Fibre reactive dyes, their preparation and their use

Abstract

A reactive dye of formula ##STR00001##
wherein M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, Z.sub.1 is vinyl, ?-sulfatoethyl or the radical NHCO(CH.sub.2).sub.3SO.sub.2CH.sub.2CH.sub.2Cl; R.sub.1 denotes H or sulfo; and R.sub.2 is H, methyl, methoxy or sulfo, n is the number 3; Y is vinyl or a radical CH.sub.2CH.sub.2-U and U is Cl or OSO.sub.3H, is suitable for dyeing and printing cellulosic or amide-group-containing fibre materials.

Claims

1. A reactive dye of formula ##STR00012## wherein M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, Z1 is vinyl, ?-sulfatoethyl, ?-sulfatoethylsulfonyl or the radical NHCO(CH.sub.2).sub.3SO.sub.2CH.sub.2CH.sub.2Cl, R1 denotes H or sulfo, and R2 is H, methyl, methoxy or sulfo, n is the number 3, Y is vinyl or a radical CH.sub.2CH.sub.2-U and U is Cl or OSO.sub.3H.

2. The reactive dye of formula (1) according to claim 1, wherein Z1 is ?-sulfatoethyl or NHCO(CH.sub.2).sub.3SO.sub.2CH.sub.2CH.sub.2Cl.

3. The reactive dye of formula (1) according to claim 1, wherein R.sub.1 denotes H.

4. The reactive dye of formula (1) according to claim 1, wherein Y is a radical CH.sub.2CH.sub.2-U and U is Cl or OSO.sub.3H.

5. The reactive dye according to claim 1, wherein the reactive dye of formula (1) is a dye of formula ##STR00013## wherein M is as defined in claim 1, Z1 is ?-sulfatoethyl, ?-sulfatoethylsulfonyl or NHCO(CH.sub.2).sub.3SO.sub.2CH.sub.2CH.sub.2Cl, R.sub.1 denotes H or sulfo, and R.sub.2 is H, methyl, methoxy or sulfo.

6. A dye mixture comprising: (A) 20-60% by weight of one or more reactive dyes of formula (1) according to claim 1, and (B) 40-80% by weight of at least one blue, yellow, orange or brown dyeing reactive dye different from the dye of formula (1), each percentage being based on the sum total of all dyes.

7. The dye mixture according to claim 6 comprising one or more dyes selected from C.I. R BL 220, C.I. R BL 235, C.I. R BL 19 and C.I. R BL 279 as component (B).

8. A process for the preparation of the reactive dye of formula (1), which comprises: (a) diazotising a compound of the formula ##STR00014## wherein R.sub.1, R.sub.2 and Z.sub.1 have the meanings as defined in claim 1 and R.sub.6 denotes H or C.sub.1-C6 alkyl; and reacting the diazonium salt so obtained with a coupling component of formula ##STR00015## wherein M is as defined in claim 1; whereby an azo compound of formula ##STR00016## is obtained, wherein R.sub.1, R.sub.2, Z.sub.1, R.sub.6 and M are as defined in claim 1; (b) reacting a compound of formula ##STR00017## wherein M is as defined in claim 1, with a compound of formula
ClCO(CH.sub.2).sub.nSO.sub.2Y(7), wherein Y and n are as defined in claim 1, thereby providing a compound of formula ##STR00018## wherein M, Y and n are as defined in claim 1; (c) diazotising the compound of the formula (5) prepared in step (a) and reacting the diazonium salt so obtained with the coupling component of formula (8) prepared in step (b); and (d) reacting the bisazo dye prepared in step (c) with a Cu(II) salt in aqueous solution at pH <7 thus providing the copper complex dye of formula (1) according to claim 1.

9. A process for the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre materials, wherein a reactive dye according to claim 1 or a mixture of reactive dyes according to claim 6 or 7 is used.

10. An aqueous ink comprising at least one dye of formula (1).

11. A reactive dye of formula ##STR00019##

12. A process for the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre materials, wherein the reactive dye according to claim 11 is used.

13. An aqueous ink comprising at least one dye according to claim 11.

14. A reactive dye of formula ##STR00020##

15. A process for the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre materials, wherein the reactive dye according to claim 14 is used.

