FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
Title of the invention - "BLACK MIXTURES OF FIBRE REACTIVE AZO REACTIVE
DYESTUFFS"
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 novel mixtures of fiber reactive dyestuffs comprising reactive groups of vinylsulfone type represented by Formula 1 and Formula 2 that are suitable for dyeing from aqueous bath and for printing of fiber materials containing cellulose, polyamide or protein fiber materials, and blends containing such fiber materials, in deep black shades.

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 black shades, presently known dyes are mostly mixtures of trisazo, bisazo and monoazo dyes, containing reactive groups of the vinylsulfone types.
The Patent/Patent Applications may be considered in the context are WO 2000/06652, DE 19620415 DE 19655283, KR 94-2560, US 7,455,699, JP 17810/1988, JP 160362/1983, EP 870807, EP 1669415, US 6319291, US

7524368, US 7704286, WO 2004/069937, US 2657205, US 20030229952 , WO 2007/039573, EP 785237, US6537332 and US 6011140.
The state of the art pertaining to the aforementioned category are binary or ternary mixtures of bisazo navy blue dyes, mostly C.I. Reactive Black 5, with yellow, orange, red, rubine or scarlet monoazo, bisazo or trisazo dyestuffs.
However, these dyes have certain technical disadvantages and technical limitations such as limited wash fastness as well as contact fastness, due to staining on white adjacent fibre materials such as cotton and/or polyamide, and limited build-up in deep shades. In many of these dyes, further technical disadvantages are low stability to storage in acidic conditions, limited stability in aqueous solution, high dependency of colour strength and obtained shade on changes in the dyeing conditions, and poor dischargeabilty.
WO 2007/039573 and EP 1669415 outline black mixtures containing C.I. Reactive Black 5 with redbrown, respectively rubine or scarlet bisazo dyestuffs, and additional orange based on trisazo and bisazo dyestuffs. WO 2007/039573, in general description, also includes bisazo orange dyestuffs of the following formula

wherein Z is Sulfatoethyl or Vinyl, R201 and R202 are amino.

that give navy blue shades.
US 2657205 and US 2003/0229952 relates to dyestuffs of the formula

US5849887 relates to dye mixtures of formula

that give dyeings having good fastness properties on nitrogen containing or hydroxyl group-containing fiber materials.
EP1669415 and US7524368 outlines black compositions containing bisazo orange dyestuffs of the formula

wherein R is hydrogen or carboxy, and Dl and D2 are benzene radicals containing fibre reactive groups of the vinylsulfone types.
US 6319291 as well as EP 870807 contains navy blue, respectively black, mixtures including structures of the formula

wherein the coupling component contains one sulfo group, in comparison with the inventive compounds containing a C1-4 alkyl radical.

As noted above, all the known dyes of state of the art have certain technical disadvantages and technical limitations such as limited wash fastness as well as contact fastness, limited build-up in deep shades, low stability to storage in acidic conditions, and limited stability in aqueous solution, high dependency of color strength and obtained shade on changes in the dyeing conditions, and poor dischargeabilty. Consequences of these deficiencies include poor reproducibility, which ultimately affects the economics of the dyeing.
Thus, there arises a need for a dye mixture for black reactive dyes which would address the above issues and highlight optimal color properties.
The inventors of the present invention have surprisingly found by means of methodical study that the predicaments highlighted above, are addressed by means of new dyestuff mixtures based on already known navy dyestuffs of formula (1) of bisazo vinylsulfone reactive type, and new orange-brown bisazo dyestuffs of formula (2) of bisazo vinylsulfone reactive type, and optionally additional shading dyestuffs.
A further advantage of the dyestuff of the present invention is that the desired deep neutral black shades can be achieved simply as binary mixtures of dyestuffs of formula 1 and 2, whereas binary dyestuff compositions of state of the art, as mentioned above, would typically yield only greenish black shades and require additional red dyes for achieving a deep neutral black shade. The binary mixtures of the present invention are simpler to manufacture and therefore of technical and commercial benefit.
OBJECT OF THE INVENTION
It is an object of the present invention to provide novel mixtures of fibre reactive dyestuffs which are suitable for dyeing from aqueous bath and printing of fibre materials containing cellulose, polyamide or protein fibre materials, and blends containing such fibre materials, in deep black shades.

