Indian Patents. 190717:"A PROCESS FOR COLOURING SYNTHETIC TEXTILE MATERIAL"

Title of Invention	"A PROCESS FOR COLOURING SYNTHETIC TEXTILE MATERIAL"
Abstract	A process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a dye, which is free from water solubilising groups, carrying at least one -S02F group provided that the dye is not an azo, bisazo or anthraquinone dye.

Full Text	The present invention relates to a process for colouring synthetic textile material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof. ]P A-54-050681 discloses, in general terms, the use of fluorosulphonyl group-containing reactive disperse dyes for dyeing cellulose-containing textiles but discloses specifically only certain azo and anthraquinone dyes for this purpose. US-A-5503956 discloses a black laser dye-ablative recording element comprising a support, which may be a polyester, having thereon a dye layer comprising a mixture of at least one cy.in, magenta and yellow dye dispersed in a polymeric binder and having an infra red absorbing material associated therewith. There is no reference therein to dyes containing a fluorosulphonyl group. According to the present invention there is provided a process for colouring synthetic textile material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof, which comprises applying to the synthetic textile material a dye, which is free from water solubilising groups, carrying at least one -SO2F group provided that the dye is not an azo, bisazo, or anthraquinone dye. 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. 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, such as polyhexamethylene adipamide or polyethylene terephthalate more preferably aromatic polyester and especially poiyethlene terephthalate. Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are these of polyester cellulose such as polyester-cotton. The textile materials or blends thereof ma y be in the form of filaments, loose fibres, yarn, woven or knitted fibres. The present dyes preferably have low solubility in water, typically less than 1% preferably les.s than 0.5% and especially less than 0.2% solubility in water. They are thus free from wa ler solubilising groups such as -SO3H, -CO2H, -PO3H and quaternary amino. The dyes of the present invention as herein described optionally in admixture with each other and optionally in conjunction with other disperse dyes such as azo, bisazo or anthraquinone 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. For example, the dyes of the present invention, in the form of an aqueous dispersion, may be applied by dyeing, padding or printing processes using the conditions and additives conventionally used in carrying out such processes. 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 125°C to 140°C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, in which a sequesterant may optionally be added; li) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 190°C to 225°C for from 15 seconds to 5 minutes, in which a migration inhibitor may optionally be added; iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 160°C to 185°C for 4 to 15 minutes for high temperature steaming, or at a temperature of from 190°C to 225°C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120°C to 140°C and 1 to 2 bar for 10 to 45 minutes for pressure steaming, in which wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may be optionally be added; tv) discharge printing (by padding the dye onto the textile material, drying and overprinting) at a pH of from 4 to 6.5, in which 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 95°C to 100°C using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, in which sequesterants may optionally be added; and ri) atmospheric dyeing of ace;tate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 85°C for acetate or at a temperature of 90°C for triacetate and nylon for from 15 to 90 minutes, in which sequesterants may optionally be added. In all the above processes the dye is applied as a dispersion comprising from 0.001% to 4% of the dye in acfueous medium. The present compounds generally provide coloured textile material which shows good fastness to washing, light and heat. The dye may be a heterocyclic or carbocyclic compound and is preferably selected from one of the following dye classes benzothioxanthene, styryl, coumarin, naphtholactam, quincphthalone, aminodicyanobenzanthrone, pyrrole, thiophene-1,1-dioxide, benzodifuranone, isoindole, thiazole, triphenodioxazine, anthraisothiazolone, nitrodiphenylamine, isoquinolinone, isoquinolinedione, isoindolqperimidone and indoaniline. Where the dye is ai benzothioxanthene it is preferably of Formulae (2A) , (2B) or (2C): (Formula Removed) in which: R is -H, alkyl or aryl in which the alkyl and axyl may be further substituted; each of R1 to Ru independently is -H, -NOj, -SOjF, alkyl, . alkoxy, -Saryl, halo, -SOjNHalkyl or -SQJSHaryl; and R14 is -H, alkoxy or -SQ.F. Where the dye is a styryl dye it is preferably of Formula (3) . (Formula Removed) in which: R1 to R3 are as hereinbefore defined; R15 is -H or -CN; each of R16 and R17 independently is -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrol idino, piperidino or morpholino ring; and R18 is -H, alkyl, -SO2F, -NHCOalkyl. Where the dye is a coumarin dye it is preferably of Formulae (4A) or (4B) : (Formula Removed) in which: R' to R8, R15, Rls and R17 are as hereinbefore defined. Where the dye is a naphtholactam dye it is preferably of Formulae (5A), (5B) or (5C) : (Formula Removed) in -which: X1 is a heteroatom; n is 1 or 2; Z is optionally substituted heteroaryl; and R1 to R6 and R16 are as hereinbefore defined. Where the dye is a quinophthalone dye it is preferably of "ormula (6) : (Formula Removed) n which: V. and R1 to R9 are as hereinbefore defined. Where the dye is an anunciicYanobenzanthrone dye it is preferably of Formula (7): Formula [7] ixi which: R1 to R6, R16 and R17 are as hereinbefore defined. Where the dye is a pyrrole dye it is preferably of Formulae (8A) or (8B) : (Formula Removed) Formula [8B] Formula [8A] in which: X2 is O or S; W is a direct link or -NR; R, R1 to R3, R1S and R17 are as hereinbefore defined; R18 is -H, alkyl, -NHOOalkyl; R19 is an electron withdrawing group; and each of R20 to R23 independently is -H, alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted. Where the dye is a thiophene-1,1-dioxide dye it is preferably of Formulae (9A) or (9B) : (Formula Removed) Formula [9B] in which: R1 to R7, R" to R18, R20 to R23 and W are as hereinbefore defined. Where the dye is a benzodifuranone dye it is preferably of the Formula (10) : (Formula Removed) in which: each X3 independently is -H, halo, -SO^F, alkyl or alkoxy; and each Ring B independently is unsubstituted or is substituted by from 1 to 5 groups. Where the dye is an isoindole dye it is preferably of Formula (11): (Formula Removed) Formula [11 ] in which: R1 to R7 and R" to R18 are as hereinbefore defined. Where the dye is a thiazole dye it is preferably of Formula (12) : (Formula Removed) Formula {12] in which: X4 is CH or N; and R1 to R3, R5 to R8, R11, R16 to R18 are as hereinbefore defined. Where the dye is a triphenodioxazine dye it is preferably of Formula (13): (Formula Removed) Formula [13] in which: (Formula Removed) R24 and R25 each independently is alkyl; and R1 to Rs and R15 are as hereinbefore defined. Where the dye is an anthraisothiazolone dye it is preferably of Formula (14): (Formula Removed) Formula [14] in which: R1 to R6 an R16 are as hereinbefore defined, R26 is H, alkyl, cycloalkyl, aryl, aralkyl each of which may be optionally substituted or a group -COR in which R is as hereinbefore defined. Where the dye is a nitrodiphenylamine it is preferably of Formula (15): Formula [15] in which: Rx to R10 each independently is as hereinbefore defined provided that at least one of R1 to R10 is -NCX.. Where the dye is an indoaniline it is preferably of ForrraiLae (16A) , (16B) or (16C): (Formula Removed) in which: R, R1 to R10r R16 and R17 are as hereinbefore defined. Where the dye is an isoquinolinone it is preferably of Formula (23) : (Formula Removed) in which: R1 to R10 are as hereinbefore? defined preferred dyes of Formula (23) are those in which R2 is alkoxy, R3 is -SO2F and R1, R4 to R10 are -H. Where the dye is an isoquinolinedione it is preferably of Formula (24): (Formula Removed) in which R1 to RE, R16 and R17 are as hereinbefore defined. Preferred dyes of Formula (24) are those in which R1, R3 to Rs and R16 are H, R2 is -SC2,F, R6 is alkyl and R17 is cycloalkyl. Where the dye is an isoindoloperimidone it is preferably of Formula (25) : (Formula Removed) in which R1 to R10 are as hereinbefore defined. Preferred dyes of Formula (25) are those in which R1 to R10 are -H or ~S02F, more preferably those in which one of R1 to R4 is -SC^F, one of R5 to R7 is -S02F or one of R8 to R10 is -SO^F. The electron withdrawing group represented by R19 is preferably --CN, -SO2F, -GOOalkyl, -C0N(alkyl)2 or -S02alkyl. Where any of the groups represented by R, R1 to R14, R1S to R26 or X3 is or contains alkyl or alkoxy the alkyl or alkoxy preferably contains from 1 to 10 and more preferably from 1 to 6 carbon atoms and may be straight or branched chain and may carry one or more substituents. Where any of the groups represented by R, R1 to R13, R16, R17, R20 to R23 and R26 is or contains aryl the aryl is preferably phenyl or naphthyl, more preferably phenyl and may carry one or more substituents. The cycloalkyl group represented by R", R17, R20 to R23 and R26 is preferat)ly C5-7 cycloalkyl, more preferably cyclohexyl and may carry one or more substituents. The alkenyl group represented by R16, R17 and R20 to R23 is preferably C5-7-alkenyl, more preferably C2-3-alkenyl and especially C2-3 alkenyl which may be straight or branched chain and may carry one or more substituents. The aralkyl group represented by R1S, R17, R20 to R23 and R26 is preferably phenylC1-6-alkyl, more preferably phenylC1-3-alkyl and especially ben2yl, phenyl ethyl, chlorobenzyl or nitrobenzyl and may carry one or more substituents. The halo group represented by R1 to R° or X3 is preferably -CI, -Br or -I more preferably -CI or -Br. The heteroaryl group represented by Z is preferably pyridyl, thienyl, thiazolyl or isothiazolyl. Where X1 is a heteroatom it is preferably O or N. Where any of the groups represented by R, R1 to R14, R1S to R26, Ring B, Z or X3 is substituted by one or more substituents, suitable substituents may be selected from cyano, hydroxy, nitro, halo such as fluoro, chloro and bromo, fluorosulphonyl, trifluoromethyl, alkyl, ' alkoxy, aryl, (fluorosulphonyl)aryl , aryloxy, (fluorosulphonyl) aryloxy, -COalkyl, -NHCOalkyl, -NHSOjalkyl, -OCOalkyl, -COOalkyl, -Salkyl, -Saryl, -SQjalkyl, -SC^aryl, NR^R28 in which R27 and R28 each independently is -H, cycloalkyl, alkyl or alkyl substituted by -CH, -CN, halo such as -F, -CI and -Br, phenyl, -OCOalkyl, -COOalkyl, (Formula Removed) -OCOphenyl, -COOphenyl, alkyl (f luorosulphonylphenyl), -OaXfluorosulphonylphenyl), alkenyl, -COOalkylOalkyl, -OalkylCN, aryloxy or -OalkylOCOalkylOalkyl, in which each alkyl is C1-10-alkyl and each alkoxy is C1-10alkoxy each of which may be straight or branched chain and each alkyl, alkoxy, aryl or phenyl group may carry an -SO2F substituent or R27 and R28 together with the -N atom to which they are attached form a 5- or 6-membered ring such as morpholino or piperidino. Preferred substituents are cyano, nitro, chloro, bromo, fluorosulphonyl, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyI, -NHCOC1-6-alkyl, -OCOC1-6-alkyl, -COOC1-6-alkyl, -NR27R28 in which R27 and R28 each independently is -H, C1-6-allcyl or C1.6-alkyl substituted by -OH, -CN, -CI, phenyl, -OCOC1-6-alkyl, -COOC1-6-alkyl, C1-4-alJcyl (4-fluorosulphonylphenyl), -OCO (3-f luorosulphonylphenyl) , -0C0(4-fluorosulphonylphenyl) , -C1-4-alkenyl, -COOC1-6-alkylOC1-6-alkyl, -OC^-alkylCN or -CC1-6-alkylOC1-6-alkylCC1-6alkyl or where R27 and R28 together with the -N atom to which they are attached form a morpholino or piperidino. The dyes of the present invention preferably carry a total of from one to three -SC^F groups, more preferably from one to two -SOL,F groups and especially one -SCt,F group. The dyes of Formulae (2) to (16) and (23) to (25) used in the above coloration process are novel and form a further feature of the present invention. Compounds of Formulae (2) to (16) and (23) to (25) may be mixed with structurally similar compounds or the compounds of Formulae (2) to (16) and (23) to (25) may be mixed with dyes which do not contain an -SCLF 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 Formulae (2) to (16) and (23) to (25) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment. Compositions conprising dispersions of the dyes of the present invention in aqueous media are novel and form a further feature of the present invention. The compositions typically comprise from 1% to 30% of dye and are preferably buffered at a pH from 2 to 7, more preferably at a pH from 4 to 6. 