FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
Title of the invention - "BLUE DYE STUFF MIXTURES CONTAINING BISAZO AND
BISAZO OR FORMAZANE REACTIVE DYESTUFFS WITH POLYFUNCTIONAL REACTIVE GROUPS"
2. Applicant(s)
(a) NAME : COLOURTEX INDUSTRIES LIMITED
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Survey No 91, Paikee Bhestan, Navasari-Surat Road, Surat - 395 023,
Gujarat (India)
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

FIELD OF THE INVENTION
The present invention relates to new blue dyestuffs and new blue mixtures of fiber reactive dyestuffs, containing polyfunctional reactive groups.
BACKGROUND OF THE INVENTION
Dyes have been used over the years in various applications. However, with the evolution of technology and consumer demand, today's requirements in reactive dyes, especially for coloration of cellulose fibres, are high colour yield and good build-up with excellent fastness.
Specifically, in the arena of blue, navy blue and dark blue shades, presently known dyes are mostly bisazo dyes, anthraquinone or copper formazane dyes, containing reactive groups of the vinylsulfone and/or heterocyclic types. Bisazo dyes based on l-amino-8-hydroxynaphalene 3,6-disulfonic acid as coupling component provide high build-up, however comparably poor light fastness and dull shades. Therefore their use is mainly for deep shades, navy blue and dull ternary shades. Copper formazane dyes provide bright blue shades, excellent light, wet-light and good perspiration light fastness, however comparably poor build-up and unsatisfactory fixation yields in high concentrations, low molar absorbance and low tinctorial values. Therefore their use is mainly for pale shades. In trichromatic blues and medium shades with good fastness, mixtures of bisazo dyes with other bisazo, anthraquinone or formazane dyestuffs are known from the patent literature to provide good overall performance in regard to build-up and fastnesses, whilst also considering economical requirements.
EP735111 discloses dyestuff mixtures comprising one or more copper formazane dyes and one or more monoazodyes.
WO2005/090485 discloses dye mixtures comprising at least one biszao dye with at least one bisazo, formazane or anthraquinone dye, are suitable for dyeing or printing cellulose-containing fibre materials, while at the same time exhibiting good build-up behaviour, and yield dyeing of deep shade having good fastness properties.

WO2007003541 discloses dye mixtures that comprise at least one biszao dye with at least one bisazo, formazane or anthraquinone dye, are suitable, with good buildup behaviour, for dyeing or printing cellulose-containing fibre materials, and yield dyeings having a deep shade and good fastness properties. US20030229552 discloses reactive dye mixtures of disazo dyes. JP 57057754 discloses reactive bisazo dye capable of tinting natural and artificial fibers, particularly fibers such as cotton, linen, viscose rayon silk, etc in navy blue or black color.
US20080039614 discloses reactive dyestuff containing an alkylthio-S-triazinyl group. These dyes are suitable for exhaust dyeing, cold batch-up dyeing and continuous dyeing materials.
However, these mixtures still have limitations in regard to the above mentioned technical requirements, especially limited fastnesses, unsatisfactory build-up in deep shades, poor fixation yields, and high dependency of color strength and shade upon changes in the dyeing conditions.
Consequences of these deficiencies include poor reproducibility, which ultimately affects the economics of the dyeing, and limitations of fastness which adversely affects the quality of the dyed fabrics.
Thus, there arises a need for new dyestuffs and improved dyestuff mixtures which would address the above issues and highlight optimal color properties. The inventors of the present invention have surprisingly found that the predicaments highlighted above, are addressed by means of the novel dyes and their mixtures as disclosed hereinafter.
OBJECT OF THE INVENTION
It is an object of the present invention to provide dyestuff mixtures having excellent fixation yield and excellent build-up, which can achieve very deep shades, with good wash, high contact fastness, high light fastness, wet-light and perspiration-light fastness, high fastness to oxidation agents such as chlorine, perborate, nitrogen oxide, peroxide, as well as fastness to washing conditions using detergents with activated bleaching systems.

It is another object of the present invention to provide novel blue fibre reactive dyestuffs suitable for dyeing from aqueous bath and printing of fibre materials containing cellulose, polyamide or protein fibre materials, and blends containing such fibre materials, for use as trichromatic blue, in combination with yellow orange and red dyestuffs, in dark ternary shades, or as navy blue shade. It is yet another object of the present invention to provide new dyestuffs having excellent fixation yield and excellent build-up, which can achieve very deep shades, with good wash, high contact fastness, high light fastness, wet-light and perspiration-light fastness, high fastness to oxidation agents such as chlorine, perborate, nitrogen oxide, peroxide, as well as fastness to washing conditions using detergents with activated bleaching systems.
SUMMARY OF THE INVENTION
According to an aspect of the present invention, there is provided novel fibre reactive dyestuff mixtures comprising:
i) one bisazo dyestuff of the formula (1)

containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, Cl-C4-alkoxy, Cl-
C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyl or CH2CH2U wherein U is a leaving group such as sulfato,
phosphato, thiosulfato, chlorine, bromo, acetoxy, or benzoyloxy,
preferably SO2Y is Vinyl or ß-sulfatoethyl,

L is a leaving group selected from chloro, fluoro, pyridinyl which may be
substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from Cl-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -O- R , or -S- R
wherein R is Cl-C6-Alkyl, preferably C1-C3, which is substituted by at
least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or carboxy
substituent, and optionally by further substituents such as hydroxy, or
X is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6-
cycloaliphatic amine which may be interrupted by heteroatoms O, NH or
S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl. or a radical of the formula
0-CH2CH2-OR13 wherein Rl 3 is Methyl, Ethyl, Hydroxy or cyano;
ii) one bisazo dyestuff of the formula (2)

wherein
R6 is hydrogen, C1 -C4-aIkoxy, carboxy, halogen or sulfo, preferably
hydrogen, methoxy or sulfo,
R7 has one of the meanings of R6,

R8 is hydrogen, Cl-C4-alkoxy, Cl-C4-Alkyl, or sulfo, preferably
hydrogen, methoxy, methyl or sulfo,
R9 has one of the meanings of R8,
Y1 is Vinyl or CH2CH2U, wherein U is a leaving group which is split off
under alkaline conditions, such as sulfato, acetato, halogen, such as chloro
or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
preferably Y is Vinyl or ß-Sulfatoethyl, preferably Yl is Vinyl or ß-
Sulfatoethyl,
Y2 has one of the meanings of Y1.
According to another aspect of the invention there is provided novel fibre reactive dyestuff mixtures comprising:
i) one bisazo dyestuff of the formula (1)

containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, Cl-C4-alkoxy,
C1-C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyl or CH2CH2U wherein U is a leaving group such as
sulfato, phosphato, thiosulfato, chlorine, bromo, acetoxy, or
benzoyloxy, preferably SO2Y is Vinyl or ß-sulfatoethyl,
L is a leaving group selected from chloro, fluoro, pyridinyl which
may be substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from Cl-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -0- R , or -S- R

wherein R is Cl-C6-Alkyl, preferably C1-C3, which is substituted by at least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or
X is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6-cycloaliphatic amine which may be interrupted by heteroatoms O, NH or S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl. or a radical of the formula
0-CH2CH2-OR13 wherein R13 is Methyl, Ethyl, Hydroxy or cyano;
ii) one formazane dyestuff of the formula (3)

