F0RM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
Title of the invention - "NEW TRISAZO REACTIVE DYES AND DYESTUFF
MIXTURES"
(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 INVENTION
The present invention relates to compounds of the formula (1)
Formula (1) The present invention further relates to a process for the preparation of the compounds of the formula (1) as well as mixtures of formula (1) with formula (2) and optionally comprising further dyestuffs for shading.
BACKGROUND OF THE INVENTION
The presently known state of the art dyes of Fibre reactive dyes for orange and brown shades are trisazo reactive dyes which have been published in EP 785237 which describes reactive dyes of the formula
wherein D and Dl contain fibre reactive groups of the vinylsulfone type.
These dyestuffs mostly contain a chlorotriazinyl group in the radical M, and the radical D-N=N— is positioned between the amino groups,
The patent CH 695613 describes black mixtures including trisazo dyes of the formula

wherein either Rl or R2 contains a vinyl sulfone fibre reactive group, however,
contain in total only 1 fibre reactive group.
The patent WO2003/033599 describe dyestuffs of the formula
Wherein Y contains a vinyl sulfone fibre reactive group, and include trisazo dyestuffs, for example the dyestuff of the formula
Trisazo dyes, mostly direct dyes, are disclosed in the patents US6028179, US2259735, US3941560, GB1508041, EP0191126, GB465281A, GB513233, GB482192, GB482240, US2220397, US2259734, US2259736, and US4128497.
The known reactive dyestuffs have certain technical disadvantages, such as poor fixation yields, limited build-up, limited wash and contact fastness, especially with regard to staining on adjacent fibres such as cotton, viscose, wool, polyester or nylon, limited fastness to light and oxidation agents, and limited solubility in high concentrations.
There is a need for novel dyes with better build-up and higher fixation yields on cellulose containing textile fibres, in particular cotton and regenerated cellulose fibres, and improved technical properties, especially related to colour fastnesses,

in particular wash fastnesses, contact fastnesses, perspiration fastness, light and chlorine fastnesses, robust dyeing performance even in varying dyeing conditions and high solubility in dyeing applications such as exhaust or continuous dyeing, in order to achieve economical dyeing of high quality.
OBJECT OF INVENTION
It is an object of the present invention to provide dyestuffs with higher fixation yields, superior build-up, and improved dyeing and fastness properties, based on trisazo reactive dyestuffs of the formula (1).
It is another object of the present invention to provide trisazo dyes of the formula (1) which can be applied as single dye or as mixture, or in combination with other compatible dyestuffs, preferably applied in dichromatic or trichromatic combinations, or in black mixtures, to achieve very deep shades and excellent fastness properties.
It is yet another object of the present invention to provide a process for the preparation of trisazo dyes of the formula (1).
SUMMARY OF INVENTION
(1) wherein R1 is hydrogen, Cl-C3-alkyl, halogen, carboxy or sulfo;
According to an aspect of the present invention there is provided new fibre reactive trisazo dyestuffs of the formula (1)


K is a radical of the formulae
wherein
Qi is hydrogen, carboxy, sulfo, NHCONHR2, NHCOR2, NHR2, C1-C3-alkyl,
halogen, methoxy or hydroxy;
wherein R2 is hydrogen or C1-C3-alkyl;
Q2 is hydrogen, methyl, methoxy or sulfo;
the benzene rings A may optionally contain 1-2 substituents of sulfo, methyl,
methoxy, cyano or nitro, preferably sulfo;
the benzene rings B, independent from benzene ring A, may optionally contain 1-
2 substituents of sulfo, methyl, methoxy, cyano or nitro, preferably sulfo;
Y is vinyl, 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 two Y substituents can have identical or different meanings.
According to yet another aspect, the present invention provides mixtures of trisazo dyestuffs of formula (1) with bisazo dyes of the formula (2).
wnerein
Bl and B2 are benzene ring radical having the substituent -SO2Y,

wherein Y is Vinyl or CH2CH2L, wherein L is a leaving groups as defined above;
and
Bl and B2, independent of each other, may be further optionally substituted by
additional substituents such as methoxy, methyl, carboxy or sulfo;
And optionally the black mixtures may contain additional Yellow, Orange. Red,
Rubine or carmine coloured dyes.
According to yet another aspect, the present invention provides process for the preparation of trisazo dyes of formula (1) comprising the following steps
a. Coupling an aromatic amine carrying a SO2Y radical in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling onto a diaminobenzene derivative in aqueous medium at a pH of 1-7 and a temperature of 0-20 °C to give monoazo dye of formula (3) which is schematically represented as below
Formula (3) b. Coupling diazotized 4-azoarylamino monoazo dyestuff of formula (4) with monoazo dye of formula (3) in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling in aqueous medium at a pH of 1-8, preferably 5-7.5 and a temperature of 0-20 °C to yield new trisazo dyestuffs of the formula (1) which is schematically represented as below

DESCRIPTION OF THE INVENTION
The present invention provides new fibre reactive trisazo dyestuffs of the formula (1)


(1)

vherein
K is a radical of the formulae
wherein
Q, is hydrogen, carboxy, sulfo, NHCONHR2, NHCOR2) NHR2, C1-C3-alkyl,
halogen, methoxy or hydroxy;
wherein R2 is hydrogen or C1-C3-alkyl;
Q2 is hydrogen, methyl, methoxy or sulfo;
Ri is hydrogen, Cl-C3-alkyl, halogen, carboxy or sulfo;

the benzene rings A may optionally contain 1-2 substituents of sulfo, methyl,
methoxy, cyano or nitro, preferably sulfo;
the benzene rings B, independent from benzene ring A, may optionally contain 1-
2 substituents of sulfo, methyl, methoxy, cyano or nitro, preferably sulfo;
Y is vinyl, CH2CH2L , wherein L is a leaving group which is split off under
alkaline conditions, is a leaving group such as sulfato, acetato, halogen, such as
chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
and two Y substituents can have identical or different meanings, and preferably Y
is vinyl, β-chloroethylsulfonyl or β-sulfatoethylsulfonyl.
The new dyes of the present invention have excellent colour strength, good dyeing
performance, excellent build-up and high colour fastnesses.
Preferably R1 is hydrogen, methyl, chloro, carboxy or sulfo, and preferably R1 is
in ortho and para position to the amino groups.
Preferably at least one of the benzene rings A or B preferably contains a sulfo
substituent.
Preferred structures of the formula (1) are structures of the formulae (la), (lb),
(lc),(ld),or(le).

