Process for dyeing cellulosic fibre materials with reactive phthalocyanine dyes from bath containing colorless compounds

The invention relates to a process for dyeing cellulosic fibre materials with reactive dyes by the pad dyeing process in the process of an assistant, which process comprises the use of a mixture containing PA0 (a) at least one reactive dye of formula ##STR1## wherein Pc, W, k, R.sub.1, R.sub.2, B and R are as defined in claim 1, and PA0 (b) at least one colorless compound which contains at least one --SO.sub.2 --Z group, wherein Z is as defined in claim 1.

The present invention relates to a novel process for dyeing cellulosic 
fibre materials with a mixture of a fibre-reactive phthalocyanine dye and 
a fibre-reactive colourless compound by the pad dyeing process. 
Pad dyeing processes, especially the cold pad batch process, are known 
processes for dyeing cellulosic fibre materials. These processes make it 
possible to dye and fix textile fibre materials in bulk by impregnating 
the fibre substrates with the dye solution in a vat at the shortest 
possible liquor ratio and usually with only a single passage of the goods 
on the pad and, for example, by subsequently batching the goods for 1 to 
48 hours. 
In view of the increasingly stringent demands being made of dyeings 
obtained with reactive dyes in respect of efficiency, application 
technology and fastness standards, the current state of the art is in many 
respects not entirely satisfactory. 
Specifically, the present invention relates to a process for dyeing 
cellulosic fibre materials with reactive dyes by the pad dyeing process, 
preferably by the cold pad batch process, in the presence of an assistant, 
which process comprises dyeing from an aqueous liquor containing a mixture 
of 
(a) at least one reactive dye of formula 
##STR2## 
wherein Pc is the radical of a copper or nickel phthalocyanine, W is --OH 
and/or --N(R.sub.3)R.sub.4, K is 1, 2 or 3, and R.sub.1 is hydrogen or 
C.sub.1 -C.sub.4 alkyl which may be substituted by halogen, hydroxy, 
cyano, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, carboxy, 
sulfo or sulfato, (R.sub.2).sub.0-2 denotes 0 to 2 substituents selected 
from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, carboxy or sulfo, R.sub.3 and R.sub.4 are each 
independently of the other hydrogen or C.sub.1 -C.sub.4 alkyl which may be 
substituted by hydroxy or sulfo, or wherein R.sub.3 and R.sub.4, when 
taken together, form a C.sub.4 -C.sub.5 alkylene radical which may be 
interrupted in the chain by a nitrogen or oxygen atom, B is a direct bond 
or a radical --(CH.sub.2).sub.n -- or --O--(CH.sub.2).sub.n --, wherein n 
is 1,2,3,4,5 or 6; and R is a radical of formula 
##STR3## 
wherein R' is hydrogen or C.sub.1 -C.sub.6 alkyl, alk is a C.sub.1 
-C.sub.7 alkylene radical or the branched isomers thereof, T is hydrogen, 
halogen, hydroxy, sulfato, carboxy, cyano, C.sub.1 -C.sub.4 alkanoyloxy. 
C.sub.1 -C.sub.4 alkoxycarbonyl, carbamoyl or a --SO.sub.2 --Z radical, V 
is hydrogen, unsubstituted or substituted C.sub.1 -C.sub.4 alkyl or a 
radical of formula 
##STR4## 
wherein (alk) is as defined above, alk' is a polymethylene radical of 2 to 
6 carbon atoms or the branched isomers thereof, Z is .beta.-sulfatoethyl, 
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-acyloxyethyl, 
.beta.-haloethyl or vinyl, p, q, r and t are each independently of one 
another 1,2,3,4,5 or 6, and s is 2,3,4,5 or 6; and 
(b) at least one colourless compound which contains a --SO.sub.2 --Z group, 
wherein Z has the given meaning. 
Surprisingly, the process of this invention yields especially good results. 
Thus the addition of a fibre-reactive colourless compound which contains a 
--SO.sub.2 --Z group markedly improves the degree of fixation obtainable 
by the cold pad batch process, the resultant dyeings can be washed off 
more readily, and a greater depth of shade is obtained, i.e. to obtain 
dyeings of the same tinctorial strength, a smaller amount of dye is needed 
in the process of this invention than in the known cold pad batch 
processes of the prior art. Further, the process of this invention results 
in insignificant pollution of the wastewater. 
