Monoazo dyes which are free from water-solubilizing groups and which contain a fluorosulphonyl group and process for colouring polyamides and polyester materials therewith

A process for coloring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilizing groups, of Formula (1): EQU A--N.dbd.N--D Formula (1) wherein PA1 A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO.sub.2 F group or carries a substituent to which at least one --SO.sub.2 F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenyl-pyrazol-4-yl-5-one or ##STR1## or that one of A or D does not carry an --NCH.sub.2 CH(OH)CH.sub.2 Cl, --NCOCH.sub.2 Cl or --NCH.sub.2 CH.sub.2 SO.sub.2 F substituent. The presence of one or more --SO.sub.2 F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet fastness and light fastness properties.

This application claims benefit of international application 
PCT/GB94/02831, filed Dec. 30, 1994. 
The present invention relates to a process for colouring synthetic textile 
materials, to synthetic textiles when coloured, to a process for the mass 
coloration of plastics, to plastics when coloured, to certain novel azo 
dyes and to compositions containing azo dyes. 
GB-A-856,348 relates to water insoluble monoazo dyestuffs and discloses one 
specific dye containing a 4-fluorosulphonylnaphth-1-yl group which is 
disclaimed from the present claims. 
GB-A-819,664 relates to water insoluble monoazo dyestuffs and discloses two 
specific dyes both of which are disclaimed from the present claims. 
U.S. Pat. No. 2,576,037 relates to the coloration of cellulose acetate with 
certain --SO.sub.2 F containing azo dyes. Such dyes, particularly those 
which also contain --NC.sub.2 H.sub.4 OH groups or derivatives thereof are 
dye bath unstable and as such are unsuitable for coloration of polyester 
textile materials. 
According to the present invention there is provided a process for 
colouring polyamide and aromatic polyester textile material or fibre blend 
thereof which comprises applying to the synthetic textile material a 
compound or mixture thereof, which is free from water solubilising groups, 
of Formula (1): 
EQU A--N.dbd.N--D Formula (1) 
wherein 
A and D each independently is an optionally substituted heterocyclic or 
carbocyclic group and at least one of A or D carries directly at least one 
--SO.sub.2 F group or carries a substituent to which at least one 
--SO.sub.2 F group is attached except for 
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A 
or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 
1-phenyl-pyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or 
##STR2## 
or that one of A or D does not carry an --NCH.sub.2 CH(OH)CH.sub.2 Cl, 
--NCOCH.sub.2 Cl or --NCH.sub.2 CH.sub.2 SO.sub.2 F substituent. 
Different compounds of Formula (1) may be mixed or the compounds of Formula 
(1) may be mixed with dyes which do not contain an --SO.sub.2 F group. The 
mixtures may be simple physical mixtures or may be mixed crystals formed 
for example by co-crystallisation. Such mixtures generally show 
improvement in dyeing properties. Crystalline modifications of compounds 
of Formula (1) exist and it is intended that the present definition 
includes such crystalline modifications which may be formed by heat 
treatment. 
The presence of one or more --SO.sub.2 F groups in a dye molecule generally 
improves the properties of that dye and confers surprisingly good 
wet-fastness and light-fastness properties. 
According to a first embodiment of the present invention there is provided 
a process for colouring a synthetic textile material or fibre blend 
thereof which comprises applying to the synthetic textile material a 
compound or mixture thereof, which is free from water solubilising groups, 
of Formula (1) wherein A and D each independently is an optionally 
substituted heterocyclic or carbocyclic group in which at least one of A 
or D carries directly at least one --SO.sub.2 F group or carries a 
substituent to which at least one --SO.sub.2 F group is attached and at 
least one of A or D carries directly at least one ester group or carries a 
substituent to which at least one ester group is attached. 
Azo dyes containing both an --SO.sub.2 F and an ester group have improved 
performances in wash fastness properties over azo dyes carrying only an 
--SO.sub.2 F group. 
The synthetic textile material may be selected from secondary cellulose 
acetate, cellulose triacetate, polyamide, polyacrylonitrile and aromatic 
polyester. The synthetic textile material is preferably polyamide or 
aromatic polyester, more preferably aromatic polyester such as 
polyhexamethylene adipamide or polyethylene terephthalate and especially 
polyethlene terephthalate. Fibre blends may comprise mixtures of different 
synthetic textile materials or mixtures of synthetic and natural textile 
materials. Preferred fibre blends are those of polyester 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. 
