KR102051953B1 - Reactive Black Dye Composition and Methods for Dyeing Fiber Using the Same - Google Patents

Abstract

The present invention relates to a reactive black dye composition and a method of dyeing fibers using the same, and more particularly, to dyeing, printing, etc. of cellulose fibers and rayon fibers, having a strong color density, high dyeing rate, and excellent washing and fastness. In addition, the present invention relates to a reactive black dye composition capable of satisfying other physical properties and to provide high-quality dyeing, and a method of dyeing fibers using the same.

Description

Reactive Black Dye Composition and Methods for Dyeing Fibers Using the Same

The present invention relates to a reactive black dye composition and a method for dyeing fibers using the same, and more particularly, to a reactive black dye composition having excellent color yield and water washability and excellent fastnesses.

Reactive dyes are mainly used for cotton, hemp, ramie, rayon, silk, and Korean paper, and are dyes formed by covalent bonding with fibers in a salt bath in the presence of alkali. They are well soluble in water and have superior fastness to direct dyes. Have. In addition, because of the vivid color, excellent permeability and uniformity, and a wide range of dyeable fibers, this dye is widely used in craft dyeing.

In recent years, the practice of dyeing has increased the requirements regarding the quality of the dyeing and the economics of the dyeing process. In particular, there is a continuing need for new and readily obtainable dye compositions with improved properties in terms of applicability.

Today's dyes require reactive dyes that have a sufficient degree of substantibity and at the same time have good ease of washing of unfixed dyes. In addition, these reactive dyes should exhibit good color yield and high reactivity, and are particularly aimed at obtaining dyeings with high adhesion. In many cases, the build-up behavior of reactive dyes is not sufficient for dyeing these requirements, especially for deep tones, so dyeers need to use a suitable reactive dye in combination.

As a related art in a reactive dye composition, Korean Patent No. 10-0522164 discloses a reactive black composition in which a dye compound for adjusting color is mixed with a reactive black dye having a vinyl sulfone ester group at an appropriate ratio, which is a method of preparing the same. This has the advantage of being relatively simple and can be made at a low cost, but has the disadvantage that the color density is weak and the after bath is dark at high concentration.

In addition, Korean Patent Publication No. 10-0499448 discloses a dye composition composed of a compound used for a conventional black dye composition, a compound containing a monochloro triazine or vinyl sulfone group, and a compound containing a diazo group. The same combination of dyes is most commonly used because of their high color density and low residual bath at high concentrations, but they are unused during the rinsing and soaping (removing unfixed dyes near 100 ° C using a surfactant) after dyeing. There was a disadvantage in that time and water were required for removing the fixed dye.

Recently, due to the lack of water due to global warming, it has become an international topic in saving water during the dyeing process. In the case of synthetic fibers, a dye-free dyeing method such as the development of a supercritical carbon dioxide dyeing process is being applied. In this case, there is a limit to the fundamental application of this process.

Therefore, there is a continuous need for the development of a dye composition having a strong color density and high dyeing rate and a short washing process after dyeing.

Korean Patent Registration No. 10-0522164 (Published: Dec. 23, 2004) Korean Patent Registration No. 10-0499448 (published: 2002.03.22)

The main object of the present invention is to solve the above-mentioned problems, to provide a reactive black dye composition excellent in color yield and water washability, and excellent fastness and fiber dyeing method using the same.

In order to achieve the above object, one embodiment of the present invention is a compound represented by the formula (A); A compound represented by formula B; And it provides a reactive black dye composition comprising a compound represented by the formula (C).

[Formula A]

[Formula B]

[Formula C]

In Formulas (A) to (C), R ₁ to R ₇ are the same or different, and are each independently 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; Any one substituent, M ₁ to M ₃ , M are the same or different, and each independently selected from the group consisting of hydrogen, ammonium, lithium, sodium and potassium, Z ₁ to Z ₇ are each the same Or different from each other, and independently of each other, any one substituent selected from the group consisting of the following structural formulas 1 to 3 and hydrogen, wherein at least one of Z ₃ to Z ₅ is a substituent of any one selected from formulas 1 to 3, A substituent bonded to a meta position of an azo group (-N = N-), k and l are each 0 or 1, m to q are each an integer of 0 to 4, and m to q are each 2 or more Yiwu each of R ₃ to R ₇ are the same or different and each other, to the following structural formula in 1 to 3 X ₁ to X ₃ is a leaving group which can be removed at alkaline conditions.

[Formula 1]

[Formula 2]

[Formula 3]

In a preferred embodiment of the present invention, at least one of k and l of Formula A is 1, wherein R ₁ to R ₂ are the same or different, and each independently an alkyl group having 1 to 4 carbon atoms, 1 carbon number It may be characterized in that it is any one substituent selected from the group consisting of an alkoxy group of 4 to -SO ₃ M.

