KR0124474B1 - Black reactive dyes composition - Google Patents

Abstract

Disclosed is a reactive black dye composition which comprises 60-90wt% of one or more of dyes represented by general formula[1 and 40-10wt% of a dye represented by general formula[2 . In these formulae, R1 and R2 each represents atom of hydrogen or methyl group, and methoxy group; M represents atom of hydrogen, Na, Li, or potassium; Z represents atom of hydrogen, halogen, or amino group. This black dye composition has high dyeability of cellulose fibers.

Description

Black Reactive Dye Composition

The present invention is a dark black reactive dye composition when dyed to cellulose fibers, and is useful for dyeing, printing and cold pad dyeing. The present invention relates to a black reactive dye composition having good performance and uniformity and exhibiting excellent fastness in other fiber contamination among laundry fastnesses.

General formula [I] is widely known as a representative reactive black dye, but many researchers have made efforts to improve it due to unsatisfactory refastness and lack of black depth.

(Wherein R ₁ and R ₂ each represent a hydrogen atom, a methyl group, or a methoxy group, and M represents a hydrogen atom or Na, Li, K atoms)

Conventionally, as for the reactive black dye composition for the improvement, the dark black dye composition which mixed the dye of general formula [I] with the orange dye represented by the following general formula [A] is known.

(Wherein R ₁ means hydrogen or an acetyl group, a dichlorotriazinyl group, an arylchlorotriazinyl group)

However, such dye compositions have a relatively deep black color when dyed to cotton fibers, but not only have good leveling properties, but also have white flaws and poor flammability.

On the other hand, Japanese Unexamined Patent Publication (A) Hei 1-2898680 has an orange dye represented by the following general formula [B] in place of the orange dye represented by the general formula [A] and other yellow dyes for color control. The dark black dye composition which mix | blended with typical CI Reactive Black 5 in General formula [I] is disclosed.

Wherein X and Y are hydrogen or sulfonic acid groups, not hydrogen at the same time, either of which represents sulfonic acid groups

This composition also has good black depth, anti-fog, and flame retardancy when dyed to cotton fibers, but has poor defects in anti-radiation and exothermic properties of rayon fibers, and this composition also has limitations in use.

In addition, although similar patents are disclosed in Korean Patent Publication Nos. 90-8468 and 94-2560, there are disadvantages in that washing fastnesses and contamination fastnesses of other fibers are poor.

Therefore, the present inventors have studied for a long time in order to solve these problems, and as a result, by blending a specific orange dye in the formula [I] dye, it can be used regardless of the fiber material such as hemp, cotton, rayon, etc. The inventors have invented a multi-purpose composition which is excellent in anti-staining and printing property on cotton and rayon fibers and which can be used industrially in any dyeing technique such as dyeing, printing, dyeing, cold pad batch, printing, and printing.

That is, it has been found that the object of the present invention can be achieved by blending the dye represented by the general formula [II] with at least one dye represented by the general formula [I].

(Wherein Z represents a hydrogen atom, a halogen atom or an aminoacet group, and A and B each represent a diazo component and A represents the following general formula [A] group.)

Namely, general formula [A] represents 3-aminobenzene-beta-sulfatoethylsulfone and 4-aminobenzene-beta-sulfatoethylsulfone.

B represents the following general formula [B] group.

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, or a methoxy group)

That is, general formula [B] is 3-aminobenzene-beta-sulfatoethylsulfone, 4-aminobenzene-beta-sulfatoethylsulfone, 3-methoxy-4-aminobenzene-beta-sulfatoethyl Sulfone 2,5-dimethoxy-4-aminobenzene-beta-sulfatoethylsulfone, 2-methoxy-5-methyl-4-aminobenzene-beta-sulfatoethylsulfone, 4-methoxy-3- Aminobenzene-beta-sulfatoethylsulfone.