According to a second embodiment of the present invention there is provided 
a process for colouring a polyester textile material or fibre blend 
thereof which comprises applying to the polyester textile material a 
compound or mixture thereof, which is free from water solubilising groups, 
of Formula (1) in which A and D are as herein before defined except for 
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A 
or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 
1-phenylpyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or 
4-nitro-2-fluorosulphonylphenyl or that one of A or D does not carry an 
--NCH.sub.2 CH.sub.2 SO.sub.3 F substitutent. 
The dyes of Formula (1) preferably have low solubility in water, typically 
less than 1% preferably less than 0.5% and especially less than 0.2% 
solubility in water. The dyes of Formula (1) are thus free from water 
solubilising groups such as --SO.sub.3 H, --CO.sub.3 H, --PO.sub.3 H and 
quaternary amino. 
The compounds of Formula (1), optionally in conjunction with other disperse 
dyes may be applied to the synthetic textile materials or fibre blends 
thereof by methods which are conventionally employed in dyeing disperse 
dyes to such materials and fibre blends. 
The process conditions may be selected from the following: 
i) exhaust dyeing at a pH of from 4 to 6.5, an a temperature of from 
125.degree. C. to 140.degree. C. for from 10 to 120 minutes and under a 
pressure of from 1 to 2 bar, a sequestrant may be optionally be added; 
ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 
190.degree. C. to 225.degree. 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.degree. C. to 185.degree. C. for 4 to 15 minutes for high temperature 
steaming, or at a temperature of from 190.degree. C. to 225.degree. C. for 
15 seconds to 5 minutes for bake fixation with dry heat or at a 
temperature of from 120.degree. C. to 140.degree. 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 be optionally be 
added; 
iv) discharge printing (by padding the dye onto the textile material, 
drying and overprinting) at a pH of from 4 to 6.5, migration inhibitors 
and thickeners may optionally be added; 
v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 
95.degree. C. to 100.degree. 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.degree. C. for acetate or at a temperature 
of 90.degree. C. for triacetate and nylon for from 15 to 90 minutes, 
sequesterants may optionally be added. 
In all the above processes the 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 heterocyclic group represented by A and D may be selected from thienyl, 
thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- 
and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, 
pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, 
indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl and 
1,2,4-triazolyl. The carbocyclic group represented by A or D may be phenyl 
or naphthyl. 
For the avoidance of doubt optionally substituted isoquinolinyl represented 
by A includes structures of the formula: 
##STR3## 
in which m is from 1 to 4 and m is preferably 3. 
A and D each independently is preferably thienyl, phenol, naphthyl, 
thiazolyl, isothiazolyl, pyridonyl, quinolinyl more preferably thien-2-yl, 
phenyl, naphth-1-yl, naphth-2-yl, thiazol-2-yl, isothiazol-5-yl, 
pyrid-4-one-5-yl or quinolinyl. A is especially preferably thien-2-yl or 
phenyl and D is especially preferably phenyl or naphth-1-yl. 
Examples of suitable substituents for A and D are cyano, hydroxy, nitro, 
fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, 
alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, 
--COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, 
--NHCOalkyl, --NHCOaryl, --NHSO.sub.2 alkyl, --NHSO.sub.2 aryl, --Salkyl, 
--Saryl, --SO.sub.2 alkyl, --SO.sub.2 aryl, --SCN or --NR.sup.2 R.sup.1 in 
which R.sup.1 and R.sup.2 each independently is --H, alkyl, aryl or 
cycloalkyl all the alkyl, alkoxy, aryl, aryloxy parts of the above 
substituents for A, D, R.sup.1 and R.sup.2 may optionally be substituted 
by --OH, --CN, --F, --Cl, --Br, --I, --SO.sub.2 F, alkoxy, alkenyl, 
phenyl, phenylSO.sub.2 F, aryloxy, aryloxySO.sub.2 F, --N(alkyl).sub.2, 
--OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, 
--COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO.sub.2 F, 
--OCOphenylNO.sub.2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, 
--OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, 
--COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, 
--OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, 
--OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or 
--COOalkylCOOalkyl, 
##STR4## 
in which L is --H or alkyl. 
In all of the suitable substitutents for A and D each alkyl is preferably 
C.sub.1-10 -alkyl, each alkoxy is preferably C.sub.1-10 -alkoxy, each 
alkenyl is preferably C.sub.2-8 -alkenyl each of which may be straight or 
branched chain, each aryl is preferably phenyl or naphthyl and each 
heterocyclic group may be any of the groups described above for A and D 
and each alkyl, alkoxy, alkenyl, aryl, heterocyclic or phenyl group may 
carry an --SO.sub.2 F substituent. R.sup.1 and R.sup.2 together with the 
--N atom to which they are attached may form a 5- or 6-membered ring such 
as morpolino or piperidino. 