It is a further object of the present invention to provide dyestuff mixtures having excellent fixation yield and excellent build-up, which can achieve very deep black shades with good wash and very high contact fastness.
SUMMARY OF THE INVENTION
According to an aspect of the present invention there is provided novel dyestuff mixtures of water soluble dyes containing at least one navy blue dyestuff of formula (1) that account for 50 to 85% by weight in the form of free acid in the pure form;

and at least one orange-brown dyestuff of formula (2) that account for 15 to 50% by weight in the form of free acid in the pure form,

According to another aspect of the present invention there is provided novel dyestuff mixtures of water soluble dyes containing at least one navy blue dyestuff of formula 1, orange-brown dyestuff of formula 2, and optionally, additional dyestuffs of formula 3 for a more reddish black shade accounting for 0.1 to 20%.


According to yet another aspect of the present invention there is provided novel dyestuff mixtures of water soluble dyes containing at least one navy blue dyestuff of formula 1 and orange-brown dyestuff of formula 2 and optionally additional red monoazo dyestuffs of formula 4a or 4b or a mixture thereof accounting for about 6 % by weight of the dyestuff composition.

According to yet another aspect of the present invention there is provided novel dyestuff mixtures of water soluble dyes containing at least one navy blue dyestuff of formula 1 and orange-brown dyestuff of formula 2 and optionally additional dyestuffs of formula 5 or a mixture thereof accounting for upto 15% by weight of the dyestuff composition.

DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to black mixtures of fiber reactive azo reactive navy blue dyestuffs of formula (1) of bisazo vinylsulfone reactive type, and new orange-brown dyestuffs of formula (2) of bisazo vinylsulfone reactive type, and optionally additional shading dyestuffs, as disclosed hereinafter.
The fiber reactive dyestuff mixture of the present invention comprises:
a) 50-85% by weight of total composition, preferably 55-80% by weight of total composition, of at least one bisazo dyestuff, containing two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (1)

Wherein
Benzene rings Bl and B2 in formula (1) may carry independent from each other 1-2 additional substituents such as methoxy, methyl, carboxy or sulfo, preferably B1 and B2 carry no further substituents, and

Y is Vinyl or CH2CH2L, wherein L 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 B-Sulfatoethy],
and the two substituents Y may have identical or different meaning.
b) 15-50% by weight of total composition, preferably 20-45% by weight of total composition, of at least one orange-brown bisazo dyestuff, containing at least one fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (2)

wherein the radicals have the following meaning:
Ro is hydrogen or methyl,
R1is Cl-C4-A!kyl,
Y has one of the above defined meanings of Y, preferably is Vinyl or ß-sulfatoethyl, and the two substituents Y may have identical or different meaning,
D1 is a benzene radical of the formula (2a) or a naphthalene radical of the formula (2b), or a radical of the formula (2c),

wherein
Rc is methoxy, methyl, chloro, bromo, cyano, nitro, carboxy, hydroxy, ureido or acetylamino, preferably methoxy,
n is 0, 1 or 2, and in case of n=2 the substituents Rc are preferably methoxy or methyl, and may have identical or different meanings,
m is 0-2, preferably 1,
D2 has, independent from the meaning of Dl, one of the meanings of D1, and the radicals Dl and D2 containing together at least one sulfo substituent, preferably 2 sulfo substituents,
R2 is hydrogen, methyl, ethyl or phenyl,
W is C2-C3-Alkylen, 1,3-Phenylen, 1,4-Phenylen or (CH2)20(CH2)2-.
Suitable radicals R1 are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl, preferably methyl or ethyl, and in particular methyl is preferred.
Preferably the radical Ro is hydrogen,
Suitable radicals (2a) include 2-sulfo-l,4-phenylen, 6-sulfo-l,3-phenylen, 2-methoxy-5-methyl-1,4-phenylen, 2,5-dimethoxy-l,4-phenylen, 2-chloro-l,4-phenylen, 2-bromo-l,4-phenylen, 6-methoxy-l,3-phenylen, 6-hydroxy-l,3-

phenylen, 6-carboxy-l,3-phenylen, 6-nitro-l,3-phenylen, 6-cyano-l,3-phenylen, 2-carboxy-l,4-phenylen, 2-hydroxy-l,4-phenylen, 1,2-phenylen, and 1,3-phenylen.
In particular, the radical 2-sulfo-l,4-phenylen is preferred for (2a).
Suitable radicals (2b) include 2,6-naphthylen, l-sulfo-2,6-naphthyIen, 2,8-naphthylen and 6-sulfo-2,8-naphthylen.
Suitable radicals of the formula (2c) are

