DESC: FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)

1. TITLE OF THE INVENTION:
“A Composition for Deep Black Dye Mixtures of Fiber-Reactive Azo Dyes”

2. APPLICANT:

1. (A) KIRI INDUSTRIES LIMITED
(B) Indian
(C) 7th Floor, Hasubhai Chamber,
Opp. Town Hall, Ellis Bridge,
Ahmedabad-380006
Gujarat, India.

3. PREMABLE TO THE DESCRIPTION:
PROVISIONAL
SPECIFICATION
(See section 10 and rule 13)
The following specification describes the invention.
þCOMPLETE
SPECIFICATION
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 a composition for deep black dye mixtures of fiber- reactive azo dyes. More particularly it relates to production of intense black reactive dyes after combining mixture of reactive orange dye with reactive navy and reactive yellow dye.

BACKGROUND OF INVENTION

Over the past years many countries have committed to improve the quality of the environment by saving natural resources and reducing the emission of substances which are harmful to the climate. Retailers are transmitting these demands into real requirements and textile manufactures are continuously improving their production by investing in selecting environment friendly chemical substances.

As a result, there is a huge demand for novel reactive dye mixtures that are suitable for reproducible dyeing and printing of fibre materials while still providing dyeings of the desired colour shades with good fastness properties such as water fastness. Suitable reactive dyes should provide an inimitable combinability and a low sensitivity to various dyeing factors. Furthermore, they should have adequate substantivity and at same time have good ease of washing off unfixed dye. They should also have a good tinctorial yield and high reactivity which provides dyeing with high degrees of fixing.

Japanese Patent Application No. 160,362/1983 discloses a black reactive dye composition which contains black reactive dye and orange reactive dye. Nevertheless, when this black dye composition is used in dyeing, the dyed material can not accumulate a high build up property and have poor wash or chlorine fastness as well as solubility problems.

Japanese Patent Application No. 17,8170/1988 discloses another black reactive dye composition which contains formula for black reactive dye with any one of red or orange reactive dye. This composition has worse leveling property, less solubility and lower tinctorial strength. In a high concentrated dye solution, the black dye mixture component will precipitate out and this limits the usefulness of said composition. This dye composition still does not totally solve the above problems.

Furthermore, most reactive dyes do not have good properties when used in discharge printing. More often they can not totally discharge and this limits the usefulness of the reactive dyes. Therefore, to provide a reactive dye with better discharge printing property is another target for the dyeing industry. So far, there are no reactive dyes which can produce a high black shade build up property.

Therefore there is desperate need to find mixtures of reactive dyes especially intense black dyeing mixtures which are not subjected to above mentioned problems.

OBJECT OF THE INVENTION

The principle object of the present invention is to obtain a composition for deep black dye mixtures of fiber-reactive azo dyes.

Another object of the present invention is to obtain economical black mixtures from the reaction of reactive orange triazo dye with reactive navy disazo dyes and reactive yellow monoazo dyes.

Further object of the present invention is to deliver substantial cost advantages as the end product obtained by the reactive dye mixtures are very economical.

Yet another object of the present invention is to provide excellent reproducibility and easy washing-off to meet today's quality requirements.

Further object of the present invention is to provide intense black dye mixtures with excellent self life that is unattainable with other mixtures of dyes.

Another object of the present invention is to provide a composition for preparation of black dye mixtures with very high solubility, good diffusion and high fixation.

Still another object of the present invention is to provide a composition for deep black dye mixtures with good fastness properties with minimal colour loss and moderate to good light fastness.

SUMMARY OF THE INVENTION

The present invention discloses a composition for deep black dye mixtures of fiber- reactive azo dyes. More particularly it relates to triazo orange dye giving intense black mixtures when combined with navy and yellow reactive dyes. The present invention particularly provides reactive orange triazo dye with unique tone, when combined with reactive navy disazo dyes and reactive yellow monoazo dyes along with other excipients and antidusting oil gives economical black mixtures. Various reactive moieties are used and replaced in triazo orange dye to produce intense black dyeing which is cost effective, has strong tinctorial value for fibre and excellent self life.

DETAIL DESCRIPTION OF THE INVENTION

The nature of invention and the manner in which it is performed is clearly described in the specification. The invention has various components and they are clearly described in the following pages of the complete specification.