(le)
Wherein,
Q1 is carboxy, sulfo, NHCONH2, NHCOCH3, methyl, methoxy or chloro,
Q2 is hydrogen;
the benzene rings A and B contain each 0-2 sulfo groups, preferably combined at
least 1 sulfo group, and further the benzene rings A and B may additionally
contain each 1-2 methoxy and 1 methyl groups;
Y is vinyl or β-sulfatoethylsulfonyl.
When the radical K in structures of the formula (1) represents a radical of the
formula

for examples the following structures are included,
In particular, the following radicals are preferred for the radical K in structures of the formula (1)

Preferably, radicals of the formula
are, independent from each other, one of the following radicals
wherein Yl is vinyl or β-sulfatoethylsuIfonyl,
and especially preferred they are one of the following radicals
wherein Yl is vinyl or β-sulfatoethylsulfonyl.
The invention also covers black mixtures of the trisazo dyestuffs of formula (1) with bisazo dyes of the formula (2) providing that the ratio of the mixing components (1): (2) is in the range 10:90 to 45:55.

wherein
Bl and B2 are benzene ring radical having the substituent -SO2Y,
wherein Y is Vinyl or CH2CH2L, wherein L is a leaving groups as defined above;
and
Bl and B2, independent of each other, may be further optionally substituted by
additional substituents such as methoxy, methyl, carboxy or sulfo.
In particular, the dyestuff of the formula (2) is preferably
OS03H
One of the advantages of the dyestuff composition of the present invention is that
they provide neutral blacks even in binary mixtures, whereas most other known
binary compositions are either very weak in colour strength or they are very
greenish (when orange or yellow is applied in combination) or reddish (when
carmine or rubine is applied in combination) and require ternary mixtures to
achieve neutral black shades.
The black compositions of the present invention can be conveniently shaded while
adding further dyestuffs.
The invention also covers black mixtures of the trisazo dyestuffs of formula (1)
with bisazo dyes of the formula (2) and optionally containing additional shading
components such as yellow (formula(2a)), orange (formula(2b)), red, rubine or
carmine coloured dyes of (formula (2c)).
Suitable shading components are typical fibre reactive dyes, such as monoazo,
bisazo or trisazo yellow dyestuffs (2a) and orange dyestuffs (2b)

rY"
HQjSv ^ >50,H
Hjtr' V^

O"^^

H

SOA Orange (2b)
wherein Y has one of the above meanings.
Further suitable shading dyes are red, rubine or carmine bisazo dyestuffs of the formulae (2 c)


Y02S

S02Y
(2c)
wherein Y has one of the above meanings, the benzene ring B3 contains
optionally further methyl and methoxy substituents and Rl' is hydrogen,
sulfomethyl, β-sulfoethyl or β-carboxyethyl, and depending on the substitution
pattern the dyes are of red, carmine or rubine colour.
In particular, (2a) is preferably a dyestuff of the formula

Yellow
In particular, (2b) is preferably a dyestuff of the formula

In particular, (2c) is a dyestuff of the formulae


Carmine 3

OSO3H
Rubine 1
Shading dyestuffs may be contained in amounts of 0.1 to 15% of dyestuff composition.
The invention also includes a process for manufacturing the dyes of the formula (1) by diazotization and coupling reactions according to the process route, by first preparing a monoazo dye of the formula (3) by diazotization and coupling reaction followed by further coupling with formula (4) to yield the new dyestuffs of the formula (1).
The process steps for the preparation of trisazo dyes of formula (1) comprises the
steps of
a. Coupling an aromatic amine carrying a SO2Y radical in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling onto a diaminobenzene derivative in aqueous medium at a pH of

1-7 and a temperature of 0-20 °C to give monoazo dye of formula (3) which is schematically represented as below
NH2 R1
Formula (3) b. Coupling diazotized 4-azoarylamino monoazo dyestuff of formula (4) with monoazo dye of formula (3) in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling in aqueous medium at a pH of 1-8, preferably 5-7.5 and a temperature of 0-20 °C to yield new trisazo dyestuffs of the formula (1) which is schematically represented as below

(1)
In particular, the inventive dyestuffs of the formula (1) wherein K is a phenyl radical which is substituted by QI and Q2 and the amino groups in the double coupled component are in meta positions, which are dyestuffs of the formula (1'),

are synthesized by the following reaction sequence:
First the compound (3') is prepared by coupling a 1,3-diaminobenzene derivative in 4-position with an aromatic diazonium salt carrying a SO2Y radical, which has been prepared from the respective aromatic amine by using nitrous acid or alkali nitrite salt and a strong acid, such as sulfuric acid or hydrochloric acid at temperatures of 0-15°. Then azo coupling is carried out in aqueous medium at a pH of 1-8, preferably 5-7.5 and a temperature of 0-20 °C to yield compounds of the structure (3').
Subsequently (3') is used as coupling component for a second coupling reaction with a diazotized 4-azoarylamino monoazo dyestuff of formula (4') diazotized in the same manner as described above for (4), and coupled, in aqueous medium at a pH of 1-8. preferably 5-7,5 and a temperature of 0-20 °C according to the scheme to yield the new dyestuffs of the formula (1').