R.sub.1 and R.sub.2 as C.sub.1 -C.sub.4 alkyl are typically: methyl, ethyl, 
n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl and sec-butyl, which 
radicals may be substituted by halogen, hydroxy, cyano, C.sub.1 -C.sub.4 
alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, carboxy, sulfo and sulfato. 
Examples of such substituted radicals are: carboxymethyl, 
.beta.-carboxyethyl, .beta.-carboxypropyl, methoxycarbonylmethyl, 
.beta.-methoxyethyl, .beta.-chloroethyl, .beta.-hydroxyethyl, 
.beta.-cyanoethyl, sulfomethyl, .beta.-sulfoethyl and .beta.-sulfatoethyl. 
The preferred meaning of R.sub.1 is hydrogen, methyl or ethyl. 
R.sub.2 as C.sub.1 -C.sub.4 alkoxy is suitably: methoxy, ethoxy, 
isopropoxy, n-propoxy, isobutoxy, tertbutoxy, sec-butoxy and n-butoxy, 
which radicals may be substituted, for example by C.sub.1 -C.sub.4 alkoxy. 
Such a radical is typically the .beta.-ethoxyethoxy radical. 
R.sub.2 as halogen may be fluoro, chloro or bromo. 
Each of R.sub.3 and R.sub.4 independently of the other as C.sub.1 -C.sub.4 
alkyl is suitably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 
sec-butyl and tert-butyl, which radicals may be substituted by hydroxy or 
sulfo. Exemplary of such radicals are .beta.-hydroxyethyl, sulfomethyl, 
.beta.-sulfoethyl. 
If R.sub.3 and R.sub.4 together form a C.sub.4 -C.sub.5 alkylene radical 
which may be substituted by a --N or --O atom then R.sub.3 and R.sub.4, 
together with the linking nitrogen atom, may suitably be for example 
piperidyl, morpholinyl or piperazinyl. 
The radical B contains 1 to 6, preferably 1 to 4, carbon atoms. Examples of 
B are: methylene, ethylene, propylene, butylene, methyleneoxy, 
ethyleneoxy, propyleneoxy and butyleneoxy. Where B is a 
--O--(CH.sub.2).sub.n -- radical, B is linked to the benzene ring through 
the oxygen atom. Preferably B is a direct bond. 
A .beta.-haloethyl radical Z is preferably the .beta.-chloroethyl radical; 
and the .beta.-acyloxyethyl radical is preferably the .beta.-acetoxyethyl 
radical. The alkylene radical alk is preferably methylene, ethylene, 
methylmethylene, propylene or butylene. The substituent T as alkanoyloxy 
radical is preferably acetyloxy, propionyloxy or butyryloxy; and as 
alkoxycarbonyl radical T is preferably methoxycarbonyl, ethoxycarbonyl or 
propoxycarbonyl. An alkyl radical V may be methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. Derivatives of the 
carboxy or sulfo group are carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, 
N,N-dimethylcarbamoyl and N,N-diethylcarbamoyl, cyano, acetyl, propionyl, 
butyryl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, sulfamoyl, 
N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl and 
N,N-diethylsulfamoyl, methylsulfonyl, ethylsulfonyl and propylsulfonyl. 
The radical R' is typically methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, or is preferably 
hydrogen. The polymethylene radicals alk' are preferably ethylene, 
propylene or butylene. The indices p, q and t are independent of one 
another and are preferably 2, 3 or 4. The indices r and s are each 
independently of the other preferably 2. 
If T is a --SO.sub.2 --Z radical and R' is hydrogen, then the radical of 
formula (2) preferably has the formula 
##STR5## 
wherein Z and Z' are each independently of the other .beta.-sulfatoethyl, 
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-acyloxyethyl, 
.beta.-haloethyl or vinyl. An important variant of the formula of this 
radical is 
##STR6## 
wherein Z=Z' and Z and Z' are as defined above. Preferably Z and Z' are 
.beta.-sulfatoethyl, .beta.-chloroethyl or vinyl. 
In the process of this invention, those compounds are termed colourless 
whose absorption maximum is outside the visible range of the spectrum and 
whose absorption in the visible range is very insignificant. 
The colourless organic compound used in the process of this invention is a 
compound having "fibre-reactive" character, i.e. under dyeing conditions 
this compound behaves as a reactive dye through being capable of forming 
covalent linkage with the fibre substrate. 