In formula (2) the radicals Y02S-D]-N=N- and -N=N- D2-S02Y are derived from diazo components YO2S-D1-NH2 and YO2S-D2NH2.
The dyestuffs of the formula (2) used in the black compositions of the present invention are new and also part of the invention.
Process for Preparation of Dyestuffs of the Formula (2): The dyestuffs of the formula (2) are manufactured by diazotization of the component of the formula YO2S-D1-NH2 in aqueous acidic medium by means of sodium nitrate and hydrochloric acid or sulfuric acid, yielding the diazonium salt compound YO2S-Dl-N2+, which is subsequently coupled at a pH value of 1-3 and a temperature of 0-25°C, preferably pH 1-2.5 and 0-5°C, onto a coupling component of the formula

which yield monoazo dyes of the formula

which is subsequently coupled at a pH value of 4-8, preferably 5-7, and a temperature of 0-25°C, preferably 0-10°C, with a freshly diazotized Y02S-D2-

NH2, diazotized in the same way ad described for YO2S-DI-NH2 , to yield the inventive bisazo dyes of the formula (2).
Examples for suitable coupling components (C1) are 2,4-diaminotoluene, 2,4-
diamino-ethylbenzene, 2,4-diamino-isopropylbenzene, 2,4-diamino-n-
propylbenzene, 2,4-diamino-n-butylbenzene, 2,4-diamino-xylene and 3,5-diamino-xylene, which are known since long time and some are well established industrial products.
The inventive dyestuff mixtures of dyestuffs of the formula (1) and (2) in the ratio 85:15 to 50:50, preferably 80:20 to 55:45, provide deep black dyes with a greenish to neutral black shade.
In order to provide a more greenish black shade, optionally the reactive dyestuff compositions may contain up to 20% of additional dyestuffs of yellow, yellowbrown, or orange shades, preferably containing 0-10%, based on the total amount of dyes of the formula (1) and (2), of suitable monoazo or bisazo dyestuffs containing at least one vinylsulfone and optionally additional monochlorortriazine reactive groups.
Such suitable shading dyes are for example the following typical fibre-reactive dyestuffs:
C.I. Reactive Yellow 15, C. I. Reactive Yellow 145, C.I. Reactive Yellow 176, , C.I. Reactive Yellow 186, C.I. Reactive Yellow 201, C.I. Reactive Orange 107, C.I. Reactive Orange 131.
In order to provide a more reddish black shade, the reactive dyestuff compositions of the present invention may be mixed with red, scarlet, redbrown or rubine shading dyestuffs up to 20%, more preferably 0.1 -10%. Such dyestuffs may be one or more azo dye compounds of the following formulae:


wherein
R1 is hydrogen, methyl, sulfomethyl, ß-Sulfoethyl, Carboxymethyl, ß-Carboxyethyl,
D1 is l,4-phenylen or 2-sulfo-1,4-phenylen,
D2 is independent from the meaning of D1, 1,4-phenylen, 2-sulfo-l,4-phenylen, 2-methoxy-1,4-phenylen, 2-methoxy-5-methyl-l,4-phenylen, 2-methoxy-l,3-phenylen, or 2-5-dimethoxy-l,4-phenylen,
Y has one of the above meanings, preferably Vinyl or B-sulfatoethyl.
Optionally the black dyestuff composition of the present invention may contain up to 6 % by weight of each of the red monoazo dyestuffs of the formula (4a) or (4b), or mixture thereof

wherein the benzene ring Bl has the same meaning as defined under formula (1) and Y has one of the above meanings, preferably Vinyl or 6-Sulfatoethyl.

