, CN or -NR1R2; 12 R is NO2 or -SO2F; R" is H; and R" and R'4 each independently is -H or -Cl; provided that (iv) one of the nuclei A and D does not carry an -NCH2CH (OH) CH2Cl, -NCOCH2Cl or -NCH2CH2SO2F substituent; and (ci) (i) the synthetic textile material in an aromatic polyester or fibre blend thereof; and (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae herein R' and R2 each independently is H or optionally substituted C16alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I,-SO2F or C1~6alkyl, C16alkoxy, C1 4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; 7 8 R , R and R~' each independently is H, C1.6alkyl, NO2, -COOC16alkyl, -OCOalkyl, Cl, F, Br, I, - COC,~alkyl, -CN formyl, protected formyl or - SO2F provided that at least one of R' to P. is - SO2F or carries a substituent to which at least R13~ one -SO2F group is attached and provided that P.7 and P.9 are not both -SO2F; wherein: P.' and R2 each independently is H or optionally substituted C16alkyl or optionally substituted aryl; R', R4, P.5 and P.6 each independently is H, F, Cl, Br, I, -SO,F or C16alkyl, C,~alkoxy, C, 4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; P.'2 is —SO2F; and P.'0 , P." , P." and P.'4 each independently is H, alkoxy, alkyl, NO9, -SO,F, F, Cl, Br, I or -CN; except for 4- (4-fluorosulphonylphenylazo) -N,Ndimethylaniline; in which 2 P.' and P. substituted P.4 is alkyl in which Y direct link, each independently is optionally C16alkyl; or a group of Formula -N(R'9)-Y-X-W is a direct link or C = 0, X is a alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(P.20) -Z,-COOZ- or -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and P.20 is H, alkyl, aryl or 21 21 alkylaryl, W is -C02P. , -OCOP. or -OH in which 21 P. is alkyl, aryl, alkylaryl, alkyloalkyl or alkylOH, and R~ is H or alkyl; R5 is H, C16alkoxy, or -Ophenyl; P.'0 is NO2 or Cl; and P." and P.'4 each independently is H or Cl; and wherein: P.' and P.2 each independently is H or optionally substituted C,~alkyl; P.' is optionally substituted C16alkyl or C, 6alkoxy; P.4 is optionally substituted C,6alkyl or C, 6alkoxy; P.'0 is optionally substituted C,~alkyl, NO2 or Cl; P.'5 to P.'8 each independently is H, C,~alkyl, C, 6alkoxy, F, Cl, Br, I, SO2F, NO2, -CN or -NP.'P.2; 12 P. is NO2 or -SO2F; P." is H; and P." and P.'4 each independently is H or Cl; provided that one of the nuclei A and D does not carry an -NCH2CH2SO2F substituent; and (e) in the formula (1) , each of A and D is such as to provide a dye compound selected from compounds of the formulae whereby a coloured synthetic textile material is obtained. The invention is further illustrated by the following Examples. Example 1 Preparation of 4-(2,5—dichloro-4- fluorosulphonylphenylazO) -3-methyl-N—ethyliN (2-benzoyloxyethyl) aniline i) Preparation of 2, 5-dichloro-4-chlorosulphOnylaniline 2,5—Dichloroaniline (32.4 parts) was added portionwise to chlorosulphonic acid (93 parts) at 350C. The mixture was stirred at 1200C for 3hrs and then cooled to 700C. Dimethyl formamide (1.6 parts) and thionyl chloride (15 parts) were added, maintaining the temperature at 65 — 700C and the mixture stirred at 700C for 24 hours. The reaction mixture was cooled to ambient temperature and poured with caution onto stirred ice (1000 parts) producing a cream precipitate. The product was isolated by filtration, washed acid-free with ice/water and dried under vacuum to yield 2,5-dichloro-4-chlorosulphonylaniline (44.2 parts) ii) Preparation of ~,5~~j~hloro-4—fluOrO5ulphOnylaniline A mixture of ~ (44.2 parts), potassium flucride(3~ parts) and water (200 parts) was stirred under ref)ux fcr S hours. ~ reaction mixture was cooled to ambient temuerature and drowned into water t300parts). The cream precipitate was isc3ated by tiltraticn, washed with water and dried under vacuum to yi~ld; 2.$-dich'lorc'-4-fluorbsvlphony]an±line (37.2 parts) iii)Preparation of 3.methvJ-~-ethv]-N-f2-benzovlo~ethyl)arij3ine Fenzoyichloride (3.3g) was added to a mixture of N-ethy2-.