A REACTIVE NAVY TO BLACK DYE COMPOSITION AND DYE PRODUCT THEREOF

Abstract

A reactive navy to black dye composition comprises component A and component B, wherein component A is selected from one or more compounds of formula (I), component B is selected from one or more compounds of formula (II); D.sup.1 and D.sup.2 are each independently a group represented by the following formula (a) or (b) or (c); R.sup.1-R.sup.2 are each independently selected from the group consisting of H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy and sulfo; m, n=0-3, and every R.sup.3 is each independently selected from the group consisting of amino, sulfo, ureido, C.sub.1C.sub.4 alkanoylamino, C.sub.1C.sub.4 alkoxy and C.sub.1C.sub.4 alkyl, every R.sup.6 is each independently selected from the group consisting of amino, hydroxyl and sulfo; X.sup.1-X.sup.3 are each independently selected from the group consisting of H, C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy, SO.sub.2Y.sup.1, NHCO(CH.sub.2).sub.pSO.sub.2Y.sup.2 and CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, and at least one of D.sup.1 and D.sup.2 contains a fiber-reactive group, p, q=1-3, and Y.sup.1Y.sup.5 are each independently selected from the group consisting of CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H and CH.sub.2CH.sub.2Cl. A reactive navy to black dye product comprising the dye composition, has the properties of good washing fastness, high degree of fixation and dye-uptake, good build-up, clear remanent dyeing liquor, and the like.

##STR00001##

Claims

1. A reactive navy to black dye composition, comprising component A and component B, wherein component A is selected from one or more dye compounds of formula (I), component B is selected from one or more dye compounds of formula (II); and based on component A and component B, component A has a mass percentage of 5% to 50%, and component B has a mass percentage of 50% to 95%; ##STR00143## in formula (I): D.sup.1 and D.sup.2 are each independently a group represented by the following formula (a) or (b) or (c); ##STR00144## in the above formulae (a)(c): R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; m=0-3, and every R.sup.3 is each independently selected from the group consisting of amino, sulfo, ureido, C.sub.1C.sub.4 alkanoylamino, C.sub.1C.sub.4 alkoxy and C.sub.1C.sub.4 alkyl; n=0-3, and every R.sup.6 is each independently selected from the group consisting of amino, hydroxyl and sulfo; X.sup.1,X.sup.2 and X.sup.3 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy, SO.sub.2Y.sup.1, NHCO(CH.sub.2).sub.pSO.sub.2Y.sup.2 or -CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, and at least one of D.sup.1 and D.sup.2 contains a fiber-reactive group, that is, SO.sub.2Y.sup.1, NHCO(CH.sub.2).sub.pSO.sub.2Y.sup.2 or CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, wherein p=1-3, q=1-3, and Y.sup.1Y.sup.3 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or CH.sub.2CH.sub.2Cl; in formula (II): R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; Y.sup.4 and Y.sup.5 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or C.sub.2H.sub.4Cl.

2. The reactive navy to black dye composition as claimed in claim 1, wherein the composition comprises component A and component B, wherein component A is selected from one or more dye compounds of formula (IA), component B is selected from one or more dye compounds of formula (II); based on component A and component B, component A has a mass percentage of 5% to 50%, and component B has a mass percentage 50% to 95%; ##STR00145## in formula (IA): D.sup.1 and D.sup.2 are each independently a group represented by the following formula (a) or (b) or (c); ##STR00146## in the above formulae (a), (b) and (c): R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; m=0-3, and every R.sup.3 is each independently selected from the group consisting of sulfo, ureido and C.sub.1C.sub.4 alkanoylamino; n=0-3, and every R.sup.6 is each independently selected from the group consisting of hydroxyl and sulfo; X.sup.1, X.sup.2 and X.sup.3 are each independently SO.sub.2Y.sup.1, NHCO(CH.sub.2).sub.pSO.sub.2Y.sup.2 or CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, wherein p=1-3, q=1-3, and Y.sup.1Y.sup.3 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or CH.sub.2CH.sub.2Cl; in formula (II): R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; Y.sup.4 and Y.sup.5 are each independently -CH=CH.sub.2, -C.sub.2H.sub.4OSO.sub.3H or -C.sub.2H.sub.4C1.

3. The reactive navy to black dye composition as claimed in claim 1, wherein both D.sup.1 and D.sup.2 are the group of the general formula (a) wherein the substituents are the same or different; or D.sup.1 is selected from the group of formula (a), and D.sup.2- is selected from the group of formula (b) or formula (c).

4. The reactive navy to black dye composition as claimed in claim 1, wherein component A is selected from one or more dye compounds of the following formulae: ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164##

5. The reactive navy to black dye composition as claimed in claim 1, wherein component A is selected from at least one of formulae (I-1) (I-63), (I-88) and (I-89), preferably selected from at least one of formulae (I-1) (I-21), (I-27) (I-33), (I-41) (I-63), (I-88) and (I-89), more preferably selected from at least one of formulae (I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), (I-51), (I-52), (I-55) and (I-88), even more particularly preferably selected from at least one of formulae (I-31), (I-32), (I-51) and (I-52).

6. The reactive navy to black dye composition as claimed in claim 1, wherein component B is selected from one or more dye compounds of the following formulae: ##STR00165## ##STR00166##

7. The reactive navy to black dye composition as claimed in claim 1, wherein the reactive navy to black dye composition consists of component A and component B.

