CN113388265B - Reactive dark blue to black dye composition and dye product - Google Patents
Reactive dark blue to black dye composition and dye product Download PDFInfo
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- CN113388265B CN113388265B CN202110379867.2A CN202110379867A CN113388265B CN 113388265 B CN113388265 B CN 113388265B CN 202110379867 A CN202110379867 A CN 202110379867A CN 113388265 B CN113388265 B CN 113388265B
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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
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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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
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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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0079—Azoic dyestuff preparations
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Abstract
The invention discloses an active dark blue to black dye composition and a dye product. The active dark blue-to-black dye composition comprises a component A and a component B, wherein the component A is selected from one or more of dye compounds shown in a formula (I) and alkali metal salts thereof, and the component B is selected from one or more of dye compounds shown in a formula (II) and alkali metal salts thereof; in the formula (I), D 1 、D 2 Each independently is a group represented by the following formula (a), formula (b), formula (c) or formula (D), and D 1 、D 2 Not simultaneously being a group of the formula (a), formula (b), formula (c) or formula (d); preferably D 1 Is a group of formula (a) or (b), D 2 Is a group represented by formula (c) or formula (d). The invention provides an active navy blue to black dye product containing the dye composition, which has the characteristics of good washing fastness, good lifting force and the like.
Description
Field of the art
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 suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials.
(II) background art
Reactive black KNB has become the largest variety of black reactive dyes due to low price, good fastness and easy washing property, but the dye has low substantivity to fibers, low dye-uptake and fixation rate, and aiming at 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 existing reactive black dye color matching products still have the problems of poor lifting force, low washing fastness and the like in the practical application process.
(III) summary of the invention
In order to solve the problems, the invention aims to provide an active navy blue-black dye composition and a dye product, which have the characteristics of good washing fastness, good lifting power and the like, 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 aim of the invention, 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 dye compounds shown in a formula (I) and one or more alkali metal salts thereof, and the component B is selected from one or more dye compounds shown in a formula (II) and one or more alkali metal salts 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%:
in formula (I):
D 1 、D 2 each independently is a group represented by the following formula (a), formula (b), formula (c) or formula (D), and D 1 、D 2 Not simultaneously are groups represented by the following formulas (a), (b), (c) or (d):
in the above formulas (a) to (d):
R 1 、R 2 、R 3 、R 5 、R 6 、R 8 、R 9 h, C independently of each other 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups;
m=0-3, each R 4 Each independently selected from amino, sulfonic acid, ureido, C 1 ~C 4 Alkyl, C of (2) 1 ~C 4 Alkanoylamino or C 1 ~C 4 An alkoxy group;
n=0-3, each R 7 Each independently selected from hydroxyl, amino, or sulfonic groups;
X 1 、X 2 、X 3 、X 4 h, C independently of each other 1 ~C 4 Alkyl, 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 them contains a fibre-reactive group, 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 10 ~R 13 each independently is hydrogen, C 1 ~C 4 Alkyl, 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 invention, the C 1 ~C 4 The alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C is 1 ~C 4 The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
Further, R 1 、R 2 、R 3 、R 5 、R 6 、R 8 、R 9 Independently of one another, H, methyl, methoxy or sulphonic acid groups;
further, m is preferably 1 or 2, each R 4 Each independently is preferably methyl, sulfonate, ureido, or acetamido;
further, n is preferably 0 or 1, each R 7 Each independently selected from hydroxyl or sulfonate;
further, X 1 、X 2 、X 3 、X 4 Are independently of one another-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 The group represented by formula (c) or formula (d) is preferable.
Further, the dye compound (I) has a structure represented by the following formula (IA) or formula (IB):
the definition of each substituent in the formula (IA) and the formula (IB) is the same as that in the formula (I).
Still further, said formula (a) is preferably selected from one of the following groups:
still further, said formula (b) is preferably selected from one of the following groups:
still further, said formula (c) is preferably selected from one of the following groups:
still further, said formula (d) is preferably selected from one of the following groups:
further, R 10 ~R 13 Each independently is preferably hydrogen, methyl, methoxy or a sulfonate group.
Further, Y 4 、Y 5 Each independently is preferably-ch=ch 2 or-CH 2 CH 2 OSO 3 H。
Further, the reactive navy blue to black dye composition consists of a component A and a component B.
