KR100368989B1 - Reactive orange color dyestuff - Google Patents

Abstract

The present invention relates to a dye represented by the following general formula (I) suitable for dyeing cellulose, cellulose / nylon fabric in orange.

(Ⅰ)

In the above formula, D is a benzene or naphthalene amine compound represented by the following general formula (D-1) or (D-2), and R ₁ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, amino group or hydroxide R ₂ , R ₃ are hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group, R ₄ , R ₅ are hydrogen, methyl group, ethyl group, X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ and n is an integer of 0-3.

(D-1)

(D-2)

Description

Reactive orange color dyestuff

The present invention relates to a dye represented by the following general formula (I) suitable for dyeing cellulose, cellulose / nylon fabric in orange.

(Ⅰ)

In the above formula, D is a benzene or naphthalene amine compound represented by the following general formula (D-1) or (D-2), and R ₁ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, amino group or hydroxide R ₂ , R ₃ are hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group, R ₄ , R ₅ are hydrogen, methyl group, ethyl group, X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ and n is an integer of 0-3.

(D-1)

(D-2)

The compound represented by general formula (D-1) is as follows.

1,3-phenylene diamine 4-sulfonic acid

Aniline-o-sulfonic acid

Metanilic acid

Sulfanilic acid

o-toluidine-p-sulfonic acid

5-Aminotoluene-2-sulfonic acid

4-ethylaniline-3-sulfonic acid

Aniline-2,5-disulfonic acid

Aniline-2,4-disulfonic acid

The compound represented by general formula (D-2) is as follows.

2-naphthylamine-1,5-disulfonic acid

2-naphthylamine-4,8-disulfonic acid

2-naphthylamine-5,7-disulfonic acid

2-naphthylamine-6,8-disulfonic acid

2-Amino-5-naphthol-7-sulfonic acid

2-Amino-8-naphthol-6-sulfonic acid

1-amino-5-naphthol-7-sulfonic acid

2-Amino-3-naphthol-6-sulfonic acid

1-naphthylamine-4,6,8-trisulfonic acid

2-naphthylamine-3,6-8-trisulfonic acid

2-naphthylamine-4,6,8-trisulfonic acid

1-naphthylamine-3,6,8-trisulfonic acid

The dye of the present invention is a dye containing monochlorotriazine and vinyl sulfone group or vinyl sulfone group, which has high dyeing strength, excellent wet wash fastness, chlorine fastness, sweat-light fastness, etc., and can be used for both dyeing and printing dyeing. It is wide and there is little staining on other fibers when dyeing fabrics such as cellulose, cellulose / nylon, etc., good dyeing and dyeing are excellent. In addition, it has an excellent feature of wash-off, so it is easy to solve the waste water treatment problem, such as less water consumption when washing the water, less waste water treatment cost.

Orange dyes that are conventionally used for dyeing cellulose or cellulose / nylon fabrics include compounds represented by the following general formulas (II) and (III).

(Ⅱ)

(Ⅲ)

In the above formula, R ₁ , R ₂ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group, X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ and n is an integer of 0-3.

The dyes represented by the general formulas (II) and (III) are also used as ingredients in the preparation of the black dye compositions, wherein the black dyes have a low wash-off property, poor fastness to washing, and when used for dyeing cotton / nylon fabrics, There is a disadvantage that the pollution to the large.

The present inventors have introduced monochlorotriazine and vinyl sulfone groups or vinyl sulfone groups into the molecules of conventional orange reactive dye compounds to increase dye dyeing ability, to improve washing fastness, light fastness and the like and to fabrics such as cellulose / nylon When the dyeing is less contaminated to other fibers and excellent wash-off properties to confirm that can reduce the amount of waste water generated when washing the chlorine to complete the present invention.

The manufacturing method of the reactive dye represented by the said general formula (I) is as follows.

The diazotization of the compound represented by the following general formula (IV)

(Ⅳ)

Wherein R ₂ , R ₃ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group and X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ to be.

