WO2013021352A2

WO2013021352A2 - Black mixtures of fibre reactive azo reactive dyestuffs

Info

Publication number: WO2013021352A2
Application number: PCT/IB2012/054036
Authority: WO
Inventors: Christian Schumacher; Pankaj Desai; Ashit VASHI
Original assignee: Colourtex Industries Pvt Ltd
Current assignee: Colourtex Industries Pvt Ltd
Priority date: 2011-08-10
Filing date: 2012-08-08
Publication date: 2013-02-14
Anticipated expiration: 2014-02-10
Also published as: WO2013021352A3; IN2014MN00383A

Abstract

The present invention relates to black reactive dyestuff mixtures, containing navy blue dyestuffs of the formula (1), yellow or orange dyestuffs of the formula (3), optionally further dyestuffs of the formula (2), optionally further yellow/orange dyestuffs of the formula (4-1) to (4-6) and optionally further dyestuffs of formula (5). The black mixtures are suitable for coloration of fibre material, in particular for dyeing and printing of cellulose, polyamide or protein fibre materials or blends thereof, and produce dyeing and prints having good all- round fastness properties, especially wash and contact fastness, and excellent build up for deep black shades.

Description

BLACK MIXTURES OF FIBRE REACTIVE AZO REACTIVE DYESTUFFS

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 B1 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 sulfato, 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)

^' S0₂Y

(2)

DrS0₂Y and D₂ ^'S0₂Y are independent from each other a radical of the formula

wherein benzene ring Bi carries 0-2 additional identical of different substituents of C1 - C3-Alkoxy, preferably methoxy, C1 -C3-Alkyl, preferably methyl, Carboxy, halogen, or hydroxyl,

Y has one of the above defined meanings,

FV is hydrogen, Sulfomethyl, β-Sulfoethyl, Carboxymethyl, β-Carboxyethyl, or β- 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:

K- 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 K- one of the meanings of K_{1 ;} 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 C1 -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 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, R_a is Hydrogen or C1 -C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,

R_b has each independent from the meaning of R_a one of the meanings of R_a

Y has one of the above defined meanings,

D- is a benzene radical of the formula (3a)

wherein

R_c 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 R_c may have identical or different meanings, D2 has independent from the meaning of D1 , one of the meanings of D1 .

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 showing fastness assessment of dyestuff mixtures A and B Figure 2 showing fastness assessment of the dyestuff mixtures C,D and E

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

B1 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 β-Sulfatoethyl,

Further B1 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)

(2) wherein

DrS0₂Y and D₂ ^'S0₂Y are independent from each other radicals of the formula

wherein

Benzene ring

carries 0-2 additional identical of different substituents of C1 -C3-Alkoxy, preferably methoxy, C1 -C3-Alkyl, preferably methyl, Carboxy, halogen, or hydroxyl,

Y has one of the above defined meanings, preferably Vinyl, or β-sulfatoethyl,

Ui is hydroxyl or has one of the meanings of Y, preferably Ui is hydroxyl, vinyl or β- sulfatoethyl,

FV is hydrogen, Sulfomethylen, β-Sulfoethylen, Carboxymethyl, β-Carboxyethyl, or β- Cyanoethyl; c) 1 0-40%, 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)

wherein the radicals have the following meaning: 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 one of the meanings of K_{1 ;} providing that at least one of the radicals K1 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 C1 -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 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 β-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

R_a is Hydrogen or C1 -C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo, preferably Hydrogen or Methyl,

R_b has each independent from the meaning of R_a one of the meanings of R_a, preferably hydrogen or methyl,

Y has one of the above defined meanings, preferably is Vinyl, or β-sulfatoethyl,

D is a benzene radical of the formula (3a) which may be non substituted or substituted by one or more substituents sulfo, C1 -C4-alkyl, C1 -C4-alkoxy, halogen, or nitro,

Wherein R_c 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 R_c may have identical or different meanings,

D2 has independent from the meaning of D1 , one of the meanings of D1 .