Further, the reactive navy blue to black dye composition may further comprise a component C, wherein the component C is selected from one or more of dye compounds shown as formulas (III) to (VII) and alkali metal salts thereof, and 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, and is preferably 1-40%:
in formula (III):
R 14 ~R 17 each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, carboxyl or sulfonic acid groups, preferably H, methyl, methoxy, 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 0 or 1, preferably 1;
D 3 、D 4 are independently substituted phenyl, unsubstituted phenyl, substituted naphthyl or unsubstituted naphthyl, the number of substituents 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, C 1 ~C 4 Alkoxy or hydroxy, preferably 1 to 2 substituents each, each independently selected from amino, sulfonate, ureido, acetamido, methoxy or hydroxy;
in formula (IV):
R 18 ~R 21 each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonate, preferably H, methyl, methoxy or sulfonate;
e=0 or 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 and h are each independently 0-3, each R 22 、R 23 、R 24 Each independently is C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonate, preferably methyl, methoxy or sulfonate;
X 5 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 (e) or (f) or (g):
in the above formulas (e), (f) and (g): r is R 25 、R 26 、R 28 、R 29 、R 31 、R 32 Each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonate, preferably H, methyl, methoxy or sulfonate;
i=0-3, each R 27 Each independently selected from C 1 ~C 4 Alkyl, sulfo, ureido or C 1 ~C 4 Preferably methyl, sulfonate, ureido or acetamido;
j=0-3, each R 30 Each independently selected from hydroxyl or sulfonate;
X 6 、X 7 、X 8 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=1-3, s=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 6 、X 7 、X 8 Each independently is preferably-SO 2 Y 13 ;
In formula (VII):
k=1-3, each R 33 Each independently selected from amino, sulfonic acid, ureido, C 1 ~C 4 Alkanoylamino, C 1 ~C 4 Alkoxy or hydroxy, preferably amino, sulfonic or acetamido;
Y 12 is-CH=CH 2 、-C 2 H 4 OSO 3 H or-C 2 H 4 Cl;
l=0-2, each R 34 Each independently is C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups, preferably methyl, methoxy or sulfonic acid groups.
Further, component C is selected from at least one dye of formula (III) and/or formula (IV) and/or formula (VI), wherein a and b are together 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 to black dye composition of the present invention preferably comprises the following dye components:
component A: at least one selected from the group consisting of a dye compound represented by the formula (I) and an alkali metal salt thereof;
component B: at least one selected from the group consisting of a dye compound represented by the formula (II) and an alkali metal salt thereof;
component C: at least one dye compound selected from the group consisting of dye compounds represented by the formula (III), the formula (IV) and the formula (VI) and alkali metal salts thereof, wherein a and b are 0, or one of a and b is 0, the other is 1, c is 1, and d is 0 or 1.
Further, the reactive navy blue to black dye composition consists of a component A, a component B and a component C.
Still further, the reactive navy to black dye composition of the present invention preferably consists of the following dye components:
component A: at least one selected from the group consisting of a dye compound represented by the formula (I) and an alkali metal salt thereof;
component B: at least one selected from the group consisting of a dye compound represented by the formula (II) and an alkali metal salt thereof;
component C: at least one dye compound shown in the formula (III), the formula (IV) and the formula (VI) and alkali metal salts thereof, wherein a and b are 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 at least one of the following dye compounds and alkali metal salts thereof:
further, component A is preferably one of the compounds represented by the formulae (I-1) to (I-16), and the formulae (I-27) to (I-48) and alkali metal salts thereof.
Further, component A is preferably one of the compounds represented by the formulae (I-1) to (I-8), and the formulae (I-27) to (I-30), and alkali metal salts thereof.
Specifically, the component B is preferably at least one of the following compounds and alkali metal salts thereof:
further, component B is preferably at least one of the formula (II-1), the formula (II-3) and alkali metal salts thereof.
Specifically, the component C is preferably at least one of the following compounds and alkali metal salts thereof:
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.
Still 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.
The dye composition according to the invention particularly preferably comprises component A and component B:
component A: at least one selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-16), the formulae (I-27) to (I-48) and alkali metal salts thereof, and more particularly, at least one selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-8), the formulae (I-27) to (I-30) and alkali metal salts thereof;
component B: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (II-1), (II-3) and alkali metal salts thereof;
the mass percentage of the component A is preferably 5 to 50% and the mass percentage of the component B is preferably 50 to 95% based on the sum of the mass percentages of the components A to B.
The dye composition according to the invention also particularly preferably comprises component A, component B and component C:
component A: at least one selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-16), the formulae (I-27) to (I-48) and alkali metal salts thereof, and more particularly, at least one selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-8), the formulae (I-27) to (I-30) and alkali metal salts thereof;
component B: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (II-1), (II-3) and alkali metal salts thereof;
component C: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (III-1), (III-2), (III-4), (IV-1), (IV-3), (VI-26), (VI-27), (VI-41), (VI-42) and alkali metal salts thereof;
based on the sum of the mass of the components A and B, the mass percentage of the component A is 5-50%, the mass percentage of the component B is 50-95%, and the mass percentage of the component C is 1-50% of the total mass of the component A and the component B.
