CN113185852B - Active navy blue to black dye composition and dye product - Google Patents

Active navy blue to black dye composition and dye product Download PDF

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CN113185852B
CN113185852B CN202110379865.3A CN202110379865A CN113185852B CN 113185852 B CN113185852 B CN 113185852B CN 202110379865 A CN202110379865 A CN 202110379865A CN 113185852 B CN113185852 B CN 113185852B
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formula
component
independently
group
navy blue
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CN113185852A (en
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何旭斌
袁伟杰
袁文炳
蒋应海
彭光耀
陈沈
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Zhejiang Keyong Chemical Co ltd
Zhejiang Longsheng Group Co Ltd
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Zhejiang Keyong Chemical Co ltd
Zhejiang Longsheng Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C09B67/005—Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0079—Azoic dyestuff preparations

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses an active navy blue to black dye composition and a dye product. The dyeing composition comprises a component A and a component B, wherein the component A is selected from one or more of a dye compound shown in a formula (I) and an alkali metal salt thereof, and the component B is selected from one or more of a dye compound shown in a formula (II) and an alkali metal salt thereof; in the formula (I), D 1 、D 2 Each independently is a group of formula (a), formula (b) or formula (c), and D 1 、D 2 Not simultaneously a group represented by the following formula (a), formula (b) or formula (c). The invention provides a reactive navy blue to black dye product, which contains the reactive navy blue to black dye composition. The dye composition and the dye product provided by the invention have good lifting power and excellent color fastness, and are suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials and blended fabrics thereof.

Description

Active navy blue to black dye composition and dye product
(I) technical field
The invention relates to a reactive dye composition and a dye product, in particular to a reactive navy blue-black dye composition and a dye product which are suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials.
(II) background of the invention
The reactive black KNB is a variety with the largest usage amount in black reactive dyes due to low price, good fastness and easy washability, but the dye has low substantivity to fibers, low dye uptake and color fixing rate, and in view of the defects of the reactive black KNB, dye researchers have made a great deal of work in the research and development of the reactive black dye in recent years. The problems of poor lifting power, low fastness to washing and the like still exist in the practical application process of the existing reactive black dye color matching product.
Disclosure of the invention
In order to solve the problems, the invention aims to provide an active navy blue to black dye composition and a dye product, which have the characteristics of good lifting power and excellent color fastness (especially outstanding washing fastness), and are suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials and blended fabrics thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an active navy blue to black dye composition, which comprises a component A and a component B, wherein the component A is selected from one or more of a dye compound shown as a formula (I) and an alkali metal salt thereof, and the component B is selected from one or more of a dye compound shown as a formula (II) and an alkali metal salt thereof; based on the component A and the component B, the mass percentage of the component A is 5-50%, and the mass percentage of the component B is 50-95%;
Figure BDA0003012518150000011
in formula (I):
D 1 、D 2 each independently is a group of the formula (a), formula (b) or formula (c), and D 1 、D 2 Not both being a group represented by the following formula (a), formula (b) or formula (c):
Figure BDA0003012518150000012
in the above formulas (a) to (c):
R 1 ～R 5 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
X 1 、X 2 、X 3 are independent of each other H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, -SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 And D is 1 、D 2 At least one of which contains fibre-reactive groups, i.e. -SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 Wherein Y is 1 ～Y 3 Each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-CH 2 CH 2 Cl，p＝1-3，q＝1-3；
In formula (II):
R 6 ～R 9 each independently of the other is hydrogen, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
Y 4 、Y 5 each independently is-CH ═ CH 2 、-CH 2 CH 2 OSO 3 H or-CH 2 CH 2 Cl。
In the present invention, said C 1 ～C 4 The alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; said C 1 ～C 4 The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.
Further, R 1 ～R 5 Each independently is H, methyl, methoxy or sulfonic acid.
Further, X 1 、X 2 、X 3 Independently of one another are-SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 Wherein Y is 1 ～Y 3 Each independently is-CH ═ CH 2 、-CH 2 CH 2 Cl or-C 2 H 4 OSO 3 H，p＝1-3，q＝1-3。
Further, D 1 Preferably a group of formula (a) or (b), said D 2 Preferred are groups of formula (c).
Still further, said formula (a) is preferably selected from one of the following groups:
Figure BDA0003012518150000021
still further, said formula (b) is preferably selected from one of the following groups:
Figure BDA0003012518150000022
Figure BDA0003012518150000031
still further, said formula (c) is preferably selected from one of the following groups:
Figure BDA0003012518150000032
Figure BDA0003012518150000041
further, R 6 ～R 9 Each independently is preferably hydrogen, methyl, methoxy or sulfonic acid.
Further, Y 4 、Y 5 Each independently is preferably-CH ═ CH 2 or-CH 2 CH 2 OSO 3 H。
Further, the active navy blue to black dye composition consists of a component A and a component B.