A further suitable substituent for A and D is a group of Formula R.sup.19 
--N--Y--X--W in which 
Y is a direct link or C.dbd.O, 
X is a direct link, optionally substituted alkyl, alkenyl, aryl, 
heterocyclic, alkylOalkyl, alkylNHalkyl or --NR.sup.20 --Z-- or --O--Z-- 
in which Z is optionally substituted alkyl, alkenyl, aryl, heterocyclic, 
alkylOalkyl, alkylNHalkyl or a direct link and R.sup.20 is --H, optionally 
substituted alkyl, aryl or alkylaryl, 
W is --CO.sub.2 R.sup.21, --OCOR.sup.21, --OH or --CN in which R.sup.21 is 
optionally substituted alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, 
R.sup.19 is --H or optionally substituted alkyl. 
Where X, Z, R.sup.19, R.sup.20 or R.sup.21 is or contains alkyl it is 
preferably C.sub.1-8 -alkyl more preferably C.sub.1-6 -alkyl each of which 
may be straight or branched chain or cyclic alkyl. Where X or Z is alkenyl 
it is preferably C.sub.2-8 -alkenyl which may be straight or branched 
chain or cyclic alkenyl. Where X, Z, R.sup.20 or R.sup.21 is aryl it is 
preferably phenyl or naphthyl more preferably phenyl. Where X or Z is 
heterocyclic it may be selected from any of the heterocyclic groups 
defined above for A. Where X, Z or R.sup.21 is alkylOalkyl it is 
preferably C.sub.1-6 -alkylOC.sub.1-6 -alkyl each alkyl may be straight or 
branched chain and the alkylOalkyl group may be cyclic ether. Where X or Z 
is alkylNHalkyl it is preferably C.sub.1-6 -alkylNHC.sub.1-6 -alkyl in 
which each alkyl may be straight or branched chain and the alkylNHalkyl 
group may be a cyclic amine. Where R.sup.20 or R.sup.21 is alkylaryl it is 
preferably C.sub.1-6 -alkylaryl more preferably C.sub.1-6 -alkylphenyl and 
especially benzyl or ethylphenyl. Where R.sup.21 is alkylOH it is 
preferably C.sub.1-6 -alkylOH. 
The optional substituents for any of the groups represented by X, Z, 
R.sup.19, R.sup.20 or R.sup.21 may be selected from any of the optional 
substituents listed for A, D, R.sup.1 or R.sup.2. 
Preferred substituents for A and D are cyano, nitro, chloro, bromo, 
fluorosulphonyl, C.sub.1-6 -alkyl, C.sub.1-6 -alkoxy, --COC.sub.1-6 
-alkyl, --NHCOC.sub.1-6 -alkyl, --OCOC.sub.1-6 -alkyl, --COOC.sub.1-6 
-alkyl, phenoxy, 4--SO.sub.2 Fphenoxy, R.sup.19 N--Y--X--W in which 
R.sup.19, Y, X and W are as herein before defined, and --NR.sup.1 R.sup.2 
in which R.sup.1 and R.sup.2 each independently is --H, C.sub.1-6 -alkyl, 
C.sub.1-6 -alkyl substituted by --OH, --CN, --Cl, phenyl, --OCOC.sub.1-6 
-alkyl, --COOC.sub.1-6 -alkyl, 
##STR5## 
--C.sub.1-6 -alkyl(4-fluorosulphonylphenyl), 
--OCO(3-fluorosulphonylphenyl), --OCO(4-fluorosulphonylphenyl), 
--C.sub.2-4 -alkenyl, --COOC.sub.1-6 -alkylOC.sub.1-6 -alkyl, --OC.sub.1-6 
-alkylCN, --OC.sub.1-6 -alkylOCOC.sub.1-6 -alkylOC.sub.1-6 -alkyl, 
--COOalkylOCOalkyl and --COOalkylCOOalkyl or where R.sup.1 and R.sup.2 
together with the --N atom to which they are attached form a morpholino or 
piperidino ring. 
The compounds of Formula (1) preferably carry a total of from one to three 
--SO.sub.2 F groups, more preferably one or two --SO.sub.2 F groups and 
especially one --SO.sub.2 F groups. 
The compounds of Formula (1) more preferably carry one --SO.sub.2 F group 
and one ester group. 