8. The reactive navy to black dye composition as claimed in claim 1, wherein the reactive navy to black dye composition further comprises component C, and component C is selected from one or more compounds of formulae (III)(VI), the mass of component C in the composition is 1% to 50% of the total mass of component A and component B; ##STR00167## in formula (III): R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy, carboxyl or sulfo; Y.sup.6 and Y.sup.7 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or C.sub.2H.sub.4Cl; a is 0 or 1; b is 0 or 1; c and d are each independently 0 or 1; every D.sup.3 and D.sup.4 is each independently substituted phenyl, unsubstituted phenyl, substituted naphthyl or unsubstituted naphthyl, and the number of the substituents of the substituted phenyl and the substituted naphthyl is 1-3, respectively, and each of the substituents is independently selected from the group consisting of amino, sulfo, ureido, C.sub.1C.sub.4 alkanoylamino, C.sub.1C.sub.4 alkoxy and hydroxyl; in formula (IV): R.sup.17R.sup.20 are each independently H, linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; s=0-1, and Y.sup.8 and Y.sup.9 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or C.sub.2H.sub.4Cl; in formula (V): e, f and g are each independently selected from 0-3, and every R.sup.21, R.sup.22 and R.sup.23 is each independently linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy and sulfo; X.sup.4 is hydrogen or carboxyl; Y.sup.10 and Y.sup.11 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or C.sub.2H.sub.4Cl; in formula (VI): h=0-2, and every R.sup.24 is each independently linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; i=1-3, and every R.sup.25 is each independently selected from the group consisting of amino, sulfo, ureido, C.sub.1C.sub.4 alkanoylamino, C.sub.1C.sub.4 alkoxy and hydroxyl; Y.sup.12 is CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or C.sub.2H.sub.4Cl.

9. The reactive navy to black dye composition as claimed in claim 8, wherein component C is selected from at least one dye of formula (III) and/or formula (VI), wherein both a and b are 0, or one of a and b is 0, while the other is 1, c is 1, and d is 0 or 1.

10. The reactive navy to black dye composition as claimed in claim 8, wherein the reactive navy to black dye composition comprises the following components: component A which is selected from at least one dye of formula (I), wherein D.sup.1 and D.sup.2 are each independently the group of the general formula (a), and the substituents are the same or different; or D.sup.1 is the group of formula (a), D.sup.2 is the group of formula (b) or formula (c); and at least one of D.sup.1 and D.sup.2 contains SO.sub.2Y.sup.1; component B which is selected from at least one dye of formula (II); and component C which is selected from at least one dye of formula (III) and/or formula (IV), wherein both a and b are 0, or one of a and b is 0, while the other is 1, c is 1, and d is 0 or 1.

11. The reactive navy to black dye composition as claimed in 8, wherein component C is selected from one or more dyes of the following formulae: ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181##

12. The reactive navy to black dye composition as claimed in claim 8, wherein the reactive navy to black dye composition consists of component A, component B and component C.

13. The reactive navy to black dye composition as claimed in claim 4, wherein the dye composition comprises component A and component B, wherein component A is selected from at least one dye of formulae (I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), (I-51), (I-52), (I-55) and (I-88) more particularly preferably selected from at least one dye of formulae (I-31), (I-32), (I-51) and (I-52); and component B is selected from the dye of formula (II-1) and/or the dye of formula (II-3); based on the sum of the mass of component A and component B, the mass percentage of component A is 5% to 50%, and the mass percentage of component B is 50% to 95%, ##STR00182##

14. The reactive navy to black dye composition as claimed in claim 4, wherein the dye composition comprises component A, component B and component C, wherein component A is selected from at least one dye of formulae (I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), (I-51), (I-52), (I-55) and (I-88), more particularly preferably selected from at least one dye of formulae (I-31), (I-32), (I-51) and (I-52); component B is selected from the dye of formula (II-1) and/or the dye of formula (II-3); and component C is selected from at least one dye of formulae (III-1), (III-2), (III-4), (IV-1) and (IV-3); based on the sum of the mass of component A and component B, the mass percentage of component A is 5% to 50%, the mass percentage of component B is 50% to 95%, and the mass of component C is 1% to 50% of the total mass of component A and component B, ##STR00183##

15. The reactive navy to black dye composition as claimed in claim 1, wherein the dye of the general formula (I) contains a quinohydrazone structure of the following formula (Ia) and/or formula (Ib) and/or (Ic) and/or (Id), and the dye of the general formula (II) contains a quinohydrazone structure of the following formula (IIa): ##STR00184## the definitions of the substituents of the above formulae (Ia)(Id) are the same as that of formula (I), and the definitions of the substituents of formula (IIa) is the same as that of formula (II).

16. The reactive navy to black dye composition as claimed in claim 8, wherein the dye of the general formula (IV) contains a quinohydrazone structure of the following formula (IVa): ##STR00185## the definitions of the substituents of the above formula (IVa) is the same as that of formula (IV).

17. A reactive navy to black dye product, comprising the navy to black dye composition as claimed in claim 1.

18. The reactive navy to black dye composition as claimed in claim 1, wherein the dye compound of formula (I) or formula (II) is prepared and isolated in the form of alkali metal salt in the actual synthesis process and also used for dyeing in the form of alkali metal salt.