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-fearners 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 dye. Wetting agents may be used at from 0% to 20% on the weight of the dye . The dispersions may be prepared by bead milling the compound of Formula (1) with glass beads or sand in an aqueous medium. According to a further feature of the present invention there is provided a process for the mass coloration of plastics which comprises incorporating into a plastics material a dye except for azo. bisazo and anthracquinone dyes or mixture of dyes which is free from water solubilising groups and which carry at least one -S02F group. The plastics may be selected from polystyrene, acrylics, styrene/acrylonitrile mixtures, acrylonitrile/butadiene/styrene mixtures, polycarbonate, polyether-sulphone, nylons, rigid PVC (uPVC) and polypropylene. The dye or dye mixture may be incorporated by blending with granules or powdered plastics material, by for example, dry tumbling or high-speed mixing followed by injection moulding on a screw machine or by conventional compounding/xrasterbatching techniques. The present dyes generally dissolve or disperse readily in hot plastics melt and provide bright coloration with good clarity and good light fastness. The plastics material when coloured with the above dyes form a further feature of the present invention. Fluorosulphonyl groups may be introduced into precursors of the dyes of Formulae (2) to (16) free from fluorosulphonyl groups by methods generally available in the literature. For example reaction of such a precursor of a dye of Formulae (2) to (16) with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30°C to 140°C gives the chlorosuLphonyl derivative. The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative. Altentatively the precursor of the dye of Formulae (2) to (16) may be sulphonated with sulphuric acid or oleum to give the sulphonic acid derivative which may be converted to the chlorosulphonyl 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 oxychloride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20°C to 110°C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above. Precursors of the dyes of Formulae (2) to (16) before chlorosulphonation or sulphonation may be prepared by methods available in the literature. Dyes of Formulae (2A), (2B) and (2C) or the above precursors thereof may be prepared according to German patents 2238330 and,1569737. Dyes of Formula (3) or the above precursors thereof may be prepared according to German patent 2741392 and Japanese patents 59129264, 59129263, 59126466, 59230060 and 60031564. Dyes of Formulae (4A) and (4B) or the above precursor thereof may be prepared according to German patent 2415661 and Japanese patent 57031958. Dyes of Formulae (5A), (5B) and (5C) or the above precursor thereof may be prepared according to German patents 2341657, 2724566, 2608020, 2724567, 2606716, '724540, 2724444,' 2736914, 2924069 and 2611665. Dyes of Formula (6) or the above precursors thereof may be prepared by reaction of a naphthopyridine of Formula (17): (Formula Removed) with a phthalic anhydride of Formula (18): (Formula Removed) n the presence of a Lewis acid catalyst such as zinc chloride optionally in an inert liquid medium at temperatures up to 220°C. Dyes of Formula (7) or the above precursors thereof may be prepared by reaction of an anthraquinone of Formula (19): (Formula Removed)with dicyanomethane in the presence of TiCl4 and as described in EP-A-146280 followed by reaction, as appropriate, of the resultant amino conpound with compounds of Formulae R16-hal and R17-hal in which R1 to R6, F16 and R17 are as hereinbefore defined and hal is -CI, -Br or -I. Dyes of Formulae (8A) or (8B) or the above precursors thereof may be prepared according to UK patent 2191498 and Japanese patents 60150262 and 60156760. Dyes of Formula (9A) or (9B) or the above precursors thereof may be prepared according to German patent 2929001. Dyes of Formula (10) or the above precursors thereof may be prepared UK patent: 1557205 and European patents 23080, 146269 and European patent application 363034. Dyes of Formula (11) or the above precursors thereof may be prepared according to German patent 2912428 and Japanese patent 59184262. Dyes of Formula (12) or the above precursors thereof may be prepared according to German patent 2732221 and Japanese patents 57030760 and 57030759. Dyes of Fonnula (13) or the above precursors thereof may be prepared according to German patent 2733539 and Japanese patents 53134971, 54068478, 53026826, 52140683, 52134634 and 52030823. Dyes of Fonnula (14) or the above precursors thereof may be prepared by reaction of an anthraquinone of Formula (20): (Formula Removed) in which R1 to R3, Rs, R6, R16 and R26 are as hereinbefore defined with anmoniura hytiroxide at a tenperature of 130°C. Dyes of Formula (15) or the above precursors thereof may be prepared by reaction of a chloronitrobenzene with an aniline. Dyes of Formula (16) or the above precursors thereof may be prepared by reaction of a nitroso compound of Formula (21): (Formula Removed) with a hydroxy conpound of Formula (22A), (22B) or (22C) (Formula Removed) in the presence of acetic anhydride in which R;, R1 to R10, R16 and R17 are as hereinbefore defined. The dye of Formula (23) in which R1, R3 to R10 are -H and R2 is methoxy is commercially available as C.I. Disperse Yellow 71. The dye of Formula (24) in which R1 to Rs are -H, R6 is methyl, R16 is -H and R17 is cyclohexyl is commercially available as C.I. Disperse Yellow 100. The dye of Formula (25) in which R1 to R10 are -H is commercially available as C.I. Disperse Orange 24. The dyes of Formulae (2) to (16) and (23) to (25) 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. The dyes of Formulae (2) to (16) and (23) to (25) are also useful for the mass coloration of elastics and impart bright colours generally with good clarity and light fastness. Example 1 (Formula Removed) Dye A in which R=H (5 parts) was added to cooled concentrated sulphuric acid and stirred overnight at room temperature. The reaction mixture was poured into ice/water and the precipitate filtered off. The solid was washed with 10% brine and allowed to aix" dry (Formula Removed) before heating in pyridine (1240 parts) at 125°C for 2.5 hours. After screening the hot mixture it was evaporated to dryness. The resulting solid was stirred in POCL3 (215 parts) at 75°C for 3 hours and for a further 24 hours at room temperature. Addition to ice/water was followed by filtration, yielding a solid which was washed with water and dried in a vacuum oven. Yield of product (1.7 parts) found to be a mixture of mono and disulphonyl chloride. Potassium fluoride (3.4 parts) dissolved in water (277 parts) was added to 1,4-dioxane (290 parts) and stirred for 5 minutes before adding the sulphonyl chloride dye (0.84 parts) . After stirring at room temperature for 1 hour at 75°C and 1 hour at 120°C the reaction mixture was carefully added to ice/water which was then extracted with ethyl acetate several times. The ethyl acetate was then dried over magnesium sulphate, filtered and concentrated to yield a mixture of dyes of formula A (0.6 parts) in which one R=H and the other R=SO2F and in which both R groups were SQ,F. Example 2 (Formula Removed) Dye B in which R=H (3.7 parts) was added to chlorosulphonic acid (188 parts) with stirring at room temperature. Thionyl chloride (13.7 parts) was then added and the reaction mixture heated at 80°C for 24 hours. After cooling to room temperature, the reaction mixture was carefully drowned out into ice/water and left to stand overnight. Filtration yielded an orange solid which was washed with water then dried in a vacuum oven overnight. The sulphonyl chloride dye (6 parts) was stirred in 1,4-dioxane (870 parts) while potassium fluoride (25.4 parts) in water (277 parts) was added in one portion, the mixture was heated at 120°C for 30 hours, cooled to room temperature and filtered. The solid obtained was washed with water before drying at 50°C to give a mixture of dyes of formula B in which one R=H and two R groups = SO2F and in which two R groups = H and one R=SO2F. Example 3 (Formula Removed) Dye C in which R=H (2.6 parts) was added to chlorosulphonic acid (226 parts) with stirring at room temperature. Ihionyl chloride 13.7 parts) was then added and the reaction mixture heated at 55°C for hours. After cooling and poiiring carefully into ice/water the resulting solution was filtered. The solid obtained was washed with water and dried in the vacuum oven overnight. The sulphonyl chloride dye (2.6 parts) was stirred in 1,4-ciioxane (580 parts) while potassium fluoride (3.4 parts) in water (277 parts) was added in one portion and the mixture was heated at reflux for hours before cooling to room temperature and filtering. The filtrate . was diluted with water and re-filtered. The collected solids were combined, washed with water and dried at 50°C overnight to give a mixture of dyes of formula C (2.5 parts) in which one, two and three R qroups = SO2,F. Example 4 (Formula Removed) Dye D in which R=H (6.7 parts) was added to chlorosulphonic acid (226 parts) with stirring at room temperature. Thionyl chloride (20.5 parts) was added and the reaction mixture heated at 80°C for 3 hours. After cooling to room temperature the mixture was carefully drowned out in ice/water and the resulting solid filtered off. The solid was washed with water and dried under vacuum overnight. The dry solid (4.4 parts) was stirred in 1,4-dioxane (870 (Darts) while potassium fluoride (8.5 parts) dissolved in water (277 ,Dart:s) was added in one portion and the mixture was heated at reflux for 3 hours before cooling to room temperature and filtering. The solid was washed with water and dried under vacuum overnight to give dye D in which R=SO2. Bxanrole 5 Dye E in which R=H (2.4 parts) was added to chlorosulphonic icid (150 parts) with stirring at room tenperature. Thionyl chloride 10.3 parts) was added and the mixture heated at 70°C for 3-4 hours. After cooling to room tenperature the mixture was carefully drowned out in ice/water and the resulting solid filtered off. The solid was washed with water and dried under vacuum overnight. The sulphonyl chloride dye (0.5 parts) was stirred in 1,4-dioxane (290 parts) while potassium fluoride (1.7 parts) dissolved in water (227 parts) was added in one portion and the mixture was heated at reflux for 2-3 hours before cooling to room temperature and carefully (Irownrng in water. The precipitate was filtered off , washed with water and dried under vacuum overnight, to give dye E (0.01 parts) in which k-S02F. Example 6 Dye F in which R, and RH (10 parts) was added to a stirred mixture of chlorosulphonic acid (376 parts) and thionyl chloride (68.5 parts) at room tenperature. The reaction mixture was heated at 100°C for hours After cooling to room tenperature the mixture was carefully poured into ice/water and the precipitate filtered off. The solid was washed with water and dried under vacuum to give the sulphonyl chloride derivative. 