KR100686977B1 - Fiber-reactive dyestuffs and methods for preparing the same - Google Patents

Abstract

A fiber-reactive dyestuff and a method for dyeing fiber using the same are provided to show high adsorbing/fixing ratio and fiber-dyestuff binding stability, deep color expression, and excellent oxidative bleaching-, moisture- and light-fastness, and to be useful for dyeing cellulose fiber. The fiber-reactive dyestuff has a structure represented by the formula (1), wherein A is a C1-C6 alkyl, R1 is hydrogen, a C1-C4 alkyl, a C1-C4 alkoxy or -SO3H; and Y1 is vinyl or a radical of the formula -CH2-Ch2-Q (where, Q is -Cl, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-C6H5, -OSO2-(C1-C4 alkyl) or -OSO2-N(C1-C4 alkyl)2).

Description

Reactive dye compound and preparation method thereof {Fiber-Reactive Dyestuffs and Methods for Preparing the Same}

1 is a graph comparing the dyeing rates of reactive yellow dyes and Comparative Examples 1 and 2 that are compatible with the dye of Example 1 according to the present invention.

The present invention relates to a reactive dye compound and a method for preparing the same, and more particularly, the dyeing is superior to conventional dyes in implementing yellow to cinnabar, and has excellent wettability and fastness to chlorine water, nitrogen and hydride. The present invention relates to a reactive dye compound useful for dyeing fibrous materials, particularly cellulose fibers, comprising a hydroxy group and a process for producing the same.

C.I. of the following formula which is a conventional reactive yellow dye. CI Reactive Yellow 145 is a heterodifunctional yellow dye, which shows good fastness, but does not show sufficient build-up when deep color is implemented, and thus the fastness is lowered because unfixed dye is accumulated after dyeing. There was a problem.

In this regard, Korean Patent Application Publication No. 1989-2348, European Patent Registration No. 0974621, etc., although the accumulating property was slightly improved with the compound of the following formula, chlorine water and oxidation bleaching fastness showed a disadvantage.

Wherein R is hydrogen, methyl or methoxy, and X is an esterifiable reactor by substitution.

In addition, Korean Patent No. 03046148 improves the accumulating ability and increases the chlorine fastness with the following compounds, but still has the disadvantage of poor light fastness.

Wherein R ₁ and R ₂ are each independently hydrogen, methyl or methoxy, X is a leaving group, and A is a substituted or unsubstituted benzene or naphthalene ring without a substituent.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and technical problems that have been requested from the past.

That is, an object of the present invention is to provide a reactive dye having a high fixation rate and a high fiber-dye bonding stability, and at the same time, a dye which is not fixed to the fiber can be easily washed, and has excellent oxidation bleaching and fastness to moisture. To provide.

The inventors of the present application, after continuing in-depth research and various experiments, the new reactive dyes described hereinafter have relatively high build fastness and sufficient build-up when dyeing, compared to conventional compounds. It is possible to realize a deep color even with a small amount of dye, and it is confirmed that it can solve most of the above-mentioned objects, such as not having to put much effort in wastewater treatment because there is not much residual liquid due to excellent adsorption and fixation. It came to the following.

The fiber reactive dye of the present invention according to this object has a structure of the following formula (1).

(1)

(One)

Where

A is C ₁ -C ₆ alkyl;

R ₁ is hydrogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ alkoxy or —SO ₃ H;

Y ₁ is vinyl or a formula —CH ₂ —CH ₂ —Q; Here, Q is _{-Cl, -Br, -F, -OSO 3} H, -SSO 3 H, -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H 5, -OSO 2 - (C 1 ˜C ₄ alkyl) or —OSO ₂ —N (C ₁ -C ₄ alkyl) ₂ .

A is C ₁ ~ C ₂ Alkyl is preferred, and methyl is particularly preferred.

The present invention also provides a method of preparing a reactive dye of formula (1).

For convenience of description, the following Chemical Formula 2, Chemical Formula 3 and Chemical Formula 4 are as follows. R ₁ , A, Y ₁ and the like in the following Chemical Formulas 2, 3, and 4 are the same as those defined in Chemical Formula 1.

[Formula 2]

[Formula 3]

[Formula 4]

Exemplary methods for preparing the compound of Formula 1 are as follows.

First, the compound of formula (2) is diazotized by a known method, and the first coupling reaction with 2,4-diaminobenzenesulfonic acid to prepare a compound of formula (4). On the other hand, after the diazotization of the compound of the formula (3) by a known method, it may be subjected to a second coupling reaction with the compound of the formula (4) to obtain a compound of the formula (1).

The first and second coupling reactions in this step can be carried out in an organic medium, an aqueous medium or an aqueous-organic medium, preferably in the presence of an acid-binder in the aqueous medium. Preferred examples of the acid-binding agent include carbonates, bicarbonates, hydroxides of alkali metals, carbonates of bicarbonate, bicarbonates, hydroxides, alkali metal acetates or mixtures of two or more selected from these, or tertiary amines. Can be mentioned. Preferred examples of the alkali metal and alkaline earth metal include lithium, sodium, potassium, calcium, and the like, and preferred examples of the tertiary amine include pyridine, triethylamine, and quinoline. The coupling reaction can be carried out at -10 to 40 ℃, preferably at 0 to 20 ℃ and pH 1.0 to 8.0.

