FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. 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
This invention relates to black mixtures of fibre reactive azo reactive dyestuffs, containing reactive groups of the vinylsulfone type.
BACKGROUND OF THE INVENTION AND PRIOR ART
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 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 orange, respectively yellow, and red, respectively rubine or scarlet, dyestuffs.
Without limitation or disclaim, the following documents may be considered most relevant to the present invention.
US patent application US 6,537,332 (WO 2000/06652) teaches mixtures of C.I. Reactive Black 5 with scarlet or rubine bisazo dyestuffs and orange bisazo dyestuffs. However, these dyes have certain technical disadvantages and technical limitations such as limited wash fastness as well as contact fastness, due to critical staining on white adjacent fibre materials such as cotton and/ or polyamide.
The German patent applications DE 19620415 and DE 19655283, as well as the Korean patent application KR 94-2560 disclose ternary mixtures of C.I. Reactive Black 5 with yellow and orange monoazo dyestuffs containing vinylsulfone reactive groups. However, these dyes have certain technical disadvantages and technical limitations such as limited wash fastness as well as contact fastness, due to critical staining on white adjacent fibre materials, especially in regard to staining on polyamide.

The US patent application US 7,455,699 discloses ternary mixtures of C.I. Reactive Black 5 with red brown, respectively scarlet bisazo dyes, and additional orange, respectively yellow monoazo dyestuffs. However, these dyes have certain technical disadvantages and technical limitations such as low stability to storage in acidic conditions, and limited stability in aqueous solution, high dependency of colour strength and obtained shade on changes in the dyeing conditions, and poor dischargeability.
The Japanese patent application JP 17810/1988 discloses black mixtures of C.I. Reactive Black 5 with orange monoazo dyestuffs containing a dichlorotriazinyl fibre reactive group. However, these dyes too have limited build-up in deep shades, low stability to storage in acidic conditions, and limited stability in aqueous solution, high dependency of colour strength and obtained shade on changes in the dyeing conditions, and poor dischargeability.
The Japanese patent application JP 160362/1983 discloses black mixtures of C.I. Reactive Black 5 with orange monoazo dyestuffs containing a vinylsulfone fibre reactive group. However, these dyes have limited build-up in deep shades.
The patent applications WO 2004/069937 and WO 2007/039573 outline black mixtures containing C.I. Reactive Black 5 with red brown, respectively rubine bisazo dyes, and additional orange based on trisazo dyestuffs.
The European patent application EP 870,807 discloses black mixtures of C.I. Reactive Black 5 with orange monoazo dyestuffs containing two vinylsulfone reactive groups.
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, due to critical staining on white adjacent fibre materials such as cotton and/ or polyamide.
Moreover, the dyes of the above mentioned patent applications have further limitations such as 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.
OBJECT OF THE INVENTION
It is an object of the present invention to provide black reactive dyestuff comprising mixtures of water soluble dyes.
It is another object of the invention to provide black reactive dyestuff mixtures 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 yet another 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 one aspect of the invention there is provided Black dyestuff composition comprising dyes selected from
a) 40-90% 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 methoxy, methyl, carboxy or sulfo,
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,
b) up to 20% of at least one bis- or trisazo redbrown, scarlet or rubine dyestuff, containing at least two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (2)

wherein
D1SO2Y and D2'SO2Y are independent from each other a radical of the formula


wherein benzene ring B1 carries 0-2 additional identical of different substituents of Cl-C3-Alkoxy, preferably methoxy, Cl-C3-Alkyl, preferably methyl, Carboxy, halogen, or hydroxyl,
Y has one of the above defined meanings,
R1' is hydrogen, Sulfomethyl, ß-Sulfoethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Cyanoethyl;
c) 10-40% of at least one yellow or orange dyestuffs, containing two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (3)

wherein the radicals have the following meaning:
K1 is a radical of the benzene or naphthalene series which is substituted by amino, hydroxy, Acylamino, Ureido, and optionally further substituted by 1 or 2 Sulfo groups, and optionally substituted by Cl-C3-Alkoxy, C1-C3 Alkyl, Halogen, Nitro, or Carboxy.
K2 has independent from the meaning of K1 one of the meanings of K1, providing that at least one of the radicals K1 or K2 is a radical of the benzene series,
X is chloro, fluoro, pyridinyl which may be substituted by Carboxy or Carbamoyl, -NHCN, -NHR, -N(CH3) R, -O- R , or -S- R wherein R is Cl-C6-Alkyl which is substituted by at least one sulfo, sulfato, phosphate, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or 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,
Ra is Hydrogen or Cl-C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,
Rbhas each independent from the meaning of Ra one of the meanings of Ra
Y has one of the above defined meanings,
D1 is a benzene radical of the formula (3 a)

wherein
Rc is methoxy, methyl, chloro or bromo,
n is 0, 1 or 2, and m is 0 or 1, and
in case of n=2 the substituents Rc may have identical or different meanings,
D2 has independent from the meaning of Dl, one of the meanings of Dl.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The inventors of the present invention have surprisingly found by means of methodical study that the predicaments highlighted above, are addressed by means of the dye mixture as disclosed hereinafter.

