KR102591925B1 - Reactive Red Dye Composition and Methods for Dyeing Fiber Using the Same - Google Patents

Abstract

The present invention relates to a reactive red dye composition and a method for dyeing fibers using the same. More specifically, the present invention relates to a reactive red dye composition and a method for dyeing fibers using the same. In more detail, the present invention relates to a reactive red dye composition that improves deep coloring during dip-dyeing and printing of cellulose fibers, rayon fibers, etc., and at the same time provides appropriate washability and can be used to dye existing general-purpose red dyes. The present invention relates to a reactive red dye composition that can achieve excellent color fastness without a large color difference between the two and a method for dyeing fibers using the same.

Description

Reactive red dye composition and method for dyeing fiber using the same {Reactive Red Dye Composition and Methods for Dyeing Fiber Using the Same}

The present invention relates to a reactive red dye composition and a method for dyeing fibers using the same. More specifically, the present invention relates to a reactive red dye composition and a method for dyeing fibers using the same. More specifically, the present invention relates to a reactive red dye composition that improves deep coloring properties, provides appropriate washability at the same time, and provides excellent color fastness without significant color difference from existing general-purpose red dyes. It relates to a reactive red dye composition and a method for dyeing fibers using the same.

Reactive dyes are mainly used for cotton, linen, ramie, rayon, silk, Korean paper, etc., and are dyed by covalent bonding with fibers in a dye bath in the presence of alkali. They are easily soluble in water and have superior fastness characteristics than direct dyes. Have. In addition, it is a dye that has been widely used in recent craft dyeing due to its vivid colors, excellent penetration and leveling properties, and a wide range of fibers that can be dyed.

In recent years, in the practice of dyeing, there have been increasing requirements regarding the quality of the dyed material and the economy of the dyeing process. There is a continuing need for new and readily obtainable dye compositions with improved properties, especially with regard to applicability.

Today's dyeing requires reactive dyes with sufficient substantibity and at the same time excellent ease of cleaning of unset dyes. In addition, these reactive dyes must exhibit excellent color yield and high reactivity, and in particular, the purpose is to obtain dyes with high fixation. In many cases, the build-up behavior of reactive dyes is not sufficient to meet these requirements, especially for dyeing deep shades, so dyers need to use suitable reactive dyes in their formulations.

In particular, the conventional technology for tricolor dyeing using reactive dyes is C.I. It is known to mix red dyes such as Reactive Red 195 with yellow and blue dyes.

On the other hand, Reactive Red 195, which is a representative red dye according to the prior art and is represented by the chemical formula below, has the disadvantage of leaving a lot of residue in medium-dark color dyeing and having a low dyeing yield.

-Reactive Red 195

In order to compensate for the shortcomings of Reactive Red 195, US Patent No. 4,485,041 proposed a dye represented by Chemical Formula 2 below.

-Formula 2

The dye represented by Formula 2 has two vinylsulfone groups in the molecule, so it has excellent build-up in medium-dark colors, reduces residual bathing, and has excellent dyeing yield. However, it has the disadvantage of poor color fastness in washing because it is difficult to remove unadhered dye during the washing process. , Because it has a benzene-based diazomer, it has a problem of poor chromosomal properties compared to Reactive Red 195, which is connected to a naphthalene-based diazomer.

Meanwhile, U.S. Patent No. 5,200,511 proposes a dye as shown in Formula 3 below in order to obtain excellent washing fastness while implementing deep color properties. However, the Formula 3 dye has poor medium-dark color build-up compared to the Formula 2 dye. Compared to Reactive Red 195 dye, it shows limitations in terms of washing fastness and chlorine water fastness.

-Formula 3

Meanwhile, U.S. Patent No. 5,556,435 proposes a composition in which a dye represented by Formula 2 above is mixed with a dye represented by Formula 4 below, which is a reactive dye.

-Formula 4

However, it is known that the dye represented by Formula 4 has a completely different visible spectrum compared to general reactive red dyes, and the structural difference is very large compared to the dye of Formula 2, so there is no synergistic effect of the mixture at all, The color of the mixture also shows ambiguous limitations in using it as the three main colors.

Additionally, U.S. Patent No. 6,090,164 proposes a composition that mixes the dye represented by Formula 2 above with a component represented by Formula 5 below, which is another reactive dye.