Further, the active navy blue-black dye composition can also comprise a component C, the component C is selected from one or more of dye compounds shown in formulas (III) to (VII) and alkali metal salts thereof, in the composition, the mass of the component C accounts for 1-50% of the total mass of the component A and the component B, preferably 1-40%,
Figure BDA0003012518150000042
Figure BDA0003012518150000051
in the formula (III):
R 10 ～R 13 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, carboxyl or sulfonic acid group, preferably H, methyl, methoxy, carboxyl or sulfonic acid group;
Y 6 、Y 7 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
a is 0 or 1;
b is 0 or 1;
c. d is independently of one another 0 or 1, preferably 1;
D 3 、D 4 independently from each other, substituted phenyl, unsubstituted phenyl, substituted naphthyl or unsubstituted naphthyl, the number of the substituted phenyl and the substituted naphthyl is respectively 1-3, and each substituent is independently selected from amino, sulfonic acid group, ureido and C 1 ～C 4 Alkanoylamino of (1), C 1 ～C 4 Alkoxy or hydroxyl, preferably the number of the substituent groups is 1-2, and each substituent group is independently selected from amino, sulfonic group, ureido, acetamido, methoxy or hydroxyl;
in the formula (IV):
R 14 ～R 17 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups, preferably H, methyl, methoxy or sulfonic acid groups;
e＝0-1；
Y 8 、Y 9 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
In formula (V):
f. g, h are each independently 0 to 3, each R 18 、R 19 、R 20 Each independently is C 1 ～C 4 Alkyl radical, C 1 ～C 4 An alkoxy group or a sulfonic acid group, preferably a methyl group, a methoxy group or a sulfonic acid group;
X 4 is hydrogen or carboxyl;
Y 10 、Y 11 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
In formula (VI):
D 5 、D 6 each independently a group represented by the following formula (d) or (e) or (f):
Figure BDA0003012518150000061
in the above formulae (d), (e), (f): r 21 、R 22 、R 24 、R 25 、R 27 、R 28 Each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups, preferably H, methyl, methoxy or sulfonic acid groups;
i is 0 to 3, each R 23 Each independently selected from C 1 ～C 4 Alkyl, sulfo, ureido or C 1 ～C 4 Preferably a methyl group, a sulfonic acid group, a ureido group or an acetamido group;
j is 0 to 3, each R 26 Each independently selected from hydroxyl or sulfonic acid group;
X 5 、X 6 、X 7 each independently is-SO 2 Y 13 、-NHCO(CH 2 ) r SO 2 Y 14 or-CONH (CH) 2 ) s SO 2 Y 15 Wherein r is 1-3, s is 1-3, Y 13 ～Y 15 Each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-CH 2 CH 2 Cl, wherein, X 5 、X 6 、X 7 Each independently is preferably-SO 2 Y 13 ；
In the formula (VII):
m is 1 to 3, each R 29 Each independently selected from amino, sulfonic acid, ureido, C 1 ～C 4 Alkanoylamino of (1), C 1 ～C 4 Alkoxy or hydroxy, preferably amino, sulfonic or acetylamino;
Y 12 is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
n is 0-2, each R 30 Each independently is C 1 ～C 4 Straight or branched alkyl, C 1 ～C 4 An alkoxy group or a sulfonic acid group, preferably a methyl group, a methoxy group or a sulfonic acid group.
Further, the component C is selected from one or more of dye compounds shown in a formula (III), a formula (IV) and a formula (VI) and alkali metal salts thereof, wherein a and b are both 0, or one of a and b is 0, the other is 1, C is 1, and d is 0 or 1.
Still further, the reactive navy blue to black dye composition of the invention preferably comprises the following dye components:
component A: one or more selected from the group consisting of dye compounds represented by formula (I) and alkali metal salts thereof;
and (B) component: one or more selected from the group consisting of dye compounds represented by formula (II) and alkali metal salts thereof;
and (3) component C: one or more dye compounds selected from the dye compounds shown in formula (III), formula (IV) and formula (VI) and alkali metal salts thereof, wherein a and b are both 0, or one of a and b is 0, the other is 1, c is 1, and d is 0 or 1.
Furthermore, the active navy blue to black dye composition consists of a component A, a component B and a component C.
Still further, the reactive navy blue to black dye composition of the invention preferably consists of the following dye components:
and (2) component A: one or more selected from the group consisting of dye compounds represented by formula (I) and alkali metal salts thereof;
and (B) component: one or more selected from the group consisting of dye compounds represented by formula (II) and alkali metal salts thereof;
and (3) component C: one or more dye compounds selected from the dye compounds shown in formula (III), formula (IV) and formula (VI) and alkali metal salts thereof, wherein a and b are both 0, or one of a and b is 0, the other is 1, c is 1, and d is 0 or 1.
Specifically, the component a is preferably one or more of the following dye compounds and alkali metal salts thereof:
Figure BDA0003012518150000071
Figure BDA0003012518150000081
Figure BDA0003012518150000091
Figure BDA0003012518150000101
Figure BDA0003012518150000111
Figure BDA0003012518150000121
Figure BDA0003012518150000131
Figure BDA0003012518150000141
Figure BDA0003012518150000151
Figure BDA0003012518150000161
Figure BDA0003012518150000171
Figure BDA0003012518150000181
Figure BDA0003012518150000191
further, component A is preferably at least one of dye compounds represented by the formulae (I-1) to (I-8), the formulae (I-11) to (I-26) and alkali metal salts thereof.
Further, component A is preferably at least one of dye compounds represented by the formulae (I-1) to (I-4), the formulae (I-11) to (I-16), and alkali metal salts thereof.
Specifically, the component B is preferably one or more of the following dye compounds and alkali metal salts thereof:
Figure BDA0003012518150000192
Figure BDA0003012518150000201
Figure BDA0003012518150000211
further, component B is preferably one or more of formula (II-1), formula (II-3) and alkali metal salts thereof.