In a preferred embodiment of the present invention, in Formula B, Z ₃ to Z ₅ are the same or different and independently from each other, any one substituent selected from the group consisting of Structural Formulas 1 to 3, at least one or more of these May be a substituent bonded to a meta position of an azo group (-N = N-).

In one preferred embodiment of the present invention, in Formula B, Z ₃ to Z ₅ are the same or different and independently from each other, any one substituent selected from the group consisting of Structural Formulas 1 to 3, one is an azo group (-N It may be characterized in that it is a substituent bonded to the meta (meta) position of = N-).

In a preferred embodiment of the present invention, in Formula A k + l is 1, wherein R _{One To} R _{2 Are} the same or different, each independently represent an alkyl group of 1 to 4 carbon atoms, of 1 to 4 carbon atoms It may be characterized by one of the substituents selected from the group consisting of an alkoxy group and -SO ₃ M.

In a preferred embodiment of the present invention, the substituents in the general formula B in Z ₃ to Z ₅ do not bind to the meta position of the azo group may be characterized in that each bind to the para (para) position of the azo group.

In a preferred embodiment of the present invention, at least one substituent of Z ₁ , Z ₂ , Z ₆ and Z ₇ may be characterized in that it binds to the para position of the azo group.

In a preferred embodiment of the present invention, the Z ₁ , Z ₂ , Z ₆ and Z ₇ substituents may be characterized in that each bonded to the para (para) position of the azo group.

In a preferred embodiment of the invention, in the structural formulas 1 to 3 X ₁ to X ₃ are the same or different and each independently represents a chloro (-Cl), bromo (-Br), sulfatoethylsulfonyl (-OSO ₃ together H), iodo (-I), acetateoto (-CH ₃ COO) and phosphate (-OP0 ₃ H ₂ ) It can be characterized in that any one selected from the group consisting of.

In a preferred embodiment of the present invention, each of R ₁ to R ₇ are the same or different, and are each independently composed of hydrogen, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group and -SO ₃ H It may be characterized in that it is any one selected from the group.

In one preferred embodiment of the present invention, in Formula A R ₁ and R ₂ are the same as or different from each other, it may be characterized in that each independently hydrogen or -SO ₃ H.

In a preferred embodiment of the present invention, Z ₁ to Z ₇ are the same or different, each independently may be characterized in that the substituent represented by the formula (1).

In a preferred embodiment of the present invention, the reactive black dye composition is 30 wt% to 80 wt% of the compound represented by Formula A, 10 wt% to 45 wt% of the compound represented by Formula B and compound 5 represented by Formula C It may be characterized by including wt% to 20wt%.

Another embodiment of the present invention provides a method of dyeing or printing a fiber material containing a hydroxyl group or a nitrogen group using the reactive black dye composition.

The reactive black dye composition according to the present invention has a high color density at the time of dyeing and printing of cellulose fibers, rayon fibers, etc., high dyeing rate, excellent washing and fastness, and can also satisfy other physical properties. It is effective to provide a dyeing of.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

Throughout this specification, "fiber" is used in the concept including fabric.

The present invention is a compound represented by the formula (A); A compound represented by formula B; And it relates to a reactive black dye composition comprising a compound represented by the formula (C).

[Formula A]

[Formula B]

[Formula C]

In Formulas (A) to (C), R ₁ to R ₇ are the same or different, and are each independently 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; Any one substituent, M ₁ to M ₃ , M are the same or different, and each independently selected from the group consisting of hydrogen, ammonium, lithium, sodium and potassium, Z ₁ to Z ₇ are each the same Or different from each other, and independently of each other, any one substituent selected from the group consisting of the following structural formulas 1 to 3 and hydrogen, wherein at least one of Z ₃ to Z ₅ is a substituent of any one selected from formulas 1 to 3, A substituent bonded to a meta position of an azo group (-N = N-), k and l are each 0 or 1, m to q are each an integer of 0 to 4, and m to q are each 2 or more Yiwu each of R ₃ to R ₇ are the same or different and each other, to the following structural formula in 1 to 3 X ₁ to X ₃ is a leaving group which can be removed at alkaline conditions.

[Formula 1]

[Formula 2]

[Formula 3]

In this case, specific examples of the alkyl group having 1 to 4 carbon atoms among the substituents of R ₁ to R ₇ in Formulas A to C may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. Specific examples of the alkoxy group of Groups 4 to 4 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and the like.

In addition, the R ₁ to R ₇ substituents are the same or different, and each independently, selected from the group consisting of hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy and -SO ₃ H It may be one, more preferably any one selected from the group consisting of methyl group, ethyl group, methoxy group, ethoxy group and -SO ₃ H, even more preferably may be -SO ₃ H.