-Formula 5

However, the dye represented by Chemical Formula 5 also has a very large structural difference compared to Chemical Formula 2, so it is known that there is almost no synergistic effect of the mixture, so there is no significant advantage in using it as a reactive red dye.

Therefore, compared to the red dyes of the prior art, there is a need to develop a reactive red dye composition that can improve color depth, provide appropriate washability, and achieve excellent color fastness without significant color difference from existing general-purpose red dyes. is continuously being demanded.

US Patent No. 4,485,041 (Patent Date: 1984.11.27) US Patent No. 5,200,511 (Patent date: 1993.04.06) US Patent No. 5,556,435 (Patent Date: 1996.09.17.) US Patent No. 6,090,164 (Patent date: July 18, 2000)

The main purpose of the present invention is to solve the above-mentioned problems, and is a reactive red dye composition that increases deep coloring properties, provides appropriate washability, and provides excellent color fastness without significant color difference from existing general-purpose red dyes; and The aim is to provide a method for dyeing fibers using this.

In order to achieve the above object, one embodiment of the present invention includes a compound represented by the following formula (A); and a compound represented by Formula B. It provides a reactive red dye composition comprising a.

[Formula A]

[Formula B]

In Formula A and Formula B above,

R ₁ to R ₃ are each the same or different and are independently any one substituent selected from the group consisting of hydrogen, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and -SO ₃ M, wherein R 1 and one of R2 must be an alkoxy group having 1 to 4 carbon atoms,

M ₁ to M ₈ and M are each the same or different and are independently selected from the group consisting of hydrogen, ammonium group, lithium, sodium and potassium,

Y ₁ to Y ₃ are each the same or different, and are independently substituents represented by structural formula 1 below,

[Structural Formula 1]

In structural formula 1, ‘*’ refers to a binding site that binds to a sulfur atom, and X is a leaving group that can be removed by alkali,

In Formula A, one of SO ₂ Y ₁ and SO ₂ Y ₂ is bonded to the para position of the azo group, and the other is bonded to the meta position of the azo group.

In Formula B, D is one of the naphthalene-based substituents represented by structural formula 2 below.

[Structural Formula 2]

‘*’ in structural formula 2 refers to a binding site that binds to a nitrogen atom,

M ₉ to M ₁₁ are the same or different, and are independently selected from the group consisting of hydrogen, ammonium, lithium, sodium, and potassium.

As an example, in Structural Formula 2 in Chemical Formula B, M ₉ to M ₁₁ are the same or different, and may independently be any one selected from the group consisting of hydrogen, lithium, sodium, and potassium.

As an example, in Formula A and Formula B, the substituents R ₁ to R ₃ are each the same or different, and are independently selected from the group consisting of hydrogen, methyl group, methoxy group, and -SO ₃ M. It may be a substituent.

As _an example, in Formula A and Formula B, It may be any one substituent selected from ₃ COO-) and phosphate (-OP0 ₃ H ₂ ).

As an example, in Formula A, R ₁ may be hydrogen or -SO ₃ M, and R ₂ may be a methoxy group. In this case, phenyl containing R ₁ (hydrogen or -SO ₃ M) SO ₂ Y ₂ bonded to the group is bonded to the para position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group containing R ₂ (methoxy group) is bonded to the meta position of the azo group, or the R ₁ (hydrogen Or, SO ₂ Y ₂ bonded to the phenyl group containing -SO ₃ M) is bonded to the meta position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group containing R ₂ (methoxy group) is bonded to the para position of the azo group. can be combined with

As an example, the content ratio of the compound represented by Formula A and the compound represented by Formula B in the reactive black dye composition may range from 1:9 to 9:1, based on the weight of each component.

Additionally, the present invention can provide a reactive black dye composition comprising the reactive red dye composition according to the present invention as a red component.

In addition, the present invention provides a method for dyeing or printing or digital inkjet printing a textile material containing a hydroxyl group or a nitrogen group using a dye composition containing the reactive red dye composition according to the present invention. You can.

The reactive black dye composition according to the present invention increases deep coloring in dip dyeing, printing, and digital printing of cellulose fibers, rayon fibers, etc., and at the same time provides appropriate washability and provides excellent overall color fastness without significant color difference from existing general-purpose red dyes. This has the effect of providing high-quality dyeing materials.