In addition, the composition of the present invention may be used alone or in combination of two or more dyes of the general formula [I] and the dyes of each of the general formulas [A] and [B]. good.

The black dye crystals of the present invention have good build-up and leveling properties when dyed to cellulose fibers such as cotton, hemp and rayon, and are superior to conventional black dye compositions in terms of overall fastness, especially washing fastness, and especially in cotton and rayon. It has good spreadability, and its application is suitable for all fields such as dyeing, cold pad batch, dyeing and printing.

A dark black color was obtained at the composition ratio of 60 to 90% by weight of the general formula [I] dye and 10 to 40% by weight of the general formula [II] dye. May be mixed).

The composition of the present invention is absorbed at around 40 ° C in the presence of neutral salt sodium sulfate or sodium chloride when dyeing cellulose fibers (e.g. cotton, rayon, hemp, etc.) and an alkali binder (e.g. sodium hydroxide, sodium carbonate, bicarbonate) Dyeing at 60 ° C for 1 hour with the addition of sodium, potassium hydroxide, sodium tribenzoate, etc., followed by washing with soap and non-ionic surfactant at 95-100 ° C for 10 minutes, drying and printing After mixing with a paste, an alkalizing agent, an anti-reducing agent and other preparations, the mixture was pre-dried (10 minutes at 95 ° C.) and steamed (10 minutes at 103 ° C.), washed with water, soaped and dried to obtain a dark black chlorine.

For white or flame retardant, a good germination or flame retardant effect was obtained by making and treating a fired arc with long garrit or the like, or by treating a fired arc with Cleantex PWC.

In addition, when dyeing the dye composition of the present invention in cold pad batch dyeing mixed with acid binders, inorganic salts, penetrants and the like (padding), and after the batch is placed on the rollers to stop the stains for more than 3 hours, washed with water, drying treatment The dark black chlorine was obtained by doing the following.

The composition of the present invention is spray-dried the reaction solution, or salted with sodium chloride, sodium chloride, and the like, filtered and then dried and mixed in powder form, or after desalting and stabilization by a reverse osmosis membrane device to prepare a stable liquid dye, and then mix. You may.

Specific embodiments of the present invention by examples are as follows. By part means part by weight.

Example 1

Dissolve 28.1 parts of 4-aminobenzene-beta-sulfatoethylsulfone in 200 parts of water and dissolve in 6 parts of sodium carbonate. After adding ice and cooling to 0-5 DEG C, 25 parts of 35% hydrochloric acid was added, and 24 ml of 30% aqueous 30% sodium nitrite solution was added dropwise over about 30 minutes, followed by stirring for 1 hour to diazotize. When diazotization is complete, sulfamic acid is used to remove excess nitrite.

In a separate vessel, 34.1 parts of NN-di-beta-sulfatoethylaniline are dispersed in 100 parts of ice water. The diazo solution prepared above was added with a dispersion, adjusted to pH 5-6 with sodium bicarbonate, and the coupling was completed. The reaction was completed by salting with chlorine chloride, filtered and dried under vacuum at 60 ° C. to give an orange dye powder 80 Got wealth.

The orange dye powder prepared by a known method and the powder of C.I Reactive Black 5 of the following structural formula

The black dye composition blended in a ratio of 25% to 75% by weight was applied to the cellulose fibers by dyeing, printing, cold pad batch, continuous dyeing, etc. in a well-known method. The dye was excellent in washing fastness.

Example 2

Dissolve 28.1 parts of 3-aminobenzene-beta-sulfatoethylsulfone in 200 parts of water and dissolve in 6 parts of sodium carbonate. After adding ice and cooling to 0-5 DEG C, 25 parts of 35% hydrochloric acid was added, and 24 ml of 30% aqueous 30% sodium nitrite solution was added dropwise over about 30 minutes, followed by stirring for 1 hour to diazotize. When diazotization is complete, sulfamic acid is used to remove excess nitrite.