On the other hand, the substituent represented by the structural formulas 1 to 3 may use a leaving group in which the terminal portion can be removed in alkaline conditions. Here, the leaving group which can be removed in the alkaline conditions means a substituent that can be removed in an aqueous solution condition of pH 7 or higher, or under basic conditions in an organic solvent. For example, in Formulas 1 to 3, X ₁ to X ₃ may represent chloro (-Cl), bromo (-Br), sulfato (-OSO ₃ H), iodo (-I), and acetate. -OCO-CH ₃ ) and phosphate (-OPO ₃ H ₂ ), fluoro (-F), -SSO ₃ H, -OCO-C ₆ H ₅ , -OSO ₂ -R (R: C1-C4 alkyl ) And -OSO ₂ -NR ₂ (R ₂ : C1 ~ C4 alkyl) and the like may be used, preferably chloro (-Cl), bromo (-Br), sulfato (-OSO ₃ H) , Iodo (-I), acetateoto (-OCO-CH ₃ ), phosphate (-OPO ₃ H ₂ ) and the like can be used.

In addition, as the preferred examples of Z ₁ to Z ₇ in the formula A to C may be a substituent represented by the formula (1).

The reactive black dye composition according to the present invention includes a compound represented by Formula A, a compound represented by Formula B, and a compound represented by Formula C.

In addition, the reactive black dye composition according to the present invention, as shown in Figures 1 and 2, in the compounds represented by Formula A and Formula B constituting the dye composition, the substituent position contained in the phenylene group bonded to the azo group In the compound represented by Formula A (whether the substituent corresponds to the position of ortho, meta or para based on the azo group), at least one of substituents R ₁ and R ₂ is an azo group In the compound represented by the formula (B), at least one of the substituents Z ₃ to Z ₅ is a compound bonded to the meta position of the azo group (-N = N-) It features.

<Picture 1>

<Picture 2>

That is, the reactive black dye composition according to the present invention includes a compound represented by the formula (C), wherein at least one of the substituents R ₁ and R ₂ is represented by the formula (A) bonded to the ortho (ortho) position of the azo group Since at least one of the substituents Z ₃ to Z ₅ includes the compound represented by the formula (B) bonded to the meta position of the azo group, the color yield and water washability are excellent, and the color fastness is excellent.

In the present invention, the compound represented by the formula (A) is a blue dye, at least one of the substituents R ₁ and R ₂ included in the phenylene group bonded to the azo group (-N = N-) at the ortho position of the azo group By combining and partially canceling the linearity generated by the bond groups (Z ₁ and Z ₂ ) of the azo group at the para or meta positions by the twisting effect, the flushing ability can be increased, generally giving a resonance effect to the phenylene structure, By increasing the electron density, the energy level between HOMO and LUMO can be close to give deep color.

In addition, the subscripts k and l representing the number of bonds to the phenylene ring in the compound represented by Formula A may be the same or different, and may be independently 0 or 1, and preferably at least one of k and l is 1 , More preferably one of k or 1 may be 1. In this case, each of R ₁ to R ₂ is the same as or different from each other, and each independently a substituent selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms and -SO ₃ M, R The substituent of one of ₁ and R ₂ is bonded to the ortho position of the azo group to be included in the phenylene group, so that water flushing, deep colorability, and the like are improved.

In this case, in Formula A, at least one substituent of Z ₁ and Z ₂ may be bonded to a para position of an azo group, and preferably, both substituents Z ₁ and Z ₂ may be bonded to a para position of an azo group. Can be.

The compound represented by Formula A may be included in an amount of 30 wt% to 80 wt%, preferably 45 to 75 wt%, based on the total weight of the reactive black dye composition. If the compound represented by Formula (A) is used in less than 30 wt% with respect to the total weight of the composition, the color may be colored brown, and when used in excess of 80 wt%, color may be dark blue.

In the present invention, the compound represented by the formula (B) is a yellow (orange) series dye, and at least one of substituents Z ₃ to R ₅ included in the phenylene group bonded to an azo group (-N = N-) is represented by Structural Formula 1 As any substituent selected from 3 to 3, it is bonded to the meta position of the azo group.

In general, in the azo dye compound, when two substituents in one compound are bonded to the para position of the azo group, linearity is increased to increase the affinity between the dye and the fiber, while at least three substituents are used at the para position of the azo group. If these are combined, the affinity may be excessively increased, making it difficult to remove disproportionate or unfixed dyes.

On the other hand, when a substituent is present in the meta position of the azo group, linearity is weaker than that of the para position, and when the compound having a meta position substituent is bonded at the same time, the affinity increase is less than that of the compound of the para position, and the dyeing yield increase effect Stand out. Thus, when the azo compound having a substituent in the para position and the azo compound having a substituent in the meta position coexist, of course, the dyeing yield and the water washability can be increased.

Accordingly, the compound represented by Formula B is a compound in which at least one of the substituents Z ₃ to Z ₅ included in the phenylene group bonded to the azo group is bonded to the meta position of the azo group (-N = N-), and is represented by Formula B By containing the compound represented by the compound represented by the formula (A) and the compound represented by the formula (C), it is possible to further improve the dyeing yield, water washability, and overall fastness of the dye composition.

