KR101864363B1 - Reactive dye composition - Google Patents

Abstract

The present invention relates to a composition comprising 30 to 85 wt% of a compound represented by the formula (A), 10 to 10 wt% of a compound represented by the following formula (B) based on the total sum of the compound represented by the formula (A) To 60 wt% of a compound represented by the following formula (C) and 2 to 45 wt% of a compound represented by the following formula (C), wherein the above formulas (A) to (C) are each the same as defined in the detailed description of the invention.

Description

REACTIVE DYE COMPOSITION [0001]

The present invention relates to a reactive dye composition, and more particularly, to a reactive dye composition having excellent color yield and washability and excellent fastness properties.

Reactive dyes are dyes mainly used in cotton, hemp, rayon, rayon, dogs and hanji, and are dyed by covalent bonding with fibers in a salt bath in the presence of alkali. They are well soluble in water and have better fastness than direct dyes Have. In addition, it is a dyestuff which is used for dyeing crafts recently because it has a clear color, excellent permeability and uniformity, and a wide range of dyeable fibers.

Recently, in the practice of dyeing, there are increasing requirements regarding the quality of dyeing and the economics of the dyeing process. In particular, there is a continuing need for new and easily obtainable dye compositions having improved properties with respect to applicability.

Today, dyeing requires reactive dyes that have sufficient substantivity and are easy to clean unfixed dyes. In addition, these reactive dyes should exhibit excellent color yield and high reactivity, in particular, to obtain a dye with high fixability. In many cases, the build-up behavior of reactive dyes is not sufficient to dye these requirements, especially for deep shades, so dyeers need to mix and use suitable reactive dyes.

Korean Patent Registration No. 10-0522164 (Oct. 18, 2005) discloses a reactive black composition obtained by mixing a reactive black dye having a vinyl sulfone ester group with a dye compound for controlling the chromaticity in an appropriate ratio as a conventional technique in a reactive dye composition. Which has a merit that the manufacturing method thereof is comparatively simple and can be made at a low cost, but has a disadvantage that the color density is weak and the darkness after the dyeing is dense at a high concentration.

Korean Patent Laid-Open Publication No. 10-0499448 (Jul. 7, 2005) discloses a dye composition comprising a compound used in a conventional black dye composition, a compound containing a monochlorotriazine or a vinyl sulfone group, and a compound containing a diazo group The above combination of dyes is most widely used because it has a high color density and a low concentration at a high concentration. However, after the dyeing is finished, rinsing and soaping (using a surfactant to remove unfixed dyes near 100 deg. The removal of unfixed dyes in the process of removal of the time and water is a drawback.

In recent years, water shortage caused by global warming has become an international hot topic for water reduction in the dyeing process. Synthetic fibers have been applied to dyeing methods that do not use water, such as development of supercritical carbon dioxide dyeing process. However, There is a limit in which such a process can not be applied.

Accordingly, there is a continuing need for the development of a dye composition which is strong in color density and has a high dyeing rate and short wash cycle after dyeing.

Korean Patent Registration No. 10-0522164 (Oct. 18, 2005) Korean Patent Publication No. 10-0499448 (Jul. 2005)

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a reactive dye composition excellent in color yield and washability and excellent in fastness and dyeing method using the same.

The present invention provides a dye composition comprising a compound represented by the formula (A), a compound represented by the formula (B) and a compound represented by the formula (C), wherein the compound represented by the formula (A) 30 to 85 wt% of the compound represented by the formula (A), 10 to 60 wt% of the compound represented by the formula (B) and 2 to 45 wt% of the compound represented by the formula (C) based on the total sum of the compounds represented by the following formula To provide a dye composition.

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

In Formulas A to C,

R 1 to R 6 are each The same or different and is a substituent of one another are independently selected from hydrogen, alkoxy group and a -SO ₃ M for the alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, wherein M1 to M4, M is the same or different, respectively, and And Z 1 to Z 6 are each independently selected from the group consisting of hydrogen, an ammonium group, lithium, sodium and potassium, and each of Z 1 to Z 6 is independently any one of substituents selected from the following structural formulas 1 to 3,

[Structural formula 1] [Structural formula 2]

[Structural Formula 3]

X1 to X3 are leaving groups which can be removed under alkaline conditions,

At least one of Z1 and Z2 is a substituent bonded to a meta position of an azo group (-N = N-), at least one of Z3 and Z4 is a substituent bonded to a meta position of an azo group (-N = N-) At least one of Z5 and Z6 is a substituent bonded to the meta position of an azo group (-N = N-), each of k to p is an integer of 0 to 4, and each of k to p is 2 or more, R1 to R6 are the same as or different from each other.