1,4-Dioxane (58 parts) /potassium fluoride (5.9 parts)/water (27.7 parts) were stirred together before the sulphonyl chloride derivative (0.75 parts) was added. The reaction mixture was heated at 70°C for 20 hours. After cooling to room temperature the solution was filtered and the resulting solid obtained washed with water. The solid was dried under vacuum overnight to yield a mixture of sulphonyl fluoride containing dyes (0.2 parts) of structure F in which R1= CI, R2= SO.F, and in which R1= R SO2F. Example 7 (Formula Removed) Dye G in which R=H (2 parts) was added to chlorosulphonic acid (300 parts) at room temperature then heated at 50°C for 3 hours. After cooling, the reaction mixture was poured into ice/water and the precipitate formed filtered off. The solid was washed with water several times before being dried under vacuum, yielding the sulphonyl chloride derivative (1.45 parts). The potassium fluoride (10 parts)/water (22 parts) /l, 4-dioxane (23.2 parts) were stirred together before the sulphonyl chloride derivative (1.25 parts) was added in one portion. The reaction mixture was heated at 60°C for 5 hours, cooled and filtered. After washing with water and drying overnight under vacuum at 50°C a dye (0.03 parts) of structure G in which R=Sp2F was obtained. Example 8 (Formula Removed) Dye H in which R=H (0.75 parts) was added to chlorosulphonic acid (300 parts) at room temperature then heated at 70°C for 5 hours. After cooling, the reaction mixture was poured into ice/water and the (Formula Removed) precipitate formed filtered off. The solid was washed with water several times before being dried under vacuum, yielding the sulphonyl chloride dye. The potassium fluoride (5.1 parts)/water (111 parts)/p-dioxane (93 parts) were stirred together before the sulphonyl chloride dye (0.6 parts) was added and the reaction mixture was heated at 60°C for 5-6 hours. On cooling, the solution was filtered and the solid washed with water. After drying the solid overnight at 50°C, purification was carried out using flash chromatography (eluent: dichloromethane/ethyl acetate) to give dye in which R = S02F. Example 9 (Formula Removed) The di-sodium salt of 4-cyano-5-dicyanomethylidene-3-hydroxy-2-co-2,5-dihydropyrrole (10 parts) was dissolved in DMF (388 parts). N- Ethyl -N-ß- (4- fluorosulphonylphenoxy) -ethyl -m-toluidine (10 parts) was then added at 0°C, followed by the dropwise addition of POCL, (24 parts) . After the reaction exothermed slightly, stirring was continued ait 0°C for 30 minutes followed by 2 hours at room temperature. The reaction mixture was carefully drowned out in ice/water, filtered and the solid obtained washed with water before drying at 40°C. The dye was dissolved in an acetone (2 parts) /methanol (5 parts) mixture before pouring into water (27 parts) . The solid filtered off was washed with water and dried at 50°C, yielding dye J (3.4 parts) . λmax 637 nm. Example 10 (Formula Removed) N-Ethyl-N-(2-(4-fluorosulphonylphenyl)ethyl)-aniline (12.5 arts) was dissolved in DMF (323 parts) and cooled to 0°C before adding POCl3 (32 parts) drcpwise. The reaction mixture was heated at 80°C for 3 hours, cooled to room temperature and carefully drowned out into ice/water. The aqueous solution was neutralised with concentrated sodium hydroxide and then extracted with toluene (5 x 500mls) . The toluene extracts were combined, dried over MgSO4, and concentrated on a rotary evaporator to yield the aldehyde intermediate (10.5 parts). The aldehyde intermediate (3 parts) and 3-dicyanomethylidene-2,3-dihydrobenzothiophene-l,1-dioxide (3.3 parts) were refluxed in ethanol (170 parts) for 4 hours. On cooling the solvent was removed on the rotary evaporator and the dye purified by column chromatography (eluent: dichloromethane) to yield dye K (0.1 parts). λmax 581nm. Example 11 (Formula Removed) The procedure for example 10 was repeated except that in place of 12.5 parts of N-ethyl-N- (2- (4-fluorosulphonylphenyl)ethyl) -aniline, 12.5 parts of N-ethyl-N- (4-fluorosulphonyl-phenyl ethyl)-m-toluidine was used to yield dye L (0.12 parts) . λmax 596nm. Example 12 The procedure for exanple 10 was repeated except that in place of 12.5 parts of N-ethyl-N-(2-(4-fluorosulphonylphenyl)ethyl)-aniline; 12.5 parts of N-ethyl-N-(4-fluorosulphonyl-benzyl)-aniline was used to yie:ld dye M (0.6 parts) λmax 566nm. Example 13 (Formula Removed) The procedure for exanple 10 was repeated except that in place of 12.5 parts of N-ethyl-N-(2-(4-fluorosulphonylphenyl) ethyl) -aniline,- 12.5 parts of N-isobutyl-N-(3-(4-fluorosulphonylphenyl)propyl) m-toluidine was used to yield dye N (0.08 parts) .λmax 607nm. WE CLAIM:- 1). A process for colouring synthetic textile material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof, which comprises applying to the synthetic textile material a dye, which is free from water solubilising groups as herein described, carrying at least one -SO2F group provided that the dye is not an azo, bisazo, or anthraquinone dye. 2 A process as claimed in claim 1, wherein the dye is applied in the form of an aqueous dispersion. 3 A process as claimed in claim 1 or claim 2, in which the dye is selected from a benzothioxanthene, styryl, coumarin, naphtholactam, quinophthalone, aminodicyanobenzanthrone, pyrrole, thiophene-1,1 -dioxide, benzodi-furanone, isoindole, thiazole, triphenodioxazine, anthraisothiazolone, nitrodiphenylamine, isoquinolinone, isoquinolinedione, isoindolo-perimidone and indoaniline. 4 A process as claimed in claim 3, in which the dye is of Formula 2A, 2B or 2C (Formula removed) in which: R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; each of R1 to R13 is independently -H, i -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and R14 is -H, alkoxy or S02F. 5. A process as claimed in Claim 3, in which the dye is of Formula 3: (Formula removed) in which: R1 to R3 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; P.15 is -H or -CN; each of R16 and R17 independently is -H, alkyl, cycloalkyl, aryl, alkenyl, araikyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidno, piperidino or morpholinio ring; and R18 is -H, -S02F, NHCOalkyl. (Formula removed) 6. A process as claimed in Claim 3, in which the dye is of Formula 4A or Formula 4B (Formula removed) in which: R1 to R8 are independently -H, -N02, S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; R15 is -H or -CN; and each of R16 and R17 independently is -H, aJkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidine, piperidino or morpholino ring. 7. A process as claimed in Claim 3, in which the dye is of Formula 5A, 5B or 5C: i n which: X' is a heteroatom; n is 1 or 2; Z is optionally substituted heteroaryl; R: to R6 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and R3 is -H, alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted. 8. A process as claimed in Claim 3, in which the dye is of Formula 6: (Formula removed) in which: R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; and R1 to R9 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl. y. A process as claimed in Claim 3, in which the dye is of Formula 7: (Formula removed) in which: R1 to Rb are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and R and R17 independently are -H, alkyl, cycloalkyl, aryi, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring. 10. A process as claimed in Claim 3, in which the dye is of Formula 8A or 8B: Formula [8B] X2 is 0 or S; (Formula removed) W is a direct link or -Nr; R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; R1 to R3 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; R16 and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring R1 is -H, alkyl or -NHCOalkyl; R' is an electron withdrawing group; and each of R20 to R23 independently is -H, alkyl., cycloalkyJ, aryl, alkenyl or aralkyl each of which may be optionally substituted. 11. A process as claimed in claim 3, in which the dye is Formula 9A or 9B: (Formula removed) in which: R1 to R7 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; RIb and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom which they are attached form a pyrrolidino, piperidino or morpholino ring R18 is -H, alkyl or -NHCOalkyl; R'° and R23 are independently -H, alkyl, cydoalkyl, aryl, a 1kenyl or aralkyl each of which may be optionally substituted; and W is a direct link or -NR. 12. A process as claimed in claim 3, in which the dye is of Formula 10: Formula [10] in which:: each X3 independently is -H, halo, -S02F, alkyl or alkoxy; and each Ring B independently is unsubstituted or is substituted by from 1 to 5 groups. 13. .. A process as claimed in Claim 3, in which the dye is of Formula 11: (Formula removed) in which: R1 to R7 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; R16 and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R and R together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring R18 is -H, alkyl or -NCHOalkyl. 14 A process as claimed in claim 3, in which the dye is of Formula 12: (Formula removed) in which v4 Xs is CH or N R1 to R3, R5 to R8 and R11 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; R16 and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring R1B is -H, alkyl or -NHCOalkyl. 15 A process as claimed in Claim 3, in which the dye is of Formula 13: (Formula removed) in which: -.25 R" and R each independently is alkyl; R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and ,15 is -H or -CN. 16* A process as claimed in claim 3, in which the dye is of Formula 14: (Formula removed) NR15R2e Formula [14] in which: R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; Rlfe is -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted; and R26 is H, alkyl, cycloalkyl, aryl, aralkyl each of which may be optionally substituted or a group -COR in which R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted. 17.. A process as claimed in claim 3, in which the dye is of Formula 15: (Formula removed) in which: ,10 R to R each independently is -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl, provided that at least one of R1 to R10 is -N02. 18. A process as claimed in Claim 3, in which the dye is of Formula 16A, 16B or 16C: (Formula removed) in which: R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; R1 to R10 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and R16 and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring. A process as claimed in Claim 3, in which the dye is of Formula 23: (Formula removed) in which R1 to R10 are independently -H, -N02, -So2F, alkyl, alkoxy, -Saryl, halo, ~S02NHalkyl or -S02NHaryl. 20. A process as claimed in Claim 3, in which the dye is of Formula 24: (Formula removed) in which: R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy, --Saryl, halo, -S02NHalkyl or -S02NHaryl; R16 and R17 independently is -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring. 11. A process as claimed in claim 3, in which the dye is of Formula 25: (Formula removed) in which R» to Ri° are independently -H, -NC)2, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -SOzNHaryl. 2.1. A process for colouring synthetic textile material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof substantially as herein described with reference to the foregoing examples.

