KR960005800B1 - Process for producing reactive black dyes - Google Patents

Abstract

The dye is composed of 60-80wt% compound(I-1), 8-15 wt% compound(I-2) and 12-25 wt% compound(I-3), made by coupling diazo compound obtained from diazofication of aromatic amine(II) compound of 2 mole, 1-amino-8-naphtol-3,6-disulfuric acid(III-1) of 1mole, 1,3-diaminobenzen-4-sulfuric acid of 1mole and 1-aminonaphtalene sulfuric acid of 2mole. The dye doesn't generate precipition in case of storing for long time at low temperature.

Description

Method for preparing reactive black dye

The present invention relates to a method for producing a reactive black dye comprising a compound of the following general formulas (I-1), (I-2) and (I-3) in the form of a free acid and dyed black on cellulose fibers. will be.

The formula (I-1), (I -2) R 1 and R _2, and in (I-3) is hydrogen, methyl group or methoxy group, X is _{-CH 2 CH 2 OSO 3 H,} -CH = CH 3 M and n are integers 0-2 and m + n≥1.

The present invention relates to a method for preparing a new reactive black dye composition, which is an improvement of the method for preparing a reactive black dye, which is proposed in Korean Patent Publication No. 90-8468. To provide.

The method proposed in Korean Patent Publication No. 90-8468 prepares a reactive black dye by reacting 1 mole of 2 or 3-amino-5-natpol-7-sulfonic acid with 1 mole of a compound of Formula (II). In contrast, the present invention is characterized by using a complex of 1-aminonaphthalene-4-sulfonic acid and 1-aminonaphthalene-5-sulfonic acid (compound of formula III) in the following compound of formula (II).

Reactive black dye composition prepared by reacting 1 mole of the compound of the following general formula (III-3) with 1 mole of the compound of the following general formula (II) is wash fastness compared to the dye proposed in Korean Patent Publication No. 90-8468 Not only is excellent (0.5 grade increase) but also shows a significant difference in solubility and color.

The composition of the present invention is excellent in water fastness and washing fastness in terms of color fastness, even if stored for a long time in a low temperature in a liquid state does not generate precipitates and the dye solution is stable and convenient for use in an automatic dyeing device as well as economical in terms of It can be made cheaper than conventional dyes, and has the characteristic of obtaining a high-density powder dye by drying.

In addition, the dye composition of the present invention is obtained by causing a coupling reaction at one time by containing a bifunctional vinyl sulfone group in order to enhance the affinity to the fiber, improve solubility, and increase the absorbency as a fiber reactor.

Hereinafter, the method for preparing the reactive black dye of the present invention will be described in detail.

Hydrochloric acid was added to 2 moles of the aromatic amine compound of the general formula (II) at 0-10 ° C. to diazotize with sodium acetate, and 1-amino-8-naphthol-3,6-disulfonic acid of the following structural formula (III-1) 1 mole, 1 mole of 1,3-diaminobenzene-4-sulfonic acid of the following general formula (III-2), 2 mole of 1-aminonaphthalenesulfonic acid compound of the following general formula (III-3) are adjusted with a neutral aqueous solution. By coupling to the above diazo solution at 5 ~ 15 ℃ and pH adjusted to 5 ~ 6.5 ℃ to obtain the dye composition of the present invention.

In Formulas (II) and (III-3), R ₁ and R ₂ are hydrogen, a methyl group or a methoxy group, X is -CH ₂ CH ₂ OSO ₃ H, -CH = CH ₂ , and m and n are 0 to Is an integer of 2 and m + n ≧ 1.

In the composition of the present invention, the compound composition ratio of the structural formula to be coupled is 60 to 80 wt% of the structural formula (III-1), the structural formula (III-2) is 8 to 15 wt%, and the general formula (III-3) is 12 to 25wt%.

The amine compound of the polyazo compound of the general formula (II) used in the present invention is 1-aminobenzene-3, β-sulfateethylsulfone, 1-aminobenzene-4, β-sulfateethylsulfone, 1-amino-2- Methylbenzene-5, β-sulfateethylsulfone, 1-amino-2-methoxy-5-methylsulfone-4, β-sulfateethylsulfone, 1-amino-4-methoxybenzene-5, β-sulfateethylsulfone , 1-amino-2,5-dimethoxybenzene-4, β-sulfateethylsulfone.

In the present invention, the compound of formula (III-1), which is a coupling component, is 1-amino-8-naphthol-3,6-disulfonic acid, and the compound of formula (III-2) is 1,3-diaminobenzene-4 -Sulfonic acid, and the compound of general formula (III-3) is a complex of 1-aminonaphthalene-4-sulfonic acid and 1-aminonaphthalene-5-sulfonic acid.

