1. Patent Search
  2. Details

A REACTIVE NAVY TO BLACK DYE COMPOSITION AND DYE PRODUCT THEREOF

20240002669 ยท 2024-01-04

    Inventors

    Cpc classification

    International classification

    Abstract

    A reactive navy to black dye composition comprises component A and component B. Component A is one or more selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof, and component B is one or more selected from the group consisting of dye compounds of formula (II) and alkali metal salts thereof, 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%. The present invention also provides a reactive navy to black dye product comprising the reactive navy to black dye composition. The reactive navy to black dye composition and dye product thereof with properties such as good fastness to washing, high degree of fixation and good build-up, which is suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials and blended fabrics thereof.

    ##STR00001##

    Claims

    1. A reactive navy to black dye composition, comprising component A and component B, wherein component A is one or more selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof, and component B is one or more selected from the group consisting of dye compounds of formula (II) and alkali metal salts thereof, 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%, ##STR00134## in formula (I): D.sup.1 and D.sup.2 are each independently a group represented by the following formula (a) or (b); ##STR00135## in the above formulae (I), (a) and (b): R.sup.1 and R.sup.2 are each independently hydrogen, COR.sup.7, C.sub.1C.sub.4 alkyl or C.sub.1C.sub.4 alkyl substituted by hydroxyl, sulfo or carboxyl, in which R.sup.7 is C.sub.1C.sub.4 alkyl, C.sub.2C.sub.4 alkenyl or NH.sub.2; R.sup.3 is hydrogen, C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy, carboxyl or sulfo; R.sup.4R.sup.6 are each independently hydrogen, C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; X.sup.1 and X.sup.2 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 Y.sup.1Y.sup.3 are each independently CHCH.sub.2, CH.sub.2CH.sub.2OSO.sub.3H or CH.sub.2CH.sub.2Cl, p=1-3 and q=1-3; in formula (II): R.sup.8R.sup.11 are each independently hydrogen, 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, CH.sub.2CH.sub.2OSO.sub.3H or CH.sub.2CH.sub.2Cl.

    2. 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.

    3. The reactive navy to black dye composition as claimed in claim 1, wherein the reactive navy to black dye composition also comprises component C and component D; component C is one or more selected from the group consisting of compounds of formulae (III)(IV) and alkali metal salts thereof, and the mass of component C is 1% to 50% of the total mass of component A and component B; component D is one or more selected from the group consisting of dye compounds of formulae (V)(VII) and alkali metal salts thereof, and the mass of component D is 1% to 50% of the total mass of component A and component B; ##STR00136## in formula (III): R.sup.12R.sup.15 are each independently H, 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; each of D.sup.3 and D.sup.4 is 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.16R.sup.19 are each independently H, C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; e=0-1; 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): f, g and h are each independently selected from 0-3, and every R.sup.20, R.sup.21 and R.sup.22 is each independently C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; X.sup.3 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): D.sup.5 and D.sup.6 are each independently a group of the following formula (c), (d) or (f): ##STR00137## in the above formulae (c), (d) and (f): R.sup.23, R.sup.24, R.sup.26, R.sup.27, R.sup.29 and R.sup.30 are each independently H, C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo; i=0-3, and every R.sup.25 is each independently selected from the group consisting of C.sub.1C.sub.4 alkyl, sulfo, ureido and C.sub.1C.sub.4 alkanoylamino; j=0-3, and every R.sup.28 is each independently selected from the group consisting of hydroxyl and sulfo; X.sup.4, X.sup.5 and X.sup.6 are each independently SO.sub.2Y.sup.13, NHCO(CH.sub.2).sub.rSO.sub.2Y.sup.14 or CONH(CH.sub.2).sub.sSO.sub.2Y.sup.15, wherein r and s are integers, r=1-3, s=1-3, Y.sup.13Y.sup.15 are each independently CHCH.sub.2, C.sub.2H.sub.4OSO.sub.3H or CH.sub.2CH.sub.2Cl; in formula (VII): m=1-3, and every R.sup.31 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; n=0-2, and every R.sup.32 is each independently linear or branched C.sub.1C.sub.4 alkyl, C.sub.1C.sub.4 alkoxy or sulfo.