~-hvdro'ethyl-~methylani2ine (2.lg) in acetone (25cm3) and pyridine (2cm3) an~.st~rred at ref2ux ~t I ~ The react.ion mixture was coo2ed and used ~irect2v in iv) ~e3dw iv) Preparat cn o: 4- (2.5-dichloro-4-f2ucrosui~honv2ohenvlazo~~3-inethv]-N-ethv>N- (2'benzovlcxvethv] )ani2ine • Nitrosy) su~.phuric acid (3cm3 of 4O~) was added to a mixture of 2,5-dichIoro-4-fluorosulphon~lanh].ine (29) in acetic/propionic acid (eE:24, 25cm3) at 00C to 50C. The mixture was stirred at OW to 50C for 2 hours before'addino the reaction mixture from iii) above in methanol (200cm3) at 00C to 50C. The precipitated solid •was collected by fi2t~'ation, washed with water. slurried with methanol, ~Qlle.~tedby fi2tz~ation and washed with inethanol to give 4- (2,5~dichloro-4-f2uorosulphonylphenylazo)-3-rnethyl-N-ethyl-N- (2-ben~oy]oxyethy2)aniline (2.lg) when applied to polyester rn~terials from aqueous dispersion gives bluish-red shades with ~xce]lent wet apd light fastness prdperti.es. The followin9 exampJes of dyes of Formula: Prenarat ion of N, N-diethylani line -'-I 4- ~ Prenaration of 2,6-dibromo ~ ~l"'~osulohorrvlaniline To a solution of 4-amincbenzenesulphonyl fluoride (10 parts) in acetic acid (100 parts), stirring at 0-50C, was added gradually a solution of bromine (18 parts) in acetic acid (50 parts); keeping the temuerature below 50C. The temperature was allowed to warm to ambient and the mixture was stirred at this temoerature for a further lhr. The reaction mass was drowned into water (500 parts) , the product was isolated by filtration, washed with cold water and dried at 500C to yield; 2,C-dibromo-4-fluorosulphonylaniline (17.5 parts). ii) Preoarataon of 4- (2,6-dibromc-~-fluorosulohonvlrhenvlazo)-3-acetamido-N N—diethvlani line A mixture of 2,6-dibromo-4-fluorosulphonylanll2ne (2.7 parts) and acetic-/Propionic acid mixture (15 parts, 86/24 yol,/vol) was stirred and heated until a complete solution was formed The solution was set stirrino at 0-50C, and nitrosyl sulphuric acid soln (5 parts) was added dropwise The mixture was stirred at this temperature for a further 3Omin The diazo solution was added slowly to a mixture of 3-N,N-diethviamincacetanilide (1.7 parts) irethanol (50 Oarts) and sulchamic acid (0.5 parts); stirrino at 0~BcC After starrrng for lhr at this temperature, water (50 carts) was added and the mixture was starred a further 30mm at ambient terroerature. The product was isolated by filtration, washed with water ano methanol and then dried at 50CC to yield; 4- (2,6-dibrcmo-4-fltiOYOSiilOlnVlOh&nVlaZo)-3-aOCtCmidO-N,N-diethvlaniline (1.8 oarts.~ -2maxr480nm. When applied to polyester materials from an aqueous dispersion, the dye gaves oufl orange shades with excellent light fastness and excellent fastness to wet treatme•nts The following examples of dyes of Formula: Br were prepared by the procedure of Example 87: / WE CLAIM: 1. A process for the manufacture of a coloured synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a dispersion comprising an aqueous medium and, dispersed therein, from 0.001% to 4% of a dye compound or mixture thereof, which is free from water solubilising groups, comprising: exhaust dyeing at a pH of from 4 to 6.5 at a temperature of from 125°C to 140°C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, in which process a sequestrant of the kind such as herein described may be optionally added; which dye compound has the formula (Formula Removed) wherein A and D each independently is an optionally substituted heterocyclic or carboxylic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached; and (b) (i) the synthetic textile material is a polyester or fibre blend thereof; (ii) each of A and D independently is an optionally substituted phenyl group; and (iii) one of A and D carries a 4-SO2F group; except for (iv) 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline; provided that (v) one of A and D does not carry an -NCH2CH(OH)CH2C1, -NCOCH2C1 OR -NCH2CH2SO2F substituent; and (c) (i) the synthetic textile material is a polyamide or aromatic polyester or fibre blend thereof