In particular, the component C is preferably one or more of the following dye compounds and alkali metal salts thereof:
Figure BDA0003012518150000212
Figure BDA0003012518150000221
Figure BDA0003012518150000231
Figure BDA0003012518150000241
Figure BDA0003012518150000251
Figure BDA0003012518150000261
Figure BDA0003012518150000271
Figure BDA0003012518150000281
Figure BDA0003012518150000291
Figure BDA0003012518150000301
Figure BDA0003012518150000311
Figure BDA0003012518150000321
Figure BDA0003012518150000331
Figure BDA0003012518150000341
Figure BDA0003012518150000351
Figure BDA0003012518150000361
Figure BDA0003012518150000371
Figure BDA0003012518150000381
Figure BDA0003012518150000391
Figure BDA0003012518150000401
Figure BDA0003012518150000411
Figure BDA0003012518150000421
Figure BDA0003012518150000431
further, component C is preferably one or more of the formulae (III-1) to (III-33), (IV-1) to (IV-10), (VI-1), (VI-3) (VI-4), (VI-26), (VI-27), (VI-31), (VI-38), (VI-41), (VI-42), (VI-45), (VI-54) and alkali metal salts thereof.
Further, component C is preferably at least one of the formulae (III-1), (III-2), (III-4), (IV-1), (IV-3), (VI-26), (VI-27), (VI-41), (VI-42) and alkali metal salts thereof.
Particularly preferred dye compositions according to the invention comprise component a and component B:
and (2) component A: at least one selected from the group consisting of dye compounds represented by formulae (I-1) to (I-8) and formulae (I-11) to (I-26) and alkali metal salts thereof, more preferably at least one selected from the group consisting of dye compounds represented by formulae (I-1) to (I-4) and formulae (I-11) to (I-16) and alkali metal salts thereof;
and (B) component: at least one dye compound selected from the group consisting of dye compounds represented by the formulae (II-1) and (II-3) and alkali metal salts thereof;
based on the mass sum of the components A to B, the mass percentage of the component A is preferably 5 to 50 percent, and the mass percentage of the component B is preferably 50 to 95 percent.
The invention also particularly preferably relates to a dye composition which comprises a component A, a component B and a component C:
and (2) component A: one or more selected from the group consisting of dye compounds represented by formulae (I-1) to (I-8), formulae (I-11) to (I-26) and alkali metal salts thereof, more particularly one or more selected from the group consisting of dye compounds represented by formulae (I-1) to (I-4), formulae (I-11) to (I-16) and alkali metal salts thereof;
and (B) component: one or more selected from the group consisting of dye compounds represented by the formulae (II-1) and (II-3) and alkali metal salts thereof;
and (3) component C: one or more selected from dye compounds shown in formulas (III-1), (III-2), (III-4), (IV-1), (IV-3), (VI-26), (VI-27), (VI-41) and (VI-42) and alkali metal salts thereof;
based on the sum of the mass of the components A to B, the mass percentage of the component A is 5-50%, the mass percentage of the component B is 50-95%, and the mass of the component C is 1-50% of the total mass of the component A and the component B.
The reactive navy blue to black dye compositions according to the invention, the dye compounds (II) to (VII) used are known dyes which can be synthesized by customary methods, for example by using suitable components known to the person skilled in the art and in the necessary proportions by means of customary diazotisation and coupling reactions, or by reference to the methods or approximations in patents CN101250334A, CN105176139A, CN105524485A, CN1266869A, CN 109971208A.
The reactive dye compound shown in the formula (I) can also be prepared according to a conventional diazo coupling method of a reactive dye, for example, the invention provides a preparation method of the dye compound shown in the formula (I), which comprises the following steps:
(1) diazotization:
diazotizing the arylamine compounds shown in the formula (Ia), the formula (Ib) and/or the formula (ic) respectively according to requirements to obtain respective diazonium salts;
(2) coupling reaction:
adding water into 3, 5-dihydroxy benzoic acid for pulping, performing primary coupling on the pulped solution and one of the diazonium salt of the formula (Ia), the diazonium salt of the formula (Ib) and the diazonium salt of the formula (ic) in the step (1), and performing secondary coupling on the pulped solution and one of the diazonium salt of the formula (Ia), the diazonium salt of the formula (Ib) and the diazonium salt of the formula (ic), wherein the diazonium salts adopted in the primary coupling and the secondary coupling can not be the diazonium salt of the formula (Ia), the diazonium salt of the formula (Ib) or the diazonium salt of the formula (ic), so as to obtain the dye compound (I);
Figure BDA0003012518150000441
the substituents in the above formulae (Ia) to (ic) are as defined for formula (I).