Figure 1 is a diagram showing build-up evaluation data according to examples and comparative examples of the present invention, where the horizontal axis represents o.w.f. values and the vertical axis represents K/S values.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

Throughout this specification, “fiber” is used to include fabric.

The reactive red dye composition according to the present invention includes a compound represented by the following formula (A); and a compound represented by Formula B.

[Formula A]

[Formula B]

In Formula A and Formula B above,

R ₁ to R ₃ are each the same or different and are independently any one substituent selected from the group consisting of hydrogen, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and -SO ₃ M, wherein R 1 and one of R2 must be an alkoxy group having 1 to 4 carbon atoms,

M ₁ to M ₈ and M are each the same or different and are independently selected from the group consisting of hydrogen, ammonium group, lithium, sodium and potassium,

Y ₁ to Y ₃ are each the same or different, and are independently substituents represented by structural formula 1 below,

[Structural Formula 1]

In structural formula 1, ‘*’ refers to a binding site that binds to a sulfur atom, and X is a leaving group that can be removed by alkali,

In Formula A, one of SO ₂ Y ₁ and SO ₂ Y ₂ is bonded to the para position of the azo group, and the other is bonded to the meta position of the azo group.

In Formula B, D is one of the naphthalene-based substituents represented by structural formula 2 below.

[Structural Formula 2]

‘*’ in structural formula 2 refers to a binding site that binds to a nitrogen atom,

M ₉ to M ₁₁ are the same or different, and are independently selected from the group consisting of hydrogen, ammonium, lithium, sodium, and potassium.

As described in the previous background art, in the case of a typical red dye component, a single compound such as Reactive Red 195, Chemical Formula 2, or Chemical Formula 3 known in the prior art can be used alone, but as already described above, a lot of residual bath remains. There are disadvantages such as low dyeing yield, build-up problem, poor washing fastness and deep color resistance, so in the process of finding a dye composition that can solve these problems and has improved properties, the inventors of the present invention found the formula In the structure of the dye represented by A, one of the two phenyl groups at the terminal is necessarily bonded to an alkoxy group having 1 to 4 carbon atoms, and also the two reactive groups at the terminal in the formula A, SO ₂ Y ₁ and SO ₂ When a dye component having a structure in which one of Y ₂ binds to the para position of the azo group and the other binds to the meta position of the azo group is combined with the red dye component represented by the formula B, the deep color is further increased. At the same time, it was discovered that it can provide appropriate water washing properties and also achieve excellent color fastness without a large color difference from Reactive Red 195, an existing general-purpose ingredient, leading to the completion of the present invention.

Meanwhile, among the substituents of R ₁ to R ₃ in Formula A and Formula B, specific examples of alkyl groups having 1 to 4 carbon atoms may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc., Specific examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and isobutoxy.

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

Meanwhile, the substituent represented by Structural Formula 1 may use a leaving group whose terminal X can be removed under alkaline conditions. Here, the leaving group that can be removed under alkaline conditions refers to a substituent that can be removed under aqueous solution conditions of pH 7 or higher, or under basic conditions in an organic solvent. _For example, in structural formula 1 _, and phosphato (-OPO ₃ H ₂ ), fluoro (-F), -SSO ₃ H, -OCO-C ₆ H ₅ , -OSO ₂ -R(R: C1 to C4 alkyl) and -OSO ₂ - Substituents such as NR ₂ (R: C1 to C4 alkyl) may be used, preferably chloro (-Cl), bromo (-Br), sulfato (-OSO ₃ H), and iodo (-I). , acetate (-OCO-CH ₃ ), phosphatide (-OPO ₃ H ₂ ), etc. may be used.

In addition, in Structural Formula 2 in Formula B of the present invention, M ₉ to M ₁₁ are the same or different, and may be independently selected from the group consisting of hydrogen, lithium, sodium, and potassium.

As a preferred embodiment corresponding to the first technical feature of Formula A according to the present invention, in the case where one of the two terminal phenyl groups in Formula A is necessarily bonded to an alkoxy group having 1 to 4 carbon atoms, the other one Hydrogen or SO ₃ M may be bonded to the phenyl group. For example, in Formula A, R ₁ may be hydrogen or -SO ₃ M, and R ₂ may be a methoxy group.