and; (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae: (Formula Removed)wherein R1 and R2 each independently is H or optionally substituted C1-6alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1-6alkyl, C1-6alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R7, R8 and R9 each independently is H, C1-6alkyl, NO2, -COOC1-6alkyl, -OCOlakyl, Cl, F, Br, I, -COC1-6alkyl, -CN, formyl, protected formyl or SO2F provided that at least one of R1 to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F; and (Formula Removed)wherein R1 and R2 each independently is H or optionally substituted C1-6alkyl; R3 is optionally substituted C1-6alkyl or C1-6alkoxy; R4 is optionally substituted C1-6alkyl or C1-6alkoxy; R10 is optionally substituted C1-6alkyl, NO2 or Cl; R15 to R18 each independently is H, C1-6alkyl, C1-6alkoxy, F, Cl, Br, I, -SO2F, NO2, CN or -NR1R2; R12 is NO2 or -SO2F; R11 is H; and R13 and R14 each independently is -H or -Cl; provided that (iii) one of the nuclei A and D does not carry an -NCH2CH(OH)CH2C1, -NCOCH2C1 or -NCH2CH2SO2F substituent; and (d) (i) the synthetic textile material in an aromatic polyester or fibre blend thereof; and (ii) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formula (Formula Removed)wherein R1 and R2 each independently is H or optionally substituted C1-6alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1-6alkyl, C1-6alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R7, R8 and R9 each independently is H, Ci-ealkyl, NO2, - COOC1-6alkyl, -OCOalkyl, Cl, F, Br, I, -COC1-6alkyl, -CN formyl, protected formyl or -SO2F provided that at least one of R1 to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F; (Formula Removed)wherein: R1 and R2 each independently is H or optionally substituted C1-6alkyl or optionally substituted aryl; R3, R4, R5 and RG each independently is H, F, Cl, Br, I, -SO2F or C1-6alkyl, C1-6alkoxy, C1-6alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R12 is -SO2F; and R10, R11, R13 and R14 each independently is H, alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or -CN; except for 4-(4-fluorosulphonylphenylazo)-N,N- dimethylaniline; (Formula Removed)in which R1 and R2 each independently is optionally substituted C1-6alkyl; R4 is alkyl or a group of Formula -N(R19)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z, -COOZ- or -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is H, alkyl, aryl or alkylaryl, W is -CO2R21, -OCOR21 or -OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is H or alkyl; R5 is H, C1-6alkoxy, or -Ophenyl; R10 is NOa or Cl; and R13 and R14 each independently is H or Cl; and (Formula Removed)wherein: R1 and R2 each independently is H or optionally substituted Ci-ealkyl; R3 is optionally substituted C1-6alkyl or Ci-ealkoxy; R4 is optionally substituted C1-6alkyl or Ci-ealkoxy; R10 is optionally substituted C1-6alkyl, NO2 or Cl; R15 to R18 each independently is H, C1-6alkyl, C1-6alkoxy, F, Cl, Br, I, SO2F, NO2, -CN or -NR'R2; R12 is NO2 or -SO2F; R11sH; and R13 and R14 each independently is H or Cl; provided that one of the nuclei A and D does not carry an -NCH2CH2SO2F substituent; and (e) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formula (Formula Removed) whereby a coloured synthetic textile material is obtained. 2. A process as claimed in claim 1, wherein requirement (a) is satisfied and in which A and D each independently is selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4-and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and naphthyl. 3. A process as claimed in claim 2, wherein A and D each independently is selected from thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl and quinolinyl. 4. A process as claimed in claim 3, wherein A and D each independently is selected from thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol- 2-yl, isothiazol-5-yl, pyrid-4-one-5-yl and quinolinyl. 