Wherein
Z2 is S02Y, wherein Y has one of the above meanings as defined under
(1), preferably Vinylsulfonyl, ß-Sulfatoethylsulfonyl,
Or
Z2 is a radical of the formula (3a) to (3d)


wherein
L2 has one of the meanings of L1, preferably chloro or fluoro,
Ph is phenyl, preferably 1,3 -or 1,4-phenyl,
alk is C1-C3 alkylene, or -(CH2)20(CH2)2-,
R1O is hydrogen, Cl-C4-alkyl, preferably methyl or ethyl, Rll is
hydrogen, Cl-C4-alkyl, or phenyl,
R12 is hydrogen or chloro,
Hall is chloro or fluoro,
Hal2 is chloro or fluoro, Y has one of the above defined meanings, preferably Vinyl, ß-Sulfatoethyl or 13-chlororethyl.
According to yet another aspect of the invention there is provided novel fibre reactive dyestuff mixtures comprising:
i) at least one bisazo dyestuff of the formula (1)

Formula (1) containing 2 fibre reactive groups, wherein
R1i and R2 are independent from each other hydrogen, Cl-C4-alkoxy, Cl-
C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyi or CH2CH2U wherein U is a leaving group such as sulfato,
phosphato, thiosulfato, chlorine, bromo, acetoxy, or benzoyloxy,
preferably SO2Y is Vinyl or ß-sulfatoethyl,
L is a leaving group selected from chloro, fluoro, pyridinyl which may be
substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from Cl-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -O- R, or -S- R
wherein R is C1-C6-Alkyl, preferably C1-C3, which is substituted by at
least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or carboxy
substituent, and optionally by further substituents such as hydroxy, or
X is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6-
cycloaliphatic amine which may be interrupted by heteroatoms O, NH or
S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl. or a radical of the formula
0-CH2CH2-OR13 wherein Rn is Methyl, Ethyl, Hydroxy or cyano;


ii) one bisazo dyestuff of the formula (2)
wherein
R6 is hydrogen, Cl-C4-alkoxy, carboxy, halogen or sulfo, preferably
hydrogen, methoxy or sulfo,
R7 has one of the meanings of R6,
R8 is hydrogen, Cl-C4-alkoxy, Cl-C4-Alkyl, or sulfo, preferably
hydrogen, methoxy, methyl or sulfo,
R9 has one of the meanings of R8,
Y1 is Vinyl or CH2CH2U, wherein U is a. leaving group which is split off
under alkaline conditions, such as sulfato, acetato, halogen, such as chloro
or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
preferably Y is Vinyl or ß-Sulfatoethyl, preferably Yl is Vinyl or ß-
Sulfatoethyl,
Y2 has one of the meanings of Y1.
iii) one formazane dyestuff of the formula (3)


Formula (3) Wherein
Z2 is S02Y, wherein Y has one of the above meanings as defined under
(1), preferably Vinylsulfonyl, ß-Sulfatoethyl sulfonyl,
Or
Z2 is a radical of the formula (3a) to (3d)

wherein
L2 has one of the meanings of L1, preferably chloro or fluoro,
Ph is phenyl, preferably 1,3 -or 1,4-phenyl,
alk is C1-C3 alkylene, or -(CH2)20(CH2)2-,
R1O is hydrogen, Cl-C4-alkyl, preferably methyl or ethyl, R11 is
hydrogen, Cl-C4-alkyl, or phenyl,
R12 is hydrogen or chloro,
Hall is chloro or fluoro,
Hal2 is chloro or fluoro, Y has one of the above defined meanings, preferably Vinyl, ß-Sulfatoethyl or ß-chlororethyl.

According to yet another aspect of the present invention, there is provided Novel fibre reactive bisazo dyestuff of the formula (1) represented by



DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides novel dyestuff mixtures of at least bisazo dyestuffs of the formula (1)

and at least one bisazo dyestuff from the group of the formula (2)


The bisazo dyestuffs of the formula (1) which form a part of the novel mixtures are

containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, Cl-C4-alkoxy, C1-C4 alkyl,
halogen, carboxy or sulfo,
one of the radicals Q1 and Q2 is hydroxyl, the other one is amino, preferably Ql is
hydroxyl and Q2 is amino,
the substituent -S02Y is preferably in para position to the azo linkage,
Y is Vinyl or CH2CH2U wherein U is a leaving group such as sulfato, phosphato,
thiosulfato, chlorine, bromo, acetoxy, or benzoyloxy, preferably SO2Y is Vinyl or
ß-sulfatoethyl,
L is a leaving group such as chloro, fluoro, pyridinyl which may be substituted by
Carboxy or Carbamoyl,
X is a non-fibre reactive radical Cl-C8-Alkoxy, Cyanamino, -NHR, -N(CH3) R,
-O- R , or -S- R wherein R is Cl-C6-AIkyl, preferably C1-C3, which is
substituted by at least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or
carboxy substituent, and optionally by further substituents such as hydroxy, or X

is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6- cycloaliphatic amine which may be interrupted by heteroatoms O, NH or S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl.
Suitable radicals X is selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-
butoxy, s-butoxy, allyloxy, 2-Methoxyethoxy, 2-Hydroxyethoxy, 2-Ethoxyethoxy,
2-cyanoethoxy, cyanamino, ß-sulfoethylamino, N-methyl -ß-sulfoethyl-amino,
morpholino, piperidino, pyrrolidino, N-(ß-sulfatoethyl)-piperidino,
Carboxymethylthio-, ß-Sulfatoethylamino, ß-Carboxyethylamino. Preferably the dyes of the formula (1) are structures of the formula (1')

Wherein
Rl is hydrogen, sulfo, chloro, bromo, carboxy, methoxy or ethoxy;
R2 is hydrogen, methyl or methoxy;
the substituent -SO2Y is preferably in para position to the azo linkage;
Y is Vinyl, ß-Chloroethyl or ß-Sulfatoethyl,
L1 has one of the above meanings of L,
X1 is C1-C3 Alkoxy, cyanamino, ß-Sulfoethylamino, N-methyl-ß-
Sulfoethylamino, morpholino, piperidino,
or a radical of the formula


or a radical of the formula
0-CH2CH2-OR,3 wherein R13 is Methyl, Ethyl, Hydroxy or cyano. Preferably, in the formula (1) the radical

has one of the following structures :