K NR_a- is preferably 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),

(3b-1 ) (3b-2)

Wherein

Ro is hydrogen or methyl, preferably hydrogen

Ri is hydrogen, Methyl, or Ethyl, preferably hydrogen,

R₂ is amino or methyl, r is 0-1 .

Preferably K₂-NR_b has one of the meanings of (3b-1 ), (3b-2) or (3b-3) wherein the radicals R₀, Ri, R2 and r have one of the above meanings.

In particular, the radicals (3b-1 ) are especially preferred meanings for KiNR_a and K₂NR_b. 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-D NH₂ and YO2S-D2NH2, whereas the radicals -K1 NR_a- and K2NHR_b- 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%.

(4-3)

(4-5)

In the formula (4-1 ) thru (4-6) the radicals have the following meaning: Q is hydrogen or carboxy, Ac is C1 -C3-Acyl, preferably Acetyl, dichlorotriazinyl or a monohalogen triazinyl ring which is substituted by phenylamino carrying 1 -2 sulfo groups and 0-1 substituents S0₂Y 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 β-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,

(5b)

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 β-Sulfatoethyl.

In formula (3), preferably the radical (3b-1 ) is one of the following radicals

Preferably formula (3b-2) is the following radical

Preferably formula (3b-3) 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-Sulfatoethyl, 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 -DiS0₂Y, -D₂S0₂Y, -Di ^'S0₂Y and -D₂ S0₂Y in the formulae (2) and (3) are 4-(2^'-Sulfatoethylsulfonyl)phenyl-,

2- Sulfo-4-(2^'-Sulfatoethylsulfonyl)phenyl-,

3- (2^'-Sulfatoet ylsulfonyl)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)p enyl-,

2,6-Dichloro-4-(2^'-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-met yl-4-(2^'-Sulfatoethylsulfonyl)phenyl-, 4-Methyl-5-(2^'-Sulfatoethylsulfonyl)phenyl-

2.6- Dimethyl-4-(2^'-Sulfatoethylsulfonyl)phenyl-,

Suitable radicals -Di ^'S0₂Y and -D₂ ^'S0₂Y are also

In particular, preferred radicals -D₁S0₂Y and -D₁ ^'S0₂Y are 4-(2^'-Sulfatoethylsulfonyl) phenyl- and 2-Sulfo-4-(2^'-Sulfatoethylsulfonyl) phenyl-.

In particular, preferred radicals -D₂S0₂Y, and -D₂ S0₂Y 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

- and -NR_b-K₂-N=N-D₂-S0₂Y in dyestuffs of the formula (3) are, independent from each other, radicals of the formula

wherein the reactive group β-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 (K1 oK2 and/or D1 oD2).

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 -N=N-K1 and K2-N=N-D2 at least 1 Sulfo group.

In the dyestuffs of the formula (1 ) the benzene radicals B1 and B2 include 1 ,4-Phenylen, 2-Sulfo-1 ,4-Phenylen, 2-Carboxy-1 ,4-Phenylen, 2, 5-dimethoxy-1 ,4-Phenylen, 2-Methoxy- 5-methyl-1 ,4-Phenylen 2-Methoxy-1 ,4-Phenylen, 2-Chloro-1 ,4-Phenylen, 2-Bromo-1 ,4- Phenylen, 1 ,3-Phenylen, 2-Methoxy-1 ,5-phenylen and 2-Sulfo-1 ,5-phenylen of which the radicals 1 ,4-Phenylen, 2-Sulfo-1 ,4-Phenylen and 2, 5-dimethoxy-1 ,4-Phenylen are especially preferred. Preferred dyestuffs of the formula (1 ) are:

Wherein

Y is Vinyl or β-Sulfatoethyl, and two Y substituents can have identical or different meaning, and in particular, the dyestuff is of the formula

C. I. Reactive Black 5 is especially preferred. In the dyestuffs of the formula (2) the radicals D1 ^' and D2^'are preferably a radical of the formula

wherein

Y is Vinyl or β-Sultatoethyl,

B1 has one of the above meanings as defined under formula(2).