Here, when one of R1 and R2, which are substituents bonded to the two terminal phenyl groups in the formula A according to the present invention, is an alkoxy group having 1 to 4 carbon atoms, the dye The colorfastness is high and the fastness to chlorine water can be improved.

In addition, corresponding to the second technical feature of the formula A according to the present invention, one of the SO ₂ Y ₁ and SO ₂ Y ₂ in the formula A is bonded to the para position of the azo group, and the other is bonded to the meta position of the azo group. Through the structure that is bonded to, it is possible to have the advantage of easy removal of unfixed dye after dyeing, compared to dyes in which both ends of Formula 2, etc., are bonded to the para position of the azo group.

That is, as shown in Figure 1 below, the substituent positions of each SO ₂ Y ₁ and SO ₂ Y ₂ included in the phenylene group bonded to the azo group (the substituent is ortho, meta, or relative to the azo group) Depending on which position of the para (para) it corresponds to, the effect of affinity between dye and fiber and the advantage of easy removal of unfixed dye after dyeing may be displayed differently.

<Figure 1>

This is because in azo dye compounds, when there is a substituent such as SO ₂ Y _1, SO ₂ Y ₂ , etc. at the para position of the azo group, linearity increases and the affinity between the dye and fiber increases, but the affinity is excessive. However, if a substituent exists in the meta position of the azo group, the linearity is weaker than that in the para position, so the compound with a substituent in the meta position is stronger than the compound in the para position. The increase in affinity is small and removal of unfixed dye may become easier.

Accordingly, when both a substituent at the para position of the azo group and a substituent at the meta position coexist, such as the compound represented by formula A in the present invention, the affinity between the dye and the fiber and the washability can be considered together. can be obtained.

Here, one of the two terminal reactive groups in Formula A, SO ₂ Y ₁ and SO ₂ Y ₂ , is bonded to the para position of the azo group, and the other is bonded to the meta position of the azo group. The structure is, for example, In Formula A, when R ₁ is hydrogen or -SO ₃ M and R ₂ is a methoxy group, SO ₂ Y is bonded to a phenyl group containing R ₁ (hydrogen or -SO ₃ M) in Formula A. ₂ is bonded to the para position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group containing R ₂ (methoxy group) may be bonded to the meta position of the azo group, or the R ₁ (hydrogen or -SO SO ₂ Y ₂ bonded to the phenyl group containing R 2 (methoxy group) is bonded to the meta _position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group containing R ₂ (methoxy group) is bonded to the para position of the azo group. It could be a structure.

Here, according to the first technical feature, when a methoxy group is bonded to the terminal benzene ring, when the azo group and sulfone group (-S(=O)(=O)-) bonded to the benzene ring are in the para position, it is purple. tends to be close to Therefore, in the case where a methoxy group is bonded to the terminal benzene ring, it may be more preferable if the azo group and sulfone group (-S(=O)(=O)-) bonded to the benzene ring are in the meta position.

Meanwhile, the structure of Chemical Formula B of the present invention has the same triazine structure at the center and the naphthalene structure bonded thereto compared to the compound represented by Chemical Formula A, and the benzene ring containing R1 and the benzene ring portion containing R3 are also the same. The difference is that the benzene ring portion containing R2 in Chemical Formula A is D (Structural Formula 2) in Chemical Formula B. Here, when it has a naphthalene-based structure, which is the structure of D (Structural Formula 2) in Chemical Formula B, Compared to the benzene structure, the spectrum in the visible region can absorb longer wavelengths and produce highly saturated colors, and overall fastness can be excellent. Overall, Chemical Formula B has better washability compared to the compound represented by Chemical Formula A. do.

Here, in the D structure in the above Chemical Formula B, it may be advantageous for the -SO ₃ M group to be located at a position adjacent to the azo group, especially at position 1 of the naphthalene ring, due to high fastness to chlorine water and/or washing fastness.

In addition, due to the structural similarity between Formula A and Formula B, when the two structures are mixed, a synergistic effect can be realized in which the disadvantages of each dye are offset and the advantages are highlighted.

Meanwhile, the compounds represented by Formula A and Formula B in the present invention can be prepared by forming azo groups on both sides of a naphthalene ring bonded to the central part of the triazine through a diazotization reaction with amine groups on both sides, Compounds represented by Formula A and Formula B can be easily produced through this diazotization reaction.