Further, the reactive dye compound (I) is preferably synthesized by the following steps:
(1) diazotization:
according to requirements, pulping the compounds shown in the formula (Ia), (Ib) and/or (ic) together with water and ice for 1-2 h, adding a certain amount of hydrochloric acid after pulping is finished, then adding a sodium nitrite solution within 20-30min, controlling the pH to be 0.5-3.0 (preferably 0.5-2.0) and the temperature T to be 0-30 ℃ (preferably 0-20 ℃) to perform diazotization reaction, and detecting the end point by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s); after the diazo end point is reached, eliminating excessive sodium nitrite by using sulfamic acid to respectively obtain diazo liquid of the formula (Ia), the formula (Ib) or the formula (ic), and storing for later use; wherein the molar ratio of the compound shown in the formula (Ia), the compound shown in the formula (Ib) or the compound shown in the formula (ic) to the hydrochloric acid and the sodium nitrite is 1 (1-3) to 1-1.1, preferably 1 (1-1.8) to 1-1.02;
(2) coupling reaction:
adding water into 3, 5-dihydroxy benzoic acid, pulping and dispersing, and controlling the temperature to be 15-25 ℃. Adding the dispersed 3, 5-dihydroxybenzoic acid into the diazo liquid of the formula (Ia), the diazo liquid of the formula (Ib) or the diazo liquid of the formula (ic) prepared in the step (1), controlling the pH value to be 2.0-5.0 and the temperature to be 0-30 ℃ (preferably 0-20 ℃) by using liquid alkali or sodium bicarbonate to carry out coupling reaction, testing diazo by using an H acid test solution, and obtaining a coupling product 1 after the diazo has completely reacted and is colorless at a ring penetration position;
adding the diazo liquid of the formula (Ia), the diazo liquid of the formula (Ib) or the diazo liquid of the formula (ic) obtained in the step (1) into the coupling product 1, controlling the pH value to be 5.0-8.0 and the temperature to be 0-30 ℃ (preferably 0-20 ℃) by using liquid alkali or baking soda to carry out coupling reaction, testing diazo by using H acid test solution, and obtaining the reactive dye compound of the formula (I) after the diazo has reacted completely to the end point and being colorless at the position of a seepage ring;
the diazo liquids used in the two coupling reactions can not be all the diazo liquids of formula (Ia), formula (Ib) or formula (ic); wherein the molar ratio of the compound of formula (Ia), formula (Ib) or formula (ic) to the 3, 5-dihydroxybenzoic acid is (0.95-1.2): 1, preferably (0.98-1.08): 1.
it should be emphasized that in the reactive navy blue to black dye composition of the present invention, the dye compound monomer coupled at the ortho-position of the phenolic hydroxyl group often exists in a stable state of quinone hydrazone structure, that is, the dye of the general formula (i) substantially contains quinone hydrazone structure represented by the following formula (ie) and/or formula (if) and/or (ig) and/or (ih), the dye of the general formula (ii) and (iv) substantially contains quinone hydrazone structure represented by the following formula (iia) and (iva), the dye of the general formula (vi) substantially contains quinone hydrazone structure represented by the following formula (via) and/or formula (vib) and/or (vic) and/or (vid), considering the writing habit of those skilled in the art, the writing form of the azo body is still adopted in the summary and the examples, which does not affect the essence of the invention:
Figure BDA0003012518150000451
Figure BDA0003012518150000461
the substituents in the above formulae (ie) to (ih) are as defined for formula (I), the substituents in the formulae (IIa) and (IVa) are as defined for formulae (II) and (IV), respectively, and the substituents in the formulae (VIa) to (VId) are as defined for formula (VI).
In addition, the active navy blue to black dye compositions according to the invention, formulae (I) to (VII) are all embodied in the form of the free acids, and in the actual synthesis process are generally prepared and isolated in the form of their alkali metal salts, preferably sodium or potassium salts, and are also used for dyeing in the form of their salts, which are also known to the person skilled in the art, i.e. the carboxyl and sulfonic acid groups in formulae (I) to (VII) can be present in the form of sodium carboxylates or sodium sulfonates.
The reactive navy blue to black dye composition of the invention is prepared by mixing the dye components A, B or A, B, C according to the above-mentioned ratio, the mixing can be carried out by conventional mechanical means, such as in a grinder, kneader or homogenizer, during the mixing process, the single dye compound can be in the form of powder, granule, aqueous solution or synthetic solution, when the single dye compound is mixed in the form of synthetic solution, the separation of the complex reactive navy blue to black dye of the invention from the synthetic solution can be carried out by generally known methods, such as salting out the dye from the reaction medium by an electrolyte (such as sodium chloride or potassium chloride), or evaporating and spray-drying the mixed solution, therefore, the dye component A, B, C and the dye composition thereof usually comprise the electrolyte salt (such as sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium, Sodium sulfate, etc.).
In the second aspect, when the active navy blue to black dye composition of the invention is sold as a commodity, no auxiliary agent is added, and conventional auxiliary agents in the commodity dye, such as a cosolvent, a dispersing agent, an alkali-resistant auxiliary agent, a dust-proof agent, a surfactant, a buffering agent, an accelerating agent and the like, can also be added. Therefore, the invention also provides a reactive navy blue to black dye product which contains the reactive navy blue to black dye composition. Preferably, the reactive navy blue to black dye product contains the reactive navy blue to black dye composition and an auxiliary agent, and the weight of the auxiliary agent is not more than 45 percent, preferably not more than 40 percent of the weight of the reactive navy blue to black dye composition. The auxiliary agent is preferably one or the combination of any several of the following components: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), dispersant CNF (benzylnaphthalenesulfonate formaldehyde condensate), sodium sulfate (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogen carbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, and the like. The auxiliary agents are all conventional commercial varieties.
The active navy blue to black dye product is suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials, wherein the nitrogen-containing and/or hydroxyl-containing fiber materials can be cellulose fibers, polyamide fibers and fabrics thereof, the cellulose fibers are preferably cotton fibers or regenerated fibers, and can also comprise other plant fibers such as hemp fibers or fabrics; the polyamide fiber is preferably an animal fiber material including a sheath, a wool or a silk, and a synthetic fiber material such as nylon 6 and nylon 66. When the fiber material is printed and dyed by using the active navy blue to black dye product, the dyeing can be carried out according to the known active dye dyeing method, such as the commonly used active dye dip dyeing method and pad dyeing method, wherein the dip dyeing method is a method for dipping the fabric into a dye solution to gradually dye the fabric, and the procedures of dyeing, fixing color, washing, soaping, washing, dewatering, drying and the like are usually required.