19. The reactive navy to black dye composition as claimed in claim 17, wherein the alkali metal salt is sodium or potassium salt.

20. The reactive navy to black dye composition as claimed in claim 18, wherein the alkali metal salt is sodium salt.

21. The reactive navy to black dye composition as claimed in claim 8, wherein the dye compound of formula (III), formula (IV) or formula (V) is prepared and isolated in the form of alkali metal salt in the actual synthesis process and also used for dyeing in the form of alkali metal salt.

22. The reactive navy to black dye composition as claimed in claim 20, wherein the alkali metal salt is sodium or potassium salt.

23. The reactive navy to black dye composition as claimed in claim 21, wherein the alkali metal salt is sodium salt.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0067] FIG. 1 is the 1HNMR spectrum of the reactive orange dye compound (I-1) obtained in example 1;

[0068] FIG. 2 is the LC-MS spectrum of the reactive orange dye compound (I-1) obtained in example 1;

[0069] FIG. 3 is the 1HNMR spectrum of the compound (I-31) obtained in example 1;

[0070] FIG. 4 is the 13C NMR spectrum of the compound (I-31) obtained in example 1;

SPECIFIC EMBODIMENTS

[0071] The present invention will be further described in conjunction with the specific examples, but the scope of protection of the present invention is not limited thereto. In the range of the general formulae of the present invention, dye compositions having similar properties obtained by corresponding group replacement should be included in the scope of protection of the present invention.

EXAMPLE 1

[0072] 1) Diazotization: 100 g of water and 100 g of ice were added into 32.5 g (0.2 mol) of cristidine para-ester (2-methoxy-5-methyl-para-ester) and beaten for 1 h, then 40 g of 31% hydrochloric acid (containing 0.34 mol of HCl) were added, 48 g of a 30% sodium nitrite solution (containing 0.208 mol of sodium nitrite) were added within 20-30 minutes, the diazotization reaction was carried out by controlling pH between 0.5 and 2.0 and temperature T at 0 C. to 20 C., and the end point was detected using an ethanol solution of 4-dimethylaminobenzaldehyde (ie, no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the diazo solution was stored for use.

[0073] 2) First-coupling: 15.4 g (0.1mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating. After the beating, the diazo solution of 0.1 mol cristidine di-ester was added to 3,5-dihydroxybenzoic acid solution. Meanwhile, the pH was controlled at 4.0 with 30% liquid alkali, the temperature was controlled at 0 C. to 20 C., the reaction was carried out for 0.5-2 h, and when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction was ended. Otherwise, the reaction time was extended until the reaction came to the end. And the obtained first-coupling product was stored for use.

[0074] 3) Second-coupling: the diazo solution of 0.1 mol cristidine di-ester was added to the first-coupling product, the pH was controlled at 5.0 to 8.0 with 30% liquid alkali, the temperature was controlled at 0 C. to 20 C., the reaction was carried out for 0.5-2 h, when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction was ended. And the mixture was dried to obtain the orange reactive dye compound (I-1), whose .sub.max in water was 465 nm.

##STR00044##

EXAMPLES 230

[0075] Referring to the preparation method of the disazo dye described in example 1, the dye compounds of the structures shown in table 1 and table 2 were obtained by stepwise coupling:

TABLE-US-00001 1 TABLE 1 Wavelength Examples Reactive dye compound (nm) 2 [00045] 430 3 [00046] 420 4 [00047] 425 5 [00048] 425 6 [00049] 420 7 [00050] 420 8 [00051] 420 9 [00052] 455 10 [00053] 435 11 [00054] 440 12 [00055] 435 13 [00056] 445 14 [00057] 425 15 [00058] 420 16 [00059] 425 17 [00060] 430 18 [00061] 435 19 [00062] 435

TABLE-US-00002 2 Table 2 Wavelength Examples Reactive dye compounds (nm) 20 [00063] 450 21 [00064] 450 22 [00065] 450 23 [00066] 420 24 [00067] 420 25 [00068] 420 26 [00069] 425 27 [00070] 425 28 [00071] 435 29 [00072] 435 30 [00073] 435

EXAMPLE31

[0076] 1) Diazotization:

[0077] 28.1 g (0.1 mol) of para-ester (p--hydroxyethylsulfone sulfate aniline) were added into 100 g of water and 100 g of ice, beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and added with 24 g of a 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) within 20min to 30min. The diazotization reaction was carried out for 1-2 hours by controlling pH between 0.5 and 2.0 and temperature T at 0 C. to 20 C., and the end point was detected using an ethanol solution of 4-dimethylaminobenzaldehyde (ie, no no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained diazo solution of para-ester was stored for use.

[0078] 36.1 g (0.1 mol) of sulfonated para-ester (2-sulfonic acid-4--hydroxyethylsulfone sulfate aniline) were added into 100 g of water and 100 g of ice, beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and added with 24 g of a 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 1 hour to 2 hours by controlling pH between 0.5 and 2.0 and temperature T at 0 C. to 20 C., and the end point was detected using an ethanol solution of 4-dimethylaminobenzaldehyde (ie, no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained diazo solution of sulfonated para-ester was stored for use.