[Formula A]

[Formula B]

Hereinafter, as a representative structural formula of Chemical Formula A in the dye composition of the present invention, any one compound selected from the group represented by [Formula A-1] to [Formula A-6] below, and a representative structural formula of Chemical Formula B, Any one compound selected from the group represented by the following [Formula B-1] to [Formula B-7] is shown, but the compounds represented by Formula A and the compounds represented by Formula B according to the present invention are not limited thereto. and may result in modification of various substituents.

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

[Formula A-6]

[Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

[Formula B-5]

[Formula B-6]

[Formula B-7]

Meanwhile, the content ratio of the compound represented by Formula A and the compound represented by Formula B in the reactive red dye composition according to the present invention may range from 1:9 to 9:1, based on the weight of each component, and is preferably may be in the range of 2:8 to 8:2, more preferably in the range of 3:7 to 7:3, and most preferably the total of the compound represented by Formula A and the compound represented by Formula B Based on the sum, it may range from 30 to 50 wt% of the compound represented by Formula A and 50 to 70 wt% of the compound represented by Formula B.

Additionally, the present invention can provide a reactive black dye composition comprising the reactive red dye composition according to the present invention as a red component. More specifically, the red dye composition can be mixed with a yellow (orange)-based dye and a blue-based dye to produce a black dye composition. In this case, the content of each component can be adjusted to a known composition or an appropriate composition. By modification, it can be adjusted to have colors such as brown, dark blue, purple, and green, or to be dark black.

In addition, the reactive red dye composition according to the present invention may further include additives in an amount of 1% to 50% by weight based on the total weight of the reactive red dye composition, as long as it does not impair the purpose and effect of the present invention. The additive may consist of, for example, electrolyte salts, buffering agents, anti-freezing agents, etc., but is not limited thereto.

In addition, the present invention provides a method for dyeing or printing or digital inkjet printing a textile material containing a hydroxyl group or containing a nitrogen group using a dye composition comprising the reactive red dye composition according to the present invention. You can.

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

Additionally, the reactive red dye composition according to the present invention is suitable as a colorant used in recording systems. Examples of such recording systems include digital inkjet printers or recording devices commercially available for paper or fabric printing, fountain pens, or ballpoint pens.

As described above, in order to use the reactive red 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 suitable forms include water-based ink containing the dye composition as a colorant. You can. The water-based ink can be prepared in a conventional manner by mixing individual components, depending on the purpose.

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

The dyeing method may be used by various methods such as, for example, an adsorption method, a cold pad placement method, a continuous dyeing method, a dip dyeing method, a printing method, or a discharge dyeing method. In detail, the adsorption method and the continuous dyeing method may be used.

Specifically, dyeing by the adsorption method is generally carried out in an aqueous medium, based on 100 parts by weight of the aqueous medium (water), 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, of the reactive red dye composition, and the reaction It 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 examined in more detail through examples and comparative examples related to the preparation of compounds for the dyeing composition of the present invention and the evaluation of the dye composition. However, the scope of protection of the present invention is not limited to the following examples.

<Preparation example of compound for reactive red dye composition>

Preparation Example 1: Synthesis of a compound represented by Formula A-1

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 18.1 g of 2-sulfo-4-(2-sulfatoethylsulfone)aniline, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. , added to the reaction solution and adjusted to 5-10°C and pH 6-7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 70 g of the compound represented by Formula A-1 was prepared by spray drying.

Preparation Example 2: Synthesis of a compound represented by Formula A-2

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.1 g of 4-(2-sulfatoethylsulfone)aniline, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the reaction solution. After adding it, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 67 g of the compound represented by Formula A-2 was prepared by spray drying.

Preparation Example 3: Synthesis of a compound represented by Formula A-3

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 18.1 g of 2-sulfo-5-(2-sulfatoethylsulfone)aniline, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-4-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 70 g of the compound represented by Formula A-3 was prepared by spray drying.

Preparation Example 4: Synthesis of a compound represented by Formula A-4

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.1 g of 3-(2-sulfatoethylsulfone)aniline, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the reaction solution. After adding it, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-4-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 67 g of the compound represented by Formula A-4 was prepared by spray drying.

