Mixtures of at least three anionic dyes and their use for dyeing natural and synthetic polyamides

Dye mixtures comprising PA0 (i) as a yellow component, at least one compound of the formula ##STR1## or a salt thereof, wherein R.sub.1 is hydrogen, C.sub.1-4 alkoxy, C.sub.1-4 alkyl or C.sub.1-4 alkyl monosubstituted by halo, PA1 R.sub.2 is C.sub.1-4 alkyl or --COR.sub.6, PA2 wherein R.sub.6 is C.sub.1-6 alkyl, C.sub.1-6 alkoxy or --NR.sub.7 R.sub.8, PA3 wherein each of R.sub.7 and R.sub.8 is independently hydrogen, C.sub.1-6 -alkyl or C.sub.2-6 alkyl mono-substituted by hydroxy, PA1 R.sub.4 is hydrogen, halo, C.sub.1-4 alkyl, C.sub.1-4 alkoxy or --NR.sub.3 R.sub.9, PA1 R.sub.5 is c.sub.1-4 alkyl or C.sub.2-6 alkyl monosubstituted by hydroxy, PA1 R.sub.10 is hydrogen, halo, C.sub.1-4 alkyl, C.sub.1-4 alkoxy or --NR.sub.3 R.sub.9, and PA1 R.sub.11 is hydrogen, halo, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, wherein PA2 each R.sub.3 is independently hydrogen or C.sub.1-4 alkyl, and PA2 each R.sub.9 is independently (C.sub.1-6 alkyl)carbonyl or (C.sub.1-6 alkoxy)carbonyl, PA0 (ii) as a red component, at least one compound of the formula ##STR2## or a salt thereof, wherein R.sub.21 is hydrogen, halo or (C.sub.1-4 alkyl)carbonylamino, and PA1 R.sub.22 is trifluoromethyl, --SO.sub.2 Z.sub.1 or --SO.sub.2 Z.sub.2, wherein PA2 Z.sub.1 is phenyl, phenoxy or --NR.sub.19 R.sub.20, wherein PA3 R.sub.19 is methyl or ethyl, and PA3 R.sub.20 is phenyl or cyclohexyl, and PA2 Z.sub.2 is --N(C.sub.4 H.sub.9).sub.2 or ##STR3## (iii) as a blue component, at least one compound of the formula ##STR4## or a salt thereof, wherein R.sub.23 is hydrogen or methyl, and PA1 one of R.sub.24 and R.sub.25 is C.sub.2-4 hydroxyalkylsulfamoyl or --NR.sub.26 --COC.sub.1-4 alkyl and the other is hydrogen or methyl, wherein R.sub.26 is hydrogen, methyl or ethyl, useful for dyeing and printing nitrogen-containing organic substrates, especially natural and synthetic polyamides.

The invention relates to combinable anionic dye mixtures and their use for 
dyeing or printing nitrogen-containing organic substrates, especially in 
trichromatic dyeing processes. 
More particularly, this invention provides a process for the trichromatic 
dyeing or printing of a nitrogen-containing organic substrate, preferably 
natural or synthetic polyamide material, comprising applying to a 
substrate an anionic dye mixture containing 
(i) at least one dyestuff of formula Ia as yellow component 
##STR5## 
which is in free acid or salt form, in which R.sub.1 is hydrogen, 
C.sub.1-4 alkoxy, unsubstituted C.sub.1-4 alkyl or C.sub.1-4 alkyl 
monosubstituted by halogen, 
R.sub.2 is C.sub.1-4 alkyl or --COR.sub.6, 
wherein R.sub.6 is C.sub.1-6 alkyl, --OC.sub.1-6 alkyl or --NR.sub.7 
R.sub.8, 
wherein each of R.sub.7 and R.sub.8 is independently hydrogen, 
unsubstituted C.sub.1-6 alkyl or monohydroxy-substituted C.sub.2-6 alkyl, 
R.sub.3 is hydrogen or C.sub.1-4 alkyl, 
R.sub.4 is hydrogen, halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy or 
--NR.sub.3 R.sub.9 in which R.sub.3 is as defined above but independent 
thereof and R.sub.9 is --COC.sub.1-6 alkyl or --COOC.sub.1-6 alkyl, 
R.sub.5 is C.sub.1-4 alkyl or monohydroxy-substituted C.sub.2-6 alkyl, 
R.sub.10 is hydrogen, halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy or 
--NR.sub.3 R.sub.9 in which R.sub.3 and R.sub.9 are as defined above but 
independent thereof, and 
R.sub.11 is hydrogen, halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy; 
optionally together with at least one yellow to orange dyestuff of the 
following formulae Ib to Ie, 
##STR6## 
in which X is hydroxy or --NHSO.sub.2 C.sub.1-4 alkyl, and 
R.sub.12 is hydrogen or C.sub.1-4 alkyl; 
##STR7## 
in which each of R.sub.13, R.sub.14 and R.sub.15 is independently 
hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, and 
R.sub.16 is C.sub.1-4 alkyl or C.sub.2-4 hydroxyalkyl; 
##STR8## 
in which each of R.sub.17 and R.sub.18 is independently hydrogen, halogen 
or C.sub.1-4 alkyl; 
##STR9## 
in which Z.sub.1 is phenyl, phenoxy or --NR.sub.19 R.sub.20, 
wherein R.sub.19 is methyl or ethyl, and 
R.sub.20 is phenyl or cyclohexyl; 
which dyestuffs of formulae Ib to Ie are in free acid or salt form; 
together with 
(ii) at least one dyestuff of formula II as red component 
##STR10## 
which is in free acid or salt form, in which R.sub.21 is hydrogen, halogen 
or --NHCOC.sub.1-4 alkyl, and 
R.sub.22 is trifluoromethyl, --SO.sub.2 Z.sub.1 or --SO.sub.2 Z.sub.2 in 
which 
Z.sub.1 is as defined above and 
Z.sub.2 is --N(C.sub.4 H.sub.9).sub.2 or 
##STR11## 
(iii) at least one dyestuff of formula III as blue component 
##STR12## 
which is in free acid or salt form, in which R.sub.23 is hydrogen or 
methyl, 
one of R.sub.24 and R.sub.25 is --SO.sub.2 NHC.sub.2-4 hydroxyalkyl or 
--NR.sub.26 COC.sub.1-4 alkyl in which R.sub.26 is hydrogen, methyl or 
ethyl, and 
the other is hydrogen or methyl. 
In the specification, any unsubstituted or substituted alkyl or alkoxy 
group present is linear or branched unless indicated to the contrary. 
Any halogen is preferably fluorine, chlorine or bromine, especially 
chlorine. 
In any hydroxy-substituted alkyl group which is attached to nitrogen, the 
hydroxy group is preferably bound to a carbon atom which is not directly 
attached to the nitrogen atom. 
In any hydroxy-substituted alkyl group as R.sub.5 or R.sub.16, the hydroxy 
group is preferably bound to a carbon atom which is not directly attached 
to the phenoxy group. 
In a compound of formula Ia: 
R.sub.1 is preferably R.sub.1a, where R.sub.1a is hydrogen, methyl or 
methoxy. Most preferably R.sub.1 is hydrogen. 
Preferably each of R.sub.7 and R.sub.8 is R.sub.7a and R.sub.8a, where each 
of R.sub.7a and R.sub.8a is independently hydrogen, C.sub.1-2 alkyl or 
C.sub.2-3 hydroxyalkyl. More preferably R.sub.7 is R.sub.7b, where 
R.sub.7b is hydrogen or methyl and R.sub.8 is hydrogen. 
R.sub.6 is preferably R.sub.6a, where R.sub.6a is C.sub.1-2 alkyl, 
--OC.sub.1-2 alkyl or --NHR.sub.7b in which R.sub.7b is as defined above; 
more preferably it is R.sub.6b, where R.sub.6b is C.sub.1-2 alkyl or 
--NH.sub.2. Most preferably R.sub.6 is methyl. 
R.sub.2 is preferably R.sub.2a, where R.sub.2a is --COR.sub.6b in which 
R.sub.6b is as defined above. Most preferably R.sub.2 is --COCH.sub.3. 
Each R.sub.3 is preferably R.sub.3a, where each R.sub.3a is independently 
hydrogen or methyl. Most preferably each R.sub.3 is hydrogen. 
R.sub.9 is preferably R.sub.9a, where R.sub.9a is --COC.sub.1-2 alkyl or 
--COOC.sub.1-2 alkyl. More preferably R.sub.9 is --COCH.sub.3. 
R.sub.4 is preferably R.sub.4a, where R.sub.4a is hydrogen, chlorine, 
methyl, methoxy or --NHCOCH.sub.3 ; more preferably R.sub.4 is R.sub.4b, 
where R.sub.4b is hydrogen or methyl. Most preferably R.sub.4 is hydrogen. 
R.sub.5 is preferably R.sub.5a, where R.sub.5a is methyl, ethyl or 
monohydroxy-substituted C.sub.3-5 alkyl; more preferably it is R.sub.5b, 
where R.sub.5b is methyl or monohydroxy-substituted C.sub.4 alkyl; most 
preferably R.sub.5 is 
##STR13## 
Alternatively, R.sub.5 is preferably C.sub.2-6 hydroxyalkyl. 
R.sub.10 is preferably R.sub.10a, where R.sub.10a is hydrogen, chlorine, 
methyl, methoxy or --NHCOCH.sub.3 ; most preferably R.sub.10 is hydrogen. 
R.sub.11 is preferably hydrogen. 
Preferred compounds of formula Ia correspond to formula Ia' 
##STR14## 
which compounds are in free acid or salt form, in which the sulpho group 
is meta or para to the carbon atom to which the azo group is attached, and 
R.sub.1a, R.sub.2a, R.sub.3a, R.sub.4b, R.sub.5b and R.sub.10a are as 
defined above. 