This route is applied, for example, for the preferred dyestuffs of the formulae (la). (lb), (lc) and (Id).

Likewise, the inventive dyestuffs of the formulae (1) wherein K is a naphtyl
radical, of the formula (1")
/=\ H2N\^V/NH2
Y02S^Xw> -N=N^T/ Jl N
R1 f B V-S02Y
VL) \=y
S03H
(1")
are prepared in the following manner by diazotization and coupling reactions by first preparing a monoazo dye of the formula (3') by diazotization and coupling reaction in the same manner as described above, which is subsequently used as coupling component for a second coupling reaction with a diazotized 4-azonapthylamino monoazo dyestuff of formula (4"), diazotized in the same manner as described above for (4), and coupled in aqueous medium at a pH of 1-8, preferably 5-7.5, and a temperature of 0-20 °C according to the scheme to yield the new dyestuffs of the formula (1)

This route is applied, for example, for the preferred dyestuffs of the formulae (le).
Examples for dyestuffs of the formula (3') are
4-{4 '-(β-sulfatoethyl)suIfonyl-phenylazo}-l ,3-diaminobenzene;
4-{4r-(β-sulfatoethyl)sulfonyl-phenylazo}-6-sulfo-l,3-diaminobenzene;
4-{4r-(β-sulfatoethyl)sulfonyI-phenylazo}-6-methyl-l,3-diaminobenzene;
4-{2'sulfo-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-l ,3-diaminobenzene;
4-{2'-sulfo-4'-(ft-sulfatoethyl)sulfonyl-phenylazo}-6-sulfo-l ,3-diaminobenzene;
4-{2'sulfo-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-6-methyl-l,3-diaminobenzene.
Examples for dyestuffs of the formula (4') are 4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-methyl-aniline; 4-{4'-(fi-sulfaroethyl)suifonyl-phenylazo}-3-methyl-aniline; 4-{-4'-(6-sulfatoethyl)sulfonyl-phenylazo}-2-methoxy-aniline; 4-{ 4'-(B-suIfatoethyl)sulfonyl-phenylazo}-3-methoxy-aniline; 4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-chloro-aniline; 4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-chloro-aniline; 4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-carboxy-aniline; 4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-carboxy-aniline;

4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-acetylamino-aniline;
4-{4'-(β-sulfatoethyl)sulfonyl-phenyIazo}-3-ureido-aniline;
4-{ 4'-(β-sulfatoethyl)sulfonyl-phenyla2o}-2-sulfo-aniline;
4-{ 4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-sulfo-aniline;
4-{2'sulfo-4'-(β-sulfatoethyl)sulfonyl-phenyiazo}-2-methyl-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenyla2o}-3-methyl-aniline;
4-{2'sulfo-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-methoxy-aniline;
4- {2 'sulfo 4 '-(β-sulfatoethyl)sulfonyl-phenylazo} -3 -methoxy-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-chloro-aniline;
4-{2'sulfo 4'-(β-sulfatoethyl)suIfonyl-phenylazo}-3-chloro-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-carboxy-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-carboxy-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-acetylamino-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-ureido-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-sulfo-aniline;
4-{2'sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-sulfo-aniline;
4-{3'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-carboxy-aniline;
4-{3'-(β-sulfatoethyl)suIfonyI-phenyIazo}-2-suIfo-aniIine;
4-{3'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-methyl-aniline;
4-{3'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-acetylamino-aniline;
4-{3'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-ureido-aniline;
4-{2'-methoxy-5'-(β-sulfatoethyl)sulfony]-phenylazo}-2-carboxy-aniline;
4-{2'-methoxy-5'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-sulfo-aniline;
4-{2'-methoxy-5'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-methyl-aniline;
4-{2'-methoxy-5'- (β-sulfatoethyl)sulfonyl-phenylazo}-3-acetylamino-aniline;
4-{2'-methoxy-5r-(β-sulfatoethyl)sulfonyl-phenylazo}-3-ureido-aniline;
4-{2',5'-dimethoxy-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-carboxy-aniline;
4-{2',5'-dimethoxy-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-2-sulfo-aniline; *
4-{2',5'-dimethoxy-4'-(β-sulfatoethyl)sulfonyI-phenylazo}-2-methyl-aniline;
4-{2',5'-dimethoxy-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-acetylaminoaniiine;
4-{2'55'-dimethoxy-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-3-ureido-aniline.

Examples for dyestuffs of the formula (4") are
4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-6-sulfo-l-amino-naphthalene;
4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-7-sulfo-l-amino-naphthalene;
4-{4'-(β-sulfatoethyl)sulfonyl-phenylazo}-8-sulfo-l-amino-naphthalene;
4-{2'-sulfo-4'-(β-sulfatoethyl)sulfonyl-phenylazo}-6-sulfo-l-amino-naphthalene;
4- {2 '-sulfo 4'-(β-sulfatoethyl)sulfonyl-phenylazo} -7-sulfo-1 -amino-naphthalene;
4-{2'-sulfo4'-(β-sulfatoethyl)sulfonyl-phenylazo}-8-sulfo-l-amino-naphthalene.
The so prepared dyestuffs are then isolated in the usual manner, by salting out in a concentrated salt solution or by spray drying.
The invention also includes a process for application in dyeing or printing of the dyes of the formula (1) on hydroxy!, amino or carbonamino group containing fibres such as cellulose, protein fibres such as wool or silk, and polyamide fibres. In particular, 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 dyes are also suitable for dyeing and printing of fibre blends containing the mentioned cellulose, polyamide or protein fibre materials.
The dyes 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 method, 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 dye and prints are rinsed and thoroughly washed with cold or hot water containing auxiliary agents such as detergents or surfactants that promote the wash-off of unfixed portions.
Coloration in deep shades is often a challenge, especially when high fastness to washing, contact and perspiration is concerned. All known dyes have limitations in this respect.
The following examples illustrate the invention which however does not limit the scope of the invention. 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 1
361 parts by weight of freshly diazotized 2-sulfo-4-(β-sulfatoethylsulfonyl) phenylamine- diazotizing fromula (3) using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1-1.5 - in 1600 parts per volume of water is charged into a solution containing 173 parts per weight of the coupling component 2-sulfo-aniline in 1200 parts per volume of water. The azo coupling is carried out within 3-4 hrs at pH 5-6 and 0-5 °C which yields the monoazo dyestuff of stage 1 of the formula