The pad dyeing is a dyeing method that a fabric is soaked in a dye solution, then the fabric passes through a roller, the dye solution is uniformly rolled into the fabric, and then the fabric is steamed or hot-melted and the like, and generally the procedures of pad dyeing, drying- (pad fixing solution), steaming or baking, washing, soaping, washing, drying and the like are needed.
Generally, the dye usage amount is different due to different dyeing requirements on fabrics, when a dip dyeing method is used for dyeing, the dyeing depth (owf) is generally 0.1-10% (the dye accounts for the weight percent of the fabrics), the bath ratio is 1: 2-1: 60 (the weight ratio of the fabrics to the dye liquor is preferably 1: 10-1: 30), the initial dyeing temperature is controlled to be 30-60 ℃, the dyeing time is 10-30 minutes, the soaping temperature is 85-95 ℃, the soaping time is 10-15 minutes, the color fixing temperature is 60-100 ℃, the color fixing time is 10-50 minutes, and the color fixing pH value is 9-11. When the pad dyeing method is used for dyeing, the pad retention rate of the cellulose fiber is generally 60-80%, the steaming temperature is 100-103 ℃, and the steaming time is 1-3 minutes. In the pad dyeing method, a cold pad-batch dyeing method is frequently used at present, and a dye and an alkaline substance are introduced into a pad dyeing machine, coiled and stacked at room temperature for 2-30 hours for color fixation, and then thoroughly rinsed.
The invention has the following beneficial effects: the active navy blue to black dye composition and the product of the invention have the characteristics of good promotion, excellent color fastness, especially prominent washing fastness and the like when being used for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials.
(IV) description of the drawings
FIG. 1 is a UV-Vis spectrum of a reactive dye compound prepared in example 3;
FIG. 2 is a mass spectrum of the reactive dye compound prepared in example 3, wherein m/Z-432.96 is a target molecule double charge ionization peak.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
the dye compound prepared in the embodiment of the invention is sodium salt and is applied in the form of sodium salt, but for the convenience of writing, all structural formulas in the embodiment are embodied in the form of free acid, and the substantial dyeing performance of the free acid and the sodium salt is known to be equivalent by persons skilled in the art.
Example 1
(1) Diazotization:
41.1g (0.1mol) of 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid was put into 100g of water and 100g of ice and slurried for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol) was added thereto, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) was added thereto within 20 to 30 minutes, diazotization was carried out at a pH of 0.5 to 2.0 and a temperature T of 0 to 20 ℃ for 1 to 2 hours, and the end point was detected by an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., no discoloration was observed within 5 seconds). And after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid diazotization liquid for later use.
36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate aniline) is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at the pH value of 0.5-2.0 and the temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.
(2) Coupling:
firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled to be 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the diazo liquid of 2-amino-6-hydroxyethyl sulfone sulfate-based-1-naphthalenesulfonic acid obtained in the step (1), the pH is controlled to be 2.0-4.0 by 30% liquid alkali, the temperature is controlled to be 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled to be below 3% by HPLC to obtain the end point, thus obtaining the chromophore 1 shown in the following formula (A).
Figure BDA0003012518150000481
And (2) adding the sulfonated para-ester diazo solution prepared in the step (1) into a chromophore 1, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining an orange reactive dye compound (I-1) when the diazo reaction is completely finished, wherein the lambda max in an aqueous solution is 440 nm.
Figure BDA0003012518150000482
Example 2
(1) Diazotization:
40.0g (0.1mol) of 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at a pH of 0.5-2.0 and a temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no discoloration occurs within 5 s). After the diazotization end point is reached, sulfamic acid is used for eliminating excessive sodium nitrite to obtain 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline diazo liquid for storage and standby.
36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate ester aniline) is put into 100g of water and 100g of ice and beaten for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at a pH of 0.5-2.0 and a temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change is generated within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.
(2) Coupling:
firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled to be 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) phenylamine obtained in the step (1), the pH is controlled to be 2.0-4.0 by 30 percent liquid alkali, the temperature is controlled to be 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled to be below 3 percent by HPLC to obtain the end point, thus obtaining the chromophore 2 shown in the following formula (B).
Figure BDA0003012518150000491
And (2) adding the sulfonated para-ester diazo solution prepared in the step (1) into a chromophore 2, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining an orange reactive dye compound (I-11) when the diazo reaction is completely finished, wherein the lambda max in an aqueous solution is 420 nm.
Figure BDA0003012518150000492
Examples 3 to 63:
dye compounds having the structures shown in Table 1 below were prepared by stepwise diazotization and coupling reactions using intermediate raw materials well known in the art according to the azo dye preparation methods described in example 1 or example 2, respectively.
TABLE 1
Figure BDA0003012518150000493
Figure BDA0003012518150000501
Figure BDA0003012518150000511
Figure BDA0003012518150000521
Figure BDA0003012518150000531
Figure BDA0003012518150000541
Figure BDA0003012518150000551
Figure BDA0003012518150000561
Figure BDA0003012518150000571
Figure BDA0003012518150000581
Figure BDA0003012518150000591
Example 64:
20 parts of the dye compound of the formula (I-1), 80 parts of the dye compound of the formula (II-1) and 10 parts of anhydrous sodium sulphate are mechanically mixed, and the obtained reactive dye product is dyed black by a conventional dip-dyeing method, has the fastness to washing and staining of more than 4 grades (refer to ISO 105C 10-2006) and has excellent lifting force (refer to GB/T21875-2016).