Especially preferred structures of the formula (1') are dyestuffs of the formula are structures of the formula (1.1) to (1.5)



wherein
LI is a leaving group chloro, fluoro, or pyridinyl which may be substituted by
Carboxy or Carbamoyl, in particular preferably chloro;
the substituent -S02Y is preferably in para position to the azo linkage,
Y is Vinyl or ß-Sulfatoethyl,
Ro is hydrogen or methyl,
R3 is hydrogen, sulfo, or methoxy,
R4 is hydrogen, methyl or methoxy, preferably hydrogen,
R5 is methyl, ethyl, n-propyl, isopropyl, CH2CH2OCH3, preferably methyl, ethyl
or isopropyl, and in particular preferably methyl,
Gl is a direct bond, methylene or a heteroatom 0-
Dyestuffs of the formula (2) are of the structure


wherein
R6 is hydrogen, Cl-C4-alkoxy, carboxy, halogen or sulfo, preferably hydrogen,
methoxy or sulfo,
R7 has one of the meanings of R6,
R8 is hydrogen, Cl-C4-alkoxy, Cl-C4-Alkyl, or sulfo, preferably hydrogen,
methoxy, methyl or sulfo,
R9 has one of the meanings of R8,
Y1 is Vinyl or CH2CH2U, wherein U is a leaving group which is split off under
alkaline conditions, such as sulfato, acetato, haiogen, such as chloro or bromo,
phosphate, thiosulfato, acyloxy, such as acetoSy or phenoxy, preferably Y is
Vinyl or ß-Sulfatoethyl, preferably Yl is Vinyl or ß-Sulfatoethyl,
Y2 has one of the meanings of Y1.
Preferably the substituents S02Y1 and S02Y2 are in para or meta position to the
azo bond, and in particular dyes are preferred wherein the substituent S02Y2 is in
para position.
The present invention also provides novel dye mixtures of at least one dye of the
formula (1) and at least one dye formula (3).
Dyestuffs of the formula (3) are of the structure


Wherein
Z2 is S02Y, wherein Y has one of the above meanings as defined under (1),
preferably Vinylsulfonyl, ß-Sulfatoethylsulfonyl,
Or
Z2 is a radical of the formula (3a) to (3d)

wherein
L2 has one of the meanings of L1, preferably chloro or fluoro,
Ph is phenyl, preferably 1,3 -or 1,4-phenyl,
alk is C1-C3 alkylene, or -(CH2)20(CH2)2-,
R1O is hydrogen, Cl-C4-alkyl, preferably methyl or ethyl, Rll is hydrogen, Cl-
C4-alkyl, or phenyl,
R12 is hydrogen or chloro,

Hall is chloro or fluoro,
Hal2 is chloro or fluoro,
Y has one of the above defined meanings, preferably Vinyl, ß-Sulfatoethyl or ß-
chlororethyl.

Of the radicals (3b) are especially preferred

Of the radicals (3c) are especially preferred

Of the radicals (3d) are especially preferred
Of the radicals (3a) are especially preferred


The dye stuffs of formula (1) in combination with dyestuffs of formula (2) or
formula (3) provide inventive mixtures which are attractive in shade and have
superior colour fastness and dyeing performance.
The dyes of the present invention are mixtures of at least one bisazo dyestuffs of
the formula (1) with at least one bisazo dyestuffs of the formula (2) and/or at least
one formazane dyestuffs of the formula (3), providing that the ratio of the
dyestuffs of the formula (1) to formula (2) or formula (3) or the sum of (2) and (3)
is 20:80 to 80:20.
Especially preferred are mixtures are binary dyestuff mixtures containing at least
one bisazo dyestuffs of the formula (1) and at least one bisazo dyestuffs of the
formula (2) in a ratio 65:35 to 35:65.
Furthermore, especially preferred are mixtures are binary dyestuff mixtures
containing at least one bisazo dyestuffs of the formula (1) and at least one
formazane dyestuffs of the formula (3) in a ratio 65:35 to 35:65
The contents of the dyes in the mixtures are given by mole of dye in the form of
the free acid.
The present invention further provides novel dyestuffs of the formula (la) and
(lb),(lc),(ld)and(le).



wherein
L1 has one of the above defined meanings of L1, preferably chloro,
R3' has one of the meanings of Rl, excluding hydrogen, preferably R3' is sulfo or
methoxy,
R3" is hydrogen, methoxy or sulfo,
R4' has one of the above defined meanings of R2, preferably hydrogen, methyl or
methoxy,

R5' is methoxy, ethoxy or isopropoxy,
R0 is methyl or hydrogen,
G1 is a direct bond, methylene or a heteroatom 0,
Y is R-sulfatoethyl or vinyl and the substituent SO2Y is preferably located in para
position to the azo linkage.
In particular, of the formula (la) to (le) dyestuffs are preferred wherein the
substituents L1 'is chloro and R3' is sulfo.
Dyestuffs of the formula (1.1) wherein R3 and R4 are hydrogen are already known
from the European patent application EU 264.878, example 1. Dyestuffs of the
formula (1.2) wherein R3 and R4 are hydrogen are already known from the US
patent application US 5.349.057, example 58. However, these known dyestuffs, as
self dyes, have unsatisfactory light, perspiration-light and wet-light fastness. They
also have unsatisfactory contact and washing fastnesses.
Surprisingly it has been found that the new dyestuffs of the formula (la), (lb),
(1c), (d) and (le) provide better fastnesses, in particular light, perspiration-light
and wet-light fastness, contact and washing fastnesses, compared to similar
dyestuffs of state of the art.
Examples for preferred structures of dyestuffs of formula (1.1) are

Examples for preferred structures of dyestuffs of formula (2) are dyestuffs of the formula are

The dyestuffs of the formula (2.1) to (2.6) are known in the form of the vinylsulfone type from the patent application US 2657205 (Hoechst, 1953). Examples of preferred structures of formazane dyestuffs of formula (3) are

The dyestuffs of the formula (3.1) to (3.5) are known from the patent applications EP 144766, EP 70807 and EP 568860.
Synthesis:
The new dyestuffs of the present invention of formula (la) are made by diazotation of the compound of formula (5.1 a) in the usual manner by means of sodium nitrite in presence of hydrochloric or sulfuric acid, followed by coupling

on the previously prepared coupling component of the formula (5.1b) in the usual manner, e.g. at pH 4-6 and 0-20 °C.

LI', R5', R3'and R4' in the formula (5.1a) and (5.1b) have one of the above meanings.
The new dyestuffs of the present invention of formula (lb) are made by diazotization of the compound of formula (5.2 a) in the usual manner by means of sodium nitrite in presence of hydrochloric or sulfuric acid, followed by coupling on the previously prepared coupling component of the formula (5.1 b) in the usual manner, e.g. at pH 4-6 and 0-20 °C.

The compounds of the formula (5.1a) and (5.2a) are already known as intermediate from the above listed patent documents, e.g. from US 5349057 and EP 264878.
The compounds of the formula (5.1b) are made by coupling of an aromatic amine of the formula (5.3) in the usual manner, by means of sodium nitrite in presence of hydrochloric or sulfuric acid, followed by coupling on coupling component 1-

amino-8-hydroxynapthalene-3,6, disulfonic acid in the usual manner, e.g. at pH 0.5-2 and 0-5 °C.
The new dyestuffs of the present invention of formula (lc), (1d) and (le) are made by diazotation of the compound of formula (5.1 c) onto a coupling component of the formula (5.1b) in a similar manner as described for (la).

