Title of Invention

"A DISPERSION COMPOSITION AND A PROCESS FOR PREPARING THE SAME"

Abstract

This invention relates to a process for the preparation of a dispersion composition comprises: i) a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, ii) a dispersing agent present in an amount of 10 to 200% by weight of the dye compound and iii) optionaHy additionally comprising ingredients selected from conventional components such as wetting agents and defoamers, which dye compound is free from water solubilizing groups and is of formula (1):

Full Text

The present invention relates to a dispersion composition and a process for preparing the same. The dispersion composition contains a disazo dye compound having a fluorosulphonyl group for colouring synthetic textile materials, especially aromatic polyesters and fibre blends thereof and the invention also relates particularly to a process for preparing such dispersion compositions containing disazo dye compounds. Disazo dyes including water soulbilizing groups are described 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 a reactive disperse dyes for cellulose. According to the present invention there is provided a dispersion composition comprising: i) a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, ii) a dispersing agent present in an amount of 10 to 200% by weight of the dye compound and iii) optionally additionally comprising ingredients selected from conventional components such as wetting agents and defoamers, which dye compound is free from water solubilizing groups and is of formula (1) : (Formula Removed) wherein, each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A, D and E carries directly at least one -SO2F group or carries a substitutent to which at least one -SO2F group is attached, and wherein, in the formula (1), each of A, D and E is such as to provide a dye compound selected from compounds of the formulae 2, 3 and 4 as given below: (Formula Removed) in which: R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -CI, -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, -0C0(3-fluorosulphonylphenyl), -0CO(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, -N02/ -S02F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, ' -CONRaR2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined; in which: R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -C1, -Br, -S02F, phenyl, phenylS02F, -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, -0C0(3-fluorosulphonylphenyl), -0C0(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl; R3 is -H, -S02F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6- alkyl; R5 and R6 each independently is -H, Ci_6-alkyl, C!_6-alkoxy or -SO2F; 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, -C1, -Br, -CF3, -NRXR2, -CONR1R2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined; R16 is -H, -CN, -S02F, -COOCi-e-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; and in which: R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, Ci-e-alkyl, C1-6-alkoxy or -NHCOC1-6- alkyl; R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, Ci-e-alkoxy or -SO2F; and R", R12, R13, R14 and Rl5 each independently is -H, -CN, -NO2,-SO2F, C1-6-alkyl, Ci-e-alkoxy, COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, CF3, NR1R2, -CONR1R2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined. 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 invention also relates to a process for the preparation of dispersion composition, comprising mixing homogeneously i) a dye compound of formula (1) in an amount of from 1 to 30% by weight of the composition , ii) a dispersing agent in an amount of 10 to 200% by weight of the dye compound and iii) conventional components such as wetting agents and defoamers in an aqueous medium in a manner such as herein described, to obtain a dispersion composition in the form of homogenous mixture. The dispersion composition is neither a product of chemical reaction nor a mere admixture resulting in the aggregation of the properties of the individual components but is in fact a synergistic composition having improved and unexpected properties in that the respective components of the dispersion cooperate together so as to provide, in application thereof to a textile fabric, a dyed product having surprisingly good fastness to washing, light and heat. 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 are a feature 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 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; 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; and vi) atmospheric dyeing of acetate, 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; 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 present compounds generally provide coloured textile material which shows good fastness to washing, light and heat. The dye compounds of Formula (1) preferably carry a total of from one to three -SO2F groups, more preferably from one to two -SO2F groups and especially one -S02F group. As indicated above, a 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 Ci-6-alkyl substituted by -OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylS02F, -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, -SOzF, 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 -S02F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -N02, -SO2F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, -CONR1R2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined. In