In one embodiment, the dye composition can be used to dye or print fiber materials containing hydroxyl groups or containing nitrogen groups.

The improved reactive dye compositions according to the present invention have excellent color fastness and wash fastness and excellent fastness properties.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of comparison of dyeing rates of the dye compositions of the present invention and the dye compositions of Comparative Examples. FIG.
2 is a graph showing the results of comparing the fastness of the dye composition of the present invention and the dye composition of the comparative example.
FIG. 3 is a graph showing the results of comparison of washability of the dye composition of the present invention and the dye composition of the comparative example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Unless otherwise defined in this invention, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

The dye composition according to the present invention comprises a compound represented by the following general formulas (A), (B) and (C) and, based on the total sum thereof, 30 to 85% by weight of a compound represented by the general formula (A) 10 to 60 wt% of a compound and 2 to 45 wt% of a compound represented by the following formula (C).

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

In Formulas A to C,

R 1 to R 6 are each The same or different and is a substituent of one another are independently selected from hydrogen, alkoxy group and a -SO ₃ M for the alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, wherein M1 to M4, M is the same or different, respectively, and , Z 1 to Z 6 are each independently selected from the group consisting of hydrogen, lithium, sodium and potassium, and each of Z 1 to Z 6 is independently any one selected from the following structural formulas 1 to 3,

[Structural formula 1] [Structural formula 2]

[Structural Formula 3]

X1 to X3 are leaving groups which can be removed under alkaline conditions,

At least one of Z1 and Z2 is a substituent bonded to a meta position of an azo group (-N = N-), at least one of Z3 and Z4 is a substituent bonded to a meta position of an azo group (-N = N-) At least one of Z5 and Z6 is a substituent bonded to the meta position of an azo group (-N = N-), each of k to p is an integer of 0 to 4, and each of k to p is 2 or more, R1 to R6 are the same as or different from each other.

As can be seen from the reference to the compound represented by the chemical formula A in the following FIG. 1, in the compounds constituting the dye composition, the substituent groups Z1 to Z6 contained in the perylene group bonded to the azo group (Where the substituent corresponds to ortho, meta or para on the azo group), in formula A, at least one of Z1 and Z2 is bonded to the meta position of the azo group (-N = N-) And at least one of Z3 and Z4 is a substituent bonded to the meta position of an azo group (-N = N-), and in formula (C), at least one of Z5 and Z6 is an azo group (-N = N-) Is a substituent bonded to the meta position of the < RTI ID = 0.0 >

<Figure 1>

That is, at least one of the substituents Z1 and Z2 in the formula (A) is a compound bonded to the meta position of the azo group, and the compounds having the same structure are also used in the formulas (B) and (C).

In general, when a linker such as Z1 or Z2 is present at the para position of the azo group, the linearity increases and the affinity between the dye and the fiber increases. However, when two or more para-azo compounds are bonded to a coupler, the affinity may be excessively increased, which may make it difficult to remove the unstable or unfixed dyes.

On the other hand, in general, when the linker is present at the meta position of the azo group, the linearity is weaker than that of the para position, so that when the azo compounds of plural meta positions are bonded at the same time, the affinity is less increased than that of the para- It stands out. When the azo compound at the para position and the azo compound at the meta position coexist, the dyeing yield and washability increase as well.

In one embodiment, the Z1 to Z6 substituents in the formulas (A) to (C) are each bonded to the meta position of the azo group, whereby all of them can be bonded to the meta position of the azo group.

In yet another embodiment, the subscripts k to p each representing the number of the substituents R 1 to R 6 bonded to the phenylene ring may be the same or different, and may be an integer of 0 to 2.