In this case, the compound represented by the formula (B) is a substituent Z ₃ to Z ₅ are the same or different, each independently of one another selected from the group consisting of structural formulas 1 to 3, at least one or more of these, preferably Preferably, one is a substituent bonded to a meta position of an azo group (-N = N-), and a substituent not bonded to a meta position of an azo group among the substituents Z ₃ to Z ₅ is each a para of azo group. And a phenylene group including the para or meta position bonded substituent in this case includes at least one substituent of one of R ₃ to R ₅ other than hydrogen at the ortho or meta position of the azo group. can do.

The compound represented by Formula B may be included in an amount of 10 wt% to 45 wt%, preferably 15 wt% to 35 wt%, based on the total weight of the reactive black dye composition. If the compound represented by the formula (B) is used in less than 10 wt% with respect to the total weight of the composition, the color is purple-based, when used in excess of 45 wt% may be a brown color.

In the present invention, the compound represented by the formula (C) is a yellow (orange) -based dye, at least one of the substituents Z ₆ to Z ₇ included in the phenylene group bonded to the azo group (-N = N-) is azo group (- N = N-) may be a compound bonded to the para position, preferably the substituents Z ₆ to Z ₇ may each bind to the para position of the azo group, in this case The phenyl group including a substituent may include at least one substituent of one of R ₆ and R ₇ which is not hydrogen at the ortho or meta position of the azo group.

The compound represented by Formula C may be included in an amount of 5 wt% to 20 wt%, preferably 5 wt% to 15 wt%, based on the total weight of the reactive black dye composition. If the compound represented by the formula (B) is used in less than 5 wt% with respect to the total weight of the composition, the color is green color, when used in excess of 20 wt% may be a brown color.

On the other hand, the compounds represented by formulas (A) to (C) in the present invention can be produced by forming azo groups on both sides by diazotization reaction with amine groups on both sides, centered on the benzene ring or naphthalene ring at the center.

Table 1 below describes a coupler compound having an amine compound for diazo reaction and a benzene ring or naphthalene ring in the central portion of the dye composition of the present invention in Formulas (A) to (C), the compounds for the following diazo reaction (Diazo 1 and Diazo 2) each may be interchangeable with each other. In addition, the compound of Formula A to the compound of Formula C according to the present invention is not limited to the compounds shown in Table 1 below and may bring about various modifications of substituents.

Chemical formula Diazo 1 Coupler Diazo 2 compound Formula A

Formula 1

〃 〃 Formula 2 〃 〃

Formula 3

〃 〃 Formula 4

〃 〃 Formula 5

〃

Formula 6

〃 〃 Formula 7

〃 〃 Formula 8

〃

Formula 9

Chemical formula Diazo 1 Diazo 2 Diazo 3 Coupler compound Chemical formula
B

Formula 10 〃

〃 〃 Formula 11

〃 〃 〃 Formula 12

〃 〃 Formula 13 〃 〃

〃 Formula 14

〃 Formula 15

〃 〃 〃 Formula 16

〃 〃 〃 Formula 17

〃 Formula 18

Chemical formula Diazo 1 Coupler Diazo 2 compound Chemical formula
C

Formula 19 〃 〃

Formula 20

〃

Formula 21 〃 〃

Formula 22

〃

Formula 23 〃 〃

Formula 24

〃

Formula 25

〃

Formula 26

Hereinafter, as a representative structural formula of the dye composition of the present invention, specific compounds of the compounds represented by [Formula A] to [Formula C], any one selected from the group represented by the following [Formula 1] to [Formula 26] Although the compounds are shown, the compounds according to the invention are not limited thereto.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

 In addition, the reactive black dye composition according to the present invention may further include an additive in an amount of 5 wt% to 30 wt% with respect to the total weight of the reactive black dye composition within a range that does not impair the purpose and effect of the present invention. The additive may be composed of, for example, an electrolyte salt, a buffer, an anti-icing agent, and the like, but is not limited thereto.

The electrolyte salt may be inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and the like.

The buffer salt is a salt that is adjusted to pH 3 to 7 of the aqueous solution in which the mixture dye is dissolved in order to prevent decomposition of the dye during storage and storage, for example, sodium carbonate, sodium bicarbonate, sodium acetate (sodium acetate), sodium monohydrogen phosphate, sodium dihydrogenphosphate, and the like can be used.

The present invention also relates to a method for dyeing or printing a fiber material containing a hydroxyl group or a nitrogen group using the reactive black dye composition described above.

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

In addition, the reactive black dye composition according to the present invention is suitable as a colorant for use in a recording system. Such recording systems include, for example, inkjet printers or recording apparatuses, fountain pens or ballpoint pens, which are commercially available for paper or textile printing.