The dyestuff compositions may further contain, besides the dyestuffs of the formula (2), up to 15%, preferably upto 8%, of compounds of the formula (5)

wherein Ro, Rl, Dl and D2 have one of the above meanings as defined under formula (2), preferably Ro is hydrogen, Rl is methyl, Dl and D2 have one of the meanings of (2a), in particular (2a') or (2a").
These dyestuffs of the formula (5) are derived from the 2,6-diaminobenzenes coupling components which may be contained as by-products in the 2,4-diaminobenzenes coupling components, underlying the dyes of the formula (2).
Suitable radicals Y in the formula (1), (2), (3), (4a) and (4b) include Vinyl, ß-Sulfatoethyl, ß-Chloroethyl, ß-Bromoethyl, ß-acetoxyethyl, ß-Phenoxyethyl, ß-Phosphatoethyl, and ß-Thiosulfatoethyl, and in particular, Vinyl, and ß-Sulfatoethyl.
Suitable dyestuffs of the formula (1) include

wherein
Y is Vinyl or ß-Sulfatoethyl, and the two substituents Y can have identical or different meanings,
and in particular, the dyestuff of the formula (la) is preferred.

In the radicals -SO2Y the reactive group ß-Sulfatoethylsulfonyl is drawn in the form of its sulfuric acid form but can likewise be the alkali metal salt thereof, especially sodium salt, or it can be in the form of vinylsulfonyl to which it is easily converted upon exposure to alkaline medium, and the sulfo groups are drawn in the form of its sulfuric acid form as well, but can likewise be the alkali metal salt thereof, especially sodium salt. This illustration form is used in all further structures drawn of preferred embodiments or preferred radicals.
The dyestuffs containing one or more sulfo groups are drawn in the form of its sulfuric acid form -S03H, but can likewise be the alkali metal salt thereof, especially sodium salt or potassium or lithium salt, preferably sodium salt. This illustration form is used in all further structures drawn of preferred embodiments or preferred radicals, and examples.
Of the structures of the formula (2) the following structures (2-1) are preferred


wherein
Ro is methyl or hydrogen,
Rl is methyl or ethyl,
Y is ß-sulfatoethyl or vinyl,
D1 and D2 have one of the above defined meanings, provided that at least one of the radicals Dl and D2 is a radical of the formula (2a), and preferably at least one of the radicals D1 and D2 is a radical of the formula (2a') or (2a"), and moreover such radicals of Dl and D2 are preferred carrying combined at least one sulfo group, preferably 2 sulfo groups.

Suitable dyestuffs of the formula (2) include the following structures (2-1 a) to (2-lh).

wherein
Rl has one of the above meanings, preferably methyl, R3 is methyl or methoxy,
Wl' is 1,2-ethylen or 1,3-propylen, 1,3-Phenylen, 1-4-Phenylen or a radical of the formula -(CH2)20(CH2)2-
R2' is hydrogen or methyl.
In particular, of the dyestuffs of the formula (2) the following dyestuff is especially preferred:


wherein Rl and Y have one of the meanings as defined in formula (2).
Of these dyestuffs of the formula (5) the structures of (5-1) are preferred.
In particular preferred are the binary mixtures containing 55-80% of a dyestuff of the formula (la), C.I. Reactive Black 5, and 20-45% of a dyestuff of the formula
(2-la).
Moreover, of these preferred compositions, the binary mixtures containing 65-77% of a dyestuff of the formula (la), C.I. Reactive Black 5, and 23-35% of a dyestuff of the formula (2-la) are especially preferred.
Surprisingly it was found by the inventors that build-up, wash fastness and contact fastness are superior to dyestuff mixtures of state of the art.

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.
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.
These dyestuff mixtures are also suitable for dyeing and printing of fibre blends containing the mentioned cellulose, polyamide or protein fibre materials. The dyestuff mixtures of the present invention can further 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 amounts wherein the dyes are applied in the dye baths can vary according to the desired depth of shade, generally amounts of 1% to 12 % per weight of fabric are suitable, preferably 3% to 11%, and in particular 5% to 10% for achieving deep black shades.
The dye bath may contain addition 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, preferably 50-90 g/L of 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 atemperature of 40-90, 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 light fastness and very good wash fastness, even in deep shades, as well as good contact fastness to water, and good acid as well as alkaline perspiration fastness.
Moreover, the dyeing obtained with the dyes of the present invention is dischargeable and can be applied in discharge printing.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Examples
The following examples illustrate the invention.
Parts are given, unless specified otherwise, in parts per weights, such as grams.