Full Text

The present invention relates to a process for colouring synthetic textile material selected
from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and
polyacrylonitrile or fibre blend thereof.
]P A-54-050681 discloses, in general terms, the use of fluorosulphonyl group-containing
reactive disperse dyes for dyeing cellulose-containing textiles but discloses specifically
only certain azo and anthraquinone dyes for this purpose.
US-A-5503956 discloses a black laser dye-ablative recording element comprising a support,
which may be a polyester, having thereon a dye layer comprising a mixture of at least one
cy.in, magenta and yellow dye dispersed in a polymeric binder and having an infra red
absorbing material associated therewith. There is no reference therein to dyes containing a
fluorosulphonyl group.
According to the present invention there is provided a process for colouring synthetic textile
material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate,
polyamide and polyacrylonitrile or fibre blend thereof, which comprises applying to the
synthetic textile material a dye, which is free from water solubilising groups, carrying at
least one -SO2F group provided that the dye is not an azo, bisazo, or anthraquinone dye.
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.
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, such as polyhexamethylene
adipamide or polyethylene terephthalate more preferably aromatic polyester and especially
poiyethlene terephthalate. Fibre blends may comprise mixtures of different synthetic textile
materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are
these of polyester cellulose such as polyester-cotton. The textile materials or blends thereof
ma y be in the form of filaments, loose fibres, yarn, woven or knitted fibres.
The present dyes preferably have low solubility in water, typically less than 1% preferably
les.s than 0.5% and especially less than 0.2% solubility in water. They are thus free from
wa ler solubilising groups such as -SO3H, -CO2H, -PO3H and quaternary amino.