As described above, in order to use the reactive black dye composition according to the present invention in a recording system, it must be made into a form suitable for use in a recording system, and a suitable form includes an aqueous ink containing the dye composition as a colorant. Can be. The aqueous ink can be prepared in a conventional manner by mixing together the individual components as desired.

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

As the dyeing method, for example, it can be used by various methods such as adsorption method, cold pad placement method, continuous dyeing method, dyeing method, printing method, printing method, in detail, adsorption method and continuous dyeing method can be used.

Specifically, the dyeing by the adsorption method is generally 0.1 parts to 50 parts by weight, preferably 0.5 parts to 30 parts by weight, and preferably 0.5 parts to 30 parts by weight of the reactive black dye composition, based on 100 parts by weight of the aqueous medium (water) under an aqueous medium. Is carried out at a temperature of 20 ° C to 105 ° C, preferably 30 ° C to 90 ° C, more preferably 40 ° C to 80 ° C.

Hereinafter, the present invention will be described in more detail through examples and comparative examples regarding the preparation of compounds for dyeing compositions of the present invention and evaluation of dye compositions. However, the protection scope of the present invention is not limited to the following examples.

<Preparation Example of Compound for Reactive Black Dye Composition>

Preparation Example 1 Synthesis of Compound Represented by Formula 1

28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) were dispersed in water, and then diazotized by slowly adding a solution of 7 g of sodium nitrite dissolved in water while maintaining the temperature below 10 ° C under a hydrochloric acid catalyst. , 31 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid was added and acid coupling was performed at pH 2-3. When the reaction was completed, a solution of 7 g of sodium nitrite dissolved in water while dispersing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) in water and maintaining the temperature below 10 ° C under a hydrochloric acid catalyst Was added slowly to diazotize, and then added to the acidic coupling solution to the coupling at pH 5-7, and spray-dried after the reaction was completed to prepare 131 g of the compound represented by the formula (1).

Preparation Example 2 Synthesis of Compound Represented by Chemical Formula 10

After diazotizing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) using the same conditions as in Production Example 1, 15 g of 3,5-diaminobenzoic acid was added at a pH of 2 ~. Perform primary coupling at 4, and upon completion of the reaction, diazotize 28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) to secondary coupling at pH 4-6, then complete the reaction. 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) were diazotized to effect tertiary coupling at pH 5-7. Spray drying after the reaction was completed to prepare 154 g of the compound represented by the formula (10).

Preparation Example 3 Synthesis of Compound Represented by Chemical Formula 19

Using the same conditions as in Production Example 1, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized and then 1-hydroxy-6-aminonaphthalene-3-sulfonic acid 23 g of acid coupling was performed at pH 2-3, and 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized to complete the coupling at pH 5-6. Was performed. After the reaction was completed by spray drying to prepare a compound represented by 131 g of the formula (19).

Preparation Example 4 Synthesis of Compound Represented by Chemical Formula 2

Using the same conditions as in Production Example 1, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized, and then 1-amino-8-hydroxynaphthalene-3,6 After adding 31 g of disulfonic acid, acid coupling was performed at pH 2-3, and when the reaction was completed, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized to pH 3 ~. Coupling was carried out at 5. After the reaction was completed by spray drying to prepare 141 g of the compound represented by the formula (2).

Preparation Example 5 Synthesis of Compound Represented by Chemical Formula 3

Using the same conditions as in Production Example 1, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized, and then 1-amino-8-hydroxynaphthalene-3,6 After adding 31 g of disulfonic acid, acid coupling was performed at pH 2-3, and when the reaction was completed, 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized to pH. Coupling was performed at 6-7. After the reaction was completed by spray drying to prepare a compound represented by 134 g of the formula (3).

Preparation Example 6 Synthesis of Compound Represented by Chemical Formula 4

Using the same conditions as in Production Example 1, 28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) was diazotized, and then 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid After adding 31 g, acid coupling was performed at pH 2-3, and when the reaction was completed, diazotized 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) to pH 6-7 Coupling was performed at. 125 g of the compound represented by Chemical Formula 4 was prepared by spray drying after the reaction was completed.

Preparation Example 7 Synthesis of Compound Represented by Chemical Formula 5

Using the same conditions as described in Preparation Example 1, 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized, and then 1-amino-8-hydroxynaphthalene-3 After addition of 31 g of 6-disulfonic acid, acid coupling was performed at pH 2-3, and when the reaction was completed, 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized. Coupling was performed at pH 6-7. After the reaction was completed by spray drying to prepare a compound represented by 129 g of the formula (5).

Preparation Example 8 Synthesis of Compound Represented by Formula 11

Using the same conditions as in Preparation Example 1, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized in a conventional manner, and then 15 g of 3,5-diaminobenzoic acid. Primary coupling at pH 2 to 4, and upon completion of the reaction, diazotize 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) to form secondary coupling at pH 4 to 6 On completion of the reaction, 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) was diazotized to perform tertiary coupling at pH 5-7. Spray drying after the reaction was completed to prepare 154 g of the compound represented by the formula (11).