The colourless organic compounds contain one or more fibre-reactive 
--SO.sub.2 --Z groups. 
Surprisingly, the process of this invention can be used equally well both 
for dyeing pure cellulosic fibres, such as mercerised or causticised or 
bleached cotton or viscose rayon, and for dyeing cellulose-containing 
fibre blends such as polyester/cellulose blends. 
The amount of dye used in the process of this invention will depend as a 
rule on the desired depth of shade. Amounts ranging from 0.05 g/l to 100 
g/l in the aqueous padding liquor have proved useful. 
It is also possible to use mixtures of reactive dyes of formula (1) and 
mixtures of colourless fibre-reactive compounds in the process of the 
invention. 
The fibre material to be dyed should exhibit neutral reaction and have a 
good absorption capacity. The reactive dye and the colourless compound are 
added, with stirring, to water of, for example, 20.degree. to 30.degree. 
C. For padding, it is possible to use for example known vats of U- or 
V-shaped cross-section and having divider inserts. The volume of the 
liquor should preferably be kept small in order to ensure a rapid liquor 
uptake. The immersion time is usually from 1 to 4 seconds. A padding 
temperature range from 20.degree. to 30.degree. C. has proved very 
suitable. The pick-up is normally 50 to 120%, preferably 60 to 80%, for 
cotton, and 80 to 100% for viscose rayon. The normal procedure is that dye 
and alkali solution are prepared separately and fed overnight into the 
padding vat by means of a mixing or metering device. Mixing of the two 
solutions is thus effected immediately before padding. After padding, the 
goods are batched up evenly and wrapped in a plastic sheet. During 
fixation, the goods must be protected from cooling or heating and from 
loss of moisture. The fixation rate depends on the chosen substrate and 
the temperature. Fixation times of 3 to 24, preferably from 3 to 8, hours 
at room temperature suffice as a rule. 
The fixation alkalies customarily used for cold pad batch processes can be 
used as fixation alkalies. For carrying out the process of this invention 
in the alkaline pH range it has proved especially useful to use, for 
example, sodium hydroxide, potassium hydroxide, trisodium phosphate, 
disodium phosphate, sodium carbonate or mixtures of sodium carbonate with 
neutral salts such as sodium chloride and, in particular, water glass, as 
alkaline acid acceptors. Water glass is the term given to the vitreous 
solidified melts of alkali metal silicates. It is also possible to use 
mixtures of the cited acid acceptors. In the process of this invention it 
is preferred to use a mixture of water glass and sodium hydroxide. 
In the process of this invention the liquor contains one or more of the 
cited acid acceptors and, if desired, conventional additives such as 
wetting agents, for example dioctyl sulfosuccinate, and thickeners, for 
example alginate thickeners, and neutral inorganic salts such as alkali 
metal chlorides or alkali metal sulfates. 
After fixation, the dyeings are rinsed thoroughly with cold and hot water, 
with the optional addition of an agent which acts as dispersant and 
promotes the diffusion of unfixed dye. 
The preferred procedure is that the dyed goods are washed off in an aqueous 
washing liquor at a pH of 8.5 to 9 and at elevated temperature, preferably 
in the range from 70.degree. to 85.degree. C., in the absence or in the 
presence of a nonionic detergent. 
A preferred embodiment of the process of this invention comprises using, as 
colourless compound, a cycloaliphatic amine or, in particular, an aromatic 
amine, which contains a --SO.sub.2 --Z group. 
A suitable cycloaliphatic amine is, for example, a piperazine compound 
which contains a --SO.sub.2 --Z group. A suitable aromatic amine is, for 
example, an aniline or naphthylamine which contains a --SO.sub.2 --Z 
group. 
An especially preferred embodiment of the process of the invention 
comprises using mixtures of at least one reactive dye of formula (1) with 
at least one colourless compound of formula 
##STR7## 
wherein R.sub.1, (R.sub.2).sub.0-2, B, R, Z and n are as defined for 
formula (1), but are independent of the corresponding radicals and indices 
in formula (1). 