In formula (5.1c) L1 'has one of the above meanings and Q is a radical of the formulae

wherein Ro is hydrogen or methyl, and Gl is methylene, a direct bond or -0-. The inventors have come across the find that the dyestuffs used in the mixtures of the present invention can be in the form of the free acid or in the form of their salts. They are preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts. The dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials.
Application
The present invention further provides a process for dyeing from an aqueous bath and printing of fibre materials with the dyestuff mixtures of the present invention.

Cellulose, natural cellulose fibres such as cotton, linen or hemp, especially cotton,
and regenerated cellulose such as viscose or Lyocell, polyamide fibres such as
nylon 6, nylon 6.6 or protein fibres such as wool or silk are preferred fibre
materials.
The inventors have arrived at the conclusion that these dyestuff mixtures are also
suitable for dyeing and printing of fibre blends containing the mentioned
cellulose, polyamide or protein fibre materials. Moreover, it was also found that
the dyestuff mixtures of the invention can be applied to and fixed on the fibre
material in various ways, in particular in the form of aqueous dye solutions and
print pastes.
They are suitable for known application techniques which are established for the
application of reactive dyes, in particular exhaust method, padding methods,
whereby the material is impregnated with aqueous salt containing or salt free
solutions of the dyes, and fixed after alkali treatment or in presence of alkali with
or without heating, and printing methods, conventional or digital (ink jet) printing.
After fixing, the dyeing and prints are rinsed and thoroughly washed with cold or
hot water, preferably at 60-98°C, containing auxiliary agents such as detergents
or surfactants that promote the wash-off of unfixed portions.
Examples for suitable alkali used for fixation include alkali hydroxide, alkali
carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium
silicate are in particular preferred.
The dyes and dyestuff mixtures of the present invention can be used in self shade,
dichromatic or preferably in trichromatic combination with yellow, orange and
red dyes. The amounts wherein the dyes and dye mixtures of the present invention
are applied in the dye baths can vary according to the desired depth of shade,
generally amounts of 0.1% to 10 % per weight of fabric are suitable, preferably
0.2% to 8%, and in particular 0.5% to 5% for achieving medium to dark ternary
shades.
The dye bath may contain additions of auxiliaries such as inorganic salt,
preferably sodium chloride or sodium sulfate, to support the exhaustion of the

dyes onto the fibre material, and in case of padding process urea, and in case of
printing applications thickening pastes such as alginate thickenings.
In case of exhaust dyeing process, the preferred procedure is dyeing from an
aqueous batch, in presence of 20-100 g/L salt, sodium chloride or sodium sulfate,
and a liquor ratio of 1:2 to 1:50, preferably 1:3 to 1:30, at a dye bath pH of 7-13,
preferably 9-11, and a temperature of 40-90°C, preferably 45-70 °C.
The dyeing obtained with the dyes of the present invention has excellent fixation
yield and excellent build-up. The obtained dye-fibre bond is of high stability not
only in the acid but also in the alkaline range, also good wash fastness, even in
deep shades, as well as good contact fastness to water, and good acid as well as
alkaline perspiration fastness.
Furthermore, the dyeing obtained with the dyes of the present invention has good
light-fastness, wet-light fastness in presence of oxidation agents and bleaching
agents such as perborate, bleaching activators such as peracids, and perspiration
light fastness (light fastness in presence of artificial perspiration solution
containing histidine, salt and buffer solution). Moreover, the dyeing obtained with
the dyes of the present invention have good stability to oxidation agents, which is
exhibited for example in good fastness to chlorinated water.
Moreover, the dyeing obtained with the dyes of the present invention is
dischargeable and can be applied in discharge printing.
Examples for binary dyestuff mixtures of the present invention:
Example 1:
50 parts per weight of the dyestuff of the formula (1.1a)



are physically mixed in a blender, and a dyestuff mixture with high color strength and good color build-up is obtained which yields a navy blue shade when applied on cotton fabric.
Example 2:
45 parts per weight of a the dyestuffof the formula (1.1a) and
55 parts per weight of a dyestuff of the formula (3.8)

are physically mixed in a blender, cut with 10 parts per weight of a dispersing agent and 20 parts per weight of sodium chloride. A dyestuff mixture with high color strength and good light fastness is obtained which yields a blue shade when applied on cotton fabric.
Further examples of binary mixtures of the compositions

Dyestuff of formula (1) Dyestuffof formula(2) Dyestuffof
formula (3) Shade on cotton
3 50% of (1.1a) 50% of (2.2) Navy blue
4 60% of (1.1b) 40% of (2.3) Greenish Navy
5 50% of (1.1c) 50% of (2.1) Navy blue
6 50%of(l.l.d) 50% of (2.5) Navy
7 45 %of(l.le) 55% of (2.6) Greenish Navy
8 45%of(l.lg) 55% of (3.1) Blue
9 60% of (1.1a) 40% of (3.2) Blue
10 50%of(l.lg) 50% of (3.7) Blue
11 50% of (1.1b) 50% of (3.8) Blue

12 42% of (Lie) 58% of (3.9) Blue
13 45% of (L If) 55% of (3.1) Blue
Example 14:
50 parts per weight of the dyestuff of the formula (1.3a)

and 50 parts of the dyestuff of the formula (2.2)

are physically mixed in a blender, and a dyestuff mixture with high color strength and good color build-up is obtained which yields a navy blue shade when applied on cotton or viscose fabric, in exhaust or padding applications similar to the conditions given in the dyeing examples 1-3.
Example 15:
58 parts per weight of a the dyestuff of the formula (1.2b) and
42 parts per weight of a dyestuff of the formula (3.1)

are mixed in respective amounts to achieve the above specified mixing ratio, as a solution containing 80 parts per weight of the respective dyestuffs in 1000 parts per volume of water, and 5 parts per weight of a sodium phosphate buffer at pH 6.5-7, stirred for 15 min. and the solution is subsequently spray dried. A dyestuff mixture with good light fastness is obtained which yields a blue shade when applied on cotton or viscose fabric, in exhaust or padding applications similar to the conditions given in the dyeing examples 1-3.
Example 16:
50 parts per weight of a the dyestuff of the formula (1.1b) and
50 parts per weight of a dyestuff of the formula (3.2)

are mixed in respective amounts to achieve the above specified mixing ratio as a solution containing 100 parts per weight of the respective dyestuffs in 1000 parts per volume of water, and 5 parts per weight of a sodium phosphate buffer at pH 6-6.5. The mixed solutions are stirred for 30 min and spray dried. A dyestuff mixture with good light fastness is obtained which yields a blue shade when applied on cotton or viscose fabric, in exhaust or padding applications.similar to the conditions given in the dyeing examples 1-3.