Various methods for preparing the dye compound of Formula 1 in addition to the above-described method is possible, and even if there is no separate description, those skilled in the art to which the present invention pertains those methods through You will be able to recognize it.

The present invention also provides a method of dyeing a fiber material using the dye of formula (1). The fiber reactive dyes according to the present invention can be used for dyeing fiber materials containing nitrogen or hydroxy groups, and representative examples of such fiber materials include cellulose fibers.

The compounds of formula 1 according to the invention are suitable as dyes for dyeing or printing all types of cellulose fiber materials. Such cellulose fiber materials include, for example, natural cellulose fibers such as cotton, flax, and hemp, pulp and regenerated cellulose, and are particularly suitable for dyeing cotton. The dye compounds of formula 1 according to the invention are also suitable for dyeing or printing cellulose blend fabrics, for example cotton / polyester, cotton / nylon blend fabrics and the like.

In the dye solution, the content of the reactive dye, such as the compound of Formula 1, may vary depending on the desired degree of coloring. The dye compounds according to the invention can be used at 0.01 to 10% by weight, preferably 0.01 to 6% by weight, based on the fabric to be dyed.

The fiber reactive compounds according to the invention are particularly suitable for dyeing by the absorption method.

The dyeing by the adsorption method generally has a weight ratio of water to dye in an aqueous medium of from 1: 2 to 1:60, preferably from 1: 5 to 1:20, from 20 to 105 ° C, preferably from 30 to 90 ° C, more Preferably it is performed at the temperature of 40-80 degreeC.

Other suitable dyeing methods include pad dyeing, in which the fabric is generally immersed in an aqueous solution, saline solution, saline solution or the like. In this case, the pick-up is 20 to 150%, in particular 40 to 120%, preferably 50 to 100% by weight of the fiber material to be dyed. In some cases, the aqueous liquid already contains a fixed alkali, or after impregnation, the fiber material is treated with a fixed alkali. Suitable alkali metals are, for example, mixtures of sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium borate, aqueous ammonia, sodium trichloroacetate or sodium silicate solution, among others alkali hydroxides and alkali carbonates. This is preferred, with sodium hydroxide and sodium carbonate being particularly preferred.

Fixation can be carried out, for example, by means of steaming the impregnated fibrous material at a temperature of 100 to 120 ° C., in particular through thermal action such as saturated steam. Alternatively, the dye can be placed in a padder with alkali and stored at room temperature for several hours, for example 3 to 40 hours, in accordance with a cold pad-batch method. After fixation, a dispersant is added to the dye or printed material as necessary and thoroughly washed.

The dyeings and printings obtained according to the present invention not only have excellent accumulation and levelness, but also have high fixing properties, and non-fixed dyes can be easily washed off, and the difference between adsorption and fixing properties, That means less soap loss. Moreover, the dyeings and printings obtained are excellent in coloration, high in fiber-dye binding stability, and excellent water fastness, wrinkles, ironing and rubbing such as fastness to washing, seawater, cross-dyeing and sweating, etc. The fastness to daylight is also excellent as well.

Although the content of the present invention will be described with reference to the following Examples, the scope of the present invention is not limited thereto.

Example  One

After cooling by adding 32 g of ice to 23.7 g of 4-sulfatoethylsulfone-1-aminobenzene, 7.6 g of sodium nitrite and 31.3 g of hydrochloric acid (35%) were stirred and mixed at 0-5 ° C. and about pH 2 The mixture was stirred for 3 hours to diazotize. After dissolving 15.0 g of 2,4-diaminobenzenesulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5 to 10 ° C. at about pH 6 for about 1 hour. The resulting solution is stirred at 5-10 ° C., about pH 6 for 2 hours to prepare a coupling. 36 g of ice was added to 14.3 g of 6-amino metatoluene sulfonic acid, and then cooled. After cooling, 8.2 g of sodium nitrite and 21.3 g of hydrochloric acid (35%) were mixed and stirred at 5 ° C. and pH 2 for 3 hours to diazotize. The coupling reaction mixture and the diazo body of 6-amino metatoluenesulfonic acid were stirred at 5 to 20 ° C. and pH 6.5 for 2 hours to complete the coupling reaction. The product was dried to give 88.0 g of a compound of formula 5 showing λ _max = 411 nm.

(5)

(5)

Example 2

47 g of ice was added to 37.2 g of 3-sulfatoethylsulfone-6-aminobenzenesulfonic acid, followed by cooling. 15 g of sodium nitrite and 47 g of hydrochloric acid (35%) were stirred and mixed. It was diazotized by stirring for 2 to 3 hours. After dissolving 18.8 g of 2,4-diaminobenzenesulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5-10 ° C., about pH 6, for about 1 hour. The resulting solution is stirred at 5-10 ° C., about pH 6 for 2 hours to prepare a coupling. 36 g of ice was added to 21.5 g of 6-amino metatoluene sulfonic acid, followed by cooling. Then, 8.2 g of sodium nitrite and 21.3 g of hydrochloric acid (35%) were mixed and stirred, and stirred at 5 ° C. and pH 2 for 3 hours to diazotize. The coupling reaction mixture and the diazo compound of 6-amino metatoluenesulfonic acid were stirred at 5 to 20 ° C. and pH 6.5 for 2 hours to complete the coupling reaction. The product was dried to give 95.1 g of a compound of formula 6 showing λ _max = 418 nm.