Preparation Example 9 Synthesis of Compound Represented by Chemical Formula 12

After diazotizing 36.1 g of 2-aminobenzenesulfonic acid-4- (2-sulfatoethylsulfone) in a conventional manner using the same conditions as in Production Example 1, 15 g of 3,5-diaminobenzoic acid was used. Primary coupling at pH 2 to 4, and upon completion of the reaction, diazotize 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) to form secondary coupling at pH 4 to 6 On completion of the reaction, 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) was diazotized to perform tertiary coupling at pH 5-7. Spray drying after the reaction was completed to prepare 154 g of the compound represented by the formula (12).

Preparation Example 10 Synthesis of Compound Represented by Chemical Formula 13

After diazotizing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) by a conventional method using the same conditions as in Preparation Example 1, 15 g of 3,5-diaminobenzoic acid was used. Primary coupling at pH 2-4, and upon completion of the reaction diazotized 36.1 g of 2-aminobenzenesulfonic acid-4- (2-sulfatoethylsulfone) to secondary coupling at pH 3-5 After completion of the reaction, 28.1 g of 3-aminobenzene- (2-sulfatoethylsulfone) was diazotized to perform tertiary coupling at pH 5-7. After the reaction was completed by spray drying to prepare a compound represented by 164 g of the formula (13).

Preparation Example 11 Synthesis of Compound Represented by Chemical Formula 14

After diazotizing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) by a conventional method using the same conditions as in Preparation Example 1, 15 g of 3,5-diaminobenzoic acid was used. Primary coupling at pH 2-4, and upon completion of the reaction diazotized 36.1 g of 2-aminobenzenesulfonic acid-4- (2-sulfatoethylsulfone) to secondary coupling at pH 3-5 After completion of the reaction, 36.1 g of 2-aminobenzenesulfonic acid-4- (2-sulfatoethylsulfone) was diazotized to perform tertiary coupling at pH 5-7. After the reaction was completed by spray drying to prepare a compound represented by 173 g of the formula (14).

Preparation Example 12 Synthesis of Compound Represented by Chemical Formula 20

Using the same conditions as in Production Example 1, 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized and then 1-hydroxy-6-aminonaphthalene-3-sulfonic acid 23 g of acidic coupling was performed at pH 2-3, and when the reaction was completed, 28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) was diazotized to perform coupling at pH 6-7. After the reaction was completed by spray drying to prepare a compound represented by 121 g of the formula (20).

Preparation Example 13 Synthesis of Compound Represented by Chemical Formula 21

Using the same conditions as in Production Example 1, 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized, and then 1-hydroxy-6-aminonaphthalene-3 Acidic coupling of 23 g of sulfonic acid at pH 2-3, and 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) were diazotized at pH 5-7 when the reaction was complete. Ring was performed. After the reaction was completed by spray drying to prepare a compound represented by 125 g of the formula (21).

Preparation Example 14 Synthesis of Compound Represented by Chemical Formula 22

Using the same conditions as in Production Example 1, 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized, and then 1-hydroxy-6-aminonaphthalene-3 Acidic coupling of 23 g of sulfonic acid at pH 2.5 to 3; diazotizing 31.1 g of 3-methoxy-4-aminobenzene- (2-sulfatoethylsulfone) when the reaction is complete to pH 6-7 Coupling was performed at. After the reaction was completed by spray drying to prepare a compound represented by the formula (22) of 119 g.

Preparation Example 15 Synthesis of Compound Represented by Chemical Formula 23

Using the same conditions as in Production Example 1, 29.5 g of 3-methyl-4-aminobenzene- (2-sulfatoethylsulfone) was diazotized, and then 1-hydroxy-6-aminonaphthalene-3- Acidic coupling of 23 g of sulfonic acid was performed at pH 2.5 to 3, and 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) was diazotized to coupling at pH 5 to 6 when the reaction was completed. Was performed. After the reaction was completed by spray drying to prepare a compound represented by 123 g of the formula (23).

<Example 1>

As the compound corresponding to the above-mentioned formula (A), 60 wt% of the compound represented by formula (1), 30 wt% of the compound represented by formula (10) as the compound corresponding to formula (B) and the compound represented by formula (19) as the compound corresponding to formula (C) 10 wt% was mixed.

<Examples 2 to 7>

The dye composition was prepared by the method described in Example 1 below, and each component is described in Table 4 below.

Comparative Example 1

A reactive black dye composition was prepared using a compound represented by Formula 19 and a compound represented by Formulas 27 and 28 below.

[Formula 27]

[Formula 28]

Comparative Example 2

Reactive black dye compositions were prepared using the compounds represented by Formulas 19 and 27 and the compounds represented by Formula 29 below.