A still more preferred embodiment of the process of this invention 
comprises using mixtures containing 
(a) at least one reactive dye of formula 
##STR8## 
wherein Pc is the radical of a copper phthalocyanine, W is as defined for 
formula (1) and is preferably --OH or --NH.sub.2, R.sub.1 is hydrogen, 
methyl or ethyl, R.sub.5 is hydrogen, methyl, methoxy, chloro or sulfo, B 
is a direct bond, --CH.sub.2 -- or --O--CH.sub.2 CH.sub.2 --, R is a 
radical of formula 
##STR9## 
Z is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl, T is hydrogen or a 
--SO.sub.2 --Z radical, wherein Z has the given meaning, and V is hydrogen 
or methyl, or V is a radical of formula 
##STR10## 
wherein Z has the given meaning, T is hydrogen, alk is C.sub.1 -C.sub.3 
alkylene, R' is hydrogen, p is 2 and q is 2, and 
(b) at least one of the colourless compound of formula 
##STR11## 
wherein R.sub.1, R.sub.5, B, R and Z have the given meanings but are 
independent of the corresponding radicals in formula (4). 
An important embodiment of the process of this invention comprises using 
mixtures containing 
(a) at least one reactive dye of formula (4), wherein Pc, W, k, R.sub.1, 
R.sub.5 and B are as defined for formula (4), R is a radical of formula 
(2a), (2b) or (2c), Z, T, (alk), R', p and q are as defined for formula 
(4), and V is hydrogen or a radical of formula (2g), and 
(b) at least one colourless compound of formula (5a) or (5b). 
A particularly important embodiment of the process of this invention 
comprises using mixtures containing 
(a) a reactive dye of formula 
##STR12## 
wherein R.sub.1 is hydrogen or methyl, k is 1.5 to 2.5, and R is a radical 
of formula 
##STR13## 
(b) a compound of formula 
##STR14## 
wherein Z is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl. 
A particularly preferred embodiment of the process of this invention 
comprises using mixtures containing 
(a) a reactive dye of formula 
##STR15## 
wherein Pc is as defined for formula (4), and 
(b) a compound of formula 
##STR16## 
In the process of this invention it is preferred to use mixtures wherein 
the ratio of the reactive dyes to the colourless compounds is from 1:1 to 
100:1, preferably from 10:1 to 100:1, parts by weight. 
The invention further relates to mixtures containing 
(a) at least 50 parts by weight of at least one reactive dye of formula 
(1), wherein Pc, W, k, R.sub.1, R.sub.2, B and R are as defined for 
formula (1), and 
(b) at least 0.5 part by weight of at least one colourless compound which 
contains at least one --SO.sub.2 --Z group, wherein Z is as defined for 
formula (1). 
Preferred mixtures are those wherein the colourless compound is a 
cycloaliphatic amine or, preferably, an aromatic amine, conveniently a 
compound of formula (3a), (3b), (3c) or (3d). 
Particularly preferred mixtures are those which contain at least one 
reactive dye of formula (4) and at least one colourless compound of 
formula (5a) or (5b). 
More particularly preferred mixtures are those which contain (a) a reactive 
dye of formula (6) and (b) a colourless compound of formula (11), (12) or 
(13). 
The most preferred mixtures are those which contain (a) a reactive dye of 
formula (14) and (b) a colourless compound of formula (15) or (16). 
The ratio of the reactive dyes to the colourless compounds is preferably 
from 1:1 to 100:1, most preferably from 10:1 to 100:1, parts by weight. 
The invention further relates to aqueous dye formulations which contain a 
mixture of (a) at least one reactive dye of formula 
##STR17## 
wherein Pc is the radical of a copper or nickel phthalocyanine, W is --OH 
and/or --N(R.sub.3)R.sub.4, k is 1,2 or 3, and R.sub.1 is hydrogen or 
C.sub.1 -C.sub.4 alkyl which may be substituted by halogen, hydroxy, 
cyano, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, carboxy, 
sulfo or sulfato, (R.sub.2).sub.0-2 denotes 0 to 2 substituents selected 
from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, carboxy or sulfo, R.sub.3 and R.sub.4 are each 
independently of the other hydrogen or C.sub.1 -C.sub.4 alkyl which may be 
substituted by hydroxy or sulfo, or wherein R.sub.3 and R.sub.4, when 
taken together, form a C.sub.4 -C.sub.5 alkylene radical which may be 
interrupted in the chain by a nitrogen or oxygen atom, B is a direct bond 
or a radical --(CH.sub.2).sub.n -- or --O--(CH.sub.2 (.sub.n --, wherein n 
is 1, 2, 3 4, 5 or 6; and R is a radical of formula 
##STR18## 
wherein R' is hydrogen or C.sub.1 -C.sub.6 alkyl, alk is a C.sub.1 
-C.sub.7 alkylene radical or the branched isomers thereof, T is hydrogen, 
halogen, hydroxy, sulfato, carboxy, cyano, C.sub.1 -C.sub.4 alkanoyloxy. 