In a separate vessel, 280 parts by weight of freshly diazotized 4-(B-suIfatoethylsuIfonyl)phenylamine - diazotized using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1-1.5 - in 1800 parts per volume of water. To this reaction mass is charged 210 parts per weight of the sodium salt of 2-sulfo-1,3-diaminobenzene. The reaction mass of stage 2 is stirred at 0-5°C over a period of 2 hours, then pH is raised to pH 6-6.5 to complete the azo coupling reaction. A monoazo dyestuff of stage 2, of the formula


O—S03H

is obtained.
The monoazo dyestuff of stage 1 is further diazotized in the usual manner, by means of sodium nitrite and hydrochloric acid at 0-5°C and pH 1-1.5, and this diazonium salt solution is charged into the solution of the monoazo dyestuff of stage 2. The reaction mass is stirred for 2-3 hours at 8-12°C and a pH of 7. A trisazo dye of the

HCXjSO
OSO3H
is obtained and isolated in the usual manner, by salting out with sodium chloride or by spray drying. The dyestuff has a orange shade and dyes on cotton fibres with excellent fastnesses, such as wash fastness at 60° in presence of detergents as well as excellent contact fastnesses such as perspiration fastness. More specifically, at in 1/1 standard depth on a level of 4-5 to 5 with respect to staining on adjacent fibres such as cotton, polyester or nylon is achieved in ISO105-C03 (60°C) or ISO105-E04 colour fastness tests.
Example 2;
281 parts by weight of freshly diazotized 4-(β-sulfatoethylsulfonyl)phenylamine suspension - diazotized using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1-1.5 - in 1500 parts per volume of water is charged into a solution containing 137 parts per weight of the coupling component 2-carboxy-aniline in 1000 parts

per volume. The azo coupling is carried out within 3 hrs at pH 5-5.5 and 0-5 °C which will yield the monoazo dye stuff offstage 1 of the formula
In a separate vessel, 361 parts by weight of freshly diazotized 2-sulfo-4-(β--suIfatoethylsulfonyl)phenylamine - diazotized using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1-1.5 - in 2000 parts per volume of water. To this reaction mass is charged 108 parts per weight of 1, 3-diaminobenzene. The reaction mass of stage 2 is stirred at 0-5°C over a period of 2 hours, then pH is raised to pH 6.5-7 to complete the azo coupling reaction. A monoazo dye stuff of stage 2, of the formula
l2N
-O—S03H
HO3S
is obtained. The monoazo dyestuff of stage 1 is further diazotized in the usual manner, by means of sodium nitrite and hydrochloric acid at 0-6°C and pH 1-1.5, and this diazonium salt solution is charged into the solution of the monoazo dyestuff of stage 2. The reaction mass is stirred for 2-4 hours at 10-15°C and a pH of 7-7.5. A trisazo dye of the
HOjSO

HOjS
brown, ^max = 478 nm
is obtained and isolated in the usual manner, by salting out with sodium chloride or by spray drying. The dyestuff has a brown shade and dyes on cotton fibres with outstandingly high colour strength and very good fixation yield of 88% while

applying a dyeing procedure as in dyeing example 1 at a depth of 2.2 % of weight of fibre.
Example 3:
361 parts by weight of freshly diazotized 2-sulfo-4-(β-sulfatoethylsulfonyl)phenylamine, diazotized in same manner as in example 1, in 2000 parts per volume of water is charged into a solution containing 151 parts per weight of the coupling component 3-ureido-aniline in 1000 parts per volume of water. The azo coupling is carried out within 2-3 hrs at pH 6,5-7 and 0-5 °C which yields the monoazo dyestuff of stage 1 of the formula
NH,
>°
SQ3H NH
The monoazo dyestuff of stage 1 is further diazotized in the usual manner, by means of sodium nitrite and hydrochloric acid at 0-5°C and pH 1-1.5, and this diazonium salt solution is charged into the solution of the monoazo dyestuff 4-(fi-sulfatoethylsulfonyl)phenylazo-6-sulfo-1,3-diaminobenzene), corresponding to stage 2 of example 1 and prepared as described in example 1. To complete the azo coupling of stage 3, the reaction mass is stirred for 2-3 hours at 10-15°C and apH of 7. A trisazo dye of the
o
SO3H 2-sulfo-5-acetylamino-aniline

1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H)

2-Sulfo-4-(6-sulfatoethyl) sulfonyl-aniline

SOaH
brown



%//
VO^fS

S03H

HfO

NH COCH3
\\ "I
S03H

2-Sulfo-4-(B-
SuIfatoethyl)sulfon
yl-aniline-> 2-
methoxy-5-acetylamino-aniline

1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H)