The mixtures of the present invention contain
a) 40-90%, preferably 55-80%, 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
Bl and B2 are benzene ring radical bearing the substituent -So2Y,
wherein Y is Vinyl or CH2CH2L, wherein L is a leaving groupsuch as sulfato, acetato, halogen, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy; preferably Y is Vinyl or B-Sulfatoethyl,
Further Bl and B2 independent of each other, may be further optionally substituted by additional substituents such as methoxy, methyl, carboxy or sulfo;
b) up to 20%, preferably 8-18%, of at least one bis-or trisazo redbrown, scarlet or rubine dyestuff, containing at least two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (2)


wherein
D2'SO2Y and D2'SO2Y are independent from each other radicals of the formula

wherein
Benzene ring B1 carries 0-2 additional identical of different substituents of C1-C3-Alkoxy5 preferably methoxy, Cl-C3-AlkyL preferably methyl, Carboxy, halogen, or hydroxyl,
Y has one of the above defined meanings, preferably Vinyl, or B-sulfatoethyl,
U1 is hydroxyl or has one of the meanings of Y, preferably U1 is hydroxyl, vinyl or ß-sulfatoethyl,
R1' is hydrogen, Sulfomethylen, ß-Sulfoethylen, Carboxymethyl, ß-Carboxyethyl, or ß-Cyanoethyl;
wherein the radicals have the following meaning:
c) 10-40%, preferably 12-30%, of at least one yellow or orange dyestuffs, containing two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (3)


K1 is a radical of the benzene or naphthalene series which is substituted by amino, hydroxy, Acylamino, Ureido, and optionally further substituted by 1 or 2 Sulfo groups, and optionally substituted by Cl-C3-Alkoxy, C1-C3 Alkyl, Halogen, Nitro, or Carboxy.
K.2 has independent from the meaning of K1 one of the meanings of K1, providing that at least one of the radicals Kl or K2 is a radical of the benzene series,
X is halogen, preferably chloro or fluoro, pyridinyl which may be substituted by Carboxy or Carbamoyl, -NHCN, -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, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or 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, and in particular,
X is preferably Cyanamino, 2-Sulfoethylamino, N-Methyl- 2-Sulfoethyl-amino, carboxymethylthio, chloro, fluoro, or morpholino, or a radical of the formula

Ra is Hydrogen or Cl-C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo, preferably Hydrogen or Methyl,

Rb has each independent from the meaning of Ra one of the meanings of Ra, preferably hydrogen or methyl,
Y has one of the above defined meanings, preferably is Vinyl, or ß-sulfatoethyl,
D1 is a benzene radical of the formula (3a) which may be non substituted or substituted by one or more substituents sulfo, Cl-C4-alkyl, Cl-C4-alkoxy, halogen, or nitro,

Wherein
Rc is preferably methoxy, methyl, chloro or bromo,
n is 0,1 or 2, and m is 0 or 1, and
in case of n=2 the substituents Rc may have identical or different meanings,
D2 has independent from the meaning of D1, one of the meanings of D1.
K1-NRa- is preferably a radical of the formula (3b-l), (3b-2) and (3b-3) of the benzene or series or a radical of the naphthalene series (3b-4),



Wherein
Ro is hydrogen or methyl, preferably hydrogen
R1 is hydrogen, Methyl, or Ethyl, preferably hydrogen,
R2 is amino or methyl,
ris 0-1.
Preferably K2-NRb has one of the meanings of (3b-1), (3b-2) or (3b-3) wherein the radicals RO, R1, R2 and r have one of the above meanings.
In particular, the radicals (3b-1) are especially preferred meanings for K1NRa and K2NRb.
In the design of the structures of formula (3) the radicals Y02S-D1-N=N- and -N=N- D2-S02Y are derived from diazo components Y02S-D1-NH2 and YO2S-D2NH2, whereas the radicals -KlNRa- and K2NHRb- are derived from coupling components.
Optionally the black dyestuff composition may contain up to 20%, preferably 0-10%, of at least one further yellow or orange dyestuffs which have in the form of the free acid the formula the formula (4-1) to (4-6), containing at least one vinylsulfone reactive group, providing that the total amount of yellow and orange dyestuffs according to the sum of the components of formula (3) and (4-1) to (4-6) is not exceeding 40%.


In the formula (4-1) thru (4-6) the radicals have the following meaning:
Q is hydrogen or carboxy,
Ac is Cl-C3-Acyl, preferably Acetyl, dichlorotriazinyl or a monohalogen triazinyl ring which is substituted by phenylamino carrying 1-2 sulfo groups and 0-1 substituents SO2Y wherein Y has one of the above defined meanings, preferably Ac is 2,4-dichlorotriazinyl,
R4 is hydrogen, methyl or methoxy,
R5 is hydrogen or has one of the meanings of Ac, preferably hydrogen or acetyl,
Y has one of the above defined meanings, preferably Vinyl, or ß-sulfatoethyl.