[0079] The above diazo solution of 0.1 mol sulfonated para-ester was added to 15.1 g (0.1 mol) of m-urea (m-ureidoaniline), the pH was controlled between 4.0 and 6.0 with 30% liquid alkali, and the temperature T was controlled at 0 C. to 20 C., the coupling reaction was carried out for 0.5 h to 2 h. The reaction solution was tested with H acid test solution, if the bleed circle was colorless, it meant that the diazo had been reacted completely to the end point (if not, the reaction continued to the end point), thereby obtaining chromophore 1. Chromophore 1 was added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), added with 24 g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20-30 min. The diazotization reaction was carried out for lhour to 2 hours by controlling pH between 0.5 and 2.0 and temperature T at 0 C. to 20 C., and the end point was detected using an ethanol solution of 4-dimethylaminobenzaldehyde (ie, no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained solution of chromophore 1 in diazo was stored for use.

[0080] 2) Coupling:

[0081] Firstly, 154 g (0.1 mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating, pH was adjusted to 8.0-9.0 with soda ash, the temperature was 20 C. to 25 C., and the beaten 3,5-dihydroxybenzoic acid solution was added to the diazo solution of 0.1 mol para-ester obtained in step 1), the pH was controlled at 4.0 with 30% liquid alkali, the temperature was controlled at 0 C. to 20 C., the reaction was carried out for 0.5h to 2.5 h, and when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction was ended, and chromophore 2 represented by the following formula (A) was obtained, and characterized by H1-NHR spectra[.sup.1HNMR (DMSO-d6) [3.68-3.71 ppm 2H(t), 3.98-4.01 ppm 2H(t), 6.42ppm 1H(s), 6.62 ppm 1H(s), 7.96-7.97 ppm 2H (d), 8.05-8.07 ppm 2H (d)].

##STR00074##

[0082] The diazo solution of chromophore 1 obtained in step (1) was added to the chromophore 2, the pH was controlled between 5.0 and 8.0 with 30% liquid alkali, and the temperature T was controlled at 0 C. to 20 C., the coupling reaction was further carried out for 0.5 h to 10 h. The diazotization was tested with H acid test solution, and if the bleed circle was colorless, it meant that the diazo had been reacted completely to the end point, thereby obtaining the orange reactive dye compound (I-31). In aqueous solution its max=485 nm, the mass spectrum (ESI-MS) m/z (): 325.84 ([M-3H].sup.3/3), 488.96 ([M-2H].sup.2/2), 978.89 ([M-H].sup.1). The dye (in terms of free sulfonic acid) had the molecular weight M of 980.0, and was characterized by H1-NHR spectrar[.sup.1HNMR(DMSO-d6)[3.61-3.74 ppm 4H(m), 3.96-4.04 ppm 4H(m), 6.22 ppm 1H(s), 7.48-8.20 ppm 8H(m), 8.40 ppm 1H(s), 9.02 ppm 1H (s), 11.1 ppm 1H (s)].

##STR00075##

EXAMPLE 3290

[0083] Referring to the preparation method of the azo dye described in example 31, the dye compounds of the structures shown in the following tables 3-7 were respectively obtained by stepwise diazotization and coupling reactions as needed.

TABLE-US-00003 TABLE 3 Wavelength Example Reactive dye compounds (nm) 32 [00076] 480 33 [00077] 485 34 [00078] 490 35 [00079] 495 36 [00080] 490 37 [00081] 465 38 [00082] 470 39 [00083] 465 40 [00084] 465 41 [00085] 480 42 [00086] 480 43 [00087] 475 44 [00088] 470 45 [00089] 485 46 [00090] 475 47 [00091] 470 48 [00092] 485 49 [00093] 520 50 [00094] 510 51 [00095] 510 52 [00096] 525

TABLE-US-00004 Wavelength Example Reactive dye compounds (nm) 53 [00097] 500 54 [00098] 510 55 [00099] 470 56 [00100] 510 57 [00101] 520 58 [00102] 510 59 [00103] 500 60 [00104] 510 61 [00105] 535 62 [00106] 535 63 [00107] 485 64 [00108] 485 65 [00109] 485

TABLE-US-00005 TABLE 5 Wavelength Example Reactive dye compounds (nm) 66 [00110] 500 67 [00111] 510 68 [00112] 515 69 [00113] 475 70 [00114] 480 71 [00115] 465 72 [00116] 485 73 [00117] 485 74 [00118] 480 75 [00119] 465 76 [00120] 480 77 [00121] 475

TABLE-US-00006 TABLE 6 Wavelength Example Reactive dye compounds (nm) 78 [00122] 455 79 [00123] 455 80 [00124] 465 81 [00125] 500 82 [00126] 505 83 [00127] 510 84 [00128] 455

TABLE-US-00007 TABLE 7 Wavelength Example Reactive dye compounds (nm) 85 [00129] 465 86 [00130] 485 87 [00131] 480 88 [00132] 500 89 [00133] 455 90 [00134] 520

EXAMPLE 91

[0084] 25 parts of the dye of formula (I-1), 75 parts of the dye of formula (II-3) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye mixture dyed cotton black by the conventional dip dyeing method, and the staining fastness to washing of the dyeings, especially on nylon, polyester and acrylon, was not lower than grade 4-5 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00135##