The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise.
Example A:
64.5 parts by weight of 2-Sulfo-4-(ß-sulfatoethylsulfonyl)phenylamine is diazotized in the usual manner using 14.5 parts per weight of sodium nitrite at 0-5°C and pH 1-1.5, adjusted with hydrochloric acid, in 300 parts per volume of water over a period of 1 hour. The so prepared diazonium salt is charged to the solution containing 12 parts per weight of the coupling component 2,4-Diaminotoluene. The 1 st azo coupling stage is then carried out within 2 hours at pH 1.5 at 0-5°C, then pH is raised to pH 7 and the 2nd coupling stage is completed to yield the dyestuff of the formula

Brown 1 (type 2-la),λmax = 490 nm
This dyestuff can be used for colouration of cellulosic fibres in dark reddish brown shades, and the same dyestuff is also perfectly suitable as components for the black composition of the present invention.
Example B:
32.2 parts by weight of 2-Sulfo-4-(ß-sulfatoethylsulfonyl)phenylamine is diazotized in the usual manner using 7.3 parts per weight of sodium nitrite at 0-5°C and pH 1-1.5, adjusted with hydrochloric acid, in 120 parts per volume of water over a period of 1 hour. The so prepared diazonium salt is charged to the solution containing 12 parts per weight of the coupling component 2,4-

Diaminotoluene. The 1st azo coupling stage is then carried out within 2 hours at pH1.5 at O-5°C.
The monoazo dyestuff of the formula is obtained

which is converted without further isolation by adding a freshly diazotized suspension of 28 parts per weight 4-(ß-sulfatoethylsulfonyl)phenylamine, diazotized in the usual manner using 7.1 parts per weight of sodium nitrite at 0-5°C and pH 1-1.5, adjusted with hydrochloric acid, in 160 parts per volume of water over a period of 2 hours. Then pH is raised to pH 6-7 and the 2nd coupling stage is completed, and finally the dyestuff of the formula

Brown 4 (type 2-la), λmax = 402 nm
is obtained. This dyestuff can be used for colouration of cellulosic fibres in dark reddish brown shades, and the same dyestuff is also perfectly suitable as components for the black composition of the present invention.
The following dyestuffs are obtained when the diazo and coupling components specified in the table are used. Likewise these dyes can be used as components for the black composition of the present invention.

Example
Diazogw m Diazo component Coupling Product and
. , -,■: component 1 2 component shade
c 2-Sulfo-4-(ß- 2-Sulfo-4-(ß- 2,4-Diamino- Brown 2
sulfatoethyl-
sulfonyl)
phenylamine sulfatoethyl-
sulfonyl)
phenylamine ethylbenzene
D Ditto dito 3,5-Diamino-xylene Brown 3
E 4-(ß- 2-Methoxy-5-(ß- 2,4-Diami no- Brown 6
sulfatoethyl- sulfatoethyl- toluene λmax = 415
sulfonyl) phenylamine sulfonyl) phenylamine nm
F Ditto 3-(ß-sulfatoethyl-
sulfonyl)
phenylamine Ditto Brown 7
G Ditto 2-methoxy-5-
methyl-4-(ß-
sulfatoethyl-
sulfonyl)
phenylamine Ditto Brown 8
λmax = 425 nm
H Ditto 2,5-dimethoxy-4-(ß-sulfatoethyt-sulfonyl) phenylamine Ditto Brown 11
λmax = 490 nm
The following examples illustrate the black compositions of the present invention.
Example 1:
70 parts per weight of the dyestuff Navy la and 30 parts per weight of the dyestuff Brown 1 are mixed as dry powders in a mill. The following composition is obtained:



A neutral black shade is obtained which exhibits excellent build-up, even in very deep black shades, excellent contact fastness, and superb washing fastness.
When in example 1 the navy and brown dyes is replaced by any the following dyestuffs, and optionally additional shading dyes are added, more useful dye mixtures are obtained. Specific examples of such variations are shown in the following tables.
Examples of binary mixtures:

32 Navy 2, 70% Brown 1,30%
33 Navy 3, 75% Brown 1,25%
34 Navy 4,66% Brown 1,34%
35 Navy 5, 72% Brown 1,28%
36 Navy 6, 71% Brown 1,29%
37 Navy 7, 65% Brown 1,35%
The following examples illustrate the black compositions of the present invention, for ternary mixtures:
Example 38:
Navy la 70% is mixed with 22% Brown I (Bisazo-2,4 isomer) and 8% of the respective Bisazo-2,6 isomer.