The reactive navy to black dye compositions according to the invention, the dye compounds (II) to (VII) used being known dyes, can be synthesized by conventional methods, for example by using suitable components known to those skilled in the art and using the necessary proportions by means of customary diazotisation and coupling reactions, or by reference to the process or approximation of the process of patent 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 reactive dyes, for example, the invention provides a preparation method of the dye compound shown in the formula (I), which comprises the following steps:
(1) Diazotisation is carried out according to the following steps A and B and/or C:
A. diazotizing an aromatic amine compound shown in a formula (Ia), a formula (Ib), a formula (ic-1) and/or a formula (Id-1) respectively according to requirements to obtain respective diazonium salts;
B. coupling diazonium salt of formula (ic-1) with aromatic amine of formula (ic-2) to obtain compound of formula (ic), diazotizing compound of formula (ic) to obtain diazonium salt for standby;
C. coupling diazonium salt of formula (Id-1) with aromatic amine of formula (Id-2) to obtain compound of formula (Id), and diazotizing the compound of formula (Id) to obtain diazonium salt for later use;
(2) Coupling reaction: pulping 3, 5-dihydroxybenzoic acid in water, and performing primary coupling on the pulped solution and one of diazonium salt of the formula (Ia), diazonium salt of the formula (Ib) and diazonium salt of the formula (Id) in the step (1), and performing secondary coupling on the pulped solution and one of diazonium salt of the formula (Ia), diazonium salt of the formula (Ib) and diazonium salt of the formula (Id) in the step (1), wherein the diazonium salt adopted in the primary coupling and the secondary coupling cannot be the diazonium salt of the formula (Ia), the diazonium salt of the formula (Ib) or the diazonium salt of the formula (Id) to obtain the dye compound (I); :
the substituents in the above formulae (Ia) to (Id), formulae (Id-1), formula (Id-2) and formula (Id-2) are as defined in formula (I).
(1) Diazotization:
A. pulping the compounds shown in the formula (Ia), the formula (Ib), the formula (ic-1) and/or the formula (id-1) with water and ice respectively for 1-2h as required, adding a certain amount of hydrochloric acid after pulping, then adding sodium nitrite solution in 20-30min, controlling pH=0.5-3.0 (preferably 0.5-2.0) and temperature T=0-30 ℃ (preferably 0-20 ℃) for diazotization reaction, and detecting the end point by using ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change in 5 s); after the diazo end point is reached, excessive sodium nitrite is eliminated by sulfamic acid, and diazo solutions of the formula (Ia), the formula (Ib), the formula (ic-1) or the formula (id-1) are respectively obtained and stored for later use; wherein the molar ratio of the compound of the formula (Ia), the formula (Ib), the formula (ic-1) or the formula (Id-1) to the hydrochloric acid and the sodium nitrite is 1 (1-3): 1-1.1, preferably 1 (1-1.8): 1-1.02;
B. adding a compound of formula (ic-2) into the prepared diazonium solution of formula (ic-1), controlling the pH to be 4.0-6.0 by using liquid alkali and the temperature to be 0-30 ℃ (preferably 0-20 ℃), performing coupling reaction, testing diazonium by using an H acid test solution, and obtaining the compound of formula (ic) after colorless at a permeation ring, namely, the diazonium has completely reacted to the end point, wherein the molar ratio of the compound of formula (ic-2)) to the compound of formula (ic-1) is 1 (0.95-1.2), preferably 1 (0.98-1.08);
adding a certain amount of hydrochloric acid into the compound shown in the formula (ic), then adding sodium nitrite solution within 20-30min, controlling pH to be 0.5-3.0 (preferably 0.5-2.0) and temperature T to be 0-30 ℃ (preferably 0-20 ℃) to carry out diazotization reaction, detecting an end point (namely, no color change within 5 s) by using ethanol solution of 4-dimethylaminobenzaldehyde, eliminating excessive sodium nitrite by using sulfamic acid after the end point of diazotization is reached, and obtaining diazonium solution shown in the formula (ic) for storage for later use;
C. adding a compound of formula (Id-2) into the prepared diazonium solution of formula (Id-1), controlling the pH to be 4.0-6.0 by using liquid alkali and the temperature to be 0-30 ℃ (preferably 0-20 ℃), performing coupling reaction, testing diazonium by using an H acid test solution, and obtaining the compound of formula (Id) after colorless at a permeation ring, namely, the diazonium has completely reacted to the end point, wherein the molar ratio of the compound of formula (Id-2) to the compound of formula (Id-1) is 1 (0.95-1.2), preferably 1 (0.98-1.08);
adding a certain amount of hydrochloric acid into the compound shown in the formula (Id), then adding sodium nitrite solution within 20-30min, controlling pH to be 0.5-3.0 (preferably 0.5-2.0) and temperature T to be 0-30 ℃ (preferably 0-20 ℃) to carry out diazotization reaction, detecting an end point (namely, no color change within 5 s) by using ethanol solution of 4-dimethylaminobenzaldehyde, eliminating excessive sodium nitrite by using sulfamic acid after the end point of diazotization is reached, and obtaining a diazonium solution of the compound shown in the formula (Id) for later use;