    4. The reactive navy to black dye composition as claimed in claim 3, wherein the reactive navy to black dye composition consists of component A, component B, component C and component D.

    5. 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 formula (a) or (b).

    6. The reactive navy to black dye composition as claimed in claim 1, wherein component A is at least one selected from the group consisting of dye compounds of the following formulae (I-1)(I-65) and alkali metal salts thereof: ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159##

    7. The reactive navy to black dye composition as claimed in claim 1, wherein component B is at least one selected from the group consisting of the following compounds and alkali metal salts thereof: ##STR00160## ##STR00161##

    8. The reactive navy to black dye composition as claimed in claim 3, wherein component C is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, 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.

    9. The reactive navy to black dye composition as claimed in claim 3, wherein component C is at least one selected from the group consisting of the following compounds and alkali metal salts thereof: ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174##

    10. The reactive navy to black dye composition as claimed in claim 3, wherein component D is at least one selected from the group consisting of the following compounds and alkali metal salts thereof: ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187##

    11. The reactive navy to black dye composition as claimed in claim 1, wherein component A is at least one selected from the group consisting of dye compounds of formulae (I-1)(I-28) and (I-48)(I-55) and alkali metal salts thereof; component B is at least one selected from the group consisting of dye compounds of formulae (II-1) and (II-3) and alkali metal salts thereof, component C is at least one selected from the group consisting of dye compounds of formulae (III-1), (III-2), (III-4), (IV-1) and (IV-3) and alkali metal salts thereof; and component D is at least one selected from the group consisting of compounds of formulae (VI-26), (VI-27), (VI-41) and (VI-42) and alkali metal salts thereof, based on the sum of the masses of components A and B, the mass percentage of component A is 5-50%, the mass percentage of component B is 50-95%, the mass of component C is 1-50% of the total mass of components A and B, and the mass of component D is 1-50% of the total mass of components A and B; ##STR00188## ##STR00189##

    12. The reactive navy to black dye composition as claimed in claim 1, wherein the alkali metal salt is sodium salt or potassium salt.

    13. The reactive navy to black dye composition as claimed in claim 1, wherein in the reactive navy to black dye composition, the dye compound of the formula (II) contains a quinohydrazone structure of the following formula (IIa), ##STR00190## the definitions of the substituents of the above formulae (IIa) are respectively the same as those of formula (II).

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

    15. The reactive navy to black dye composition as claimed in claim 3, wherein the mass of component C is 1% to 40% of the total mass of component A and component B; and the mass of component D is 1% to 40% of the total mass of component A and component B.

    16. The reactive navy to black dye composition as claimed in claim 3, wherein in formula (III): R.sup.12R.sup.15 are each independently H, methyl, methoxy, carboxyl or sulfo; c and d are each independently 1; each of D.sup.3 and D.sup.4 is 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 1-2, respectively, and each of the substituents is independently selected from the group consisting of amino, sulfo, ureido, acetylamino, methoxy and hydroxyl; in formula (IV): R.sup.16R.sup.19 are each independently H, methyl, methoxy or sulfo; in formula (V): f, g and h are each independently selected from 0-3, and every R.sup.20, R.sup.21 and R.sup.22 is each independently methyl, methoxy or sulfo; in formula (VI): R.sup.23, R.sup.24, R.sup.26, R.sup.27, R.sup.29 and R.sup.30 are each independently H, methyl, methoxy or sulfo; i=0-3, and every R.sup.25 is each independently methyl, sulfo, ureido or acetylamino; j=0-3, and every R.sup.28 is each independently selected from the group consisting of hydroxyl and sulfo; X.sup.4, X.sup.5 and X.sup.6 are each independently SO.sub.2Y.sup.13; in formula (VII): m=1-3, and every R.sup.31 is each independently amino, sulfo or acetylamino; n=0-2, and every R.sup.32 is each independently methyl, methoxy or sulfo.

    17. The reactive navy to black dye composition as claimed in claim 5, wherein both D.sup.1 and D.sup.2 are the group of formula (a).

    18. The reactive navy to black dye composition as claimed in claim 11, wherein component A is at least one selected from the group consisting of dye compounds of formulae (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and alkali metal salts thereof.