A number of compounds of Formula (1) used in the above coloration process 
are novel and according to a further feature of the present invention 
there is provided a compound which is free from watersolubilising groups 
of Formula (2): 
EQU A.sup.1 --N.dbd.N--D.sup.1 Formula ( 2) 
in which: 
A.sup.1 and D.sup.1 each independently is an optionally substituted 
heterocyclic or carbocyclic group and at least one of A.sup.1 or D.sup.1 
carries directly at least one --SO.sub.2 F group or carries a substituent 
to which at least one --SO.sub.2 F group is attached except for 
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, 
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, 
4-(4-fluorosulphonylphenylazo)-N-ethyl-N-acetoxyethylaniline, 
1-(5-fluorosulphonyl-2-methylphenylazo)-2-hydroxynaphthalene, 
4-(4-fluorosulphonylphenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-2 
-methoxyethyl)aniline, 
4-(4-fluorosulphonylphenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-2 
-cyanoethyl)aniline, 
4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyethyl)anili 
ne, 
4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-cyanoethyl)aniline 
4-(4-fluorosulphonylphenylazo)-N-ethyl-N-(2-fluorosulphonylethyl)aniline, 
4-(4-fluorosulphonylphenylazo)-N,N-di(2-fluorosulphonylethyl)aniline, 
4-(3-fluorosulphonyl-4-methylphenylazo)-3-(trifluoromethylcarbonylamino)-N- 
ethyl-N-(2-methoxyethyl)aniline, 
4-(3-fluorosulphonyl-4-methylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyet 
hyl)aniline, 
4-(3-fluorosulphonyl-4-chlorophenylazo)-3-(trifluoromethylcarbonylamino)-N- 
ethyl-N-(2-methoxyethyl)aniline, 
4-(3-fluorosulphonyl-4-chlorophenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyet 
hyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-1-aminonaphthalene, 
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline, 
4-(3-fluorosulphonylphenylazo)-2,5-dimethoxyaniline, 
4-(2-chloro-4-nitrophenylazo)-2-methyl-5-fluorosulphonylaniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylanil 
ine, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline, 
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl--N(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anili 
ne, 
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anilin 
e, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N((2-methoxy)-2-ethoxy)eth 
yl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine, 
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline, 
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline, provided that A.sup.1 
is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 
pyrazol-4-yl-5-one or N-allylpyrid-2-one-5-yl and provided that A.sup.1 is 
not 
##STR6## 
when D.sup.1 carries an --NCH.sub.2 CH(OH)CH.sub.2 Cl substituent and 
provided than one of A.sup.1 or D.sup.1 is not 
4-fluorosulphonylnaphth-1-yl, substituted 4-hydroxynapth-1-yl or 
##STR7## 
and provided than A.sup.1 is not a fluorosulphonylphenyl group when 
D.sup.1 is an arylamide of an aromatic 2-hydroxycarboxylic acid. 
A.sup.1 and D.sup.1 each independently may be any of the heterocyclic 
groups defined for A above. A.sup.1 and D.sup.1 each independently may be 
any of the carbocyclic groups defined for A and D above. 
A.sup.1 and D.sup.1 each independently is preferably thienyl, phenyl, 
naphthyl, thiazolyl, isothiazolyl or pyridonyl, more preferably thienyl, 
phenyl, thiazolyl, isothiazolyl or pyridonyl and especially thien-2-yl, 
phenyl, thiazol-2-yl, isothiazol-5-yl or pyrid-4-one-5-yl. 
D.sup.1 is preferably phenyl. 
Preferred compounds of Formulae (1) and (2) are those in which A or A.sup.1 
is phenyl and D or D.sup.1 is phenyl; A or A.sup.1 is thien-2-yl and D or 
D.sup.1 is phenyl; and A or A.sup.1 is phenyl and D or D.sup.1 is 
naphth-1-yl. 
The optional substituents for A.sup.1 and D.sup.1 are any of those defined 
for A and D above. 
A preferred sub-group of compounds of Formula (1) are those of Formula (3): 
##STR8## 
wherein R.sup.1 and R.sup.2 each independently is --H or optionally 
substituted C.sub.1-6 -alkyl or optionally substituted aryl; 
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each independently is --H, --F, --Cl, 
--Br, --I, --SO.sub.2 F or C.sub.1-6 -alkyl, C.sub.1-6 -alkoxy, C.sub.1-6 
-alkanoylamino, --NHSO.sub.2 alkyl or Ophenyl each of which may be 
optionally substituted; 
R.sup.7, R.sup.8 and R.sup.9 each independently is --H, C.sub.1-6 -alkyl, 
--NO.sub.2, --COOC.sub.1-6 -alkyl, --OCOalkyl, 
--Cl, --F, --Br, --I, --COC.sub.1-6 -alkyl, --CN, formyl, protected formyl 
or --SO.sub.2 F provided that at least one of R.sup.1 to R.sup.9 is 
--SO.sub.2 F or carries a substituent to which at least one --SO.sub.2 F 
group is attached and provided that R.sup.7 and R.sup.9 are not both 
--SO.sub.2 F. 