(2) Coupling reaction: 3, 5-dihydroxybenzoic acid is added with water, beaten and dispersed, and the temperature is controlled to be 15-25 ℃. Adding the dispersed 3, 5-dihydroxybenzoic acid into the diazonium liquid of the formula (Ia), the diazonium liquid of the formula (Ib), the diazonium liquid of the formula (ic) or the diazonium liquid of the formula (Id) prepared in the step (1), controlling the pH value to be 2.0-5.0 by liquid alkali or sodium bicarbonate, controlling the temperature to be 0-30 ℃ (preferably 0-20 ℃), carrying out coupling reaction, testing diazonium by using an H acid test solution, and obtaining a coupling product 1 after the diazonium is completely reacted at a permeation ring part;
adding the diazonium solution of the formula (Ia), the diazonium solution of the formula (Ib), the diazonium solution of the formula (ic) compound or the diazonium solution of the formula (Id) compound obtained in the step (1) into a coupling product 1, controlling the pH value to be 5.0-8.0 by liquid alkali or sodium bicarbonate, controlling the temperature to be 0-30 ℃ (preferably 0-20 ℃) for coupling reaction, testing the diazonium by using an H acid test solution, and obtaining the reactive dye compound of the formula (I) in the invention after the diazonium has completely reacted to the end point after colorless permeation ring;
the diazonium liquids used in the above two coupling reactions cannot be the diazonium liquid of formula (ia), the diazonium liquid of formula (ib), the diazonium liquid of formula (ic) or the diazonium liquid of formula (id); wherein the molar ratio of formula (Ia), formula (Ib), formula (ic) or formula (Id) to 3, 5-dihydroxybenzoic acid is from (0.95 to 1.2): 1, preferably (0.98-1.08): 1.
it is emphasized that in the reactive navy to black dye compositions according to the invention, the dye compound monomers coupled in the ortho-position to the phenolic hydroxyl groups are frequently present in the stable state of the quinone hydrazone, i.e. the dyes of the general formula (I) substantially contain the quinone hydrazone structures of the following formulae (ie) and/or (if) and/or (ih), the dyes of the general formulae (II), (IV) substantially contain the quinone hydrazone structures of the following formulae (IIa), (IVa), the dyes of the general formula (VI) substantially contain the quinone hydrazone structures of the following formulae (VIa) and/or (VIb) and/or (VIc) and/or (VId), and the writing forms of the azo bodies are still employed in the description and examples, taking into account the writing habits of the person skilled in the art, without affecting the essence of the invention:
the definition of each substituent in the formulas (ie) to (ih) is the same as that in the formula (I), the definition of each substituent in the formulas (IIa) and (IVa) is the same as that in the formulas (II) and (IV), and the definition of each substituent in the formulas (VIa) to (VId) is the same as that in the formula (VI).
In addition, the reactive navy to black dye compositions according to the invention are of the free acid type, whereas in the actual synthesis, they are usually prepared and isolated in the form of their alkali metal salts, such as 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 carboxylic groups, sulfonic acid groups in the formulae (i) to (vii) may be present in the form of sodium carboxylates, sodium sulfonates.
The reactive navy blue to black dye composition of the present invention is prepared by mixing the dye components A, B or A, B, C according to the above-mentioned ratio, and the mixing may be performed by a conventional mechanical means such as a mill, kneader or homogenizer, and during the mixing, the individual dye compounds of the formulas (i) to (vii) may exist in the form of powder, granule, aqueous solution or synthetic solution, and when the individual dye compounds are blended in the form of synthetic solution, the separation of the reactive navy blue to black dye of the present invention from the synthetic solution may be performed by a generally known method such as salting out the dye from the reaction medium with an electrolyte such as sodium chloride or potassium chloride, or evaporating and spray-drying the mixed solution, and thus the dye component A, B, C and the dye composition thereof usually contain a conventional electrolyte salt (such as sodium chloride, sodium sulfate, etc.) in the reactive dye.
In a second aspect, the reactive navy blue to black dye composition of the present invention may be sold as a commercial product without adding any auxiliary agents, or may be added with conventional auxiliary agents in commercial dyes, such as a cosolvent, a dispersant, an alkali-resistant auxiliary agent, a dust-proof agent, a surfactant, a buffer, a dye accelerator, and the like. Thus, the present invention also provides a reactive navy to black dye preparation comprising the reactive navy to black dye composition. Preferably, the active navy blue to black dye product contains the active navy blue to black dye composition and an auxiliary agent. The weight of the auxiliary does not exceed 45%, preferably not more than 40% of the weight of the active navy to black dye composition. The auxiliary agent is preferably one or a combination of any of the following: naphthalene sulfonic acid formaldehyde condensate (NNO), methyl naphthalene sulfonic acid formaldehyde condensate (dispersant MF), diffusant CNF (benzyl naphthalene sulfonate formaldehyde condensate), anhydrous sodium sulfate (industrial sodium sulfate), lignin sulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, and the like. The auxiliary agents are all commercially available conventional varieties.