Here, in the Z1 to Z6 substituents in the above-mentioned formulas (A) to (C), when they are not meta positions, these substituents are each bonded to the para position of the azo group. In this case, the substituent The ring may contain at least one substituent of one of R &lt; 1 &gt; to R &lt; 6 &gt; other than hydrogen at the ortho or meta position of the azo group.

That is, referring to FIG. 2, the substituent R 1 bonded to the ortho and meta positions when the substituent Z 1 in the round root is bonded to the para position of the azo group is an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms An alkoxy group of -O-M &lt; ₃ &gt; and -SO &lt; ₃ &gt; M.

 <Figure 2>

When the phenylene group containing a substituent bonded to the para position contains at least one substituent of one of R 1 to R 6, which is not hydrogen, at the ortho or meta position of the azo group, the dye composition according to the present invention may contain azo group para The linearity generated by the presence of the coupler at the position can be partially canceled by the distortion effect due to the substituent, and thus the water repellency can be increased. Generally, the resonance effect is given to the phenylene structure or the electron density is increased to increase the energy level between HOMO and LUMO It is possible to give a cardiovascular property.

The compound represented by the formula (A), the compound represented by the formula (B) and the compound represented by the formula (C) can be used as a component of the black dye composition, wherein the content ratio thereof is 30 to 85 wt 10 to 60 wt% of the compound represented by the formula (B) and 2 to 45 wt% of the compound represented by the formula (C), more preferably the dye composition is used in an amount of 45 to 75 wt% 10 to 25 wt% and C to 5 to 40 wt%.

Specific examples of the alkyl group in the R 1 to R 6 substituents used in the present invention include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. Specific examples of the alkoxy group include Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and the like.

In one embodiment, the present invention of the R1 to R6 are the same or different and each independently represent a methyl group each, an ethyl group, a propyl group, a methoxy group, and the substituent of any one selected from an ethoxy group, a propoxy group and a -SO ₃ H Lt; / RTI &gt;

On the other hand, when the substituent Z1 to Z6 are bonded to the para position of the azo group of the R1 to R6 can be a preferable example substituents each a methyl group, an ethyl group, a methoxy group, an ethoxy group and selected from -SO ₃ H.

The substituents represented by Structural Formulas 1 to 3 in Z1 to Z6 above may be a leaving group in which the terminal portion can be removed under alkaline conditions.

Herein, the leaving group which can be removed in the above alkaline condition means a substituent which can be removed under an aqueous solution condition of pH 7 or more, or under basic conditions under an organic solvent. For example, X1 to X3 in the above Structural Formulas 1 to 3 are chloro (-Cl), bromo (-Br), sulfato (-OSO3H), iodo (-I), acetato ) And phosphato (-OPO3H2), fluoro (-F), -SSO3H, -OCO-C6H5, -OSO2- (C1-C4alkyl) and -OSO2-N (C1- (-Cl), bromo (-Br), sulfato (-OSO3H), iodo (-I), acetato (-OCO-CH3) and phosphato OPO3H2) can be used.

As preferred examples of the substituents Z1 to Z6 in the above formulas A to C in the present invention, the substituent represented by the formula 1 may be used.

In this case, the dye compositions according to the present invention are advantageous in environmental friendliness because the intermediate compounds used for preparing the compounds represented by the formulas (A) to (C) do not use p-chloroaniline as a raw material, respectively.

 In the present invention, substituents -SO3M1, -SO3M2, -SO3M3, -SO3M, -SO3M 'and the like in the compounds represented by the formulas A to C are sulfonic acids or salts thereof (for example, sodium, lithium, Ammonium salt).

The compounds represented by the formulas (A) to (C) constituting the dye composition according to the present invention can be produced by forming azo groups on both sides of the diazotization reaction with amine groups on both sides of the center naphthalene ring.

Table 1 below shows amine compounds for the diazo reaction and coupler compounds having a naphthalene ring at the center in the above-mentioned formulas A to C which are the dye compositions of the present invention. The compounds for diazo reaction 1 and diazo 2) may be mutually interchangeable. Further, the compounds A to C according to the present invention are not limited to the compounds listed in the following Table 1, and may have various substituent modifications.

