Title of Invention | "A PROCESS FOR THE MANUFACTURE OF A COLOURED AROMATIC POLYESTER TEXTILE MATERIALS" |
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Abstract | A process for the manufacture of a coloured aromatic polyester textile material or fibre blend thereof comprises applying to the aromatic polyester textile material a dispersion comprising an aqueous medium and, dispersed therein, from 0.001 to 4% of a dye compound of Formula (1): A-N=N-D-N=N-E Formula (1) wherein: A, D and E each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A, D and E carries directly at least one -S02F group or carries a substituent to which at least one -S02F group is attached. The dye compound is free from water solubilising groups. |
Full Text | The present invention relates to a process for the manufacture of a coloured aromatic polyester textile material. The present invention is a divisional out of Indian Patent Application No. 113/DEL/95. The present invention relates to a process for the manufacture of coloured synthetic textile materials, especially synthetic textile materials of aromatic polyester fibres or fibre blends thereof, by application thereto of a dispersion, in an aqueous medium of a disazo dye compound. Disazo dyes including water solubilizing groups are disclosed in FR-A-1307200 and US-A-3131021. Disazo dyes including ice colour coupling components are disclosed in US-A-2427995. JP-A-54-050021 discloses a disazo dye in the context of reactive disperse dyes for cellulose. According to the present invention there is provided a process for the manufacture of a coloured aromatic polyester textile material or fibre blend thereof which comprises applying to the aromatic polyester textile material a dispersion comprising an aqueous medium and characterized in that dispersed therein is 0.001 to 4% of a dye compound which is free from water solubilising groups which dye compound has the Formula (1) (Formula Removed) where in each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A, D or E carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached. 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. Different dye compounds of Formula (1) may be mixed or the dye compounds of Formula (1) may be mixed with dyes which do not contain an --SO2F group; such mixtures may be used in a process of the present invention. 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 the dye 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 synthetic textile material to be manufactured by the process of the invention iS of aromatic polyester fibres or a fibre blend thereof . Other fibres in the blend thereof may be selected from secondary cellulose acetate, cellulose triacetate, polyamide, such as polyhexamethylene adipamide, pOlyacrylonitrile, in addition to the aromatic polyester. The aromatic polyester is especially preferably polyethylene 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 cellulose such as polyester-cotton. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn, woven or knitted fibres. 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 dye compounds of Formula (1) are thus free from water solubilising groups such as -SO2H, -C02H, -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 as an aqueous dispersion by methods which are conventionally employed in dye ing disperse dyes to such materials and fibre blends. For example, the dye compounds of Formula (1) 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; a sequestrant may optionally be added; ii) 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; 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; wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may 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; and 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; sequesterants may optionally be added. In all 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 clisazo dye compounds of Formula (1) used in a process of the invention generally provide coloured textile material which shows good fastness to washing, light and heat. The heterocyclic group represented by A, D or E 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- and 1,2,4-triazolyl. The carbocyclic group represented by A, D or E may be phenyl or naphthyl. A