Dyestuffof
formula (1) Dyestuff of formula (2) Dyestuff of
formula (3) Shade on cotton
17 50% of (1.2a) 50% of (2.1)
18 60% of (1.2b) 40% of (2.2) Greenish navy
19 50% of (1.2c) 50% of (2.3) Greenish navy
20 50% of (1.2d) 50% of (2.6) Greenish navy
21 45% of (1.3a) 55% of (2.5) Navy
22 45% of (1.3b) 55% of (3.1) Blue
23 60% of (1.3c) 40% of (3.2) Blue
24 50% of (1.3d) 50% of (3.7) Blue
25 45% of (1.4a) 55% of (3.8) Blue
26 60% of (1.4b) 40% of (3.9) Blue
27 50% of (1.4c) 50% of (3.10) Blue
28 48%of(1.4d) 52% of (3.11) Blue
29 60%of(1.4e) 40% of (3.12) Blue
30 50% of (1.5a) 50% of (3.1) Blue
31 50% of (1.5b) 50% of (3.1) Blue
32 50% of (1.5c) 50% of (3.3) Blue
33 50%of(1.5d) 50% of (3.6) Blue
34 50%of(1.5e) 50% of (3.7) Blue
Examples for ternary dyestuff mixtures of the present invention:
Example 35:

25 parts of the dyestuff of the formula (2.1)

35 parts per weight of the dyestuff of the formula (1.1a)

And 40 parts of the dyestuff of the formula (3.1)
are physically mixed in a blender, and a dyestuff mixture with high color strength and good color build-up is obtained which yields a blue shade when applied on cotton fabric.
More examples for ternary mixtures:

Dyestuffof formula (1) Dyestuffof
formula (2) Dyestuffof formula (3) Shade on cotton
36 50% of (1.1a) 5% of (2.1) 45% of (3.1) Blue
37 30% of (1.1a) 20% of (2.1) 50% of (3.8) Blue
38 30% of (1.1b) 20% of (2.2) 50% of (3.1) Blue
39 30%of(Ug) 20% of (2.2) 50% of (3.1) Blue
40 30%of(l.lg) 20% of (2.7) 50% of (3.2) Blue
41 30% of (1.2a) 20% of (2.7) 50% of (3.1) Blue
42 21% of (1.3a) 19% of (2.1) 60% of (3.5) Blue
43 30% of (1.4a) 20% of (2.1) 50% of (3.9) Blue
44 20% of (1.5a) 20% of (2.1) 60% of (3.10) Blue
Examples for dyestuff intermediates used in the present invention:
Example Al:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethyisulfonyl-aniline in 500 parts per volume of water is charged while stirring 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazionium salt is obtained, and charged slowly over a period of 1 h to a freshly prepared solution of the sodium salt of 32 parts of l-amino-8-naphthol-3,6-disulfonic acid ("H-acid") in 500 parts per volume of water, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted

hydrochloride acid, and temperature is kept at 0-5 °C. The diazonium salt is charged to the extent until the first coupling stage is completed. The compound of the formula

is obtained as red monoazo dyestuff and is used without isolation in subsequent azo coupling reactions for the secondary coupling.

Example Bl:
In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1,3,5-Trichlorotriazine. To this dispersion is added 42 parts per weight of Cyanamide. While the reaction mass is stirred at 0 °C, the pH value falls down and is held at pH 1.5-2 by constantly dosing diluted 10% soda ash solution. This procedure will yield the primary condensation product 2-Cyanamino-4,6-dichlorotriazin. The reaction mass is stirred for 2 h. To this is then added 190 parts per weight of l,3-Phenylendiamin-4-sulfonic acid and the reaction is

conducted at pH 5.8-6.2 and a temperature of 45-50 °C, to yield the compound of the formula

The compound is obtained in solution and is used without further isolation as intermediate for subsequent azo coupling reactions as diazo component.
Example B2:
In 100 parts by volume of water containing 50 parts of crushed ice is charged 25 parts per weight of 1,3,5-Trichlorotriazine. To this dispersion is added 60 parts per weight of ethanol, and 25 parts per weight of sodium bicarbonate. While the reaction mass is stirred at 0-5 °C. The reaction mass is stirred for 4 hours. To this is then added 27 parts per weight of l,3-Phenylendiamin-4-sulfonic acid and the reaction is conducted at pH 5.8-6.2 and a temperature of 30-35 °C while stirred for another 4 hours. The reaction mass is allowed to cool down to 15-20°C and filtered to yield the compound of the formula

The compound is used as intermediate for subsequent azo coupling reactions.
Example B3:
The compound of the formula

is prepared as described in the European patent application EP 264.878 example 1.
The compound is used as intermediate for subsequent azo coupling reactions.

Example B13:
In 500 parts by volume of water, 500 parts of ice, buffered with sodium phosphate to pH 4-5 is charged 17 parts per weight of 1,3,5-Trifluortriazine. Under vigorous stirring 15 parts per weight of N-methyl-taurine is added. While the reaction mass is stirred at 0 °C, the pH value falls down and is held at pH 4-5 by dosing 10% soda ash solution. The reaction mass is stirred for 20 min. To this reaction mass is then added 19.5 parts per weight of meta phenylene-diamine 4-Sulfonic Acid, and the reaction is conducted at pH 5.8-6.2 and a temperature of 0-10 °C, to yield the compound of the formula

The compound is used as intermediate for subsequent azo coupling reactions. Example for one pot synthesis of dyestuff mixtures of the present invention:
Example 45:
33.2 parts per weight of the compound of example B3 is dissolved in 500 parts per volume of water, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged under stirring at a temperature of 0-5 °C. After stirring the reaction mass for further 30 min, a freshly prepared diazonium salt solution is obtained.

In the same manner 29 parts per weight of 4-Sulfatoethylsulfonyl-aniline is
diazotized.
Both diazonium salt solutions are then charged slowly in parallel, over a period of
1 h, to 61 parts per weight of the red coloured monoazo coupling component of
the formula,

which is a common intermediate in the synthesis of C.I. Reactive Black 5, to carry out the 2nd coupling stage in one reaction vessel. During that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salts are charged to the extent until the second coupling stage is completed. A dyestuff mixture, coupled in one reaction vessel, containing the same dyestuffs as in example 1, of the formulae

are obtained.
The dyestuff mixture is subsequently isolated by spray drying. This dyestuff mixture is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, especially in deep shades, and provides navy blue dyeings with good all round good fastness properties.
Example 46:
33.2 parts per weight of the compound of example B3 is dissolved in 500 parts per volume of water, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged while stirred at a temperature of 0-5 °C. After stirring the reaction mass for 45 min, a freshly prepared diazonium salt is obtained.