C.sub.1 -C.sub.4 alkoxycarbonyl, carbamoyl or a --SO.sub.2 --Z radical, V 
is hydrogen, unsubstituted or substituted C.sub.1 -C.sub.4 alkyl or a 
radical of formula 
##STR19## 
wherein (alk) is as defined above, alk' is a polymethylene radical of 2 to 
6 carbon atoms or the branched isomers thereof, Z is .beta.-sulfatoethyl, 
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-acyloxyethyl, 
.beta.-haloethyl or vinyl, p, q, r and t are each independently of one 
another 1, 2, 3, 4, 5 or 6, and s is 2, 3, 4, 5 or 6; and 
(b) at least one colourless compound which contains a --SO.sub.2 --Z group, 
wherein Z has the given meaning. 
The same preferences apply to the aqueous dye formulations as to the 
mixtures of this invention. 
The dye formulations normally have a dye concentration of 5 to 20% by 
weight and a salt content (inorganic salts) of 1 to 30% by weight, 
especially 4 to 10% by weight. The pH is normally in the range from 3 to 
10, preferably from 3 to 7. Insoluble constituents are separated by 
microfiltration. Enrichment and deionisation can be carried out until the 
dye concentration is in the range from 10 to 50% by weight. The salt 
content then falls to below 5% by weight, preferably to below 2% by weight 
and, most preferably, to below 1% by weight. 
The temperature of the dye formulations may be in the range from 10.degree. 
to 80.degree. C., preferably from 20.degree. to 60.degree. C. 
The concentrated dye formulations are distinguished by their high 
concentration of dye, their homogeneity and their good stability (over 
several months) in a wide temperature range (0.degree. C. to 50.degree. 
C.). 
To prepare the concentrated dye formulations it is expedient to perform 
different separating operations, for example using membranes: 
microfiltration of the aqueous solution of the crude dye to separate 
undissolved constituents 
ultrafiltration/hyperfiltration of the dye solution, whereby the solution 
is deionised to values below 1% by weight and the dye concentration is 
enriched to 15 to 45% by weight 
microfiltration of the concentrated dye solution to remove undissolved 
constituents subsequent preparation of the ready-for-use liquid or solid 
dye formulation. 
The liquid dye formulations are usually aqueous and may contain, aside from 
water and the mixture of this invention, components conventionally used in 
liquid formulations, for example solubilisers, foam inhibitors, antifreeze 
agents, humectants, surfactants, buffer substances and/or microbicides. 
To prepare a liquid physical form, the concentrated dye formulation, after 
addition of the optional conventional components and adjusting the pH, 
must only be brought to a predetermined final dye concentration by 
dilution and/or with the aid of extenders. Alternatively, however, the dye 
formulation, after the addition of optional auxiliaries such as binders, 
dust inhibitors, wetting agents, buffer substances and/or extenders, can 
also be converted into a solid dye formulation by dehydration. Because of 
the high dye concentration, less energy is need for drying. Conventional 
drying methods are used, preferably spray drying. 
The dyeings obtained with the reactive dyes used in the practice of this 
invention have clear shades. High fixation rates and very good build-up 
are achieved, and the dyeings have good lightfastness and very good 
wetfastness properties. 
The invention is illustrated by the following Examples in which parts and 
percentages are by weight.

EXAMPLE 1 
A bleached cotton fabric is padded at 25.degree. C. with a solution which 
contains 30 g/l of the dye of formula 
##STR20## 
wherein Pc is the radical of a copper phthalocyanine, 21 ml/l of a 30% 
aqueous solution of NaOH, 70 ml/l of a water glass solution having a 
density of 1.356 at 15.degree. (38 Be), and 3 g/l of the compound of 
formula 
##STR21## 
The cotton fabric is padded to a pick-up of 70% and then batched up on a 
roll, wrapped airtight in plastic, and stored for 24 hours at 25.degree. 