The dyes of the present invention as herein described optionally in admixture with each other and optionally in conjunction with other disperse dyes such as azo, bisazo or anthraquinone 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. For example, the dyes of the present invention, in the form of an aqueous dispersion, may be applied by dyeing, padding or printing processes using the conditions and
additives conventionally used in carrying out such processes. 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 125°C to 140°C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, in which a sequesterant may optionally be added; li) continuous dyeing at a pH of from 4 to 6.5, at a temperature of
from 190°C to 225°C for from 15 seconds to 5 minutes, in which a migration inhibitor may optionally be added; iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 160°C to 185°C for 4 to 15 minutes for high temperature steaming, or at a temperature of from 190°C to 225°C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120°C to 140°C and 1 to 2 bar for 10 to 45 minutes for pressure steaming, in which wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may be optionally be added; tv) discharge printing (by padding the dye onto the textile material, drying and overprinting) at a pH of from 4 to 6.5, in which 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 95°C to 100°C using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, in which sequesterants may optionally be added; and ri) atmospheric dyeing of ace;tate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 85°C for acetate or at a temperature of 90°C for triacetate and nylon for from 15 to 90 minutes, in which sequesterants may optionally be added.
In all the above processes the dye is
applied as a dispersion comprising from 0.001% to 4% of the dye in acfueous medium.
The present compounds generally provide coloured textile material which shows good fastness to washing, light and heat.
The dye may be a heterocyclic or carbocyclic compound and is preferably selected from one of the following dye classes benzothioxanthene, styryl, coumarin, naphtholactam, quincphthalone, aminodicyanobenzanthrone, pyrrole, thiophene-1,1-dioxide, benzodifuranone, isoindole, thiazole, triphenodioxazine, anthraisothiazolone, nitrodiphenylamine, isoquinolinone, isoquinolinedione, isoindolqperimidone and indoaniline.
Where the dye is ai benzothioxanthene it is preferably of
Formulae (2A) , (2B) or (2C):
(Formula Removed)
in which:
R is -H, alkyl or aryl in which the alkyl and axyl may be further substituted; each of R1 to Ru independently is -H, -NOj, -SOjF, alkyl, . alkoxy, -Saryl, halo, -SOjNHalkyl or -SQJSHaryl; and R14 is -H, alkoxy or -SQ.F.
Where the dye is a styryl dye it is preferably of Formula (3) .
(Formula Removed)
in which:
R1 to R3 are as hereinbefore defined; R15 is -H or -CN; each of R16 and R17 independently is -H, alkyl, cycloalkyl, aryl,
alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrol idino, piperidino or morpholino ring; and
R18 is -H, alkyl, -SO2F, -NHCOalkyl.
Where the dye is a coumarin dye it is preferably of Formulae (4A) or (4B) :
(Formula Removed)
in which:
R' to R8, R15, Rls and R17 are as hereinbefore defined.
Where the dye is a naphtholactam dye it is preferably of Formulae (5A), (5B) or (5C) :
(Formula Removed)
in -which:
X1 is a heteroatom;
n is 1 or 2;
Z is optionally substituted heteroaryl; and R1 to R6 and R16 are as hereinbefore defined.
Where the dye is a quinophthalone dye it is preferably of "ormula (6) :
(Formula Removed)
n which:
V. and R1 to R9 are as hereinbefore defined.
Where the dye is an anunciicYanobenzanthrone dye it is preferably of Formula (7):
Formula [7]
ixi which:
R1 to R6, R16 and R17 are as hereinbefore defined.
Where the dye is a pyrrole dye it is preferably of Formulae (8A) or (8B) :

(Formula Removed)
Formula [8B]
Formula [8A]
in which:
X2 is O or S;
W is a direct link or -NR; R, R1 to R3, R1S and R17 are as hereinbefore defined;
R18 is -H, alkyl, -NHOOalkyl;
R19 is an electron withdrawing group; and each of R20 to R23 independently is -H, alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted. Where the dye is a thiophene-1,1-dioxide dye it is preferably of Formulae (9A) or (9B) :
(Formula Removed)
Formula [9B]
in which:
R1 to R7, R" to R18, R20 to R23 and W are as hereinbefore defined.
Where the dye is a benzodifuranone dye it is preferably of
the Formula (10) :
(Formula Removed)
in which:

each X3 independently is -H, halo, -SO^F, alkyl or alkoxy; and each Ring B independently is unsubstituted or is substituted by from 1
to 5 groups.

Where the dye is an isoindole dye it is preferably of Formula (11):

(Formula Removed)
Formula [11 ]
in which:
R1 to R7 and R" to R18 are as hereinbefore defined.
Where the dye is a thiazole dye it is preferably of Formula
(12) :

(Formula Removed)
Formula {12]
in which:
X4 is CH or N; and R1 to R3, R5 to R8, R11, R16 to R18 are as hereinbefore defined.
Where the dye is a triphenodioxazine dye it is preferably of Formula (13):

(Formula Removed)
Formula [13]

in which:

(Formula Removed)
R24 and R25 each independently is alkyl; and R1 to Rs and R15 are as hereinbefore defined.
Where the dye is an anthraisothiazolone dye it is preferably of Formula (14):
(Formula Removed)
Formula [14]
in which:
R1 to R6 an R16 are as hereinbefore defined,
R26 is H, alkyl, cycloalkyl, aryl, aralkyl each of which
may be optionally substituted or a group -COR in which R is as hereinbefore defined. Where the dye is a nitrodiphenylamine it is preferably of Formula (15):

Formula [15]
in which:
Rx to R10 each independently is as hereinbefore defined provided that at least one of R1 to R10 is -NCX..
Where the dye is an indoaniline it is preferably of ForrraiLae (16A) , (16B) or (16C):
(Formula Removed)
in which:
R, R1 to R10r R16 and R17 are as hereinbefore defined.
Where the dye is an isoquinolinone it is preferably of Formula (23) :
(Formula Removed)
in which:
R1 to R10 are as hereinbefore? defined preferred dyes of Formula (23) are
those in which R2 is alkoxy, R3 is -SO2F and R1, R4 to R10 are -H.

Where the dye is an isoquinolinedione it is preferably of Formula (24):
(Formula Removed)
in which R1 to RE, R16 and R17 are as hereinbefore defined. Preferred dyes of Formula (24) are those in which R1, R3 to Rs and R16 are H, R2 is -SC2,F, R6 is alkyl and R17 is cycloalkyl.
Where the dye is an isoindoloperimidone it is preferably of Formula (25) :

(Formula Removed)
in which R1 to R10 are as hereinbefore defined. Preferred dyes of Formula (25) are those in which R1 to R10 are -H or ~S02F, more preferably those in which one of R1 to R4 is -SC^F, one of R5 to R7 is -S02F or one of R8 to R10 is -SO^F.
The electron withdrawing group represented by R19 is preferably --CN, -SO2F, -GOOalkyl, -C0N(alkyl)2 or -S02alkyl.
Where any of the groups represented by R, R1 to R14, R1S to R26 or X3 is or contains alkyl or alkoxy the alkyl or alkoxy preferably contains from 1 to 10 and more preferably from 1 to 6 carbon atoms and may be straight or branched chain and may carry one or more substituents.
Where any of the groups represented by R, R1 to R13, R16, R17, R20 to R23 and R26 is or contains aryl the aryl is preferably phenyl or naphthyl, more preferably phenyl and may carry one or more substituents.
The cycloalkyl group represented by R", R17, R20 to R23 and R26 is preferat)ly C5-7 cycloalkyl, more preferably cyclohexyl and may carry one or more substituents.
The alkenyl group represented by R16, R17 and R20 to R23 is preferably C5-7-alkenyl, more preferably C2-3-alkenyl and especially C2-3 alkenyl which may be straight or branched chain and may carry one or more substituents.
The aralkyl group represented by R1S, R17, R20 to R23 and R26 is preferably phenylC1-6-alkyl, more preferably phenylC1-3-alkyl and especially ben2yl, phenyl ethyl, chlorobenzyl or nitrobenzyl and may carry one or more substituents.
The halo group represented by R1 to R° or X3 is preferably -CI, -Br or -I more preferably -CI or -Br.
The heteroaryl group represented by Z is preferably pyridyl, thienyl, thiazolyl or isothiazolyl.
Where X1 is a heteroatom it is preferably O or N.
Where any of the groups represented by R, R1 to R14, R1S to R26, Ring B, Z or X3 is substituted by one or more substituents, suitable substituents may be selected from cyano, hydroxy, nitro, halo such as fluoro, chloro and bromo, fluorosulphonyl, trifluoromethyl, alkyl, ' alkoxy, aryl, (fluorosulphonyl)aryl , aryloxy, (fluorosulphonyl) aryloxy, -COalkyl, -NHCOalkyl, -NHSOjalkyl, -OCOalkyl, -COOalkyl, -Salkyl, -Saryl, -SQjalkyl, -SC^aryl, NR^R28 in which R27 and R28 each independently is -H, cycloalkyl, alkyl or alkyl substituted by -CH, -CN, halo such as -F, -CI and -Br, phenyl, -OCOalkyl, -COOalkyl,