    19. The reactive navy to black dye composition as claimed in claim 12, wherein the alkali metal salt is sodium salt.

    20. The reactive navy to black dye composition as claimed in claim 3, wherein in the reactive navy to black dye composition, the dye compound of the formula (II) contains a quinohydrazone structure of the following formula (IIa), the dye compound of the formula (IV) contains a quinohydrazone structure of the following formula (IVa), and the dye compound of the formula (VI) contains a quinohydrazone structure of the following formulae (VIa) and/or (VIb) and/or (VIc) and/or (VId), ##STR00191## the definitions of the substituents of the above formulae (IIa) and (IVa) are respectively the same as those of formulae (II) and (IV), and the definitions of the substituents of formulae (VIa)(VId) are the same as those of formula (VI).

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0128] FIG. 1 is the mass spectrum of the compound (I-1) obtained in example 1.

    [0129] FIG. 2 is the mass spectrum of the chromophore (A) obtained in example 1.

    SPECIFIC EMBODIMENTS

    [0130] 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:

    [0131] The dye compounds used in the examples of the present invention were prepared and separated in the form of their sodium salt in the actual synthesis process, and are also used for dyeing in the form of sodium salt, but for the convenience of writing, all the chemical formulae of the dye compounds in the examples are expressed in the form of free acid, and their substantial dyeing properties are equivalent to the form of sodium salt.

    Example 1

    [0132] (1) Diazotization:

    [0133] 23.0 g (0.1 mol) of 4-(acetylamino)-2-amino-benzenesulfonic acid 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 0.104 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 12 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0 C. and 20 C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of 4-(acetylamino)-2-amino-benzenesulfonic acid was obtained and stored for use.

    [0134] 56.2 g (0.2 mol) of para-ester (p--hydroxyethylsulfone sulfate aniline) were added into 200 g of water and 200 g of ice, beaten for about 1 h, added with 35 g of 31% hydrochloric acid (containing 0.3 mol of HCl), and added with 48 g of a 30% sodium nitrite solution (containing 0.208 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 12 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0 C. and 20 C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of the para-ester was obtained and stored for use.

    [0135] (2) Coupling Reaction:

    [0136] 15.2 g (0.1 mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating, the pH of the solution was controlled to be between 8.0 and 9.0, and the temperature of the solution was controlled to be between 20 C. and 25 C. After the beating, the diazonium solution of 0.1 mol 4-(acetylamino)-2-amino-benzenesulfonic acid obtained in step (1) was added to the 3,5-dihydroxybenzoic acid solution. The pH was controlled to be between 5 and 5.5 with 30% liquid alkali, the temperature was controlled to be between 5 C. and 10 C., the reaction was carried out for 0.52 h, and when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction reached the end point, thereby obtaining chromophore of the following formula (A) whose mass spectrum is shown in FIG. 2.

    ##STR00059##

    [0137] The diazonium solution of the para-ester obtained in step (1) was added to the chromophore of formula (A), the pH was controlled to be between 5 and 5.5 with 30% liquid alkali, and the temperature T was controlled to be between 5 C. and 10 C., the coupling reaction was further carried out for 0.5 h to 10 h. The reaction solution was tested with H acid test solution, if the bleed circle was colorless, it meant that the diazonium had been reacted completely to the end point, thereby obtaining an orange reactive dye compound (I-1) whose max is 420 nm in water. And the mass spectrum of the compound (I-1) is shown in FIG. 1.

    ##STR00060##

    Example 266

    [0138] Referring to the preparation method of the azo dye described in example 1, the dye compounds of the structures shown in the following table 1 were respectively obtained by stepwise diazotization and coupling reactions using raw materials of intermediates well known in the art.