5. A process as claimed in claim 4, wherein A is thien-2-yl or phenyl and D is phenyl or naphth-1-yl. 6. A process as claimed in claim 1, wherein the requirement (a), (c) and (d) is satisfied and in which the compound of Formula (1) has the formula (3) (Formula Removed) wherein R1 and R2 each independently is H or optionally substituted C1-6alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1- 6alkyl, C1-6alkoxy, C1-4alkanoylamino, -NHSO2alkyl or-Ophenyl, each of which may be optionally substituted; R7, R8 and R9 each independently is H, C1-6alkyl, NO2, -COOC1-6alkyl, -OCOalkyl, Cl, F, Br, I, -COC1-6alkyl, -CN, formyl, protected formyl or -SO2F provided that at least one of R1 to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F. 7. A process as claimed in claim 1, wherein requirement (b) or (d) is satisfied and in which the compound of Formula (1) has the formula (4) (Formula Removed) wherein: R1 and R2 each independently is H or optionally substituted Ci-ealkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1- 6alkyl, C1-6alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R12 is -SO2F; and R10, R11, R13 and R14 each independently is H, alkoxy, alkyl, NO2, - S02F, F, Cl, Br, I or -CN. 8. A process as claimed in claim 1, wherein requirement (b), (c) or (d) is satisfied and in which the compound of Formula (1) has the formula (Formula Removed) (7) in which R1 and R2 each independently is optionally substituted C1-6alkyl; R4 is alkyl or a group of Formula -N(R19)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z-, -COOZ- or -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is H, alkyl, aryl or alkylaryl, W is -CO2R21, -OCOR21 or -OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is H or alkyl; R5 is H, Ci-6alkoxy or -Ophenyl; R10 is NO2 or Cl; and R13 and R14 each independently is H or Cl. 9. A process as claimed in claim 1, wherein requirement (a), (c) or (d) is satisfied and in which the compound of Formula (1) has the formula (5) (Formula Removed)wherein R1 and R2 each independently is H or optionally substituted Ci-ealkyl; R3 is optionally substituted C1-6alkyl or Ci-ealkoxy; R4 is optionally substituted C1-6alkyl or Ci-ealkoxy; R10 is optionally substituted C1-6alkyl, NO2 or Cl; R15 to R18 each independently is H, C1-6alkyl, Ci-ealkoxy, F, Cl, Br, I, -S02F, N02, -CN or -NR'R2; R12 is NO2 or -SO2F; R11 is H; and R13 and R14 each independently is H or Cl. 10. A process as claimed in claim 1, wherein requirement (a) is satisfied and in which the compound of Formula (1) has the formula (41): (Formula Removed)wherein: R1 and R2 each independently is H or optionally substituted C1-6alkyl t or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1- 6alkyl, C1-6alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; and R10 to R14 each independently is H, alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or -CN; provided that when R10 is SO2F, R12 is not NOa and R11, R13 and R14 are not all H. 11. A process as claimed in claim 1, wherein requirement (a) is satisfied and in which the compound of Formula (1) has the formula (7) (Formula Removed) in which R1 and R2 each independently is optionally substituted Ci-ealkyl; R4 is alkyl or a group of Formula -N(R19)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z-, - COOZ- or -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or direct link and R20 is H, alkyl, aryl or alkyaryl, W is -CO2R21, or -OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is H or alkyl; R5 is H, C1-6alkoxy or -Ophenyl; R10 is NO2 or Cl; and R13 and R14 each independently is H or Cl. 12. A process for the manufacture of a coloured synthetic textile material or fibre blend thereof substantially as herein described with reference to and as illustrated in the foregoing examples.

Documents:

935-del-2002-abstract.pdf

935-del-2002-claims.pdf

935-del-2002-correspondence-others.pdf

935-del-2002-correspondence-po.pdf

935-del-2002-description (complete).pdf

935-DEL-2002-Form-1.pdf

935-del-2002-form-13.pdf

935-DEL-2002-Form-2.pdf

935-del-2002-form-3.pdf

935-DEL-2002-Form-4.pdf

935-DEL-2002-Form-5.pdf

935-del-2002-form-6.pdf

935-del-2002-gpa.pdf

935-del-2002-petition-137.pdf

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