Hereinafter, as a representative structural formula of the dye composition of the present invention, any one compound selected from the group consisting of the following Chemical Formulas 1 to 27 is shown. The compounds according to the present invention are not limited thereto.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

The present invention can also be used for dyeing or printing fiber materials containing or containing hydroxyl groups in the dye composition.

Examples of the fiber material containing the hydroxyl group or containing the nitrogen group include, but not limited to, paper, linen, hemp, silk, leather, mother fiber, polyamide fiber and polyurethane.

The dye compositions according to the present invention can be applied to fiber materials and can be fixed to fibers in various ways in the form of aqueous dye solutions and dye printing pastes.

Thus, the dye compositions according to the invention are suitable for both dyeing by the adsorption process and pad-dyeing process.

The dye compositions according to the invention are also suitable as colorants for use in recording systems. Examples of such a recording system include inkjet printers or recording devices, fountain pens, ballpoint pens, etc., which are commercially available for printing paper or cloth.

As described above, in order to use the dye composition according to the present invention in a recording system, the dye composition should be in a form suitable for use in a recording system, and a suitable example thereof is an aqueous ink containing the dye composition as a coloring agent . The aqueous ink may be prepared in a conventional manner by mixing together with the respective components as desired.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples relating to the preparation of a compound for a dyeing composition of the present invention and the evaluation of a dye composition. However, the scope of protection of the present invention is not limited to the following examples.

Synthesis Example of Compound for Dye Composition

Synthesis Example 1. Synthesis of the formula 4

31.1 g of 5- (2-sulfatoethylsulfone) -2-methoxyaniline was slowly added to a solution of sodium nitrite (7 g) in water while maintaining the temperature at 10 ° C or less under acid catalyst, -3-hydroxynaphthalene-3,6-disulfonic acid are acid-coupled at pH 3.5.

After completion of the reaction, 36.1 g of 2-amino-4- (2-sulfatoethylsulfonyl) benzenesulfone was slowly added to a solution of sodium nitrite (7 g) in water while maintaining the temperature at 10 ° C or lower, Coupling at pH 7 in combination. After the reaction is completed, spray drying is performed to obtain about 110 g of Formula (4).

Synthesis Example 2. Synthesis of Compound (13)

31.1 g of 5- (2-sulfatoethylsulfone) -2-methoxyaniline was diazotized using the same conditions as in Synthesis Example 1, and 23 g of 1-hydroxy-6-aminonaphthalene- Is acid-coupled at pH 3.5. When the reaction is complete, 36.1 g of 2-amino-4- (2-sulfatoethylsulfonyl) benzenesulfone is diazotized and coupled at pH 7.

After the reaction is completed, spray drying is carried out to obtain about 105 g of formula (13).

Synthesis Example 3. Synthesis of Compound (22)

31.1 g of 5- (2-sulfatoethylsulfone) -2-methoxyaniline was diazotized by a conventional method using the same conditions as in Synthesis Example 1, and 1,3-phenylenediamine-4- 18 g of sulfone is subjected to primary coupling at pH 5.5. When the reaction is completed, 36.1 g of 2-amino-4- (2-sulfatoethylsulfonyl) benzenesulfonic acid is diazotized and subjected to secondary coupling at pH 7.

After the reaction is complete, spray drying yields about 100 g of Formula 22.

Synthesis Examples 4 to 7

(1), (3), (10) and (19) were prepared in the same manner as in Synthesis Example 1.

Evaluation Example of Dye Composition

Example 1

60% by weight of the compound represented by the formula (4), 15% by weight of the compound of the formula (13) as the compound corresponding to the formula (B), and 25% by weight of the compound % By weight.

Examples 2 to 6

A dye composition was prepared by the method described in Example 1 below, and the respective components are shown in Table 2 below.

Comparative Example 1

As Comparative Example 1, a black dye composition was prepared using the compounds of the formulas (28) to (30) wherein the substituents Z1 to Z6 in the structural formulas (A) to (C) each have a substituent at the para position.

28

Formula 29

Formula 30

Comparative Example 2

As Comparative Example 2, a black dye composition was prepared using the compounds of Formulas (31) to (33).