More preferred are compounds of formula Ia' in which 
(1) R.sub.1a and R.sub.3a are hydrogen and R.sub.2a is --COCH.sub.3 ; 
(2) R.sub.10a is hydrogen; 
(3) R.sub.4b is hydrogen; 
(4) those of (1) to (3) in which R.sub.5b is 
##STR15## 
(5) those of (4) in which the sulpho group is meta to the carbon atom to 
which the azo group is attached; 
(6) each of R.sub.1a, R.sub.3a and R.sub.4b is hydrogen, and R.sub.5b is 
##STR16## 
(7) those of (6) wherein R.sub.10a is hydrogen, and the sulpho group is 
meta to the --N.dbd.N-- radical. 
In a compound of formula Ib: 
X is preferably hydroxy or --NHSO.sub.2 CH.sub.3 and 
R.sub.12 is preferably hydrogen, methyl or ethyl. 
In a compound of formula Ic: 
The sulpho group is preferably meta or para to the carbon atom to which the 
azo group is attached. 
R.sub.13 is preferably hydrogen or methoxy, and R.sub.14 is preferably 
hydrogen or methyl. 
R.sub.15 is preferably hydrogen. 
R.sub.16 is preferably methyl, ethyl or C.sub.2-4 hydroxyalkyl; more 
preferably R.sub.16 is methyl or C.sub.3-4 hydroxyalkyl; and the 
--OR.sub.16 radical is preferably ortho or para to the carbon atom to 
which the azo group is attached. 
In a compound of formula Id: 
The phenyl substituents R.sub.17 and R.sub.18 are preferably para to each 
other; more preferably they are both chlorine. 
In a compound of formula Ie: 
Z.sub.1 is preferably phenyl. 
In a compound of formula II: 
R.sub.21 is preferably hydrogen, chlorine or --NHCOCH.sub.3 ; more 
preferably R.sub.21 is hydrogen and R.sub.22 is --SO.sub.2 Z.sub.1 or 
--SO.sub.2 Z.sub.2. 
Preferred compounds of formula III are those in which 
(3a) R.sub.23 is hydrogen, one of R.sub.24 and R.sub.25 is acetylamino or 
propionylamino and the other is hydrogen; or 
(3b) R.sub.23 is hydrogen or methyl, R.sub.24 is methyl and R.sub.25 is 
--SO.sub.2 NHCH.sub.2 CH.sub.2 OH. 
Most preferred is a compound of formula III in which 
(3c) R.sub.23 is hydrogen, R.sub.24 is methyl and R.sub.25 is --SO.sub.2 
NHCH.sub.2 CH.sub.2 OH. 
Preferably, in the dye mixture used in the process according to the 
invention, the yellow component of formula Ia is used alone or together 
with a compound of formula Ib. 
The dyes of formulae Ia to Ie, II and III used in the dyeing or printing 
process may be in free acid or preferably salt form. When they are in salt 
form, the cation associated with the sulpho group is not critical and may 
be any one of those non-chromophoric cations conventional in the field of 
anionic dyes. Examples of such cations are alkali metal cations and 
unsubstituted or substituted ammonium cations, e.g., lithium, sodium, 
potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, 
triethylammonium and mono-, di- and tri-ethanolammonium. 
The preferred cations are the alkali metal cations and ammonium, with 
sodium being the most preferred cation. 
The cations associated with the sulpho group can also be a mixture of the 
above mentioned cations meaning that these compounds can be in a mixed 
salt form. 
The compounds of formulae Ia to Ie, II and III are either known or may be 
prepared by analogy with known processes. For example, the compounds of 
formula Ia may be obtained as described in U.S. Pat. No. 4,384,870 by 
etherifying a compound of formula IV 
##STR17## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.10 and R.sub.11 are as 
defined above, with the corresponding dialkylsulphate or alkylene oxide. 
This etherification is suitably carried out in an aqueous alkaline medium, 
preferably at pH 9-11, and at a reaction temperature of 
30.degree.-100.degree. C., preferably at 50.degree.-80.degree. C. The 
reaction may also be effected under elevated pressure. 
The compounds of formula Ib may be obtained as described in British Patent 
1,454,475 and U.S. Pat. No. 4,060,383, the compounds of formula Ic as 
described in U.S. Pat. Nos. 3,862,119 and 3,932,378 and in British Patent 
1,423,629, the compounds of formula Id as described in U.S. Pat. No. 
3,891,619, and the compounds of formula Ie as described in European Patent 
121495. 
The compounds of formula II may be prepared as described in German Patent 
702932, U.S. Pat. No. 4,312,808 and British Patent 1,579,414. 
The compounds of formula III may be prepared as described in British Patent 
1,568,928 and U.S. Pat. No. 3,778,453. 