compounds of Formula (2) R7, R8, R9 and R10 each independently is preferably -H, C1-6-alkyl or C1-6-alkoxy. A further sub-group of dye 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 compounds of Formula (2); and R16 is -H, -CN, -S02F, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR1R2 in v/hich R1 and R2 are as hereinbefore defined; and R17 is -H, -CN, -SO2F or C1-6-alkyl. In compounds of Formula (3) R is preferably -H, -CN, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR1R2 and R17 is preferably -H, -CN or C1-6-alkyl. A further subgroup of dye compounds of Formula (11 is that of dye compounds of Formula (4): (Formula Removed) in which R3 to Ri5 are as hereinbefore defined, except for 4-(2'-methoxyphenylazo-4'-(4'-fluorosulphonylphenylazo)) phenol, which may alternatively be named as l-(4'-hydroxyphenylazo)-2-methoxy-4-(4'-fluorosulphonylphenylazo)benzene. In a further preferred embodiment of the present invention the dye compounds of Formulae (1), (2), (3) and (4) carry directly at least one -SO2F group or carry a substituent to which at least one -SO2F group is attached and carry at least one 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 in accordance with the invention 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 further comprise ingredients conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl ethoxylates which may be sulphonated or phosphated, inorganic salts, de-foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the 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 I-(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-1-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 or propionic acid or mixtures thereof using a nitrosating agent such as nitrosyl sulphuric acid at a temperature 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 thicnylchloride 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 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 pentachioride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20°C to 110°C. The chlorosulphonyl derivative 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-Aminobenzenesuiphonyl 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-thiophene-azo)-N-(2-cyanoethyl)-N-(2-methoxy-carbonylethyl)-m-toluidine (3.8 parts) which when applied to polyester materials from an aqueous dispersion qave 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. Amax 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-thiophene-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-acetanilide (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 36/14 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 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-(3'-sulphonyl fluoro-phenylazo)-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 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-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-diethyl aniline; 15 parts of N-ethyl-N-(2-cyanoethyl) aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-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 λmax 585 nm. Example 9 The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl 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'-sulphonylfluoro-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'-sulphonylfluorophenylazo)-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 acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.2 parts of 2-amino-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 (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-(2-cyanoethyl)-N-acetoxyethylaniline (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-cyano-5-(2'-methoxy-5'-sulphonylfluorophenyl-azo)-2-thiophene-azo)-N-(2- cyanoethyl)-N-acetoxyethyl aniline (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 to yield the product 4-(3-cyano-5-(2'-methoxy-5'-sulphonylfluorophenylazo)-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% nitrosyl 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 further 2 hours filtration yielded 3.3 parts of 2-amino-3-ethoxycarbonyl-5-(3'-sulphonylfluoro-phenylazo)thiophene. 2-Amino-3-ethoxycarbonyl-5-(3'-sulphonylfluorophenylazo) -thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid ;3"75 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'-sulphonylfluoro-phenyl-azo)-2-thiophene-azo)-N-ethyl-N-(2-cyanoethyl)-aniline (2.7 parts) which when applied to polyester materials from an aqueous 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, Amax 649 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'-sulphonylfluorophenyl 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 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) vzas 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'-sulphonylfluorophenyl-azo)-aniline. 