Figure BDA0003012518150000601
Example 65:
20 parts of the dye compound of the formula (I-2), 75 parts of the dye compound of the formula (II-3), 5 parts of the dye compound of the formula (VI-26) and 10 parts of anhydrous sodium sulphate are mechanically mixed, and the obtained reactive dye product is dyed into black cotton by a conventional dip dyeing method, has the fastness to washing and staining of more than 4 grades (refer to ISO 105C 10-2006), and has excellent lifting force (refer to GB/T21875-2016).
Figure BDA0003012518150000602
Example 66:
20 parts of the dye compound of the formula (I-1), 70 parts of the dye compound of the formula (II-3), 10 parts of the dye compound of the formula (IV-1) and 10 parts of anhydrous sodium sulphate are mechanically mixed, and the obtained reactive dye product is dyed into dark black cotton by a conventional dip-dyeing method, has the fastness to washing and staining of more than 4 grades (refer to ISO 105C 10-2006), and has excellent lifting force (refer to GB/T21875-2016).
Figure BDA0003012518150000611
Example 67:
20 parts of the dye compound of the formula (I-1), 75 parts of the dye compound of the formula (II-3), 2 parts of the dye compound of the formula (IV-1), 3 parts of the dye compound of the formula (VI-26), 10 parts of anhydrous sodium sulphate and 10 parts of a dispersing agent MF are mechanically mixed, and the obtained reactive dye product is dark black dyed cotton, has the color fastness to washing of more than 4 grades (refer to ISO 105C 10-2006) and has excellent lifting force (refer to GB/T21875-2016).
Figure BDA0003012518150000612
Figure BDA0003012518150000621
Example 68:
the active dye product obtained by mechanically mixing 14 parts of the dye compound of the formula (I-11), 70 parts of the dye compound of the formula (II-3), 8 parts of the dye compound of the formula (IV-1), 8 parts of the dye compound of the formula (VI-26), 10 parts of anhydrous sodium sulphate and 10 parts of a dispersing agent MF has dark black dyed cotton and excellent lifting force and has the color fastness to washing up to more than 4 levels (refer to ISO 105C 10-2006) (refer to GB/T21875-2016).
Figure BDA0003012518150000622
Figure BDA0003012518150000631
Example 69:
20 parts of the dye compound shown in the formula (I-12), 70 parts of the dye compound shown in the formula (II-1), 10 parts of the dye compound shown in the formula (III-1), 10 parts of anhydrous sodium sulphate and 10 parts of a dispersing agent MF are mechanically mixed, and the obtained reactive dye product is dark black in dyed cotton, has the fastness to washing of more than 4 grades (refer to ISO 105C 10-2006), and is excellent in lifting force (refer to GB/T21875-2016).
Figure BDA0003012518150000632
Examples 70 to 223
According to the method of one of the embodiments 64 to 69, the dyes with the proportions listed in the table 2 are mechanically mixed, and the dyed cotton is dark blue to black according to the conventional reactive dye dyeing method, has the color fastness to washing of more than 4 grade (refer to ISO 105C 10-2006), and has excellent lifting force (refer to GB/T21875-2016).
TABLE 2
Figure BDA0003012518150000633
Figure BDA0003012518150000641
Figure BDA0003012518150000651
Figure BDA0003012518150000661
Figure BDA0003012518150000671
Figure BDA0003012518150000681
Figure BDA0003012518150000691
Figure BDA0003012518150000701

Claims (21)

1. An active navy blue to black dye composition comprises a component A and a component B, wherein the component A is selected from one or more of a dye compound shown as a formula (I) and an alkali metal salt thereof, and the component B is selected from one or more of a dye compound shown as a formula (II) and an alkali metal salt thereof; based on the component A and the component B, the mass percentage of the component A is 5-50%, and the mass percentage of the component B is 50-95%;
Figure FDA0003638144880000011
in formula (I):
D 1 、D 2 each independently is a group of formula (a), formula (b) or formula (c), and D 1 、D 2 Not simultaneously a group represented by the following formula (a), formula (b) or formula (c):
Figure FDA0003638144880000012
in the above formulas (a) to (c):
R 1 ～R 5 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
X 1 、X 2 、X 3 are independent of each other H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, -SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 And D is 1 、D 2 At least one of which contains fibre-reactive groups, i.e. -SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 Wherein Y is 1 ～Y 3 Each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-CH 2 CH 2 Cl，p＝1-3，q＝1-3；
In formula (II):
R 6 ～R 9 each independently of the other is hydrogen, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
Y 4 、Y 5 each independently is-CH ═ CH 2 、-CH 2 CH 2 OSO 3 H or-CH 2 CH 2 Cl。
2. The reactive navy to black dye composition of claim 1, wherein: the active navy blue to black dye composition consists of a component A and a component B.