    TABLE-US-00001 TABLE 1 max Examples Reactive dye compounds (nm) 2 [00061]embedded image 420 3 [00062]embedded image 420 4 [00063]embedded image 412 5 [00064]embedded image 412 6 [00065]embedded image 420 7 [00066]embedded image 420 8 [00067]embedded image 425 9 [00068]embedded image 425 10 [00069]embedded image 425 11 [00070]embedded image 425 12 [00071]embedded image 415 13 [00072]embedded image 415 14 [00073]embedded image 415 15 [00074]embedded image 420 16 [00075]embedded image 415 17 [00076]embedded image 415 18 [00077]embedded image 410 19 [00078]embedded image 410 20 [00079]embedded image 415 21 [00080]embedded image 415 22 [00081]embedded image 415 23 [00082]embedded image 410 24 [00083]embedded image 410 25 [00084]embedded image 415 26 [00085]embedded image 415 27 [00086]embedded image 425 28 [00087]embedded image 425 29 [00088]embedded image 420 30 [00089]embedded image 415 31 [00090]embedded image 410 32 [00091]embedded image 410 33 [00092]embedded image 410 34 [00093]embedded image 415 35 [00094]embedded image 410 36 [00095]embedded image 418 37 [00096]embedded image 418 38 [00097]embedded image 418 39 [00098]embedded image 435 40 [00099]embedded image 435 41 [00100]embedded image 430 42 [00101]embedded image 435 43 [00102]embedded image 435 44 [00103]embedded image 440 45 [00104]embedded image 440 46 [00105]embedded image 435 47 [00106]embedded image 435 48 [00107]embedded image 415 49 [00108]embedded image 425 50 [00109]embedded image 418 51 [00110]embedded image 418 52 [00111]embedded image 415 53 [00112]embedded image 425 54 [00113]embedded image 422 55 [00114]embedded image 422 56 [00115]embedded image 428 57 [00116]embedded image 425 58 [00117]embedded image 430 59 [00118]embedded image 420 60 [00119]embedded image 430 61 [00120]embedded image 425 62 [00121]embedded image 415 63 [00122]embedded image 420 64 [00123]embedded image 430 65 [00124]embedded image 430 66 [00125]embedded image 420

    Example 67

    [0139] 25 parts of the dye of formula (I-1), 75 parts of the dye of formula (II-1) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00126##

    Example 68

    [0140] 20 parts of the dye of formula (I-1), 76 parts of the dye of formula (II-3), 4 parts of the dye of formula (VI-26) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00127##

    Example 69

    [0141] 22 parts of the dye of formula (I-1), 75 parts of the dye of formula (II-3), 3 parts of the dye of formula (IV-1) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton dark black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00128##

    Example 70

    [0142] 21 parts of the dye of formula (I-1), 76 parts of the dye of formula (II-3), 1 part of the dye of formula (IV-1), 2 parts of the dye of formula (VI-26), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00129##

    Example 71

    [0143] 17 parts of the dye of formula (I-1), 68 parts of the dye of formula (II-3), 7 parts of the dye of formula (IV-1), 8 parts of the dye of formula (VI-26), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00130##

    Example 72

    [0144] 20 parts of the dye of formula (I-1), 70 parts of the dye of formula (II-1), 10 parts of the dye of formula (III-1), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (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).