and E each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl, more preferably thien-2-yl, phonyl, naphthyl, thiazol-2-yl, isothiazol-5-yl or pyrid-4-one-5-yl and especially phenyl or naphthyl. D is preferably phenyl, naphthyl, biphenyl, thienyl or thiazolyl, more preferably phen-1,4-ylene, naphth-1,4- ylene, 4,4'-biphenylene, 3,3'-dichloro-4,4'-biphenylene, thien-2,5-ylene or thiazol-2,5-ylene and especially phen-1,4-ylene, naphth-1,4-ylene or thien-2,5-ylene. Examples of suitable substituents for A, D and E are cyano, hydroxy, nitro, halo such as fluoro, chloro and bromo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryloxy, -COalkyl, -NHCOalkyl, -NHS02alkyl, -OCOalkyl, -COOalkyl, -Salkyl, -Saryl, -S02alkyl, -S02aryl, NRXR2, -CONR1R2, -S02NR1R2 in which R1 and R2 each independently is -H or cycloalkyl, alkyl, alkyl or alkoxy substituted by -OH, -CN, halo such as -F, -Cl and -Br, phenyl, -S02F, -OCOalkyl, -COOalkyl, (Formula Removed) -OCOphenyl, -COOphenyl, -OCO(f1uorosulphonylphenyl), alkyl(fluorosulphonylphenyl), -OCO(fluorosulphonyl-phenyl), -COOalkoxyalkoxy, alkoxyalkoxy, -OCalkyl, -OCalkoxyalkoxy, alkenyl, -OCOalkenyl, -COOalkylOalkyl, -OalkylCN, alkoxy, aryloxy, -OalkylOCOalkylOalkyl in which each alkyl is C1-10-alkyl and each alkoxy is C1-10-alkoxy each of which may be straight or branched chain and each alkyl, alkoxy, aryl or phenyl group may carry an -S02F substituent or R1 and R2 together with the -N atom to which they are attached form a 5- or 6-membered ring such as morpholino or piperidino. Preferred substituents for A, D and E are cyano, nitro, chloro, bromo, f luorosulphonyl, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -NHCOC1-6-alkyl, -OCOC1-6-alkyl, -COOC1-6-alkyl, -NRTR2 in which R1 and R2 each independently is -H, C1-6-alkyl, C1-6-alkyl substituted by -OH, -CN, -Cl, phenyl, -OCOC1-6-alkyl, -COOC1-6-a Ikyl, (Formula Removed) C1-4-alkyl (4-fluorosulphonylphenyl) , OCO(3- fluorosulphonylphenyl), -OCOphenyl, -OCO(4- fluorosulphonylphenyl) , -C2-4-alkenyl, -COOC1-6-alkylOC1-6- alkyl, -OC1-6-alkylCN, -OC1-6-alky 1.0COCC1-6-alkylOC1-6-alkyl or where R1 and R2 together with the -N atom to which they are attached form a morpholino or piperidino. The dye compounds of Formula (1) preferably carry a total of from one to three -S02F groups, more preferably from one to two -S02F groups and especially one -S02F group. A preferred sub-group of dye compounds of Formula (1) is that of dye compounds of Formula (2): (Formula Removed) in which: R1 and R2 each independently is -H, C1-8-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -Cl, -Br, -SQ2F, phenyl, pheny!S02F, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOC1-6 alkoxyC1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO(3-fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4--alkenyl; R3 is -H, -S02F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -S02F, CC1-6-alkyi, C1-6-alkoxy or -NHCOC1-6- alkyl; R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -S02F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -N02, -S02F, C1-6-alkyi, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, -F, -Cl, -Br, -CF3, -NRaR2, -CONR^2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined. In compounds of Formula (2) R1 R8, R9 and R10 each independently is preferably -H, C1-6-alkyl or C1-6-alkoxy A further preferred sub-group of compounds of Formula (1) is that of dye compounds of Formula (3): (Formula Removed) in which: R1, R2, R3, R4, R5, R6, R11, R12, R13, R14 and R15 are as hereinbefore defined for compound;: of Formula (2); and R16 is -H, -CN, -S02F, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR1R2 in which R1 and R2 are as hereinbefore defined; and R17 is -H, -CN, -S02F or C1-6.