The reactive 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, and 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 fibers are preferably animal fiber materials including sheath, fur or filament, and synthetic fiber materials such as nylon 6 and nylon 66. When the reactive navy blue to black dye product is used for printing and dyeing the fiber materials, the method can be carried out according to the known reactive dye dyeing method, such as the common reactive dye dip dyeing method and pad dyeing method, wherein the dip dyeing method is a method for dipping the fabric in a dye solution to gradually dye the fabric, and the working procedures of dyeing, fixation, washing, soaping, washing, dehydration, drying and the like are generally required.
The pad dyeing is a dyeing method that firstly, fabrics are immersed in dye liquor, then the fabrics pass through a roller, the dye liquor is uniformly padded into the fabrics, and then the fabrics are subjected to steaming or hot melting treatment and the like, and the dyeing method generally needs the procedures of padding dye liquor-drying- (padding color fixing liquor) -steaming or baking-washing-soaping-washing-drying and the like.
Generally, due to different dyeing requirements on fabrics, the dye usage amount is also different, when the dip dyeing method is used for dyeing, the dyeing depth (owf) is generally 0.1-10 percent (the dye accounts for the weight percentage of the fabric), the bath ratio is 1:2-1:60 (the weight ratio of the fabric to the dye liquor is preferably 1:10-1:30), the primary 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 fixation temperature is 60-100 ℃, the fixation time is 10-50 minutes, and the fixation pH value is 9-11. When the pad dyeing method is used for dyeing, the pad ratio 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 used at present, dye and alkaline substances are introduced into a pad dyeing machine, and are coiled and piled for 2-30 hours at room temperature to fix colors, and then thoroughly rinsed.
The beneficial effects of the invention are mainly as follows: the active navy blue to black dye composition and the product thereof are used for printing and dyeing of fiber materials containing nitrogen and/or hydroxyl, and have the characteristics of good lifting property, excellent color fastness, particularly outstanding washing fastness and the like.
(IV) description of the drawings
FIG. 1 is an ultraviolet-visible 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, m/z= 553.82 is a target molecule double charge ionization peak.
(fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
the dye compound prepared in the examples of the present invention is sodium salt, but for convenience of writing, all structural formulas in the examples are embodied in the form of free acid, and the substantial dyeing properties of the free acid and sodium salt are known to those skilled in the art to be equivalent.
Example 1
(1) Diazotization:
41.1g (0.1 mol) of 2-amino-6-hydroxyethyl sulfone sulfate-1-naphthalene sulfonic acid is put into 100g of water and 100g of ice to be beaten for about 1h, 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 reaction is carried out for 1-2h at the temperature of T=0-20 ℃ by controlling pH value to be 0.5-2.0, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change is caused within 5 s). And after the diazo end point is reached, removing excessive sodium nitrite by sulfamic acid, and preserving the obtained 2-amino-6-hydroxyethyl sulfone sulfate-1-naphthalene sulfonic acid diazonium solution for later use.
36.1g (0.1 mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethylsulfone sulfate aniline) is put into 100g of water and 100g of ice to be pulped for about 1h, 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 reaction is carried out for 1-2h at the temperature of T=0-20 ℃ by controlling pH value to be 0.5-2.0, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change is caused within 5 s). And after the diazo end point is reached, removing excessive sodium nitrite by sulfamic acid, and preserving the obtained sulfonated para-ester diazo liquid for later use.
Adding the 0.1mol of sulfonated para-ester diazonium solution into 15.1g (0.1 mol) of m-urea (m-ureido aniline), controlling the pH to be 4.0-6.0 by 30% of liquid alkali, controlling the temperature T to be 0-20 ℃, carrying out coupling reaction for 0.5-2H, testing diazonium by using H acid test solution, namely, colorless at a permeation ring until the diazonium is reacted completely to an end point (if not, continuing the reaction to the end point), obtaining a chromophore 1, adding 20g of 31% hydrochloric acid (containing HCl 0.17 mol) into the chromophore 1, adding 24g of 30% sodium nitrite solution (containing sodium nitrite 0.104 mol) within 20-30min, carrying out diazotization reaction for 1-2H by controlling the pH to be 0.5-2.0 and controlling the temperature T to be 0-20 ℃, detecting the end point by using ethanol solution of 4-dimethylaminobenzaldehyde (namely, not changing color within 5 s), eliminating excessive sodium nitrite by sulfamic acid after the end point of diazonium is reached, and obtaining the chromophore 1 for storage.
(2) Coupling:
firstly, 154g (0.1 mol) 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 2-amino-6-hydroxyethyl sulfone sulfate-1-naphthalene sulfonic acid diazonium liquid 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 less than 3% to reach the end point by HPLC, thus obtaining the chromophore 2 shown in the following formula (A).