    ##STR00131##

    Examples 73-224

    [0145] According to the method described in one of examples 67-72, the dyes with listed ratio in Table 2 were mechanically mixed, and the obtained dye mixture dyed cotton navy to black by the conventional reactive dyeing method, and the color fastness to washing of the dyeings especially on nylon and wool was not lower than grade 4 (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-00002 TABLE 2 custom-character 2 custom-character custom-character custom-character custom-character custom-character Examples Component A Component B Component C Ratio 73 (I -1) (II -3) 50:50 74 (I -1) (II -1) 45:55 75 (I -1) (II -1) + 40:(30 + 30) (II -3) 76 (I -4) (II -3) 35:65 77 (I -4) (II -1) 30:70 78 (I -4) (II -1) + 20:(40 + 40) (II -3) 79 (I -6) (II -3) 25:75 80 (I -6) (II -1) 15:85 81 (I -6) (II -1) + 10:(45 + 45) (II -3) 82 (I -2) (II -3) 5:95 83 (I -2) (II -1) 12:88 84 (I -2) (II -1) + 18:(46 + 46) (II -3) 85 (I -5) (II -3) 24:76 86 (I -5) (II -1) 36:64 87 (I -5) (II -1) + 30:(35 + 35) (II -3) 88 (I -7) (II -3) 38:62 89 (I -7) (II -1) 44:56 90 (I -7) (II -1) + 40:(30 + 30) (II -3) 91 (I -1) (II-3) (III-1) 20:80:5 92 (I -1) (II-3) (IV-1) 25:75:10 93 (I -1) (II-3) (IV-3) 30:70:15 94 (I -1) (II-3) (VI-26) 40:60:20 95 (I -1) (II-1) (III-1) 45:55:25 96 (I -1) (II-1) (IV-1) 35:65:30 97 (I -1) (II-1) (IV-3) 50:50:10 98 (I -1) (II-1) (VI-26) 20:(40 + 40):15 99 (I -1) (II -1) + (III-1) 30:(35 + 35):10 (II -3) 100 (I -1) (II -1) + (IV-1) 40:(30 + 30):5 (II -3) 101 (I -1) (II -1) + (IV-3) 10:(45 + 45):10 (II -3) 102 (I -1) (II -1) + (VI-26) 50:(25 + 25):20 (II -3) 103 (I -1) (II-3) (III-1) + 5:95:(10 + 10) (IV-1) 104 (I -1) (II-3) (III-1) + 15:85:(15 + 15) (IV-3) 105 (I -1) (II-3) (III-1) + 25:75:(5 + 5) (VI-26) 106 (I -1) (II-3 (IV-1) + 35:65:(3 + 3) (IV-3) 107 (I -1) (II-3) (IV-1) + 45:55:(10 + 10) (VI-26) 108 (I -1) (II-3) (IV-3) + 22:78:(7 + 8) (VI-26) 109 (I -1) (II-1) (III-1) + 24:76:(10 + 10) (IV-1) 110 (I -1) (II-1) (III-1) + 28:72:(8 + 8) (IV-3) 111 (I -1) (II-1) (III-1) + 34:68:(12 + 12) (VI-26) 112 (I -1) (II-1) (IV-1) + 36:64:(15 + 15) (IV-3) 113 (1-1) (II-1) (IV-1) + 38:62:(5 + 5) (VI-26) 114 (I -1) (II-1) (IV-3) + 40:60:(7 + 8) (VI-26) 115 (I -1) (II -1) + (III-1) + 20:(40 + 40):(10 + 10) (II -3) (IV-1) 116 (I -1) (II -1) + (III-1) + 30:(35 + 35):(2 + 3) (II -3) (IV-3) 117 (I -1) (II -1) + (III-1) + 10:(45 + 45):(5 + 5) (II -3) (VI-26) 118 (I -1) (II -1) + (IV-1) + 40:(30 + 30):(6 + 6) (II -3) (IV-3) 119 (I -1) (II -1) + (IV-1) + 28:(36 + 36):(10 + 10) (II -3) (VI-26) 120 (I -1) (II -1) + (IV-3) + 32:(34 + 34):(4 + 4) (II -3) (VI-26) 121 (I -1) (II-1) (III-1) + 30:70:(5 + 5 + 5) (IV-1) + (IV-3) 122 (I -1) (II-1) (III-1) + 35:65:(8 + 8 + 8) (IV-1) + (VI-26) 123 (I -1) (II-1) (III-1) + 25:75:(3 + 3 + 3) (IV-3) + (VI-26) 124 (I -1) (II-1) (IV-1) + 20:80:(9 + 9 + 9) (IV-3) + (VI-26) 125 (I -1) (II-1) (III-1) + 15:85:(5 + 5 + 5 + 5) (IV-1) + (IV-3) + (VI-26) 126 (I -1) (II-3) (III-1) + 10:90:(6 + 6 + 6) (IV-1) + (IV-3) 127 (I -1) (II-3) (III-1) + 22:78:(7 + 7 + 