31

(32)

Formula 33

Example 1 compound Formula 4 Formula 13 Formula 22 Weight (wt%) 60 15 25 Example 2 compound (3) 10 Formula 19 Weight (wt%) 55 15 30 Example 3 compound Formula 1 10 Formula 22 Weight (wt%) 60 15 25 Example 4 compound Formula 4 10 25 Weight (wt%) 60 10 30 Example 5 compound Formula 7 Formula 16 25 Weight (wt%) 65 10 25 Example 6 compound 6 Formula 15 24 Weight (wt%) 55 15 30 Comparative Example 1 compound 28 Formula 29 Formula 30 Weight (wt%) 60 15 25 Comparative Example 2 compound 31 (32) Formula 33 Weight (wt%) 55 15 30

Salinity rate  evaluation

1 g of the dye compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were dissolved in 100 g of water, 10 g of anhydrous gum was added, and 10 g of cotton fibers were added. Make 11 samples under the same conditions.

After heating at 60 캜 for about 20 minutes, 4 g of sodium carbonate is added to this bath and dyeing is carried out at about 60 캜 for 1 hour. The samples belonging to the composition of the example and the composition of the comparative example were taken out at 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes and 80 minutes, Add 0.5 g of nonionic surfactant to 100 g of water, shake at 95-100 ° C for 5 minutes to remove unfixed dyestuff, wash it thoroughly with cold water, dry it, and colorize it to calculate the salt content.

In this case, at the time of 80 minutes, the reflectance of the darkest dye in each sample was set at a maximum value of 100, and the remainder was converted into a relative value, which is graphically shown in FIG.

Salinity rate 5 minutes 10 minutes 15 minutes 20 minutes 25 minutes 30 minutes 40 minutes 50 minutes 60 minutes 80 minutes Example 1 15 39 57 69 83 90 94 96 97 97 Example 2 16 38 56 69 82 91 95 98 99 99 Example 3 15 39 58 71 84 92 95 97 99 100 Example 4 17 39 59 70 80 90 94 96 97 97 Example 5 15 37 58 68 81 91 94 96 97 98 Example 6 14 38 55 70 80 90 93 96 97 97 Comparative Example 1 15 37 49 60 69 77 82 84 85 85 Comparative Example 2 16 36 53 66 76 84 89 90 91 92

The results of Table 3 and FIG. 1 show that the dyeing compositions of the dyeing compositions of the examples according to the present invention are high.

Fastness evaluation

The fastness is compared with a dyeing cloth having the same K / S value, and it is shown in Table 4 and FIG. 2 below.

Example Comparative Example One 2 3 4 5 6 One 2 Wet friction fastness
(ISO 105-X12-N) 4 3-4 3-4 4 4 3-4 3 3 Light fastness
(ISO 105-B02) 4 4 4-5 4-5 4 4 4 4 Chlorine water fastness
(ISO 105-E03) 4 4 4 4 4 4 4 3 Wash fastness
(ISO 105-C06- C2S ) 5 5 5 5 5 5 3 4

According to Table 4 and FIG. 2, it can be seen that the fastness of the dyeing cloth stained with the dyeing composition of the example according to the present invention is excellent.

Water Resistance Evaluation

The fabric fibers were dyed using Examples 1 to 6 and Comparative Examples 1 and 2, and the color change with washing was measured.

After dyeing the dyes of Examples 1 to 6 and Comparative Examples 1 and 2 in the same ratio as the dyeing rate evaluation test, remove the dyed cloth from the pot and shake it in 100 g of water at 25 DEG C for 10 minutes. Remove the dyeing cloth again and shake for 10 minutes in water containing 0.2 g of glacial acetic acid in 100 g of water at 25 ° C. The dyed cloth is shaken for 10 minutes at 80 ° C, shaken for 10 minutes, removed, shaken for 10 minutes in water containing 100 g of water at 95 ° C and 0.2 g of soaping agent, and the concentration of the residue is measured by UV-Vis spectrophotometer (primary / Soaping). The dyeing cloth is shaken for 10 minutes in 100 g of water at 80 ℃, taken out, and the concentration of the residue is measured (2nd / hot water tax). Finally, the dyeing cloth is shaken for 10 minutes by adding 100 g of water at 25 ° C, and the concentration of the remaining solution is measured (third / cold water).