Optionally the black dyestuff composition may contain up to 6% of each of the red monoazo dyestuffs of the formula (5a) or (5b), or a mixture of both,

Wherein the benzene ring B1 has the same meaning as defined under formula (1) and Y has one of the above meanings, preferably Vinyl or ß-Sulfatoethyl.
Preferably formula (3b-2) is the following radical
Preferably formula (3b-3) is one of the following radicals
In formula (3), preferably the radical (3b-1) is one of the following radicals




Preferably formula (3b-4) is one of the following radicals

Examples of suitable radicals X in formula (3) include Cyanamino,
sulfomethylamino-, 2-sulfoethylamino, N-Methyl-2-sulfoethylamino, 3-
sulfopropylamino-, 2-sulfato-ethylamino-, 3-sulfato-propylamino, 2-
carboxyethylamino, Carboxymethylthio-, 2-Carboxyethylthio , 2-
Carboxyethyloxy-, Carboxymethyloxy-, 2-phosphatoethylamino, 2-thiosulfoethylamino, 3-phosphatopropylamino, 3-thiosulfopropylamino, Chloro, fluoro, 2-Hydroxyethylamino, 3- hydroxypropylamino, 3-carboxy-pyridinyl, 3-Carbamoyl-pyridinyl, piperidino, or morpholino.
Suitable radicals Y include Vinyl, 2-SuIfatoethyl, 2-Chloroethyl, 2-Bromoethyl, 2-acetoxyethyl, 2-Phenoxyethyl, 2-Phosphatoethyl, and 2-Thiosulfatoethyl.
In particular, Y is preferably Vinyl or 2-Sulfatoethyl.
Examples for radicals -D1SO2Y, -D1SO2Y, -D1SO2Y and -D1SO2Y in the formulae (2) and (3) are
4-(2'-Sulfatoethylsulfonyl)phenyl-, 2-Sulfo-4-(2'-Sulfatoethylsulfonyl)phenyl-, 3 -(2 '-Sulfatoethylsulfony l)phenyl-,

2-Sulfo-5-(2'-Sulfatoethylsulfonyl)phenyl-,
2-(2'-Sulfatoethylsulfonyl)phenyl-,
2-methoxy-5-(2'-Sulfatoethylsulfonyl)phenyl-,
2-methoxy-4-(2' -Sulfatoethylsulfonyl)phenyl-,
4-methoxy-3-(2'-Sulfatoethylsulfonyl)phenyl-,
2-Chloro-4-(2'-Sulfatoethylsulfonyl)phenyl-,
2,6-Dichloro-4-(2r-Sulfatoethylsulfonyl)phenyl-,
2-Brom-4-(2'-Sulfatoethylsulfonyl)phenyl-,
2,6-dibromo-4-(2'-Sulfatoethylsulfonyl)phenyl-,
2,5-Dimethoxy-4-(2'-Sulfatoethylsulfonyl)phenyl-,
2-Methoxy-5-methyl-4-(2'-Sulfatoethylsulfonyl)phenyl-,
4-Methyl-5-(2'-Sulfatoethylsulfonyl)phenyl-
2,6-Dimethyl-4-(2'-Sulfatoethylsulfonyl)phenyl-,
Suitable radicals -D1SO2Y and -D1SO2Y are also


In particular, preferred radicals -D1SO2Y and D1SO2Y are 4-(2'-Sulfatoethylsulfonyl) phenyl- and 2-Sulfo-4-(2'-Sulfatoethylsulfonyl) phenyl-.
In particular, preferred radicals -D1SO2Y, and -D1SO2Y are
4-(2 '-Sulfatoethylsulfonyl)phenyl-, 2-Sulfo-4-(2 '-Sulfatoethylsulfonyl)phenyl-, 2-methoxy-5-(2'-Sulfatoethylsulfonyl) phenyl-, and 2-Methoxy-5-methyl-4-(2'-Sulfatoethylsulfonyl) phenyl-.
Preferred radicals of the formula Y02S-D1-N=N-K1-NRa - and -NRb-K2-N=N-D2-SO2Y in dyestuffs of the formula (3) are, independent from each other, radicals of the formula

wherein the reactive group fi-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 dyes of the formula (3) can be symmetrical (K1=K2 and D1=D2) or asymmetrical (KloK2 and/or DK>D2).
Of the dyes of the formula (3) outlined in the present invention, such dyes are especially preferred which contain in each of the radicals D1-NHM-K1 and K2-N=N-D2 at least 1 Sulfo group.
In the dyestuffs of the formula (1) the benzene radicals Bl and B2 include 1,4-Phenylen, 2-SuIfo-l,4-Phenylen, 2-Carboxy-l,4-Phenylen, 2,5-dimethoxy-l,4-Phenylen, 2-Methoxy-5-methyl-l,4-Phenylen 2-Methoxy-l,4-Phenylen, 2-Chloro-1,4-Phenylen, 2-Bromo-l,4-Phenylen, 1,3-Phenylen, 2-Methoxy-l,5-phenylen and 2-Sulfo-l,5-phenylen of which the radicals 1,4-Phenylen, 2-Sulfo-l,4-Phenylen and 2,5-dimethoxy-l,4-Phenylen are especially preferred.
Preferred dyestuffs of the formula (1) are:


Wherein
Y is Vinyl or ß-Sulfatoethyl, and two Y substituents can have identical or different meaning, and
C.I. Reactive Black 5 is especially preferred.
in particular, the dyestuff is of the formula


In the dyestuffs of the formula (2) the radicals Dl' and D2'are preferably a radical of the formula

wherein
Y is Vinyl or ß-Sultatoethyl,
Bl has one of the above meanings as defined under formula(2).
The benzene radical Bl includes 1,4-Phenylen, 2-Sulfo-l,4-Phenylen, 2-Carboxy-1,4-Phenylen, 2,5-dimethoxy-1,4-Phenylen, 2-Methoxy-5-methyl-1,4-Phenylen 2-Methoxy-l,4-Phenylen, 2-Chloro-l,4-Phenylen, 2-Bromo-l,4-Phenylen, 1,3-Phenylen, 2-Methoxy-l,5-phenylen, and 2-Sulfo-l,5-phenylen of which the radicals 1,4-Phenylen and 2-Sulfo-l,4-Phenylen are especially preferred.
Preferred dyes of the formula (2) are:

wherein
The benzene ring B3 carries 0-2 substituents methyl, methoxy or sulfo. The dyestuff of the formula (2a) may be particularly selected from


wherein Rl' is hydrogen Sulfomethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Sulfoethyl and R2'is hydrogen, methyl ormethoxy.
In particular, preferred are dyes of the formula (2a) are

Wherein
Y is Vinyl or ß-Sulfatoethyl and two Y substituents can have identical or different meanings,
Dyestuff of the present invention may contain two dyes of the formula (2), in total 5-20%, and the two dyes being of the formula (2a°) and (2a1), within the range of (2a°): (2a1) of 10:90 to 50:50, and the sum of (2a°) and (2a') being 100%

wherein Rl' is Sulfomethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Sulfoethyl,
Y is Vinyl or ß-Sulfatoethyl, and the benzene ring B3 has one of the above defined meanings.

Of the dyestuffs of the formula (3) the following dyestuffs are preferred:

Preferred dyes of the formula (4-1) are

Preferred dyes of the formula (4-2) are

Preferred dyes of the formula (4-6) are
Preferred dyestuffs of formula (5a) and (5b) are


Preferred binary black dyestuff compositions according to the present invention are compositions containing 60-80% of one dye of the formula (1) and 20-40% of a dyestuff of the formula (3), but not containing any dyestuffs of the formula (2).
Preferred are ternary black dyestuff compositions according to the present
invention, containing 50-85%, especially 62-76%, of a dyestuff of the formula (1), 8-20% of a dyestuff of the formula (2a) and 10-30% of a dyestuff of the

formula (3), and especially preferred are dyestuff compositions wherein Rl' in formula (2a) is 6-Sulfoethyl or B-Carboxyethyl.
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.
The dyestuff mixtures of the present invention can be mixed physically by mixing the respective components as dry powder in a blender, or, by mixing aqueous solutions thereof, or, in case of identical diazo components, by one pot synthesis of coupling the respective diazonium components YO2S-D1-N2+ and/or YO2S-D2-N2+ made from aromatic amines of the formula YO2S-D1-NH2 and/or YO2S-D2-NH2 onto a mixture of the respective coupling components of the formulae.

of the underlying dyestuffs, in the respective ratio of the mixing ration in the dyestuff composition, at conditions which are typically applied for azo coupling reactions, in aqueous medium at a temperature of 0-20°C and a pH range of 1-7.

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 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 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, 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.
Examples of Black mixtures
Example 1: Binary black composition containing 75% Navyblue 1 and 25% Orange 1
An electrolyte containing dye powder containing 75 parts per weight of navy dyeing disazo dyestuff of the formula

Navyblue 1
is mechanically mixed in a blender with an electrolyte containing dye powder containing 25 parts per weight of the orange azo dyestuff of the formula


Orange 1
The resulting dye mixture according to the invention, when employed according to the application and fixation methods customary in the art for fibre reactive dyes, produces for example on cellulose fibre material such as cotton dyeings and prints in deep black shades high colour depth.
The table examples which follow describe further novel binary dyestuff mixtures and can be prepared in a similar way as outlined in the above examples. Percentages are given in % of parts per weight.
Table of binary dyestuff mixtures:

Example no. Dyestuff 1 Dyestuff 2 Shade
2 75% Navyblue 1 25% Yellow 1 Greenish black
3 73% Navyblue 1 27% Yellow 2 Greenish black
4 78% Navyblue 1 22% Yellow 3 Greenish black
5 75% Navyblue 1 25% Yellow 4 Greenish black
6 75% Navyblue 1 25% Yellow 5 Greenish black
7 75% Navyblue 1 25% Yellow 6 Greenish black
8 75% Navyblue 1 25% Yellow 8 Greenish black
9 75% Navyblue 1 25% Yellow 9 Greenish black
10 75%> Navyblue 1 25% Yellow 10 Greenish black
11 75% Navyblue 1 25% Yellow 11 Greenish black
12 75% Navyblue 1 25% Orange 2 Greenish black

Example 13: Black composition containing 65% Navyblue 1, 15% Yellow 3 and 20% Orange 3
An electrolyte containing dye powder containing 65 parts per weight of navy dyeing disazo dyestuff of the formula

is mechanically mixed in a blender with an electrolyte containing dye powder containing 20 parts per weight of the orange disazo dyestuff of the formula

Orange 3
and an electrolyte containing dye powder containing 15 parts per weight of the yellow azo dyestuff of the formula

Yellow 3
The resulting dye mixture according to the invention, when employed according to the application and fixation methods customary in the art for fibre reactive

Yellow 4
in 150 parts per weight of water. The solution is buffered to pH 6-6.5 using a phosphate buffer and spry dried in the usual manner or standardized as a liquid formulation.
The resulting dye mixture according to the invention, when employed according to the application and fixation methods customary in the art for fibre reactive dyes, produces for example on cellulose fibre material such as cotton dyeings and prints.
Example 15: Black composition containing 66% Navyblue 1, 17% Yellow 5 and 17%Redbrown 1
281 parts per weight of 4-(ß-sulfatoethylsulfonyl)aniline is diazotized in 1000 parts ice water and 180 parts 30% aqueous hydrochloric acid with 69 parts per weight of sodium nitrite. After 1h stirring at 0 °C, the suspension of the diazonium salt is charged into a solution containing



dissolved in 2000 parts per weight of water at pH 6 and 0-5 °C. The first coupling is carried out at a pH value of 1-1.5 and a temperature of 0-10 °C. The pH value during coupling is then slowly raised to pH 6.5 by adding small portions of soda ash 20% solution. After the coupling is completed, the reaction mass is spry dried.
A black composition containing 66% Navyblue 1, 17% Yellow 5 and 17% Redbrown 1 is obtained wherein Navyblue 1 and Redbrown 1 are of the above composition and Yellow 5 is of the following structure

Yellow 5
The resulting dye mixture according to the invention, when employed according to the application and fixation methods customary in the art for fibre reactive dyes, produces for example on cellulose fibre material such as cotton dyeings and prints.
The table examples which follow describe further novel ternary dyestuff mixtures and can be prepared in a similar way as outlined in the above examples. Percentages are given in % of parts per weight.

Table of ternary dvestuff ] mixtures:
Example no. Dyestuff 1 Dyestuff 2 Dyestuff 3 Shade
16 70% Navyblue 1 10% Red brown 1 20% Yellow 5 Greenish black
17 57% Navyblue 1 15%Redbrown2 28% Yellow 5 Greenish black
18 70% Navyblue 1 20% Redbrown 2 10% Yellow 5 Reddish black
19 75% Navyblue 1 15%Redbrown3 10% Yellow 5 Reddish black
20 70% Navyblue 1 15% Redbrown 3 15% Yellow 2 Greenish black
21 68% Navyblue 1 12% Rubine 1 20% Yellow 1 Greenish black
22 72% Navyblue 1 8% Rubine 2 20% Yellow 2 Greenish black
23 70% Navyblue 1 10% Rubine 2 20% Yellow 3 Greenish black
24 70% Navyblue 1 20% Rubine 2 10% Yellow 3 Reddish black
25 70% Navyblue 1 20% Rubine 3 10% Yellow 3 Reddish black
26 70% Navyblue 1 15% Rubine 3 15% Yellow 4 neutral black
27 70% Navyblue 1 15% Rubine 4 15% Yellow 4 neutral black
28 70% Navyblue 1 15% Rubine 3 15% Yellow 6 Neutral Black
29 70% Navyblue 1 15% Rubine 3 15% Yellow 7 Neutral Black
30 70% Navyblue 1 15% Rubine 2 15% Yellow 8 Neutral Black
31 70% Navyblue 1 15% Rubine 2 15% Yellow 9 Neutral Black
32 70% Navyblue 1 15% Rubine 1 15% Yellow 10 Neutral Black
33 70% Navyblue 1 15% Rubine 1 15% Yellow 11 Neutral Black
34 65% Navyblue 1 15% Rubine 2 20% Orange 1 Reddish black
35 65% Navyblue 1 17% Rubine 4 18% Orange 2 Reddish black
36 70% Navyblue 1 15% Orange 3 15% Yellow 2 Neutral Black
37 70% Navyblue 1 15% Orange 3 15% Yellow 5 Neutral Black
38 70% Navyblue 1 15% Redbrown 4 15% Yellow 5 Neutral Black
39 70% Green 1 20% Rubine 2 10% Yellow 3 Greenish black
40 70% Green 1 20% Rubine 3 10% Yellow 4 Greenish black
41 70% Green 1 20% Rubine 4 10% Yellow 5 Greenish black
42 58% Navyblue2 20% Rubine 3 22% Yellow 1 Greenish black
43 72% Navyblue2 10% Rubine 4 18% Yellow 1 Greenish black
44 70% Navyblue2 15% Rubine 1 15% Yellow 2 Greenish black
45 70% Navyblue2 15% Rubine 2 15% Yellow 2 Greenish black