The benzene radical B1 includes 1 ,4-Phenylen, 2-Sulfo-1 ,4-Phenylen, 2-Carboxy-1 ,4- Phenylen, 2, 5-dimethoxy-1 ,4-Phenylen, 2-Methoxy-5-methyl-1 ,4-Phenylen 2-Methoxy-1 ,4- Phenylen, 2-Chloro-1 ,4-Phenylen, 2-Bromo-1 ,4-Phenylen, 1 ,3-Phenylen, 2-Methoxy-1 ,5- phenylen, and 2-Sulfo-1 ,5-phenylen of which the radicals 1 ,4-Phenylen and 2-Sulfo-1 ,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 R1 ^' is hydrogen Sulfomethyl, Carboxymethyl, β-Carboxyethyl, or β-Sulfoethyl and R2^'is hydrogen, methyl or methoxy.

21

Wherein

Y is Vinyl or β-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 (2a¹) being 100%

wherein R1 ^' is Sulfomethyl, Carboxymethyl, β-Carboxyethyl, or β-Sulfoethyl,

Y is Vinyl or β-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 (4-3) are

Preferred dyes of the formula (4-4) are

Preferred dyes of the formula (4-5) 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 R1 ^' in formula (2a) is β-Sulfoethyl or β- 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 Y0₂S-DrN₂ ⁺ and/or Y0₂S-D₂-N₂ ⁺ made from aromatic amines of the formula Y0₂S-D NH₂ and/or Y0₂S-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^ 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 1 1 %, 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 9-1 1 , 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 contai 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:

1 8 black

75% Navyblue 25% Yellow Greenish 1 9 black

75% Navyblue 25% Yellow Greenish 1 10 black

75% Navyblue 25% Yellow Greenish 1 1 1 black

75% Navyblue 25% Orange Greenish 1 2 black

Yellow 3

Yellow 4

Yellow 5

Yellow 7

Yellow 11

Orange 2

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

Navyblue 1

is mechanically mixed in a blender with an electrolyte containing dye powder contai 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

Example 14: Black composition containing 67% Navyblue 1 , 18% Yellow 4 and 15% Redbrown 1

To an electrolyte containing dye solution containing 800 party per weight of water, 67 parts per weight of navy dyeing disazo dyestuff of the formula

Navyblue 1

is added a solution of 15 parts per weight of the redbrown disazo dyestuff of the formula

Redbrown 1

in 200 parts per weight of water, and 18 parts per weight of the yellow azo dyestuff of the formula

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-(B-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 1 h stirring at 0 °C, the suspension of the diazonium salt is charged into a solution containing

84.1 parts per weight of

52.9 parts per weight of

and 213 parts per weight of 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 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 dyestuff mixtures:

Navyblue 1 Redbrown 2 5 black

70% 20% 10% Yellow Reddish

Navyblue 1 Redbrown 2 5 black

75% 15% 10% Yellow Reddish

Navyblue 1 Redbrown 3 5 black

70% 15% 15% Yellow Greenish

Navyblue 1 Redbrown 3 2 black

68% 12% Rubine 1 20% Yellow Greenish

Navyblue 1 1 black

72% 8% Rubine 2 20% Yellow Greenish

Navyblue 1 2 black

70% 10% Rubine 2 20% Yellow Greenish

Navyblue 1 3 black

70% 20% Rubine 2 10% Yellow Reddish

Navyblue 1 3 black

70% 20% Rubine 3 10% Yellow Reddish

Navyblue 1 3 black

70% 15% Rubine 3 15% Yellow neutral black

Navyblue 1 4

70% 15% Rubine 4 15% Yellow neutral black

Navyblue 1 4

70% 15% Rubine 3 15% Yellow Neutral

Navyblue 1 6 Black

70% 15% Rubine 3 15% Neutral

Navyblue 1 Yellow 7 Black

70% 15% Rubine 2 15% Yellow Neutral

Navyblue 1 8 Black

70% 15% Rubine 2 15% Yellow Neutral

Navyblue 1 9 Black

70% 15% Rubine 1 15% Yellow Neutral

Navyblue 1 10 Black

70% 15% Rubine 1 15% Yellow Neutral Navyblue 1 1 1 Black

34 65% 15% Rubine 2 20% Reddish

Navyblue 1 Orange 1 black

35 65% 17% Rubine 4 18% Reddish

Navyblue 1 Orange 2 black

36 70% 15% Orange 3 15% Yellow Neutral

Navyblue 1 2 Black

37 70% 15% Orange 3 15% Yellow Neutral

Navyblue 1 5 Black

38 70% 15% 15% Yellow Neutral

Navyblue 1 Redbrown 4 5 Black

39 70% Green 1 20% Rubine 2 10% Yellow Greenish

3 black

40 70% Green 1 20% Rubine 3 10% Yellow Greenish

4 black

41 70% Green 1 20% Rubine 4 10% Yellow Greenish

5 black

42 58% 20% Rubine 3 22% Yellow Greenish

Navyblue2 1 black

43 72% 10% Rubine 4 18% Yellow Greenish

Navyblue2 1 black

44 70% 15% Rubine 1 15% Yellow Greenish

Navyblue2 2 black

45 70% 15% Rubine 2 15% Yellow Greenish

Navyblue2 2 black

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

Greenl

Red brown 2

Red brown 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

HC SO

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

Navyblue 1 4 Yellow 5 black 1

65% 10% Orange 15% 10% Neutral

Navyblue 7 Redbrown 2 Yellow 5 black 1

65% 9% Orange 15% 1 1 % Neutral

Navyblue 7 Redbrown 3 Yellow 5 black 1

65% 8% Orange 15% 12% Neutral

Navyblue 7 Redbrown 4 Yellow 5 black 1

65% 10% Orange 15% Rubine 10% Neutral

Navyblue 7 2 Yellow 5 black 1

65% 10% Orange 15% Rubine 10% Neutral

Navyblue 7 4 Yellow 5 black 1

66% 7% Orange 15% 12% Reddish

Navyblue 8 Redbrown 3 Yellow 5 black 1

64% 8% Orange 15% 13% Reddish

Navyblue 9 Redbrown 3 Yellow 5 black 1

65% 12% Orange 7% 16% Neutral

Navyblue 10 Redbrown 1 Yellow 3 black 1

65% 9% Orange 7% 19% Neutral

Navyblue 10 Redbrown 2 Yellow 4 black 1

65% 10% Orange 7% 18% Neutral

Navyblue 10 Redbrown 3 Yellow 5 black 1 45% 17% 12% 26% Greenish

Navyblue Navyblue 3 Redbrown 1 Yellow 5 black 1

45% 20% 15% 20% Greenish

Navyblue Navyblue 2 Redbrown 2 Yellow 5 black 1

34% 33% 13% 20% Greenish

Navyblue Navyblue 4 Redbrown 3 Yellow 5 black 1

34% 33% 13% 20% Greenish

Navyblue Navyblue 2 Redbrown 4 Yellow 1 black 1

34% 33% Green 13% 20% Greenish

Navyblue 1 Redbrown 4 Yellow 2 black 1

34% 33% 13% 20% Greenish

Navyblue Navyblue 3 Redbrown 4 Yellow 3 black 1

34% 33% 13% 20% Greenish

Navyblue Navyblue 4 Redbrown 4 Yellow 4 black 1

65% 10% Yellow 10% 15% Greenish

Navyblue 12 Redbrown 1 Yellow 3 black 1

70% 10% Yellow 10% 10% Greenish

Navyblue 12 Redbrown 2 Yellow 4 black 1

65% 10% Yellow 12% 13% Greenish

Navyblue 13 Redbrown 3 Yellow 5 black 1

65% 10% Yellow 10% 15% Greenish

Navyblue 13 Redbrown 4 Yellow 7 black 1

76 36% 24% 19% 21 % Neutral

Navyblue Navyblue 4 Redbrown3 Yellow 5 black

2

77 25% 36% 19% 20% Greenish

Green 1 Navyblue 4 Redbrown3 Yellow 5 black