Azo dyes are classified as to indicate the chief method of application into use as acid, base (cationic), direct, disperse, mordent and especially reactive dyeing classes. From the chemistry viewpoint the disperse azo dyes are divided according to number of azo groups as monoazo, bisazo, trisazo, tetrakis or polyazo dyes and as further subdivided into carbocyclic and heterocyclic (heteroaryl) azo dyes according to the aromatic or heterocyclic radical present in a dye molecule. Because of its cost effectiveness, tinctorial strength, brightness
and high fastness properties, they are used to color the vast majorities of apparel and household textiles as well as non textile materials such as paper, leather, foods, drugs, cosmetics and colour photography and constitute the largest group of synthetic dyes.

The present invention comprises 10% to 20% triazo dyes is selected from the formula (Ia), (Ib), (Ic), (Id), (Ie), 50% to 60% disazo dyes of the formula (II), and 5% to 10% monoazo dyes is selected from the formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf) along with 1% to 2% antidusting oil and 10% to 35% other excipients. These requisite individual dyes of formula (I) to (III) are mechanically mixed with excipients in desired blend ratio leading to intense black mixtures that is used commercially in cost-effective means.
Further it also includes other excipients that are selected but not limiting to, sodium sulphate, sodium chloride, Tammol (formaldehyde naphthalene sulphontes), lignine sulphontes.
One aspect of the present invention relates to a triazo orange reactive dye. It has very good fiber-reactive dyestuff properties and dyeing properties on fiber materials in particular cellulose fiber materials, such as cotton, with good fastness properties and a very low dependence of shade and strengths on the dyeing temperature. The present invention relates to dye mixtures comprising from an orange triazo dye of formula (Ia), (Ib), (Ic), (Id), (Ie) suitable for reaction with the fibre material. An orange reactive dye is a compound comprises of the formula (Ia), (Ib), (Ic), (Id), (Ie) that are as follows:

Formula (Ia)

Formula (Ib)

Formula (Ic)

Formula (Id)

Formula (Ie)

In the present invention corresponding to formula (I), R1 and R2 are replaced with distinct and defined reactive moeity to obtain a deep black dye mixture of fibre reactive azo dyes which are as follows:

The formula (I) for preparation of triazo orange dye is developed through various trials to get enhance in deep black shades with good color build-up and good wash-off in respect of unfixed dye portions.

Another aspect of the present invention refers to a reactive navy dye which is disazo in nature. Navy reactive dye of good property is having wash fastness, colour fastness and good fixation. Structure of reactive disazo navy dye is a compound derived as the formula (II):

Formula (II)
Structure of reactive disazo navy dye is a compound derived as the formula (II) comprises the following steps as follows:
(i) The amino compound of formula (x) undergoes diazotization and then coupled with amino compound of formula (y) under acidic pH values of 1-3 at 10-20° C temperature.
(ii) Subsequently on the other side the diazonium salt derived from the formula (z) is coupled with the reaction mixture formed in step (i) under acidic to neutral pH values such as 4.5-6.5 at 10-20° C temperature.
(iii) The final product is obtained having navy disazo dye of formula (II).

Further the structures of reactive navy compound of formula (II) having X is selected from following reactive anchor:

Further the structures of reactive navy compound of formula (II) having Z is selected from following reactive anchor:

Further the synthesis of largest group of dyes is mono azo group as a chromophore in an aromatic system. These groups of dyes cover a bright shade with good fastness properties. The reactive yellow dye composition is not limited and can be applied to dye leather, wool, silk, nylon and cellulose fibers. About 50% of the disperse dyes available are of mono azo type. Mono azo yellow dye is a compound represented as formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf) are represented as follows:

(IIIa) (IIIb)

(IIIc) (IIId)

(IIIe) (IIIf)

In the present invention mono azo yellow dye is a compound represented as formula (IIIa-f) comprises the following steps as follows:
(i) Diazotizing the amino compound and then proceeding a coupling reaction between the diazotized formula and amino compound under acidic pH values of 1-7 at 0-30° C temperature to obtain the formula (III) compound of present invention.
The above reactive yellow component is synthesized in the subsequent manner and the said compound is to be added along with any of orange reactive triazo dye of formula (Ia), (Ib), (Ic), (Id), (Ie) and reactive disazo navy dye compound derived as the formula (II) to achieve intense deep black dye mixtures of fibre reactive azo dyes.
The resulting dye, when employed according to the application and fixing methods of the dyes component of the formulae (I), (II) & (III) each listed in the form of the alkali metals salts.
The invention is illustrated more in detail in the following example. The example describes and demonstrates embodiments within the scope of the present invention. This example is given solely for the purpose of illustration and is not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the scope.
The parts by weight bear the same relation to parts by volume as the kilogram to the liter. A dyestuff of formula (I) is described with following reactive moieties:

Example 1:

The process for preparation of orange reactive triazo dye of formula (I) comprises following steps:
Preparation of first coupling product:
i) In the reaction vessel with high speed constant stirrer 21 parts of 2-sulfonic-5-acetylamino-aniline was dispersed in 200 parts of ice water followed by addition of 24.3 parts of 30% HCL and added 6.9 parts of sodium nitrite and maintained 0-5° C temperature and sufficiently stirred until diazotization was complete.
ii) After the above diazotization was complete in step (i) remove the excess nitrous acid with sulfamic acid and the precipitation mass as a diazonium compound was obtained for coupling reaction.
iii) In the vessel containing diazonium compound formed in step (ii), 15.2 parts of 3,5 –diaminobenzoic acid was added as an aqueous solution with high speed constant stirrer until coupling reaction was complete and first coupling product was obtained.

Preparation of Second diazonium compound:

iv) In another vessel with constant stirrer 56.2 parts of the 4-ß-sulfatoethylsulfone-aniline was dispersed in 350 parts of ice-water followed by addition of 24.3 parts of 30% HCL sufficiently stirred, then added 13.8 parts of sodium nitrite maintained between 0-5° C temperature with constant stirring until the diazotization was completed and the second diazonium compound was obtained.

Preparation of final product:

v) The second diazonium compound formed was added to above first coupling product and sodium bicarbonate was added to adjust the pH value to 5.5 and maintained temperature of 10-20° C with constant stirring until the coupling reaction was complete.
vi) After the above said coupling reaction (precipitation) method, the filtration was carried out.
vii) Further the product formed in step (vi) was washed with brine filtration procedures for removal of dissolved contaminants or subjected to desalination by reverse osmosis procedure.
viii) Final product was collected as an orange dye and stored.

The structure of reactive orange compound of formula (I) was as follows:

Example 2:
The process for preparation of orange reactive triazo dye of formula (I) comprises following steps:
Preparation of first coupling product:
i) In the reaction vessel with high speed constant stirrer 23 parts of 2-sulfonic-4-acetylamino-aniline was dispersed in 200 parts of ice water followed by addition of 24.3 parts of 30% HCL and added 6.9 parts of sodium nitrite and maintained 0-5° C temperature and sufficiently stirred until diazotization was complete.
ii) After the above step (i) follow the procedure for remaining steps as shown in example 1.
The structure of reactive orange compound of formula (I) was as follows:

Example 3:
The process for preparation of orange reactive triazo dye of formula (I) comprises following steps:
Preparation of first coupling product:
i) In the reaction vessel with high speed constant stirrer 31 parts of 2, 4-disulfonic-3-acetylamino-aniline was dispersed in 200 parts of ice water followed by addition of 24.3 parts of 30% HCL and added 6.9 parts of sodium nitrite and maintained between 0-5° C temperature and sufficiently stirred until diazotization was complete.
ii) After the above step (i) follow the procedure for remaining steps as shown in example 1.
The structure of reactive orange compound of formula (I) was as follows:

Example 4:
The process for preparation of orange reactive triazo dye of formula (I) comprises following steps:
Preparation of first coupling product:
i) In the reaction vessel with high speed constant stirrer 31 parts of 2, 5-disulfonic-4-acetylamino-aniline was dispersed in 200 parts of ice water followed by addition of 24.3 parts of 30% HCL and added 6.9 parts of sodium nitrite and maintained between 0-5° C temperature and sufficiently stirred until diazotization was complete.
ii) After the above step (i) follow the procedure for remaining steps as shown in example 1.

The structure of reactive orange compound of formula (I) was as follows:

Example 5:
The process for preparation of orange reactive triazo dye of formula (I) comprises following steps:
Preparation of first coupling product:
i) In the reaction vessel with high speed constant stirrer 36 parts of 4, 8-disulfonic-6-acetylamino-2 naphthylamine was dispersed in 200 parts of ice water followed by addition of 24.3 parts of 30% HCL and added 6.9 parts of sodium nitrite and maintained between 0-5° C temperature and sufficiently stirred until diazotization was complete.
ii) After the above step (i) follow the procedure for remaining steps as shown in example 1.
The structure of reactive orange compound of formula (I) was as follows:

The synthesis procedure indicated in Example 1 of reactive orange compound of formula (I), there were likewise the following examples from 6-65 as shown below as follows:

REACTIVE ANCHOR DYE COMPOUND FORMULAE

Exp-6

Exp-7

Exp-8

Exp-9

Exp-10

Exp-11

Exp-12

Exp-13

Exp-14


Exp-15

Exp-16

Exp-17

Exp-18

Exp-19

Exp-20

Exp-21

Exp-22

Exp-23

Exp-24

Exp-25

Exp-26

Exp-27

Exp-28

Exp-29

Exp-30

Exp-31

Exp-32

Exp-33

Exp-34

Exp-35

Exp-36

Exp-37

Exp-38

Exp-39

Exp-40

Exp-41

Exp-42

Exp-43

Exp-44

Exp-45

Exp-46

Exp-47

Exp-48

Exp-49

Exp-50

Exp-51

Exp-52

Exp-53

Exp-54

Exp-55

Exp-56

Exp-57

Exp-58

Exp-59

Exp-60

Exp-61

Exp-62

Exp-63

Exp-64

Exp-65

The resulting product according to the above mentioned examples, when employed produces yellow-orange dye.

Further the structures of reactive navy compound of formula (II) as examples from 66-92 having X.Y. and Z as the reactive anchor with its dye compound formulae are shown in below table as follows:
Exp-66.

Exp-67.

Exp-68.

Exp-69.

Exp-70.

Exp-71.

Exp-72.

Exp-73.

Exp-74.

Exp-75.

Exp-76.

Exp-77.

Exp-78.

Exp-79.

Exp-80.

Exp-81.

Exp-82.

Exp-83.

Exp-84.

Exp-85.

Exp-86.

Exp-87.

Exp-88.

Exp-89.

Exp-90.

Exp-91.

Exp-92.

The above mentioned examples shows the structural reactive navy compound of formula (II) having highly distinguished synthesis manner and was further utilized in mixture of producing deep black dye mixtures of fibre reactive azo dyes.

Further, for the examples of mono azo yellow dye is a compound represented as formula 93 (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf) as follows:
Exp-93(IIIa) Exp-93(IIIb)

Exp-93(IIIc) Exp- 93(IIId)

Exp-93(IIIe) Exp-93(IIIf)

The above reactive mono azo dye of yellow component was synthesized in the subsequent manner and the said compound is to be added along with orange reactive triazo dye of formula (I) and reactive disazo navy dye compound derived as the formula (II) to achieve intense deep black dye mixtures of fibre reactive azo dyes.

Similar to the methods described in the examples 1-93 the following examples 94-305 mentions the dyestuffs that were prepared and mixed with one another in the ratios given in table 1 to afford bluish gray to intense black dye mixtures with superior wash fastness even at dyeing on cotton as well as on wool as substrate and reactive dyes for printing methods.
Table 1:

Example Dye of formulae (I) Orange component Dye of formulae (II) Navy component Dye of formulae (III) Yellow component Ratio in parts
94 exp-1 exp-66 exp-93(IIIa) 25:65:10
95 exp-1 exp-66 exp-93(IIIb) 27:66:7
96 exp-1 exp-66 exp-93(IIIc) 26:70:4
97 exp-1 exp-66 exp-93(IIId) 27:67:6
98 exp-1 exp-66 exp-93(IIIe) 25:67:8
99 exp-1 exp-66 exp-93(IIIf) 28:65:7
100 exp-1 exp-66 - 30:70
101 exp-1 exp-72 exp-93(IIIa) 23:68:9
102 exp-1 exp-72 exp-93(IIIb) 25:69:6
103 exp-1 exp-72 exp-93(IIIc) 24:73:3
104 exp-1 exp-72 exp-93(IIId) 25:70:5
105 exp-1 exp-72 exp-93(IIIe) 23:70:7
106 exp-1 exp-72 exp-93(IIIf) 26:68:6
107 exp-1 exp-72 - 33:67
108 exp-1 exp-76 exp-93(IIIa) 22:69:9
109 exp-1 exp-76 exp-93(IIIb) 24:70:6
110 exp-1 exp-76 exp-93(IIIc) 23:74:3
111 exp-1 exp-76 exp-93(IIId) 24:71:5
112 exp-1 exp-76 exp-93(IIIe) 22:71:7
113 exp-1 exp-76 exp-93(IIIf) 25:69:6
114 exp-1 exp-76 - 32:68
115 exp-1 exp-81 exp-93(IIIa) 23:67:10
116 exp-1 exp-81 exp-93(IIIb) 25:68:7
117 exp-1 exp-81 exp-93(IIIc) 24:72:4
118 exp-1 exp-81 exp-93(IIId) 25:69:6
119 exp-1 exp-81 exp-93(IIIe) 23:69:8
120 exp-1 exp-81 exp-93(IIIf) 26:67:7
121 exp-1 exp-81 - 34:66
122 exp-1 exp-86 exp-93(IIIa) 24:65:11
123 exp-1 exp-86 exp-93(IIIb) 26:66:8
124 exp-1 exp-86 exp-93(IIIc) 25:70:5
125 exp-1 exp-86 exp-93(IIId) 26:67:7
126 exp-1 exp-86 exp-93(IIIe) 24:67:9
127 exp-1 exp-86 exp-93(IIIf) 27:65:8
128 exp-1 exp-86 - 36:64
129 exp-1 exp-92 exp-93(IIIa) 25:64:11
130 exp-1 exp-92 exp-93(IIIb) 27:65:8
131 exp-1 exp-92 exp-93(IIIc) 26:69:5
132 exp-1 exp-92 exp-93(IIId) 27:66:7
133 exp-1 exp-92 exp-93(IIIe) 25:66:9
134 exp-1 exp-92 exp-93(IIIf) 28:66:8
135 exp-1 exp-92 - 37:63
136 exp-2 exp-66 exp-93(IIIa) 28:65:7
137 exp-2 exp-66 exp-93(IIIb) 30:66:4
138 exp-2 exp-66 exp-93(IIIc) 29:70:1
139 exp-2 exp-66 exp-93(IIId) 30:67:3
140 exp-2 exp-66 exp-93(IIIe) 28:67:5
141 exp-2 exp-66 exp-93(IIIf) 31:65:4
142 exp-2 exp-66 - 32:68
143 exp-2 exp-72 exp-93(IIIa) 26:68:6
144 exp-2 exp-72 exp-93(IIIb) 28:69:3
145 exp-2 exp-72 exp-93(IIIc) 26:73:1
146 exp-2 exp-72 exp-93(IIId) 28:70:2
147 exp-2 exp-72 exp-93(IIIe) 26:70:4
148 exp-2 exp-72 exp-93(IIIf) 29:68:3
149 exp-2 exp-72 - 31:69
150 exp-2 exp-76 exp-93(IIIa) 25:69:6
151 exp-2 exp-76 exp-93(IIIb) 27:70:3
152 exp-2 exp-76 exp-93(IIIc) 25:74:1
153 exp-2 exp-76 exp-93(IIId) 27:71:2
154 exp-2 exp-76 exp-93(IIIe) 25:71:4
156 exp-2 exp-76 exp-93(IIIf) 28:69:3
157 exp-2 exp-76 - 33:67
158 exp-2 exp-81 exp-93(IIIa) 26:67:7
159 exp-2 exp-81 exp-93(IIIb) 28:68:4
160 exp-2 exp-81 exp-93(IIIc) 27:72:1
161 exp-2 exp-81 exp-93(IIId) 28:69:3