In the same manner 31 parts per weight of 4-Sulfatoethylsulfonyl-2,5-
Dimethoxyaniline is diazotized.
Both diazonium salts are then charged slowly in parallel, over a period of 1 h, to
the reaction mass of example Al, containing 69 parts per weight of the compound
of the formula Al, while during that time the pH value is adjusted to pH 6.2-6.7
by adding portion wise sodium carbonate and sodium bicarbonate, and the
temperature is maintained at 5-10°C. The diazonium salts are charged to the
extent until the second coupling stage is completed.
An dyestuff mixture, coupled in one reaction vessel, containing the dyestuffs of
the formula

is obtained. The dyestuff mixture is subsequently isolated by spray drying. This dyestuff mixture is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with excellent color fastness to light and washing.

Example Dyestuff of formula (1) Dyestuff of formula (2) Shade on cotton
47 l.ld 2.7 Navy
48 1.2a 2.1 Navy blue
49 1.3a 2.2 Greenish navy
50 1.4c 2.3 Greenish navy
51 l.,5d 2.4 Greenish navy
52 1.4d 2.6 Greenish navy

Examples for new dyestuffs of the present invention:
Example 53:
34.2 parts per weight of the compound Bl is dissolved in 750 parts per volume of water, then 7 parts per weight of sodium nitrite, and 28 parts per weight of hydrochloric acid, 32% grade by weight, are charged while stirred at a temperature of -2 to 8 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained.
This diazonium salt is then charged slowly over a period of 1 h to the reaction mass of example Al, containing 69 parts per weight of compound Al, while during that time the pH value is adjusted to pH 6.5-7.0 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-12°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula

(1.2b) Navy Blue (λmax 595 nm) is obtained. The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with color fastness to good light and washing.
Example 54:
In a similar manner as in the previous examples, 34.2 parts per weight of the compound of the formula Bl is diazotized and coupled onto 67.2 parts per weight of the coupling component of the formula A2 at a temperature of 5-15 °C and a pH value of 6.2-6.8. A dyestuff of the formula


is obtained. The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with high fixation yields and good color fastness properties.
In a similar manner, the following dyestuffs are prepared.

Example W shade on cotton
55 1.2d 2-methoxy-5-methyl-1,4-phenylen Reddish navy
56 1.2e 2-methoxy-1,4-phenylen Reddish navy
57 6-methoxy-l,3-phenylen Navy
58 6-sulfo-l ,3-phenylen Navy
Example 59:
34.6 parts per weight of the compound of example B2 is dissolved in 500 parts per volume of water, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C while the reaction mass is vigorously stirred. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained.
This diazonium salt is then charged slowly over a period of 1 h to the reaction mass of example Al, containing 68.5 parts per weight of example Al, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate, and the temperature is maintained in the range 5-15°C. The

diazonium salt is charged to the extent until the second coupling stage is
completed.
The dyestuff of the formula

(l.ld) navy blue, λmax 623 nm is obtained. The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with color fastness to good light and washing.
Example 60:
33.2 parts per weight of the compound of example B3 is dissolved in 600 parts per volume of water, then 7 parts per weight of sodium nitrite, and 27 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of -5 to 5 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained.
This diazonium salt is then charged slowly over a period of 1 h to the reaction mass of example A], containing 68 parts per weight of example Al, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 2-8°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula

is obtained. The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with color fastness to good light and washing.

Example 61:
In a similar manner as in the previous examples, 34.6 parts per weight of the compound of the formula B2 is diazotized and coupled onto 65.6 parts per weight of the coupling component of the formula A3 at a temperature of 0-10 °C and a pH value of 5-7. A dyestuff of the formula

is obtained. The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with high fixation yields and good color fastness properties.
In a similar manner as in the previous examples, the following dyestuffs are prepared.

Example formula W R5 shade on cotton
62 1.1c 2-sulfo-l,4-phenylen Isopropyl Navy λmax 607 nm
63 l.1e 6-sulfo-l,3-phenylen Methyl Navy
λmax 557 nm
64 l.lh 2-methoxy-5-methyl-1,4-phenylen Ethoxy Navy
65 1.lg 2-sulfo-l,4-phenylen -CH2-CH2-OCH3 Navy

66 2,5-dimethoxy-1,4-phenylen Isopropyl Greenish
Navy
67 2-methoxy-5-methyl- 1,4-phenylen Isopropyl Navy
68 2,5-dimethoxy-l,4-phenylen Ethyl Greenish
Navy
69 2-methoxy-5-methyl- 1,4-phenylen Ethyl Navy
70 2,5-dimethoxy-1,4-phenylen n-propyl Greenish
Navy
71 2-methoxy-5-methyl-1,4-phenylen -CH2-CH2-OCH3 Navy
72 6-sulfo-l,3-phenylen -CH2-CH2-OCH3 Navy
73 2-methoxy-l,4-phenylen -CH2-CH2-OCH3 Navy
74 2-sulfo-l,4-phenylen -CH2-CH2-OCH2CH3 Navy
75 2-sulfo-l,4-phenylen -CH2-CH=CH2 Navy
76 2-sulfo-l,4-phenylen n-propyl Navy
77 2-sulfo-l,4-phenylen -CH2-CH2-CN Navy
78 2-sulfo-l,4-phenylen -CH2-CH2-OH Navy
Example 79:
42 parts per weight of the compound of example B13, freshly prepared, is dissolved in 750 parts per volume of water, then 7 parts per weight of sodium nitrite is added. To this reaction mass 26 parts per weight of hydrochloric acid, 32% grade by weight, is added at a temperature of -5 to 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained. This diazonium salt is then charged slowly to the reaction mass of example Al, containing 68 parts per weight of example Al, while during that time the pH value is adjusted to pH 6.4-6.8 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-2°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula


is obtained. The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with color fastness to good light and washing.
Example 80:
51 parts per weight of the compound of example Bl 1 is dissolved in 400 parts per volume of water, then 7 parts per weight of sodium nitrite, and 27.5 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of -2 to 2 °C. After stirring the reaction mass for 45 min, a freshly prepared diazonium salt is obtained.
This diazonium salt is then charged slowly over a period of 45 min to a solution of 61 parts per weight of the coupling component of the 1st stage of example 45 in 600 parts per volume of water, while during that time the pH value is adjusted to pH 6.3-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula

(1.4a) Navy Blue (λ max 595 nm)
is obtained. The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades, and provides dyeings with color fastness to domestic laundry and excellent contact fastnesses.