The dyestuffs Navybluel, Redbrownl, Orange 1-3, Yellow 1-5 are as defined above.
Redbrown 2
The following additional dyestuffs are used in the table examples

Rubinc 4
Example 46: Black composition of 45% Navyblue 1, 20% Navyblue 2, 20% Yellow 5 and 15% Redbrown 2
An electrolyte containing dye powder containing 45 parts per weight of navy dyeing disazo dyestuff of the formula


Navyblue 1
is mechanically mixed in a blender with an electrolyte containing dye powder containing 20 parts per weight of the greenish navy blue disazo dyestuff of the formula

Navyblue 2
an electrolyte containing dye powder containing 15 parts per weight of the redbrown bis azo dyestuff of the formula

Redbrown 2
and an electrolyte containing dye powder containing 20 parts per weight of the yellow azo dyestuff of the formula


Yellow 5
The resulting dye mixture according to the invention, when employed according to the application and fixation methods customary in the art for fibre reactive dyes, produces for example on cellulose fibre material such as cotton dyeings and prints in deep black shades high colour depth.
The table examples which follow describe further novel ternary dyestuff mixtures and can be prepared in a similar way as outlined in the above examples.
Table of more quaternary dyestuff mixtures

1 Example no. I Dyestuff 1 Dyestuff 2 Dyestuff 3 Dyestuff 4 Shade
47 70% Navyblue 1 5% Orange 3 10%Redbrown 1 15% Yellow 5 Neutral black
48 70% Navyblue 1 5% Orange 3 13% Redbrown 3 12% Yellow 5 Neutral black
49 72% Navyblue 1 6% Orange 3 10% Redbrown 2 12% Yellow 5 Neutral black
50 70% Navyblue 1 6% Orange 3 12% Redbrown 2 12% Yellow 5 Neutral black
51 70% Navyblue 1 5%Rubine 1 10% Rubine 2 15% Yellow 2 Neutral black
52 67% Navyblue 1 5% Rubine 1 13% Rubine 4 15% Yellow 2 Neutral black
53 70% Navyblue 1 5% Rubine 1 10% Rubine 2 15% Yellow 5 Neutral black
54 67% Navyblue 1 5% Rubine 1 13% Rubine 4 15% Yellow 5 Neutral black

55 65% 10% Orange 7 15%Redbrown 10% Yellow 5 Neutral
Navyblue 1 2 black
56 65% 9% Orange 7 15% Red brown 11% Yellow 5 Neutral
Navyblue 1 3 black
57 65% 8% Orange 7 15% Redbrown 12% Yellow 5 Neutral
Navyblue 1 4 black
58 65% Navyblue 1 10% Orange 7 15% Rubine2 10% Yellow 5 Neutral black
59 65% Navyblue 1 10% Orange 7 15%Rubine4 10% Yellow 5 Neutral black
60 66% 7% Orange 8 15% Redbrown 12% Yellow 5 Reddish
Navyblue 1 3 black
61 64% 8% Orange 9 15% Redbrown 13% Yellow 5 Reddish
Navyblue 1 3 black
62 65% Navyblue 1 12% Orange 10 7% Redbrown 1 16% Yellow 3 Neutral black
63 65% Navyblue 1 9% Orange 10 7% Redbrown 2 19% Yellow 4 Neutral black
64 65% Navyblue 1 10% Orange 10 7% Redbrown 3 18% Yellow 5 Neutral black
65 45% 17% Navyblue 3 12% Redbrown 26% Yellow 5 Greenish
Navyblue 1 1 black
66 45% 20% Navyblue 2 15% Redbrown 20% Yellow 5 Greenish
Navyblue 1 2 black
67 34% 33% Navyblue 4 13% Redbrown 20% Yellow 5 Greenish
Navyblue 1 3 black
68 34% 33% Navyblue 13% Redbrown 20% Yellow 1 Greenish
Navyblue 1 2 4 black
69 34% 33% Green 1 13% Redbrown 20% Yellow 2 Greenish
Navyblue 1 4 black
70 34% 33% Navyblue 3 13% Redbrown 20% Yellow 3 Greenish
Navyblue 1 4 black
71 34% 33% Navyblue 4 13% Redbrown 20% Yellow 4 Greenish
Navyblue 1 4 black
72 65% 10% Yellow 12 10% Redbrown 15% Yellow 3 Greenish
Navyblue 1 1 black