4-(B-
Sulfatoethyl) sulfonyl-aniline

brown

9 M
\\ "1
SO3H
Orange 418 nm 2-Sulfo-4-(β-Sulfatoethyl)sulfon yl-aniline-> 2-sulfo-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= S03H) 2-sulfo-4-(B-Sulfatoethyl) sulfonyl-aniline
10 ^ O^^Vx
W^f HO.S SO,H
Orange 415 nm 4-(β-sulfatoethyl )
sulfonyl-aniline->
2-sulfo-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= S03H) 2-sulfo-4-(B-Sulfaroethyl) sulfonyl-aniline
11 YO=s—0~N="Vx
N
SOJH
Orange 416 nm 4-(β-sulfatoethyl )
sulfonyl-aniline->
2-sulfo-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H) 4-(B-
Sulfatoethyl) sulfonyl-anitine


SOjV
YG2S
S02Y
%._M
12
13

Y02S-

{^N=N
Orange 414 nm
Orange 418 nm

HnCO

1,3- 3-(B-
4-(β-sulfatoethyl ) su Ifony I-an i I ine-> diaminobenze ne -sulfonic Sulfatoethyl) sulfonyl-
2-sulfo-aniline acid
(R,= S03H) aniline
1,3- 2-methoxy-
4-(β-sulfatoethyl ) diaminobenze 5-(β-
sulfonyl-aniline-> ne -sulfonic Sulfatoethyl)
2-sulfo-aniline acid sulfonyl-
(R,= S03H) aniiine

14 0
w "I
SOaH
brown 435 nm 4-(β-sulfatoethyl ) sulfonyl-aniline-> 3-acetylaminoaniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= S03H) 2-sulfo-4-(β-Sulfatoethyl) sulfonyl-aniline
15 0
V02S ( \-N=-N ,NH\H3
N
S03H
brown 430 nm 4-(β-sulfatoethyl )
sulfonyl-aniline->
3-ureido-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= S03H) 2-sulfo-4-(β--Sulfatoethyl) sulfonyl-aniline




W "1
\\ //
16
17

YOiS.
YOjS

SO3H

brown, A^^ = 426 nm

W "-!'
.»"^
£03H
HO3S
brown, Xmas = 431 nm
S03H
brown, "kmK = 427 nm

S02Y
SOjY

2-Sulfo-4-(β--Sulfatoethyl)sulfon yl-aniline-> 2-methyl-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H) 4-(β--
Sulfatoethyl) sulfonyl-aniline
2-Sulfo-4-((3-Sulfatoethyl)sulfon yl-aniline-> 3-methyl-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H) 4-(B-
Sulfatoethyl) sulfonyl-aniline
2-Suifo-4-(G-Sulfatoethyl)sulfon yl-aniline-> 2-methyl-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(Rt= S03H) 2-Suifo-4-(G-Sulfatoethyl) sulfonyl-aniline-

19 2-Sulfo-4-(β--Sulfatoethy l)sulfon yl-aniline-> 2-chloro-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(RL= S03H) 2-Sulfo-4-(β--Sulfatoethyl) sulfonyl-aniline-

N
\\ H,N
Hi'N T HQ3S S03H
brown, ^n,ax = 428 nm

20 2-Sulfo-4-(β--Sulfatoethyl)sulfon yl-aniline-> 2-Carboxy aniline 2,4-diamino-toluene 2-Sulfo-4-(β--Sulfatoethyl) sulfonyl-aniline-

1 HCSS CHi
brown, X™ax = 465 nm

YOjS
S02V
HOaS
21

CH3
brown, Xm^ = 470 nm

2-Sulfo-4-(β--
Sulfatoethyl)sulfon
yl-ani!ine-> 3-
ureido-aniline

2,4-diamino-toluene

2-Sulfo-4-(β--Sulfatoethyl) sulfonyl-aniline-

N=N
V //
22

YO2S-

SC^H

2-Sulfo-4-(β--
S u 1 fatoethy 1 )su 1 fon
yl-aniline-> 3-
ureido-aniline

2,4-diamino-toluene

2-Su1fo-4-(β--Suifatoethyl) sulfonyl-aniline-

brown, 478 nm

23 SOsH /^^A . u HH
YQzS ^ ^ ^^^V^
/ \\ KN
HObS \\ 1 i ,
scbH
brown, X^^ = 432 nm 2-Sulfo-4-(β--Sulfatoethyl)sulfon yI-aniline-> 2-sulfo-5-acetylamino-aniline 1,3-
diaminobenze
ne -sulfonic
acid
(R,= SO3H) 4-(β--
Sulfatoethyl) sulfonyl-aniline
24 S03H J>
ni* HO 38
brown, Xmax = 472 nm 2-Sulfo-4-(β--Sulfatoethyl)sulfon yl-aniline-> 2-sulfo-5-acetylamino-aniline 1,3-
diaminobenze ne (Ri=H) 2-Sulfo-4-(β--Sulfatoethyi) sulfonyl-aniline-

25 H03S \\ 3i
brown, ^ = 465 ntn 4-(B-Sulfatoethy1) sulfonyl-aniline-> 2-sulfo-S-acety 1 am ino-an i 1 i ne 1,4-
phenylendiami ne (Ri= H) 2-Sulfo-4-(I3-Sulfatoethyl) sulfonyl-aniline-
26 CM,
SQjH {
/ \ _. HH
YtfcS—^ A "^^V__/
HOas \\ 1
fl^[ ^^—C y—$QZY
^" J^ HCas
Chi,
brown, 478 nm 2-Sulfo-4-(fi-Sulfatoethyl)sulfon yl-aniline-> 2-sulfo-5-aceryiamino-aniline 2,4-diamino-toluene (R,= CH3) 2-Sulfo-4-(6-Sulfatoethyl) sulfonyl-aniline-