EXAMPLE 92

[0085] 35 parts of the dye of formula (I-31), 65 parts of the dye of formula (II-3) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye mixture dyed cotton black by the conventional dip dyeing method , and the staining fastness to washing of the dyeings especially on nylon, polyester and acrylon was not lower than grade 4-5 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00136##

EXAMPLE 93

[0086] 30 parts of the dye of formula (I-31), 5 parts of the dye of formula (I-4), 65 parts of the dye of formula (II-3) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye mixture dyed cotton black by the conventional dip dyeing method, and the staining fastness to washing of the dyeings, especially on nylon, polyester and acrylon, was not lower than grade 4-5 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00137##

EXAMPLE 94

[0087] 30 parts of the dye of formula (I-31), 5 parts of the dye of formula (I-3), 65 parts of the dye of formula (II-3) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye mixture dyed cotton black by the conventional dip dyeing method, and the staining fastness to washing of the dyeings, especially on nylon, polyester and acrylon, was not lower than grade 4-5 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00138##

EXAMPLE 95

[0088] 20 parts of the dye of formula (I-31), 65 parts of the dye of formula (I-3), 15 parts of the dye of formula (III-1) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye mixture dyed cotton dark black by the conventional dip dyeing method, and the staining fastness to washing of the dyeings, especially on nylon, polyester and acrylon was not lower than grade 45(referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00139##

EXAMPLE 96

[0089] 20 parts of the dye of formula (I-31), 65 parts of the dye of formula (I-3), 10 parts of the dye of formula (IV-1), 10 parts of sodium sulfate powder, and 10 parts of dispersant MF were mechanically mixed, and the obtained dye mixture dyed cotton dark black, and the staining fastness to washing of the dyeings, especially on nylon, polyester and acrylon was not lower than grade 45 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

##STR00140##

EXAMPLE 97286

[0090] According to the method described in example 91 or example 96, the dyes with listed ratio in table 7 and 8 were mechanically mixed, and the obtained dye mixture dyed cotton dark blue to black by the conventional reactive dyeing method, and the staining fastness to washing of the dyeings especially on nylon, polyester and acrylon was not lower than grade 45 (referring to ISO 105 C10-2006), and the build-up was excellent (referring to GB/T21875-2016), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).