73 70% 10% Yellow 12 10% Redbrown 10% Yellow 4 Greenish
Navyblue 1 2 black
74 65% 10% Yellow 13 12% Redbrown 13% Yellow 5 Greenish
Navyblue 1 3 black
75 65% 10% Yellow 13 10% Redbrown 15% Yellow 7 Greenish
Navyblue 1 4 black
76 36% 24% 19% 21% Neutral
Navyblue 2 Navyblue 4 Redbrown3 Yellow 5 black
77 25% 36% 19% 20% Greenish
Green 1 Navyblue 4 Red brown 3 Yellow 5 bJack
The follow wing additional dyestuffs are used in the table examples, the other dyes
are as defj ned above.

Orange 10 Comparative Example 1:
A: 70% of nayblue 1, 15% Orange 9, 15% Rubine 1 (according to WO2004/069937, example 88) in 5% depth of weight of fabric.
B: 68% of nayblue 1, 14% yellow 5, 18% Redbrown 2 (according to this invention, matched to same strength and shade as A as reddish black)
The 60° Wash fastness according to ISO 105-C03 is observed, dyeings are made according to dyeing example 1, and staining on adjacent fibres, especially cotton (CO) and polyamide (NY - nylon) is observed, rated against grey scale. On the assessment scale used, 5 denotes no staining (best rating) and 1 denotes substantial staining (worst rating).


From the above fastness assessment it is obvious that the dyestuff mixture B is superior in washing fastness, exhibiting less staining on adjacent fibres cotton (CO) and polyamide (NY) compared to the dyestuff mixture A. Moreover the undesired reddish staining of A is significantly reduced in B.
Comparative example 2:
C: 70% of nayblue 1, 15% Orange 7, 15% Redbrown 5 (according to WO2000/06652, example 124) in 6% depth of weight of fabric.
D: 68% of nayblue 1, 16% Yellow 5, 16% Redbrown 2 (according to this invention, matched to same strength and shade as C as neutral black)
E: : 68% of nayblue 1, 16% Yellow 5, 16% Redbrown 3 (according to this invention, matched to same strength and shade as C as neutral black)


From the above fastness assessment it is obvious that the dyestuff mixtures D and E are superior in washing fastness, exhibiting less staining on adjacent fibres cotton (CO) and polyamide (NY) compared to the dyestuff mixture C. Moreover the undesired reddish staining of C is significantly reduced in D and E.

Redbrown 5 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 5 parts per weight of the dyestuff composition of example 7. 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 another 45 min. The dyed fabric is then 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.
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, 80 parts per weight of sodium chloride, and 7.5 parts per weight of the dyestuff composition of example8. 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 5 ml of sodium hydroxide solution is added, then dyeing temperature is maintained at 60 °C for another 30 min. The dyed fabric is then rinsed and soaped in the same manner as outlined in dyeing example 1.
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, 100 parts per weight of the dyestuff mixture of composition as in example 9, 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.

We claim
1. Black dyestuff composition comprising dyes selected from
a) 40-90% 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 B1 and B2 in formula (1) may carry independent from each. other 1-2 additional substituents methoxy, methyl, carboxy or sulfa,
Y is Vinyl or CH2CH2L, wherein L is 2 leaving group which is split off under alkaline conditions, such as sulfato, acetate, halogen,, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
b) up to 20% of at least one bisazo redbrown, scarlet or rubinc dyestuff, containing at least two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (2)

wherein

D1'SO2Y and D1'SO2Y are independent from each other a radical of the formula

wherein benzene ring B1 carries 0-2 additional identical of different substituents of Cl-C3-Alkoxy, preferably methoxy, Cl-C3-Alkyl, preferably methyl, Carboxy, haiogen, or hydroxyl,
Y has one of the above defined meanings,
R1' is hydrogen, Sulfomethyl, ß-Sulfoethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Cyanoethyl;
c) 10-40% of at least one yellow or orange dyestuffs, containing two fibre reactive groups of the vinylsulfone type, which have in the form of the free acid the formula (3)

wherein the radicals have the following meaning:
K1 is a radical of the benzene or naphthalene series which is substituted by amino, hydroxy, Acylamino, Ureido, and optionally further substituted by 1 or 2 Sulfo groups, and optionally substituted by C1-C3-Alkoxy, C1-C3 Alkyl, Halogen, Nitro, or Carboxy.