16. An aqueous ink comprising at least one dye according to claim 14.

Description

EXAMPLE 1

(1) (a) 62.2 parts of 2-methoxy-4-(?-sulfatoethylsulfonyl)-1-aminobenzene finely dispersed in 200 parts of water, are diazotized at pH<1.5 and 20? C. by addition of 17.5 parts of sodium nitrite. The reaction mixture is stirred for one hour and excess of nitrite is destroyed by addition of sulfamic acid. (b) 63.9 parts of 2-amino-1,7-disulfo-5-hydroxynaphthalene are finely dispersed in 700 parts of water and pH is set up at 6.0 by use of sodium hydroxide 30% solution. By ice addition, temperature is kept by 5-20? C. Diazonium salt obtained in (i) is then added over 30 minutes by 5-20? C. while pH is kept at 6.0 by use of sodium hydroxide 30% solution. (c) 63.9 parts of 1-amino-3,6-disulfo-8-naphthol are finely dispersed in 400 parts of water and 100 parts of ice. By use of sodium hydroxide 30% solution, pH is set up to 7.0. After addition of 300 parts of ice, 62.5 parts of ?-chloroethylsulfonylbutyryl chloride are slowly added to the above solution by maintaining pH at 7.0-7.5 by the use of soda 20% solution and the temperature between 0-10? C. (d) 150 parts of water, 150 parts of ice and 60 parts of hydrochloric acid (32%) are mixed together. To this, is slowly added a mixture of the compound obtained according to (b) and 17.5 parts of sodium nitrite by pH<1.5 and temperature at 0-15? C. The resulting mixture is the stirred 30 minutes. Excess of nitrite is destroyed by addition of sulfamic acid. (e) the mixture obtained according to (d) is added over 1 hour at pH 6.5 and at a temperature of 0-20? C. to the mixture obtained according to (c) which is preliminary cooled with 150 parts of ice. pH is kept at value 6.5 by the use of sodium hydroxide 30% solution. After addition completion, the mixture is stirred for one additional hour. (f) The mixture obtained according to (e) is combined with 32.2 parts of copper (II) chloride and pH is set up to value 4.5 by use of soda 20% solution. The resulting mixture is then stirred at pH 4.5 kept by use of soda 20% solution for 30 hours at 95-100? C. After reaction completion, the pH is the adjusted to 6.0 and the dyestuff obtained is isolated by methods commonly known in the art, for example, by desalting using a dialysis membrane. 305 parts of the crude dyestuff are obtained (?.sub.max; 576 nm) which main component, in the form of the free acid, corresponds to the formula

(2) ##STR00009##

EXAMPLES 2-4

(3) The following dyes, each of which dyes cellulose in a blue to violet shade with good all-round fastness properties, can be prepared in a manner analogous to that described in Example 1.

(4) ##STR00010##

APPLICATION EXAMPLE 1

Pad Batch Dyeing

(5) On a padder having a squeezing effect of 75% (70%) liquor pick-up, a bleached (mercerized) cotton cretonne fabric is impregnated with an aqueous dyeing liquor containing, per litre, X g of the dyestuff of formula (104) obtained according to Example 4, 1 g of a wetting agent (ALBAFLOW? PAD), 20 ml (?) of sodium hydroxide 36? B? and 70 ml of sodium silicate (water glass) 38? B?. The immersion time is 2 seconds. After padding, the fabric is rolled up and then stored for 24 hours at a temperature of 25? C. After storage, the dyed cotton material is cold-rinsed with water (10 min), boiled in water (5 min) and subsequently cold-rinsed with water (10 min). Blue shaded fabrics of different colour depths are obtained with the dyeing liquors 1 to 3 dependent on the dyestuff concentration (X g/l).

(6) The tinctorial strengths of the dyeings are measured photospectrometrically. Table 1 summarizes the build-up properties. The dyestuff prepared according to Example 4 shows very good build-up properties.

(7) TABLE-US-00001 TABLE 1 Build-up: dependence of reference depth (RD) from dyestuff concentration Dyebath 1 2 3 Dyestuff of Ex. 3 [X g/l] 10 20 60 Co cretonne bleached 0.76 1.27 2.28 Co cretonne mercerized 1.12 1.88 3.11

APPLICATION EXAMPLE 2

(8) As described in Application Example 1, a cotton cretonne fabric is dyed with a mixture comprising 30.0 parts by weight of a dye of formula (103) and 70.0 parts by weight of a dye of formula

(9) ##STR00011##

(10) Blue shaded fabrics of different colour depths are obtained with the dyeing liquors containing different amounts of dye mixture dependent on the dyestuff concentration (X g/l).

(11) The tinctorial strengths of the dyeings are measured photospectrometrically. Table 2 summarizes the build-up properties. The mixture of the dye of formula (103) and the dye of formula (901) shows very good build-up properties.

(12) TABLE-US-00002 TABLE 2 Build-up: dependence of reference depth (RD) from dyestuff concentration Concentration of 0.50 1.00 2.00 4.00 6.00 8.00 Dye Mixture [%] Colour Depth 0.35 0.64 1.19 2.14 2.64 3.15

(13) A bleached cotton cretonne fabric dyed according to the above method with the mixture of 30% by weight of dye of formula (103) and 70% by weight of dye of formula (901) is subjected to xenon light fastness testing (ISO 105/E03). Changes in colour are determined according to the Grey Scale. The fabric is rated 4.