(Formula Removed)
-OCOphenyl, -COOphenyl, alkyl (f luorosulphonylphenyl), -OaXfluorosulphonylphenyl), alkenyl, -COOalkylOalkyl, -OalkylCN, aryloxy or -OalkylOCOalkylOalkyl, in which each alkyl is C1-10-alkyl and each alkoxy is C1-10alkoxy each of which may be straight or branched chain and each alkyl, alkoxy, aryl or phenyl group may carry an -SO2F substituent or R27 and R28 together with the -N atom to which they are attached form a 5- or 6-membered ring such as morpholino or piperidino.
Preferred substituents are cyano, nitro, chloro, bromo, fluorosulphonyl, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyI, -NHCOC1-6-alkyl, -OCOC1-6-alkyl, -COOC1-6-alkyl, -NR27R28 in which R27 and R28 each independently is -H, C1-6-allcyl or C1.6-alkyl substituted by -OH, -CN, -CI, phenyl, -OCOC1-6-alkyl, -COOC1-6-alkyl,

C1-4-alJcyl (4-fluorosulphonylphenyl), -OCO (3-f luorosulphonylphenyl) , -0C0(4-fluorosulphonylphenyl) , -C1-4-alkenyl, -COOC1-6-alkylOC1-6-alkyl, -OC^-alkylCN or -CC1-6-alkylOC1-6-alkylCC1-6alkyl or where R27 and R28 together with the -N atom to which they are attached form a morpholino or piperidino.
The dyes of the present invention preferably carry a total of from one to three -SC^F groups, more preferably from one to two -SOL,F groups and especially one -SCt,F group.
The dyes of Formulae (2) to (16) and (23) to (25) used in the above coloration process are novel and form a further feature of the present invention.
Compounds of Formulae (2) to (16) and (23) to (25) may be mixed with structurally similar compounds or the compounds of Formulae (2) to (16) and (23) to (25) may be mixed with dyes which do not contain an -SCLF 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 Formulae (2) to (16) and (23) to (25) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment.
Compositions conprising dispersions of the dyes of the present invention in aqueous media are novel and form a further feature of the present invention. The compositions typically comprise from 1% to 30% of dye and are preferably buffered at a pH from 2 to 7, more preferably at a pH from 4 to 6.
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-fearners 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 dye.
Wetting agents may be used at from 0% to 20% on the weight of the
dye . The dispersions may be prepared by bead
milling the compound of Formula (1) with glass beads or sand in an aqueous medium.
According to a further feature of the present invention there is provided a process for the mass coloration of plastics which comprises incorporating into a plastics material a dye except for azo.
bisazo and anthracquinone dyes or mixture of dyes which is free from water solubilising groups and which carry at least one -S02F group.
The plastics may be selected from polystyrene, acrylics, styrene/acrylonitrile mixtures, acrylonitrile/butadiene/styrene mixtures, polycarbonate, polyether-sulphone, nylons, rigid PVC (uPVC) and polypropylene.
The dye or dye mixture may be incorporated by blending with granules or powdered plastics material, by for example, dry tumbling or high-speed mixing followed by injection moulding on a screw machine or by conventional compounding/xrasterbatching techniques. The present dyes generally dissolve or disperse readily in hot plastics melt and provide bright coloration with good clarity and good light fastness.
The plastics material when coloured with the above dyes form a further feature of the present invention.
Fluorosulphonyl groups may be introduced into precursors of the dyes of Formulae (2) to (16) free from fluorosulphonyl groups by methods generally available in the literature. For example reaction of such a precursor of a dye of Formulae (2) to (16) with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30°C to 140°C gives the chlorosuLphonyl derivative. The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative.
Altentatively the precursor of the dye of Formulae (2) to (16) may be sulphonated with sulphuric acid or oleum to give the sulphonic acid derivative which may be converted to the chlorosulphonyl 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 oxychloride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20°C to 110°C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above.
Precursors of the dyes of Formulae (2) to (16) before chlorosulphonation or sulphonation may be prepared by methods available in the literature.
Dyes of Formulae (2A), (2B) and (2C) or the above precursors thereof may be prepared according to German patents 2238330 and,1569737.
Dyes of Formula (3) or the above precursors thereof may be prepared according to German patent 2741392 and Japanese patents 59129264, 59129263, 59126466, 59230060 and 60031564.
Dyes of Formulae (4A) and (4B) or the above precursor thereof may be prepared according to German patent 2415661 and Japanese patent 57031958.
Dyes of Formulae (5A), (5B) and (5C) or the above precursor thereof may be prepared according to German patents 2341657, 2724566, 2608020, 2724567, 2606716, '724540, 2724444,' 2736914, 2924069 and 2611665.

Dyes of Formula (6) or the above precursors thereof may be prepared by reaction of a naphthopyridine of Formula (17):
(Formula Removed)
with a phthalic anhydride of Formula (18):
(Formula Removed)
n the presence of a Lewis acid catalyst such as zinc chloride optionally in an inert liquid medium at temperatures up to 220°C.
Dyes of Formula (7) or the above precursors thereof may be prepared by reaction of an anthraquinone of Formula (19):
(Formula Removed)with dicyanomethane in the presence of TiCl4 and as described in EP-A-146280 followed by reaction, as appropriate, of the resultant amino conpound with compounds of Formulae R16-hal and R17-hal in which R1 to R6, F16 and R17 are as hereinbefore defined and hal is -CI, -Br or -I.

Dyes of Formulae (8A) or (8B) or the above precursors thereof may be prepared
according to UK patent 2191498 and Japanese patents 60150262 and 60156760.
Dyes of Formula (9A) or (9B) or the above precursors thereof may be prepared
according to German patent 2929001.
Dyes of Formula (10) or the above precursors thereof may be prepared UK patent:
1557205 and European patents 23080, 146269 and European patent application 363034.
Dyes of Formula (11) or the above precursors thereof may be prepared according to
German patent 2912428 and Japanese patent 59184262.
Dyes of Formula (12) or the above precursors thereof may be prepared according to
German patent 2732221 and Japanese patents 57030760 and 57030759.
Dyes of Fonnula (13) or the above precursors thereof may be prepared according to
German patent 2733539 and Japanese patents 53134971, 54068478, 53026826, 52140683,
52134634 and 52030823.
Dyes of Fonnula (14) or the above precursors thereof may be prepared by reaction
of an anthraquinone of Formula (20):
(Formula Removed)
in which R1 to R3, Rs, R6, R16 and R26 are as hereinbefore defined with anmoniura hytiroxide at a tenperature of 130°C.
Dyes of Formula (15) or the above precursors thereof may be prepared by reaction of a chloronitrobenzene with an aniline.
Dyes of Formula (16) or the above precursors thereof may be prepared by reaction of a nitroso compound of Formula (21):
(Formula Removed)
with a hydroxy conpound of Formula (22A), (22B) or (22C)

(Formula Removed)
in the presence of acetic anhydride
in which R;, R1 to R10, R16 and R17 are as hereinbefore defined.
The dye of Formula (23) in which R1, R3 to R10 are -H and R2 is methoxy is commercially available as C.I. Disperse Yellow 71. The dye of Formula (24) in which R1 to Rs are -H, R6 is methyl, R16 is -H and R17 is cyclohexyl is commercially available as C.I. Disperse Yellow 100. The dye of Formula (25) in which R1 to R10 are -H is commercially available as C.I. Disperse Orange 24.
The dyes of Formulae (2) to (16) and (23) to (25) 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.
The dyes of Formulae (2) to (16) and (23) to (25) are also useful for the mass coloration of elastics and impart bright colours generally with good clarity and light fastness.
Example 1
(Formula Removed)
Dye A in which R=H (5 parts) was added to cooled concentrated sulphuric acid and stirred overnight at room temperature. The reaction mixture was poured into ice/water and the precipitate filtered off. The solid was washed with 10% brine and allowed to aix" dry

(Formula Removed)
before heating in pyridine (1240 parts) at 125°C for 2.5 hours. After screening the hot mixture it was evaporated to dryness. The resulting solid was stirred in POCL3 (215 parts) at 75°C for 3 hours and for a further 24 hours at room temperature. Addition to ice/water was followed by filtration, yielding a solid which was washed with water and dried in a vacuum oven. Yield of product (1.7 parts) found to be a mixture of mono and disulphonyl chloride.
Potassium fluoride (3.4 parts) dissolved in water (277 parts) was added to 1,4-dioxane (290 parts) and stirred for 5 minutes before adding the sulphonyl chloride dye (0.84 parts) . After stirring at room temperature for 1 hour at 75°C and 1 hour at 120°C the reaction mixture was carefully added to ice/water which was then extracted with ethyl acetate several times. The ethyl acetate was then dried over magnesium sulphate, filtered and concentrated to yield a mixture of dyes of formula A (0.6 parts) in which one R=H and the other R=SO2F and in which both R groups were SQ,F.
Example 2
(Formula Removed)
Dye B in which R=H (3.7 parts) was added to chlorosulphonic acid (188 parts) with stirring at room temperature. Thionyl chloride (13.7 parts) was then added and the reaction mixture heated at 80°C for 24 hours. After cooling to room temperature, the reaction mixture was carefully drowned out into ice/water and left to stand overnight. Filtration yielded an orange solid which was washed with water then dried in a vacuum oven overnight.
The sulphonyl chloride dye (6 parts) was stirred in 1,4-dioxane (870 parts) while potassium fluoride (25.4 parts) in water (277 parts) was added in one portion, the mixture was heated at 120°C for 30 hours, cooled to room temperature and filtered. The solid obtained was washed with water before drying at 50°C to give a mixture of dyes of formula B in which one R=H and two R groups = SO2F and in which two R groups = H and one R=SO2F.