C. The dyed fabric is then rinsed, soaped at the boil for a quarter of an 
hour with 2 g/l of a nonionic detergent (obtained by addition of 10 
equivalents of ethylene oxide to p-nonylphenol), rinsed once more and 
dried. 
For comparison purposes, the degree of fixation is determined (calculated 
from the extinction values (at .lambda. max.) of the extraction solutions 
of the samples of the dyeings which have not been washed off, each time 
fixed and unfixed). The degree of fixation in this Example is 81%. 
EXAMPLE 2 
The procedure of Example 1 is repeated, using 6 g/l instead of 3 g/l of the 
compound of formula (102). The dyeing so obtained with the dye of formula 
(101) has a degree of fixation of 83.7%. 
EXAMPLE 3 
The procedure of Example 1 is repeated, replacing 3 g/l of the compound of 
formula (102) with 6 g/l of the compound of formula 
##STR22## 
The dyeing so obtained with the dye of formula (101) has a degree of 
fixation of 83.6%. 
COMISON EXAMPLE 
The procedure of Example 1 is repeated, except that the cotton fabric is 
padded without the addition of the compound of formula (102). The dyeing 
so obtained with the compound of formula (101) has a degree of fixation of 
only 68% and a markedly lighter shade than the dyeings of Examples 1 to 3. 
EXAMPLE 4 
A mercerised cotton fabric is padded at 25.degree. C. with a solution which 
contains 60 g/l of the salt-free dye of formula 
##STR23## 
wherein Pc is the radical of a copper phthalocyanine, 31 ml/l of a 30% 
aqueous solution of NaOH, 70 ml/l of a water glass solution having a 
density of 1.356 at 15.degree. (38 Be). The cotton fabric is padded to a 
pick-up of 70% and then batched up on a roll, wrapped airtight in plastic, 
and stored for 24 hours at 25.degree. C. The dyed fabric is then rinsed, 
soaped at the boil for a quarter of an hour with 2 g/l of a nonionic 
detergent (obtained by addition of 10 equivalents of ethylene oxide to 
p-nonylphenol), rinsed once more and dried. 
By repeating the above procedure and using 53 g/l instead of 60 g/l of the 
dye of formula (104) and 7 g/l of the compound of formula (101) of Example 
1, then a cotton fabric dyed in the same depth of shade and having 
enhanced washfastness properties is obtained. 
EXAMPLE 5 
The procedure of Example 4 is repeated, replacing 60 g/l of the dye of 
formula (104) with 83 g/l of the salt-free dye of formula 
##STR24## 
wherein Pc is the radical of a phthalocyanine radical and k is 1.75, to 
give a dyeing of the same depth of shade as that obtained with 70 g/l of 
the dye of formula (105) and 10 g/l of the compound of formula 
##STR25## 
Comparably good results are obtained by repeating the above procedure and 
using dyes wherein k=2.0 to k=2.5. 
EXAMPLES 6 TO 17 
The procedures described in Examples 1 to 5 are repeated, using a dye of 
formula 
##STR26## 
wherein Pc is the radical of a copper phthalocyanine, R.sub.x, R.sub.y and 
k are as defined in columns 2, 3 and 4, respectively, of the following 
Table, and, as colourless compound, at least 5% by weight, based on the 
dye employed, of the compounds listed in column 5 of the Table. Compared 
with the dyeings obtained without colourless compounds, the resultant 
dyeings have markedly better fixation and depth of shade values. 
Table 
__________________________________________________________________________ 
colourless 
compound of 
Example 
R.sub.x 
R.sub.y k formula 
__________________________________________________________________________ 
6 H 4-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
2.0 
(102) 
7 H 3-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.5 
(106) 
8 H 3-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
2.5 
(106) 
9 H 4-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.75 
(103) 
10 H 4-CONHCH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2 
2.0 
(106) 
11 H 4-CONHCH.sub.2 CH(SO.sub.2 CHCH.sub.2)C.sub.3 H.sub.6 SO.sub.2 
CHCH.sub.2 1.0 
(102) 
12 H 
##STR27## 1.5 
(106) 
13 H 4-CON(CH.sub.3)CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 
CHCH.sub.2 1.75 
(106) 
14 CH.sub.3 
3-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.75 
(102) 
15 CH.sub.3 
4-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.5 
(103) 
16 H 4-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.5 
(103) 
17 H 2-CONHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 
1.5 
(102) 
__________________________________________________________________________