27 P-CH,
V02s—Q-=N
CHS
brown, A^* = 480 nm 2,4-dimethoxy-4-(G-Sulfatoethyl) sulfonyl-aniline-> 2-carboxy-aniline 2,4-diamino-toluene (R,= CH3) 2-Sulfo-4-
(A-Sulfatoethyl)
sulfonyl-
aniline-
28 vo,s—Q-N=Vs
brown, X,,,^ = 470 nm 2-Sulfo-4-(6-Sulfato-ethyl)su!fonyl-aniline -> aniline 2,4-diamino-toluene (RL= CH3) 2-Sulfo-4-(B-Sulfatoethyl) sulfonyl-aniline-
The following examples 29-31 are obtained by treatment of the triaszo dyestuffs of examples 1-3 at pt
of 20-25 °C. 10-10.5 for 1 h at a temperature

brown, X,nax = 476 nm

S03H

as example 1

as example 1 as example I
as example 2 as example 2 as example 2

w
H,N
"- V^-^v-s^
SO?
H,N'
SO]H
brown, ^ = 436 nm

example 3 as example 3 as example 3

Example 32:
361 parts by weight of freshly diazotized 2-sulfo-4-(B-sulfatoethylsulfonyl)phenylamine, diazotized in same manner as in example 1, in 2000 parts per volume of water is charged, into a solution containing 223 parts per weight of the coupling component 6-sulfo-l-naphthylamine in 2000 parts per volume of water. The azo coupling is carried out within 2-3 hrs at pH 6.5-7 and 0-5 °C which yields the monoazo dyestuff of stage 1 of the formula

HO3S
The monoazo dyestuff of stage 1 is further diazotized in the usual manner, by means of sodium nitrite and hydrochloric acid at 0-5°C and pH 1-1.5, and this diazonium salt solution is charged into the solution of the monoazo dyestuff 4-(ft-sulfatoethylsulfonyl)phenylazo-6-sulfo-1,3-diaminobenzene), corresponding to stage 2 of example 1 and prepared as described in example 1. To complete the azo coupling of stage 3, the reaction mass is stirred for 2-3 hours at 10-15°C and apH
15 of 7. A trisazo dye of the

SO3H Brown, A™* 461 nm



H,N
N^N.
33
34

SO3H
Brown, Km3f. 464 nm
Brown, Xmax 480 nm

^N—(/ \y_so2Y

HO3S
HOaS

4-(fJ-
Sulfatoethyl)
sulfonyl-
aniline-> 6-
sulfo-1-
naphthylamine 1,3-
diaminobenze ne -sulfonic acid 2-sulfo-4-
(B-
Sulfatoethy 1) sulfonyl-aniline
2-Sulfo-4-(B-
Sulfatoethyl)sul
fonyl-aniline->
6-sulfo-l-
naphthylamine 1,3-
diaminobenze
ne 2-sulfo-4-(6-
Sulfatoethy 1) sulfonyl-aniline


^N^f VS02Y
YOzS

35
36

Y02S-

S03H
1>HO3S

CH,
Brown, A.majt 490 nm
S03H
Brown, A.max 465 nm

HO3S

2-Sulfo-4-(B- 2-sulfo-4-
Sulfatoethyl)sul 2,4-diamino- (6-
fonyl-aniline->
6-sulfo-l- toluene Sulfatoethy
naphthylamine 1) sulfonyl-aniline
4-(fi-
Sulfatoethyl) sulfonyl- 1,3-diaminobenze 4-(G-
aniline-> 6- ne -sulfonic Sulfatoethy
sulfo-1- acid 1) sulfonyl-
naphthylamine aniline

H03S
SOzY
37

S03H

SO3H
Brown, Xmax 465 rim

2-sulfo-4-(B-
Sulfatoethyl)
sulfonyl-
aniline-> 6
sulfo-1-
naphthylamine

1,3-
diaminobenze ne -sulfonic acid

2-methoxy-5-(6-
Sulfatoethy 1) sulfonyl-aniline

Y02S
HO3S
38

SO3H Brown, Xmm 462 nm

2-sulfo-4-(fJ-
Sulfatoethyl)
sulfonyl-
aniline-> 7-
sulfo-1-
naphthylamine

1,3-
diaminobenze ne -sulfonic acid

4-(6-
Sulfatoethy 1) sulfonyl-aniline


39

Y02S

S03H
Brown, A,max466 nm

S02Y

2-Sulfo-4-(B-
Sulfatoethyl)sul
fonyl-aniline->
8-sulfo-l-
naphthylamine

U3-
diaminobenze ne -sulfonic acid

4-(B-
Sulfatoethy 1) sulfonyl-aniline

YO2S
40

HO3S

2-Sulfo-4-(6-
Sulfatoethyl)sul
fonyl-aniline->
8-sulfo-l-
naphthylamine

1,3-
diaminobenze
ne

2-sulfo-4-(B-
Sulfatoethy I) sulfonyl-aniline

brown, A.ma)(480 nm

Y02S
H03S

41
42

SO3H Brown, ^.max 438 nm
S03H
Brown, Xm!tx 462 nm

2-Sulfo-4-(6-
Sulfatoethyl)sul
fonyl-ani!ine->
8-sulfo-l-
naphthylamine
2-sutfo-4-(6-
Sulfatoethyl)
sulfonyl-
aniline-> 6
sulfo-1-
naphthylamine

1,3-
diaminobenze ne -sulfonic acid
1,3-
diaminobenze ne -sulfonic acid

2-suIfo-4-(fi-
Sulfatoethy I) sulfonyl-aniline
Vinylsulfon yl-aniline


H03S
S^ ^-^ ^
HaCO
43

YOjS

OCHj

SO3H Brown, Xnax 450 nm

SOjY

2-Methoxy-4-
(β-sulfatoethyl)
sulfonyl- 1,3- 2-Methoxy-
aniline-> 6- diaminobenze 4-(6-
sulfo-1- ne -sulfonic Sulfatoethy
naphthylamine
1 acid 1) sulfonyl-aniline

Dyes based on 1,4-diamino-aniline derivatives
The following dyestuffs based on 1,4-diamino-aniline derivatives are prepared in the same manner as described above for the 1,3-diamino-aniline derivatives.