The invention further relates to dye mixtures containing at least one 
yellow dyestuff of formula Ia optionally together with one or more 
dyestuffs of formulae Ib to Ie, preferably a dye of formula Ib, together 
with at least one red dyestuff of formula II and at least one blue 
dyestuff of formula III, which dyestuffs of formulae Ia to Ie, II and III 
are as defined above. The dyestuffs are preferably in sodium salt form. 
Preferred dye mixtures consist of at least one dye of formula Ia as yellow 
component, at least one dye of formula II as red component and at least 
one dye of formula III as blue component, each of which dyes is 
independently in free acid or salt form. 
Also preferred are dye mixtures consisting essentially of at least one dye 
of formula Ia as yellow component, at least one dye of formula II as red 
component and at least one dye of formula III as blue component together 
with at least one dye selected from those of formulae Ib-Ie, each of which 
dyes is independently in free acid or salt form. 
In preferred dye mixtures, the ratio of the individual pure dyestuffs used 
in the mixture is as follows: 
______________________________________ 
at least of the yellow component, a dye of 
10 parts by weight 
formula Ia alone or together with 
one or more dyes of formulae Ib to 
Ie; and 
5 to 85 parts by weight 
of each of the red and blue compo- 
nents, at least one dye of formula 
II and at least one dye of formula 
III, 
______________________________________ 
based on 100 parts total weight of the three components and calculated as 
if each component were in sodium salt form. 
More preferred are trichromatic mixtures in which the ratio of the pure 
individual dyestuffs is in the range 
10-60, more preferably 20-50, parts by weight of the yellow component, 
20-70, more preferably 20-45, parts by weight of the red component, and 
10-50, more preferably 15-40, parts by weight of the blue component, 
based on 100 parts total weight of the three components and calculated as 
if each component were in sodium salt form (which preferably it is). 
With these dye mixtures as described above, dyeings or prints on a natural 
or synthetic polyamide substrate are obtained showing a wide range of 
shades, e.g., from pale yellowish-brown to dark bluish-grey. 
For use in dyeing as dye mixtures, the individual dyes are mixed together. 
Stock solutions of the individual dyes of the mixtures may be prepared and 
used in the dyeing process or, preferably, the dyes may be formulated 
together in a single stock solution. 
Such dye mixtures include, for example, mixtures of appropriate commercial 
dry (powder, granules) or liquid forms, aqueous stock solutions which 
contain such mixtures and are obtained, e.g., by dilution with water, and 
dye liquors or printing pastes which contain the dyestuffs as defined 
above as a dye mixture. 
The dyestuff mixtures may be applied in the appropriate commercial form as 
described above. They may contain suitable standardising agents such as 
water-soluble salts (particularly sodium chloride, sodium carbonate and 
sodium sulphate), non-electrolyte type of standardising agents such as 
dextrin and urea, and optionally further additives which are suitable for 
the formulation of solid or liquid preparations. If dyestuffs which are 
especially low in electrolytes are required, these may be obtained by 
purification in accordance with known osmotic methods. 
Any anionically dyeable substrates are suitable for the dyeing or printing 
process according to the invention, particularly natural or synthetic 
polyamides, especially wool, silk, polyamide 6, polyamide 6.6, polyamide 
11, Qiana (a polyamide fibre which may be obtained by reacting 
4,4'-methylene-bis(cyclohexylamine) with a C.sub.12 dicarboxylic acid) and 
mixtures thereof. These substrates may be in any form usually dyed from an 
aqueous medium, e.g., as loose fibres, yarns, threads, filaments, hanks, 
spools, fabrics, texture, felts, fleeces, velvet, especially carpets, 
tufting ware, and semifinished or fully fashioned goods. The fibres may 
also be pre-treated mechanically or with heat, for example, they may be 
crimped or stretched. Furthermore, even mixtures of different fibres or 
fibres which are treated in a different way may be used, particularly, 
when the differential dyeing method is used. 
The above mentioned substrates may be dyed according to conventional dyeing 
methods, for example in accordance with exhaust dyeing from an aqueous dye 
liquor or by impregnating with an aqueous dye liquor or a dye preparation. 
Exhaust dyeing may be effected in accordance with conventional conditions, 
for example at a temperature of from 40.degree. to 120.degree. C. and at 
pH 3.5 to 10, preferably at pH 4 to 7. The pH of the dyebath may be 
adjusted by adding acids usually employed such as formic acid, acetic 
acid, tartaric acid or citric acid, or a buffer solution such as a 
phosphate, tartrate or acetate buffer. In case of pH-controlled dyeing 
processes, the process can be started at pH 7-10 and, subsequently, in the 
course of the dyeing process, the pH may be lowered to a pH up to 3.5 to 
5.5. For the dyeing of synthetic polyamides, the pH of the dyebath is 
preferably adjusted to a weakly acid or neutral reaction, and is more 
preferably held at pH 4.5-6. For the dyeing of wool a lower pH is 
preferred, more particularly in the range of pH 4-5.5. Using an 
impregnation process, any conventional method is suitable, whereby the 
substrate is impregnated by an aqueous dye liquor or paste, for example by 
a dipping, padding or printing process. Subsequently, the obtained dyeing 
is fixed in accordance with conventional means, e.g., by the cold dwell 
method suitably at temperatures of from 15.degree.-40.degree. C., 
preferably at 20.degree.-30.degree. C., or by steaming for example at 
100.degree.-105.degree. C. 