(6)

(6)

Example 3

After cooling by adding 35 g of ice to 29.5 g of 3-sulfatoethylsulfone-1-aminobenzene, stirring was carried out by mixing 8.5 g of sodium nitrite and 25.3 g of hydrochloric acid (35%) at 0 to 5 DEG C and about pH 2. The mixture was stirred for 3 hours to diazotize. After dissolving 18.8 g of 2,4-diaminobenzenesulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5-10 ° C., about pH 6, for about 1 hour. The resulting solution is stirred at 5-10 ° C., about pH 6 for 2 hours to prepare a coupling. After cooling by adding 30 g of ice to 20.4 g of 6-amino-3-methoxybenzenesulfonic acid, the mixture was stirred and mixed with 8.9 g of sodium nitrite and 26.2 g of hydrochloric acid (35%), followed by stirring at 5 ° C. and pH 2 for 3 hours. Diazotized. The coupling reaction mixture and the diazo compound of 6-amino-3-methoxybenzenesulfonic acid were stirred at 5 to 20 ° C. and pH 6.5 for 2 hours to complete the coupling reaction. The product was dried to give 85.2 g of a compound of formula 7 showing λ _max = 422 nm.

(7)

(7)

Example 4

28 g of ice was added to 23.7 g of 2-methoxy-4-sulfatoethylsulfone-1-aminobenzene and cooled, followed by stirring and mixing 8.5 g of sodium nitrite and 25.3 g of hydrochloric acid (35%), followed by mixing at 0 to 5 ° C. And diazotized by stirring at about pH 2 for 3 hours. After dissolving 18.8 g of 2,4-diaminobenzenesulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5-10 ° C., about pH 6, for about 1 hour. The resulting solution is stirred at 5-10 ° C., about pH 6 for 2 hours to prepare a coupling. After cooling by adding 30 g of ice to 20.4 g of 6-amino-3-methoxybenzenesulfonic acid, the mixture was stirred and mixed with 8.9 g of sodium nitrite and 26.2 g of hydrochloric acid (35%), followed by stirring at 5 ° C. and pH 2 for 3 hours. Diazotized. The coupling reaction mixture and the diazo compound of 6-amino-3-methoxybenzenesulfonic acid were stirred at 5 to 20 ° C. for about 2 hours to complete the coupling reaction. The product was dried to give 89.8 g of a compound of Formula 8 showing λ _max = 427 nm.

(8)

(8)

Example  5 to 84

Based on the above examples, it was possible to synthesize the compounds of Examples 5 to 84 described in Table 1 below, their specific preparation method can be sufficiently expected through the examples based on the chemical structure of the product Therefore, detailed description thereof will be omitted.

For convenience of description, the following Chemical Formula 9 is provided to indicate D ₂ , and Table ₂ describes D ₂ in each example.

(9)

(9)

Experimental Example  : Measurement of dyeing intensity by adsorption dyeing method

The dyes of Comparative Example 1 and Comparative Example 2, C.I. Reactive Yellow 145 and the dye of Example 1 were used to dye each other under the same conditions by the above-mentioned adsorption method, and the dyeing strengths of the dyes stained at the above conditions were measured and compared. The result is shown in FIG.

Comparative Example 1

Comparative Example 2

As can be seen in Figure 1, the dye of Example 1 according to the present invention is C.I. It was confirmed that the dyeing strength is superior to the dyes of Reactive Yellow 145 and Comparative Examples 1 and 2.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

As described above, the novel compounds according to the present invention are dyes having very good fiber reactivity properties, and are effective for dyeing and printing fiber materials, especially cellulose fiber materials by fixing methods commonly used in the field of fiber reactive dyes. It has excellent adsorption / settling rate and very good fastness to oxidative bleaching and wet treatment.

Claims (4)

A fiber reactive dye having the structure of Formula 1

(One) Where A is C ₁ to C ₆ Alkyl, R ₁ is hydrogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ alkoxy or —SO ₃ H; Y ₁ is vinyl or a formula —CH ₂ —CH ₂ —Q; Here, Q is _{-Cl, -Br, -F, -OSO 3} H, -SSO 3 H, -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H 5, -OSO 2 - (C 1 ˜C ₄ alkyl) or —OSO ₂ —N (C ₁ -C ₄ alkyl) ₂ . The fiber reactive dye according to claim 1, wherein R ₁ is hydrogen, sulfonic acid or methoxy. The fiber reactive dye according to claim 1, wherein A is methyl. A method of dyeing a fiber material containing nitrogen or a hydroxyl group using the reactive dye compound of formula 1 according to any one of claims 1 to 3.

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