2,5-Dimethoxy-4-(4'-sulphonylfluorophenyl-azo)-aniline (8 parts) was stirred in 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 being 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, Amax 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 the product 4-(2',5'- dimethoxy-4-(4'-sulphonylfluorophenyl-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 heated 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'-chlorosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-benzenesulphonyl 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-ben^©n&sulphonyl fluoride (1.6 parts). Example 2 4 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 2 5 The procedure for Example 23 was repeated except that the starting dye was l-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-methyl-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 2 8 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-methyl-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 dispersion composition comprising: i) a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, ii) a dispersing agent present in an amount of 10 to 200% by weight of the dye compound and iii) optionally additionally comprising ingredients selected from conventional components such as wetting agents and defoamers, which dye compound is free from water solubilizing groups and is of formula (1) : (Formula Removed) wherein each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A, D and E carries directly at least one -SO2F group or carries a substitutent to which at least one -SO2F group is attached, and wherein, in the formula (1), each of A, D and E is such as to provide a dye compound selected from compounds of the formulae 2, 3 and 4 as given below: (Formula Removed) R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -CI, -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, -0C0(3-fluorosulphonylphenyl), -0C0(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl; R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-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 -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -N02, -SO2F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F,-CI, -Br, -CF3, -NRXR2, -CONRV or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined; (Formula Removed) in which: R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by -OH, -CN, -F, -CI, -Br, -S02F, phenyl, phenylSO2F, -0COC1-6-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, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6- alkyl; R5 and R6 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F; 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,-CI, -Br, -CF3, -NRXR2, -CONRV or -S02NR1R2 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-alky!; and (Formula Removed) in which: R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -S02F, Ci-e-alkyl, Ci_6-alkoxy or -NHCOCi_6- alkyl; R5 and R6 each independently is -H, C1-6-alkyl, C1-6alkoxy or -SO2F; R1X, 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, -CI, -Br, -CF3, -NR1R2, -CONRiR2 or -SO2NR1R2 in which R1 and R2 are as hereinbefore defined. 2. A dispersion composition as claimed in claim 1, wherein, where the dye compound of formula (1) is a compound of formula (2) or (3), R1 or R2 is a C1-6alkyl group substituted by -OCOC1-6alkyl, -COOCi-6alkyl, -COOC1-6alkoxyC1-6alkyl, -OCO(3-fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4alkenyl or wherein, where the dye compound of formula (1) is a compound of formula (2), (3) or (4), R11, R12, R13, R14 or R15 is -COOC1-6alkyl, whereby the dye compound of Formula (1) carries at least one ester group or carries a substituent to which at least one ester group is attached. 3. A dispersion composition as claimed in claim 1, wherein the dye compound of formula (1) is a compound of formula (4) other than 4-(2-methoxyphenylazo-4( 4-fluorosulphonylphenylazo)) phenol. 4. A dispersion composition as claimed in any preceding claim, wherein the dispersing' agent is selected from the group consisting of lignosulophonates, naphthalene sulphonic acid formaldehyde condensates, phenol, cresol and sulphanilic acid formaldehyde condensates and surfactants. 5. A dispersion composition as claimed in any preceding claim, wherein the wetting agent comprises upto 20% of the weight of compound of formula (1) and is selected from the group consisting of alkyl aryl ethoxylates. 6. A dispersion as claimed in claim 5, wherein the ethoxylates are sulphonated or phosphated. 7. A dispersion composition as claimed in any preceding claim, wherein the defoamers are selected from the group consisting of mineral oil, nonanol, organic liquids and buffers. 8. A process for the preparation of a dispersion composition as claimed in claim 1, comprising mixing homogeneously i) a dye compound of formula (1) in an amount of from 1 to 30% by weight of the composition , ii) a dispersing agent in an amount of 10 to 200% by weight of the dye compound and iii) conventional components such as wetting agents and defoamers in an aqueous medium in a manner such as herein described, to obtain a dispersion composition in the form of homogenous mixture. 9. A process as claimed in claim 8, wherein the said step of homogeneously mixing the said dye compound of formula (1), dispersing agent and conventional components is carried out by bead milling the said dye compound of formula (1), dispersing agent and conventional components with glass beads or sand in an aqueous medium. 10. A dispersion composition substantially as herein described with reference to the foregoing examples. 11. A process for the preparation of the dispersion composition substantially as herein described with reference to the foregoing examples.

Documents:

113-del-1995-abstract.pdf

113-del-1995-claims.pdf

113-del-1995-correspondence-others.pdf

113-del-1995-correspondence-po.pdf

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

113-del-1995-form-1.pdf

113-del-1995-form-13.pdf

113-del-1995-form-2.pdf

113-del-1995-form-3.pdf

113-del-1995-form-4.pdf

113-del-1995-form-6.pdf

113-del-1995-form-9.pdf

113-del-1995-gpa.pdf

113-del-1995-petition-123.pdf

113-del-1995-petition-124.pdf