Adding the diazonium solution of the chromophore 1 prepared in the step (1) into the chromophore 2, controlling the pH value to be 5.0-8.0 by 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further carrying out coupling reaction for 5-10H, testing diazonium by using an H acid test solution, and obtaining an orange active dye compound (I-1) after colorless at a permeation ring, namely, complete diazonium reaction, wherein λmax=505 nm in an aqueous solution.
Example 2
(1) Diazotization:
40.0g (0.1 mol) of 4-acetyl (4' -beta-hydroxyethyl sulfonyl sulfate aniline) aniline is added into 100g of water and 100g of ice to be pulped for about 1h, 20g of 31 percent hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30 percent sodium nitrite solution (containing 0.104mol of sodium nitrite) is added in 20 to 30min, diazotization reaction is carried out for 1 to 2 hours at the temperature of T=0 to 20 ℃ by controlling the pH value to be 0.5 to 2.0, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change is caused in 5 seconds). And after the diazo end point is reached, excessive sodium nitrite is eliminated by sulfamic acid, and the obtained 4-acetyl (4' -beta-hydroxyethyl sulfonyl sulfate aniline) base aniline diazonium solution is stored for later use.
36.1g (0.1 mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethylsulfone sulfate aniline) is put into 100g of water and 100g of ice to be pulped for about 1h, 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 reaction is carried out for 1-2h at the temperature of T=0-20 ℃ by controlling pH value to be 0.5-2.0, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no color change is caused within 5 s). And after the diazo end point is reached, removing excessive sodium nitrite by sulfamic acid, and preserving the obtained sulfonated para-ester diazo liquid for later use.
Adding the 0.1mol of sulfonated para-ester diazonium solution into 15.1g (0.1 mol) of m-urea (m-ureido aniline), controlling the pH to be 4.0-6.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, carrying out coupling reaction for 0.5-2H, testing diazonium by using H acid test solution, namely, colorless at a permeation ring until the diazonium reaction is completed to an end point (if not, continuing to react to the end point), obtaining chromophore 3, adding 20g of 31% hydrochloric acid (containing HCl 0.17 mol) into the chromophore 3, adding 24g of 30% sodium nitrite solution (containing sodium nitrite 0.104 mol) within 20-30min, carrying out diazotization reaction for 1-2H by using ethanol solution of 4-dimethylaminobenzaldehyde, detecting the end point (namely, not changing color within 5 s), eliminating excessive sodium nitrite by using sulfamic acid after the end point of diazonium is reached, and storing the chromophore 3 for standby.
(2) Coupling:
firstly, 154g (0.1 mol) 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 4-acetyl (4' -beta-hydroxyethyl sulfonyl sulfate aniline) base aniline diazonium liquid obtained in the step (1), 30% liquid alkali is used for controlling the pH to be 2.0-4.0, the temperature is controlled to be 0-20 ℃, the reaction is carried out for 15-20h, and HPLC is used for controlling the free 3, 5-dihydroxybenzoic acid to reach the end point after the free 3, 5-dihydroxybenzoic acid reaches the end point after the free 3, the chromophore 4 shown in the following formula (B) is obtained.
Adding the diazonium solution of the chromophore 3 prepared in the step (1) into the chromophore 4, controlling the pH value to be 5.0-8.0 by 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further carrying out coupling reaction for 5-10H, testing diazonium by using an H acid test solution, and obtaining a red-light orange active dye compound (I-27) after colorless at a permeation ring, namely complete diazonium reaction, wherein lambda max=495 nm in an aqueous solution.
Examples 3 to 112:
with reference to the azo dye preparation process described in example 1 or example 2, the dye compounds having the structures shown in Table 1 below can be prepared by fractional diazo and coupling reactions, respectively, using intermediate starting materials well known in the art.
TABLE 1
Example 113:
20 parts of dye compound of formula (I-2), 80 parts of dye compound of formula (II-1) and 10 parts of anhydrous sodium sulfate are mechanically mixed, and the obtained composite dye is dyed black by a conventional dip dyeing method, has water washing staining resistance reaching more than 4 levels (refer to ISO 105C 10-2006), and has excellent lifting force (refer to GB/T21875-2016).
Example 114:
20 parts of a dye compound of formula (I-1), 75 parts of a dye compound of formula (II-3), 5 parts of a dye compound of formula (VI-26) and 10 parts of anhydrous sodium sulfate are mechanically mixed, and the obtained composite dye is dyed into black by a conventional dip dyeing method, and has excellent lifting force (refer to GB/T21875-2016) due to washing resistance of more than 4 levels (refer to ISO 105C 10-2006).
Example 115:
22 parts of a dye compound of formula (I-3), 70 parts of a dye compound of formula (II-3), 8 parts of a dye compound of formula (IV-1) and 10 parts of anhydrous sodium sulfate are mechanically mixed, and the obtained composite dye is dyed into deep black by a conventional dip dyeing method, has a washing resistance staining of more than 4 levels (refer to ISO 105C 10-2006), and is excellent in lifting power (refer to GB/T21875-2016).