The diazonium compound obtained here is coupled with the aromatic amine compound of the following general formula (V)

(Ⅴ)

In the formula, R ₁ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, amino group or hydroxyl group, R ₄ , R ₅ is hydrogen, methyl group, ethyl group and n is an integer of 0-3.

The monoazo compound represented by following General formula (VI) is obtained.

(Ⅵ)

In formula, R ₁ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, imoni group or hydroxyl group, R ₂ , R ₃ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group, R ₄ , R ₅ are hydrogen, methyl, ethyl, X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ and n is an integer of 0-3.

The azo dye represented by the general formula (I) can be prepared by coupling the diazonium compounds represented by the general formula D to the monoazo compound represented by the general formula (VI).

Examples of the aromatic amine compound of the general formula (IV) used in the present invention include the following.

1-aminobenzene-3-β-sulfatoethylsulfone

1-aminobenzene-4-β-sulfatoethylsulfone

1-hydroxybenzene-3-β-sulfoitoethylsulfone

1-hydroxybenzene-4-β-sulphoitoethylsulfone

1-amino-2-methylbenzene-5-β-sulfatoethylsulfone

1-amino-4-methylbenzene-3-β-sulfatoethylsulfone

1-amino-2-methylbenzene-4-β-sulfatoethylsulfone

1-amino-3-methylbenzene-4-β-sulfatoethylsulfone

1-amino-2,5-dimethylbenzene-4-β-sulfatoethylsulfone

1-amino-2-methylbenzene-5-β-sulfatoethylsulfone

1-amino-4-methylbenzene-3-β-sulfatoethylsulfone

1-amino-2-methylbenzene-4-β-sulfatoethylsulfone

1-amino-3-methylbenzene-4-β-sulfatoethylsulfone

1-amino-2-carboxybenzene-5-β-sulfatoethylsulfone

1-amino-2-carboxybenzene-4-β-sulfatoethylsulfone

1-amino-3-carboxybenzene-4-β-sulfatoethylsulfone

1-amino-2,5-dimethoxybenzene-4-β-sulfatoethylsulfone

1-amino-2-ethoxybenzene-5-β-sulfatoethylsulfone

1-amino-2-ethoxybenzene-4-β-sulfatoethylsulfone

1-amino-3-ethoxybenzene-4-β-sulfatoethylsulfone

1-amino-2-methyl-5-methoxy-4-β-sulfatoethylsulfone

1-aminobenzene-3-β-thiosulfatoethylsulfone

1-aminobenzene-4-β-thiosulfatoethylsulfone

1-hydroxybenzene-3-β-thiosulfatoethylsulfone

1-hydroxybenzene-4-β-thiosulfatoethylsulfone

1-amino-2-methylbenzene-5-β-thiosulfatoethylsulfone

1-amino-4-methylbenzene-3-β-thiosulfatoethylsulfone

1-amino-2-methylbenzene-4-β-thiosulfatoethylsulfone

1-amino-3-methylbenzene-4-β-thiosulfatoethylsulfone

1-amino-2,5-dimethylbenzene-4-β-thiosulfatoethylsulfone

1-amino-2-methoxybenzene-5-β-thiosulfatoethylsulfone

1-amino-4-methoxybenzene-3-β-thiosulfatoethylsulfone

1-amino-2-methoxybenzene-4-β-thiosulfatoethylsulfone

1-amino-3-methoxybenzene-4-β-thiosulfatoethylsulfone

1-amino-2-carboxybenzene-5-β-thiosulfatoethylsulfone

1-amino-2-carboxybenzene-4-β-thiosulfatoethylsulfone

1-amino-3-carboxybenzene-4-β-thiosulfatoethylsulfone

1-amino-2,5-dimethoxybenzene-4-β-thiosulfatoethylsulfone

1-amino-2-ethoxybenzene-5-β-thiosulfatoethylsulfone

1-amino-2-ethoxybenzene-4-β-thiosulfatoethylsulfone

1-amino-3-ethoxybenzene-4-β-thiosulfatoethylsulfone

1-amino-2-methyl-5-methoxy-4-β-thiosulfatoethylsulfone

Moreover, the example of General formula (V) as a coupling component is as follows.

m-phenylenediamine

1,3-phenylenediamine-4-sulfonic acid

m-hydroxyaniline

3-Aminomethanesulfonylaminobenzene-4-sulfonic acid

3-hydroxyl-1-aniline-6-sulfonic acid

Hereinafter, the method for preparing the dye compound represented by Formula (I) of the present invention will be described in detail.