Structure

D2
2nd diazo
component

Coupling component

Dl
Is' diazo
component

NHCONH2
S02Y
HO3S
44

YC^S

2-Su!fo-4-(B-Sulfatoethyl)sulf onyl-aniline-> 3-ureido-aniline

1,4-
diaminobenzen e -sulfonic acid
(R,= SO3H)

4-(fl-
Sulfatoethyl) sulfonyl-aniline

brown


N N
W //
S02Y
45

Y02S-

SO-,H

NHCOCHj

2-Sulfo-4-(B-Sulfatoethyl)sulf onyl-aniline-> 3-acety lam i no-aniline

1,4-
diaminobenzen e -sulfonic acid
(R,= SO,H)

4-(B-
Sulfatoethyl)
sulfonyl-
amline

brown



H03S
46
47

i
Y02S (v \—N=N

H03s
brown
brown

NH-

S02Y

4-(B-
Sulfatoethyl) sulfonyl-aniline-> 2-carboxy-aniline 1,4-
diaminobenzen e -sulfonic acid
(R,= SO3H) 2-sulfo-4-(B-Sulfatoethyl) sulfonyl-aniline
4-(fl-
Sulfatoethyl) sulfonyl-aniline-> 2-sulfo-aniline 1,4-
diaminobenzen e -sulfonic acid
(R,= S03H) 2-sulfo-4-(6-Sulfatoethyl) sulfonyl-aniline

48

Y02S-

:N PHS


N^V^N-fVs02Y

HO3S
NH-

4-(B-
Sulfatoethyl)
sulfonyl-aniline-
> 3-methyl-
aniline

1,4-
diaminobenzen e -sulfonic acid
(Rt= S03H)

2-sulfo-4-(6-Sulfatoethyl) sulfonyl-aniline

brown

The present dyes are of orange to brown colour and are especially suitable for dyeing in deep shades such as dark brown and black shades, applied as single dye or as mixture in the present invention, or in combination with other compatible dyestuffs containing vinylsulfone and/or heterocyclic reactive groups, preferably applied in dichromatic or trichromatic combinations and in black mixtures, while exhibiting superior properties in coloration technology compared to known mixtures of state of the art, with regard to achieving very deep shades, and excellent fastness properties.
Examples of mixtures
Example 49:
Composition of the formula
75 parts per weight of C.I. Reactive Black 5 (Component of formula 2), 25% per weight of Brown according to example 2 (component of formula 1) provides a neutral black shade.
Structures of shading dyes used in table:

S02-CH2-CH2-0SO3H

HOjS.

^

N II
N SQjH

S02-CH2CH2-OS03H

Orange 1

Example
No. Component 2 Component I Shade
50 70% Reactive Black 5 30% Brown of example 3 Neutral black
51 75% Reactive Black 5 25% Brown of example 4 Neutral black
52 67% Reactive Black 5 33% Brown of example 6 Neutral black
53 71% Reactive Black 5 29% Brown of example 3, shaded with 5% of Red 1 Neutral black
54 70% Reactive Black 5 22% Brown of example 3, shaded with 8% of Red 1 Reddish black
55 72% Reactive Black 5 18% Brown of example 3, shaded with 10% of Carmine 1 Reddish black
56 68% Reactive Black 5 26% Brown of example 2, shaded with 6% of Carmine 2 Reddish black
57 68% Reactive Black 5 26% Brown of example 4, shaded with 6% of Carmine 3 Reddish black
58 73% Reactive Black 5 20% Brown of example 3, shaded with 7% of Rubine 1 Reddish black
59 67% Reactive Black 5 33% Brown of example 36 Neutral black
60 70% Reactive Black 5 23% Orange of example 1 shaded with 7% of Red 1 Neutral black
61 70% Reactive Black 5 30% Orange of example 1 Greenish black
62 70% Reactive Black 5 25% Orange of example 2, shaded with 5% yellow 1 Greenish black
63 70% Reactive Black 5 23% Orange of example 3, shaded with 7% Orange 1 Greenish black
64 70% Reactive Black 5 22% Orange of example 4, shaded with 8% Orange 1 Greenish black
65 60% Reactive Black 5 40% brown of example 5 Neutral black , bronzy
66 60% Reactive Black 5 35% brown of example 6, 5% Carmine 1 Blueish black

67 85% Reactive Black 5 15% brown of example 6 Blueish black
68 84% Reactive Black 5 13% brown of example 7 3% Rubine 1 Blueish black
Examples of suitable alkali used for fixation include alkali hydroxide, alkali
carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium
silicate are preferred.
The amount of dye applied in the dye bath can vary according to the desired depth
of shade, generally an amount of 0.01 to 10 % per weight of fabric is suitable, and
in particular 0.2 to 8% per weight of fabric is preferred. Especially preferred are
1% to 6% depth of dyeing.
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 padding process urea, and in printing
applications thickening pastes such as alginate thickenings.
In exhaust dyeing process, the preferred procedure is dyeing from an aqueous
batch, in the 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 10-12, and at a temperature of 40-90°C, preferably 45-65 °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 perspiration.
Moreover, the dyeing obtained with the dyes of the present invention is
dischargeable and can be applied in discharge printing.
Dyeing example 1:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 1000 parts of water, 50 parts per weight of sodium chloride, and 3 parts per weight of the dyestuff of example 2. After 30 min at 60°C, 10 parts per weight of sodium carbonate is added, the dyeing temperature is