162 exp-2 exp-81 exp-93(IIIe) 26:69:5
163 exp-2 exp-81 exp-93(IIIf) 29:67:4
164 exp-2 exp-81 - 35:65
165 exp-2 exp-86 exp-93(IIIa) 27:65:8
166 exp-2 exp-86 exp-93(IIIb) 29:66:5
167 exp-2 exp-86 exp-93(IIIc) 28:70:2
168 exp-2 exp-86 exp-93(IIId) 29:67:4
169 exp-2 exp-86 exp-93(IIIe) 27:67:6
170 exp-2 exp-86 exp-93(IIIf) 30:65:5
171 exp-2 exp-86 - 37:63
172 exp-2 exp-92 exp-93(IIIa) 28:64:8
173 exp-2 exp-92 exp-93(IIIb) 30:65:5
174 exp-2 exp-92 exp-93(IIIc) 29:69:2
175 exp-2 exp-92 exp-93(IIId) 30:66:4
176 exp-2 exp-92 exp-93(IIIe) 28:66:6
177 exp-2 exp-92 exp-93(IIIf) 31:66:5
178 exp-2 exp-92 - 39:61
179 exp-3 exp-66 exp-93(IIIa) 29:65:6
180 exp-3 exp-66 exp-93(IIIb) 31:66:3
181 exp-3 exp-66 exp-93(IIIc) 29:70:1
182 exp-3 exp-66 exp-93(IIId) 31:67:2
183 exp-3 exp-66 exp-93(IIIe) 29:67:4
184 exp-3 exp-66 exp-93(IIIf) 32:65:3
185 exp-3 exp-66 - 33:67
186 exp-3 exp-72 exp-93(IIIa) 27:68:5
187 exp-3 exp-72 exp-93(IIIb) 29:69:2
188 exp-3 exp-72 exp-93(IIIc) 26:73:1
189 exp-3 exp-72 exp-93(IIId) 29:70:1
190 exp-3 exp-72 exp-93(IIIe) 27:70:3
191 exp-3 exp-72 exp-93(IIIf) 30:68:2
192 exp-3 exp-72 - 31:69
193 exp-3 exp-76 exp-93(IIIa) 26:69:5
194 exp-3 exp-76 exp-93(IIIb) 28:70:2
195 exp-3 exp-76 exp-93(IIIc) 26:73:1
196 exp-3 exp-76 exp-93(IIId) 28:71:1
197 exp-3 exp-76 exp-93(IIIe) 26:71:3
198 exp-3 exp-76 exp-93(IIIf) 29:69:2
199 exp-3 exp-76 - 32:68
200 exp-3 exp-81 exp-93(IIIa) 27:67:6
201 exp-3 exp-81 exp-93(IIIb) 29:68:3
202 exp-3 exp-81 exp-93(IIIc) 28:71:1
203 exp-3 exp-81 exp-93(IIId) 29:69:2
204 exp-3 exp-81 exp-93(IIIe) 27:69:4
205 exp-3 exp-81 exp-93(IIIf) 30:67:3
206 exp-3 exp-81 - 36:64
207 exp-3 exp-86 exp-93(IIIa) 28:65:7
208 exp-3 exp-86 exp-93(IIIb) 30:66:4
209 exp-3 exp-86 exp-93(IIIc) 29:70:1
210 exp-3 exp-86 exp-93(IIId) 29:68:3
211 exp-3 exp-86 exp-93(IIIe) 28:67:5
212 exp-3 exp-86 exp-93(IIIf) 31:65:4
213 exp-3 exp-86 - 38:62
214 exp-3 exp-92 exp-93(IIIa) 29:64:7
215 exp-3 exp-92 exp-93(IIIb) 31:65:4
216 exp-3 exp-92 exp-93(IIIc) 30:69:1
217 exp-3 exp-92 exp-93(IIId) 31:66:3
218 exp-3 exp-92 exp-93(IIIe) 29:66:5
219 exp-3 exp-92 exp-93(IIIf) 32:66:4
220 exp-3 exp-92 - 40:60
221 exp-4 exp-66 exp-93(IIIa) 27:67:6
222 exp-4 exp-66 exp-93(IIIb) 29:68:3
223 exp-4 exp-66 exp-93(IIIc) 27:72:1
224 exp-4 exp-66 exp-93(IIId) 29:69:2
225 exp-4 exp-66 exp-93(IIIe) 27:69:4
226 exp-4 exp-66 exp-93(IIIf) 30:67:3
227 exp-4 exp-66 - 31:69
228 exp-4 exp-72 exp-93(IIIa) 25:70:5
229 exp-4 exp-72 exp-93(IIIb) 27:71:2
230 exp-4 exp-72 exp-93(IIIc) 25:74:1
231 exp-4 exp-72 exp-93(IIId) 27:72:1
232 exp-4 exp-72 exp-93(IIIe) 25:72:3
233 exp-4 exp-72 exp-93(IIIf) 28:70:2