Preparation Example 5: Synthesis of a compound represented by Formula A-5

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.9 g of 2-methyl-4-(2-sulfatoethylsulfone)aniline, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 68 g of the compound represented by Formula A-5 was prepared by spray drying.

Preparation Example 6: Synthesis of a compound represented by Formula A-6

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.9 g of 2-methyl-5-(2-sulfatoethylsulfone)aniline, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.6 g of 2-methoxy-4-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. Afterwards, the secondary reaction solution is cooled to 15°C, the diazo solution is added, and the temperature is adjusted to 10-15°C and pH 6-7 to obtain a final red solution.

After the reaction was completed, 68 g of the compound represented by Formula A-6 was prepared by spray drying.

Preparation Example 7: Synthesis of a compound represented by Formula B-1

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.1 g of 4-(2-sulfatoethylsulfone)aniline, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the reaction solution. After adding it, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.2 g of 2-aminonaphthalene-4,8-disulfonic acid, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the secondary reaction solution. After cooling to 15 ℃, add diazo solution and adjust the temperature to 10~15 ℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 75 g of the compound represented by Formula B-1 was prepared by spray drying.

Preparation Example 8: Synthesis of a compound represented by Formula B-2

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.1 g of 4-(2-sulfatoethylsulfone)aniline, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the reaction solution. After adding it, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.2 g of 2-aminonaphthalene-1,5-disulfonic acid, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the solution. After cooling to 15℃, add diazo solution and adjust the temperature to 10~15℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 75 g of the compound represented by Formula B-2 was prepared by spray drying.

Preparation Example 9: Synthesis of a compound represented by Formula B-3

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 14.1 g of 3-(2-sulfatoethylsulfone)aniline, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the reaction solution. After adding it, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.2 g of 2-aminonaphthalene-4,8-disulfonic acid, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the secondary reaction solution. After cooling to 15 ℃, add diazo solution and adjust the temperature to 10~15 ℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 75 g of the compound represented by Formula B-3 was prepared by spray drying.

Preparation Example 10: Synthesis of a compound represented by Formula B-4

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, the temperature is adjusted to 5-10°C and pH is 6-7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 15.2 g of 2-aminonaphthalene-4,8-disulfonic acid, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, and then diazotizing the secondary reaction solution. After cooling to 15 ℃, add diazo solution and adjust the temperature to 10~15 ℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 77 g of the compound represented by Formula B-4 was prepared by spray drying.

Preparation Example 11: Synthesis of a compound represented by Formula B-5

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 18.1 g of 2-sulfo-4-(2-sulfatoethylsulfone)aniline, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, adjust the temperature to 5~10℃ and pH to 6~7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 19.3 g of 2-aminonaphthalene-4,6,8-trisulfonic acid, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, followed by secondary dispersion. After cooling the reaction solution to 15℃, add diazo solution and adjust the temperature to 10~15℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 80 g of the compound represented by Formula B-5 was prepared by spray drying.

Preparation Example 12: Synthesis of a compound represented by formula B-6

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, the temperature is adjusted to 5-10°C and pH is 6-7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 19.3 g of 2-aminonaphthalene-3,6,8-trisulfonic acid, diazotization was performed by gradually adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, followed by secondary dispersion. After cooling the reaction solution to 15 ℃, add the diazo solution and adjust the temperature to 10~15 ℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 78 g of the compound represented by Formula B-6 was prepared by spray drying.

Preparation Example 13: Synthesis of a compound represented by Formula B-7

After dispersing 9.3 g of trichlorotriazine using water, a small amount of ice, and a dispersant, a solution of 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dissolved at pH 7 was slowly added dropwise, followed by 5~10 drops. Complete the reaction by adjusting pH to 2~3 at ℃.

After dispersing 15.6 g of 2-methoxy-5-(2-sulfatoethylsulfone)aniline, diazotization was carried out by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst. After adding it to the reaction solution, the temperature is adjusted to 5-10°C and pH is 6-7 to obtain a red solution.

Add 16 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid to the solution and adjust the temperature to 30-50°C and pH 3-5 to complete the secondary reaction.