-alkyl. In compounds of Formula ( :!) R16 is preferably -H, -CN, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR1R2 and R17 is preferably -H, -CN or C1-6-alkyJ.. A further preferred subgroup of dye compounds of Formula (1) is that of dye compounds of Formula (4): (Formula Removed) in which R3 to R15 are as hereinbefore defined. Such compounds, other than 4-(2'-mel hoxyphenylazo-4'-(fluorosulphonylphenylazo)) phenol, which may be otherwise named as 1-(4'-hydroxyphenylazo)-2-methoxy-4-(4'-fluorosulphonylphenylazo) benzene, are novel compounds. In a further preferred embodiment of the present invention the dye compounds of Formulae (1), (2), (3) and (4) applied carry directly at least one -S02F group or carry a substituent to which at least one -SO2F group is attached and carry at least one1 ester group or carry a substituent: to which at least one ester group is attached. Such dyes with both -SO2F and ester groups show improved dyeing properties, particularly wet-fastness and light-fastness. Compositions comprising dispersions of the dye compounds of Formulae (1), (2), (3) and (4) in which A, D and E are as hereinbefore defined in aqueous media are novel. The compositions typically comprise from 1% to 30% of a compound of Formula (1), (2) or (3) and are preferably buffered at a pH from 2 to 7, more preferably at a pH from 4 to 6. These dispersions may furt her comprise ingredients conventionally used in dyeing applications such as dispersing agents for example 1ignosulphonates, naphthalene sulphoriic 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 dye compound of Formula (1). Wetting agents may be used at from 0% to 20% on the weight of the dye compound of Formula (1). The dispersions may be prepared by bead milling the dye compound of Formula (1) with glass beads or sand in an aqueous medium. A number of compounds of Formula (1) used in the above coloration process are novel except for 1-(4-hydroxyphenylazo)~2-methoxy-4-(4-fluorosulphonylphenylazo)benzene; 1-(2-chloro-4-nitrophenylazo)-5-methyl-2-fluorosulphonyl-4 -(2-hydroxy-3-(carbonyl(n-phenyl)amino)naphth-1-ylazo)benzene; 1-(2-methyl-5-fluorosulphonylphenylazo)-3-ethoxy-4-(2-hydroxy-3-(carbonyl(N-phenyl)amino)naphth-1-ylazo)benzene; 1-(3-fluorosulphonylphenylazo)- 2,5-dimethoxy-4-(2-hydroxy-3- (carbonyl (N-naphth-l--yl) amino) naphth-1-ylazo)benzene; and 1-(2-methyl-5-fluorosulphonylphenylazo)-4-(2-hydroxy-3-(carbonyl(N-phenyl)amino)naphth-1-ylazo)naphthalene. The dye compounds of Formula (1) may be prepared by usual methods for the preparation of disazo compounds such as by diazotisation of an amine A-NH2 and coupling onto a component X-D-NH2 in which A and D are as hereinbefore defined and X is a group displaceable by a diazotised amine, followed by diazotisation of the resultant monoazo compound A-N=N-D-NH2 and coupling onto a component E-X in which E and X are as hereinbefore defined. Typically the amine A-NH2 may be diazotised in an acidic medium such as acetic 01 propionic acid or mixtures thereof using a nitrosating agent such as nitrosyl sulphuric acid at a temperature of from -5°C to 5°C. The diazotised amine may be coupled onto the component X-D-NH2 in an alkanol such as methanol and water at a temperature of from 0°C to 5°C. The monoazo compound A-N=N-D-NH2 may be recovered from the reaction mixture by filtration. The compound A-N=N-D-NH2 may be diazotised in an acidic medium such as acetic or sulphuric acid or mixtures thereof using a nitrosating agent as described above and coupled onto a component E-X in aqueous medium preferably whilst maintaining the pH at about 3. The A-N=N-D-N=N-E product may be recovered from the reaction mixture by filtration and may be purified by slurrying in an alkanol such as methanol and refiltering. Fluorosulphonyl groups may be introduced into the dye compounds of Formula (1) or into the A, D and E components prior to coupling by methods generally available in the literature. For example reaction of the dye compound of Formula (1), A-NH2, the NH2 being protected as 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 30°C to 100°C gives the chlorosulphonyl derivative. The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative. Alternatively the dye compound of Formula (1), A-NH2, or D-X may be sulphonated with sulphuric acid or oleum to give the sulphonic ac:id 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. The chlorosulphonyl der ivative may then be converted to the fluorosulphonyl derivative as described above. The dye compound of Formula (1) is useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which are excellent in wet and light fastness properties. The invention is further illustrated by the following Examples. Example 1 4-Aminobenzenesulphonyl fluoride (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts) and ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.3 parts of 2-amino-3-cyano-5-(4'-sulphonylfluorophenylazo)thiophene. 