234 exp-4 exp-72 - 29:71
235 exp-4 exp-76 exp-93(IIIa) 24:71:5
236 exp-4 exp-76 exp-93(IIIb) 26:72:2
237 exp-4 exp-76 exp-93(IIIc) 25:74:1
238 exp-4 exp-76 exp-93(IIId) 26:73:1
239 exp-4 exp-76 exp-93(IIIe) 24:73:3
240 exp-4 exp-76 exp-93(IIIf) 27:71:2
241 exp-4 exp-76 - 30:70
242 exp-4 exp-81 exp-93(IIIa) 25:69:6
243 exp-4 exp-81 exp-93(IIIb) 27:70:3
244 exp-4 exp-81 exp-93(IIIc) 26:73:1
245 exp-4 exp-81 exp-93(IIId) 27:71:2
246 exp-4 exp-81 exp-93(IIIe) 25:71:4
247 exp-4 exp-81 exp-93(IIIf) 28:69:3
248 exp-4 exp-81 - 34:66
249 exp-4 exp-86 exp-93(IIIa) 26:67:7
250 exp-4 exp-86 exp-93(IIIb) 28:68:4
251 exp-4 exp-86 exp-93(IIIc) 27:72:1
252 exp-4 exp-86 exp-93(IIId) 27:70:3
253 exp-4 exp-86 exp-93(IIIe) 26:69:5
254 exp-4 exp-86 exp-93(IIIf) 29:67:4
256 exp-4 exp-86 - 36:64
257 exp-4 exp-92 exp-93(IIIa) 27:66:7
258 exp-4 exp-92 exp-93(IIIb) 29:67:4
259 exp-4 exp-92 exp-93(IIIc) 28:71:1
260 exp-4 exp-92 exp-93(IIId) 29:68:3
261 exp-4 exp-92 exp-93(IIIe) 27:68:5
262 exp-4 exp-92 exp-93(IIIf) 30:68:4
263 exp-4 exp-92 - 38:62
264 exp-5 exp-66 exp-93(IIIa) 21:70:9
265 exp-5 exp-66 exp-93(IIIb) 23:71:6
266 exp-5 exp-66 exp-93(IIIc) 21:75:4
267 exp-5 exp-66 exp-93(IIId) 23:72:5
268 exp-5 exp-66 exp-93(IIIe) 21:72:7
269 exp-5 exp-66 exp-93(IIIf) 24:70:6
270 exp-5 exp-66 - 25:75
271 exp-5 exp-72 exp-93(IIIa) 19:73:8
272 exp-5 exp-72 exp-93(IIIb) 21:74:5
273 exp-5 exp-72 exp-93(IIIc) 18:78:4
274 exp-5 exp-72 exp-93(IIId) 21:75:4
275 exp-5 exp-72 exp-93(IIIe) 19:75:6
276 exp-5 exp-72 exp-93(IIIf) 22:73:5
277 exp-5 exp-72 - 23:77
278 exp-5 exp-76 exp-93(IIIa) 18:74:8
279 exp-5 exp-76 exp-93(IIIb) 20:75:5
280 exp-5 exp-76 exp-93(IIIc) 18:78:4
281 exp-5 exp-76 exp-93(IIId) 20:76:4
282 exp-5 exp-76 exp-93(IIIe) 18:76:6
283 exp-5 exp-76 exp-93(IIIf) 21:74:5
284 exp-5 exp-76 - 24:76
285 exp-5 exp-81 exp-93(IIIa) 19:72:9
286 exp-5 exp-81 exp-93(IIIb) 21:73:6
287 exp-5 exp-81 exp-93(IIIc) 20:76:4
288 exp-5 exp-81 exp-93(IIId) 21:74:5
289 exp-5 exp-81 exp-93(IIIe) 19:74:7
290 exp-5 exp-81 exp-93(IIIf) 22:72:6
291 exp-5 exp-81 - 28:72
292 exp-5 exp-86 exp-93(IIIa) 20:70:10
293 exp-5 exp-86 exp-93(IIIb) 22:71:7
294 exp-5 exp-86 exp-93(IIIc) 21:75:4
295 exp-5 exp-86 exp-93(IIId) 21:73:6
296 exp-5 exp-86 exp-93(IIIe) 20:72:8
297 exp-5 exp-86 exp-93(IIIf) 23:70:7
298 exp-5 exp-86 - 30:70
299 exp-5 exp-92 exp-93(IIIa) 21:69:10
300 exp-5 exp-92 exp-93(IIIb) 23:70:7
301 exp-5 exp-92 exp-93(IIIc) 22:74:4
302 exp-5 exp-92 exp-93(IIId) 23:71:6
303 exp-5 exp-92 exp-93(IIIe) 21:71:8
304 exp-5 exp-92 exp-93(IIIf) 22:71:7
305 exp-5 exp-92 - 30:70