The dye mixtures according to the invention are well suited for using in 
exhaust dyeing wool and/or synthetic polyamide, e.g., in stock-, hank- or 
piece-dyeing; furthermore, in conventional as well as in special printing 
processes such as displace or resist processes; in continuous carpet 
dyeing, differential dyeing and space dyeing and in pH-controlled dyeing 
processes. 
Due to the notably good levelness of their dyeing behaviour, these dye 
mixtures are particularly suited for the exhaust and immersion processes. 
With the above mentioned dye mixtures, optimum dyeings, especially on 
natural and synthetic polyamides, are obtained which show good constancy 
in shade, high yield in tinctorial strength, very good fastness properties 
and a notably good migrating power. These dyeings do not show catalytic 
fading. Their colorimetrically calculated recipes, even when done by 
computers, are well reproducible. It has been found that these 
characteristics are a surprising result of the specific mixture of dyes of 
this invention. 
Furthermore, the dyes are compatible with conventional dyeing auxiliaries, 
such as wetting agents, levelling agents, carriers, thickening agents and 
absorption assistants. In addition, the dyeings thus obtained can be 
treated with common finishing agents such as antistatic agents, softening 
agents, agents to improve the sewability or raising assistants.

The following examples further serve to illustrate the invention. In the 
examples all parts and percentages are by weight unless indicated to the 
contrary. The temperatures are in degrees Centigrade. In the Application 
Examples the dyestuff components are used in commercial powder form and 
the amounts of dye component given in parts or as percent refer to the 
concentration of pure dyestuff based on the dry weight of substrate. 
PREATION EXAMPLE 
44 Parts of the disazo dyestuff of formula (1a) 
##STR18## 
which may be prepared in accordance with the method described in Example 1 
of U.S. Pat. No. 4,384,870, are dissolved in 500 parts of water at 
60.degree. by the addition of 30% sodium hydroxide solution to adjust the 
pH of the mixture at 10. To this solution 30 parts of n-butylene oxide-1,2 
are added whilst stirring, and the reaction temperature is elevated to 
62.degree.-65.degree.. Simultaneously, the pH is maintained at 10-10.5 by 
adding 30% sodium hydroxide solution. After 15 to 20 hours at 
62.degree.-65.degree., the etherification is complete. The precipitation 
of the dyestuff is completed by added sodium chloride. The dyestuff is 
isolated by filtration, washed with 10% sodium chloride solution and 
dried. The disazo dye which, in free acid form, corresponds to formula 
(1b) 
##STR19## 
is obtained in sodium salt form. It dyes natural and synthetic polyamides 
a yellow shade. 
When a mixture of 1-aminobenzene-3- and -4-sulphonic acids (in a ratio of 
approximately 1:1) is used instead of 1-aminobenzene-3-sulphonic acid to 
prepare the starting dye (1a) and otherwise etherification is carried out 
in accordance with the method described above, the corresponding dye 
mixture is obtained. It dyes natural and synthetic polyamides a yellow 
shade. 
By analogy with the method described in the Preparation Example, using 
appropriate starting compounds, further compounds of formula Ia may be 
prepared which are listed in the following Table. They correspond to 
formula IA, 
##STR20## 
in which the symbols are as defined in the Table below. In the last column 
J of this Table the shade of the dyeings on natural and synthetic 
polyamides obtained with each of Compounds 2 to 10 is given whereby 
a is yellow and 
b is brownish orange. 
TABLE 
__________________________________________________________________________ 
Compounds of formula IA 
SO.sub.3 H in 
R.sub.10, R.sub.11 R.sub.4 
Cpd. No. 
position 
(position) 
R.sub.1 
R.sub.2 
R.sub.3 
(position) 
J 
__________________________________________________________________________ 
2 4 H H --COCH.sub.3 
H H a 
3 3 H H --COCH.sub.3 
H 3-CH.sub.3 
a 
4 3 H H --CONH.sub.2 
H H b 
5 4 H CH.sub.3 
--COCH.sub.3 
H 2-CH.sub.3 
a 
6 3 H H --COCH.sub.3 
CH.sub.3 
H a 
7 4 2-CH.sub.3 
H --COCH.sub.3 
H H a 
8 5 2-CH.sub.3 
H --COCH.sub.3 
H 3-CH.sub.3 
a 
9 4 2-Cl H --COCH.sub.3 
CH.sub.3 
H a 
10 4 2,5-di-CH.sub.3 
H --COCH.sub.3 
H H b 
__________________________________________________________________________ 
In the following Application Examples in which the mixtures according to 
the invention are used, the following individual dyestuffs are employed: 
A: a yellow component of formula Ia having the formula (1b) according to 
the Preparation Example; 
B: a red component of formula II consisting of a mixture of two dyes (in a 
ratio of approximately 1:1) having the formulae 
##STR21## 
C: a blue component of formula III consisting of a mixture of two dyes (in 
a ratio of approximately 1:1) having the formulae 
##STR22## 
D: a blue component of formula III having the formula 
##STR23## 
E: a red component of formula II having the formula 
##STR24## 
F: a blue component of formula III consisting of a mixture of dyes IC and 
IIC according to C but using 90% IC together with 10% IIC; 
G: a yellow component of formula Ib having the formula 
##STR25## 
Each of the individual dyestuffs of components A to G is in sodium salt 
form. 