2-Amino-3-cyano-5-(4'-sulphonylfluorophenylazo) thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 parts) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N,N~bis-(acetoxyethyl)-aniline (15 parts) in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered and dried overnight to yield 4-(3-cyano-5-(4'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-bis-(acetoxyethyl)-aniline (4 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 2 The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis - (acetoxyethyl)-aniline; 15 parts of N-(2-cyanoethyl)-N-(2-methoxy-carbonylethyl)-m-toluidine were used to yield 4-(3-cyano-5-(4'-sulphonylfluorophenylazo)-2-th:ophene-azo)-N-(2-cyanoethyl)-N-(2-methoxy-carbonylethyl)-m-toluidine (3.8 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 3 The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts N,N-bis-(2-cyanoethyl)-aniline were used to yield the product 4-(3-cyano-5-(4'-sulphonylfluoro-phenyl azo)-2-thiophene-azo)-N,N-bis-(2-cyanoethyl)-aniline (2.2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. λmax 575nm. Example 4 The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N-ethyl-N-(2-carboxyethyl)-aniline were used to yield the product 4-(3-cyano-5-(4'- sulphonylfluorophenylazo)-2-thJ ophene-azo)-N-ethyl-N-(2-carboxyethyl)-aniline (2.4 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. λmax 637 nm. Example 5 The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N,N-diethyl m-acetanilide were used to yield the product 4-(3-cyano-5-(4'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-diethyl m-aoetanilide (6.5 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 6 3-Aminobenzenesulphonyl fluoride hydrochloride hydrate (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0 -5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts), ice/water (840 parts). The pH was maintained at 3 by I he addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.3 parts of 2-arnino-3-cyano-5- (3 ' sulphonyl fluorophenylazo) -thiophene. 2-Amino-3-cyano-5-(3'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 pa:its) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N,N-diethylaniline (15 parts) stirred in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The diazo (12.5 parts) was then added slowly. The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-cyano-5-( 3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-diethyl aniline (1.7 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades. Example 7 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diet;hyl aniline; 15 parts of N-ethyl-N-(2-cyanoethyl) aniline were used to yield the product 4-(3-cyano-5-(3'-sulphoriylfluoropheriylazo)-2-thiophene-azo)-N-ethyl-N-(2-cyanoethyl) aniline (7 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 8 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-(2-cyanoethyl)-N-(acetoxyethyl)aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo) -2-thiophene-azo)-N-(2-cyanoethyl)-N-(acetoxyethyl)aniline (2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades Araax 585 nm. Example 9 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diet:hyl aniline; 15 parts of N-octyl-N-(sec)butyl-aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N-octyl-N-(sec)butyl-aniline (1.5 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades. Example 10 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N,N-diethyl m-acetanilide were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-diethyl m-acetanilide (3 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades. Example 11 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-butyl-N-secbutyl m-acetanilide were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N-butyl-N-sec-butyl m-acetanilide (8.5 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades. Example 12 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-ethyl-N-benzyl-aniline were used to yield the product 4- (3-cyano-5-(3'-sulphonylfluoio-phenylazo)-2-thiophene-azo)-N-ethyl-N-benzyl-aniline (2.3 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 13 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethylaniline; 15 parts of N-ethyl-N-2-isopropenoxycarbonylethylaniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluoro-phenylazo)-2-thiophene-azo)N-ethyl-N-2-iso-propenoxycarbonyl-ethyl-aniline (2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 14 3-Amino-4-methoxybenzenesulphonylfluoride (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts) ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetfite and 50% sodium hydroxide solution. After Stirling at 0-5°C for a further 2 hours filtration yielded 3.2 parts of 2-aniino-3-cyano-5-(2'methoxy-5'-sulphonylfluoro-phenylazo)-thiophene. 