Mixtures containing additional red or redbrown shading dyes:
Example 42:
65% of Navy la, 25% of a brown dye of the structure and 10% of a rubine dyestuff the structure are mixed to obtain reddish black shades when dyed on cotton fabric.

Examples for mixtures of formula 1, formula 2 and formula 4



Comparative example 1:
70% Navy la, 30% of a dyestuff of the structure is mixed similar as outlined in example 1


(disclosed in EP 870807)

.K/S @l% owf dyeing K/S @3% owf dyeing K/S @6% owf dyeing
Example 1 79.6 202 290
Comparative ex.1 92.2 207 229.5
The above table shows a comparison of the build-up in a typical exhaust dyeing process at a liquor ratio of 1:10, a temperature of 60°C, using 20 g/L sodium carbonate ash as fixation alkali, and 80 g/L of sodium chloride to facilitate exhaustion, of cotton fabric.
The evaluation of the colour strength was done by Kubelka Munk function K/S,

according to http://de.wikipedia.org/wiki/Kubelka-Munk-Theorie), based on "of weight fabrics" (owf) dyeing after normalizing the dye bath to same absorbance in solution.
From the comparative example it is obvious that the dyestuff mixtures exhibit a significantly better build-up, which means with increasing dye concentration comparably deeper dyeing are obtained. Specifically it is shows that despite of lower strength at 1% and similar strength at 3%, the inventive dye misture provides much darker dyeing at 6% which is in the range of the relevant dye concentration for black shades (5-10%).
Comparative Example 2:
Example of patent application US 6.537.332 example 124, components adjusted to achieve same shade as example 1.

Comparison of a 8% owf dyeing, rinsed warm once and soaped once at 95 °C at a liquor ratio of 1:20. Checked the wash fastness ISO 105-C03 (60°C) for staining on multifibre strip:

It is clearly visible in the scan that the inventive dyestuff composition provides a better wash fastness in regard to staining on adjacent fibre material.
Comparative dyeing example:
Normalized dyeing in similar colour strength, taken in exhaust dyeing at 60°C temperature rise process, at liquor ration 1:10 and using 50 g/L sodium chloride and 20 g/L sodium carbonate as fixation alkali after dyeing rinsed warm and soaped once at 95°C.


WO2007/039573 example 6 is the dyestuff of the formula

containing even one more solubilising groups (S03H), and the same number of fibre reactive groups of vinylsulfone type as brown 1. It is surprising that Brown 1 (dyes of formula 2of the present invention) exhibits a better washing fastness.
US 6160101, example 38 is the trisazo dyestuff of the structure


containing the same number of solubilising groups (COOH or S03H), and the same number of fibre reactive groups of vinylsulfone type as brown 1. It is surprising that Brown 1 exhibits a better washing fastness.

We Claim
1. Fiber reactive dyestuff mixtures comprising
a) 50-85% by weight of total composition, of at least one bisazo dyestuff, containing two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (1)

Wherein
benzene rings Bl and B2 in formula (1) may carry independent from each other additional substituents selected from methoxy, methyl, carboxy or sulfo, and
Y is Vinyl or CH2CH2L, wherein L 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,
and the two substituents Y may have identical or different meaning.
b) 15-50% by weight of total composition by weight of total composition, of at least one orange-brown bisazo dyestuff, containing at least one fibre reactive groups of the vinyl sulfone type, which have in the form of the free acid the formula (2)


wherein the radicals have the following meaning:
Ro is hydrogen or methyl,
Rl is Cl-C4-AIkyl,
Y has one of the above defined meanings of Y, preferably is Vinyl or ß-sulfatoethyl, and the two substituents Y may have identical or different meaning,
D1 is a benzene radical of the formula (2a) or a naphthalene radical of the formula (2b), or a radical of the formula (2c),

wherein
Rc is methoxy, methyl, chloro, bromo, cyano, nitro, carboxy, hydroxy, ureido or acetylamino,
n is 0, 1 or 2, and in case of n=2 the substituents Rc may have identical or different meanings,

m is 0-2,
D2 has, independent from the meaning of Dl, one of the meanings of Di, and the radicals Dl and D2 containing together at least one sulfo substituent,
R2 is hydrogen, methyl, ethyl or phenyl,
W is C2-C3-Alkylen, 1,3-Phenylen, 1,4-Phenylen or (CH2)20(CH2)2-.
2. Fiber reactive dyestuff mixtures as claimed in claim 1, wherein Y is Vinyl or ß-Sulfatoethyl.
3. Fiber reactive dyestuff mixtures as claimed in any one of the preceding claims, wherein Dl is a radical of the formula (2a') or (2a")