The above results are shown in Table 5 and Fig.

Soaping Hot water tax Cold water tax 400 500 600 400 500 600 400 500 600 Example 1 1.4 1.3 1.5 0.3 0.4 0.5 0.1 0.1 0.1 Example 2 1.3 1.3 1.6 0.4 0.5 0.4 0.1 0.2 0.1 Example 3 1.3 1.2 1.5 0.4 0.4 0.5 0.1 0.1 0.1 Example 4 1.4 1.3 1.6 0.3 0.5 0.4 0.1 0.2 0.1 Example 5 1.3 1.4 1.7 0.3 0.4 0.5 0.1 0.1 0.1 Example 6 1.4 1.2 1.5 0.4 0.4 0.5 0.2 0.1 0.1 Comparative Example 1 2.5 2.2 2.0 0.7 0.8 0.6 0.2 0.3 0.2 Comparative Example 2 1.9 2.0 2.2 0.6 0.6 0.7 0.2 0.2 0.2

[Table 5] shows the absorbance values at the wavelengths of 400 nm, 500 nm and 600 nm of the concentrations of the soaping, hot water and cold water in each of the examples and the comparative examples. The higher the value, the darker the concentration and the poorer the water repellency And the results of Table 3 show that the dyeing compositions of the examples according to the present invention are highly washable.

Claims (9)

A dye composition comprising a compound represented by the formula (A), a compound represented by the formula (B) and a compound represented by the formula (C), wherein the compound represented by the formula A, the compound represented by the formula B and the compound represented by the formula C 30 to 85 wt% of a compound represented by the formula (A), 10 to 60 wt% of a compound represented by the following formula (B), and 2 to 45 wt% of a compound represented by the following formula (C), based on the total sum.
(A)

[Chemical Formula B]

&Lt; RTI ID = 0.0 &

In Formulas A to C,
R 1 to R 6 are each Each independently any one substituent selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and -SO ₃ M,
M 1 to M 4 and M are the same or different and independently selected from hydrogen, an ammonium group, lithium, sodium and potassium,
Each of Z1 to Z6 is the same or different and independently selected from the following Substituents 1 to 3,
[Structural formula 1] [Structural formula 2]

[Structural Formula 3]

X1 to X3 are leaving groups which can be removed under alkaline conditions,
At least one of Z1 and Z2 is a substituent bonded to the meta position of an azo group (-N = N-)
At least one of Z3 and Z4 is a substituent bonded to the meta position of an azo group (-N = N-)
At least one of Z5 and Z6 is a substituent bonded to the meta position of an azo group (-N = N-)
Wherein k to p are the same or different and are an integer of 0 to 2,
When each of k to p is 2, each of R 1 to R 6 is the same or different from each other,
The substituents not bonded to the meta positions of the azo group in Z1 to Z6 are bonded to the para position of the azo group,
In this case, the phenylene group containing a substituent bonded to the para position includes at least one substituent of one of R1 to R6, which is not hydrogen, at the ortho or meta position of the azo group. delete The method according to claim 1,
Wherein X1 to X3 each are any one selected from chloro, bromo, sulfato, iodo, acetato, and phosphato. The method according to claim 1,
Wherein the Z1 to Z6 substituents are each bonded to the meta position of the azo group. The method according to claim 1,
Wherein R 1 to R 6 are the same or different and are each independently any one substituent selected from the group consisting of methyl, ethyl, propyl, methoxy, ethoxy, propoxy and -SO ₃ H. The method according to claim 1,
The substituents Z1-Z6 are to R1 when bonded to the para position of the azo group and R6 is each a methyl group, an ethyl group, a methoxy group, a dye composition, wherein the substituent is selected from an ethoxy group and a -SO ₃ H. The method according to claim 1,
Wherein the dye composition comprises from 45 to 75 wt% of the formula A, from 10 to 25 wt% of the formula B and from 5 to 40 wt% of the formula C. The method according to claim 1,
Wherein each of the substituents Z1 to Z6 is a substituent represented by the structural formula (1). 9. The method according to any one of claims 1 to 8,
Wherein the dye composition is used for dyeing or printing a fiber material containing or containing a hydroxyl group.

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