3. The reactive navy blue to black dye composition of claim 1, wherein: the active navy blue to black dye composition also comprises a component C, wherein the component C is selected from one or more of dye compounds shown in formulas (III) to (VII) and alkali metal salts thereof, in the composition, the mass of the component C accounts for 1-50% of the total mass of the component A and the component B,
Figure FDA0003638144880000021
in the formula (III):
R 10 ～R 13 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, carboxyl or sulfonic acid groups;
Y 6 、Y 7 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
a is 0 or 1;
b is 0 or 1;
c. d is independently of each other 0 or 1;
D 3 、D 4 independently of one another, is a substituted phenyl group, an unsubstituted phenyl group, a substituted naphthyl group or an unsubstituted naphthyl group, the number of the substituents of the substituted phenyl group and the substituted naphthyl group is 1 to 3, and each substituent is independently selected from the group consisting of an amino group, a sulfonic acid group, a salt, and a salt, a,Ureido group, C 1 ～C 4 Alkanoylamino of (1), C 1 ～C 4 Alkoxy or hydroxy;
in the formula (IV):
R 14 ～R 17 each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
e＝0-1；
Y 8 、Y 9 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
In formula (V):
f. g, h are each independently 0-3, each R 18 、R 19 、R 20 Each independently is C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
X 4 is hydrogen or carboxyl;
Y 10 、Y 11 each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
In formula (VI):
D 5 、D 6 each independently is a group represented by the following formula (d) or (e) or (f):
Figure FDA0003638144880000031
in the above formulae (d), (e), (f): r is 21 、R 22 、R 24 、R 25 、R 27 、R 28 Each independently is H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy or sulfonic acid groups;
i is 0 to 3, each R 23 Each independently selected from C 1 ～C 4 Alkyl, sulfo, ureido or C 1 ～C 4 Alkanoylamino of (a);
j is 0 to 3, each R 26 Each independently selected from hydroxyl or sulfonic acid group;
X 5 、X 6 、X 7 each independently is-SO 2 Y 13 、-NHCO(CH 2 ) r SO 2 Y 14 or-CONH (CH) 2 ) s SO 2 Y 15 Wherein r is 1-3, s is 1-3, Y 13 ～Y 15 Each independently is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-CH 2 CH 2 Cl；
In the formula (VII):
m is 1-3, each R 29 Each independently selected from amino, sulfonic acid, ureido, C 1 ～C 4 Alkanoylamino of (1), C 1 ～C 4 Alkoxy or hydroxy;
Y 12 is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl；
n is 0-2, each R 30 Each independently is C 1 ～C 4 Straight or branched alkyl, C 1 ～C 4 Alkoxy groups or sulfonic acid groups.
4. A reactive navy blue to black dye composition according to claim 3, characterized in that: the active navy blue to black dye composition consists of a component A, a component B and a component C.
5. A reactive navy blue to black dye composition according to any of claims 1 to 4, characterized in that: d 1 Is a group of formula (a) or (b), said D 2 Is a group of formula (c).
6. A reactive navy blue to black dye composition according to any of claims 1 to 4, characterized in that:
in formula (I):
R 1 ～R 5 each independently is H, methyl, methoxy or sulfonic group;
X 1 、X 2 、X 3 independently of one another are-SO 2 Y 1 、-NHCO(CH 2 ) p SO 2 Y 2 or-CONH (CH) 2 ) q SO 2 Y 3 Wherein Y is 1 ～Y 3 Each independently is-CH ═ CH 2 、-CH 2 CH 2 Cl or-C 2 H 4 OSO 3 H；
In formula (II):
R 6 ～R 9 each independently is hydrogen, methyl, methoxy or sulfonic group;
Y 4 、Y 5 each independently is-CH ═ CH 2 or-CH 2 CH 2 OSO 3 H。
7. A reactive navy blue to black dye composition according to any of claims 1 to 4, characterized in that: the alkali metal salt is sodium salt or potassium salt.
8. A reactive navy blue to black dye composition according to claim 3 or 4, characterized in that: in the active dark blue-black dye composition, the mass of the component C accounts for 1-40% of the total mass of the component A and the component B.
9. A reactive navy blue to black dye composition according to claim 3 or 4, characterized in that: the component C is selected from one or more of dye compounds shown in a formula (III), a formula (IV) and a formula (VI) and alkali metal salts thereof, wherein a and b are both 0, or one of a and b is 0, the other is 1, C is 1, and d is 0 or 1.
10. A reactive navy blue to black dye composition according to claim 3 or 4, characterized in that:
in the formula (III):
R 10 ～R 13 each independently is H, methyl, methoxy, carboxyl or sulfonic group;
c. d is 1;
D 3 、D 4 independently of one another, is substituted phenyl, unsubstituted phenyl, substituted naphthyl or unsubstituted naphthyl, the number of substituents of the substituted phenyl and the substituted naphthyl is respectively 1-2, and each substituent is independently selected from aminoSulfonic acid group, ureido group, acetamido group, methoxy group or hydroxyl group;
in the formula (IV):
R 14 ～R 17 each independently is H, methyl, methoxy or sulfonic group;
in formula (V):
f. g, h are each independently 0 to 3, each R 18 、R 19 、R 20 Each independently is methyl, methoxy or sulfonic group;
in formula (VI):
in formulas (d), (e), (f): r 21 、R 22 、R 24 、R 25 、R 27 、R 28 Each independently is H, methyl, methoxy or sulfonic group;
i is 0 to 3 and each R 23 Each independently selected from methyl, sulfonic acid, ureido or acetamido;
X 5 、X 6 、X 7 each independently is-SO 2 Y 13 ，Y 13 is-CH ═ CH 2 、-C 2 H 4 OSO 3 H or-CH 2 CH 2 Cl；
In the formula (VII):
m is 1-3, each R 29 Each independently selected from amino, sulfonic acid or acetylamino;
n is 0-2, each R 30 Each independently being a methyl group, a methoxy group or a sulfonic group.