More dyestuffs of the following structures are prepared in a similar manner :

Exa mpl
e formula W Q L - shade on cotton
81 1.3a 2-sulfo-1,4-phenylen N-Methyl-ß-Sulfoethylamino Chlorine Navy
82 1.3b 2-sulfo-1,4-phenylen ß-Sulfoethyl-amino Chlorine Navy
83 1.3c 2,5-dimethoxy-l ,4-phenylen ß-Sulfoethyl-amino Chlorine Navy
84 1.4b 2-methoxy-5-methyl-1,4-phenylen Chlorine Navy
85 1.4c 2-sulfo-1,4-phenylen Ditto Chlorine Navy
86 1.4d 2,5-dimethoxy-l,4-phenylen Ditto Chlorine Navy
87 1.5b 2-sulfo-1,4-phenylen Morpholino Chlorine Navy
88 1.5c 2-methoxy-l,4-phenylen Morpholino Chlorine Navy
89 1.5d 2-sulfo-l ,4-phenylen Pyrrolidino Chlorine Navy
90 1.5e 2,5-dimethoxy-l ,4-phenylen Piperidino Chlorine Navy
91 1.5f 2-sulfo-1,4-phenylen Morpholino Fluoro Navy
92 2-sulfo-1,4-phenylen Methoxy Pyridinyl Navy
93 2-sulfo-l ,4-phenylen Methoxy 3-Carboxy-Pyridinyl Navy
94 2-methoxy-5-methyl-1,4-phenylen Methoxy 3-Carboxy-
Pyridinyl Navy
95 2,5-dimethoxy-1,4-phenylen Methoxy 3-Carboxy-Pyridinyl Navy

Application examples:
Dyeing example 1:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 800 parts of water, 50 parts per weight of sodium chloride, and 3 parts per weight of the dyestuff of example 1. After 30 min at 60°C, 10 parts per weight of sodium carbonate is added, the dyeing temperature is maintained at 60 °C for 15 min, then 2 parts per volume of sodium hydroxide 50% solution is added, then dyeing temperature is'maintained at 60 °C for another 30 min. Then the dyed fabric is rinsed in a fresh bath of 2000 parts warm water, neutralized by adding 1 part per weight of acetic acid, and soaped in another fresh bath of 2000 parts of water in presence of a conventional detergent for 5 min. at 95°C, and dried. A navy blue dyeing with good all round fastness properties is obtained.
Dyeing Example 2:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 1000 parts of water, 50 parts per weight of sodium chloride, and 1.2 parts per weight of the dyestuff of example 2. After 30 min at 60°C, 15 parts per weight of sodium carbonate is added, and the dyeing temperature is maintained at 60 °C for 60 min. The dyed fabric is then rinsed and soaped in the same manner as outlined in dyeing example 1. A blue dyeing with good light fastnesses is obtained.
Dyeing Example 3:
100 parts per weight of cotton fabric is padded with a padding liquor, applying a liquor pickup of 70% per weight of fabric, in a freshly prepared padding liquor containing 1000 parts of water, 25 parts per weight of the dyestuff of example 44, 30 parts per weight of sodium carbonate and 10 parts per weight of sodium hydroxide 50% solution. The padded fabric is then rolled, covered to keep it wet, and stored for a period of 16 to 24 h. Finally the fabric is rinsed and soaped in the

same manner as outlined in dyeing example 1. A navy blue dyeing with good all round fastness properties is obtained.
The following comparative examples illustrate that the new dyestuffs of the present invention surprisingly exhibit significantly superior wash fastnesses, and distinctively superior light fastnesses, as compared to know dyestuffs of state of the art. In regard to wash fastness the difference is significant. In regard to light fastness it is noted that retailers typically reject ratings of lower than 4 level, and even a half grade different is therefore crucial.
The dyeing conditions and aftertreatment of the dyed cotton knitware fabrics as tested in the fastness tests were according to dyeing example 1. The wash fastness was evaluated at a temperature of 60 °C according to the norm of ISO105-C03. Light fastness was assessed according to the norm of AATCC 16A. All fastness tests are obtained from 6% of weight fabric (owf) with dyes of the present invention of formula in comparison with structural similar known dyestuffs. In the wash fastness test, the staining of adjacent cotton fabric is assessed. On the assessment scale used, 5 denotes to no staining whatsoever and 1 denotes to substantial staining.

Fastnesses in 6% owf (strength adjusted to comparative) Rl = R5= Light fastness AATCC 20h Wash Fastness ISO105-C03(60°C)
(see scan below) Staining:
Example 60 sulfo methyl 5 Excellent CO 4-5

Comparative 1: hydrogen methyl 4-5 Poor, blue stain on
Example 1 of CO 2
EP 264.878
Comparative Example 2:

Fastnesses in 6% Rl = R5= Light fastness Wash Fastness
owf (strength adjusted to AATCC40h ISO105-C03(60°C), (see scan below)
comparative) Staining :
Example 59 sulfo ethyl 4 Excellent CO 5
Comparative 2: hydrogen ethyl 3-4 Poor, blue stain on
Example 3-1 of EP 264.878 CO 2-3
Washfastness ISO 105 C03 at 6% dyeing (strength adjusted), staining on adjacent fibre material (CO=cotton)


We claim:
1. Novel fibre reactive dyestuff mixtures comprising:
i) one bisazo dyestuff of the formula (1)

Formula (1) containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, Cl-C4-alkoxy, Cl-
C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyl or CH2CH2U wherein U is a leaving group such as sulfato,
phosphato, thiosulfato, chlorine, bromo, acetoxy, or benzoyloxy,
preferably SO2Y is Vinyl or 13-sulfatoethyl,
L is a leaving group selected from chloro, fluoro, pyridinyl which may be
substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from Cl-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -0- R , or -S- R
wherein R is Cl-C6-Alkyl, preferably C1-C3, which is substituted by at
least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or carboxy
substituent, and optionally by further substituents such as hydroxy, or
X is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6-
cycloaliphatic amine which may be interrupted by heteroatoms O, NH or
wherein W has one of the meanings of R, preferably ß-Sulfatoethyl.
S, or a heterocyclic radical of the formula


or a radical of the formula
0-CH2CH2-OR13
wherein R13 is Methyl, Ethyl, Hydroxy or cyano;
ii) one bisazo dyestuff of the formula (2)

wherein
R6 is hydrogen, Cl-C4-alkoxy, carboxy, halogen or sulfo, preferably
hydrogen, methoxy or sulfo,
R7 has one of the meanings of R6,
R8 is hydrogen, Cl-C4-alkoxy, Cl-C4-Alkyl, or sulfo, preferably
hydrogen, methoxy, methyl or sulfo,
R9 has one of the meanings of R8,
Y1 is Vinyl or CH2CH2U, wherein U is a leaving group which is split off
under alkaline conditions, such as sulfate, acetato, halogen, such as chloro
or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
preferably Y is Vinyl or ß-Sulfatoethyl, preferably Yl is Vinyl or ß-
Sulfatoethyl,
Y2 has one of the meanings of Y1
2. Novel fibre reactive dyestuff mixtures comprising:
i) one bisazo dyestuff of the formula (1)