The aromatic amine compound represented by the general formula (IV) is diazotized according to a method well known in the art and couples with the general formula (V), which is a coupling component, to pH 2.0 to 7.0 at a temperature of 0 to 25 ° C Ring reaction is carried out to obtain a monoazo compound represented by the general formula (VI). The monoazo compound is adjusted to pH 4.0-9.0 by adding sodium bicarbonate or sodium carbonate, filtered by salting with sodium chloride or potassium chloride. The diazonium product of the aromatic amine compounds of general formula (D) is then subjected to a coupling reaction for several hours with monoazo compound (VI), which is a coupling component, at a pH of 2.0 to 7.0 at a temperature of 0 to 25 ° C. The reaction solution is then adjusted to pH 6.0-7.5, and then filtered by salting out with sodium chloride or potassium chloride to obtain an orange reactive dye composition of general formula (I).

Hereinafter, the specific preparation method of the compound represented by general formula (I) is given in detail.

Herein, "parts" means "parts by weight".

Example 1

<Preparation of a compound represented by the following structural formula (VII)>

(Ⅶ)

1-aminobenzene-4-β-sulfato ethylsulfone of 14.1 was stirred and dispersed in 100 parts of water, and 6 parts of concentrated hydrochloric acid was added thereto and cooled to 0-20 ° C with ice. 3.6 parts of sodium nitrite was made into a 10% aqueous solution, and then slowly added dropwise at the same temperature to diazotize the 1-aminobenzene-4-β-sulfato ethylsulfone. Excess sodium nitrite is removed by adding a small amount of sulfamic acid.

9.4 parts of 1,3-phenylenediamine-4-sulfonic acid was made into 100 parts of a neutral aqueous solution, and added to the diazonium solution. The mixture was adjusted to pH 2.0 to 9.0 with sodium bicarbonate to undergo coupling reaction for several hours.

Again, 12 parts of 2-amino-5-naphthol-7-sulfonic acid are stirred and dispersed in 200 parts of water, and 6 parts of concentrated hydrochloric acid is added to the bath to cool down to 0-20 ° C with ice. 3.6 parts of sodium nitrite is made into a 10% aqueous solution, and then slowly added dropwise at the same temperature to diazotize. Excess sodium nitrite is removed by adding a small amount of sulfamic acid.

An aqueous solution of the above monoazo dye, which is a coupling component, is added to the diazonium product of the crude product, and the mixture is adjusted to pH 4.0-9.0 with sodium bicarbonate for several hours.

The reaction solution was adjusted to pH 6.0-7.5, and the stock solution was spray dried or potassium chloride or sodium chloride was added to separate dyes, filtered, and dried to obtain 52 parts by weight of a red powder dye compound represented by the above formula.

Example 2

<Preparation of a compound represented by the following structural formula (VII)>

(Ⅷ)

12.6 parts of aniline-2,4-disulfonic acid is stirred and dispersed in 100 parts of water, and 6 parts of concentrated hydrochloric acid are added and cooled to 0-20 ° C with ice. 3.6 parts of sodium nitrite is made into a 10% aqueous solution, and then slowly added dropwise at the same temperature to diazotize the aniline 2,4-disulfonic acid. Excess sodium nitrite is removed by adding a small amount of sulfamic acid.

In a separate tank, 9.4 parts of 1,3-phenylenediamine-4-sulfonic acid was made into 100 parts of a neutral aqueous solution, and added to the diazonium solution described above. Obtain an aqueous solution of the dye.