TABLE-US-00008 TABLE 7 Ex- Component Component Component ample A B C Ratio Shade 97 (I-31) (II-3) (III-1) 5:95:(35 + 20) Black (IV-1) 98 (I-31) (II-3) (V-1) 10:90:15 Navy 99 (I-31) (II-3) (V-7) 15:85:20 Black 100 (I-31) (II-3) (V-8) 20:80:25 Black 101 (I-31) (II-3) (III-8) 25:75:10 Black 102 (I-31) (II-3) (III-9) 30:70:20 Black 103 (I-31) (II-3) (III-10) 35:65:5 Black 104 (I-31) (II-3) (III-33) 40:60:10 Black 105 (I-31) (II-3) (III-32) 45:55:5 Black 106 (I-31) (II-3) (III-31a) 50:50:5 Black 107 (I-31) (II-3) (III-31b) 35:65:1 Black 108 (I-31) (II-13) (III-1) 5:95:30 Black 109 (I-31) (II-13) (IV-1) 5:95:35 Black 110 (I-31) (II-13) (III-1) 5:95:(20 + 20) Black (IV-1) 111 (I-31) (II-12) (III-1) 10:90:15 Black 112 (I-31) (II-12) (IV-1) 15:85:20 Black 113 (I-31) (II-12) (III-1) 15:85:15 Black (IV-1) 114 (I-31) (II-3) (IV-3) 20:80:5 Black 115 (I-31) (II-3) (IV-10) 25:75:5 Black 116 (I-1) (II-3) (III-1) 25:75:10 Black 117 (I-2) (II-1) (III-1) 30:70:(5 + 5) Black (IV-1) 118 (I-3) (II-3) (III-1) 30:70:10 Black 119 (I-4) (II-3) (III-1) 25:75:15 Black 120 (I-5) (II-3) (III-1) (10 + 25):65:5 Black (I-6) 121 (I-7) (II-3) (III-1) 9:91:15 Navy 122 (I-8) (II-3) (III-1) 19:81:5 Black 123 (I-9) (II-3) (III-1) 30:70:10 Black 124 (I-10) (II-3) (III-1) 25:75:10 Black 125 (I-11) (II-3) (III-1) 35:65:5 Black 126 (I-12) (II-3) (III-1) 25:75:10 Black 127 (I-13) (II-3) (III-1) 25:75:15 Black 128 (I-14) (II-3) (III-1) (10 + 25):65:5 Black (I-15) 129 (I-31) (II-3) (III-1) (10 + 10):80:10 Black (I-16) 130 (I-33) (II-3) (III-1) (30 + 15):55:5 Black (I-17) 131 (I-34) (II-3) (III-1) (10 + 10):80:10 Black (I-18) 132 (I-35) (II-3) (III-1) (10 + 15):75:5 Black (I-19) 133 (I-36) (II-3) (III-1) (10 + 10):80:20 Black (I-20) 134 (I-37) (II-3) (III-1) (15 + 15):70:5 Black (I-21) 135 (I-38) (II-3) (III-1) (15 + 15):70:5 Black (I-22) 136 (I-39) (lI-3) (III-1) (10 + 10):80:20 Black (I-23) 137 (I-40) (II-3) (III-1) (10 + 10):80:10 Black (I-24) 138 (I-41) (II-3) (III-1) (10 + 15):75:5 Black (I-25) 139 (I-42) (II-3) (III-1) (10 + 10):80:10 Black (I-26) 140 (I-43) (II-3) (III-1) (20 + 15):65:5 Black (I-27) 141 (I-44) (II-3) (III-1) (10 + 10):80:10 Black (I-28) 142 (I-88) (II-3) (III-1) (15 + 15):70:10 Black (I-29) 143 (I-89) (II-1) (III-2) (15 + 15):70:5 Black (I-30) 144 (I-31) (II-1) (III-3) 25:75:10 Black 145 (I-32) (II-1) (III-4) 30:70:20 Black 146 (I-33) (II-1) (III-5) 35:65:5 Black 147 (I-34) (II-1) (III-6) 25:75:10 Black 148 (I-35) (II-1) (III-7) 30:70:20 Black 150 (I-36) (II-1) (III-31) 35:65:5 Black 151 (I-37) (II-2) (III-11) 25:75:10 Black 152 (I-38) (II-2) (III-12) 30:70:20 Black 153 (I-39) (II-2) (III-13) 35:65:5 Black 154 (I-40) (II-2) (III-14) 25:75:(5 + 15) Black (III-15) 155 (I-41) (II-2) (III-16) 25:75:(5 + 5) Black (III-17) 156 (I-42) (II-2) (III-18) 20:80:(5 + 15) Black (III-19) 157 (I-43) (II-3) (III-20) 30:70:20 Black 158 (I-44) (II-3) (III-21) 30:70:(5 + 8) Black (III-22) 160 (I-88) (II-3) (III-23) 25:75:(15 + 5) Black (III-24) 161 (I-89) (II-3) (III-25) 20:80:(10 + 5) Black (III-26) 162 (I-45) (II-3) (III-27) 35:65:(5 + 5) Black (III-28) 163 (I-46) (II-4) (III-29) 30:70:(5 + 15) Black (III-30) 164 (I-47) (II-4) (III-31) 20:80:(10 + 5) Black (III-32) 165 (I-48) (II-4) (III-33) 35:65:20 Black 166 (I-49) (II-4) (III-34) 30:70:20 Black 167 (I-50) (II-5) (III-35) 35:65:5 Black 168 (I-51) (II-5) (III-36) 25:75:10 Black 169 (I-52) (II-5) (III-37) 35:65:20 Black 170 (I-53) (II-5) (III-38) 30:70:20 Black 171 (I-54) (II-6) (III-39) 35:65:5 Black 172 (I-55) (II-6) (III-40) 25:75:10 Black 173 (I-56) (II-6) (III-41) 35:65:5 Black 174 (I-57) (II-6) (III-42) 30:70:20 Black 175 (I-58) (II-6) (III-43) 35:65:5 Black 176 (I-59) (II-6) (III-44) (10 + 10):80:10 Black (I-60) 177 (I-61) (II-6) (III-45) (10 + 15):75:5 Black (I-2) 178 (I-62) (II-7) (III-46) (10 + 10):80:10 Black (I-4) 179 (I-63) (II-7) (III-47) (10 + 15):75:15 Black (I-3) 180 (I-55) (II-7) (III-48) (10 + 10):80:10 Black (I-10) 181 (I-55) (II-7) (IV-1) (10 + 15):75:20 Black (I-12) 182 (I-52) (II-8) (IV-2) (15 + 15):70:5 Black (I-15) 183 (I-51) (II-8) (IV-3) (10 + 10):80:10 Black (I-1) 184 (I-48) (II-9) (IV-4) (10 + 15):75:20 Black (I-22) 185 (I-6) (II-9) (IV-5) (10 + 10):80:10 Black (I-60) 186 (I-3) (II-10) (IV-6) (10 + 15):75:20 Black (I-2) 187 (I-1) (II-10) (IV-7) (10 + 10):80:10 Black (I-31) 188 (I-1) (II-11) (IV-8) (10 + 15):75:20 Black (I-32) 189 (I-32) (II-11) (IV-9) (15 + 15):70:5 Black (I-59) 190 (I-32) (II-1) (IV-10) (10 + 15): Black (I-2) (II-3) (40 + 35):10 191 (I-31) (II-1) (V-1) (10 + 10): Black (I-6) (II-3) (40 + 40):10 192 (I-88) (II-1) (V-2) 25:(40 + 35):15 Black (II-3) 193 (I-32) (II-3) (V-3) 25:(40 + 35):15 Black (II-10) 194 (I-41) (II-4) (V-4) 25:(40 + 35):15 Black (II-5) 195 (I-32) (II-13) (V-5) 25:(40 + 35):15 Black (II-1) 196 (I-32) (II-13) (V-6) 30:70:20 Black 197 (I-32) (II-12) (V-7) 35:65:5 Black 198 (I-89) (II-1) (V-8) (10 + 10):80:10 Black (I-30) 199 (I-31) (II-1) (III-1) 30:70:(5 + 8) Black (VI-1) 200 (I-32) (II-1) (III-1) 25:75:(15 + 5) Black (VI-2) 201 (I-33) (II-1) (III-1) 20:80:(10 + 5) Black (VI-3) 202 (I-34) (II-1) (III-1) 25:75:(15 + 5) Black (IV-1) 203 (I-35) (II-1) (III-1) 40:60:(5 + 5) Black (V-1) 204 (I-62) (II-7) (VI-1) (20 + 10):70: Black (I-4) (V-1) (5 + 8) 205 (I-63) (II-7) (III-1) (5 + 20):75: Black (I-3) (IV-1) (5 + 5 + 5) (V-1) 206 (I-1) (II-1) (15 + 5):80 Navy (I-31) 207 (I-2) (II-1) 45:(25 + 30) Black (II-3) 208 (I-32) (II-1) 40:(30 + 30) Black (II-5) 209 (I-3) (II-1) 45:(25 + 30) Black (II-3) 210 (I-5) (II-1) 40:(30 + 30) Black (II-3) 211 (I-41) (II-1) 35:(30 + 35) Black (II-3) 212 (I-49) (II-1) 20:80 Navy 213 (I-1) (II-1) (15 + 5):80 Navy (I-32) 214 (I-31) (II-1) 40:(30 + 30) Black (II-5) 215 (I-66) (II-1) 35:(30 + 35) Black (II-3) 216 (I-74) (II-1) 20:80 Navy