Formula (1) containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, Cl-C4-alkoxy,
C1-C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyl or CH2CH2U wherein U is a leaving group such as
sulfate, phosphato, thiosulfato, chlorine, bromo, acetoxy, or
benzoyloxy, preferably S02Y is Vinyl or ß-sulfatoethyl,
L is a leaving group selected from chloro, fluoro, pyridinyl which
may be substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from Cl-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -O- R, or -S- R
wherein R is C1-C6-Alkyl, preferably C1-C3, which is substituted
by at least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato
or carboxy substituent, and optionally by further substituents such
as hydroxy, or
X is the radical of a Cl-C6-primary or secondary aliphatic or C5-C6-
cycloaliphatic amine which may be interrupted by heteroatoms O,
NH or S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl. or a radical of the formula
0-CH2CH2-OR13
wherein R13 is Methyl, Ethyl, Hydroxy or cyano;

ii) one formazane dyestuff of the formula (3)

Wherein
Z2 is S02 Y, wherein Y has one of the above meanings as defined under
(1), preferably Vinylsulfonyl, ß-Sulfatoethylsulfonyl,
Or
Z2 is a radical of the formula (3a) to (3d)

wherein
L2 has one of the meanings of L1, preferably chloro or fluoro,
Ph is phenyl, preferably 1,3 -or 1,4-phenyl,
alk is C1-C3 alkylene, or -(CH2)20(CH2)2-,

R1O is hydrogen, Cl-C4-alkyl, preferably methyl or ethyl, Rll is
hydrogen, Cl-C4-alkyl, or phenyl,
R12 is hydrogen or chloro,
Hall is chloro or fluoro,
Hal2 is chloro or fluoro,
Y has one of the above defined meanings, preferably Vinyl, ß-Sulfatoethyl
or ß-chlororethyl.
3. Novel fibre reactive dyestuff mixtures comprising:
i) at least one bisazo dyestuff of the formula (1)

Formula (1) containing 2 fibre reactive groups, wherein
R1 and R2 are independent from each other hydrogen, C1 -C4-alkoxy, Cl-
C4 alkyl, halogen, carboxy or sulfo,
the radicals Q1 and Q2 are selected from hydroxyl and amino;
Y is Vinyl or CH2CH2U wherein U is a leaving group such as sulfato,
phosphato, thiosulfato, chlorine, bromo, acetoxy, or benzoyloxy,
preferably S02Y is Vinyl or ß-sulfatoethyl,
L is a leaving group selected from chloro, fluoro, pyridinyl which may be
substituted by Carboxy or Carbamoyl,
X is a non-fibre reactive radical seclected from C1-C8-Alkoxy,
Cyanamino, -NHR, -N(CH3) R, -O- R, or -S- R
wherein R is Cl-C6-Alkyl, preferably C1-C3, which is substituted by at
least one sulfo, sulfato, phosphate, alkoxy, cyano, thiosulfato or carboxy
substituent, and optionally by further substituents such as hydroxy, or

X is the radical of a C1-C6-primary or secondary aliphatic or C5-C6-cycloaliphatic amine which may be interrupted by heteroatoms O, NH or S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably ß-Sulfatoethyl. or a radical of the formula
0-CH2CH2-OR13 wherein R13 is Methyl, Ethyl, Hydroxy or cyano;
ii) one bisazo dyestuff of the formula (2)

R6 is hydrogen, Cl-C4-alkoxy, carboxy, halogen or sulfo, preferably
hydrogen, methoxy or sulfo,
R7 has one of the meanings of R6,
R8 is hydrogen, Cl-C4-alkoxy, C1-C4-Alkyl, or sulfo, preferably
hydrogen, methoxy, methyl or sulfo,
R9 has one of the meanings of R8,
Y1 is Vinyl or CH2CH2U, wherein U is a leaving group which is split off
under alkaline conditions, such as sulfato, acetato, halogen, such as chloro
or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
preferably Y is Vinyl or 13-Sulfatoethyl, preferably Yl is Vinyl or ß-
Sulfatoethyl,

Y2 has one of the meanings of Y1;
in) one formazane dyestuff of the formula (3)

Wherein
Z2 is S02Y, wherein Y has one of the above meanings as defined under
(1), preferably Vinylsulfonyl, ß-Sulfatoethylsulfonyl,
Or
Z2 is a radical of the formula (3a) to (3d)

wherein
L2 has one of the meanings of L1, preferably chloro or fluoro,
Ph is phenyl, preferably 1,3 -or 1,4-phenyl,

alk is C1-C3 alkylene, or -(CH2)20(CH2)2-,
R1O is hydrogen, Cl-C4-alkyl, preferably methyl or ethyl, R11 is
hydrogen, Cl-C4-alkyl, or phenyl,
R12 is hydrogen or chloro,
Hall is chloro or fluoro,
Hal2 is chloro or fluoro, Y has one of the above defined meanings, preferably Vinyl, ß-Sulfatoethyl or ß-chlororethyl.
4. Novel fibre reactive dyestuff mixtures as claimed in any one of the preceding claims wherein dyes of the formula (1) are structures of the formula (1')

(1)
Wherein
Rl is hydrogen, sulfo, chloro, bromo, carboxy, methoxy or ethoxy;
R2 is hydrogen, methyl or methoxy;
the substituent -SO2Y is preferably in para position to the azo linkage;
Y is Vinyl, ß-Chloroethyl or ß-Sulfatoethyl,
L1 has one of the above meanings of L,
X1 is C1-C3 Alkoxy, cyanamino, ß-Sulfoethylamino, N-methyl-ß-
Sulfoethylamino, morpholino, piperidino,
or a radical of the formula


or a radical of the formula
-O-CH2CH2-OR13
wherein R6 is Methyl, Ethyl, Hydroxy or cyano.
in the dyes of formula (1) or formula (1') is selected from

5. Novel fibre reactive dyestuff mixtures as claimed in claim 4 wherein the radical



6. Novel fibre reactive dyestuff mixtures as claimed in claim 2 and claim 3 wherein: i) radical (3a) in formula (3) is selected from

ii) radical (3b) in formula (3) is selected from


iii) radical (3 c) in formula (3) is selected from

iii) radical (3d) in formula (3) is selected from




L1 has one of the above defined meanings of L1, preferably chloro,

R3' has one of the meanings of Rl, excluding hydrogen, preferably R3' is
sulfo or methoxy,
R3" is hydrogen, methoxy or sulfo,
R4' has one of the above defined meanings of R2, preferably hydrogen,
methyl or methoxy,
R5' is methoxy, ethoxy or isopropoxy,
Ro is methyl or hydrogen,
Gi is a direct bond, methylene or a heteroatom O,
Y is ß-sulfatoethyl or vinyl and
the substituent S02Y is preferably located in para position to the azo
linkage.
8. Novel dyestuff mixtures as claimed in claim 1 and claim 5 wherein the ratio of the dyestuffs of the formula (1) to formula (2) is 20:80 to 80:20.
9. Novel dyestuff mixtures as claimed in claim 2, claim 5 and claim 6 wherein the ratio of the dyestuffs formula (1) to formula (3) is 20:80 to 80:20.
10. Novel dyestuff mixtures as claimed in claim 3, claim 5 and claim 6 wherein the ratio of the dyestuffs formula (1) to the sum of dyestuffs of the formula (2) and (3) is 20:80 to 80:20.