14.1 parts of 1-aminobenzene-4-β-sulfatoethylsulfone was further dispersed and dispersed in 100 parts of water, and 6 parts of concentrated hydrochloric acid was added thereto, followed by cooling with ice at 0 to 20 ° C. 3.6 parts of sodium nitrite is made into a 10% aqueous solution, and then slowly added dropwise at the same temperature to diazotize. Excess sodium nitrite is removed by adding a small amount of sulfamic acid. The diazonium product is added to an aqueous solution of the above monoazo dye which is a coupling component, adjusted to pH 2.0 to 9.0 with sodium bicarbonate, and subjected to a coupling reaction for several hours.

The reaction solution was adjusted to pH 6.0-7.5, and then the stock solution was spray-dried or potassium chloride or sodium chloride was added to separate dyes, filtered, and dried to obtain 52 parts by weight of a dye compound of red powder represented by the above formula.

Printing, dyeing test

The orange dye composition according to the present invention is present in the form of free acid or metal salt, and dyeing or dyeing the cellulose-based fiber gives an orange dye having excellent overall fastness.

Further, by absorbing cellulose fibers at about 60 ° C. in the presence of sodium chloride or sodium sulfate, which is a neutral inorganic salt, and dyeing and dyeing by adding an acid binder sodium carbonate or sodium hydroxide, orange dyeings having excellent fastnesses can be obtained.

As a result of washing fastness with the dye obtained by dyeing or printing dyeing using the dye composition obtained in Example 1 it showed an improved fourth grade than the conventional dye of the third grade.

Application examples of printing dyeing and dyeing dyeing are as follows.

Printing dyeing test example

2 g of the dye composition of the present invention obtained in Example 1, 30 g of sodium alginate, 1 g of sodium bicarbonate, 10 g of urea and water were added to make the whole amount 50 g, followed by mixing and stirring, followed by printing on a cotton cloth. The cloth is dried in a drier, steamed and heat-fixed at 103 to 105 占 폚 for 15 minutes, washed at 100 占 폚 for 10 minutes, washed with water and dried to obtain a bright orange printing dyeing.

Dyeing dye test example

20 ml of a 0.4% dye solution of the dye composition of the present invention obtained in Example 1, 32 ml of water, and 20 ml of 20% sodium sulfate were added to a triangle flask, and 4 g of cotton cloth was added thereto and dyed at 60 ° C. After 30 minutes, 8 ml of 20% sodium carbonate is added and dyed again for 60 minutes. The dyed cloth is washed with boiling water for 10 minutes, washed with water and dried to obtain 2% (o.w.f) dyed cloth. In case of 4% dyeing (o.w.f), 40ml of the same dye composition, 40% of dye solution, 12ml of water, and 20cc of 20% sodium sulfate are added to a triangle flask and the same dyeing process is performed.

As a result of the fastness test with the dyed dyeing as above, the water fastness and washing fastness were 4 to 5 grade, showing high fastness.

The dye of the present invention is a dye containing monochlorotriazine and vinyl sulfone group or vinyl sulfone group, which has high dyeing strength, excellent wet wash fastness, chlorine fastness, sweat-light fastness, etc. It is wide and there is little staining on other fibers when dyeing fabrics such as cellulose, cellulose / nylon, etc., good dyeing and dyeing are excellent. In addition, it has an excellent wash-off, so it is easy to solve the problem of wastewater treatment, such as less water consumption when washing, and less wastewater treatment cost.

Claims (1)

The reactive orange dye represented by the following general formula (I). (Ⅰ) In the above formula, D is a benzene or naphthalene amine compound represented by the following general formula (D-1) or (D-2), and R ₁ is hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, amino group or hydroxide R ₂ , R ₃ are hydrogen, methyl group, ethyl group, methoxy group, ethoxy group or hydroxyl group, R ₄ , R ₅ are hydrogen, methyl group, ethyl group, X is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ SSO ₃ H or -CH ₂ = CH ₂ and n is an integer of 0-3. (D-1) (D-2)