In any dye mixture used in the following Application Examples, the dye of 
formula (1b) as yellow component A can be replaced with each of Compounds 
2 to 10 set forth in the Table above. Each of Compounds 2 to 10 is used in 
sodium salt form. 
APPLICATION EXAMPLE 1 
Exhaust Dyeing on Polyamide Fabric 
100 Parts of pre-wetted synthetic polyamide, for example polyamide 6.6 
fabric, are entered at 40.degree. into a dyebath consisting of 4000 parts 
of water, 10 parts of anhydrous sodium sulphate and a dye mixture 
containing 
0.07% of A 
0.05% of B and 
0.03% of C. 
The dye liquor is heated over the course of 30 minutes to boiling 
temperature and kept at this temperature for 1 hour. 4 Parts of glacial 
acetic acid are then added thereto and dyeing is completed with heating 
for a further 30 minutes at boiling temperature. During dyeing, the water 
that evaporates is continuously replaced. The nylon cloth dyed in a brown 
shade is then removed from the liquor, rinsed with water and dried. 
Wool or wool/synthetic polyamide blends may also be dyed by the same 
process. 
The polyamide dyeings thus obtained are evenly dyed and show good light 
fastness and wet fastness properties. 
APPLICATION EXAMPLE 2 
Following the method described in Example 1 but using a dye mixture 
containing 
0.02% of A 
0.025% of B and 
0.025% of D, 
an evenly dyed nylon cloth is obtained having a grey shade and good 
fastness properties. 
APPLICATION EXAMPLE 3 
Printing of Polyamide Fabric 
Polyamide 6 is printed with a printing paste containing: 
15 parts of a dye mixture consisting of 
5.7 parts of A 
6.0 parts of E and 
3.3 parts of F, 
50 parts of urea 
50 parts of a solubilising agent (e.g., thiodiethylene glycol) 
305 parts of water 
500 parts of a thickening agent (for example based on carob bean gum in 
form of a 10% aqueous solution) 
20 parts of an acid-donating agent (e.g., ammonium tartrate) and 
60 parts of thiourea. 
The printed textile goods are steamed for 40 minutes at 102.degree. 
(saturated steam), rinsed cold, washed at 60.degree. with a dilute 
solution of a conventional detergent for 5 minutes, and then rinsed again 
with cold water. A brown print having good light and wet fastness 
properties is obtained. 
APPLICATION EXAMPLE 4 
Continuous Dyeing of Polyamide Carpet 
Polyamide (e.g., regular polyamide 6.6 fibres) carpet is wetted with a 
composition consisting of 1.5 parts of a product obtained by reacting 4 
moles of ethylene oxide with 1 mole of decyl alcohol and 998.5 parts of 
water and squeezed to impregnate the wetting agent and reduce the total 
pick-up to 90% (by weight of the dry substrate). 
A dye liquor consisting of 
0.15 parts of a dye mixture containing 
0.035 parts of A 
0.035 parts of G 
0.05 parts of B and 
0.03 parts of F, 
1.5 parts of a thickener based on guar (e.g., Celca Gum D-49-D) 
1.5 parts of decyl alcohol ethoxylated with 4 moles of ethylene oxide per 
mole of alcohol, 
96.85 parts of water, and 
a sufficient amount of monosodium phosphate to adjust the pH of the liquor 
at 5, 
is applied to the wetted polyamide carpet using a continuous applicator 
(e.g., Kusters) to achieve a wet pick-up of 500% (based on dry weight of 
the substrate). The polyamide carpet thus treated is then steamed in a 
vertical streamer for 7 minutes at 102.degree., rinsed with warm water at 
40.degree. and then dried. 
When continuous impregnation is effected to a pick-up of 300% or 600%, 
lower or deeper dyeings may be obtained. Instead of a vertical steamer, a 
horizontal steamer may be employed. 
Very evenly dyed brown dyeings are obtained which have good light fastness 
(even when exposed to light in the heat) and wet fastness properties. 