The following additional dyestuffs are used in the table examples, the other dyes are as defined above.

Navyblue

Navyblue 4

SO3H

Yellow 12

Orange 7

Orange 8

Orange 9

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 Figure 1 showing 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 Figure 2 showing 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 .

Claims

CLAIMS:

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

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, b) up to 20% of at least one bisazo 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

Di ^'S0₂Y and D₂ ^'S0₂Y are independent from each other a radical of the formula

Y has one of the above defined meanings,

K₂ has independent from the meaning of

one of the meanings of K_{1 ;} 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 C1 -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 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 N— W wherein W has one of the meanings of R,

R_a is Hydrogen or C1 -C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,

R_b has each independent from the meaning of R_a one of the meanings of R_a

Y has one of the above defined meanings,

D- is a benzene radical of the formula (3a)

wherein

2. Black dyestuff composition according to claim 1 , wherein Y is Vinyl or β-Sulfatoethyl

3. Black dyestuff composition according to claim 1 - 2, wherein at least one of the dyes of the formula (1 ) is a dyestuff of the formula

4. Black dyestuff composition according to claims 1 -3, wherein K NR_a- 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),

wherein

R₀ is hydrogen or methyl, Ri is hydrogen, Methyl, or Ethyl, R₂ is amino or methyl, r is 0-1 , and K₂-NR_b has one of the meanings of (3b-1 ), (3b-2) or (3b-3) wherein the radicals R₀, Ri , R₂ and r have one of the above meanings.

5. Black dyestuff composition according to claim 4 wherein K NR_a- and K₂-NR_b in formula (3) are both radicals of the formula (3b-1 ) of one of the following radicals

6. Black dyestuff composition according to claim 1 wherein the radical X is chloro, fluoro, Cyanamino, Sulfoethylamino, N-Methyl- β-Sulfoethylamino, morpholino, or is a radical of the formula

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

wherein X is Cyanamino, β-Sulfoethylamino, or N-Methyl- β-Sulfoethylamino.

8. Black dyestuff composition according to claims 1 -7 containing at least one dyestuff of the formula (2), of the formula

wherein

Y is β-Sulfatoethylsulfonyl or Vinylsulfonyl,

the benzene ring B3 carries 0-2 substituents methyl, methoxy or sulfo,

FM ^'is hydrogen, Sulfomethyl, Carboxymethyl, β-Carboxyethyl, or β-Sulfoethyl

9. Black dyestuff composition according to claim 8 wherein formula (2) is

wherein R1 ^' is hydrogen Sulfomethyl, Carboxymethyl, β-Carboxyethyl, or β-Sulfoethyl

10. Black dyestuff composition according to claim 8 wherein formula (2) is

wherein R1 ^' is hydrogen, Sulfomethyl, Carboxymethyl, β-Carboxyethyl, or β-Sulfoethyl, and R2^'is hydrogen, methyl or methoxy.

1 1 . Black dyestuff composition according to claims 9 and 10, wherein R1 ^' is β- Carboxyethyl or β-Sulfoethyl, and R2^'is hydrogen.

12. Black dyestuff composition according to claims 8-1 1 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, β-Carboxyethyl, or β-Sulfoethyl,

Y is Vinyl or β-Sulfatoethyl, and the benzene ring B3 has one of the above defined meanings.

13. Black dyestuff composition according to 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 according to 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 according to 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%.