Example 3
(Formula Removed)
Dye C in which R=H (2.6 parts) was added to chlorosulphonic acid (226 parts) with stirring at room temperature. Ihionyl chloride
13.7 parts) was then added and the reaction mixture heated at 55°C for hours. After cooling and poiiring carefully into ice/water the resulting solution was filtered. The solid obtained was washed with water and dried in the vacuum oven overnight.
The sulphonyl chloride dye (2.6 parts) was stirred in 1,4-ciioxane (580 parts) while potassium fluoride (3.4 parts) in water (277 parts) was added in one portion and the mixture was heated at reflux for hours before cooling to room temperature and filtering. The filtrate . was diluted with water and re-filtered. The collected solids were combined, washed with water and dried at 50°C overnight to give a mixture of dyes of formula C (2.5 parts) in which one, two and three R qroups = SO2,F.
Example 4
(Formula Removed)
Dye D in which R=H (6.7 parts) was added to chlorosulphonic acid (226 parts) with stirring at room temperature. Thionyl chloride (20.5 parts) was added and the reaction mixture heated at 80°C for 3 hours. After cooling to room temperature the mixture was carefully drowned out in ice/water and the resulting solid filtered off. The solid was washed with water and dried under vacuum overnight.
The dry solid (4.4 parts) was stirred in 1,4-dioxane (870 (Darts) while potassium fluoride (8.5 parts) dissolved in water (277 ,Dart:s) was added in one portion and the mixture was heated at reflux for 3 hours before cooling to room temperature and filtering. The solid was washed with water and dried under vacuum overnight to give dye D in which R=SO2.
Bxanrole 5

Dye E in which R=H (2.4 parts) was added to chlorosulphonic icid (150 parts) with stirring at room tenperature. Thionyl chloride 10.3 parts) was added and the mixture heated at 70°C for 3-4 hours. After cooling to room tenperature the mixture was carefully drowned out in ice/water and the resulting solid filtered off. The solid was washed with water and dried under vacuum overnight.
The sulphonyl chloride dye (0.5 parts) was stirred in 1,4-dioxane (290 parts) while potassium fluoride (1.7 parts) dissolved in water (227 parts) was added in one portion and the mixture was heated at reflux for 2-3 hours before cooling to room temperature and carefully (Irownrng in water. The precipitate was filtered off , washed with water and dried under vacuum overnight, to give dye E (0.01 parts) in which k-S02F.
Example 6
Dye F in which R, and RH (10 parts) was added to a stirred mixture of chlorosulphonic acid (376 parts) and thionyl chloride (68.5 parts) at room tenperature. The reaction mixture was heated at 100°C for hours After cooling to room tenperature the mixture was carefully
poured into ice/water and the precipitate filtered off. The solid was washed with water and dried under vacuum to give the sulphonyl chloride derivative.
1,4-Dioxane (58 parts) /potassium fluoride (5.9 parts)/water (27.7 parts) were stirred together before the sulphonyl chloride derivative (0.75 parts) was added. The reaction mixture was heated at 70°C for 20 hours. After cooling to room temperature the solution was filtered and the resulting solid obtained washed with water. The solid was dried under vacuum overnight to yield a mixture of sulphonyl fluoride containing dyes (0.2 parts) of structure F in which R1= CI, R2= SO.F, and in which R1= R SO2F.
Example 7

(Formula Removed)
Dye G in which R=H (2 parts) was added to chlorosulphonic acid (300 parts) at room temperature then heated at 50°C for 3 hours. After cooling, the reaction mixture was poured into ice/water and the precipitate formed filtered off. The solid was washed with water several times before being dried under vacuum, yielding the sulphonyl chloride derivative (1.45 parts).
The potassium fluoride (10 parts)/water (22 parts) /l, 4-dioxane (23.2 parts) were stirred together before the sulphonyl chloride derivative (1.25 parts) was added in one portion. The reaction mixture was heated at 60°C for 5 hours, cooled and filtered. After washing with water and drying overnight under vacuum at 50°C a dye (0.03 parts) of structure G in which R=Sp2F was obtained.
Example 8

(Formula Removed)
Dye H in which R=H (0.75 parts) was added to chlorosulphonic acid (300 parts) at room temperature then heated at 70°C for 5 hours. After cooling, the reaction mixture was poured into ice/water and the
(Formula Removed)
precipitate formed filtered off. The solid was washed with water several times before being dried under vacuum, yielding the sulphonyl chloride dye.
The potassium fluoride (5.1 parts)/water (111 parts)/p-dioxane (93 parts) were stirred together before the sulphonyl chloride dye (0.6 parts) was added and the reaction mixture was heated at 60°C for 5-6 hours. On cooling, the solution was filtered and the solid washed with water. After drying the solid overnight at 50°C, purification was carried out using flash chromatography (eluent: dichloromethane/ethyl acetate) to give dye in which R = S02F.
Example 9
(Formula Removed)
The di-sodium salt of 4-cyano-5-dicyanomethylidene-3-hydroxy-2-co-2,5-dihydropyrrole (10 parts) was dissolved in DMF (388 parts). N- Ethyl -N-ß- (4- fluorosulphonylphenoxy) -ethyl -m-toluidine (10 parts) was then added at 0°C, followed by the dropwise addition of POCL, (24 parts) . After the reaction exothermed slightly, stirring was continued ait 0°C for 30 minutes followed by 2 hours at room temperature. The reaction mixture was carefully drowned out in ice/water, filtered and the solid obtained washed with water before drying at 40°C. The dye was dissolved in an acetone (2 parts) /methanol (5 parts) mixture before pouring into water (27 parts) . The solid filtered off was washed with water and dried at 50°C, yielding dye J (3.4 parts) . λmax 637 nm.
Example 10

(Formula Removed)
N-Ethyl-N-(2-(4-fluorosulphonylphenyl)ethyl)-aniline (12.5 arts) was dissolved in DMF (323 parts) and cooled to 0°C before adding POCl3 (32 parts) drcpwise. The reaction mixture was heated at 80°C for 3 hours, cooled to room temperature and carefully drowned out into ice/water. The aqueous solution was neutralised with concentrated sodium hydroxide and then extracted with toluene (5 x 500mls) . The toluene extracts were combined, dried over MgSO4, and concentrated on a rotary evaporator to yield the aldehyde intermediate (10.5 parts).
The aldehyde intermediate (3 parts) and 3-dicyanomethylidene-2,3-dihydrobenzothiophene-l,1-dioxide (3.3 parts) were refluxed in ethanol (170 parts) for 4 hours. On cooling the solvent was removed on the rotary evaporator and the dye purified by column chromatography (eluent: dichloromethane) to yield dye K (0.1 parts). λmax 581nm.
Example 11

(Formula Removed)
The procedure for example 10 was repeated except that in place of 12.5 parts of N-ethyl-N- (2- (4-fluorosulphonylphenyl)ethyl) -aniline, 12.5 parts of N-ethyl-N- (4-fluorosulphonyl-phenyl ethyl)-m-toluidine was used to yield dye L (0.12 parts) . λmax 596nm.
Example 12

The procedure for exanple 10 was repeated except that in place of 12.5 parts of N-ethyl-N-(2-(4-fluorosulphonylphenyl)ethyl)-aniline; 12.5 parts of N-ethyl-N-(4-fluorosulphonyl-benzyl)-aniline was used to yie:ld dye M (0.6 parts) λmax 566nm.
Example 13

(Formula Removed)
The procedure for exanple 10 was repeated except that in place of 12.5 parts of N-ethyl-N-(2-(4-fluorosulphonylphenyl) ethyl) -aniline,- 12.5 parts of N-isobutyl-N-(3-(4-fluorosulphonylphenyl)propyl) m-toluidine was used to yield dye N (0.08 parts) .λmax 607nm.