2-Amino-3-cyano-5-(2'-methoxy-5'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (1H parts) was added carefully and the reaction stiired for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N-(2-cyanoethyl)-N-acetoxyethylaniline (15 parts) stirred in ice/water (960 part.s), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by fiJtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-cyano-5-(2'-methoxy-5'-sulphonylfluorophenyl-azo)-2-thiophene-azo)-N- (2-cyanoethyl)-N-acetoxyethyl aniJ.ine (3 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 15 The procedure for Example 14 was repeated except that in place of 15 parts of N-- (2-cyanoethyl) -N-acetoxyethyl aniline; 15 parts of N-butyl-N- (2-cyanoethyl) aniline were used t.o yield the product 4-(3-cyano-5- (2 ' -methoxy-5 ' -sulphonylf luorophenylazo) -2-thiophene-azo) -N-butyl-N-(2-cyanoethyl)aniline (6 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. Example 16 3-Aminobenzenesulphonylfluoride hydrochloride hydrate (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nilrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-ethoxycarbonyl-thiophene (4.2 parts) in methanol (625 parts), ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a :f urther 2 hours filtration yielded 3.3 parts of 2-amino-3-ethoxycarbonyl-5-(3'-sulphonylfluoro-phenylazo)thiophene. 2-Amino-3-ethoxycarbonyl-5-(3'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 parts) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to N-ethyl-N-(2-cyanoethyl)-aniline (15 parts) stirred in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-ethoxycarbonyl-5-(3'-sulphonylf1uoro-phenyl-azo)-2-thiophene-azo)-N-ethyl-N-(2-cyanoethyl)-aniline (2.7 parts) which when applied to polyester materials from an agueous dispersion gave blue shades. Example 17 The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-propyl) -aniline was used to yield the product 4-(3-cyano-5-(4'-sulphonylfluoro-phenylazo)-2-thiophene-azo)-N-ethyl-N-( (4-sulphonylfluorophenyl)-propyl)-aniline (0.25 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades, λmax649 nm. Example 18 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethylaniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline was used to yield the product 4-(3 cyano-5-(3'- sulphonylfluoro-phenylazo)-2-thiophene-azo)-N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline (4 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades, Amax 629 nm. Example 19 The procedure for Example 14 was repeated except that in place of 15 parts of N-(2-cyanoethyl)-N-acetoxyethylaniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline was used to yield the product 4- ( 3-cyano-5- (2 ' -methoxy-5 ' -sulphonylf luorophenyl azo)-2-thiophene-azo)-N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline (1.6 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades, λmax 627 nm. Example 20 The procedure for Example 16 was repeated except that in place of 4 parts of 3-aminobenzenesulphonyl fluoride hydrochloride hydrate; 4 parts of 4-nitroaniline was used and in place of 15 parts of N-ethyl-N-(2-cyanoethyl)-aniline; 15 parts of! N-ethyl-N-( (4-sulphonylfluorophenyl)-ethyl)-aniline was used. This yielded 4-(3-ethoxycarbonyl-5-(4'-nitro-phenyl-azo)-2-thiophene-azo)-N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline (1.9 parts), which when applied to polyester materials from an aqueous dispersion gave blue colours. Example 21 Sulphanilyl fluoride (4 parts) was stirred in acetic/propionic acid 86/14 vo.l/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours. The diazo component was then added slowly to 2,5-dimethoxyaniline (4.1 parts) in methanol (625 parts) and ice/water (840 parts). The pH was maintained at 5-6 by the addition of sodium acetate. After stirring at 0-5°C for 2 hours the mixture was alLowed to warm to room temperature before being filtered to yield 3.8 parts of 2,5-dimethoxy-4-(4'-sulphonylf1uorophenyl-azo)-aniline. 