The following Application Examples 5 to 14 illustrate conventional or more 
specific dyeing or printing methods for polyamide carpet in which 
particular assisting agents are used. These assistants may be listed as 
follows: 
Levelling agents LA1) to LA6), where 
LA1) is an amphoteric levelling agent consisting essentially of a 
quaternary sulphonated higher amino fatty acid amide; 
LA2) is an anionic levelling agent consisting essentially of a saturated 
C.sub.12-13 -alcohol polyglycol ethersulphate as sodium salt; 
LA3) is an anionic levelling agent consisting essentially of a mixture 
consisting of 
sulphonated polyphenyl sulfone, 
ethoxylated amino C.sub.22 fatty amine and 
ethoxylated higher alkyl alcohol; 
LA4) is an amphoteric levelling agent consisting essentially of a sulphated 
ethoxylated C.sub.18-22 fatty amine as ammonium salt; 
LA5) is a cation-active levelling agent consisting essentially of the 
reaction product of 1 mole C.sub.22 fatty acid aminopropylamine and 105 
moles ethylene oxide; 
LA6) is a non-ionic levelling agent consisting essentially of a mixture 
consisting of 
tridecylalcohol polyglycol ether 
LA1) and 
hexylene glycol. 
Acid-donating agents AD1) to AD3), where 
AD1) consists essentially of butyrolactone; 
AD2) consists essentially of a glycol mono- or di-ester of formic acid; 
AD3) consists essentially of a mixture of C.sub.4-6 dicarboxylic acids. 
Reserving agent RA1), where 
RA1) consists essentially of the quaternary reaction product of a higher 
fatty amine reacted with ethylene oxide and 1 mole styrene oxide. 
APPLICATION EXAMPLES 5 TO 8 
Exhaust Dyeing 
In each of these Application Examples a liquor to goods ratio of 20:1 is 
used. 
EXAMPLE 5 
Differential Dyeing on Polyamide 6.6 
50 Parts of polyamide carpet of deep dye, regular, basic fibres are used. 
The aqueous liquor contains 
a trichromatic dye mixture consisting of 
0.16% of A 
0.15% of B and 
0.30% of F, 
a basic dye mixture consisting of 
0.006% of C.I. Basic Yellow 45 
0.002% of C.I. Basic Red 23 and 
0.01% of C.I. Basic Blue 22, 
1% of LA5), and 
1 g/l of AD2) which is added when starting the dyeing process. 
The pH of the liquor is 7 at the beginning. During the course of dyeing 
which is effected at 98.degree. for 60 minutes, the pH of the liquor 
decreases to 5.5. 
The resulting grey-rose polyamide carpet is very evenly dyed. 
EXAMPLE 6 
Dyeing is effected by analogy with the method described in Example 5 but 
using 1 g/l of AD1) instead of AD2) which is added to the dyebath only at 
boiling temperature. The dyeing process is started at pH 8.0 and the 
liquor is heated to 98.degree. within 30 minutes. Then the appropriate 
amount of AD1) is added whereby the pH of 8 when starting is adjusted to 6 
over 30 minutes. 
EXAMPLE 7 
Plain Dyeing on Polyamide 6.6 
50 Parts of polyamide carpet of regular fibres are employed. The aqueous 
dye liquor contains 
a trichromatic dye mixture which consists of 
0.044% of A 
0.035% of B and 
0.028% of F, 
1% LA5), and 
1 g/l of AD1). 
Dyeing is effected in accordance with the method described in Example 6. An 
evenly dyed pale-brown carpet is obtained. 
EXAMPLE 8 
Plain Dyeing on Polyamide 6 
50 Parts of polyamide carpet of deep dye fibres are employed. The aqueous 
liquor contains 
a trichromatic dye mixture consisting of 
0.014% of A 
0.025% of B and 
0.08% of F, 
1% of LA3), and 
1 g/l of AD2) which is added from the beginning. 
Dyeing is carried out starting at pH 8.0 and 20.degree.. In accordance with 
a low temperature dyeing process, the bath is heated to 60.degree. and is 
kept at 60.degree. for 60 minutes. At the end of the dyeing procedure, the 
pH of the liquor is 5.5. An evenly dyed carpet of grey-blue shade is 
obtained. 
APPLICATION EXAMPLES 9 TO 11 
Continuous and Semi-Continuous Dyeing 
In each of these Application Examples (Examples 9 and 10 show a continuous 
and Example 11 a semi-continuous process), the liquor to goods ratio is 
2.8:1. 
EXAMPLE 9 
--Differential Dyeing on Polyamide 6 
A polyamide carpet of deep dye, regular, basic fibres is used. A dye liquor 
consisting of 
0.395 parts of a trichromatic dye mixture containing 
0.055 parts of A 
0.27 parts of B and 
0.07 parts of F, 
1.06 parts of a basic dye mixture containing 
0.06 parts of C.I. Basic Yellow 45 
0.10 parts of C.I. Basic Red 23 and 
0.90 parts of C.I. Basic Blue 22, 
1.5 g/l of LA6), 
1.5 g/l of AD3), and 
2.0 g/l of AD2), 
is applied to the polyamide carpet at pH 7.5 and a pick-up of 280% (based 
on the dry weight of substrate) is achieved. The dyed carpet is then 
steamed for 5 minutes at 102.degree. (saturated steam). The resultant 
carpet is evenly dyed in a reddish violet-blue tone. 