The manufacturing method of the 1-amino naphthalene sulfonic acid complex of general formula (III-3) is as follows.

7.15 parts by weight of 1-aminonaphthalene is added to 30 parts by weight and sulfuric acid (98% or more), and the temperature is maintained at 90-120 ° C. for several hours, and then the reaction mass is discharged into water in 100 parts by weight, followed by stirring. Obtained by filtration.

The dye composition of the present invention is present in the form of a free acid or salt (metal salt), and absorbs cellulose fibers such as cotton, hemp, and viscose ray at 30 to 40 ° C. in the presence of a neutral inorganic salt, sodium chloride or sodium sulfate, and is an alkali binder. (For example, sodium hydroxide, sodium carbonate, etc.), when the dye is fixed and dyed, a dark black color can be obtained. If the dyeing method is carried out according to a known method, a black dye with excellent color fastness can be obtained.

Example 1

23.42 parts by weight of 1-aminobenzene-4 and β-sulfate ethyl sulfone were dispersed in 120 parts by weight of water, and 8.84 parts by weight of hydrochloric acid (35%) was added at a temperature of 0 to 5 ° C., and 5.80 parts by weight of sodium acetate was injected. Diazotize. When diazotization is complete, a small amount of sulfamic acid is added to remove excess nitrite.

And then 0.97 parts by weight of separate 1,3-diaminobenzene-4-sulfonic acid and 2.94 parts by weight of 1-aminonaphthalenesulfonic acid complex and 10.72 parts by weight of 1-amino-8-naphthol-3,6-disulfonic acid (MW = 341) was added to 80 parts by weight of water, and 2.60 parts by weight of sodium carbonate was added thereto to make a neutral aqueous solution. The solution was injected into the diazo solution at 5 to 15 ° C. for 30 to 40 minutes, and then the pH was adjusted to 5.5 to 6.5 with sodium carbonate. After the coupling reaction was carried out, the reaction solution was spray dried, and 73 wt% of the compound of formula (I-1), 10 wt% of the compound of formula (I-2), and 17 wt% of compound of formula (I-3). A dye composition was obtained.

Absorption dyeing and printing dyeing are performed on the cellulose fibers of the dye obtained in the presence of an acid binder to obtain a black dye having excellent color fastness.

Example 2

23.42 parts by weight of 1-aminobenzene-3, β-sulfateethylsulfone are dispersed in 120 parts by weight of water, 8.84 parts by weight of hydrochloric acid (35%) is added, and 5.80 parts by weight of sodium acetate are infused to diazotize at 0-5 ° C. .

80 weight parts of 0.97 parts by weight of separate 1,3-diaminobenzene-4-sulfonic acid and 2.94 parts by weight of 1-aminonaphthalenesulfonic acid complex and 10.72 parts by weight of 1-amino-8-naphthol-3,6-disulfonic acid It was added to the negative water, and sodium carbonate was added thereto to make a neutral aqueous solution, and this was injected into the diazo solution at 5 to 15 ° C. for 40 to 50 minutes, and the coupling reaction was performed for several hours while adjusting the pH to 5.5 to 7.0. The same dye composition as in 1 was obtained.

The examples enumerated below were carried out in the same manner as in Examples 1-2.

Claims (2)

To a diazo product diazotized with 2 moles of the aromatic amine compound of formula (II), 1 mole of a compound of formula (III-1) and a compound of formula (III-2), respectively, A method for producing a reactive black dye composition composed of general formulas (I-1), (I-2) and (I-3) obtained by coupling in a bath at 2 molar ratios. In formulas (I-1), (I-2) and (I-3), R ₁ and R ₂ are hydrogen, a methyl group or a methoxy group, and X is —CH ₂ CH ₂ OSO ₃ H, —CH = CH ₂ M and n are integers 0-2, and m + n≥1. Wherein R ₁ and R ₂ are hydrogen, a methyl group or a methoxy group, X is —CH ₂ CH ₂ OSO ₃ H, —CH═CH ₂ , m, n is an integer of 0 to 2, and m + n ≧ 1 to be. The compound of formula (III-1) is 1-amino-8-naphthol-3,6-disulfonic acid, and the compound of (III-2) is 1.3-diaminobenzene-4-sulfonic acid. (III-3) The compound is a 1-aminonaphthalene sulfonic acid complex, and the ratio of the compounds of the general formula (I-1), the general formula (I-2), and the general formula (I-3) is 60 to 80 wt%, respectively. , 8 ~ 15wt%, 12 ~ 25wt% method of producing a reactive black dye composition.