maintained at 60 °C for 15 min, then 2 ml/L of sodium hydroxide solution is added, then dyeing temperature is maintained at 60 °C for another 30 min. The dyed fabric is then rinsed, neutralized with acetic acid and soaped in 2 wash baths with each 1L of water at 95°C. A dark brown dyeing is obtained.
Dyeing example 2:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 1000 parts of water, 70 parts per weight of sodium chloride, and 6 parts per weight of the dyestuff of example 50. After 30 min at 60°C, 10 parts per weight of sodium carbonate is added, the dyeing temperature is maintained at 60 °C for 15 min, then 2 ml/L of sodium hydroxide solution is added, then dyeing temperature is maintained at 60 CC for another 30 min. The dyed fabric is then rinsed, neutralized with acetic acid and soaped in 2 wash baths with each 1L of water at 95°C. A deep black dyeing is obtained.
Dyeing example 3:
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 parts per weight of the dyestuff of example 54. After 30 min at 60°C, 10 parts per weight of sodium carbonate is added, the dyeing temperature is maintained at 60 °C for 15 min, then 2 ml/L of sodium hydroxide solution is added, then dyeing temperature is maintained at 60 °C for another 40 min. The dyed fabric is then rinsed, neutralized with acetic acid and soaped in 2 wash baths with each 1L of water at 95°C. A reddish deep black dyeing is obtained.

We claim:
1. New fibre reactive trisazo dyestuffs of the formula (1)
wherein
R1 is hydrogen, Cl-C3-alkyl, halogen, carboxy or sulfo;
K is a radical of the formulae
Q2
wherein
Q1 is hydrogen, carboxy, sulfo, NHCONHR2, NHCOR2, NHR2, C1-C3-alkyl,
halogen, methoxy or hydroxy;
wherein R2 is hydrogen or C1-C3-alkyl;
Q2 is hydrogen, methyl, methoxy or sulfo;
the benzene rings A is further optionally substituted by substituents selected
from sulfo, methyl, methoxy, cyano or nitro;
the benzene rings B, independent from benzene ring A is further optionally
substituted by substituents selected from sulfo, methyl, methoxy, cyano or
nitro;
Y is vinyl, 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,
and two Y substituents can have identical or different meanings.

2. Fibre reactive trisazo dyestuffs as claimed in claim 1 wherein Rl is selected from hydrogen, methyl, chloro, carboxy or sulfo and R1 is in ortho and para position to the amino groups.
3. Fibre reactive trisazo dyestuffs as claimed in claim 1 wherein Y is vinyl, β--chloroethylsulfonyl or β--sulfatoethylsulfonyl.
4. Fibre reactive trisazo dyestuffs Trisazo dyestuff as claimed in any one of the preceding claim wherein formula (1) is of the formula

(le) wherein, Q1 is carboxy, sulfo, NHCONH2, NHCOCH3, methyl, methoxy or chloro;
Q2 is hydrogen,
each of the benzene rings A and B contain 0-2 sulfo groups and each of the
rings is further optionally substituted by 1-2 methoxy group and 1 methyl
group;
Y is vinyl or β-sulfatoethylsulfonyl.
5. Fibre reactive trisazo dyestuffs as claimed in any one of the preceding claim wherein atleast one of the benzene rings A and B contains a sulfo group.
6. Fibre reactive trisazo dyestuffs as claimed in any one of the preceding claim wherein radicals of the formula
independent from each other have one of the following radicals

wherein Yl is vinyl or β-sulfatoethyl. 7. Fibre reactive trisazo dyestuffs as claimed in any of the preceding claim wherein the radical K having the formula
Mixtures of trisazo dyestuffs of formula (1) as defined in any one of the preceding claims with bisazo dyes of the formula (2)
wherein
Bl and B2 are benzene ring radical having the substituent -SO2Y,
wherein Y is Vinyl or CH2CH2L, wherein L is a leaving groups as defined
above;
Bl and B2, independent of each other, may be further optionally substituted
by additional substituents such as methoxy, methyl, carboxy or sulfo and

the ratio of the mixing components formula (1): formula (2) is in the range 10:90 to 45:55.
9. Mixtures of trisazo dyestuffs of formula (1) with bisazo dyes of the formula (2) as claimed in claim 8 may optionally further comprise additional shading components of the yellow dye of formula(2a), wherein Y has one of the above meanings;

orange dye (formula(2b)), wherein Y has one Of the above meanings;
red, rubine or carmine coloured dyes of (formula (2c)),
wherein Y has one of the above meanings;

the benzene ring B3 contains optionally further methyl and methoxy
substituents and Rl' is hydrogen, sulfomethyl, β-sulfoethyl or β-
carboxyethyl.
10. A process for the preparation of trisazo dyes of formula (1) comprising the steps:
a. Coupling an aromatic amine carrying a SO2Y radical in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling onto a diaminobenzene derivative in aqueous medium at a pH of 1-7 and a temperature of 0-20 °C to give monoazo dye of formula (3) which is schematically represented as below

H2N.
Formula (3) b. Coupling diazotized 4-azoarylamino monoazo dyestuff of formula (4) with monoazo dye of formula (3) in the presence of nitrous acid or alkali nitrite salt and a strong acid selected from sulfuric acid or hydrochloric acid at temperatures of 0-15° followed by azo coupling in aqueous medium at a pH of 1-8, preferably 5-7.5 and a temperature of 0-20 °C to yield new trisazo dyestuffs of the formula (1) which is schematically represented as below