7) (IV-1) + (VI-26) 128 (I -1) (II-3) (III-1) + 30:70:(4 + 4 + 4) (IV-3) + (VI-26) 129 (I -1) (II-3) (IV-1) + 33:67:(5 + 5 + 5) (IV-3) + (VI-26) 130 (I -1) (II-3) (III-1) + 40:60:(5 + 5 + 5 + 5) (IV-1) + (IV-3) + (VI-26) 131 (I -1) (II -1) + (III-1) + 45:(20 + 35):(4 + 4 + 4) (II -3) (IV-1) + (IV-3) 132 (I -1) (II -1) + (III-1) + 50:(25 + 25):(2 + 2 + 2) (II -3) (IV-1) + (VI-26) 133 (I -1) (II -1) + (III-1) + 30:(35 + 35):(10 + 10 + 10) (II -3) (IV-3) + (VI-26) 134 (I -1) (II -1) + (IV-1) + 28:(36 + 36):(3 + 3 + 3) (II -3) (IV-3) + (VI-26) 135 (I -1) (II -1) + (III-1) + 38:(31 + 31):(5 + 5 + 5 + 5) (II -3) (IV-1) + (IV-3) + (VI-26) 136 (I -2) (II-1) (III-2) 5:95:10 137 (I -2) (II-1) (III-4) 10:90:30 138 (1-2) (II-1) (VI-27) 15:85:25 139 (I -4) (II-1) (VI-41) 20:80:15 140 (I -4) (II-3) (VI-42) 25:75:25 141 (I -4) (II-3) (III-2) + 30:70:(15 + 15) (VI-27) 142 (I -7) (II-3) (III-4) + 35:65:(10 + 10) (VI-41) 143 (I -7) (II-3) (VI-26) + 40:60:(5 + 5) (VI-27) 144 (I -7) (II-3) (VI-41) + 45:55:(2 + 3) (VI-42) 145 (I -5) (II-1) (III-2) + 50:50:(3 + 3) (IV-1) 146 (I -5) (II-1) (III-4) + 34:66:(10 + 10) (IV-3) 147 (I -5) (II -1) + (III-2) + 32:(34 + 34):(5 + 5 + 5) (II -3) (IV-3) + (VI-27) 148 (I -6) (II -1) + (III-4) + 30:(35 + 35):(7 + 7 + 7) (II -3) (IV-1) + (VI-41) 150 (I -6) (II -1) + (IV-1) + 25:(40 + 35):(10 + 10) (II -3) (VI-27) 151 (I -1) + (II-2) (V-1) (10 + 10):80:30 (I -2) 152 (I -3) (II-4) (VII-1) 10:90:40 153 (I -8) (II-5) (III-1) + 20:80:(15 + 15) (III-2) 154 (I -9) + (II-6) (III-3) + (15 + 15):70:(10 + 10) (I -10) (III-4) 155 (I -11) (II-7) (III-4) 25:75:15 156 (I -12) (II-8) (III-5) 30:70:20 157 (I -13) + (II-9) + (III-6) (20 + 20):(30 + 30):18 (I -14) (II -10) 158 (I -15) (II-11) (III-7) 35:65:12 160 (I -16) + (II-12) (III-8) + (10 + 10):80:(10 + 10) (I -17) (III-9) 161 (I -18) + (II-13) (III-10) (10 + 15):75:10 (I -19) 162 (I -20) + (II-9) (III-11) (5 + 5):90:50 (I -21) 163 (I -23) (II-10) (IV-2) 15:85:40 164 (I -24) (II-1) (IV-4) 25:75:10 165 (I -22) (II-1) (V -1) + 35:65:(10 + 10) (V -2) 166 (I -25) (II-2) (V -3) + 28:72:(5 + 5) (V -4) 167 (I -26) (II-2) (V -5) 32:68:5 168 (I -27) + (II-3) (VI-1) (9 + 9):82:45 (I -28) 169 (I -48) (II-3) (VI-3) + 22:78:(10 + 25) (VI-4) 170 (I -49) (II-4) (VII-2) 23:77:20 171 (I -50) (II-4) (VII-3) 32:68:10 172 (I -51) (II-5) (III-13) + 38:62:(5 + 5 + 5) (III-15) + (IV-5) 173 (I -52) + (II-5) (III-14) + (10 + 10):80:(10 + 10) (I -53) (IV-6) 174 (I -54) (II-6) (III-16) + 30:70:(5 + 5) (V-1) 175 (I -55) (II-6) (III-17) + 25:75:(15 + 10) (V-2) 176 (I -56) (II-7) (III-18) + 5:95:(15 + 15 + 15) (III-19) + (VI-5) 177 (I -57) (I I-7) (III-20) + 10:90:(25 + 25) (VI-6) 178 (I -58) (II-8) (III-21) + 15:85:(20 + 20) (VII-1) 179 (I -59) (II-8) (III-22) + 20:80:(15 + 15) (VII-2) 180 (I -60) (II-9) (IV-2) + 25:75:(10 + 10) (V -3) 181 (I -61) (II-9) (IV-4) + 30:70:(12 + 12) (V -4) 182 (I -62) + (II-10) (IV-5) + (15 + 15):70:(5 + 5 + 5) (I -63) (VI-7) + 183 (I -64) + (II-10) (IV-6) + (18 + 18):64:(5 + 5) (I -65) (VI-9) 184 (I -66) (II-11) (IV-7) + 21:79:(10 + 10) (VI-3) 185 (I -29) (II-11) (V-5) + 27:73:(8 + 8) (VI-10) 186 (I -30) (II-12) (V-6) + 35:65:(7 + 7) (VII-1) 187 (I -31) + (II-12) VI-10) + (20 + 20):60:(10 + 10) (I -32) (VII-2) 188 (I -33) (II-13) (III-23) + 45:55:(2 + 2 + 2) (I V-7) + (V-7) 189 (I -34) (II-13) (III-24) + 38:62:(5 + 5 + 5) (IV-8) + (VI-11) 190 (I -35) (II-2) + (III-25) + 34:66:(8 + 8 + 8) (II-6) (IV-9) + (VII-3) 191 (I -36) + (II-5) (IV-4) + (15 + 15):70:(6 + 6 + 6) (I -37) (V-8) + (VI-12) 192 (I -38) (II-4) + (IV-5) + 20:(40 + 40):(10 + 10 + 10) (II-7) (V-1) + (VII-1) 193 (I -39) (II-1) + (V-2) + 15:(40 + 45):(15 + 15 + 15) (II-3) (VI-13) + (VI-14) 194 (I -40) (II-2) (III-26) + 20:80:(5 + 5 + 5 + 5) (IV-10) + (V-3) + (VI-9) 195 (I -41) (II-8) (III-27) + 10:90:(10 + 10 + 10 + 10) (IV-11) + (V-4) + (VI-2) 196 (I -42) (II-10) (IV-2) + 25:75:(12 + 12 + 12 + 12) (V-5) + (VI-15) + (VII-3) 197 (I -43) (II-9) (III-28) + 35:65:(5 + 5 + 5 + 5 + 5) (IV-6) + (V-6) + (VI-16) + (VII-1) 198 (I -44) (II-11) (III-29) + 40:60:(5 + 5 + 5 + 5 + 5) (IV-5) + (V-7) + (VI-17) + (VII-2) 199 (I -47) (II-12) (III-30) + 40:60:(10 + 10 + 10) (IV-4) + (VI-20) 200 (I -46) (II-13) (III-31) + 50:50:(4 + 4 + 4 + 4) (IV-10) + (VI-18) + (VI-19) 201 (I -45) (II-8) (III-32) + 45:55 (5 + 5 + 5) (IV-3) + (VI-21) 202 (I -48) + (I I-7) (III-33) + (20 + 20):60:(10 + 10 + 10) (I -49) (IV-2) + (VI-22) 203 (I -50) (II-6) (III-34) + 35:65:(12 + 12 + 12) (IV-1) + (VI-23) 204 (I -51) (II-5) (III-35) + 25:75:(10 + 10 + 10 + 10) (IV-2) + (VI-24) + (VI-25) 205 (I -52) (II-4) (III-36) + 30:70:(12 + 12 + 12 + 12) (III-37) + (IV-4) + (VI-28) 206 (I -53) (II-3) (III-39) + 20:80:(15 + 15 + 15) (IV-5) + (VI-29) 207 (I -54) + (II-2) (III-38) + (20 + 20):60:(5 + 5 + 5 + 5) (I -55) (III-40) + (IV-6) + (VI-30) 208 (I -56) (II-1) (III-41) + 35:65:(10 + 10 + 10 + 10) (IV-7) + (VI-31) + (VI-32) 209 (I -57) (II-9) (III-42) + 25:75:(10 + 10 + 10) (IV-8) + (VI-33) 210 (I -58) (II-10) (III-43) + 40:60:(10 + 10 + 10 + 10) (III-44) + (IV-9) + (VI-34) 211 (I -59) (II-11) (III-45) + 30:70:(7 + 7 + 7 + 7) (III-47) + (IV-10) + (VI-36) 212 (I -60) (II-12) (III-46) + 38:62:(8 + 8 + 8 + 8) (IV-4) + (VI-35) + (VI-37) 213 (I -61) (II-13) (III-47) + 26:74:(6 + 6 + 6 + 6) (IV-11) + (VI-38) + (VI-39) 214 (I -62) + (II-2) (III-48) + (15 + 15):70:(10 + 10 + 10) (I -63) (IV-5) + (VI-40) 215 (I -64) (II-2) (III-49) + 40:60:(10 + 10 + 10) (IV-6) + (VI-45) 216 (I -65) (I -4) (III-50) + 50:50:(3 + 3 + 3 + 3) (IV-7) + (VI-46) + (VI-47) 217 (I -66) (II-4) (III-51) + 48:52:(4 + 4 + 4 + 4) (III-52) + (IV-10) + (VI-43) 218 (I -55) (II-5) (III-50) + 45:55:(5 + 5 + 5) (IV-11) + (VI-44) 219 (I -54) (II-2) + (III-40) + 40:(30 + 30):(10 + 10 + 10) (II-6) (IV-9) + (VI-50) 220 (I -53) (II-4) + (III-30) + 30:(35 + 35):(10 + 10 + 10) (II-7) (IV-8) + (VI-48) 221 (I -52) (II-8) (III-20) + 50:50:(5 + 5 + 5) (IV-7) + (VI-49) 222 (I -51) (II-9) (III-1) + 30:70:(10 + 10 + 10 + 10) (IV-6) + (VI-51) + (VI-52) 223 (I -50) (II-10) (III-2) + 40:60:(10 + 10 + 10) (IV-5) + (VI-53) 224 (I -48) (II-11) (III-4) + 35:65:(5 + 5 + 5 + 5) (IV-4) + (VI-54) + (VI-55)