After dispersing 19.3 g of 2-aminonaphthalene-4,6,8-trisulfonic acid, diazotization was performed by slowly adding a solution of 3.5 g of sodium nitrite dissolved in water while maintaining the temperature below 10°C under a hydrochloric acid catalyst, followed by secondary dispersion. After cooling the reaction solution to 15 ℃, add the diazo solution and adjust the temperature to 10~15 ℃ and pH 6~7 to obtain the final red solution.

After the reaction was completed, 78 g of the compound represented by Chemical Formula B-7 was prepared by spray drying.

<Example 1>

A red dye composition is prepared by mixing 40% by weight of the compound represented by Formula A-1 as a compound corresponding to the above-mentioned Formula A and 60% by weight of the compound represented by Formula B-1 as a compound corresponding to Formula B at room temperature. did.

<Examples 2 to 5>

The method described in Example 1 was followed, but each component was listed in Table 1 below.

<Comparative Examples 1 to 5>

As Comparative Example 1, Reactive Red 195, the most commonly used red dye in the prior art, was used alone, and as Comparative Example 2, a red dye composition was prepared by mixing Reactive Red 195 and Chemical Formula 2, and Comparative Example As 3, a red dye composition was prepared and used by mixing Reactive Red 195 and Chemical Formula 3, and as Comparative Example 4, a red dye composition was prepared and used by mixing Reactive Red 195 and Chemical Formula A-1, and as Comparative Example 5 , a red dye composition was prepared and used by mixing Reactive Red 195 and Chemical Formula B-1.

Compounds of Formula A Compounds of Formula B compound Content (% by weight) compound Content (% by weight) Example 1 Formula A-1 40 Formula B-1 60 Example 2 Formula A-2 35 Formula B-2 65 Example 3 Formula A-3 35 Formula B-3 65 Example 4 Formula A-1 40 Formula B-2 60 Example 5 Formula A-1 45 Formula B-1 55 Comparative Example 1 Reactive Red 195 100 - - Comparative Example 2 Reactive Red 195 40 Formula 2 60 Comparative Example 3 Reactive Red 195 45 Formula 3 55 Comparative Example 4 Reactive Red 195 40 Formula A-1 60 Comparative Example 5 Reactive Red 195 40 Formula B-1 60

<Experimental Example 1: Build-up evaluation>

In order to evaluate the build-up of the reactive red dye compositions of Examples 1 to 5 and Comparative Examples 1 to 5 according to the present invention, each dye and dye composition was subjected to o.w.f. Prepare 1.0% to 9.0% as shown in Table 2 below.

o.w.f.(%) 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 White cloth (g) 10 10 10 10 10 10 10 10 10 water (ml) 100 100 100 100 100 100 100 100 100 Na ₂ SO ₄ (g) 3 4 5 6 7 8 8 8 8 dye (g) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Na ₂ CO ₃ (g) 1.5 1.5 2 2 2 2 2 2 2

Water, white cloth, dye, and Na ₂ SO ₄ were added to the 9 pots corresponding to each example and comparative example as shown in the table, then shaken at 60°C for 20 minutes, and then Na ₂ CO ₃ was added as shown in the table. Shake for another 60 minutes at the same temperature.

After dyeing is completed, take out the sample, wash it thoroughly in cold water, place it in 100 g of water containing 0.5 g of non-ionic surfactant, shake at 100°C for 5 minutes to remove unadhered dye, wash it thoroughly in cold water again, and then dry it. Then, the color was measured and the K/S value for each o.w.f. was measured using a CCM (computer color matching) machine.

Here, the dyeing rate was calculated by setting the reflectance of the darkest dyed cloth among each sample at 80 minutes as the maximum value of 100 and converting the remainder into relative values, which are shown in Table 3 and Figure 1.

K/S value by concentration o.w.f. One 2 3 4 5 6 7 8 9 Example 1 18 36 53 69 82 93 101 107 111 Example 2 19 37 54 70 83 93 102 109 115 Example 3 19 37 54 69 82 93 100 106 110 Example 4 19 37 54 69 82 92 99 104 108 Example 5 18 36 53 69 81 91 99 105 108 Comparative Example 1 17 32 47 58 67 72 83 74 74 Comparative example 2 20 38 52 65 75 82 86 89 89 Comparative Example 3 18 34 49 59 68 72 73 74 75 Comparative Example 4 18 33 48 59 68 72 73 74 75 Comparative Example 5 17 35 49 63 72 80 84 85 85

As a result, as shown in Table 3, the color density value of the samples dyed with the reactive red dye compositions of Examples 1 to 5 according to the present invention was higher than that of the samples dyed with the compositions of Comparative Examples 1 to 5. As the concentration increases (the larger the o.w.f. value), the build-up becomes more excellent. In this way, if the color density of high-concentration dyeing is high compared to low-concentration dyeing, the dyeing time can be shortened, the permeability in dense fabrics is high, and it can have the advantage of being particularly advantageous for low bath ratio dyeing.