Where R.sup.7, R.sup.8 and R.sup.9 is or contains alkyl the alkyl may be 
optionally subustituted. 
Protected formyl groups include for example oxazolidone, imidazoline, 
thiazolidine, bisulphite, cyanohydrin, hydrazone and oxime. 
The compounds of Formula (3) are novel and accordingly are a further aspect 
of the present invention. 
The optional substituents for groups represented by R.sup.1 to R.sup.9 may 
be selected from any of the substituents described above for A and D. The 
optional substituents for R.sup.1 to R.sup.9 are preferably --CN, --OH, 
--OCOC.sub.1-6 -alkyl, --COOC.sub.1-6 -alkyl, phenyl, --OCOphenyl, 
--OCOphenylSO.sub.2 F, phenylSO.sub.2 F, --OphenylSO.sub.2 F, --CO.sub.2 
phenylSO.sub.2 F, --COOC.sub.1-6 -alkylOCOC.sub.1-6 -alkyl and 
--COOC.sub.1-6 -alkylCOOC.sub.1-6 -alkyl. 
Preferred compounds of Formula (3) are those in which R.sup.1 and R.sup.2 
each independently is --CH.sub.2, --C.sub.2 H.sub.5, --C.sub.2 H.sub.4 CN, 
--C.sub.2 H.sub.4 OH, --CH(CH.sub.2)CH.sub.2 CH.sub.3, --C.sub.4 H.sub.9, 
--CH.sub.2 (4-fluorosulphonylphenyl), --C.sub.2 H.sub.4 
(4-fluorosulphonylphenyl), --C.sub.3 H.sub.7 (4-fluorosulphonylphenyl), 
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each independently is --H, --Cl, 
--CH.sub.2, --OCH.sub.2, --NHCOCH.sub.2, --NHCOC.sub.2 H.sub.5, 
--NHSO.sub.2 CH.sub.3 or --SO.sub.2 F and R.sup.7, R.sup.8 and R.sup.9 
each independently is --H, --NO.sub.2, --CN, --COCH.sub.2, --COOC.sub.2 
H.sub.5, --SO.sub.2 F or --CH.sub.3 provided that both R.sup.7 and R.sup.9 
are not --SO.sub.2 F. 
Especially preferred compounds of Formula (3) are those in which 
R.sup.1 and R.sup.2 each independently is --C.sub.2 H.sub.4 CN, --C.sub.2 
H.sub.5 or (4-fluorosulphonylphenyl ) C.sub.1-6 -alkyl; 
R.sup.3 is --H, --OCH.sub.3, --CH.sub.3 or --SO.sub.2 F; 
R.sup.4 and R.sup.5 each independently is --H, --Cl or --SO.sub.2 F; 
R.sup.6 is --H, --NHCOCH.sub.3, --NHCOC.sub.2 H.sub.5, --CH.sub.3 or 
--SO.sub.2 F; 
R.sup.7 is --NO.sub.2, --COCH.sub.3, --COOC.sub.2 H.sub.5 or --SO.sub.2 F; 
R.sup.8 is --H, --SO.sub.2 F or --Cl; 
R.sup.9 is --NO.sub.2, --SO.sub.2 F or --CHO. 
A further preferred sub-group of compounds of Formula (1) are those of 
Formula (4): 
##STR9## 
wherein R.sup.1 to R.sup.6 are as hereinbefore defined; 
R.sup.10 to R.sup.14 each independently is --H, alkoxy, alkyl, --NO.sub.2, 
--SO.sub.2 F, --F, --Cl, --Br, --I or --CN; 
provided that when R.sup.10 is SO.sub.2 F, R.sup.12 is not --NO.sub.2 and 
R.sup.11, R.sup.13 and R.sup.14 are not all --H. 
Where a group represented by R.sup.10 to R.sup.14 is alkyl it is preferably 
C.sub.1-10 -alkyl, more preferably C.sub.1-6 -alkyl. Where a group 
represented by R.sup.10 to R.sup.14 is alkoxy it is preferably C.sub.1-10 
-alkoxy more preferably C.sub.1-6 -alkoxy. 