EXAMPLE 10--Plain Dyeing of Polyamide 6.6 
A polyamide carpet of regular fibres is used. A dye liquor consisting of 
0.62 parts of a trichromatic dye mixture containing 
0.16 parts of A 
0.24 parts of B and 
0.22 parts of F, 
1 g/l of LA3), 
2 g/l of LA6), 
2 g/l of LA2), and 
1 g/l of AD3), 
is applied to the polyamide carpet at pH 7.0. A pick-up to 250% (based on 
the dry weight of substrate) is achieved. Then the dyeing is steamed at 
102.degree. (saturated steam) for fixation. A brown dyeing is obtained 
showing the same shade at the fibre ends as well as on both sides due to 
the homogeneous dispersing effect of colour promoting good ground/pile tip 
levelness. 
EXAMPLE 11--Semi-Continuous Plain Dyeing on Polyamide 6.6 
Carpet material of regular fibres is used. A dye liquor consisting of 
0.94 parts of a trichromatic dye mixture containing 
0.38 parts of A 
0.34 parts of B and 
0.22 parts of F, 
2 g/l of LA2), 
4 g/l of LA4), and 
1 g/l acetic acid 60%, 
is applied to the carpet and a pick-up of 250% is achieved. The retention 
time is 20 hours at room temperature. An evenly dyed brown carpet is 
obtained which show no difference in shade with respect to both sides and 
the fibre ends. 
APPLICATION EXAMPLES 12-15 
Printing Processes 
EXAMPLE 12--Conventional Printing of Polyamide 6 
A carpet material of polyamide 6 endless velvet is employed. Fond dyeing is 
effected by padding with a liquor containing 
0.23 parts of a dye mixture consisting of 
0.02 parts of A 
0.10 parts of B and 
0.11 parts of F, 
1 g/l of LA2), and 
2 g/l of a thickening agent (based on locust bean gum), 
at pH 5.0 to a pick-up of 100%. 
Subsequently, overprinting with a rotary screen is effected using a 
printing paste which consists of 
0.76 parts of a dye mixture containing 
0.2 parts of A 
0.11 parts of B and 
0.45 parts of F, 
400 g/kg of an alginate thickening agent 4% 
4 g/kg of LA1), and 
5 cm.sup.3 /kg of acetic acid 80%. 
Dyeing is effected by padding the carpet to yield a pale-blue fond followed 
by printing of designs using the green overprinting paste and fixing the 
resultant prints with saturated steam for 10 minutes. 
A pale-blue carpet fond with green printing designs is obtained showing 
good penetration and a homogeneous colour distribution with respect to the 
printing appearance. 
EXAMPLE 13--Displace Printing 
A carpet material of polyamide 6.6 heat set yarns (velvet) is used. Fond 
dyeing is effected by padding with a liquor containing 
4.12 parts of a dye mixture consisting of 
0.64 parts of C.I. Acid Yellow 235 
0.28 parts of C.I. Acid Red 399 and 
3.2 parts of C.I. Acid Black 218 
100 g/l of an alginate thickening agent 4% 
3 g/l of LA1), and 
1 g/l of a defoaming agent, 
at pH 5.0 to a pick-up of 100%. 
Overprinting is effected with a rotary screen using a printing paste which 
consists of 
1.77 parts of a dye mixture containing 
1.0 parts of A 
0.6 parts of B and 
0.17 parts of F, 
10 g/kg of RA1), and 
500 g/kg of an alginate thickener 4%, 
at pH 7.0. 
The printing process is analogous to that described in Example 12. A carpet 
with a dark-grey fond and clear yellowish-brown printing designs is 
obtained showing a homogeneous colour distribution in the structure of the 
fibres. 
EXAMPLE 14--Spray Printing 
A carpet material of polyamide 6.6 heat set velvet is employed. A printing 
paste consisting of 
0.126 parts of a dye mixture containing 
0.045 parts of A 
0.045 parts of B and 
0.036 parts of F, 
an appropriate amount of citric acid to adjust the pH at 4.5, 
an appropriate amount of thickening agent to yield a viscosity of 300 cps, 
and 
2 g/l of LA5), 
is applied to achieve a pick-up of 350%. The carpet is locally printed 
using a spray printing machine and fixed with saturated steam for 10 
minutes. A brown printing pattern is obtained. 
An optimum colour distribution is obtained without any differences in shade 
regarding the pile ground/pile tip levelness. 
EXAMPLE 15 
The printing process according to Example 14 is repeated with the exception 
that printing is effected over the whole surface without a pattern instead 
of locally printing, whereby a plain brown carpet is obtained. The whole 
carpet surface is evenly dyed and the pile levelness is notably good.