WE CLAIM:-
1). A process for colouring synthetic textile material selected from aromatic
polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof, which comprises applying to the synthetic textile material a dye, which is free from water solubilising groups as herein described, carrying at least one -SO2F group provided that the dye is not an azo, bisazo, or anthraquinone dye.
2 A process as claimed in claim 1, wherein the dye is applied in the form of an aqueous dispersion.
3 A process as claimed in claim 1 or claim 2, in which the dye is selected from a benzothioxanthene, styryl, coumarin, naphtholactam, quinophthalone, aminodicyanobenzanthrone, pyrrole, thiophene-1,1 -dioxide, benzodi-furanone, isoindole, thiazole, triphenodioxazine, anthraisothiazolone, nitrodiphenylamine, isoquinolinone, isoquinolinedione, isoindolo-perimidone and indoaniline.
4 A process as claimed in claim 3, in which the dye is of Formula 2A, 2B or 2C
(Formula removed)
in which:
R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; each of R1 to R13 is independently -H, i -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; and R14 is -H, alkoxy or S02F.
5. A process as claimed in Claim 3, in which the dye is of Formula 3:
(Formula removed)
in which:
R1 to R3 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; P.15 is -H or -CN;
each of R16 and R17 independently is -H, alkyl, cycloalkyl, aryl, alkenyl, araikyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidno, piperidino or morpholinio ring; and R18 is -H, -S02F, NHCOalkyl.
(Formula removed)
6. A process as claimed in Claim 3, in which the dye is of Formula 4A or Formula 4B

(Formula removed)
in which:

R1 to R8 are independently -H, -N02, S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl; R15 is -H or -CN; and
each of R16 and R17 independently is -H, aJkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidine, piperidino or morpholino ring.
7. A process as claimed in Claim 3, in which the dye is of Formula 5A, 5B or 5C:
i n which:
X' is a heteroatom;
n is 1 or 2;
Z is optionally substituted heteroaryl;
R: to R6 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl; and
R3 is -H, alkyl, cycloalkyl, aryl, alkenyl or aralkyl each
of which may be optionally substituted.
8. A process as claimed in Claim 3, in which the dye is of Formula 6:
(Formula removed)
in which:
R is -H, alkyl or aryl in which the alkyl and aryl may be further substituted; and
R1 to R9 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl.
y. A process as claimed in Claim 3, in which the dye is of
Formula 7:
(Formula removed)
in which:
R1 to Rb are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl; and
R and R17 independently are -H, alkyl, cycloalkyl, aryi,
alkenyl, aralkyl each of which may be optionally
substituted or R16 and R17 together with the nitrogen atom to
which they are attached form a pyrrolidino, piperidino or
morpholino ring.
10. A process as claimed in Claim 3, in which the dye is of
Formula 8A or 8B:

Formula [8B]
X2 is 0 or S;
(Formula removed)
W is a direct link or -Nr;
R is -H, alkyl or aryl in which the alkyl and aryl may be
further substituted;
R1 to R3 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl;
R16 and R17 independently are -H, alkyl, cycloalkyl, aryl,
alkenyl, aralkyl each of which may be optionally
substituted or R16 and R17 together with the nitrogen atom to
which they are attached form a pyrrolidino, piperidino or
morpholino ring
R1
is -H, alkyl or -NHCOalkyl;
R' is an electron withdrawing group; and
each of R20 to R23 independently is -H, alkyl., cycloalkyJ,
aryl, alkenyl or aralkyl each of which may be optionally
substituted.
11. A process as claimed in claim 3, in which the dye is Formula 9A or 9B:

(Formula removed)
in which:
R1 to R7 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl;
RIb and R17 independently are -H, alkyl, cycloalkyl, aryl,
alkenyl, aralkyl each of which may be optionally
substituted or R16 and R17 together with the nitrogen atom
which they are attached form a pyrrolidino, piperidino or
morpholino ring
R18 is -H, alkyl or -NHCOalkyl;
R'° and R23 are independently -H, alkyl, cydoalkyl, aryl, a 1kenyl or aralkyl each of which may be optionally substituted; and W is a direct link or -NR.
12. A process as claimed in claim 3, in which the dye is of
Formula 10:
Formula [10] in which::
each X3 independently is -H, halo, -S02F, alkyl or alkoxy;
and
each Ring B independently is unsubstituted or is
substituted by from 1 to 5 groups.
13. .. A process as claimed in Claim 3, in which the dye is of
Formula 11:
(Formula removed)
in which:
R1 to R7 are independently -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl;
R16 and R17 independently are -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of which may be optionally
substituted or R and R together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring R18 is -H, alkyl or -NCHOalkyl.
14 A process as claimed in claim 3, in which the dye is of Formula 12:
(Formula removed)
in which
v4
Xs is CH or N
R1 to R3, R5 to R8 and R11 are independently -H, -N02, -S02F,
alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl;
R16 and R17 independently are -H, alkyl, cycloalkyl, aryl,
alkenyl, aralkyl each of which may be optionally
substituted or R16 and R17 together with the nitrogen atom to
which they are attached form a pyrrolidino, piperidino or
morpholino ring
R1B is -H, alkyl or -NHCOalkyl.
15 A process as claimed in Claim 3, in which the dye is of Formula 13:
(Formula removed)
in which:
-.25
R" and R each independently is alkyl;
R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl; and
,15
is -H or -CN.
16* A process as claimed in claim 3, in which the dye is of
Formula 14:
(Formula removed)
NR15R2e Formula [14] in which:
R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl;
Rlfe is -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl each of
which may be optionally substituted; and
R26 is H, alkyl, cycloalkyl, aryl, aralkyl each of which may
be optionally substituted or a group -COR in which R is -H,
alkyl or aryl in which the alkyl and aryl may be further
substituted.
17.. A process as claimed in claim 3, in which the dye is of Formula 15:
(Formula removed)

in which:
,10
R to R each independently is -H, -N02, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -S02NHaryl, provided that at least one of R1 to R10 is -N02.
18. A process as claimed in Claim 3, in which the dye is of Formula 16A, 16B or 16C:

(Formula removed)
in which:
R is -H, alkyl or aryl in which the alkyl and aryl may be
further substituted;
R1 to R10 are independently -H, -N02, -S02F, alkyl, alkoxy,
-Saryl, halo, -S02NHalkyl or -S02NHaryl; and
R16 and R17 independently are -H, alkyl, cycloalkyl, aryl,
alkenyl, aralkyl each of which may be optionally
substituted or R16 and R17 together with the nitrogen atom to
which they are attached form a pyrrolidino, piperidino or
morpholino ring.
A process as claimed in Claim 3, in which the dye is of
Formula 23: (Formula removed)

in which

R1 to R10 are independently -H, -N02, -So2F, alkyl, alkoxy, -Saryl, halo, ~S02NHalkyl or -S02NHaryl.
20. A process as claimed in Claim 3, in which the dye is of
Formula 24:
(Formula removed)
in which:
R1 to R6 are independently -H, -N02, -S02F, alkyl, alkoxy, --Saryl, halo, -S02NHalkyl or -S02NHaryl;
R16 and R17 independently is -H, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, each of which may be optionally substituted or R16 and R17 together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring.

11. A process as claimed in claim 3, in which the dye is of Formula 25:
(Formula removed)
in which
R» to Ri° are independently -H, -NC)2, -S02F, alkyl, alkoxy, -Saryl, halo, -S02NHalkyl or -SOzNHaryl.
2.1. A process for colouring synthetic textile material selected from aromatic polyester, secondary cellulose acetate, cellulose triacetate, polyamide and polyacrylonitrile or fibre blend thereof substantially as herein described with reference to the foregoing examples.

Documents:

129-del-1995-abstract.pdf

129-del-1995-claims.pdf

129-del-1995-correspondence-others.pdf

129-del-1995-correspondence-po.pdf

129-del-1995-description (complete).pdf

129-del-1995-form-1.pdf

129-del-1995-form-13.pdf

129-del-1995-form-2.pdf

129-del-1995-form-3.pdf

129-del-1995-form-4.pdf

129-del-1995-form-6.pdf

129-del-1995-form-9.pdf

129-del-1995-gpa.pdf

129-del-1995-pct-210.pdf

129-del-1995-pct-408.pdf

129-del-1995-petition-others.pdf

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Patent Number

190717

Indian Patent Application Number

129/DEL/1995

PG Journal Number

33/2003

Publication Date

16-Aug-2003

Grant Date

15-Mar-2004

Date of Filing

30-Jan-1995

Name of Patentee

ZENECA LIMITED

Applicant Address

15 STANHOPE GATE, LONDON, W1Y 6LN, ENGLAND.

Inventors:

#	Inventor's Name	Inventor's Address
1	NIGEL HALL	ZENECA SPECIALTIES, P.O.BOX 42, HEXAGON HOUSE, BLACKLEY, MANCHESTER M9 8ZS, UNITED KINGDOM.

PCT International Classification Number

D06B

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9404020.1	1994-03-02	U.K.