[Formula 29]

Compound of Formula A Compound of formula (B) Compound of formula (C) compound Content (% by weight) compound Content (% by weight) compound Content (% by weight) Example 1 Formula 1 60 Formula 10 30 Formula 19 10 Example 2 Formula 1 60 Formula 11 30 Formula 20 10 Example 3 Formula 2 60 Formula 11 30 Formula 20 10 Example 4 Formula 3 60 Formula 12 30 Formula 21 10 Example 5 Formula 4 60 Formula 13 30 Formula 22 10 Example 6 Formula 5 50 Formula 14 30 Formula 23 10 Example 7 Formula 1 35 Formula 11 45 Formula 20 20 Comparative Example 1 Formula 27 60 Formula 28 30 Formula 19 10 Comparative Example 2 Formula 27 60 Formula 29 30 Formula 19 10

Experimental Example 1 Evaluation of Dyeing Ratio

0.5 g of the reactive black dye compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were dissolved in 100 g of water, 8 g of dry forget-me-not was added, and 10 g of cotton fiber was added thereto. Seven samples were obtained under the same conditions.

After heating at 60 ° C. for 20 minutes, 1.5 g of sodium carbonate was added to the salt bath, and staining was performed at about 60 ° C. for 1 hour. At this time, 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, respectively, and then washed sufficiently with cold water. 0.5 g of an ionic surfactant was added to 100 g of water, shaken at 100 ° C. for 5 minutes to remove the unfixed dye, washed with cold water, and then dried and measured to calculate the dyeing rate.

Here, the dyeing ratio was set to the maximum value of the reflectance of the darkest dyed cloth of each sample at 80 minutes, and the rest was converted into a relative value, which is shown in Table 5.

division Dyeing rate 5 minutes 10 minutes 15 minutes 20 minutes 25 minutes 30 minutes 40 minutes 50 minutes 60 minutes 80 minutes Example 1 21 56 77 86 91 94 97 99 100 100 Example 2 20 52 75 85 90 93 96 97 98 98 Example 3 19 50 70 81 88 92 94 95 95 95 Example 4 20 51 73 85 89 91 92 93 93 93 Example 5 18 48 69 80 87 90 91 92 92 92 Example 6 20 48 69 79 86 89 90 91 91 91 Example 7 18 47 68 78 85 87 88 89 90 90 Comparative Example 1 22 49 57 59 76 81 82 82 82 82 Comparative Example 2 23 49 56 69 76 80 81 81 81 81

As a result, as shown in Table 5, the dyeing rate of the samples dyed with the reactive black dye compositions of Examples 1 to 7 is stronger than that of the samples dyed with the Comparative Examples 1 and 2 compositions according to Examples 1 to It was confirmed that the reactive black dye composition of 7 is superior in terms of dyeing rate than the Comparative Examples 1 and 2. In addition, it was found that the compositions of Examples 1 to 7 were lower than the compositions of Comparative Examples 1 and 2 in terms of initial dyeing rate. Thus, when the slope of the final dyeing ratio relative to the initial dyeing ratio is large, higher saturation value can be expected, in particular, it can be expected to be more advantageous for low bath ratio dyeing.

Experimental Example 2 Evaluation of Color Fastness

Since it is very difficult to match the same K / S value in normal dyeing, the difference in dyeing rate of ± 5% or so is generally regarded as the same, and the fastness test was performed.

division Fastness rating Wet Friction Fastness
(ISO 150-X12-N) Daylight fastness
(ISO 105-B02) Chlorine water fastness
(ISO 105-E03) Color fastness
(ISO 105-C06-C2S) Example 1 4 4 4-5 4-5 Example 2 4 4 4-5 4-5 Example 3 3-4 4 4-5 4-5 Example 4 3-4 4 4 4 Example 5 3-4 4 4 4 Example 6 3-4 4 4 4 Example 7 3-4 4 4 4 Comparative Example 1 3 4 4 3-4 Comparative Example 2 3 4 4 3-4

As a result, as shown in Table 6, the fastness of the sample dyed with the reactive black dye composition of Examples 1 to 7 was found to be excellent on average, there was no problem in use. The fastness grade means that the higher the number, the less the change or the contamination of other fibers.

Experimental Example 3: Flushability Evaluation

The color change with water washing was measured using the sample of Examples 1-7 and Comparative Examples 1 and 2.

After dyeing the reactive black dye compositions of the Examples and Comparative Examples in the same ratio as the dyeing rate evaluation test, the dyeing cloth was removed from the pot, and then shaken for 10 minutes in water containing 0.2 g of glacial acetic acid in 100 g of 25 ℃ water. The dyeing cloth was taken out again and placed in 100 g of water at 60 ° C. for 10 minutes of shaking, and the concentrations of the second, third and fourth rounds were measured by UV-Vis spectrophotometer. Table 7 shows the absorbance values at wavelengths of 400 nm, 500 nm, and 600 nm at 60 ° C shaking for the second, third, and fourth rounds of the Examples and Comparative Examples, respectively. It means bad world.