Further the above mentioned examples serve to illustrate the invention by parts in weight it bears the same relation to parts by volume as the kilogram to the litre.

It relates to the use of compounds of the formula (I), (II) and (III) for dyeing or printing fibre materials containing hydroxyl groups or containing nitrogen, in particular containing cotton. The dyes according to the invention can be applied to the fibre material and fixed to the fibre in various ways, in particular in the form of aqueous dye solutions and printing pastes.

The said dyes are also suitable for printing, in particular on cotton, but likewise also for printing fibres containing nitrogen, for example wool, silk or blend fabrics containing wool. The dyeing instructions particular for application on cotton as well as wool and on printing are described below:

Dyeing Instructions particularly for cotton fabric:
• 100 parts of cotton fabric are introduced at temperature 60° C into 1000 parts of a dye bath which comprises 45 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 94-128,136-171,179-213,221-256& 264-298.
• After 45 minutes at 60° C temperature, 20 g/l of calcined sodium carbonate are added.
• Further dyeing is continued at this temperature for another 45 minutes. Thereafter, the dyed goods are rinsed, soaped with a nonionic detergent while boiling for a quarter an hour, rinsed again and dried. As an alternative to the above step, dyeing can also be carried out at 80° C instead of at 60° C.

Dyeing Instructions particularly for woollen fabric:
• Part of the dye according to Example 129-135,172-178,214-220,257-263 & 299-305 are dissolved in 200 parts of water and 0.5 part of sodium sulfate, 0.1 part of a levelling assistant (based on the condensation product of a higher aliphatic amine and ethylene oxide) and 0.5 part of sodium acetate are added.
• The pH is then brought to a value of 5.5 with acetic acid. The dyebath is heated to 50° C for 10 minutes and 10 parts of a woollen fabric is then added.
• The dyebath is heated to a temperature of 100° C in the course of about 50 minutes and dyeing is carried out at this temperature for 60 minutes.
• Thereafter, the bath is allowed to cool to 90° C and the dyed goods are removed. The woollen fabric is washed with warm and cold water and then spun and dried.

Dyeing Instructions particularly for printing fabric:

• 3 parts of the dye obtained according to Example 94-305 are sprinkled with rapid stirring into 100 parts of a stop thickener comprising 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium bicarbonate.
• A cotton fabric is printed with the printing paste thus obtained, dried, and the resulting printed material is steamed in saturated steam at 102° C for 2 minutes.
• The said printed fabric is then rinsed, can be soaped at the boil and rinsed again and is then dried.

The dyeing and prints obtainable with the dye mixture possess bright shades; more particularly, the dyeing and prints on cellulose fiber materials possess good light fastness and especially good wet fastness properties.

The dyeing and prints produced with the dyes, in particular the reactive dyes, have high colour strength and high fibre-dye bond stability and furthermore a good fastness to light and very good wet fastness properties, such as fastness to washing, water, sea water, cross dyeing and perspiration.

The said dye mixture is applied and fixed on the substrates especially the cotton, wool, silk, cellulose and fiber materials by the appliance method known especially for water soluble dyes and fiber-reactive dyes. It mainly produces dyeing of intense black shades having good color build-up properties and good wash-off properties.

While the present invention has been described with respect to what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, the invention is intended to cover various modifications and equivalent ranges included within the spirit and scope of those skilled in the art. It is expressly understood, however, that such modifications and range are within the spirit and scope of the present invention as set forth in the following claims.

Dated this 9th day of March 2019. ,CLAIMS:We claim:-
1. A composition for deep black dye mixture of fiber-reactive azo dyes comprises: 10% to 20% triazo dye selected from formula (Ia), (Ib), (Ic), (Id), (Ie), 50% to 60% of disazo dyes of the formula (II), 5% to 10% monoazo dyes selected from formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), 10% to 35% of antidusting oil and other excipients;
wherein the formula (Ia), (Ib), (Ic), (Id), (Ie) are represented as follows:

Formula (Ia),

Formula (Ib),

Formula (Ic),

Formula (Id),

Formula (Ie),

wherein the formula (II) is represented as follows:

Formula (II),

wherein the formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf) are represented as follows:

(IIIa) (IIIb)

, ,
(IIIc) (IIId)
, ,

(IIIe) (IIIf)
, ,

2. The composition for deep black dye mixture of fiber-reactive azo dyes as claimed in claim 1, wherein R1 and R2 of triazo dye of formula (Ia), (Ib), (Ic), (Id), (Ie) are selected from following reactive moieties:


, ,

, ,

,
, , ,
, ,

, ,

, ,



.

3. The composition for deep black dye mixture of fiber-reactive azo dyes as claimed in claim 1, wherein x of formula (II) is selected from following reactive moieties:

, , ,

, , ,

, , ,

, , ,

, ,

.

4. The composition for deep black dye mixture of fiber-reactive azo dyes as claimed in claim 1, wherein z of formula (II) is selected from following reactive moieties:
, , ,

, , ,

, ,

, ,

, ,

, , .

5. The composition for deep black dye mixture of fiber-reactive azo dyes as claimed in claim 1, wherein other excipients is selected from sodium sulphate, sodium chloride, Tammol (formaldehyde naphthalene sulphontes) and lignine sulphontes.