Example 116:
19 parts of a dye compound of the formula (I-4), 75 parts of a dye compound of the formula (II-3), 3 parts of a dye compound of the formula (IV-1), 3 parts of a dye compound of the formula (VI-26), 10 parts of anhydrous sodium sulfate and 10 parts of a dispersing agent MF are mechanically mixed to obtain a composite dye which is dark black and has excellent lifting power (see GB/T21875-2016) due to the fact that the composite dye is resistant to washing and staining of 4 or more levels (see ISO 105C 10-2006).
Example 117:
17 parts of a dye compound of the formula (I-27), 68 parts of a dye compound of the formula (II-3), 7 parts of a dye compound of the formula (IV-1), 8 parts of a dye compound of the formula (VI-26), 10 parts of anhydrous sodium sulfate and 10 parts of a dispersing agent MF are mechanically mixed to obtain a composite dye which is dark black and has excellent lifting power (see GB/T21875-2016) due to the fact that the composite dye is resistant to washing and staining of 4 or more levels (see ISO 105C 10-2006).
Example 118:
20 parts of a dye compound of the formula (I-28), 70 parts of a dye compound of the formula (II-1), 10 parts of a dye compound of the formula (III-1), 10 parts of anhydrous sodium sulfate and 10 parts of a dispersing agent MF are mechanically mixed to obtain a composite dye which is dark black and resistant to washing and staining to 4 or more levels (refer to ISO 105C 10-2006), and has excellent lifting power (refer to GB/T21875-2016).
Examples 119 to 271
According to the method of one of examples 113 to 118, the dye compounds in the proportions shown in Table 2 were mechanically mixed, and according to the conventional dyeing method with reactive dyes, the dyed cotton was dark blue to black, and the washing resistance and staining were up to 4 or more (see ISO 105C 10-2006), and the lifting power was excellent (see GB/T21875-2016).
TABLE 2
Claims (19)
1. A reactive 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 dye compounds shown in a formula (I) and alkali metal salts thereof, and the component B is selected from one or more of dye compounds shown in a formula (II) and alkali metal salts 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%:
in formula (I):
D 1 is a group of formula (a) or (b), D 2 Is a group of formula (c) or formula (d):
in the above formulas (a) to (d):
R 1 、R 2 、R 3 、R 5 、R 6 、R 8 、R 9 h, C independently of each other 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups;
m=0-3, each R 4 Each independently selected from amino, sulfonic acid, ureido, C 1 ~C 4 Alkyl, C of (2) 1 ~C 4 Alkanoylamino or C 1 ~C 4 An alkoxy group;
n=0-3, each R 7 Each independently selected from hydroxyl, amino, or sulfonic groups;
X 1 、X 2 、X 3 、X 4 h, C independently of each other 1 ~C 4 Alkyl, 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 them contains a fibre-reactive group, 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 10 ~R 13 each independently is hydrogen, C 1 ~C 4 Alkyl, 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 dark blue-to-black dye composition consists of a component A and a component B.
3. The reactive navy to black dye composition of claim 1, wherein: the reactive 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 as formulas (III) - (VII) and alkali metal salts thereof, and 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:
in formula (III):
R 14 ~R 17 each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, carboxyl or sulfonic 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 0 or 1;
D 3 、D 4 are independently substituted phenyl, unsubstituted phenyl, substituted naphthyl or unsubstituted naphthyl, the number of substituents 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, C 1 ~C 4 Alkoxy or hydroxy;
in formula (IV):
R 18 ~R 21 each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups;
e=0 or 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 and h are each independently 0-3, each R 22 、R 23 、R 24 Each independently is C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups;
X 5 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 (e) or (f) or (g):
in the above formulas (e), (f) and (g): r is R 25 、R 26 、R 28 、R 29 、R 31 、R 32 Each independently H, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonic acid groups;
i=0-3, each R 27 Each independently selected from C 1 ~C 4 Alkyl, sulfo, ureido or C 1 ~C 4 Alkanoylamino groups of (2);
j=0-3, each R 30 Each independently selected from hydroxyl or sulfonate;
X 6 、X 7 、X 8 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=1-3, s=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 formula (VII):
k=1-3, each R 33 Each independently selected from amino, sulfonic acid, ureido, C 1 ~C 4 Alkanoylamino, 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;
l=0-2, each R 34 Each independently is C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy or sulfonate.
4. The reactive navy to black dye composition of claim 3, wherein: the reactive navy blue to black dye composition consists of a component A, a component B and a component C.