<Experimental Example 2: Evaluation of fastness to washing>

Since it is very difficult to achieve the same K/S value in normal dyeing, a difference in dyeing rate of approximately ±5% is generally considered the same. In this experiment, o.w.f. of each comparative example and example. A fastness test was conducted with 3% dye and is shown in Table 4 below.

division Washing fastness
(ISO 105-C06-C2S) Example 1 4 Example 2 4-5 Example 3 4 Example 4 4 Example 5 4 Comparative Example 1 4 Comparative Example 2 3-4 Comparative Example 3 3-4 Comparative Example 4 4 Comparative Example 5 3-4

The higher the number, the faster the fastness rating, the less deterioration or contamination of other fibers. As shown in Table 4 above, the samples dyed with the reactive red dye compositions of Examples 1 to 5 according to the present invention It was found that fastness was excellent on average.

Any simple modification or change of the present invention can be easily implemented by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (10)

A compound represented by the following formula (A); And a compound represented by Formula B; A reactive red dye composition comprising a.
[Formula A]


[Formula B]

In Formula A and Formula B above,
R ₁ is hydrogen or -SO ₃ M,
R ₂ is a methoxy group,
R ₃ is any one substituent selected from the group consisting of hydrogen, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and -SO ₃ M,
M ₁ to M ₈ and M are each the same or different and are independently selected from the group consisting of hydrogen, ammonium group, lithium, sodium and potassium,
Y ₁ to Y ₃ are each the same or different, and are independently substituents represented by structural formula 1 below,
[Structural Formula 1]

In structural formula 1, '*' refers to a binding site that binds to a sulfur atom, and X is a leaving group that can be removed by alkali,
In Formula A, one of SO ₂ Y ₁ and SO ₂ Y ₂ is bonded to the para position of the azo group, and the other is bonded to the meta position of the azo group.
In Formula B, D is one of the naphthalene-based substituents represented by structural formula 2 below,
The content ratio of the compound represented by Formula A and the compound represented by Formula B in the reactive red dye composition ranges from 3:7 to 7:3, based on the weight of each component.
[Structural Formula 2]

'*' in the structural formula 2 refers to a binding site that binds to a nitrogen atom, and M ₉ to M ₁₀ are the same or different, and are independently selected from the group consisting of hydrogen, ammonium group, lithium, sodium and potassium. It is one.
According to paragraph 1,
In structural formula 2 in formula B,
M ₉ to M ₁₀ are each the same or different and are independently selected from the group consisting of hydrogen, lithium, sodium, and potassium.
According to paragraph 1,
In Formula B,
The substituent R ₃ is a reactive red dye composition, characterized in that any one substituent selected from the group consisting of hydrogen, methyl group, methoxy group and -SO ₃ M.
According to paragraph 1,
In Formula A and Formula B above,
_{and _ _ 2} ) A reactive red dye composition, characterized in that it has any one substituent selected from among.
delete According to paragraph 1,
SO ₂ Y ₂ bonded to the phenyl group containing R ₁ is bonded to the para position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group including R ₂ is bonded to the meta position of the azo group. Reactive red dye composition.
According to paragraph 1,
SO ₂ Y ₂ bonded to the phenyl group containing R ₁ is bonded to the meta position of the azo group, and SO ₂ Y ₁ bonded to the phenyl group including R ₂ is bonded to the para position of the azo group. Reactive red dye composition.

delete A reactive black dye composition comprising the reactive red dye composition according to any one of claims 1 to 4 and 6 to 7 as a red component.
Dyeing or printing a textile material containing a hydroxyl group or a nitrogen group using a dye composition containing the reactive red dye composition of any one of claims 1 to 4 and 6 to 7. Or how to do digital inkjet printing.