2,S-Dimethoxy-4-(4'-sulphonylfluorophenyl-azo)-aniline (8 parts) was stirred i ri cone, sulphuric acid (750 parts). On cooling to 0-5"C, 40% nitrosyl sulphuric acid (12 parts) was added carefully and the reaction stirred for 1 hour before beinq allowed to warm to room temperature. N-Ethyl-N-(4'-fluorosulphonylbenzyl)-aniline (14 parts) was stirred in ice/water (960 parts), sulphamic acid (10 parts) and methanol (1250 parts). The diazo (8 parts) was then added slowly while maintaining the pH at 5-6 by the addition of sodium acetate and sodium carbonate solution. The oil obtained was then taken up in the dichloromethane and purified by column chromatography to yield 0.1 parts of the product 4-(2',5'-dimethoxy-4-(4'-sulphonylfluorophenyl-azo)-phenylazo)-N-ethyl-N-(4' -f luorosulphonylbenzyl)-aniline, λmax 536 nm. Example 22 The procedure for Example 21 was repeated except that in place of 14 parts of N-ethyl-N-(4'-fluorosulphonylbenzyl)-aniline; 14 parts of N,N-dibutyl-m-toluidine was used to yield I:he product 4-(2',5'-dimethoxy-4-(4' '-sulphonylfluo rophenyl-azo)-phenylazo)-N,N-dibutyl-m-toluidine (0.27 parts). Example 23 2-Methyl-4-) (4'-phenylazo-phenylazo)-phenol (3.2 parts) was carefully added to chlorosulphonic acid (376 parts), while stirring, Thionyl chloride (82 parts) was then added and the mixture heal.ed at 90°C for 28 hours. The reaction mixture was then drowned out into ice/water very carefully and filtered. The solid was washed several times with water until the washings were neutral before drying to yield 5-(4'-(4'-chlurosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-l>enzenesulphonyl chloride (3.1 parts). 5- (4 '- (4 ' '-Chlorosulphonyl.-phenylazo) -phenylazo) -2-hydroxy-3-methyl-benzenesulphonyl chloride (1.95 parts) was stirred in 1,4-dioxan (117.5 parts) before potassium fluoride (34 parts) dissolved in water (440 parts) was added over 2-3 minutes. After heating at 50-60°C for 2 hours the reaction mixture was cooled and filtered. The solid was washed with water and dried to yield 5-(4'-(4'-fluorosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-benzenesulphonyl fluoride (1.6 parts). Example 24 The procedure for Example 23 was repeated except that the starting dye was 4-(4 '-phenylazo-naphth-1-ylazo)-phenol (5.7 parts) and the treatment with chlorosulphonic acid was carried out at 75°C. The product (2.1 parts) was found to be a mixture of two compounds, 5-(4'-(4'-fluorosulphonyl-phenylazo)-naphth-1-ylazo)-2-hydroxy-benzene sulphonyl fluoride and 5-(4'-(4'-fluorosulphonyl-phenylazo)-naphth-1-ylazo)-2-hydroxy-benzene-1,3-disulphonyl fluoride. Example 25 The procedure for Example 23 was repeated except that the starting dye was 1-methyl-3-(4-phenylazo)-1H-quinolin-2-one (2.2 parts) and heating with chlorosulphonic acid was carried out for 2 hours. The product (0.6 parts) was found to be a mixture of 1-methy1-3-(4'-(4'-fluorosulphonyl-phenylazo)-phenylazo)-4-(lH-quinolin-2-onyl)-sulphonyl fluoride and l-methyl-3-(4-phenylazo-phenylazo)-4-(lH-quinolin-2-onyl)-sulphonyl fluoride. Example 26 The procedure for Example 23 was repeated except that the starting dye was 4-(4'-(4'-nitro-phenylazo)-phenylazo)-phenol (11.5 parts) and that the dye was heated at 75-80°C with the chlorosulphonic acid. The product (5.5 parts) was found to be a mixture of two compounds, 2-hydroxy-5-(4'-(4'-nitro-phenylazo)-phenylazo)-benzenesulphonyl fluoride and 2-hydroxy-5-(4'-(4'-nitro-phenylazo)-phenylazo)-benzene-1,3-disulphonyl fluoride. Example 27 The procedure for Example 23 was repeated except that the starting dye was 2-methyl-4-(2',5'-dimethyl-4'-(4'-nitro-phenylazo)-phenylazo)-phenol (3.85 parts) and that the dye was heated for only 3 hours with chlorosulphonic acid. The product of the reactions was found to be 2-hydroxy-3-methyl- 5-(2',5'-dimethyl-4'-(4 ' '-nitro-phenylazo)-phenylazo)-benzenesulphonyl fluoride (0.2 parts). Example 28 The procedure for Example 23 was repeated except that the starting dye was 2-methyl-(3,3'-dichloro-4'-(4-hydroxy-3-methyl-phenylazo)-biphenyl-4-ylazo)-phenol (3.05 parts) and the dye was heated for only 3 hours. The product (2.95 parts) was found to be a mixture of two compounds, 5-(3,3'-dichloro-4'-(3-fluorosulphonyl-4-hydroxy-5-rnet hyl -phenylazo) -biphenyl-4-ylazo) -2-hydroxy-3-methyl-benzenesulphonyl fluoride and 5-(3,3'-dichloro-4'-(3-methyl-4-hydroxy-phenylazo)-biphenyl-4-ylazo)-2-hydroxy-3-methyl-benzenesulphonyl fluoride. WE CLAIM:- 1. A process for the manufacture of a coloured aromatic polyester textile material or fibre blend thereof which comprises applying to the aromatic polyester textile material a dispersion comprising an aqueous medium and characterized in that dispersed therein is 0.001 to 4% of a dye compound which is free from water solubilising groups which dye compound has the Formula (1) (Formula Removed) where in each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A, D or E carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached. 2. A process as claimed in Claim 1 wherein the dye compound of Formula (1) is of Formula (2) (Formula Removed) in which R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -Cl, -Br, -SO2F, phenyl, phenyl SO2F, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOCC1-6-alkoxy C1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO (3-fluorosulphonylphenyl), -OCO (4-fluorosulphonylphenyl), -OCOphenyl or-OCOC2-4-alkenyl; R3 is -H, -SO2F,C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-alkyl; R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, NO2, -SO2F, C1-6-alkyl, C1-6- alkoxy, COC1-6-alkyl, -COOC1-6-alkyl, F, -Cl, -Br, -CF3, -NR1R2, -CONR1R2 or -SOaNR1R2 in which R1 and R2 are as hereinbefore defined. 3. A process as claimed in claim 1 wherein the dye compound of Formula (1) is of Formula (3): (Formula Removed) in which: R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -Cl, -Br, -SO2F, phenyl, phenylSO2F, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO(3-nuorosulphonylphenyl), -OCO (4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl; R3 is -H, -SO2F,C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, Ci-6-alkyl, Ci-6-alkoxy or -NHCOC1-6-alkyl; R5 and R6 each independently is -H, Ci-6-alkyl,C1-6-alkoxy or -SO2F; R11, R12, R13, R14and R15 each independently is -H, -CN, -NO2, -SOaF, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -Cl, -Br, -CF3, -NR1R2 -CONR1R2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined; R16 is -H, -CN, -SO2F, -COOC1-6-alkyl, COC1-6-alkyl or -CONR1R2 in which R1 and R2 are as hereinbefore defined; and R17 is -H, -CN, -SO2F or C1-6-alkyl. 4. A process as claimed in claim 1 wherein the dye compound of Formula (1) is of Formula (4): (Formula Removed) in which: R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, Ci-6-alkyl, C1-6-alkoxy or -NHCOC1-6- alkyl; R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -NO2, -SO2F,C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -Cl, -Br, -CF3, -NR1R2, -CONR1R2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined. 5. A process as claimed in anyone of Claims 1 to 4 wherein the dye compound carries at leat pne ester group or carries a substituent to which at least one ester group is attached. 6.Aprocess for the manufacture of a coloured aromatic polyester textile material substantially as herein described with reference to the foregoing examples. . |
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1248-del-2002-correspondence-others.pdf
1248-del-2002-correspondence-po.pdf
1248-del-2002-description (complete).pdf
1248-del-2002-petition-137.pdf
Patent Number | 216977 | |||||||||
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Indian Patent Application Number | 1248/DEL/2002 | |||||||||
PG Journal Number | 13/2008 | |||||||||
Publication Date | 31-Mar-2008 | |||||||||
Grant Date | 24-Mar-2008 | |||||||||
Date of Filing | 12-Dec-2002 | |||||||||
Name of Patentee | ZENECA LIMITED | |||||||||
Applicant Address | 15 STANHOPE GATE, LONDON W1Y 6LN, ENGLAND. | |||||||||
Inventors:
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PCT International Classification Number | D06P 3/52 | |||||||||
PCT International Application Number | N/A | |||||||||
PCT International Filing date | ||||||||||
PCT Conventions:
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