Compounds of Formula (4) are preferably those in which R.sup.1 and R.sup.2 
each independently is --CH.sub.3, --C.sub.2 H.sub.5, --C.sub.3 H.sub.7, 
--C.sub.4 H.sub.9, --C.sub.5 H.sub.11, --C.sub.6 H.sub.13, 
--CH(CH.sub.3)CH.sub.2 CH.sub.3, --CH.sub.2 phenyl, --C.sub.2 H.sub.4 
phenyl, --C.sub.3 H.sub.6 phenyl, --C.sub.2 H.sub.4 CN, --C.sub.2 H.sub.4 
OH, --C.sub.2 H.sub.4 OCH.sub.3, --C.sub.2 H.sub.4 COCH.sub.3, --C.sub.4 
H.sub.8 COCH.sub.3, --C.sub.2 H.sub.4 COCH.sub.3, --C.sub.2 H.sub.4 
OCOCH.sub.3, --C.sub.3 H.sub.6 OCOCH.sub.3, --C.sub.4 H.sub.8 OCOCH.sub.3, 
--C.sub.2 H.sub.4 OCOphenyl, --C.sub.2 H.sub.4 OCOphenyl (SO.sub.2 F), 
--C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3, --C.sub.2 H.sub.4 OC.sub.2 
H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3, allyl, --C.sub.2 H.sub.4 Ophenyl, 
--C.sub.2 H.sub.4 O(fluorosulphonylphenyl), --CH.sub.2 CH(CN) (OC.sub.2 
H.sub.4), C.sub.1-6 -alkylphenylSO.sub.2 F, 
##STR10## 
--COOC.sub.1-6 -alkylOCOC.sub.1-6 -alkyl or --COOC.sub.1-6 -alkyl 
COOC.sub.1-6 -alkyl 
R.sup.3 is --H, --OCH.sub.3 or --Cl; 
R.sup.4 is --H, --CH.sub.3, --NHCOCH.sub.3, --NHCOC.sub.2 H.sub.5, 
--NHCOCH(CH.sub.3).sub.2, --NHCOC.sub.3 H.sub.6 Cl, 
--NHCOC(CH.sub.3).sub.3, --OCH.sub.3, --OC.sub.4 H.sub.9, --F, --Cl, --Br, 
--I or --NHSO.sub.2 C.sub.1-6 -alkyl; 
R.sup.5 is --H , --OCH.sub.3, --OC.sub.2 H.sub.5 or --Cl; 
R.sup.6 is --H, --CH.sub.3, --OCH.sub.3, --F, --Cl, Br, --I or --NHSO.sub.2 
C.sub.1-6 -alkyl; 
R.sup.10 is --H, --OCH.sub.3, --NO.sub.2, --Cl, --Br or --CN; 
R.sup.11 is --H; 
R.sup.12 is --SO.sub.2 F or --NO.sub.2 ; 
R.sup.13 is --H, --OCH.sub.3, --SO.sub.2 F, --Cl, --Br or --NO.sub.2 ; and 
R.sup.14 is --H, --OCH.sub.3, --Cl, --Br or --CN, provided that at least 
one of R.sup.3 or R.sup.5 is --H and that at least one of R.sup.4 or 
R.sup.6 is --H. 
More preferably compounds of Formula (4) are those in which R.sup.1 and 
R.sup.2 each independently is --C.sub.2 H.sub.5, --C.sub.4 H.sub.9, 
--CH(CH.sub.3)CH.sub.2 CH.sub.3, --C.sub.2 H.sub.4 OCOCH.sub.3, --C.sub.4 
H.sub.8 OCOCH.sub.3, --C.sub.2 H.sub.4 OCOphenyl, --CH.sub.2 phenyl, 
C.sub.1-6 -alkylphenylSO.sub.2 F, C.sub.1-6 -alkylOphenylSO.sub.2 F, 
##STR11## 
--COOC.sub.1-6 -alkylOCOC.sub.1-6 -alkyl or --COOC.sub.1-6 
-alkylCOOC.sub.1-6 -alkyl 
R.sup.4 is --H, --CH.sub.3 or --NHCOCH.sub.3 ; 
R.sup.3, R.sup.5, R.sup.6 and R.sup.11 is --H; 
R.sup.10 and R.sup.13 each independently is --H, --Cl, --Br or --NO.sub.2 ; 
R.sup.12 is --SO.sub.2 F; and 
R.sup.14 is --H, --Cl or --Br. 
An especially preferred compound of Formula (4) is that in which R.sup.1 is 
--C.sub.2 H.sub.5 ; R.sup.2 is --C.sub.2 H.sub.4 OCOphenyl; R.sup.4 is 
--CH.sub.3 ; R.sup.10 and R.sup.13 are both --Cl; R.sup.12 is --SO.sub.2 
F; and R.sup.3, R.sup.5, R.sup.6, R.sup.11 and R.sup.14 are all --H. 