4. Fiber reactive dyestuff mixtures as claimed in any one of the preceding claims, wherein the dyestuff of the formula (1) is the dyestuff of the structure

5. Fiber reactive dyestuff mixtures as claimed in any one of the preceding claims, wherein the dyestuff of the formula (2) is a dyestuff of the structures

wherein
Rl is methyl or ethyl,
R3 is methyl or methoxy,
Wl 'is 1,2-ethylen or 1,3-propylen} 1,3-Phenylen, 1,4-Phenylen or (CH2)20(CH2)2-
R2' is hydrogen or methyl,
Y is Vinyl or ß-Sulfatoethyl.
6. Fiber reactive dyestuff mixtures as claimed in claim 5, wherein the dyestuff of the formula (2) is a dyestuff of the structure (2-1 a)

wherein
Rl is Methyl and
Y is Vinyl or G-Sulfatoethyl.
7. Fiber reactive dyestuff mixtures as claimed in claim 6, wherein the dyestuff of the formula (2) is a dyestuff of the structure


wherein Y is Vinyl or fl-Sulfatoethyl.
8. Fiber reactive dyestuff mixtures as claimed in any one of the preceding claims 1-7 optionally comprising up to 20 % of dyestuffs of formula 3

wherein
R1 is hydrogen, methyl, sulfomethyl, ß-Sulfoethyl, Carboxymethyl, or ß-Carboxyethyl,
D1 is 1,4-phenylen or 2-sulfo- 1,4-phenylen,
D2 independent from the meaning of D1 is selected from 1,4-phenylen, 2-sulfo-1,4-phenylen, 2-methoxy-1,4-phenylen, 2-methoxy-5-methyl-1,4-phenylen, 2-methoxy-1,3-phenylen, or 2-5-dimethoxy-l,4-phenylen;
Y is Vinyl or li-sulfatoethyl.
9. Fiber reactive dyestuff mixtures as claimed in any one of the claims 1-7, optionally comprising upto 6% of red monoazo dyestuffs of formula (4a) or Formula (4b)


Wherein
benzene rings Bl and B2 in formula (1) may carry independent from each other additional substituents selected from methoxy, methyl, carboxy or sulfo, and
Y is Vinyl or CH2CH2L, wherein L 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.
10. Fiber reactive dyestuff mixtures as claimed in any one of the claims 1-7, optionally comprising up to 15 % of dyestuffs of formula 5

Formula (5)
wherein Ro, Rl, Dl and D2 have one of the meanings as defined under formula (2).
11. Dyestuffs of the formula (2-1 a), (2-1 b), (2-1 c), (2-1 d), (2-1 e), (2-1 f), (2-lg) and (2-lh) as defined in claim 5.

12. A process for preparing the fiber reactive dyestuff composition as claimed in
any one of the claims 1-10 by mechanically mixing the individual dyes in the
required proportions, or by synthesizing the dyes by diazotization and
coupling reactions in one bath using mixtures for diazo and coupling
components.
13. A process for manufacturing the dyestuffs of formula 2 as claimed in claim
11 by diazotization and coupling reactions based on the components of the
formulaY02S-Dl-NH2 in aqueous acidic medium by means of sodium nitrate
and hydrochloric acid or sulfuric acid, yielding the diazonium salt compound
Y02S-D1-N2+, which is subsequently coupled at a pH value of 1-3 and a
temperature of 0-25°C, onto a coupling component of the formula

which is subsequently coupled at a pH value of 4-8, and a temperature of 0-25°C, with a freshly diazotized YO2S-D2-NH2, diazotized in the same way as described for YO2S-DI-NH2, to yield the inventive bisazo dyes of the formula (2).
14. A process for using the fiber reactive dyestuff compositions as claimed in any one of the claims 1-10 for dyeing and printing of fibre materials containing

cellulose, polyamide or protein fibres, wherein the fibre material is cotton or regenerated cellulose, viscose or Lyocell, a polyamide fibre, nylon 6 or nylon 6,6, or a protein fibre, wool or silk.