In a separate vessel, 34.1 parts of NN-di-beta-sulfatoethyl-meth-chloroaniline are dispersed in 100 parts of ice water. The diazo solution prepared above was added with a dispersion, the pH was adjusted to 5-6 with sodium bicarbonate, coupling, and spray drying when the reaction was completed to obtain 95 parts of the following orange dye powder.

In addition, 28.1 parts of 4-aminobenzene-beta-sulfatoethylsulfone are dispersed in 350 parts of water, and 6 parts of sodium carbonate are added to dissolve it. After adding ice and cooling to 0-5 ° C, 25 parts of 35% hydrochloric acid was added, and 24 ml of 30% aqueous sodium nitrite solution was added dropwise over about 30 minutes, followed by stirring for 1 hour to diazotize. When diazotization is complete, sulfamic acid is used to remove excess nitrite.

In a separate vessel, 32.4 parts of H acid was added to 200 parts of water and 6 parts of sodium carbonate to dissolve and stirred for 3 hours to couple, followed by 33.3 parts of 3-methoxy-4-aminobenzene-beta-sulfatoethylsulfone. After diazotization, 20 parts of sodium carbonate was added to terminate the coupling, followed by spray drying to obtain 155 parts of a black powder dye having the following structural formula.

The black dye powder obtained by incorporating the powder of CI Reactive Black 5 and the above-mentioned orange dye powder into the weight ratio of 35%: 45%: 20%, respectively, is immersed in a cellulose fiber by a known method. Dyeing by printing, printing, cold pad batch, continuous dyeing, etc. resulted in a high-depth black, anti-fogging, printing and printing fastness.

Example 3

Dissolve 28.1 parts of 3-aminobenzene-beta-sulfatoethylsulfone in 200 parts of water and dissolve in 6 parts of sodium carbonate. After adding ice and cooling to 0-5 DEG C, 25 parts of 35% hydrochloric acid was added, and 24 ml of 30% aqueous 30% sodium nitrite solution was added dropwise over about 30 minutes, followed by stirring for 1 hour to diazotize. When diazotization is complete, sulfamic acid is used to remove excess nitrite.

In a separate vessel 39.8 parts of NN-di-beta-sulfatoethyl amino acetanilide are dispersed in a bottle of 100 parts. The diazo solution prepared above was added with a dispersion, adjusted to pH 5-6 with sodium bicarbonate, coupling, and the reaction was completed by desalting and concentrating with a reverse osmosis membrane to obtain 250 parts of an orange liquid dye (40% of powder).

The stable liquid black dye composition obtained by mixing the liquid dye obtained in this way with a liquid product of CI Reactive Black 5 (40% of the powder) and a weight ratio of 30%: 70%, respectively, is immersed in a cellulose fiber by a known method. As a result of dyeing by printing, cold pad batch, continuous dyeing, etc., a high-depth black, anti-foaming, printing and printing fastness were obtained.

Example 4-26

By synthesizing the dye represented by the general formula [II] in the same manner as in Examples (1) to (3), and then blending the dye represented by the general formula [I], it is possible to obtain a black color of the various color shades. there was.

Experimental Example 1

The black dye composition obtained in Examples [I] to [26], and the composition of the above general formula [A], Japanese Grain Patent Publication (A) Hei 1-2898680, Korean Patent Publication No. 90-8468, and 94-2560 To dye the cellulose-based fiber as shown in the following table.

As can be seen from the above table, the black reactive dye composition of the present invention was superior in various dyeing properties as compared with the conventionally known black dye composition.

Claims (1)

Black dye composition comprising at least one dye represented by the following general formula [I] 60 to 90% by weight and 40 to 10% by weight dye represented by the general formula [II] (Wherein R₁R₂ represents hydrogen atom or methyl group, methoxy group, M represents hydrogen atom, Na, Li or K atom respectively) (Wherein Z is hydrogen, a halogen atom or an aminoacet group, and M is the same as in general formula [I])