An especially preferred sub-group of compounds of Formula (1) are those of 
Formula (7): 
##STR12## 
in which R.sup.1 and R.sup.2 each independently is optionally substituted 
C.sub.1-6 -alkyl; 
R.sup.4 is alkyl or a group of Formula R.sup.19 --N--Y--X--W in which Y is 
a direct link or C.dbd.O, X is a direct link, alkyl, alkenyl, aryl, 
heterocyclic, alkylOalkyl, --NR.sup.20 --Z--, --COOZ or --O--Z in which Z 
is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl or a direct link and 
R.sup.20 is --H, alkyl, aryl or alkylaryl, W is --CO.sub.2 R.sup.21, 
--OCOR.sup.21 or --OH in which R.sup.21 is alkyl, aryl, alkylaryl, 
alkylOalkyl or alkylOH, and R.sup.19 is --H or alkyl; 
R.sup.5 is --H, C.sub.1-6 -alkoxy or --Ophenyl; 
R.sup.10 is --NO.sub.2 or --Cl; and 
R.sup.13 and R.sup.14 each independently is --H or --Cl. 
The dyes of Formula (7) are novel and form a further feature of the present 
invention. 
In the dyes of Formula (7) 
R.sup.1 and R.sup.2 each independently is preferably C.sub.1-6 -alkyl or 
C.sub.1-6 -alkyl substituted by phenyl or --COOC.sub.1-6 -alkyl, and more 
preferably is ethyl, propyl, butyl, 1-methylpropyl, hexyl, benzyl, 
ethylphenyl or propylphenyl. 
R.sup.4 is preferably a group of Formula R.sup.19 --N--Y--X--W in which 
R.sup.19 is preferably --H or C.sub.1-6 -alkyl more preferably --H; Y is 
preferably a direct link or C.dbd.O more preferably C.dbd.O; 
X is preferably a direct link, C.sub.1-8 -alkyl, C.sub.2-8 -alkenyl, any of 
the carbocyclic or heterocyclic groups defined above for A, C.sub.1-6 
-alkylOC.sub.1-6 -alkyl, --NR.sup.20 --Z--, --COOZ or --O--Z-- in which 
R.sup.20 is preferably --H, C.sub.1-6 -alkyl, phenyl or benzyl and 
Z is preferably a direct link or C.sub.1-6 -alkyl, C.sub.2-8 -alkenyl, 
phenyl, benzyl or any of the heterocyclic groups defined above for A; 
X is more preferably a direct link, CH.sub.2, C.sub.2 H.sub.4, CH.sub.2 
C(CH.sub.3).sub.2, cyclohexyl, CH.dbd.CH, phenyl, --NR.sup.20 --Z, --COOZ 
or --O--Z-- in which 
R.sup.20 is preferably --H, Z is preferably a direct link, C.sub.1-6 alkyl 
or benzyl. 
W is --CO.sub.2 .sup.R.sup.21, --OCOR.sup.21 or --OH in which R.sup.21 is 
C.sub.1-6 -alkyl, phenyl, chlorobenzyl, C.sub.1-6 -alkoxybenzyl, benzyl, 
C.sub.1-6 -alkylOC.sub.1-6 -alkyl or C.sub.1-6 -alkylOH more preferably 
ethyl, methyl, butyl, or 1,3-dimethylbutyl. 
Dyes in which both A and D are phenyl and in which one of A and D carries a 
4-SO.sub.2 F group are generally more stable and build up better on 
polyester textile material than do the corresponding 2-SO.sub.2 F dyes. 
A further preferred sub-group of compounds of Formula (1) are those of 
Formula (5); 
##STR13## 
wherein R.sup.1 to R.sup.4 and R.sup.10 to R.sup.14 are as herein before 
defined; and 
R.sup.15 to R.sup.18 each independently is --H, --F, --Cl, --Br, --I, 
--SO.sub.2 F, --NO.sub.2, --CN, --NR.sub.1 R.sub.2, OH or optionally 
substituted --C.sub.1-6 -alkyl or --C.sub.1-6 -alkoxy. 
The optional substituents for any of the groups represented by R.sup.15 to 
R.sup.18 may be selected from any of optional substituents described above 
for A, D, R.sup.1 and R.sup.2. 