5. The reactive navy to black dye composition according to any one of claims 1 to 4, wherein:
in the above formulas (a) to (d):
R 1 、R 2 、R 3 、R 5 、R 6 、R 8 、R 9 independently of one another, H, methyl, methoxy or sulphonic acid groups;
m is 1 or 2, each R 4 Each independently is methyl, sulfonate, ureido, or acetamido;
n is 0 or 1, each R 7 Each independently selected from hydroxyl or sulfonate;
X 1 、X 2 、X 3 、X 4 are independently of one another-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;
In formula (II):
R 10 ~R 13 each independently is hydrogen, methyl, methoxy or a sulfonate group.
6. The reactive navy to black dye composition of claim 3 or 4, wherein:
in formula (III):
R 14 ~R 17 each independently is H, methyl, methoxy, carboxyl or sulfonate;
c. d is 1;
D 3 、D 4 each of which is independently a substituted phenyl group, an unsubstituted phenyl group, a substituted naphthyl group or an unsubstituted naphthyl group, wherein the number of substituents of the substituted phenyl group and the substituted naphthyl group is 1 to 2, and each substituent is independently selected from amino group, sulfonic acid group, ureido group, acetamido group, methoxy group or hydroxyl group;
in formula (IV):
R 18 ~R 21 each independently is H, methyl, methoxy or sulfonate;
in formula (V):
f. g and h are each independently 0-3, each R 22 、R 23 、R 24 Each independently is a nailA group, methoxy or sulfonate;
in formula (VI):
D 5 、D 6 each independently is a group represented by the following formula (e) or (f) or (g):
in the above formulas (e), (f) and (g): r is R 25 、R 26 、R 28 、R 29 、R 31 、R 32 Each independently is H, methyl, methoxy or sulfonate;
i=0-3, each R 27 Each independently selected from methyl, sulfonate, ureido, or acetamido;
X 6 、X 7 、X 8 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 formula (VII):
k=1-3, each R 33 Each independently selected from amino, sulfonic or acetamido;
l=0-2, each R 34 Each independently is a methyl, methoxy or sulfonic acid group.
7. The reactive navy to black dye composition of claim 3 or 4, wherein: the mass of the component C accounts for 1-40% of the total mass of the component A and the component B.
9. The reactive navy to black dye composition of claim 3 or 4, wherein: the component C is selected from at least one dye shown in the formula (III) and/or the formula (IV) and/or the formula (VI), wherein a and b are 0, or one of a and b is 0, the other is 1, C is 1, and d is 0 or 1.
13. the reactive navy to black dye composition according to claim 1 or 2, characterized in that:
component A: at least one dye compound selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-16), the formulae (I-27) to (I-48) and alkali metal salts thereof;
component B: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (II-1), (II-3) and alkali metal salts thereof;
based on the sum of the mass percentages of the components A and B, the mass percentage of the component A is 5-50%, and the mass percentage of the component B is 50-95%;
14. the reactive navy to black dye composition of claim 13, wherein:
the component A is at least one selected from the group consisting of dye compounds represented by the formulae (I-1) to (I-8), and the formulae (I-27) to (I-30) and alkali metal salts thereof.
15. The reactive navy to black dye composition of claim 12, wherein:
component A: at least one dye compound selected from the group consisting of the dye compounds represented by the formulae (I-1) to (I-16), the formulae (I-27) to (I-48) and alkali metal salts thereof;
component B: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (II-1), (II-3) and alkali metal salts thereof;
component C: at least one dye compound selected from the group consisting of dye compounds represented by the formulas (III-1), (III-2), (III-4), (IV-1), (IV-3), (VI-26), (VI-27), (VI-41), (VI-42) and alkali metal salts thereof;
based on the sum of the mass of the components A and 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;
16. the reactive navy to black dye composition of claim 15, wherein:
the component A is at least one selected from the group consisting of dye compounds represented by the formulae (I-1) to (I-8), and the formulae (I-27) to (I-30) and alkali metal salts thereof.
17. The reactive navy to black dye composition according to claim 1 or 2, characterized in that: the dye compounds of the formula (I) contain a quinone hydrazone structure of the following formulae (ie) and/or (if) and/or (ig) and/or (ih), the dye compounds of the formula (II) contain a quinone hydrazone structure of the following formula (IIa), respectively,
the substituents in the formulae (ie) to (ih) are as defined in the formula (I), and the substituents in the formula (IIa) are as defined in the formula (II).
18. The reactive navy to black dye composition of claim 3 or 4, wherein: the dye compound represented by the formula (IV) contains a quinone hydrazone structure represented by the following formula (IVa), the dye compound represented by the formula (VI) contains a quinone hydrazone structure represented by the following formula (VIa) and/or formula (VIb) and/or formula (VIc) and/or formula (VId),
the definition of the substituent in the formula (IVa) is the same as that of the formula (IV), and the definition of the substituent in the formulas (VIa) to (VId) is the same as that of the formula (VI).
19. A reactive navy to black dye preparation comprising the reactive navy to black dye composition of claim 1.
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