11. A reactive navy blue to black dye composition according to any of claims 1 to 4, characterized in that: the component A is one or more of the following dye compounds and alkali metal salts thereof:
Figure FDA0003638144880000051
Figure FDA0003638144880000061
Figure FDA0003638144880000071
Figure FDA0003638144880000081
Figure FDA0003638144880000091
Figure FDA0003638144880000101
Figure FDA0003638144880000111
Figure FDA0003638144880000121
Figure FDA0003638144880000131
Figure FDA0003638144880000141
Figure FDA0003638144880000151
Figure FDA0003638144880000161
Figure FDA0003638144880000171
12. a reactive navy blue to black dye composition according to any of claims 1 to 4, characterized in that: the component B is one or more of the following dye compounds and alkali metal salts thereof:
Figure FDA0003638144880000172
Figure FDA0003638144880000181
Figure FDA0003638144880000191
13. a reactive navy blue to black dye composition according to claim 3 or 4, characterized in that: the component C is one or more of the following dye compounds and alkali metal salts thereof:
Figure FDA0003638144880000192
Figure FDA0003638144880000201
Figure FDA0003638144880000211
Figure FDA0003638144880000221
Figure FDA0003638144880000231
Figure FDA0003638144880000241
Figure FDA0003638144880000251
Figure FDA0003638144880000261
Figure FDA0003638144880000271
Figure FDA0003638144880000281
Figure FDA0003638144880000291
Figure FDA0003638144880000301
Figure FDA0003638144880000311
Figure FDA0003638144880000321
Figure FDA0003638144880000331
Figure FDA0003638144880000341
Figure FDA0003638144880000351
Figure FDA0003638144880000361
Figure FDA0003638144880000371
Figure FDA0003638144880000381
Figure FDA0003638144880000391
Figure FDA0003638144880000401
Figure FDA0003638144880000411
14. a reactive navy to black dye composition according to claim 1 or 2, characterized in that:
component A: one or more dye compounds selected from the group consisting of dye compounds represented by formulae (I-1) to (I-8), formulae (I-11) to (I-26), and alkali metal salts thereof;
and (B) component: one or more selected from dye compounds represented by formulas (II-1) and (II-3) and alkali metal salts thereof;
based on the sum of the components A to B, the mass percentage of the component A is 5-50%, and the mass percentage of the component B is 50-95%;
Figure FDA0003638144880000412
Figure FDA0003638144880000421
Figure FDA0003638144880000431
Figure FDA0003638144880000441
Figure FDA0003638144880000451
Figure FDA0003638144880000461
15. a reactive navy blue to black dye composition according to claim 3 or 4, characterized in that:
and (2) component A: one or more selected from the group consisting of dye compounds represented by formulae (I-1) to (I-8) and formulae (I-11) to (I-26), and alkali metal salts thereof;
and (B) component: one or more selected from the group consisting of dye compounds represented by the formulae (II-1) and (II-3) and alkali metal salts thereof;
and (3) component C: one or more selected from dye compounds shown in formulas (III-1), (III-2), (III-4), (IV-1), (IV-3), (VI-26), (VI-27), (VI-41) and (VI-42) and alkali metal salts thereof;
based on the sum of the mass of the components A to B, the mass percentage of the component A is 5-50%, the mass percentage of the component B is 50-95%, and the mass of the component C is 1-50% of the total mass of the component A and the component B;
Figure FDA0003638144880000462
Figure FDA0003638144880000471
Figure FDA0003638144880000481
Figure FDA0003638144880000491
Figure FDA0003638144880000501
Figure FDA0003638144880000511
Figure FDA0003638144880000521
16. a reactive navy blue to black dye composition according to claim 1 or 2, characterized in that: the dye compound shown in the formula (I) contains quinone hydrazone structures shown in the following formula (ie) and/or the formula (if) and/or the formula (Ig) and/or the formula (ih), the dye compounds shown in the formula (II) respectively contain quinone hydrazone structures shown in the following formula (IIa),
Figure FDA0003638144880000531
the substituents in the above formulae (ie) to (ih) are as defined for formula (I), and the substituents in formula (IIa) are as defined for formula (II).
17. A reactive navy blue to black dye composition according to claim 3 or 4, characterized in that: the dye compound shown in the formula (I) contains a quinone hydrazone structure shown in the following formula (ie) and/or the formula (if) and/or the formula (Ig) and/or the formula (ih), the dye compounds shown in the formulae (II) and (IV) respectively contain the quinone hydrazone structures shown in the formulae (IIa) and (IVa), the dye compound shown in the formula (VI) contains the quinone hydrazone structure shown in the formula (VIa) and/or the formula (VIb) and/or the formula (VIc) and/or the formula (VI d),
Figure FDA0003638144880000532
Figure FDA0003638144880000541
the substituents in the above formulae (ie) to (ih) are as defined for formula (I), the substituents in the formulae (IIa) and (IVa) are as defined for formulae (II) and (IV), respectively, and the substituents in the formulae (VIa) to (VId) are as defined for formula (VI).
18. A reactive navy blue to black dye preparation comprising a reactive navy blue to black dye composition according to any of claims 1 to 4.
19. The reactive navy blue to black dye preparation of claim 18, wherein: the active navy blue to black dye product contains the active navy blue to black dye composition and an auxiliary agent, and the weight of the auxiliary agent is not more than 45 percent of the weight of the active navy blue to black dye composition.
20. A reactive navy to black dye preparation according to claim 19, characterized in that: the weight of the auxiliary agent is not more than 40% of the weight of the active navy blue-black dye composition.
21. A reactive navy to black dye preparation according to claim 19 or 20, characterized in that: the auxiliary agent is selected from one or a combination of any of the following components: naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, a dispersing agent CNF, anhydrous sodium sulphate, lignosulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate and a thickening agent.
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