TABLE-US-00009 TABLE 8 Ex- Component Component Component ample A B C Ratio Shade 217 (I-32) (II-3) (III-1 ) (10 + 10):80:10 Black (I-16) 218 (I-56) (II-3) (III-1) (30 + 15):55:5 Black (I-17) 219 (I-37) (II-3) (III-1) (10 + 10):80:10 Black (I-18) 220 (I-39) (II-3) (III-1) (10 + 15):75:5 Black (I-19) 221 (I-40) (II-3) (III-1) (10 + 10):80:20 Black (I-20) 222 (I-64) (II-3) (III-1) (15 + 15):70:5 Black (I-21) 223 (I-65) (II-3) (III-1) (15 + 15):70:5 Black (I-22) 224 (I-48) (II-3) (III-1) (10 + 10):80:20 Black (I-23) 225 (I-49) (II-3) (III-1) (10 + 10):80:10 Black (I-24) 226 (I-66) (II-3) (III-1) (10 + 15):75:5 Black (I-25) 227 (I-67) (II-3) (III-1) (10 + 10):80:10 Black (I-26) 228 (I-68) (II-3) (III-1) (20 + 15):65:5 Black (I-27) 229 (I-69) (II-3) (III-1) (10 + 10):80:10 Black (I-28) 230 (I-32) (II-1) (III-3) 25:75:10 Black 231 (I-31) (II-1) (III-4) 30:70:20 Black 232 (I-56) (II-1) (III-5) 35:65:5 Black 233 (I-37) (II-1) (III-6) 25:75:10 Black 234 (I-39) (II-1) (III-7) 30:70:20 Black 235 (I-40) (II-1) (III-31) 35:65:5 Black 236 (I-64) (II-2) (III-11) 25:75:10 Black 237 (I-65) (II-2) (III-12) 30:70:20 Black 238 (I-48) (II-2) (III-13) 35:65:5 Black 239 (I-49) (II-2) (III-14) 25:75:(5 + 15) Black (III-15) 240 (I-66) (II-2) (III-16) 25:75:(5 + 5) Black (III-17) 241 (I-67) (II-2) (III-18) 20:80:(5 + 15) Black (III-19) 242 (I-68) (II-3) (III-20) 30:70:20 Black 243 (I-69) (II-3) (III-21) 30:70:(5 + 8) Black (III-22) 244 (I-70) (II-3) (III-27) 35:65:(5 + 5) Black (III-28) 245 (I-71) (II-4) (III-29) 30:70:(5 + 15) Black (III-30) 246 (I-72) (II-4) (III-31) 20:80:(10 + 5) Black (III-32) 247 (I-73) (II-4) (III-33) 35:65:20 Black 248 (I-74) (II-4) (III-34) 30:70:20 Black 249 (I-75) (II-5) (III-35) 35:65:5 Black 250 (I-76) (II-5) (III-36) 25:75:10 Black 251 (I-77) (II-5) (III-37) 35:65:20 Black 252 (I-63) (II-5) (III-38) 30:70:20 Black 253 (I-78) (II-6) (III-39) 35:65:5 Black 254 (I-79) (II-6) (III-40) 25:75:10 Black 255 (I-80) (II-6) (III-41) 35:65:5 Black 256 (I-81) (II-6) (III-42) 30:70:20 Black 257 (I-82) (II-6) (III-43) 35:65:5 Black 258 (I-83) (II-6) (III-44) (10 + 10):80:10 Black (I-84) 259 (I-85) (II-6) (III-45) (10 + 15):75:5 Black (I-2) 260 (I-86) (II-7) (III-46) (10 + 10):80:10 Black (I-4) 261 (I-54) (II-7) (III-47) (10 + 15):75:15 Black (I-3) 262 (I-87) (II-7) (III-48) (10 + 10):80:10 Black (I-10) 263 (I-57) (II-7) (IV-1) (10 + 15):75:20 Black (I-12) 264 (I-58) (II-8) (IV-2) (15 + 15):70:5 Black (I-15) 265 (I-59) (II-8) (IV-3) (10 + 10):80:10 Black (I-1) 266 (I-60) (II-9) (IV-4) (10 + 15):75:20 Black (I-22) 267 (I-6) (II-9) (IV-5) (10 + 10):80:10 Black (I-84) 268 (I-89) (II-1) (V-8) (10 + 10):80:10 Black (I-30) 269 (I-1) (II-10) (IV-7) (10 + 10):80:10 Black (I-32) 270 (I-1) (II-11) (IV-8) (10 + 15):75:20 Black (I-31) 271 (I-31) (II-11) (IV-9) (15 + 15):70:5 Black (I-83) 272 (I-31) (II-1) (IV-10) (10 + 15):(40 + Black (I-2) (II-3) 35):10 273 (I-32) (II-1) (V-1) (10 + 10):(40 + Black (I-6) (II-3) 40):10 274 (I-31) (II-1) (V-2) 25:(40 + 35):15 Black (II-3) 275 (I-31) (II-3) (V-3) 25:(40 + 35):15 Black (II-10) 276 (I-31) (II-4) (V-4) 25:(40 + 35):15 Black (II-5) 277 (I-31) (II-13) (V-5) 25:(40 + 35):15 Black (II-1) 278 (I-31) (II-13) (V-6) 30:70:20 Black 279 (I-31) (II-12) (V-7) 35:65:5 Black 280 (I-32) (II-1) (III-1) 30:70:(5 + 8) Black (VI-1) 281 (I-31) (II-1) (III-1) 25:75:(15 + 5) Black (VI-2) 282 (I-56) (II-1) (III-1) 20:80:(10 + 5) Black (VI-3) 283 (I-37) (II-1) (III-1) 25:75:(15 + 5) Black (IV-1) 284 (I-39) (II-1) (III-1) 40:60:(5 + 5) Black (V-1) 285 (I-86) (II-7) (VI-1) (20 + 10):70: Black (I-4) (V-1) (5 + 8) 286 (I-54) (II-7) (III-1) (5 + 20):75: Black (I-3) (IV-1) (5 + 5 + 5) (V-1)