Compositions comprising dispersions of the compounds which are free from 
water solubilising groups of Formula (1) in which A is an optionally 
substituted heterocyclic or carbocyclic group; and D is an optionally 
substituted carbocyclic group; and at least one of A or D carries directly 
at least one --SO.sub.2 F group or carried a substituent to which at least 
one --SO.sub.2 F group is attached in aqueous media are novel and form a 
further feature of the present invention provided that one of A or D is 
not 3,5-difluorosulphonylthien-2-yl, 4-fluorosulphonylnaphth-1-yl, 
optionally substituted 1-phenylpyrazol-4-yl-5-one or 
##STR14## 
or that one of A or D does not carry an --NCH.sub.2 CH(OH)CH.sub.2 Cl, 
--NCOCH.sub.2 Cl or --NCH.sub.2 CH.sub.2 SO.sub.2 F substituent except for 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylanil 
ine, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline, 
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)eth 
yl)aniline, 
4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anilin 
e, 
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anilin 
e, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine, 
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline, 
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline Compositions 
comprising dispersions of compounds of Formulae (2), (3), (4), (5) and (7) 
are also novel. The compositions typically comprise form 1% to 30% of a 
compound of Formulae (1), (2), (3), (4), (5) or (6) in an aqueous medium. 
The compositions are preferably buffered at pH 2 to 7 more preferably at 
pH 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 am from 10% 
to 200% on the weight of the compound of Formulae (1), (2), (3), (4), (5) 
or (7). Wetting agents may be used at from 0% to 20% on the weight of the 
compound (1), (2), (3), (4), (5) or (7). The dispersions may be prepared 
by bead milling the compound of Formula (1). (2), (3 , (4), (5) or (7) 
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 compound or mixture thereof which is free from 
water solubilising groups, of Formula (1) wherein A and D each 
independently is an optionally substituted heterocyclic or carbocyclic 
group and at least one of A or D carries directly at least one --SO.sub.2 
F group or carries a substituent to which at least one --SO.sub.2 F group 
is attached provided that one of A or D is not 
4-fluorosulphonylnaphth-1-yl, except for 
4-(2-chloro-4-nitrophenylazo)-2-methyl-4-fluorosulphonylaniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylanil 
ine, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline, 
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)eth 
yl)aniline, 
4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anilin 
e, 
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)anilin 
e, 
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)et 
hyl)aniline, 
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine, 
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline, 
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline, 
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 compound or mixture thereof which is free from 
water solubilising groups, of Formula (1) wherein A and D each 
independently is an optionally substituted heterocyclic or carbocyclic 
group and at least one of A or D carries directly a least one --SO.sub.2 F 
group or carries a substituent to which at least one --SO.sub.2 F group is 
attached and at least one of A or D carries directly at least one ester 
group or carries a substituent to which at least one ester group is 
attached. 
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 compound 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/masterbatching techniques. The present dyes generally dissolve 
or disperse readily in hot plastics melt and provide bright coloration 
generally with good clarity and good light fastness. 
The plastics materials when coloured with the above dyes form a further 
feature of the present invention. 
The compounds of Formula (1) may be obtained by usual methods for the 
preparation of azo compounds such as by diazotisation of an amine of 
Formula A--NH.sub.2 or A.sup.1 --NH.sub.2 and coupling onto a component 
D--X or D.sup.1 --X in which A, A.sup.1, D and D.sup.1 are as hereinbefore 
defined and X is a group displaceable by a diazotised amine. Typically the 
amine, A--NH.sub.2 or A.sup.1 --NH.sub.2 may be diazotised in an acidic 
medium, such as acetic, propionic or hydrochloric acid using a nitrosating 
agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a 
temperature from -10.degree. C. to 10.degree. C. Coupling onto the 
component D--X or D.sup.1 --X may be achieved by adding the diazotised 
amine to a mixture of D--X or D.sup.1 --X in an alkanol such as methanol 
at a temperature from 0.degree. C. to 10.degree. C. After coupling the 
compound of Formula (1) may be recovered from the reaction mixture by any 
convenient means such as by filtration. 
Fluorosulphonyl groups may be introduced into the compounds of Formula (1) 
or Formula (2) or into the A, A.sup.1, D and D.sup.1 components prior to 
coupling by methods generally available in the literature. For example 
reaction of the compound of Formula (1) or Formula (2), A--NH.sub.2, 
A.sup.1 --NH.sub.2, the NH.sub.2 being protected as necessary, D--X or 
D.sup.1 --X, in which A, A.sup.1, D and D.sup.1 are as hereinbefore 
defined, with chlorosulphonic acid optionally in the presence of 
dimethylformamide and thionylchloride at a temperature of from 30.degree. 
C. to 140.degree. 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 compound of Formula (1) or Formula (2), A--NH.sub.2, 
A.sup.1 --NH.sub.2, D--X or D.sup.1 --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 pentachloride in an organic liquid such as an aromatic 
hydrocarbon at a temperature of from 20.degree. C. to 110.degree. 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. 
The compounds of Formulae (1), (2), (3), (4), (5) and (7) 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 compounds of Formula (1), (2), (3), (4), (5) or (7) are also useful for 
the mass coloration of plastics as described above and impart bright 
colours generally with good clarity and light fastness.