    Comparative Example 1: According to Example 1 in Patent CN100582168A, the Reactive Black Dye Comprising the Following Two Components was Prepared

    [0146] ##STR00132##

    Comparative Example 2: According to Example 6 in Patent CN1730566A, the Reactive Black Dye Comprising the Following Three Components was Prepared

    [0147] ##STR00133##

    Application Example 1

    [0148] The dried reactive black dyes obtained in examples 67-72 (closest to the prior art) and comparative examples 1 and 2 were respectively dissolved in water and added with sodium sulfate powder with a final concentration of 50 g/L to prepare a dyeing solution. 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. Tests of fastnesses to washing, perspiration and rubbing were carried out according to methods in ISO 105 C10, ISO 105-E04 and ISO 105 X12. The results are shown in table 2:

    TABLE-US-00003 TABLE 2 Fastness to washing Perspiration Rubbing Color Color Cotton Nylon Wool resistence fastness Examples strength change staining staining staining Acid Alkli Dry Wet 67 4.0% 4 5 4-5 4 4-5 4-5 5 4 68 4.0% 4 5 4-5 4 4-5 4-5 5 4 69 4.0% 4 5 4-5 4 4-5 4-5 5 4 70 4.0% 4 5 4-5 4 4-5 4-5 5 4 71 4.0% 4 5 4-5 4 4-5 4-5 5 4 72 4.0% 4 5 4-5 4 4-5 4-5 5 4 comparative 4.0% 4 4 4 3-4 4 4 4 3-4 example 1 comparative 4.0% 4 3-4 3-4 3 4 4 4-5 3-4 example 2

    [0149] The build-up property of the reactive dyes obtained in the representative examples 67-72 of the present invention and comparative examples 1 and 2 was tested according to a method specified in the GB/T 21875-2016 standard, and it was found that the build-up of the reactive dyes of examples 67-72 was obviously better than that of the comparative examples 1 and 2, and that under the same dyeing conditions, the amount of the dye can be reduced by 5% to 15%, which led to remarkable economic effect.

    Application Example 3

    [0150] The degree of fixation of the reactive dyes obtained in examples 6772 of the present invention and comparative examples 12 was tested according to the method specified in GB/T2391-2014 standard, and the results are shown in Table 3:

    TABLE-US-00004 TABLE 3 Examples Example Example Example Example Example Example Comparative Comparative 67 68 69 70 71 72 example1 example 2 Degree of 81.1% 80.9% 81.5% 82.0% 81.8% 80.5% 72.3% 70.5% fixation

    [0151] In summary, the dyes of the present invention are significantly superior to those of the comparative examples, and for the industry it has a significant improvement in fastness, build-up and degree of fixation.