COMPARATIVE EXAMPLE 1

[0091] according to example 2 in patent CN1858118, the reactive black dye comprising the following three components was prepared:

##STR00141##

COMPARATIVE EXAMPLE 2

[0092] according to example 6 in patent CN1730566, the reactive black dye comprising the following three components was prepared:

##STR00142##

APPLICATION EXAMPLE 1

[0093] The dried reactive black dyes obtained in examples 91-96 (closest to the prior art) and comparative examples 1 and 2 were respectively dissolved in water, and sodium sulfate powder was added to prepare a dyeing solution with a final concentration of 50 g/L. The dyeing concentration (dye to cloth weight) was set at 4%, the bath ratio (gram weight of cloth to milliliter volume of dyeing solution) was set at 1:20, cotton was placed in the bath for adsorption at 60 C. for 30 minutes, alkali (sodium carbonate 20 g / L) was added for dye fixation for 45 minutes, the dyed fabric was washed with water, soaped, and dried to obtain a navy to black dyed fabric. The staining fastness to washing test was carried out according to the method of ISO 105 C10-2006. The results were shown in table 9:

TABLE-US-00010 TABLE 9 Staining fastness to Washing (ISO 105 C10-2006) 95 C. 30 min Exam- Dyeing Vinegar Poly- ples depth fiber Cotton Nylon ester Acrylon Wool 91 4.0% 4~5 4~5 5 5 4~5 4 92 4.0% 4~5 4~5 4~5 5 4~5 4 93 4.0% 4~5 4~5 5 5 4~5 4 94 4.0% 4~5 4~5 5 5 4~5 4 95 4.0% 4~5 4~5 5 5 4~5 4 96 4.0% 4~5 4~5 4~5 5 4~5 4 Compar- 4.0% 4 3~4 3~4 4 4 3 ative example 1 Compar- 4.0% 4 3~4 3~4 4 3~4 3 ative example 2

APPLICATION EXAMPLE 2

[0094] The build-up property of the reactive dyes obtained in the representative examples 9196 of the present invention and comparative examples 12 was tested according to the method specified in the GB/T 21875-2016 standard, and it was found that the build-up of the reactive dyes of examples 91-96 was obviously better than that of the comparative examples 12, and that under the same dyeing conditions, the amount of dye can be reduced by 5% to 15%, which led to remarkable economic effect.

APPLICATION EXAMPLE 3

[0095] The degree of fixation of the reactive dyes obtained in examples 91-96 of the present invention and comparative examples 1-2 was tested according to the method specified in the GB/T2391-2014 standard, and the results were shown as table 10:

TABLE-US-00011 TABLE 10 Examples 91Example Example Example Example Example Example Comparative Comparative 91 92 93 94 95 96 example 1 example 2 Degree of 76.1% 75.9% 75.2% 76.5% 75.7% 76.3% 71.6% 70.5% fixation

[0096] In summary, the dye of the present invention was significantly superior to that of the comparative examples, and for the industry it has a significant improvement in fastness, build-up and degree of fixation.