2nd round 3rd round 4th round 400 nm 500 nm 600 nm 400 nm 500 nm 600 nm 400 nm 500 nm 600 nm Example 1 0.52 0.39 0.72 0.25 0.12 0.23 0.04 0.03 0.03 Example 2 0.53 0.38 0.77 0.23 0.13 0.22 0.04 0.04 0.03 Example 3 0.55 0.39 0.71 0.24 0.13 0.25 0.05 0.03 0.04 Example 4 0.55 0.40 0.69 0.23 0.12 0.24 0.05 0.04 0.05 Example 5 0.53 0.39 0.70 0.21 0.12 0.24 0.06 0.03 0.06 Example 6 0.54 0.38 0.71 0.23 0.13 0.25 0.07 0.03 0.06 Example 7 0.54 0.38 0.72 0.23 0.14 0.26 0.07 0.04 0.06 Comparative Example 1 0.60 0.38 0.69 0.38 0.12 0.39 0.20 0.04 0.17 Comparative Example 2 0.51 0.37 0.68 0.39 0.13 0.40 0.21 0.04 0.19

As a result, as shown in Table 7, the residual concentration of the sample stained with the reactive black dye composition of Examples 1 to 7 was slightly higher than that of Comparative Example 1 and Comparative Example 2, but It was found that the number of steps in the washing process could be reduced by approaching almost zero.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (14)

A compound represented by formula (A); A compound represented by formula B; And a compound represented by formula (C); a reactive black dye composition comprising:
[Formula A]

[Formula B]

[Formula C]

In Chemical Formulas A to C,
R ₁ to R ₇ are the same as or different from each other, and are each independently a 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 ₃ , M are the same or different, and each independently selected from the group consisting of hydrogen, ammonium group, lithium, sodium and potassium,
m to q are each an integer of 0 to 4, and when m to q are each 2 or more, each of R ₃ to R ₇ is the same as or different from each other,
In Formula A
k and l are each 0 or 1, where k + l is 1,
In this case, each of R1 to R2 is the same or different, and each independently a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and -SO3M,
Z ₁ and Z ₂ are each any one substituent selected from Structural Formulas 1 to 3, wherein both Z ₁ and Z ₂ are bonded to a para position of an azo group,
In Formula B
Z ₃ to Z ₅ are each any one substituent selected from Structural Formulas 1 to 3, at least one of which is a substituent bonded to a meta position of the azo group (-N = N-),
Substituents not bonded to the meta position of the azo group in Z ₃ to Z ₅ are each bonded to a para position of the azo group,
In Formula C
Z ₆ and Z ₇ are the same or different and are each independently a substituent selected from the group consisting of the following structural formulas 1 to 3 and hydrogen.
[Formula 1]

[Formula 2]

[Formula 3]

In the structural formulas 1 to 3 X ₁ to X ₃ is a leaving group which can be removed at alkaline conditions.
delete delete The method of claim 1,
In Formula B, Z ₃ to Z ₅ are the same as or different from each other, and independently of each other, any one substituent selected from the group consisting of Structural Formulas 1 to 3, one of which is meta of an azo group (-N = N-) Reactive black dye composition, characterized in that the substituent bonded to the position.
delete delete delete The method of claim 1,
The Z ₁ , Z ₂ , Z ₆ and Z ₇ substituents are each reactive black dye composition, characterized in that bonded to the para (para) position of the azo group.
The method of claim 1,
In Formulas 1 to 3, X ₁ to X ₃ are the same as or different from each other, and independently from each other, chloro (-Cl), bromo (-Br), sulfato (-OSO ₃ H), and iodo (-I). Reactive black dye composition, characterized in that any one selected from the group consisting of acetate (-CH ₃ COO) and phosphate (-OP0 ₃ H ₂ ).
The method of claim 1,
R ₁ to R ₇ are the same as or different from each other, and are each independently selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy and -SO ₃ H Reactive black dye composition.
The method of claim 1,
In Formula A, R ₁ and R ₂ are the same as or different from each other, and each independently is a reactive black dye composition, which is -SO ₃ H.
The method of claim 1,
Z ₁ to Z ₇ are the same or different, respectively, reactive black dye composition, characterized in that the substituent represented by the formula (1).
The method of claim 1,
The reactive black dye composition comprises 30 wt% to 80 wt% of a compound represented by Formula A, 10 wt% to 45 wt% of a compound represented by Formula B, and 5 wt% to 20 wt% of a compound represented by Formula C. Reactive black dye composition, characterized in that.
 14. A method of dyeing or printing a fiber material containing hydroxyl groups or nitrogen groups using the reactive black dye composition of any one of claims 1, 4 and 8-13.