K2 has independent from the meaning of K1 one of the meanings of K1, providing that at least one of the radicals K1 or K2 is a radical of the benzene series,
X is chloro, fluoro, pyridinyl which may be substituted by Carboxy or Carbamoyl, -NHCN, -NHR, -N(CH3) R, -O- R , or -S- R wherein R is Cl-C6-Alkyl which is substituted by at least one sulfo, sulfato, phosphate, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or the radical of a Cl-C6-primary or secondary aliphatic or C5-C6- cycloaliphatic amine which may be interrupted by heteroatoms 0, NH or S, or a heterocyclic radical of the formula

wherein W has one of the meanings of R,
Ra is Hydrogen or C1-C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,
Rbhas each independent from the meaning of Ra one of the meanings of Ra
Y has one of the above defined meanings,
D1 is a benzene radical of the formula (3 a)

wherein
Rc is methoxy, methyl, chloro or bromo,
n is 0,1 or 2, and m is 0 or 1, and

in case of n=2 the substituents Rc may have identical or different meanings, D2 has independent from the meaning of D1, one of the meanings of D1.
2. Black dyestuff composition as claimed in claim 1, wherein Y is Vinyl or B-Sulfatoethyl
3. Black dyestuff composition as claimed in claim 1 - 2, wherein at least one of the dyes of the formula (1) is a dyestuff of the formula

wherein
4. Black dyestuff composition as claimed in claims 1-3, wherein K1-NRa- in the formula (3) is a radical of the formula (3b-1), (3b-2) and (3b-3) of the benzene or series or a radical of the naphthalene series (3b-4),


Ro is hydrogen or methyl,
R1 is hydrogen, Methyl, or Ethyl,
R2 is amino or methyl,
r is 0-1,
and K2-NRb has one of the meanings of (3b-l), (3b-2) or (3b-3) wherein the radicals Ro, R1, R2 and r have one of the above meanings.
5. Black dyestuff composition as claimed in claim 4 wherein K1-NRa- and K2-NRb in formula (3) are both radicals of the formula (3b-l) of one of the following radicals

6. Black dyestuff composition as claimed in claim 1 wherein the radical X is chloro, fluoro, Cyanamino, Sulfoethylamino, N-Methyl- ß-Sulfoethylamino, morpholino, or is a radical of the formula

7. Black dyestuff composition as claimed in claims 1-6 containing at least one dyestuff of the formula (3) of any of the formula


wherein X is Cyanamino, ß-Sulfoethylamino, or N-Methyl- ß-Sulfoethylamino.
8. Black dyestuff composition as claimed in claims 1-7 containing at least one dyestuff of the formula (2), of the formula


wherein
Y is ß-Sulfatoethylsulfonyl or Vinylsulfonyl,
the benzene ring B3 carries 0-2 substituents methyl, methoxy or sulfo,
R1'is hydrogen, Sulfomethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Sulfoethyl
9. Black dyestuff composition as claimed in claim 8 wherein formula (2) is

wherein R1' is hydrogen Sulfomethyl, Carboxymethyl, B-Carboxyethyl, or ß-Sulfoethyl
10. Black dyestuff composition as claimed in claim 8 wherein formula (2) is


wherein R1' is hydrogen, Sulfomethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Sulfoethyl, and R2'is hydrogen, methyl or methoxy.
11. Black dyestuff composition as claimed in claims 9 and 10, wherein R1' is ß-Carboxyethyl or ß-Sulfoethyl, and R2'is hydrogen.
12. Black dyestuff composition as claimed in claims 8-11 containing two dyes of the formula (2), in total 5-20%, and the two dyes being of the formula (2a°) and (2a1), within the range of (2a°) : (2a1) of 10:90 to 50:50, and the sum of (2a°) and (2a1) being 100%


wherein R1' is Sulfomethyl, Carboxymethyl, ß-Carboxyethyl, or ß-Sulfoethyl,
Y is Vinyl or ß-Sulfatoethyl, and the benzene ring B3 has one of the above defined meanings.
13. Black dyestuff composition as claimed in claims 1-7, containing 60-80% of a dyestuff of the formula (1), 20-40% of a dyestuff of the formula (3), but not containing any dyes of the formula (2).
14. Black dyestuff composition as claimed in claims 1-12, containing 50-85% of a dyestuff of the formula (1), 8-20% of a dyestuff of the formula (2) and 10-30% of at least one dye of the formula (3).
15. Black dyestuff composition as claimed in claims 13-14 wherein the black composition contains up to 20% an additional yellow or orange dyestuff of at least one dye of the formula (4-1), (4-2), (4-3), (4-4), (4-5) or (4-6) providing that the total amount of yellow and orange dyestuffs according to the sum of the components of formula (3) and (4-1) to (4-6) is not exceeding 40%.


16. Black dyestuff composition as claimed in claim 15 containing the bisazo dyestuff of the formula


17. Black dyestuff composition as claimed in claim 15 containing at least one trisazo dye of the formula (4-2) of the formula

18. A process for preparing the black dyestuff composition as claimed in any one of the claims 1-17 by mechanically mixing the individual dyes in the required proportions, or by synthesizing the dyes by diazotation and coupling reactions in one bath using mixtures for diazo and coupling components.
19. A process for using the black dyestuff compositions as claimed in any one of the claims 1-17 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.